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Pd was deposited using a Na2CO3 solution followed by the addition of Na2PdCl4, heated to evaporate water, calcined, and reduced with NaBH4.","phase":"Cubic zirconia support phase; metallic Pd nanoparticles.","particleSize":"5.2 ± 1.2 nm (fresh); 5.9 ± 0.9 nm (used)","surfaceStates":"Pd0 and Pd2+ species identified; both are noted as required to activate the catalytic reaction.","structureLink":"Sintering at 1200 °C provided an optimal balance between high porosity (86%) for anchoring Pd nanoparticles and compressive strength (3.7 MPa) for stability in a fixed-bed reactor.","reactionConditions":"Continuous dehydrogenation of formic acid (FA) in a fixed-bed reactor.","selectivity":"CO-free H2; H2 and CO2 were the unique species detected; H2/CO2 molar ratio ~ 1.2","stability":"Activity decreased from 1 h of operation, completely deactivated after 3 h on stream; activity restored after drying at 60 °C overnight (2nd use)","deactivation":"Fouling of Pd active sites by water and FA (or HCOO- species); slight loss of Pd loading from 5.0 to 4.5 wt%","whyPerformsWell":"Presence of both Pd0 and Pd2+ species; robust structured catalyst conformation reduces pressure drop compared to powders","metricCount":"2"},{"paperId":"P003","catalystId":"P003_PERF_001","name":"3D Pd/AC","support":"activated carbon (AC) and alumina (Al2O3)","matchedSynthesis":"3D Pd/AC","matchedCharacterization":"3D Pd/AC","role":"catalyst for the dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"3D AC supports were submerged in a PdCl2/HCl solution, evaporated at 95 °C, washed with Milli-Q water, dried at 60 °C, and reduced under H2/N2 stream.","phase":"Pd0 and PdO","particleSize":"1.9 ± 0.4 nm (fresh); increased to 2.8 nm after 5th use at 25 °C and 4.4 nm after 5th use at 55 °C.","surfaceStates":"Pd0 (335.9 and 341.1 eV) and Pd2+ (337.6 and 342.8 eV, ascribed to PdO); fresh catalyst Pd2+/Pd0 ratio was ~1.4.","structureLink":"The progressive reduction of Pd2+ species into Pd0 with time-on-stream is identified as the main factor responsible for permanent loss of activity; particle agglomeration occurred but had less impact on performance than the change in oxidation state.","reactionConditions":"Fixed-bed reactor, continuous mode, spatial time (s) = 160 gCAT hL-1, carrier gas He at 17 N mL min-1, ambient pressure (1 atm), liquid flow rate (QL) = 0.25 mL min-1","selectivity":"100% selective for the dehydrogenation of FA; CO-free hydrogen produced","stability":"Good catalytic stability and recyclability. Activity could be totally recovered after 1st use via dry treatment at 60 °C. Irreversible deactivation observed from 4th use at 25 °C and 3rd use at 55 °C.","deactivation":"No Pd leaching detected in aqueous effluent. Deactivation caused by progressive reduction of Pd2+ species into Pd0 with time-on-stream and agglomeration of Pd nanoparticles (particle size increased from 1.9 nm to 2.8-4.4 nm).","whyPerformsWell":"High porosity (86%), small Pd particle size (~2 nm), and high Pd2+/Pd0 ratio (1.4) in fresh catalyst.","metricCount":"6"},{"paperId":"P004","catalystId":"P004_PERF_001","name":"Pd0.8Au0.2/1'","support":"MOF 1' ([(CH3)2NH2][Cd(L)])","matchedSynthesis":"Pd0.8Au0.2/1'","matchedCharacterization":"Pd0.8Au0.2/1'","role":"Catalyst for formic acid dehydrogenation","composition":"Pd:Au = 0.8:0.2 (molar ratio)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of MOF 1' in n-hexane with aqueous metal precursors, followed by vacuum drying and liquid-phase reduction using NaBH4.","phase":"Fresh catalyst shows no distinct alloy peaks due to high dispersion; spent catalyst exhibits an alloy structure signal at 39.1° (between Au and Pd characteristic peaks).","particleSize":"0.8 nm to 2.3 nm (fresh); 2.2 nm to 6.8 nm (spent)","surfaceStates":"Electron transfer from support to metal NPs indicated by shift in N 1s XPS binding energy from 398.75 eV (pristine 1') to 400.30 eV.","structureLink":"High activity is attributed to the high surface area of the MOF support, ultra-small particle size, alloying effect of Au on Pd electronic structure, and Lewis basic N sites promoting FA activation.","reactionConditions":"Dehydrogenation of formic acid at 333 K","selectivity":"No CO detected; H2 and CO2 generated with a 1:1 volume ratio","stability":"Activity decreased after the fourth run at 333 K","deactivation":"Aggregation of metal NPs (size increased from 2.2 nm to 6.8 nm)","whyPerformsWell":"High surface area (527 m2 g-1) for NP encapsulation; double-solvent method ensures tiny NPs; uncoordinated N atoms act as Lewis base sites promoting HCOO- generation and anchor PdAu NPs; alloying effect of PdAu modifies electronic structure of Pd","metricCount":"2"},{"paperId":"P005","catalystId":"P005_PERF_001","name":"Pd/BPC (optimal: C:B ratio 1:5, calcined at 900 °C, reduced at 60 °C)","support":"Boron-Doped Porous Carbon (BPC)","matchedSynthesis":"Pd/BPC","matchedCharacterization":"Pd/BPC","role":"main catalyst","composition":"Pd; precursor to support ratio 1:9","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Porous carbon (PC) was synthesized from petroleum asphalt using alpha-Fe2O3 as a template at 800 °C. BPC was prepared by calcining PC and boron acid (1:5 ratio) at 900 °C under N2. Pd nanoparticles were then loaded onto BPC via reduction of palladium acetate in methanol at 60 °C.","phase":"Pd crystal planes (111), (200), and (220) identified by XRD (JCPDS No. 88-2335).","particleSize":"3.6 nm","surfaceStates":"XPS shows C-B bonds at 283.8 eV. Pd 3d XPS peaks at 335.7/341.0 eV (Pd(0)) and 337.2/342.5 eV (Pd2+). DFT indicates strong charge transfer between B and C atoms regulates metal-support interaction, reducing electron density of Pd 3d orbitals.","structureLink":"Boron doping induces a stronger support-metal interaction (adsorption energy -1.10 eV) compared to undoped or N-doped carbon, optimizing the electronic density of Pd and facilitating homogeneous nanoparticle distribution for enhanced formic acid dehydrogenation.","reactionConditions":"50 °C water bath, 30 mg catalyst, 10 mL deionized water, 1 mL sodium formate solution (5 mol/L), 90 min reaction time","selectivity":"no poisonous CO gas produced","stability":"excellent recyclability with no significant reduction after five consecutive cycles","deactivation":"slight reduction in performance due to catalyst loss during filtration recovery","whyPerformsWell":"Boron doping facilitates homogenous distribution of Pd nanoparticles and induces a stronger support-metal interaction, modifying electronic properties (reduction of electron density of Pd 3d orbitals) and preventing agglomeration/sintering. DFT calculations show higher adsorption energy of Pd on B-graphene (-1.10 eV) compared to N-graphene and undoped graphene.","metricCount":"1"},{"paperId":"P005","catalystId":"P005_PERF_002","name":"Pd/PC","support":"Porous Carbon (PC)","matchedSynthesis":"Pd/PC","matchedCharacterization":"Pd/PC","role":"control sample","composition":"Pd; precursor to support ratio 1:9","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar to Pd/BPC but without the boron doping step for the support.","phase":"Pd crystal planes (111), (200), and (220) identified by XRD.","particleSize":"Larger than Pd/BPC","structureLink":"Lack of boron doping results in larger particle size and weaker metal-support interaction, leading to lower catalytic activity than Pd/BPC.","reactionConditions":"50 °C water bath, 30 mg catalyst, 10 mL deionized water, 1 mL sodium formate solution (5 mol/L), 90 min reaction time","metricCount":"1"},{"paperId":"P005","catalystId":"P005_PERF_003","name":"commercial Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"50 °C water bath, 30 mg catalyst, 10 mL deionized water, 1 mL sodium formate solution (5 mol/L), 90 min reaction time","metricCount":"1"},{"paperId":"P005","catalystId":"P005_PERF_004","name":"Pd/NPC","support":"Nitrogen-Doped Porous Carbon (NPC)","matchedSynthesis":"Pd/NPC","matchedCharacterization":"Pd/NPC","role":"comparison sample","composition":"Pd; precursor to support ratio 1:9","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar to Pd/BPC, but urea was used instead of boron acid for the support doping step.","surfaceStates":"DFT suggests N-doping increases charge density on surrounding C atoms, promoting electronic interaction between Pd and C.","structureLink":"N-doping improves performance over Pd/PC but is less effective than B-doping due to lower adsorption energy (-0.49 eV vs -1.10 eV).","reactionConditions":"50 °C water bath, 30 mg catalyst, 10 mL deionized water, 1 mL sodium formate solution (5 mol/L), 90 min reaction time","metricCount":"1"},{"paperId":"P006","catalystId":"P006_PERF_001","name":"Pd/NMP-360-t","matchedCharacterization":"Pd/NMP-360","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Monometallic Pd","particleSize":"2.3 ± 0.5 nm","reactionConditions":"FA dehydrogenation in a two-necked round-bottomed flask (10 mL) under ambient atmosphere","metricCount":"1"},{"paperId":"P006","catalystId":"P006_PERF_002","name":"Pd1Au1/16-NMP-360-t","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation in a two-necked round-bottomed flask (10 mL) under ambient atmosphere","metricCount":"1"},{"paperId":"P006","catalystId":"P006_PERF_003","name":"Pd1Au1/8-NMP-360-t","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation in a two-necked round-bottomed flask (10 mL) under ambient atmosphere","metricCount":"1"},{"paperId":"P006","catalystId":"P006_PERF_004","name":"Pd1Au1/4-NMP-360-t (powder)","matchedCharacterization":"Pd1Au1/4/NMP-360","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Alloy phase; XRD shows a broad symmetric diffraction peak between Pd and Au peaks; HRTEM interplanar spacing is 0.23 nm (larger than Pd(111) at 0.22 nm).","particleSize":"2.5 ± 0.5 nm","surfaceStates":"XPS shows negative shifts in binding energy for both Au 4f and Pd 3d levels, indicating electron transfer between Pd and Au (Pd gains d electrons).","structureLink":"Enhanced catalytic performance in formic acid dehydrogenation compared to monometallic analogues is attributed to the electronic interaction/synergistic effect between Pd and Au.","reactionConditions":"FA dehydrogenation in a two-necked round-bottomed flask (10 mL) under ambient atmosphere","selectivity":"no detectable CO found, excellent H2 selectivity","whyPerformsWell":"electronic interaction between Pd and Au in the bimetallic PdAu nanoparticles","metricCount":"4"},{"paperId":"P006","catalystId":"P006_PERF_005","name":"Pd1Au1/2-NMP-360-t","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation in a two-necked round-bottomed flask (10 mL) under ambient atmosphere","metricCount":"1"},{"paperId":"P006","catalystId":"P006_PERF_006","name":"monolithic Pd1Au1/4-NMP-360-t","matchedCharacterization":"Pd1Au1/4/NMP-360","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Alloy phase; XRD shows a broad symmetric diffraction peak between Pd and Au peaks; HRTEM interplanar spacing is 0.23 nm (larger than Pd(111) at 0.22 nm).","particleSize":"2.5 ± 0.5 nm","surfaceStates":"XPS shows negative shifts in binding energy for both Au 4f and Pd 3d levels, indicating electron transfer between Pd and Au (Pd gains d electrons).","structureLink":"Enhanced catalytic performance in formic acid dehydrogenation compared to monometallic analogues is attributed to the electronic interaction/synergistic effect between Pd and Au.","reactionConditions":"FA dehydrogenation in a two-necked round-bottomed flask (10 mL) under ambient atmosphere","stability":"recycled five times without considerable changes in activity","whyPerformsWell":"coral-like structure allows molding into monolith without binders; abundant macropores benefit mass transfer","metricCount":"1"},{"paperId":"P007","catalystId":"P007_PERF_001","name":"Ag@Pd/N-GCNT aerogel (optimized as Ag1@Pd1)","support":"nitrogen-doped graphene carbon nanotube (N-GCNT) aerogel","matchedSynthesis":"Ag@Pd/N-GCNT aerogel","matchedCharacterization":"Ag@Pd/N-GCNT aerogel","role":"catalyst for the dehydrogenation of formic acid","composition":"Ag:Pd molar ratios of 1:1, 1:2, and 2:1","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"sequential_impregnation","synthesis":"N-GCNT aerogel and AgNO3 were dissolved in ethylene glycol and heated to 120 °C under N2 for 30 min; then a solution of PdCl2 in ethylene glycol was added and the mixture was heated to 90 °C for 2 h under N2.","phase":"Ag core Pd shell structure with face-centered cubic (fcc) phase; XRD pattern is described as Pd-like.","particleSize":"3–12 nm","surfaceStates":"Metallic Pd (Pd 3d5/2 at 335.2 eV, Pd 3d3/2 at 340.0 eV) and metallic Ag (Ag 3d5/2 at 367.6 eV, Ag 3d3/2 at 374.1 eV).","structureLink":"The N-GCNT aerogel support enhances activity by inhibiting aggregation through strong metal-support interactions and providing anchoring points via nitrogen doping. A synergistic effect exists between Ag and Pd due to electronic promotion and charge transfer from Ag to Pd.","reactionConditions":"Dehydrogenation of formic acid in aqueous solution, 3 mg catalyst, 1.5 mL of 1 mmol/mL FA solution, 2 mL distilled water","selectivity":"Excellent H2 selectivity; generation of only CO2 and H2 (1:1 ratio); no CO detected by GC spectrum","stability":"No significant change in catalytic efficiency after four runs","deactivation":"Heterogeneous nature confirmed; Ag and Pd contents in filtrate were below the detection limit of AAS","whyPerformsWell":"Synergistic effect between Ag and Pd (electronic promotion and charge transfer from Ag to Pd); N-GCNT aerogel support prevents nanoparticle aggregation, provides high surface area/porosity, and weakly basic amino groups facilitate OH bond cleavage of FA","metricCount":"4"},{"paperId":"P007","catalystId":"P007_PERF_002","name":"support-free Ag@Pd nanoparticles","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Dehydrogenation of formic acid in aqueous solution","whyPerformsWell":"Decreased efficiency compared to supported catalyst due to lack of immobilization and increased aggregation","metricCount":"1"},{"paperId":"P008","catalystId":"P008_PERF_001","name":"PdMg","matchedSynthesis":"PdMg","matchedCharacterization":"PdMg","role":"catalyst for formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-step replacement reaction where Mg powder is added to a Pd(NO3)2 solution at room temperature, followed by acid treatment to remove residual Mg.","phase":"Face-centered-cubic (fcc) palladium","particleSize":"5 nm to 20 nm; primary nanoparticles fused into larger particles in the range of 10-20 nm","surfaceStates":"Presence of steps, corners, kinks, and edges with lower coordination atoms; specific surface area of 36.0 m2/g","structureLink":"The larger nanopores compared to PdHCOONa provide a larger surface area and more active sites that benefit O-H bond dissociation.","reactionConditions":"Room temperature (ca. 25 °C), aqueous solution of 6.64 mol/L HCOOH and 3.32 mol/L HCOONa","selectivity":"CO content in reformed gases was 17.18 mg/m3; decomposition mainly proceeded via HCOOH -> H2 + CO2","stability":"Reused for 3 cycles; activity reduced slightly in the 2nd and 3rd cycle but not changed obviously overall","deactivation":"Reduced catalytic activity may be attributed to Pd active sites being poisoned during the initial run","whyPerformsWell":"Spongelike structure with larger nanopores providing more active sites that benefit O-H bond dissociation and subsequent C-H bond cleavage","metricCount":"3"},{"paperId":"P008","catalystId":"P008_PERF_002","name":"PdNaBH4","matchedSynthesis":"PdNaBH4","matchedCharacterization":"PdNaBH4","role":"catalyst for formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-step reduction of Pd(NO3)2 solution using NaBH4 at room temperature.","phase":"Face-centered-cubic (fcc) palladium","particleSize":"5 nm to 20 nm; contains small nano-sized grains","surfaceStates":"Presence of steps, corners, kinks, and edges; interplanar fringes of 0.225 nm corresponding to (111) planes","structureLink":"Larger nanopores compared to PdHCOONa may lead to larger surface areas and more active sites for O-H bond dissociation.","reactionConditions":"Room temperature (ca. 25 °C), aqueous solution of 6.64 mol/L HCOOH and 3.32 mol/L HCOONa","whyPerformsWell":"Larger nanopores compared to PdHCOONa catalyst","metricCount":"1"},{"paperId":"P008","catalystId":"P008_PERF_003","name":"PdHCOONa","matchedSynthesis":"PdHCOONa","matchedCharacterization":"PdHCOONa","role":"catalyst for formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-step reduction of Pd(NO3)2 solution using HCOONa at room temperature.","phase":"Face-centered-cubic (fcc) palladium","particleSize":"5 nm to 20 nm; nanoparticles are relatively big and dense compared to PdNaBH4","surfaceStates":"Presence of steps, corners, kinks, and edges; interplanar fringes of 0.225 nm corresponding to (111) planes","structureLink":"Smaller nanopores and denser nanoparticles result in lower catalytic activity compared to PdMg and PdNaBH4.","reactionConditions":"Room temperature (ca. 25 °C), aqueous solution of 6.64 mol/L HCOOH and 3.32 mol/L HCOONa","deactivation":"Distinct deactivation effect after 20 min, possibly due to formation of poisoning intermediates on the catalyst surface","whyPerformsWell":"Lower activity compared to PdMg and PdNaBH4 due to smaller nanopores and more closely packed ligament-pore network structure","metricCount":"1"},{"paperId":"P009","catalystId":"P009_PERF_001","name":"Ag1Pd9–(MnOx)1.5/A-CS","matchedCharacterization":"Ag1Pd9–(MnOx)1.5/A-CS","activeMetals":"Ag-Pd-Mn","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"AgPd alloy (fcc structure confirmed by XRD diffraction peak between Ag(111) and Pd(111), and HRTEM lattice spacing of 0.23 nm)","particleSize":"< 5 nm","surfaceStates":"Ag: Ag0 (3d5/2 at 367.75 eV); Pd: Pd0 (3d5/2 at 335.78 eV) and Pd2+ (3d5/2 at 337.78 eV); Mn: Mn2+ (2p3/2 at 640.3 eV), Mn3+ (2p3/2 at 641.6 eV), and Mn4+ (2p3/2 at 642.8 eV). Negative binding energy shifts for Ag 3d and Pd 3d indicate electron transfer from Ag to Pd.","structureLink":"MnOx acts as a CO-sponge enhancing activity and CO-resistivity; alloy formation and ultrafine particle size (< 5 nm) are critical for high catalytic activity; air activation preserves spherical morphology and oxygen-containing functional groups which benefit performance.","reactionConditions":"Dehydrogenation of formic acid (FA) in aqueous solution with potassium formate (PF) additive, conducted in a 25 mL round-bottom flask in a water bath.","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 82% of initial catalytic activity and provided 95% conversion after the fifth consecutive cycle/run.","deactivation":"No leaching of metals into the solution (determined by ICP-AES).","whyPerformsWell":"MnOx nanoparticles act as CO-sponges enhancing catalytic activity and CO-resistivity; air activation maintains spherical morphology and provides more oxygen-containing functional groups.","metricCount":"3"},{"paperId":"P009","catalystId":"P009_PERF_002","name":"Ag1Pd9–(MnOx)1.5/K-CS","activeMetals":"Ag-Pd-Mn","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Same as Ag1Pd9–(MnOx)1.5/A-CS","whyPerformsWell":"Lower activity than A-CS due to destruction of spherical structure during KOH activation and metal particle aggregation.","metricCount":"0"},{"paperId":"P009","catalystId":"P009_PERF_003","name":"Ag1Pd9/A-CS","activeMetals":"Ag-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Same as Ag1Pd9–(MnOx)1.5/A-CS","whyPerformsWell":"Lower activity than Ag1Pd9–MnOx/A-CS because it lacks the CO-sponge effect of MnOx.","metricCount":"0"},{"paperId":"P010","catalystId":"P010_PERF_001","name":"Pd/NH2-KIE-11-k","support":"NH2-functionalized mesoporous silica (NH2-KIE-11)","matchedSynthesis":"Pd/NH2-KIE-11","matchedCharacterization":"Pd/NH2-KIE-11-k","role":"formic acid dehydrogenation catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KIE-11 support was functionalized with APTMS, impregnated with palladium(II) nitrate hydrate solution, and reduced using aqueous NaBH4.","phase":"Pd nanoparticles","particleSize":"1.60 nm","structureLink":"Highest catalytic activity (TOF: 860.7 mol H2 mol Pd-1 h-1) due to a trade-off pore structure providing both easy diffusion of molecules and confinement of active metal nanoparticles to suppress aggregation","reactionConditions":"Additive-free dehydrogenation of formic acid at room temperature in a 100 mL Teflon-lined reactor.","selectivity":"volumetric ratio of H2 to CO2 was 50.9:49.1; CO not detected (<10 ppm)","whyPerformsWell":"Trade-off pore structure between easy diffusion of molecules and confinement of active metal nanoparticles (Pd particle size 1.60 nm).","metricCount":"1"},{"paperId":"P010","catalystId":"P010_PERF_002","name":"Pd/NH2-KIE-11-c","support":"NH2-functionalized mesoporous silica (NH2-KIE-11)","matchedSynthesis":"Pd/NH2-KIE-11","matchedCharacterization":"Pd/NH2-KIE-11-c","role":"formic acid dehydrogenation catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KIE-11 support was functionalized with APTMS, impregnated with palladium(II) nitrate hydrate solution, and reduced using aqueous NaBH4.","phase":"Pd nanoparticles","particleSize":"1.75 nm","structureLink":"Lower catalytic activity compared to Pd/NH2-KIE-11-k due to small pore size restricting easy diffusion of reactant and product molecules","reactionConditions":"Additive-free dehydrogenation of formic acid at room temperature in a 100 mL Teflon-lined reactor.","whyPerformsWell":"Pore size did not provide easy diffusion of reactant and product molecules.","metricCount":"1"},{"paperId":"P010","catalystId":"P010_PERF_003","name":"Pd/NH2-KIE-11-l","support":"NH2-functionalized mesoporous silica (NH2-KIE-11)","matchedSynthesis":"Pd/NH2-KIE-11","matchedCharacterization":"Pd/NH2-KIE-11-l","role":"formic acid dehydrogenation catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KIE-11 support was functionalized with APTMS, impregnated with palladium(II) nitrate hydrate solution, and reduced using aqueous NaBH4.","phase":"Pd nanoparticles","particleSize":"2.58 nm","structureLink":"Lowest catalytic activity due to increased Pd nanoparticle size and aggregation resulting from lack of confinement in the large pores of KIE-11-l","reactionConditions":"Additive-free dehydrogenation of formic acid at room temperature in a 100 mL Teflon-lined reactor.","whyPerformsWell":"Large pore size did not give the confinement effect of active metal nanoparticles, resulting in increased Pd nanoparticle size (2.58 nm) and aggregation.","metricCount":"1"},{"paperId":"P011","catalystId":"P011_PERF_001","name":"Pd1Au2/AC-LA","support":"active carbon (AC)","matchedSynthesis":"Pd1Au2/AC-LA","matchedCharacterization":"Pd1Au2/AC-LA","role":"active catalyst for ambient hydrogen storage and release","composition":"Pd:Au = 1:2","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"L-arginine was dissolved in water, followed by the addition of active carbon and sonication for 10 min. An aqueous solution of Na2PdCl4 and AuCl3 was slowly added to the mixture. After 1 hour, a fresh NaBH4 solution was rapidly added under magnetic stirring for 25 min. The product was centrifuged, washed with water, and vacuum dried.","phase":"Uniform PdAu alloy","particleSize":"5.2 nm","surfaceStates":"Pd and Au peaks shift to lower binding energies compared to monometallic catalysts, indicating electron transfer from the support and L-arginine (LA) to PdAu NPs; Pd becomes more electron-rich as Au content increases.","structureLink":"Synergistic effect between PdAu alloy and basic LA regulates reactant adsorption. Lewis acidity of Au adsorbs lone-pair electrons of bicarbonate intermediate, while electron-rich Pd facilitates nucleophilic attack on the positive C atom of bicarbonate. The guanidine group of LA enhances CO2 capture and activation.","reactionConditions":"Ambient conditions (25 °C, 0.1 MPa)","selectivity":"100% selectivity to H2; no CO detected","stability":"After 3 cycles of consecutive hydrogen storage and release, TOF for hydrogenation was 111 h⁻¹ and TOF for dehydrogenation was 1669 h⁻¹","deactivation":"No obvious loss of Pd (before: 1.96 wt %, after: 1.87 wt %) and Au (before: 6.38 wt %, after: 6.07 wt %)","whyPerformsWell":"Synergistic effect between PdAu alloy and strongly basic L-arginine; LA enhances adsorption/activation of CO2 and FA via guanidine and amino groups; Au increases Lewis acidity to adsorb bicarbonate intermediates, while electron-rich Pd accelerates formation of nucleophilic Pd-H species.","metricCount":"2"},{"paperId":"P011","catalystId":"P011_PERF_002","name":"PdAu/AC-LA (various ratios)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"NaHCO3 (1 M, 10 mL), catalyst (10 mg), CO2:H2 (25%:75%, 0.1 MPa), 25 °C, 12 h","metricCount":"6"},{"paperId":"P011","catalystId":"P011_PERF_003","name":"PdAu/AC","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"NaHCO3 (1 M, 10 mL), catalyst (10 mg), CO2:H2 (25%:75%, 0.1 MPa), 25 °C, 12 h","metricCount":"1"},{"paperId":"P012","catalystId":"P012_PERF_001","name":"Pd-La(OH)3/N-PCB-NH2","support":"amine-functionalized N-doped porous carbon bowl (N-PCB-NH2)","matchedSynthesis":"Pd-La(OH)3/N-PCB-NH2","matchedCharacterization":"Pd-La(OH)3/N-PCB-NH2","role":"main catalyst","composition":"Pd and La; designed molar ratio of La(OH)3/Pd = 0.2 (actual measured ratio = 0.14)","activeMetals":"Pd-La","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"N-PCB was functionalized with APTES, followed by the addition of Na2PdCl4 and La(NO3)3 precursors via sonication. Pd2+ was reduced to Pd0 using NaBH4, while La3+ was converted to La(OH)3 in situ by the alkali solution generated from NaBH4 hydrolysis.","phase":"Low crystallinity; HRTEM shows a plane distance of 0.222 nm assigned to the Pd(111) planes.","particleSize":"1.6 nm","surfaceStates":"Pd 3d binding energies (335.9 and 341.2 eV) shifted to higher values compared to support-free Pd-La(OH)3, indicating strong metal-support interaction (SMSI). La exists as La3+ in the form of La(OH)3 (La 3d5/2 at 836.1 eV).","structureLink":"The high catalytic activity is attributed to the ultrafine particle size, the strong metal-support interaction (SMSI), and the abundance of surface basic sites provided by La(OH)3 and amine groups which facilitate O-H bond dissociation of formic acid.","reactionConditions":"FA dehydrogenation in FA-SF aqueous solution, nPd/nFA = 0.04, reactor: two-necked reaction flask with inverted gas burette","selectivity":"100% H2 selectivity; CO impurity not detected","stability":"good durability with no obvious decrease in activity during recycle test","deactivation":"Pd leaching: 0.21% (single reaction), 0.23% (durability test); La leaching: 0.20% (single reaction), 0.30% (durability test); particle size increased from 1.6 to 2.4 nm","whyPerformsWell":"cooperation between Pd and La(OH)3, SMSI effect between Pd-La(OH)3 and N-PCB-NH2, ultrafine NP size (1.6 nm), deprotonation ability of La(OH)3 and amine groups, high concentration of basic sites facilitating O-H bond dissociation","metricCount":"4"},{"paperId":"P012","catalystId":"P012_PERF_002","name":"Pd/N-PCB-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation in FA-SF aqueous solution at 323 K, nPd/nFA = 0.04","metricCount":"1"},{"paperId":"P012","catalystId":"P012_PERF_003","name":"Pd-La(OH)3 (support-free)","activeMetals":"Pd-La","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation at 323 K","metricCount":"1"},{"paperId":"P012","catalystId":"P012_PERF_004","name":"Pd-La(OH)3/N-PCB (amine-free)","activeMetals":"Pd-La","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation at 323 K","metricCount":"1"},{"paperId":"P013","catalystId":"P013_PERF_001","name":"Pd/HNTs","support":"Halloysite nanotubes (HNTs)","matchedSynthesis":"Pd/HNTs","matchedCharacterization":"Pd/HNTs","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"HNTs dispersed in water, Pd precursor added and stirred for 12 h at room temperature; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","phase":"Metallic Pd nanoparticles supported on natural halloysite nanotubes","particleSize":"3.5 nm (chemisorption); >4.3 nm to 25 nm (TEM)","surfaceStates":"Pd0 and Pd2+","structureLink":"Larger particle size and aggregation lead to significantly lower catalytic activity compared to the amino-functionalized support.","reactionConditions":"Aqueous formic acid/sodium formate (FA/SF) solution, C FA + CSF = 6.0 M, T=298 K, FA/SF = 1","selectivity":"100% toward H2; no CO detected by GC","metricCount":"2"},{"paperId":"P013","catalystId":"P013_PERF_002","name":"Pd/HNTs (1.28 wt.% Pd)","support":"Halloysite nanotubes (HNTs)","matchedSynthesis":"Pd/HNTs","matchedCharacterization":"Pd/HNTs","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"HNTs dispersed in water, Pd precursor added and stirred for 12 h at room temperature; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","phase":"Metallic Pd nanoparticles supported on natural halloysite nanotubes","particleSize":"3.5 nm (chemisorption); >4.3 nm to 25 nm (TEM)","surfaceStates":"Pd0 and Pd2+","structureLink":"Larger particle size and aggregation lead to significantly lower catalytic activity compared to the amino-functionalized support.","reactionConditions":"Aqueous formic acid/sodium formate (FA/SF) solution, C FA + CSF = 6.0 M, T=298 K, FA/SF = 1","selectivity":"100% toward H2; no CO detected by GC","metricCount":"2"},{"paperId":"P013","catalystId":"P013_PERF_003","name":"Pd/NH2-HNTs","support":"Halloysite nanotubes (HNTs)","matchedSynthesis":"Pd/NH2-HNTs","matchedCharacterization":"Pd/NH2-HNTs","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd precursor added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","phase":"Metallic Pd nanoparticles supported on amino-functionalized halloysite nanotubes","particleSize":"1.2 nm (chemisorption); 1.8 ± 0.4 nm (TEM)","surfaceStates":"Pd0 and Pd2+; Pd 3d peaks shifted toward higher binding energies compared to Pd/HNTs due to interaction with -NH2 groups (electron migration from Pd to N)","structureLink":"The -NH2 groups facilitate high dispersion of ultra-fine particles and act as basic sites for formate ion formation; the electronic interaction between Pd and N enhances the combination of active centers with formate ions.","reactionConditions":"Aqueous formic acid/sodium formate (FA/SF) solution, C FA + CSF = 6.0 M, T=298 K, FA/SF = 1","selectivity":"100% toward H2; no CO detected by GC","stability":"Activity decreased slightly after the first run, then remained stable after the second run.","deactivation":"Pd NP size increased after the fifth catalytic reaction cycle.","whyPerformsWell":"-NH2 groups promote fixation and dispersion of ultra-fine Pd particles; alkalinity of -NH2 facilitates breaking O-H bonds of FA to form formate ions; synergistic interactions between Pd, -NH2, and support change electron density of Pd0, benefiting the combining of formate ions.","metricCount":"2"},{"paperId":"P013","catalystId":"P013_PERF_004","name":"Pd/NH2-HNTs (1.30 wt.% Pd)","support":"Halloysite nanotubes (HNTs)","matchedSynthesis":"Pd/NH2-HNTs","matchedCharacterization":"Pd/NH2-HNTs","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd precursor added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","phase":"Metallic Pd nanoparticles supported on amino-functionalized halloysite nanotubes","particleSize":"1.2 nm (chemisorption); 1.8 ± 0.4 nm (TEM)","surfaceStates":"Pd0 and Pd2+; Pd 3d peaks shifted toward higher binding energies compared to Pd/HNTs due to interaction with -NH2 groups (electron migration from Pd to N)","structureLink":"The -NH2 groups facilitate high dispersion of ultra-fine particles and act as basic sites for formate ion formation; the electronic interaction between Pd and N enhances the combination of active centers with formate ions.","reactionConditions":"Aqueous formic acid/sodium formate (FA/SF) solution, C FA + CSF = 6.0 M, T=298 K, FA/SF = 1","selectivity":"100% toward H2; no CO detected by GC","whyPerformsWell":"-NH2 groups promote fixation and dispersion of ultra-fine Pd particles; alkalinity of -NH2 facilitates breaking O-H bonds of FA to form formate ions; synergistic interactions between Pd, -NH2, and support change electron density of Pd0.","metricCount":"2"},{"paperId":"P013","catalystId":"P013_PERF_005","name":"PdAu/NH2-HNTs","support":"Halloysite nanotubes (HNTs)","matchedSynthesis":"PdAu/NH2-HNTs","matchedCharacterization":"PdAu/NH2-HNTs","role":"active catalyst","composition":"Pd:Au","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd and Au precursors added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","phase":"Bimetallic PdAu nanoparticles","surfaceStates":"Shift in Pd 3d binding energies relative to Pd/NH2-HNTs due to differences in work functions between Pd and Au, causing electron migration","structureLink":"Synergistic electronic effects between Pd and Au and the support significantly enhance catalytic performance for DFA.","reactionConditions":"Aqueous formic acid/sodium formate (FA/SF) solution, C FA + CSF = 6.0 M, T=298 K, FA/SF = 1","selectivity":"100% toward H2; no CO detected by GC","whyPerformsWell":"Synergistic interactions between Pd and Au (electronic effect) and the interaction between metal and support significantly enhance catalytic performance.","metricCount":"2"},{"paperId":"P013","catalystId":"P013_PERF_006","name":"PdAg/NH2-HNTs","support":"Halloysite nanotubes (HNTs)","matchedSynthesis":"PdAg/NH2-HNTs","matchedCharacterization":"PdAg/NH2-HNTs","role":"active catalyst","composition":"Pd:Ag","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd and Ag precursors added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","phase":"Bimetallic PdAg nanoparticles","surfaceStates":"Shift in Pd 3d binding energies relative to Pd/NH2-HNTs due to work function differences between Pd and Ag","structureLink":"Electronic effects modify the electron density of Pd0, influencing the activity which is lower than that of PdAu/NH2-HNTs.","reactionConditions":"Aqueous formic acid/sodium formate (FA/SF) solution, C FA + CSF = 6.0 M, T=298 K, FA/SF = 1","selectivity":"100% toward H2; no CO detected by GC","metricCount":"2"},{"paperId":"P013","catalystId":"P013_PERF_007","name":"Au/NH2-HNTs","support":"Halloysite nanotubes (HNTs)","matchedSynthesis":"PdAu/NH2-HNTs","matchedCharacterization":"PdAu/NH2-HNTs","role":"active catalyst","composition":"Pd:Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"co_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd and Au precursors added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","phase":"Bimetallic PdAu nanoparticles","surfaceStates":"Shift in Pd 3d binding energies relative to Pd/NH2-HNTs due to differences in work functions between Pd and Au, causing electron migration","structureLink":"Synergistic electronic effects between Pd and Au and the support significantly enhance catalytic performance for DFA.","reactionConditions":"Aqueous formic acid/sodium formate (FA/SF) solution, C FA + CSF = 6.0 M, T=298 K, FA/SF = 1","selectivity":"no activity","metricCount":"2"},{"paperId":"P013","catalystId":"P013_PERF_008","name":"Ag/NH2-HNTs","support":"Halloysite nanotubes (HNTs)","matchedSynthesis":"PdAg/NH2-HNTs","matchedCharacterization":"PdAg/NH2-HNTs","role":"active catalyst","composition":"Pd:Ag","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"co_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd and Ag precursors added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","phase":"Bimetallic PdAg nanoparticles","surfaceStates":"Shift in Pd 3d binding energies relative to Pd/NH2-HNTs due to work function differences between Pd and Ag","structureLink":"Electronic effects modify the electron density of Pd0, influencing the activity which is lower than that of PdAu/NH2-HNTs.","reactionConditions":"Aqueous formic acid/sodium formate (FA/SF) solution, C FA + CSF = 6.0 M, T=298 K, FA/SF = 1","selectivity":"no activity","metricCount":"2"},{"paperId":"P014","catalystId":"P014_PERF_001","name":"AgPd-NH2-SBA-15","support":"SBA-15","matchedSynthesis":"AgPd-NH2-SBA-15","matchedCharacterization":"AgPd-NH2-SBA-15","role":"dehydrogenation catalyst for generation of H2 from formic acid","composition":"Ag:Pd = 1.6 wt% : 0.8 wt%","activeMetals":"Ag-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"SBA-15 was modified with APMS to introduce amino and hydrido groups; subsequently, a mixture of PdCl2 and AgNO3 was introduced and reduced by the residual surface Si-H groups.","phase":"Ag-doped Pd nanoparticles","particleSize":"<1 nm (ultrasmall NPs); >20 nm (outer surface Ag NPs); single metal atoms","surfaceStates":"Ag: Ag+ (367.5, 373.5 eV, likely AgCl) and Ag0 (368.2, 374.2 eV); Pd: Pd0 (334.8, 340.2 eV) and Pd2+ (336.9, 342.3 eV, unreacted PdCl2)","structureLink":"High activity attributed to the synergy between amino groups (acting as Brønsted basic sites for FA deprotonation) and single metal atoms/ultrasmall Ag-doped Pd NPs (distorted crystal lattice).","reactionConditions":"ambient condition without external base","stability":"can easily be recovered after reaction and successfully reused; catalytic activity is enhanced after recycling","whyPerformsWell":"Copresence of surface amino groups (acting as Brønsted basic sites to deprotonate FA) and supported single metal atom sites/ultrasmall Ag-doped Pd NPs; incorporation of Ag distorts the Pd lattice.","metricCount":"2"},{"paperId":"P014","catalystId":"P014_PERF_002","name":"Pd-NH2-SBA-15","support":"SBA-15","matchedSynthesis":"Pd-NH2-SBA-15","matchedCharacterization":"Pd-NH2-SBA-15","role":"dehydrogenation catalyst for generation of H2 from formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"SBA-15 modified with APMS to create NH2-H-SBA-15, followed by introduction of PdCl2 for on-site reduction by surface Si-H groups.","particleSize":"ca. 1 nm (ultrasmall NPs); ca. 10 nm (outer surface NPs)","reactionConditions":"ambient condition without external base","whyPerformsWell":"Presence of Pd NPs and amino groups","metricCount":"1"},{"paperId":"P014","catalystId":"P014_PERF_003","name":"Ag-NH2-SBA-15","support":"SBA-15","matchedSynthesis":"Ag-NH2-SBA-15","matchedCharacterization":"Ag-NH2-SBA-15","role":"comparison catalyst","composition":"Ag","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"SBA-15 modified with APMS to create NH2-H-SBA-15, followed by introduction of silver ions for on-site reduction by surface Si-H groups.","particleSize":"<6 nm (average ca. 3 nm)","reactionConditions":"ambient condition without external base","metricCount":"1"},{"paperId":"P015","catalystId":"P015_PERF_001","name":"Arg-Pd/MSC-30","support":"Maxsorb MSC-30 (Mesoporous Carbon)","matchedSynthesis":"Arg-Pd/MSC-30","matchedCharacterization":"Arg-Pd/MSC-30","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Arginine was dispersed in deionized water and mixed with MSC-30; K2PdCl4 solution was added followed by sonication for 0.5 h. NaBH4 solution was then rapidly injected, and the mixture was stirred for 0.5 h at room temperature.","phase":"Metallic Pd; PXRD shows a weak broad diffraction peak at ~40° corresponding to the (111) plane.","particleSize":"1.9 ± 0.3 nm","surfaceStates":"Surface oxidation to Pd(II); presence of amine groups from arginine (N 1s at 400.5 eV).","structureLink":"Superior activity is attributed to smaller particle size (more active sites) and a synergetic effect where arginine provides an alkalized environment facilitating FA deprotonation; MSC-30 pores provide spatial confinement preventing aggregation.","reactionConditions":"Dehydrogenation of formic acid (FA) in de-ionized water using a two-necked reaction tube under ambient atmosphere.","selectivity":"100% selectivity; no CO detected","stability":"No obvious loss in catalytic activity after 5 cycles at 323 K by adding aliquots of pure FA.","whyPerformsWell":"Smaller size of ultrafine Pd NPs (average diameter ≤1.9 nm) and synergetic effect between Pd NPs and amino acid molecules providing an alkalized environment that facilitates deprotonation of FA; spatial confinement by MSC-30 pores prevents aggregation.","metricCount":"6"},{"paperId":"P015","catalystId":"P015_PERF_002","name":"Pd/MSC-30","support":"Maxsorb MSC-30 (Mesoporous Carbon)","matchedSynthesis":"Pd/MSC-30","matchedCharacterization":"Pd/MSC-30","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Synthesized using the same procedure as Arg-Pd/MSC-30 but in the absence of amino acids.","phase":"Metallic Pd; distinct characteristic diffraction peaks observed in PXRD.","particleSize":"3.9 ± 0.5 nm","surfaceStates":"Surface oxidation of ultrafine Pd NPs to Pd(II).","structureLink":"Larger particle size and lack of amino acid synergy resulted in significantly lower catalytic activity for FA dehydrogenation.","reactionConditions":"Dehydrogenation of formic acid (FA) in de-ionized water using a two-necked reaction tube under ambient atmosphere.","metricCount":"2"},{"paperId":"P016","catalystId":"P016_PERF_001","name":"PdNC/AC-NH2","support":"active carbon (AC)","matchedSynthesis":"PdNC/AC-NH2","matchedCharacterization":"PdNC/AC-NH2","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"AC was modified with APTES, soaked in Na2PdCl4 solution, and then reduced using NaBH4.","phase":"Nanoclusters","particleSize":"2.20 nm","surfaceStates":"Intermediate electronic state between single atoms and nanoparticles","structureLink":"Highest activity (TOF 40856 h-1 at 328 K) due to an optimal balance of the Pd0/Pd2+ synergistic electronic effect for C-H cleavage and a robust hydrogen spillover effect for H2 desorption.","reactionConditions":"Formic acid (FA) dehydrogenation","selectivity":"100% selectivity to H2 and CO2; dehydration to CO could be ignored","stability":"No obvious decrease in catalytic activity after five cycles at 298 K without additive","whyPerformsWell":"Optimal balance between electronic state (coexistence of Pd0 and Pd2+) and hydrogen spillover effect due to appropriate particle size (2.2 nm); amine groups act as proton scavengers promoting O-H bond dissociation.","metricCount":"4"},{"paperId":"P016","catalystId":"P016_PERF_002","name":"Pd1/AC-NH2","support":"active carbon (AC)","matchedSynthesis":"Pd1/AC-NH2","matchedCharacterization":"Pd1/AC-NH2","role":"benchmark catalyst (single atom)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Similar to PdNC/AC-NH2 but with lower Pd precursor amount.","phase":"Single atoms","particleSize":"Isolated atoms","surfaceStates":"Lowest electronic state among the three Pd species (highest binding energy in XPS)","structureLink":"Highest hydrogen spillover capacity but lower activity than nanoclusters due to lack of optimal balance between electronic properties and spillover.","reactionConditions":"Formic acid (FA) dehydrogenation","metricCount":"1"},{"paperId":"P016","catalystId":"P016_PERF_003","name":"PdNP/AC-NH2","support":"active carbon (AC)","matchedSynthesis":"PdNP/AC-NH2","matchedCharacterization":"PdNP/AC-NH2","role":"benchmark catalyst (nanoparticle)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Similar to PdNC/AC-NH2 but reduced by H2 gas instead of NaBH4.","phase":"Metallic Pd (XRD peaks at 41.12° and 46.66°, JCPDS: 46-1043)","particleSize":"5.42 nm","surfaceStates":"Richest electronic state (lowest binding energy in XPS)","structureLink":"Lowest activity among the three due to the lowest hydrogen spillover capacity, despite having the richest Pd0 electronic state.","reactionConditions":"Formic acid (FA) dehydrogenation","metricCount":"1"},{"paperId":"P016","catalystId":"P016_PERF_004","name":"Pd/AC-NH2 (unreduced)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Formic acid (FA) dehydrogenation","whyPerformsWell":"Inferior activity of bare Pd2+ compared to reduced species","metricCount":"1"},{"paperId":"P016","catalystId":"P016_PERF_005","name":"Pd/AC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Formic acid (FA) dehydrogenation","whyPerformsWell":"Modest activity; lacks amine groups for synergistic proton scavenging","metricCount":"1"},{"paperId":"P016","catalystId":"P016_PERF_006","name":"PdNC/SiO2-NH2","support":"silica (SiO2)","matchedSynthesis":"PdNC/SiO2-NH2","matchedCharacterization":"PdNC/SiO2-NH2","role":"comparison sample (nonreducing carrier)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"SiO2 was first functionalized with APTES, then loaded with Na2PdCl4 and reduced with NaBH4.","phase":"Nanoclusters","particleSize":"2.15 nm","surfaceStates":"Similar electronic properties to PdNC/AC-NH2","structureLink":"No activity for FA dehydrogenation, underscoring the critical role of the support's hydrogen spillover effect (SiO2 is a nonreducing carrier with mild spillover).","reactionConditions":"Formic acid (FA) dehydrogenation","whyPerformsWell":"Lack of activity underscores the critical role of hydrogen spillover effect provided by AC support","metricCount":"1"},{"paperId":"P017","catalystId":"P017_PERF_001","name":"Pd@KNDC(10-900)","matchedCharacterization":"Pd@KNDC(10-900)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Metallic Pd (PDF no. 89-4897) with identified planes (1 1 1), (2 0 0), and (2 2 0).","particleSize":"4.1 nm","surfaceStates":"Mainly metallic Pd0 (Pd 3d5/2 at 335.1 eV, Pd 3d3/2 at 340.3 eV) with minor surface Pd2+.","structureLink":"The superior catalytic performance is attributed to the robust synergistic interactions between Pd NPs and N sites on the KNDC(900) support (metal-support interaction, MSI), as well as the ultrafine size and high dispersion of the active Pd NPs.","reactionConditions":"Formic acid (FA) dehydrogenation with sodium formate (SF) additive at 50 °C","selectivity":"100 % H2 selectivity; no formation of CO","stability":"maintained outstanding stability enduring through five successive runs with only a marginal reduction in activity","deactivation":"increased mean size from 4.1 nm to 4.3 nm for recovered catalyst; partial loss of Pd content found","whyPerformsWell":"robust synergistic interactions between Pd NPs and N sites on the KNDC(900) together with the ultrafine size and high dispersion of Pd NPs as the catalytic active sites","metricCount":"7"},{"paperId":"P017","catalystId":"P017_PERF_002","name":"Pd@NDC(10-900)","support":"N-doped carbon (NDC)","matchedSynthesis":"Pd@NDC(10-900)","role":"reference catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd@KNDC(10-900) but using non-etched NDC support.","reactionConditions":"Same conditions as Pd@KNDC(10-900) (50 °C, FA/SF=1:2)","whyPerformsWell":"KOH solution etching on the NDC support enhances catalytic performance","metricCount":"1"},{"paperId":"P018","catalystId":"P018_PERF_001","name":"Pd0.9Ag0.1/CDs","matchedCharacterization":"Pd0.9Ag0.1/CDs","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdAg alloy; crystal plane spacing of 0.227 nm (between fcc Pd 0.224 nm and Ag 0.235 nm); XRD shows shift of Pd peaks to lower 2 theta values with increasing Ag content.","particleSize":"1.14 nm (freshly prepared); increased to approximately 1.45 nm after five cycles.","surfaceStates":"XPS shows negative shift in Pd 3d binding energy (electron-enriched Pd) and positive shift in Ag 3d binding energy (electron-depleted Ag); N 1s spectrum shifted positively by 0.11 eV compared to Pd/CDs.","structureLink":"High activity is attributed to electron transfer from Ag to Pd, strong electronic interactions between the PdAg alloy and N-doped CDs support, and the restrictive effect of CDs preventing nanoparticle aggregation.","reactionConditions":"Formic acid (FA) dehydrogenation in water without additives at ambient temperature.","selectivity":"only CO2 as a byproduct","stability":"Complete dehydrogenation achieved after five cycles; activity remained at 73.3% after five cycles (TOF decreased from 619 h-1 to 454 h-1).","deactivation":"Decrease in durability is due to the increase in particle size of the PdAg alloys and the erosion of the catalyst by the reactants.","whyPerformsWell":"Electron transfer in PdAg alloys, strong electronic interaction between PdAg alloys and CDs supports; N-doped CDs restrict growth and aggregation of nanoparticles.","metricCount":"3"},{"paperId":"P019","catalystId":"P019_PERF_001","name":"PdAu/NH2-MIL-101","support":"NH2-MIL-101","matchedSynthesis":"PdAu/NH2-MIL-101","matchedCharacterization":"PdAu/NH2-MIL-101","role":"main catalyst for formic acid dehydrogenation (FAD)","composition":"Pd:Au = 0.7:0.3 (molar ratio)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"NH2-MIL-101 was synthesized via a one-step hydrothermal method (453 K, 4 h). Pd and Au precursors were impregnated into the support suspension through sonication and stirring, followed by liquid-phase reduction using NaBH4.","phase":"Pd-Au alloy structure (verified by HRTEM lattice spacing of 0.232 nm and XRD shift of the Pd(111) peak to a lower angle)","particleSize":"1.2 nm (increased to 1.9 nm after durability tests)","surfaceStates":"Electron migration from Pd to Au; Pd0 shifted to higher binding energies (341.3 eV and 336.1 eV) and Au0 shifted to lower binding energies (87.7 eV and 84.0 eV)","structureLink":"Synergy between amino groups (acting as anchor sites and proton scavengers), electronic coupling between Pd and Au, and strong metal-support interaction (SMSI) promotes the formation of reactive ultrafine NCs and reduces activation energy to 36.3 kJ/mol","reactionConditions":"T = 323 K, FA amount = 2.5 mmol (2.0 mL aqueous solution), solvent = H2O (3 mL in flask), metal-to-FA ratio ((Pd+Au)/FA) = 0.02, reactor = double-necked round-bottom flask with water-filled inverted gas burette, ambient atmosphere","selectivity":"100 % H2 selectivity; no CO gas detected at 323 K","stability":"outstanding durability during five subsequent FAD runs; complete conversion almost sustained","deactivation":"H2 generation rate decreases slightly after cycle test; slight size increase of PdAu NCs to 1.9 nm","whyPerformsWell":"synergistic combination of promoting effect of amino groups, effective electronic coupling of Pd and Au, and strong metal-support interaction (SMSI) between PdAu NCs and NH2-MIL-101","metricCount":"3"},{"paperId":"P019","catalystId":"P019_PERF_002","name":"Pd/NH2-MIL-101","matchedCharacterization":"Pd/NH2-MIL-101","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Monometallic Pd","surfaceStates":"Pd0 3d3/2 at 341.2 eV and Pd0 3d5/2 at 335.9 eV","structureLink":"Mild catalytic activity with a higher activation energy (37.7 kJ/mol) than the PdAu alloy catalyst","reactionConditions":"T = 323 K, FA amount = 2.5 mmol (2.0 mL aqueous solution), solvent = H2O (3 mL in flask), metal-to-FA ratio (Pd/FA) = 0.02","selectivity":"null","stability":"maintains good performance after five FAD cycles, but inferior to PdAu/NH2-MIL-101","deactivation":"null","whyPerformsWell":"null","metricCount":"2"},{"paperId":"P019","catalystId":"P019_PERF_003","name":"PdAu/MIL-101","matchedCharacterization":"PdAu/MIL-101","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"3.1 nm","structureLink":"Poor activity compared to PdAu/NH2-MIL-101 due to the absence of amino groups which are necessary for stabilizing NCs and promoting FA deprotonation","reactionConditions":"T = 323 K, FA amount = 2.5 mmol (2.0 mL aqueous solution), solvent = H2O (3 mL in flask), metal-to-FA ratio ((Pd+Au)/FA) = 0.02","selectivity":"null","stability":"null","deactivation":"null","whyPerformsWell":"null","metricCount":"1"},{"paperId":"P019","catalystId":"P019_PERF_004","name":"pure PdAu NPs","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"T = 323 K, FA amount = 2.5 mmol (2.0 mL aqueous solution), solvent = H2O (3 mL in flask), metal-to-FA ratio ((Pd+Au)/FA) = 0.02","selectivity":"null","stability":"null","deactivation":"null","whyPerformsWell":"null","metricCount":"1"},{"paperId":"P020","catalystId":"P020_PERF_001","name":"Pd0.60Co0.18Ni0.22/TiO2-ALD-SiO2 (6 cycles)","activeMetals":"Pd-Co-Ni","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of aqueous formic acid solution at room temperature","selectivity":">99% dehydrogenation selectivity; CO below detection limit (<10 ppm)","stability":"Retains >=83% of initial catalytic activity and selectivity at >90% conversion even at the 20th reuse when tested at 100 °C. Lower bound TTON of >=7500 mol H2/mol catalyst.","deactivation":"No Pd, Co, or Ni detected in reaction solutions after 5th, 10th, and 20th reuse (no leaching). Minimal sintering observed: mean particle size increased from 3.52 to 3.75 nm.","whyPerformsWell":"Strong Metal-Molecular Support Interaction (SMMSI) due to free amine groups from APTS facilitating FA adsorption/storage and O-H bond cleavage; ALD-SiO2 layers protect against sintering and leaching; trimetallic alloy structure provides high CO poisoning resistivity.","metricCount":"3"},{"paperId":"P020","catalystId":"P020_PERF_002","name":"Pd0.60Co0.18Ni0.22/TiO2","activeMetals":"Pd-Co-Ni","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of aqueous formic acid solution at room temperature","stability":"Completely lost its catalytic performance (activity, selectivity and conversion) by the 20th reuse when tested at 100 °C.","deactivation":"Highly agglomerated as a result of sintering on the surface of TiO2 under forcing conditions (100 °C).","metricCount":"1"},{"paperId":"P021","catalystId":"P021_PERF_001","name":"Au0.3Pd0.7/CA-BN-NH2","support":"citric acid-modified boron nitride with amino groups (CA-BN-NH2)","matchedSynthesis":"Au0.3Pd0.7/CA-BN-NH2","matchedCharacterization":"Au0.3Pd0.7/CA-BN-NH2","role":"main catalyst","composition":"Au:Pd = 0.3:0.7 (atomic ratio)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Pristine h-BN was modified with citric acid to create defective sites, followed by APTES functionalization to introduce -NH2 groups. Aqueous solutions of HAuCl4 and Na2PdCl4 were impregnated into the CA-BN-NH2 suspension and subsequently reduced using NaBH4.","phase":"Au0.3Pd0.7 alloy (confirmed by XRD broad peaks between Pd and Au; HRTEM lattice spacing of 0.230 nm indicates lattice expansion of fcc Pd)","particleSize":"~3.6 nm","surfaceStates":"Electron-rich Pd active sites resulting from strong metal-support interaction (electron transfer from CA-BN-NH2 to AuPd) and ligand effect (charge transfer between Pd and Au)","structureLink":"Ultrafine particle size, excellent dispersion, and electronic modification (electron-rich Pd promoting C-H dissociation and weak H atom adsorption boosting H2 desorption) lead to extraordinary catalytic activity.","reactionConditions":"Formic acid (FA) dehydrogenation, 1.0 M FA (5.0 mL), aqueous solution, without any additive","selectivity":"100% hydrogen selectivity","stability":"Slight decay in activity observed over five catalytic cycles","deactivation":"Metal loading amount of AuPd NPs decreased after the fifth run","whyPerformsWell":"Comprehensive influence of ultrafine particle size (~3.6 nm), excellent dispersion, and electronic structure modification (electron transfer from CA-BN-NH2 to AuPd nanoparticles and ligand effect between Au and Pd) which makes Pd active sites electron-rich, promoting C-H dissociation; additionally, weak H atom adsorption boosts hydrogen desorption.","metricCount":"3"},{"paperId":"P021","catalystId":"P021_PERF_002","name":"Au0.3Pd0.7/BN-NH2","matchedCharacterization":"Au0.3Pd0.7/BN-NH2","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Au0.3Pd0.7 alloy","particleSize":"~4.1 nm","surfaceStates":"No significant shift in Pd 3d and Au 4f peaks compared to Au0.3Pd0.7/BN, indicating that amine groups from APTES alone do not significantly modify the electronic structure.","structureLink":"Higher activity than Au0.3Pd0.7/BN due to smaller particle size (higher active site concentration), but lower than Au0.3Pd0.7/CA-BN-NH2 due to lack of support-induced electronic modification.","reactionConditions":"Formic acid (FA) dehydrogenation, 1.0 M FA (5.0 mL), aqueous solution, without any additive","whyPerformsWell":"Better activity than Au0.3Pd0.7/BN due to more ultrafine particle size (~4.1 nm) and higher active site concentration.","metricCount":"1"},{"paperId":"P021","catalystId":"P021_PERF_003","name":"Au0.3Pd0.7/BN","matchedCharacterization":"Au0.3Pd0.7/BN","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Au0.3Pd0.7 alloy","particleSize":"~10.4 nm","surfaceStates":"Higher binding energies for Pd 3d and Au 4f compared to CA-BN-NH2 supported catalyst, indicating weaker electron density on the metal NPs.","structureLink":"Larger particle size and poor dispersion result in significantly lower catalytic activity.","reactionConditions":"Formic acid (FA) dehydrogenation, 1.0 M FA (5.0 mL), aqueous solution, without any additive","metricCount":"1"},{"paperId":"P021","catalystId":"P021_PERF_004","name":"Au0.3Pd0.7 NPs (free)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Formic acid (FA) dehydrogenation, 1.0 M FA (5.0 mL), aqueous solution, without any additive","metricCount":"1"},{"paperId":"P022","catalystId":"P022_PERF_001","name":"AuPd/n-CNS-Th-160","support":"nitrogen-decorated carbon nanosheets (n-CNS)","matchedSynthesis":"AuPd/n-CNS","matchedCharacterization":"AuPd/n-CNS-Th-160","role":"catalyst for the dehydrogenation of formic acid","composition":"AuPd (1:1 molar ratio based on precursor concentrations)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"n-CNS support was prepared from g-C3N4 and glucose; Au and Pd precursors were added to the n-CNS suspension, stirred overnight, and reduced using NaBH4.","phase":"fcc alloy structure","particleSize":"1.82 nm","surfaceStates":"Electron transfer from the support to Pd and Au, evidenced by XPS binding energy shifts to lower values (Pd 3d shift ~0.2 eV; Au 4f shift ~0.3 eV) compared to pure metals.","structureLink":"The high ratio of graphitic N to pyridinic N in the support modifies electron density distribution and minimizes nanoparticle size, which greatly enhances catalytic activity for formic acid dehydrogenation.","reactionConditions":"Dehydrogenation of FA/SF solution in deionized water under ambient atmosphere with magnetic stirring.","selectivity":"100% hydrogen generation and selectivity to CO2 and H2; CO-free","stability":"Productivity of hydrogen remained almost unchanged after two cycles; morphology and structure maintained after three cycles.","deactivation":"Possible losses of supported catalyst, nanoparticle detachment from support, or trapping of byproducts/intermediates in porous catalyst.","whyPerformsWell":"Coordinated effect from Au-Pd alloying and nitrogen-decorated carbon nanosheets; specifically, a high ratio of graphitic N to pyridinic N modifies electron density distribution and minimizes metal nanoparticle size (mean diameter ~1.82 nm).","metricCount":"3"},{"paperId":"P022","catalystId":"P022_PERF_002","name":"AuPd/AC","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA/SF solution (2.5 M/2.5 M, 2 mL) at 25 °C under ambient atmosphere.","metricCount":"1"},{"paperId":"P022","catalystId":"P022_PERF_003","name":"commercial Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"FA/SF solution (2.5 M/2.5 M, 2 mL) at 25 °C under ambient atmosphere.","metricCount":"1"},{"paperId":"P023","catalystId":"P023_PERF_001","name":"Au-Pd-SBA-15-NH2-TD","support":"SBA-15","matchedSynthesis":"Au-Pd-SBA-15-NH2-TD","matchedCharacterization":"Au-Pd-SBA-15-NH2-TD","role":"active catalyst","composition":"Au and Pd (equal mass loading based on precursor volumes)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"SBA-15 was first calcined and then functionalized with APTES in a toluene/DMF mixture. The resulting SBA-15-NH2 support was dispersed in water, mixed with Au and Pd precursors, and reduced using NaBH4.","phase":"Au-Pd bimetal alloy (HRTEM lattice fringe of 0.230 nm, between Pd(111) and Au(111))","particleSize":"3.2 nm (distribution 2.8-3.6 nm)","surfaceStates":"Metallic Au, Pd0, positively charged Pd, -NH2 groups, and protonated amine groups (NH3+).","structureLink":"Smallest nanoparticle size and highest surface amine density lead to strong metal-metal and metal-support interactions, resulting in the best catalytic performance.","reactionConditions":"308 K, 100 mg catalyst, 5 mL H2O + 0.4 mL HCOOH (0.5 M) + 70 mg sodium formate, stirred in a water bath in a two-necked round-bottom flask","selectivity":"CO was not detected; high selectivity for H2 and CO2","stability":"Activity reduced by no more than 11% after three cycles","whyPerformsWell":"Synergistic effect between amine-functionalized SBA-15 and Au-Pd bimetal (metal-support interactions), smallest nanoparticle size, and highest surface amine content facilitating deprotonation of formic acid","metricCount":"3"},{"paperId":"P023","catalystId":"P023_PERF_002","name":"Au-Pd-SBA-15-NH2-T","support":"SBA-15","matchedSynthesis":"Au-Pd-SBA-15-NH2-T","matchedCharacterization":"Au-Pd-SBA-15-NH2-T","role":"active catalyst","composition":"Au and Pd (equal mass loading based on precursor volumes)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"SBA-15 was first calcined and then functionalized with APTES in pure toluene. The resulting SBA-15-NH2 support was dispersed in water, mixed with Au and Pd precursors, and reduced using NaBH4.","phase":"Poorly formed bimetal; line scanning and mapping primarily show Au species with difficult-to-observe Pd.","particleSize":"6.2 nm","surfaceStates":"Metallic Au and Pd species.","structureLink":"Largest bimetal nanoparticle size and poorly formed bimetallic structure lead to the worst catalytic performance.","reactionConditions":"308 K, 100 mg catalyst, 5 mL H2O + 0.4 mL HCOOH (0.5 M) + 70 mg sodium formate, stirred in a water bath in a two-necked round-bottom flask","whyPerformsWell":"Worst performance among amine-functionalized catalysts due to largest bimetal nanoparticles","metricCount":"2"},{"paperId":"P023","catalystId":"P023_PERF_003","name":"Au-Pd-SBA-15-NH2-D","support":"SBA-15","matchedSynthesis":"Au-Pd-SBA-15-NH2-D","matchedCharacterization":"Au-Pd-SBA-15-NH2-D","role":"active catalyst","composition":"Au and Pd (equal mass loading based on precursor volumes)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"SBA-15 was first calcined and then functionalized with APTES in pure DMF. The resulting SBA-15-NH2 support was dispersed in water, mixed with Au and Pd precursors, and reduced using NaBH4.","phase":"Au-Pd bimetal","particleSize":"4.0 nm","surfaceStates":"Metallic Au and Pd species.","structureLink":"Larger metal particle size and lower amine content compared to the TD sample result in lower catalytic activity.","reactionConditions":"308 K, 100 mg catalyst, 5 mL H2O + 0.4 mL HCOOH (0.5 M) + 70 mg sodium formate, stirred in a water bath in a two-necked round-bottom flask","metricCount":"1"},{"paperId":"P023","catalystId":"P023_PERF_004","name":"Au-Pd-SBA-15","support":"SBA-15","matchedSynthesis":"Au-Pd-SBA-15-NH2-TD","matchedCharacterization":"Au-Pd-SBA-15-NH2-TD","role":"active catalyst","composition":"Au and Pd (equal mass loading based on precursor volumes)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"SBA-15 was first calcined and then functionalized with APTES in a toluene/DMF mixture. The resulting SBA-15-NH2 support was dispersed in water, mixed with Au and Pd precursors, and reduced using NaBH4.","phase":"Au-Pd bimetal alloy (HRTEM lattice fringe of 0.230 nm, between Pd(111) and Au(111))","particleSize":"3.2 nm (distribution 2.8-3.6 nm)","surfaceStates":"Metallic Au, Pd0, positively charged Pd, -NH2 groups, and protonated amine groups (NH3+).","structureLink":"Smallest nanoparticle size and highest surface amine density lead to strong metal-metal and metal-support interactions, resulting in the best catalytic performance.","reactionConditions":"308 K, 100 mg catalyst, 5 mL H2O + 0.4 mL HCOOH (0.5 M) + 70 mg sodium formate, stirred in a water bath in a two-necked round-bottom flask","whyPerformsWell":"Worst catalytic activity due to lack of amine groups on the SBA-15 matrix","metricCount":"1"},{"paperId":"P024","catalystId":"P024_PERF_001","name":"Au1Pd3/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Au1Pd3/rGO","role":"catalyst","composition":"Au:Pd = 1:3 molar ratio","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sol_immobilization","synthesis":"Metal salts were reduced with NaBH4 in a PVA solution, acidified to pH 2 with sulfuric acid, and immobilized by adding rGO support under vigorous stirring for 2 h.","reactionConditions":"0.5 M formic acid, 10 mL solution, 50 °C, 1 atm, nFA/nmetal = 2000, stirring at 1400 rpm in a two-necked 100 mL circular bottom flask with reflux condenser","selectivity":"100% hydrogen selectivity; CO concentrations of 5–7 ppm","stability":"Reusability test for five cycles showed an insignificant loss of 7% of its initial activity after the fifth reuse; efficiency increased by 6.5% after the first cycle.","deactivation":"Negligible leaching (Au < 0.04%; Pd < 0.05%). Deactivation attributed to agglomeration of Au-Pd particles (mean size increased from 3.5 nm to 6.8 nm), strong absorption of FA on rGO, and CO poisoning.","whyPerformsWell":"Synergetic effect of Au–Pd nanostructures, increased reaction sites evenly distributed on the rGO support, smaller mean particle size promoted by co-reduction, and moderate HCOOH adsorption/activation through alloying.","metricCount":"2"},{"paperId":"P024","catalystId":"P024_PERF_002","name":"Au1Pd1/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Au1Pd1/rGO","role":"catalyst","composition":"Au:Pd = 1:1 molar ratio","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sol_immobilization","synthesis":"Metal salts were reduced with NaBH4 in a PVA solution, acidified to pH 2 with sulfuric acid, and immobilized by adding rGO support under vigorous stirring for 2 h.","reactionConditions":"0.5 M formic acid, 10 mL solution, 50 °C, 1 atm, nFA/nmetal = 2000, stirring at 1400 rpm","whyPerformsWell":"Synergetic effect of Au-Pd nanostructures","metricCount":"2"},{"paperId":"P024","catalystId":"P024_PERF_003","name":"Au3Pd1/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Au3Pd1/rGO","role":"catalyst","composition":"Au:Pd = 3:1 molar ratio","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sol_immobilization","synthesis":"Metal salts were reduced with NaBH4 in a PVA solution, acidified to pH 2 with sulfuric acid, and immobilized by adding rGO support under vigorous stirring for 2 h.","reactionConditions":"0.5 M formic acid, 10 mL solution, 50 °C, 1 atm, nFA/nmetal = 2000, stirring at 1400 rpm","whyPerformsWell":"Synergetic effect of Au-Pd nanostructures","metricCount":"2"},{"paperId":"P025","catalystId":"P025_PERF_001","name":"Ag/AgPd CS-0.3","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"10 mL FA aqueous solution (1 M) at 50 °C","metricCount":"1"},{"paperId":"P025","catalystId":"P025_PERF_002","name":"Ag/AgPd CS-0.6","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"10 mL FA aqueous solution (1 M) at 50 °C","metricCount":"1"},{"paperId":"P025","catalystId":"P025_PERF_003","name":"Ag/AgPd CS-0.9","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Bifunctional catalysis: FA dehydrogenation and NO3-/NO2- reduction","selectivity":"CO-free H2 (no CO detected < 2 ppm); molar ratio of CO2 to H2 is 1; 99.8% selectivity for the reduction of NO3- and NO2- to N2","stability":"maintained its initial high activity toward FA dehydrogenation and conversion of NO3-/NO2- to N2 until at least the fourth run","deactivation":"no obvious changes in Ag/Pd composition or network-like morphology after 4 runs","whyPerformsWell":"more efficient electron transfer from PVPI and Ag to Pd","metricCount":"7"},{"paperId":"P025","catalystId":"P025_PERF_004","name":"Ag/AgPd CS-1.2","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"10 mL FA aqueous solution (1 M) at 50 °C","metricCount":"1"},{"paperId":"P026","catalystId":"P026_PERF_001","name":"Au1Pd3/BNNFs-A","support":"porous boron nitride nanofibers (BNNFs)","matchedSynthesis":"Au1Pd3/BNNFs-A","matchedCharacterization":"Au1Pd3/BNNFs-A","role":"catalyst","composition":"Au:Pd = 1:3","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"BNNFs were dispersed in an ethanol and deionized water mixed solution and treated with APTES. A combined solution of Na2PdCl4 and HAuCl4 was added under stirring, followed by reduction using aqueous NaBH4 in an ice-water bath.","phase":"AuPd alloy (confirmed by XRD peaks between metallic Au and Pd, HRTEM lattice spacing of ~0.228 nm, and EDS elemental mapping)","particleSize":"~2.2 nm","surfaceStates":"Partial transfer of electrons from Pd to Au; electron transfer from Au1Pd3 nanoparticles to the BNNFs-A carrier.","structureLink":"High activity is attributed to small particle size, high dispersion, modified Pd electronic structure via synergistic effect with Au, and the role of amine groups on BN surfaces as proton scavengers.","reactionConditions":"Catalytic dehydrogenation of formic acid (FA) in water at 298 K without additives.","selectivity":"Complete decomposition into H2 and CO2; no CO gas detected.","stability":"Activity not significantly reduced after five cycles.","deactivation":"Slight increase in nanoparticle size from 2.2 to 3.3 nm after cycling test.","whyPerformsWell":"Small particle sizes and high dispersion of Au1Pd3 nanoparticles on BNNFs, modified Pd electronic structure due to Au-Pd synergy, and the synergistic effect of amine groups (acting as proton scavengers) on the BN surface.","metricCount":"2"},{"paperId":"P027","catalystId":"P027_PERF_001","name":"Pd0.6Cr0.4/OPDA-SmMn2O5","matchedCharacterization":"Pd0.6Cr0.4/OPDA-SmMn2O5","activeMetals":"Pd-Cr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic PdCr NPs exist in an alloyed state, characterized by lattice contraction (lattice spacing 0.188 nm) compared to pure Pd (0.193 nm).","particleSize":"2.05 nm","surfaceStates":"XPS confirms metallic Pd0 (Pd 3d: 340.4, 335.2 eV) and Cr0 (Cr 2p: 584.3, 574.5 eV). The amino-modified support creates electron-rich PdCr NPs by modulating the electronic structure.","structureLink":"The formation of ultrafine, highly dispersed alloyed nanoparticles and the electronic modulation provided by the amino groups (OPDA) significantly enhance catalytic activity for formic acid dehydrogenation.","reactionConditions":"Formic acid dehydrogenation in a three-necked round-bottom flask placed in a thermostatic water bath.","selectivity":"Hydrogen selectivity close to 100%; no carbon monoxide detected at the detection limit of 10 ppm.","stability":"Stable and active under five cycle performance tests at 50 °C with no significant attenuation in decomposition rate or amount of gas produced.","deactivation":"No significant agglomeration after reaction confirmed by TEM.","whyPerformsWell":"Formation of small (2.05 nm) and highly dispersed PdCr NPs due to amino groups; synergistic effect between bimetal and support; electron-donor amino groups modulate the electronic structure of catalytic sites, increasing electron cloud density and alkalinity.","metricCount":"5"},{"paperId":"P027","catalystId":"P027_PERF_002","name":"Pd0.6Cr0.4/SmMn2O5","activeMetals":"Pd-Cr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation in a three-necked round-bottom flask placed in a thermostatic water bath.","whyPerformsWell":"Lacks amino groups which are necessary for high dispersion and electronic modulation of PdCr NPs.","metricCount":"1"},{"paperId":"P028","catalystId":"P028_PERF_001","name":"Pd7Ag3/SPP","matchedCharacterization":"Pd7Ag3/SPP","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdAg alloy","surfaceStates":"Formation of electronically enriched Pd by adsorption of formate anions","structureLink":"The hierarchical SPP zeolite carrier is more advantageous than bulky zeolites for making highly active catalysts; the optimized Pd/Ag ratio was found to be 7:3.","reactionConditions":"80 °C, aqueous solution of formic acid (FA) and sodium formate (SF), water solvent, 600 r/min stirring","selectivity":"100% selectivity to H2 (CO-free)","stability":"Hydrogen production rate was maintained well during three cycling tests","deactivation":"Slight increase in reaction time after three cycles may be due to the loss of catalyst during cycling","whyPerformsWell":"Hierarchical SPP zeolite allows easy encapsulation and well dispersion of metal clusters; SF additive promotes dehydrogenation by forming electronically enriched Pd via adsorption of formate anions","metricCount":"3"},{"paperId":"P028","catalystId":"P028_PERF_002","name":"PdAg/SPP (various ratios)","support":"self-pillared pentasil (SPP) zeolite","matchedSynthesis":"PdAg/SPP","matchedCharacterization":"Ag/SPP","role":"catalyst","composition":"Pd:Ag molar ratios of 9:1, 7:3, 1:1, and 3:7","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"SPP support was suspended in DI water, impregnated with Pd and Ag nitrate solutions, and then reduced using sodium borohydride in a sodium carbonate solution.","phase":"Metallic silver","structureLink":"Exhibited low activity for formic acid dehydrogenation.","reactionConditions":"80 °C, n_FA = 2.5 mmol, n_SF = 2.5 mmol, n_metal/n_FA = 0.04","whyPerformsWell":"Activity depends on Pd/Ag ratio: Pd7Ag3/SPP ≈ Pd9Ag1/SPP > Pd1Ag1/SPP > Pd3Ag7/SPP","metricCount":"0"},{"paperId":"P028","catalystId":"P028_PERF_003","name":"Pd/SPP and Ag/SPP","matchedCharacterization":"Pd/SPP","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Metallic palladium","structureLink":"Pd plays a decisive role in formic acid dehydrogenation compared to Ag.","reactionConditions":"80 °C, n_FA = 2.5 mmol, n_SF = 2.5 mmol, n_metal/n_FA = 0.04","whyPerformsWell":"Pd/SPP exhibited much higher activity than Ag/SPP, proving Pd plays a decisive role","metricCount":"0"},{"paperId":"P029","catalystId":"P029_PERF_001","name":"Pd0.8Au0.2/UiO-66-D","support":"NH2-UiO-66","matchedSynthesis":"Pd0.8Au0.2/UiO-66-D","matchedCharacterization":"Pd0.8Au0.2/UiO-66-D","role":"active catalyst","composition":"Pd:Au = 0.8:0.2","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"NH2-UiO-66 was suspended in n-hexane and sonicated; aqueous metal precursors were added dropwise and stirred. The product was dried, reduced with NaBH4 in an ice bath, washed, and dried again.","phase":"PdAu alloy","particleSize":"1.4 nm","surfaceStates":"Pd0 (3d5/2: 335.44 eV) and Au0 (4f7/2: 84.46 eV); partial electron transfer from Pd to Au due to electronegativity differences","structureLink":"High activity attributed to highly dispersed PdAu alloy NPs, electronic structure adjusted by the alloy effect and metal-support interaction, and basic amine groups promoting formic acid activation.","reactionConditions":"10 mg catalyst in 9.5 mL deionized water, 0.5 mL of 4 M aqueous formic acid (FA), ambient atmosphere, shaking water bath","selectivity":"1:1 volume ratio of H2 and CO2; no detectable CO","stability":"Conversion remains nearly unchanged after the fourth reaction and decreases slightly at the fifth test","deactivation":"Slight aggregation of PdAu NPs (average size increased to about 2 nm) over time","whyPerformsWell":"Formation of highly dispersed PdAu alloy NPs, suitable electronic structure adjusted by alloy effect and metal-support interaction, and abundant amine groups promoting FA activation via HCOO- formation","metricCount":"2"},{"paperId":"P029","catalystId":"P029_PERF_002","name":"Pd0.8Au0.2/UiO-66-S","support":"NH2-UiO-66","matchedSynthesis":"Pd0.8Au0.2/UiO-66-S","matchedCharacterization":"Pd0.8Au0.2/UiO-66-S","role":"comparison catalyst","composition":"Pd:Au = 0.8:0.2","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Activated NH2-UiO-66 was dispersed in deionized water and sonicated; aqueous metal precursors were added and stirred, followed by NaBH4 reduction in an ice bath.","phase":"PdAu alloy","particleSize":"5.6 nm","surfaceStates":"Pd0 (3d5/2: 335.64 eV) and Au0 (4f7/2: 84.74 eV)","structureLink":"Lower activity and stability compared to -D sample due to larger particle size and distribution on the external surface, leading to easier aggregation.","reactionConditions":"10 mg catalyst in 9.5 mL deionized water, 0.5 mL of 4 M aqueous formic acid (FA), ambient atmosphere, shaking water bath","selectivity":"1:1 volume ratio of H2 and CO2; no detectable CO","stability":"Catalytic activity decreases obviously with increasing recycling numbers","deactivation":"Obvious aggregation of PdAu NPs (about 10.2 nm) in spent catalyst","metricCount":"2"},{"paperId":"P029","catalystId":"P029_PERF_003","name":"Pd0.8Au0.2/UiO-66-ref-D","support":"UiO-66","matchedSynthesis":"Pd0.8Au0.2/UiO-66-ref-D","matchedCharacterization":"Pd0.8Au0.2/UiO-66-ref-D","role":"reference catalyst","composition":"Pd:Au = 0.8:0.2","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Pd0.8Au0.2/UiO-66-D using conventional UiO-66 support.","phase":"PdAu alloy","particleSize":"> 5 nm","structureLink":"Nearly inactive for formic acid decomposition, indicating that NH2 groups are crucial for activity.","reactionConditions":"10 mg catalyst in 9.5 mL deionized water, 0.5 mL of 4 M aqueous formic acid (FA), ambient atmosphere, shaking water bath","whyPerformsWell":"Nearly inactive due to absence of NH2 groups on support","metricCount":"0"},{"paperId":"P029","catalystId":"P029_PERF_004","name":"Pd0.8Au0.2/UiO-66-ref-S","support":"UiO-66","matchedSynthesis":"Pd0.8Au0.2/UiO-66-ref-S","matchedCharacterization":"Pd0.8Au0.2/UiO-66-ref-S","role":"reference catalyst","composition":"Pd:Au = 0.8:0.2","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Pd0.8Au0.2/UiO-66-S using conventional UiO-66 support.","phase":"PdAu alloy","particleSize":"> 5 nm","structureLink":"Nearly inactive for formic acid decomposition.","reactionConditions":"10 mg catalyst in 9.5 mL deionized water, 0.5 mL of 4 M aqueous formic acid (FA), ambient atmosphere, shaking water bath","whyPerformsWell":"Nearly inactive due to absence of NH2 groups on support","metricCount":"0"},{"paperId":"P030","catalystId":"P030_PERF_001","name":"PdCo0.2/EDA-HPAN","support":"EDA-HPAN (amine modified polyacrylonitrile hollow spheres)","matchedSynthesis":"PdCo0.2/EDA-HPAN","matchedCharacterization":"PdCo0.2/EDA-HPAN","role":"catalyst for formic acid dehydrogenation","composition":"Pd:Co = 1:0.2 molar ratio","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"EDA-HPAN was impregnated with Pd and Co precursors, dried, and then reduced using NaBH4.","phase":"Bimetallic alloy","particleSize":"0.81 nm","surfaceStates":"Pd0 signals shift toward lower binding energies compared to Pd/EDA-HPAN due to electron transfer from Co to Pd. Co 2p XPS peaks at 781.1 and 797.3 eV.","structureLink":"The alloy effect adjusts the electronic state of Pd, decreasing particle size and improving dehydrogenation activity compared to single metal Pd.","reactionConditions":"Additive-free dehydrogenation of formic acid aqueous solution","selectivity":"Excellent dehydrogenation selectivity; no CO signal detected by GC analysis","stability":"Very high activity after five cycles at 333 K","deactivation":"Strong capability against aggregation; spent catalyst particle size around 0.9 nm","whyPerformsWell":"Hollow structure of support provides higher specific surface area and rougher surface for high dispersion of ultra-small NPs (<1 nm). Surface amino and cyano groups act as basic sites to promote deprotonation of FA. Addition of Co adjusts the electronic state of Pd species.","metricCount":"3"},{"paperId":"P030","catalystId":"P030_PERF_002","name":"Pd/EDA-HPAN","support":"EDA-HPAN (amine modified polyacrylonitrile hollow spheres)","matchedSynthesis":"Pd/EDA-HPAN","matchedCharacterization":"Pd/EDA-HPAN","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"EDA-HPAN was impregnated with Pd precursor, dried, and then reduced using NaBH4.","phase":"Single metal nanoparticles","particleSize":"0.88 nm","surfaceStates":"Pd 3d XPS peaks: Pd2+ (342.8, 337.8 eV) and Pd0 (341.1, 335.9 eV).","structureLink":"Ultra-small particle size and high dispersion on the aminated hollow support contribute to catalytic activity.","reactionConditions":"Additive-free dehydrogenation of formic acid aqueous solution","selectivity":"Excellent dehydrogenation selectivity; no CO signal detected by GC analysis","stability":"Very high activity after five cycles at 333 K","deactivation":"Strong capability against aggregation; spent catalyst particle size around 1.0 nm","whyPerformsWell":"Hollow structure of support and surface amino/cyano groups facilitate high dispersion of ultra-small NPs and activate FA molecules.","metricCount":"2"},{"paperId":"P031","catalystId":"P031_PERF_001","name":"Pd0.7Cr0.3/NH2-MXene","matchedCharacterization":"Pd0.7Cr0.3/NH2-MXene","activeMetals":"Pd-Cr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic PdCr nanoparticles; HRTEM shows a lattice spacing of 0.230 nm, indicating lattice contraction relative to the Pd(111) plane (0.231 nm) due to Cr incorporation.","particleSize":"1.2-1.8 nm","surfaceStates":"Electron-rich metal sites; XPS reveals negative shifts in binding energies for both Pd and Cr compared to the non-amine functionalized support, indicating electron transfer from amine groups to the nanoparticles. Specific peaks: Pd 3d5/2 at 335.1 eV (Pd0), Cr 2p3/2 at 574.9 eV (Cr0) and 577.0 eV (Cr3+).","structureLink":"Amine groups act as anchors to prevent aggregation and donate electrons to the PdCr sites, accelerating O-H bond cleavage in formic acid. Cr incorporation modulates the electronic structure, local strain, and atomic coordination number of Pd active sites.","reactionConditions":"Aqueous FA system, 303-333 K, catalyst/FA molar ratio = 0.016","selectivity":"excellent selectivity for FA dehydrogenation","stability":"no apparent decay of kinetics after fifth runs at 323 K","whyPerformsWell":"Amine group benefits the formation of ultrafine and well-dispersed PdCr NPs (1.8 nm), modulates electronic structure by facilitating electron transfer from support to NPs forming electron-rich sites, and accelerates O-H bond cleavage.","metricCount":"6"},{"paperId":"P031","catalystId":"P031_PERF_002","name":"Pd0.7Cr0.3/MXene","matchedCharacterization":"Pd0.7Cr0.3/MXene","activeMetals":"Pd-Cr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"Seriously aggregated compared to Pd0.7Cr0.3/NH2-MXene","surfaceStates":"Higher binding energies for Pd and Cr compared to the amine-functionalized version, indicating a lack of electron transfer from the support.","structureLink":"Lack of amine anchors leads to nanoparticle aggregation and less electron-rich active sites, resulting in significantly lower catalytic activity (17.6 times lower TOF).","reactionConditions":"Aqueous FA system, 323 K, catalyst/FA molar ratio = 0.016","whyPerformsWell":"Inferior performance due to serious aggregation of NPs compared to NH2-MXene support","metricCount":"1"},{"paperId":"P032","catalystId":"P032_PERF_001","name":"POLITAG-20-Pd(0)","support":"macroreticular resin (POLITAG-20-L)","matchedSynthesis":"POLITAG-20-Pd(0)","matchedCharacterization":"POLITAG-20-Pd(0)","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Synthesis of macroreticular resin SP-20-Cl, functionalization with ligand 3,3-bis(1H-imidazol-1-yl)propan-1-ol and quaternization with iodomethane to form POLITAG-20-L; loading of Pd(II) using Na2PdCl4 in water to obtain POLITAG-20-Pd(II), followed by reduction to Pd(0) using NaBH4 in ethanol.","phase":"Pd nanoparticles","surfaceStates":"Pd(0) stabilized by pincer-type bis-imidazolium ionic tags on a macroreticular resin support.","structureLink":"The macroreticular polymeric matrix provides a stable and durable porous structure suitable for aqueous media. The use of pincer-type ionic tags to stabilize Pd(0) and the operation in an alkaline environment (pH 9) were linked to enhanced dehydrogenation rates and total selectivity, inhibiting the dehydration pathway.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous media, typically at 90 °C with catalyst loading of 1.2 mol%.","selectivity":"Total selectivity toward dehydrogenation; no traces of CO detected; only CO2 gas produced.","stability":"Consistent efficiency over five consecutive runs without loss of activity (evaluated at t50% conversion).","deactivation":"TEM analysis confirmed preservation of Pd nanoparticle morphology and dimensions in the recycled catalyst.","whyPerformsWell":"Stable porous macroreticular structure suitable for aqueous media; alkaline environment (pH 9) favors dehydrogenation while inhibiting dehydration; sodium ions promote Pd-catalyzed hydrogen transfer.","metricCount":"6"},{"paperId":"P033","catalystId":"P033_PERF_001","name":"1Pd/C3Ny_650_4","support":"carbon nitride (g-C3N4)","matchedSynthesis":"1Pd/C3Ny_650_4","matchedCharacterization":"1Pd/C3Ny_650_4","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Melamine was thermally polycondensed at 650 °C for 4 h to create the C3N4 support. Palladium acetate dissolved in acetone was added dropwise to the support, followed by drying and reduction under a hydrogen/nitrogen flow.","phase":"Metallic Pd","particleSize":"2.8 nm","structureLink":"Lowest activity among the series due to smallest particle size and lowest metal loading.","reactionConditions":"Formic acid decomposition in liquid phase at 60 °C","selectivity":"totally selective toward formic acid dehydrogenation; only H2 and CO2 produced","stability":"support structure is preserved after reaction","deactivation":"minimal Pd leaching; drop in rate ascribed to formation of intermediate species (COH and CHOO) blocking the active phase","metricCount":"3"},{"paperId":"P033","catalystId":"P033_PERF_002","name":"5Pd/C3Ny_650_4","support":"carbon nitride (g-C3N4)","matchedSynthesis":"5Pd/C3Ny_650_4","matchedCharacterization":"5Pd/C3Ny_650_4","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Melamine was thermally polycondensed at 650 °C for 4 h to create the C3N4 support. Palladium acetate dissolved in acetone was added dropwise to the support, followed by drying and reduction under a hydrogen/nitrogen flow.","phase":"fcc Pd0","particleSize":"4.6 nm (TEM), 4.5 nm (XRD)","surfaceStates":"Preferential orientation of the (111) facet","structureLink":"Optimal particle size (~4.6 nm) for maximum specific rate in formic acid decomposition, following a volcano relationship.","reactionConditions":"Formic acid decomposition in liquid phase at 60 °C","selectivity":"totally selective toward formic acid dehydrogenation; only H2 and CO2 produced","stability":"support structure is preserved after reaction","deactivation":"minimal Pd leaching; drop in rate ascribed to formation of intermediate species (COH and CHOO) blocking the active phase","whyPerformsWell":"Pd particle size (4.6 nm) is close to optimal sizes reported for high specific rates","metricCount":"3"},{"paperId":"P033","catalystId":"P033_PERF_003","name":"10Pd/C3Ny_650_4","support":"carbon nitride (g-C3N4)","matchedSynthesis":"10Pd/C3Ny_650_4","matchedCharacterization":"10Pd/C3Ny_650_4","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Melamine was thermally polycondensed at 650 °C for 4 h to create the C3N4 support. Palladium acetate dissolved in acetone was added dropwise to the support, followed by drying and reduction under a hydrogen/nitrogen flow.","phase":"Coexistence of metallic palladium (Pd0) and palladium hydride (PdHx)","particleSize":"10.2 nm (TEM), 11.1 nm (XRD)","surfaceStates":"Preferential orientation of the (111) facet; expanded Pd lattice (3.9123 Å vs bulk 3.8910 Å)","structureLink":"Highest TOF and cumulative H2 production; larger, thermodynamically stable single-crystalline nanoparticles are more resistant to deactivation than smaller clusters.","reactionConditions":"Formic acid decomposition in liquid phase at 60 °C","selectivity":"totally selective toward formic acid dehydrogenation; only H2 and CO2 produced","stability":"support structure is preserved after reaction","deactivation":"minimal Pd leaching; drop in rate ascribed to formation of intermediate species (COH and CHOO) blocking the active phase","whyPerformsWell":"Highest TOF attributed to thermodynamically stable aggregated nanoparticles that may expose highly active low-index planes such as Pd(111), combined with high surface area of the support enhancing effective exposure of Pd centers.","metricCount":"3"},{"paperId":"P034","catalystId":"P034_PERF_001","name":"Pd/NC-Co1%","support":"NC-Co1% (N-doped carbon decorated with Co)","matchedSynthesis":"Pd/NC-Co1%","matchedCharacterization":"Pd/NC-Co1%","role":"active catalyst","composition":"Pd:Co (approx. 4:1 by weight based on ICP)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Urea calcined to C3N4; hydrothermal with glucose to form C3N4@G; Co salt added and heated under N2 to form NC-Co support; Pd immobilized via NaBH4 reduction.","phase":"Pd nanoparticles immobilized on a support (not an alloy).","particleSize":"1.86 nm","surfaceStates":"Pd 3d peak at 336.2 eV with an increased area for Pd2+ compared to Pd/NC, indicating strong interaction between Co and Pd NPs. Co is present as Co2+-N species. N 1s spectra show pyridinic N (398.5 eV), pyrrolic N (400.5 eV), graphitic N (401 eV), and N-Co species (399.5 eV).","structureLink":"Atomically dispersed Co atoms on the support increase carbon defects, provide additional active sites for Pd dispersion, and regulate the nucleation/growth of Pd NPs to reduce their size, resulting in enhanced catalytic activity for FA dehydrogenation.","reactionConditions":"FA dehydrogenation in aqueous solution using a mixture of FA and SF","stability":"Good durability; only a slight loss in activity was observed after 5 cycles at 50 °C","whyPerformsWell":"Interaction between Pd NPs and atomically dispersed Co atoms anchored on N-doped carbon; Co doping induces more carbon defects increasing active site density and reduces the size of Pd NPs (average particle size 1.86 nm).","metricCount":"1"},{"paperId":"P034","catalystId":"P034_PERF_002","name":"Pd/NC","support":"NC (N-doped carbon)","matchedSynthesis":"Pd/NC","matchedCharacterization":"Pd/NC","role":"control sample","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"Urea calcined to C3N4; hydrothermal with glucose to form C3N4@G; Pd immobilized via NaBH4 reduction.","phase":"Pd nanoparticles","surfaceStates":"Pd 3d peak at 336.2 eV.","structureLink":"Lower activity than Pd/NC-Co1%, demonstrating the promotional effect of Co doping on the support.","reactionConditions":"FA dehydrogenation in aqueous solution using a mixture of FA and SF","whyPerformsWell":"N species on the carbon can efficiently enhance catalytic activity compared to non-doped carbon.","metricCount":"1"},{"paperId":"P034","catalystId":"P034_PERF_003","name":"PdCo1%/NC","matchedCharacterization":"PdCo1%/NC","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdCo alloy","particleSize":"2.41 nm","surfaceStates":"Binding energy of Co is 0.2 eV lower than in NC-Co1% and Pd/NC-Co1%; Pd 3d peak is 0.25 eV higher than in Pd/NC and Pd/NC-Co1%.","structureLink":"Lower catalytic activity compared to Pd/NC-Co1%, suggesting that atomically dispersed Co on the support is more effective for performance enhancement than alloying Co into the nanoparticles.","reactionConditions":"FA dehydrogenation in aqueous solution using a mixture of FA and SF","whyPerformsWell":"Inferior to Pd/NC-Co1% because alloyed NPs have larger average particle size (2.41 nm) compared to the Co-decorated support system.","metricCount":"0"},{"paperId":"P035","catalystId":"P035_PERF_001","name":"0.1Pt/MoC","support":"α-MoC","matchedSynthesis":"0.1Pt/MoC","matchedCharacterization":"0.1Pt/MoC","role":"catalyst","composition":"Pt:Mo (0.1 wt% Pt)","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"arc discharge","synthesis":"One-step ultrahigh-temperature synthesis using an arc-discharge route. Mixed Pt and Mo powders were filled in a graphite anode tube with a graphite rod as the cathode. The chamber was vacuumized to 3 Pa, then filled with pure hydrogen to 0.08 MPa. Arc discharge was performed at 80 A for approximately 30 minutes.","phase":"Single-crystal FCC α-MoC support with Pt single atoms (SAs)","particleSize":"Single atom","surfaceStates":"Pt exists as Ptδ+ species (positive charge); Mo exists in Mo2+ and Mo4+ states","structureLink":"SAs maximize FA dehydrogenation and CO2 hydrogenation efficiency due to strong Pt-MoC interactions and high adsorption energies for FA (-2.84 eV) and CO2 (-1.42 eV), but exhibit low CO oxidation activity due to CO poisoning (adsorption energy -2.35 eV).","reactionConditions":"Room-temperature FA dehydrogenation (aqueous base-free); CO2 hydrogenation to FA (aqueous amine); Room-temperature CO oxidation.","selectivity":"100% selectivity to H2 evolution through FA dehydrogenation; no toxic CO detected.","stability":"Air-stable for two years; reused up to six times without significant loss of conversion efficiency; total TON of 54,148 achieved.","deactivation":"ICP-AES analysis shows Pt and Mo contents in the filtrate are below detection limit.","whyPerformsWell":"Enhanced electron transfer from MoC to active Pt species improves surface electron density; strong Pt-MoC interactions; atomic dispersion effect of Pt SAs maximizes catalytic potential for FA dehydrogenation and CO2 hydrogenation.","metricCount":"9"},{"paperId":"P035","catalystId":"P035_PERF_002","name":"0.2Pt/MoC","support":"α-MoC","matchedSynthesis":"0.2Pt/MoC","matchedCharacterization":"0.2Pt/MoC","role":"catalyst","composition":"Pt:Mo (0.2 wt% Pt)","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"arc discharge","synthesis":"One-step ultrahigh-temperature synthesis using an arc-discharge route. Mixed Pt and Mo powders were filled in a graphite anode tube with a graphite rod as the cathode. The chamber was vacuumized to 3 Pa, then filled with pure hydrogen to 0.08 MPa. Arc discharge was performed at 80 A for approximately 30 minutes.","phase":"α-MoC support with Pt nanoclusters (NCs) and small amount of nanoparticles (NPs)","particleSize":"ca. 1.1 nm (average size of NCs)","surfaceStates":"Coexistence of metallic Pt and positively charged Ptδ+ species","structureLink":"Displays the highest performance for room-temperature CO oxidation.","reactionConditions":"Room-temperature FA dehydrogenation (aqueous base-free); CO2 hydrogenation to FA (aqueous amine); Room-temperature CO oxidation.","whyPerformsWell":"Highest performance for room-temperature CO oxidation due to optimal Pt particle size (ca. 1.1 nm NCs) avoiding the poisoning effect seen with SAs.","metricCount":"2"},{"paperId":"P035","catalystId":"P035_PERF_003","name":"1Pt/MoC","support":"α-MoC","matchedSynthesis":"1Pt/MoC","matchedCharacterization":"1Pt/MoC","role":"catalyst","composition":"Pt:Mo (1 wt% Pt)","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"arc discharge","synthesis":"One-step ultrahigh-temperature synthesis using an arc-discharge route. Mixed Pt and Mo powders were filled in a graphite anode tube with a graphite rod as the cathode. The chamber was vacuumized to 3 Pa, then filled with pure hydrogen to 0.08 MPa. Arc discharge was performed at 80 A for approximately 30 minutes.","phase":"α-MoC support with co-existing NCs and NPs","particleSize":"ca. 2.2 nm","structureLink":"Lower activity for FA dehydrogenation and CO2 hydrogenation compared to SAs.","reactionConditions":"Room-temperature FA dehydrogenation (aqueous base-free); CO2 hydrogenation to FA (aqueous amine).","metricCount":"2"},{"paperId":"P035","catalystId":"P035_PERF_004","name":"2Pt/MoC","support":"α-MoC","matchedSynthesis":"2Pt/MoC","matchedCharacterization":"2Pt/MoC","role":"catalyst","composition":"Pt:Mo (2 wt% Pt)","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"arc discharge","synthesis":"One-step ultrahigh-temperature synthesis using an arc-discharge route. Mixed Pt and Mo powders were filled in a graphite anode tube with a graphite rod as the cathode. The chamber was vacuumized to 3 Pa, then filled with pure hydrogen to 0.08 MPa. Arc discharge was performed at 80 A for approximately 30 minutes.","phase":"α-MoC support with co-existing NCs and NPs","particleSize":"ca. 3.1 nm","surfaceStates":"Dominating metallic Pt state","structureLink":"Lowest activity for FA dehydrogenation and CO2 hydrogenation among the series.","reactionConditions":"Room-temperature FA dehydrogenation (aqueous base-free); CO2 hydrogenation to FA (aqueous amine).","metricCount":"2"},{"paperId":"P036","catalystId":"P036_PERF_001","name":"Ru4/AC","support":"Vulcan XC72R carbon","matchedSynthesis":"Ru4/AC","matchedCharacterization":"Ru4/AC","role":"catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Prepared on Vulcan XC72R without any nitrogen source by a chemical reduction method.","phase":"Hexagonal-close-packed (hcp) structure of metallic Ru.","particleSize":"3–5 nm","surfaceStates":"Strong interaction between Ru nanoparticles and CO, leading to easy poisoning.","structureLink":"Lack of nitrogen coordination results in strong CO adsorption, which poisons active sites and inhibits activity.","reactionConditions":"140 °C, propylene carbonate (PC), nFA = 10 mmol, nFA/nRu = 500, 20 μmol Ru, 5 mL solvent","selectivity":"H2:CO2 = 43%/52%, CO = 5.2%","stability":"deactivated quickly","deactivation":"poisoned by generated CO","metricCount":"2"},{"paperId":"P036","catalystId":"P036_PERF_002","name":"Ru5/ACN","support":"Vulcan XC72R carbon","matchedSynthesis":"Ru5/ACN","role":"catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Prepared following the same synthesis procedure as Ru/CN but using Vulcan XC72R carbon as support and phenanthroline ligand.","reactionConditions":"140 °C, propylene carbonate (PC), nFA = 10 mmol, nFA/nRu = 500, 20 μmol Ru, 5 mL solvent","selectivity":"H2:CO2 = 49%/51%, CO = 287 ppm","whyPerformsWell":"ruthenium is coordinated to nitrogen","metricCount":"2"},{"paperId":"P036","catalystId":"P036_PERF_003","name":"Ru2/CN","support":"nitrogen-doped carbon","matchedSynthesis":"Ru2/CN","matchedCharacterization":"Ru2/CN, Ru4/CN, Ru14/CN","role":"catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Pyrolysis of RuCl3·xH2O in the presence of 1,10-phenanthroline (Phen) on C3N4 support.","phase":"Metallic Ru species on nitrogen-doped carbon; XRD peak intensity at 43.4° increases with higher Ru content.","particleSize":"2–3 nm","surfaceStates":"Electron-deficient state due to Ru-N interaction.","structureLink":"Activity increases with Ru content up to 7 wt%, then stabilizes.","reactionConditions":"140 °C, propylene carbonate (PC), nFA = 10 mmol, nFA/nRu = 500, 20 μmol Ru, 5 mL solvent","selectivity":"H2:CO2 = 47%/53%, CO = 699 ppm","whyPerformsWell":"ruthenium is coordinated to nitrogen","metricCount":"2"},{"paperId":"P036","catalystId":"P036_PERF_004","name":"Ru4/CN","support":"nitrogen-doped carbon","matchedSynthesis":"Ru4/CN","matchedCharacterization":"Ru2/CN, Ru4/CN, Ru14/CN","role":"catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Pyrolysis of RuCl3·xH2O in the presence of 1,10-phenanthroline (Phen) on C3N4 support.","phase":"Metallic Ru species on nitrogen-doped carbon; XRD peak intensity at 43.4° increases with higher Ru content.","particleSize":"2–3 nm","surfaceStates":"Electron-deficient state due to Ru-N interaction.","structureLink":"Activity increases with Ru content up to 7 wt%, then stabilizes.","reactionConditions":"140 °C, propylene carbonate (PC), nFA = 10 mmol, nFA/nRu = 500, 20 μmol Ru, 5 mL solvent","selectivity":"H2:CO2 = 47%/53%, CO = 203 ppm","whyPerformsWell":"ruthenium is coordinated to nitrogen","metricCount":"2"},{"paperId":"P036","catalystId":"P036_PERF_005","name":"Ru7/CN","support":"nitrogen-doped carbon","matchedSynthesis":"Ru7/CN","matchedCharacterization":"Ru7/CN","role":"optimal catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Pyrolysis of RuCl3·xH2O in the presence of 1,10-phenanthroline (Phen) on C3N4 support.","phase":"Metallic Ru species supported on nitrogen-doped carbon; broad XRD peaks suggest an amorphous structure or ultra-small size.","particleSize":"2–3 nm","surfaceStates":"Electron-deficient state caused by strong electronic interaction between Ru and nitrogen doping on the support.","structureLink":"Nitrogen coordination weakens CO adsorption strength via electron depletion on Ru, increasing CO tolerance and suppressing CO2 dissociation into CO.","reactionConditions":"140 °C, propylene carbonate (PC), nFA = 10 mmol, nFA/nRu = 500, 20 μmol Ru, 5 mL solvent","selectivity":"H2:CO2 = 49%/51%, CO = 56 ppm","stability":"activity stayed unchanged in the next 6 runs after second run; TON of 12,000 over 50 cycles at 140 °C","whyPerformsWell":"nitrogen-doped carbon support increases barrier for CO2 reduction to CO and weakens adsorption of CO","metricCount":"6"},{"paperId":"P036","catalystId":"P036_PERF_006","name":"Ru14/CN","support":"nitrogen-doped carbon","matchedSynthesis":"Ru14/CN","matchedCharacterization":"Ru2/CN, Ru4/CN, Ru14/CN","role":"catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Pyrolysis of RuCl3·xH2O in the presence of 1,10-phenanthroline (Phen) on C3N4 support.","phase":"Metallic Ru species on nitrogen-doped carbon; XRD peak intensity at 43.4° increases with higher Ru content.","particleSize":"2–3 nm","surfaceStates":"Electron-deficient state due to Ru-N interaction.","structureLink":"Activity increases with Ru content up to 7 wt%, then stabilizes.","reactionConditions":"140 °C, propylene carbonate (PC), nFA = 10 mmol, nFA/nRu = 500, 20 μmol Ru, 5 mL solvent","selectivity":"H2:CO2 = 50%/50%, CO = 67 ppm","whyPerformsWell":"ruthenium is coordinated to nitrogen","metricCount":"2"},{"paperId":"P036","catalystId":"P036_PERF_007","name":"Ru5/C","matchedCharacterization":"Ru5/C","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","surfaceStates":"High surface oxidation.","structureLink":"Surface oxidation leads to significantly lower TOF compared to Ru7/CN.","reactionConditions":"140 °C, propylene carbonate (PC), nFA = 10 mmol, nFA/nRu = 500, 20 μmol Ru, 5 mL solvent","selectivity":"H2:CO2 = 50%/49%, CO = 2360 ppm","metricCount":"2"},{"paperId":"P036","catalystId":"P036_PERF_008","name":"Pd5/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"140 °C, propylene carbonate (PC), nFA = 10 mmol, nFA/nPd = 500, 20 μmol Pd, 5 mL solvent","selectivity":"H2:CO2 = 44%/55%, CO = 1.6%","deactivation":"almost completely poisoned by the generated CO","metricCount":"2"},{"paperId":"P037","catalystId":"P037_PERF_001","name":"PdAu/ACB","support":"amine-functionalized carbon bowls (ACB)","matchedSynthesis":"PdAu/ACB","matchedCharacterization":"PdAu/ACB","role":"active catalyst","composition":"Pd:Au = 3:2","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"ACB was dispersed in DI water, metal precursors were added and stirred for 3 h, followed by reduction with NaBH4.","phase":"PdAu alloy (lattice spacing 0.232 nm; XRD Pd(111) peak shifted to lower angle)","particleSize":"0.9 nm","surfaceStates":"Electron-rich PdAu clusters; partial electron transfer from Pd to Au (due to electronegativity difference) and from ACB support to PdAu clusters via electronic metal-support interaction.","structureLink":"Subnanometric size provides abundant active sites; electron-rich nature facilitates rate-determining C-H activation in FAD; surface amine groups act as Brønsted basic sites (proton scavengers) boosting O-H bond cleavage in FA.","reactionConditions":"Formic acid dehydrogenation (FAD) and Cr(VI) reduction using FA as hydrogen donor.","selectivity":"100% H2 selectivity (no detectable CO)","stability":"completely decompose FA with H2 selectivity and conversion unchanged during durability test; gas generation rate shows a slight loss over ten runs","deactivation":"slightly increased particle size of PdAu clusters is responsible for the decreased activity","whyPerformsWell":"tiny size and abundant active sites of PdAu clusters, promotional effect of surface amine groups (acting as proton scavengers/Brønsted basic sites), and electronic interaction between subnanometric PdAu clusters and support forming electron-rich metal sites that facilitate C-H activation","metricCount":"4"},{"paperId":"P037","catalystId":"P037_PERF_002","name":"PdAu/CB","matchedCharacterization":"PdAu/CB","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdAu alloy","particleSize":"4.9 nm","structureLink":"Lack of amine groups on CB leads to cluster aggregation and lower catalytic activity compared to PdAu/ACB.","reactionConditions":"FAD and Cr(VI) reduction.","whyPerformsWell":"poor activity compared to PdAu/ACB due to lack of amine groups","metricCount":"2"},{"paperId":"P037","catalystId":"P037_PERF_003","name":"Pd/ACB","matchedCharacterization":"Pd/ACB","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"monometallic Pd","particleSize":"1.1 nm","reactionConditions":"FAD and Cr(VI) reduction.","metricCount":"1"},{"paperId":"P037","catalystId":"P037_PERF_004","name":"Au/ACB","support":"amine-functionalized carbon bowls (ACB)","matchedSynthesis":"PdAu/ACB","matchedCharacterization":"PdAu/ACB","role":"active catalyst","composition":"Pd:Au = 3:2","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"ACB was dispersed in DI water, metal precursors were added and stirred for 3 h, followed by reduction with NaBH4.","phase":"PdAu alloy (lattice spacing 0.232 nm; XRD Pd(111) peak shifted to lower angle)","particleSize":"0.9 nm","surfaceStates":"Electron-rich PdAu clusters; partial electron transfer from Pd to Au (due to electronegativity difference) and from ACB support to PdAu clusters via electronic metal-support interaction.","structureLink":"Subnanometric size provides abundant active sites; electron-rich nature facilitates rate-determining C-H activation in FAD; surface amine groups act as Brønsted basic sites (proton scavengers) boosting O-H bond cleavage in FA.","reactionConditions":"Cr(VI) reduction.","metricCount":"1"},{"paperId":"P037","catalystId":"P037_PERF_005","name":"PdAu (support-free)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FAD and Cr(VI) reduction.","metricCount":"1"},{"paperId":"P038","catalystId":"P038_PERF_001","name":"Pd/SiO2@SC-1:3","support":"commercial SiO2 nanoparticles","matchedSynthesis":"Pd/SiO2","matchedCharacterization":"Pd/SiO2@SC-1:3","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Pd/SiO2@SC-1:x but using commercial SiO2 nanoparticles instead of the carbon-coated support.","phase":"Metallic Pd and PdO","particleSize":"3.26 nm","surfaceStates":"Electron-deficient state of Pd0 (B.E. = 336 eV)","structureLink":"The electron-deficient state and optimal Pd0/PdO ratio weaken the Pd-H bond, accelerating hydrogen desorption (the rate-determining step), resulting in a TOF of 1138 h^-1 and Ea of 28.6 kJ/mol.","reactionConditions":"Formic acid decomposition (FAD) at 30 °C in a double-neck flask with stirring.","selectivity":"Only H2 and CO2 generated (confirmed by GC)","stability":"Activity significantly decreases after the first performance test, but Pd/SiO2@SC-1:3 displays the smallest decrease among tested catalysts.","deactivation":"Carbon layer is destroyed, particles are agglomerated, and PdO is consumed.","whyPerformsWell":"Electron-deficient state of Pd0 (induced by SiO2) and optimal ratio of Pd0/PdO (regulated by carbon layer thickness) enhance the hydrogen desorption rate, which is the rate determining step (RDS).","metricCount":"2"},{"paperId":"P038","catalystId":"P038_PERF_002","name":"Pd/SiO2","support":"commercial SiO2 nanoparticles","matchedSynthesis":"Pd/SiO2","matchedCharacterization":"Pd/SiO2","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Pd/SiO2@SC-1:x but using commercial SiO2 nanoparticles instead of the carbon-coated support.","phase":"PdO","particleSize":"20-30 nm","surfaceStates":"Pd loses electrons to SiO2 (B.E. shift)","reactionConditions":"Formic acid decomposition (FAD) at 30 °C in a double-neck flask with stirring.","metricCount":"1"},{"paperId":"P038","catalystId":"P038_PERF_003","name":"Pd/E-SiO2@SC-1:3","support":"E-SiO2@SC-1:3","matchedSynthesis":"Pd/E-SiO2@SC-1:3","matchedCharacterization":"Pd/E-SiO2@SC-1:3","role":"control catalyst (etched support)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"SiO2 core was etched from SiO2@SC-1:3 using NaOH, followed by Pd loading via the same wet impregnation reduction procedure as Pd/SiO2@SC-1:x.","phase":"Metallic Pd","surfaceStates":"Electron-deficient state is weakened compared to Pd/SiO2@SC-1:3; B.E. of Pd0 decreases.","structureLink":"Dramatic decrease in dehydrogenation performance due to the loss of the electron-deficient state induced by SiO2.","reactionConditions":"Formic acid decomposition (FAD) at 30 °C in a double-neck flask with stirring.","whyPerformsWell":"Dehydrogenation performance dramatically decreased compared with Pd/SiO2@SC-1:3 due to the absence of SiO2 core and subsequent weakening of the electron-deficient state.","metricCount":"0"},{"paperId":"P039","catalystId":"P039_PERF_001","name":"Au1–Pd11/KIT-6","support":"KIT-6","matchedSynthesis":"Au1–Pd11/KIT-6","role":"active catalyst","composition":"Au: 0.25 wt%, Pd: 2.80 wt%","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Wet impregnation of KIT-6 with Pd and Au precursors in acidic solution, followed by stirring, solvent evaporation, and calcination.","reactionConditions":"65 °C, 80 mg catalyst in 10 mL DI water, stirred at 800 rpm","whyPerformsWell":"Synergic effect of Au and Pd nanoparticles on KIT-6 support","metricCount":"1"},{"paperId":"P039","catalystId":"P039_PERF_002","name":"Au1–Pd18/KIT-6","support":"KIT-6","matchedSynthesis":"Au1–Pd18/KIT-6","role":"active catalyst","composition":"Au: 0.15 wt%, Pd: 2.70 wt%","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Wet impregnation of KIT-6 with Pd and Au precursors in acidic solution, followed by stirring, solvent evaporation, and calcination.","reactionConditions":"65 °C, 80 mg catalyst in 10 mL DI water, stirred at 800 rpm","whyPerformsWell":"Synergic effect of Au and Pd nanoparticles on KIT-6 support","metricCount":"1"},{"paperId":"P039","catalystId":"P039_PERF_003","name":"Au1–Pd14/KIT-6","support":"KIT-6","matchedSynthesis":"Au1–Pd14/KIT-6","role":"active catalyst","composition":"Au: 0.20 wt%, Pd: 2.70 wt%","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Wet impregnation of KIT-6 with Pd and Au precursors in acidic solution, followed by stirring, solvent evaporation, and calcination.","reactionConditions":"65 °C, 80 mg catalyst in 10 mL DI water, stirred at 800 rpm","whyPerformsWell":"Synergic effect of Au and Pd nanoparticles on KIT-6 support","metricCount":"1"},{"paperId":"P039","catalystId":"P039_PERF_004","name":"Au1–Pd17/KIT-6","support":"KIT-6","matchedSynthesis":"Au1–Pd17/KIT-6","role":"activated catalyst","composition":"Au: 0.10 wt%, Pd: 1.70 wt%","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Wet impregnation followed by calcination at 350 °C and subsequent activation under oxygen flow.","reactionConditions":"65 °C, 80 mg catalyst in 10 mL DI water, stirred at 800 rpm; activated by oxygen flow at 220 °C for 5 h","selectivity":"dehydrogenation pathway preferred over dehydration","stability":"Regenerated and reused for 4 successive runs; gas volumes: Run 1 (142 mL), Run 2 (98 mL), Run 3 (86 mL), Run 4 (110 mL)","deactivation":"decrease in catalytic activity over four runs","whyPerformsWell":"Oxygen treatment prohibits diffusion of Pd atoms into Au sublayers, increasing surface Pd concentration; synergic metal-metal and metal-support interactions; high surface area of KIT-6 support","metricCount":"3"},{"paperId":"P039","catalystId":"P039_PERF_005","name":"Pd/KIT-6","matchedCharacterization":"Au–Pd/KIT-6","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Formation of a Pd–Au alloy was indicated by XRD peaks appearing at intermediate values between metallic Pd and Au. Recycled catalysts showed face-centered cubic (fcc) Pd, while those calcined at 550 °C exhibited fcc PdO.","surfaceStates":"Oxygen treatment inhibits the diffusion of Pd atoms into Au sublayers, maintaining more Pd on the surface. At higher temperatures, Au nanoparticles tend to migrate to the catalyst surface.","structureLink":"Catalysts calcined at 350 °C exhibited higher activity than those calcined at 550 °C. The transition from a non-crystalline state (at 350 °C) to PdO crystal formation via oxygen treatment significantly increased gas release from 62 mL to 142 mL.","reactionConditions":"65 °C, 80 mg catalyst in 10 mL DI water, stirred at 800 rpm","whyPerformsWell":"Pd has a critical role but requires modification (e.g., by Au) for higher activity","metricCount":"1"},{"paperId":"P040","catalystId":"P040_PERF_001","name":"LS-NH2/Pd","support":"Amino-functionalized layered silicate (LS-NH2)","matchedSynthesis":"LS-NH2/Pd","matchedCharacterization":"LS-NH2/Pd","role":"Catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"LS-NH2 dispersed in ethanol was mixed with aqueous K2PdCl4, sonicated, stirred, and dried. The powder was redispersed in H2O:EtOH (1:1) and reduced by dropwise addition of methanolic NaBH4.","phase":"Pd nanoclusters","particleSize":"Average lateral size 1.1-1.3 nm; thickness < 0.5 nm","surfaceStates":"XPS Pd 3d5/2 main peak at 336.0 eV and shoulder at 338.2 eV; exhibits weaker binding with the amine-functionalized surface and retains more metallic characteristics due to minimal hybridization between Pd 4d and N 2p states.","structureLink":"Higher catalytic activity (TOF = 246 h-1 at 70 °C) is attributed to weaker Pd-N covalency, which preserves the structural integrity of the nanoclusters and maintains more available metallic 4d electrons for catalysis.","reactionConditions":"Aqueous solution of formic acid, Ar atmosphere, stirring at 20, 50, and 70 °C","stability":"Pd NCs on amine functional groups tend to agglomerate and grow in size during catalytic activity (indicated by XPS BE shift)","deactivation":"agglomeration","whyPerformsWell":"Weaker hybridization between Pd 4d electrons and N 2p orbitals resulting in weaker covalency, allowing Pd NCs to retain more metallic characteristics; ligands also act as spacers for the LS and Pd NCs.","metricCount":"2"},{"paperId":"P040","catalystId":"P040_PERF_002","name":"LS-SH/Pd","support":"Thio-functionalized layered silicate (LS-SH)","matchedSynthesis":"LS-SH/Pd","matchedCharacterization":"LS-SH/Pd","role":"Catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"LS-SH dispersed in ethanol was mixed with aqueous K2PdCl4, sonicated, stirred, and dried. The powder was redispersed in H2O:EtOH (1:1) and reduced by dropwise addition of methanolic NaBH4.","phase":"Pd nanoclusters","particleSize":"Average lateral size 1.1-1.3 nm; thickness < 1.1 nm","surfaceStates":"XPS Pd 3d5/2 peak at 337.3 eV (higher BE than LS-NH2/Pd); UV-vis absorption band at 390 nm indicates ligand-to-metal-charge-transfer (LMCT) and strong Pd 4d-S 3p hybridization.","structureLink":"Lower catalytic activity (TOF = 9 h-1 at 70 °C) is attributed to strong Pd-S covalency causing charge transfer from Pd to S, and structural deformation into a flatter, quasi-two-dimensional structure that reduces the overall surface area and number of active sites.","reactionConditions":"Aqueous solution of formic acid, Ar atmosphere, stirring at 20, 50, and 70 °C","stability":"Robustly anchored to the thiol groups and do not undergo changes during reaction (confirmed by XPS)","whyPerformsWell":"Performs poorly due to strong hybridization between Pd 4d electrons and S 3p orbitals causing greater covalency and charge transfer from Pd to S; additionally, Pd NCs undergo structural deformation (flattening) into a quasi-2D structure, reducing overall surface area.","metricCount":"2"},{"paperId":"P041","catalystId":"P041_PERF_001","name":"2 wt.% Pd/KCC-1-PDETA","support":"KCC-1","matchedSynthesis":"2 wt.% Pd/KCC-1-PDETA","matchedCharacterization":"2 wt.% Pd/KCC-1-PDETA","role":"catalyst for additive-free dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KCC-1 was functionalized with PDETA in toluene at 80 °C for 24 h, then impregnated with Na2PdCl4 solution and reduced using sodium borohydride.","phase":"Pd nanoparticles","particleSize":"2.8 nm (mean diameter; 90% in range 2–4 nm)","surfaceStates":"Pd(0) peaks at 339.9 and 334.6 eV; Pd(2+) peaks at 337.5 and 342.8 eV","structureLink":"The unique fibrous morphology of KCC-1 and presence of amine groups reduced particle size and improved reactant access to active sites, resulting in the highest TOF (332 h-1).","reactionConditions":"Additive-free dehydrogenation of formic acid in aqueous solution, nPd/nFA = 0.01, 5 mmol FA, 15 mL water, vigorous stirring under inert conditions (Ar)","selectivity":"100% selectivity towards hydrogen; practically CO-free","stability":"Good reusability up to five times; ~7% decline in catalytic activity after the fifth run","deactivation":"No Pd leaching detected (limit: ~0.01 ppm); Pd particle size grew from 2.8 nm to 3.3 nm after reuse","whyPerformsWell":"Unique fibrous morphology of KCC-1 and presence of amine groups reduced Pd particle size and improved reactant access to active sites","metricCount":"4"},{"paperId":"P041","catalystId":"P041_PERF_002","name":"2 wt.% Pd/MSF-PDETA","support":"MSF","matchedSynthesis":"2 wt.% Pd/MSF-PDETA","matchedCharacterization":"2 wt.% Pd/MSF-PDETA","role":"comparison catalyst for support effect study","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"MSF support functionalized with PDETA, then impregnated with Na2PdCl4 solution and reduced using sodium borohydride.","phase":"Pd nanoparticles","particleSize":"4.9 nm","surfaceStates":"Higher fraction of Pd(2+) than 2 wt.% Pd/KCC-1-PDETA","structureLink":"Larger particle size and lower nitrogen content compared to KCC-1 resulted in lower catalytic activity (TOF 147 h-1).","reactionConditions":"Additive-free dehydrogenation of formic acid in aqueous solution, nPd/nFA = 0.01, 5 mmol FA, 15 mL water, vigorous stirring under inert conditions (Ar)","metricCount":"1"},{"paperId":"P041","catalystId":"P041_PERF_003","name":"2 wt.% Pd/KIT-6-PDETA","support":"KIT-6","matchedSynthesis":"2 wt.% Pd/KIT-6-PDETA","matchedCharacterization":"2 wt.% Pd/KIT-6-PDETA","role":"comparison catalyst for support effect study","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KIT-6 support functionalized with PDETA, then impregnated with Na2PdCl4 solution and reduced using sodium borohydride.","phase":"Pd nanoparticles","particleSize":"14.5 nm","surfaceStates":"Higher fraction of Pd(2+) than 2 wt.% Pd/KCC-1-PDETA","structureLink":"Significantly larger particle size compared to KCC-1 resulted in the lowest catalytic activity (TOF 97 h-1).","reactionConditions":"Additive-free dehydrogenation of formic acid in aqueous solution, nPd/nFA = 0.01, 5 mmol FA, 15 mL water, vigorous stirring under inert conditions (Ar)","metricCount":"1"},{"paperId":"P041","catalystId":"P041_PERF_004","name":"5 wt.% Pd/KCC-1-PDETA","support":"KCC-1","matchedSynthesis":"5 wt.% Pd/KCC-1-PDETA","matchedCharacterization":"5 wt.% Pd/KCC-1-PDETA","role":"catalyst for additive-free dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same as 2 wt.% Pd/KCC-1-PDETA with adjusted Na2PdCl4 amount.","phase":"Pd nanoparticles (characteristic Pd(111) peak at 39.1° in XRD)","particleSize":"5.6 nm","surfaceStates":"Higher portion of unreduced Pd(2+) compared to 2 wt.% loading","structureLink":"Increased particle size and agglomeration, along with a higher fraction of unreduced Pd(2+), contributed to lower catalytic activity (TOF 242 h-1).","reactionConditions":"Additive-free dehydrogenation of formic acid in aqueous solution, nPd/nFA = 0.01, 5 mmol FA, 15 mL water, vigorous stirring under inert conditions (Ar)","whyPerformsWell":"Decreased activity compared to 2 wt.% due to bigger particle size and agglomeration of Pd nanoparticles","metricCount":"1"},{"paperId":"P041","catalystId":"P041_PERF_005","name":"10 wt.% Pd/KCC-1-PDETA","support":"KCC-1","matchedSynthesis":"10 wt.% Pd/KCC-1-PDETA","matchedCharacterization":"10 wt.% Pd/KCC-1-PDETA","role":"catalyst for additive-free dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same as 2 wt.% Pd/KCC-1-PDETA with adjusted Na2PdCl4 amount.","phase":"Pd nanoparticles (characteristic Pd(111) peak at 39.1° in XRD)","particleSize":"8.0 nm","surfaceStates":"Highest portion of unreduced Pd(2+) among KCC-1 samples","structureLink":"Largest particle size and highest fraction of unreduced Pd(2+) led to the lowest activity among KCC-1 catalysts (TOF 222 h-1).","reactionConditions":"Additive-free dehydrogenation of formic acid in aqueous solution, nPd/nFA = 0.01, 5 mmol FA, 15 mL water, vigorous stirring under inert conditions (Ar)","whyPerformsWell":"Decreased activity compared to 2 wt.% due to bigger particle size and agglomeration of Pd nanoparticles","metricCount":"1"},{"paperId":"P042","catalystId":"P042_PERF_001","name":"2% Pd/Al2O3","support":"Al2O3","matchedSynthesis":"2% Pd/Al2O3","matchedCharacterization":"2% Pd/Al2O3","role":"comparison catalyst","composition":"Pd (2%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Ex situ synthesis of PVP-stabilized Pd nanoparticles using 1-ascorbic acid as reducing agent at 368 K, followed by incipient wetness impregnation on Al2O3 support.","phase":"Pure Pd nanoparticles","particleSize":"8.2 ± 3.3 nm","surfaceStates":"Single Pd atoms on edges (weak band at 2060 cm-1), hollow Pd sites (<1920 cm-1), and double coordinated Pd sites (>1920 cm-1).","structureLink":"Lower hydrogen selectivity (91.1%) compared to Pd/ZnO, attributed to the absence of PdZn alloy and higher activity for the reverse water-gas shift reaction.","reactionConditions":"Vapor phase formic acid decomposition in a fixed-bed flow reactor; 2 vol.% formic acid/He mixture; total flow rate of 51 cm3 (STP) min−1; catalyst amount 0.035 g.","selectivity":"91.1 ± 0.3% (H2 selectivity)","metricCount":"2"},{"paperId":"P042","catalystId":"P042_PERF_002","name":"2% Pd/ZnO","support":"ZnO","matchedSynthesis":"2% Pd/ZnO","matchedCharacterization":"2% Pd/ZnO","role":"main catalyst","composition":"Pd (2%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Ex situ synthesis of PVP-stabilized Pd nanoparticles using 1-ascorbic acid as reducing agent at 368 K, followed by incipient wetness impregnation on ZnO support.","phase":"PdZn alloy","particleSize":"9.8 ± 4.1 nm (reduced at 573 K)","surfaceStates":"High concentration of single Pd sites surrounded by Zn atoms (DRIFTS band at ~2080 cm-1) and double coordinated Pd sites due to dilution of surface Pd with Zn.","structureLink":"Formation of PdZn alloy directs formic acid decomposition toward dehydrogenation, resulting in high hydrogen selectivity (up to 99.3%) and reducing the reverse water-gas shift reaction compared to pure Pd.","reactionConditions":"Vapor phase formic acid decomposition in a fixed-bed flow reactor; 2 vol.% formic acid/He mixture; total flow rate of 51 cm3 (STP) min−1; catalyst amount 0.035 g.","selectivity":"98.8 ± 0.3% (reduced at 573 K); 99.3 ± 0.3% (after in situ reduction at 773 K)","whyPerformsWell":"Formation of PdZn alloy during reductive pre-treatment directs formic acid decomposition to dehydrogenation and reduces the reverse water-gas shift reaction compared to pure Pd.","metricCount":"3"},{"paperId":"P042","catalystId":"P042_PERF_003","name":"1% Pd/ZnO","support":"ZnO","matchedSynthesis":"1% Pd/ZnO","matchedCharacterization":"1% Pd/ZnO","role":"comparison catalyst (ionic precursor)","composition":"Pd (1%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Aqueous solution of PdCl2(HCl) added to ZnO suspension, stirred for 24 h at room temperature, filtered, washed and dried.","phase":"PdZn alloy","particleSize":"6.5 ± 2.2 nm (at 573 K); 11.6 ± 4.1 nm (at 773 K)","structureLink":"Catalytic activity is independent of the reduction temperature and resulting particle size, suggesting the ZnO support plays a key role in the rate-determining step.","reactionConditions":"Vapor phase formic acid decomposition in a fixed-bed flow reactor; 2 vol.% formic acid/He mixture; total flow rate of 51 cm3 (STP) min−1; catalyst amount 0.070 g.","selectivity":"96.5 ± 0.1% (reduced at 573 K); 98.0 ± 0.1% (reduced at 773 K)","whyPerformsWell":"Formation of PdZn alloy; activity is independent of reduction temperature/particle size.","metricCount":"0"},{"paperId":"P042","catalystId":"P042_PERF_004","name":"1.2% Pt/ZnO","support":"ZnO","matchedSynthesis":"1.2% Pt/ZnO","matchedCharacterization":"1.2% Pt/ZnO","role":"comparison catalyst (ionic precursor)","composition":"Pt (1.2%)","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Aqueous solution of hexachloroplatinic acid added to ZnO suspension, stirred for 24 h at room temperature, filtered, washed and dried.","phase":"PtZn alloy (for reduced samples); pure Pt nanoparticles (for air-treated sample)","particleSize":"2.3 ± 0.5 nm (at 573 K); 5.9 ± 2.0 nm (at 773 K); 5.0 ± 1.7 nm (air treated)","structureLink":"Hydrogen selectivity increases with reduction temperature (from 95.3% to 96.3%).","reactionConditions":"Vapor phase formic acid decomposition in a fixed-bed flow reactor; 2 vol.% formic acid/He mixture; total flow rate of 51 cm3 (STP) min−1; catalyst amount 0.070 g.","selectivity":"95.3 ± 0.5% (reduced at 573 K); 96.3 ± 0.5% (reduced at 773 K); 93.1 ± 0.5% (treated in air)","metricCount":"0"},{"paperId":"P042","catalystId":"P042_PERF_005","name":"ZnO support","activeMetals":"Zn","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Vapor phase formic acid decomposition in a fixed-bed flow reactor; 2 vol.% formic acid/He mixture; total flow rate of 51 cm3 (STP) min−1; catalyst amount 0.035 g.","selectivity":"< 70% (H2 selectivity)","metricCount":"2"},{"paperId":"P043","catalystId":"P043_PERF_001","name":"Au0.4Pd0.6Pt0.2/CNC-NH2","support":"amino-modified cellulose nanocrystals (CNC-NH2)","matchedSynthesis":"Au0.4Pd0.6Pt0.2/CNC-NH2","matchedCharacterization":"Au0.4Pd0.6Pt0.2/CNC-NH2","role":"main catalyst","composition":"Au:Pd:Pt = 0.4:0.6:0.2","activeMetals":"Au-Pd-Pt","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Metal precursors were added to a CNC-NH2 aqueous solution, stirred, and then reduced using sodium borohydride in an ice water bath.","phase":"Ternary alloy (confirmed by lattice spacing of 0.23 nm, XRD after heat treatment, and absence of Au nanoparticles in UV-vis spectra)","particleSize":"Average size 2.28 nm","surfaceStates":"Binding energy shifts observed via XPS: Pt 4f increased (71.0 to 72.6 eV), Au 4f decreased (83.8 to 82.9 eV), and Pd 3d decreased (335.2 to 334.5 eV) upon loading on CNC-NH2.","structureLink":"The optimized local electron environment facilitates O-H bond cleavage (the rate-determining step) and reduces the binding energy barrier between H*; ultrafine size and high dispersion further enhance catalytic activity.","reactionConditions":"FA/SF mixed solution at 323K","selectivity":"100% selectivity for hydrogen; CO not detected","stability":"Cycle stability studied at 313K; activity decreased slightly after the second cycle, then did not decrease significantly.","deactivation":"Degradation attributed to poor dispersion stability leading to particle aggregation and loss of metal particles that fail to bind to carrier during centrifugation/washing cycles.","whyPerformsWell":"Introduction of Pt optimizes the electronic structure (electron transfer from Pt to Au and Pd) creating a Pd-rich electron center; amine-modified CNC support ensures ultrafine size (~2.28nm) and high dispersion; DFT shows reduced energy barrier for O-H bond cleavage (RDS).","metricCount":"2"},{"paperId":"P044","catalystId":"P044_PERF_001","name":"Pd/C-H2P","support":"activated carbon","matchedSynthesis":"Pd/C-H2P","matchedCharacterization":"Pd/C-H2P","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Pre-oxidized activated carbon was impregnated with PdCl2 solution, dried, calcined under H2, and then treated with H2 working gas in a dielectric barrier discharge (DBD) cold plasma reactor.","phase":"Metallic Pd (fcc)","particleSize":"2.6 ± 1.0 nm (TEM)","surfaceStates":"Pd0: 50.8%, PdII: 29.2%, PdIV: 20.0%; presence of Pd-C bonds at 282.5 eV indicating strong metal-support interaction.","structureLink":"Small particle size, high metallic Pd content, and high Pd/C atomic ratio (0.0229) contribute to the highest HCOOH dehydrogenation activity.","reactionConditions":"50 °C, deionized water, 4 M HCOOH and 4 M sodium formate (SF), magnetic stirring","selectivity":"No CO was detected during the reaction.","whyPerformsWell":"High Pd/C atomic ratio (0.0229), high content of metallic Pd (50.8%), small average particle size (2.6 ± 1.0 nm), and strong metal-support interaction.","metricCount":"2"},{"paperId":"P044","catalystId":"P044_PERF_002","name":"Pd/C-ArP","support":"activated carbon","matchedSynthesis":"Pd/C-ArP","matchedCharacterization":"Pd/C-ArP","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Pre-oxidized activated carbon was impregnated with PdCl2 solution, dried, calcined under H2, and then treated with Ar working gas in a dielectric barrier discharge (DBD) cold plasma reactor.","phase":"Metallic Pd (fcc)","particleSize":"3.2 ± 1.1 nm (TEM)","surfaceStates":"Pd0: 46.3%, PdII: 28.5%, PdIV: 25.2%; Pd/C atomic ratio: 0.0141","structureLink":"Activity is inferior to Pd/C-H2P due to milder discharge and weaker regulation effect of Ar plasma.","reactionConditions":"50 °C, deionized water, 4 M HCOOH and 4 M sodium formate (SF), magnetic stirring","selectivity":"No CO was detected during the reaction.","whyPerformsWell":"Discharge in Ar plasma was mild and regulation effect not as strong as H2 plasma.","metricCount":"1"},{"paperId":"P044","catalystId":"P044_PERF_003","name":"Pd/C-AirP","support":"activated carbon","matchedSynthesis":"Pd/C-AirP","matchedCharacterization":"Pd/C-AirP","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Pre-oxidized activated carbon was impregnated with PdCl2 solution, dried, calcined under H2, and then treated with compressed air working gas in a dielectric barrier discharge (DBD) cold plasma reactor.","phase":"Metallic Pd (fcc)","particleSize":"5.2 ± 1.8 nm (TEM); 4.9 nm (XRD crystallite size)","surfaceStates":"Pd0: 50.1%, PdII: 24.6%, PdIV: 25.3%; presence of adsorbed [NOy]s at 405.9 eV; Pd/C atomic ratio: 0.0087","structureLink":"Poor activity due to large particle size (> 4 nm) and harmful adsorbed NOx species.","reactionConditions":"50 °C, deionized water, 4 M HCOOH and 4 M sodium formate (SF), magnetic stirring","selectivity":"No CO was detected during the reaction.","whyPerformsWell":"Poor activity due to severe ablation of carbon support and agglomeration of Pd nanoparticles (5.2 ± 1.8 nm), exceeding optimal size range (< 4 nm).","metricCount":"1"},{"paperId":"P044","catalystId":"P044_PERF_004","name":"Pd/C-O2P","support":"activated carbon","matchedSynthesis":"Pd/C-O2P","matchedCharacterization":"Pd/C-O2P","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Pre-oxidized activated carbon was impregnated with PdCl2 solution, dried, calcined under H2, and then treated with O2 working gas in a dielectric barrier discharge (DBD) cold plasma reactor.","phase":"Metallic Pd (fcc)","particleSize":"7.0 ± 2.4 nm (TEM); 8.0 nm (XRD crystallite size)","surfaceStates":"Pd0: 46.6%, PdII: 26.7%, PdIV: 26.7%; Pd/C atomic ratio: 0.0115","structureLink":"Poor activity due to large particle size (approx. 2.7 times that of Pd/C-H2P) exceeding the optimal range for HCOOH dehydrogenation.","reactionConditions":"50 °C, deionized water, 4 M HCOOH and 4 M sodium formate (SF), magnetic stirring","selectivity":"No CO was detected during the reaction.","whyPerformsWell":"Poor activity due to severe ablation of carbon support and agglomeration of Pd nanoparticles (7.0 ± 2.4 nm), exceeding optimal size range (< 4 nm).","metricCount":"1"},{"paperId":"P045","catalystId":"P045_PERF_001","name":"Pd/C (5 wt % Pd)","support":"activated carbon","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"commercial","synthesis":"Commercially available Pd/C was purchased from Merck-Sigma and used as received.","phase":"Metallic Pd nanoparticles on activated carbon","particleSize":"3.2 nm","surfaceStates":"Fresh: 78% Pd0, 22% PdII; Used/Regenerated: 100% Pd0","structureLink":"Deactivation is attributed to pore fouling (92% loss of micropore area) and active site poisoning by formate ions rather than changes in particle size or oxidation state. Metallic Pd was found to be the most active species.","reactionConditions":"Additive-free dehydrogenation of aqueous formic acid","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","deactivation":"No Pd leaching observed via ICP-MS. Deactivation attributed to pore fouling and poisoning by formate ions; CO is an effective poison but not the primary cause during standard operation.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","metricCount":"9"},{"paperId":"P046","catalystId":"P046_PERF_001","name":"Pd/TC","support":"templated carbon","matchedSynthesis":"Pd/TC","matchedCharacterization":"Pd/TC (Pd/templated carbon)","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Templated carbon was synthesized via CVD of acetylene on NaY zeolite and HF washing. Pd was deposited onto the TC support using wet impregnation from an aqueous PdCl2 solution, dried at room temperature, and reduced under H2 flow.","phase":"Small Pd particles (evidenced by a broad and low amplitude XRD peak at 39.9°)","particleSize":"Around 2 nm and below","structureLink":"The high surface area (965 m2/g) and uniformly dispersed small Pd nanoparticles on the nanostructured templated carbon are linked to superior activity in FA decomposition at room temperature. TGA showed that Pd nanoparticles significantly decreased the combustion temperature of the TC support from 500-600 °C down to 290 °C.","reactionConditions":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","deactivation":"Activity decrease observed during reuse cycles.","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","metricCount":"20"},{"paperId":"P047","catalystId":"P047_PERF_001","name":"AP-SiO2@NGO-PDA@Pd0.51Au0.49","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) in aqueous solution at 50 °C","selectivity":"selective dehydrogenation","whyPerformsWell":"combination of the bimetallic synergistic effect and the carrier effect; cooperation of the PDA ligand effect (accelerating O-H bond splitting and H* association) and modulated geometric/electronic structures of Pd after Au incorporation","metricCount":"1"},{"paperId":"P047","catalystId":"P047_PERF_002","name":"AP-SiO2@NGO-PDA@Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) in aqueous solution at 50 °C","whyPerformsWell":"Pd is the active site; Au alone exhibits slight activity","metricCount":"1"},{"paperId":"P047","catalystId":"P047_PERF_003","name":"AP-SiO2@NGO-PDA@Pd5Au5 (higher loading)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) in aqueous solution at 50 °C","whyPerformsWell":"Activity decreased due to the size effect (average cluster size increased from 1.9 to 2.5 nm)","metricCount":"1"},{"paperId":"P048","catalystId":"P048_PERF_001","name":"Au0.28Pd0.47Co0.25/MIL-101-NH2","support":"MIL-101-NH2","matchedSynthesis":"Au0.28Pd0.47Co0.25/MIL-101-NH2","matchedCharacterization":"Au0.28Pd0.47Co0.25/MIL-101-NH2","role":"catalyst for formic acid dehydrogenation","composition":"Au:Pd:Co = 0.283:0.467:0.250","activeMetals":"Au-Pd-Co","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Metal precursors were dispersed in deionized water, followed by the addition of activated MIL-101-NH2 and stirring for 2 h. Reduction was then performed by adding NaBH4 solution and stirring under Ar atmosphere for 2 h.","phase":"Homogeneous AuPdCo alloy with a face-centered cubic (fcc) structure similar to metallic Au; lattice spacing of 0.230 nm.","particleSize":"2.3 ± 0.4 nm","surfaceStates":"XPS shows binding energies for Pd 3d and Au 4f shifted to lower values and Co 2p shifted to higher values compared to monometallic counterparts, indicating electron transfer from Co to Au and Pd.","structureLink":"The NH2 group effectively immobilizes metal ions via coordination or electrostatic interactions, inducing small particle size and high dispersion; the H2N-Co complex acts as a proton scavenger facilitating FA decomposition.","reactionConditions":"FA-SF aqueous solution, ambient atmosphere","selectivity":"100% H2 selectivity; no CO detected by GC","stability":"Activity and H2 selectivity remained with no significant change after the first run (recycled by adding same amount of FA); activity significantly decreased after nine cycles (980 min)","deactivation":"Aggregations of AuPdCo NPs; acidic catalytic environment of FA-SF aqueous solution weakened interaction force between AuPdCo NPs and MIL-101-NH2","whyPerformsWell":"Electron-donating NH2 group bonded to Co forming a complex H2N-Co which acts as a proton scavenger, facilitating the cleavage of O-H bond in FA; synergistic interaction among different metals.","metricCount":"1"},{"paperId":"P048","catalystId":"P048_PERF_002","name":"Au0.28Pd0.47Fe0.25/MIL-101-NH2","support":"MIL-101-NH2","matchedSynthesis":"Au0.28Pd0.47Fe0.25/MIL-101-NH2","matchedCharacterization":"Au0.28Pd0.47Fe0.25/MIL-101-NH2","role":"catalyst for formic acid dehydrogenation","composition":"Au:Pd:Fe = 0.281:0.473:0.246","activeMetals":"Au-Pd-Fe","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Same process as Au0.28Pd0.47Co0.25/MIL-101-NH2 using Fe(NO3)2·6H2O instead of cobalt source.","phase":"AuPdFe alloy nanoparticles","particleSize":"5.2 ± 0.5 nm","surfaceStates":"Fe in oxidation state","reactionConditions":"FA-SF aqueous solution, ambient atmosphere","selectivity":"Complete and selective decomposition of FA into H2 and CO2; no CO detected by GC","metricCount":"1"},{"paperId":"P048","catalystId":"P048_PERF_003","name":"Au0.28Pd0.47Ni0.25/MIL-101-NH2","support":"MIL-101-NH2","matchedSynthesis":"Au0.28Pd0.47Ni0.25/MIL-101-NH2","matchedCharacterization":"Au0.28Pd0.47Ni0.25/MIL-101-NH2","role":"catalyst for formic acid dehydrogenation","composition":"Au:Pd:Ni = 0.284:0.475:0.241","activeMetals":"Au-Pd-Ni","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Same process as Au0.28Pd0.47Co0.25/MIL-101-NH2 using Ni(NO3)2·6H2O instead of cobalt source.","phase":"AuPdNi alloy nanoparticles","particleSize":"4.2 ± 0.5 nm","surfaceStates":"Ni in oxidation state","reactionConditions":"FA-SF aqueous solution, ambient atmosphere","selectivity":"Complete and selective decomposition of FA into H2 and CO2","metricCount":"1"},{"paperId":"P048","catalystId":"P048_PERF_004","name":"Au0.28Pd0.47Co0.25/MIL-101-NO2","matchedCharacterization":"Au0.28Pd0.47Co0.25/MIL-101-NO2","activeMetals":"Au-Pd-Co","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"2.6 ± 0.3 nm","surfaceStates":"Co in oxidation state","structureLink":"Electron-accepting NO2 group leads to stronger bonding of intermediates (CO2 and H2) on the surface, hindering desorption and reducing activity.","reactionConditions":"FA-SF aqueous solution, 298 K","selectivity":"Very low H2 selectivity","whyPerformsWell":"Low activity and selectivity due to strong bonding of Co-OOCH-, Co-H- and Pd-H+ making desorption of CO2 and H2 difficult","metricCount":"0"},{"paperId":"P048","catalystId":"P048_PERF_005","name":"Au0.28Pd0.47Co0.25/MIL-101-SO3H","matchedCharacterization":"Au0.28Pd0.47Co0.25/MIL-101-SO3H","activeMetals":"Au-Pd-Co","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"5.3 ± 0.5 nm","surfaceStates":"Co in oxidation state","reactionConditions":"FA-SF aqueous solution, 298 K","selectivity":"Drastically lower H2 selectivity than Au0.28Pd0.47Co0.25/MIL-101-NH2","whyPerformsWell":"Drastically lower activity compared to NH2 functionalized support","metricCount":"0"},{"paperId":"P048","catalystId":"P048_PERF_006","name":"Au0.28Pd0.47Co0.25/MIL-101 (bare)","matchedCharacterization":"Au0.28Pd0.47Co0.25/MIL-101","activeMetals":"Au-Pd-Co","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"3.6 ± 0.5 nm","reactionConditions":"FA-SF aqueous solution, 298 K","selectivity":"Drastically lower H2 selectivity than Au0.28Pd0.47Co0.25/MIL-101-NH2","whyPerformsWell":"Drastically lower activity compared to NH2 functionalized support","metricCount":"0"},{"paperId":"P048","catalystId":"P048_PERF_007","name":"Au0.28Pd0.47Co0.25/SBA-15-NH2","activeMetals":"Au-Pd-Co","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA-SF aqueous solution, 298 K","selectivity":"95% H2 selectivity","whyPerformsWell":"Low activity compared to MIL-101-NH2 but better than bare SBA-15 due to NH2 group","metricCount":"0"},{"paperId":"P048","catalystId":"P048_PERF_008","name":"Au0.28Pd0.47Co0.25/SBA-15","activeMetals":"Au-Pd-Co","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA-SF aqueous solution, 298 K","whyPerformsWell":"Almost no activity","metricCount":"0"},{"paperId":"P049","catalystId":"P049_PERF_001","name":"Co5Pd5/CTF-600","matchedCharacterization":"Co5Pd5/CTF-600","activeMetals":"Co-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Amorphous or ultrafine nanoparticles (no characteristic XRD peaks for Co or Pd); synergistic bimetallic effect observed between Co and Pd.","particleSize":"approximately 2 nm","surfaceStates":"Pd exists as both Pd0 (335.75, 340.95 eV) and Pd2+ (338.1, 343.35 eV); Co exists as Co2+ (781.4, 797.2 eV). Positive shift in N 1s binding energy indicates electron transfer between metal NPs and the CTF support.","structureLink":"High catalytic activity is attributed to the ultrafine particle size (~2 nm), the synergistic effect between Co and Pd, and the nitrogen-rich CTF support (specifically pyridinic-N) which enhances electron transfer and provides coordination sites for metal anchoring.","reactionConditions":"10 mL round-bottomed flask in a water bath with magnetic stirrer, connected to a gas burette; solvent: distilled water","selectivity":"100% H2 selectivity; no CO detected at the level of 1 ppm","stability":"no significant decrease of activity observed after 5 runs","whyPerformsWell":"synergetic effect between CoPd nanoparticles and nitrogen-rich CTF support; ultrafine sizes of CoPd (mean size ~2 nm); high pore volume and pore size of CTF-600 facilitate metal nanoparticle entry and reaction medium transmission","metricCount":"4"},{"paperId":"P049","catalystId":"P049_PERF_002","name":"Co5Pd5/CTF-500","matchedCharacterization":"Co5Pd5/CTF-500","activeMetals":"Co-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"3.86 nm","structureLink":"Activity is higher than CTF-400 but lower than CTF-600 due to particle size and support pore volume differences.","reactionConditions":"Same as Co5Pd5/CTF-600","whyPerformsWell":"larger BET surface area and pore volume than CTF-400","metricCount":"1"},{"paperId":"P049","catalystId":"P049_PERF_003","name":"Co5Pd5/CTF-400","matchedCharacterization":"Co5Pd5/CTF-400","activeMetals":"Co-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"4.51 nm","structureLink":"Lower activity than CTF-600 due to larger particle size and inferior dispersion.","reactionConditions":"Same as Co5Pd5/CTF-600","metricCount":"1"},{"paperId":"P049","catalystId":"P049_PERF_004","name":"Co5Pd5/XC-72","matchedCharacterization":"Co5Pd5/XC-72","activeMetals":"Co-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","structureLink":"Exhibited torpid catalytic activity compared to CTF-supported catalysts, highlighting the role of nitrogen doping in the support.","reactionConditions":"Same as Co5Pd5/CTF-600","metricCount":"1"},{"paperId":"P050","catalystId":"P050_PERF_001","name":"Pd/a_MSC-30","matchedCharacterization":"Pd/a_MSC-30","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pd nanoparticles","structureLink":"Acid activation of the MSC-30 carbon support improves catalytic activity for formic acid dehydrogenation compared to non-activated supports.","reactionConditions":"Formic acid dehydrogenation with sodium formate (SF) additive, Pd/FA molar ratio = 0.01, solvent: water","selectivity":"absence of CO at the detection limit in the released gas (at 60 °C)","stability":"tested by recollecting catalyst via centrifugation and washing with DI water; reused in aqueous solution containing FA (3.0 M) and SF (7.5 M)","metricCount":"6"},{"paperId":"P051","catalystId":"P051_PERF_001","name":"Pd/a_MSC-30","support":"MSC-30","matchedSynthesis":"Pd/a_MSC-30","matchedCharacterization":"Pd/a_MSC-30","role":"benchmark catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Porous carbon was treated with HNO3 at room temperature, washed, and dispersed in water; K2PdCl4 precursor was added and shaken for 1 hour, followed by reduction with sodium borohydride.","phase":"Metallic palladium (Pd^0)","particleSize":"~2.4 nm","surfaceStates":"Pd 3d binding energies at 335.5 and 340.8 eV; stabilized by oxygen-containing functional groups introduced via HNO3 treatment.","structureLink":"Ultrafine feature and high dispersibility lead to a record-high TOF of 13333 h^-1 for formic acid dehydrogenation.","reactionConditions":"aqueous FA-SF system, nFA:nSF = 1 : 2.5, nPd/nFA = 0.01, FA amount = 3 mmol","selectivity":"exclusive formation of H2 and CO2 without CO impurity","stability":"only a slight decrease in the activity is observed after five cycles at 60 °C","deactivation":"slight increase in particle size of Pd NPs","whyPerformsWell":"ultrafine feature and high dispersibility that originated from the stabilization effect of HNO3-treated carbon","metricCount":"7"},{"paperId":"P051","catalystId":"P051_PERF_002","name":"Pd/MSC-30","support":"MSC-30","matchedSynthesis":"Pd/MSC-30","matchedCharacterization":"Pd/MSC-30","role":"control experiment","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Prepared by the same procedure as Pd/a_MSC-30 but using pristine MSC-30 support.","phase":"Metallic palladium","particleSize":"Much larger than Pd/a_MSC-30","structureLink":"Lower catalytic activity (TOF) compared to the ultrafine Pd/a_MSC-30 due to larger particle size.","reactionConditions":"aqueous FA-SF system, nFA:nSF = 1 : 2.5, nPd/nFA = 0.01, 60 °C","metricCount":"1"},{"paperId":"P051","catalystId":"P051_PERF_003","name":"Pd/C_commercial","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"aqueous FA-SF system, nFA:nSF = 1 : 2.5, nPd/nFA = 0.01, 60 °C","metricCount":"1"},{"paperId":"P052","catalystId":"P052_PERF_001","name":"Pd6Cr4@NH2-MIL-101","support":"NH2-MIL-101","matchedSynthesis":"Pd6Cr4@NH2-MIL-101","matchedCharacterization":"Pd6Cr4@NH2-MIL-101","role":"active catalyst","composition":"Pd:Cr = 6:4","activeMetals":"Pd-Cr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"NH2-MIL-101 was dispersed in deionized water via ultrasonication; Cr and Pd precursors were added under stirring for 2 h, followed by liquid-phase reduction with NaBH4 solution.","phase":"Bimetallic nanoparticles with crystalline nature; lattice spacing of 0.294 nm (close to the (101) crystal plane of Cr)","particleSize":"0.29 nm","surfaceStates":"Strong interaction between Pd nanoparticles and NH2-MIL-101, evidenced by a shift in the binding energy of Pd 3d compared to Pd6Cr4@MIL-101; weak interaction between Cr nanoparticles and NH2-MIL-101","structureLink":"Catalyst deactivation (decrease in TOF) is attributed to the agglomeration of Pd and Cr atoms on the outer surface, with particle sizes increasing from 0.29 nm to approximately 300 nm after two cycles and up to 800 nm after four cycles.","reactionConditions":"Dehydrogenation of formic acid aqueous solution at 323 K, stirring at 600 rpm in a two-port round-bottom flask.","selectivity":"Carbon monoxide content in gaseous products: < 0.5 ppm (Cycle 1), ~1.3 ppm (Cycles 2 and 3), 7.4 ppm (Cycle 4).","stability":"Catalyst cannot be reused more than three times because CO concentration may exceed 10 ppm (especially if CO2 is removed by alkali absorption).","deactivation":"Deactivation is caused by agglomeration of Pd and Cr atoms on the outer surface of the catalyst; ICP-OES analysis confirmed that leaching of active metals into the liquid was very low.","whyPerformsWell":"Strong interaction between Pd nanoparticles and NH2-MIL-101, which is enhanced by the NH2 group modification of MIL-101.","metricCount":"2"},{"paperId":"P053","catalystId":"P053_PERF_001","name":"1 wt% Pd/g-C3N4","support":"graphitic carbon nitride (g-C3N4)","matchedSynthesis":"Pd/g-C3N4","matchedCharacterization":"Pd/g-C3N4","role":"Catalyst","composition":"Pd (1 wt%, 3 wt%, and 5 wt%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Metal precursor and support were sonicated for 30 min and stirred for 4 h; pH adjusted to 8-9 using 0.5M NaOH; reduced by droplet addition of NaBH4 solution; re-sonicated for 20 min and stirred for 1 h at 10°C; centrifuged, washed with ethanol and distilled water, and dried.","phase":"Metallic phase (Pd0)","particleSize":"8.14 nm (1 wt%), 11.14 nm (3 wt%), 17.63 nm (5 wt%)","surfaceStates":"Nitrogen atoms in g-C3N4 support transfer electrons to Pd NPs, increasing electron cloud density.","structureLink":"Higher Pd loading increases active sites but leads to particle agglomeration and lower activity at high temperatures due to possible passive layer formation (PdCO or Pd formate).","reactionConditions":"Decomposition of formic acid; 0.03 g catalyst, 1.0 mL FA (98%), temperature range 30-70 °C","metricCount":"1"},{"paperId":"P053","catalystId":"P053_PERF_002","name":"3 wt% Pd/g-C3N4","support":"graphitic carbon nitride (g-C3N4)","matchedSynthesis":"Pd/g-C3N4","matchedCharacterization":"Pd/g-C3N4","role":"Catalyst","composition":"Pd (1 wt%, 3 wt%, and 5 wt%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Metal precursor and support were sonicated for 30 min and stirred for 4 h; pH adjusted to 8-9 using 0.5M NaOH; reduced by droplet addition of NaBH4 solution; re-sonicated for 20 min and stirred for 1 h at 10°C; centrifuged, washed with ethanol and distilled water, and dried.","phase":"Metallic phase (Pd0)","particleSize":"8.14 nm (1 wt%), 11.14 nm (3 wt%), 17.63 nm (5 wt%)","surfaceStates":"Nitrogen atoms in g-C3N4 support transfer electrons to Pd NPs, increasing electron cloud density.","structureLink":"Higher Pd loading increases active sites but leads to particle agglomeration and lower activity at high temperatures due to possible passive layer formation (PdCO or Pd formate).","reactionConditions":"Decomposition of formic acid; 0.03 g catalyst, 1.0 mL FA (98%), temperature range 30-70 °C","metricCount":"1"},{"paperId":"P053","catalystId":"P053_PERF_003","name":"5 wt% Pd/g-C3N4","support":"graphitic carbon nitride (g-C3N4)","matchedSynthesis":"Pd/g-C3N4","matchedCharacterization":"Pd/g-C3N4","role":"Catalyst","composition":"Pd (1 wt%, 3 wt%, and 5 wt%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Metal precursor and support were sonicated for 30 min and stirred for 4 h; pH adjusted to 8-9 using 0.5M NaOH; reduced by droplet addition of NaBH4 solution; re-sonicated for 20 min and stirred for 1 h at 10°C; centrifuged, washed with ethanol and distilled water, and dried.","phase":"Metallic phase (Pd0)","particleSize":"8.14 nm (1 wt%), 11.14 nm (3 wt%), 17.63 nm (5 wt%)","surfaceStates":"Nitrogen atoms in g-C3N4 support transfer electrons to Pd NPs, increasing electron cloud density.","structureLink":"Higher Pd loading increases active sites but leads to particle agglomeration and lower activity at high temperatures due to possible passive layer formation (PdCO or Pd formate).","reactionConditions":"Decomposition of formic acid; 0.03 g catalyst, 1.0 mL FA (98%), temperature range 30-70 °C","selectivity":"Hydrogen: 95.3%, Carbon Dioxide: 4.7%; no carbon monoxide or methane detected","stability":"Gas produced over three cycles at 30 °C: 1st cycle = 3.3 mL, 2nd cycle = 3.0 mL, 3rd cycle = 2.7 mL","deactivation":"At higher temperature (70 °C), total gas decreased for 5 wt% Pd/g-C3N4 compared to lower loadings; attributed to early dehydration reaction producing PdCO or Pd formate causing inhibition","whyPerformsWell":"Higher content of Pd metal provides more active sites; rich electrons of nitrogen atoms in g-C3N4 support transfer to Pd NPs increasing electron cloud density and promoting dissociation of hydrogen atom","metricCount":"6"},{"paperId":"P053","catalystId":"P053_PERF_004","name":"5 wt% Cu/g-C3N4","support":"graphitic carbon nitride (g-C3N4)","matchedSynthesis":"Cu/g-C3N4","matchedCharacterization":"Cu/g-C3N4","role":"Catalyst","composition":"Cu (5 wt%)","activeMetals":"Cu","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Same method as Pd/g-C3N4: sonication, stirring, pH adjustment to 8-9 with NaOH, NaBH4 reduction, re-sonication and stirring at 10°C, centrifugation, washing, and drying.","phase":"Oxide phase (CuO)","particleSize":"20.39 nm","surfaceStates":"Presence of CuO promotes passive layer formation on the catalyst surface.","structureLink":"Low catalytic activity attributed to high metal oxide (CuO) content and small amount of metallic Cu.","reactionConditions":"Decomposition of formic acid; 0.03 g catalyst, 1.0 mL FA (98%), temperature range 30-70 °C","selectivity":"Hydrogen: 92.0%, Carbon Dioxide: 6.7%","whyPerformsWell":"Low activity attributed to large formation of metal oxide (CuO) which is a less active species","metricCount":"2"},{"paperId":"P053","catalystId":"P053_PERF_005","name":"5 wt% Zn/g-C3N4","support":"graphitic carbon nitride (g-C3N4)","matchedSynthesis":"Zn/g-C3N4","matchedCharacterization":"Zn/g-C3N4","role":"Catalyst","composition":"Zn (5 wt%)","activeMetals":"Zn","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Same method as Pd/g-C3N4: sonication, stirring, pH adjustment to 8-9 with NaOH, NaBH4 reduction, re-sonication and stirring at 10°C, centrifugation, washing, and drying.","phase":"Oxide phase (ZnO)","particleSize":"25.24 nm","surfaceStates":"Presence of ZnO promotes passive layer formation on the catalyst surface.","structureLink":"Low catalytic activity attributed to high metal oxide (ZnO) content and larger crystal size leading to poor dispersion.","reactionConditions":"Decomposition of formic acid; 0.03 g catalyst, 1.0 mL FA (98%), temperature range 30-70 °C","selectivity":"Hydrogen: 87.5%, Carbon Dioxide: 10.5%","whyPerformsWell":"Low activity attributed to large formation of metal oxide (ZnO) which is a less active species","metricCount":"2"},{"paperId":"P054","catalystId":"P054_PERF_001","name":"5Ni–SiO2 (P123)","support":"SiO2","matchedSynthesis":"5Ni–SiO2(P123)","matchedCharacterization":"5Ni–SiO2(P123)","role":"active catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"one-pot synthesis","synthesis":"P123 mixed in HNO3 and water at 50 °C; Ni salt added, followed by dropwise addition of TEOS. Mixed for 24 h, then hydrothermally treated at 80 °C for 24 h, and evaporated at 80 °C.","phase":"Metallic Ni (111) plane","particleSize":"22.6 nm","surfaceStates":"Lewis acid sites; lower intensity peaks in terms of acidity compared to other catalysts.","structureLink":"Highest H2 concentration and selectivity among 5 wt% Ni catalysts.","reactionConditions":"Gas-phase decomposition of formic acid at 350 °C, space velocity of 27 L/hr.g cat, FA/Ar molar ratio of 1/2","selectivity":"H2: 51.5%, CO: 2.4%, CO2: 46.1% product distribution","stability":"stable catalytic activity in the experiments carried out for 180 min","whyPerformsWell":"The absence of CO after 90 min indicated only dehydrogenation occurred; acidic-basic properties may be more dominant than pore properties, surface area, or Ni crystallite size.","metricCount":"2"},{"paperId":"P054","catalystId":"P054_PERF_002","name":"2.5Ni–SiO2 (P123)","support":"SiO2","matchedSynthesis":"2.5Ni–SiO2(P123)","matchedCharacterization":"2.5Ni–SiO2(P123)","role":"active catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"one-pot synthesis","synthesis":"P123 mixed in HNO3 and water at 50 °C; Ni salt added, followed by dropwise addition of TEOS. Mixed for 24 h, then hydrothermally treated at 80 °C for 24 h, and evaporated at 80 °C.","phase":"Metallic Ni (111) plane","particleSize":"18.4 nm","surfaceStates":"Highest Lewis acidity among the catalysts.","structureLink":"Lower H2 distribution and selectivity compared to 5Ni–SiO2(P123) due to reduced nickel content.","reactionConditions":"Gas-phase decomposition of formic acid at 350 °C, space velocity of 27 L/hr.g cat, FA/Ar molar ratio of 1/2","selectivity":"H2: 29.5%, CO: 24.5%, CO2: 46.0% product distribution","stability":"stable catalytic activity in the experiments carried out for 180 min","whyPerformsWell":"Higher Lewis acidity was associated with lower catalytic activity.","metricCount":"2"},{"paperId":"P054","catalystId":"P054_PERF_003","name":"5Ni–SiO2 (NH3-CA)","support":"SiO2","matchedSynthesis":"5Ni–SiO2(NH3-CA)","matchedCharacterization":"5Ni–SiO2(NH3-CA)","role":"active catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"one-pot synthesis","synthesis":"TEOS added to ethanol and mixed at 50 °C; ammonia solution added and stirred for 3 h. Citric acid added and stirred at RT for 30 min, then Ni salt added and mixed for 30 min.","phase":"Metallic Ni dispersed as small crystals in the SiO2 lattice structure","surfaceStates":"Lewis and Brønsted acid sites.","structureLink":"Highest total pore volume; H2 selectivity of 0.69.","reactionConditions":"Gas-phase decomposition of formic acid at 350 °C, space velocity of 27 L/hr.g cat, FA/Ar molar ratio of 1/2","selectivity":"H2: 40.8%, CO: 6.7%, CO2: 52.5% product distribution","stability":"stable catalytic activity in the experiments carried out for 180 min","metricCount":"2"},{"paperId":"P054","catalystId":"P054_PERF_004","name":"5Ni–SiO2 (Tw80–NaF)","support":"SiO2","matchedSynthesis":"5Ni–SiO2(Tw80–NaF)","matchedCharacterization":"5Ni–SiO2(Tw80–NaF)","role":"active catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"one-pot synthesis","synthesis":"Tween-80 solution mixed with HCl (pH 2) at 65 °C for 2 h. Ni salt dissolved in water added dropwise, followed by TEOS addition. NaF added while stirring at 65 °C, then evaporated at 65 °C.","phase":"Metallic Ni (111) plane","particleSize":"15.4 nm","surfaceStates":"Lewis acid sites.","structureLink":"Lowest surface area and pore volume; H2 selectivity of 0.56.","reactionConditions":"Gas-phase decomposition of formic acid at 350 °C, space velocity of 27 L/hr.g cat, FA/Ar molar ratio of 1/2","selectivity":"H2: 34.9%, CO: 16.9%, CO2: 48.1% product distribution","stability":"stable catalytic activity in the experiments carried out for 180 min","whyPerformsWell":"H2 selectivity was close to that of 5Ni–SiO2(Tw80) despite having much lower surface area and pore volume.","metricCount":"2"},{"paperId":"P054","catalystId":"P054_PERF_005","name":"5Ni–SiO2 (Tw80)","support":"SiO2","matchedSynthesis":"5Ni–SiO2(Tw80)","matchedCharacterization":"5Ni–SiO2(Tw80)","role":"active catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"one-pot synthesis","synthesis":"Tween-80 added to HCl solution at 65 °C. Ni salt dissolved in water added dropwise, followed by TEOS addition. Stirred under reflux at 65 °C and evaporated at 65 °C.","phase":"Metallic Ni (111) plane","particleSize":"34.8 nm","surfaceStates":"Lewis and Brønsted acid sites.","structureLink":"Highest Ni crystallite size; H2 selectivity of 0.55.","reactionConditions":"Gas-phase decomposition of formic acid at 350 °C, space velocity of 27 L/hr.g cat, FA/Ar molar ratio of 1/2","selectivity":"H2: 33.7%, CO: 22.1%, CO2: 44.3% product distribution","stability":"stable catalytic activity in the experiments carried out for 180 min","metricCount":"2"},{"paperId":"P055","catalystId":"P055_PERF_001","name":"Au@SiO2 2.8 ± 0.5 nm (Entry A)","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Vapour phase decomposition of HCOOH in a 3 mm quartz fixed-bed reactor at atmospheric pressure; Ar (40 ml/min) bubbled through pure formic acid at 20 °C (~7% HCOOH); WHSV ~138 g formic acid / gAu h-1","selectivity":"85-87% selectivity towards H2 and CO2 at full conversion","stability":"Activity was higher during initial heating ramp; subsequent cycles resulted in similar light-off curves","deactivation":"Partial chemical deactivation attributed to irreversible formation of amide species between grafted amines and formic acid (substrate poisoning)","whyPerformsWell":"Low-coordinated Au corner atoms and amine functionalised sites facilitate OH bond cleavage and H-assisted formate decomposition","metricCount":"2"},{"paperId":"P055","catalystId":"P055_PERF_002","name":"Au@SiO2 2.6 ± 0.3 nm (Entry B)","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Vapour phase decomposition of HCOOH in a 3 mm quartz fixed-bed reactor at atmospheric pressure; Ar (40 ml/min) bubbled through pure formic acid at 20 °C (~7% HCOOH); WHSV ~138 g formic acid / gAu h-1","selectivity":"85-87% selectivity towards H2 and CO2 at full conversion","stability":"Activity was higher during initial heating ramp; subsequent cycles resulted in similar light-off curves","deactivation":"Partial chemical deactivation attributed to irreversible formation of amide species between grafted amines and formic acid (substrate poisoning)","whyPerformsWell":"Low-coordinated Au corner atoms and amine functionalised sites facilitate OH bond cleavage and H-assisted formate decomposition","metricCount":"2"},{"paperId":"P055","catalystId":"P055_PERF_003","name":"Au@SiO2 2.2 ± 0.3 nm (Entry C)","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Vapour phase decomposition of HCOOH in a 3 mm quartz fixed-bed reactor at atmospheric pressure; Ar (40 ml/min) bubbled through pure formic acid at 20 °C (~7% HCOOH); WHSV ~138 g formic acid / gAu h-1","selectivity":"Slightly better selectivity towards H2 than other catalysts; 85-87% at full conversion","stability":"Activity was higher during initial heating ramp; subsequent cycles resulted in similar light-off curves","deactivation":"Partial chemical deactivation attributed to irreversible formation of amide species between grafted amines and formic acid (substrate poisoning)","whyPerformsWell":"Smallest Au nanoparticles increase the relative number of low-coordinated corner atoms; amine functionalised sites facilitate OH bond cleavage","metricCount":"2"},{"paperId":"P055","catalystId":"P055_PERF_004","name":"Au@SiO2 2.7 ± 0.4 nm (Entry D)","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Vapour phase decomposition of HCOOH in a 3 mm quartz fixed-bed reactor at atmospheric pressure; Ar (40 ml/min) bubbled through pure formic acid at 20 °C (~7% HCOOH); WHSV ~138 g formic acid / gAu h-1","selectivity":"85-87% selectivity towards H2 and CO2 at full conversion","stability":"Activity was higher during initial heating ramp; subsequent cycles resulted in similar light-off curves","deactivation":"Partial chemical deactivation attributed to irreversible formation of amide species between grafted amines and formic acid (substrate poisoning)","whyPerformsWell":"Lower activity compared to others due to increased SiO2 shell thickness, which may limit diffusion of formic acid","metricCount":"2"},{"paperId":"P056","catalystId":"P056_PERF_001","name":"Pd/rGO-SI","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd/rGO-SI","matchedCharacterization":"Pd/rGO-SI","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sol_immobilization","synthesis":"PdCl2 and PVA were mixed in water, reduced with NaBH4, acidified to pH 2 with sulfuric acid, then rGO was added under dynamic stirring for 1 h.","phase":"fcc Pd","particleSize":"2.51 ± 0.3 nm (fresh), 3.11 ± 0.3 nm (used)","surfaceStates":"Higher metallic Pd content and higher atomic percentage of Pd (0.93%) compared to IMP","structureLink":"Smaller particle size, higher dispersion, and higher metallic Pd content lead to superior catalytic activity (TOF = 910-911 h⁻¹).","reactionConditions":"30 °C, 0.5 M FA aqueous solution, mol substrate/mol metal ratio 2000:1, stirring at 800 rpm","selectivity":"H2:CO2 molar ratio 1.0; no CO formation","stability":"no decline of activity witnessed after five runs","whyPerformsWell":"smaller mean particle size (2.28 nm), higher Pd exposure, higher atomic percentage of Pd on rGO sheets and higher metallic Pd content; PVA ligand inhibited surface oxidation","metricCount":"3"},{"paperId":"P056","catalystId":"P056_PERF_002","name":"Pd/rGO-IMP","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd/rGO-IMP","matchedCharacterization":"Pd/rGO-IMP","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PdCl2 solution was added to rGO and stirred for 6 h, followed by reduction with aqueous NaBH4 and further stirring for 6 h.","phase":"fcc Pd","particleSize":"12.81 ± 0.5 nm (fresh), 13.29 ± 0.5 nm (used)","surfaceStates":"Contains Pd0 and PdII; atomic percentage of Pd is 0.65%","structureLink":"Larger particle size, lower metallic content, and lower dispersion result in lower catalytic activity (TOF = 503-506 h⁻¹).","reactionConditions":"30 °C, 0.5 M FA aqueous solution, mol substrate/mol metal ratio 2000:1, stirring at 800 rpm","selectivity":"H2:CO2 molar ratio 1.0; no CO formation","stability":"no decline of activity witnessed after five runs","whyPerformsWell":"Pd nanoparticles anchored on rGO nanosheets increased interactions between FA and Pd","metricCount":"3"},{"paperId":"P056","catalystId":"P056_PERF_003","name":"Pd/rGO-SI-Used","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd/rGO-SI","matchedCharacterization":"Pd/rGO-SI","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sol_immobilization","synthesis":"PdCl2 and PVA were mixed in water, reduced with NaBH4, acidified to pH 2 with sulfuric acid, then rGO was added under dynamic stirring for 1 h.","phase":"fcc Pd","particleSize":"2.51 ± 0.3 nm (fresh), 3.11 ± 0.3 nm (used)","surfaceStates":"Higher metallic Pd content and higher atomic percentage of Pd (0.93%) compared to IMP","structureLink":"Smaller particle size, higher dispersion, and higher metallic Pd content lead to superior catalytic activity (TOF = 910-911 h⁻¹).","reactionConditions":"30 °C, 0.5 M FA aqueous solution, mol substrate/mol metal ratio 2000:1, stirring at 800 rpm","stability":"recovered catalyst used five times","metricCount":"2"},{"paperId":"P056","catalystId":"P056_PERF_004","name":"Pd/rGO-IMP-Used","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd/rGO-IMP","matchedCharacterization":"Pd/rGO-IMP","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PdCl2 solution was added to rGO and stirred for 6 h, followed by reduction with aqueous NaBH4 and further stirring for 6 h.","phase":"fcc Pd","particleSize":"12.81 ± 0.5 nm (fresh), 13.29 ± 0.5 nm (used)","surfaceStates":"Contains Pd0 and PdII; atomic percentage of Pd is 0.65%","structureLink":"Larger particle size, lower metallic content, and lower dispersion result in lower catalytic activity (TOF = 503-506 h⁻¹).","reactionConditions":"30 °C, 0.5 M FA aqueous solution, mol substrate/mol metal ratio 2000:1, stirring at 800 rpm","stability":"recovered catalyst used five times","metricCount":"2"},{"paperId":"P057","catalystId":"P057_PERF_001","name":"Pd-ZrO2/RUB-15-NH2","support":"RUB-15-NH2","matchedSynthesis":"Pd-ZrO2/RUB-15-NH2","matchedCharacterization":"Pd-ZrO2/RUB-15-NH2","role":"hydrogen production from formic acid decomposition","composition":"Pd (1–4 wt%) and Zr (0.2–2 wt%); optimal ratio Pd: 2.5 wt%, Zr: 0.2 wt%","activeMetals":"Pd-Zr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Pd and Zr precursors were dissolved in HCl, added to a mixture of RUB-15 support, distilled water, and APTES, reduced using NaBH4, centrifuged, and dried.","phase":"Pd-ZrO2 nanoparticles","particleSize":"3.75 nm","surfaceStates":"Functionalized with amine groups (-NH2) via APTES, which provide strong adsorption capacity for Pd2+ and Zr4+ ions","structureLink":"The confinement of ultrasmall Pd-ZrO2 NPs within the layered RUB-15-NH2 structure provides numerous and accessible active sites for formic acid molecules","reactionConditions":"Formic acid (2.4 M), sodium formate (300 mg), water (8–20 mL), 100 mg catalyst in a 50 mL double-necked flask, N2 atmosphere for stabilization, magnetic stirring at 2500 rpm","selectivity":"No CO was found; FA completely broken down into H2 and CO2","whyPerformsWell":"Strong adsorption capacity of amine groups (-NH2) for Pd2+ and Zr4+ ions leads to ultrasmall and highly dispersed Pd-ZrO2 NPs (average diameter 3.75 nm) confined within the layered structure, providing numerous accessible active sites.","metricCount":"4"},{"paperId":"P058","catalystId":"P058_PERF_001","name":"Bare Pd octahedrons","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"1 M aqueous FA solution (10 mL), 120 min, 365 K","selectivity":"No CO has been detected in GC","metricCount":"3"},{"paperId":"P058","catalystId":"P058_PERF_002","name":"Bare Pd tetrahedrons","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"1 M aqueous FA solution (10 mL), 120 min, 365 K","selectivity":"No CO has been detected in GC","metricCount":"3"},{"paperId":"P058","catalystId":"P058_PERF_003","name":"Bare Pd cuboctahedrons","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"1 M aqueous FA solution (10 mL), 120 min, 365 K","selectivity":"No CO has been detected in GC","metricCount":"3"},{"paperId":"P058","catalystId":"P058_PERF_004","name":"Octahedrons-TiO2","support":"TiO2","matchedSynthesis":"Pd octahedrons-TiO2","matchedCharacterization":"Pd octahedrons-TiO2","role":"catalyst","composition":"Pd","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"One-step synthesis of Pd nano-octahedrons using K2PdCl4, PVP, ascorbic acid (AA), and formaldehyde in aqueous media with a precursor feeding rate of 90 mL/h, followed by loading onto TiO2 via an in-situ growth protocol.","phase":"Single-crystal nano-octahedrons covered by {111} facets","particleSize":"8 nm (average edge length)","surfaceStates":"Electron accumulation on the Pd side due to interfacial polarization with TiO2; Schottky junction formed under light traps photoexcited electrons on Pd.","structureLink":"Enhanced activity compared to bare Pd due to interface polarization, but lower than tetrahedrons due to a smaller interface angle (70.5°) increasing steric effects.","reactionConditions":"1 M aqueous FA solution (10 mL), 120 min, 365 K","selectivity":"No CO has been detected in GC","stability":"morphology of hybrid nanostructures is well maintained after the FA decomposition reaction","whyPerformsWell":"interfacial polarization between metal and semiconductor (accumulation of electrons at Pd side)","metricCount":"5"},{"paperId":"P058","catalystId":"P058_PERF_005","name":"Tetrahedrons-TiO2","support":"TiO2","matchedSynthesis":"Pd tetrahedrons-TiO2","matchedCharacterization":"Pd tetrahedrons-TiO2","role":"catalyst","composition":"Pd","activeMetals":"Te-Ti","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"One-step synthesis of Pd nano-tetrahedrons using K2PdCl4, PVP, ascorbic acid (AA), and formaldehyde in aqueous media with a precursor feeding rate of 5–45 mL/h, followed by loading onto TiO2 via an in-situ growth protocol.","phase":"Single-crystal nano-tetrahedrons covered by {111} facets","particleSize":"8 nm (average edge length)","surfaceStates":"Electron accumulation on the Pd side due to interfacial polarization with TiO2; Schottky junction formed under light traps photoexcited electrons on Pd.","structureLink":"Highest activity in FA dehydrogenation attributed to a large interface angle (109.5°) which reduces steric effects during molecular bond whirligig/wrench processes, combined with electronic polarization from the TiO2 interface.","reactionConditions":"1 M aqueous FA solution (10 mL), 120 min, 365 K","selectivity":"No CO has been detected in GC","stability":"morphology of hybrid nanostructures is well maintained after the FA decomposition reaction","whyPerformsWell":"interfacial polarization and steric effect (larger interface angle 109.5° provides more space for molecular bond whirligig/wrench)","metricCount":"5"},{"paperId":"P058","catalystId":"P058_PERF_006","name":"Cuboctahedrons-TiO2","support":"TiO2","matchedSynthesis":"Pd cuboctahedrons-TiO2","matchedCharacterization":"Pd cuboctahedrons-TiO2","role":"catalyst","composition":"Pd","activeMetals":"Cu-Ti","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"One-step synthesis of Pd cuboctahedron nanocrystals using K2PdCl4, PVP, ascorbic acid (AA), and formaldehyde in aqueous media with a precursor feeding rate of 360 mL/h, followed by loading onto TiO2 via an in-situ growth protocol.","phase":"Nanocrystals enclosed by a mix of {111} and {100} facets","particleSize":"about 5 nm","surfaceStates":"Electron accumulation on the Pd side due to interfacial polarization with TiO2.","structureLink":"Lower catalytic activity than octahedrons-TiO2 attributed to a small interface angle (54.7°) which hinders the catalytic reaction via steric effects.","reactionConditions":"1 M aqueous FA solution (10 mL), 120 min, 365 K","selectivity":"No CO has been detected in GC","stability":"morphology of hybrid nanostructures is well maintained after the FA decomposition reaction","whyPerformsWell":"interfacial polarization; however, small interface angle (54.7°) may hinder catalytic reaction compared to tetrahedrons","metricCount":"2"},{"paperId":"P058","catalystId":"P058_PERF_007","name":"Tetrahedrons-C","activeMetals":"Te","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"1 M aqueous FA solution (10 mL), 120 min, 365 K","selectivity":"No CO has been detected in GC","whyPerformsWell":"comparable performance to bare Pd tetrahedron as no interfacial polarization takes place on carbon substrate","metricCount":"1"},{"paperId":"P058","catalystId":"P058_PERF_008","name":"Tetrahedrons-Al2O3","activeMetals":"Te-Al","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"1 M aqueous FA solution (10 mL), 120 min, 365 K","selectivity":"No CO has been detected in GC","whyPerformsWell":"comparable performance to bare Pd tetrahedron as no interfacial polarization takes place on Al2O3 substrate","metricCount":"1"},{"paperId":"P059","catalystId":"P059_PERF_001","name":"Pd-PCN-350R","support":"polymeric carbon nitride (PCN)","matchedSynthesis":"Pd-PCN-350R","matchedCharacterization":"Pd-PCN-350R","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Synthesized via stepwise annealing to form Pd-PCN, followed by reduction at 350 °C in an H2 atmosphere.","phase":"Pd nanoparticles and single atoms on PCN","particleSize":"ca. 2-3 nm (specifically 2.4 nm)","surfaceStates":"Average charge QPd = 2.6; metallic Pd fingerprint at 335.3 eV","structureLink":"Optimal activity associated with a moderate average charge (QPd = 2.6) and ultrafine particle size","reactionConditions":"Formic acid dehydrogenation in various solvents (Propylene Carbonate, Toluene, Triglyme) at temperatures from 90 to 130 °C.","selectivity":"1:1 H2/CO2 analyzed by GC","stability":"Robust catalyst performance up to ca. 350 h without obvious deactivation; active after 15 days of operation.","deactivation":"Leaching of Pd was excluded by analyzing the metal content in the recovered solvent. Average particle size slightly increased from 2.5 to 3.0 nm.","whyPerformsWell":"Strong interaction between Pd and carbon nitride support; tunable electronic properties via stepwise annealing and reduction strategy; presence of numerous basic nitrogen sites on PCN promotes H2 production.","metricCount":"9"},{"paperId":"P059","catalystId":"P059_PERF_002","name":"Pd-PCN","support":"polymeric carbon nitride (PCN)","matchedSynthesis":"Pd-PCN","matchedCharacterization":"Pd-PCN","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"stepwise annealing","synthesis":"PCN support was prepared via calcination of melamine and cyanuric acid complex; Pd was loaded using a modified stepwise annealing approach.","phase":"Pd nanoparticles and single atoms on polymeric carbon nitride (PCN)","particleSize":"ca. 4-5 nm","surfaceStates":"Average charge QPd = 3.4; XPS peaks at 338.3 eV (Pd4+) and 336.6 eV (Pd2+)","structureLink":"Lower activity compared to Pd-PCN-350R due to higher average charge","reactionConditions":"T = 110 °C, Solvent = Propylene Carbonate (PC)","metricCount":"1"},{"paperId":"P059","catalystId":"P059_PERF_003","name":"Pd-PCN-500R","support":"polymeric carbon nitride (PCN)","matchedSynthesis":"Pd-PCN-500R","matchedCharacterization":"Pd-PCN-500R","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Synthesized via stepwise annealing to form Pd-PCN, followed by reduction at 500 °C in an H2 atmosphere.","phase":"Pd nanoparticles on PCN","particleSize":"slightly below 6 nm","surfaceStates":"Average charge QPd = 1.1; metallic Pd (335.3 eV) is the main contribution","structureLink":"Lower activity compared to Pd-PCN-350R, following a volcano relationship with average charge","reactionConditions":"T = 110 °C, Solvent = Propylene Carbonate (PC)","metricCount":"1"},{"paperId":"P059","catalystId":"P059_PERF_004","name":"5 wt % Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"T = 110 °C, Solvent = Propylene Carbonate (PC)","metricCount":"1"},{"paperId":"P060","catalystId":"P060_PERF_001","name":"1%Pd@HHT","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","matchedSynthesis":"1 %Pd@HHT","matchedCharacterization":"1 %Pd@HHT","role":"monometallic catalyst for formic acid decomposition","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sol_immobilization","synthesis":"Precursor salt dissolved in water, PVA added as capping agent, reduced with NaBH4. HHT nanofibers added to the colloid and acidified to pH 2 using sulfuric acid.","phase":"Monometallic","particleSize":"3.9 ± 1.2 nm","surfaceStates":"Pd0 (B.E. 336.70 eV) and PdII (B.E. 337.80 eV)","structureLink":"Rapidly deactivates due to coalescence, agglomeration (size increase from 3.0 to 4.7 nm), and CO-poisoning","reactionConditions":"30 °C, 1400 rpm, 0.5 M FA in water, FA/metal molar ratio of 2000/1","selectivity":"77% selectivity to H2","stability":"quickly deactivates after the first run","deactivation":"coalescence and agglomeration of particles (average size increase from 3.0 to 4.7 nm) and CO poisoning","metricCount":"1"},{"paperId":"P060","catalystId":"P060_PERF_002","name":"1%Au@HHT","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","matchedSynthesis":"1 %Au@HHT","matchedCharacterization":"1 %Au@HHT","role":"monometallic catalyst for formic acid decomposition","composition":"Au only","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"sol_immobilization","synthesis":"Precursor salt dissolved in water, PVA added as capping agent, reduced with NaBH4. HHT nanofibers added to the colloid and acidified to pH 2 using sulfuric acid.","phase":"Monometallic","particleSize":"3.4 ± 1.2 nm","surfaceStates":"Au0 (B.E. 84.22 eV) and Auδ+ (B.E. 85.60 eV)","structureLink":"Extremely low activity in formic acid decomposition","reactionConditions":"30 °C, 1400 rpm, 0.5 M FA in water, FA/metal molar ratio of 2000/1","metricCount":"2"},{"paperId":"P060","catalystId":"P060_PERF_003","name":"1%Pd8Au2@HHT","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","matchedSynthesis":"1 %Pd8Au2@HHT, 1 %Pd6Au4@HHT, 1 %Pd4Au6@HHT, 1 %Pd2Au8@HHT","matchedCharacterization":"1 %Pd8Au2@HHT","role":"bimetallic catalysts for formic acid decomposition","composition":"Pd:Au nominal molar ratios of 8:2, 6:4, 4:6, and 2:8","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sol_immobilization","synthesis":"Precursor salts were dissolved in water, PVA was added as a capping agent, and the solution was reduced with NaBH4. HHT nanofibers were then added to the colloidal solution, which was acidified to pH 2 using sulfuric acid to ensure nanoparticle immobilization.","phase":"Au-Pd alloy; surface enrichment of Pd atoms","particleSize":"3.5 ± 0.9 nm (fresh), 3.9 ± 1.1 nm (used)","surfaceStates":"Pd0, PdII, Au0, Auδ+; decrease in Pd0 binding energy (~1.1-1.2 eV) relative to monometallic Pd","structureLink":"High stability over 6 cycles with minimal morphology changes","reactionConditions":"30 °C, 1400 rpm, 0.5 M FA in water, FA/metal molar ratio of 2000/1","selectivity":"> 99% for H2 (only CO2 detected in gas phase)","stability":"good stability up to 6 cycles of reaction","deactivation":"no significant modifications of catalyst morphology; mean particle size increase from 3.5 nm to 3.9 nm","whyPerformsWell":"alloying Pd with Au inhibits the dehydration pathway and suppresses CO poisoning","metricCount":"2"},{"paperId":"P060","catalystId":"P060_PERF_004","name":"1%Pd6Au4@HHT","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","matchedSynthesis":"1 %Pd8Au2@HHT, 1 %Pd6Au4@HHT, 1 %Pd4Au6@HHT, 1 %Pd2Au8@HHT","matchedCharacterization":"1 %Pd6Au4@HHT","role":"bimetallic catalysts for formic acid decomposition","composition":"Pd:Au nominal molar ratios of 8:2, 6:4, 4:6, and 2:8","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sol_immobilization","synthesis":"Precursor salts were dissolved in water, PVA was added as a capping agent, and the solution was reduced with NaBH4. HHT nanofibers were then added to the colloidal solution, which was acidified to pH 2 using sulfuric acid to ensure nanoparticle immobilization.","phase":"Au-Pd alloy; surface enrichment of Pd atoms","particleSize":"2.9 ± 0.7 nm (fresh), 3.1 ± 0.8 nm (used)","surfaceStates":"Pd0, PdII, Au0, Auδ+; decrease in Pd0 binding energy (~1.1-1.2 eV) relative to monometallic Pd","structureLink":"Highest initial activity (3539 h-1) and high selectivity (>99% H2); DFT suggests optimal balance between lattice and ligand effects and stronger interaction with support for superior stability","reactionConditions":"30 °C, 1400 rpm, 0.5 M FA in water, FA/metal molar ratio of 2000/1","selectivity":"> 99% for H2 (only CO2 detected in gas phase)","stability":"good stability up to 6 cycles of reaction","deactivation":"no significant modifications of catalyst morphology; mean particle size increase from 2.9 nm to 3.1 nm","whyPerformsWell":"perfect balance between the lattice and ligand effect; more exothermic FA adsorption compared to monometallic Pd (DFT)","metricCount":"1"},{"paperId":"P060","catalystId":"P060_PERF_005","name":"1%Pd4Au6@HHT","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","matchedSynthesis":"1 %Pd8Au2@HHT, 1 %Pd6Au4@HHT, 1 %Pd4Au6@HHT, 1 %Pd2Au8@HHT","matchedCharacterization":"1 %Pd4Au6@HHT","role":"bimetallic catalysts for formic acid decomposition","composition":"Pd:Au nominal molar ratios of 8:2, 6:4, 4:6, and 2:8","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sol_immobilization","synthesis":"Precursor salts were dissolved in water, PVA was added as a capping agent, and the solution was reduced with NaBH4. HHT nanofibers were then added to the colloidal solution, which was acidified to pH 2 using sulfuric acid to ensure nanoparticle immobilization.","phase":"Au-Pd alloy; surface enrichment of Pd atoms","particleSize":"4.0 ± 0.8 nm","surfaceStates":"Pd0, PdII, Au0, Auδ+; decrease in Pd0 binding energy (~1.1-1.2 eV) relative to monometallic Pd","structureLink":"High initial activity (1983 h-1)","reactionConditions":"30 °C, 1400 rpm, 0.5 M FA in water, FA/metal molar ratio of 2000/1","selectivity":"> 99% for H2 (only CO2 detected in gas phase)","whyPerformsWell":"alloying Pd with Au inhibits the dehydration pathway","metricCount":"2"},{"paperId":"P060","catalystId":"P060_PERF_006","name":"1%Pd2Au8@HHT","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","matchedSynthesis":"1 %Pd8Au2@HHT, 1 %Pd6Au4@HHT, 1 %Pd4Au6@HHT, 1 %Pd2Au8@HHT","matchedCharacterization":"1 %Pd2Au8@HHT","role":"bimetallic catalysts for formic acid decomposition","composition":"Pd:Au nominal molar ratios of 8:2, 6:4, 4:6, and 2:8","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sol_immobilization","synthesis":"Precursor salts were dissolved in water, PVA was added as a capping agent, and the solution was reduced with NaBH4. HHT nanofibers were then added to the colloidal solution, which was acidified to pH 2 using sulfuric acid to ensure nanoparticle immobilization.","phase":"Au-Pd alloy; surface enrichment of Pd atoms","particleSize":"3.1 ± 0.6 nm","surfaceStates":"Pd0, PdII, Au0, Auδ+; decrease in Pd0 binding energy (~1.1-1.2 eV) relative to monometallic Pd","structureLink":"Lower activity compared to other bimetallics (878 h-1)","reactionConditions":"30 °C, 1400 rpm, 0.5 M FA in water, FA/metal molar ratio of 2000/1","selectivity":"> 99% for H2 (only CO2 detected in gas phase)","whyPerformsWell":"alloying Pd with Au inhibits the dehydration pathway","metricCount":"1"},{"paperId":"P061","catalystId":"P061_PERF_001","name":"Pd@CMK3","support":"CMK3","matchedSynthesis":"Pd@CMK3","matchedCharacterization":"Pd@CMK3","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of CMK3 with K2PdCl4 aqueous solution, followed by NaBH4 reduction and drying.","phase":"Monometallic Pd nanoparticles","particleSize":"Fresh: average 2.7 nm; Used (batch and fixed bed): average 3.3 nm, with some particles > 5 nm.","surfaceStates":"Adsorption of poison species such as CO","structureLink":"Confinement effects within CMK3 mesopores provide higher stability and activity compared to Pd@HHT (where NPs are only on external surfaces). Fixed bed reactors exhibit more severe metal leaching and faster deactivation than batch reactors due to the continuous flow of reactants removing leached species.","reactionConditions":"Liquid-phase formic acid (FA) decomposition in batch and fixed bed reactors at 30 °C using 0.5 M HCOOH.","stability":"More stable behavior over 6 reaction cycles in batch reactor compared to Pd@HHT; activity reduced by 50% after six cycles.","deactivation":"Severe leaching of Pd (59 wt% loss) in fixed bed reactor. In batch reactor, 23 wt% Pd was lost with significant redeposition and aggregation on the external surface. Deactivation also attributed to CO poisoning.","whyPerformsWell":"Confinement effects of the mesopores of CMK3 reduce particle growth/sintering and enhance stability compared to catalysts with particles only on external surfaces.","metricCount":"5"},{"paperId":"P061","catalystId":"P061_PERF_002","name":"Pd@HHT","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Liquid-phase FA decomposition in batch reactor at 30 °C using 0.5 M HCOOH.","stability":"Rapidly deactivated over 6 reaction cycles in batch reactor.","whyPerformsWell":"Performs worse than Pd@CMK3 because all Pd particles are located on the external surface of the support, lacking confinement effects.","metricCount":"1"},{"paperId":"P062","catalystId":"P062_PERF_001","name":"Pd@MHCP-2","support":"MHCP-2 (m-phenylenediamine-based hypercrosslinked polymer)","matchedSynthesis":"Pd@MHCP-2","matchedCharacterization":"Pd@MHCP-2","role":"optimized catalyst for formic acid dehydrogenation","composition":"Pd-Fe bimetallic species (residual Fe from support synthesis)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Synthesis of MHCP support via Friedel-Crafts alkylation, followed by Pd precursor impregnation and NaBH4 reduction.","phase":"Bimetallic Pd-Fe species; low-crystallinity ultrafine Pd nanoparticles embedded in HCP pores.","particleSize":"1.21 ± 0.35 nm","surfaceStates":"XPS shows electron transfer between Fe and Pd atoms (decrease in Fe 2p binding energy) and interaction between amino groups and Pd NPs (N 1s shift).","structureLink":"Ultrafine particle size and bimetallic synergistic effect with oxidized Fe lower the O-H bond dissociation barrier to 0.040 eV (vs 0.06 eV for pure Pd), resulting in a TOF of 1486 h^-1.","reactionConditions":"Formic acid dehydrogenation in aqueous solution at ambient atmospheric pressure.","selectivity":"No detection of CO; generated gas is a combination of H2 and CO2.","stability":"Evaluated over 5 cycles; activity increased in the second cycle, decreased after the third, but remained relatively high after the fifth cycle.","deactivation":"Particle agglomeration observed (some particles > 3 nm) as internal Pd nanoparticles escape from pores and attach to external amino groups.","whyPerformsWell":"Dual optimization strategy: reduced Fe3+ content optimizes nitrogen exposure and BET surface area, leading to smaller Pd nanoparticle size (1.21 nm). Residual oxidized Fe species act as electron acceptors that lower the energy barrier for O-H bond dissociation in the rate-determining step.","metricCount":"2"},{"paperId":"P062","catalystId":"P062_PERF_002","name":"Pd@MHCP-X (X=1, 3, 4)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation in aqueous solution at ambient atmospheric pressure.","whyPerformsWell":"Performance correlates with BET surface area and nitrogen atom exposure; excessive or insufficient Fe3+ content during synthesis adversely affects these properties.","metricCount":"1"},{"paperId":"P062","catalystId":"P062_PERF_003","name":"Pd@MHCP-2(s)","support":"MHCP-2 (m-phenylenediamine-based hypercrosslinked polymer)","matchedSynthesis":"Pd@MHCP-2","matchedCharacterization":"Pd@MHCP-2","role":"optimized catalyst for formic acid dehydrogenation","composition":"Pd-Fe bimetallic species (residual Fe from support synthesis)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Synthesis of MHCP support via Friedel-Crafts alkylation, followed by Pd precursor impregnation and NaBH4 reduction.","phase":"Bimetallic Pd-Fe species; low-crystallinity ultrafine Pd nanoparticles embedded in HCP pores.","particleSize":"1.21 ± 0.35 nm","surfaceStates":"XPS shows electron transfer between Fe and Pd atoms (decrease in Fe 2p binding energy) and interaction between amino groups and Pd NPs (N 1s shift).","structureLink":"Ultrafine particle size and bimetallic synergistic effect with oxidized Fe lower the O-H bond dissociation barrier to 0.040 eV (vs 0.06 eV for pure Pd), resulting in a TOF of 1486 h^-1.","reactionConditions":"Formic acid dehydrogenation in aqueous solution at ambient atmospheric pressure.","whyPerformsWell":"Lower activity than Pd@MHCP-2 due to the removal of Fe3+ via Soxhlet extraction, confirming that Fe species enhance Pd catalytic activity.","metricCount":"1"},{"paperId":"P062","catalystId":"P062_PERF_004","name":"Fe@MHCP-2","activeMetals":"Fe","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Formic acid dehydrogenation in aqueous solution at ambient atmospheric pressure.","whyPerformsWell":"Minimal catalytic activity compared to Pd@MHCP-2, suggesting that Pd species serve as the active sites.","metricCount":"1"},{"paperId":"P063","catalystId":"P063_PERF_001","name":"NiCu/rGO10","support":"reduced graphene oxide (rGO10)","matchedSynthesis":"NiCu/rGO10","matchedCharacterization":"NiCu/rGO10","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"7 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 showed only Cu0/+ species (no Cu2+).","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Quite stable conversion profile along the experiment time","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_002","name":"NiCu/rGO325","support":"reduced graphene oxide (rGO325)","matchedSynthesis":"NiCu/rGO325","matchedCharacterization":"NiCu/rGO325","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"8 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"High stability evaluated at 145 and 190 °C","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_003","name":"NiCu/SXC","support":"spheres of xerogel carbons (SXC)","matchedSynthesis":"NiCu/SXC","matchedCharacterization":"NiCu/SXC","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"8 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 binding energy at 932.99 eV (reduced copper species).","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Quite stable conversion profile along the experiment time","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_004","name":"NiCu/MWCNT","support":"multi-walled carbon nanotubes (MWCNT)","matchedSynthesis":"NiCu/MWCNT","matchedCharacterization":"NiCu/MWCNT","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"7 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Quite stable conversion profile along the experiment time","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_005","name":"NiCu/SWCNT","support":"single-walled carbon nanotubes (SWCNT)","matchedSynthesis":"NiCu/SWCNT","matchedCharacterization":"NiCu/SWCNT","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"7 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Conversion decreases slightly with time, but the decrease is below 10%","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_006","name":"NiCu/HSAG","support":"high surface area graphite (HSAG)","matchedSynthesis":"NiCu/HSAG","matchedCharacterization":"NiCu/HSAG","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Conversion decreases slightly with time, but the decrease is below 10%","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_007","name":"NiCu/NrGO10","support":"N-doped reduced graphene oxide (NrGO10)","matchedSynthesis":"NiCu/NrGO10","matchedCharacterization":"NiCu/NrGO10","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 showed a shift to lower binding energy (0.2 eV) compared to undoped counterpart; contains Cu0/+ and Cu2+.","structureLink":"Lower activity attributed to metal particles located on pyridinic N atoms, making them less positively charged and less capable of stabilizing formate species.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Quite stable conversion profile along the experiment time","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_008","name":"NiCu/NrGO325","support":"N-doped reduced graphene oxide (NrGO325)","matchedSynthesis":"NiCu/NrGO325","matchedCharacterization":"NiCu/NrGO325","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"Lower activity attributed to metal particles located on pyridinic N atoms, making them less positively charged and less capable of stabilizing formate species.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Quite stable conversion profile along the experiment time","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_009","name":"NiCu/NCNT","support":"N-doped carbon nanotubes (NCNT)","matchedSynthesis":"NiCu/NCNT","matchedCharacterization":"NiCu/NCNT","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 atomic ratio of Cu0/+ to Cu2+ is close to 1.","structureLink":"Most active catalyst; attributed to metal nanoparticles located on defect sites rather than N atoms, and the presence of pyrrolic nitrogen acting as activation sites for formic acid.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Conversion decreases slightly with time, but the decrease is below 10%","whyPerformsWell":"Most active and selective catalyst; attributed to pyrrolic nitrogen acting as activation sites for formic acid while metal nanoparticles are located on defect sites other than nitrogen.","metricCount":"2"},{"paperId":"P063","catalystId":"P063_PERF_010","name":"NiCu/NSXC","support":"N-doped spheres of xerogel carbons (NSXC)","matchedSynthesis":"NiCu/NSXC","matchedCharacterization":"NiCu/NSXC","role":"catalyst","composition":"Ni:Cu = 1:1","activeMetals":"Ni-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 binding energy at 932.47 eV (reduced copper species).","structureLink":"Lower activity attributed to metal particles located on pyridinic N atoms, making them less positively charged and less capable of stabilizing formate species.","reactionConditions":"Vapor phase formic acid decomposition, fixed-bed flow reactor, 5.5 vol % FA/N2 feed, total flow rate of 25 cm3 (STP)/min, catalyst amount 75 mg","selectivity":"94-98% selectivity to H2 at conversions above 95%","stability":"Quite stable conversion profile along the experiment time","metricCount":"2"},{"paperId":"P064","catalystId":"P064_PERF_001","name":"1% Pt/N-graphene (Pt(NO3)4)","support":"N-graphene","matchedSynthesis":"Pt/N-graphene (Pt(NO3)4)","matchedCharacterization":"Pt/N-graphene (Pt(NO3)4)","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","phase":"nanocrystals","particleSize":"10-16 nm","structureLink":"lower catalytic activity and selectivity compared to catalysts prepared with H2PtCl6 due to lower dispersion","reactionConditions":"Gas-phase decomposition of formic acid; 5 vol.% HCOOH/He; flow rate 20 cm3/min; catalyst amount 20 mg mixed with 0.5 cm3 quartz sand; reduced in 10% H2/He at 200 °C for 1 h before reaction","selectivity":"99.6% at 105 °C to 97.7% at 235 °C (to H2 and CO2)","stability":"stable for at least 5 h at 150 °C","metricCount":"1"},{"paperId":"P064","catalystId":"P064_PERF_002","name":"0.2% Pt/N-graphene (Pt(NO3)4)","support":"N-graphene","matchedSynthesis":"Pt/N-graphene (Pt(NO3)4)","matchedCharacterization":"Pt/N-graphene (Pt(NO3)4)","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","phase":"nanocrystals","particleSize":"10-16 nm","structureLink":"lower catalytic activity and selectivity compared to catalysts prepared with H2PtCl6 due to lower dispersion","reactionConditions":"Gas-phase decomposition of formic acid; 5 vol.% HCOOH/He; flow rate 20 cm3/min; catalyst amount 20 mg mixed with 0.5 cm3 quartz sand; reduced in 10% H2/He at 200 °C for 1 h before reaction","selectivity":"97.3% at 150 °C to 93.4% at 290 °C (to H2 and CO2)","metricCount":"1"},{"paperId":"P064","catalystId":"P064_PERF_003","name":"N-graphene","support":"N-graphene","matchedSynthesis":"Pt/N-graphene (Pt(NO3)4)","matchedCharacterization":"Pt/N-graphene (Pt(NO3)4)","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","phase":"nanocrystals","particleSize":"10-16 nm","structureLink":"lower catalytic activity and selectivity compared to catalysts prepared with H2PtCl6 due to lower dispersion","reactionConditions":"Gas-phase decomposition of formic acid; 5 vol.% HCOOH/He; flow rate 20 cm3/min; catalyst amount 20 mg mixed with 0.5 cm3 quartz sand","selectivity":"96.4% at 160 °C to 92.3% at 290 °C (to H2 and CO2)","metricCount":"1"},{"paperId":"P064","catalystId":"P064_PERF_004","name":"1% Pt/N-graphene (H2PtCl6)","support":"N-graphene","matchedSynthesis":"Pt/N-graphene (H2PtCl6)","matchedCharacterization":"Pt/N-graphene (H2PtCl6)","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","phase":"atomically dispersed platinum","particleSize":"2 ± 0.5 Å","surfaceStates":"Pt2+ (72.4 eV) and Pt4+ (73.5 eV); predominantly Pt2+ after reduction","structureLink":"Atomically dispersed state leads to higher catalytic activity and selectivity (up to 100% for H2/CO2) compared to nanocrystalline form; atomically dispersed platinum is unable to adsorb CO","reactionConditions":"Gas-phase decomposition of formic acid; 5 vol.% HCOOH/He; flow rate 20 cm3/min; catalyst amount 20 mg mixed with 0.5 cm3 quartz sand; reduced in 10% H2/He at 200 °C for 1 h before reaction","selectivity":"99.8-100% (to H2 and CO2)","stability":"stable for at least 5 h at 150 °C","whyPerformsWell":"higher platinum dispersion; atomically dispersed platinum stabilized on the N-graphene surface","metricCount":"2"},{"paperId":"P064","catalystId":"P064_PERF_005","name":"0.4% Pt/N-graphene (H2PtCl6)","support":"N-graphene","matchedSynthesis":"Pt/N-graphene (H2PtCl6)","matchedCharacterization":"Pt/N-graphene (H2PtCl6)","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","phase":"atomically dispersed platinum","particleSize":"2 ± 0.5 Å","surfaceStates":"Pt2+ (72.4 eV) and Pt4+ (73.5 eV); predominantly Pt2+ after reduction","structureLink":"Atomically dispersed state leads to higher catalytic activity and selectivity (up to 100% for H2/CO2) compared to nanocrystalline form; atomically dispersed platinum is unable to adsorb CO","reactionConditions":"Gas-phase decomposition of formic acid; 5 vol.% HCOOH/He; flow rate 20 cm3/min; catalyst amount 20 mg mixed with 0.5 cm3 quartz sand; reduced in 10% H2/He at 200 °C for 1 h before reaction","selectivity":"99.8-100% (to H2 and CO2)","stability":"stable for at least 5 h at 150 °C","whyPerformsWell":"higher platinum dispersion; atomically dispersed platinum stabilized on the N-graphene surface","metricCount":"1"},{"paperId":"P064","catalystId":"P064_PERF_006","name":"0.2% Pt/N-graphene (H2PtCl6)","support":"N-graphene","matchedSynthesis":"Pt/N-graphene (H2PtCl6)","matchedCharacterization":"Pt/N-graphene (H2PtCl6)","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","phase":"atomically dispersed platinum","particleSize":"2 ± 0.5 Å","surfaceStates":"Pt2+ (72.4 eV) and Pt4+ (73.5 eV); predominantly Pt2+ after reduction","structureLink":"Atomically dispersed state leads to higher catalytic activity and selectivity (up to 100% for H2/CO2) compared to nanocrystalline form; atomically dispersed platinum is unable to adsorb CO","reactionConditions":"Gas-phase decomposition of formic acid; 5 vol.% HCOOH/He; flow rate 20 cm3/min; catalyst amount 20 mg mixed with 0.5 cm3 quartz sand; reduced in 10% H2/He at 200 °C for 1 h before reaction","selectivity":"99.5% at 120 °C to 97.5% at 290 °C (to H2 and CO2)","stability":"stable for at least 5 h at 150 °C","whyPerformsWell":"higher platinum dispersion; atomically dispersed platinum stabilized on the N-graphene surface","metricCount":"1"},{"paperId":"P065","catalystId":"P065_PERF_001","name":"Pd/rutile","support":"rutile TiO2","matchedSynthesis":"Pd/rutile","matchedCharacterization":"Pd/rutile","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of Pd onto rutile TiO2 support, followed by drying, calcination, and reduction.","phase":"Metallic Pd nanoparticles on rutile TiO2 support","particleSize":"3.0 nm","surfaceStates":"Higher proportion of Pd(111) crystal plane; linear adsorption of CO on corner and edge Pd atoms.","structureLink":"Highest catalytic performance due to smallest particle size, high metallic Pd content, and easier transformation of bidentate formate to monodentate formate, resulting in the lowest activation energy (21.1 kJ/mol).","reactionConditions":"Transfer hydrogenation of p-nitrophenol (p-NP) using formic acid (HCOOH)","whyPerformsWell":"Lowest activation energy; easier transformation of bidentate formate into monodentate formate due to smaller Pd nanoparticle size.","metricCount":"4"},{"paperId":"P065","catalystId":"P065_PERF_002","name":"Pd/anatase","support":"anatase TiO2","matchedSynthesis":"Pd/anatase","matchedCharacterization":"Pd/anatase","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of Pd onto anatase TiO2 support, followed by drying, calcination, and reduction.","phase":"Metallic Pd nanoparticles on anatase TiO2 support","particleSize":"3.3 nm","surfaceStates":"Higher proportion of Pd(111) crystal plane; linear adsorption of CO on corner and edge Pd atoms.","structureLink":"High catalytic performance linked to relatively small particle size and high metallic Pd content (Ea = 37.2 kJ/mol).","reactionConditions":"Transfer hydrogenation of p-nitrophenol (p-NP) using formic acid (HCOOH)","metricCount":"4"},{"paperId":"P065","catalystId":"P065_PERF_003","name":"Pd/brookite","support":"brookite TiO2","matchedSynthesis":"Pd/brookite","matchedCharacterization":"Pd/brookite","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of Pd onto brookite TiO2 support, followed by drying, calcination, and reduction.","phase":"Metallic Pd nanoparticles on brookite TiO2 support","particleSize":"4.7 nm","surfaceStates":"Higher proportion of Pd(100) crystal plane.","structureLink":"Highest selectivity for HCOOH dehydration to CO due to higher proportion of Pd(100) planes, which inhibits dehydrogenation and increases activation energy (65.9 kJ/mol).","reactionConditions":"Transfer hydrogenation of p-nitrophenol (p-NP) using formic acid (HCOOH)","selectivity":"Highest selectivity of HCOOH dehydration (forming CO)","deactivation":"By-product CO can be strongly absorbed on the Pd surface to inhibit the absorption and reaction of HCOOH","whyPerformsWell":"Performance is sensitive to the large pre-exponential factor (A).","metricCount":"4"},{"paperId":"P065","catalystId":"P065_PERF_004","name":"Pd/TiO2(B)","support":"TiO2(B)","matchedSynthesis":"Pd/TiO2(B)","matchedCharacterization":"Pd/TiO2(B)","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of Pd onto TiO2(B) support, followed by drying, calcination, and reduction.","phase":"Metallic Pd nanoparticles on TiO2(B) support","particleSize":"4.5 nm","surfaceStates":"Higher proportion of Pd(100) crystal plane.","structureLink":"Lowest catalytic performance attributed to the lowest metallic Pd content, poor dispersion state, and preference for HCOOH dehydration over dehydrogenation.","reactionConditions":"Transfer hydrogenation of p-nitrophenol (p-NP) using formic acid (HCOOH)","selectivity":"Significant occurrence of HCOOH dehydration","whyPerformsWell":"Lowest catalytic performance due to lowest metallic Pd content, poor dispersion state (fewest active sites), and preference for dehydration over dehydrogenation.","metricCount":"4"},{"paperId":"P066","catalystId":"P066_PERF_001","name":"Pd/c-Al2O3","support":"c-Al2O3","matchedSynthesis":"Pd/c-Al2O3","matchedCharacterization":"Pd/c-Al2O3","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support was calcined, suspended in water at pH 9, impregnated with Pd precursor, dried via rotary evaporation, calcined in air, and reduced under H2/N2.","particleSize":"2.8 nm","surfaceStates":"Pd0/Pd2+ ratio of 2.3; ATR-IR detected linear bonded (2110 cm-1) and bridged bonded (1830 cm-1) CO on the Pd surface.","structureLink":"Small Pd particles oxidize easily in air. Catalyst deactivation is caused by the strong adsorption of CO on the Pd surface, which can be suppressed by trace oxygen via oxidation of adsorbed CO to CO2.","reactionConditions":"T = 20 °C, atmospheric pressure, aqueous phase, stirring speed 625 rpm, gas flow rate 50 mL/min NTP, catalyst amount 0.1 g in 0.3 L water","selectivity":"H2 and CO2 produced in equal amounts under inert conditions; hydrogen yield is maximal at 0.1 vol% O2 but decreases significantly as oxygen concentration increases further due to H2 oxidation or direct formic acid oxidation.","stability":"Catalyst deactivates significantly under inert atmosphere (Ar); stability is maintained for three runs with the addition of 0.1 vol% O2, showing only mild deactivation in the fourth run.","deactivation":"Deactivation is caused by CO poisoning; adsorbed CO on Pd surface was confirmed via ATR-IR and pretreatment with CO led to complete deactivation.","whyPerformsWell":"Traces of oxygen (below 0.1 vol%) suppress deactivation by removing adsorbed CO through oxidation to CO2, thereby maintaining active Pd sites for formic acid decomposition.","metricCount":"1"},{"paperId":"P067","catalystId":"P067_PERF_001","name":"Pt–PVP","matchedSynthesis":"Pt–PVP","matchedCharacterization":"Pt–PVP (colloidal platinum nanoparticles dispersed in polyvinylpyrrolidone)","role":"catalyst for formic acid decomposition","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Colloidal platinum nanoparticles were prepared via the chemical reduction of chloroplatinic acid in the presence of polyvinylpyrrolidone (PVP) as a dispersant to maintain nanoscale particle size.","phase":"colloidal platinum nanoparticles","particleSize":"2.3 nm","structureLink":"The catalytic activity of platinum nanoparticles is controlled by the dispersing agent.","reactionConditions":"Formic acid decomposition into H2 and CO2 using isochoric or isobaric process systems","selectivity":"Selectively decomposed into H2 and CO2","stability":"H2 production resumed when the reaction solution was replaced with nitrogen gas after deactivation","deactivation":"Deactivation of the catalyst due to the adsorption of simultaneously produced CO2 onto Pt-PVP","whyPerformsWell":"Isobaric process prevents reaching equilibrium pressure, reducing activation energy (41.0 vs 52.0 kJ/mol) and increasing H2 production efficiency compared to isochoric systems; activity is maximized near pKa of formic acid (3.75).","metricCount":"8"},{"paperId":"P068","catalystId":"P068_PERF_001","name":"Au/NdZrO2","support":"NdZrO2","matchedSynthesis":"Au/NdZrO2","matchedCharacterization":"Au/NdZrO2","role":"catalyst","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"ZrO2 was doped with Nd3+ by partial substitution of Zr4+ to form a solid solution support, followed by the loading of Au nanoparticles.","phase":"Tetragonal phase ZrO2 solid solution; lattice expansion induced by Nd3+ incorporation.","particleSize":"< 1.0 nm","surfaceStates":"Au 4f peak shifted to lower binding energy (83.4 eV), indicating electron-enrichment due to oxygen vacancies in support.","structureLink":"Stronger metal-support interaction and charge transfer from support to Au enhance catalytic activity for FA dehydrogenation, resulting in the highest TOF (2452.5 h-1) and lowest Ea (35.6 kJ mol-1).","reactionConditions":"Dehydrogenation of formic acid (FA) in NEt3 solution at 50 °C","selectivity":"Only H2 and CO2 produced; no CO detected (detection limit: 10 ppm)","stability":"Good stability and reusability after 5 cycles at 323 K with no obvious loss of catalytic activity","deactivation":"Slight Au leaching determined by ICP","whyPerformsWell":"Rare earth metal doping stabilizes the tetragonal phase of zirconia, promotes oxygen vacancies, enhances metal-support interaction, and facilitates electron transfer from support to gold.","metricCount":"2"},{"paperId":"P068","catalystId":"P068_PERF_002","name":"Au/CeZrO2","support":"CeZrO2","matchedSynthesis":"Au/CeZrO2","matchedCharacterization":"Au/CeZrO2","role":"catalyst","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"ZrO2 was doped with Ce3+ by partial substitution of Zr4+ to form a solid solution support, followed by the loading of Au nanoparticles.","phase":"Tetragonal phase ZrO2 solid solution; lattice expansion induced by Ce3+ incorporation.","particleSize":"< 1.0 nm","surfaceStates":"Au 4f peak shifted to lower binding energy (83.5 eV), indicating electron-enrichment due to oxygen vacancies in support.","structureLink":"Enhanced metal-support interaction via oxygen vacancy formation promotes charge transfer to Au, improving activity over Au/ZrO2.","reactionConditions":"Dehydrogenation of formic acid (FA) in NEt3 solution at 50 °C","selectivity":"Only H2 and CO2 produced; no CO detected (detection limit: 10 ppm)","whyPerformsWell":"Rare earth metal doping promotes oxygen vacancies and enhances metal-support interaction.","metricCount":"2"},{"paperId":"P068","catalystId":"P068_PERF_003","name":"Au/SmZrO2","support":"SmZrO2","matchedSynthesis":"Au/SmZrO2","matchedCharacterization":"Au/SmZrO2","role":"catalyst","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"ZrO2 was doped with Sm3+ by partial substitution of Zr4+ to form a solid solution support, followed by the loading of Au nanoparticles.","phase":"Tetragonal phase ZrO2 solid solution; lattice expansion induced by Sm3+ incorporation.","particleSize":"< 1.0 nm","surfaceStates":"Au 4f peak shifted to lower binding energy (83.6 eV), indicating electron-enrichment due to oxygen vacancies in support.","structureLink":"Enhanced metal-support interaction via oxygen vacancy formation promotes charge transfer to Au, improving activity over Au/ZrO2.","reactionConditions":"Dehydrogenation of formic acid (FA) in NEt3 solution at 50 °C","selectivity":"Only H2 and CO2 produced; no CO detected (detection limit: 10 ppm)","whyPerformsWell":"Rare earth metal doping promotes oxygen vacancies and enhances metal-support interaction.","metricCount":"2"},{"paperId":"P068","catalystId":"P068_PERF_004","name":"Au/ZrO2","support":"ZrO2","matchedSynthesis":"Au/ZrO2","matchedCharacterization":"Au/ZrO2","role":"catalyst","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"other","synthesis":"Gold nanoparticles were supported on a ZrO2 support.","phase":"Support exhibits mixed monoclinic and tetragonal phases (tetragonal is main phase).","particleSize":"< 1.0 nm","surfaceStates":"Au 4f peak located at 83.8 eV.","structureLink":"Baseline catalyst with lowest TOF (1524.9 h-1) and highest activation energy (45.5 kJ mol-1).","reactionConditions":"Dehydrogenation of formic acid (FA) in NEt3 solution at 50 °C","selectivity":"Only H2 and CO2 produced; no CO detected (detection limit: 10 ppm)","metricCount":"2"},{"paperId":"P069","catalystId":"P069_PERF_001","name":"Pd2.3/C-N","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA and sodium formate aqueous solution","selectivity":"nearly 100% (no CO signal detected)","metricCount":"1"},{"paperId":"P069","catalystId":"P069_PERF_002","name":"Pd4.6/C-N","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA and sodium formate aqueous solution","selectivity":"nearly 100% (no CO signal detected)","metricCount":"2"},{"paperId":"P069","catalystId":"P069_PERF_003","name":"Pd9.2/C-N","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Room temperature to 333 K, FA and sodium formate aqueous solution","selectivity":"nearly 100% (no CO signal detected)","stability":"In the second run, produced 90% volume of H2 in 20 min and TOF decreased to 92.52%. In the third cycle, produced 65% volume of H2 in 20 min and TOF decayed by about 25% (to 74.95%).","deactivation":"Deactivation attributed to destruction of N active sites on support surface (N content decreased from 4.13% to 2.29%), contamination with other components, and agglomeration of Pd particles.","whyPerformsWell":"Well-distributed ultrafine palladium nanoparticles (2.2-2.6 nm), proper metal-carrier interaction enhancing C-H bond cleavage, electron transfer from graphitic-N and pyridinic-N to Pd, and high specific surface area of the support.","metricCount":"5"},{"paperId":"P069","catalystId":"P069_PERF_004","name":"Pd18.4/C-N","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA and sodium formate aqueous solution","selectivity":"nearly 100% (no CO signal detected)","metricCount":"2"},{"paperId":"P069","catalystId":"P069_PERF_005","name":"Pd23.1/C-N","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA and sodium formate aqueous solution","selectivity":"nearly 100% (no CO signal detected)","metricCount":"1"},{"paperId":"P070","catalystId":"P070_PERF_001","name":"Pd@TU-PMO","support":"TU-PMO","matchedSynthesis":"Pd@TU-PMO","matchedCharacterization":"Pd@TU-PMO","role":"catalyst for the catalytic dehydrogenation of formic acid in water","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"TU-PMO was dispersed in a tetrachloropalladate solution to incorporate Pd2+ into the pore channels, followed by reduction with sodium borohydride.","phase":"metallic palladium","particleSize":"ca. 2.3 nm","surfaceStates":"XPS peaks at 337.16 and 342.51 eV assigned to metallic palladium.","structureLink":"High activity is attributed to small, highly dispersed Pd nanoparticles resulting from strong interactions between the Pd precursors and thiourea groups; metallic Pd is more active than Pd2+ ions.","reactionConditions":"Catalytic dehydrogenation of formic acid in water","selectivity":"almost 100% selectivity for formic acid dehydrogenation; CO was not detected","stability":"Excellent recyclability was observed.","deactivation":"no significant leaching from support into the reaction media (verified by hot-filtration test)","whyPerformsWell":"stable immobilization of the Pd nanoparticles on the surface of the mesopores via interactions between the Pd and the thiourea functionalities","metricCount":"2"},{"paperId":"P070","catalystId":"P070_PERF_002","name":"Pd2+@TU-PMO","matchedCharacterization":"Pd2+@TU-PMO","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"ionic Pd2+","surfaceStates":"XPS peaks at 337.90 and 343.14 eV assigned to ionic species (Pd2+).","structureLink":"Lower rate of H2 generation compared to metallic Pd; may consume produced H2 to deposit metallic Pd.","reactionConditions":"Catalytic dehydrogenation of formic acid in water","whyPerformsWell":"Pd2+ may consume part of the produced H2 to deposit metallic Pd","metricCount":"1"},{"paperId":"P071","catalystId":"P071_PERF_001","name":"Pd/HTNC-950","matchedCharacterization":"Pd/HTNC-950","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","particleSize":"2.8 ± 0.1 nm (fresh); 3.3 nm (after 5 runs)","surfaceStates":"Pd0 binding energy at 335.8 eV and Pd2+ at 337.8 eV; electronic enrichment of Pd0 due to interaction with N species.","structureLink":"High TOF (1631 h-1) attributed to well-dispersed NPs and the synergy between Pd2+ sites for formate ion adsorption and Pd0 sites for C-H bond activation.","reactionConditions":"FA/SF aqueous solution, 30 °C","selectivity":"no CO (< 1 ppm) detected","stability":"did not show an obvious loss of catalytic activity even after the fifth run","deactivation":"particle size increased from 2.8 nm to 3.3 nm after five runs","whyPerformsWell":"N species adjusted electronic properties of Pd (Pd2+ for formate adsorption and Pd0 for C-H bond activation) and promoted dispersion of small Pd NPs","metricCount":"5"},{"paperId":"P071","catalystId":"P071_PERF_002","name":"Pd/HTNC-O","support":"Activated carbon (AC)","matchedSynthesis":"Pd/HTNC-O","matchedCharacterization":"Pd/HTNC-O","role":"Control catalyst (parental AC support)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Parental AC sonicated in deionized water, mixed with H2PdCl4 solution at room temperature, reduced using NaBH4 after pH adjustment, then centrifuged, washed, and dried.","particleSize":"5.8 nm (fresh); 6.4 nm (after 5 runs)","structureLink":"Lower activity and stability compared to Pd/HTNC-950 due to larger particle size and poor dispersion.","reactionConditions":"FA/SF aqueous solution, 30 °C","stability":"decreased significantly during recycling","deactivation":"particle size increased from 5.8 nm to 6.4 nm after five runs","metricCount":"2"},{"paperId":"P071","catalystId":"P071_PERF_003","name":"Pd/AC-950","support":"Activated carbon (AC)","matchedSynthesis":"Pd/AC-950","matchedCharacterization":"Pd/AC-950","role":"Control catalyst (non-nitrogen doped high temp AC)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"AC treated with N2 at 950 °C, then Pd deposited via the same impregnation and NaBH4 reduction method as Pd/HTNC.","particleSize":"4.3 nm","structureLink":"Lower activity than Pd/HTNC-950 indicates that high surface area of the support is not the decisive factor for catalytic performance.","reactionConditions":"FA/SF aqueous solution, 30 °C","whyPerformsWell":"lower activity confirmed that SSA of the support might not be decisive","metricCount":"0"},{"paperId":"P072","catalystId":"P072_PERF_001","name":"Ag16Pd1/C","support":"carbon","matchedSynthesis":"Ag16Pd1/C","matchedCharacterization":"Ag16Pd1/C","role":"catalyst for sodium formate decomposition","composition":"Ag:Pd = 16:1","activeMetals":"Ag-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"deposition_precipitation","synthesis":"Commercial Pd/C was mixed with an aqueous solution of Ag salt at an atomic Ag/Pd ratio of 16, followed by reduction using sodium borohydride at 30 °C.","phase":"PdAg alloy (confirmed by HRTEM lattice fringe distance of 0.238 nm for PdAg (111) and EDX mapping/line scanning)","particleSize":"3.36 nm (increased to 3.61 nm after 5 reuses)","surfaceStates":"Metallic Ag0 (Ag 3d 5/2 at 368.42 eV) and Pd0 (Pd 3d 5/2 at 335.98 eV)","structureLink":"The formation of the PdAg alloy significantly enhances catalytic activity for sodium formate decomposition compared to commercial Pd/C.","reactionConditions":"Decomposition of sodium formate (SF) in the presence of acetic acid (AcOH) in water.","selectivity":"100% H2 selectivity; CO-free (GC: 52.34% CO2 and 49.95% H2)","stability":"Continuously reused at least 5 times without any significant decrease of activity","deactivation":"Particle size slightly increased from 3.36 nm to 3.61 nm after 5th reuse","whyPerformsWell":"Formation of PdAg alloy; weak acid (AcOH) creates a mixture of SF and FA, where SF increases electron density on the catalyst surface favoring beta-H elimination of formate.","metricCount":"4"},{"paperId":"P072","catalystId":"P072_PERF_002","name":"Pd/C","matchedCharacterization":"Pd/C (commercial)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","particleSize":"3.08 nm","structureLink":"Less active than Ag16Pd1/C for SF decomposition.","reactionConditions":"Decomposition of sodium formate (SF) in the presence of acetic acid (AcOH).","metricCount":"2"},{"paperId":"P072","catalystId":"P072_PERF_003","name":"Cu16Pd1/C","support":"carbon","matchedSynthesis":"Cu16Pd1/C","matchedCharacterization":"Cu16Pd1/C","role":"catalyst for sodium formate decomposition","composition":"Cu:Pd = 16:1","activeMetals":"Cu-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"deposition_precipitation","synthesis":"Commercial Pd/C was mixed with an aqueous solution of Cu salt at an atomic Cu/Pd ratio of 16, followed by reduction using sodium borohydride at 30 °C.","phase":"Alloyed onto the surface of Pd/C","particleSize":"3.43 nm","structureLink":"Catalytically inactive for SF decomposition.","reactionConditions":"Decomposition of sodium formate (SF) in the presence of acetic acid (AcOH).","whyPerformsWell":"catalytically inactive","metricCount":"0"},{"paperId":"P072","catalystId":"P072_PERF_004","name":"Ag/C","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Decomposition of sodium formate (SF) in the presence of acetic acid (AcOH).","whyPerformsWell":"catalytically inactive","metricCount":"0"},{"paperId":"P073","catalystId":"P073_PERF_001","name":"8 wt.% Pd/NHPC-150","support":"N-doped hierarchical porous carbon (NHPC-150)","matchedSynthesis":"Pd/NHPC-150","matchedCharacterization":"Pd/NHPC-150","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support dispersed in ethylene glycol (EG) and H2O (2:3 ml ratio) via ultrasonication; PdCl2/NaOH solution added under ultrasonication, followed by reduction with NaBH4 aqueous solution.","phase":"Face-centered cubic (FCC) structure","particleSize":"3.61 ± 0.24 nm","surfaceStates":"Pd 3d binding energy is 0.6 eV higher than metallic Pd, indicating strong interaction between Pd particles and N functional groups of NHPC-150.","structureLink":"The synergistic interface between Pd NPs and NHPC-150 sites, combined with the small particle size effect and N-doping, modifies the electronic environment of Pd atoms, facilitating C-H bond cleavage and lowering activation energy (21.39 kJ/mol).","reactionConditions":"Additive-free formic acid dehydrogenation (FAD) in distilled water at 25-40 °C.","selectivity":"100% selectivity for CO-free FAD; absence of CO confirmed at a detection limit of 10 ppm","stability":"Maintained 95% of initial activity after 8 successive reaction cycles; achieved 100% FAD even after 200 days of storage at room temperature.","deactivation":"Outstanding durability to leaching; average Pd NP size grew marginally from 3.54 nm (after 8th run) to 3.99 nm (after 10th cycle).","whyPerformsWell":"Synergistic interface between small-sized Pd NPs (3.61 nm) and N-doped hierarchical porous carbon (NHPC-150); N-doping modifies electronic properties of Pd, facilitates C-H bond cleavage, lowers activation energy (21.39 kJ/mol), and stabilizes intermediates.","metricCount":"5"},{"paperId":"P074","catalystId":"P074_PERF_001","name":"Pd/AS","support":"biomass-derived activated carbon (AS)","matchedSynthesis":"Pd/AS","matchedCharacterization":"Pd/AS","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of AS support with Pd precursor followed by reduction with NaBH4.","phase":"Monometallic Pd","particleSize":"3.8 ± 2.1 nm (fresh), 4.4 ± 1.9 nm (used)","surfaceStates":"Pd0 main species; Pd2+ content is 17% (fresh) and 11% (used)","reactionConditions":"75 °C, 30 min, aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration), 0.150 g catalyst","stability":"good stability preserved after six consecutive reaction cycles","metricCount":"2"},{"paperId":"P074","catalystId":"P074_PERF_002","name":"Pd/N-AS","support":"N-doped biomass-derived activated carbon (N-AS)","matchedSynthesis":"Pd/N-AS","matchedCharacterization":"Pd/N-AS","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of N-AS support with Pd precursor followed by reduction with NaBH4.","phase":"Monometallic Pd","particleSize":"3.2 ± 0.9 nm (fresh), 3.6 ± 1.0 nm (used)","surfaceStates":"Higher Pd2+ content than Pd/AS: 46% (fresh) and 21% (used)","structureLink":"Nitrogen functional groups serve as anchoring sites to maintain smaller nanoparticle size compared to N-free support.","reactionConditions":"75 °C, 30 min, aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration), 0.150 g catalyst","stability":"good stability preserved after six consecutive reaction cycles","whyPerformsWell":"Nitrogen functional groups modify basicity favoring FA interaction and can be involved in deprotonation of FA.","metricCount":"2"},{"paperId":"P074","catalystId":"P074_PERF_003","name":"PdAg/AS","support":"biomass-derived activated carbon (AS)","matchedSynthesis":"PdAg/AS","matchedCharacterization":"PdAg/AS","role":"catalyst","composition":"Pd/Ag molar ratio = 1/0.5","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of AS support with Pd and Ag precursors followed by reduction with NaBH4.","phase":"Bimetallic PdAg alloy","particleSize":"5.0 ± 2.0 nm (fresh), 6.6 ± 2.6 nm (used)","surfaceStates":"Only Pd0 present; electronic enrichment of Pd surface atoms due to alloying with Ag","structureLink":"Poor stability and activity in non-reduced version attributed to formation of Ag-rich surface nanoparticles.","reactionConditions":"75 °C, 30 min, aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration), 0.150 g catalyst","stability":"catalytic activity decay of ~43% after 6 cycles (745 to 425 mLgas/gcat)","deactivation":"slight increase in average nanoparticle size from 5.0 ± 2.0 nm to 6.6 ± 2.6 nm","whyPerformsWell":"Presence of Ag modifies electronic properties and size of nanoparticles, favoring electron-rich Pd species.","metricCount":"2"},{"paperId":"P074","catalystId":"P074_PERF_004","name":"PdAg/N-AS","support":"N-doped biomass-derived activated carbon (N-AS)","matchedSynthesis":"PdAg/N-AS","matchedCharacterization":"PdAg/N-AS","role":"catalyst","composition":"Pd/Ag molar ratio = 1/0.5","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of N-AS support with Pd and Ag precursors followed by reduction with NaBH4.","phase":"Bimetallic PdAg alloy","particleSize":"2.8 ± 0.5 nm (fresh), 4.0 ± 0.7 nm (used)","surfaceStates":"Presence of Pd2+ due to strong Pd2+-N interaction: 52% (fresh) and 11% (used)","structureLink":"Superior performance attributed to the smallest nanoparticle size, high dispersion, and coexistence of metallic Pd0 and electron-deficient Pd species.","reactionConditions":"75 °C, 30 min, aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration), 0.150 g catalyst","stability":"excellent stability; activity loss almost negligible (~3%) after 6 cycles (988 to 954 mLgas/gcat)","deactivation":"small increase in particle size from 2.8 ± 0.5 nm to 4.0 ± 0.7 nm","whyPerformsWell":"Synergistic effect of N and Ag; small well-dispersed nanoparticles (2.8 nm); basic character of support; presence of both metallic Pd and electron-deficient Pd species.","metricCount":"2"},{"paperId":"P074","catalystId":"P074_PERF_005","name":"Pd/AS(n.r.)","support":"biomass-derived activated carbon (AS)","matchedSynthesis":"Pd/AS","matchedCharacterization":"Pd/AS","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of AS support with Pd precursor followed by reduction with NaBH4.","phase":"Monometallic Pd","particleSize":"3.8 ± 2.1 nm (fresh), 4.4 ± 1.9 nm (used)","surfaceStates":"Pd0 main species; Pd2+ content is 17% (fresh) and 11% (used)","reactionConditions":"75 °C, 30 min, aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration), 0.150 g catalyst","stability":"better activity than pre-reduced Pd/AS","whyPerformsWell":"In-situ reduction with H2 produced in reaction may result in more active 'clean' Pd species compared to NaBH4 reduction.","metricCount":"1"},{"paperId":"P074","catalystId":"P074_PERF_006","name":"Pd/N-AS(n.r.)","support":"N-doped biomass-derived activated carbon (N-AS)","matchedSynthesis":"Pd/N-AS","matchedCharacterization":"Pd/N-AS","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of N-AS support with Pd precursor followed by reduction with NaBH4.","phase":"Monometallic Pd","particleSize":"3.2 ± 0.9 nm (fresh), 3.6 ± 1.0 nm (used)","surfaceStates":"Higher Pd2+ content than Pd/AS: 46% (fresh) and 21% (used)","structureLink":"Nitrogen functional groups serve as anchoring sites to maintain smaller nanoparticle size compared to N-free support.","reactionConditions":"75 °C, 30 min, aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration), 0.150 g catalyst","stability":"better activity than pre-reduced Pd/N-AS","whyPerformsWell":"In-situ reduction with H2 produced in reaction; nitrogen atoms stabilize cationic Pd species and serve as anchoring sites.","metricCount":"1"},{"paperId":"P074","catalystId":"P074_PERF_007","name":"PdAg/AS(n.r.)","support":"biomass-derived activated carbon (AS)","matchedSynthesis":"PdAg/AS","matchedCharacterization":"PdAg/AS","role":"catalyst","composition":"Pd/Ag molar ratio = 1/0.5","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of AS support with Pd and Ag precursors followed by reduction with NaBH4.","phase":"Bimetallic PdAg alloy","particleSize":"5.0 ± 2.0 nm (fresh), 6.6 ± 2.6 nm (used)","surfaceStates":"Only Pd0 present; electronic enrichment of Pd surface atoms due to alloying with Ag","structureLink":"Poor stability and activity in non-reduced version attributed to formation of Ag-rich surface nanoparticles.","reactionConditions":"75 °C, 30 min, aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration), 0.150 g catalyst","stability":"significantly hindered activity compared to pre-reduced PdAg/AS","whyPerformsWell":"Poor performance attributed to possible formation of non-interacting/segregated species or Ag-rich surface nanoparticles (surface Pd/Ag ratio 0.45).","metricCount":"0"},{"paperId":"P074","catalystId":"P074_PERF_008","name":"PdAg/N-AS(n.r.)","support":"N-doped biomass-derived activated carbon (N-AS)","matchedSynthesis":"PdAg/N-AS","matchedCharacterization":"PdAg/N-AS","role":"catalyst","composition":"Pd/Ag molar ratio = 1/0.5","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of N-AS support with Pd and Ag precursors followed by reduction with NaBH4.","phase":"Bimetallic PdAg alloy","particleSize":"2.8 ± 0.5 nm (fresh), 4.0 ± 0.7 nm (used)","surfaceStates":"Presence of Pd2+ due to strong Pd2+-N interaction: 52% (fresh) and 11% (used)","structureLink":"Superior performance attributed to the smallest nanoparticle size, high dispersion, and coexistence of metallic Pd0 and electron-deficient Pd species.","reactionConditions":"75 °C, 30 min, aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration), 0.150 g catalyst","stability":"significantly hindered activity compared to pre-reduced PdAg/N-AS","whyPerformsWell":"Poor performance attributed to possible formation of non-interacting/segregated species or Ag-rich surface nanoparticles (surface Pd/Ag ratio 1.06).","metricCount":"0"},{"paperId":"P075","catalystId":"P075_PERF_001","name":"Pd/NHPC-AC","support":"NHPC-AC (N-doped porous carbon)","matchedSynthesis":"Pd/NHPC-AC","matchedCharacterization":"Pd/NHPC-AC","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"NHPC-AC dispersed in water, PdCl2 added, pH adjusted to 8 with Na2CO3, stirred for 2 h, heated to 60 °C, reduced by dropwise addition of HCOOH, pH adjusted to 9-10 with Na2CO3, stirred for 1 h, filtered, washed and dried.","phase":"Metallic Pd (111 plane)","particleSize":"1.88 ± 0.48 nm","surfaceStates":"Pd0 (54%) and Pd2+","structureLink":"Nitrogen doping prevents nanoparticle aggregation, increases metal dispersion, and enhances the proportion of active Pd0 sites via electron effects, resulting in higher TOF.","reactionConditions":"Decomposition of formic acid (FA) in deionized water using a 25 mL two-necked round-bottom flask with magnetic stirrer connected to a gas buret.","selectivity":"no generating of CO at the level of detection limit","stability":"reused for more than 5 times without significant activity lost; constantly in use for more than 2 h","deactivation":"nitrogen doping prevents Pd nanoparticles from aggregation and leaching from the support surface","whyPerformsWell":"N-doping increases proportion of Pd0 (54%) providing more active sites, and anchors noble metal via affinity of nitrogen to prevent aggregation.","metricCount":"4"},{"paperId":"P075","catalystId":"P075_PERF_002","name":"Pd/HPC-AC","support":"HPC-AC (porous carbon)","matchedSynthesis":"Pd/HPC-AC","matchedCharacterization":"Pd/HPC-AC","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Same methodology as Pd/NHPC-AC using HPC-AC support.","phase":"Metallic Pd (111 and 200 planes)","particleSize":"2.56 nm","surfaceStates":"Pd0 (41%) and Pd2+","structureLink":"Lower nitrogen-free support leads to larger particle size, lower dispersion, and fewer active Pd0 sites compared to Pd/NHPC-AC.","reactionConditions":"Decomposition of formic acid (FA) in deionized water using a 25 mL two-necked round-bottom flask with magnetic stirrer connected to a gas buret.","stability":"activity decreased after 3 times","metricCount":"2"},{"paperId":"P075","catalystId":"P075_PERF_003","name":"Pd/AC","support":"AC (activated carbon)","matchedSynthesis":"Pd/AC","matchedCharacterization":"Pd/AC","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Same methodology as Pd/NHPC-AC using AC support.","phase":"Metallic Pd (111 and 200 planes)","particleSize":"3.31 nm","surfaceStates":"Pd0 (39%) and Pd2+","structureLink":"Lack of nitrogen doping results in the largest particle size, lowest dispersion, and lowest proportion of active Pd0 sites.","reactionConditions":"Decomposition of formic acid (FA) in deionized water using a 25 mL two-necked round-bottom flask with magnetic stirrer connected to a gas buret.","stability":"activity decreased after 3 times","metricCount":"2"},{"paperId":"P076","catalystId":"P076_PERF_001","name":"PdAg/CNT (various Pd:Ag molar ratios including Pd/CNT, Ag/CNT, Pd9Ag1/CNT, Pd8Ag2/CNT, Pd7Ag3/CNT, Pd6Ag4/CNT)","matchedCharacterization":"PdAg/CNT","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdAg alloy; XRD showed a shift of the combined Pd-Ag peak from 40° (metallic Pd) toward 38° (metallic Ag) as the Ag/Pd molar ratio increased.","particleSize":"Average particle sizes were 3.0 nm for Pd/CNT and 3.1 nm for Pd7Ag3/CNT.","surfaceStates":"Electronic modification of Pd by Ag; XPS revealed a red shift (lower binding energy) in Pd 3d spectra with increasing Ag content, peaking at a Pd:Ag ratio of 7:3.","structureLink":"The electronic modification of Pd (maximized at Pd7Ag3/CNT) correlates with the highest TOF calculated based on surface Pd sites. KIE experiments suggest this effect weakens the C-H bond of adsorbed formate, facilitating its cleavage and enhancing overall activity.","reactionConditions":"Semi-batch reaction system; 0.03 g catalyst loaded into a two-necked reactor connected to a burette with mineral oil; 9 mL reactant solution.","selectivity":"FT-IR analysis revealed the absence of CO in produced gases, indicating dehydration was negligible.","deactivation":"Absence of micropores in CNT excludes fouling as a deactivation cause.","whyPerformsWell":"Electronic modification of Pd by Ag (maximized at 7:3 ratio) weakens the C-H bond of adsorbed formate, facilitating its cleavage and enhancing overall activity.","metricCount":"3"},{"paperId":"P077","catalystId":"P077_PERF_001","name":"PdMn0.6@S-1","matchedCharacterization":"PdMn0.6@S-1","activeMetals":"Pd-Mn","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Pd-Mn alloy structures.","particleSize":"< 0.7 nm","surfaceStates":"Electron-enriched Pd surfaces (indicated by CO-DRIFTS shift to 2076–2082 cm-1 and lower XANES white-line intensity).","structureLink":"Synergistic effect between Pd and Mn creates electron-enriched Pd surfaces that enhance bicarbonate hydrogenation and prevent overly strong binding of HCOO* and H* intermediates during FA dehydrogenation.","reactionConditions":"CO2 hydrogenation: H2/CO2 (20/20 bar), catalyst 5 mg, aqueous solution 2 mL; FA dehydrogenation: 2 M FA (1.5 mL)","selectivity":"CO-free (< 10 ppm) for FA decomposition; CO2/H2 ratio of 1:1","stability":"Formate generation rate remains unchanged after five consecutive runs (CO2 hydrogenation); no decrease in activity observed after five successive recycling tests (FA dehydrogenation)","whyPerformsWell":"Synergistic effect between Pd and Mn species leading to electron-enriched Pd surfaces; alloying of Pd with Mn favored a more compact 3D structure and slightly passivated Pd active sites, preventing overly strong binding with intermediates in FA decomposition.","metricCount":"6"},{"paperId":"P077","catalystId":"P077_PERF_002","name":"Pd@S-1","support":"silicalite-1 (S-1) zeolite","matchedSynthesis":"Pd/S-1-im","matchedCharacterization":"Pd@S-1","role":"control sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Prepared by incipient wetness impregnation method.","phase":"Monometallic sub-nanometer clusters.","particleSize":"< 0.7 nm","surfaceStates":"Linear-adsorbed CO peak at 2089 cm-1.","structureLink":"Sub-nanometer size increases the number of accessible active sites compared to larger nanoparticles, though TOF is similar to bulk Pd.","reactionConditions":"CO2 hydrogenation: H2/CO2 (20/20 bar), catalyst 5 mg, aqueous solution 2 mL; FA dehydrogenation: 2 M FA (1.5 mL)","whyPerformsWell":"Sub-nanometer Pd clusters confined inside the zeolite stay in a close to metallic state, providing an enhanced number of active sites compared to larger nanoparticles.","metricCount":"3"},{"paperId":"P077","catalystId":"P077_PERF_003","name":"Pd/Al2O3","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"CO2 hydrogenation: H2/CO2 (20/20 bar), 1.5 M aqueous NEt3 solution, 298 K","metricCount":"2"},{"paperId":"P077","catalystId":"P077_PERF_004","name":"Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"CO2 hydrogenation: H2/CO2 (20/20 bar), 1.5 M aqueous NEt3 solution, 298 K","metricCount":"2"},{"paperId":"P077","catalystId":"P077_PERF_005","name":"Mn@S-1","matchedCharacterization":"Mn@S-1","activeMetals":"Mn","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Monometallic clusters.","particleSize":"Sub-nanometer","surfaceStates":"No CO adsorption observed via DRIFTS.","structureLink":"Inactive for both CO2 hydrogenation and FA dehydrogenation without Pd.","reactionConditions":"CO2 hydrogenation and FA dehydrogenation tests","whyPerformsWell":"Not active; Mn species only modulate the reactivity of Pd.","metricCount":"1"},{"paperId":"P078","catalystId":"P078_PERF_001","name":"Co&CoN-0.5","matchedCharacterization":"Co&CoN-0.5","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Metallic Co phase (diffraction peaks at 2θ = 44°, 53°, and 76° corresponding to (111), (211), and (311) planes) coexisting with single atomic Co-N-C sites.","particleSize":"Mean size of ~10 nm for nanoparticles; some clusters < 3 nm observed.","surfaceStates":"Co0 and Co2+ coexist; high concentration of metal Co-N bonds identified via XPS N 1s spectra.","structureLink":"The hybrid core-shell structure optimizes the adsorption energy of intermediates, lowering the dehydrogenation energy barrier (81.48 kJ/mol) and increasing the dehydration energy barrier (227.54 kJ/mol), thereby enhancing activity and suppressing CO formation.","reactionConditions":"0.4 mL formic acid (10.4 mmol), 6 mL propylene carbonate solvent, 30 mg catalyst, helium atmosphere","selectivity":"92 ppm CO","stability":"maintained original activity for 5 cycles","deactivation":"high antiacid leaching stability; no metal found in reaction solution via ICP-MS; only neat formic acid resulted in a 10% loss of Co","whyPerformsWell":"synergy effect between cobalt nanoparticles and single atomic Co sites in the hybrid core-shell structure optimizes adsorption energy of intermediates, lowering the dehydrogenation energy barrier and increasing the dehydration energy barrier","metricCount":"1"},{"paperId":"P078","catalystId":"P078_PERF_002","name":"Co SAC","support":"carbon derived from ZIFs-2","matchedSynthesis":"Co SAC","matchedCharacterization":"Co SAC","role":"comparison catalyst","composition":"Co and Zn (Zn/Co = 2)","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"ZIFs-2 precursor synthesized from Co/Zn nitrates and 2-methylimidazole in methanol, then pyrolyzed at 800 °C under argon.","phase":"Single atomic Co sites coordinated with N atoms (Co-N-C).","particleSize":"No metal particles observed.","surfaceStates":"Co2+ valence state; pyridinic N accounts for > 50% of total N.","structureLink":"Single atomic Co sites facilitate the dehydration reaction, leading to high CO concentration (1644 ppm) compared to hybrid structures.","reactionConditions":"0.4 mL formic acid (10.4 mmol), 6 mL propylene carbonate solvent, 30 mg catalyst, helium atmosphere","selectivity":"1644 ppm CO","stability":"null","deactivation":"null","whyPerformsWell":"null","metricCount":"1"},{"paperId":"P078","catalystId":"P078_PERF_003","name":"Co&CoN-2","matchedCharacterization":"Co&CoN-2","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Single atomic Co sites; no metal Co peaks observed in XRD.","particleSize":"No nanoparticles present (high dispersion).","surfaceStates":"Co exists in Co2+ valence state; pyridinic N accounts for > 50% of total N.","structureLink":"Despite higher Co load than Co SAC, mass activity is similar because many single atomic sites are wrapped inside and inaccessible to reactants.","reactionConditions":"0.4 mL formic acid (10.4 mmol), 6 mL propylene carbonate solvent, 30 mg catalyst, helium atmosphere","selectivity":"similar to Co SAC (1644 ppm CO)","stability":"null","deactivation":"null","whyPerformsWell":"most of the Co single atomic sites are wrapped inside and not accessible for reactant","metricCount":"1"},{"paperId":"P078","catalystId":"P078_PERF_004","name":"Co&CoN-0","matchedCharacterization":"Co&CoN-0.5","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Metallic Co phase (diffraction peaks at 2θ = 44°, 53°, and 76° corresponding to (111), (211), and (311) planes) coexisting with single atomic Co-N-C sites.","particleSize":"Mean size of ~10 nm for nanoparticles; some clusters < 3 nm observed.","surfaceStates":"Co0 and Co2+ coexist; high concentration of metal Co-N bonds identified via XPS N 1s spectra.","structureLink":"The hybrid core-shell structure optimizes the adsorption energy of intermediates, lowering the dehydrogenation energy barrier (81.48 kJ/mol) and increasing the dehydration energy barrier (227.54 kJ/mol), thereby enhancing activity and suppressing CO formation.","reactionConditions":"0.4 mL formic acid (10.4 mmol), 6 mL propylene carbonate solvent, 30 mg catalyst, helium atmosphere","selectivity":"493 ppm CO","stability":"null","deactivation":"null","whyPerformsWell":"null","metricCount":"1"},{"paperId":"P078","catalystId":"P078_PERF_005","name":"Co NPs","support":"carbon black","matchedSynthesis":"Co NPs","matchedCharacterization":"Co NPs","role":"comparison catalyst","composition":"Co","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Co nitrate solution was poured into a carbon black methanol slurry, stirred for 6 h, centrifuged, washed, dried, and then reduced under H2 gas.","phase":"Metallic cobalt nanoparticles on nitrogen-free active carbon support.","particleSize":"~10 nm","surfaceStates":"Co0 and Co2+ coexist.","structureLink":"Low mass activity due to particle aggregation, low metal load, and lack of single atomic sites.","reactionConditions":"0.4 mL formic acid (10.4 mmol), 6 mL propylene carbonate solvent, 30 mg catalyst, helium atmosphere","selectivity":"relatively high CO","stability":"null","deactivation":"acid leaching stability is intractable for supported Co nanoparticle catalysts","whyPerformsWell":"low activity due to particle aggregation and low metal load","metricCount":"1"},{"paperId":"P079","catalystId":"P079_PERF_001","name":"Pd0.95Co0.05/CK-BN","support":"CK-BN","matchedSynthesis":"Pd0.95Co0.05/CK-BN","matchedCharacterization":"Pd0.95Co0.05/CK-BN","role":"optimal catalyst","composition":"Pd:Co = 0.95:0.05 (atomic ratio)","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CK-BN support was mixed with Pd and Co precursor solutions in water, stirred for 1 h, then reduced by adding NaBH4 solution and stirring for 90 min.","phase":"PdCo alloy nanoparticles","particleSize":"2.34 nm","surfaceStates":"Pd0 binding energy is 0.25 eV higher than in Pd/CK-BN due to interaction with Co; support contains pyridine N (398.5 eV), pyrrole N (400.5 eV), BC2O (191.2 eV), and BCO2 (192.4 eV).","structureLink":"Alloying Pd with Co modulates the electronic structure of Pd, increasing TOF to 3123 h-1; KCl etching and B,N co-doping increase surface area, defects, and hydrophilicity, facilitating NP immobilization.","reactionConditions":"Aqueous FA/SF solution at 30, 40, 50, and 60 °C","stability":"Good catalytic performance; only a slight decrease in activity observed after five cycles at 50 °C","deactivation":"Decreased activity attributed to surface and structure change of alloy NPs (agglomeration) and weakening signal of Co","whyPerformsWell":"Combination of KCl etching (large BET surface area, pore volume, and defects), B and N co-doping (improved hydrophilicity and abundance of accessible active sites), and PdCo alloying (optimal electronic structure due to electron redistribution on Pd)","metricCount":"1"},{"paperId":"P079","catalystId":"P079_PERF_002","name":"Pd/CK-BN","support":"CK-BN","matchedSynthesis":"Pd/CK-BN","matchedCharacterization":"Pd/CK-BN","role":"comparison catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar to Pd0.95Co0.05/CK-BN but without Co precursor.","phase":"Pd nanoparticles","surfaceStates":"Pd0 peak at 336.1 eV.","structureLink":"B and N co-doping improves support hydrophilicity and provides accessible active sites, resulting in a TOF of 1808 h-1.","reactionConditions":"Aqueous FA/SF solution","whyPerformsWell":"Abundance of accessible active sites such as N and B species; rich defects from KCl etching","metricCount":"1"},{"paperId":"P079","catalystId":"P079_PERF_003","name":"Pd/CK-B","support":"CK-BN","matchedSynthesis":"Pd/CK-BN","matchedCharacterization":"Pd/CK-BN","role":"comparison catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar to Pd0.95Co0.05/CK-BN but without Co precursor.","phase":"Pd nanoparticles","surfaceStates":"Pd0 peak at 336.1 eV.","structureLink":"B and N co-doping improves support hydrophilicity and provides accessible active sites, resulting in a TOF of 1808 h-1.","reactionConditions":"Aqueous FA/SF solution","whyPerformsWell":"B doping on carbon support regulates surface-interface property","metricCount":"1"},{"paperId":"P079","catalystId":"P079_PERF_004","name":"Pd/CK-N","matchedCharacterization":"Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pd nanoparticles on carbon","structureLink":"Lower catalytic activity compared to Pd/CK-BN due to the absence of alkaline etching and heteroatom doping in the support.","reactionConditions":"Aqueous FA/SF solution","whyPerformsWell":"N doping on carbon support regulates surface-interface property","metricCount":"1"},{"paperId":"P080","catalystId":"P080_PERF_001","name":"Pd/DMSNs-1.0-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation (FAD) in a 25 mL two-necked round-bottom flask with stirring; FA-SF mixed solution (2 mL, molar ratio FA:SF = 1:2, containing 2.5 mmol FA); catalyst dispersed in deionized water (3 mL).","selectivity":"100% H2 selectivity; no detectable CO formation observed","stability":"Good recyclability across five consecutive tests: TOF values were 473.8, 468.5, 466.6, 462.5, and 460.3 h-1; total reaction times were 24.00, 24.30, 24.45, 24.48, and 24.55 min.","deactivation":"Minor decrease in catalytic performance attributed to an increase in Pd NP size from 1.6 nm to 2.8 nm after five cycles.","whyPerformsWell":"Dendritic center-radial 3D pore channels with high surface area, notable pore volume, and concentrative pore size distribution for modulated mass transfer; ultrasmall Pd NPs (1.6 nm) with high dispersion; suitable metal-support interaction (MSI) between Pd NPs and DMSNs-1.0-NH2 support.","metricCount":"4"},{"paperId":"P080","catalystId":"P080_PERF_002","name":"Pd/DMSNs-0.25-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/DMSNs-1.0-NH2","selectivity":"100% FA conversion","metricCount":"2"},{"paperId":"P080","catalystId":"P080_PERF_003","name":"Pd/DMSNs-0.5-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/DMSNs-1.0-NH2","selectivity":"100% FA conversion","metricCount":"2"},{"paperId":"P080","catalystId":"P080_PERF_004","name":"Pd/DMSNs-2.0-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/DMSNs-1.0-NH2","selectivity":"100% FA conversion","metricCount":"2"},{"paperId":"P080","catalystId":"P080_PERF_005","name":"Pd/DMSNs-3.0-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/DMSNs-1.0-NH2","selectivity":"100% FA conversion","metricCount":"2"},{"paperId":"P081","catalystId":"P081_PERF_001","name":"C2N-Co","support":"C2N","matchedSynthesis":"C2N-Co-Sn","matchedCharacterization":"C2N-Co","role":"theoretical catalyst model","composition":"Co:Sn = 1:1 (per cavity)","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Density Functional Theory (DFT) calculations","synthesis":"Theoretical construction of C2N cluster models by anchoring one Co atom and one Sn atom in the same cavity.","phase":"Single atom catalyst","particleSize":"single atom","surfaceStates":"low-spin (S = 1/2) and high-spin ground state","structureLink":"Low-spin state is active for HCOOH dehydrogenation but higher in energy than the high-spin ground state.","reactionConditions":"HCOOH dehydrogenation","metricCount":"2"},{"paperId":"P081","catalystId":"P081_PERF_002","name":"C2N-Co-Sn","support":"C2N","matchedSynthesis":"C2N-Co-Sn","matchedCharacterization":"C2N-Co-Sn","role":"theoretical catalyst model","composition":"Co:Sn = 1:1 (per cavity)","activeMetals":"Co-Sn","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Density Functional Theory (DFT) calculations","synthesis":"Theoretical construction of C2N cluster models by anchoring one Co atom and one Sn atom in the same cavity.","phase":"Single atom catalyst with noncontact single atom promoter","particleSize":"single atom","surfaceStates":"Degenerate low-spin (S = 1/2) and high-spin (S = 3/2) states; d-band center closer to Fermi level at high-spin (-3.02 eV)","structureLink":"The noncontact Sn promoter facilitates spin manipulation, where the high-spin state of Co remarkably lowers the reaction barrier for HCOOH dehydrogenation compared to C2N-Co.","reactionConditions":"HCOOH dehydrogenation","stability":"nitrogen-doped porous-carbon-supported Co or Sn could maintain intact under 450−650 °C","whyPerformsWell":"Noncontact single atom promoter (Sn) manipulates the electronic state of Co via charge redistribution of C2N support, making high-spin and low-spin states almost degenerate. High-spin Co provides a lower reaction barrier due to increased charge transfer from HCOOH to Co and d-band center shifting closer to the Fermi level.","metricCount":"4"},{"paperId":"P081","catalystId":"P081_PERF_003","name":"C2N-Co-Ge","support":"C2N","matchedSynthesis":"C2N-Co-Ge","matchedCharacterization":"C2N-Co","role":"theoretical catalyst model","composition":"Co:Ge = 1:1 (per cavity)","activeMetals":"Co-Ge","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Density Functional Theory (DFT) calculations","synthesis":"Theoretical construction of C2N cluster models by anchoring one Co atom and one Ge atom in the same cavity.","phase":"Single atom catalyst","particleSize":"single atom","surfaceStates":"low-spin (S = 1/2) and high-spin ground state","structureLink":"Low-spin state is active for HCOOH dehydrogenation but higher in energy than the high-spin ground state.","reactionConditions":"HCOOH dehydrogenation","whyPerformsWell":"Similar to C2N-Co-Sn, Ge acts as a noncontact SAP manipulating the spin state of Co.","metricCount":"1"},{"paperId":"P081","catalystId":"P081_PERF_004","name":"C2N-Co-Pb","support":"C2N","matchedSynthesis":"C2N-Co-Pb","matchedCharacterization":"C2N-Co","role":"theoretical catalyst model","composition":"Co:Pb = 1:1 (per cavity)","activeMetals":"Co-Pb","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Density Functional Theory (DFT) calculations","synthesis":"Theoretical construction of C2N cluster models by anchoring one Co atom and one Pb atom in the same cavity.","phase":"Single atom catalyst","particleSize":"single atom","surfaceStates":"low-spin (S = 1/2) and high-spin ground state","structureLink":"Low-spin state is active for HCOOH dehydrogenation but higher in energy than the high-spin ground state.","reactionConditions":"HCOOH dehydrogenation","whyPerformsWell":"Similar to C2N-Co-Sn, Pb acts as a noncontact SAP manipulating the spin state of Co.","metricCount":"1"},{"paperId":"P082","catalystId":"P082_PERF_001","name":"PdNi-WOx/KIT-6-NH2","support":"KIT-6-NH2","matchedSynthesis":"PdNi-WOx/KIT-6-NH2","matchedCharacterization":"PdNi-WOx/KIT-6-NH2","role":"active catalyst","composition":"Pd:Ni = 8:2","activeMetals":"Pd-Ni-W","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Aqueous solutions of Pd, Ni, and W precursors were added to KIT-6-NH2 support under magnetic stirring and subsequently reduced with NaBH4 at room temperature.","phase":"fcc PdNi alloy (XRD peak at 40.9°; HRTEM lattice spacing 0.216 nm)","particleSize":"1.4 nm","surfaceStates":"Electron-rich Pd active sites resulting from: 1) electronic coupling (electron transfer from WOx to PdNi), 2) electronic metal-support interaction (EMSI, electron transfer from KIT-6-NH2 to PdNi-WOx), and 3) alloying effect (partial electron transfer from Ni to Pd).","structureLink":"Ultrafine size increases exposed active sites; electron-rich Pd surface favors C-H bond cleavage of the Pd-formate intermediate. WOx stabilizes low-coordination surface Pd atoms, improving stability.","reactionConditions":"Additive-free formic acid dehydrogenation, n_metal/n_FA = 0.04, FA amount = 2.5 mmol, double-necked round-bottomed flask in a water bath","selectivity":"100% hydrogen selectivity; no CO detected by GC","stability":"Maintains almost 100% hydrogen selectivity and conversion during five recycling tests at 323 K, with a slight loss in gas-releasing rate.","deactivation":"Leaching percentages after durability test: Pd (0.12 wt%), Ni (0.43 wt%), W (0.10 wt%). Particle size increased from 1.4 to 2.3 nm.","whyPerformsWell":"Ultrafine and highly dispersed electron-rich PdNi-WOx nanoclusters; synergistic effect between PdNi-WOx and KIT-6-NH2; amino groups provide Brønsted basic sites for FA deprotonation; WOx promoter creates oxygen vacancies and inhibits NP growth.","metricCount":"2"},{"paperId":"P082","catalystId":"P082_PERF_002","name":"PdNi/KIT-6-NH2","support":"KIT-6-NH2","matchedSynthesis":"Pd/KIT-6-NH2, Pd-WOx/KIT-6-NH2, PdNi/KIT-6-NH2","matchedCharacterization":"PdNi/KIT-6-NH2","role":"comparative catalysts","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared according to the same experimental conditions as PdNi-WOx/KIT-6-NH2.","phase":"fcc PdNi alloy","particleSize":"2.2 nm","reactionConditions":"Additive-free formic acid dehydrogenation, n_metal/n_FA = 0.04, FA amount = 2.5 mmol","stability":"Shows good reusability but inferior to PdNi-WOx/KIT-6-NH2","deactivation":"Leaching percentages: Pd (0.52 wt%), Ni (0.99 wt%)","whyPerformsWell":"Electron-rich Pd active sites induced by Pd-Ni alloying effect","metricCount":"1"},{"paperId":"P082","catalystId":"P082_PERF_003","name":"Pd-WOx/KIT-6-NH2","support":"KIT-6-NH2","matchedSynthesis":"Pd/KIT-6-NH2, Pd-WOx/KIT-6-NH2, PdNi/KIT-6-NH2","matchedCharacterization":"Pd-WOx/KIT-6-NH2","role":"comparative catalysts","activeMetals":"Pd-W","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared according to the same experimental conditions as PdNi-WOx/KIT-6-NH2.","particleSize":"2.3 nm","reactionConditions":"Additive-free formic acid dehydrogenation, n_metal/n_FA = 0.04, FA amount = 2.5 mmol","whyPerformsWell":"WOx dopant promotes the metal NPs for FDR","metricCount":"1"},{"paperId":"P082","catalystId":"P082_PERF_004","name":"Pd/KIT-6-NH2","support":"KIT-6-NH2","matchedSynthesis":"Pd/KIT-6-NH2, Pd-WOx/KIT-6-NH2, PdNi/KIT-6-NH2","matchedCharacterization":"Pd/KIT-6-NH2","role":"comparative catalysts","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared according to the same experimental conditions as PdNi-WOx/KIT-6-NH2.","particleSize":"2.6 nm","reactionConditions":"Additive-free formic acid dehydrogenation, n_metal/n_FA = 0.04, FA amount = 2.5 mmol","metricCount":"1"},{"paperId":"P082","catalystId":"P082_PERF_005","name":"PdNi-WOx/KIT-6","support":"KIT-6-NH2","matchedSynthesis":"PdNi-WOx/KIT-6-NH2","matchedCharacterization":"PdNi-WOx/KIT-6","role":"active catalyst","composition":"Pd:Ni = 8:2","activeMetals":"Pd-Ni-W","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Aqueous solutions of Pd, Ni, and W precursors were added to KIT-6-NH2 support under magnetic stirring and subsequently reduced with NaBH4 at room temperature.","particleSize":"7.7 nm","structureLink":"Larger particle size leads to poorer catalytic activity compared to the amino-modified support version.","reactionConditions":"Additive-free formic acid dehydrogenation, n_metal/n_FA = 0.04, FA amount = 2.5 mmol","whyPerformsWell":"Poorer activity due to larger particle size (7.7 nm) and lack of amino groups","metricCount":"1"},{"paperId":"P083","catalystId":"P083_PERF_001","name":"Pd/Al2O3-HS","support":"Al2O3 hollow spheres (HS)","matchedSynthesis":"Pd/Al2O3-HS","matchedCharacterization":"Pd/Al2O3-HS","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"Al2O3-HS support dispersed in deionized water, PdCl2/NaCl mixture added, pH adjusted to 10.8 with NaOH, filtered, washed, dried, and reduced.","phase":"gamma-Al2O3 support with Pd nanoparticles/PdO","particleSize":"3.1 nm (fresh), 4.5 nm (spent)","surfaceStates":"High density of weak (<300 °C) and moderate (300-450 °C) basic sites on the support; Pd exists as PdO in fresh state (CN Pd-O = 4.0, Pd-Pd = 0.7).","structureLink":"High density of engineered basic sites promotes formic acid dissociation into formate ions and facilitates the formation of reactive Pd-HCOO* intermediates, leading to superior TOF (4606 h-1).","reactionConditions":"60 °C (333 K), atmospheric conditions, 600 rpm stirring in a two-necked flask","selectivity":"no detectable CO formation; exclusively produced H2 and CO2","stability":">90% of the initial activity was maintained during the first five reaction cycles","deactivation":"pronounced activity decline after the fifth cycle, attributed to possible Pd leaching and/or nanoparticle aggregation","whyPerformsWell":"high density of basic sites on the hollow spherical Al2O3 support enhances deprotonation of formic acid to formate (HCOO-), promotes the formation of reactive Pd-HCOO* intermediates, and accelerates formate decomposition","metricCount":"1"},{"paperId":"P083","catalystId":"P083_PERF_002","name":"Pd/Al2O3-NB","support":"Al2O3 nanobelts (NB)","matchedSynthesis":"Pd/Al2O3-NB","matchedCharacterization":"Pd/Al2O3-NB","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"Al2O3-NB support dispersed in deionized water, PdCl2/NaCl mixture added, pH adjusted to 10.8 with NaOH, filtered, washed, dried, and reduced.","phase":"gamma-Al2O3 support with Pd nanoparticles/PdO","particleSize":"2.8 nm (fresh), 3.9 nm (spent)","surfaceStates":"Intermediate basicity with a complete distribution of weak, moderate, and strong (>450 °C) basic sites.","structureLink":"Moderate density of basic sites results in lower activity compared to Pd/Al2O3-HS but higher than Pd/Al2O3-NP.","reactionConditions":"60 °C (333 K), atmospheric conditions, 600 rpm stirring in a two-necked flask","selectivity":"no detectable CO formation; exclusively produced H2 and CO2","whyPerformsWell":"intermediate level of basicity compared to HS and NP catalysts","metricCount":"1"},{"paperId":"P083","catalystId":"P083_PERF_003","name":"Pd/Al2O3-NP","support":"Al2O3 nanoparticles (NP)","matchedSynthesis":"Pd/Al2O3-NP","matchedCharacterization":"Pd/Al2O3-NP","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"Al2O3-NP support dispersed in deionized water, PdCl2/NaCl mixture added, pH adjusted to 10.8 with NaOH, filtered, washed, dried, and reduced.","phase":"gamma-Al2O3 support with Pd nanoparticles/PdO","particleSize":"3.0 nm (fresh), 4.1 nm (spent)","surfaceStates":"Lowest concentration of surface basicity, exhibiting only weak basic sites.","structureLink":"Low content of weak basic sites correlates with the lowest catalytic performance (TOF = 1842 h-1).","reactionConditions":"60 °C (333 K), atmospheric conditions, 600 rpm stirring in a two-necked flask","selectivity":"no detectable CO formation; exclusively produced H2 and CO2","whyPerformsWell":"poor activity attributed to low content of weak basic sites","metricCount":"1"},{"paperId":"P084","catalystId":"P084_PERF_001","name":"Pd/ZrO2@C","support":"ZrO2@C (t-ZrO2 embedded in amorphous carbon)","matchedSynthesis":"Pd/ZrO2@C","matchedCharacterization":"Pd/ZrO2@C","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"ZrO2@C support was synthesized via pyrolysis of UiO-66. Pd was loaded using wet impregnation with K2PdCl4, followed by NaOH addition and NaBH4 reduction.","phase":"fcc Pd; tetragonal ZrO2 embedded in amorphous carbon.","particleSize":"2.5 ± 0.3 nm","surfaceStates":"Electron-rich Pd surfaces indicated by negative shift in XPS binding energies compared to Pd/AC.","structureLink":"Uniform dispersion of smaller nanoparticles and electron-rich surfaces promote the dissociation of O-H bonds in formic acid and favor the formation of Pd-formate intermediates, enhancing catalytic activity.","reactionConditions":"Decomposition of formic acid (FA) in the presence of sodium formate (SF) promoter.","selectivity":"100% H2 selectivity","stability":"significant decrease in catalytic activity in the process of reuse","deactivation":"slight aggregation of the catalyst","whyPerformsWell":"uniform dispersion of smaller palladium nanoparticles and a synergistic effect between the metal NPs and support; ZrO2 modifies electronic structure to generate more electron-rich Pd surfaces promoting FA dissociation.","metricCount":"4"},{"paperId":"P084","catalystId":"P084_PERF_002","name":"Pd/AC","support":"activated carbon (AC)","matchedSynthesis":"Pd/AC","matchedCharacterization":"Pd/AC","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Prepared using the same method as Pd/ZrO2@C (impregnation with K2PdCl4 and NaBH4 reduction).","particleSize":"Similar to Pd/ZrO2@C (~2.5 nm)","surfaceStates":"Less electron-rich than Pd/ZrO2@C.","structureLink":"Higher fraction of oxidized Pd species and less electron-rich surface lead to lower activity compared to Pd/ZrO2@C despite similar particle size.","reactionConditions":"Decomposition of formic acid (FA) in the presence of sodium formate (SF) promoter.","metricCount":"2"},{"paperId":"P084","catalystId":"P084_PERF_003","name":"Pd/ZrO2","support":"ZrO2","matchedSynthesis":"Pd/ZrO2","matchedCharacterization":"Pd/ZrO2","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Prepared using the same method as Pd/ZrO2@C on a ZrO2 support derived from thermal decomposition of ZrO2@C.","structureLink":"Lowest activity attributed to the lowest BET surface area and poor Pd NP dispersion.","reactionConditions":"Decomposition of formic acid (FA) in the presence of sodium formate (SF) promoter.","whyPerformsWell":"lowest activity attributed to poor dispersion of Pd NPs due to lowest surface area","metricCount":"1"},{"paperId":"P084","catalystId":"P084_PERF_004","name":"Pd/UiO-66","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Decomposition of formic acid (FA) in the presence of sodium formate (SF) promoter.","metricCount":"1"},{"paperId":"P085","catalystId":"P085_PERF_001","name":"PVPI-capped networked Pd5Ag5 NWs","matchedCharacterization":"PVPI-capped networked Pd5Ag5 NWs","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Homogeneously alloyed fcc PdAg; polycrystalline structure with (111) facet lattice fringe distance of 0.23 nm","surfaceStates":"High density of low coordination atoms; extensive defects around kinks and steps; electron-rich Pd centers due to interfacial electron transfer from PVPI imino groups","structureLink":"Electron donation from PVPI imino groups increases electron density of Pd active centers, facilitating O-H cleavage and strengthening formate adsorption; the imino group also acts as a proton scavenger promoting b-hydride elimination","reactionConditions":"Room temperature, aqueous formic acid solution, ambient atmosphere","selectivity":"No CO detected (detection limit <= 2 ppm); molar ratio of CO2 to H2 is 1","stability":"Maintained initial activity and excellent dispersity after the sixth run","whyPerformsWell":"Interfacial electron transfer from PVPI imino group to PdAg NW surface increases electron density of Pd active centers; imino group acts as a proton scavenger for O-H bond dissociation and promotes C-H cleavage.","metricCount":"7"},{"paperId":"P085","catalystId":"P085_PERF_002","name":"PVP-capped networked Pd5Ag5 NWs","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Aqueous formic acid solution","metricCount":"1"},{"paperId":"P086","catalystId":"P086_PERF_001","name":"1 wt%Pd@O-HHT","support":"Oxygen Functionalised High Heat Treated carbon nanofibers (O-HHT)","matchedSynthesis":"1 wt%Pd@O-HHT","matchedCharacterization":"1 wt%Pd@O-HHT","role":"active catalyst","composition":"Pd, 1 wt%","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sol_immobilization","synthesis":"Pd precursor salt was mixed with PVA capping agent and reduced by NaBH4. The resulting colloidal solution was added to O-HHT nanofibers, acidified to pH 2 using sulphuric acid, filtered, washed, and dried.","phase":"Pd nanoparticles","particleSize":"2.3 nm","surfaceStates":"Surface Pd exposure of 1.14%; preferential deposition on O functionalities","structureLink":"Smaller particle size, higher dispersion, and electronic interaction between Pd and oxygen functional groups enhance activity, stability, and selectivity for the dehydrogenation pathway.","reactionConditions":"Liquid-phase formic acid decomposition at 30 °C, 0.5 M HCOOH aqueous solution, FA/metal molar ratio 2000:1, stirring at 1400 rpm in a two-necked round-bottom flask with reflux condenser.","selectivity":"75% selectivity for the dehydrogenation pathway","stability":"Remarkable stability up to six cycles of reaction (12 h total)","deactivation":"Avoids leaching of Pd; no signs of deactivation observed during 2h kinetic profiles","whyPerformsWell":"Smaller Pd particles, higher particle dispersion, increased Pd exposure leading to more surface active sites, and electronic interaction between Pd and oxygen functional groups on the support.","metricCount":"2"},{"paperId":"P086","catalystId":"P086_PERF_002","name":"1 wt%Pd@P-HHT","support":"Phosphorous Functionalised High Heat Treated carbon nanofibers (P-HHT)","matchedSynthesis":"1 wt%Pd@P-HHT","matchedCharacterization":"1 wt%Pd@P-HHT","role":"active catalyst","composition":"Pd, 1 wt%","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sol_immobilization","synthesis":"Pd precursor salt was mixed with PVA capping agent and reduced by NaBH4. The resulting colloidal solution was added to P-HHT nanofibers, acidified to pH 2 using sulphuric acid, filtered, washed, and dried.","phase":"Pd nanoparticles","particleSize":"2.3 nm","surfaceStates":"Surface Pd exposure of 1.57%; preferential deposition on P functionalities (confirmed by STEM-EDS)","structureLink":"Smaller particle size, higher dispersion, and electronic interaction between Pd and phosphorous functional groups enhance stability and activity compared to non-functionalized HHT.","reactionConditions":"Liquid-phase formic acid decomposition at 30 °C, 0.5 M HCOOH aqueous solution, FA/metal molar ratio 2000:1, stirring at 1400 rpm in a two-necked round-bottom flask with reflux condenser.","selectivity":"65% selectivity for the dehydrogenation pathway","stability":"Remarkable stability up to six cycles of reaction (12 h total)","deactivation":"Avoids leaching of Pd; no signs of deactivation observed during 2h kinetic profiles","whyPerformsWell":"Smaller Pd particles, higher particle dispersion, increased Pd exposure leading to more surface active sites, and electronic interaction between Pd and phosphorous functional groups on the support.","metricCount":"2"},{"paperId":"P086","catalystId":"P086_PERF_003","name":"1 wt%Pd@HHT","support":"High Heat Treated carbon nanofibers (HHT)","matchedSynthesis":"1 wt%Pd@HHT","matchedCharacterization":"1 wt%Pd@HHT","role":"reference catalyst","composition":"Pd, 1 wt%","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sol_immobilization","synthesis":"Pd precursor salt was mixed with PVA capping agent and reduced by NaBH4. The resulting colloidal solution was added to HHT nanofibers, acidified to pH 2 using sulphuric acid, filtered, washed, and dried.","phase":"Pd nanoparticles","particleSize":"3 nm","surfaceStates":"Surface Pd exposure of 0.77%","structureLink":"Larger particle size and lower dispersion compared to functionalized supports result in lower activity and stability.","reactionConditions":"Liquid-phase formic acid decomposition at 30 °C, 0.5 M HCOOH aqueous solution, FA/metal molar ratio 2000:1, stirring at 1400 rpm in a two-necked round-bottom flask with reflux condenser.","selectivity":"55% selectivity for the dehydrogenation pathway","stability":"Rapidly deactivates after the first run","deactivation":"Sintering (average particle size increased from 3.0 to 4.7 nm during 9 h), CO poisoning of NPs, and leaching of Pd","metricCount":"1"},{"paperId":"P087","catalystId":"P087_PERF_001","name":"Cr0.4Pd0.6/M-β-CD-A","support":"3-aminopropyl triethoxysilane functionalized monochlortriazinyl β-cyclodextrin (M-β-CD-A)","matchedSynthesis":"Cr0.4Pd0.6/M-β-CD-A","matchedCharacterization":"Cr0.4Pd0.6/M-β-CD-A","role":"main catalyst","composition":"Cr:Pd = 0.4:0.6 (molar ratio)","activeMetals":"Cr-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"M-β-CD was functionalized with APTES via ultrasonication; Cr and Pd precursors were added to the suspension and stirred, followed by reduction with NaBH4.","phase":"Alloy structure; HRTEM shows lattice spacing of 0.222 nm (smaller than Pd(111) at 0.224 nm); XRD shows a broad diffraction peak between characteristic peaks of Pd and Cr.","particleSize":"~2.8 nm","surfaceStates":"Binding energies of Pd 3d 5/2 and Cr 2p 3/2 are shifted to lower values compared to free NPs, indicating electron transfer from the M-β-CD-A support to CrPd NPs; charge transfer occurs between Pd and Cr due to alloying, resulting in an electron-rich Pd surface.","structureLink":"Strong metal/organic interfacial interactions control particle size and distribution while modifying the electronic structure of Pd active centers, which promotes the rate-determining C–H dissociation of the Pd-formate intermediate.","reactionConditions":"Formic acid dehydrogenation, 1.0 M FA aqueous solution (5.0 mL), ambient atmosphere, magnetic stirring (600 r/min)","selectivity":"100% H2 selectivity; no CO detected (detection limit: ~10 ppm)","stability":"Slight decrease in activity after three cycles","whyPerformsWell":"Strong metal/organic interfacial interactions between CrPd NPs and M-β-CD-A support; electron transfer from M-β-CD-A to CrPd NPs through the interface; synergistic alloying effect between Pd and Cr modulating electronic structure of Pd active centers.","metricCount":"2"},{"paperId":"P087","catalystId":"P087_PERF_002","name":"Cr0.4Pd0.6 NPs (free)","matchedCharacterization":"Cr0.4Pd0.6 NPs (free)","activeMetals":"Cr-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"~4.8 nm","reactionConditions":"Formic acid dehydrogenation, 1.0 M FA aqueous solution (5.0 mL), ambient atmosphere, magnetic stirring (600 r/min)","metricCount":"1"},{"paperId":"P087","catalystId":"P087_PERF_003","name":"Cr0.4Pd0.6/M-β-CD","support":"3-aminopropyl triethoxysilane functionalized monochlortriazinyl β-cyclodextrin (M-β-CD-A)","matchedSynthesis":"Cr0.4Pd0.6/M-β-CD-A","matchedCharacterization":"Cr0.4Pd0.6/M-β-CD","role":"main catalyst","composition":"Cr:Pd = 0.4:0.6 (molar ratio)","activeMetals":"Cr-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"M-β-CD was functionalized with APTES via ultrasonication; Cr and Pd precursors were added to the suspension and stirred, followed by reduction with NaBH4.","particleSize":"~3.8 nm","reactionConditions":"Formic acid dehydrogenation, 1.0 M FA aqueous solution (5.0 mL), ambient atmosphere, magnetic stirring (600 r/min)","metricCount":"1"},{"paperId":"P087","catalystId":"P087_PERF_004","name":"Cr0.4Pd0.6-A","matchedCharacterization":"Cr0.4Pd0.6-A","activeMetals":"Cr-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"3.1 nm","reactionConditions":"Formic acid dehydrogenation, 1.0 M FA aqueous solution (5.0 mL), ambient atmosphere, magnetic stirring (600 r/min)","metricCount":"1"},{"paperId":"P088","catalystId":"P088_PERF_001","name":"Pd@MC(2)-P","support":"MC(2)-P","matchedSynthesis":"Pd@MC(2)-P","matchedCharacterization":"Pd@MC(2)-P","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CMC, NaHCO3, and (NH4)2C2O4 were calcined at 973 K to form MC(2). MC(2) was then hydrothermally treated with concentrated H3PO4 at 403 K for 12 h to produce MC(2)-P. Pd precursor solution was added to the support dispersion, followed by reduction with NaBH4 in NaOH solution.","phase":"Metallic Pd nanoparticles","particleSize":"2.8 nm","surfaceStates":"Pd0 peaks at 339.9 and 334.7 eV; Pd2+ peaks at 341.6 and 335.9 eV. A distinct downshift of Pd0 peaks indicates stronger interaction with the N-doped carbon support compared to control samples.","structureLink":"Ultra-fine particle size, high dispersion, and exposure of active Pd-cluster-edge (edges of Pd-cluster-100 and Pd-cluster-111 surfaces) reduce H poisoning and lower energy barriers for formic acid dehydrogenation.","reactionConditions":"Formic acid (FA) dehydrogenation in FA/SF solution; In situ hydrogenation of phenol to cyclohexanone.","selectivity":"High selectivity for cyclohexanone (>90%) in phenol hydrogenation.","stability":"Maintains high initial catalysis activity and conversion of phenol to cyclohexanone with five recycled uses.","whyPerformsWell":"Ultra-fine Pd NPs (avg 2.8 nm) on N-doped porous biochar; phosphate-mediation ensures fine dispersion; reduced H poisoning and more exposed (100) surface/Pd-cluster-edge.","metricCount":"10"},{"paperId":"P088","catalystId":"P088_PERF_002","name":"Pd@MC(0)-P","support":"MC(0)-P","matchedSynthesis":"Pd@MC(0)-P","matchedCharacterization":"Pd@MC(0)-P","role":"control catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Pd@MC(2)-P, but using MC(0)-P support (CMC calcined without NaHCO3 and (NH4)2C2O4, then treated with H3PO4).","phase":"Metallic Pd nanoparticles","particleSize":"4.8 nm","surfaceStates":"Pd0 peaks at 340.4 and 335.3 eV.","reactionConditions":"Formic acid (FA) dehydrogenation in FA/SF solution.","whyPerformsWell":"Lower activity than Pd@MC(2)-P due to absence of foaming agent leading to inferior pore structure and lower N-doping.","metricCount":"8"},{"paperId":"P088","catalystId":"P088_PERF_003","name":"Pd@MC(2)-0","support":"MC(2)-0","matchedSynthesis":"Pd@MC(2)-0","matchedCharacterization":"Pd@MC(2)-0","role":"control catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Pd@MC(2)-P, but using MC(2)-0 support (CMC calcined with foaming agents, without H3PO4 hydrothermal treatment).","phase":"Metallic Pd nanoparticles","particleSize":"5.7 nm","surfaceStates":"Pd0 peaks at 342.5 and 335.9 eV.","reactionConditions":"Formic acid (FA) dehydrogenation in FA/SF solution.","whyPerformsWell":"Lowest activity due to severe agglomeration of Pd particles (avg 5.7 nm) and absence of phosphate-mediated dispersion.","metricCount":"8"},{"paperId":"P089","catalystId":"P089_PERF_001","name":"PdAu/Al2O3–CO (1)","support":"g-Al2O3","matchedSynthesis":"PdAu/Al2O3–CO (1)","matchedCharacterization":"PdAu/Al2O3–CO (1)","role":"active catalyst","composition":"Pd:Au = 1:1","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Impregnation of g-Al2O3 with Pd and Au precursors, drying, calcination, reduction under H2, followed by heat treatment under CO.","phase":"PdAu alloy (verified by XPS shift of Pd 3d 5/2 peak from 335.2 eV to 335.4 eV)","particleSize":"1.2–1.3 nm","surfaceStates":"High population of Pd 3-fold hollow sites (1800–1900 cm-1 in DRIFT) compared to H2 or N2 treated samples.","structureLink":"Highest activity for FA dehydrogenation due to the synergistic effect of a high density of Pd hollow sites (ensemble effect) and electronic perturbation from Au sublayers (ligand effect).","reactionConditions":"Aqueous FA solution (~1.0 M) at 50 °C, stirred at 300 rpm","whyPerformsWell":"High quantity of 3-fold hollow Pd sites (ensemble effect) and electronic perturbation induced by Au-containing sublayers (ligand effect).","metricCount":"1"},{"paperId":"P089","catalystId":"P089_PERF_002","name":"PdAu/Al2O3–H2 (2)","support":"g-Al2O3","matchedSynthesis":"PdAu/Al2O3–H2 (2)","matchedCharacterization":"PdAu/Al2O3–H2 (2)","role":"active catalyst","composition":"Pd:Au = 1:1","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Impregnation of g-Al2O3 with Pd and Au precursors, drying, calcination, and reduction under H2.","phase":"PdAu alloy (verified by XPS shift of Pd 3d 5/2 peak from 335.2 eV to 335.4 eV)","particleSize":"1.2–1.3 nm","surfaceStates":"Moderate population of Pd hollow sites (2.8 times greater than catalyst 3).","structureLink":"Moderate activity for FA dehydrogenation, correlating with the intermediate density of Pd hollow sites.","reactionConditions":"Aqueous FA solution (~1.0 M) at 50 °C, stirred at 300 rpm","whyPerformsWell":"Possesses fewer Pd hollow sites than catalyst 1.","metricCount":"1"},{"paperId":"P089","catalystId":"P089_PERF_003","name":"PdAu/Al2O3–N2 (3)","support":"g-Al2O3","matchedSynthesis":"PdAu/Al2O3–N2 (3)","matchedCharacterization":"PdAu/Al2O3–N2 (3)","role":"active catalyst","composition":"Pd:Au = 1:1","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Impregnation of g-Al2O3 with Pd and Au precursors, drying, calcination, reduction under H2, followed by heat treatment under N2.","phase":"PdAu alloy (verified by XPS shift of Pd 3d 5/2 peak from 335.2 eV to 335.4 eV)","particleSize":"1.2–1.3 nm","surfaceStates":"Negligible intensity of CO vibration at Pd hollow sites (1800–1900 cm-1).","structureLink":"Lowest activity for FA dehydrogenation due to low surface Pd coverage and lack of Pd hollow sites.","reactionConditions":"Aqueous FA solution (~1.0 M) at 50 °C, stirred at 300 rpm","whyPerformsWell":"Lowest activity among PdAu catalysts due to high Au surface concentration inhibiting the formation of Pd hollow sites.","metricCount":"1"},{"paperId":"P089","catalystId":"P089_PERF_004","name":"Pd/Al2O3 (4)","support":"g-Al2O3","matchedSynthesis":"Pd/Al2O3 (4)","matchedCharacterization":"Pd/Al2O3 (4)","role":"comparison sample","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Prepared for comparison; specific steps not detailed but implied to follow similar protocol as PdAu catalysts.","phase":"Pure Pd","surfaceStates":"High quantity of 3-fold hollow sites, but lower relative ratio than catalyst 1 because CO adsorption on bridge sites is more favorable at high coverage.","structureLink":"Lower activity compared to Catalyst 1 despite higher total hollow site count, demonstrating the positive ligand effect provided by Au sublayers in PdAu alloys.","reactionConditions":"Aqueous FA solution (~1.0 M) at 50 °C, stirred at 300 rpm","whyPerformsWell":"Lower H2-release activity compared to catalyst 1 despite higher quantity of 3-fold hollow Pd sites, indicating the importance of the ligand effect from Au sublayers.","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_001","name":"Pd1Ag0.5/NAS","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","matchedSynthesis":"Pd1Ag0.5/NAS","matchedCharacterization":"Pd1Ag0.5/NAS","role":"bimetallic catalyst","composition":"Pd:Ag = 1:0.5","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","phase":"Fresh: Ag crystalline facets (38°, 44°, 64°, 77°) and incomplete alloy; Used: PdAg alloy (XRD signals at 38.4° and 44.4°)","particleSize":"2.8 ± 1.1 nm","surfaceStates":"Highest relative proportion of Pd2+/Pd0 among all catalysts; Ag species electronic charge redistribution","structureLink":"Outstanding performance (TOF 1716 h-1) linked to the highest Pd2+/Pd0 ratio and small particle size.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","stability":"Maintained substantial activity over 6 consecutive reaction cycles; loss of 25% of initial activity in the sixth cycle. Initial reaction rates for cycles 1-6: 22.7, 20.5, 19.6, 20.0, 17.4, and 17.0 mL min-1.","deactivation":"No Pd leaching observed via ICP-OES. Deactivation attributed to sintering (average nanoparticle size increased by 39%) and reduction of Pd2+ species to Pd0 under reaction conditions.","whyPerformsWell":"Nitrogen functional groups in NAS support serve as anchoring sites for smaller, well-distributed bimetallic nanoparticles; increase surface basicity favoring HCOOH interaction; stabilize Pd2+ species which, along with Pd0, are needed for the dehydrogenation mechanism via formate intermediate. Ag incorporation modifies electronic properties of Pd.","metricCount":"2"},{"paperId":"P090","catalystId":"P090_PERF_002","name":"Pd1Ag0.5/AS","support":"Almond shell-derived activated carbon (AS)","matchedSynthesis":"Pd1Ag0.5/AS","matchedCharacterization":"Pd1Ag0.5/AS","role":"bimetallic catalyst","composition":"Pd:Ag = 1:0.5","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","phase":"PdAg alloy (XRD signals at 38.4° and 44.4°)","particleSize":"4.0 ± 1.3 nm","surfaceStates":"Predominantly Pd0; Ag species enriched in electronic charge","structureLink":"Optimal bimetallic composition for AS support, showing maximum gas volume among AS-supported catalysts.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","stability":"Loss of 57% of initial activity in the sixth cycle. Initial reaction rates for cycles 1-6: 23.5, 19.6, 17.9, 12.6, 12.2, and 10.0 mL min-1.","deactivation":"No Pd leaching observed via ICP-OES. Deactivation attributed to sintering (average nanoparticle size increased by 55%) and complete reduction of Pd species to Pd0.","whyPerformsWell":"PdAg alloy formation modifies electronic properties compared to monometallic Pd.","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_003","name":"Pd/AS","support":"Almond shell-derived activated carbon (AS)","matchedSynthesis":"Pd/AS","matchedCharacterization":"Pd/AS","role":"monometallic catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Standard impregnation followed by reduction with NaBH4.","phase":"Monometallic Pd","particleSize":"3.8 ± 2.1 nm","surfaceStates":"Pd0 and Pd2+; Pd0 3d5/2 at 335.6 eV, Pd2+ 3d5/2 at 337.5 eV","structureLink":"Lower activity compared to bimetallic and NAS-supported counterparts due to larger particle size and lower Pd2+/Pd0 ratio.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","stability":"Active after 6 cycles but less stable than Pd/NAS","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_004","name":"Pd1Ag0.3/AS","support":"Almond shell-derived activated carbon (AS)","matchedSynthesis":"Pd1Ag0.3/AS","matchedCharacterization":"Pd1Ag0.3/AS","role":"bimetallic catalyst","composition":"Pd:Ag = 1:0.3","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","phase":"PdAg alloy","particleSize":"4.5 ± 0.9 nm","surfaceStates":"Pd0 and Pd2+; Ag species enriched in electronic charge (shift of ~0.4 eV towards lower binding energies)","structureLink":"Increased activity compared to monometallic Pd/AS due to alloy formation.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_005","name":"Pd1Ag0.7/AS","support":"Almond shell-derived activated carbon (AS)","matchedSynthesis":"Pd1Ag0.7/AS","matchedCharacterization":"Pd1Ag0.7/AS","role":"bimetallic catalyst","composition":"Pd:Ag = 1:0.7","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","phase":"PdAg alloy","particleSize":"4.1 ± 1.2 nm","surfaceStates":"Pd0 and Pd2+; Ag species enriched in electronic charge","structureLink":"Activity lower than Pd1Ag0.5/AS, following a volcano-type relationship with Ag content.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_006","name":"Pd1Ag1/AS","support":"Almond shell-derived activated carbon (AS)","matchedSynthesis":"Pd1Ag1/AS","matchedCharacterization":"Pd1Ag1/AS","role":"bimetallic catalyst","composition":"Pd:Ag = 1:1","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","phase":"PdAg alloy","particleSize":"5.0 ± 2.0 nm","surfaceStates":"Purely Pd0; Ag species enriched in electronic charge","structureLink":"Lower activity than Pd1Ag0.5/AS due to larger particle size and absence of Pd2+.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_007","name":"Pd/NAS","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","matchedSynthesis":"Pd/NAS","matchedCharacterization":"Pd/NAS","role":"monometallic catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Standard impregnation followed by reduction with NaBH4.","phase":"Monometallic Pd","particleSize":"3.2 ± 0.9 nm","surfaceStates":"Pd0 and Pd2+; shift towards higher binding energies (Pd0 3d5/2 at 336.0 eV, Pd2+ 3d5/2 at 338.0 eV) due to N-groups","structureLink":"Enhanced activity over Pd/AS attributed to smaller particle size and higher concentration of Pd2+ species.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","stability":"Active after 6 cycles; stability better than Pd/AS","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_008","name":"Pd1Ag0.3/NAS","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","matchedSynthesis":"Pd1Ag0.3/NAS","matchedCharacterization":"Pd1Ag0.3/NAS","role":"bimetallic catalyst","composition":"Pd:Ag = 1:0.3","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","phase":"PdAg alloy","particleSize":"2.7 ± 0.7 nm","surfaceStates":"Pd0 and Pd2+; Ag species electronic charge redistribution influenced by electronegative N-groups","structureLink":"Higher activity than Pd1Ag0.3/AS due to smaller particle size and higher Pd2+ content.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_009","name":"Pd1Ag0.7/NAS","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","matchedSynthesis":"Pd1Ag0.7/NAS","matchedCharacterization":"Pd1Ag0.7/NAS","role":"bimetallic catalyst","composition":"Pd:Ag = 1:0.7","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","phase":"PdAg alloy","particleSize":"2.7 ± 0.6 nm","surfaceStates":"Pd0 and Pd2+; Ag species electronic charge redistribution","structureLink":"High activity but lower than Pd1Ag0.5/NAS, correlating with a lower Pd2+/Pd0 ratio.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","metricCount":"1"},{"paperId":"P090","catalystId":"P090_PERF_010","name":"Pd1Ag1/NAS","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","matchedSynthesis":"Pd1Ag1/NAS","matchedCharacterization":"Pd1Ag1/NAS","role":"bimetallic catalyst","composition":"Pd:Ag = 1:1","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","phase":"PdAg alloy","particleSize":"2.8 ± 0.5 nm","surfaceStates":"Pd0 and Pd2+; Ag species electronic charge redistribution","structureLink":"Activity lower than Pd1Ag0.5/NAS, following the volcano trend with Ag content.","reactionConditions":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","metricCount":"1"},{"paperId":"P091","catalystId":"P091_PERF_001","name":"Pd/CMS-ZnCl2","support":"CMS-ZnCl2","matchedSynthesis":"Pd/CMS-ZnCl2","matchedCharacterization":"Pd/CMS-ZnCl2","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3 and ZnCl2, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","phase":"Metallic Pd (weak diffraction peaks due to small particle size)","particleSize":"XRD: 2.8 nm; TEM: 2.9 ± 0.5 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Smallest particle size, high specific surface area (1081 m2/g), and uniform honeycomb morphology led to the highest TON value due to more active sites and uncapped surfaces.","reactionConditions":"Mixed solution of 1.0 mol·L−1 FA and 1.0 mol·L−1 SF in deionized water; n Pd/nFA = 0.2%; three-necked flask with gas burette.","selectivity":"100% hydrogen selectivity; CO below detection limit (< 1 ppm)","stability":"Catalytic activity decreased after three cycles","deactivation":"Average Pd particle size increased from 2.9 nm to 3.2 nm; content of Pd0 decreased","whyPerformsWell":"High specific surface area (1081 m2·g−1), uniform honeycomb morphology, stronger hydrophilicity, smaller Pd nanoparticles with more active sites and clean surfaces, increased oxygen-containing functional groups reducing surface acidity.","metricCount":"6"},{"paperId":"P091","catalystId":"P091_PERF_002","name":"Pd/CPS-ZnCl2","support":"CPS-ZnCl2","matchedSynthesis":"Pd/CPS-ZnCl2","matchedCharacterization":"Pd/CPS-ZnCl2","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Peanut seed shell was pretreated with HNO3 and ZnCl2, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","phase":"Metallic Pd (weak diffraction peaks due to small particle size)","particleSize":"XRD: 3.8 nm; TEM: 3.6 ± 0.6 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"ZnCl2 activation increased surface O content, providing nucleation points that reduced particle size and improved dispersion, increasing activity.","reactionConditions":"Mixed solution of 1.0 mol·L−1 FA and 1.0 mol·L−1 SF in deionized water; n Pd/nFA = 0.2%; three-necked flask with gas burette.","whyPerformsWell":"ZnCl2 activation reduced Pd particle size and increased surface oxygen content.","metricCount":"2"},{"paperId":"P091","catalystId":"P091_PERF_003","name":"Pd/CMS","support":"CMS","matchedSynthesis":"Pd/CMS","matchedCharacterization":"Pd/CMS","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites.","reactionConditions":"Mixed solution of 1.0 mol·L−1 FA and 1.0 mol·L−1 SF in deionized water; n Pd/nFA = 0.2%; three-necked flask with gas burette.","metricCount":"2"},{"paperId":"P091","catalystId":"P091_PERF_004","name":"Pd/CPS","support":"CPS","matchedSynthesis":"Pd/CPS","matchedCharacterization":"Pd/CPS","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Peanut seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 7.2 nm; TEM: 6.7 ± 0.6 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites.","reactionConditions":"Mixed solution of 1.0 mol·L−1 FA and 1.0 mol·L−1 SF in deionized water; n Pd/nFA = 0.2%; three-necked flask with gas burette.","metricCount":"2"},{"paperId":"P091","catalystId":"P091_PERF_005","name":"Pd/CMS-2gZnCl2","support":"CMS","matchedSynthesis":"Pd/CMS","matchedCharacterization":"Pd/CMS","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites.","reactionConditions":"Mixed solution of 1.0 mol·L−1 FA and 1.0 mol·L−1 SF in deionized water; n Pd/nFA = 0.2%; three-necked flask with gas burette.","metricCount":"1"},{"paperId":"P091","catalystId":"P091_PERF_006","name":"Pd/CMS-6gZnCl2","support":"CMS","matchedSynthesis":"Pd/CMS","matchedCharacterization":"Pd/CMS","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites.","reactionConditions":"Mixed solution of 1.0 mol·L−1 FA and 1.0 mol·L−1 SF in deionized water; n Pd/nFA = 0.2%; three-necked flask with gas burette.","metricCount":"1"},{"paperId":"P091","catalystId":"P091_PERF_007","name":"Pd/CMS-ZnCl2 (carbonized at 500 °C)","support":"CMS","matchedSynthesis":"Pd/CMS","matchedCharacterization":"Pd/CMS","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites.","reactionConditions":"Mixed solution of 1.0 mol·L−1 FA and 1.0 mol·L−1 SF in deionized water; n Pd/nFA = 0.2%; three-necked flask with gas burette.","metricCount":"1"},{"paperId":"P091","catalystId":"P091_PERF_008","name":"Pd/CMS-900","support":"CMS","matchedSynthesis":"Pd/CMS","matchedCharacterization":"Pd/CMS","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites.","reactionConditions":"Mixed solution of 1.0 mol·L−1 FA and 1.0 mol·L−1 SF in deionized water; n Pd/nFA = 0.2%; three-necked flask with gas burette.","metricCount":"1"},{"paperId":"P092","catalystId":"P092_PERF_001","name":"AuPd/TiO2 nanosheets-400","support":"TiO2 nanosheets","matchedSynthesis":"AuPd/TiO2 nanosheets","matchedCharacterization":"AuPd/TiO2 nanosheets-400","role":"catalyst for dehydrogenation of formic acid","composition":"Au:Pd = 1:1 molar ratio in precursor solution","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"TiO2 nanosheets were first synthesized and calcined; then Au and Pd precursors were impregnated onto the support followed by liquid-phase reduction with NaBH4.","phase":"AuPd alloy with face-centered cubic (fcc) structure; HRTEM lattice fringe distance of 0.231 nm is between fcc Pd (0.224 nm) and Au (0.235 nm).","particleSize":"2.8 nm","surfaceStates":"XPS shows binding energies of Au 4f and Pd 3d shifted to lower values compared to pure metals (reduced by approximately 1.8 eV and 1.1 eV, respectively), indicating electron transfer from the TiO2 support to the metal nanoparticles.","structureLink":"Superior activity is attributed to the alloy structure of AuPd centers, the low crystallinity anatase phase of the TiO2 nanosheets, and strong electron transfer interaction between the AuPd nanoparticles and the TiO2 substrate.","reactionConditions":"Dehydrogenation of formic acid (FA) in FA/SF aqueous solution at 25 °C under ambient atmosphere using a gas burette system.","selectivity":"CO2 as the only by-product","stability":"little deactivation of catalytic performance after two cycles","deactivation":"little deactivation observed over two cycles","whyPerformsWell":"alloy structure of AuPd centers, low crystallinity anatase phase and layered morphology of TiO2 nanosheets, and strong electron transfer from the support to Pd and Au nanoparticles.","metricCount":"4"},{"paperId":"P092","catalystId":"P092_PERF_002","name":"AuPd","support":"TiO2 nanosheets","matchedSynthesis":"AuPd/TiO2 nanosheets","matchedCharacterization":"AuPd/TiO2 nanosheets-400","role":"catalyst for dehydrogenation of formic acid","composition":"Au:Pd = 1:1 molar ratio in precursor solution","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"TiO2 nanosheets were first synthesized and calcined; then Au and Pd precursors were impregnated onto the support followed by liquid-phase reduction with NaBH4.","phase":"AuPd alloy with face-centered cubic (fcc) structure; HRTEM lattice fringe distance of 0.231 nm is between fcc Pd (0.224 nm) and Au (0.235 nm).","particleSize":"2.8 nm","surfaceStates":"XPS shows binding energies of Au 4f and Pd 3d shifted to lower values compared to pure metals (reduced by approximately 1.8 eV and 1.1 eV, respectively), indicating electron transfer from the TiO2 support to the metal nanoparticles.","structureLink":"Superior activity is attributed to the alloy structure of AuPd centers, the low crystallinity anatase phase of the TiO2 nanosheets, and strong electron transfer interaction between the AuPd nanoparticles and the TiO2 substrate.","reactionConditions":"FA/SF (2.5/2.5 M, 2 ml) at 25 °C under ambient atmosphere","deactivation":"aggregate severely without the support","metricCount":"1"},{"paperId":"P092","catalystId":"P092_PERF_003","name":"Pd/TiO2 nanosheets-400","matchedCharacterization":"AuPd/TiO2 nanosheets-400","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"AuPd alloy with face-centered cubic (fcc) structure; HRTEM lattice fringe distance of 0.231 nm is between fcc Pd (0.224 nm) and Au (0.235 nm).","particleSize":"2.8 nm","surfaceStates":"XPS shows binding energies of Au 4f and Pd 3d shifted to lower values compared to pure metals (reduced by approximately 1.8 eV and 1.1 eV, respectively), indicating electron transfer from the TiO2 support to the metal nanoparticles.","structureLink":"Superior activity is attributed to the alloy structure of AuPd centers, the low crystallinity anatase phase of the TiO2 nanosheets, and strong electron transfer interaction between the AuPd nanoparticles and the TiO2 substrate.","reactionConditions":"FA/SF (2.5/2.5 M, 2 ml) at 25 °C under ambient atmosphere","metricCount":"1"},{"paperId":"P092","catalystId":"P092_PERF_004","name":"Au/TiO2 nanosheets-400","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"FA/SF (2.5/2.5 M, 2 ml) at 25 °C under ambient atmosphere","metricCount":"1"},{"paperId":"P092","catalystId":"P092_PERF_005","name":"AuPd/TiO2 nanotubes-250","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA/SF (2.5/2.5 M, 2 ml) at 25 °C under ambient atmosphere","metricCount":"1"},{"paperId":"P092","catalystId":"P092_PERF_006","name":"AuPd/TiO2 nanoparticles-N","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA/SF (2.5/2.5 M, 2 ml) at 25 °C under ambient atmosphere","metricCount":"1"},{"paperId":"P093","catalystId":"P093_PERF_001","name":"Au2Pd8/SBA-15-Amine","matchedCharacterization":"Au2Pd8/SBA-15-Amine","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Au-Pd alloy structure","particleSize":"4.5 ± 0.5 nm","surfaceStates":"Metallic Au0 and Pd0; XPS shows binding energy shifts (Au shifted to lower values: 83.5, 87.1 eV; Pd shifted to higher values: 336.1, 341.5 eV) compared to monometallic counterparts, indicating alloying.","structureLink":"Alloy formation between Au and Pd exerts a positive synergistic effect on the dehydrogenation of formic acid.","reactionConditions":"303–333 K, ambient atmosphere, stirred glass tube, aqueous FA-SF mixture solution","selectivity":"100% H2 selectivity; no CO detected by GC and NaOH trap","stability":"excellent catalytic performance without a distinct decrease for dehydrogenation activity after five runs at 323 K","whyPerformsWell":"synergy between Au-Pd alloy and SBA-15-Amine; promotion effect of SF; formation of Au-Pd alloy structure (lattice spacing 0.230 nm)","metricCount":"3"},{"paperId":"P094","catalystId":"P094_PERF_001","name":"Pd@CN900K","support":"N-doped hierarchically porous carbon (CN900K)","matchedSynthesis":"Pd@CN900K","matchedCharacterization":"Pd@CN900K","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"Al-MIL-101-NH2 was carbonized at 900 °C in argon to form CN900, which was then etched with aq KOH via ultrasonication to produce the hierarchically porous support CN900K. Pd nanoparticles were subsequently immobilized on this support using a wet chemical reduction process with NaBH4.","phase":"Metallic Pd0 phase (JCPDS: 46-1043)","particleSize":"1.1 ± 0.2 nm","surfaceStates":"Pd exists as Pd0 and Pd2+; the carbon support contains pyridinic, pyrrolic, and graphitic nitrogen species, as well as C=O and C-OH groups.","structureLink":"Smaller particle size compared to other samples provides more accessible active sites. Rich mesoporosity facilitates effective mass transport. N-doping stabilizes Pd NPs against aggregation and exerts an electronic effect that facilitates the rate-determining step (C-H bond cleavage).","reactionConditions":"Dehydrogenation of aqueous solution of formic acid (FA) and sodium formate (SF)","selectivity":"100% H2 selectivity; no CO detected (detection limit 10 ppm)","stability":"No significant loss in activity over 5 cycles; reused for 15 times with TON of 2700","whyPerformsWell":"Ultra fine Pd NPs (1.1 ± 0.2 nm) provide more accessible active sites; rich mesoporosity favors effective mass transport; electronic effect between N atoms and Pd NPs facilitates C-H bond cleavage.","metricCount":"4"},{"paperId":"P094","catalystId":"P094_PERF_002","name":"Pd@CN600K","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA at 30 °C","metricCount":"1"},{"paperId":"P094","catalystId":"P094_PERF_003","name":"Pd@CN700K","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA at 30 °C","metricCount":"1"},{"paperId":"P094","catalystId":"P094_PERF_004","name":"Pd@CN800K","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA at 30 °C","metricCount":"1"},{"paperId":"P094","catalystId":"P094_PERF_005","name":"Pd@CN1000K","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA at 30 °C","metricCount":"1"},{"paperId":"P095","catalystId":"P095_PERF_001","name":"Pd−Cr(OH)3/NH2-rGO","support":"amino-modified reduced graphene oxide (NH2-rGO)","matchedSynthesis":"Pd-Cr(OH)3/NH2-rGO","matchedCharacterization":"Pd-Cr(OH)3/NH2-rGO","role":"active catalyst","composition":"Pd/Cr molar ratio = 0.1/0.06","activeMetals":"Pd-Cr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sequential_impregnation","synthesis":"GO was modified with APTMS to form NH2-rGO, followed by the addition of Pd and Cr precursors under stirring, and finally reduced using NaBH4.","phase":"Non-alloyed nanoclusters with strong electronic coupling between Pd and Cr(OH)3","particleSize":"1.6 nm","surfaceStates":"Electron-rich Pd0 (Pd0/(Pd0+Pd2+) = 0.76); partial electron transfer from Cr(OH)3 to Pd and from NH2-rGO to the nanoclusters.","structureLink":"Ultrafine size increases exposed active sites; electron-rich Pd NCs facilitate C-H bond dissociation (RDS); basic amino groups and Cr(OH)3 promote O-H bond dissociation of FA molecules.","reactionConditions":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","selectivity":"100% H2 selectivity; CO-free","stability":"Robust durability with no significant decline in activity and aggregation of metal NCs even after 10 cycles.","whyPerformsWell":"Well-distributed ultrafine Pd−Cr(OH)3 nanoclusters (1.6 nm), strong electronic coupling of Pd with Cr(OH)3 making Pd electron-rich, synergistic interaction of Pd−Cr(OH)3 with NH2-rGO, and the promotion effect of amino groups acting as Brønsted basic sites to accelerate O-H bond dissociation.","metricCount":"3"},{"paperId":"P095","catalystId":"P095_PERF_002","name":"Pd/NH2-rGO","support":"amino-modified reduced graphene oxide (NH2-rGO)","matchedSynthesis":"Pd/NH2-rGO","matchedCharacterization":"Pd/NH2-rGO","role":"comparative catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sequential_impregnation","synthesis":"Prepared using the same method as Pd-Cr(OH)3/NH2-rGO but without Cr precursor.","particleSize":"1.8 nm","surfaceStates":"Pd0/(Pd0+Pd2+) = 0.71","reactionConditions":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","stability":"Good durability, but an obvious loss of activity was observed after the 9th and 10th runs.","whyPerformsWell":"Amino groups on NH2-rGO serve as anchoring sites for ultrafine metal NCs and act as Brønsted basic sites.","metricCount":"2"},{"paperId":"P095","catalystId":"P095_PERF_003","name":"Pd−Cr(OH)3/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd-Cr(OH)3/rGO","matchedCharacterization":"Pd-Cr(OH)3/rGO","role":"comparative catalyst","composition":"Pd/Cr = 0.1/0.06","activeMetals":"Pd-Cr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"sequential_impregnation","synthesis":"Prepared using the same method as Pd-Cr(OH)3/NH2-rGO but without APTMS modification of GO.","particleSize":"2.3 nm","reactionConditions":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","whyPerformsWell":"Integration of Cr(OH)3 significantly enhances the catalytic performance of Pd compared to Pd/rGO.","metricCount":"1"},{"paperId":"P095","catalystId":"P095_PERF_004","name":"Pd/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd/rGO","matchedCharacterization":"Pd/rGO","role":"comparative catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sequential_impregnation","synthesis":"Prepared using the same method as Pd-Cr(OH)3/NH2-rGO but without APTMS and Cr precursor.","particleSize":"4.8 nm","reactionConditions":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","metricCount":"1"},{"paperId":"P095","catalystId":"P095_PERF_005","name":"Cr(OH)3/NH2-rGO","support":"amino-modified reduced graphene oxide (NH2-rGO)","matchedSynthesis":"Pd-Cr(OH)3/NH2-rGO","matchedCharacterization":"Pd-Cr(OH)3/NH2-rGO","role":"active catalyst","composition":"Pd/Cr molar ratio = 0.1/0.06","activeMetals":"Cr","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"sequential_impregnation","synthesis":"GO was modified with APTMS to form NH2-rGO, followed by the addition of Pd and Cr precursors under stirring, and finally reduced using NaBH4.","phase":"Non-alloyed nanoclusters with strong electronic coupling between Pd and Cr(OH)3","particleSize":"1.6 nm","surfaceStates":"Electron-rich Pd0 (Pd0/(Pd0+Pd2+) = 0.76); partial electron transfer from Cr(OH)3 to Pd and from NH2-rGO to the nanoclusters.","structureLink":"Ultrafine size increases exposed active sites; electron-rich Pd NCs facilitate C-H bond dissociation (RDS); basic amino groups and Cr(OH)3 promote O-H bond dissociation of FA molecules.","reactionConditions":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","metricCount":"1"},{"paperId":"P096","catalystId":"P096_PERF_001","name":"AgPd@MIL-125-NH2-PDA","support":"MIL-125-NH2 modified with polydopamine (PDA)","matchedSynthesis":"AgPd@MIL-125-NH2-PDA","matchedCharacterization":"AgPd@MIL-125-NH2-PDA","role":"active catalyst","composition":"Ag and Pd; atomic ratio 0.283:0.717","activeMetals":"Ag-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"MIL-125-NH2 was synthesized solvothermally and then coated with PDA. Ag and Pd precursors were adsorbed onto the MOF-PDA surface followed by NaBH4 induced reduction.","phase":"Bimetallic nanoalloy confirmed by d-spacing of 0.23 nm (between FCC Pd 0.22 nm and FCC Ag 0.24 nm), XPS binding energy shifts (Ag0 downshifted to 373.7 eV, Pd0 upshifted to 341.1 eV), and the complete disappearance of the Ag plasmon resonance peak in UV-Vis spectroscopy.","particleSize":"2.2 ± 0.3 nm","surfaceStates":"Pd is electronically promoted due to nanoalloying with Ag; strong metal-support interaction (SMSI) between the bimetallic nanoparticles and the PDA-coated MOF support.","structureLink":"The thin PDA layer provides abundant catechol and amino groups that act as nucleation sites, preventing nanoparticle agglomeration and leaching. DFT calculations indicate that alloying Ag with Pd lowers the energy barrier for hydrogen desorption (0.76 eV vs 0.94 eV for pure Pd), which is the rate-determining step in formic acid dehydrogenation.","reactionConditions":"Multifunctional catalysis including formic acid dehydrogenation, Suzuki-Miyaura coupling, and aldehyde hydrogenation.","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th cycle; no significant decrement in aldehyde hydrogenation activity after 6 consecutive cycles.","deactivation":"ICP-MS analysis of filtrate showed less than 0.001 ppb Ag and 0.0015 ppb Pd, confirming negligible leaching.","whyPerformsWell":"Ultrafine dispersion (2.2 nm), synergistic effects between Ag and Pd, strong metal-support interaction (SMSI) with PDA coating, strain effect from nanoalloying, and lower energy path for hydrogen desorption as shown by DFT calculations.","metricCount":"9"},{"paperId":"P096","catalystId":"P096_PERF_002","name":"Pd@MIL-125-NH2-PDA","support":"MIL-125-NH2 modified with polydopamine (PDA)","matchedSynthesis":"Pd@MIL-125-NH2-PDA","matchedCharacterization":"AgPd@MIL-125-NH2-PDA","role":"control sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar approach to AgPd@MIL-125-NH2-PDA using only palladium precursor.","phase":"Bimetallic nanoalloy confirmed by d-spacing of 0.23 nm (between FCC Pd 0.22 nm and FCC Ag 0.24 nm), XPS binding energy shifts (Ag0 downshifted to 373.7 eV, Pd0 upshifted to 341.1 eV), and the complete disappearance of the Ag plasmon resonance peak in UV-Vis spectroscopy.","particleSize":"2.2 ± 0.3 nm","surfaceStates":"Pd is electronically promoted due to nanoalloying with Ag; strong metal-support interaction (SMSI) between the bimetallic nanoparticles and the PDA-coated MOF support.","structureLink":"The thin PDA layer provides abundant catechol and amino groups that act as nucleation sites, preventing nanoparticle agglomeration and leaching. DFT calculations indicate that alloying Ag with Pd lowers the energy barrier for hydrogen desorption (0.76 eV vs 0.94 eV for pure Pd), which is the rate-determining step in formic acid dehydrogenation.","reactionConditions":"Formic acid dehydrogenation ([FA] = 0.3 M, [SF] = 1 M in 10.0 mL aqueous dispersion, catalyst amount 10 mg) at 35 °C.","metricCount":"1"},{"paperId":"P097","catalystId":"P097_PERF_001","name":"Zn51.9Pd48.1","matchedSynthesis":"Zn51.9Pd48.1","matchedCharacterization":"Bulk Zn51.9Pd48.1 / Zn49.8Pd50.2 (Zn-rich)","role":"bulk catalyst","composition":"Zn: 51.9 at.%, Pd: 48.1 at.%","activeMetals":"Zn-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"solid-vapor synthesis","synthesis":"Reactants placed in a quartz glass ampoule with a neck to avoid direct contact; heated at 60 °C/min to 500 °C, annealed for 1 day, then raised to 900 °C and held for 10 days, followed by water quenching.","phase":"Single-phase intermetallic compound ZnPd","surfaceStates":"Surface consists of a layer of oxidized Zn species (Zn 3d5/2 at 10.5 eV) and intermetallic Zn (Zn 3d5/2 at 9.65 or 9.49 eV); formate carbon detected at 289.2 eV during reaction.","structureLink":"Surface oxidation to ZnO and subsequent zinc formate formation hinders the overall reaction rate compared to Pd-rich samples.","reactionConditions":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","selectivity":"98.5-99.9% CO2 selectivity","stability":"Undergoes reversible oxidation/reduction during heating/cooling in formic acid; H2/CO2 ratio drops to ~0.8 above 240 °C","whyPerformsWell":"Oxidation of Zn and formation of zinc formate hinders the overall reaction rate compared to Pd-rich samples.","metricCount":"2"},{"paperId":"P097","catalystId":"P097_PERF_002","name":"Zn49.8Pd50.2","matchedSynthesis":"Zn49.8Pd50.2","matchedCharacterization":"Bulk Zn51.9Pd48.1 / Zn49.8Pd50.2 (Zn-rich)","role":"bulk catalyst","composition":"Zn: 49.8 at.%, Pd: 50.2 at.%","activeMetals":"Zn-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"solid-vapor synthesis","synthesis":"Reactants placed in a quartz glass ampoule with a neck to avoid direct contact; heated at 60 °C/min to 500 °C, annealed for 1 day, then raised to 900 °C and held for 10 days, followed by water quenching.","phase":"Single-phase intermetallic compound ZnPd","surfaceStates":"Surface consists of a layer of oxidized Zn species (Zn 3d5/2 at 10.5 eV) and intermetallic Zn (Zn 3d5/2 at 9.65 or 9.49 eV); formate carbon detected at 289.2 eV during reaction.","structureLink":"Surface oxidation to ZnO and subsequent zinc formate formation hinders the overall reaction rate compared to Pd-rich samples.","reactionConditions":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","selectivity":"Reversible decrease of CO2 selectivity down to 96% with increasing reaction temperature","stability":"Undergoes reversible oxidation/reduction during heating/cooling in formic acid; H2/CO2 ratio drops to ~0.9 above 240 °C","whyPerformsWell":"Oxidation of Zn and formation of zinc formate hinders the overall reaction rate compared to Pd-rich samples.","metricCount":"2"},{"paperId":"P097","catalystId":"P097_PERF_003","name":"Zn42.0Pd58.0","matchedSynthesis":"Zn42.0Pd58.0","matchedCharacterization":"Bulk Zn42.0Pd58.0 (Pd-rich)","role":"bulk catalyst","composition":"Zn: 42.0 at.%, Pd: 58.0 at.%","activeMetals":"Zn-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"solid-vapor synthesis","synthesis":"Reactants placed in a quartz glass ampoule with a neck to avoid direct contact; heated at 60 °C/min to 500 °C, annealed for 1 day, then raised to 900 °C and held for 10 days, followed by water quenching.","phase":"Single-phase intermetallic compound ZnPd","surfaceStates":"Predominantly intermetallic Zn (Zn 3d5/2 at 9.30 eV).","structureLink":"Higher stability against oxidation correlates with higher catalytic activity in formic acid decomposition.","reactionConditions":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","selectivity":"99.5-99.9% CO2 selectivity","stability":"More resistant against surface oxidation; H2/CO2 ratio remains approximately 1.0","whyPerformsWell":"Higher Pd content leads to higher stability against oxidation and prevents the formation of hindering zinc formate species.","metricCount":"2"},{"paperId":"P097","catalystId":"P097_PERF_004","name":"ZnPd/ZnO","support":"ZnO","matchedSynthesis":"ZnPd/ZnO","matchedCharacterization":"ZnPd/ZnO (Supported)","role":"supported catalyst","composition":"nominal Pd loading of 9.7 at.% (ICP-OES: 7.8(3) at.%)","activeMetals":"Zn-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Standard incipient wetness impregnation of Pd nitrate on ZnO, followed by calcination and reduction to induce reactive metal-support interaction (RMSI) for ZnPd formation.","phase":"Intermetallic compound ZnPd nanoparticles supported on ZnO","surfaceStates":"Dynamic formation and decomposition of zinc formate species during catalysis.","structureLink":"Significantly higher activity than bulk ZnPd; performance is linked to the modification of ZnO crystallinity through the zinc formate cycle.","reactionConditions":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: calcined at 500 °C in synthetic air for 3h and reduced in 5 vol.% H2 at 500 °C for 2h","selectivity":"99.2-99.8% CO2 selectivity","stability":"H2/CO2 ratio change similar to Zn-rich bulk samples; reproducible and reversible upon second heating","deactivation":"Modification of ZnO support observed via SEM (fine pores, less compact morphology) attributed to zinc formate formation/decomposition","whyPerformsWell":"Highest activity among tested materials due to the supported ZnPd nanoparticles on ZnO.","metricCount":"2"},{"paperId":"P098","catalystId":"P098_PERF_001","name":"Pd/C3N4","support":"carbon nitride (C3N4)","matchedSynthesis":"Pd/C3N4","matchedCharacterization":"Pd/C3N4","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"C3N4 support was prepared by melamine calcination. Pd was deposited via wetness impregnation, followed by thermal treatment in N2 and reduction in N2/H2.","phase":"Face-centered cubic Pd0 and H-loaded Pd species (PdHx)","particleSize":"2.8 nm (TEM), 17.2 nm (XRD crystallite size)","surfaceStates":"Hydrogen atoms diffused into the Pd lattice; nitrogen species on C3N4 support reduce electron density on the Pd surface","structureLink":"Nitrogen species stabilize Pd particles and provide adsorption sites, facilitating reactant adsorption.","reactionConditions":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C, stirring at 1036 rpm; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","selectivity":"Liquid-phase: complete selectivity towards dehydrogenation (no CO, CH4 detected). Gas-phase: negligible CO at low temperatures; CO production increased above 300 °C.","stability":"Stable performance for 30 h at 250 °C in gas phase, conversion > 90%.","deactivation":"No signs of catalytic deactivation; cumulative H2 volume increased linearly.","whyPerformsWell":"Nitrogen species on C3N4 surface stabilize Pd particles and provide adsorption sites while reducing electron density on the Pd surface, allowing easier adsorption of reactives.","metricCount":"5"},{"paperId":"P098","catalystId":"P098_PERF_002","name":"Ru/C3N4","support":"carbon nitride (C3N4)","matchedSynthesis":"Ru/C3N4","matchedCharacterization":"Ru/C3N4","role":"catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"C3N4 support was prepared by melamine calcination. Ru was deposited via wetness impregnation, followed by thermal treatment in N2 and reduction in N2/H2.","phase":"Hexagonal Ru crystal structure","particleSize":"4.2 nm (TEM), 15.3 nm (XRD crystallite size)","structureLink":"Inactive in liquid-phase FAD due to competitive absorption of water and surface hydroxylation.","reactionConditions":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","selectivity":"Liquid-phase: inactive. Gas-phase: CO produced at low temperatures (< 275 °C) via dehydration; above 275 °C, selectivity shifts to CH4 production via CO methanation.","stability":"Stable performance for 30 h at 250 °C in gas phase, conversion > 90%.","deactivation":"No signs of catalytic deactivation; cumulative H2 volume increased linearly.","metricCount":"1"},{"paperId":"P098","catalystId":"P098_PERF_003","name":"PdRu/C3N4","support":"carbon nitride (C3N4)","matchedSynthesis":"PdRu/C3N4","matchedCharacterization":"PdRu/C3N4","role":"catalyst","composition":"Pd:Ru = 1:1 molar ratio","activeMetals":"Pd-Ru","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"C3N4 support was prepared by melamine calcination. Pd and Ru were deposited via wetness impregnation, followed by thermal treatment in N2 and reduction in N2/H2.","phase":"Hexagonal Ru crystal structure; no alloy formation detected","particleSize":"3.6 nm (TEM), 9.8 nm (XRD crystallite size for Ru)","structureLink":"Presence of Ru facilitates carboxyl formation on Pd sites; presence of Pd diminishes Ru particle size.","reactionConditions":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","selectivity":"Liquid-phase: complete selectivity towards dehydrogenation. Gas-phase: CO formation similar to monometallic Pd at low temperatures and similar to Ru catalysts at high temperature (where CO is switched to methane). H2 selectivity around 100%.","stability":"Stable performance for 30 h at 250 °C in gas phase, conversion > 90%.","deactivation":"No signs of catalytic deactivation; cumulative H2 volume increased linearly.","whyPerformsWell":"Presence of Ru facilitates carboxyl formation on Pd sites, generating a similar TOF as monometallic Pd despite lower total hydrogen production. Bimetallic catalyst combines the action of both metals in gas phase (WGS at low T and methanation at high T).","metricCount":"4"},{"paperId":"P099","catalystId":"P099_PERF_001","name":"Pd 5","support":"activated carbon (AC) DARCO G-60","matchedSynthesis":"Pd 5","matchedCharacterization":"Pd 5","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Precursor dissolved in acetone, mixed with support, solvent evaporated via rotary evaporator, dried at 100 °C, and reduced under N2:H2 flow at 350 °C.","phase":"Metallic Pd","particleSize":"1.64 nm","structureLink":"Higher surface availability compared to Pd 10 leads to higher initial hydrogen production velocity.","reactionConditions":"FA 1 M, 60 °C, 100 mg catalyst, semi-batch reactor, N2 flow carrier","selectivity":"Only CO2 and H2 detected; no CO observed. H2/CO2 ratio close to 1.","stability":"Activity completely recovered after heating post-reacted samples at 150 °C in an oven for a few hours.","deactivation":"Surface progressively covered by reaction intermediates, leading to decrease in gas flow; bidentate formate adsorption is responsible for deactivation.","whyPerformsWell":"Addition of formates (especially ammonium formate) increases intermediate concentration and stabilizes monodentate adsorption, inhibiting bidentate deactivation.","metricCount":"6"},{"paperId":"P099","catalystId":"P099_PERF_002","name":"Pd 10","support":"activated carbon (AC) DARCO G-60","matchedSynthesis":"Pd 10","matchedCharacterization":"Pd 10","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Precursor dissolved in acetone, mixed with support, solvent evaporated via rotary evaporator, dried at 100 °C, and reduced under N2:H2 flow at 350 °C.","phase":"Metallic Pd","particleSize":"5.62 nm","structureLink":"Larger average particle size indicates lower Pd surface availability, resulting in lower initial hydrogen production velocity compared to Pd 5.","reactionConditions":"FA 1 M, 60 °C, 100 mg catalyst, semi-batch reactor, N2 flow carrier","selectivity":"Only CO2 and H2 detected; no CO observed.","whyPerformsWell":"Higher total Pd loading increases global production, but larger particle size reduces surface availability compared to Pd 5.","metricCount":"2"},{"paperId":"P099","catalystId":"P099_PERF_003","name":"PdCo 3:1","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA 1 M, 60 °C, 100 mg catalyst, semi-batch reactor, N2 flow carrier","selectivity":"Only CO2 and H2 detected; no CO observed.","metricCount":"2"},{"paperId":"P099","catalystId":"P099_PERF_004","name":"PdCo 2:1","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA 1 M, 60 °C, 100 mg catalyst, semi-batch reactor, N2 flow carrier","selectivity":"Only CO2 and H2 detected; no CO observed.","whyPerformsWell":"Metal-metal synergy; possible formation of ordered Pd2Co structure decreases the role of formate as an intermediate.","metricCount":"2"},{"paperId":"P099","catalystId":"P099_PERF_005","name":"PdCo 1:1","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA 1 M, 60 °C, 100 mg catalyst, semi-batch reactor, N2 flow carrier","selectivity":"Only CO2 and H2 detected; no CO observed.","metricCount":"2"},{"paperId":"P099","catalystId":"P099_PERF_006","name":"PdCo 1:3","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA 1 M, 60 °C, 100 mg catalyst, semi-batch reactor, N2 flow carrier","selectivity":"Only CO2 and H2 detected; no CO observed.","whyPerformsWell":"Metal-metal synergy; presence of Co/CoOx sites influences initial hydrogen production velocity.","metricCount":"2"},{"paperId":"P099","catalystId":"P099_PERF_007","name":"Co 5","support":"activated carbon (AC) DARCO G-60","matchedSynthesis":"Co 5","matchedCharacterization":"Co 5","role":"reference catalyst","composition":"Co","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Precursor dissolved in acetone, mixed with support, solvent evaporated via rotary evaporator, dried at 100 °C, and reduced under N2:H2 flow at 350 °C.","phase":"Metallic Co / Co3O4","particleSize":"28 nm","structureLink":"Inactive in FAD conditions.","reactionConditions":"FA 1 M, 60 °C, semi-batch reactor","whyPerformsWell":"Inactive in these particular FAD conditions.","metricCount":"0"},{"paperId":"P100","catalystId":"P100_PERF_001","name":"1 wt.% Pd/C","support":"C","matchedSynthesis":"1 wt.% Pd/C","matchedCharacterization":"1 wt.% Pd/C","role":"unpromoted catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"commercial","synthesis":"Supplied by Sigma-Aldrich","particleSize":"3.6 ± 1.7 nm","reactionConditions":"Fixed-bed flow reactor, 2 vol.% formic acid in He, total flow rate of 51 cm3 (STP) min−1, catalyst amount chosen to give 0.68 mg of Pd","selectivity":"hydrogen selectivity remained above 92%","metricCount":"2"},{"paperId":"P100","catalystId":"P100_PERF_002","name":"10:1 K–Pd/C","support":"C","matchedSynthesis":"10:1 K–Pd/C","matchedCharacterization":"10:1 K–Pd/C","role":"promoted catalyst","composition":"K:Pd = 10:1 (weight ratio)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Potassium carbonate was deposited on commercial 1.0 wt.% Pd/C via incipient wetness impregnation.","particleSize":"3.7 ± 1.3 nm","structureLink":"K-promotion increases TOF and hydrogen selectivity via formation of a buffer solution of potassium formate and formic acid in pores","reactionConditions":"Fixed-bed flow reactor, 2 vol.% formic acid in He, total flow rate of 51 cm3 (STP) min−1, catalyst amount chosen to give 0.68 mg of Pd","selectivity":"hydrogen selectivities well above 96%","whyPerformsWell":"The existence of mobile formate ions present in the buffer solution and stabilized by K ions in a K-doped catalyst is an essential factor in the promotion of its activity.","metricCount":"2"},{"paperId":"P100","catalystId":"P100_PERF_003","name":"1 wt.% Pd/SiO2","support":"SiO2","matchedSynthesis":"1 wt.% Pd/SiO2","matchedCharacterization":"1 wt.% Pd/SiO2","role":"unpromoted catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"commercial","synthesis":"Supplied by Johnson Matthey","particleSize":"7.4 ± 2.4 nm","surfaceStates":"Condensed HCOOH on SiO2; very small concentrations of formate species (1578 cm-1)","reactionConditions":"Fixed-bed flow reactor, 2 vol.% formic acid in He, total flow rate of 51 cm3 (STP) min−1, catalyst amount chosen to give 0.68 mg of Pd","selectivity":"hydrogen selectivity remained above 92%","metricCount":"2"},{"paperId":"P100","catalystId":"P100_PERF_004","name":"4:1 K–Pd/SiO2","support":"SiO2","matchedSynthesis":"4:1 K–Pd/SiO2","matchedCharacterization":"4:1 K–Pd/SiO2","role":"promoted catalyst","composition":"K:Pd = 4:1 (weight ratio)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Potassium carbonate was deposited on commercial 1.0 wt.% Pd/SiO2 via incipient wetness impregnation.","surfaceStates":"Formate anions in solution (1586 cm-1) and bulk potassium formate (crystalline or molten KHCOO, 1606 cm-1)","structureLink":"Presence of mobile formate ions stabilized by K ions in a buffer-like solution is an essential factor in promoting activity","reactionConditions":"Fixed-bed flow reactor, 2 vol.% formic acid in He, total flow rate of 51 cm3 (STP) min−1, catalyst amount chosen to give 0.68 mg of Pd","selectivity":"hydrogen selectivities well above 96%","whyPerformsWell":"The existence of mobile formate ions present in the buffer solution and stabilized by K ions in a K-doped catalyst is an essential factor in the promotion of its activity.","metricCount":"2"},{"paperId":"P100","catalystId":"P100_PERF_005","name":"1 wt.% Pd/Al2O3","support":"Al2O3","matchedSynthesis":"1 wt.% Pd/Al2O3","matchedCharacterization":"1 wt.% Pd/Al2O3","role":"unpromoted catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"commercial","synthesis":"Supplied by Johnson Matthey","particleSize":"4.2 ± 1.0 nm","reactionConditions":"Fixed-bed flow reactor, 2 vol.% formic acid in He, total flow rate of 51 cm3 (STP) min−1, catalyst amount chosen to give 0.68 mg of Pd","selectivity":"hydrogen selectivities fell in the range of only 79–83%","metricCount":"2"},{"paperId":"P100","catalystId":"P100_PERF_006","name":"2:1 K–Pd/Al2O3","support":"Al2O3","matchedSynthesis":"2:1 K–Pd/Al2O3","matchedCharacterization":"2:1 K–Pd/Al2O3","role":"promoted catalyst","composition":"K:Pd = 2:1 (weight ratio)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Potassium carbonate was deposited on commercial 1.0 wt.% Pd/Al2O3 via incipient wetness impregnation.","structureLink":"Promotion by K increases TOF and hydrogen selectivity","reactionConditions":"Fixed-bed flow reactor, 2 vol.% formic acid in He, total flow rate of 51 cm3 (STP) min−1, catalyst amount chosen to give 0.68 mg of Pd","selectivity":"hydrogen selectivities well above 96%","whyPerformsWell":"The existence of mobile formate ions present in the buffer solution and stabilized by K ions in a K-doped catalyst is an essential factor in the promotion of its activity.","metricCount":"2"},{"paperId":"P101","catalystId":"P101_PERF_001","name":"Pd–CeO2","support":"CeO2","matchedSynthesis":"Pd–CeO2","matchedCharacterization":"Pd–CeO2","role":"monometallic catalyst","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd precursor mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","phase":"Monometallic Pd nanoparticles","particleSize":"~7 nm","surfaceStates":"High surface coverage of atomic oxygen under ambient conditions.","structureLink":"Surface atomic oxygen promotes H2O formation and decreases H2 selectivity; apparent activation barrier is 25 ± 3 kJ mol−1.","reactionConditions":"Aqueous formic acid (FA) decomposition in a batch reactor under ambient pressure and air atmosphere.","selectivity":"Low H2 selectivity (10%) against water formation; negligible CO production.","whyPerformsWell":"Performs poorly due to high surface coverage of oxygen on Pd–CeO2 which promotes H2O formation and decreases H2 selectivity.","metricCount":"3"},{"paperId":"P101","catalystId":"P101_PERF_002","name":"0.5 PdAg–CeO2","support":"CeO2","matchedSynthesis":"0.5 PdAg–CeO2","matchedCharacterization":"0.5 PdAg–CeO2","role":"alloy catalyst","composition":"Pd:Ag = 0.5 (atomic ratio)","activeMetals":"Pd-Ag-Ce","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd and Ag precursors mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","phase":"Alloyed PdAg nanoparticles (confirmed by HR-TEM elemental detection)","particleSize":"~7 nm","surfaceStates":"Increased surface coverage of reduced Pd0 compared to monometallic Pd; decreased atomic oxygen coverage.","structureLink":"Alloying increases Pd0 coverage and reduces atomic oxygen, suppressing oxidative dehydrogenation and decreasing the apparent activation barrier to 8 ± 4 kJ mol−1, increasing H2 TOF and selectivity.","reactionConditions":"Aqueous formic acid (FA) decomposition in a batch reactor under ambient pressure and air atmosphere.","selectivity":"Higher H2 selectivity (22%) compared to Pd–CeO2; negligible CO production.","stability":"Recovered catalysts show comparable catalytic reactivity to fresh catalysts after washing once.","deactivation":"Surface intermediates, such as formate ions, possibly lead to deactivation during the FA reaction.","whyPerformsWell":"Ag alloying increases surface coverage of reduced Pd (Pd0) and reduces surface atomic oxygen coverage, suppressing oxidative dehydrogenation and decreasing the apparent activation barrier for H2 formation.","metricCount":"3"},{"paperId":"P101","catalystId":"P101_PERF_003","name":"Pd–TiO2","support":"TiO2","matchedSynthesis":"Pd–TiO2","matchedCharacterization":"Pd–TiO2","role":"monometallic catalyst","composition":"Pd","activeMetals":"Pd-Ti","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd precursor mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","phase":"Monometallic Pd nanoparticles","particleSize":"~7 nm","structureLink":"Low H2 TOF (5 h−1) and selectivity (3%) compared to alloyed version.","reactionConditions":"Aqueous formic acid (FA) decomposition in a batch reactor under ambient pressure and air atmosphere.","selectivity":"Low H2 selectivity (3%); negligible CO gas formed.","metricCount":"2"},{"paperId":"P101","catalystId":"P101_PERF_004","name":"0.5 PdAg–TiO2","support":"TiO2","matchedSynthesis":"0.5 PdAg–TiO2","matchedCharacterization":"0.5 PdAg–TiO2","role":"alloy catalyst","composition":"Pd:Ag = 0.5 (atomic ratio)","activeMetals":"Pd-Ag-Ti","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd and Ag precursors mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","phase":"Alloyed PdAg nanoparticles","particleSize":"~7 nm","structureLink":"Higher H2 TOF (115 h−1) and selectivity (26%) than Pd–TiO2; performance comparable to 0.5 PdAg–CeO2 due to similar support basicity (PZC).","reactionConditions":"Aqueous formic acid (FA) decomposition in a batch reactor under ambient pressure and air atmosphere.","selectivity":"Higher H2 selectivity (26%) than Pd–TiO2; negligible CO gas formed.","whyPerformsWell":"Alloying Pd with Ag induces electronic and ensemble effects that promote reactivity. Comparable performance to 0.5 PdAg–CeO2 due to similar support basicity (PZC).","metricCount":"2"},{"paperId":"P101","catalystId":"P101_PERF_005","name":"Pd–Al2O3","support":"Al2O3","matchedSynthesis":"Pd–Al2O3","matchedCharacterization":"Pd–Al2O3","role":"monometallic catalyst","composition":"Pd","activeMetals":"Pd-Al","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd precursor mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","phase":"Monometallic Pd nanoparticles","particleSize":"~12 nm","surfaceStates":"Adsorbed atomic oxygen present on surface.","structureLink":"H2 TOF of 113 h−1 and selectivity of 17%; apparent activation energy is 25 ± 3 kJ mol−1.","reactionConditions":"Aqueous formic acid (FA) decomposition in a batch reactor under ambient pressure and air atmosphere.","selectivity":"H2 selectivity of 17%; negligible presence of CO.","metricCount":"3"},{"paperId":"P101","catalystId":"P101_PERF_006","name":"0.5 PdAg–Al2O3","support":"Al2O3","matchedSynthesis":"0.5 PdAg–Al2O3","matchedCharacterization":"0.5 PdAg–Al2O3","role":"alloy catalyst","composition":"Pd:Ag = 0.5 (atomic ratio)","activeMetals":"Pd-Ag-Al","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd and Ag precursors mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","phase":"Alloyed PdAg nanoparticles","particleSize":"~12 nm","surfaceStates":"CO binds stronger in bridging mode compared to Pd–Al2O3; strongly adsorbed atomic oxygen.","structureLink":"Lower H2 TOF (5 h−1) and selectivity (8%) than Pd–Al2O3; higher apparent activation energy (42 ± 5 kJ mol−1) due to stronger adsorption of intermediates like HCOO* and H*.","reactionConditions":"Aqueous formic acid (FA) decomposition in a batch reactor under ambient pressure and air atmosphere.","selectivity":"Low H2 selectivity (8%); negligible presence of CO.","whyPerformsWell":"Performs worse than Pd–Al2O3 due to larger nanoparticle size (12 nm vs 7 nm) and electronic modifications that increase the binding energy of intermediates like HCOO* and H*, thereby increasing the apparent activation barrier.","metricCount":"3"},{"paperId":"P102","catalystId":"P102_PERF_001","name":"5Pd-M1U3-600","support":"graphitic carbon nitride (C3N4)","matchedSynthesis":"5Pd-M1U3-600","matchedCharacterization":"5Pd-M1U3-600","role":"active catalyst","composition":"Pd","activeMetals":"Pd-U","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine/urea mixture; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","phase":"fcc cubic metallic Pd","particleSize":"2.8 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm; presence of cyano defects enhances N-to-Pd transfer.","structureLink":"Highest BET surface area (94 m2/g) and smallest particle size result in almost complete FA conversion (98%) and highest 2,5-DMF yield in HDO by suppressing humins formation.","reactionConditions":"Formic acid dehydrogenation (FAD) in aqueous solution or hydrodeoxygenation (HDO) of 5-HMF in THF.","selectivity":"High selectivity to CO2 and H2 in FAD; highest 2,5-DMF yield in HDO","whyPerformsWell":"Highest BET surface area (94 m2/g) and smallest Pd particle size (2.8 nm), facilitating adsorption of reactants and enhancing N-to-Pd electron transfer via cyano defects.","metricCount":"3"},{"paperId":"P102","catalystId":"P102_PERF_002","name":"5Pd-M1U3-550","support":"graphitic carbon nitride (C3N4)","matchedSynthesis":"5Pd-M1U3-550","matchedCharacterization":"5Pd-M1U3-550","role":"active catalyst","composition":"Pd","activeMetals":"Pd-U","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine/urea mixture; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","phase":"fcc cubic metallic Pd","particleSize":"3.6 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm","structureLink":"High dispersion and small particle size contribute to high FA conversion (96%).","reactionConditions":"Formic acid dehydrogenation (FAD) in aqueous solution.","whyPerformsWell":"High surface area and small Pd particle size (3.6 nm).","metricCount":"3"},{"paperId":"P102","catalystId":"P102_PERF_003","name":"5Pd-M-600","support":"graphitic carbon nitride (C3N4)","matchedSynthesis":"5Pd-M-600","matchedCharacterization":"5Pd-M-600","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","phase":"fcc cubic metallic Pd","particleSize":"9.1 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm; higher aromaticity (lower C/H ratio) increases electron density on Pd.","structureLink":"Higher specific activity compared to 5Pd-M-550 attributed to increased support surface area and decreased C/H ratio.","reactionConditions":"Formic acid dehydrogenation (FAD) in aqueous solution or hydrodeoxygenation (HDO) of 5-HMF in THF.","whyPerformsWell":"Higher aromaticity (lower C/H ratio) and increased support surface area compared to 5Pd-M-550.","metricCount":"4"},{"paperId":"P102","catalystId":"P102_PERF_004","name":"5Pd-M-550","support":"graphitic carbon nitride (C3N4)","matchedSynthesis":"5Pd-M-550","matchedCharacterization":"5Pd-M-550","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","phase":"fcc cubic metallic Pd","particleSize":"6.7 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm","structureLink":"Lower BET surface area (12 m2/g) and larger particle size compared to M1U3 series correlate with lower FA conversion.","reactionConditions":"Formic acid dehydrogenation (FAD) in aqueous solution.","whyPerformsWell":"Lowest surface area (12 m2/g) among the series leads to lower performance.","metricCount":"3"},{"paperId":"P102","catalystId":"P102_PERF_005","name":"5Pd-M3U1-600","support":"graphitic carbon nitride (C3N4)","matchedSynthesis":"5Pd-M3U1-600","matchedCharacterization":"5Pd-M3U1-600","role":"active catalyst","composition":"Pd","activeMetals":"Pd-U","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine/urea mixture; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","phase":"fcc cubic metallic Pd","particleSize":"9.1 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm","structureLink":"Moderate performance; lower gas pressure in HDO compared to M1U3 series.","reactionConditions":"Formic acid dehydrogenation (FAD) in aqueous solution or hydrodeoxygenation (HDO) of 5-HMF in THF.","selectivity":"Small amount of CO formed through dehydration in FAD","metricCount":"2"},{"paperId":"P102","catalystId":"P102_PERF_006","name":"5Pd-M3U1-550","support":"graphitic carbon nitride (C3N4)","matchedSynthesis":"5Pd-M3U1-550","matchedCharacterization":"5Pd-M3U1-550","role":"active catalyst","composition":"Pd","activeMetals":"Pd-U","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine/urea mixture; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","phase":"fcc cubic metallic Pd","particleSize":"15.4 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm","structureLink":"Poor FA conversion despite high metal loading (11 wt%) due to largest particle size and lowest dispersion.","reactionConditions":"Formic acid dehydrogenation (FAD) in aqueous solution.","whyPerformsWell":"Poor conversion despite high metal content (11 wt% Pd) due to largest particle size (15.4 nm).","metricCount":"2"},{"paperId":"P102","catalystId":"P102_PERF_007","name":"5Pd-U-600","activeMetals":"Pd-U","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation (FAD) in aqueous solution or hydrodeoxygenation (HDO) of 5-HMF in THF.","whyPerformsWell":"Presence of urea in support improves HMF conversion and reduces humins fraction.","metricCount":"2"},{"paperId":"P102","catalystId":"P102_PERF_008","name":"5Pd-U-550","activeMetals":"Pd-U","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation (FAD) in aqueous solution.","metricCount":"1"},{"paperId":"P103","catalystId":"P103_PERF_001","name":"Pd/MWCNT","support":"MWCNT","matchedSynthesis":"Pd/MWCNT","matchedCharacterization":"Pd/MWCNTs","role":"reference catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Prepared using the same experimental procedure as Pd/MWCNT-C3N4 catalysts.","phase":"Metallic Pd","particleSize":"4 ± 4 nm","surfaceStates":"Metallic state and Pd2+","structureLink":"Poor activity compared to composite supports.","reactionConditions":"Dehydrogenation of formic acid in liquid phase at 75 ºC using an aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration) with 0.15 g catalyst, stirred at ~700 rpm in a 50 mL reactor.","metricCount":"3"},{"paperId":"P103","catalystId":"P103_PERF_002","name":"Pd/C3N4","support":"g-C3N4","matchedSynthesis":"Pd/C3N4","matchedCharacterization":"Pd/C3N4","role":"reference catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Prepared using the same experimental procedure as Pd/MWCNT-C3N4 catalysts.","phase":"Metallic Pd","particleSize":"6 ± 2 nm","surfaceStates":"Mainly Pd2+","structureLink":"Moderate activity; low surface area and layer stacking limit available N ligand sites.","reactionConditions":"Dehydrogenation of formic acid in liquid phase at 75 ºC using an aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration) with 0.15 g catalyst, stirred at ~700 rpm in a 50 mL reactor.","metricCount":"3"},{"paperId":"P103","catalystId":"P103_PERF_003","name":"Pd/MWCNT-C3N4(63)","support":"MWCNT","matchedSynthesis":"Pd/MWCNT","matchedCharacterization":"Pd/MWCNT-C3N4(63)","role":"reference catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Prepared using the same experimental procedure as Pd/MWCNT-C3N4 catalysts.","phase":"Metallic Pd","particleSize":"2.4 ± 0.8 nm","surfaceStates":"Metallic state, Pd2+, electron-deficient species (~338.7 eV), and electron-rich Pd species (Pdδ-) at 334.3 eV.","structureLink":"Highest activity attributed to the presence of both electron-deficient species (for formate adsorption) and electron-rich species (for C-H bond cleavage).","reactionConditions":"Dehydrogenation of formic acid in liquid phase at 75 ºC using an aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration) with 0.15 g catalyst, stirred at ~700 rpm in a 50 mL reactor.","whyPerformsWell":"Basicity of the materials, better dispersibility in reaction solution compared to Pd/MWCNT, control of NP size (smaller NPs), and modification of electronic properties: electron-deficient Pd species facilitate formate adsorption, while electron-rich Pd species participate in the rate-determining step (cleavage of C-H bond).","metricCount":"3"},{"paperId":"P103","catalystId":"P103_PERF_004","name":"Pd/MWCNT-C3N4(38)","support":"MWCNT","matchedSynthesis":"Pd/MWCNT","matchedCharacterization":"Pd/MWCNT-C3N4(38)","role":"reference catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Prepared using the same experimental procedure as Pd/MWCNT-C3N4 catalysts.","phase":"Metallic Pd","particleSize":"2.2 ± 0.4 nm","surfaceStates":"Metallic state, Pd2+, and electron-deficient species (~338.7 eV).","structureLink":"Improved Pd-N interaction due to efficient distribution of C3N4 layers on MWCNTs.","reactionConditions":"Dehydrogenation of formic acid in liquid phase at 75 ºC using an aqueous solution of formic acid and sodium formate (9:1 molar ratio, 1 M final concentration) with 0.15 g catalyst, stirred at ~700 rpm in a 50 mL reactor.","metricCount":"1"},{"paperId":"P104","catalystId":"P104_PERF_001","name":"Pd/N–C","support":"nitrogen-doped carbon (N–C)","matchedSynthesis":"Pd/N–C","matchedCharacterization":"Pd/N–C","role":"comparison catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Pd1Nix/N–C using only the Pd precursor.","phase":"Crystalline Pd nanoparticles","surfaceStates":"Baseline Pd 3d binding energies for comparison with alloys","structureLink":"Lower activity than PdNi alloys due to lack of synergistic electronic/geometric effects from Ni","reactionConditions":"Aqueous solution of 1.0 M HCO2H and 1.0 M sodium formate, stirring under ambient conditions in a two-neck glass tube with Ar gas supply.","metricCount":"2"},{"paperId":"P104","catalystId":"P104_PERF_002","name":"Pd1Ni0.37/N–C","matchedCharacterization":"Pd1Ni0.37/N–C","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdNi isomorphous alloy with face-centered cubic (fcc) structure","particleSize":"3.0 nm","surfaceStates":"Increased Pd 3d binding energies relative to Pd/N–C indicating electronic interactions between Pd and Ni","structureLink":"Ni alloying perturbs the Pd electronic structure, facilitating H2 release from aqueous FA solution","reactionConditions":"Aqueous solution of 1.0 M HCO2H and 1.0 M sodium formate, stirring under ambient conditions in a two-neck glass tube with Ar gas supply.","selectivity":"H2 and CO2, with no CO gas formed","whyPerformsWell":"Synergistic effect of Pd-Ni alloying; electronic interaction shifts d-band center closer to Fermi level.","metricCount":"1"},{"paperId":"P104","catalystId":"P104_PERF_003","name":"Pd1Ni1.3/N–C","matchedCharacterization":"Pd1Ni1.3/N–C","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdNi isomorphous alloy with face-centered cubic (fcc) structure","particleSize":"3.1 nm","surfaceStates":"Increased Pd 3d binding energies relative to Pd/N–C indicating electronic interactions between Pd and Ni","structureLink":"Highest activity attributed to optimum Ni content, synergistic interaction between Pd and Ni atoms creating new active sites, and compressive strain weakening H* adsorption facilitating desorption","reactionConditions":"Aqueous solution of 1.0 M HCO2H and 1.0 M sodium formate, stirring under ambient conditions in a two-neck glass tube with Ar gas supply.","selectivity":"H2 and CO2, with no CO gas formed","whyPerformsWell":"Synergistic effect of Pd-Ni alloying; Ni facilitates the HCOO pathway (rotation of HCOO intermediate) and activates C-H bonds while blocking the unfavorable COOH dehydration pathway; N-doped carbon support improves dispersion and donates charge density to active sites.","metricCount":"5"},{"paperId":"P104","catalystId":"P104_PERF_004","name":"Pd1Ni3.6/N–C","matchedCharacterization":"Pd1Ni3.6/N–C","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdNi isomorphous alloy with face-centered cubic (fcc) structure","particleSize":"2.5 nm","surfaceStates":"Increased Pd 3d binding energies relative to Pd/N–C indicating electronic interactions between Pd and Ni","structureLink":"Ni alloying perturbs the Pd electronic structure, facilitating H2 release from aqueous FA solution","reactionConditions":"Aqueous solution of 1.0 M HCO2H and 1.0 M sodium formate, stirring under ambient conditions in a two-neck glass tube with Ar gas supply.","selectivity":"H2 and CO2, with no CO gas formed","whyPerformsWell":"Synergistic effect of Pd-Ni alloying.","metricCount":"1"},{"paperId":"P104","catalystId":"P104_PERF_005","name":"Ni/N–C","support":"nitrogen-doped carbon (N–C)","matchedSynthesis":"Ni/N–C","matchedCharacterization":"Ni/N–C","role":"comparison catalyst","composition":"Ni only","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Same procedure as Pd1Nix/N–C using only the Ni precursor.","phase":"Ni nanoparticles","structureLink":"Negligible FA dehydrogenation activity compared to Pd-based catalysts","reactionConditions":"Aqueous solution of 1.0 M HCO2H and 1.0 M sodium formate, stirring under ambient conditions in a two-neck glass tube with Ar gas supply.","metricCount":"1"},{"paperId":"P104","catalystId":"P104_PERF_006","name":"Pd1Ni1.3/C","support":"commercial carbon (Ketjen)","matchedSynthesis":"Pd1Ni1.3/C","matchedCharacterization":"Pd1Ni1.3/C","role":"comparison catalyst","composition":"Pd:Ni = 1:1.3","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Pd1Nix/N–C but using commercial Ketjen carbon instead of N-doped carbon.","phase":"PdNi alloy","particleSize":"7.9 nm","structureLink":"Larger particle size and lower dispersion on commercial carbon support result in lower activity than N-doped carbon support","reactionConditions":"Aqueous solution of 1.0 M HCO2H and 1.0 M sodium formate, stirring under ambient conditions in a two-neck glass tube with Ar gas supply.","metricCount":"1"},{"paperId":"P104","catalystId":"P104_PERF_007","name":"Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Aqueous solution of 1.0 M HCO2H and 1.0 M sodium formate, stirring under ambient conditions in a two-neck glass tube with Ar gas supply.","metricCount":"1"},{"paperId":"P105","catalystId":"P105_PERF_001","name":"Pd0.5Au0.5/AC","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous FA/SF solution","selectivity":"high selectivity; inhibits the generation of CO","stability":"complete conversion maintained after 5 cycles at 313 K","whyPerformsWell":"strong metal-support interaction (SMSI) between PdAu and AC; electron transfer from Pd to Au; ultra-small alloy NPs with polydispersity; uniform mixing states of Pd and Au; large specific surface area of AC support","metricCount":"3"},{"paperId":"P105","catalystId":"P105_PERF_002","name":"Pd NPs/AC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous FA/SF solution","metricCount":"1"},{"paperId":"P106","catalystId":"P106_PERF_001","name":"10 wt% Pd/AC (commercial Noblyst® P1070)","support":"activated carbon","matchedSynthesis":"Pd/AC","matchedCharacterization":"10 wt% Pd/AC","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"commercial","synthesis":"Commercial catalyst (Noblyst ® P1070) supplied by Evonik in powder form.","phase":"Metallic Pd and PdO","particleSize":"Fresh: 1.6 ± 0.2 nm; Used (55 °C): 3.7 nm; Used (85 °C): 4.8 nm","surfaceStates":"Pd0 and Pd2+ species; Fresh Pd2+/Pd0 ratio is ~2.4, which decreases to 0.88 (at 55 °C) and 0.79 (at 85 °C) after the 3rd use.","structureLink":"Irreversible deactivation at T > 55 °C is primarily caused by CO2 chemisorption on Pd active sites; loss of Pd2+ species and Pd-PdO interfaces also contributes to quicker deactivation, while sintering of Pd nanoparticles does not significantly affect activity.","reactionConditions":"CFA,0 = 0.25 – 2 M, CCAT = 0.5 – 2 g L-1, T = 25 – 85 °C, P = 1 atm, stirring speed (ω) = 200 – 900 rpm","selectivity":"H2 and CO2 were the only reaction products detected; CO was never detected.","stability":"Maintains activity during four cycles at 55 °C (XFA slightly decreases by 15% in last cycle); progressive deactivation at 85 °C (XFA drops by 60% after three cycles).","deactivation":"No Pd leaching detected. Deactivation caused by fouling of active sites and chemisorption of CO2 on Pd nanoparticles at T > 55-65 °C; sintering of Pd particles (1.6 to 4.8 nm) occurs but does not significantly affect activity.","whyPerformsWell":"Presence of Pd-PdO interfaces increases activity and selectivity towards dehydrogenation; SF promoter favors FA deprotonation, the rate determining step.","metricCount":"5"},{"paperId":"P107","catalystId":"P107_PERF_001","name":"Pd/Cdarco","support":"Cdarco","matchedSynthesis":"Pd/Cdarco","matchedCharacterization":"Pd/Cdarco","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Wetness impregnation of Pd(II) acetate in acetone onto commercial activated carbon, followed by drying and reduction.","phase":"Cubic palladium metal phase","particleSize":"4.6 nm (XRD), 5 nm (TEM)","structureLink":"Intermediate external surface area and intermediate catalytic activity.","reactionConditions":"50°C, 1M HCOOH in distilled water, 0.1g catalyst, semi-batch reactor, N2 flow (100 mL/min), stirring (1036 rpm)","selectivity":"100% selectivity towards dehydrogenation; CO not detected","whyPerformsWell":"Intermediate external surface area","metricCount":"2"},{"paperId":"P107","catalystId":"P107_PERF_002","name":"Pd/Ccel","support":"Ccel","matchedSynthesis":"Pd/Ccel","matchedCharacterization":"Pd/Ccel","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support prepared via CO2 pyrolysis of cellulose, followed by wetness impregnation of Pd(II) acetate in acetone, drying, and reduction.","phase":"Cubic palladium metal phase","particleSize":"18.4 nm (XRD), 20 nm (TEM)","structureLink":"High microporosity leads to higher particle size and poor catalytic performance due to palladium being inaccessible within pores.","reactionConditions":"50°C, 1M HCOOH in distilled water, 0.1g catalyst, semi-batch reactor, N2 flow (100 mL/min), stirring (1036 rpm)","selectivity":"100% selectivity towards dehydrogenation; CO not detected","whyPerformsWell":"Poor catalytic performance due to poor textural properties (microporous)","metricCount":"2"},{"paperId":"P107","catalystId":"P107_PERF_003","name":"Pd/CcelZnCl2","support":"CcelZnCl2","matchedSynthesis":"Pd/CcelZnCl2","matchedCharacterization":"Pd/CcelZnCl2","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support prepared via ZnCl2 chemical activation and CO2 pyrolysis of cellulose, followed by wetness impregnation of Pd(II) acetate in acetone, drying, and reduction.","phase":"Cubic palladium metal phase","particleSize":"2.3 nm (XRD), 2.7 nm (TEM)","structureLink":"ZnCl2 treatment enhances meso-macroporosity and surface area, facilitating high metal dispersion and improving catalytic activity.","reactionConditions":"50°C, 1M HCOOH in distilled water, 0.1g catalyst, semi-batch reactor, N2 flow (100 mL/min), stirring (1036 rpm)","selectivity":"100% selectivity towards dehydrogenation; CO not detected","stability":"After 25h of reaction, overall conversion is 30% and TOF is 145 h-1. Activity maintained in first two cycles, slightly decreases in the last cycle.","deactivation":"Specific speed drops sharply after six hours of reaction; partial and continuous deactivation observed over repeated cycles","whyPerformsWell":"Meso-macroporous surface improves mass transfer and accessibility to active sites; isoelectric point close to neutral pH facilitates formate adsorption","metricCount":"2"},{"paperId":"P107","catalystId":"P107_PERF_004","name":"Pd/Cvin","support":"Cvin","matchedSynthesis":"Pd/Cvin","matchedCharacterization":"Pd/Cvin","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support prepared via HNO3 demineralization and CO2 pyrolysis of vine shoots, followed by wetness impregnation of Pd(II) acetate in acetone, drying, and reduction.","phase":"Cubic palladium metal phase","particleSize":"30.4 nm (XRD), 24 nm (TEM)","structureLink":"High microporosity leads to higher particle size and poor catalytic performance.","reactionConditions":"50°C, 1M HCOOH in distilled water, 0.1g catalyst, semi-batch reactor, N2 flow (100 mL/min), stirring (1036 rpm)","selectivity":"100% selectivity towards dehydrogenation; CO not detected","whyPerformsWell":"Poor catalytic performance due to poor textural properties (microporous)","metricCount":"2"},{"paperId":"P107","catalystId":"P107_PERF_005","name":"Pd/CvinZnCl2","support":"CvinZnCl2","matchedSynthesis":"Pd/CvinZnCl2","matchedCharacterization":"Pd/CvinZnCl2","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support prepared via HNO3 demineralization, ZnCl2 chemical activation and CO2 pyrolysis of vine shoots, followed by wetness impregnation of Pd(II) acetate in acetone, drying, and reduction.","phase":"Cubic palladium metal phase","particleSize":"2.3 nm (XRD), 2.4 nm (TEM)","structureLink":"ZnCl2 treatment increases pore volume and surface area, leading to the highest dispersion and high catalytic activity.","reactionConditions":"50°C, 1M HCOOH in distilled water, 0.1g catalyst, semi-batch reactor, N2 flow (100 mL/min), stirring (1036 rpm)","selectivity":"100% selectivity towards dehydrogenation; CO not detected","whyPerformsWell":"Meso-macroporous surface improves mass transfer and accessibility to active sites; isoelectric point close to neutral pH facilitates formate adsorption","metricCount":"2"},{"paperId":"P108","catalystId":"P108_PERF_001","name":"Pd/MWCNTs-AP","support":"MWCNTs","matchedSynthesis":"Pd/MWCNTs-AP","matchedCharacterization":"Pd/MWCNTs-AP","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"plasma synthesis","synthesis":"MWCNTs were amino-modified with APTES to obtain MWCNTs-A; H2PdCl4 solution was added to MWCNTs-A in a quartz reactor and treated with surface dielectric barrier discharge (DBD) plasma using an Ar/H2 working gas mixture, followed by drying.","phase":"Face-centered cubic (fcc) Pd; HRTEM shows lattice spacing of 0.220 nm corresponding to the Pd(111) crystal plane.","particleSize":"2.9 ± 0.8 nm (TEM); 2.9 nm (CO pulse chemisorption)","surfaceStates":"Metallic Pd0 with higher binding energy than Pd/MWCNTs-AH, suggesting electron transfer from Pd to MWCNTs; nitrogen mainly exists as pyridinic N (53.1%) and pyrrolic N (27.3%).","structureLink":"Ultrasmall particle size, high surface Pd concentration (high Pd/C ratio), abundant -OH groups, and highly active pyridinic N facilitate formic acid adsorption and the breakage of C-H and O-H bonds.","reactionConditions":"Liquid-solid reaction in a round-bottomed flask under atmospheric pressure, stirring at 500 r min-1, using deionized water as solvent.","selectivity":"No CO was detected","stability":"Activity not reduced during six reaction cycles","deactivation":"Slight agglomeration of Pd nanoparticles observed by XRD after 6 cycles; no loss of active components (Pd mass fraction remained within error range: 4.6 to 4.8 wt%)","whyPerformsWell":"Ultrasmall-sized Pd, high Pd/C and N/C atomic ratios, abundant -OH groups facilitating C-H and O-H bond breakage; pyridinic N coordinating with Pd for strong interaction with formic acid; amino groups acting as proton scavengers promoting O-H bond breaking.","metricCount":"5"},{"paperId":"P108","catalystId":"P108_PERF_002","name":"Sigma-Aldrich Pd/C","activeMetals":"Al-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Liquid-solid reaction in a round-bottomed flask under atmospheric pressure, stirring at 500 r min-1, using deionized water as solvent.","stability":"Activity decreased over six cycles; gas volume produced after 6th cycle was 48% of initial (116 mL)","metricCount":"5"},{"paperId":"P108","catalystId":"P108_PERF_003","name":"Pd/MWCNTs-P","support":"MWCNTs","matchedSynthesis":"Pd/MWCNTs-P","matchedCharacterization":"Pd/MWCNTs-P","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"plasma synthesis","synthesis":"Prepared via the same plasma-assisted method as Pd/MWCNTs-AP but without APTES amino-modification of the MWCNTs support.","phase":"Face-centered cubic (fcc) Pd; XRD peaks at 40.1, 46.7, 68.1, and 82.1 degrees corresponding to (111), (200), (220), and (311) planes.","particleSize":"8.6 ± 1.3 nm (TEM); 8.6 nm (CO pulse chemisorption)","surfaceStates":"Metallic Pd0, Pd2+, and Pd4+; negligible nitrogen content compared to amino-modified samples.","structureLink":"Large particle size and poor dispersion lead to lower catalytic activity compared to Pd/MWCNTs-AP.","reactionConditions":"Liquid-solid reaction in a round-bottomed flask under atmospheric pressure, stirring at 500 r min-1, using deionized water as solvent.","metricCount":"1"},{"paperId":"P108","catalystId":"P108_PERF_004","name":"Pd/MWCNTs-AH","support":"MWCNTs","matchedSynthesis":"Pd/MWCNTs-AH","matchedCharacterization":"Pd/MWCNTs-AH","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"MWCNTs were amino-modified with APTES; H2PdCl4 was supported on MWCNTs-A via equivalent volume impregnation, followed by hydrogen thermal reduction.","phase":"Face-centered cubic (fcc) Pd; HRTEM shows lattice spacing of 0.220 nm corresponding to the Pd(111) crystal plane.","particleSize":"3.0 ± 0.5 nm (TEM); 3.0 nm (CO pulse chemisorption)","surfaceStates":"Metallic Pd0, Pd2+, and Pd4+; lower N/C ratio (0.028) compared to Pd/MWCNTs-AP.","structureLink":"Despite small particle size, the high-temperature reduction process caused significant damage to support functional groups (-OH, -NH2), resulting in poor catalytic activity.","reactionConditions":"Liquid-solid reaction in a round-bottomed flask under atmospheric pressure, stirring at 500 r min-1, using deionized water as solvent.","metricCount":"1"},{"paperId":"P109","catalystId":"P109_PERF_001","name":"Pd/BC","support":"BC","matchedSynthesis":"Pd/BC","matchedCharacterization":"Pd/BC","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"The carbon support was dispersed in acetone, and an aqueous solution of 0.01 M Pd(OAc)2 was added; the mixture was stirred at room temperature, washed with distilled water, and dried.","phase":"Pd nanoparticles","particleSize":"3.6 ± 1.8 nm (spent)","surfaceStates":"Fresh: Pd2+; Spent: Pd0 and Pd2+","reactionConditions":"75 °C, aqueous solution of FA and sodium formate (SF) with a molar ratio of 9:1 and final concentration of 1 M, catalyst amount 0.15 g","stability":"Great stability even after six consecutive reaction runs at 75 °C","deactivation":"No significant leaching of Pd after six reaction runs; no significant sintering","metricCount":"4"},{"paperId":"P109","catalystId":"P109_PERF_002","name":"Pd/BC_TT","support":"BC_TT","matchedSynthesis":"Pd/BC_TT","matchedCharacterization":"Pd/BC_TT","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"The carbon support was dispersed in acetone, and an aqueous solution of 0.01 M Pd(OAc)2 was added; the mixture was stirred at room temperature, washed with distilled water, and dried.","phase":"Pd nanoparticles","particleSize":"3.7 ± 1.3 nm (spent)","surfaceStates":"Fresh: Pd2+; Spent: Pd0 and Pd2+","structureLink":"Small Pd clusters in the fresh catalyst are highly active in FA decomposition; thermal treatment reduced surface acidity, favoring interaction with FA molecules.","reactionConditions":"75 °C, aqueous solution of FA and sodium formate (SF) with a molar ratio of 9:1 and final concentration of 1 M, catalyst amount 0.15 g","stability":"Great stability even after six consecutive reaction runs at 75 °C","deactivation":"No significant leaching of Pd after six reaction runs; no significant sintering","whyPerformsWell":"Thermal treatment reduced surface acidic groups (increased pHPZC from 4.8 to 6.6), favoring interaction with FA molecules; formation of small, highly active Pd nanoclusters/species due to strong metal-support interaction.","metricCount":"4"},{"paperId":"P109","catalystId":"P109_PERF_003","name":"Pd/N-BC","support":"N-BC","matchedSynthesis":"Pd/N-BC","matchedCharacterization":"Pd/N-BC","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"The carbon support was dispersed in acetone, and an aqueous solution of 0.01 M Pd(OAc)2 was added; the mixture was stirred at room temperature, washed with distilled water, and dried.","phase":"Pd nanoparticles","particleSize":"3.5 ± 2.2 nm (spent)","surfaceStates":"Fresh: Pd2+; Spent: Pd0 and Pd2+. XPS shows a shift towards higher binding energies attributed to Pd-N interaction.","structureLink":"Nitrogen functionalization helps in attaining promising catalysts with outstanding stability during reaction cycles.","reactionConditions":"75 °C, aqueous solution of FA and sodium formate (SF) with a molar ratio of 9:1 and final concentration of 1 M, catalyst amount 0.15 g","stability":"Good activity and outstanding stability during the six cycles of reaction","deactivation":"No significant leaching of Pd after six reaction runs; no significant sintering","whyPerformsWell":"Incorporation of N functional groups increased pHPZC (basic character), favoring interaction with FA molecules and stabilizing Pd species.","metricCount":"3"},{"paperId":"P109","catalystId":"P109_PERF_004","name":"Pd/N-BC_TT","support":"N-BC_TT","matchedSynthesis":"Pd/N-BC_TT","matchedCharacterization":"Pd/N-BC_TT","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"The carbon support was dispersed in acetone, and an aqueous solution of 0.01 M Pd(OAc)2 was added; the mixture was stirred at room temperature, washed with distilled water, and dried.","phase":"Pd nanoparticles","particleSize":"2.6 ± 0.9 nm (spent)","surfaceStates":"Fresh: Pd2+; Spent: Pd0 and Pd2+. XPS shows a shift towards higher binding energies attributed to Pd-N interaction.","structureLink":"Lowest average particle size and narrowest distribution among samples, contributing to preserved activity over multiple cycles.","reactionConditions":"75 °C, aqueous solution of FA and sodium formate (SF) with a molar ratio of 9:1 and final concentration of 1 M, catalyst amount 0.15 g","stability":"Good activity and outstanding stability during the six cycles of reaction; most promising catalyst as its activity was preserved across cycles","deactivation":"No significant leaching of Pd after six reaction runs; no significant sintering","whyPerformsWell":"Combination of thermal treatment (reducing surface acidity) and nitrogen functionalization (introducing basic groups), resulting in the lowest average particle size and narrowest distribution among spent catalysts.","metricCount":"3"},{"paperId":"P110","catalystId":"P110_PERF_001","name":"Pd/CN-B1.5M","matchedCharacterization":"Pd/CN-B1.5M","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Face-centered cubic (fcc) palladium","particleSize":"1.8 nm","surfaceStates":"High Pd2+/Pd0 ratio (0.590); strong metal-support interaction via Pd-N coordination with high pyrrolic N content (0.406).","structureLink":"Synergistic effect of Pd and pyrrolic N interactions induces electron transfer from Pd to N, creating electron-deficient Pd sites that strengthen interactions with formic acid and accelerate activation; small particle size and high dispersion further enhance activity.","reactionConditions":"Formic acid dehydrogenation in FA/SF mixture (n(FA):n(SF)= 1:8, total FA= 2 mmol) using 50 mg catalyst in 10 mL deionized water at various temperatures.","selectivity":"trace CO formation was undetectable by GC-TCD analysis","stability":"maintained complete formic acid conversion (approximate 100%) through three consecutive reaction cycles","deactivation":"increase in Pd nanoparticle size observed after three cycles; reduction in both Pd2+ species and pyrrolic nitrogen content","whyPerformsWell":"synergistic effect of Pd and pyrrolic N interactions, coupled with the small particle size (1.8 nm) and high dispersion of Pd nanoparticles; electron-deficient Pd sites strengthen interactions with formic acid","metricCount":"3"},{"paperId":"P110","catalystId":"P110_PERF_002","name":"Pd/CN-M","support":"Nanotubular carbon nitride (CN)","matchedSynthesis":"Pd/CN-BxM (x = 1, 1.5, 2), Pd/CN-M, Pd/CN-B","matchedCharacterization":"Pd/CN-M","role":"Catalyst for hydrogen production from formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Nanotubular CN was synthesized by dispersing melamine and barbituric acid in DI water, hydrothermal treatment, drying at 353 K, and annealing at 823 K. Pd nanoparticles were then loaded by dispersing the support in DI water, adding palladium acetate, stirring for 1 h, and reducing with NaBH4 solution.","phase":"fcc palladium","particleSize":"Larger than Pd/CN-B1.5M (indicated by sharper XRD peaks)","surfaceStates":"Lower Pd2+/Pd0 ratio (0.298) compared to B1.5M.","reactionConditions":"Formic acid dehydrogenation in FA/SF mixture (n(FA):n(SF)= 1:8, total FA= 2 mmol) using 50 mg catalyst in 10 mL deionized water at 348 K.","metricCount":"1"},{"paperId":"P110","catalystId":"P110_PERF_003","name":"Pd/CN-B1M","matchedCharacterization":"Pd/CN-B1M","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"fcc palladium","surfaceStates":"Pd2+/Pd0 ratio of 0.475.","reactionConditions":"Formic acid dehydrogenation in FA/SF mixture (n(FA):n(SF)= 1:8, total FA= 2 mmol) using 50 mg catalyst in 10 mL deionized water at 348 K.","metricCount":"1"},{"paperId":"P110","catalystId":"P110_PERF_004","name":"Pd/CN-B2M","matchedCharacterization":"Pd/CN-B2M","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"fcc palladium","particleSize":"Increased particle size due to aggregation (indicated by sharpening/intensification of Pd(111) XRD peak)","surfaceStates":"Pd2+/Pd0 ratio of 0.433.","structureLink":"Excessive barbituric acid promotes Pd particle growth and disrupts uniform active-site distribution, diminishing catalytic activity.","reactionConditions":"Formic acid dehydrogenation in FA/SF mixture (n(FA):n(SF)= 1:8, total FA= 2 mmol) using 50 mg catalyst in 10 mL deionized water at 348 K.","metricCount":"1"},{"paperId":"P110","catalystId":"P110_PERF_005","name":"Pd/CN-B","support":"Nanotubular carbon nitride (CN)","matchedSynthesis":"Pd/CN-BxM (x = 1, 1.5, 2), Pd/CN-M, Pd/CN-B","matchedCharacterization":"Pd/CN-B","role":"Catalyst for hydrogen production from formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Nanotubular CN was synthesized by dispersing melamine and barbituric acid in DI water, hydrothermal treatment, drying at 353 K, and annealing at 823 K. Pd nanoparticles were then loaded by dispersing the support in DI water, adding palladium acetate, stirring for 1 h, and reducing with NaBH4 solution.","phase":"fcc palladium","surfaceStates":"Pd2+/Pd0 ratio of 0.300.","structureLink":"Poor maintenance of carbon nitride structure when pure barbiturate is used as precursor leads to lower activity.","reactionConditions":"Formic acid dehydrogenation in FA/SF mixture (n(FA):n(SF)= 1:8, total FA= 2 mmol) using 50 mg catalyst in 10 mL deionized water at 348 K.","metricCount":"1"},{"paperId":"P111","catalystId":"P111_PERF_001","name":"Pd-Ag nanoplate (nPd:nAg = 8.33 x 10^-4) supported on Vulcan XC-72 carbon black","support":"Vulcan XC-72 carbon black","matchedSynthesis":"Pd-Ag nanoplate catalyst","role":"active catalyst","composition":"nPd:nAg from 4.17 x 10^-4 to 1.0","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Ag nanoplates were synthesized by adding AgNO3 and trisodium citrate to water, followed by rapid injection of NaBH4 and dropwise addition of H2O2 at room temperature. Pd was then deposited onto the Ag nanoplates by injecting PdCl2 and ascorbic acid into the nanoplate solution and heating at 40 °C for 2 h. The resulting nanoparticles were supported on Vulcan XC-72 carbon black.","reactionConditions":"90 °C, 5 M formic acid, 2.5 M sodium formate, 30 mg catalyst in 5 mL solution","whyPerformsWell":"Attributed to the average activity of three facets: Pd-Ag{111}, Pd-Ag{100}, and Pd-Ag{hcp} at the edges.","metricCount":"2"},{"paperId":"P111","catalystId":"P111_PERF_002","name":"Pd-Ag nanoplate (nPd:nAg = 0.33) supported on Vulcan XC-72 carbon black","support":"Vulcan XC-72 carbon black","matchedSynthesis":"Pd-Ag nanoplate catalyst","role":"active catalyst","composition":"nPd:nAg from 4.17 x 10^-4 to 1.0","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Ag nanoplates were synthesized by adding AgNO3 and trisodium citrate to water, followed by rapid injection of NaBH4 and dropwise addition of H2O2 at room temperature. Pd was then deposited onto the Ag nanoplates by injecting PdCl2 and ascorbic acid into the nanoplate solution and heating at 40 °C for 2 h. The resulting nanoparticles were supported on Vulcan XC-72 carbon black.","reactionConditions":"90 °C, 5 M formic acid, 2.5 M sodium formate, 30 mg catalyst in 5 mL solution","whyPerformsWell":"Attributed to the activity of the Pd-Ag{111} facet in the mid part of the nanoplate.","metricCount":"2"},{"paperId":"P111","catalystId":"P111_PERF_003","name":"Pd-Ag nanowire (nPd:nAg = 8.33 x 10^-3)","support":"Vulcan XC-72 carbon black","matchedSynthesis":"Pd-Ag nanowire catalyst","role":"comparison catalyst","composition":"nPd:nAg varied (e.g., 8.33 x 10^-3)","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"polyol_reduction","synthesis":"Ag nanowires were synthesized by adding NaCl and PVP to ethylene glycol, followed by dropwise addition of AgNO3 and heating at 160 °C for 6 h in an autoclave. Pd was deposited onto the Ag nanowires using ascorbic acid and PdCl2 at 40 °C for 2 h, then supported on Vulcan XC-72 carbon black.","reactionConditions":"90 °C, 5 M formic acid, 2.5 M sodium formate","whyPerformsWell":"Activity is dominated by the Pd-Ag{100} facet on the side wall.","metricCount":"1"},{"paperId":"P111","catalystId":"P111_PERF_004","name":"Pd-Ag{hcp} nanofacet","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"90 °C or 60 °C, 5 M formic acid, 2.5 M sodium formate","selectivity":"k1/k2 = 2070","stability":"Activity can reach a plate after 15 min","whyPerformsWell":"Extremely active in activating the C-H bond (high k1) and comparable binding affinity of CO ad compared to Pd-Ag{100}.","metricCount":"4"},{"paperId":"P111","catalystId":"P111_PERF_005","name":"quasi-spherical Pd-Ag alloy nanocatalyst","matchedCharacterization":"quasi-spherical Pd-Ag alloy nanocatalyst","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Pd-Ag alloy","structureLink":"Significantly lower activity (TOF = 22 h^-1 at 92 °C) compared to nanofacet catalysts.","reactionConditions":"92 °C, 5 M formic acid, 2.5 M sodium formate","metricCount":"2"},{"paperId":"P112","catalystId":"P112_PERF_001","name":"Pd/C650","support":"Vulcan XC-72 carbon black","matchedSynthesis":"Pd/C650","matchedCharacterization":"Pd/C650","role":"control catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Similar to Pd0.9Co0.1/C650 but without the addition of cobalt acetate.","phase":"Pure Pd phase (JCPDS: 65-2867)","particleSize":"13.50 nm","surfaceStates":"Pd0 and Pd2+; Pd2+/Pd0 ratio of 1.2","structureLink":"Larger particle size and lower Pd2+ content result in lower catalytic activity (TOF = 7257 h-1) compared to the Co-doped catalyst.","reactionConditions":"FA dehydrogenation in FA–SF solution at 333 K","selectivity":"almost no CO was generated (< 100 ppm)","stability":"cyclic catalytic activity of 41.7% after ten cycles","metricCount":"1"},{"paperId":"P112","catalystId":"P112_PERF_002","name":"Pd0.9Co0.1/C650","support":"Vulcan XC-72 carbon black","matchedSynthesis":"Pd0.9Co0.1/C650","matchedCharacterization":"Pd0.9Co0.1/C650","role":"active catalyst","composition":"Pd:Co = 9:1","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Pretreated Vulcan XC-72 was mixed with water and APTS, followed by the addition of Pd and Co precursors. The mixture was reduced using NaOH and NaBH4, then centrifuged and vacuum dried.","phase":"Pd-Co alloy (lattice spacing 0.222 nm)","particleSize":"3.41 nm","surfaceStates":"Pd0, Pd2+, and Co0; Pd2+/Pd0 ratio of 5.43; Pd2+ binding energy shifted to 337.5 eV due to Co presence","structureLink":"Formation of Pd-Co alloy reduces particle size and increases the amount of Pd2+, which promotes O-H fracture and enhances formic acid decomposition (TOF = 8117 h-1).","reactionConditions":"FA dehydrogenation in FA–SF solution at 333 K","stability":"cyclic catalytic activity of 55.3% after ten cycles","deactivation":"particle size increased after 10 cycles; Pd2+ to Pd0 ratio decreased significantly","whyPerformsWell":"Formation of Pd-Co alloy reduced particle size (from 13.50 nm to 3.41 nm) and increased the amount of Pd2+, which promotes O-H fracture and FA decomposition.","metricCount":"2"},{"paperId":"P113","catalystId":"P113_PERF_001","name":"PdCe0.2/SP-S-1","support":"self-pillared silicalite-1 (SP-S-1) zeolite nanosheets","matchedSynthesis":"PdCe0.2/SP-S-1","matchedCharacterization":"PdCe0.2/SP-S-1","role":"optimized catalyst","composition":"Pd and Ce (molar ratio Ce/Pd = 0.2)","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"SP-S-1 zeolite nanosheets were synthesized hydrothermally and calcinated. Pd and Ce precursors were dissolved in deionized water, co-impregnated into the support, and then reduced under H2.","phase":"Bimetallic nanoparticles with a heterojunction interface; no metal peaks in PXRD indicate high dispersion.","particleSize":"Average size of 2.0 nm; maintains 2.4–2.7 nm after thermal treatment at 700 °C in H2.","surfaceStates":"Electron-enriched state compared to Pd/SP-S-1 due to electron transfer from Ce to Pd atoms.","structureLink":"The interfacial effect between Pd and cerium oxide clusters reduces activation barriers for both FA dehydrogenation and CO2 hydrogenation, enhancing catalytic performance.","reactionConditions":"Formic acid (FA) dehydrogenation and CO2 hydrogenation to formate","selectivity":"perfect H2 selectivity in FA dehydrogenation; no CO detected","stability":"FA dehydrogenation: initial rate maintained over 70% after five consecutive runs; CO2 hydrogenation: performance and metal size basically unchanged over five cycles","deactivation":"decrease of catalytic performance in FA dehydrogenation may be related to the oxidation of some Pd species in air during drying","whyPerformsWell":"Interfacial effect between Pd and cerium oxide clusters reduces activation barriers; electron transfer from Ce to Pd creates an electron-enriched state; high dispersion on SP-S-1 zeolite nanosheets due to abundant isolated silanol groups enhancing mass transfer and hydrophilicity.","metricCount":"7"},{"paperId":"P113","catalystId":"P113_PERF_002","name":"Pd/SP-S-1","support":"self-pillared silicalite-1 (SP-S-1) zeolite nanosheets","matchedSynthesis":"Pd@SP-S-1","matchedCharacterization":"Pd/SP-S-1","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"direct hydrothermal synthesis","synthesis":"Prepared under direct hydrothermal conditions using [Pd(NH2CH2CH2NH2)2]Cl2 as metal precursor and TBAOH as template.","phase":"Metallic Pd nanoparticles; no metal peaks in PXRD indicate high dispersion.","particleSize":"Average size of 2.0 nm; maintains 2.4–2.7 nm after thermal treatment at 700 °C in H2.","surfaceStates":"Positively charged Pdδ+ species.","structureLink":"Small particle size and high dispersion on the hydrophilic SP-S-1 surface provide more exposed active sites compared to Con-S-1 support.","reactionConditions":"FA dehydrogenation; CO2 hydrogenation","whyPerformsWell":"Smaller Pd species on SP-S-1 zeolites offer more exposed active sites and a hydrophilic surface facilitating FA accumulation.","metricCount":"1"},{"paperId":"P113","catalystId":"P113_PERF_003","name":"Pd/Con-S-1","support":"conventional silicalite-1 (Con-S-1)","matchedSynthesis":"Pd/Con-S-1","matchedCharacterization":"Pd/Con-S-1","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Pd precursor dissolved in deionized water, impregnated into Con-S-1 zeolites, followed by H2 reduction.","phase":"Large-sized metal species; PXRD shows a weak diffraction peak assigned to Pd foil.","particleSize":"Mean size of 12.5 nm; increases significantly to 26.0 nm after thermal treatment at 700 °C in H2.","structureLink":"Larger particle size and lower dispersion lead to inferior catalytic activity compared to SP-S-1 supported catalysts.","reactionConditions":"FA dehydrogenation; CO2 hydrogenation","deactivation":"activity for nitrobenzene hydrogenation decreased by approximately 38% after treatment at 700 °C","metricCount":"1"},{"paperId":"P113","catalystId":"P113_PERF_004","name":"Pd@SP-S-1","support":"self-pillared silicalite-1 (SP-S-1) zeolite nanosheets","matchedSynthesis":"Pd@SP-S-1","matchedCharacterization":"Pd/SP-S-1","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"direct hydrothermal synthesis","synthesis":"Prepared under direct hydrothermal conditions using [Pd(NH2CH2CH2NH2)2]Cl2 as metal precursor and TBAOH as template.","phase":"Metallic Pd nanoparticles; no metal peaks in PXRD indicate high dispersion.","particleSize":"Average size of 2.0 nm; maintains 2.4–2.7 nm after thermal treatment at 700 °C in H2.","surfaceStates":"Positively charged Pdδ+ species.","structureLink":"Small particle size and high dispersion on the hydrophilic SP-S-1 surface provide more exposed active sites compared to Con-S-1 support.","reactionConditions":"FA dehydrogenation","whyPerformsWell":"Poor performance due to large-sized Pd species and phase separation from the zeolite support.","metricCount":"1"},{"paperId":"P114","catalystId":"P114_PERF_001","name":"PdP/NC","support":"N-doped carbon (NC)","matchedSynthesis":"PdP/NC","matchedCharacterization":"PdP/NC","role":"active nanocatalyst","composition":"Pd/P = 86:14 (molar ratio)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"other","synthesis":"NC support was first prepared via soft-nitriding. H2PdCl4 solution was mixed with dispersed NC and dried under vacuum filtration. NaH2PO2 solution was then injected to grow PdP alloy nanoclusters in situ.","phase":"fcc PdP alloy; XRD shows a shift toward higher angle in the (111) plane compared to Pd/NC, indicating decreased interplanar spacing due to amorphous P alloying.","particleSize":"1.59 ± 0.24 nm","surfaceStates":"Pd 3d5/2 binding energy at 336.3 eV; P exists as elemental P0 (131.4 eV) and oxidized P5+ (134.0 eV); NC support contains quaternary N (14.82%), amine/amide groups (71.44%), and pyridine N (13.74%).","structureLink":"Synergistic effect of alloyed P and doped N modifies Pd electronic states to optimize FA adsorption energy, weaken CO poisoning, and strengthen HCOO* intermediate adsorption; optimal particle size (1.59 nm) and P content follow the Sabatier principle for maximum TOF.","reactionConditions":"Dehydrogenation of formic acid (FA) with sodium formate (SF) additive at various temperatures.","selectivity":"100% selectivity toward CO2 and H2 (no CO produced)","stability":"Kept 56% of the initial activity after four cycles; TOF decreased from 3253 to 1822 h-1","deactivation":"Phosphorus content decreased from 14 to 1 at. % over four cycles; particle diameter increased during recycling.","whyPerformsWell":"Synergistic effect of alloyed P in Pd crystals and doped N in carbon support tailored the electronic states of the Pd surface, optimizing adsorption energy of FA/intermediates (Sabatier principle) and lowering activation energy to 27.2 kJ mol-1.","metricCount":"5"},{"paperId":"P114","catalystId":"P114_PERF_002","name":"Pd/NC","matchedCharacterization":"Pd/NC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"fcc Pd","surfaceStates":"Pd 3d5/2 binding energy at 336.5 eV.","structureLink":"Lower activity than PdP/NC due to lack of P-alloying electronic modification.","reactionConditions":"Dehydrogenation of FA with sodium formate (SF) additive at 30 °C.","stability":"Activity dramatically decreased during durability tests","deactivation":"Gradually increased particle diameters","metricCount":"1"},{"paperId":"P114","catalystId":"P114_PERF_003","name":"PdP/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA with sodium formate (SF) additive at 30 °C.","metricCount":"1"},{"paperId":"P114","catalystId":"P114_PERF_004","name":"commercial Pd/C","matchedCharacterization":"commercial Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","surfaceStates":"Pd 3d5/2 binding energy at 335.6 eV.","structureLink":"Lowest activity and highest reduction temperature; susceptible to CO poisoning.","reactionConditions":"Dehydrogenation of FA with sodium formate (SF) additive at 30 °C.","stability":"Activity dramatically decreased during durability tests","deactivation":"Gradually increased particle diameters; low-coverage COads accumulation on Pd surface especially at higher temperatures","metricCount":"1"},{"paperId":"P115","catalystId":"P115_PERF_001","name":"Pd/NH2-P-GC","support":"NH2-functionalized phosphorous-doped glucose-based porous carbon (NH2-P-GC)","matchedSynthesis":"Pd/NH2-P-GC","matchedCharacterization":"Pd/NH2-P-GC","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"P-GC support synthesized by heating glucose, MgO template, and sodium hypophosphite at 120 °C followed by annealing at 800 °C under N2; MgO removed via HCl washing. Support then grafted with APTES. Pd precursor was impregnated onto the modified support and reduced using NaBH4.","phase":"Metallic Pd nanoparticles; HRTEM/IFFT shows lattice fringes of 0.229 nm corresponding to Pd {111} planes.","particleSize":"1.47 nm (increased to 1.86 nm after use)","surfaceStates":"Electron-deficient Pd species, indicated by a positive shift in XPS binding energies (336.6 and 338.9 eV) compared to Pd/NH2-GC.","structureLink":"High activity is attributed to the small particle size, high dispersion, SMSI from amine groups, and P doping which acts as an electronic promoter creating electron-deficient active centers; amine groups also act as Brønsted basic sites for proton scavenging.","reactionConditions":"Additive-free dehydrogenation of aqueous FA solution, magnetic stirring (600 rpm), two-necked round-bottom flask connected to a gas burette","selectivity":"100% H2 selectivity, CO generation undetectable","stability":"excellent stability; H2 generation rate and production remained almost unchanged after five cycles","deactivation":"minor activity attenuation due to small loss of surface amine functional groups and slight increase in Pd particle size from 1.47 nm to 1.86 nm","whyPerformsWell":"Synergy between NH2-P-GC support and Pd NPs; amino groups act as proton scavengers for FA deprotonation and stabilize Pd2+ species via SMSI; P doping acts as a pore expander and electronic promoter to maintain electron-deficient Pd active centers","metricCount":"5"},{"paperId":"P115","catalystId":"P115_PERF_002","name":"Pd/NH2-GC","support":"NH2-functionalized glucose-based porous carbon (NH2-GC)","matchedSynthesis":"Pd/NH2-GC","matchedCharacterization":"Pd/NH2-GC","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Similar to Pd/NH2-P-GC but without sodium hypophosphite during support synthesis.","phase":"Metallic Pd nanoparticles.","particleSize":"2.54 nm","surfaceStates":"Less electron-deficient than Pd/NH2-P-GC (XPS binding energies at 336.2 and 338.0 eV).","structureLink":"Inferior catalytic activity compared to Pd/NH2-P-GC due to larger particle size and absence of P doping.","reactionConditions":"Additive-free dehydrogenation of aqueous FA solution, magnetic stirring (600 rpm), two-necked round-bottom flask connected to a gas burette","whyPerformsWell":"amino groups act as proton scavengers and facilitate electron transport to Pd NPs","metricCount":"2"},{"paperId":"P115","catalystId":"P115_PERF_003","name":"Pd/GC","support":"glucose-based porous carbon (GC)","matchedSynthesis":"Pd/GC","matchedCharacterization":"Pd/GC","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Similar to Pd/NH2-P-GC but without sodium hypophosphite and APTES.","phase":"Metallic Pd nanoparticles.","structureLink":"Nearly inactive for FA dehydrogenation due to the absence of both amine groups and P doping.","reactionConditions":"Additive-free dehydrogenation of aqueous FA solution","metricCount":"1"},{"paperId":"P115","catalystId":"P115_PERF_004","name":"Pd/P-GC","support":"phosphorous-doped glucose-based porous carbon (P-GC)","matchedSynthesis":"Pd/P-GC","matchedCharacterization":"Pd/P-GC","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Similar to Pd/NH2-P-GC but without APTES functionalization.","phase":"Metallic Pd nanoparticles.","surfaceStates":"XPS shows binding energies for zero-valent Pd 3d shifted towards higher values compared to Pd/NH2-GC.","structureLink":"Nearly inactive for FA dehydrogenation due to the absence of amine groups acting as proton scavengers.","reactionConditions":"Additive-free dehydrogenation of aqueous FA solution","metricCount":"1"},{"paperId":"P116","catalystId":"P116_PERF_001","name":"0.2 wt % Pd/N-CNTs","support":"N-CNTs","matchedSynthesis":"Pd/N-CNTs","matchedCharacterization":"Pd/N-CNTs","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Palladium was deposited onto N-CNT supports via incipient wetness impregnation using an acetone solution of palladium acetate.","phase":"Single-atom isolated ions at low loading; nanoparticles at high loading.","particleSize":"Not visible for <1 wt%; 1.2–1.4 nm for 1–2 wt%.","surfaceStates":"Isolated Pd2+ ions coordinated by pyridinic nitrogen sites.","structureLink":"Single-atom ionic Pd sites provide maximum TOF and higher selectivity to hydrogen in formic acid decomposition compared to nanoparticles.","reactionConditions":"gas-phase formic acid decomposition","selectivity":"improved selectivity to hydrogen compared to metal nanoparticles","stability":"stable up to 500 °C in hydrogen atmosphere; activity not influenced by pretreatment temperature in hydrogen up to 400 °C","whyPerformsWell":"Pd2+ ions coordinated by two pyridinic nitrogen atoms at the edges of graphite planes facilitate C-H bond cleavage and subsequent interaction to produce H2 and CO2","metricCount":"1"},{"paperId":"P116","catalystId":"P116_PERF_002","name":"2 wt % Pd/N-CNTs","support":"N-CNTs","matchedSynthesis":"Pd/N-CNTs","matchedCharacterization":"Pd/N-CNTs","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Palladium was deposited onto N-CNT supports via incipient wetness impregnation using an acetone solution of palladium acetate.","phase":"Single-atom isolated ions at low loading; nanoparticles at high loading.","particleSize":"Not visible for <1 wt%; 1.2–1.4 nm for 1–2 wt%.","surfaceStates":"Isolated Pd2+ ions coordinated by pyridinic nitrogen sites.","structureLink":"Single-atom ionic Pd sites provide maximum TOF and higher selectivity to hydrogen in formic acid decomposition compared to nanoparticles.","reactionConditions":"gas-phase formic acid decomposition","whyPerformsWell":"less active than 0.2 wt % Pd/N-CNTs due to formation of metallic nanoparticles","metricCount":"0"},{"paperId":"P116","catalystId":"P116_PERF_003","name":"2 wt % Pd/CNTs","support":"CNTs","matchedSynthesis":"Pd/CNTs","matchedCharacterization":"Pd/CNTs","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Palladium was deposited onto CNT supports via incipient wetness impregnation using an acetone solution of palladium acetate.","phase":"Metallic palladium nanoparticles","particleSize":"1.2–2.3 nm","surfaceStates":"Surface oxidized PdO","structureLink":"Less active in formic acid decomposition compared to N-doped counterparts.","reactionConditions":"gas-phase formic acid decomposition","stability":"TOF decreases by a factor of roughly 1.5 upon pretreatment in hydrogen to 400 °C","whyPerformsWell":"less active than N-doped counterparts","metricCount":"0"},{"paperId":"P116","catalystId":"P116_PERF_004","name":"0.2 wt % Pd/CNTs","support":"CNTs","matchedSynthesis":"Pd/CNTs","matchedCharacterization":"Pd/CNTs","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Palladium was deposited onto CNT supports via incipient wetness impregnation using an acetone solution of palladium acetate.","phase":"Metallic palladium nanoparticles","particleSize":"1.2–2.3 nm","surfaceStates":"Surface oxidized PdO","structureLink":"Less active in formic acid decomposition compared to N-doped counterparts.","reactionConditions":"gas-phase formic acid decomposition","whyPerformsWell":"less active than N-doped counterparts","metricCount":"0"},{"paperId":"P117","catalystId":"P117_PERF_001","name":"Pd/CN-U1W5","support":"carbon nitride (CN)","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","matchedCharacterization":"Pd/CN-U1W5","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","phase":"fcc Pd(111)","particleSize":"2.4 nm","surfaceStates":"Electron-deficient palladium with a higher percentage of cationic Pd (Pd2+ = 46.2%, Pd0 = 53.8%) compared to Pd/CN-U; electronic properties regulated by pyridinic N via Pd-N covalent bonds causing electron transfer from Pd to N.","structureLink":"High catalytic activity is attributed to the high amount of pyridinic N, small particle size (2.4 nm), and high dispersion, which increases the surface Pd2+/Pd0 ratio.","reactionConditions":"Formic acid dehydrogenation at 348 K in aqueous solution","stability":"retained about 90% of its initial TOF after three times of recycling","deactivation":"decrease in catalytic activity attributed to decrease in Pd2+ and pyridinic N content in recovered catalyst","whyPerformsWell":"high amount of pyridinic N, high Pd dispersion, small Pd particle sizes (average 2.4 nm), and strong interaction between Pd nanoparticles and pyridinic N regulating electronic properties","metricCount":"3"},{"paperId":"P117","catalystId":"P117_PERF_002","name":"Pd/CN-U","support":"carbon nitride (CN)","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","matchedCharacterization":"Pd/CN-U","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","phase":"fcc Pd(111)","particleSize":"3.0 nm","surfaceStates":"Pd0 (64.8%) and Pd2+ (35.2%)","reactionConditions":"Formic acid dehydrogenation at 348 K in aqueous solution","metricCount":"2"},{"paperId":"P117","catalystId":"P117_PERF_003","name":"Pd/CN-U1W3","support":"carbon nitride (CN)","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","matchedCharacterization":"Pd/CN-U","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","phase":"fcc Pd(111)","particleSize":"3.0 nm","surfaceStates":"Pd0 (64.8%) and Pd2+ (35.2%)","reactionConditions":"Formic acid dehydrogenation at 348 K in aqueous solution","metricCount":"1"},{"paperId":"P117","catalystId":"P117_PERF_004","name":"Pd/CN-U1W1","support":"carbon nitride (CN)","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","matchedCharacterization":"Pd/CN-U","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","phase":"fcc Pd(111)","particleSize":"3.0 nm","surfaceStates":"Pd0 (64.8%) and Pd2+ (35.2%)","reactionConditions":"Formic acid dehydrogenation at 348 K in aqueous solution","metricCount":"1"},{"paperId":"P117","catalystId":"P117_PERF_005","name":"Pd/CN-U1W7","support":"carbon nitride (CN)","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","matchedCharacterization":"Pd/CN-U","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","phase":"fcc Pd(111)","particleSize":"3.0 nm","surfaceStates":"Pd0 (64.8%) and Pd2+ (35.2%)","reactionConditions":"Formic acid dehydrogenation at 348 K in aqueous solution","metricCount":"1"},{"paperId":"P118","catalystId":"P118_PERF_001","name":"Pd@S-1-H","support":"silicalite-1 (S-1) zeolite","matchedSynthesis":"Pd@S-1-H","matchedCharacterization":"Pd@S-1-H","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Synthesized via hydrothermal method at 170 °C for 3 days using a reaction gel, followed by direct reduction in H2 flow.","phase":"Single and pseudo-single atoms; atomically dispersed.","particleSize":"Subnanometer","surfaceStates":"Pd valence state of +1.83; higher oxidation state than Pd foil and Pd@S-1-C.","structureLink":"Decreased size and increased dispersion expose more accessible active sites (especially corner sites), resulting in superior methane combustion activity (complete combustion temperature of 390 °C).","reactionConditions":"Methane combustion: GHSV = 36,000 mL gcat-1 h-1, feed gas 2% CH4–20% O2–78% N2; FA dehydrogenation: 333 K, no additives, 2 M FA, nmetal/nFA = 0.012","stability":"100% methane conversion remains unchanged after 100 h on stream at 470 °C; no degradation of catalytic activities for FA dehydrogenation observed after five cycles at 333 K","whyPerformsWell":"decreased sizes of Pd species exposing more accessible active sites (especially the corner site); unique microenvironment and highly dispersed Pd(d+) species due to confinement effect of zeolites","metricCount":"3"},{"paperId":"P118","catalystId":"P118_PERF_002","name":"Pd@S-1-C","support":"silicalite-1 (S-1) zeolite","matchedSynthesis":"Pd@S-1-C","matchedCharacterization":"Pd@S-1-C","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Synthesized via hydrothermal method at 170 °C for 3 days, then calcinated and reduced.","phase":"Subnanometer Pd clusters; Pd-Pd metallic bonds observed.","particleSize":"Subnanometer (larger than Pd@S-1-H)","surfaceStates":"Pd valence state of +1.67.","structureLink":"Larger metal size compared to Pd@S-1-H leads to lower methane combustion activity (complete combustion temperature of 416 °C).","reactionConditions":"Methane combustion: GHSV = 36,000 mL gcat-1 h-1; FA dehydrogenation: 333 K, no additives, 2 M FA, nmetal/nFA = 0.012","metricCount":"2"},{"paperId":"P118","catalystId":"P118_PERF_003","name":"Pd/S-1-im","support":"silicalite-1 (S-1) zeolite","matchedSynthesis":"Pd/S-1-im","matchedCharacterization":"Pd/S-1-im","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Prepared by incipient wetness impregnation with the same metal loading as Pd@S-1.","phase":"Pd nanoparticles (NPs)","particleSize":"4–5 nm","structureLink":"Large particle size and aggregation lead to poor methane combustion activity (complete combustion temperature of 513 °C).","reactionConditions":"Methane combustion: GHSV = 36,000 mL gcat-1 h-1; FA dehydrogenation: 333 K, no additives, 2 M FA, nmetal/nFA = 0.012","stability":"methane conversion decreases rapidly from 88.0% to 68.7% within 65 h on stream at 470 °C","metricCount":"2"},{"paperId":"P118","catalystId":"P118_PERF_004","name":"0.8Pd0.2Ni(OH)2@S-1-H","support":"silicalite-1 (S-1) zeolite","matchedSynthesis":"0.8Pd0.2Ni(OH)2@S-1-H","matchedCharacterization":"0.8Pd0.2Ni(OH)2@S-1-H","role":"optimized bimetallic catalyst","composition":"Pd/Ni = 0.8/0.2 (molar ratio)","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Synthesized via hydrothermal method at 170 °C for 3 days using a reaction gel, followed by direct reduction in H2 flow.","phase":"Partial formation of Pd–Ni alloy structure (Pd–Ni metallic bond CN = 0.13); Pd is dimer- or single-atomic dispersion (Pd–Pd CN = 0.9).","particleSize":"Subnanometer / pseudo-single atoms; remains small (1.6 nm) after calcination at 700 °C under N2.","surfaceStates":"Pd valence state of +1.17; electron-enriched Pd surfaces due to electron transfer from Ni to Pd.","structureLink":"Synergistic effect of the bimetallic Pd–Ni(OH)2 interface and electron-rich Pd surface lowers the energy barrier for FA dehydrogenation, affording a TOF up to 9308 h⁻¹.","reactionConditions":"FA dehydrogenation: 333 K, no additives, 2 M FA, nmetal/nFA = 0.012; Cr(VI) reduction: 323 K, aqueous solution with K2Cr2O7 and HCOOH","selectivity":"H2 generation from FA decomposition: CO impurity < 10 ppm","stability":"No degradation of catalytic activities for FA dehydrogenation after five cycles at 333 K; activity remains unchanged after five consecutive cycles during Cr(VI) reductions","whyPerformsWell":"formation of ultrasmall and highly-dispersed metal species coupled with the synergistic effect of the Pd–Ni(OH)2 interface that lowers energy barrier; electron-rich Pd surface favors C–H activation of the Pd-formate intermediate","metricCount":"3"},{"paperId":"P119","catalystId":"P119_PERF_001","name":"Pd/BNC","support":"B, N co-doped carbon (BNC)","matchedSynthesis":"Pd/BNC","matchedCharacterization":"Pd/BNC","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"BNC support was synthesized by physical grinding of EDTA-2Na and H3BO3 followed by pyrolysis at 800 C in N2. Pd was loaded via deposition-precipitation using an H2PdCl4 solution, pH adjusted to 10 with NaOH, then reduced under H2/N2 flow.","phase":"Highly dispersed Pd nanoparticles; no XRD signals for Pd nanocrystals observed","particleSize":"1.3 nm","surfaceStates":"Strong interaction between Pd and pyridinic-N as well as BC2O species","structureLink":"B and N co-doping provides more anchor sites (BC2O, pyridinic-N), resulting in smaller Pd particle size and optimized electronic properties (Pd2+/Pd0 ratio), which lowers the activation barrier to 31.84 kJ/mol and increases TOF.","reactionConditions":"Hydrogen evolution from formic acid (FA) aqueous solution at 50 °C without additives.","selectivity":"almost 100% H2 selectivity; no CO detected","stability":"activity almost unchanged after five cycles of reaction","whyPerformsWell":"High doping content of B and N provides more anchor sites for Pd, resulting in ultrafine Pd NPs (1.3 nm) and optimized electronic properties; strong interaction between support and Pd nanoparticles.","metricCount":"3"},{"paperId":"P119","catalystId":"P119_PERF_002","name":"Pd/NC","support":"N-doped carbon (NC)","matchedSynthesis":"Pd/NC","matchedCharacterization":"Pd/NC","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NC support prepared by pyrolysis of EDTA-2Na at 800 C in N2. Pd loaded and reduced using the same route as Pd/BNC.","phase":"Highly dispersed Pd nanoparticles; no XRD signals for Pd nanocrystals observed","particleSize":"2.3 nm","surfaceStates":"Pd0 and Pd2+ states present with weaker support interaction compared to Pd/BNC","structureLink":"Larger particle size and less optimized electronic properties lead to lower activity (TOF = 747 h-1) and higher activation energy (50.88 kJ/mol).","reactionConditions":"Hydrogen evolution from formic acid (FA) aqueous solution at 50 °C without additives.","selectivity":"almost 100% H2 selectivity; no CO detected","metricCount":"2"},{"paperId":"P119","catalystId":"P119_PERF_003","name":"BNC","support":"B, N co-doped carbon (BNC)","matchedSynthesis":"Pd/BNC","matchedCharacterization":"Pd/BNC","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"BNC support was synthesized by physical grinding of EDTA-2Na and H3BO3 followed by pyrolysis at 800 C in N2. Pd was loaded via deposition-precipitation using an H2PdCl4 solution, pH adjusted to 10 with NaOH, then reduced under H2/N2 flow.","phase":"Highly dispersed Pd nanoparticles; no XRD signals for Pd nanocrystals observed","particleSize":"1.3 nm","surfaceStates":"Strong interaction between Pd and pyridinic-N as well as BC2O species","structureLink":"B and N co-doping provides more anchor sites (BC2O, pyridinic-N), resulting in smaller Pd particle size and optimized electronic properties (Pd2+/Pd0 ratio), which lowers the activation barrier to 31.84 kJ/mol and increases TOF.","reactionConditions":"Hydrogen evolution from formic acid (FA) aqueous solution at 50 °C without additives.","metricCount":"1"},{"paperId":"P119","catalystId":"P119_PERF_004","name":"Pd/BNC-700","support":"B, N co-doped carbon (BNC-700)","matchedSynthesis":"Pd/BNC-700","matchedCharacterization":"Pd/BNC-700","role":"comparison catalyst (temperature effect)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"Same route as Pd/BNC but support pyrolysis temperature changed to 700 C.","particleSize":"1.0 nm","surfaceStates":"Excessively strong interaction between carrier and Pd NPs","structureLink":"Too high a Pd2+/Pd0 ratio hinders the reaction compared to Pd/BNC.","reactionConditions":"Hydrogen evolution from formic acid (FA) aqueous solution at 50 °C without additives.","whyPerformsWell":"Inferior to Pd/BNC because the interaction between carrier and Pd NPs is too strong (Pd2+/Pd0 ratio = 2.08), which might hinder the reaction.","metricCount":"0"},{"paperId":"P119","catalystId":"P119_PERF_005","name":"Pd/BNC-900","support":"B, N co-doped carbon (BNC-900)","matchedSynthesis":"Pd/BNC-900","matchedCharacterization":"Pd/BNC-900","role":"comparison catalyst (temperature effect)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"Same route as Pd/BNC but support pyrolysis temperature changed to 900 C.","particleSize":"1.8 nm","structureLink":"Larger Pd size compared to Pd/BNC provides fewer active sites, reducing performance.","reactionConditions":"Hydrogen evolution from formic acid (FA) aqueous solution at 50 °C without additives.","whyPerformsWell":"Inferior to Pd/BNC because the Pd size is larger (1.8 nm vs 1.3 nm), providing fewer active sites.","metricCount":"0"},{"paperId":"P120","catalystId":"P120_PERF_001","name":"Pd1Ag1-NH2/C","support":"pristine carbon supports","matchedSynthesis":"Pd1Ag1-NH2/C","matchedCharacterization":"Pd1Ag1-NH2/C","role":"active catalyst","composition":"Pd:Ag = 1:1 (molar ratio of precursors)","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"L-histidine was dissolved in Na2PdCl4 aqueous solution to form a Pd-based complex, followed by the addition of AgNO3 and subsequent co-reduction using NaBH4 on carbon support at room temperature.","phase":"PdAg alloy (confirmed by XRD peaks located between pristine Ag and Pd, and HRTEM lattice spacing of 0.229 nm)","particleSize":"4.03 ± 0.08 nm (fresh); 5.2 ± 0.35 nm (after cycling)","surfaceStates":"L-histidine coordinated at the metal surface; electron density transferred from metal nanoparticles to L-histidine/complexes (indicated by positive shifts in Pd0 and Ag0 XPS signals); presence of -NH2 groups (N1s peak at 400.5 eV).","structureLink":"L-histidine acts as a 'transfer station' for protons, promoting formic acid deprotonation via acid-base interactions and reducing energy barriers for the rate-determining steps (bi-HCOO to mo-HCOO isomerization and H-H coupling) through optimized electronic structure.","reactionConditions":"Aqueous solution containing formic acid (FA) and sodium formate (SF) at 333 K","selectivity":"H2 selectivity approaches nearly 100% without detecting other gases","stability":"TOF slightly decreased from 6493.5 to 5683.2 h-1 within five cycles","deactivation":"Slight coarsening of nanoparticles (average size increased to 5.2 ± 0.35 nm) responsible for decreased TOF during stability test","whyPerformsWell":"L-histidine at metal sites promotes rapid binding of FA via acid-base interactions, local enrichment of protons and formate promoting decomposition and hydride transfer; reduces energy barriers of RDSs (isomerization of bi-HCOO to mo-HCOO and H-H coupling) through optimized electronic structure.","metricCount":"3"},{"paperId":"P120","catalystId":"P120_PERF_002","name":"Pd1Ag1/C","support":"pristine carbon supports","matchedSynthesis":"Pd1Ag1/C","matchedCharacterization":"Pd1Ag1/C","role":"control sample","composition":"Pd:Ag = 1:1 (molar ratio of precursors)","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Co-reduction of Na2PdCl4 and AgNO3 using NaBH4 on carbon support without L-histidine.","phase":"PdAg alloy (confirmed by XRD)","particleSize":"7.8 ± 0.3 nm","surfaceStates":"Binding energy of Pd0 is negatively shifted by 0.25 eV compared to Pd/C due to electron transfer from Ag to Pd.","reactionConditions":"Aqueous solution containing FA and SF at 333 K","selectivity":"Shows CO generation","stability":"Sharp decay in four cycles","deactivation":"Catalyst poisoning by CO generated as a side product","metricCount":"1"},{"paperId":"P120","catalystId":"P120_PERF_003","name":"Pd/C","support":"pristine carbon supports","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"control sample","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Reduction of Na2PdCl4 using NaBH4 on carbon support without L-histidine or Ag precursor.","phase":"Pure Pd nanoparticles","particleSize":"4.8 ± 0.06 nm","reactionConditions":"Aqueous solution containing FA and SF at 333 K","selectivity":"Shows CO generation","stability":"Sharp decay in three cycles","deactivation":"Irreversible poisoning by CO generated as a side product (via dehydration)","metricCount":"2"},{"paperId":"P120","catalystId":"P120_PERF_004","name":"Pd-NH2/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Aqueous solution containing FA and SF at 333 K","whyPerformsWell":"Beneficial role of L-histidine in enhancing the FAD process","metricCount":"2"},{"paperId":"P120","catalystId":"P120_PERF_005","name":"Pd1Ag2-NH2/C","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Aqueous solution containing FA and SF at 333 K","metricCount":"1"},{"paperId":"P120","catalystId":"P120_PERF_006","name":"Pd2Ag1-NH2/C","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Aqueous solution containing FA and SF at 333 K","metricCount":"1"},{"paperId":"P120","catalystId":"P120_PERF_007","name":"Pd1Ag1/C-NH2","support":"carbon blacks","matchedSynthesis":"Pd1Ag1/C-NH2","matchedCharacterization":"Pd1Ag1/C-NH2","role":"control sample","composition":"Pd:Ag = 1:1","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Bare Pd1Ag1 nanoparticles were loaded onto L-histidine modified carbon blacks.","phase":"PdAg alloy (confirmed by EDS mapping)","particleSize":"4.33 ± 0.05 nm","structureLink":"Lower activity compared to Pd1Ag1-NH2/C due to the larger distance between resulting H species (protonated -NH2 at carbon vs. metal surface), retarding H-H coupling.","reactionConditions":"Aqueous solution containing FA and SF at 333 K (implied)","whyPerformsWell":"Lower TOF attributed to initial protonation of -NH2 at carbon and thus far distance between the resulting two H species from the FA molecule, which retards the H-H coupling","metricCount":"1"},{"paperId":"P121","catalystId":"P121_PERF_001","name":"Pd/D201","support":"D201 resin","matchedSynthesis":"Pd/D201","matchedCharacterization":"Pd/D201","role":"FA dehydrogenation catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Resin pretreatment -> impregnation with PdCl2 solution at room temperature for 24 h -> filtration/washing -> liquid-phase reduction with NaBH4 -> vacuum drying","phase":"Monometallic Pd nanoparticles","particleSize":"2.3 nm","surfaceStates":"Pd 0, Pd 2+","structureLink":"The optimized particle size (~2.3 nm) and higher content of metallic Pd 0 are beneficial for superior catalytic performance in FA dehydrogenation.","reactionConditions":"50 °C, 5 mL of 0.25 M FA solution, atmospheric pressure, magnetic stirring at ~850 rpm","selectivity":"~100% selectivity toward FA dehydrogenation; no trace of CO detected","stability":"Decent stability; only a minor reduction in catalytic performance after the fourth run","whyPerformsWell":"Optimized Pd NP size (~2.3 nm), higher content of metallic Pd0 on surface, and electrostatic interaction between positively charged -N+(CH3)3 groups and HCOO- species which increases localized concentration of HCOO-","metricCount":"3"},{"paperId":"P121","catalystId":"P121_PERF_002","name":"Pd/D301","support":"D301 resin","matchedSynthesis":"Pd/D301","matchedCharacterization":"Pd/D301","role":"FA dehydrogenation catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Resin pretreatment -> impregnation with PdCl2 solution at room temperature for 24 h -> filtration/washing -> liquid-phase reduction with NaBH4 -> vacuum drying","phase":"Monometallic Pd nanoparticles","particleSize":"5.6 nm","surfaceStates":"Pd 0, Pd 2+","structureLink":"Larger particle size (~5.6 nm) and lower metallic Pd 0 content compared to Pd/D201 correlate with poorer catalytic activity.","reactionConditions":"50 °C, 5 mL of 0.25 M FA solution, atmospheric pressure, magnetic stirring at ~850 rpm","selectivity":"~100% selectivity toward FA dehydrogenation; no trace of CO detected","whyPerformsWell":"Lower activity compared to Pd/D201 due to larger Pd NP size (~5.6 nm) and lower metallic Pd0 content","metricCount":"3"},{"paperId":"P121","catalystId":"P121_PERF_003","name":"Pd/D311","support":"D311 resin","matchedSynthesis":"Pd/D311","matchedCharacterization":"Pd/D311","role":"FA dehydrogenation catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Resin pretreatment -> impregnation with PdCl2 solution at room temperature for 24 h -> filtration/washing -> liquid-phase reduction with NaBH4 -> vacuum drying","phase":"Monometallic Pd nanoparticles","particleSize":"4.4 nm","surfaceStates":"Pd 0, Pd 2+","structureLink":"Larger particle size (~4.4 nm) and lowest metallic Pd 0 content correlate with poor catalytic performance.","reactionConditions":"50 °C, 5 mL of 0.25 M FA solution, atmospheric pressure, magnetic stirring at ~850 rpm","selectivity":"~100% selectivity toward FA dehydrogenation; no trace of CO detected","whyPerformsWell":"Lower activity compared to Pd/D201 due to larger Pd NP size (~4.4 nm) and lower metallic Pd0 content","metricCount":"3"},{"paperId":"P122","catalystId":"P122_PERF_001","name":"AuNPs-PPO","support":"poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)","matchedSynthesis":"AuNPs-PPO","matchedCharacterization":"AuNPs-PPO","role":"catalyst for formic acid decomposition (FAD)","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"PPO was swollen in anhydrous THF, followed by the addition of HAuCl4·3H2O and reduction with sodium triethylborohydride. The resulting catalyst was precipitated in methanol, filtered, washed with methanol, and dried under vacuum.","phase":"face-centered cubic (fcc) gold","particleSize":"4-6 nm","surfaceStates":"Cubic morphology with exposed <220> planes of fcc gold.","structureLink":"The cubic geometry and <220> crystalline facets are attributed to high catalytic activity due to the low coordination number of the metal atoms.","reactionConditions":"Formic acid decomposition in aqueous or mixed solvent media, catalyst amount 100 mg (1 x 10^-5 mol Au), solvent volume 4 mL.","selectivity":"High selectivity for dehydrogenation; exclusive formation of H2 and CO2, no CO detected.","stability":"Reusable for five consecutive tests in neat water (FA/Au = 100, 80 °C, 45 min) with consistent conversion and activity. WAXD patterns before and after reuse were identical.","whyPerformsWell":"Complete encapsulation of AuNPs (4-6 nm) within the PPO matrix ensures uniform distribution; active cubic morphology exposing fcc gold 220 planes. DMAc cosolvent swells PPO to enhance reagent access.","metricCount":"6"},{"paperId":"P123","catalystId":"P123_PERF_001","name":"3Ni@KIT-6","support":"KIT-6","matchedSynthesis":"3Ni@KIT-6","matchedCharacterization":"3Ni@KIT-6","role":"catalyst","composition":"Ni: 3 wt.%","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Ni precursor solution was added dropwise and stirred until dry, followed by calcination and H2 reduction.","phase":"Metallic Ni","particleSize":"9.9 nm (crystallite size)","surfaceStates":"Lewis acid sites present; lower Lewis acidity compared to Co-based catalysts.","structureLink":"Highest H2 selectivity linked to relatively higher surface area (851 m2/g), pore volume (1.35 cm3/g), and smaller crystallite size compared to 5Ni@KIT-6.","reactionConditions":"Packed-bed continuous-flow reactor, 250 °C, FA/Ar ratio 1/2 or 1/1, total flow rate 45 mL/min","selectivity":"Product distribution at 250 °C, FA/Ar=1/2: H2 42.4%, CO 6.58%, CO2 51.0%; at FA/Ar=1/1: H2 34.8%, CO 19.6%, CO2 45.6%","stability":"Stable catalytic activity for 150 min","whyPerformsWell":"Higher surface area (851 m2/g), pore volume (1.35 cm3/g) and smaller crystallite size (9.54 nm) compared to 5Ni@KIT-6","metricCount":"3"},{"paperId":"P123","catalystId":"P123_PERF_002","name":"5Ni@KIT-6","support":"KIT-6","matchedSynthesis":"5Ni@KIT-6","matchedCharacterization":"5Ni@KIT-6","role":"catalyst","composition":"Ni: 5 wt.%","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Ni precursor solution was added dropwise and stirred until dry, followed by calcination and H2 reduction.","phase":"Metallic Ni","particleSize":"10.6 nm (crystallite size)","surfaceStates":"Lewis acid sites present; slight increase in Lewis acidity compared to 3Ni@KIT-6.","structureLink":"Lower H2 selectivity than 3Ni@KIT-6 attributed to larger crystallite size and lower surface area/pore volume.","reactionConditions":"Packed-bed continuous-flow reactor, 250 °C, FA/Ar ratio 1/2, total flow rate 45 mL/min","selectivity":"Product distribution at 250 °C, FA/Ar=1/2: H2 41.9%, CO 7.93%, CO2 50.1%","stability":"Stable catalytic activity for 150 min","deactivation":"Coke accumulation weight loss of about 7.1% (TG analysis)","metricCount":"2"},{"paperId":"P123","catalystId":"P123_PERF_003","name":"3Co@KIT-6","support":"KIT-6","matchedSynthesis":"3Co@KIT-6","matchedCharacterization":"3Co@KIT-6","role":"catalyst","composition":"Co: 3 wt.%","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Co precursor solution was added dropwise and stirred until dry, followed by calcination and H2 reduction.","phase":"Metallic Co","particleSize":"4.5 nm (crystallite size)","surfaceStates":"Lewis acid sites present; higher Lewis acidity than Ni-based catalysts.","structureLink":"Higher H2 selectivity compared to 5Co@KIT-6 linked to lower metal loading and associated surface properties.","reactionConditions":"Packed-bed continuous-flow reactor, 250 °C, FA/Ar ratio 1/2, total flow rate 45 mL/min","selectivity":"Product distribution at 250 °C, FA/Ar=1/2: H2 40.6%, CO 10.6%, CO2 48.8%","stability":"Stable catalytic activity for 150 min","metricCount":"2"},{"paperId":"P123","catalystId":"P123_PERF_004","name":"5Co@KIT-6","support":"KIT-6","matchedSynthesis":"5Co@KIT-6","matchedCharacterization":"5Co@KIT-6","role":"catalyst","composition":"Co: 5 wt.%","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Co precursor solution was added dropwise and stirred until dry, followed by calcination and H2 reduction.","phase":"Metallic Co","particleSize":"6.5 nm (crystallite size)","surfaceStates":"Lewis acid sites present; slight increase in Lewis acidity compared to 3Co@KIT-6.","structureLink":"Lower catalytic activity associated with increased coke formation (9.6% weight loss in TG analysis).","reactionConditions":"Packed-bed continuous-flow reactor, 250 °C, FA/Ar ratio 1/2, total flow rate 45 mL/min","selectivity":"Product distribution at 250 °C, FA/Ar=1/2: H2 40.2%, CO 10.5%, CO2 49.2%","stability":"Stable catalytic activity for 150 min","deactivation":"Coke accumulation weight loss of 9.6% (TG analysis)","metricCount":"2"},{"paperId":"P123","catalystId":"P123_PERF_005","name":"4Ni1Co@KIT-6","support":"KIT-6","matchedSynthesis":"4Ni1Co@KIT-6","matchedCharacterization":"4Ni1Co@KIT-6","role":"catalyst","composition":"Ni: 4 wt.%, Co: 1 wt.%","activeMetals":"Ni-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Ni and Co precursor solutions were added dropwise and stirred until dry, followed by calcination and H2 reduction.","phase":"Bimetallic (Ni-Co)","particleSize":"10.1 nm (crystallite size)","surfaceStates":"Lewis acid sites present.","structureLink":"Decreased H2 selectivity and increased CO production compared to monometallic Ni, attributed to the active role of Co in coke formation.","reactionConditions":"Packed-bed continuous-flow reactor, 250 °C, FA/Ar ratio 1/2, total flow rate 45 mL/min","selectivity":"Product distribution at 250 °C, FA/Ar=1/2: H2 38.7%, CO 11.5%, CO2 49.9%","stability":"Stable catalytic activity for 150 min","metricCount":"2"},{"paperId":"P124","catalystId":"P124_PERF_001","name":"Au/C","support":"N-free porous carbon","matchedSynthesis":"Au/C","matchedCharacterization":"Au/C","role":"catalyst for hydrogen production from formic acid","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"Carbon support was placed in HAuCl4 water solution, interacted for 1 h at 343 K, centrifuged, and treated with a 10 wt% NH3-water solution at 333 K for 1 h.","phase":"Metallic nanoparticles and single atoms","particleSize":"10 ± 6 nm","surfaceStates":"Metallic state (Au 4f7/2 ~ 84.1 eV); narrower XPS lines attributed to larger particle size","structureLink":"Lower activity compared to Au/N-C due to significantly lower dispersion and larger particle size","reactionConditions":"Gas-phase formic acid decomposition in a fixed-bed tubular glass reactor at atmospheric pressure.","selectivity":"99.5% (to H2 at 448 K)","metricCount":"2"},{"paperId":"P124","catalystId":"P124_PERF_002","name":"Au/N-C","support":"N-doped porous carbon","matchedSynthesis":"Au/N-C","matchedCharacterization":"Au/N-C","role":"catalyst for hydrogen production from formic acid","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"Carbon support was placed in HAuCl4 water solution, interacted for 1 h at 343 K, centrifuged, and treated with a 10 wt% NH3-water solution at 333 K for 1 h.","phase":"Metallic nanoparticles and single atoms","particleSize":"2.2 ± 0.9 nm","surfaceStates":"Metallic state (Au 4f7/2 ~ 83.9 eV); support contains pyridinic N (30 at%), pyrrolic N (49 at%), graphitic N (15 at%), and pyridine-N-oxide (6 at%)","structureLink":"High activity attributed to high Au dispersion and the presence of pyridinic nitrogen which activates formic acid via protonation to form pyridinium formate species that interact with Au","reactionConditions":"Gas-phase formic acid decomposition in a fixed-bed tubular glass reactor at atmospheric pressure.","selectivity":"96.6% (to H2 at 448 K)","whyPerformsWell":"High Au dispersion (~2 nm) and presence of pyridinic nitrogen on the support which activates formic acid via protonation to form formate species that interact with Au.","metricCount":"2"},{"paperId":"P124","catalystId":"P124_PERF_003","name":"Au/Al2O3","support":"Al2O3","matchedSynthesis":"Au/Al2O3","matchedCharacterization":"Au/Al2O3","role":"catalyst for hydrogen production from formic acid","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"Support mixed with HAuCl4 solution, stirred at 343 K for 2 h, treated with 4 M ammonia solution, stirred again for 1 h at 343 K, filtered and washed.","phase":"Metallic nanoparticles","particleSize":"2.2 ± 1.0 nm","surfaceStates":"Metallic state (Au 4f7/2 ~ 83.9 eV)","reactionConditions":"Gas-phase formic acid decomposition in a fixed-bed tubular glass reactor at atmospheric pressure.","selectivity":"98.0% (to H2 at 448 K)","metricCount":"2"},{"paperId":"P124","catalystId":"P124_PERF_004","name":"Au/SiO2","support":"SiO2","matchedSynthesis":"Au/SiO2","matchedCharacterization":"Au/SiO2","role":"catalyst for hydrogen production from formic acid","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"Support mixed with HAuCl4 solution, stirred at 343 K for 2 h, treated with 4 M ammonia solution, stirred again for 1 h at 343 K, filtered and washed.","phase":"Metallic nanoparticles","particleSize":"1.6 ± 0.8 nm","surfaceStates":"Metallic state (Au 4f7/2 ~ 84.1 eV)","reactionConditions":"Gas-phase formic acid decomposition in a fixed-bed tubular glass reactor at atmospheric pressure.","selectivity":"83.0% (to H2 at 448 K)","metricCount":"2"},{"paperId":"P125","catalystId":"P125_PERF_001","name":"Pd/C","support":"Vulcan XC72 carbon","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"Control catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Pd was impregnated on carbon using deposition-precipitation with Na2CO3 and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"2.5 nm","surfaceStates":"XPS shows 25.1% Pd0 and 74.9% Pd2+","reactionConditions":"10 mL 1 M formic acid, 60 °C, 0.05 g catalyst","selectivity":"100% H2 selectivity (no CO detected)","metricCount":"2"},{"paperId":"P125","catalystId":"P125_PERF_002","name":"Pd/Ceria0.4/C","support":"Vulcan XC72 carbon","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"Control catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Pd was impregnated on carbon using deposition-precipitation with Na2CO3 and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"2.5 nm","surfaceStates":"XPS shows 25.1% Pd0 and 74.9% Pd2+","reactionConditions":"10 mL 1 M formic acid, 60 °C, 0.05 g catalyst","selectivity":"100% H2 selectivity (no CO detected)","deactivation":"Ceria was dissolved by the acidic formic acid solution (Ce content decreased from 3.5 wt % to 0.1 wt % after reaction)","whyPerformsWell":"Dissolution of ceria produces formate anions and released cerium ions interact with formate anions to reduce the activation barrier for C-H bond cleavage.","metricCount":"2"},{"paperId":"P125","catalystId":"P125_PERF_003","name":"Physical mixture of Pd/C and Ceria0.4/C","support":"Vulcan XC72 carbon","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"Control catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Pd was impregnated on carbon using deposition-precipitation with Na2CO3 and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"2.5 nm","surfaceStates":"XPS shows 25.1% Pd0 and 74.9% Pd2+","reactionConditions":"10 mL 1 M formic acid, 60 °C, 0.05 g each component","whyPerformsWell":"Promoting effect originates from dissolved cerium ions and formate anions produced during ceria dissolution.","metricCount":"2"},{"paperId":"P125","catalystId":"P125_PERF_004","name":"Pd/C with added Ce precursors","support":"Vulcan XC72 carbon","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"Control catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Pd was impregnated on carbon using deposition-precipitation with Na2CO3 and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"2.5 nm","surfaceStates":"XPS shows 25.1% Pd0 and 74.9% Pd2+","reactionConditions":"10 mL 1 M formic acid, 40 °C, 0.03 g catalyst, 5 mM metal-based cerium precursor","whyPerformsWell":"Ce(III) species are more effective than Ce(IV), indicating the charge of cerium ions affects the electronic state of the formate anion.","metricCount":"1"},{"paperId":"P126","catalystId":"P126_PERF_001","name":"Pd/200-8-1.5","matchedCharacterization":"Pd/MIL-88 (Pd/200-8-1.5)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Highly dispersed Pd on MIL-88 support","surfaceStates":"Pd 3d5/2 peaks at 335.3 eV (Pd(0)) and 336.6 eV (Pd(II))","structureLink":"The rod-like MIL-88 crystal structure provides better hydrogen production performance than the octahedral MIL-101; Pd(II) species strengthen the dispersion of active sites and enhance formate ion adsorption.","reactionConditions":"Potassium formate hydrolysis in a round-bottom three-necked flask with magnetic stirring (400 rpm) under N2 flow (10 mL min-1).","selectivity":"CO2/H2 ratio ranges from 0.16 to 0.24 depending on temperature","whyPerformsWell":"rod-like MIL-88 crystal structure is more effective at inhibiting bicarbonate decomposition compared to octahedral structures (MIL-101)","metricCount":"3"},{"paperId":"P126","catalystId":"P126_PERF_002","name":"Pd1Ni2/200-8-1.5","matchedCharacterization":"Pd-Ni/MIL-88 (Pd1Ni2/200-8-1.5)","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Pd-Ni alloy confirmed by HRTEM lattice fringes (d = 0.223 nm and 0.205 nm, between Pd(111) and Ni(111))","particleSize":"Highly dispersed fine particles","surfaceStates":"Electron transfer from Ni to Pd; binding energies of Pd(0) and Pd(II) are lower than in Pd/MIL-88, while the Ni(0) peak is higher than nickel metal.","structureLink":"Pd-Ni alloying creates electron-rich Pd active sites that facilitate C-H bond activation in the Pd-formate intermediate, resulting in a TOF of 863.6 h-1 and lower activation energy (42.47 kJ/mol).","reactionConditions":"Potassium formate hydrolysis in a round-bottom three-necked flask with magnetic stirring (400 rpm) under N2 flow (10 mL min-1).","selectivity":"lower CO2-to-H2 ratio in comparison to Pd/200-8-1.5","whyPerformsWell":"Pd-Ni alloying effect leads to electron transfer from Ni to Pd; electron-rich Pd surface facilitates activation of the C-H bond in the Pd-formate intermediate","metricCount":"3"},{"paperId":"P127","catalystId":"P127_PERF_001","name":"Ag3Pd12/MOF-5-C-900","support":"MOF-5 derived porous carbon (MOF-5-C)","matchedSynthesis":"Ag3Pd12/MOF-5-C-900","matchedCharacterization":"Ag3Pd12/MOF-5-C-900","role":"active catalyst","composition":"Ag:Pd = 1:4 (mass ratio)","activeMetals":"Ag-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"MOF-5 was carbonized to create the support, then impregnated with Ag and Pd salts, followed by NaBH4 reduction.","phase":"Co-existence of AgPd bimetallic alloy, Ag0, and Pd0; HRTEM lattice spacings (0.22, 0.23, 0.24 nm) and XRD patterns confirm the presence of fcc Pd(111), AgPd alloy(111), and Ag(111). UV-Vis DRS shows a red-shift of the Ag surface plasmon absorption peak from 406 nm to 414 nm, confirming alloy formation.","particleSize":"approximately 4 nm","surfaceStates":"Metallic Pd0 and Ag0","structureLink":"Enhanced catalytic performance is attributed to the special composition (Pd0, Ag0, and AgPd alloy), small particle size, and high dispersion on the MOF-5-C support.","reactionConditions":"Dehydrogenation of formic acid (FA) in FA/SF solution at ambient conditions.","selectivity":"100% H2 selectivity; no CO detected","stability":"Catalysts are not deactivated (surge of hydrogen gas production observed after further addition of FA after 20 min)","whyPerformsWell":"Special composition (Pd0, Ag0 and AgPd alloy), small particle size (~4 nm) and well dispersion of nanoparticles on the MOF-5-C support.","metricCount":"3"},{"paperId":"P127","catalystId":"P127_PERF_002","name":"Pd15/MOF-5-C-900","support":"MOF-5 derived porous carbon (MOF-5-C)","matchedSynthesis":"Pd15/MOF-5-C-900","role":"active catalyst","composition":"Ag:Pd = 0:5 (mass ratio)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Ag3Pd12/MOF-5-C-900 but with only Pd precursor.","reactionConditions":"Dehydrogenation of FA in FA/SF solution at 30 °C.","metricCount":"1"},{"paperId":"P127","catalystId":"P127_PERF_003","name":"physical mixture of Ag15/MOF-5-C-900 and Pd15/MOF-5-C-900 (m ratio 1:4)","support":"MOF-5 derived porous carbon (MOF-5-C)","matchedSynthesis":"Pd15/MOF-5-C-900","role":"active catalyst","composition":"Ag:Pd = 0:5 (mass ratio)","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Same procedure as Ag3Pd12/MOF-5-C-900 but with only Pd precursor.","reactionConditions":"Dehydrogenation of FA in FA/SF solution at 30 °C.","metricCount":"1"},{"paperId":"P127","catalystId":"P127_PERF_004","name":"Ag3/Pd12/MOF-5-C-900","support":"MOF-5 derived porous carbon (MOF-5-C)","matchedSynthesis":"Ag3Pd12/MOF-5-C-900","matchedCharacterization":"Ag3Pd12/MOF-5-C-900","role":"active catalyst","composition":"Ag:Pd = 1:4 (mass ratio)","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"MOF-5 was carbonized to create the support, then impregnated with Ag and Pd salts, followed by NaBH4 reduction.","phase":"Co-existence of AgPd bimetallic alloy, Ag0, and Pd0; HRTEM lattice spacings (0.22, 0.23, 0.24 nm) and XRD patterns confirm the presence of fcc Pd(111), AgPd alloy(111), and Ag(111). UV-Vis DRS shows a red-shift of the Ag surface plasmon absorption peak from 406 nm to 414 nm, confirming alloy formation.","particleSize":"approximately 4 nm","surfaceStates":"Metallic Pd0 and Ag0","structureLink":"Enhanced catalytic performance is attributed to the special composition (Pd0, Ag0, and AgPd alloy), small particle size, and high dispersion on the MOF-5-C support.","reactionConditions":"Dehydrogenation of FA in FA/SF solution at 30 °C.","metricCount":"1"},{"paperId":"P127","catalystId":"P127_PERF_005","name":"Ag3Pd12/XC-72","support":"Vulcan XC-72 Carbon","matchedSynthesis":"Ag3Pd12/XC-72","role":"active catalyst","composition":"Ag:Pd = 1:4 (mass ratio)","activeMetals":"Ag-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Same procedure as Ag3Pd12/MOF-5-C-900 but using Vulcan XC-72 Carbon support.","reactionConditions":"Dehydrogenation of FA in FA/SF solution at 30 °C.","metricCount":"1"},{"paperId":"P127","catalystId":"P127_PERF_006","name":"Ag3Pd12/MOF-5","support":"MOF-5 derived porous carbon (MOF-5-C)","matchedSynthesis":"Ag3Pd12/MOF-5-C-900","matchedCharacterization":"Ag3Pd12/MOF-5-C-900","role":"active catalyst","composition":"Ag:Pd = 1:4 (mass ratio)","activeMetals":"Ag-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"MOF-5 was carbonized to create the support, then impregnated with Ag and Pd salts, followed by NaBH4 reduction.","phase":"Co-existence of AgPd bimetallic alloy, Ag0, and Pd0; HRTEM lattice spacings (0.22, 0.23, 0.24 nm) and XRD patterns confirm the presence of fcc Pd(111), AgPd alloy(111), and Ag(111). UV-Vis DRS shows a red-shift of the Ag surface plasmon absorption peak from 406 nm to 414 nm, confirming alloy formation.","particleSize":"approximately 4 nm","surfaceStates":"Metallic Pd0 and Ag0","structureLink":"Enhanced catalytic performance is attributed to the special composition (Pd0, Ag0, and AgPd alloy), small particle size, and high dispersion on the MOF-5-C support.","reactionConditions":"Dehydrogenation of FA in FA/SF solution at 30 °C.","deactivation":"Low activity ascribed to moisture sensitivity of MOF-5 material; crystal structure can decompose in moist atmosphere/FA-SF solution.","metricCount":"1"},{"paperId":"P127","catalystId":"P127_PERF_007","name":"Ag15/MOF-5-C-900","support":"MOF-5 derived porous carbon (MOF-5-C)","matchedSynthesis":"Ag15/MOF-5-C-900","role":"active catalyst","composition":"Ag:Pd = 5:0 (mass ratio)","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Same procedure as Ag3Pd12/MOF-5-C-900 but with only Ag precursor.","reactionConditions":"Dehydrogenation of FA in FA/SF solution at 30 °C.","whyPerformsWell":"cannot catalyze the reaction","metricCount":"0"},{"paperId":"P127","catalystId":"P127_PERF_008","name":"AgPd alloy (m Ag:mPd = 1:4)","activeMetals":"Ag-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA in FA/SF solution at 30 °C.","whyPerformsWell":"single AgPd alloy only has low catalytic activity","metricCount":"0"},{"paperId":"P128","catalystId":"P128_PERF_001","name":"Pt/AC","support":"activated carbon","matchedSynthesis":"Pt/AC","matchedCharacterization":"Pt/AC","role":"comparison catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"H2PtCl6 solution was added dropwise to activated carbon, dried in an oven and then in a flow reactor, followed by heating under nitrogen flow to 500 °C.","phase":"Platinum metal","particleSize":"dXRD: 2.66 nm; dTEM: 5.00 nm","surfaceStates":"Active Pt surface area of 14.6 m2/g-Pt; metal accessibility of 26.1%.","structureLink":"Lower activity compared to Pt@C catalysts due to larger particle size and nonuniform dispersion; hydrogen adsorption on the Pt surface may inhibit reaction.","reactionConditions":"80 °C, aqueous formic acid solution, batch reactor, ambient atmosphere, 300 rpm stirring, N2 purge at 50 mL/min","stability":"activity decreased in reusability tests","deactivation":"Pt particle size increased slightly after reaction; hydrogen adsorption may inhibit the reaction particularly at the initial stage","metricCount":"2"},{"paperId":"P128","catalystId":"P128_PERF_002","name":"Pt@C 500 °C","support":"carbon derived from WA-30 resin","matchedSynthesis":"Pt@C","matchedCharacterization":"Pt@C500°C","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"ion-exchange resin method","synthesis":"WA-30 resin was dispersed in HCl; H2PtCl6 solution was added dropwise and stirred for 24 h at room temperature. The resulting Pt@WA-30 was filtered, air dried, and then carbonized in a nitrogen stream.","phase":"Platinum metal","particleSize":"dXRD: 1.76 nm; dTEM: 2.91 nm","surfaceStates":"Active Pt surface area of 26.3 m2/g-Pt; metal accessibility of 27.3%.","structureLink":"High activity attributed to small particle size and uniform dispersion achieved via the ion-exchange resin method.","reactionConditions":"80 °C, aqueous formic acid solution, batch reactor, ambient atmosphere, 300 rpm stirring, N2 purge at 50 mL/min","selectivity":"hydrogen selectivity above 99.99% (CO and methane < 0.5 ppm)","stability":"activity per exposed Pt surface area remained almost unchanged between first and second runs","deactivation":"decrease in hydrogen production rate during initial 150 min ascribed to gaseous products stuck inside the pores of the carbon support","whyPerformsWell":"uniform dispersion of small Pt particles; high metal loading (26-28 wt%) achieved via ion-exchange resin method","metricCount":"2"},{"paperId":"P128","catalystId":"P128_PERF_003","name":"Pt@C 700 °C","support":"carbon derived from WA-30 resin","matchedSynthesis":"Pt@C","matchedCharacterization":"Pt@C700°C","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"ion-exchange resin method","synthesis":"WA-30 resin was dispersed in HCl; H2PtCl6 solution was added dropwise and stirred for 24 h at room temperature. The resulting Pt@WA-30 was filtered, air dried, and then carbonized in a nitrogen stream.","phase":"Platinum metal","particleSize":"dXRD: 1.69 nm; dTEM: 2.61 nm","surfaceStates":"Active Pt surface area of 20.6 m2/g-Pt; metal accessibility of 19.2%.","structureLink":"High activity due to small particle size and uniform dispersion; exhibits good durability over 24 h.","reactionConditions":"80 °C, aqueous formic acid solution, batch reactor, ambient atmosphere, 300 rpm stirring, N2 purge at 50 mL/min","selectivity":"hydrogen selectivity above 99.99% (CO and methane < 0.5 ppm)","stability":"activity per exposed Pt surface area remained stable after 150 min in a 24 h continuous reaction test; activity unchanged between first and second runs","deactivation":"initial decrease in hydrogen production rate during first 150 min attributed to product retention in micropores; deactivation less pronounced at higher FA concentrations (e.g., 100 wt%)","whyPerformsWell":"uniform dispersion of small Pt particles; high metal loading achieved via ion-exchange resin method","metricCount":"2"},{"paperId":"P128","catalystId":"P128_PERF_004","name":"Pt@C 900 °C","support":"carbon derived from WA-30 resin","matchedSynthesis":"Pt@C","matchedCharacterization":"Pt@C900°C","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"ion-exchange resin method","synthesis":"WA-30 resin was dispersed in HCl; H2PtCl6 solution was added dropwise and stirred for 24 h at room temperature. The resulting Pt@WA-30 was filtered, air dried, and then carbonized in a nitrogen stream.","phase":"Platinum metal","particleSize":"dXRD: 2.62 nm; dTEM: 3.24 nm","surfaceStates":"Active Pt surface area of 5.90 m2/g-Pt; metal accessibility of 6.83%.","structureLink":"Lowest activity among Pt@C catalysts due to increased particle size and decreased metal accessibility (platinum particles become more embedded in the carbon support at higher carbonization temperatures).","reactionConditions":"80 °C, aqueous formic acid solution, batch reactor, ambient atmosphere, 300 rpm stirring, N2 purge at 50 mL/min","selectivity":"hydrogen selectivity above 99.99% (CO and methane < 0.5 ppm)","stability":"activity per exposed Pt surface area remained almost unchanged between first and second runs","whyPerformsWell":"uniform dispersion of small Pt particles; high metal loading achieved via ion-exchange resin method","metricCount":"2"},{"paperId":"P129","catalystId":"P129_PERF_001","name":"NP","support":"activated carbon","matchedSynthesis":"NP","matchedCharacterization":"NP","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"Colloidal Pd nanoparticles were synthesized via polyol method using PVP and ethylene glycol, purified with acetone, redispersed in methanol, and then adsorbed onto activated carbon.","phase":"FCC Pd, [111]/[200] ratio = 21.9","particleSize":"3.4 ± 0.9 nm","surfaceStates":"Pd0 and Pd2+","structureLink":"Moderate catalytic performance; part of a volcano-type relationship with particle size.","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","selectivity":"CO was not detected","whyPerformsWell":"Volcano-type dependence on Pd particle size.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_002","name":"AR","support":"activated carbon","matchedSynthesis":"AR","matchedCharacterization":"AR","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Metal precursor was adsorbed onto activated carbon suspended in deionized water, followed by hydrogen reduction.","phase":"FCC Pd, [111]/[200] ratio = 2.9","particleSize":"9.4 ± 1.4 nm","surfaceStates":"Pd0 and Pd2+","structureLink":"Poor activity attributed to larger particle size.","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","selectivity":"CO was not detected","whyPerformsWell":"Poor activity compared to ADR due to larger particle size.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_003","name":"ADR","support":"activated carbon","matchedSynthesis":"ADR","matchedCharacterization":"ADR","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Pd precursor was adsorbed on activated carbon, heated to 393 K, treated with NaOH to form Pd(OH)2, and then reduced with H2.","phase":"FCC Pd, [111]/[200] ratio = 12.9","particleSize":"4.4 ± 0.7 nm","surfaceStates":"Pd0, Pd2+, and PdO species","structureLink":"Activity improved over AR due to smaller particle size.","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","selectivity":"CO was not detected","whyPerformsWell":"Formation of smaller Pd nanoparticles via NaOH addition.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_004","name":"IR","support":"activated carbon","matchedSynthesis":"IR","matchedCharacterization":"IR","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Activated carbon was suspended in sodium carbonate solution, mixed with Pd precursor, and reduced with H2.","phase":"FCC Pd, [111]/[200] ratio = 4.4","surfaceStates":"Pd0 and Pd2+","structureLink":"Best performance (TOF = 87 h-1); attributed to higher [200] phase content.","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","selectivity":"CO was not detected","whyPerformsWell":"Higher Pd [200] phase content and optimal particle size.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_005","name":"IDR","support":"activated carbon","matchedSynthesis":"IDR","matchedCharacterization":"IDR","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar to IR, but included a deposition step using NaOH to adjust pH to 12 before H2 reduction.","phase":"FCC Pd, [111]/[200] ratio = 9.7","surfaceStates":"Pd0, Pd2+, and PdO species","structureLink":"Lower activity than IR; attributed to higher [111]/[200] ratio.","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","selectivity":"CO was not detected","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_006","name":"SR","support":"activated carbon","matchedSynthesis":"SR","matchedCharacterization":"SR","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"sol_immobilization","synthesis":"In-situ colloidal Pd sols were formed by adding Na2CO3 to the metal precursor, adsorbed on activated carbon, and reduced with H2.","phase":"FCC Pd, [111]/[200] ratio = 13.4","surfaceStates":"Pd0 and Pd2+","structureLink":"Higher activity than SDR; attributed to higher [200] phase content.","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","selectivity":"CO was not detected","whyPerformsWell":"Higher Pd [200] phase content.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_007","name":"SDR","support":"activated carbon","matchedSynthesis":"SDR","matchedCharacterization":"SDR","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Similar to SR, but pH was adjusted to 12 using NaOH after impregnation and before H2 reduction.","phase":"FCC Pd, [111]/[200] ratio = 43.9","surfaceStates":"Pd0, Pd2+, and PdO species","structureLink":"Lower activity than SR; attributed to higher [111]/[200] ratio.","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","selectivity":"CO was not detected","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_008","name":"Pd2+/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","whyPerformsWell":"Pd2+ ion is ineffective in liquid-phase reaction.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_009","name":"Pd(OH)2/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","stability":"total evolved gas volume was considerably smaller than that of Pd0/C","whyPerformsWell":"Oxidized Pd(OH)2 species may act as Lewis acid sites for formate ion adsorption.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_010","name":"Pd/C (untreated support)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","whyPerformsWell":"pH of reaction medium (8.3) is basic, leading to competitive adsorption between formate and hydroxyl ions.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_011","name":"Pd/C (1 wt% HNO3 treated support)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","stability":"catalytic activity was maintained without any apparent loss of activity after the third recycle run","deactivation":"activity can be almost fully recovered by drying at an elevated temperature (383 K)","whyPerformsWell":"Reaction medium pH (5.6) is closer to neutral, minimizing competitive adsorption and proton-induced recombination.","metricCount":"2"},{"paperId":"P129","catalystId":"P129_PERF_012","name":"Pd/C (10 wt% HNO3 treated support)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","whyPerformsWell":"Low pH (3.2) promotes recombination of formate ion with a proton and/or retards deprotonation.","metricCount":"1"},{"paperId":"P129","catalystId":"P129_PERF_013","name":"Pd/C (10 wt% HNO3 + 10 wt% H2O2 treated support)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"323 K, 15 ml water, 5 ml formic acid, Pd:FA molar ratio = 0.004, Ar atmosphere, vigorous stirring","metricCount":"1"},{"paperId":"P130","catalystId":"P130_PERF_001","name":"Pd/NMC1","support":"nitrogen-doped mesoporous carbon (NMC1)","matchedSynthesis":"Pd/NMC1","matchedCharacterization":"Pd/NMC1","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"4.2 nm (TEM), 4.8 nm (CO chemisorption)","surfaceStates":"Pd0: 52.4%, Pd2+: 47.6%; highest binding energy for both species compared to N-doped samples.","structureLink":"Largest particle size and lack of nitrogen dopant result in the lowest catalytic activity and highest activation energy.","reactionConditions":"0.03g catalyst, 9mL of 2M FA solution, semi-batch reaction system in a water bath","selectivity":"No CO detected","metricCount":"1"},{"paperId":"P130","catalystId":"P130_PERF_002","name":"Pd/NMC2","support":"nitrogen-doped mesoporous carbon (NMC2)","matchedSynthesis":"Pd/NMC2","matchedCharacterization":"Pd/NMC2","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"3.8 nm (TEM), 4.1 nm (CO chemisorption)","surfaceStates":"Pd0: 45.2%, Pd2+: 54.8%; binding energy shifted lower by 0.11-0.18 eV relative to Pd/NMC1 due to electron transfer from N dopants.","structureLink":"Low TOF attributed to difficulty in C-H bond cleavage and high activation barrier despite some nitrogen doping.","reactionConditions":"0.03g catalyst, 9mL of 2M FA solution, semi-batch reaction system in a water bath","selectivity":"No CO detected","metricCount":"1"},{"paperId":"P130","catalystId":"P130_PERF_003","name":"Pd/NMC3","support":"nitrogen-doped mesoporous carbon (NMC3)","matchedSynthesis":"Pd/NMC3","matchedCharacterization":"Pd/NMC3","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"3.3 nm (TEM), 3.3 nm (CO chemisorption)","surfaceStates":"Pd0: 40.9%, Pd2+: 59.1%; binding energy shifted lower relative to Pd/NMC1.","structureLink":"Optimum nitrogen doping and small particle size result in the lowest activation barrier for hydrogen desorption, enhancing activity.","reactionConditions":"0.03g catalyst, 9mL of 2M FA solution, semi-batch reaction system in a water bath","selectivity":"No CO detected","whyPerformsWell":"Optimum nitrogen doping reduces the activation barrier of hydrogen desorption; electronic modification via electron transfer from pyridinic-N to Pd.","metricCount":"4"},{"paperId":"P130","catalystId":"P130_PERF_004","name":"Pd/NMC4","support":"nitrogen-doped mesoporous carbon (NMC4)","matchedSynthesis":"Pd/NMC4","matchedCharacterization":"Pd/NMC4","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"3.6 nm (TEM), 3.7 nm (CO chemisorption)","surfaceStates":"Pd0: 43.9%, Pd2+: 56.1%; binding energy shifted lower relative to Pd/NMC1.","structureLink":"Lower activation energy than Pd/NMC2 attributed to higher nitrogen content despite similar particle size.","reactionConditions":"0.03g catalyst, 9mL of 2M FA solution, semi-batch reaction system in a water bath","selectivity":"No CO detected","metricCount":"1"},{"paperId":"P130","catalystId":"P130_PERF_005","name":"Pd/NMC5","support":"nitrogen-doped mesoporous carbon (NMC5)","matchedSynthesis":"Pd/NMC5","matchedCharacterization":"Pd/NMC5","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","phase":"Metallic Pd","particleSize":"2.9 nm (TEM), 2.9 nm (CO chemisorption)","surfaceStates":"Pd0: 28.7%, Pd2+: 71.3%; binding energy shifted lower relative to Pd/NMC1; highest proportion of Pd2+ correlated with smallest particle size.","structureLink":"Excessive nitrogen interaction raises the activation barrier for hydrogen desorption, offsetting the benefit of the smallest particle size.","reactionConditions":"0.03g catalyst, 9mL of 2M FA solution, semi-batch reaction system in a water bath","selectivity":"No CO detected","whyPerformsWell":"Small Pd size due to nitrogen dopant; however, excessive interaction between N and Pd can raise the activation barrier.","metricCount":"1"},{"paperId":"P131","catalystId":"P131_PERF_001","name":"30 sc% Pd-on-Au/C","support":"activated carbon (Darco-G60)","matchedSynthesis":"30 sc% Pd-on-Au/C","matchedCharacterization":"30 sc% Pd-on-Au/C","role":"catalyst","composition":"Pd: 1 wt%, Au: 13.5 wt%","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"adsorption_or_loading","synthesis":"Pd-on-Au nanoparticles were synthesized via previously reported protocols and then immobilized onto activated carbon.","phase":"Core-shell (Au core, Pd shell)","surfaceStates":"Small Pd ensembles","structureLink":"Low activity due to linear binding of formate on small Pd ensembles favoring dehydration and CO poisoning.","reactionConditions":"23 °C, 1 M formic acid, semi-batch reactor, 1200 rpm stirring","selectivity":"CO:CO2 molar ratio = 1.03 x 10^-2 after 20 min reaction time; generated the most CO (~8 ppm)","stability":"deactivated","deactivation":"in situ CO poisoning of the Pd atoms","whyPerformsWell":"Low activity due to isolated metallic Pd atoms favoring linear binding and dehydration pathway leading to CO formation","metricCount":"3"},{"paperId":"P131","catalystId":"P131_PERF_002","name":"60 sc% Pd-on-Au/C","support":"activated carbon (Darco-G60)","matchedSynthesis":"60 sc% Pd-on-Au/C","matchedCharacterization":"60 sc% Pd-on-Au/C","role":"catalyst","composition":"Pd: 1 wt%, Au: 6.8 wt%","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"adsorption_or_loading","synthesis":"Pd-on-Au nanoparticles were synthesized via previously reported protocols and then immobilized onto activated carbon.","phase":"Core-shell (Au core, Pd shell)","surfaceStates":"Partially oxidized","structureLink":"Low activity; small Pd ensembles favor dehydration pathway.","reactionConditions":"23 °C, 1 M formic acid, semi-batch reactor, 1200 rpm stirring","selectivity":"CO:CO2 molar ratio = 3.01 x 10^-4 after 20 min reaction time; generated ~5 ppm CO","stability":"deactivated","deactivation":"correlated to the dehydration pathway (due to CO formation)","metricCount":"3"},{"paperId":"P131","catalystId":"P131_PERF_003","name":"150 sc% Pd-on-Au/C","support":"activated carbon (Darco-G60)","matchedSynthesis":"150 sc% Pd-on-Au/C","matchedCharacterization":"150 sc% Pd-on-Au/C","role":"catalyst","composition":"Pd: 1 wt%, Au: 2.5 wt%","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"adsorption_or_loading","synthesis":"Pd-on-Au nanoparticles were synthesized via previously reported protocols and then immobilized onto activated carbon.","phase":"Core-shell (Au core, Pd shell)","surfaceStates":"Partially oxidized ex situ; reduced in situ","structureLink":"Moderate activity; increased ensemble size reduces CO formation.","reactionConditions":"23 °C, 1 M formic acid, semi-batch reactor, 1200 rpm stirring","selectivity":"CO:CO2 molar ratio = 6.86 x 10^-6 after 20 min reaction time; generated ~1 ppm CO","stability":"deactivated","deactivation":"correlated to the dehydration pathway (due to CO formation)","metricCount":"3"},{"paperId":"P131","catalystId":"P131_PERF_004","name":"300 sc% Pd-on-Au/C","support":"activated carbon (Darco-G60)","matchedSynthesis":"300 sc% Pd-on-Au/C","matchedCharacterization":"300 sc% Pd-on-Au/C","role":"catalyst","composition":"Pd: 1 wt%, Au: 1.4 wt%","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"adsorption_or_loading","synthesis":"Pd-on-Au nanoparticles were synthesized via previously reported protocols and then immobilized onto activated carbon.","phase":"Core-shell (Au core, Pd shell)","surfaceStates":"Partially oxidized ex situ; reduced in situ","structureLink":"Highest activity and selectivity for dehydrogenation due to large Pd ensembles favoring bridging binding of formate.","reactionConditions":"23 °C, 1 M formic acid, semi-batch reactor, 1200 rpm stirring","selectivity":"CO:CO2 molar ratio = 0 after 20 min reaction time; no detectable amount of CO","stability":"no apparent deactivation after 3 h","whyPerformsWell":"Large 3-D Pd ensembles favor bridging binding conformation for dehydrogenation pathway; electronic effect of Au stabilizes Pd from oxidation","metricCount":"3"},{"paperId":"P131","catalystId":"P131_PERF_005","name":"Pd/C","support":"activated carbon (Darco-G60)","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"control catalyst","composition":"Pd: 1 wt%","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"Pd nanoparticles were immobilized onto activated carbon.","phase":"Monometallic Pd nanoparticles","particleSize":"2-3 nm (in situ); 3-4 nm (after H2 treatment at 200 °C)","surfaceStates":"Partially oxidized ex situ; reduced in situ","structureLink":"Slightly active; prone to CO formation and deactivation.","reactionConditions":"23 °C, 1 M formic acid, semi-batch reactor, 1200 rpm stirring","selectivity":"CO:CO2 molar ratio = 3.70 x 10^-6 after 20 min reaction time; reached ~1 ppm CO after 3 h","metricCount":"3"},{"paperId":"P131","catalystId":"P131_PERF_006","name":"Au/C","support":"activated carbon (Darco-G60)","matchedSynthesis":"Au/C","matchedCharacterization":"Au/C","role":"control catalyst","composition":"Au: 1 wt%","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"Au nanoparticles were immobilized onto activated carbon.","phase":"Monometallic Au nanoparticles","particleSize":"~4.3 nm","surfaceStates":"Metallic","structureLink":"Inactive for formic acid decomposition.","reactionConditions":"23 °C, 1 M formic acid, semi-batch reactor, 1200 rpm stirring","selectivity":"no gas formation observed after 3 h; did not generate any CO","whyPerformsWell":"inactive","metricCount":"0"},{"paperId":"P132","catalystId":"P132_PERF_001","name":"Pd/NCZIF-8-25","support":"NCZIF-8","matchedSynthesis":"Pd/NCZIF-8","matchedCharacterization":"Pd/NCZIF-8","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"ZIF-L was synthesized using Zn(NO3)2, 2-dimethylimidazole, and CTAB; ZIF-L underwent phase transition to ZIF-8 at 70 °C in DMF/ethanol for 48 h; ZIF-8 was calcined at 900 °C in N2 for 2 h to form NCZIF-8; Pd was deposited via impregnation of H2PdCl4 followed by NaBH4 reduction.","phase":"HRTEM identified an interplanar spacing of 0.224 nm, corresponding to the Pd(111) facet.","particleSize":"Average Pd NP size varied with CTAB dosage: 2.85 nm (0 mg), 1.84 nm (25 mg), and 2.32 nm (35 mg).","surfaceStates":"XPS showed electron-rich Pd NPs with binding energy shifting from 335.46 to 334.81 eV as CTAB increased. Surface contains pyridinic N (enriched by CTAB), pyrrolic N, graphitic N, and hydrophilic oxygen-containing groups (carboxyl and hydroxyl).","structureLink":"The combination of ultrafine Pd NPs (minimized in Pd/NCZIF-8-25), high hydrophilicity (contact angle reduced to 15.7° for Pd/NCZIF-8-25), and a hierarchical pore structure significantly enhanced the TOF (1925 h-1) by improving mass transfer and metal-support interaction.","reactionConditions":"Ambient temperature (30 °C), 1 M FA/SF solution in water, 40 mg catalyst","selectivity":"almost no CO release","stability":"no remarkable reduction of the catalyst activity in three consecutive cycles","whyPerformsWell":"Notable hydrophilicity and ultrafine Pd nanoparticles; high content of pyridinic N and carbon defects enhance metal-support interaction and dispersion; FA-H2O hydrogen-bonding network facilitates proton shuttling via the Grotthuss mechanism.","metricCount":"4"},{"paperId":"P132","catalystId":"P132_PERF_002","name":"Pd/NCZIF-8-35","support":"NCZIF-8","matchedSynthesis":"Pd/NCZIF-8","matchedCharacterization":"Pd/NCZIF-8","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"ZIF-L was synthesized using Zn(NO3)2, 2-dimethylimidazole, and CTAB; ZIF-L underwent phase transition to ZIF-8 at 70 °C in DMF/ethanol for 48 h; ZIF-8 was calcined at 900 °C in N2 for 2 h to form NCZIF-8; Pd was deposited via impregnation of H2PdCl4 followed by NaBH4 reduction.","phase":"HRTEM identified an interplanar spacing of 0.224 nm, corresponding to the Pd(111) facet.","particleSize":"Average Pd NP size varied with CTAB dosage: 2.85 nm (0 mg), 1.84 nm (25 mg), and 2.32 nm (35 mg).","surfaceStates":"XPS showed electron-rich Pd NPs with binding energy shifting from 335.46 to 334.81 eV as CTAB increased. Surface contains pyridinic N (enriched by CTAB), pyrrolic N, graphitic N, and hydrophilic oxygen-containing groups (carboxyl and hydroxyl).","structureLink":"The combination of ultrafine Pd NPs (minimized in Pd/NCZIF-8-25), high hydrophilicity (contact angle reduced to 15.7° for Pd/NCZIF-8-25), and a hierarchical pore structure significantly enhanced the TOF (1925 h-1) by improving mass transfer and metal-support interaction.","reactionConditions":"Ambient temperature (30 °C), 1 M FA/SF solution in water, 40 mg catalyst","selectivity":"almost no CO release","whyPerformsWell":"Highest surface unit efficiency due to superior hydrophilicity.","metricCount":"1"},{"paperId":"P133","catalystId":"P133_PERF_001","name":"Pd0.8Ag0.2/NH2-MIL-101(Cr)","support":"NH2-MIL-101(Cr)","matchedSynthesis":"Pd0.8Ag0.2/NH2-MIL-101(Cr)","matchedCharacterization":"Pd0.8Ag0.2/NH2-MIL-101(Cr)","role":"catalyst","composition":"Pd:Ag = 0.8:0.2 (nominal); Pd:Ag = 0.78:0.22 (actual)","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"NH2-MIL-101(Cr) was dispersed in water and sonicated; an aqueous solution of Pd and Ag precursors was added and stirred, followed by reduction with NaBH4, centrifugation, and vacuum drying.","phase":"Alloy; HRTEM shows a lattice spacing of 2.3 Å, which differs from pure Pd (2.25 Å) and Ag (2.35 Å), indicating lattice contraction induced by alloying.","particleSize":"2.2 nm","surfaceStates":"Electron-rich PdAg catalytic sites formed via electron transfer from the amine groups of the support, evidenced by negatively shifted binding energies in XPS compared to Pd0.8Ag0.2/MIL-101.","structureLink":"Excellent kinetics are attributed to ultrafine size and high dispersion of PdAg NPs, synergistic electronic effects between Pd and Ag (modulating atomic coordination and local strain), and the presence of amine groups acting as Brønsted basic sites to facilitate O-H bond dissociation of formic acid.","reactionConditions":"Formic acid/sodium formate (FA/SF) solution, n(Pd+Ag)/n(FA) = 0.0083","selectivity":"100% H2 selectivity","stability":"almost maintain its kinetics activity after fifth runs","deactivation":"no apparent aggregation was observed","whyPerformsWell":"ultrafine size and high dispersion of PdAg NPs; amine group from NH2-MIL-101(Cr) support facilitates OAH bond dissociation and acts as Bronsted basic sites to facilitate cleavage of CAH bond; electron synergetic effect between Pd and Ag","metricCount":"6"},{"paperId":"P134","catalystId":"P134_PERF_001","name":"Pd@CN","support":"Nitrogen-doped carbon (CN)","matchedSynthesis":"Pd@CN","matchedCharacterization":"Pd@CN","role":"target catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"TAT monomer was polymerized to PTAT. Pd NPs were formed by reducing Pd(OAc)2 in diethylene glycol at 130 °C in the presence of PTAT for adsorption (forming Pd/PTAT). The resulting complex was pyrolyzed at 450 °C under N2 to produce Pd@CN.","phase":"Face centered cubic crystal phases of Pd NPs ((111), (200), and (220)); HR-TEM confirms (111) lattice spacing of 0.212 nm for Pd0","particleSize":"6–8 nm","surfaceStates":"Negatively charged Pd NPs induced by strong electronic coupling with pyridinic-N; XPS shows coexistence of Pd0 and Pd2+.","structureLink":"Superior activity is attributed to electronically modulated Pd NPs (via pyridinic-N), an accessible mesoporous structure, and an optimal particle size of 6–8 nm which improves reactant binding energy compared to smaller particles.","reactionConditions":"Formic acid dehydrogenation and alkene hydrogenation at 90 °C","selectivity":"Almost 100% selectivity toward H2 production in FA dehydrogenation (no CO detected); exclusively yielding phenylethane in styrene hydrogenation.","stability":"Conversion of styrene remained at 95% after 5 cycles; reused five runs without significant decrease of activity.","deactivation":"No obvious leaching of Pd species (recovered Pd content 2.36%, almost unchanged).","whyPerformsWell":"Prominent surface electronic modulation with pyridinic-N in CN, accessible mesoporous structure of CN support, and appropriate Pd particle size (6-8 nm).","metricCount":"3"},{"paperId":"P134","catalystId":"P134_PERF_002","name":"Pd/PTAT","matchedCharacterization":"Pd/PTAT","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","particleSize":"3–4 nm","surfaceStates":"Pd0 state (XPS binding energy peaks at 340.1 and 334.7 eV)","reactionConditions":"Formic acid dehydrogenation and alkene hydrogenation at 90 °C","selectivity":"100% selectivity in styrene hydrogenation.","stability":"Conversion of styrene decreased from 99% (first run) to 85% after 5 cycles.","metricCount":"3"},{"paperId":"P134","catalystId":"P134_PERF_003","name":"Pd/pre-CN","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation at 90 °C","metricCount":"1"},{"paperId":"P135","catalystId":"P135_PERF_001","name":"Pd/YSMSNs-NH2(10-3)","support":"yolk-shell mesoporous silica nanospheres (YSMSNs)","matchedSynthesis":"Pd/YSMSNs-NH2(10-3)","matchedCharacterization":"Pd/YSMSNs-NH2(10-3)","role":"optimized catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"YSMSNs were functionalized with APTES in anhydrous toluene at 80 °C for 24 h, then Pd was immobilized via ultrasonic treatment and reduction using NaBH4 in deionized water.","phase":"Face-centered cubic (fcc) Pd (111) plane","particleSize":"1.5 nm (average); increased to 2.2 nm after recovery","surfaceStates":"Electron-rich surface on Pd NPs due to metal-support interaction (MSI) where YSMSNs-NH2 acts as an electron donor. XPS peaks for Pd0 shifted to lower binding energies: 335.7 eV (Pd0 3d5/2) and 340.9 eV (Pd0 3d3/2).","structureLink":"The combination of ultrafine Pd NPs, high dispersion, electron-rich surface via MSI, and radially oriented mesoporous channels for rapid mass transfer enhances FA dehydrogenation activity. Amine groups act as Brønsted basic sites promoting O-H bond cleavage.","reactionConditions":"Two-necked round-bottom flask (20 mL), catalyst dissolved in 3 mL deionized water, FA:SF mixed solution (2 mL) added, vigorous stirring.","selectivity":"100% H2 selectivity; no detectable formation of CO","stability":"Remarkable stability throughout six successive runs at 323 K with no discernible alterations in initial TOF or total reaction duration.","deactivation":"Recovered catalyst showed increased particle size (1.5 nm to 2.2 nm) due to Pd NPs aggregation and partial reduction in grafted amine groups.","whyPerformsWell":"Radially oriented pore channels facilitate mass transfer; amine groups promote O-H bond cleavage as Brønsted basic sites; ultrafine Pd NP size and high dispersion provide wealth of active sites; metal-support interaction (MSI) creates electron-rich surface on Pd NPs.","metricCount":"8"},{"paperId":"P135","catalystId":"P135_PERF_002","name":"Pd/YSMSNs","support":"yolk-shell mesoporous silica nanospheres (YSMSNs)","matchedSynthesis":"Pd/YSMSNs-NH2(10-3)","matchedCharacterization":"Pd/YSMSNs","role":"optimized catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"YSMSNs were functionalized with APTES in anhydrous toluene at 80 °C for 24 h, then Pd was immobilized via ultrasonic treatment and reduction using NaBH4 in deionized water.","particleSize":"2.9 nm","surfaceStates":"Pd0 peaks located at 336.0 eV (Pd0 3d5/2) and 341.2 eV (Pd0 3d3/2).","structureLink":"Larger particle size and lack of MSI from amine groups result in nearly negligible catalytic activity.","reactionConditions":"Two-necked round-bottom flask (20 mL), catalyst dissolved in 3 mL deionized water, FA:SF mixed solution (2 mL) added, vigorous stirring.","whyPerformsWell":"Lacks surface amine groups which are necessary for O-H bond dissociation and stabilizing ultrafine Pd NPs.","metricCount":"3"},{"paperId":"P135","catalystId":"P135_PERF_003","name":"Pd/SBA-15-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Two-necked round-bottom flask (20 mL), catalyst dissolved in 3 mL deionized water, FA:SF mixed solution (2 mL) added, vigorous stirring.","whyPerformsWell":"Conventional porous structure leads to slower mass transfer compared to radial oriented pores of YSMSNs.","metricCount":"1"},{"paperId":"P136","catalystId":"P136_PERF_001","name":"Pd@PNCNCs-900","matchedCharacterization":"Pd@PNCNCs-900","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Metallic Pd phase; XRD peaks at 40.12°, 46.66°, and 68.12° correspond to (111), (200), and (220) planes of Pd (PDF no. 87-0641). HRTEM shows a lattice fringe of 0.222 nm corresponding to the Pd(111) crystal plane.","particleSize":"2.0 nm","surfaceStates":"XPS N 1s reveals pyridinic N, pyrrolic N, graphitic N, and oxidized N. Pyridinic N acts as an electron donor to the Pd NPs, creating electron-rich active sites. CO2-TPD confirms strong basic properties.","structureLink":"The high degree of graphitization and defects in PNCNCs-900 enhances electrical conductivity for FA adsorption and electron migration. Strong metal-support interaction (MSI) via electron transfer from pyridinic N to Pd creates electron-rich active sites. Bronsted basic N sites promote the cleavage of O-H bonds in formic acid molecules.","reactionConditions":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","deactivation":"Slight decline in activity attributed to the increase of Pd NP size from 2.0 nm to 2.9 nm after consecutive tests.","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","metricCount":"10"},{"paperId":"P136","catalystId":"P136_PERF_002","name":"Pd@PNCNCs-700","matchedCharacterization":"Pd@PNCNCs-700","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","particleSize":"2.4 nm","reactionConditions":"FA dehydrogenation, 60 °C, FA/SF ratio 1:2.","metricCount":"1"},{"paperId":"P136","catalystId":"P136_PERF_003","name":"Pd@PNCNCs-800","matchedCharacterization":"Pd@PNCNCs-800","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","particleSize":"2.2 nm","reactionConditions":"FA dehydrogenation, 60 °C, FA/SF ratio 1:2.","metricCount":"1"},{"paperId":"P136","catalystId":"P136_PERF_004","name":"Pd@PNCNCs-1000","matchedCharacterization":"Pd@PNCNCs-1000","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","particleSize":"2.3 nm","reactionConditions":"FA dehydrogenation, 60 °C, FA/SF ratio 1:2.","metricCount":"1"},{"paperId":"P137","catalystId":"P137_PERF_001","name":"Pd/OB-C1","support":"OB-C1","matchedSynthesis":"Pd/OB-C1","matchedCharacterization":"Pd/OB-C1","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"Support synthesized via one-step coannealing of XC-72R and boric acid at 800 °C; Pd immobilized by NaOH-assisted NaBH4 reduction.","phase":"Metallic Pd (JCPDS 46-1043)","particleSize":"~ 1.7 nm","surfaceStates":"Pd0 and Pd2+; binding energy shift observed compared to Pd/C due to charge transfer caused by B doping.","structureLink":"Strong interaction between B species and Pd NPs leads to small particle size and uniform dispersion, improving catalytic activity for FA dehydrogenation.","reactionConditions":"FA/SF system, nPd/nFA = 0.02, nFA:nSF = 1:2.5","whyPerformsWell":"positive effect of B-O functionality of the carbon nanosphere support","metricCount":"1"},{"paperId":"P137","catalystId":"P137_PERF_002","name":"Pd/C","support":"XC-72R","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"reference catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Immobilization of Pd nanoparticles on pristine XC-72R via wet chemical impregnation and NaBH4 reduction.","phase":"Metallic Pd (JCPDS 46-1043)","particleSize":"~ 3.1 nm","surfaceStates":"Pd0 (340.1 and 334.7 eV) and Pd2+ (342.2 and 336.5 eV)","reactionConditions":"FA/SF system, nPd/nFA = 0.02, nFA:nSF = 1:2.5","metricCount":"1"},{"paperId":"P137","catalystId":"P137_PERF_003","name":"Pd/OB-C-N1","support":"OB-C-N1","matchedSynthesis":"Pd/OB-C-N1","matchedCharacterization":"Pd/OB-C-N1","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"Support synthesized via coannealing of XC-72R, boric acid, and melamine at 800 °C; Pd immobilized by NaOH-assisted NaBH4 reduction.","phase":"Metallic Pd","particleSize":"~ 1.4 nm","surfaceStates":"Pd0 and Pd2+; presence of O-B-C (BCO2, BC2O) and N-C (pyridinic, pyrrolic, graphitic-N) species on support.","structureLink":"Ultrafine Pd particle size combined with high levels of B-O and N functionalities enhances activity; B-O species strengthen support-metal interaction while N dopants provide basic sites facilitating FA deprotonation.","reactionConditions":"FA/SF system, nPd/nFA = 0.02, nFA:nSF = 1:2.5","selectivity":"100% selectivity of H2 toward CO-free generation; no CO impurity detected (< 10 ppm)","stability":"no apparent loss in catalytic activity over 5 runs","whyPerformsWell":"high level of B-O and N doping and small Pd particle size (~1.4 nm); B-O species capture precursors and strengthen interaction; N dopants provide basic sites facilitating deprotonation of FA","metricCount":"4"},{"paperId":"P138","catalystId":"P138_PERF_001","name":"Au0.3Pd0.7/NH2–N-HMCS","support":"NH2–N-HMCS (amino and nitrogen functionalized mesoporous hollow carbon spheres)","matchedSynthesis":"Au0.3Pd0.7/NH2–N-HMCS","matchedCharacterization":"Au0.3Pd0.7/NH2–N-HMCS","role":"main catalyst","composition":"Au:Pd = 0.3:0.7 (molar ratio)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"HMCS was synthesized via a template method, oxidized using APS/H2SO4, and functionalized with APTMS. Au and Pd precursors were added to the support suspension, followed by liquid-phase reduction with NaBH4.","phase":"AuPd alloy (confirmed by XRD broad diffraction peak between Au and Pd peaks and HRTEM lattice spacing of 0.234 nm).","particleSize":"2.2 nm","surfaceStates":"Pd is in an electron depletion state caused by metal-support interactions (electron transfer to NH2–N-HMCS) and synergistic effects with Au.","structureLink":"The combination of hollow mesoporous structure, ultra-fine particle size, high dispersion, and the electron-depleted state of Pd accelerates C-H cleavage in adsorbed formate, leading to superior H2 evolution activity.","reactionConditions":"Formic acid dehydrogenation at 298 K under ambient atmosphere with magnetic stirring, without additives.","stability":"Slight decay in catalytic activity after four cycles.","deactivation":"Particle size increased from 2.2 to 2.7 nm after the 4th run.","whyPerformsWell":"Hollow mesoporous structure facilitates mass diffusion and enriches reactants; NH2-functionalized N-doped support immobilizes metal ions for ultra-fine particle sizes (2.2 nm) and high dispersion; amine groups act as proton scavengers to facilitate O-H bond cleavage; electron depletion state of Pd caused by metal-support interactions and Au-Pd synergistic effect accelerates C-H cleavage.","metricCount":"2"},{"paperId":"P138","catalystId":"P138_PERF_002","name":"Au xPd1/C0x/NH2–N-HMCS","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation at 298 K under ambient atmosphere with magnetic stirring, without additives.","whyPerformsWell":"Electron synergetic effect between Pd and Au; optimal molar ratio of Au to Pd (x=0.3) modulates the electronic structure of Pd.","metricCount":"1"},{"paperId":"P138","catalystId":"P138_PERF_003","name":"Au0.3Pd0.7/N-HMCS","support":"N-HMCS (nitrogen-doped hollow mesoporous carbon spheres)","matchedSynthesis":"Au0.3Pd0.7/N-HMCS","matchedCharacterization":"Au0.3Pd0.7/N-HMCS","role":"comparison catalyst","composition":"Au:Pd = 0.3:0.7 (molar ratio)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"N-HMCS support was prepared by hydrothermal treatment, then Au and Pd precursors were added followed by NaBH4 reduction.","phase":"Alloy","particleSize":"Contains a mixture of various large-sized nanoparticles","structureLink":"Lower activity compared to NH2-functionalized support due to larger particle sizes and lack of amino groups to facilitate FA adsorption/O-H cleavage.","reactionConditions":"Formic acid dehydrogenation at 298 K under ambient atmosphere with magnetic stirring, without additives.","whyPerformsWell":"Hollow morphology and interconnected mesopores facilitate mass diffusion; N-doped support helps form highly dispersed nanoparticles.","metricCount":"1"},{"paperId":"P138","catalystId":"P138_PERF_004","name":"Au0.3Pd0.7/HMCS","support":"HMCS (non-modified hollow mesoporous carbon spheres)","matchedSynthesis":"Au0.3Pd0.7/HMCS","matchedCharacterization":"Au0.3Pd0.7/HMCS","role":"comparison catalyst","composition":"Au:Pd = 0.3:0.7 (molar ratio)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Synthesized using a method similar to Au0.3Pd0.7/NH2–N-HMCS but without support functionalization.","structureLink":"Poor catalytic performance attributed to low metal dispersion.","reactionConditions":"Formic acid dehydrogenation at 298 K under ambient atmosphere with magnetic stirring, without additives.","whyPerformsWell":"Low activity due to lack of coordination sites on non-functionalized HMCS leading to low particle dispersity.","metricCount":"1"},{"paperId":"P138","catalystId":"P138_PERF_005","name":"unsupported Au0.3Pd0.7","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation at 298 K under ambient atmosphere with magnetic stirring, without additives.","whyPerformsWell":"Much lower catalytic activity compared to supported catalysts.","metricCount":"1"},{"paperId":"P139","catalystId":"P139_PERF_001","name":"Pd/TBT/rGO","support":"TBT/rGO","matchedSynthesis":"Pd/TBT/rGO","matchedCharacterization":"Pd/TBT/rGO","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"TBT/rGO was dispersed in DI water, H2PdCl4 was added and stirred for 3 h, pH adjusted to 11 with NaOH, then reduced using NaH2PO2 solution.","phase":"Metallic Pd on tetragonal-phase barium titanate (TBT) and reduced graphene oxide (rGO)","particleSize":"4.6 nm","surfaceStates":"Electron-rich Pd (Pd 3d binding energy shifted to 335.3 eV) due to metal-support interaction (MSI) where BaTiO3 acts as a strong electron donor.","structureLink":"Small particle size improves mass activity; electron-rich Pd facilitates C-H bond cleavage in HCOO*; internal electric field from TBT promotes hydrogen desorption on Pd(111); rGO enhances interfacial charge transport capacity.","reactionConditions":"1.1 M FA / 0.8 M SF, reaction temperature 303 K (default)","selectivity":"100% H2 selectivity; CO level below the limit of detection","stability":"Poor stability: total gas production in 60 min decreased from 93.5 to 18.5 mL over three cycles.","deactivation":"Mass loss (reduced from 50 to 25 mg after three tests), Pd nanoparticle agglomeration, and TBT completely separated from rGO.","whyPerformsWell":"Small-size Pd NPs; internal electric field from TBT promotes hydrogen desorption on Pd(111); electron-rich Pd facilitates C-H bond cleavage in HCOO*; rGO enhances interfacial charge transport capacity.","metricCount":"4"},{"paperId":"P139","catalystId":"P139_PERF_002","name":"Pd/rGO(3.6)","support":"rGO","matchedSynthesis":"Pd/rGO","matchedCharacterization":"Pd/rGO","role":"control catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared by the same method as Pd/TBT/rGO using rGO as support.","phase":"Metallic Pd on reduced graphene oxide (rGO)","particleSize":"35.8 nm","surfaceStates":"Electron-deficient compared to TBT-supported catalysts (Pd 3d binding energy of 335.8 eV).","structureLink":"Larger particle size and lack of internal electric field/electron-donating support lead to lower catalytic activity for FAD.","reactionConditions":"1.1 M FA / 0.8 M SF, reaction temperature 303 K","metricCount":"1"},{"paperId":"P139","catalystId":"P139_PERF_003","name":"Pd/TBT","support":"TBT","matchedSynthesis":"Pd/TBT","matchedCharacterization":"Pd/TBT","role":"control catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared by the same method as Pd/TBT/rGO using TBT as support.","phase":"Metallic Pd on tetragonal-phase barium titanate (TBT)","particleSize":"4.0 nm","surfaceStates":"Electron-rich Pd (Pd 3d binding energy shifted to 335.3 eV) due to MSI with BaTiO3.","structureLink":"Small particle size and electron-rich state facilitate activity, but lacks the charge transfer enhancement provided by rGO.","reactionConditions":"1.1 M FA / 0.8 M SF, reaction temperature 303 K","metricCount":"1"},{"paperId":"P139","catalystId":"P139_PERF_004","name":"Pd/rGO","support":"rGO","matchedSynthesis":"Pd/rGO","matchedCharacterization":"Pd/rGO","role":"control catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared by the same method as Pd/TBT/rGO using rGO as support.","phase":"Metallic Pd on reduced graphene oxide (rGO)","particleSize":"35.8 nm","surfaceStates":"Electron-deficient compared to TBT-supported catalysts (Pd 3d binding energy of 335.8 eV).","structureLink":"Larger particle size and lack of internal electric field/electron-donating support lead to lower catalytic activity for FAD.","reactionConditions":"1.1 M FA / 0.8 M SF, reaction temperature 303 K","metricCount":"1"},{"paperId":"P139","catalystId":"P139_PERF_005","name":"TBT/rGO","support":"TBT/rGO","matchedSynthesis":"Pd/TBT/rGO","matchedCharacterization":"Pd/TBT/rGO","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"TBT/rGO was dispersed in DI water, H2PdCl4 was added and stirred for 3 h, pH adjusted to 11 with NaOH, then reduced using NaH2PO2 solution.","phase":"Metallic Pd on tetragonal-phase barium titanate (TBT) and reduced graphene oxide (rGO)","particleSize":"4.6 nm","surfaceStates":"Electron-rich Pd (Pd 3d binding energy shifted to 335.3 eV) due to metal-support interaction (MSI) where BaTiO3 acts as a strong electron donor.","structureLink":"Small particle size improves mass activity; electron-rich Pd facilitates C-H bond cleavage in HCOO*; internal electric field from TBT promotes hydrogen desorption on Pd(111); rGO enhances interfacial charge transport capacity.","reactionConditions":"1.1 M FA / 0.8 M SF, reaction temperature 303 K","metricCount":"1"},{"paperId":"P140","catalystId":"P140_PERF_001","name":"Pd/C–SiO2","support":"C–SiO2","matchedSynthesis":"Pd/C–SiO2","matchedCharacterization":"Pd/C–SiO2","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"C–SiO2 was dispersed in distilled water via ultrasound; H2PdCl4 precursor was added and stirred at room temperature, followed by reduction with NaBH4 and vacuum drying.","phase":"Metallic Pd (111) plane","particleSize":"1.8 nm (TEM); 2.5 nm (XRD)","surfaceStates":"Electron-rich Pd catalytic sites formed by electron transfer from the C–SiO2 support to Pd (indicated by negative shift in Pd 3d binding energy).","structureLink":"Small particle size, high dispersion, and electron-rich surface enhance FA dehydrogenation activity; oxygen-rich species provided by SiO2 limit CO adsorption on the Pd surface; Pd–O–Si coordination stabilizes NPs against agglomeration.","reactionConditions":"Dehydrogenation of formic acid (FA) using a 1M FA/SF mixture in deionized water at 30 °C.","selectivity":"100% H2 selectivity; no CO detected","stability":"Retains about 93% of initial activity after the fifth recycle.","deactivation":"No loss of Pd (ICP-OES showed 4.9% after 5 cycles); particle size increased slightly from 1.8 to 2.0 nm","whyPerformsWell":"Small Pd NPs (1.8 nm), synergistic effect between carbon and SiO2 promoting electron transfer to form electron-rich Pd surface, high hydrophilicity due to O2 and O3 functional groups acting as proton scavengers, and oxygen-rich species from SiO2 limiting CO adsorption.","metricCount":"3"},{"paperId":"P140","catalystId":"P140_PERF_002","name":"Pd/C","support":"C","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Prepared according to the same experimental operation as Pd/C–SiO2.","phase":"Metallic Pd (111) plane","particleSize":"3.7 nm (TEM); 5.0 nm (XRD)","structureLink":"Larger particle size and lower Pd0/Pd2+ ratio compared to Pd/C–SiO2 result in lower catalytic activity.","reactionConditions":"Dehydrogenation of formic acid (FA) using a 1M FA/SF mixture in deionized water at 30 °C.","whyPerformsWell":"Large specific surface area of carbon carrier provides space for Pd NP dispersion.","metricCount":"1"},{"paperId":"P140","catalystId":"P140_PERF_003","name":"Pd/SiO2","support":"SiO2","matchedSynthesis":"Pd/SiO2","matchedCharacterization":"Pd/SiO2","role":"comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Prepared according to the same experimental operation as Pd/C–SiO2.","phase":"Metallic Pd (111) plane","particleSize":"3.1 nm (TEM); 3.8 nm (XRD)","structureLink":"Lower specific surface area and larger particle size compared to Pd/C–SiO2 lead to the lowest FA conversion rate.","reactionConditions":"Dehydrogenation of formic acid (FA) using a 1M FA/SF mixture in deionized water at 30 °C.","metricCount":"1"},{"paperId":"P141","catalystId":"P141_PERF_001","name":"Pd/TiO2","support":"TiO2","matchedSynthesis":"Pd/TiO2","matchedCharacterization":"Pd/TiO2","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PdCl2 and HCl aqueous solution were added dropwise to dried TiO2 powders, placed statically overnight, dried, calcined, and then reduced.","phase":"Highly dispersed Pd species on anatase and rutile TiO2 support","particleSize":"Slight increase observed after reaction (not statistically significant)","surfaceStates":"Pristine catalyst contains 93.1% Pd0, which decreases slightly after reaction; CO-DRIFTS shows linear, bridge, and tri-coordination adsorption of CO on Pd","structureLink":"Rapid deactivation is attributed to the accumulation of formate species on the surface (HCOOH -> HCOO + H), which blocks active sites from interacting with reactants","reactionConditions":"25 °C, atmospheric pressure, N2 atmosphere, vigorously stirred","stability":"Rapid deactivation; nearly complete loss of catalytic activity in five rounds of the reaction (k value remains below 10% of pristine state at fifth cycle).","deactivation":"Reversible deactivation caused by accumulation of formate on the catalyst surface, which hinders contact between active sites and reactants. No significant Pd leaching observed via ICP-MS.","metricCount":"3"},{"paperId":"P141","catalystId":"P141_PERF_002","name":"Zn-Pd/TiO2","support":"TiO2","matchedSynthesis":"Zn-Pd/TiO2","matchedCharacterization":"Zn-Pd/TiO2","role":"catalyst","composition":"Zn/Pd molar ratio of 1","activeMetals":"Zn-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"ZnCl2 was added to the PdCl2 and HCl aqueous solution, followed by the same steps as Pd/TiO2: dropwise addition to TiO2, static overnight, drying, calcination, and reduction.","phase":"Zn-Pd alloy structure; HAADF-STEM mapping shows Zn elements distributed on Pd nanoparticles","particleSize":"Approximately 2.8 nm (remains essentially constant across reaction cycles)","surfaceStates":"Pristine catalyst contains 57.9% Pd0, increasing to 63.3% after reaction; CO-DRIFTS confirms presence of multi-atomic Pd ensembles","structureLink":"The alloy structure facilitates an alternative HCOOH decomposition pathway (HCOOH -> COOH + H -> CO2 + 2H), preventing formate accumulation and maintaining high catalytic stability","reactionConditions":"25 °C, atmospheric pressure, N2 atmosphere, vigorously stirred","stability":"Excellent stability; decrease in k value of < 10% after five cycles.","deactivation":"No significant metal leaching. Minimal decline in activity attributed to unavoidable catalyst loss during recycling process.","whyPerformsWell":"Incorporation of Zn alters the reaction pathway (HCOOH → COOH + H → CO2 + 2H), enabling complete decomposition of formic acid and preventing the accumulation of formate on the catalyst surface.","metricCount":"4"},{"paperId":"P142","catalystId":"P142_PERF_001","name":"Pd/4N-CX-meso","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","matchedCharacterization":"Pd/4N-CX-meso","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","phase":"Metallic Pd","particleSize":"2.3 nm","surfaceStates":"Electron deficient Pd (XPS shift to higher binding energy)","structureLink":"Optimal nitrogen content (4 wt%) and micro-mesoporous texture lead to high TOF (2014 h-1).","reactionConditions":"75 °C, aqueous solution of HCOOH and HCOONa (HCOOH/HCOONa = 9/1; 1 M), reaction vessel with reflux condenser and gas burette","whyPerformsWell":"Optimal nitrogen content (4 wt.%) promotes small and well-distributed Pd NPs; N-functionalities increase Lewis basicity and create electron deficient Pd species that interact better with formate intermediates; micro-mesoporous texture improves accessibility of FA molecules.","metricCount":"2"},{"paperId":"P142","catalystId":"P142_PERF_002","name":"Pd/CX-meso","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","matchedCharacterization":"Pd/CX-meso","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","phase":"Metallic Pd","particleSize":"3.4 nm","surfaceStates":"Metallic state","structureLink":"Poor catalytic ability compared to N-doped counterparts.","reactionConditions":"75 °C, aqueous solution of HCOOH and HCOONa (HCOOH/HCOONa = 9/1; 1 M)","deactivation":"reaction ceased after 5 min","metricCount":"1"},{"paperId":"P142","catalystId":"P142_PERF_003","name":"Pd/4N-CX-macro","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","matchedCharacterization":"Pd/4N-CX-macro","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","phase":"Metallic Pd","particleSize":"2.2 nm","surfaceStates":"Electron deficient Pd (XPS shift to higher binding energy)","structureLink":"Lower activity than the meso-porous counterpart due to micro-macroporous texture impacting accessibility.","reactionConditions":"75 °C, aqueous solution of HCOOH and HCOONa (HCOOH/HCOONa = 9/1; 1 M)","deactivation":"reaction was dramatically sluggish after 5 min","metricCount":"1"},{"paperId":"P142","catalystId":"P142_PERF_004","name":"Pd/8N-CX-macro","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","matchedCharacterization":"Pd/8N-CX-macro","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","phase":"Metallic Pd","particleSize":"8.3 ± 5.2 nm","surfaceStates":"Less important Pd-N interaction compared to low/moderate N catalysts","structureLink":"High nitrogen content (8 wt%) and lower surface area lead to Pd aggregation and poor catalytic activity.","reactionConditions":"75 °C, aqueous solution of HCOOH and HCOONa (HCOOH/HCOONa = 9/1; 1 M)","deactivation":"behavior very similar to that of the N-free sample","metricCount":"0"},{"paperId":"P142","catalystId":"P142_PERF_005","name":"Pd/2N-CX-meso","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","matchedCharacterization":"Pd/2N-CX-meso","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","phase":"Metallic Pd","particleSize":"2.7 nm","surfaceStates":"Electron deficient Pd (XPS shift to higher binding energy)","structureLink":"Small particle size and electron deficiency enhance catalytic activity.","reactionConditions":"75 °C, aqueous solution of HCOOH and HCOONa (HCOOH/HCOONa = 9/1; 1 M)","whyPerformsWell":"micro-mesoporous texture provides better behavior than micro-macroporous","metricCount":"0"},{"paperId":"P143","catalystId":"P143_PERF_001","name":"Pd0.50Au0.50/PDA-rGO","support":"phenylenediamine-alkalized reduced graphene oxide (PDA-rGO)","matchedSynthesis":"Pd0.50Au0.50/PDA-rGO","matchedCharacterization":"Pd0.50Au0.50/PDA-rGO","role":"main catalyst","composition":"Pd:Au = 1:1 molar ratio","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","phase":"Bimetallic PdAu nanoparticles; XRD peaks at 38.14° and 44.50° are slightly shifted from Au reference peaks, and TEM-EDS confirms bimetallic composition with no monometallic particles.","particleSize":"Two populations: smaller nanoparticles (1.8 ± 0.5 nm) and larger nanoparticles (ca. 5-8 nm).","surfaceStates":"Amine groups on the PDA-rGO support act as proton scavengers; XPS shows Au and Pd(0) signals shifted to lower energy compared to monometallic counterparts, indicating electronic interaction/alloying.","structureLink":"High activity is attributed to nanosized particles, amine groups acting as proton scavengers for O-H cleavage, and the Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","reactionConditions":"Hydrogenation of KHCO3 in aqueous solution; Dehydrogenation of PF or FA in aqueous solution.","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","deactivation":"PDA in the support was transformed and removed during reaction under high pressure H2 conditions.","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","metricCount":"15"},{"paperId":"P143","catalystId":"P143_PERF_002","name":"Pd/PDA-rGO","support":"phenylenediamine-alkalized reduced graphene oxide (PDA-rGO)","matchedSynthesis":"Pd/PDA-rGO","matchedCharacterization":"Pd/PDA-rGO","role":"monometallic comparison catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","phase":"Monometallic Pd","particleSize":"2.3 ± 0.5 nm","reactionConditions":"Hydrogenation of KHCO3; Dehydrogenation of FA.","stability":"No gas generation observed at 25 °C for FA dehydrogenation.","metricCount":"2"},{"paperId":"P143","catalystId":"P143_PERF_003","name":"Au/PDA-rGO","support":"phenylenediamine-alkalized reduced graphene oxide (PDA-rGO)","matchedSynthesis":"Au/PDA-rGO","role":"monometallic comparison catalyst","composition":"Au only","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","reactionConditions":"Hydrogenation of KHCO3.","metricCount":"1"},{"paperId":"P143","catalystId":"P143_PERF_004","name":"Pd0.57(Low)Au0.43(Low)/PDA-rGO","support":"phenylenediamine-alkalized reduced graphene oxide (PDA-rGO)","matchedSynthesis":"Pd0.57(Low)Au0.43(Low)/PDA-rGO","matchedCharacterization":"Pd0.57(Low)Au0.43(Low)/PDA-rGO","role":"low loading comparison catalyst","composition":"Pd:Au = 0.57:0.43 molar ratio","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","phase":"Bimetallic PdAu","particleSize":"1.7 ± 0.5 nm","reactionConditions":"Hydrogenation of KHCO3.","whyPerformsWell":"Low metal loading catalyst has comparable catalytic activity for the hydrogenation of KHCO3 to PF.","metricCount":"2"},{"paperId":"P143","catalystId":"P143_PERF_005","name":"Pd0.49Au0.51/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd0.49Au0.51/rGO","matchedCharacterization":"Pd0.49Au0.51/rGO","role":"support comparison catalyst (without PDA)","composition":"Pd:Au = 0.49:0.51 molar ratio","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","phase":"Bimetallic PdAu","particleSize":"2.7 ± 0.8 nm","structureLink":"Larger particle size compared to PDA-supported catalysts suggests PDA acts as a stabilizer during synthesis.","reactionConditions":"Hydrogenation of KHCO3 (without PDA).","stability":"PF yields are maintained until the third cycle.","metricCount":"1"},{"paperId":"P144","catalystId":"P144_PERF_001","name":"Pd/C","matchedCharacterization":"Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Metallic Pd","particleSize":"4.6 nm","surfaceStates":"Binding energy of Pd 3d5/2 is 336.13 eV; contains 0.402 mmol g-1 of Pd2+ species (49.2 mol%)","reactionConditions":"10 mL 1 M formic acid at 60 °C","metricCount":"1"},{"paperId":"P144","catalystId":"P144_PERF_002","name":"Pd1NiO1.3/C (co)","matchedCharacterization":"Pd1NiO1.3/C (co)","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Metallic Pd phase; interacts directly with neighboring Ni atoms","particleSize":"3.6 nm","surfaceStates":"Binding energy of Pd 3d5/2 is 335.80 eV (more negative than Pd/C); contains 0.276 mmol g-1 of Pd2+ species (32.2 mol%)","structureLink":"More negative Pd cannot interact well with negatively charged intermediates, which counteracts the promoting effect of its smaller particle size compared to Pd/C.","reactionConditions":"10 mL 1 M formic acid at 60 °C","whyPerformsWell":"Smaller particle size than Pd/C but more negative Pd state counteracts the promoting effect","metricCount":"1"},{"paperId":"P144","catalystId":"P144_PERF_003","name":"Pd1/NiOx/C (seq)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"10 mL 1 M formic acid at 60 °C","selectivity":"No CO gas generated for x=1.3","stability":"Reduced activity after reuse (for x=1.3)","deactivation":"Loss of Ni metal (6.2 wt% to 0.5 wt%) and Pd particle agglomeration","whyPerformsWell":"Synergetic effect of small particle size and electronic modification of Pd to a positively charged ion (Pd2+ species) induced by pre-impregnated Ni","metricCount":"1"},{"paperId":"P145","catalystId":"P145_PERF_001","name":"Cp*Ir-HMDAbpy@PAA","support":"cross-linked polyacrylic acid (PAA)","matchedSynthesis":"Cp*Ir-HMDAbpy@PAA","matchedCharacterization":"Cp*Ir-HMDAbpy@PAA","role":"release-and-catch catalyst for continuous formic acid dehydrogenation","composition":"Ir","activeMetals":"Ir","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"sequential_impregnation","synthesis":"Synthesis of cross-linked PAA support followed by immobilization of 4-hmdabpy ligand, and subsequent coordination of the iridium precursor.","particleSize":"10 μm to several hundred μm","surfaceStates":"XPS analysis after reaction showed no peak shifts compared to the homogeneous Cp*Ir(HMDAbpy) complex, indicating minimal degradation.","structureLink":"The release-and-catch mechanism allows the catalyst to function as a homogeneous species during FA dehydrogenation (high TOF) and be recaptured by PAA carboxylic acid groups via electrostatic or coordination interactions for recovery. Optimal activity was linked to a ligand content of 212 μmol g−1 and Ir loading of 1.16 wt%.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution at 80 °C","selectivity":"H2 and CO2 in a 1:1 ratio","stability":"Recycled 5 times in batch (TOF maintained between 63,000-76,000 h-1) and 10 times in flow system with no deterioration in gas production rate.","deactivation":"Ir remaining in solution < 0.1 ppm after batch cycles; below ICP-AES detection limit after flow recycles. Ir recovery rate between 99.39% and 99.98%.","whyPerformsWell":"Release-and-catch mechanism: the immobilized complex dissolves into the solution as a homogeneous catalyst during FA dehydrogenation (triggered by acid) and is recaptured by the PAA support once FA is consumed.","metricCount":"4"},{"paperId":"P145","catalystId":"P145_PERF_002","name":"free Cp*Ir-HMDAbpy ([Cp*Ir(HMDAbpy)(H2O)]SO4)","activeMetals":"Ir","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution at 80 °C","whyPerformsWell":"Homogeneous nature allows high activity.","metricCount":"1"},{"paperId":"P145","catalystId":"P145_PERF_003","name":"pre-Cp*Ir-HMDAbpy@PAA","support":"cross-linked polyacrylic acid (PAA)","matchedSynthesis":"pre-Cp*Ir-HMDAbpy@PAA","matchedCharacterization":"Cp*Ir-HMDAbpy@PAA","role":"comparison catalyst","composition":"Ir","activeMetals":"Ir","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"[Cp*Ir(4HMDAbpy)(H2O)]SO4 was prepared before immobilization on cross-linked PAA.","particleSize":"10 μm to several hundred μm","surfaceStates":"XPS analysis after reaction showed no peak shifts compared to the homogeneous Cp*Ir(HMDAbpy) complex, indicating minimal degradation.","structureLink":"The release-and-catch mechanism allows the catalyst to function as a homogeneous species during FA dehydrogenation (high TOF) and be recaptured by PAA carboxylic acid groups via electrostatic or coordination interactions for recovery. Optimal activity was linked to a ligand content of 212 μmol g−1 and Ir loading of 1.16 wt%.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution at 80 °C","deactivation":"Lower elution of complex (34% compared to Cp*Ir-HMDAbpy@PAA) leads to lower activity.","metricCount":"1"},{"paperId":"P146","catalystId":"P146_PERF_001","name":"PdAu-VOx/NHMS","support":"amino-functionalized hollow mesoporous carbon sphere (NHMS)","matchedSynthesis":"PdAu-VOx/NHMS","matchedCharacterization":"PdAu-VOx/NHMS","role":"best catalyst","composition":"Pd: 0.60 wt.%, Au: 1.11 wt.%, V: 0.92 wt.%","activeMetals":"Pd-Au-V","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"VOx species were first deposited onto HMS via impregnation of aqueous VCl3 followed by calcination. Subsequently, (3-aminopropyl) triethoxysilane (APTS), Na2PdCl4, and HAuCl4·3H2O were introduced in succession, and the Pd and Au cations were reduced using NaBH4.","phase":"Binary PdAu nanoclusters","particleSize":"1.94 nm","surfaceStates":"XPS shows Pd (Pd0 main, Pd2+), Au (Au0 main, Au3+), and V (V5+, V4+, V2+). V5+ exhibits a positive shift of 0.25 eV compared to VOx/NHMS, indicating electron transfer from V to PdAu. Amino groups act as Brønsted base sites; V atoms act as Lewis acid sites.","structureLink":"Synergy between Lewis acidic VOx (facilitates HCOO* adsorption and C-H bond activation), PdAu clusters, and Brønsted basic amino groups (promotes O-H bond cleavage) reduces activation energy to 31.2 kJ/mol.","reactionConditions":"Formic acid (FA) dehydrogenation, room temperature, additive-free","selectivity":"100% selectivity; no obvious CO signal observed within the detection limit of GC","stability":"Maintains 100% conversion and selectivity in the tenth cycle reaction (reaction time: 9.25 min)","deactivation":"Slight decrease in activity due to aggregation of nanoparticles (mean size increased from 1.94 nm to 2.07 nm) and valence change of metal species; trace amounts of CO may adsorb on Pd sites","whyPerformsWell":"Synergistic effect of VOx, PdAu clusters, and amino groups: electron-rich amino groups act as Brønsted base sites for O-H bond cleavage, while electron-deficient V atoms (Lewis acid sites) regulate HCOO* adsorption and facilitate C-H bond activation.","metricCount":"8"},{"paperId":"P146","catalystId":"P146_PERF_002","name":"PdAu/NHMS","matchedCharacterization":"PdAu/NHMS","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdAu nanoclusters","particleSize":"1.88 nm","surfaceStates":"Contains Pd0, Pd2+, Au0, and Au3+ species.","structureLink":"Lower activity than PdAu-VOx/NHMS due to lack of VOx Lewis acid sites; higher activation energy (33.2 kJ/mol).","reactionConditions":"Formic acid (FA) dehydrogenation, room temperature, additive-free","metricCount":"3"},{"paperId":"P146","catalystId":"P146_PERF_003","name":"Pd/NHMS","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Formic acid (FA) dehydrogenation, room temperature, additive-free","metricCount":"3"},{"paperId":"P146","catalystId":"P146_PERF_004","name":"PdAu-VOx/HMS","matchedCharacterization":"VOx/HMS","activeMetals":"Pd-Au-V","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"VOx species","particleSize":"~1 nm","surfaceStates":"Contains V5+, V4+, and V2+ species.","reactionConditions":"Formic acid (FA) dehydrogenation, room temperature, additive-free","whyPerformsWell":"Almost inert, proving the necessity of amino modification on catalysts for FA dehydrogenation","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_001","name":"Co(1)/phen(2)/C","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Liquid-phase dehydrogenation of formic acid (FA)","metricCount":"1"},{"paperId":"P147","catalystId":"P147_PERF_002","name":"Co@NC-W","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-W","matchedCharacterization":"Co@NC (including Co@NC-W, Co@NC-ZIF, and Co@NC-Gr series)","role":"reference catalyst","composition":"Co1/L1 = 1:2","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of carbon with Co(II) complex with 1,10-phenanthroline followed by pyrolysis.","phase":"Cubic metallic Co","particleSize":"20 ± 10 nm","surfaceStates":"Co2+ (XPS peaks at 781 and 797 eV) and metallic Co (778 eV). Nitrogen species include pyridinic (398.9 eV), pyrrolic/graphitic (400.8 eV), and NOx (402.5, 405.4 eV).","structureLink":"Cobalt nanoparticles do not play a significant role in FA dehydrogenation; activity is attributed to sub-nanosized cobalt species or CoNx centers.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.5% (gas phase at 100 °C)","stability":"Considerable but not entirely perfect catalytic stability in liquid phase","deactivation":"Cobalt leaching upon corrosive action of FA; lost about 12% of Co after 20 h of reaction, gas production rate decreased by ~7%","whyPerformsWell":"Highly dispersed Co centers incorporated in carbon are more resilient to leaching","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_003","name":"Co@NC-ZIF","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-ZIF","matchedCharacterization":"Co@NC (including Co@NC-W, Co@NC-ZIF, and Co@NC-Gr series)","role":"reference catalyst","composition":"Co2/L2 = 1:40","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Carbonization of ZIF-67 metal-organic framework.","phase":"Cubic metallic Co","particleSize":"20 ± 10 nm","surfaceStates":"Co2+ (XPS peaks at 781 and 797 eV) and metallic Co (778 eV). Nitrogen species include pyridinic (398.9 eV), pyrrolic/graphitic (400.8 eV), and NOx (402.5, 405.4 eV).","structureLink":"Cobalt nanoparticles do not play a significant role in FA dehydrogenation; activity is attributed to sub-nanosized cobalt species or CoNx centers.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.2% (gas phase at 100 °C)","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_004","name":"Co@NC-Gr1","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-Gr1","matchedCharacterization":"Co@NC-WSA and Co@NC-Gr1SA","role":"active catalyst","composition":"Co1/L1 = 1:2","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","phase":"Single atomic Co species","particleSize":"Sub-nanosized / single atom","structureLink":"Retention of considerable catalytic activity after nanoparticle removal confirms that sub-nanosized/single atomic cobalt species are the primary active sites.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.5% (gas phase at 100 °C)","stability":"Exceptional selectivity (~99.9%) after 8 h of reaction at 94 °C in gas phase","deactivation":"Gas production rate showed a gradual and slowing drop-off to around 90% of the initial value over 8h; attributed to hydrogen accumulation, formate species accumulation, or slow formation of cobalt salts","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_005","name":"Co@NC-Gr2","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-Gr2","role":"active catalyst","composition":"Co1/L1 = 1:2","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.3% (gas phase at 100 °C)","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_006","name":"Co@NC-Gr3","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-Gr3","role":"active catalyst","composition":"Co1/L1 = 1:2.5","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.5% (gas phase at 100 °C)","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_007","name":"Co@NC-Gr4","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-Gr4","role":"active catalyst","composition":"Co2/L2 = 1:2","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.6% (gas phase at 100 °C)","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_008","name":"Co@NC-Gr5","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-Gr5","role":"active catalyst","composition":"Co2/L2 = 1:5","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.4% (gas phase at 100 °C)","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_009","name":"Co@NC-Gr6","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-Gr6","role":"active catalyst","composition":"Co1/L2 = 1:5","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.7% (gas phase at 100 °C)","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_010","name":"Co@NC-WSA","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-WSA","matchedCharacterization":"Co@NC-WSA and Co@NC-Gr1SA","role":"acid-treated catalyst","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"acid leaching","synthesis":"Treatment of Co@NC-W with sulfuric acid to dissolve cobalt nanoparticles.","phase":"Single atomic Co species","particleSize":"Sub-nanosized / single atom","structureLink":"Retention of considerable catalytic activity after nanoparticle removal confirms that sub-nanosized/single atomic cobalt species are the primary active sites.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.5% (gas phase at 100 °C)","whyPerformsWell":"Treatment with mineral acids can have a positive impact on gas-phase decomposition","metricCount":"2"},{"paperId":"P147","catalystId":"P147_PERF_011","name":"Co@NC-Gr1SA","support":"VulcanXC72R carbon powder","matchedSynthesis":"Co@NC-Gr1SA","matchedCharacterization":"Co@NC-WSA and Co@NC-Gr1SA","role":"acid-treated catalyst","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"acid leaching","synthesis":"Treatment of Co@NC-Gr1 with sulfuric acid to dissolve cobalt nanoparticles.","phase":"Single atomic Co species","particleSize":"Sub-nanosized / single atom","structureLink":"Retention of considerable catalytic activity after nanoparticle removal confirms that sub-nanosized/single atomic cobalt species are the primary active sites.","reactionConditions":"Liquid- and gas-phase dehydrogenation of FA","selectivity":"99.6% (gas phase at 100 °C)","metricCount":"2"},{"paperId":"P148","catalystId":"P148_PERF_001","name":"Pd/AC (Commercial 10 wt% Pd/AC)","support":"activated carbon","matchedSynthesis":"Pd/AC","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"commercial purchase","synthesis":"Commercial catalyst purchased from Sigma Aldrich, dried and activated in a reducing atmosphere.","reactionConditions":"50 °C, 1 M formic acid aqueous solution, 0.1 g catalyst, N2 flow (100 mL min-1), stirring at 1036 rpm","selectivity":"Totally selective to dehydrogenation (only H2 and CO2 produced). H2/CO2 ratio is ~1 for pH ≤ 3.5, but increases up to 15 at pH 6.5 due to CO2 retention as bicarbonate/carbonate species.","stability":"Ammonium formate addition improves Pd catalyst stability.","whyPerformsWell":"Activity depends on the hydrated cationic radii of the base; smaller hydrated radii (e.g., K+) increase activity via stronger Coulomb interactions and easier formate formation. NH4OH enhances activity through amine groups facilitating proton elimination and reducing inhibition by stable hydrogen-bonded formate-formic acid complexes.","metricCount":"3"},{"paperId":"P149","catalystId":"P149_PERF_001","name":"Pd/CB","support":"CD-6008 carbon black (CB)","matchedSynthesis":"Pd/CB","matchedCharacterization":"Pd/CB","role":"catalyst for the dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto carbon black support.","phase":"Metallic and oxidized Pd species","particleSize":"3.3 ± 0.9 nm","surfaceStates":"43% Pd(0), 57% Pdδ+","structureLink":"PVP capping provides N-containing groups and increases hydrophilicity, enhancing interface contact with formic acid.","reactionConditions":"80 °C, 1 M solution of formic acid and sodium formate (9:1 molar ratio), 0.15 g catalyst","stability":"lack of good stability under reaction conditions","whyPerformsWell":"PVP provides N-containing groups that increase local FA concentration and hydrophilicity; PVP interaction with Pd surface avoids repulsive adsorbate-adsorbate interaction.","metricCount":"3"},{"paperId":"P149","catalystId":"P149_PERF_002","name":"Pd/Vulcan","support":"XC-72F Vulcan carbon black (Vulcan)","matchedSynthesis":"Pd/Vulcan","matchedCharacterization":"Pd/Vulcan","role":"catalyst for the dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto Vulcan carbon black support.","phase":"Metallic and oxidized Pd species","particleSize":"2.6 ± 0.7 nm","surfaceStates":"57% Pd(0), 43% Pdδ+","structureLink":"PVP capping provides N-containing groups and increases hydrophilicity, enhancing interface contact with formic acid.","reactionConditions":"80 °C, 1 M solution of formic acid and sodium formate (9:1 molar ratio), 0.15 g catalyst","stability":"lack of good stability under reaction conditions","whyPerformsWell":"PVP provides N-containing groups that increase local FA concentration and hydrophilicity; PVP interaction with Pd surface avoids repulsive adsorbate-adsorbate interaction.","metricCount":"3"},{"paperId":"P149","catalystId":"P149_PERF_003","name":"Pd/MWCNT","support":"multiwall carbon nanotubes (MWCNT)","matchedSynthesis":"Pd/MWCNT","matchedCharacterization":"Pd/MWCNT","role":"catalyst for the dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto MWCNT support.","phase":"Metallic and oxidized Pd species","particleSize":"2.5 ± 0.9 nm","surfaceStates":"60% Pd(0), 40% Pdδ+","structureLink":"MWCNT's 1D structure and high available external surface area, combined with PVP capping, result in the highest TOF.","reactionConditions":"80 °C, 1 M solution of formic acid and sodium formate (9:1 molar ratio), 0.15 g catalyst","stability":"lack of good stability under reaction conditions","whyPerformsWell":"MWCNTs 1D structure and high available surface area; lower contribution of micropores results in fewer diffusion problems. PVP provides N-containing groups that increase local FA concentration and hydrophilicity.","metricCount":"3"},{"paperId":"P149","catalystId":"P149_PERF_004","name":"Pd/CB(t)","support":"CD-6008 carbon black (CB)","matchedSynthesis":"Pd/CB","matchedCharacterization":"Pd/CB(t)","role":"catalyst for the dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto carbon black support.","phase":"Metallic and oxidized Pd species","particleSize":"3.3 ± 0.8 nm","surfaceStates":"81% Pd(0), 19% Pdδ+","structureLink":"Removal of PVP leads to a significant decay in catalytic performance.","reactionConditions":"80 °C, 1 M solution of formic acid and sodium formate (9:1 molar ratio), 0.15 g catalyst","stability":"lack of good stability under reaction conditions","whyPerformsWell":"PVP-free catalyst; performance significantly decayed compared to PVP-containing counterpart.","metricCount":"1"},{"paperId":"P149","catalystId":"P149_PERF_005","name":"Pd/Vulcan(t)","support":"XC-72F Vulcan carbon black (Vulcan)","matchedSynthesis":"Pd/Vulcan","matchedCharacterization":"Pd/Vulcan(t)","role":"catalyst for the dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto Vulcan carbon black support.","phase":"Metallic and oxidized Pd species","particleSize":"3.5 ± 1.6 nm","surfaceStates":"82% Pd(0), 18% Pdδ+","structureLink":"Removal of PVP leads to a significant decay in catalytic performance.","reactionConditions":"80 °C, 1 M solution of formic acid and sodium formate (9:1 molar ratio), 0.15 g catalyst","stability":"lack of good stability under reaction conditions","whyPerformsWell":"PVP-free catalyst; performance significantly decayed compared to PVP-containing counterpart.","metricCount":"1"},{"paperId":"P149","catalystId":"P149_PERF_006","name":"Pd/MWCNT(t)","support":"multiwall carbon nanotubes (MWCNT)","matchedSynthesis":"Pd/MWCNT","matchedCharacterization":"Pd/MWCNT(t)","role":"catalyst for the dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto MWCNT support.","phase":"Metallic and oxidized Pd species","particleSize":"4.0 ± 1.9 nm","surfaceStates":"78% Pd(0), 22% Pdδ+","structureLink":"Removal of PVP decreases initial activity compared to the as-synthesized counterpart.","reactionConditions":"80 °C, 1 M solution of formic acid and sodium formate (9:1 molar ratio), 0.15 g catalyst","stability":"lack of good stability under reaction conditions","whyPerformsWell":"PVP-free catalyst; although it is the best among PVP-free catalysts, its initial activity is significantly lower than Pd/MWCNT.","metricCount":"2"},{"paperId":"P151","catalystId":"P151_PERF_001","name":"AuT-MA","support":"titania from metatitanic acid","matchedSynthesis":"AuT-MA","matchedCharacterization":"AuT / AuT-MA","role":"reference catalyst","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Titania was synthesized using metatitanic acid as precursor, calcined, and then impregnated with gold.","phase":"Anatase phase","particleSize":"Gold particles: 5-7 nm; Anatase crystallite size: ~15 nm (for AuT-MA)","structureLink":"Baseline activity for formic acid decomposition.","reactionConditions":"Formic acid decomposition, 750 ppm FA, total flow rate 750 l h-1, washcoat loading ~2.5 g L-1","selectivity":"65% CO2 selectivity at 300 °C","metricCount":"2"},{"paperId":"P151","catalystId":"P151_PERF_002","name":"Au2.3LT-CP","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Formic acid decomposition, 750 ppm FA, total flow rate 750 l h-1, washcoat loading ~2.5 g L-1","selectivity":"~88% CO2 selectivity at 300 °C","whyPerformsWell":"Lanthana modification increases CO2 selectivity and activity compared to unmodified Au/TiO2","metricCount":"2"},{"paperId":"P151","catalystId":"P151_PERF_003","name":"Au15LT-CP","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Formic acid decomposition, 750 ppm FA, total flow rate 750 l h-1, washcoat loading ~2.5 g L-1","selectivity":"~98% CO2 selectivity at 300 °C; nearly 100% ammonia yield for AmFo decomposition","whyPerformsWell":"Optimal lanthana loading (15 wt%) induces C-H bond weakening of bidentate formates and increases the concentration of hydroperoxy species (OOH*) at interfacial Au-Ti4+ sites; smaller gold particle size also contributes.","metricCount":"4"},{"paperId":"P151","catalystId":"P151_PERF_004","name":"AuXLT-WI","support":"La-modified titania","matchedSynthesis":"AuXLT-WI","matchedCharacterization":"AuXLT-WI (Wet Impregnated)","role":"catalyst for formic acid decomposition","composition":"Au and La (X wt% lanthana)","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Lanthana was wet-impregnated onto anatase titania, dried and calcined to form the support; subsequently, gold was impregnated via pore volume method, aged, washed, and calcined.","phase":"Anatase phase; lanthanum phases are amorphous and/or well-dispersed","particleSize":"Gold particles: 2-3 nm (for Au5LT-WI and Au15LT-WI); Anatase crystallite size: reduced from 25 nm to ~18 nm (at 2.3 wt% La) and stabilized at ~14 nm (at 29 wt% La)","surfaceStates":"Higher density and coverage of formates compared to coprecipitated catalysts due to high surface basicity","structureLink":"Lower activity than CP counterparts because excessive lanthana surface coverage blocks active sites for hydroperoxy species (OOH*) formation and impedes Au-Ti synergy.","reactionConditions":"Formic acid decomposition, 750 ppm FA, total flow rate 750 l h-1, washcoat loading ~2.5 g L-1","selectivity":"Similar CO2 selectivity pattern as coprecipitated catalysts; suppresses carbon monoxide formation","whyPerformsWell":"Less active than CP analogues due to high surface lanthana concentrations causing extensive blockage of active sites by formates and reducing Au-Ti synergy.","metricCount":"1"},{"paperId":"P152","catalystId":"P152_PERF_001","name":"Pd0.6Ag0.4@ZrO2/C/rGO","matchedCharacterization":"Pd0.6Ag0.4@ZrO2/C/rGO","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic PdAg nanoparticles","particleSize":"2.5 ± 0.03 nm","surfaceStates":"Electron-rich PdAg NP surface resulting from electron transfer from ZrO2 to the metal nanoparticles.","structureLink":"Ultrafine particle size provides more active sites; the electron-rich surface (induced by ZrO2) facilitates O–H bond dissociation of formic acid and favors the formation of the PdAg-formate intermediate.","reactionConditions":"Dehydrogenation of formic acid (FA) at 303–333 K","selectivity":"100% H2 selectivity; absence of CO in gas mixture","stability":"No obvious decrease in catalytic performance over five cycles (adding aliquots of 1.5 mmol FA)","whyPerformsWell":"Synergistic interaction between Pd and Ag; high dispersion of ultrafine PdAg NPs (average size 2.5 nm) on ZrO2/C/rGO support; electron transfer from ZrO2 to PdAg NPs creates an electron-rich surface that favors O-H bond dissociation of FA.","metricCount":"3"},{"paperId":"P152","catalystId":"P152_PERF_002","name":"Pd0.6Ag0.4@C/rGO","matchedCharacterization":"Pd0.6Ag0.4@C/rGO","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic PdAg nanoparticles","particleSize":"2.4 ± 0.04 nm","surfaceStates":"Less electron-rich than Pd0.6Ag0.4@ZrO2/C/rGO, evidenced by a positive shift in binding energies of Pd 3d and Ag 3d in XPS.","structureLink":"Lower activity compared to ZrO2-supported catalyst despite similar particle size and larger surface area (862 m2 g-1), highlighting the electronic role of ZrO2.","reactionConditions":"Dehydrogenation of FA at 323 K, nPd+Ag/nFA = 0.027","metricCount":"1"},{"paperId":"P152","catalystId":"P152_PERF_003","name":"Pd0.6Ag0.4@ZrO2/C","matchedCharacterization":"Pd0.6Ag0.4@ZrO2/C/rGO","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic PdAg nanoparticles","particleSize":"2.5 ± 0.03 nm","surfaceStates":"Electron-rich PdAg NP surface resulting from electron transfer from ZrO2 to the metal nanoparticles.","structureLink":"Ultrafine particle size provides more active sites; the electron-rich surface (induced by ZrO2) facilitates O–H bond dissociation of formic acid and favors the formation of the PdAg-formate intermediate.","reactionConditions":"Dehydrogenation of FA at 323 K, nPd+Ag/nFA = 0.027","metricCount":"1"},{"paperId":"P152","catalystId":"P152_PERF_004","name":"Pd0.6Ag0.4@UiO-66/rGO","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA at 323 K, nPd+Ag/nFA = 0.027","metricCount":"1"},{"paperId":"P152","catalystId":"P152_PERF_005","name":"Pd0.6Ag0.4@rGO","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA at 323 K, nPd+Ag/nFA = 0.027","metricCount":"1"},{"paperId":"P152","catalystId":"P152_PERF_006","name":"Pd0.6Ag0.4@UiO-66","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of FA at 323 K, nPd+Ag/nFA = 0.027","metricCount":"1"},{"paperId":"P153","catalystId":"P153_PERF_001","name":"Pd 0.5 Cu 0.5 / MIL-101","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Reduction of Cr(VI) to Cr(III) using formic acid; Carboxylation of terminal alkynes with CO2","selectivity":"10% alkyne dimerization yield","stability":"recycled five times with no loss of activity (Cr reduction)","whyPerformsWell":"MOF captures CO2 around catalytic centers; Lewis acidity of unsaturated chromium sites in MIL-101 enhances adsorption of aromatic substrates","metricCount":"3"},{"paperId":"P153","catalystId":"P153_PERF_002","name":"Pd 0.2 Cu 0.8 / MIL-101","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Reduction of Cr(VI) to Cr(III) using formic acid; Carboxylation of terminal alkynes with CO2","selectivity":"No alkyne dimerization detected","stability":"regenerated and reused at least five times without obvious decreases in catalytic activity (alkyne carboxylation)","whyPerformsWell":"MOF captures CO2 around catalytic centers; Lewis acidity of unsaturated chromium sites in MIL-101 enhances adsorption of aromatic substrates","metricCount":"3"},{"paperId":"P153","catalystId":"P153_PERF_003","name":"Pd 0.3 Cu 0.7 / MIL-101","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Reduction of Cr(VI) to Cr(III) using formic acid; Carboxylation of terminal alkynes with CO2","selectivity":"10% alkyne dimerization yield","stability":"recycled five times with no loss of activity (Cr reduction)","whyPerformsWell":"MOF captures CO2 around catalytic centers; Lewis acidity of unsaturated chromium sites in MIL-101 enhances adsorption of aromatic substrates","metricCount":"3"},{"paperId":"P153","catalystId":"P153_PERF_004","name":"Pd 0.7 Cu 0.3 / MIL-101","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Reduction of Cr(VI) to Cr(III) using formic acid; Carboxylation of terminal alkynes with CO2","selectivity":"20% alkyne dimerization yield","stability":"recycled five times with no loss of activity (Cr reduction)","whyPerformsWell":"MOF captures CO2 around catalytic centers; Lewis acidity of unsaturated chromium sites in MIL-101 enhances adsorption of aromatic substrates","metricCount":"3"},{"paperId":"P153","catalystId":"P153_PERF_005","name":"Pd 0.8 Cu 0.2 / MIL-101","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Reduction of Cr(VI) to Cr(III) using formic acid; Carboxylation of terminal alkynes with CO2","selectivity":"15% alkyne dimerization yield","stability":"recycled five times with no loss of activity (Cr reduction)","whyPerformsWell":"MOF captures CO2 around catalytic centers; Lewis acidity of unsaturated chromium sites in MIL-101 enhances adsorption of aromatic substrates","metricCount":"3"},{"paperId":"P153","catalystId":"P153_PERF_006","name":"Pd-Cu NCs (various ratios)","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Reduction of Cr(VI) to Cr(III) using formic acid; Carboxylation of terminal alkynes with CO2","selectivity":"25-45% alkyne dimerization yield","whyPerformsWell":"Bimetallic catalytic systems show higher activities than single-metal systems due to electron transfer across the metal-metal interface","metricCount":"3"},{"paperId":"P154","catalystId":"P154_PERF_001","name":"Fe@C-Pd","support":"Fe@C","matchedSynthesis":"Fe@C-Pd","matchedCharacterization":"Fe@C-Pd","role":"unmodified catalyst","composition":"Pd","activeMetals":"Fe","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Reduction of Pd2+ in Fe@C suspension using ethylene glycol.","phase":"Monometallic Pd nanoparticles","particleSize":"5-10 nm","surfaceStates":"Pd 3d peaks correspond to majority Pd0; CO-DRIFT showed susceptibility to CO poisoning.","structureLink":"Low activity for FA dehydrogenation and high susceptibility to CO poisoning compared to modified versions.","reactionConditions":"TCE dechlorination in 42 mL serum vials (21 mL deionized water, 21 mL headspace) at 25 °C with rotary shaker (40 rpm)","selectivity":"Ethane was the primary product","metricCount":"2"},{"paperId":"P154","catalystId":"P154_PERF_002","name":"Fe@C-Pd-B","support":"Fe@C","matchedSynthesis":"Fe@C-Pd-B","matchedCharacterization":"Fe@C-Pd-B","role":"modified catalyst","composition":"Pd-B","activeMetals":"Fe","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Liquid-phase reduction in ice-water using Fe@C, DMAB, and Pd(NO3)2 as precursors.","phase":"B atoms penetrated into the Pd lattice, causing expansion and lattice defects.","particleSize":"5-10 nm","surfaceStates":"Pd 3d peak shifted to lower binding energies, indicating electron transfer from B to Pd d orbitals; increased corrosion current (Icorr) compared to Fe@C-Pd.","structureLink":"Expanded lattice spacing (0.239 and 0.237 nm) and electronic effects induced by work function discrepancy enhance electron transfer, promoting FA dehydrogenation and TCE dechlorination stability.","reactionConditions":"TCE dechlorination in 42 mL serum vials (21 mL deionized water, 21 mL headspace) at 25 °C with rotary shaker (40 rpm)","selectivity":"Ethane >95.5%","stability":"Good stability; catalytic activity remained ~157 ± 7 L·g-1·h-1 throughout 10 consecutive experiments","whyPerformsWell":"B incorporation induced charge redistribution and elevated electron density of Pd atoms, promoting FA dehydrogenation and H spillover; B/Pd molar ratio remained unchanged after cycling.","metricCount":"2"},{"paperId":"P154","catalystId":"P154_PERF_003","name":"Fe@C-Pd-Ag","support":"Fe@C","matchedSynthesis":"Fe@C-Pd-Ag","matchedCharacterization":"Fe@C-Pd-Ag","role":"modified catalyst","composition":"Pd-Ag","activeMetals":"Fe","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Liquid-phase reduction using Fe@C, Pd(NO3)2, and AgNO3 as precursors.","phase":"Pd-Ag alloy structure","particleSize":"5-10 nm","surfaceStates":"Pronounced shift of Pd 3d peak to lower binding energies (larger than B modification), indicating significant electron transfer from Ag to Pd; highest Icorr among catalysts.","structureLink":"Lattice expansion (0.230 and 0.235 nm) and large work function discrepancy facilitate H*ads formation and spillover, leading to the highest initial TCE dechlorination rate but poor stability due to Ag leaching.","reactionConditions":"TCE dechlorination in 42 mL serum vials (21 mL deionized water, 21 mL headspace) at 25 °C with rotary shaker (40 rpm)","selectivity":"Ethene ~45.5%, Ethane ~55.5%","stability":"Poor stability; reactivity dramatically decreased since the 2nd cycle","deactivation":"Leaching of Ag atoms from Pd-Ag NPs induced by accumulated Cl- during TCE dechlorination, destroying the alloy structure","whyPerformsWell":"Larger work function discrepancy between Ag and Pd compared to B/Pd induced a larger shift in Pd peaks, lower reductive onset potential, higher current density, and suppressed H2 accumulation promoting H spillover.","metricCount":"2"},{"paperId":"P155","catalystId":"P155_PERF_001","name":"Au0.4Pd0.6/PEI-PDA@CNCs","support":"PEI-PDA@CNC","matchedSynthesis":"Au0.4Pd0.6/PEI-PDA@CNC","matchedCharacterization":"Au0.4Pd0.6/PEI-PDA@CNC","role":"optimized catalyst","composition":"Au:Pd = 0.4:0.6","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Metal precursors were added to the modified CNC suspension, stirred at room temperature and in an ice bath, followed by reduction with NaBH4.","phase":"AuPd alloy; confirmed by XRD (post-heating peaks between Au and Pd), HRTEM lattice spacing of 0.229 nm, absence of Au plasma resonance peak at 516 nm in UV-Vis, and EDS mapping showing co-localization of Au and Pd.","particleSize":"2.18 ± 0.4 nm","surfaceStates":"Electron transfer from Pd to Au (Au 4f shifted to lower binding energy 83.0 eV, Pd 3d shifted to higher binding energy 336.3 eV); strong metal-support interaction (SMSI) between the alloy and PEI-PDA@CNC carrier.","structureLink":"The optimized local electronic structure promotes bi-HCOO* rearrangement and lowers the energy barrier for H* binding; high dispersion increases metal utilization rates.","reactionConditions":"Mixed aqueous solution of formic acid (FA) and sodium formate (SF) in a two-necked flask with water bath heating.","selectivity":"100% hydrogen selectivity; no CO detected by FID detector","stability":"Activity did not decrease significantly after 5 cycles at 323 K","deactivation":"Slight increase in particle size from ~2 nm to 2.29 nm after 5 cycles","whyPerformsWell":"Modified CNCs enhance electron transfer between metal particles; optimization of local electronic structure improves adsorption of key intermediates; strong metal-support interaction (SMSI) effect; amine groups promote the breakage of O-H bonds.","metricCount":"2"},{"paperId":"P155","catalystId":"P155_PERF_002","name":"Au/PEI-PDA@CNC","matchedCharacterization":"Au/PEI-PDA@CNC","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Monometallic Au","particleSize":"Relatively large nanoparticles compared to Pd/PEI-PDA@CNC","surfaceStates":"Au 4f binding energy at 83.3 eV","structureLink":"Low catalytic activity for FA dehydrogenation due to weak adsorption of H.","reactionConditions":"323 K, mixed aqueous (FA, SF)","whyPerformsWell":"Au has a low catalytic activity for FA","metricCount":"1"},{"paperId":"P155","catalystId":"P155_PERF_003","name":"Pd/PEI-PDA@CNC","matchedCharacterization":"Pd/PEI-PDA@CNC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Monometallic Pd","particleSize":"Smallest average size among the tested catalysts","surfaceStates":"Pd 3d binding energy at 335.3 eV","structureLink":"Poor activity due to high surface energy of tiny particles increasing the energy required for hydrogen desorption.","reactionConditions":"323 K, mixed aqueous (FA, SF)","whyPerformsWell":"Tiny size of Pd particles increases surface energy and requires more energy for hydrogen desorption","metricCount":"1"},{"paperId":"P155","catalystId":"P155_PERF_004","name":"carrier-free Au0.4Pd0.6","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"323 K, mixed aqueous (FA, SF)","whyPerformsWell":"Aggregation of metal particles","metricCount":"1"},{"paperId":"P155","catalystId":"P155_PERF_005","name":"unmodified Au0.4Pd0.6/CNC","matchedCharacterization":"Au0.4Pd0.6/CNC","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","structureLink":"Poor catalytic activity attributed to metal particle aggregation.","reactionConditions":"323 K, mixed aqueous (FA, SF)","whyPerformsWell":"Aggregation of metal particles; no good interaction between metals and carrier","metricCount":"1"},{"paperId":"P156","catalystId":"P156_PERF_001","name":"Ti3C2Tx-250","matchedSynthesis":"Ti3C2Tx-250","matchedCharacterization":"Ti3C2Tx-250","role":"catalyst","composition":"Ti","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Etching and thermal treatment","synthesis":"Ti3C2Tx-25 was treated in a muffle furnace with air at 250 °C for 1 h.","phase":"Ti3C2Tx MXene phase","particleSize":"Lattice spacing of 2.6 Å corresponding to (0110) crystal plane","surfaceStates":"High surface oxygen coverage: Surface O-Ti species (26.5% relative proportion), surface OH groups, and surface-adsorbed oxygen.","structureLink":"Increased oxygen coverage promotes the conversion from HCOO* to CO2* by lowering the energy barrier and weakens the adsorption energy of CO2 and H2; active sites are identified as surface [O-Ti-C] species.","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","selectivity":"100% selectivity for H2; no CO detected","stability":"almost 90% of the original activity was preserved after four rounds","whyPerformsWell":"Increasing oxygen coverage promotes conversion from HCOO* to CO2* by lowering the energy barrier and weakens adsorption energy of CO2 and H2","metricCount":"3"},{"paperId":"P156","catalystId":"P156_PERF_002","name":"Ti3C2Tx-25","matchedSynthesis":"Ti3C2Tx-25","matchedCharacterization":"Ti3C2Tx-25","role":"catalyst","composition":"Ti","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Etching","synthesis":"Commercial Ti3AlC2 powder was immersed in 40% HF for 72 h at room temperature, washed with ethanol and water to pH 6.0, centrifuged, dried, and ultrasonicated in water for 24 h.","phase":"Ti3C2Tx MXene phase","surfaceStates":"Surface O-Ti species (3.4% relative proportion)","structureLink":"Low oxygen coverage results in lower catalytic activity for HCOOH dehydrogenation compared to Ti3C2Tx-250.","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"1"},{"paperId":"P156","catalystId":"P156_PERF_003","name":"Ti3C2Tx-150","matchedSynthesis":"Ti3C2Tx-150","matchedCharacterization":"Ti3C2Tx-150","role":"catalyst","composition":"Ti","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Etching and thermal treatment","synthesis":"Ti3C2Tx-25 was treated in a muffle furnace with air at 150 °C for 1 h.","phase":"Ti3C2Tx MXene phase","surfaceStates":"Surface O-Ti species (7.3% relative proportion)","structureLink":"Moderate increase in oxygen coverage slightly improves activity over Ti3C2Tx-25.","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"1"},{"paperId":"P156","catalystId":"P156_PERF_004","name":"Ti3C2Tx-350","matchedSynthesis":"Ti3C2Tx-350","matchedCharacterization":"Ti3C2Tx-350","role":"catalyst","composition":"Ti","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Etching and thermal treatment","synthesis":"Ti3C2Tx-25 was treated in a muffle furnace with air at 350 °C for 1 h.","phase":"MXene/TiO2 mixture","surfaceStates":"Dominated by lattice oxygen in TiO2; negligible Ti-C and Ti-F peaks in XPS.","structureLink":"Excessive oxidation to TiO2 phase leads to a decrease in catalytic activity compared to Ti3C2Tx-250.","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"1"},{"paperId":"P156","catalystId":"P156_PERF_005","name":"Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"2"},{"paperId":"P156","catalystId":"P156_PERF_006","name":"Pt/C","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"2"},{"paperId":"P156","catalystId":"P156_PERF_007","name":"Ti2CTx-250","matchedSynthesis":"Ti2CTx-250","matchedCharacterization":"Ti2CTx series (Ti2CTx-25, Ti2CTx-150, Ti2CTx-250, Ti2CTx-350)","role":"catalyst","composition":"Ti","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Etching and thermal treatment","synthesis":"Ti2CTx-25 was treated in a muffle furnace with air at 250 °C for 1 h.","phase":"Ti2CTx MXene","surfaceStates":"Oxygen coverage modulated by thermal treatment","structureLink":"Catalytic activity is modulated by surface oxygen coverage, with Ti2CTx-250 exhibiting the highest activity among the series.","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"1"},{"paperId":"P156","catalystId":"P156_PERF_008","name":"Ti2CTx-25","matchedSynthesis":"Ti2CTx-25","matchedCharacterization":"Ti2CTx series (Ti2CTx-25, Ti2CTx-150, Ti2CTx-250, Ti2CTx-350)","role":"catalyst","composition":"Ti","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Etching","synthesis":"Commercial Ti2AlC powder was immersed in 16% HF for 72 h at room temperature, washed with ethanol and water to pH 6.0, centrifuged, dried, and ultrasonicated in water for 24 h.","phase":"Ti2CTx MXene","surfaceStates":"Oxygen coverage modulated by thermal treatment","structureLink":"Catalytic activity is modulated by surface oxygen coverage, with Ti2CTx-250 exhibiting the highest activity among the series.","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"1"},{"paperId":"P156","catalystId":"P156_PERF_009","name":"Ti2CTx-150","matchedSynthesis":"Ti2CTx-150","matchedCharacterization":"Ti2CTx series (Ti2CTx-25, Ti2CTx-150, Ti2CTx-250, Ti2CTx-350)","role":"catalyst","composition":"Ti","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Etching and thermal treatment","synthesis":"Ti2CTx-25 was treated in a muffle furnace with air at 150 °C for 1 h.","phase":"Ti2CTx MXene","surfaceStates":"Oxygen coverage modulated by thermal treatment","structureLink":"Catalytic activity is modulated by surface oxygen coverage, with Ti2CTx-250 exhibiting the highest activity among the series.","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"1"},{"paperId":"P156","catalystId":"P156_PERF_010","name":"Ti2CTx-350","matchedSynthesis":"Ti2CTx-350","matchedCharacterization":"Ti2CTx series (Ti2CTx-25, Ti2CTx-150, Ti2CTx-250, Ti2CTx-350)","role":"catalyst","composition":"Ti","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"Etching and thermal treatment","synthesis":"Ti2CTx-25 was treated in a muffle furnace with air at 350 °C for 1 h.","phase":"Ti2CTx MXene","surfaceStates":"Oxygen coverage modulated by thermal treatment","structureLink":"Catalytic activity is modulated by surface oxygen coverage, with Ti2CTx-250 exhibiting the highest activity among the series.","reactionConditions":"80 °C, 2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","metricCount":"1"},{"paperId":"P157","catalystId":"P157_PERF_001","name":"Pd0/CeO2","support":"nanoceria (CeO2)","matchedSynthesis":"Pd0/CeO2","matchedCharacterization":"Pd0/CeO2","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Ceria was stirred in an aqueous solution of palladium(II) nitrate for 18 h, followed by dropwise addition of NaBH4 at room temperature. The resulting catalyst was isolated via centrifugation, washed with distilled water, and vacuum dried.","phase":"Monometallic Pd(0) nanoparticles supported on nanoceria; XRD showed no observable peaks for Pd due to low loading and small particle size.","particleSize":"1.6–4.0 nm (mean diameter: 1.9 ± 0.4 nm) for 2.27% wt Pd; mean diameter 2.5 ± 0.6 nm for 4.73% wt Pd.","surfaceStates":"Pd(0) identified by XPS peaks at 335.3 eV (3d5/2) and 340.6 eV (3d3/2).","structureLink":"The higher catalytic activity of the 2.27% wt Pd sample compared to the 4.73% wt Pd sample is attributed to its smaller mean particle size (1.9 nm vs 2.5 nm). The overall superb activity is ascribed to the reducible nature of ceria and the redox cycling between Ce4+ and Ce3+.","reactionConditions":"Dehydrogenation of formic acid (FA) in aqueous solution with sodium formate (SF), molar ratio FA/SF = 1/9, temperature 25.0 ± 0.1 °C, stirring at 1200 rpm, atmospheric pressure 0.91 atm, N2 atmosphere.","selectivity":"No carbon monoxide was detected; selectively promotes dehydrogenation over dehydration.","stability":"Provided only 50% conversion of FA in the second run.","deactivation":"No leaching of palladium into solution. Deactivation attributed to agglomeration of nanoparticles on ceria surface and deposition of sodium formate species.","whyPerformsWell":"Ascribed to the reducible nature of ceria (redox cycling between Ce4+ and Ce3+) during FA decomposition.","metricCount":"5"},{"paperId":"P157","catalystId":"P157_PERF_002","name":"Pd0/SiO2, Pd0/Al2O3, Pd0/TiO2, Pd0/ZrO2, Pd0/HfO2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd0/CeO2: 1.6 mM Pd concentration, SF/FA = 9:1, 25 °C.","whyPerformsWell":"Lower activity compared to Pd0/CeO2.","metricCount":"0"},{"paperId":"P158","catalystId":"P158_PERF_001","name":"AuPd/T-g-C3N4","support":"T-g-C3N4","matchedSynthesis":"AuPd/T-g-C3N4","matchedCharacterization":"AuPd/T-g-C3N4","role":"catalyst","composition":"AuPd (molar ratio Au/Pd = 1/3)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Precursors dissolved in deionized water, support added, reduced with NaBH4 at room temperature for 12 h.","phase":"Alloy particles","particleSize":"5.4 nm","surfaceStates":"Electron transfer from g-C3N4 support to Au.","structureLink":"Highest catalytic activity attributed to the confinement effect of the one-dimensional nanotubular geometry, which increases reactant concentration inside the nanoreactor.","reactionConditions":"Dehydrogenation of formic acid at 25, 40, 50, and 60 °C under atmospheric pressure.","stability":"Reasonably high stability over three cycles; activity almost unchanged in the second cycle and slightly decreased in the third cycle.","deactivation":"Slight decrease in activity during the third cycle due to by-products and intermediates trapped on AuPd surface and support pores.","whyPerformsWell":"Confinement effect of the one-dimensional nanotubular structure which increases reactant concentration inside the nanoreactor, combined with electron donation from nitrogen species in g-C3N4 to AuPd particles.","metricCount":"4"},{"paperId":"P158","catalystId":"P158_PERF_002","name":"AuPd/S-g-C3N4","support":"S-g-C3N4","matchedSynthesis":"AuPd/S-g-C3N4","matchedCharacterization":"AuPd/S-g-C3N4","role":"catalyst","composition":"AuPd (molar ratio Au/Pd = 1/3)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Precursors dissolved in deionized water, support added, reduced with NaBH4 at room temperature for 12 h.","phase":"Alloy particles","particleSize":"2.7 nm","surfaceStates":"Electron transfer from g-C3N4 support to Au; highest graphitic N content helps modify electron density for smaller particle size.","structureLink":"Higher activity than bulk B-g-C3N4 attributed to smaller nanoparticle size and higher surface area.","reactionConditions":"Dehydrogenation of formic acid at 25 °C and atmospheric pressure.","whyPerformsWell":"Smaller and well-distributed AuPd particle size induced by the nanosheet morphology and higher graphitic N content.","metricCount":"1"},{"paperId":"P158","catalystId":"P158_PERF_003","name":"AuPd/B-g-C3N4","support":"B-g-C3N4","matchedSynthesis":"AuPd/B-g-C3N4","matchedCharacterization":"AuPd/B-g-C3N4","role":"catalyst","composition":"AuPd (molar ratio Au/Pd = 1/3)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Precursors dissolved in deionized water, support added, reduced with NaBH4 at room temperature for 12 h.","phase":"Alloy particles","particleSize":"4.6 nm","surfaceStates":"Electron transfer from g-C3N4 support to Au (lower binding energies in XPS)","structureLink":"Higher activity than AuPd/g-C due to nitrogen anchoring and electron donation effects.","reactionConditions":"Dehydrogenation of formic acid at 25 °C and atmospheric pressure.","whyPerformsWell":"Nitrogen species act as anchoring points and donate electrons to AuPd particles.","metricCount":"0"},{"paperId":"P158","catalystId":"P158_PERF_004","name":"AuPd/g-C","support":"graphene nanoplatelets","matchedSynthesis":"AuPd/g-C","matchedCharacterization":"AuPd/g-C","role":"catalyst","composition":"AuPd (molar ratio Au/Pd = 1/3)","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Precursors dissolved in deionized water, support added, reduced with NaBH4 at room temperature for 12 h.","phase":"Alloy particles","particleSize":"5.5 nm","structureLink":"Lowest activity among the tested catalysts; rapid deactivation possibly due to adsorption of reactants or intermediates.","reactionConditions":"Dehydrogenation of formic acid at 25 °C and atmospheric pressure.","deactivation":"Deactivated rapidly, possibly due to the adsorption of reactants or intermediates on the metal surface.","metricCount":"1"},{"paperId":"P159","catalystId":"P159_PERF_001","name":"Pd/AC–CP (250 W, 10 min)","support":"activated carbon (AC)","matchedSynthesis":"Pd/AC-CP (250 W, 10 min)","matchedCharacterization":"Pd/AC–CP (250 W, 10 min)","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation followed by vacuum drying, H2 thermal reduction, and N2 RF cold plasma treatment.","phase":"Face-centered cubic metallic Pd(111)","particleSize":"1.9 ± 0.4 nm","surfaceStates":"Pd0 (336.0 eV) and Pd2+ (337.8 eV); shifted to lower binding energies compared to Pd/AC–C, indicating electron transfer from N species to Pd.","structureLink":"Smallest particle size, highest specific surface area (877.6 m2/g), high pyridine nitrogen content (39.8%), and electron-rich Pd0 sites lead to the lowest activation energy (29.67 kJ/mol) and highest TOF.","reactionConditions":"Formic acid dehydrogenation at 50 °C, stirring at 200 r·min-1","selectivity":"No CO was detected during the reactions.","stability":"Significantly enhanced stability; gas generation for the third cycle was 87.8% of that in the first cycle.","whyPerformsWell":"Surface-enriched and redispersed Pd species (small particle size 1.9 nm), large specific surface area (877.6 m2·g-1), high Pd/C atomic ratio, and enhanced N-doping (specifically pyridine nitrogen) acting as a Lewis base to promote deprotonation of FA.","metricCount":"4"},{"paperId":"P159","catalystId":"P159_PERF_002","name":"Pd/AC–C","support":"activated carbon (AC)","matchedSynthesis":"Pd/AC-C","matchedCharacterization":"Pd/AC–C","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation, vacuum drying, and H2 thermal reduction.","phase":"Face-centered cubic metallic Pd(111) and (200)","particleSize":"2.1 ± 0.5 nm","surfaceStates":"Pd0 (336.2 eV) and Pd2+ (338.0 eV)","structureLink":"Small size and uniform dispersion anchored by oxygen-rich functional groups on AC support contribute to high catalytic performance.","reactionConditions":"Formic acid dehydrogenation at 50 °C, stirring at 200 r·min-1","selectivity":"No CO was detected during the reactions.","stability":"Activity decreased with increasing number of cycles; gas generation for the third cycle was 63.9% of that in the first cycle.","whyPerformsWell":"Plentiful oxygen-containing groups on AC surface anchored metal precursors, resulting in small Pd NP size and better dispersion.","metricCount":"4"},{"paperId":"P159","catalystId":"P159_PERF_003","name":"Pd/AC-P (250 W, 10 min)","support":"activated carbon (AC)","matchedSynthesis":"Pd/AC-P (250 W, 10 min)","matchedCharacterization":"Pd/AC-P (250 W, 10 min)","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation, vacuum drying, and N2 RF cold plasma treatment without thermal reduction.","phase":"Face-centered cubic metallic Pd","particleSize":"5.4 ± 1.9 nm","surfaceStates":"Pd0 (336.2 eV) and Pd2+ (338.0 eV)","structureLink":"Poor activity attributed to larger particle size, lower reduction degree, and reduced specific surface area (733.9 m2/g).","reactionConditions":"Formic acid dehydrogenation at 50 °C","whyPerformsWell":"Poor catalytic activity because plasma treatment destroyed the interaction between oxygen-rich groups on AC and metal precursors, leading to reduced pore volume/surface area and larger Pd NPs.","metricCount":"0"},{"paperId":"P160","catalystId":"P160_PERF_001","name":"Ni0.4@Pd0.6/NH2-Fe3O4","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Formic acid dehydrogenation in aqueous solution at 60 °C, using a two-neck round-bottom flask with magnetic stirring and gas volume measurement via water displacement.","selectivity":"Volume ratio of CO2 and H2 is 1:1; GC spectrum demonstrated no CO from the evolved gas.","stability":"Utilized for four runs with no considerable loss of activity.","whyPerformsWell":"Synergic effect between Ni and Pd; presence of more active Pd nanoparticles on shell and less expensive Ni nanoparticles on core; well dispersion due to NH2 groups on magnetic nanoparticles.","metricCount":"6"},{"paperId":"P161","catalystId":"P161_PERF_001","name":"Pd/C","matchedCharacterization":"Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pure Pd NPs (fcc)","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II)","structureLink":"Lowest FAD activity despite having the highest ECSA (323 m2 g-1).","reactionConditions":"Room-temperature formic acid decomposition (FAD)","metricCount":"2"},{"paperId":"P161","catalystId":"P161_PERF_002","name":"Pd0.90Au0.10/C","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content.","reactionConditions":"Room-temperature formic acid decomposition (FAD)","metricCount":"2"},{"paperId":"P161","catalystId":"P161_PERF_003","name":"Pd0.82Au0.18/C","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content.","reactionConditions":"Room-temperature formic acid decomposition (FAD)","metricCount":"2"},{"paperId":"P161","catalystId":"P161_PERF_004","name":"Pd0.75Au0.25/C","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content.","reactionConditions":"Room-temperature formic acid decomposition (FAD)","metricCount":"2"},{"paperId":"P161","catalystId":"P161_PERF_005","name":"Pd0.69Au0.31/C","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content.","reactionConditions":"Room-temperature formic acid decomposition (FAD)","selectivity":"Gas composed of 46.91% H2, 1.45% O2, 6.82% N2 and 44.82% CO2; no CO detectable","stability":"No obvious change in catalytic activity after five cycles","whyPerformsWell":"Optimized balance of lattice strain and ligand effects induced by Au alloying, promoting the formation of surface active species (PdO)","metricCount":"2"},{"paperId":"P161","catalystId":"P161_PERF_006","name":"Pd0.64Au0.36/C","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content.","reactionConditions":"Room-temperature formic acid decomposition (FAD)","whyPerformsWell":"Activity decreased compared to Pd0.69Au0.31/C due to the ligand effect of Au becoming dominant at high Au ratios (>0.31), weakening the capability of Pd towards dissociative adsorption of O2","metricCount":"2"},{"paperId":"P161","catalystId":"P161_PERF_007","name":"Au/C","support":"carbon powder","matchedSynthesis":"PdAu/C","matchedCharacterization":"Au/C","role":"catalyst for room-temperature formic acid decomposition (FAD)","composition":"Pd and Au; atomic ratios of Au varied from 0 to 0.36 (samples: Pd/C, Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"PdAu/C alloyed catalysts were synthesized via a modified coprecipitation-reduction method using carbon powder as support and Pd(H2PdCl4) and Au(HAuCl4) precursors.","phase":"Pure Au NPs","structureLink":"No detectable gas generated during FAD.","reactionConditions":"Room-temperature formic acid decomposition (FAD)","metricCount":"1"},{"paperId":"P162","catalystId":"P162_PERF_001","name":"PdAu/NH2-W18O49","matchedCharacterization":"PdAu/NH2-W18O49","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"fcc PdAu alloy","particleSize":"~2.9 nm","surfaceStates":"Electron-rich Pd sites (negative XPS binding energy shift); surface modified with -NH2 groups (Lewis base sites); abundant oxygen vacancies (W5+ species in XPS and EPR signal at g = 2.004).","structureLink":"The O_v-rich W18O49 support enables a highly efficient hydrogen spillover effect, facilitating the storage of dissociated H atoms and desorption of adsorbates, which reduces activation energy for FA dehydrogenation (21.8 kJ/mol) and CO2 hydrogenation (11.8 kJ/mol).","reactionConditions":"Formic acid (FA) dehydrogenation and CO2 hydrogenation to formate","selectivity":"CO-free FA dehydrogenation (only H2 and CO2 detected); no gaseous products (CO or CH4) detectable for CO2 hydrogenation","stability":"FA dehydrogenation: conversion unchanged after 4 consecutive runs at 323 K; CO2 hydrogenation: maintained 88% of initial activity after 5 consecutive runs","deactivation":"Slight decrease in FA dehydrogenation rate and loss of active sites in long-term CO2 hydrogenation (up to 36 h) attributed to PdAu NP agglomeration and possible CO poisoning","whyPerformsWell":"Synergistic effect from bimetallic PdAu NPs, -NH2 groups (facilitating O-H bond dissociation and capturing CO2/HCO3-), and W18O49 support with abundant oxygen vacancies which enhance the hydrogen spillover effect, facilitating H atom storage and adsorbate desorption","metricCount":"2"},{"paperId":"P162","catalystId":"P162_PERF_002","name":"Pd/NH2-W18O49","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","metricCount":"3"},{"paperId":"P162","catalystId":"P162_PERF_003","name":"PdAu/NH2-WO3","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","metricCount":"3"},{"paperId":"P162","catalystId":"P162_PERF_004","name":"PdAu/W18O49","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","deactivation":"Dramatic activity decline for CO2 hydrogenation due to aggregated PdAu NPs and lack of -NH2 groups","metricCount":"1"},{"paperId":"P162","catalystId":"P162_PERF_005","name":"Au/NH2-W18O49","matchedCharacterization":"PdAu/NH2-W18O49","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"fcc PdAu alloy","particleSize":"~2.9 nm","surfaceStates":"Electron-rich Pd sites (negative XPS binding energy shift); surface modified with -NH2 groups (Lewis base sites); abundant oxygen vacancies (W5+ species in XPS and EPR signal at g = 2.004).","structureLink":"The O_v-rich W18O49 support enables a highly efficient hydrogen spillover effect, facilitating the storage of dissociated H atoms and desorption of adsorbates, which reduces activation energy for FA dehydrogenation (21.8 kJ/mol) and CO2 hydrogenation (11.8 kJ/mol).","metricCount":"1"},{"paperId":"P162","catalystId":"P162_PERF_006","name":"bare W18O49","activeMetals":"W","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","metricCount":"1"},{"paperId":"P163","catalystId":"P163_PERF_001","name":"PdCuCr/resin (Pd1Cu0.5Cr0.5/resin)","support":"IRA96SB resin","matchedSynthesis":"PdCuCr/resin","matchedCharacterization":"PdCuCr/resin","role":"ternary catalyst","composition":"Pd/Cu/Cr = 1:0.5:0.5","activeMetals":"Pd-Cu-Cr","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Resin was crushed, mixed with an aqueous solution of metal precursors, stirred at room temperature for 1 hour, evaporated under vacuum, dried overnight, and then prereduced with NaBH4.","phase":"Random ternary alloy structure with Pd, Cu, and Cr distributed homogeneously throughout the NPs, though Cr specifically constitutes surface clusters.","particleSize":"8.1 nm (fresh/pretreated); 2.3 nm (isolated after induction period/reaction)","surfaceStates":"Electron-rich Pd species (XPS binding energy shifted to 335.4 eV compared to 335.8 eV for monometallic Pd).","structureLink":"In situ construction of highly dispersed NPs and the synergistic alloying effect of Cr boost C-H bond dissociation (KIE = 1.37). Surface Cr clusters act as anchors to inhibit agglomeration, enhancing durability. Electron-rich Pd stabilizes bridging formate intermediates, suppressing CO production.","reactionConditions":"HCOOH/HCOONa (9:1) aqueous solution, 348 K, magnetic stirring, Ar atmosphere","selectivity":"CO concentration: 1.4 ppm after 1h","stability":"High durability; volume of evolved gas increased linearly with reaction time; particles remained at 2.3 nm without agglomeration after 1h","deactivation":"No metal leaching observed by ICP-OES","whyPerformsWell":"Synergistic alloying effect induced by Cr atoms boosts C-H bond dissociation step; surface Cr clusters act as anchors to inhibit NP agglomeration; electron-rich Pd species stabilize bridging formate intermediate","metricCount":"4"},{"paperId":"P163","catalystId":"P163_PERF_002","name":"PdCu/resin (Pd1Cu0.5/resin)","matchedCharacterization":"PdCu/resin","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic alloy","particleSize":"2.0 nm (initial); 3.7 nm (after reaction)","surfaceStates":"Electron-rich Pd species (XPS binding energy of 335.4 eV).","structureLink":"Suppresses CO production (2.0 ppm) better than monometallic Pd but exhibits more agglomeration and lower activity than the ternary PdCuCr system.","reactionConditions":"HCOOH/HCOONa (9:1) aqueous solution, 348 K","selectivity":"CO concentration: 2.0 ppm after 1h","stability":"Activity decreased gradually over time; particle size increased from 2.0 nm to 3.7 nm after 1h","whyPerformsWell":"Electron-rich Pd species minimize CO production compared to monometallic Pd","metricCount":"2"},{"paperId":"P163","catalystId":"P163_PERF_003","name":"Pd/resin","matchedCharacterization":"Pd/resin","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Monometallic","particleSize":"2.4 nm (initial); 4.6 nm (after reaction)","surfaceStates":"XPS binding energy of 335.8 eV.","structureLink":"Prone to significant agglomeration and higher CO poisoning (7.0 ppm) compared to alloyed systems.","reactionConditions":"HCOOH/HCOONa (9:1) aqueous solution, 348 K","selectivity":"CO concentration: 7.0 ppm after 1h","stability":"Significant enlargement of particles from 2.4 nm to 4.6 nm after 1h","deactivation":"Durability decreased due to CO poisoning","metricCount":"2"},{"paperId":"P164","catalystId":"P164_PERF_001","name":"Pd/CS","support":"Chitosan (CS)","matchedSynthesis":"Pd/CS","matchedCharacterization":"Pd/CS","role":"Catalyst for hydrogen generation from formate","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CS beads were impregnated with Pd precursor, converted to alcogels via ethanol exchange, reduced with NaBH4 in ethanol, and dried using supercritical CO2.","phase":"Pd nanoparticles","particleSize":"1.7 ± 0.5 nm (fresh); grew to 3.67–6.17 nm after reaction","structureLink":"Gradual deactivation attributed to Pd NP agglomeration and increase in average particle size.","reactionConditions":"Ammonium formate decomposition in aqueous solution, 25-60 °C","selectivity":"no formation of CO or methane detected","stability":"gradual deactivation upon reuse; initial reaction rate and final hydrogen production at 24 h decreased","deactivation":"Pd NP size increased from 1.7 nm to 3.67–6.17 nm after reaction","metricCount":"1"},{"paperId":"P164","catalystId":"P164_PERF_002","name":"Pd/CS-GO2","support":"Chitosan-Graphene Oxide (CS-GO)","matchedSynthesis":"Pd/CS-GO2","matchedCharacterization":"Pd/CS-GO2","role":"Catalyst for hydrogen generation from formate","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CS-GO beads were impregnated with Pd precursor, converted to alcogels via ethanol exchange, reduced with NaBH4 in ethanol, and dried using supercritical CO2.","phase":"Pd nanoparticles","particleSize":"1.8 ± 0.8 nm (fresh); grew to 3.67 nm after reuse","surfaceStates":"Pd(0) at 336.05 eV and PdO (Pd2+) at 338.21 eV; Pd(0)/Pd2+ ratio of 1.35","structureLink":"Deactivation caused by agglomeration of Pd NPs; optimal particle size for activity suggested to be ~2 nm.","reactionConditions":"Ammonium formate decomposition in methanol, 60 °C","selectivity":"no formation of CO or methane detected","stability":"gradual deactivation upon reuse","deactivation":"Pd leached was <0.006% of initial total Pd content; average particle size increased from 1.7 nm to 3.67 nm upon reuse","whyPerformsWell":"GO acts as crosslinker enhancing mechanical stability and maintaining surface area/porosity, favoring better metal-support interaction with Pd NPs","metricCount":"1"},{"paperId":"P164","catalystId":"P164_PERF_003","name":"10% Pd/AC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Ammonium formate decomposition in water, 60 °C","metricCount":"1"},{"paperId":"P164","catalystId":"P164_PERF_004","name":"Pd/CS-GO1","support":"Chitosan-Graphene Oxide (CS-GO)","matchedSynthesis":"Pd/CS-GO1","matchedCharacterization":"Pd/CS-GO1","role":"Catalyst for hydrogen generation from formate","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CS-GO beads were impregnated with Pd precursor, converted to alcogels via ethanol exchange, reduced with NaBH4 in ethanol, and dried using supercritical CO2.","phase":"Pd nanoparticles","particleSize":"1.6 ± 0.9 nm","reactionConditions":"Ammonium formate decomposition in methanol, 60 °C","metricCount":"0"},{"paperId":"P164","catalystId":"P164_PERF_005","name":"Pd/CS-GO3","support":"Chitosan-Graphene Oxide (CS-GO)","matchedSynthesis":"Pd/CS-GO3","matchedCharacterization":"Pd/CS-GO3","role":"Catalyst for hydrogen generation from formate","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CS-GO beads were impregnated with Pd precursor, converted to alcogels via ethanol exchange, reduced with NaBH4 in ethanol, and dried using supercritical CO2.","phase":"Pd nanoparticles","particleSize":"1.7 ± 0.5 nm","reactionConditions":"Ammonium formate decomposition in methanol, 60 °C","metricCount":"0"},{"paperId":"P165","catalystId":"P165_PERF_001","name":"Pd/PPy-S1","support":"polypyrrole (PPy)","matchedSynthesis":"Pd/PPy-S1","matchedCharacterization":"Pd/PPy-S1","role":"catalyst for hydrogen production from formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PPy-S1 was dispersed in deionized water, followed by dropwise addition of H2PdCl4 solution. After stirring for 30 min, sodium formate (HCOONa) solution was added as a reducing agent and stirred at room temperature for 5 hours.","phase":"Pd nanoparticles (low crystallinity/fine particles)","particleSize":"5-30 nm","surfaceStates":"XPS Pd 3d peaks: Pd(0) at 335.4 eV and 340.6 eV; Pd(II) at 338.0 eV and 343.4 eV","structureLink":"Higher catalytic activity compared to Pd/PPy-S2 despite smaller specific surface area (7.8 m2/g), attributed to different valence ratios of Pd 3d and distinctive interaction between Pd and the in situ polymerized PPy support.","reactionConditions":"60 °C, aqueous solution, with sodium formate additive","stability":"Maintained high activity even at the fourth recycle","whyPerformsWell":"Distinctive interaction of Pd and PPy resulting from different valence ratios of Pd 3d","metricCount":"1"},{"paperId":"P165","catalystId":"P165_PERF_002","name":"Pd/PPy-S2","support":"polypyrrole (PPy)","matchedSynthesis":"Pd/PPy-S2","matchedCharacterization":"Pd/PPy-S2","role":"comparison catalyst for hydrogen production from formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Commercial PPy-S2 was dispersed in deionized water, followed by dropwise addition of H2PdCl4 solution. After stirring for 30 min, sodium formate (HCOONa) solution was added as a reducing agent and stirred at room temperature for 5 hours.","phase":"Pd nanoparticles (good crystal shape and larger particles; XRD peaks at 2 theta = 40, 46, 68)","particleSize":"5-30 nm","surfaceStates":"XPS Pd 3d peaks: Pd(0) at 336.2 eV and 341.6 eV; Pd(II) at 338.6 eV and 344.0 eV","structureLink":"Lower catalytic activity than Pd/PPy-S1 despite larger specific surface area (384.3 m2/g) and better dispersion, attributed to different valence ratios of Pd 3d.","reactionConditions":"60 °C, aqueous solution, with sodium formate additive","stability":"Catalytic activity was slightly decreased after four cycles","deactivation":"Pd particles were slightly grown (indicated by XRD)","metricCount":"1"},{"paperId":"P166","catalystId":"P166_PERF_001","name":"Pd/NMC-8","support":"nitrogen-doped mesoporous carbon (NMC-8)","matchedSynthesis":"Pd/NMC-8","matchedCharacterization":"Pd/NMC-8","role":"bifunctional catalyst for formate-based hydrogen storage","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Support fabricated by hard templating with Zr-SBA-15, template removed via HF washing, and nitridated under ammonia flow at 873 K. Palladium was then loaded using wet-chemical reduction.","phase":"Pd0 (111) crystal plane","particleSize":"2.4 ± 0.5 nm","surfaceStates":"Electron-enriched metallic palladium; binding energy is 0.4 eV lower than Pd/MC-8 due to electron donation from nitrogen species (pyridine, nitrile, pyrrole, and quaternary N).","structureLink":"High activity is attributed to the good dispersion and small size of Pd NPs resulting from interactions between palladium and nitrogen functional groups in the support.","reactionConditions":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","selectivity":"No CO signal detected by gas-phase chromatography or TPD-MS during dehydrogenation of formate.","stability":"For hydrogenation: conversion decreases after first run then levels off; yield after 4th run remains superior to Pd/MC-8 and Pd/AC. For dehydrogenation at 353 K: activity slightly higher in second run, falling again in third run.","deactivation":"Deactivation tentatively attributed to adsorption of reaction product HCO3- blocking active sites; can be circumvented by washing with deionized water and drying in vacuum at 333–353 K.","whyPerformsWell":"Nitrogen functionalities (especially pyridine N) interact with Pd precursors leading to well-dispersed, small nanoparticles (~2.4 nm). Electron donation from the support increases electron density of Pd NPs. Potential electrostatic interaction between nitrogen species and positively polarized carbon in reactants.","metricCount":"6"},{"paperId":"P166","catalystId":"P166_PERF_002","name":"Pd/MC-8","support":"mesoporous carbon (MC-8)","matchedSynthesis":"Pd/MC-8","matchedCharacterization":"Pd/MC-8","role":"reference catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Support fabricated by hard templating with Zr-SBA-15, template removed via HF washing, and carbonized under nitrogen flow at 873 K. Palladium was then loaded using wet-chemical reduction.","phase":"Pd0 (111) crystal plane","particleSize":"3.1 ± 0.8 nm","surfaceStates":"Metallic palladium binding energy is higher than that of Pd/NMC-8 by 0.4 eV.","structureLink":"Lower activity compared to Pd/NMC-8 due to larger particle size and poorer dispersion.","reactionConditions":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","whyPerformsWell":"Poor dispersion and larger particle size (3.1 nm) compared to Pd/NMC-8.","metricCount":"3"},{"paperId":"P166","catalystId":"P166_PERF_003","name":"Pd/AC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Hydrogenation of bicarbonate in aqueous solution","metricCount":"1"},{"paperId":"P166","catalystId":"P166_PERF_004","name":"Pd/NMC-9","support":"nitrogen-doped mesoporous carbon (NMC-9)","matchedSynthesis":"Pd/NMC-9","matchedCharacterization":"Pd/NMC-9","role":"bifunctional catalyst for formate-based hydrogen storage","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Support fabricated by hard templating with Zr-SBA-15, template removed via HF washing, and nitridated under ammonia flow at 973 K. Palladium was then loaded using wet-chemical reduction.","particleSize":"2.2 ± 0.5 nm","structureLink":"Highest activity among the NMC series due to highest nitrogen content facilitating better dispersion and smallest particle size.","reactionConditions":"Decomposition of formate","whyPerformsWell":"Highest nitrogen concentration among NMCs leads to the highest activity and better dispersion/smaller mean size of Pd NPs (2.2 nm).","metricCount":"0"},{"paperId":"P167","catalystId":"P167_PERF_001","name":"Pd/BCNTs","support":"BCNTs","matchedSynthesis":"Pd/BCNTs","matchedCharacterization":"Pd/BCNTs","role":"catalyst for formic acid hydrogen production","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Acidification of CNTs, hydrothermal treatment with boric acid to form BCNTs, followed by impregnation with H2PdCl4 and NaBH4 reduction.","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"6.28 nm","surfaceStates":"Pd0 core-level binding energy is slightly upshifted compared to Pd/CNTs, suggesting effective electron transfer from B to Pd.","structureLink":"Highest performance attributed to the largest specific surface area (128.1273 m2/g), large mesopore volume (0.894 cm3/g), smallest particle size, and synergetic interaction between PdNPs and BCNTs.","reactionConditions":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","selectivity":"product primarily comprises CO2 and H2 in a ratio of approximately 1:1","stability":"Regenerated catalyst reused three times showed an 11.69% decrease in catalytic activity.","deactivation":"Long-term stability test without regeneration showed reduction of 52.92% in second injection and complete deactivation by fourth injection; attributed to CO poisoning, fouling of reactants/products on Pd surface, and agglomeration of PdNPs.","whyPerformsWell":"High SBET (128.1273 m2 g-1), large Vmeso, highly dispersed PdNPs with smallest particle size (6.28 nm), and synergetic interaction between PdNPs and BCNTs involving electron transfer from B to Pd.","metricCount":"6"},{"paperId":"P167","catalystId":"P167_PERF_002","name":"Pd/CNTs","support":"CNTs","matchedSynthesis":"Pd/CNTs","matchedCharacterization":"Pd/CNTs","role":"catalyst for formic acid hydrogen production","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of unmodified CNTs with H2PdCl4 followed by NaBH4 reduction.","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"7.25 nm","surfaceStates":"Pd0 (3d5/2 ~ 335.3 eV), PdO (~ 337.2 eV), and PdO2 (~ 333.8 eV).","structureLink":"Lowest catalytic performance attributed to aggregation of Pd particles, leading to fewer accessible active sites.","reactionConditions":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","deactivation":"Aggregation of Pd particles leading to fewer accessible exposed active sites","metricCount":"2"},{"paperId":"P167","catalystId":"P167_PERF_003","name":"Pd/NCNTs","support":"NCNTs","matchedSynthesis":"Pd/NCNTs","matchedCharacterization":"Pd/NCNTs","role":"catalyst for formic acid hydrogen production","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Acidification of CNTs, hydrothermal treatment with urea to form NCNTs, followed by impregnation with H2PdCl4 and NaBH4 reduction.","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"8.31 nm","surfaceStates":"Negative shift in Pd0 core-level binding energy due to electron-donating effects of N, increasing stability of Pd0.","structureLink":"Moderate performance; electronic properties modified by N enhance the stability of Pd0 and prevent agglomeration.","reactionConditions":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","stability":"Regenerated catalyst reused three times showed a 12.41% decrease in catalytic activity.","metricCount":"1"},{"paperId":"P167","catalystId":"P167_PERF_004","name":"Pd/OCNTs","support":"OCNTs","matchedSynthesis":"Pd/OCNTs","matchedCharacterization":"Pd/OCNTs","role":"catalyst for formic acid hydrogen production","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Acidification of CNTs to form OCNTs, followed by impregnation with H2PdCl4 and NaBH4 reduction.","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"8.95 nm","surfaceStates":"Strong interaction between Pd and surface O-containing functionalities facilitates electron transfer from metallic Pd nanoparticles to the CNTs support.","structureLink":"Higher Pd loading compared to Pd/CNTs but inferior catalytic performance relative to B/N doped versions despite strong anchoring.","reactionConditions":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","stability":"Regenerated catalyst reused three times showed a 9.4% decrease in catalytic activity.","whyPerformsWell":"Excellent anchoring ability of Pd/OCNTs to PdNPs is the main reason for its minimal activity loss during reuse.","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_001","name":"KCC-1/IL/PbS","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/PbS","matchedCharacterization":"KCC-1/IL/PbS","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"PbS","activeMetals":"Pb","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"KCC-1/IL NPs were dispersed in lead dichloride solution for 0.5 h to adsorb Pb2+ ions, washed, then dispersed in thioacetamide solution and heated at 45 °C for 1 h.","phase":"cubic phase of PbS (JCPDS card No. 05-0592)","particleSize":"about 250 nm","surfaceStates":"XPS confirmed presence of Si, O, C, N, S, Cl and Pb; FT-IR confirmed imidazolium IL introduction via C=N (1635 cm-1) and CH2 (2905 cm-1) stretching vibrations","structureLink":"The dendritic fibrous morphology of KCC-1 makes active sites accessible, while the ionic liquid units prevent agglomeration of PbS nanoparticles, maintaining high catalytic activity.","reactionConditions":"Dehydrogenation of aqueous solutions of HCOOH/HCOONa to H2 and CO2 gas at 40 °C, stirring at ca. 750 rpm.","selectivity":"Excellent H2 selectivity; minimal amount of CO detected by GC analyses.","stability":"Recycled ten times without any significant loss in catalytic activity.","deactivation":"PbS leaching after ten repeated recycling was 1.3%.","whyPerformsWell":"Synergistic effect between KCC-1/IL and small PbS NPs; unique dendritic fibrous morphology of the support makes active sites accessible; IL units prevent agglomeration of PbS nanoparticles.","metricCount":"2"},{"paperId":"P168","catalystId":"P168_PERF_002","name":"KCC-1/IL/ZnS","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/ZnS","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"ZnS","activeMetals":"Zn","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"Similar to KCC-1/IL/PbS synthesis using Zn2+ and thioacetamide.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_003","name":"KCC-1/IL/HgS","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/HgS","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"HgS","activeMetals":"Hg","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"Similar to KCC-1/IL/PbS synthesis using Hg2+ and thioacetamide.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_004","name":"KCC-1/IL/Au","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/Au","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"KCC-1/IL suspension was stirred with HAuCl4.3H2O for 1 h at room temperature, followed by dropwise addition of ice-cold NaBH4.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_005","name":"KCC-1/IL/Cu","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/Cu","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"Cu","activeMetals":"Cu","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"KCC-1/IL was dispersed in water, Cu(NO3)2.3H2O added and sonicated for 2 h, then stirred at room temperature for 24 h.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_006","name":"KCC-1/IL/Pd","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/Pd","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"KCC-1/IL was dispersed in water, PdCl2 added and sonicated for 2 h, then stirred at room temperature for 24 h.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_007","name":"KCC-1/IL/Ag","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/Ag","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"Ag","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"KCC-1/IL was dispersed in water, AgNO3 added and stirred for 30 min, then NaBH4 solution added dropwise.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_008","name":"KCC-1/IL/Pt","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/Pt","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"KCC-1/IL was dispersed in water, H2PtCl6 added and stirred for 30 min, then NaBH4 solution added dropwise.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_009","name":"KCC-1/IL/Mn","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/Mn","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"Mn","activeMetals":"Mn","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"KCC-1/IL was dispersed in water, Mn(NO3)2 added and sonicated for 2 h, then stirred at room temperature for 24 h.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_010","name":"KCC-1/IL/Ni","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/Ni","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"KCC-1/IL was dispersed in water, Ni(NO3)2 added and sonicated for 2 h, then stirred at room temperature for 24 h.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_011","name":"KCC-1/IL/Zn","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/ZnS","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"ZnS","activeMetals":"Zn","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"adsorption_or_loading","synthesis":"Similar to KCC-1/IL/PbS synthesis using Zn2+ and thioacetamide.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P168","catalystId":"P168_PERF_012","name":"KCC-1/IL/Co","support":"KCC-1/IL","matchedSynthesis":"KCC-1/IL/Co","role":"heterogeneous catalyst for the dehydrogenation of formic acid","composition":"Co","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"synthesis_precursors","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"KCC-1/IL was dispersed in water, CoCl2 added and stirred for 1 h at room temperature, then ice-cold NH4Cl solution (0.1 mmol) delivered dropwise.","reactionConditions":"Same as KCC-1/IL/PbS","metricCount":"1"},{"paperId":"P169","catalystId":"P169_PERF_001","name":"Pd/hatnCTF","support":"hatnCTF","matchedSynthesis":"Pd/hatnCTF","matchedCharacterization":"Pd/hatnCTF","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"The hatnCTF support was synthesized using the corresponding linker and ZnCl2 at 773 K, followed by impregnation with a Pd(acac)2 solution in acetone and final pretreatment.","phase":"Single atoms and dimers","particleSize":"Nanoparticles are rarely seen","surfaceStates":"Pd 3d5/2 components at 338.2 eV (Pd2+ stabilized by N) and 336.8 eV (attributed to Pd2+ in PdO or small clusters); surface Pd2+/Pdtotal ratio is 0.77","structureLink":"High activity attributed to the prevalence of single-atom Pd2+−C1N3 sites; high tolerance to CO poisoning due to weak adsorption on Pd2+ sites.","reactionConditions":"Gas-phase decomposition of formic acid in a fixed-bed glass reactor; feed: 2.5 vol % formic acid in Ar flow (saturated at 303 K); total flow rate: 67 mL min⁻¹; catalyst loading: 16 mg; pretreatment: formic acid/Ar mixture at 573 K for 30 min.","selectivity":">98% toward H2 at temperatures > 500 K","stability":"No deactivation observed at 473 K within 5 h; recyclability test showed conversions in two sets of runs were very close.","deactivation":"High tolerance to CO poisoning as Pd2+ sites do not adsorb CO as strongly as metallic Pd.","whyPerformsWell":"Presence of single-atom Pd2+-C1N3 sites.","metricCount":"2"},{"paperId":"P169","catalystId":"P169_PERF_002","name":"Pd/acacCTF","support":"acacCTF","matchedSynthesis":"Pd/acacCTF","matchedCharacterization":"Pd/acacCTF","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"The acacCTF support was synthesized using the corresponding linker and ZnCl2 at 773 K, followed by impregnation with a Pd(acac)2 solution in acetone and final pretreatment.","phase":"Metallic Pd nanoparticles and isolated Pd2+ atoms","particleSize":"5.2 ± 0.6 nm","surfaceStates":"Pd 3d5/2 components at 336.0 eV (metallic Pd) and 338.0 eV (isolated Pd2+ attached to O-atoms); surface Pd2+/Pdtotal ratio is 0.54","structureLink":"Lower activity than Pd/hatnCTF; metallic nanoparticles are relatively large and low active, while Pd2+−O4 sites may have negligible activity.","reactionConditions":"Gas-phase decomposition of formic acid in a fixed-bed glass reactor; feed: 2.5 vol % formic acid in Ar flow (saturated at 303 K); total flow rate: 67 mL min⁻¹; catalyst loading: 16 mg; pretreatment: formic acid/Ar mixture at 573 K for 30 min.","selectivity":">98% toward H2 at temperatures > 500 K","deactivation":"High tolerance of single-atom Pd2+-O4 sites with respect to CO.","whyPerformsWell":"Contains both single-atom Pd2+-O4 sites and metallic Pd nanoparticles (~5.2 nm); activity is lower than Pd/hatnCTF because the Pd-O4 sites may have negligible activity and the nanoparticles are relatively large and low active.","metricCount":"0"},{"paperId":"P169","catalystId":"P169_PERF_003","name":"Pd/g-C3N4","support":"g-C3N4","matchedSynthesis":"Pd/g-C3N4","matchedCharacterization":"Pd/g-C3N4","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"g-C3N4 was synthesized via heat treatment of dicyandiamide and chemical exfoliation in H2SO4, followed by impregnation with Pd(acac)2 in acetone and final pretreatment.","phase":"Metallic Pd nanoparticles","particleSize":"3.0 ± 1.2 nm","surfaceStates":"Pd 3d5/2 components at 335.0 eV (metallic Pd) and 337.4 eV (isolated Pd2+); surface Pd2+/Pdtotal ratio is 0.31","structureLink":"Poor performance in formic acid decomposition compared to Pd/hatnCTF due to the prevalence of metallic sites.","reactionConditions":"Gas-phase decomposition of formic acid in a fixed-bed glass reactor; feed: 2.5 vol % formic acid in Ar flow (saturated at 303 K); total flow rate: 67 mL min⁻¹; catalyst loading: 16 mg; pretreatment: formic acid/Ar mixture at 573 K for 30 min.","selectivity":">98% toward H2 at temperatures > 500 K","whyPerformsWell":"Contains mainly metallic Pd nanoparticles (~3.0 nm), resulting in lower activity compared to the single-atom sites of Pd/hatnCTF.","metricCount":"0"},{"paperId":"P170","catalystId":"P170_PERF_001","name":"Pd/AC_C3N4(19)","support":"AC","matchedSynthesis":"Pd/AC","matchedCharacterization":"Pd/AC_C3N4(19)","role":"reference","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","phase":"Pd nanoparticles","particleSize":"2.3 ± 0.6 nm","surfaceStates":"Electron-deficient Pd species stabilized by high nitrogen content (signals shifted to higher binding energies).","structureLink":"Combination of small particle size, modified electronic properties (Pd2+ favoring formate adsorption), and high surface area leads to highest TOF (2893 h-1) and high stability.","reactionConditions":"Dehydrogenation of formic acid in the liquid phase at 75 °C using an aqueous solution of formic acid and sodium formate (1 M, 9:1 molar ratio) with a burette system.","stability":"preserved most of its catalytic activity for at least six consecutive reaction cycles","deactivation":"low Pd loss (fresh 0.7 wt% to used 0.6 wt%)","whyPerformsWell":"Combination of large surface area from AC and nitrogen functional groups from C3N4 providing anchorage sites for metal species, basicity, small and well-distributed nanoparticles, and modified electronic properties favoring electron-deficient Pd2+ species.","metricCount":"1"},{"paperId":"P170","catalystId":"P170_PERF_002","name":"Pd/AC","support":"AC","matchedSynthesis":"Pd/AC","matchedCharacterization":"Pd/AC","role":"reference","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","phase":"Pd nanoparticles","surfaceStates":"Reduced Pd species (Pd0)","structureLink":"Poor performance compared to C3N4-modified catalysts due to lack of nitrogen functional groups and poor dispersion.","reactionConditions":"Dehydrogenation of formic acid in the liquid phase at 75 °C using an aqueous solution of formic acid and sodium formate (1 M, 9:1 molar ratio) with a burette system.","deactivation":"Pd loss from 0.9 wt% (fresh) to 0.7 wt% (used)","whyPerformsWell":"poor performance compared to C3N4-modified catalysts; large aggregates found in TEM","metricCount":"1"},{"paperId":"P170","catalystId":"P170_PERF_003","name":"Pd/C3N4","support":"g-C3N4","matchedSynthesis":"Pd/C3N4","matchedCharacterization":"Pd/C3N4","role":"reference","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Standard impregnation of g-C3N4 with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","phase":"Pd nanoparticles","particleSize":"4.2 ± 2.0 nm","surfaceStates":"Reduced species (334.8 eV) and electron-deficient species (336.5, 337.9 eV)","reactionConditions":"Dehydrogenation of formic acid in the liquid phase at 75 °C using an aqueous solution of formic acid and sodium formate (1 M, 9:1 molar ratio) with a burette system.","deactivation":"Pd content remained at 0.3 wt%","whyPerformsWell":"poor performance compared to C3N4-modified AC catalysts","metricCount":"1"},{"paperId":"P170","catalystId":"P170_PERF_004","name":"Pd/AC_C3N4(3)","support":"AC","matchedSynthesis":"Pd/AC","matchedCharacterization":"Pd/AC_C3N4(3)","role":"reference","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","phase":"Pd nanoparticles","particleSize":"4.8 ± 2.0 nm","surfaceStates":"Electronic properties dependent on support composition; lower N content results in signals shifted to lower binding energies compared to Pd/AC_C3N4(19) and (22).","reactionConditions":"Dehydrogenation of formic acid in the liquid phase at 75 °C using an aqueous solution of formic acid and sodium formate (1 M, 9:1 molar ratio) with a burette system.","deactivation":"Pd loss from 0.8 wt% (fresh) to 0.7 wt% (used)","metricCount":"0"},{"paperId":"P170","catalystId":"P170_PERF_005","name":"Pd/AC_C3N4(10)","support":"AC","matchedSynthesis":"Pd/AC","matchedCharacterization":"Pd/AC_C3N4(10)","role":"reference","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","phase":"Pd nanoparticles","particleSize":"3.8 ± 1.4 nm","surfaceStates":"Electronic properties dependent on support composition; lower N content results in signals shifted to lower binding energies compared to Pd/AC_C3N4(19) and (22).","reactionConditions":"Dehydrogenation of formic acid in the liquid phase at 75 °C using an aqueous solution of formic acid and sodium formate (1 M, 9:1 molar ratio) with a burette system.","deactivation":"Pd content remained at 0.7 wt%","metricCount":"0"},{"paperId":"P170","catalystId":"P170_PERF_006","name":"Pd/AC_C3N4(22)","support":"AC","matchedSynthesis":"Pd/AC","matchedCharacterization":"Pd/AC_C3N4(22)","role":"reference","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","phase":"Pd nanoparticles","particleSize":"3.5 ± 1.2 nm","surfaceStates":"Electron-deficient Pd species stabilized by high nitrogen content (signals shifted to higher binding energies).","structureLink":"Decay in activity compared to Pd/AC_C3N4(19) likely due to significant blockage of AC porosity and C3N4 stacking.","reactionConditions":"Dehydrogenation of formic acid in the liquid phase at 75 °C using an aqueous solution of formic acid and sodium formate (1 M, 9:1 molar ratio) with a burette system.","deactivation":"Pd loss from 0.7 wt% (fresh) to 0.5 wt% (used)","whyPerformsWell":"decay in catalytic activity compared to Pd/AC_C3N4(19), probably due to significant blockage of the porosity and C3N4 stacking","metricCount":"0"},{"paperId":"P171","catalystId":"P171_PERF_001","name":"0.2% Pd/N-CNTs","support":"bamboo-like nitrogen-doped carbon nanotubes (N-CNTs)","matchedSynthesis":"Pd/N-CNTs","matchedCharacterization":"0.2% Pd/N-CNTs","role":"hydrogen production via gas phase formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"N-CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","phase":"Isolated palladium ions","particleSize":"not detectable","surfaceStates":"Pd2+-NPy (BE Pd 3d = 337.7 eV)","structureLink":"Maximum activity observed for this catalyst as isolated palladium ions are more active than metallic nanoparticles.","reactionConditions":"Gas phase formic acid decomposition, 5 vol.% HCOOH/He feed, flow rate 20 cm3/min, catalyst amount 20 mg mixed with 0.5 cm3 quartz sand","selectivity":"97%","stability":"high stability in the course of the reaction as compared to the N-free catalyst","whyPerformsWell":"consists predominantly of isolated palladium ions (Pd2+-NPy species) which are more active than metallic nanoparticles; strong interaction with pyridinic centers","metricCount":"2"},{"paperId":"P171","catalystId":"P171_PERF_002","name":"0.5% Pd/N-CNTs","support":"bamboo-like nitrogen-doped carbon nanotubes (N-CNTs)","matchedSynthesis":"Pd/N-CNTs","role":"hydrogen production via gas phase formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"N-CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","reactionConditions":"Gas phase formic acid decomposition, 5 vol.% HCOOH/He feed, flow rate 20 cm3/min, catalyst amount 20 mg mixed with 0.5 cm3 quartz sand","selectivity":"97%","metricCount":"2"},{"paperId":"P171","catalystId":"P171_PERF_003","name":"1% Pd/N-CNTs","support":"bamboo-like nitrogen-doped carbon nanotubes (N-CNTs)","matchedSynthesis":"Pd/N-CNTs","role":"hydrogen production via gas phase formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"N-CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","reactionConditions":"Gas phase formic acid decomposition, 5 vol.% HCOOH/He feed, flow rate 20 cm3/min, catalyst amount 20 mg mixed with 0.5 cm3 quartz sand","selectivity":"98%","metricCount":"2"},{"paperId":"P171","catalystId":"P171_PERF_004","name":"2% Pd/N-CNTs","support":"bamboo-like nitrogen-doped carbon nanotubes (N-CNTs)","matchedSynthesis":"Pd/N-CNTs","matchedCharacterization":"0.2% Pd/N-CNTs","role":"hydrogen production via gas phase formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"N-CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","phase":"Isolated palladium ions","particleSize":"not detectable","surfaceStates":"Pd2+-NPy (BE Pd 3d = 337.7 eV)","structureLink":"Maximum activity observed for this catalyst as isolated palladium ions are more active than metallic nanoparticles.","reactionConditions":"Gas phase formic acid decomposition, 5 vol.% HCOOH/He feed, flow rate 20 cm3/min, catalyst amount 20 mg mixed with 0.5 cm3 quartz sand","selectivity":"98%","stability":"stabilization of both palladium species (isolated ions and metal nanoparticles) by nitrogen centers","whyPerformsWell":"contains highly dispersed Pd0 and Pd2+-NPy states","metricCount":"2"},{"paperId":"P171","catalystId":"P171_PERF_005","name":"0.2% Pd/CNTs","support":"carbon nanotubes (CNTs)","matchedSynthesis":"Pd/CNTs","role":"comparison catalysts for hydrogen production via gas phase formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","reactionConditions":"Gas phase formic acid decomposition, 5 vol.% HCOOH/He feed, flow rate 20 cm3/min, catalyst amount 20 mg mixed with 0.5 cm3 quartz sand","selectivity":"92%","metricCount":"3"},{"paperId":"P171","catalystId":"P171_PERF_006","name":"2% Pd/CNTs","support":"carbon nanotubes (CNTs)","matchedSynthesis":"Pd/CNTs","matchedCharacterization":"0.2-2% Pd/CNTs","role":"comparison catalysts for hydrogen production via gas phase formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","phase":"Metallic Pd","particleSize":"1.2 nm (for 0.2% Pd), 2.3 nm (for 2% Pd)","surfaceStates":"Pd0 (BE Pd 3d = 335.6 eV)","structureLink":"Lower activity and selectivity compared to Pd/N-CNTs; TOF decreases as particle size increases from 1.2 nm to 2.3 nm.","reactionConditions":"Gas phase formic acid decomposition, 5 vol.% HCOOH/He feed, flow rate 20 cm3/min, catalyst amount 20 mg mixed with 0.5 cm3 quartz sand","selectivity":"92%","metricCount":"3"},{"paperId":"P172","catalystId":"P172_PERF_001","name":"Pd/BN_{C,O}-1-A","matchedCharacterization":"Pd/BN_{C,O}-1-A","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Cubic-phase Pd; XRD shows primarily (111) diffraction peaks around 2θ = 40.1°.","particleSize":"~2.1 nm","surfaceStates":"Strong metal-support interaction enhanced by combined effect of -NH2 functionalization and C/O doping, resulting in electron transfer from Pd to BN_{C,O}-1-A.","structureLink":"Synergistic effect of heteroatom doping and -NH2 groups (acting as proton scavengers) leads to the smallest particle size, strongest metal-support interaction, lowest activation energy (23.6 kJ/mol), and highest TOF (522.0 h-1 at 298 K).","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution without additives.","selectivity":"nearly 100% hydrogen selectivity; no CO observed","stability":"performance showed a significant decrease at the third time of cycling, but gas volume gradually increased with increase in number of cycles","deactivation":"agglomeration of Pd nanoparticles (size increased from ~2.1 to ~2.6 nm); possible CO poison accumulation; mass loss of catalyst","whyPerformsWell":"Synergistic interaction between heteroatoms (C, O) and -NH2 groups strengthens metal-support connection; formation of small (~2.1 nm), highly dispersed Pd nanoparticles; -NH2 groups act as proton scavengers promoting cleavage of O-H bonds.","metricCount":"4"},{"paperId":"P172","catalystId":"P172_PERF_002","name":"Pd/BN_{C,O}-3","matchedCharacterization":"Pd/BN_{C,O}-3","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Cubic-phase Pd (PDF #46-1043)","particleSize":"~2.6 nm","surfaceStates":"Strong metal-support interaction characterized by electron transfer from Pd to the BN_{C,O}-3 support (Pd0 peak shifted 0.67-0.7 eV higher than pure Pd).","structureLink":"C and O doping introduces defects in BN, facilitating smaller particle size and better dispersion compared to unmodified BN, which lowers activation energy (32.9 kJ/mol) and increases TOF.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution without additives.","stability":"no significant decrease in catalytic activity even after five catalytic cycles","whyPerformsWell":"Doping with C and O atoms lowers the activation barrier; more uniform dispersion of Pd nanoparticles (~2.6 nm) compared to unmodified support.","metricCount":"2"},{"paperId":"P172","catalystId":"P172_PERF_003","name":"Pd/BN_{C,O}-0","matchedCharacterization":"Pd/BN_{C,O}-0","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Cubic-phase Pd (PDF #46-1043)","particleSize":"~9.9 nm","surfaceStates":"Lower binding energy for Pd2+ compared to Pd/BN_{C,O}-3, indicating weaker metal-support interaction.","structureLink":"Larger particle size and poor dispersion result in higher activation energy (41.4 kJ/mol) and significantly lower catalytic activity.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution without additives.","whyPerformsWell":"Poor performance due to larger Pd nanoparticles (~9.9 nm) and lack of C/O doping defects.","metricCount":"2"},{"paperId":"P173","catalystId":"P173_PERF_001","name":"Pd/PNCC","support":"porous nitrogen-doped carbon cages (PNCC)","matchedSynthesis":"Pd/PNCC","matchedCharacterization":"Pd/PNCC","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"ZIF-8@ZIF-67 was mixed with KCl and pyrolyzed at 750 °C under N2 to form PNCC after HF etching. Pd nanoparticles were then immobilized via sonication of K2PdCl4 followed by NaBH4 reduction.","phase":"Metallic Pd with a lattice spacing of 0.232 nm corresponding to the (110) crystal face.","particleSize":"2.5 nm","surfaceStates":"Electron-rich Pd sites characterized by a negative shift in XPS signals compared to pure Pd NPs, indicating electron transfer from the PNCC support to Pd.","structureLink":"The strong electronic metal–support interaction (EMSI) optimizes the electron configuration of Pd active sites to accelerate O-H bond cleavage. The hierarchical porous structure improves mass transfer and accessibility of FA molecules to the catalytic sites.","reactionConditions":"Aqueous formic acid solution in a two-necked round-bottom flask (50 mL) placed in a water bath; gas volume measured via water-filled gas burette.","selectivity":"no CO was detected at the level of detection limit","whyPerformsWell":"Strong electronic metal-support interaction (EMSI) between PNCC and Pd NPs optimizes electron configuration of Pd active sites; multi-dimensional hierarchical structure accelerates mass transfer and provides accessible active sites.","metricCount":"5"},{"paperId":"P173","catalystId":"P173_PERF_002","name":"Pd/ZIF-8@ZIF-67","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/PNCC","metricCount":"1"},{"paperId":"P173","catalystId":"P173_PERF_003","name":"Pd/KB","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/PNCC","metricCount":"1"},{"paperId":"P173","catalystId":"P173_PERF_004","name":"Pd/GO","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/PNCC","metricCount":"1"},{"paperId":"P173","catalystId":"P173_PERF_005","name":"Pd/super P","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/PNCC","metricCount":"1"},{"paperId":"P173","catalystId":"P173_PERF_006","name":"Pd/CNT","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/PNCC","metricCount":"1"},{"paperId":"P173","catalystId":"P173_PERF_007","name":"Pd/NCC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/PNCC","metricCount":"1"},{"paperId":"P173","catalystId":"P173_PERF_008","name":"Pd and PNCC mixture","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Same as Pd/PNCC","metricCount":"1"},{"paperId":"P174","catalystId":"P174_PERF_001","name":"Pd/CNT-base-4","support":"Carbon Nanotubes (CNTs)","matchedSynthesis":"Pd/CNT","matchedCharacterization":"Pd/CNT-base-4","role":"Catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CNTs were dispersed in water, Na2PdCl4 solution was added, pH adjusted to 1 using NaOH, stirred, dried, and reduced under H2/Ar.","phase":"Metallic Pd (fcc), characteristic peak at 40° corresponding to the (111) crystal plane.","particleSize":"5.4 nm","surfaceStates":"Predominantly electron-deficient Pdδ+ (up to 81% of sample); XPS shows a shift in Pd0 3d5/2 binding energy to 335.0 eV (+0.4 eV) due to electron transfer from Pd to carbonyl C=O groups.","structureLink":"The formation of the Pd0-Pdδ+ interface and Pd-PdO interfaces reduces the activation energy for formic acid dehydrogenation (27.1 kJ/mol) and increases TOF (1702 h-1).","reactionConditions":"Formic acid dehydrogenation at 40 °C with HCOOK additive","selectivity":"Excellent dehydrogenation selectivity; no CO signal detected in exhaust gas","stability":"Conversion rate remained consistently high over six consecutive runs","whyPerformsWell":"Carbonyl C=O groups on the CNT surface facilitate electron transfer from Pd to the carrier, forming slightly positively charged Pdδ+ nanoparticles and Pd-PdO interfaces, which reduce the activation energy barrier.","metricCount":"2"},{"paperId":"P174","catalystId":"P174_PERF_002","name":"Pd/CNT-acid","support":"Carbon Nanotubes (CNTs)","matchedSynthesis":"Pd/CNT-acid","matchedCharacterization":"Pd/CNT-acid","role":"Catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CNTs were pretreated with HNO3 reflux. The resulting support was dispersed in water, Na2PdCl4 solution was added, pH adjusted to 1 using NaOH, stirred, dried, and reduced under H2/Ar.","phase":"Metallic Pd","particleSize":"4.1 nm","surfaceStates":"Contains both Pd0 and Pd2+ states.","structureLink":"Higher activity than Pd/CNT due to higher metal dispersion, but lower activity than Pd/CNT-base-4 because it lacks the specific electronic modulation provided by carbonyl groups.","reactionConditions":"Formic acid dehydrogenation at 40 °C with HCOOK additive","whyPerformsWell":"Higher dispersion of Pd nanoparticles compared to Pd/CNT provides a greater number of catalytic active sites.","metricCount":"2"},{"paperId":"P174","catalystId":"P174_PERF_003","name":"Pd/CNT","support":"Carbon Nanotubes (CNTs)","matchedSynthesis":"Pd/CNT","matchedCharacterization":"Pd/CNT","role":"Catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"CNTs were dispersed in water, Na2PdCl4 solution was added, pH adjusted to 1 using NaOH, stirred, dried, and reduced under H2/Ar.","phase":"Metallic Pd (fcc), characteristic peak at 40° corresponding to the (111) crystal plane.","particleSize":"6.7 nm","surfaceStates":"Predominantly zerovalent metallic Pd (Pd0 3d5/2 binding energy at 334.6 eV).","structureLink":"Highest activation energy (33.3 kJ/mol) and lowest TOF (425.1 h-1) due to lack of support-induced electronic modulation.","reactionConditions":"Formic acid dehydrogenation at 40 °C with HCOOK additive","metricCount":"2"},{"paperId":"P175","catalystId":"P175_PERF_001","name":"Pd/N,P-C","support":"N,P-co-doped carbon (N,P-C)","matchedSynthesis":"Pd/N,P-C","matchedCharacterization":"Pd/N,P-C","role":"Catalyst for reversible formate-based chemical hydrogen storage","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"N,P-C support was synthesized by pyrolyzing a mixture of 1,10-phenanthroline (PAH) and triphenylphosphine (TPP) with an MgO template. Pd was loaded via impregnation of PdCl2 in HCl, followed by pH adjustment to ~10 and reduction with NaBH4.","phase":"Metallic Pd {111} crystal plane (lattice fringe 2.20 Å).","particleSize":"2.2 nm","surfaceStates":"Electron-enriched Pd0 active sites due to charge transfer from the N,P-co-doped carbon support, evidenced by a shift in Pd 3d5/2 XPS peaks to lower binding energies compared to Pd/AC.","structureLink":"Synergistic effects of N and P co-dopants modulate the electronic state of Pd via metal-support interactions, enhancing activity for formate dehydrogenation (TOF 3248 h-1) and bicarbonate hydrogenation; a correlation exists between TON and Pd 3d5/2 binding energy.","reactionConditions":"Formate dehydrogenation: potassium formate in water; Bicarbonate hydrogenation: KHCO3 in water under H2/CO2 atmosphere.","selectivity":"100% selectivity toward hydrogen production; no CO formation observed.","stability":"Excellent stability during dehydrogenation reactions, with no signs of deactivation after five cycles. High stability without loss of activity after three hydrogenation cycles.","whyPerformsWell":"Synergistic coupling effect between N and P co-dopants modulated the electronic properties of the carbon support; metal-support interactions enriched electron density at Pd active sites via charge transfer from the doped carbon support.","metricCount":"6"},{"paperId":"P175","catalystId":"P175_PERF_002","name":"Pd/NC","support":"Nitrogen-doped porous carbon (NC)","matchedSynthesis":"Pd/NC","matchedCharacterization":"Pd/NC","role":"Comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support synthesized using PAH via the same method as N,P-C; metal loading followed the same procedure as Pd/N,P-C.","particleSize":"Similar to Pd/N,P-C (~2 nm)","surfaceStates":"Pd0 peaks shifted to lower binding energies compared to Pd/AC, but less so than Pd/N,P-C.","reactionConditions":"Bicarbonate hydrogenation: 5 mL H2O, 20 mmol KHCO3, 20 mg catalyst, p(H2) = 6.0 MPa, T = 80 °C, t = 1.5 h.","metricCount":"2"},{"paperId":"P175","catalystId":"P175_PERF_003","name":"Pd/PC","support":"Phosphorus-doped porous carbon (PC)","matchedSynthesis":"Pd/PC","matchedCharacterization":"Pd/PC","role":"Comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support synthesized using TPP via the same method as N,P-C; metal loading followed the same procedure as Pd/N,P-C.","particleSize":"Similar to Pd/N,P-C (~2 nm)","surfaceStates":"Pd0 peaks shifted to lower binding energies compared to Pd/AC, but less so than Pd/N,P-C.","reactionConditions":"Bicarbonate hydrogenation: 5 mL H2O, 20 mmol KHCO3, 20 mg catalyst, p(H2) = 6.0 MPa, T = 80 °C, t = 1.5 h.","metricCount":"2"},{"paperId":"P175","catalystId":"P175_PERF_004","name":"Pd/AC","support":"Activated carbon (AC)","matchedSynthesis":"Pd/AC","matchedCharacterization":"Pd/AC","role":"Comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Metal loading followed the same procedure as Pd/N,P-C.","particleSize":"Similar to Pd/N,P-C (~2 nm)","surfaceStates":"Reference binding energy for Pd0; lacks the electron enrichment seen in doped carbon supports.","reactionConditions":"Bicarbonate hydrogenation: 5 mL H2O, 20 mmol KHCO3, 20 mg catalyst, p(H2) = 6.0 MPa, T = 80 °C, t = 1.5 h.","metricCount":"2"},{"paperId":"P176","catalystId":"P176_PERF_001","name":"Pd/NHPC-NH2","support":"amino-functionalized hierarchically porous carbon (NHPC-NH2)","matchedSynthesis":"Pd/NHPC-NH2","matchedCharacterization":"Pd/NHPC-NH2","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"NHPC was functionalized with APTMS to form NHPC-NH2; PdCl2 aqueous solution was then added under magnetic stirring, followed by reduction using NaBH4.","phase":"fcc Pd (lattice fringe distance 0.224 nm)","particleSize":"2.5 nm","surfaceStates":"Zero-valent Pd (Pd 3d 3/2 at 341.4 eV, Pd 3d 5/2 at 336.1 eV) shifted to higher binding energies due to strong metal-support interaction (SMSI); positively charged Pd surface.","structureLink":"Synergy between amino groups (acting as proton scavengers for O-H bond dissociation) and positively charged Pd (promoting HCOO- adsorption) enables additive-free FA dehydrogenation at room temperature.","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) aqueous solution at room temperature","selectivity":"100% H2 selectivity; no CO detected by gas chromatography","stability":"No significant loss in activity observed over 5 cycles","whyPerformsWell":"Synergy between amino groups acting as proton scavengers to promote O-H bond dissociation and positively charged Pd caused by strong metal-support interaction (SMSI) promoting the adsorption of HCOO-.","metricCount":"2"},{"paperId":"P176","catalystId":"P176_PERF_002","name":"Pd/NHPC","support":"N-doped hierarchically porous carbon (NHPC)","matchedSynthesis":"Pd/NHPC","matchedCharacterization":"Pd/NHPC","role":"control catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar to Pd/NHPC-NH2 but without APTMS functionalization of the support.","phase":"fcc Pd (planes 111, 200, 220)","particleSize":"6.7 nm","surfaceStates":"Zero-valent Pd (Pd 3d 3/2 at 341.2 eV, Pd 3d 5/2 at 335.9 eV)","structureLink":"Inert under test conditions due to relatively weak alkalinity of doped nitrogen and larger particle size.","reactionConditions":"Additive-free dehydrogenation of formic acid aqueous solution at 298 K","whyPerformsWell":"relatively weak alkalinity of the doped nitrogen makes the breaking of the O-H bond in HCOOH difficult","metricCount":"1"},{"paperId":"P176","catalystId":"P176_PERF_003","name":"Pd/NHPC H2","support":"N-doped hierarchically porous carbon (NHPC)","matchedSynthesis":"Pd/NHPC H2","matchedCharacterization":"Pd/NHPC H2","role":"comparison catalyst (particle size effect)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Pd deposited on NHPC and reduced using hydrogen gas.","particleSize":"1.75 nm","surfaceStates":"Lower Pd 3d binding energy compared to Pd/NHPC-NH2","structureLink":"Negligible catalytic activity despite small particle size, indicating that particle size alone is not the key factor for performance.","reactionConditions":"Additive-free dehydrogenation of formic acid aqueous solution at 298 K","whyPerformsWell":"relatively weak alkalinity of the doped nitrogen makes the breaking of the O-H bond in HCOOH difficult","metricCount":"1"},{"paperId":"P177","catalystId":"P177_PERF_001","name":"Pd/HNDC (20 wt% Pd)","support":"HF-etched N-doped carbon (HNDC)","matchedSynthesis":"Pd/HNDC","matchedCharacterization":"Pd/HNDC","role":"optimized catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"HNDC support and Na2PdCl4 were dispersed in DI water via ultrasonication, stirred for 3 h, reduced with NaBH4, centrifuged, washed, and dried.","phase":"fcc Pd (111)","particleSize":"3.0 nm","surfaceStates":"Electron-rich active Pd centers induced by graphitic N and pyridinic N from the HNDC support; XPS identified graphitic N (401.3 eV), pyrrolic N (399.7 eV), and pyridinic N (398.5 eV).","structureLink":"The high surface area and hierarchical pore characteristics of HNDC facilitate mass transfer, while the strong synergistic interaction between Pd NPs and N sites on HNDC, along with ultrasmall size and high dispersion, enhance catalytic activity.","reactionConditions":"FA dehydrogenation in DI water, atmospheric pressure, stirring, n_metal/n_FA = 0.02","selectivity":"100% H2 selectivity; no CO is formed","stability":"Maintained good stability after 5 consecutive cycles; TOF decreased to 91% of the initial value.","deactivation":"Partial loss of Pd content in recycled catalyst; average Pd NP size increased from 3.0 nm to 3.3 nm due to aggregation.","whyPerformsWell":"Unique structure of HNDC support with high surface area and hierarchical pore characteristic, strong synergistic interaction between Pd NPs and N sites on HNDC, ultrasmall size and high dispersion of Pd NPs.","metricCount":"6"},{"paperId":"P177","catalystId":"P177_PERF_002","name":"Pd/HNDC (10 wt% Pd)","support":"HF-etched N-doped carbon (HNDC)","matchedSynthesis":"Pd/HNDC","matchedCharacterization":"Pd/HNDC","role":"optimized catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"HNDC support and Na2PdCl4 were dispersed in DI water via ultrasonication, stirred for 3 h, reduced with NaBH4, centrifuged, washed, and dried.","phase":"fcc Pd (111)","particleSize":"3.0 nm","surfaceStates":"Electron-rich active Pd centers induced by graphitic N and pyridinic N from the HNDC support; XPS identified graphitic N (401.3 eV), pyrrolic N (399.7 eV), and pyridinic N (398.5 eV).","structureLink":"The high surface area and hierarchical pore characteristics of HNDC facilitate mass transfer, while the strong synergistic interaction between Pd NPs and N sites on HNDC, along with ultrasmall size and high dispersion, enhance catalytic activity.","reactionConditions":"n_FA/n_SF = 1:2; n_metal/n_FA = 0.02","selectivity":"100% FA conversion","metricCount":"2"},{"paperId":"P177","catalystId":"P177_PERF_003","name":"Pd/HNDC (15 wt% Pd)","support":"HF-etched N-doped carbon (HNDC)","matchedSynthesis":"Pd/HNDC","matchedCharacterization":"Pd/HNDC","role":"optimized catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"HNDC support and Na2PdCl4 were dispersed in DI water via ultrasonication, stirred for 3 h, reduced with NaBH4, centrifuged, washed, and dried.","phase":"fcc Pd (111)","particleSize":"3.0 nm","surfaceStates":"Electron-rich active Pd centers induced by graphitic N and pyridinic N from the HNDC support; XPS identified graphitic N (401.3 eV), pyrrolic N (399.7 eV), and pyridinic N (398.5 eV).","structureLink":"The high surface area and hierarchical pore characteristics of HNDC facilitate mass transfer, while the strong synergistic interaction between Pd NPs and N sites on HNDC, along with ultrasmall size and high dispersion, enhance catalytic activity.","reactionConditions":"n_FA/n_SF = 1:2; n_metal/n_FA = 0.02","selectivity":"100% FA conversion","metricCount":"2"},{"paperId":"P177","catalystId":"P177_PERF_004","name":"Pd/HNDC (25 wt% Pd)","support":"HF-etched N-doped carbon (HNDC)","matchedSynthesis":"Pd/HNDC","matchedCharacterization":"Pd/HNDC","role":"optimized catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"HNDC support and Na2PdCl4 were dispersed in DI water via ultrasonication, stirred for 3 h, reduced with NaBH4, centrifuged, washed, and dried.","phase":"fcc Pd (111)","particleSize":"3.0 nm","surfaceStates":"Electron-rich active Pd centers induced by graphitic N and pyridinic N from the HNDC support; XPS identified graphitic N (401.3 eV), pyrrolic N (399.7 eV), and pyridinic N (398.5 eV).","structureLink":"The high surface area and hierarchical pore characteristics of HNDC facilitate mass transfer, while the strong synergistic interaction between Pd NPs and N sites on HNDC, along with ultrasmall size and high dispersion, enhance catalytic activity.","reactionConditions":"n_FA/n_SF = 1:2; n_metal/n_FA = 0.02","selectivity":"100% FA conversion","metricCount":"2"},{"paperId":"P177","catalystId":"P177_PERF_005","name":"Pd/ZrO2/NDC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"n_FA/n_SF = 1:2; n_metal/n_FA = 0.02","selectivity":"incomplete reaction","metricCount":"1"},{"paperId":"P178","catalystId":"P178_PERF_001","name":"Pd/MCTP-1","support":"MCTP-1","matchedSynthesis":"Pd/MCTP-1","matchedCharacterization":"Pd/MCTP-1","role":"catalyst for H2 production via formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"MCTP-1 support was synthesized via Friedel-Crafts reaction. Pd nanoparticles were loaded using a deposition-reduction method where the anionic palladium precursor was deposited, followed by the addition of a strong base to form Pd(OH)2 before reduction.","phase":"Pd nanoparticles","particleSize":"2.4 ± 0.5 nm","surfaceStates":"Triazine groups regularly distributed on the MCTP-1 structure offer selective adsorption sites for anionic palladium precursors.","structureLink":"Superior activity is attributed to the formation of the smallest Pd NPs and the maintenance of a neutral reaction pH provided by triazine groups.","reactionConditions":"ambient conditions without additives","stability":"maintained without losses for three recycle runs","whyPerformsWell":"formation of monodisperse and smallest Pd NPs (2.4 ± 0.5 nm) and maintenance of a neutral pH throughout the reaction","metricCount":"3"},{"paperId":"P178","catalystId":"P178_PERF_002","name":"Pd/MIL-101-DETA","matchedCharacterization":"Pd/MIL-101-DETA","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pd nanoparticles","particleSize":"3.5-5 nm","surfaceStates":"Basic amine groups provide selective adsorption for anionic palladium precursors, suppressing agglomeration during reduction.","structureLink":"Improved activity due to smaller Pd NPs and a pH shift toward neutral values via basic amine groups.","reactionConditions":"ambient conditions without additives","whyPerformsWell":"formation of smaller Pd NPs and pH shift to neutral values upon incorporation of basic amine groups","metricCount":"1"},{"paperId":"P178","catalystId":"P178_PERF_003","name":"Pd/UiO-66-NH2","matchedCharacterization":"Pd/UiO-66-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pd nanoparticles","particleSize":"3.5-5 nm","surfaceStates":"Basic amine groups provide selective adsorption for anionic palladium precursors, suppressing agglomeration during reduction.","structureLink":"Improved activity due to smaller Pd NPs and a pH shift toward neutral values via basic amine groups.","reactionConditions":"ambient conditions without additives","whyPerformsWell":"formation of smaller Pd NPs and pH shift to neutral values upon incorporation of basic amine groups","metricCount":"1"},{"paperId":"P179","catalystId":"P179_PERF_001","name":"Pd/BCNTs","support":"BCNTs","matchedSynthesis":"Pd/BCNTs","matchedCharacterization":"Pd/BCNTs","role":"catalyst for formic acid hydrogen production","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Acidification of CNTs, B-doping via hydrothermal treatment with boric acid, followed by impregnation with H2PdCl4 and NaBH4 reduction.","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"6.28 nm","surfaceStates":"Pd0 core-level binding energy is slightly upshifted compared to Pd/CNTs, suggesting effective electron transfer from B to Pd.","structureLink":"Highest performance attributed to largest specific surface area (128.1273 m2/g), large mesopore volume (0.894 cm3/g), smallest particle size, and synergetic interaction between PdNPs and BCNTs.","reactionConditions":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","selectivity":"product primarily comprises CO2 and H2 in a ratio of approximately 1:1","stability":"Regenerated catalyst reused three times showed an 11.69% decrease in catalytic activity.","deactivation":"Long-term stability test without regeneration showed reduction of 52.92% in second injection and complete deactivation by fourth injection; attributed to CO poisoning, fouling of reactants/products on Pd surface, and agglomeration of PdNPs.","whyPerformsWell":"High SBET (128.1273 m2 g-1), large Vmeso, highly dispersed PdNPs with smallest particle size (6.28 nm), synergetic interaction between PdNPs and BCNTs, and electron transfer from B to Pd.","metricCount":"5"},{"paperId":"P179","catalystId":"P179_PERF_002","name":"Pd/CNTs","support":"CNTs","matchedSynthesis":"Pd/CNTs","matchedCharacterization":"Pd/CNTs","role":"catalyst for formic acid hydrogen production","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Impregnation of unmodified CNTs with H2PdCl4 followed by NaBH4 reduction at ambient temperature.","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"7.25 nm","surfaceStates":"Pd0 (3d5/2 ~ 335.3 eV), PdO (~ 337.2 eV), and PdO2 (~ 333.8 eV).","structureLink":"Lowest catalytic performance attributed to aggregation of Pd particles, leading to fewer accessible active sites.","reactionConditions":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","deactivation":"Aggregation of Pd particles leads to fewer accessible exposed active sites.","metricCount":"2"},{"paperId":"P179","catalystId":"P179_PERF_003","name":"Pd/NCNTs","support":"NCNTs","matchedSynthesis":"Pd/NCNTs","matchedCharacterization":"Pd/NCNTs","role":"catalyst for formic acid hydrogen production","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Acidification of CNTs, N-doping via hydrothermal treatment with urea, followed by impregnation with H2PdCl4 and NaBH4 reduction.","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"8.31 nm","surfaceStates":"Negative shift in Pd0 core-level binding energy due to electron-donating effects of N, increasing stability of Pd0.","structureLink":"Moderate performance; electronic properties modified by N-doping enhance Pd0 stability and prevent agglomeration.","reactionConditions":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","stability":"Regenerated catalyst reused three times showed a 12.41% decrease in catalytic activity.","metricCount":"1"},{"paperId":"P179","catalystId":"P179_PERF_004","name":"Pd/OCNTs","support":"OCNTs","matchedSynthesis":"Pd/OCNTs","matchedCharacterization":"Pd/OCNTs","role":"catalyst for formic acid hydrogen production","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Acidification of CNTs to form OCNTs, followed by impregnation with H2PdCl4 and NaBH4 reduction at ambient temperature.","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"8.95 nm","surfaceStates":"Strong interaction between Pd and surface O-containing functionalities facilitates electron transfer from metallic Pd nanoparticles to the CNTs support.","structureLink":"Higher Pd loading achieved via anchor points, but performance is moderate/poor compared to doped versions.","reactionConditions":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","stability":"Regenerated catalyst reused three times showed a 9.4% decrease in catalytic activity.","whyPerformsWell":"Excellent anchoring ability of Pd/OCNTs to PdNPs is the main reason for its minimal activity loss during reuse.","metricCount":"1"},{"paperId":"P180","catalystId":"P180_PERF_001","name":"10 wt% Pd*CeO2","support":"CeO2 nanospheres","matchedSynthesis":"Pd*CeO2","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","reactionConditions":"Dehydrogenation of additive-free formic acid in aqueous solution","selectivity":"nearly 100% hydrogen selectivity (only H2 and CO2 detected)","stability":"excellent stability; HRTEM images after first run demonstrated no distinct change in particle size and morphological","whyPerformsWell":"high dispersion of Pd NPs, more electron-rich Pd active sites, and Strong Metal-Support Interactions (SMSI) between Pd and CeO2","metricCount":"2"},{"paperId":"P180","catalystId":"P180_PERF_002","name":"0.5 wt% Pd*CeO2","support":"CeO2 nanospheres","matchedSynthesis":"Pd*CeO2","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","reactionConditions":"Dehydrogenation of additive-free formic acid in aqueous solution","metricCount":"0"},{"paperId":"P180","catalystId":"P180_PERF_003","name":"1 wt% Pd*CeO2","support":"CeO2 nanospheres","matchedSynthesis":"Pd*CeO2","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","reactionConditions":"Dehydrogenation of additive-free formic acid in aqueous solution","metricCount":"0"},{"paperId":"P180","catalystId":"P180_PERF_004","name":"3 wt% Pd*CeO2","support":"CeO2 nanospheres","matchedSynthesis":"Pd*CeO2","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","reactionConditions":"Dehydrogenation of additive-free formic acid in aqueous solution","metricCount":"0"},{"paperId":"P180","catalystId":"P180_PERF_005","name":"5 wt% Pd*CeO2","support":"CeO2 nanospheres","matchedSynthesis":"Pd*CeO2","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","reactionConditions":"Dehydrogenation of additive-free formic acid in aqueous solution","metricCount":"0"},{"paperId":"P180","catalystId":"P180_PERF_006","name":"CeO2","support":"CeO2 nanospheres","matchedSynthesis":"Pd*CeO2","matchedCharacterization":"CeO2 nanospheres","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Ce","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","phase":"Fluorite structure with face centered cubic (FCC) lattice","particleSize":"80-200 nm (nanosphere size); 14.1 nm (crystallite size)","surfaceStates":"Ce3+/Ce4+ ratio of 0.161; Oads/Olatt ratio of 0.597","structureLink":"Low catalytic activity due to lack of active Pd species","reactionConditions":"Dehydrogenation of additive-free formic acid in aqueous solution","whyPerformsWell":"exhibited the lowest catalytic activity because of lack of active Pd species","metricCount":"0"},{"paperId":"P181","catalystId":"P181_PERF_001","name":"7C","support":"SiC monolith foam / silicon wafer","matchedSynthesis":"7C","matchedCharacterization":"7C","role":"catalyst for formic acid decomposition","composition":"Pd:C = 93:7 (at%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"Magnetron sputtering","synthesis":"One-step co-deposition using a single magnetron with a homemade target (C target with 5 Pd strips) under Ar process gas (10-2 mbar working pressure) and bias voltage (150–220 V).","phase":"PdCx phase (x < 0.13)","particleSize":"13.8 nm (crystal size)","structureLink":"Lower carbon content resulted in larger column width and lower surface roughness compared to 12C and 65C, correlating with the lowest activity.","reactionConditions":"Gas phase formic acid decomposition on SiC foam monoliths; carrier gas N2 (193.5 mL·min−1), FA flow rate 0.8 g·h−1 (3.2 mol% in N2); pre-reduction with H2 (50 mL·min−1) and N2 (100 mL·min−1) at 400°C for 1.5 h.","selectivity":"100% selectivity to CO2 at 300°C","metricCount":"2"},{"paperId":"P181","catalystId":"P181_PERF_002","name":"12C","support":"SiC monolith foam / silicon wafer","matchedSynthesis":"12C","matchedCharacterization":"12C","role":"catalyst for formic acid decomposition","composition":"Pd:C = 88:12 (at%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"Magnetron sputtering","synthesis":"One-step co-deposition using a single magnetron with a homemade target (C target with 5 Pd strips) under Ar process gas (10-2 mbar working pressure) and bias voltage (150–220 V).","phase":"PdCx phase (x = 0.13–0.15)","particleSize":"32.5 nm (crystal size)","surfaceStates":"Pd0 (93%) and PdII (7%)","structureLink":"Intermediate carbon content led to intermediate column width and surface roughness, resulting in moderate activity.","reactionConditions":"Gas phase formic acid decomposition on SiC foam monoliths; carrier gas N2 (193.5 mL·min−1), FA flow rate 0.8 g·h−1 (3.2 mol% in N2); pre-reduction with H2 (50 mL·min−1) and N2 (100 mL·min−1) at 400°C for 1.5 h.","selectivity":"95% selectivity to CO2 at 300°C","metricCount":"2"},{"paperId":"P181","catalystId":"P181_PERF_003","name":"65C","support":"SiC monolith foam / silicon wafer","matchedSynthesis":"65C","matchedCharacterization":"65C","role":"catalyst for formic acid decomposition","composition":"Pd:C = 35:65 (at%)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"activity_metric_denominator","metalClass":"Pd-only","pdBased":"True","method":"Magnetron sputtering","synthesis":"One-step co-deposition using a two-magnetron configuration under Ar process gas (10-2 mbar working pressure) and bias voltage (150–220 V). Magnetron 1 used a homemade target (C with 2 Pd strips); Magnetron 2 used a single carbon target.","phase":"PdCx phase (x = 0.13–0.15)","particleSize":"10.2 nm (crystal size)","surfaceStates":"Pd0 (87%) and PdII (13%)","structureLink":"Highest carbon content led to the smallest column width, highest surface roughness and dispersion, and formation of PdCx phase, resulting in the highest activity but reduced CO2 selectivity.","reactionConditions":"Gas phase formic acid decomposition on SiC foam monoliths; carrier gas N2 (193.5 mL·min−1), FA flow rate 0.8 g·h−1 (3.2 mol% in N2); pre-reduction with H2 (50 mL·min−1) and N2 (100 mL·min−1) at 400°C for 1.5 h.","selectivity":"92% selectivity to CO2 at 300°C","stability":"Deactivates upon cycling; conversion and selectivity decrease after use.","deactivation":"Pd sintering due to elimination of carbon and/or segregation and agglomeration of Pd (crystal size increased from 10.2 nm to 58 nm).","whyPerformsWell":"Decreasing the column width and increasing surface roughness by adding carbon together with the formation of the PdCx phase.","metricCount":"2"},{"paperId":"P181","catalystId":"P181_PERF_004","name":"Pd particles supported on carbon (Norit)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Identical conditions to 65C; prepared by incipient wetness impregnation (5 nm Pd particles).","metricCount":"1"},{"paperId":"P182","catalystId":"P182_PERF_001","name":"Pd(NO3)2","matchedSynthesis":"Pd(NO3)2","matchedCharacterization":"Pd(NO3)2","role":"Catalyst precursor","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Pd(NO3)2 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","phase":"metallic Pd0","structureLink":"The activity is highly dependent on the coordinating ligands; nitrate ligands facilitate ligand exchange with formate more effectively than chloride or bipyridine ligands, promoting both Pd2+ reduction and FA decomposition.","reactionConditions":"60 °C, aqueous solution of formic acid and sodium formate","selectivity":"selective for H2 and CO2","deactivation":"Pd2+ was in situ reduced to Pd0 species (black particles)","whyPerformsWell":"Highest activity among the complexes employed; coordinating ligands are important for FA decomposition kinetics.","metricCount":"1"},{"paperId":"P182","catalystId":"P182_PERF_002","name":"PdCl2","matchedSynthesis":"PdCl2","matchedCharacterization":"Pd chloride complexes (PdCl2, Na2PdCl4, Pd(NH3)4Cl2)","role":"Catalyst precursor","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"PdCl2 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","phase":"metallic Pd0","structureLink":"Chloride ligands resulted in nearly no activity over 1 hour, possibly due to rapid nanoparticle aggregation induced by weakened zeta-potential.","reactionConditions":"60 °C, aqueous solution of formic acid and sodium formate","whyPerformsWell":"Showed nearly no activity; potentially due to rapid aggregation following reduction induced by weakening zeta-potential of initially formed Pd nanoparticles.","metricCount":"1"},{"paperId":"P182","catalystId":"P182_PERF_003","name":"Na2PdCl4","matchedSynthesis":"Na2PdCl4","matchedCharacterization":"Pd chloride complexes (PdCl2, Na2PdCl4, Pd(NH3)4Cl2)","role":"Catalyst precursor","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Na2PdCl4 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","phase":"metallic Pd0","structureLink":"Chloride ligands resulted in nearly no activity over 1 hour, possibly due to rapid nanoparticle aggregation induced by weakened zeta-potential.","reactionConditions":"60 °C, aqueous solution of formic acid and sodium formate","whyPerformsWell":"Showed nearly no activity.","metricCount":"1"},{"paperId":"P182","catalystId":"P182_PERF_004","name":"Pd(NH3)4Cl2","matchedSynthesis":"Pd(NH3)4Cl2","matchedCharacterization":"Pd chloride complexes (PdCl2, Na2PdCl4, Pd(NH3)4Cl2)","role":"Catalyst precursor","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Pd(NH3)4Cl2 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","phase":"metallic Pd0","structureLink":"Chloride ligands resulted in nearly no activity over 1 hour, possibly due to rapid nanoparticle aggregation induced by weakened zeta-potential.","reactionConditions":"60 °C, aqueous solution of formic acid and sodium formate","whyPerformsWell":"Showed nearly no activity.","metricCount":"1"},{"paperId":"P182","catalystId":"P182_PERF_005","name":"Pd(OAc)2","matchedSynthesis":"Pd(OAc)2","matchedCharacterization":"Pd(OAc)2","role":"Catalyst precursor","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Pd(OAc)2 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","phase":"metallic Pd0","structureLink":"Showed significantly improved dehydrogenation kinetics compared to chloride-based complexes.","reactionConditions":"60 °C, aqueous solution of formic acid and sodium formate","whyPerformsWell":"Dehydrogenation kinetics improved significantly compared to chloride complexes.","metricCount":"0"},{"paperId":"P183","catalystId":"P183_PERF_001","name":"Pd@UIO-66/NH2-SEP","support":"UIO-66/NH2-SEP","matchedSynthesis":"Pd@UIO-66/NH2-SEP","matchedCharacterization":"Pd@UIO-66/NH2-SEP","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"UIO-66 was synthesized on NH2-SEP via hydrothermal method (393 K, 48 h). Pd nanoparticles were then loaded onto the dual support using an anionic exchange method followed by chemical reduction with NaBH4.","phase":"Pd nanoparticles supported on a composite of sepiolite (SEP) and UIO-66; XRD identifies monoclinic (m-ZrO2) and tetragonal (t-ZrO2) phases of zirconia characteristic of the UIO-66 structure.","particleSize":"2.3 nm","surfaceStates":"Electronic states of Pd NPs are modified by the surface MOF framework and amino functionalities on SEP; synergistic effects exist between Pd NPs, Zr species, and amino groups.","structureLink":"The UIO-66 framework exerts a sacrificial effect, preventing the agglomeration of Pd nanoparticles on the fibrous NH2-SEP structure, which maintains high catalytic activity and reusability over 8 cycles.","reactionConditions":"Dehydrogenation of formic acid (FA) in aqueous solution under ambient pressure.","selectivity":"No CO was detected; CO2 to H2 molar ratio is about 1:1.","stability":"Consistent catalytic activity over 8th recycled use.","deactivation":"UIO-66 framework prevents agglomeration of Pd nanoparticles on NH2-SEP through a sacrificial effect.","whyPerformsWell":"Synergistic effects and electronic modification between Pd NPs, Zr species, and amino groups; dual-support structure stabilizes small Pd NP size and dispersion.","metricCount":"5"},{"paperId":"P183","catalystId":"P183_PERF_002","name":"Pd@NH2-SEP","support":"NH2-SEP","matchedSynthesis":"Pd@NH2-SEP","matchedCharacterization":"Pd@NH2-SEP","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Synthesized using the same anionic exchange and chemical reduction process as Pd@UIO-66/NH2-SEP, replacing the support with NH2-SEP.","particleSize":"2.0 nm (fresh); increases to over 3.6 nm after 3 cycles due to serious aggregation.","surfaceStates":"Amino groups on SEP modify the electronic states of Pd NPs.","structureLink":"Lack of MOF framework leads to rapid particle aggregation and poor reusability after 3 cycles.","reactionConditions":"Dehydrogenation of formic acid in aqueous solution.","stability":"Unsatisfactory reusability; initial TOF reduced to almost half after three cycles.","deactivation":"Serious aggregation of Pd particles observed (average size increased from 2.0 nm to over 3.6 nm) after three repeated cycles.","whyPerformsWell":"High initial activity attributed to amino groups on SEP surface modifying electronic states of Pd NPs, but lacks structural stability provided by UIO-66.","metricCount":"1"},{"paperId":"P183","catalystId":"P183_PERF_003","name":"Pd@UIO-66","support":"UIO-66","matchedSynthesis":"Pd@UIO-66","matchedCharacterization":"Pd@UIO-66","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Synthesized using the same anionic exchange and chemical reduction process as Pd@UIO-66/NH2-SEP, replacing the support with UIO-66.","phase":"Pd nanoparticles on UIO-66; XRD matches simulated pure UIO-66 crystal structure.","structureLink":"The single MOF support is less stable than the dual-support system, leading to structural changes and poor reusability.","reactionConditions":"Dehydrogenation of formic acid in aqueous solution.","stability":"Poor reusability; activity dropped dramatically after the third recycling use.","deactivation":"Lamellar structure becomes evidently thinner after 3 uses and particle agglomeration is very obvious.","metricCount":"0"},{"paperId":"P184","catalystId":"P184_PERF_001","name":"Pd0.8Au0.2/UiO-66-(NH2)2","support":"UiO-66-(NH2)2","matchedSynthesis":"Pd0.8Au0.2/UiO-66-(NH2)2","matchedCharacterization":"Pd0.8Au0.2/UiO-66-(NH2)2","role":"active catalyst","composition":"Pd:Au = 4:1","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"UiO-66-(NH2)2 was suspended in n-hexane, followed by dropwise addition of aqueous Pd and Au precursors, drying, and reduction with NaBH4.","phase":"Alloy; HRTEM lattice spacing of ~0.229 nm is between Pd(111) (0.224 nm) and Au(111) (0.235 nm).","particleSize":"0.5 - 1.1 nm","surfaceStates":"XPS shows Pd 0 (340.51 and 334.77 eV) and Au 0 (86.37 and 84.23 eV); N 1s binding energy shift from 399.46 eV to 400.47 eV indicates interaction between NPs and amino groups.","structureLink":"The higher concentration of amino groups in the diamine support increases hydrophilicity and coordination ability, resulting in tinier nanoparticles (<1.1 nm) and better stability against aggregation compared to monoamine supports, which leads to a higher TOF (3660 h-1).","reactionConditions":"Formic acid dehydrogenation in aqueous solution","selectivity":"H2 and CO2 (1:1 volume ratio); no CO signal detected","stability":"recycled seven times without obvious loss in catalytic activity; drops slightly at the eighth cycling","deactivation":"no obvious loss of noble metal ingredients ((Au+Pd)/Zr molar ratio 0.060 fresh vs 0.059 spent); BET surface area decreased from 745 to 522 m2/g and pore volume from 0.61 to 0.49 cm3/g, suggesting some cavities were blocked","whyPerformsWell":"higher concentration of amino groups promotes formation of tinier AuPd NPs (below 1.1 nm), inhibits aggregation via stronger coordination, and provides more basic sites for FA activation","metricCount":"3"},{"paperId":"P184","catalystId":"P184_PERF_002","name":"Pd0.8Au0.2/UiO-66-NH2","support":"UiO-66-(NH2)2","matchedSynthesis":"Pd0.8Au0.2/UiO-66-(NH2)2","matchedCharacterization":"Pd0.8Au0.2/UiO-66-(NH2)2","role":"active catalyst","composition":"Pd:Au = 4:1","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"UiO-66-(NH2)2 was suspended in n-hexane, followed by dropwise addition of aqueous Pd and Au precursors, drying, and reduction with NaBH4.","phase":"Alloy; HRTEM lattice spacing of ~0.229 nm is between Pd(111) (0.224 nm) and Au(111) (0.235 nm).","particleSize":"0.5 - 1.1 nm","surfaceStates":"XPS shows Pd 0 (340.51 and 334.77 eV) and Au 0 (86.37 and 84.23 eV); N 1s binding energy shift from 399.46 eV to 400.47 eV indicates interaction between NPs and amino groups.","structureLink":"The higher concentration of amino groups in the diamine support increases hydrophilicity and coordination ability, resulting in tinier nanoparticles (<1.1 nm) and better stability against aggregation compared to monoamine supports, which leads to a higher TOF (3660 h-1).","reactionConditions":"Formic acid dehydrogenation in aqueous solution","stability":"activity decreases obviously after the fifth recycling","deactivation":"AuPd NPs aggregated to a mean size of 2.4 nm","metricCount":"1"},{"paperId":"P185","catalystId":"P185_PERF_001","name":"Pd60Au40/ZrSBA-15-AP","support":"ZrSBA-15","matchedSynthesis":"Pd60Au40/ZrSBA-15","matchedCharacterization":"Pd60Au40/ZrSBA-15-AP","role":"control catalyst (pristine support)","composition":"Pd:Au = 60:40","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Pristine ZrSBA-15 was impregnated with an aqueous solution of Pd and Au precursors, followed by liquid-phase reduction using NaBH4.","phase":"PdAu alloy NPs","particleSize":"Below 2 nm","surfaceStates":"Partial electron transfer from Au to Pd, evidenced by XPS binding energy shifts (Pd 3d shifted to lower values; Au 4f shifted to higher values)","structureLink":"The coexistence of small PdAu alloy NPs and suitable amino groups provides highly efficient bifunctional sites for synergistic activation of formic acid molecules.","reactionConditions":"Dehydrogenation of formic acid (FA) in aqueous solution without additives; 0.15 g catalyst and 9.5 mL water mixed, then 0.5 mL FA aqueous solution (0.2 M) injected; magnetic stirring in a two-neck round bottom flask connected to a gas burette.","selectivity":"nearly 100% for H2; no CO detected; H2:CO2 ratio almost 1:1","stability":"reused at least five times without an obvious change in the catalytic activity","whyPerformsWell":"Co-existence of small PdAu alloy NPs and suitable amino groups on ZrSBA-15 support (high surface area, large pore volume, short channels) providing bifunctional sites for synergistic activation of FA molecules; amino groups act as proton scavengers.","metricCount":"5"},{"paperId":"P185","catalystId":"P185_PERF_002","name":"Pd60Au40/ZrSBA-15","support":"ZrSBA-15","matchedSynthesis":"Pd60Au40/ZrSBA-15","matchedCharacterization":"Pd60Au40/ZrSBA-15","role":"control catalyst (pristine support)","composition":"Pd:Au = 60:40","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Pristine ZrSBA-15 was impregnated with an aqueous solution of Pd and Au precursors, followed by liquid-phase reduction using NaBH4.","phase":"PdAu alloy NPs","particleSize":"7 nm","structureLink":"Inactive under test conditions due to larger particle size and lack of amino groups.","reactionConditions":"298 K, 0.2 M FA aqueous solution, additive-free","whyPerformsWell":"lacks amino groups","metricCount":"1"},{"paperId":"P185","catalystId":"P185_PERF_003","name":"Pd60Au40/ZrSBA-15-MAP, Pd60Au40/ZrSBA-15-AEAEAP, Pd60Au40/ZrSBA-15-AEAP, Pd60Au40/ZrSBA-15-DMAP","support":"ZrSBA-15","matchedSynthesis":"Pd60Au40/ZrSBA-15-AEAP","matchedCharacterization":"Pd60Au40/ZrSBA-15","role":"active catalyst","composition":"Pd:Au = 60:40","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Amine-modified ZrSBA-15 was impregnated with an aqueous solution of Pd and Au precursors, followed by liquid-phase reduction using NaBH4.","phase":"PdAu alloy NPs","particleSize":"7 nm","structureLink":"Inactive under test conditions due to larger particle size and lack of amino groups.","reactionConditions":"298 K, 0.2 M FA aqueous solution, additive-free","whyPerformsWell":"Activity varies with the basicity and accessibility of the amino groups.","metricCount":"1"},{"paperId":"P186","catalystId":"P186_PERF_001","name":"1Pd-SS","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"H2 production from HCOONa/HCOOH mixture in aqueous solution at 80 °C","selectivity":"H2:CO2 ratio near 9:1; CO below detection limit (0.6 ppm)","stability":"lost ~40% of catalytic activity after three sequential uses","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition","metricCount":"2"},{"paperId":"P186","catalystId":"P186_PERF_002","name":"5Pd-SS","matchedCharacterization":"15Pd-SS","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pd/TiO2 (anatase/rutile mixture)","particleSize":"< 2 nm","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"Higher activation energy (Ea = 34.5 kJ/mol) compared to SD-FSP counterparts due to lower PdO:Pd0 ratio.","reactionConditions":"H2 production from HCOONa/HCOOH mixture in aqueous solution at 80 °C","selectivity":"H2:CO2 ratio near 9:1; CO below detection limit (0.6 ppm)","stability":"lost ~40% of catalytic activity after three sequential uses","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition","metricCount":"2"},{"paperId":"P186","catalystId":"P186_PERF_003","name":"15Pd-SS","matchedCharacterization":"15Pd-SS","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pd/TiO2 (anatase/rutile mixture)","particleSize":"< 2 nm","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"Higher activation energy (Ea = 34.5 kJ/mol) compared to SD-FSP counterparts due to lower PdO:Pd0 ratio.","reactionConditions":"H2 production from HCOONa/HCOOH mixture in aqueous solution at 80 °C","selectivity":"H2:CO2 ratio near 9:1; CO below detection limit (0.6 ppm)","stability":"lost ~40% of catalytic activity after three sequential uses","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition","metricCount":"2"},{"paperId":"P186","catalystId":"P186_PERF_004","name":"35Pd-SD","matchedCharacterization":"35Pd-SD","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Tetragonal crystalline PdO phase (confirmed by XRD and Raman); TiO2 support","particleSize":"Aggregated particles; low SSA (49.3 m2/g)","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"Lowest activation energy (Ea = 23.2 kJ/mol) due to highest [PdO:Pd0] ratio, but lower overall rate than 15Pd-SD due to low SSA.","reactionConditions":"H2 production from HCOONa/HCOOH mixture in aqueous solution at 80 °C","selectivity":"H2:CO2 ratio near 9:1; CO below detection limit (0.6 ppm)","stability":"lost ~40% of catalytic activity after three sequential uses","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition","whyPerformsWell":"High [PdO:Pd0] ratio lowers Ea barrier; however, overall rate is limited by low SSA due to high Pd loading","metricCount":"2"},{"paperId":"P186","catalystId":"P186_PERF_005","name":"15Pd-SD","matchedCharacterization":"15Pd-SD","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Tetragonal crystalline PdO; TiO2 support","particleSize":"Aggregated formations on TiO2 surface","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"High [PdO:Pd0] ratio leads to high H2 production rate (534 mmol/g Pd/min) and lower activation energy (Ea = 26.5 kJ/mol).","reactionConditions":"H2 production from HCOONa/HCOOH mixture in aqueous solution at 80 °C","selectivity":"H2:CO2 ratio near 9:1; CO below detection limit (0.6 ppm)","stability":"lost ~40% of catalytic activity after three sequential uses","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition","whyPerformsWell":"High [PdO:Pd0] ratio significantly lowers the activation energy barrier Ea and enhances selectivity toward dehydrogenation path","metricCount":"2"},{"paperId":"P186","catalystId":"P186_PERF_006","name":"5Pd-Lean","matchedCharacterization":"5Pd-Lean","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pd/TiO2 (predominantly rutile phase TiO2)","particleSize":"Large rutile TiO2 particles (~29.7 nm); tendency to form large Pd particles","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"Lowest [PdO:Pd0] ratio correlates with the highest activation energy (Ea = 55.1 kJ/mol) and lowest efficiency.","reactionConditions":"H2 production from HCOONa/HCOOH mixture in aqueous solution at 80 °C","selectivity":"H2:CO2 ratio near 9:1; CO below detection limit (0.6 ppm)","stability":"lost ~40% of catalytic activity after three sequential uses","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition","metricCount":"2"},{"paperId":"P187","catalystId":"P187_PERF_001","name":"Pd/ZrO2-F","support":"ZrO2 (hollow nanoframes)","matchedSynthesis":"Pd/ZrO2-F","matchedCharacterization":"Pd/ZrO2-F","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"ZrO2-F support was prepared via hydrothermal method and calcined; Pd was loaded via impregnation of H2PdCl4, reduced with NaBH4, and vacuum dried.","phase":"Metallic Pd nanoparticles on ZrO2 support.","particleSize":"Support particle size approximately 200 nm.","surfaceStates":"Dominantly zerovalent Pd (Pd0) with minor oxidized states (Pd2+); oxygen vacancy content is 15.98%.","structureLink":"Synergistic effect of m-ZrO2 and t-ZrO2 phases promotes FA dehydrogenation, achieving the highest TOF (1348 h-1) due to balanced dissociation and recombination steps.","reactionConditions":"30 °C, 1 M FA/SF (10 mL), 40 mg catalyst, 50 mL closed flask","stability":"excellent stability; slight decline after three cycles","whyPerformsWell":"Synergistic effect between m-ZrO2 and t-ZrO2 phases; enrichment of oxygen vacancies (Ov) accelerates desorption and spillover of H species.","metricCount":"3"},{"paperId":"P187","catalystId":"P187_PERF_002","name":"Pd/ZrO2-S","support":"ZrO2 (hollow spheres)","matchedSynthesis":"Pd/ZrO2-S","matchedCharacterization":"Pd/ZrO2-S","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"ZrO2-S support was prepared via hydrothermal method and calcined; Pd was loaded via impregnation of H2PdCl4, reduced with NaBH4, and vacuum dried.","phase":"Metallic Pd nanoparticles on ZrO2 support.","particleSize":"Hollow sphere structure with diameter of 100 nm; total particle size range 100-200 nm.","surfaceStates":"Dominantly zerovalent Pd (Pd0); electron-rich state due to interaction with m-ZrO2; oxygen vacancy content is 11.38%.","structureLink":"High specific surface area (194.8 m2/g) and electron-rich Pd sites facilitate FA dissociation but lack the synergistic recombination advantage of mixed phases.","reactionConditions":"30 °C, 1 M FA/SF (10 mL), 40 mg catalyst, 50 mL closed flask","metricCount":"2"},{"paperId":"P187","catalystId":"P187_PERF_003","name":"Pd/ZrO2-P","support":"ZrO2 (irregular particles)","matchedSynthesis":"Pd/ZrO2-P","matchedCharacterization":"Pd/ZrO2-P","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"ZrO2-P support was prepared via precipitation and calcined; Pd was loaded via impregnation of H2PdCl4, reduced with NaBH4, and vacuum dried.","phase":"Metallic Pd nanoparticles on ZrO2 support.","particleSize":"Irregular particles with size approximately 20 nm.","surfaceStates":"Dominantly zerovalent Pd (Pd0); electron-deficient state due to interaction with t-ZrO2; highest oxygen vacancy content at 21.65%.","structureLink":"Strong metal-support interaction and electron-deficient Pd sites facilitate H recombination but inhibit the rate-determining FA dissociation step, leading to lower TOF (577 h-1).","reactionConditions":"30 °C, 1 M FA/SF (10 mL), 40 mg catalyst, 50 mL closed flask","metricCount":"2"},{"paperId":"P188","catalystId":"P188_PERF_001","name":"Au2Pd3@(P)N-C","support":"nitrogen (N)-doped porous carbon","matchedSynthesis":"Au2Pd3@(P)N-C","matchedCharacterization":"Au2Pd3@(P)N-C","role":"main catalyst","composition":"Au:Pd = 2:3","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"phosphate-mediation approach","synthesis":"ZIF-8 was carbonized at 1000 °C and acid etched to produce N-doped porous carbon (N-C). N-C underwent a hydrothermal process with H3PO4 at 130 °C for 12 h to form phosphate-anchored carbon (PN-C). Au and Pd precursors were then anchored onto PN-C and reduced in an alkaline solution, which simultaneously removed the phosphate species.","phase":"AuPd alloy","particleSize":"1.5 ± 0.4 nm","surfaceStates":"Surface contains pyridinic, pyrrolic, and graphitic N; Au 4f and Pd 3d doublets shift to lower binding energies compared to monometallic counterparts; addition of Au decreases the oxidation of Pd.","structureLink":"The phosphate-mediation approach ensures a uniform distribution of ultrafine AuPd NPs, which results in significantly higher catalytic activity (TOF of 5400 h−1 at 30 °C) compared to catalysts prepared without phosphate mediation (Au2Pd3@N-C).","reactionConditions":"FA/SF (sodium formate) solution, 10–50 °C","selectivity":"100% H2 selectivity; CO not detected (below 10 ppm)","stability":"No activity loss observed over ten cycles","whyPerformsWell":"Uniform distribution of ultrafine AuPd NPs introduced by the phosphate-mediation approach and synergetic effect between N atoms and metal NPs.","metricCount":"3"},{"paperId":"P188","catalystId":"P188_PERF_002","name":"Au2Pd3@N-C","matchedCharacterization":"Au2Pd3@N-C","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"2.1 ± 0.6 nm","structureLink":"Larger particle size and poor dispersion lead to much lower catalytic activity (TOF of 1350 h−1 at 30 °C) compared to the phosphate-mediated catalyst.","reactionConditions":"FA/SF (sodium formate) solution, 30 °C","metricCount":"1"},{"paperId":"P188","catalystId":"P188_PERF_003","name":"Au2Pd3/N-C-hydrogen phosphate","matchedCharacterization":"Au2Pd3@N-C","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"2.1 ± 0.6 nm","structureLink":"Larger particle size and poor dispersion lead to much lower catalytic activity (TOF of 1350 h−1 at 30 °C) compared to the phosphate-mediated catalyst.","reactionConditions":"FA/SF (sodium formate) solution, 30 °C","metricCount":"1"},{"paperId":"P188","catalystId":"P188_PERF_004","name":"AuPd/ZIF-8","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA/SF system (pH = 5)","deactivation":"ZIF-8 is totally decomposed in the FA/SF system (pH = 5)","metricCount":"1"},{"paperId":"P189","catalystId":"P189_PERF_001","name":"Pd/PAN","support":"Polyacrylonitrile (PAN) beads","matchedSynthesis":"Pd/PAN","matchedCharacterization":"Pd/PAN","role":"catalyst for dehydrogenation of formic acid and reduction of organic dyes","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PAN beads were impregnated with an aqueous Pd precursor solution, followed by reduction with NaBH4.","phase":"Pd nanoparticles","particleSize":"9 nm","surfaceStates":"Metallic Pd(0) (binding energies at 335.1 and 340.7 eV)","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) in aqueous solution at 323 K","selectivity":"Excellent dehydrogenation selectivity; no CO detected, H2/CO2 volume ratio almost 1:1","whyPerformsWell":"eCN groups on PAN act as proton scavengers to provide a basic environment for O-H bond dissociation; porous structure enhances accessibility of eCN groups","metricCount":"1"},{"paperId":"P189","catalystId":"P189_PERF_002","name":"PdCo0.6/PAN","matchedCharacterization":"PdCo0.6/PAN","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic alloy NPs","particleSize":"1.6 nm","surfaceStates":"Predominantly metallic Pd(0) and Co (778.3 eV), with minor oxidized species (Pd 2+ at 336.3/341.6 eV, Co at 782.0 eV)","structureLink":"Addition of Co reduces particle size and influences chemical states or forms novel basic sites to enhance FA activation; eCN groups stabilize NPs against aggregation or leaching.","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) in aqueous solution at 323 K; reduction of organic dyes at 298 K","selectivity":"Excellent dehydrogenation selectivity; no CO detected, H2/CO2 volume ratio almost 1:1","stability":"Reused for at least six times without obvious decrease in catalytic activity (FA dehydrogenation); recyclable for the reduction of dyes with FA","deactivation":"Strong chemical affinity of eCN groups stabilizes Pd NPs against aggregation or leaching","whyPerformsWell":"eCN groups act as proton scavengers; Co doping reduces particle size, influences chemical states of Pd, or forms novel basic sites (metal oxides/hydroxides) to enhance FA activation","metricCount":"3"},{"paperId":"P189","catalystId":"P189_PERF_003","name":"PdFe0.9/PAN","matchedCharacterization":"PdFe0.9/PAN","activeMetals":"Pd-Fe","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic alloy NPs","particleSize":"2.5 nm","surfaceStates":"Predominantly metallic Pd(0) and Fe (707.3 eV), with minor oxidized species (Pd 2+ at 336.3/341.6 eV, Fe at 711.5 eV)","structureLink":"Addition of Fe reduces particle size and influences chemical states or forms novel basic sites to enhance FA activation; eCN groups stabilize NPs against aggregation or leaching.","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) in aqueous solution at 323 K","selectivity":"Excellent dehydrogenation selectivity; no CO detected, H2/CO2 volume ratio almost 1:1","whyPerformsWell":"eCN groups act as proton scavengers; Fe doping reduces particle size, influences chemical states of Pd, or forms novel basic sites (metal oxides/hydroxides) to enhance FA activation","metricCount":"1"},{"paperId":"P190","catalystId":"P190_PERF_001","name":"Pd@M1/20NB","matchedCharacterization":"Pd@M1/20NB","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Cubic Pd (XRD peaks attenuated due to small particle size)","particleSize":"Mean size 0.762 nm (range 0.4-1.4 nm)","surfaceStates":"Pd0 and PdII species present","structureLink":"Ultrafine particles, high dispersion, and hierarchical pore structure (1-3 nm) of the NPC support facilitate fast mass transfer and provide more surface sites, leading to a TOF of 446 h-1. Pyridinic N in the support modulates electronic properties of Pd.","reactionConditions":"Formic acid dehydrogenation in aqueous solution, typically at 303 K with [FA] = 1.0 mol·L⁻¹ and catalyst dosage of 16.7 g·L⁻¹.","selectivity":"Composed totally of H2 and CO2 at 303 K; trace CO (0.018% by volume of CO2) detected at 323 K.","stability":"Reused for at least five runs: first run reached 95% conversion in 30 min; fifth run reached 70% conversion in 85 min.","deactivation":"Gradual deactivation attributed to agglomeration of Pd particles (size increased from ~0.762 nm to 1.67 nm after first run and 2.21 nm after second run).","whyPerformsWell":"Hierarchical pore structure (especially mesopores) facilitating mass transfer; ultrafine Pd nanoparticles (~0.762 nm) with high dispersion (31.5%) anchored by pyridinic N; electronic modulation of Pd surface by pyridinic N.","metricCount":"5"},{"paperId":"P190","catalystId":"P190_PERF_002","name":"Pd@U1/20NB","matchedCharacterization":"Pd@U1/20NB","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Cubic Pd (XRD peaks attenuated)","particleSize":"Mean size 1.06 nm","surfaceStates":"Pd0 and PdII species present","structureLink":"Smaller particle size and higher dispersion compared to Pd@WBA result in enhanced activity (TOF = 307 h-1).","reactionConditions":"Formic acid dehydrogenation in aqueous solution, typically at 303 K with [FA] = 1.0 mol·L⁻¹ and catalyst dosage of 16.7 g·L⁻¹.","whyPerformsWell":"N-doping and developed porosity; Pd nanoparticles mean size of 1.06 nm with dispersion of 29.2%.","metricCount":"3"},{"paperId":"P190","catalystId":"P190_PERF_003","name":"Pd@WBA","support":"Undoped porous carbon (WBA)","matchedSynthesis":"Pd@WBA","matchedCharacterization":"Pd@WBA","role":"Control catalyst (undoped support)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Undoped woodchar was coactivated with NaHCO3 and air at 700 °C for 3 h in air/N2 flow, followed by Pd loading via K2PdCl4 impregnation and NaBH4 reduction.","phase":"Cubic Pd (sharp XRD peaks at 2θ = 40.3° and 46.7°)","particleSize":"Larger than Pd@NPC catalysts","surfaceStates":"Pd0 and PdII species present","structureLink":"Lower dispersion and larger particle size result in the lowest activity (TOF = 156 h-1).","reactionConditions":"Formic acid dehydrogenation in aqueous solution, typically at 303 K with [FA] = 1.0 mol·L⁻¹ and catalyst dosage of 16.7 g·L⁻¹.","whyPerformsWell":"Undoped porous carbon support; lower dispersion (19.2%) and larger Pd particles compared to NPC-supported catalysts.","metricCount":"1"},{"paperId":"P191","catalystId":"P191_PERF_001","name":"Pd/C in situ reduction","support":"Vulcan carbon powder XC-72","matchedSynthesis":"Pd/C in situ reduction","matchedCharacterization":"Pd/C in situ reduction","role":"main catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Precursor prepared by precipitation: Pd precursor added to support slurry, stirred 4h, pH adjusted to 10.9 with NaOH, stirred 4h for nucleation/maturation, filtered and dried; catalyst then prepared by reducing the precursor with sodium formate.","phase":"Pd crystal, specifically the Pd(111) plane (lattice spacing 0.22–0.23 nm).","particleSize":"1.86 nm","surfaceStates":"Pd(II) to Pd(0) ratio of 0.49:0.51 (approximately 1:1).","structureLink":"The optimum valence composition (1:1 Pd(0)/Pd(II)) and ultra-small size result in high mass-specific activity (8.94 mol H2/(gPd·h)) and low activation energy (33.1 kJ/mol). Pd(0) sites facilitate adsorption while Pd(II) promotes desorption of formic acid and inhibits CO production.","reactionConditions":"1.1 M formic acid + 0.8 M sodium formate, 303 K","selectivity":"High selectivity; few CO molecules produced; released about 250 mL of gas (ideal yield 270 mL)","stability":"Enhanced stability compared to commercial Pd/C and Pd/C-EG","deactivation":"Did not fully deactivate before complete decomposition of formic acid; decrease in rate attributed to dilute formic acid rather than activity loss","whyPerformsWell":"High density of Pd(0)-Pd(II) interface sites, optimum valence composition (ratio ~1:1), and ultra-small particle size (1.86 nm)","metricCount":"2"},{"paperId":"P191","catalystId":"P191_PERF_002","name":"Pd/C-EG reduction","support":"Vulcan carbon powder XC-72","matchedSynthesis":"Pd/C-EG reduction","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"polyol_reduction","synthesis":"Support mixed with ethylene glycol, Pd precursor added and stirred 3h, pH adjusted to 10.8 with NaOH, microwave treatment applied, followed by 8h stirring/ripening, filtration, washing, and drying.","reactionConditions":"1.1 M formic acid + 0.8 M sodium formate","selectivity":"Higher CO yield compared to Pd/C in situ reduction","stability":"Fully deactivated before the complete decomposition of formic acid","deactivation":"Deactivated by CO poisoning","metricCount":"0"},{"paperId":"P191","catalystId":"P191_PERF_003","name":"Pd/C-30% commercial","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"1.1 M formic acid + 0.8 M sodium formate","selectivity":"Higher CO yield compared to Pd/C in situ reduction","stability":"Fully deactivated before the complete decomposition of formic acid","deactivation":"Deactivated by CO poisoning","metricCount":"0"},{"paperId":"P192","catalystId":"P192_PERF_001","name":"Pd/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd/rGO","matchedCharacterization":"Pd/rGO","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"GO was impregnated with PdCl2 solution, dried at room temperature, thermally reduced in Ar, and then treated in a H2+Ar mixture.","phase":"Pd","particleSize":"3.7 nm (TEM), 5 nm (XRD)","structureLink":"Activation energy for FA dehydrogenation is 28.5 kJ/mol without SF and 24.4 kJ/mol with SF promoter.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution; catalyst amount 10 mg; volume 5 mL; magnetic stirring 1000 rpm; ambient air atmosphere.","selectivity":"No detectable traces of CO; generated gases are H2 and CO2.","stability":"Preserved initial activity even after 5 recycling runs at 313 K and 363 K.","metricCount":"6"},{"paperId":"P192","catalystId":"P192_PERF_002","name":"PdAu/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"PdAu/rGO","matchedCharacterization":"PdAu/rGO","role":"catalyst","composition":"Pd:Au = 7.5:2.5 wt%","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"GO was impregnated with a mixture of PdCl2 and HAuCl4 aqueous solutions, dried at room temperature, and thermally treated in a H2+Ar mixture.","phase":"PdAu alloy","particleSize":"2.9 nm (TEM), 3.5 nm (XRD)","surfaceStates":"STEM-EDX suggests segregation with gold concentrated on the surface and palladium in the core.","structureLink":"Smaller particles, good dispersion, and synergistic effect lead to superior activity and a significantly lower activation energy of 13.4 kJ/mol.","reactionConditions":"Formic acid (FA) dehydrogenation in FA/SF aqueous solution; catalyst amount 11.25 mg; volume 5 mL; magnetic stirring 1000 rpm; ambient air atmosphere.","selectivity":"No CO detected in the evolved gas (H2 + CO2).","whyPerformsWell":"Smaller particles, good dispersion and synergistic effect with reduced graphene oxide.","metricCount":"2"},{"paperId":"P193","catalystId":"P193_PERF_001","name":"Pd0.90Ag0.10B/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd0.90Ag0.10B/rGO","matchedCharacterization":"Pd0.90Ag0.10B/rGO","role":"active","composition":"Pd:Ag = 0.90:0.10 (molar ratio)","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Co-reduction of metal ions deposited on GO using NaBH4 as the reducing agent and boron source.","phase":"Low crystallinity PdAgB alloy; exhibits lattice expansion with a (1 1 1) spacing of 0.233 nm; HAADF-STEM indicates an alloy structure rather than core-shell.","surfaceStates":"Electron-rich Pd active sites (Pd 3d binding energies: 341.0 eV and 335.8 eV) resulting from electron transfer from Ag, B, and rGO to Pd atoms.","structureLink":"The combination of engineered alloy nanostructure and electronic modification by boron promotes C–H scission in the absorbed HCOO* intermediate, which is the rate-determining step for formic acid dehydrogenation.","reactionConditions":"Dehydrogenation of FA/SF aqueous solution at 298 K under ambient atmosphere in a round-bottomed flask.","selectivity":"Excellent H2 selectivity; no CO detected (detection limit ≈10 ppm).","stability":"Little decrease in the second run; obvious activity loss observed in the third run.","deactivation":"Activity loss possibly attributed to the aggregation of rGO during the reaction process.","whyPerformsWell":"Combination of engineered alloy nanostructure, electronic modification effect of boron species (creating electron-rich Pd active sites), and support effects of rGO providing uniform adhesion and modifying electronic structure.","metricCount":"3"},{"paperId":"P193","catalystId":"P193_PERF_002","name":"Pd0.90Ag0.10/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"Pd0.90Ag0.10/rGO","matchedCharacterization":"Pd0.90Ag0.10/rGO","role":"comparison","composition":"Pd:Ag = 0.90:0.10 (molar ratio)","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Co-reduction of metal ions deposited on GO using N2H4·H2O as the reducing agent.","phase":"PdAg alloy with face-centered cubic (fcc) structure; lattice spacing of (1 1 1) is 0.230 nm.","particleSize":"3.47 nm","surfaceStates":"Pd 3d binding energies are higher than those of Pd0.90Ag0.10B/rGO.","structureLink":"Displays lower activity compared to the boron-doped version despite smaller particle size, highlighting the promotional effect of B.","reactionConditions":"Dehydrogenation of FA/SF aqueous solution at 298 K under ambient atmosphere.","metricCount":"1"},{"paperId":"P193","catalystId":"P193_PERF_003","name":"PdB/rGO","support":"reduced graphene oxide (rGO)","matchedSynthesis":"PdB/rGO","matchedCharacterization":"PdB/rGO","role":"comparison","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Reduction of Pd ions on GO using NaBH4.","phase":"Low crystallinity PdB alloy; XRD shows diffraction peaks shifted toward lower 2θ values, indicating enlargement of Pd–Pd interatomic distance due to B incorporation.","particleSize":"9.45 nm","surfaceStates":"Pd 3d binding energies: 341.25 eV and 336.05 eV.","structureLink":"Relatively low activity attributed to uneven dispersion and large mean particle size.","reactionConditions":"Dehydrogenation of FA/SF aqueous solution at 298 K under ambient atmosphere.","whyPerformsWell":"Relatively low activity due to uneven dispersion and large mean particle size of PdB alloy.","metricCount":"1"},{"paperId":"P194","catalystId":"P194_PERF_001","name":"Pd/C-Li, Pd/C-Na, Pd/C-Ca, Pd/C-Ba","support":"Vulcan XC-72","matchedSynthesis":"Pd/C-Li","matchedCharacterization":"Pd/C-Li","role":"catalyst for formic acid decomposition","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Synthesized via the cation dipole adjustment method using microwave-assisted reduction in ethylene glycol (EG) with LiOH as the pH-adjustment agent.","phase":"fcc Pd crystal","particleSize":"3.0-6.5 nm (range for series)","surfaceStates":"Pd(0) (67% ± 1%) and Pd(II) (33% ± 1%)","structureLink":"Small particle size inhibits formic acid dehydration and extends catalyst life by reducing adjacent Pd(0) face sites.","reactionConditions":"Formic acid decomposition (FAD) at 303 K using a mixture of formic acid and sodium formate.","selectivity":"Formic acid dehydration produces CO, which causes surface blockage.","stability":"Divergence in H2 production rate noted after 50 min; smaller particle size extends catalyst life.","deactivation":"Deactivation occurs via the formic acid dehydration pathway (CO formation); deactivation rate increases with increasing particle size.","whyPerformsWell":"Intrinsic activity is determined by Pd surface valence states; stability is enhanced in smaller particles due to a larger proportion of corner and edge sites, which reduces adjacent Pd(0) sites required for the dehydration reaction.","metricCount":"1"},{"paperId":"P195","catalystId":"P195_PERF_001","name":"Pd-ZrO2/SBA-15-NH2","support":"SBA-15","matchedSynthesis":"Pd-ZrO2/SBA-15-NH2","matchedCharacterization":"Pd-ZrO2/SBA-15-NH2","role":"main catalyst","composition":"Pd/ZrO2 molar ratio = 0.9/0.1","activeMetals":"Pd-Zr","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-step coreduction strategy at ambient conditions using NaBH4.","phase":"Pd(111) phase identified; ZrO2 present but not detected by wide-angle XRD due to low content","particleSize":"1.5 nm (increased to 1.9 nm after reusability test)","surfaceStates":"Electron-rich metallic Pd surface due to electron donation from ZrO2; strong metal-support interaction (SMSI) between NPs and SBA-15-NH2 substrate indicated by positive shift in N 1s XPS peak; abundant basic sites from ZrO2 and -NH2 groups","structureLink":"Synergistic electronic effects of Pd and ZrO2, SMSI with the support, and high density of surface basic sites promote C-H bond splitting and FA deprotonation, leading to a TOF of 1408 h-1 and 100% H2 selectivity","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) in H2O","selectivity":"100% hydrogen selectivity (CO-free)","stability":"Well retained after one cycle; slight decrease after five cycles; obvious decrease after ten cycles. Durability test showed TOF drop from 1408 h-1 to 131 h-1 by the fourth cycle.","deactivation":"Mean particle size increased from 1.5 to 1.9 nm after reusability tests; possible catalyst loss during recycle process and adsorption of impurities on surface.","whyPerformsWell":"Synergistic electronic effects of Pd and ZrO2, strong metal-support interaction (SMSI) between Pd-ZrO2 NPs and SBA-15-NH2 substrate, abundant basic sites from ZrO2 and -NH2 groups promoting C-H bond splitting and FA deprotonation, and high dispersion of ultrasmall nanoparticles.","metricCount":"5"},{"paperId":"P195","catalystId":"P195_PERF_002","name":"Pd/SBA-15-NH2","support":"SBA-15","matchedSynthesis":"Pd/SBA-15-NH2","matchedCharacterization":"Pd/SBA-15-NH2","role":"comparative catalyst","composition":"Pd only","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar to Pd-ZrO2/SBA-15-NH2 but omitting Zr precursor.","particleSize":"1.7 nm","structureLink":"Lower activity and selectivity compared to Pd-ZrO2/SBA-15-NH2 due to lack of ZrO2 promoter","reactionConditions":"Additive-free dehydrogenation of formic acid (FA) in H2O","selectivity":"Lower hydrogen selectivity than Pd-ZrO2/SBA-15-NH2","metricCount":"1"},{"paperId":"P196","catalystId":"P196_PERF_001","name":"Pd6Ir4/KIT-6-NH2","activeMetals":"Pd-Ir","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA-SF aqueous solution at 303 K","selectivity":"100% H2 selectivity; no CO detected","stability":"H2 selectivity and productivity remain unchanged after four runs, but activity shows a slight decrease","deactivation":"Slight increase in the size of PdIr NPs and small decrease of amino-groups amounts","whyPerformsWell":"Synergistic effect between Pd and Ir; strong interaction between PdIr and KIT-6-NH2; amino-groups act as proton scavenger to promote O-H bond breaking; 3D cubic structure of KIT-6 facilitates mass transfer compared to SBA-15","metricCount":"4"},{"paperId":"P196","catalystId":"P196_PERF_002","name":"Pd/KIT-6-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"FA-SF aqueous solution","metricCount":"1"},{"paperId":"P196","catalystId":"P196_PERF_003","name":"PdIr/KIT-6 (bare)","support":"KIT-6","matchedSynthesis":"PdIr/KIT-6","matchedCharacterization":"PdIr/KIT-6","role":"comparative sample (bare support)","composition":"Pd and Ir","activeMetals":"Pd-Ir","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Pd and Ir loaded onto bare KIT-6 via impregnation-reduction.","phase":"PdIr alloy","particleSize":"7.4 nm","structureLink":"Almost no catalytic activity compared to amino-modified support due to larger particle size and lack of amino-group promotion.","reactionConditions":"FA-SF aqueous solution","whyPerformsWell":"almost no activity due to lack of amino-groups","metricCount":"0"},{"paperId":"P196","catalystId":"P196_PERF_004","name":"Pd6Ir4/SBA-NH2","activeMetals":"Pd-Ir","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA-SF aqueous solution","whyPerformsWell":"lower activity than Pd6Ir4/KIT-6-NH2 due to 2D hexagonal structure of SBA-15 being less conducive to mass transfer","metricCount":"0"},{"paperId":"P197","catalystId":"P197_PERF_001","name":"Ru/CNTs (3 wt.%)","support":"Carbon nanotubes (CNTs)","matchedSynthesis":"Ru/CNTs","matchedCharacterization":"Ru/CNTs","role":"Catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Ru(NO)(NO3)3 aqueous solution added to dried CNTs, stirred, stored in a closed vessel for 30 min, dried in air, and reduced under hydrogen flow.","phase":"Metallic Ru nanoparticles","particleSize":"2.3 ± 0.6 nm","surfaceStates":"Metallic Ru0 (XPS Ru3p3/2 main maximum at 462.6–462.9 eV)","reactionConditions":"CWAO of phenol: 160 °C, 50 atm, 20%O2/80%N2; Gas-phase FAD: quartz reactor, 5 vol.% FA/He feed at 20 cm3/min","metricCount":"4"},{"paperId":"P197","catalystId":"P197_PERF_002","name":"Ru/1.9%N-CNTs (3 wt.%)","matchedCharacterization":"Ru/1.9%N-CNTs","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Metallic Ru nanoparticles","particleSize":"1.7 ± 0.3 nm","surfaceStates":"Positively charged small metal particles (Ruδ+); XPS Ru3p3/2 main peak shifted toward higher binding energies by 0.2–0.3 eV compared to Ru/CNTs due to interaction with pyridinic nitrogen centers (Ruδ+–NPy)","reactionConditions":"CWAO of phenol: 160 °C, 50 atm, 20%O2/80%N2","metricCount":"2"},{"paperId":"P197","catalystId":"P197_PERF_003","name":"Ru/3.0%N-CNTs (3 wt.%)","matchedCharacterization":"Ru/3.0%N-CNTs","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Metallic Ru nanoparticles","particleSize":"1.6 ± 0.3 nm","surfaceStates":"Positively charged small metal particles (Ruδ+); XPS Ru3p3/2 main peak shifted toward higher binding energies by 0.2–0.3 eV compared to Ru/CNTs due to interaction with pyridinic nitrogen centers (Ruδ+–NPy)","reactionConditions":"CWAO of phenol: 160 °C, 50 atm, 20%O2/80%N2","metricCount":"2"},{"paperId":"P197","catalystId":"P197_PERF_004","name":"Ru/4.8%N-CNTs (3 wt.%)","matchedCharacterization":"Ru/4.8%N-CNTs","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Metallic Ru nanoparticles and single atoms","particleSize":"1.5 ± 0.3 nm","surfaceStates":"Positively charged small metal particles (Ruδ+) and single atoms stabilized by pyridinic nitrogen centers (Ruδ+–NPy); HAADF-STEM confirms coexistence of nanoparticles and single Ru atoms","structureLink":"Presence of sub-nanoparticles and single atoms increases catalytic activity and selectivity in formic acid decomposition (FAD) but has no effect on catalytic wet air oxidation (CWAO) of phenol.","reactionConditions":"CWAO of phenol: 160 °C, 50 atm, 20%O2/80%N2; Gas-phase FAD: quartz reactor, 5 vol.% FA/He feed at 20 cm3/min","selectivity":"Selectivity to hydrogen increased by 13% compared to Ru/CNTs (2-fold decrease in CO concentration)","stability":"Stable operation during 6 h of FAD at ~150 °C; unstable in CWAO of phenol, showing sequential deactivation over three cycles","deactivation":"In CWAO: partial oxidation/destruction of N-CNTs leading to carbonaceous deposits blocking Ru surface; iron leaching (3 wt.%) and minor ruthenium loss (0.05 wt.%) observed","whyPerformsWell":"Presence of sub-nanoparticles and single atoms in Ru/4.8%N-CNTs positively contributes to rate and selectivity in FAD","metricCount":"7"},{"paperId":"P198","catalystId":"P198_PERF_001","name":"Pd0.6Co0.2Ni0.2/CNSC","support":"Schiff base conjugated carbon nitride (CNSC)","matchedSynthesis":"Pd0.6Co0.2Ni0.2/CNSC","matchedCharacterization":"Pd0.6Co0.2Ni0.2/CNSC","role":"optimized catalyst","composition":"Pd:Co:Ni = 0.6:0.2:0.2","activeMetals":"Pd-Co-Ni","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CNSC support was prepared by urea/terephthalaldehyde pyrolysis. Metal precursors were added to a CNSC aqueous suspension, pH adjusted to 9.8, and reduced using NaBH4.","phase":"Trimetallic alloy phase; lattice spacing of 0.216 nm (between fcc Pd, Co, and Ni).","particleSize":"1.70 nm","surfaceStates":"Electron-rich Pd species resulting from electron transfer from Co and Ni (due to electronegativity differences) and from the CNSC support to the metal NPs.","structureLink":"The Schiff base conjugation enhances affinity between the support and metals, leading to smaller, well-dispersed nanoparticles and increased electron density on Pd active sites, which promotes FA dehydrogenation activity.","reactionConditions":"Room temperature, FA/SF reaction liquid in deionized water","selectivity":"100% hydrogen selectivity; no CO detected (< 10 ppm)","stability":"Good recycling performance over five runs; activity decreases slightly during the second run and fifth run","deactivation":"Slight degradation attributed to agglomeration of metal nanoparticles; ICP-AES ruled out metal leaching","whyPerformsWell":"Schiff base groups provide conjugated active sites for anchoring metals, leading to ultra-fine (1.70 nm) and well-dispersed NPs; electron-rich Pd species due to charge transfer from Co, Ni, and CNSC support; Schiff base facilitates O-H bond dissociation of FA","metricCount":"3"},{"paperId":"P198","catalystId":"P198_PERF_002","name":"Pd0.6Co0.2Ni0.2/g-C3N4","support":"graphitic carbon nitride (g-C3N4)","matchedSynthesis":"Pd0.6Co0.2Ni0.2/g-C3N4","matchedCharacterization":"Pd0.6Co0.2Ni0.2/g-C3N4","role":"comparison catalyst","composition":"Pd:Co:Ni = 0.6:0.2:0.2","activeMetals":"Pd-Co-Ni","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Similar to PdCoNi/CNSC but using g-C3N4 support.","phase":"Trimetallic phase","particleSize":"2.00 nm","surfaceStates":"Lower electron density on Pd active sites compared to the CNSC-supported catalyst.","structureLink":"Larger particle size and lower electron density on Pd lead to significantly lower catalytic activity (TOF = 33 h-1) compared to Pd0.6Co0.2Ni0.2/CNSC.","reactionConditions":"Room temperature, FA/SF reaction liquid in deionized water","metricCount":"1"},{"paperId":"P198","catalystId":"P198_PERF_003","name":"Pd/CNSC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA/SF reaction liquid in deionized water","metricCount":"1"},{"paperId":"P198","catalystId":"P198_PERF_004","name":"Pd0.8Co0.1Ni0.1/CNSC","activeMetals":"Pd-Co-Ni","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA/SF reaction liquid in deionized water","metricCount":"1"},{"paperId":"P198","catalystId":"P198_PERF_005","name":"Pd0.4Co0.3Ni0.3/CNSC","activeMetals":"Pd-Co-Ni","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA/SF reaction liquid in deionized water","metricCount":"1"},{"paperId":"P198","catalystId":"P198_PERF_006","name":"Pd0.2Co0.4Ni0.4/CNSC","activeMetals":"Pd-Co-Ni","activeMetalCount":"3","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA/SF reaction liquid in deionized water","metricCount":"1"},{"paperId":"P198","catalystId":"P198_PERF_007","name":"Pd0.6Co0.4/CNSC","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA/SF reaction liquid in deionized water","metricCount":"1"},{"paperId":"P198","catalystId":"P198_PERF_008","name":"Pd0.6Ni0.4/CNSC","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Room temperature, FA/SF reaction liquid in deionized water","metricCount":"1"},{"paperId":"P199","catalystId":"P199_PERF_001","name":"γ-Mo2N/ 0.2 NK-C","matchedCharacterization":"γ-Mo2N/x NK-C (specifically γ-Mo2N/0.2 NK-C)","activeMetals":"Mo","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"γ-Mo2N (cubic phase, PDF #25-1366)","particleSize":"2.1 nm","surfaceStates":"Surface contains Moδ+ (nitride), Mo6+ (oxide), K+, pyridinic-N, and pyrrolic-N. Acid-base properties include Brønsted and Lewis acid sites (B/L ratio 0.17) and three distinct basic sites (desorption temperatures at 174, 268, and 402 °C).","structureLink":"γ-Mo2N nanoparticles are responsible for the rate-limiting H-C bond cleavage of adsorbed HCOO-. K-containing sites promote HCOO- generation and adsorption; N-doped sites act as Lewis base sites for H+ adsorption. Water molecules occupy Brønsted acid sites, inhibiting FA dehydration to CO.","reactionConditions":"Aqueous formic acid dehydrogenation in a three-neck round-bottom flask connected with a condenser (reflux temperature 10 °C) and graduated cylinder, purged with Ar gas.","selectivity":"H2/CO2 molar ratios maintained at ca. 1/1; no detectable CO for aqueous FA concentrations of 1.9, 7.7, and 40 vol%; CO/CO2 ratio increases to 0.003 (>50 vol%), 0.037 (75 vol%), and 0.748 (neat FA).","stability":"Stable activity observed during a 108 h stability test with 40 vol% aqueous FA.","deactivation":"Significant K leaching (80.6%) occurred after the stability test; Mo leaching was negligible (2.5 mg/L). Air oxidation at 400 °C caused remarkable deactivation.","whyPerformsWell":"Cooperation of K-containing sites (HCOO- generation and adsorption), N-doped sites (H+ adsorption), and γ-Mo2N active sites (H-C bond cleavage). H2O prevents FA dehydration by occupying Brønsted acid sites.","metricCount":"2"},{"paperId":"P200","catalystId":"P200_PERF_001","name":"Pd-NPs@TA-COP","support":"TA-COP (Triazine-based covalent organic polymer)","matchedSynthesis":"Pd-NPs@TA-COP","matchedCharacterization":"Pd-NPs@TA-COP","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PdCl2 was sonicated in methanol, added to a dispersion of TA-COP in ethanol, stirred, and then reduced using NaBH4.","phase":"Metallic Pd (XRD peaks at 2θ = 38.32°, 44.55°, 64.73°, 77.81°, and 81.92° corresponding to planes 111, 200, 220, 311, and 222)","particleSize":"2.52 nm","surfaceStates":"Pd(0)","structureLink":"Synergistic effects between the nitrogen-rich TA-COP support and Pd nanoparticles enhance catalytic activity; the N-rich support prevents nanoparticle aggregation.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution using a 100 mL glass reactor under nitrogen atmosphere.","selectivity":"High hydrogen selectivity; selective production of CO2 and H2 (Route A); CO-free dehydrogenation.","stability":"Catalytic activity retained for 7 times of recovery.","deactivation":"Lack of Pd NPs aggregations after six runs verified by TEM image.","whyPerformsWell":"Synergistic effects between the nitrogen-rich TA-COP support and Pd nanoparticles; well dispersion of Pd NPs on N-rich support prevents aggregation.","metricCount":"6"},{"paperId":"P201","catalystId":"P201_PERF_001","name":"PdAg/CA-5","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of formic acid in D2O","selectivity":"D2 selectivity 84-87%; CO formation suppressed to <2 ppm","stability":"spent catalyst could be reused while keeping its activity and preferential D2 selectivity","whyPerformsWell":"Weakly basic phenylamine groups promote O-H bond dissociation and facilitate H-D exchange at both Pd and amine sites; carbon support (Ketjen Black) allows efficient adsorption of reactants.","metricCount":"4"},{"paperId":"P201","catalystId":"P201_PERF_002","name":"PdAg/CA-1","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of formic acid in D2O","selectivity":"51% D2 selectivity","whyPerformsWell":"Strongly basic /C0NEt2 groups lead to preferential H-D exchange at the Pd site, favoring HD over D2.","metricCount":"1"},{"paperId":"P201","catalystId":"P201_PERF_003","name":"PdAg/C","support":"Amine-functionalized carbon (CA-x)","matchedSynthesis":"PdAg/CA-x (x=1-5)","matchedCharacterization":"PdAg/CA-x (x=1-5)","role":"catalyst","composition":"Pd:Ag = 1:1","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CA-x support was dispersed in an aqueous solution of Pd(NH3)4Cl2 and AgNO3, stirred at RT for 1 h, followed by the injection of aqueous NaBH4 for reduction.","phase":"PdAg alloy nanoparticles; confirmed by Pd and Ag K-edge EXAFS showing Pd-Ag bonds with longer interatomic distances than pure Pd-Pd or Ag-Ag bonds.","particleSize":"5.6 nm for PdAg/CA-5; 4.5-6.5 nm for other PdAg/CA-x specimens.","surfaceStates":"XPS shows Pd 3d and Ag 3d peaks shifted to higher binding energies in amine-functionalized supports compared to PdAg/C, indicating altered electronic states due to surface amine groups.","structureLink":"D2 selectivity correlates with the basicity of grafted amine groups (measured by FA adsorption energy Ead); alloying with Ag promotes C-H bond dissociation; surface amine groups promote O-H bond dissociation and govern isotope selectivity.","reactionConditions":"Dehydrogenation of formic acid in D2O","selectivity":"66% D2 selectivity","whyPerformsWell":"Lower activity and reduced D2 selectivity compared to amine-functionalized supports due to lack of surface amine groups for O-H bond dissociation.","metricCount":"1"},{"paperId":"P201","catalystId":"P201_PERF_004","name":"Pd/CA-5","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of formic acid in D2O","whyPerformsWell":"Low activity; alloying with Ag is required to promote C-H bond dissociation.","metricCount":"0"},{"paperId":"P201","catalystId":"P201_PERF_005","name":"unsupported PdAg NPs","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of formic acid in D2O","deactivation":"aggregation into larger particles under the catalytic reaction conditions","whyPerformsWell":"Almost no activity due to aggregation.","metricCount":"0"},{"paperId":"P202","catalystId":"P202_PERF_001","name":"Pd/CDs-III","support":"N-doped carbon dots (CDs-III)","matchedSynthesis":"Pd/CDs-III","matchedCharacterization":"Pd/CDs-III","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CDs dissolved in water, Pd precursor added via ultrasonication, reduced with NaBH4, dried, and annealed under Ar.","phase":"Cubic Pd (JCPDS: 46-1043)","particleSize":"1.94 nm","surfaceStates":"Pd0 binding energy of 335.10 eV; presence of N-Pd coordination (XPS peak at 398.3 eV)","structureLink":"Highest pyridine nitrogen content (34.7%) leads to the smallest particle size and highest electron density on Pd, facilitating C-H bond rupture; Pd2+ promotes HCOO* adsorption via Coulomb interaction.","reactionConditions":"FA aqueous solution, 298 K, air environment, closed system, magnetic stirring, two-neck round bottom flask","selectivity":"no CO signal detected; completely decompose into CO2 and H2","stability":"Good stability over five cyclic tests; volume of generated gases reached 75 mL within 21.3 min (1st cycle) to 27.6 min (5th cycle); TOF decreased from 256 h-1 (1st cycle) to a slightly lower value in the 5th cycle.","deactivation":"Slight decrease in activity due to growth of Pd particles and decrease in N content leading to decrease in electron density of metal Pd","whyPerformsWell":"Pyridine nitrogen facilitates HCOOH dissociation; electron transfer from pyridine N to Pd promotes C-H bond breaking; Pd2+ favors formate adsorption.","metricCount":"6"},{"paperId":"P202","catalystId":"P202_PERF_002","name":"Pd/CDs-II","support":"N-doped carbon dots (CDs-II)","matchedSynthesis":"Pd/CDs-II","matchedCharacterization":"Pd/CDs-II","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CDs dissolved in water, Pd precursor added via ultrasonication, reduced with NaBH4, dried, and annealed under Ar.","phase":"Cubic Pd (JCPDS: 46-1043)","particleSize":"2.28 nm","surfaceStates":"Pd0 binding energy of 335.32 eV","structureLink":"Pyridine nitrogen content (23.9%) correlates with reduced particle size and increased electron density on Pd.","reactionConditions":"FA aqueous solution, 298 K, air environment, closed system, magnetic stirring, two-neck round bottom flask","selectivity":"no CO signal detected","metricCount":"1"},{"paperId":"P202","catalystId":"P202_PERF_003","name":"Pd/CDs-I","support":"N-doped carbon dots (CDs-I)","matchedSynthesis":"Pd/CDs-I","matchedCharacterization":"Pd/CDs-I","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CDs dissolved in water, Pd precursor added via ultrasonication, reduced with NaBH4, dried, and annealed under Ar.","phase":"Cubic Pd (JCPDS: 46-1043)","particleSize":"2.65 nm","surfaceStates":"Pd0 binding energy of 335.58 eV","structureLink":"Pyridine nitrogen content (13.5%) influences Pd nanoparticle size and electron density.","reactionConditions":"FA aqueous solution, 298 K, air environment, closed system, magnetic stirring, two-neck round bottom flask","selectivity":"no CO signal detected","metricCount":"1"},{"paperId":"P202","catalystId":"P202_PERF_004","name":"Pd/XC-72","support":"commercial active carbon (XC-72)","matchedSynthesis":"Pd/XC-72","matchedCharacterization":"Pd/XC-72","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Synthesized using the same method as Pd/CDs catalysts.","phase":"Cubic Pd","surfaceStates":"Pd0 binding energy is approximately 0.8 eV higher than that of Pd/CDs-III","structureLink":"Lacks the electron-donating effect of pyridine nitrogen found in CD supports, resulting in lower catalytic activity.","reactionConditions":"FA aqueous solution, 298 K, air environment, closed system, magnetic stirring, two-neck round bottom flask","selectivity":"no CO signal detected","metricCount":"1"},{"paperId":"P203","catalystId":"P203_PERF_001","name":"Pd-loaded Tp-Azo-COF/SiO2","support":"Tp-Azo-COF/SiO2","matchedSynthesis":"Pd-loaded Tp-Azo-COF/SiO2","matchedCharacterization":"Pd-loaded Tp-Azo-COF/SiO2","role":"Catalyst for formic acid decomposition (hydrogen production)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"adsorption_or_loading","synthesis":"Pd(II) was adsorbed onto the Tp-Azo-COF/SiO2 composite via batch adsorption, then reduced to metallic Pd using sodium borohydride (NaBH4).","phase":"Pd(1 1 1) facet","particleSize":"nanoscale (referred to as Pd nanoclusters)","surfaceStates":"XPS analysis indicated the presence of two valence states: a dominant Pd0 state and some remaining adsorbed Pd2+.","structureLink":"C-NH containing carriers facilitate the decomposition of formic acid roots; Pd nanoclusters capture H+ ions from solution, where mutual collision on the Pd nanoscale surface catalyzes the formation of H2.","reactionConditions":"70 °C, 1 mL of 3.5 mol/L formic acid solution in 20 mL ultrapure water, 0.1 g catalyst","stability":"For 80 mg/g Pd-loaded catalyst: Cycle 1 (97 mL in 899 s), Cycle 2 (58 mL in 1364 s), Cycle 3 (33 mL in 2980 s). Outperformed commercial catalysts after three cycles.","deactivation":"H2, CO2 and HCOO intermediates generated by the decomposition of formic acid occupy active sites and deactivate the catalyst","whyPerformsWell":"C-NH-containing carriers facilitate the decomposition of formic acid roots","metricCount":"6"},{"paperId":"P204","catalystId":"P204_PERF_001","name":"Pd@NaA30700","support":"biochar-derived hierarchically porous carbon (HPC)","matchedSynthesis":"Pd@NaA30700","matchedCharacterization":"Pd@NaA30700","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Pd(II) salt was added dropwise to an aqueous dispersion of HPC at pH 8.5, followed by magnetic agitation and liquid-phase reduction using NaBH4.","phase":"Cubic Pd","particleSize":"3.61 nm","surfaceStates":"Pd0 and PdII","structureLink":"Hierarchical pores enhanced Pd nanoparticle dispersion and provided fast channels for reactants; the high mesopore surface area made active sites readily accessible and facilitated gas product diffusion, resulting in a TOF of 156 h-1.","reactionConditions":"Two-neck round bottom flask in a water bath at 30 °C, magnetic stirring, gas burette for measurement.","selectivity":"Conversion of FA totally to H2 and CO2 without side reaction","stability":"Maintained activity after one run, but gradually declined thereafter","deactivation":"Decline related to block of pores; recycled catalyst showed decreased surface area (SA BET = 645 m2 g-1, SA meso = 113 m2 g-1)","whyPerformsWell":"Hierarchical pore structure enhanced Pd dispersion and provided fast channels for reactants to access active sites and gas products to diffuse out; higher mesopore surface area compared to KA30700 carrier.","metricCount":"3"},{"paperId":"P204","catalystId":"P204_PERF_002","name":"Pd@KA30700","support":"biochar-derived hierarchically porous carbon (HPC)","matchedSynthesis":"Pd@KA30700","matchedCharacterization":"Pd@KA30700","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Pd(II) salt was added dropwise to an aqueous dispersion of HPC at pH 8.5, followed by magnetic agitation and liquid-phase reduction using NaBH4.","phase":"Cubic Pd","particleSize":"1.31 nm","surfaceStates":"Pd0 and PdII","structureLink":"Hierarchical pores improved nanoparticle distribution, but lower mesopore surface area compared to Pd@NaA30700 led to lower catalytic activity (TOF = 83.0 h-1).","reactionConditions":"Two-neck round bottom flask in a water bath at 30 °C, magnetic stirring, gas burette for measurement.","selectivity":"Conversion of FA totally to H2 and CO2 without side reaction","whyPerformsWell":"Hierarchical pores enhanced Pd dispersion; however, lower mesopore surface area compared to NaA30700 resulted in lower activity.","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_001","name":"0.3Pt/N-CNFs","support":"N-doped carbon nanofibers (N-CNFs)","matchedSynthesis":"0.3Pt/N-CNFs","matchedCharacterization":"Pt/N-CNFs","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Homogeneous precipitation of Pt from H2PtCl6 using NaOH as a precipitant, followed by drying and reduction.","phase":"Single atoms and clusters (monolayer to few layers thick)","particleSize":"1.0 nm (mean size from conventional TEM for 1 wt% sample)","surfaceStates":"Ionic/electron-deficient state (Pt2+); XPS Pt 4f 7/2 binding energy ~72.1 eV (1.0 eV higher than bulk Pt powder).","structureLink":"Single Pt atoms stabilized by a pair of pyridinic nitrogen atoms at graphene edges provide high activity for formic acid decomposition and nearly 100% selectivity to H2.","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1; catalyst loading: 7 mg","selectivity":"close to 100% (H2)","whyPerformsWell":"Pt is present mainly in the form of ionic species as single atoms stabilized by nitrogen sites","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_002","name":"1Pt/N-CNFs","support":"N-doped carbon nanofibers (N-CNFs)","matchedSynthesis":"1Pt/N-CNFs","matchedCharacterization":"Pt/N-CNFs","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Homogeneous precipitation of Pt from H2PtCl6 using NaOH as a precipitant, followed by drying and reduction.","phase":"Single atoms and clusters (monolayer to few layers thick)","particleSize":"1.0 nm (mean size from conventional TEM for 1 wt% sample)","surfaceStates":"Ionic/electron-deficient state (Pt2+); XPS Pt 4f 7/2 binding energy ~72.1 eV (1.0 eV higher than bulk Pt powder).","structureLink":"Single Pt atoms stabilized by a pair of pyridinic nitrogen atoms at graphene edges provide high activity for formic acid decomposition and nearly 100% selectivity to H2.","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1; catalyst loading: 7 mg","selectivity":"96-99.6% (H2)","stability":"very high stability for more than 40 h on stream at 448 K","whyPerformsWell":"stabilization of ionic Pt species by nitrogen sites prevents sintering and enhances activity","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_003","name":"1Pt/CNFs","support":"Carbon nanofibers (CNFs)","matchedSynthesis":"1Pt/CNFs","role":"active catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Homogeneous precipitation of Pt from H2PtCl6 using NaOH as a precipitant, followed by drying and reduction.","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1; catalyst loading: 7 mg","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_004","name":"1Pd/N-CNFs","support":"N-doped carbon nanofibers (N-CNFs)","matchedSynthesis":"1Pd/N-CNFs","matchedCharacterization":"Pd/N-CNFs","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of Pd precursor onto N-CNFs followed by reduction.","phase":"Single atoms and nanoparticles","particleSize":"2.3 nm (mean size from conventional TEM for 1 wt% sample)","surfaceStates":"Coexistence of metallic Pd0 (335.7 eV) and ionic Pd2+ (337.6 eV); ionic content is significantly higher in N-doped samples.","structureLink":"Unreducible Pd2+ species attached to pyridinic nitrogen are identified as the active sites for formic acid decomposition.","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1; catalyst loading: 7 mg","selectivity":"94-98% (H2)","whyPerformsWell":"presence of ionic metal sites stabilized by nitrogen species","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_005","name":"1Pd/CNFs","support":"Carbon nanofibers (CNFs)","matchedSynthesis":"1Pd/CNFs","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of Pd precursor onto CNFs followed by reduction.","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1; catalyst loading: 7 mg","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_006","name":"1Ru/N-CNFs","support":"N-doped carbon nanofibers (N-CNFs)","matchedSynthesis":"1Ru/N-CNFs","matchedCharacterization":"Ru/N-CNFs","role":"active catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of Ru precursor onto N-CNFs followed by reduction.","phase":"Nanoparticles","particleSize":"1.5 nm (mean size from conventional TEM for 1 wt% sample)","surfaceStates":"Electron-deficient Ru species; XPS Ru 3d 5/2 binding energy of 280.3 eV (0.3 eV higher than bulk Ru metal).","structureLink":"Ru interacts more strongly with the support than Pt or Pd, which correlates with lower catalytic activity for formic acid decomposition.","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1; catalyst loading: 7 mg","selectivity":"83-92% (H2)","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_007","name":"1Ru/CNFs","support":"Carbon nanofibers (CNFs)","matchedSynthesis":"1Ru/CNFs","role":"active catalyst","composition":"Ru","activeMetals":"Ru","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of Ru precursor onto CNFs followed by reduction.","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1; catalyst loading: 7 mg","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_008","name":"unsupported Pt powder","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1","selectivity":"about 99% at 50% conversion (H2)","metricCount":"1"},{"paperId":"P205","catalystId":"P205_PERF_009","name":"unsupported Pd powder","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"Vapor-phase formic acid decomposition in a fixed bed 4 mm (i.d.) quartz reactor at atmospheric pressure; feed: 1.8 vol % formic acid in He; total flow rate: 51 mL3 (STP) min-1","selectivity":"about 99% at 50% conversion (H2)","metricCount":"1"},{"paperId":"P206","catalystId":"P206_PERF_001","name":"Pd/CTF-1","support":"CTF-1","matchedSynthesis":"Pd/CTF-1","matchedCharacterization":"Pd/CTF-1","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support impregnated with Pd acetylacetonate in acetone, stirred, dried, and then treated under a formic acid/Ar flow to remove ligands and stabilize Pd.","phase":"Single-atom catalyst; EXAFS/wavelet transform indicated a low content of small Pd clusters with Pd-Pd distance of 2.74 Å.","particleSize":"Single atoms (observed as individual bright dots in HAADF/STEM)","surfaceStates":"Pd2+ state; best EXAFS model corresponds to Pd-C2N2 sites (Pd-C: 2.05 Å, Pd-N: 2.09 Å).","structureLink":"The highest catalytic activity was associated with the presence of Pd2+-C2N2 sites.","reactionConditions":"Gas-phase decomposition of formic acid (2.5 vol%/Ar) in a fixed-bed glass reactor.","selectivity":"~98%","stability":"Very stable behavior within 5 h of the test at 473 K","whyPerformsWell":"Associated with Pd2+-C2N2 sites; strong interaction of single-atom Pd sites with the support (binding energies ~6 eV).","metricCount":"2"},{"paperId":"P206","catalystId":"P206_PERF_002","name":"Pd/pyCTF","support":"pyCTF","matchedSynthesis":"Pd/pyCTF","matchedCharacterization":"Pd/pyCTF","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support impregnated with Pd acetylacetonate in acetone, stirred, dried, and then treated under a formic acid/Ar flow to remove ligands and stabilize Pd.","phase":"Single-atom catalyst; EXAFS indicated a low content of small Pd clusters with Pd-Pd distances of 2.71-2.72 Å.","particleSize":"Single atoms (observed as individual bright dots in HAADF/STEM)","surfaceStates":"Pd2+ state; EXAFS showed strong peak corresponding to Pd-N4 sites (~2.04 Å).","structureLink":"Lower catalytic activity compared to Pd/CTF-1, associated with the formation of Pd2+-N4 sites.","reactionConditions":"Gas-phase decomposition of formic acid (2.5 vol%/Ar) in a fixed-bed glass reactor.","selectivity":"up to 99.0% at 573 K","whyPerformsWell":"Pd-N4 sites","metricCount":"1"},{"paperId":"P206","catalystId":"P206_PERF_003","name":"Pd/bipyCTF","support":"bipyCTF","matchedSynthesis":"Pd/bipyCTF","matchedCharacterization":"Pd/bipyCTF","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Support impregnated with Pd acetylacetonate in acetone, stirred, dried, and then treated under a formic acid/Ar flow to remove ligands and stabilize Pd.","phase":"Single-atom catalyst; EXAFS indicated a low content of small Pd clusters with Pd-Pd distances of 2.71-2.72 Å.","particleSize":"Single atoms (observed as individual bright dots in HAADF/STEM)","surfaceStates":"Pd2+ state; EXAFS showed strong peak corresponding to Pd-N4 sites (~2.04 Å).","structureLink":"Lower catalytic activity compared to Pd/CTF-1, associated with the formation of Pd2+-N4 sites.","reactionConditions":"Gas-phase decomposition of formic acid (2.5 vol%/Ar) in a fixed-bed glass reactor.","selectivity":"up to 99.8% at 573 K","whyPerformsWell":"Pd-N4 sites","metricCount":"1"},{"paperId":"P206","catalystId":"P206_PERF_004","name":"Pd/C","support":"mesoporous Sibunit-type graphitic carbon","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"reference catalyst","composition":"Pd nanoparticles (~2.3 nm)","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Metallic Pd nanoparticles with surface oxide layer.","particleSize":"2.3 ± 0.3 nm","surfaceStates":"Mixed oxidation states: Pd0 (335.5 eV) and Pd2+ in Pd oxide (336.8 eV).","structureLink":"Active sites involve the surface of Pd metal nanoparticles; less stable and selective than single-atom CTF catalysts.","reactionConditions":"Gas-phase decomposition of formic acid (2.5 vol%/Ar) in a fixed-bed glass reactor.","selectivity":"~94%","stability":"Notable deactivation observed at 473 K, conversion decreased from 23 to 17% within 5 h","deactivation":"notable deactivation","metricCount":"2"},{"paperId":"P207","catalystId":"P207_PERF_001","name":"Pd(6 wt %)/KIE-8-d","support":"KIE-8","matchedSynthesis":"Pd(6 wt %)/KIE-8","matchedCharacterization":"Pd(6 wt %)/KIE-8","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KIE-8 was added to H2PdCl4 solution, stirred, pH adjusted to 9.5 with NaOH, further stirred at room temperature, then reduced using NaBH4.","phase":"nanoparticles","particleSize":"5.8 nm (KIE-8-f), 6.8 nm (KIE-8-g), 9.7 nm (KIE-8-e), 16.3 nm (KIE-8-d)","surfaceStates":"Electronic structure of Pd nanoparticles depends on the intensity ratio of graphitic nitrogen to pyridinic nitrogen in the support.","structureLink":"Catalytic activity for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content, pore structure (higher surface area and pore volume), and resulting Pd nanoparticle size and dispersion. Higher graphitic nitrogen content improves TOF.","reactionConditions":"Room-temperature formic acid dehydrogenation in a 100 mL Teflon-lined stainless steel reactor.","whyPerformsWell":"Pore structure and nitrogen structure of KIE-8 support.","metricCount":"2"},{"paperId":"P207","catalystId":"P207_PERF_002","name":"Pd(6 wt %)/KIE-8-e","support":"KIE-8","matchedSynthesis":"Pd(6 wt %)/KIE-8","matchedCharacterization":"Pd(6 wt %)/KIE-8","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KIE-8 was added to H2PdCl4 solution, stirred, pH adjusted to 9.5 with NaOH, further stirred at room temperature, then reduced using NaBH4.","phase":"nanoparticles","particleSize":"5.8 nm (KIE-8-f), 6.8 nm (KIE-8-g), 9.7 nm (KIE-8-e), 16.3 nm (KIE-8-d)","surfaceStates":"Electronic structure of Pd nanoparticles depends on the intensity ratio of graphitic nitrogen to pyridinic nitrogen in the support.","structureLink":"Catalytic activity for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content, pore structure (higher surface area and pore volume), and resulting Pd nanoparticle size and dispersion. Higher graphitic nitrogen content improves TOF.","reactionConditions":"Room-temperature formic acid dehydrogenation in a 100 mL Teflon-lined stainless steel reactor.","whyPerformsWell":"Pore structure and nitrogen structure of KIE-8 support.","metricCount":"2"},{"paperId":"P207","catalystId":"P207_PERF_003","name":"Pd(6 wt %)/KIE-8-f","support":"KIE-8","matchedSynthesis":"Pd(6 wt %)/KIE-8","matchedCharacterization":"Pd(6 wt %)/KIE-8","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KIE-8 was added to H2PdCl4 solution, stirred, pH adjusted to 9.5 with NaOH, further stirred at room temperature, then reduced using NaBH4.","phase":"nanoparticles","particleSize":"5.8 nm (KIE-8-f), 6.8 nm (KIE-8-g), 9.7 nm (KIE-8-e), 16.3 nm (KIE-8-d)","surfaceStates":"Electronic structure of Pd nanoparticles depends on the intensity ratio of graphitic nitrogen to pyridinic nitrogen in the support.","structureLink":"Catalytic activity for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content, pore structure (higher surface area and pore volume), and resulting Pd nanoparticle size and dispersion. Higher graphitic nitrogen content improves TOF.","reactionConditions":"Room-temperature formic acid dehydrogenation in a 100 mL Teflon-lined stainless steel reactor.","whyPerformsWell":"Higher graphitic nitrogen content and hierarchically porous structure (higher surface area and pore volume) improve Pd nanoparticle electronic structure, size, and dispersion.","metricCount":"2"},{"paperId":"P207","catalystId":"P207_PERF_004","name":"Pd(6 wt %)/KIE-8-g","support":"KIE-8","matchedSynthesis":"Pd(6 wt %)/KIE-8","matchedCharacterization":"Pd(6 wt %)/KIE-8","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"KIE-8 was added to H2PdCl4 solution, stirred, pH adjusted to 9.5 with NaOH, further stirred at room temperature, then reduced using NaBH4.","phase":"nanoparticles","particleSize":"5.8 nm (KIE-8-f), 6.8 nm (KIE-8-g), 9.7 nm (KIE-8-e), 16.3 nm (KIE-8-d)","surfaceStates":"Electronic structure of Pd nanoparticles depends on the intensity ratio of graphitic nitrogen to pyridinic nitrogen in the support.","structureLink":"Catalytic activity for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content, pore structure (higher surface area and pore volume), and resulting Pd nanoparticle size and dispersion. Higher graphitic nitrogen content improves TOF.","reactionConditions":"Room-temperature formic acid dehydrogenation in a 100 mL Teflon-lined stainless steel reactor.","whyPerformsWell":"Highest graphitic nitrogen content and optimized pore structure improve Pd nanoparticle electronic structure, size, and dispersion.","metricCount":"2"},{"paperId":"P207","catalystId":"P207_PERF_005","name":"Pd(6 wt %)/N-charcoal","support":"N-charcoal","matchedSynthesis":"Pd(6 wt %)/N-charcoal","matchedCharacterization":"Pd(6 wt %)/N-charcoal","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Same deposition method as used for Pd/KIE-8.","structureLink":"Lower catalytic activity compared to Pd/KIE-8 is attributed to the microporous structure of the activated charcoal support.","reactionConditions":"Room-temperature formic acid dehydrogenation in a 100 mL Teflon-lined stainless steel reactor.","deactivation":"Lower catalytic activity compared to Pd/KIE-8 is attributed to the microporous structure of activated charcoal.","metricCount":"2"},{"paperId":"P208","catalystId":"P208_PERF_001","name":"Pt/TiB2-600","support":"TiB2","matchedSynthesis":"Pt/TiB2","matchedCharacterization":"Pt/TiB2","role":"catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"TiB2 support was synthesized via molten-salt assisted borothermal reduction. Pt nanoparticles were loaded onto the TiB2 surface using IWI, followed by calcination in flowing N2.","phase":"Core-shell nanostructure consisting of a Pt core encapsulated by a TiB2 overlayer with distinctive Pt-B bonds at the interface.","particleSize":"Average size below 3 nm (Pt/TiB2-500: 2.28 ± 0.1 nm; Pt/TiB2-600: 2.37 ± 0.1 nm; Pt/TiB2-800: 2.43 ± 0.1 nm).","surfaceStates":"TiO x-terminated TiB2 overlayers serve as active sites; charge transfer occurs from TiB2 to Pt, evidenced by a negative shift in Pt 4f XPS binding energy.","structureLink":"Maximum HCOOH dehydrogenation activity is achieved with Pt/TiB2-600, where Pt nanoparticles are completely encapsulated by a thin layer of TiB2. The encapsulated Pt acts as an electronic modulator for the active TiO x-terminated TiB2 overlayers.","reactionConditions":"Aqueous phase formic acid dehydrogenation in N2 atmosphere","selectivity":">99.9% selectivity toward CO2 and H2; < 10 ppm CO","stability":"Sustained more than 90% of initial activity over six consecutive batch experiments (3 h each)","whyPerformsWell":"Strong metal-support interaction (SMSI) creates a thin continuous TiB2 overlayer that prevents sintering and facilitates charge transfer from TiB2 to Pt; TiO x-terminated TiB2 surfaces are the active sites.","metricCount":"2"},{"paperId":"P208","catalystId":"P208_PERF_002","name":"Pt/TiB2-300","support":"TiB2","matchedSynthesis":"Pt/TiB2","matchedCharacterization":"Pt/TiB2","role":"catalyst","composition":"Pt","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"TiB2 support was synthesized via molten-salt assisted borothermal reduction. Pt nanoparticles were loaded onto the TiB2 surface using IWI, followed by calcination in flowing N2.","phase":"Core-shell nanostructure consisting of a Pt core encapsulated by a TiB2 overlayer with distinctive Pt-B bonds at the interface.","particleSize":"Average size below 3 nm (Pt/TiB2-500: 2.28 ± 0.1 nm; Pt/TiB2-600: 2.37 ± 0.1 nm; Pt/TiB2-800: 2.43 ± 0.1 nm).","surfaceStates":"TiO x-terminated TiB2 overlayers serve as active sites; charge transfer occurs from TiB2 to Pt, evidenced by a negative shift in Pt 4f XPS binding energy.","structureLink":"Maximum HCOOH dehydrogenation activity is achieved with Pt/TiB2-600, where Pt nanoparticles are completely encapsulated by a thin layer of TiB2. The encapsulated Pt acts as an electronic modulator for the active TiO x-terminated TiB2 overlayers.","reactionConditions":"Aqueous phase formic acid dehydrogenation in N2 atmosphere","whyPerformsWell":"Lowest activity among Pt/TiB2 samples due to no observable SMSI","metricCount":"1"},{"paperId":"P208","catalystId":"P208_PERF_003","name":"bare TiB2","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Aqueous phase formic acid dehydrogenation in N2 atmosphere","whyPerformsWell":"Noble-metal-free MBene active catalyst","metricCount":"3"},{"paperId":"P209","catalystId":"P209_PERF_001","name":"PdAcet. Acet./Cdarco","support":"DARCO G-60 activated carbon","matchedSynthesis":"PdAcet. Acet./Cdarco","matchedCharacterization":"PdAcet. Acet./Cdarco","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in acetone, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","phase":"cubic palladium metal","particleSize":"2.8 nm (TEM), 3 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","reactionConditions":"Formic acid dehydrogenation in aqueous media at 50 °C","selectivity":"totally selective reaction towards formic acid dehydrogenation; H2/CO2 ratio close to 1 and absence of CO","stability":"higher deactivation resistance capacity compared to larger particles","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase","whyPerformsWell":"lowest particle size (2.8 nm) and high proportion of low coordination atoms","metricCount":"1"},{"paperId":"P209","catalystId":"P209_PERF_002","name":"PdCl2 W./Cdarco","support":"DARCO G-60 activated carbon","matchedSynthesis":"PdCl2 W./Cdarco","matchedCharacterization":"PdCl2 W./Cdarco","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd-W","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in water, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","phase":"cubic palladium metal","particleSize":"6.5 nm (TEM), 47 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","reactionConditions":"Formic acid dehydrogenation in aqueous media at 50 °C","selectivity":"totally selective reaction towards formic acid dehydrogenation; H2/CO2 ratio close to 1 and absence of CO","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase","metricCount":"1"},{"paperId":"P209","catalystId":"P209_PERF_003","name":"Pd(NO3)2 Acet./Cdarco","support":"DARCO G-60 activated carbon","matchedSynthesis":"Pd(NO3)2 Acet./Cdarco","matchedCharacterization":"Pd(NO3)2 Acet./Cdarco","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in acetone, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","phase":"cubic palladium metal","particleSize":"8.8 nm (TEM), 13 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","reactionConditions":"Formic acid dehydrogenation in aqueous media at 50 °C","selectivity":"totally selective reaction towards formic acid dehydrogenation; H2/CO2 ratio close to 1 and absence of CO","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase","metricCount":"1"},{"paperId":"P209","catalystId":"P209_PERF_004","name":"Pd(NO3)2 W./Cdarco","support":"DARCO G-60 activated carbon","matchedSynthesis":"Pd(NO3)2 W./Cdarco","matchedCharacterization":"Pd(NO3)2 W./Cdarco","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd-W","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in water, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","phase":"cubic palladium metal","particleSize":"12 nm (TEM), 25 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","reactionConditions":"Formic acid dehydrogenation in aqueous media at 50 °C","selectivity":"totally selective reaction towards formic acid dehydrogenation; H2/CO2 ratio close to 1 and absence of CO","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase","metricCount":"1"},{"paperId":"P209","catalystId":"P209_PERF_005","name":"PdAcet. W./Cdarco","support":"DARCO G-60 activated carbon","matchedSynthesis":"PdAcet. W./Cdarco","matchedCharacterization":"PdAcet. W./Cdarco","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd-W","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in water, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","phase":"cubic palladium metal","particleSize":"17 nm (TEM), 98 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","reactionConditions":"Formic acid dehydrogenation in aqueous media at 50 °C","selectivity":"totally selective reaction towards formic acid dehydrogenation; H2/CO2 ratio close to 1 and absence of CO","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase","metricCount":"1"},{"paperId":"P209","catalystId":"P209_PERF_006","name":"PdCl2 Acet./Cdarco","support":"DARCO G-60 activated carbon","matchedSynthesis":"PdCl2 Acet./Cdarco","matchedCharacterization":"PdCl2 Acet./Cdarco","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in acetone, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","phase":"cubic palladium metal","particleSize":"58 nm (TEM), 180 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","reactionConditions":"Formic acid dehydrogenation in aqueous media at 50 °C","selectivity":"totally selective reaction towards formic acid dehydrogenation; H2/CO2 ratio close to 1 and absence of CO","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase","metricCount":"1"},{"paperId":"P210","catalystId":"P210_PERF_001","name":"PdMn0.25@S-1-0.005NH2","support":"Silicalite-1 (S-1) zeolite","matchedSynthesis":"PdMny@S-1-xNH2 (e.g., PdMn0.25@S-1-0.005NH2)","role":"Optimized bimetallic catalyst","composition":"Pd and Mn; molar ratio Mn/Pd = y (optimized at 0.25)","activeMetals":"Pd-Mn","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating metal complexes and silane coupling agents, followed by freeze-drying and direct H2 reduction.","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","selectivity":"no detectable CO (< 10 ppm)","stability":"hydrogen generation rate remains unchanged during five consecutive cycles","whyPerformsWell":"High dispersion of metal species; synergy between Pd and Mn forming electron-enriched Pd surface facilitating C-H cleavage; additive alkaline sites (amino groups) acting as proton scavengers for O-H bond activation; enhanced hydrophilicity of zeolite support.","metricCount":"3"},{"paperId":"P210","catalystId":"P210_PERF_002","name":"Pd@S-1","support":"Silicalite-1 (S-1) zeolite","matchedSynthesis":"Pd@S-1","matchedCharacterization":"Pd@S-1","role":"Control catalyst (non-functionalized)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating Pd complex, followed by freeze-drying and direct H2 reduction.","phase":"Monometallic Pd clusters","particleSize":"Subnanometric/ultrasmall","surfaceStates":"Pd anchored on silanol defects of zeolite framework.","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","whyPerformsWell":"Ultrafine size and high dispersion of Pd clusters","metricCount":"1"},{"paperId":"P210","catalystId":"P210_PERF_003","name":"Pd@S-1-0.005NH2","support":"Silicalite-1 (S-1) zeolite","matchedSynthesis":"Pd@S-1","matchedCharacterization":"Pd@S-1","role":"Control catalyst (non-functionalized)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating Pd complex, followed by freeze-drying and direct H2 reduction.","phase":"Monometallic Pd clusters","particleSize":"Subnanometric/ultrasmall","surfaceStates":"Pd anchored on silanol defects of zeolite framework.","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","whyPerformsWell":"Hydrophilicity favors enriching FA molecules in pores; basicity benefits O-H bond activation.","metricCount":"1"},{"paperId":"P210","catalystId":"P210_PERF_004","name":"Pd@S-1-0.01NH2","support":"Silicalite-1 (S-1) zeolite","matchedSynthesis":"Pd@S-1","matchedCharacterization":"Pd@S-1","role":"Control catalyst (non-functionalized)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating Pd complex, followed by freeze-drying and direct H2 reduction.","phase":"Monometallic Pd clusters","particleSize":"Subnanometric/ultrasmall","surfaceStates":"Pd anchored on silanol defects of zeolite framework.","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","whyPerformsWell":"Lower TOF than 0.005NH2 due to larger zeolite size increasing transport resistance","metricCount":"1"},{"paperId":"P210","catalystId":"P210_PERF_005","name":"Pd@S-1-0.005CH3","support":"Silicalite-1 (S-1) zeolite","matchedSynthesis":"Pd@S-1","matchedCharacterization":"Pd@S-1","role":"Control catalyst (non-functionalized)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating Pd complex, followed by freeze-drying and direct H2 reduction.","phase":"Monometallic Pd clusters","particleSize":"Subnanometric/ultrasmall","surfaceStates":"Pd anchored on silanol defects of zeolite framework.","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","whyPerformsWell":"Poor performance due to hydrophobic properties of methyl groups","metricCount":"1"},{"paperId":"P210","catalystId":"P210_PERF_006","name":"PdMn0.5@S-1-0.005NH2","activeMetals":"Pd-Mn","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","whyPerformsWell":"Lower activity than PdMn0.25 due to more oxidized state of Pd sites and decreased dispersion","metricCount":"1"},{"paperId":"P210","catalystId":"P210_PERF_007","name":"PdFe@S-1-0.005NH2","activeMetals":"Pd-Fe","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","whyPerformsWell":"Bimetallic effect","metricCount":"1"},{"paperId":"P210","catalystId":"P210_PERF_008","name":"PdCo@S-1-0.005NH2","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","whyPerformsWell":"Bimetallic effect","metricCount":"1"},{"paperId":"P210","catalystId":"P210_PERF_009","name":"PdNi@S-1-0.005NH2","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","whyPerformsWell":"Bimetallic effect","metricCount":"1"},{"paperId":"P211","catalystId":"P211_PERF_001","name":"Pd/O-NCNTs-P","support":"carbon nanotubes (CNTs)","matchedSynthesis":"Pd/O-NCNTs-P","matchedCharacterization":"Pd/O-NCNTs-P","role":"formic acid dehydrogenation catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CNTs were treated with oxygen plasma to generate O-CNTs, which were then modified with APTES to prepare O-NCNTs. A mixture of O-NCNTs and H2PdCl4 solution was subsequently treated by H2/Ar surface DBD plasma.","phase":"Metallic Pd (lattice fringes ~0.220 nm corresponding to (111) plane)","particleSize":"3.5 ± 1.1 nm (fresh); 3.8 ± 0.7 nm (after 6 cycles)","surfaceStates":"Pd2+ (73.2%) and Pd0 (26.8%); electron-deficient Pd2+ with a 0.5 eV positive shift in binding energy compared to Pd/NCNTs-P","structureLink":"High Pd2+/Pd0 ratio regulates electronic structure to promote formation of active intermediates (Pd-HCOO* and H*); charge repulsion among Pd2+ species prevents agglomeration; OCGs and -NH2 enhance metal-support interaction for high stability.","reactionConditions":"Formic acid dehydrogenation in aqueous solution at 323-333 K","selectivity":"no CO but CO2 was detected during the reaction","stability":"activity remained unchanged even after six reaction cycles","deactivation":"no leaching of Pd species was observed","whyPerformsWell":"Abundant oxygen-containing functional groups (OCGs) and -NH2 promote small-sized, highly dispersed Pd nanoparticles and enhance metal-support interaction; high Pd2+/Pd0 ratio regulates electronic structure to promote formation/adsorption of active intermediates (Pd-HCOO* and H*); OCGs increase hydrophilicity for better dispersion in aqueous solution.","metricCount":"4"},{"paperId":"P211","catalystId":"P211_PERF_002","name":"Pd/NCNTs-P","support":"carbon nanotubes (CNTs)","matchedSynthesis":"Pd/NCNTs-P","matchedCharacterization":"Pd/NCNTs-P","role":"comparison catalyst (without oxygen plasma pretreatment)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CNTs were modified with APTES to prepare NCNTs, then a mixture of NCNTs and H2PdCl4 solution was treated by surface DBD plasma.","structureLink":"Lack of oxygen plasma pretreatment results in fewer anchoring sites (OCGs), leading to poor Pd nanoparticle dispersion and lower catalytic activity.","reactionConditions":"Formic acid dehydrogenation in aqueous solution at 333 K","metricCount":"1"},{"paperId":"P211","catalystId":"P211_PERF_003","name":"Pd/O-NCNTs-C","support":"carbon nanotubes (CNTs)","matchedSynthesis":"Pd/O-NCNTs-C","matchedCharacterization":"Pd/O-NCNTs-C","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"CNTs were treated with oxygen plasma and modified with APTES to form O-NCNTs. The mixture of H2PdCl4 solution and O-NCNTs was then reduced using NaBH4.","phase":"Metallic Pd (lattice fringes ~0.220 nm); after 6 cycles, XRD shows peaks for Pd (111), (200), and (220) facets","particleSize":"3.8 ± 0.6 nm (fresh); 6.2 ± 1.0 nm (after 6 cycles)","surfaceStates":"Pd2+ (37.4%) and Pd0 (62.6%); Pd2+ content decreased to 18.9% after 6 cycles","structureLink":"Excess NaBH4 reduces OCGs and -NH2 groups, weakening metal-support interaction and leading to lower Pd2+ content, which results in nanoparticle agglomeration and poor stability.","reactionConditions":"Formic acid dehydrogenation in aqueous solution at 333 K","stability":"At 120 s of the sixth cycle test, gas production was 54% of that produced in the first cycle test","deactivation":"small amount of leaching of Pd species; agglomeration of Pd species observed via XRD (peaks at 40, 47, and 68 degrees)","metricCount":"2"},{"paperId":"P211","catalystId":"P211_PERF_004","name":"Sigma-Aldrich Pd/C","activeMetals":"Al-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Formic acid dehydrogenation in aqueous solution at 333 K","metricCount":"2"},{"paperId":"P212","catalystId":"P212_PERF_001","name":"Pd-tetrahedron–TiO2","matchedCharacterization":"Pd-tetrahedron–TiO2","activeMetals":"Pd-Ti","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Pd tetrahedrons","particleSize":"6.3 nm","surfaceStates":"covered by {111} facets","structureLink":"Mott–Schottky junction allows photoexcited electrons in TiO2 to transfer to Pd, increasing electron density and promoting HCOOH dehydrogenation under UV light.","reactionConditions":"363 K, UV light illumination (4.5 mW cm-2), aqueous HCOOH solution","selectivity":"No signals for CO were observed","stability":"morphology was well-maintained after the catalytic reaction","whyPerformsWell":"Mott–Schottky junction between TiO2 and Pd promotes activity by increasing electron density of Pd via photoexcited electrons from TiO2","metricCount":"1"},{"paperId":"P212","catalystId":"P212_PERF_002","name":"Pd@Ag5%-tetrahedron–TiO2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"363 K, UV light illumination (4.5 mW cm-2), aqueous HCOOH solution","selectivity":"No signals for CO were observed","whyPerformsWell":"Surface polarization mechanism: Ag has a lower work function than Pd, increasing the electron density of Pd sites; combined with Mott-Schottky junction","metricCount":"1"},{"paperId":"P212","catalystId":"P212_PERF_003","name":"Pd@Cu5%-tetrahedron–TiO2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"363 K, UV light illumination (4.5 mW cm-2), aqueous HCOOH solution","selectivity":"No signals for CO were observed","whyPerformsWell":"Surface polarization mechanism: Cu has a lower work function than Pd, increasing the electron density of Pd sites","metricCount":"1"},{"paperId":"P212","catalystId":"P212_PERF_004","name":"Pd@Au5%-tetrahedron–TiO2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"363 K, UV light illumination (4.5 mW cm-2), aqueous HCOOH solution","selectivity":"No signals for CO were observed","whyPerformsWell":"Surface polarization mechanism: Au has a lower work function than Pd, increasing the electron density of Pd sites","metricCount":"1"},{"paperId":"P212","catalystId":"P212_PERF_005","name":"Pd@Pt5%-tetrahedron–TiO2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"363 K, UV light illumination (4.5 mW cm-2), aqueous HCOOH solution","selectivity":"No signals for CO were observed","whyPerformsWell":"Reduced activity due to Pt having a higher work function than Pd, reducing the electron density of Pd sites","metricCount":"1"},{"paperId":"P212","catalystId":"P212_PERF_006","name":"Pd@Pb-tetrahedron–TiO2","matchedCharacterization":"Pd@Pb-tetrahedron–TiO2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Pd@Pb alloy surface","surfaceStates":"Low work function but large atomic radius","structureLink":"Catalytic activity is suppressed by surface poisoning due to the large atomic radius of Pb.","reactionConditions":"363 K, UV light illumination (4.5 mW cm-2), aqueous HCOOH solution","deactivation":"suppressed by surface poisoning due to large atomic radius of Pb","metricCount":"1"},{"paperId":"P213","catalystId":"P213_PERF_001","name":"D-Pd5Ag5 NWs","matchedCharacterization":"D-Pd5Ag5 NWs","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"fcc PdAg alloy; polycrystalline structure confirmed by SAED and XRD peaks located between pure Pd and Ag","particleSize":"Seed Ag NPs diameter: 3.6 nm","surfaceStates":"Pd-rich surface; XPS shows binding energies of Ag 3d shifted to higher values and Pd 3d shifted to lower values compared to C-Pd5Ag5 NWs, indicating efficient electron transfer from Ag to Pd","structureLink":"Enhanced activity for FA dehydrogenation and ADN hydrogenation attributed to the Pd-rich surface, more efficient Ag-to-Pd electron transfer, high density of low coordination atoms/defects on kink surfaces, and a larger active surface area (0.40 cm2 mg-1)","reactionConditions":"Dehydrogenation of formic acid (FA) and subsequent hydrogenation of adiponitrile (ADN) to 1,6-hexanediamine (HDA).","selectivity":"100% selectivity toward FA dehydrogenation (no CO detected, limit > 2 ppm)","stability":"Maintains initial high activity and conversion after the eighth run","deactivation":"No Pd in liquid phase; no obvious changes in Ag/Pd composition or morphology after 8 cycles","whyPerformsWell":"Pd-rich surface of the NWs and more efficient electron transfer from Ag to Pd","metricCount":"5"},{"paperId":"P213","catalystId":"P213_PERF_002","name":"D-Pd3Ag7 NWs","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of formic acid (FA)","metricCount":"1"},{"paperId":"P213","catalystId":"P213_PERF_003","name":"D-Pd7Ag3 NWs","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Dehydrogenation of formic acid (FA)","metricCount":"1"},{"paperId":"P213","catalystId":"P213_PERF_004","name":"C-Pd5Ag5 NWs","matchedSynthesis":"C-Pd5Ag5 NWs","matchedCharacterization":"C-Pd5Ag5 NWs","role":"comparison catalyst","composition":"Pd:Ag (5:5)","activeMetals":"Pd-Ag","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared by co-reduction methods.","phase":"PdAg alloy","surfaceStates":"Less efficient electron transfer from Ag to Pd compared to D-Pd5Ag5 NWs (confirmed by XPS)","structureLink":"Lower catalytic activity and smaller active surface area (0.10 cm2 mg-1) compared to D-Pd5Ag5 NWs","reactionConditions":"Dehydrogenation of formic acid (FA)","metricCount":"1"},{"paperId":"P214","catalystId":"P214_PERF_001","name":"Pd/APC","support":"amine-implanted porous carbon (APC)","matchedSynthesis":"Pd/APC","matchedCharacterization":"Pd/APC","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"PPC was functionalized via hydrothermal treatment with ammonium hydroxide to create APC; Pd precursor was then loaded onto the support and reduced using NaBH4 in a NaOH solution.","phase":"Pd0 crystalline phase","particleSize":"about 2.3 nm","surfaceStates":"Amine groups (-NH-, -NH2) identified by N 1s signal at 399.9 eV; surface Pd atoms are partially oxidized (Pd2+).","structureLink":"Amine species promote the anchoring and dispersion of ultrafine Pd NPs, while providing an alkaline, electron-donating environment that facilitates formic acid deprotonation.","reactionConditions":"Dehydrogenation of formic acid (FA) in a FA/sodium formate (SF) system under ambient conditions.","selectivity":"100% selectivity for H2 and CO2; no CO detected by GC","stability":"Excellent recyclability; activity decreased slightly after four runs at 50 °C. No clear change in Pd NP crystalline phase and size.","deactivation":"Low tolerance to CO (activity decreased sharply upon exposure); no leaching of Pd observed (4.62 wt.% initial vs 4.58 wt.% recycled).","whyPerformsWell":"High dispersion of ultrafine Pd NPs and strong metal–molecular support interactions; amine groups act as proton scavengers providing an alkaline environment that promotes deprotonation of FA.","metricCount":"3"},{"paperId":"P214","catalystId":"P214_PERF_002","name":"Pd/PPC","support":"pristine porous carbon (PPC)","matchedSynthesis":"Pd/PPC","matchedCharacterization":"Pd/PPC","role":"control catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"PPC was used as support; Pd precursor was loaded and reduced using NaBH4 in a NaOH solution.","phase":"Pd0 crystalline phase","particleSize":"3.2 nm","structureLink":"Larger particle size and inferior dispersion result in lower catalytic activity relative to the amine-functionalized support.","reactionConditions":"Dehydrogenation of formic acid (FA) in a FA/sodium formate (SF) system under ambient conditions.","metricCount":"1"},{"paperId":"P214","catalystId":"P214_PERF_003","name":"Pd/APC*","support":"amine-implanted porous carbon (APC)","matchedSynthesis":"Pd/APC","matchedCharacterization":"Pd/APC","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"PPC was functionalized via hydrothermal treatment with ammonium hydroxide to create APC; Pd precursor was then loaded onto the support and reduced using NaBH4 in a NaOH solution.","phase":"Pd0 crystalline phase","particleSize":"about 2.3 nm","surfaceStates":"Amine groups (-NH-, -NH2) identified by N 1s signal at 399.9 eV; surface Pd atoms are partially oxidized (Pd2+).","structureLink":"Amine species promote the anchoring and dispersion of ultrafine Pd NPs, while providing an alkaline, electron-donating environment that facilitates formic acid deprotonation.","reactionConditions":"Dehydrogenation of formic acid (FA) in a FA/sodium formate (SF) system under ambient conditions.","whyPerformsWell":"Amine species doped within the carbon supports promoted the dehydrogenation of formic acid despite larger particle size (3.5 nm).","metricCount":"1"},{"paperId":"P215","catalystId":"P215_PERF_001","name":"Pd-Cu/TiO2-NSs (3:7)","support":"TiO2 nanosheets (TiO2-NSs)","matchedSynthesis":"Pd-Cu/TiO2-NSs","matchedCharacterization":"Pd-Cu/TiO2-NSs (3:7)","role":"catalyst","composition":"Pd:Cu atomic ratios of 10:0, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 0:10","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"TiO2-NSs were co-impregnated with Pd and Cu precursors, stirred and ultrasonicated at room temperature, then reduced using aqueous NaBH4.","phase":"Face-centered cubic (fcc) Pd-Cu alloy; XRD peaks are positioned between pure fcc Pd and pure fcc Cu with a lattice spacing of 0.217 nm for the (111) plane.","particleSize":"4.44 ± 0.08 nm","surfaceStates":"Pd 3d5/2 peaks at 334.7 eV (Pd0) and 335.9 eV (Pd2+); Cu 2p3/2 signal at approximately 932 eV; Ti exists primarily as Ti4+ with a mixed-valence Ti3+/Ti4+ state observed upon co-catalyst addition.","structureLink":"Synergistic electronic interactions, d-band center shift, and strong metal-support interaction (SMSI) lower the activation energy for O-H bond cleavage to 15 kJ/mol. Electron transfer from TiO2 support to PdCu alloy and from Cu to Pd increases electron density on Pd, enhancing catalytic activity.","reactionConditions":"Formic acid dehydrogenation in a round-bottom flask with gas burette, water bath, magnetic stirring at 700 rpm","selectivity":"High selectivity toward H2 and CO2 production","stability":"Impressive catalytic activity in the durability test for five cycles","whyPerformsWell":"Synergistic electronic interactions between Pd and Cu, d-band center shift, electron transfer from TiO2 to PdCu alloy, oxygen vacancies (VOs) on TiO2-NSs, strong metal-support interaction (SMSI), and exposure of (111) facets","metricCount":"7"},{"paperId":"P215","catalystId":"P215_PERF_002","name":"Pd-Cu/TiO2-NSs series (ratios 10:0 to 0:10)","support":"TiO2 nanosheets (TiO2-NSs)","matchedSynthesis":"Pd-Cu/TiO2-NSs","role":"catalyst","composition":"Pd:Cu atomic ratios of 10:0, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 0:10","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"co_impregnation","synthesis":"TiO2-NSs were co-impregnated with Pd and Cu precursors, stirred and ultrasonicated at room temperature, then reduced using aqueous NaBH4.","reactionConditions":"30 mg catalyst, 303 K, SF+FA = 1:1","metricCount":"2"},{"paperId":"P216","catalystId":"P216_PERF_001","name":"Ni0.2Co0.8–Soy","matchedCharacterization":"Ni0.2Co0.8–Soy","activeMetals":"Ni-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Co-rich fcc Ni–Co solid solution/alloy (lattice spacing 0.2043 nm).","particleSize":"4.8 ± 1.2 nm","surfaceStates":"Surface contains pyridinic N, pyrrolic N, graphitic N; pentavalent phosphorus (P5+) and P–O bonds; and K+ species that impart surface basicity.","structureLink":"The Ni-Co alloy structure promotes the dehydrogenation pathway and suppresses CO formation. K-derived basic sites enhance formic acid adsorption and initial decomposition, while small particle size increases active site density.","reactionConditions":"Gas-phase formic acid decomposition in a conventional fixed-bed reactor, N2 carrier gas (200 mL min-1), WHSV 4.88 h-1, FA concentration >= 88%","selectivity":"High CO2 selectivity (up to 98-99% at 523 K), effectively suppressing the dehydration pathway and CO formation.","stability":"Maintained CO2 selectivity above 98% and conversion of ~87% after ten consecutive runs at 523 K.","deactivation":"Slight decrease in K content from 4.99 wt% to 4.69 wt% after cycling; slight decline in conversion observed over cycles.","whyPerformsWell":"Synergistic Ni-Co alloy structure promotes dehydrogenation and suppresses CO formation; endogenous heteroatoms (N, P) anchor nanoparticles; K-derived basic sites enhance formic acid adsorption and activation.","metricCount":"4"},{"paperId":"P216","catalystId":"P216_PERF_002","name":"Ni-Soy","matchedCharacterization":"Ni-Soy","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"fcc Ni (PDF#87–0712)","surfaceStates":"Contains N, P, and K species from soybean precursor.","structureLink":"High conversion efficiency but poor CO2 selectivity due to dominant dehydration pathway leading to CO formation.","reactionConditions":"Gas-phase formic acid decomposition, 523 K","selectivity":"Poor CO2 selectivity; dehydration pathway dominant leading to considerable CO formation.","whyPerformsWell":"High conversion efficiency but lacks the electronic modulation of Co to suppress CO.","metricCount":"0"},{"paperId":"P216","catalystId":"P216_PERF_003","name":"Co-Soy","matchedCharacterization":"Co-Soy","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"fcc Co (PDF#15–0806)","surfaceStates":"Contains N, P, and K species from soybean precursor.","structureLink":"Higher CO2 selectivity but lower conversion efficiency than Ni-based counterparts.","reactionConditions":"Gas-phase formic acid decomposition, 523 K","selectivity":"Significantly higher CO2 selectivity compared to Ni-Soy.","whyPerformsWell":"Preference for the dehydrogenation pathway with minimal side reactions, but lower conversion efficiency than Ni-based catalysts.","metricCount":"0"},{"paperId":"P217","catalystId":"P217_PERF_001","name":"Pd/AC","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"CO2 hydrogenation to formate; ethanol solvent, triethylamine base, 383 K, 500 rpm stirring, 2 h reaction time","whyPerformsWell":"Pd is the crucial active center","metricCount":"1"},{"paperId":"P217","catalystId":"P217_PERF_002","name":"Pd-Au/AC","support":"activated carbon (AC)","matchedSynthesis":"Pd-Au/AC","matchedCharacterization":"Pd-Au/AC","role":"catalyst for CO2 hydrogenation and FA dehydrogenation","composition":"Pd:Au = 1:1 mass ratio","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"adsorption_or_loading","synthesis":"Pretreated AC was dispersed in DI water with metal salts, stirred at 363 K for 1 h, then reduced by adding Cacumen Platycladi (CP) leaf extract and stirring for another 1 h.","phase":"Bimetallic alloy structure; XRD shows a broad band at 2θ = 38.4° between Au(111) and Pd(111); HRTEM d-spacing is 2.29 Å.","particleSize":"6.83 nm","surfaceStates":"Electron-enriched Pd due to electron transfer from Au; XPS shows a downshift in Pd 0 3d binding energy (Pd 0 3d5/2 at 335.73 eV vs 335.92 eV for Pd/AC) and a positive shift in Au 4f peaks.","structureLink":"Electron-enriched Pd favors adsorption of active intermediate species during CO2 hydrogenation to FA and facilitates the formation of metal-formate composites during dehydrogenation.","reactionConditions":"CO2 hydrogenation to formate; ethanol solvent, triethylamine base, 383 K, 500 rpm stirring, 2 h reaction time","stability":"No prominent fluctuations in TOF up to five cycles for both CO2 hydrogenation and FA dehydrogenation","whyPerformsWell":"Synergistic effect between Pd and Au; electron transfer from Au to Pd increases electronic density of Pd, favoring adsorption of active intermediate species. Higher redox potential of Au makes it more durable in acidic FA solutions during dehydrogenation.","metricCount":"4"},{"paperId":"P217","catalystId":"P217_PERF_003","name":"Pd-Cu/AC","support":"activated carbon (AC)","matchedSynthesis":"Pd-Cu/AC","matchedCharacterization":"Pd-Cu/AC","role":"catalyst for CO2 hydrogenation and FA dehydrogenation","composition":"Pd:Cu = 1:1 mass ratio","activeMetals":"Pd-Cu","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"adsorption_or_loading","synthesis":"Pretreated AC was immersed in an aqueous solution of metal salts, stirred at 363 K for 1 h, then reduced by adding Cacumen Platycladi (CP) leaf extract and stirring for another 1 h.","phase":"Bimetallic alloy structure; XRD peak for (111) plane at 2θ = 40.78° (between Pd/AC and Cu/AC); HRTEM d-spacing is 2.17 Å.","particleSize":"6.12 nm","surfaceStates":"Electron-enriched Pd; XPS shows a downshift in Pd 0 3d binding energy (Pd 0 3d5/2 at 335.86 eV vs 335.92 eV for Pd/AC).","structureLink":"Smaller particle size compared to Pd-Au/AC and the presence of positively charged Cu sites (Cu2+) increase contact efficiency between reactants and active centers, enhancing hydrogenation activity.","reactionConditions":"CO2 hydrogenation to formate; ethanol solvent, triethylamine base, 383 K, 500 rpm stirring, 2 h reaction time","stability":"No prominent fluctuations in TOF up to five cycles for both CO2 hydrogenation and FA dehydrogenation","whyPerformsWell":"Synergistic effect between Pd and Cu; lower activation energy (27 kJ/mol) compared to Pd-Au/AC. Divalent Cu may act as assist active sites by attracting negatively charged HCO3-. Copper alloys provide higher mechanical strength for stability under high pressure.","metricCount":"7"},{"paperId":"P218","catalystId":"P218_PERF_001","name":"Co@Cr(OH)3/ZrO2","support":"Cr(OH)3/ZrO2","matchedSynthesis":"Co@Cr(OH)3/ZrO2","matchedCharacterization":"Co@Cr(OH)3/ZrO2","role":"catalyst for formic acid dehydrogenation","composition":"Co and Cr; optimal Co loading is 5.0 wt%","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"UiO-66 MOF was synthesized using ZrCl4 and PET-derived 1,4-benzenedicarboxylic acid (BDC), then annealed under N2 to produce ZrO2. Co and Cr precursors were added to the ZrO2 support in a water/ethylene glycol mixture and reduced with NaBH4 via sonication.","phase":"Tetragonal phase of ZrO2 (confirmed by XRD and SAED); Co present as nanoparticles.","particleSize":"3.75 nm (fresh), 4.19 ± 0.42 nm (used)","surfaceStates":"Cr exists in the 3+ state (XPS Cr 2p peaks at 577.9 and 587.8 eV). ZrO2 is tetragonal with lattice fringes d-spacing of 0.288 nm corresponding to the (111) plane.","structureLink":"High catalytic activity (TOF 7685 h-1) is attributed to the small size and uniform dispersion of Co NPs, synergistic interactions between Co NPs, Cr(OH)3 atoms, and ZrO2 sites, and a mesoporous structure with a pore size of 8.24 nm that improves mass transfer.","reactionConditions":"50 mg catalyst, 5 mL H2O, 2.5 mmol FA/SF solution","selectivity":"Prevents unfavorable dehydration processes that result in the emission of harmful CO","stability":"Recyclable over seven cycles without significant catalytic loss; minimal loss after five-cycle test","deactivation":"Slight decrease in activity in 5th cycle attributed to increase in Co NP size from 3.75 ± 0.24 nm (fresh) to 4.19 ± 0.42 nm (used)","whyPerformsWell":"Synergistic interaction between Co NPs, Cr(OH)3 atoms, and ZrO2 sites; uniform dispersion of fine metal nanoparticles (~3.75 nm); mesoporous structure (8.24 nm pore size) improving mass transfer rate","metricCount":"6"},{"paperId":"P218","catalystId":"P218_PERF_002","name":"Co/ZrO2","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"298 K, 50 mg catalyst, 5 mL H2O, 2.5 mmol FA/SF solution","metricCount":"1"},{"paperId":"P218","catalystId":"P218_PERF_003","name":"Co@Cr(OH)3","support":"Cr(OH)3/ZrO2","matchedSynthesis":"Co@Cr(OH)3/ZrO2","matchedCharacterization":"Co@Cr(OH)3/ZrO2","role":"catalyst for formic acid dehydrogenation","composition":"Co and Cr; optimal Co loading is 5.0 wt%","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"UiO-66 MOF was synthesized using ZrCl4 and PET-derived 1,4-benzenedicarboxylic acid (BDC), then annealed under N2 to produce ZrO2. Co and Cr precursors were added to the ZrO2 support in a water/ethylene glycol mixture and reduced with NaBH4 via sonication.","phase":"Tetragonal phase of ZrO2 (confirmed by XRD and SAED); Co present as nanoparticles.","particleSize":"3.75 nm (fresh), 4.19 ± 0.42 nm (used)","surfaceStates":"Cr exists in the 3+ state (XPS Cr 2p peaks at 577.9 and 587.8 eV). ZrO2 is tetragonal with lattice fringes d-spacing of 0.288 nm corresponding to the (111) plane.","structureLink":"High catalytic activity (TOF 7685 h-1) is attributed to the small size and uniform dispersion of Co NPs, synergistic interactions between Co NPs, Cr(OH)3 atoms, and ZrO2 sites, and a mesoporous structure with a pore size of 8.24 nm that improves mass transfer.","reactionConditions":"298 K, 50 mg catalyst, 5 mL H2O, 2.5 mmol FA/SF solution","metricCount":"1"},{"paperId":"P218","catalystId":"P218_PERF_004","name":"Co@Cr(OH)3/ZrO2-Air","support":"Cr(OH)3/ZrO2","matchedSynthesis":"Co@Cr(OH)3/ZrO2","matchedCharacterization":"Co@Cr(OH)3/ZrO2","role":"catalyst for formic acid dehydrogenation","composition":"Co and Cr; optimal Co loading is 5.0 wt%","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"UiO-66 MOF was synthesized using ZrCl4 and PET-derived 1,4-benzenedicarboxylic acid (BDC), then annealed under N2 to produce ZrO2. Co and Cr precursors were added to the ZrO2 support in a water/ethylene glycol mixture and reduced with NaBH4 via sonication.","phase":"Tetragonal phase of ZrO2 (confirmed by XRD and SAED); Co present as nanoparticles.","particleSize":"3.75 nm (fresh), 4.19 ± 0.42 nm (used)","surfaceStates":"Cr exists in the 3+ state (XPS Cr 2p peaks at 577.9 and 587.8 eV). ZrO2 is tetragonal with lattice fringes d-spacing of 0.288 nm corresponding to the (111) plane.","structureLink":"High catalytic activity (TOF 7685 h-1) is attributed to the small size and uniform dispersion of Co NPs, synergistic interactions between Co NPs, Cr(OH)3 atoms, and ZrO2 sites, and a mesoporous structure with a pore size of 8.24 nm that improves mass transfer.","reactionConditions":"Pyrolyzed in air atmosphere, 50 mg catalyst, 5 mL H2O, 2.5 mmol FA/SF solution","metricCount":"2"},{"paperId":"P219","catalystId":"P219_PERF_001","name":"4-PySI-Pd@Cu(BDC)","support":"OMS-Cu(BDC)","matchedSynthesis":"4-PySI-Pd@Cu(BDC)","matchedCharacterization":"4-PySI-Pd@Cu(BDC)","role":"catalyst for formic acid dehydrogenation","composition":"Pd and Cu","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"post-synthetic modification","synthesis":"Synthesis of Cu(BDC)∙nDMF -> thermal/vacuum activation to OMS-Cu(BDC) -> coordination with 4-PySI ligand -> post-synthetic metalation with PdCl2","phase":"Single-site Pd grafted on Schiff-base decorated OMS-Cu(BDC) pore cage","surfaceStates":"Initial state is Pd(II); reduced to Pd(0) during reaction.","structureLink":"The para position of the coordination bond in 4-PySI provides a more open active site compared to 2-PySI, resulting in higher catalytic activity (TOF = 412 h⁻¹). Synergistic effects between Pd and the Schiff-base group enhance dehydrogenation.","reactionConditions":"Aqueous solution of FA (5%, 5 mL), room temperature, N2 atmosphere, reactor volume 80 mL","selectivity":"H2 to CO2 ratio is 1; no CO gas generated","stability":"Stable for at least three cycles without apparent loss of activity","deactivation":"No significant activity loss during reuse; XPS indicates reduction of Pd(II) to Pd(0) during reaction","whyPerformsWell":"Synergistic effect between Pd metal and Schiff-base group; 4-PySI provides a more open active site due to the para position of the coordination bond compared to 2-PySI; porous MOF structure stabilizes Pd ions.","metricCount":"2"},{"paperId":"P219","catalystId":"P219_PERF_002","name":"2-PySI-Pd@Cu(BDC)","support":"OMS-Cu(BDC)","matchedSynthesis":"2-PySI-Pd@Cu(BDC)","matchedCharacterization":"2-PySI-Pd@Cu(BDC)","role":"catalyst for formic acid dehydrogenation","composition":"Pd and Cu","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"post-synthetic modification","synthesis":"Synthesis of Cu(BDC)∙nDMF -> thermal/vacuum activation to OMS-Cu(BDC) -> coordination with 2-PySI ligand -> post-synthetic metalation with PdCl2","phase":"Single-site Pd grafted on Schiff-base decorated OMS-Cu(BDC) pore cage","structureLink":"Lower activity (TOF = 315 h⁻¹) compared to 4-PySI-Pd@Cu(BDC) due to a less open active site resulting from the ortho position of the coordination bond.","reactionConditions":"Aqueous solution of FA (5%, 5 mL), room temperature, N2 atmosphere, reactor volume 80 mL","selectivity":"H2 to CO2 ratio is 1; no CO gas generated","stability":"Stable for at least three cycles","whyPerformsWell":"Less active than 4-PySI variant due to less open active site (ortho position of coordination bond)","metricCount":"2"},{"paperId":"P219","catalystId":"P219_PERF_003","name":"4-PySI@Cu(BDC)","activeMetals":"unknown","activeMetalCount":"0","activeMetalSource":"unknown","metalClass":"Unknown/unclear","pdBased":"False","method":"unknown","reactionConditions":"Aqueous solution of FA (5%, 5 mL), room temperature, N2 atmosphere","whyPerformsWell":"Activity is due to the chelating ligand","metricCount":"2"},{"paperId":"P219","catalystId":"P219_PERF_004","name":"OMS-Cu(BDC)","activeMetals":"Cu","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Aqueous solution of FA (5%, 5 mL), room temperature, N2 atmosphere","metricCount":"1"},{"paperId":"P219","catalystId":"P219_PERF_005","name":"Cu(BDC)∙nDMF","activeMetals":"Cu","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Aqueous solution of FA (5%, 5 mL), room temperature, N2 atmosphere","metricCount":"1"},{"paperId":"P220","catalystId":"P220_PERF_001","name":"Pd90Rh10/HHT","activeMetals":"Pd-Rh","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","selectivity":"CO under the detection limit of the instrument (5 ppm)","stability":"Deactivated during recycling tests; average particle size increased from 2.9 to 4.5 nm","deactivation":"Partial leaching of Rh in the reaction solution; coalescence of particles","whyPerformsWell":"Pd-rich catalysts were more active than Rh-rich ones","metricCount":"2"},{"paperId":"P220","catalystId":"P220_PERF_002","name":"Pd69Rh31/HHT","activeMetals":"Pd-Rh","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","selectivity":"CO under the detection limit of the instrument (5 ppm)","stability":"Good stability during 6 cycles; conversion was constant","deactivation":"Leaching of Rh in the solution; limited growing of average particle size from 2.5 to 3.0 nm","whyPerformsWell":"High stability might be attributed to a catalyst with a Pd-Rh composition similar to the most active ones after leaching","metricCount":"2"},{"paperId":"P220","catalystId":"P220_PERF_003","name":"Pd/HHT","support":"HHT CNFs (High Heat Treated carbon nanofibers)","matchedSynthesis":"Pd/HHT","matchedCharacterization":"Pd/HHT","role":"monometallic catalyst for formic acid dehydrogenation","composition":"Pd:100","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"sol_immobilization","synthesis":"Metal precursor and PVA were dissolved in H2O/EtOH, reduced by NaBH4 to form a colloid, immobilized on HHT CNFs, acidified to pH 2 with sulfuric acid, stirred for 30 min, filtered, washed, and dried.","phase":"Monometallic","particleSize":"3.2 ± 0.8 nm (fresh); 4.5 ± 1.3 nm (used)","structureLink":"Rapid deactivation attributed to particle coalescence and CO poisoning.","reactionConditions":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","selectivity":"12 ppm CO","stability":"Rapidly deactivated after the first run","deactivation":"Leaching of 5% of Pd; agglomeration and coalescence (particle size increased from 3.0 to 4.7 nm); poisoning by CO","metricCount":"2"},{"paperId":"P220","catalystId":"P220_PERF_004","name":"Pd40Rh60/HHT","activeMetals":"Pd-Rh","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","selectivity":"CO under the detection limit (5 ppm)","metricCount":"1"},{"paperId":"P220","catalystId":"P220_PERF_005","name":"Pd48Rh52/HHT","activeMetals":"Pd-Rh","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","selectivity":"CO under the detection limit (5 ppm)","metricCount":"1"},{"paperId":"P220","catalystId":"P220_PERF_006","name":"Rh/HHT","support":"HHT CNFs (High Heat Treated carbon nanofibers)","matchedSynthesis":"Rh/HHT","matchedCharacterization":"Rh/HHT","role":"monometallic catalyst for formic acid dehydrogenation","composition":"Rh:100","activeMetals":"Rh","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"sol_immobilization","synthesis":"Metal precursor and PVA were dissolved in H2O/EtOH, reduced by NaBH4 to form a colloid, immobilized on HHT CNFs, acidified to pH 2 with sulfuric acid, stirred for 30 min, filtered, washed, and dried.","phase":"Monometallic","particleSize":"3.5 ± 1.1 nm","structureLink":"Showed very low activity in formic acid dehydrogenation.","reactionConditions":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","selectivity":"CO under the detection limit (5 ppm)","metricCount":"1"},{"paperId":"P221","catalystId":"P221_PERF_001","name":"Au/N-SBA-15_K(9.5)","support":"N-SBA-15","matchedSynthesis":"Au/N-SBA-15_K(9.5)","matchedCharacterization":"Au/N-SBA-15_K(9.5)","role":"catalyst","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Support suspended in distilled water, pH adjusted to 9.5 with K2CO3, HAuCl4 added and stirred for 60 min, sodium citrate added (Na citrate:Au = 20), then stirred at 80 °C for 30 min","particleSize":"0.8 ± 0.2 nm","structureLink":"Smallest particle size correlated with highest productivity, reaching full conversion of formic acid at 115 °C.","reactionConditions":"Gas-phase dehydrogenation of formic acid, fixed-bed quartz tube (4 mm i.d.), 30 mg catalyst, N2 carrier gas at 5 mL min-1 through a saturator containing 98% formic acid, atmospheric pressure.","selectivity":"complete selectivity to hydrogen; no carbon monoxide formation detected","whyPerformsWell":"Smallest particle size (0.8 ± 0.2 nm) and amine-functionalized support which stabilizes particles and allows them to enter pores.","metricCount":"1"},{"paperId":"P221","catalystId":"P221_PERF_002","name":"Au/N-SBA-15_K(11)","support":"N-SBA-15","matchedSynthesis":"Au/N-SBA-15_K(11)","matchedCharacterization":"Au/N-SBA-15_K(11)","role":"catalyst","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Support suspended in distilled water, pH adjusted to 11 with K2CO3, HAuCl4 added and stirred for 60 min, sodium citrate added (Na citrate:Au = 20), then stirred at 80 °C for 30 min","particleSize":"0.9 ± 0.2 nm","structureLink":"Second smallest particle size correlated with high productivity, reaching full conversion of formic acid at 115 °C.","reactionConditions":"Gas-phase dehydrogenation of formic acid, fixed-bed quartz tube (4 mm i.d.), 30 mg catalyst, N2 carrier gas at 5 mL min-1 through a saturator containing 98% formic acid, atmospheric pressure.","selectivity":"complete selectivity to hydrogen; no carbon monoxide formation detected","whyPerformsWell":"Small particle size (0.9 ± 0.2 nm) and amine-functionalized support.","metricCount":"1"},{"paperId":"P221","catalystId":"P221_PERF_003","name":"Au/SBA-15","support":"SBA-15","matchedSynthesis":"Au/SBA-15","matchedCharacterization":"Au/SBA-15","role":"catalyst","composition":"Au","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Support suspended in distilled water, no pH adjustment, HAuCl4 added and stirred for 60 min, sodium citrate added (Na citrate:Au = 20), then stirred at 80 °C for 30 min","particleSize":"26 ± 18 nm","structureLink":"Largest particles did not reach full conversion at 350 °C and showed lower selectivity to hydrogen (53%) with higher CO formation (44%).","reactionConditions":"Gas-phase dehydrogenation of formic acid, fixed-bed quartz tube (4 mm i.d.), 30 mg catalyst, N2 carrier gas at 5 mL min-1 through a saturator containing 98% formic acid, atmospheric pressure.","selectivity":"53% selectivity to hydrogen and 44% selectivity to carbon monoxide at 350 °C","whyPerformsWell":"Performs poorly due to large particle size (26 ± 18 nm).","metricCount":"1"},{"paperId":"P222","catalystId":"P222_PERF_001","name":"Gly-Cu/Ag/MnO2","matchedSynthesis":"Gly-Cu/Ag/MnO2","matchedCharacterization":"Gly-Cu/Ag/MnO2","role":"catalyst for hydrogen generation from formic acid decomposition","composition":"Cu:Ag:Mn (bulk mole ratio 1:1:1)","activeMetals":"Cu","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"MnO2 was prepared by reacting KMnO4 with Na2S2O3 in the presence of CTAB at room temperature. Gly-Cu/Ag (10 ml, 5.0 x 10^-3 mol/L) was mixed with MnO2 suspension (10 ml, 5.0 x 10^-4 mol/L), stirred overnight, and treated with NaBH4.","phase":"Ternary nanocomposite","particleSize":"Crystallite size ca. 30 nm; spherical NPs 10-50 nm; overall chain/rod structures up to 100 nm","surfaceStates":"Glycine-capped; MnO2-doped Gly-Cu/Ag","structureLink":"Highest catalytic activity (TOF = 146 h-1, Ea = 56 kJ/mol) attributed to strong metal-metal interactions and synergistic electronic effects between Cu, Ag, and MnO2.","reactionConditions":"Decomposition of formic acid in aqueous solution, monitored by water displacement method.","selectivity":"H2:CO2 molar ratio = 1:1","stability":"Excellent for four consecutive cycles; performance slightly decreased in higher cyclic experiments.","deactivation":"Stability decreased due to the release of MnO2 from the surface by formic acid.","whyPerformsWell":"Synergistic electronic effect and strong interactions between the three metals (Cu, Ag, Mn).","metricCount":"4"},{"paperId":"P222","catalystId":"P222_PERF_002","name":"Gly-Cu/Ag","matchedSynthesis":"Gly-Cu/Ag","matchedCharacterization":"Gly-Cu/Ag","role":"catalyst for hydrogen generation from formic acid decomposition","composition":"Cu/Ag","activeMetals":"Cu","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"other","synthesis":"Gly-Cu nanoparticles were treated with AgNO3 solution in the presence of CTAB to deposit Ag onto the Cu surface via metal displacement.","phase":"Cu/Ag core-shell","particleSize":"15 nm","surfaceStates":"Glycine-capped","structureLink":"Higher catalytic activity than Gly-Cu due to the incorporation of Ag.","reactionConditions":"Decomposition of formic acid in aqueous solution.","selectivity":"H2:CO2 molar ratio = 1:1","metricCount":"3"},{"paperId":"P222","catalystId":"P222_PERF_003","name":"Gly-Cu","matchedSynthesis":"Gly-Cu","matchedCharacterization":"Gly-Cu","role":"catalyst for hydrogen generation from formic acid decomposition","composition":"Cu","activeMetals":"Cu","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"chemical_reduction_loading","synthesis":"Glycine solution was mixed with copper nitrate and equilibrated at room temperature for 30 min to form Cu(glycine)2 complex, followed by dropwise addition of NaBH4 solution.","particleSize":"40 nm","surfaceStates":"Glycine-capped","structureLink":"Shows no effect on the decomposition of formic acid compared to multi-metal systems.","reactionConditions":"Decomposition of formic acid in aqueous solution.","whyPerformsWell":"no effect on the decomposition of formic acid","metricCount":"0"},{"paperId":"P222","catalystId":"P222_PERF_004","name":"Gly-Ag","activeMetals":"Ag","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"Decomposition of formic acid in aqueous solution.","whyPerformsWell":"no effect on the decomposition of formic acid","metricCount":"0"},{"paperId":"P223","catalystId":"P223_PERF_001","name":"Pd/N-MSC-30-two-175","support":"N-MSC-30-two-175","matchedSynthesis":"Pd/N-MSC-30-two-175","matchedCharacterization":"Pd/N-MSC-30-two-175","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"N-functionalized MSC-30 was prepared via tandem urea heat treatment. Pd nanoclusters were immobilized by dispersing the support in water, adding K2PdCl4 solution, and reducing with NaBH4 in a NaOH solution.","phase":"Metallic palladium (111 reflection)","particleSize":"1.4 nm","surfaceStates":"Pd 3d 5/2 peaks at 335.9 eV (Pd 0) and 337.5 eV (Pd 2+); N 1s peaks at 400.0 eV (amine/amide groups) and 398.7 eV (pyridinic N).","structureLink":"The ultrasmall size, high specific surface area, and synergistic effect between Pd NCs and N-functional groups (acting as base sites for FA deprotonation) result in a high TOF of 8414 h-1. Pore confinement prevents aggregation.","reactionConditions":"Aqueous FA-SF system, nFA:nSF = 1:2.5, nPd/nFA = 0.02","selectivity":"exclusive formation of H2 and CO2 without detectable CO impurity (<5 ppm)","stability":"activity remained only slightly changed after 15 cycles; total TON of 1250","whyPerformsWell":"ultrasmall size (mean diameter 1.4 nm) and clean surface of Pd NCs, synergistic effect between Pd NCs and N-functionalized groups on MSC-30 supports, high specific surface area providing spatial confinement preventing aggregation","metricCount":"5"},{"paperId":"P223","catalystId":"P223_PERF_002","name":"Pd/N-MSC-30-one","support":"N-MSC-30-one","matchedSynthesis":"Pd/N-MSC-30-one","matchedCharacterization":"Pd/N-MSC-30-one","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Identical metal loading and reduction process as Pd/N-MSC-30-two-175, using a one-step N-functionalized support.","phase":"Pd phase (distinct diffraction peaks)","particleSize":"Contains some large particles due to aggregation","surfaceStates":"N 1s peaks at 400.0 eV and 398.7 eV.","structureLink":"Lower TOF (5408 h-1) compared to Pd/N-MSC-30-two-175 due to poorer dispersity of Pd NCs.","reactionConditions":"Aqueous FA-SF system, nFA:nSF = 1:2.5, nPd/nFA = 0.02","metricCount":"1"},{"paperId":"P223","catalystId":"P223_PERF_003","name":"Pd/MSC-30","support":"MSC-30","matchedSynthesis":"Pd/MSC-30","matchedCharacterization":"Pd/MSC-30","role":"catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Identical metal loading and reduction process as Pd/N-MSC-30-two-175, using non-functionalized MSC-30.","phase":"Pd phase (distinct diffraction peaks)","particleSize":"2.6 nm","structureLink":"Poor catalytic performance relative to the N-functionalized counterpart due to larger particle size.","reactionConditions":"Aqueous FA-SF system, nFA:nSF = 1:2.5, nPd/nFA = 0.02","whyPerformsWell":"relatively poor catalytic performance compared to Pd/N-MSC-30 catalysts","metricCount":"0"},{"paperId":"P224","catalystId":"P224_PERF_001","name":"Pd cubic nanocrystals","matchedSynthesis":"Pd cubic nanocrystals","role":"model catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"shape-controlled synthesis","synthesis":"Synthesis of Pd nanocrystals enclosed by {100} facets; surface ligands (PVP) were removed via centrifugation and washing at least 6 times.","reactionConditions":"Varies by reaction (HCOOH decomposition, styrene hydrogenation, or tandem hydrogen transfer)","selectivity":"No CO is observed in GC for HCOOH decomposition","whyPerformsWell":"Consistency of active edge sites during different step reactions (HCOOH decomposition and hydrogenation) enables cubic nanocrystals to exhibit higher activity in tandem hydrogen transfer reactions.","metricCount":"11"},{"paperId":"P224","catalystId":"P224_PERF_002","name":"Pd octahedral nanocrystals","matchedSynthesis":"Pd octahedral nanocrystals","role":"model catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"shape-controlled synthesis","synthesis":"Synthesis of Pd nanocrystals enclosed by {111} facets; surface ligands (PVP) were removed via centrifugation and washing at least 6 times.","reactionConditions":"Varies by reaction","whyPerformsWell":"The decomposition of HCOOH occurs preferentially at the plane sites of octahedral nanocrystals, while hydrogenation takes place mainly at edge sites. This spatial separation leads to lower tandem reaction efficiency compared to cubic nanocrystals.","metricCount":"11"},{"paperId":"P224","catalystId":"P224_PERF_003","name":"Pd tetrahedral nanocrystals","matchedSynthesis":"Pd tetrahedral nanocrystals","role":"model catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"shape-controlled synthesis","synthesis":"Synthesis of Pd nanocrystals enclosed by {111} facets; surface ligands (PVP) were removed via centrifugation and washing at least 6 times.","reactionConditions":"Varies by reaction","whyPerformsWell":"Similar to octahedral nanocrystals, the spatial separation of active sites for HCOOH decomposition (planes) and hydrogenation (edges) limits tandem efficiency.","metricCount":"5"},{"paperId":"P224","catalystId":"P224_PERF_004","name":"Pd@Ag nanocubes","matchedSynthesis":"Pd@Ag nanocubes","matchedCharacterization":"Pd@Ag nanocubes","role":"modified catalyst for enhanced HCOOH decomposition","composition":"Pd-Ag","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"selective overgrowth","synthesis":"Selective overgrowth of Ag atoms starting at the edges of Pd nanocubes, enabled by Br- capping of {100} facets; Ag subsequently spills over from edges to plane sites.","phase":"Bimetallic (Ag-modified Pd)","particleSize":"14.4 nm","surfaceStates":"Ag atoms modified at both edge and plane sites of the Pd nanocube","structureLink":"Ag modification accelerates HCOOH decomposition (the limiting step), promoting overall tandem reaction TOF by generating Had not only at edges but also on planes.","reactionConditions":"Tandem hydrogen transfer reaction at 323 K, 1 h","whyPerformsWell":"Ag modification accelerates the limiting step (HCOOH decomposition), forming Had not only at edge sites but also on planes, promoting overall tandem reactions.","metricCount":"1"},{"paperId":"P225","catalystId":"P225_PERF_001","name":"Pd/EDA-PAN","support":"EDA-PAN","matchedSynthesis":"Pd/EDA-PAN","matchedCharacterization":"Pd/EDA-PAN","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"EDA-PAN was dispersed in water, H2PdCl4 was added and stirred for 8 h; the resulting Pd2+/EDA-PAN was dried and then reduced by injecting NaBH4 solution into an aqueous dispersion under strong stirring for 6 h.","phase":"Pd nanoparticles","particleSize":"1.2 nm","surfaceStates":"Fresh catalyst contains both Pd0 and Pd2+, with Pd2+ as the dominant species; spent catalyst remains consistent with fresh state.","structureLink":"The coexistence of Pd0 and Pd2+ and the ultra-small particle size (1.2 nm) are linked to improved catalytic activity for formic acid dehydrogenation. Strong metal-support interaction provided by amino groups enhances chemical stability.","reactionConditions":"Dehydrogenation of formic acid (FA) aqueous solution without additives.","selectivity":"Excellent selectivity; no CO signal detected by GC analysis.","stability":"High activity maintained after recycling five times.","deactivation":"Particle size of Pd NPs increased slightly after five recycling experiments, but structural stability is excellent.","whyPerformsWell":"Surface amination with EDA achieves high dispersion of ultra-small Pd NPs (~1.2 nm) and builds strong metal-support interaction; basic features of amidinate and amino groups facilitate FA deprotonation.","metricCount":"3"},{"paperId":"P225","catalystId":"P225_PERF_002","name":"Pd/PAN","support":"PAN","matchedSynthesis":"Pd/PAN","matchedCharacterization":"Pd/PAN","role":"reference sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"PAN was dispersed in water, H2PdCl4 was added and stirred for 8 h; the resulting Pd2+/PAN was dried and then reduced by injecting NaBH4 solution into an aqueous dispersion under strong stirring for 6 h.","phase":"Pd nanoparticles","particleSize":"1.6 nm","surfaceStates":"Fresh catalyst consists primarily of Pd0 (binding energies 336.0 and 341.2 eV); spent catalyst shows formation of Pd2+ (338.1 and 343.2 eV).","reactionConditions":"Dehydrogenation of formic acid (FA) aqueous solution without additives.","selectivity":"Excellent selectivity; no CO signal detected by GC analysis.","stability":"Slight decline in catalytic activity observed with increasing recycling numbers.","deactivation":"Particle size of Pd NPs increased slightly after five recycling experiments.","metricCount":"2"},{"paperId":"P226","catalystId":"P226_PERF_001","name":"6Ni/N-LC","support":"N-doped porous carbon (N-LC)","matchedSynthesis":"6Ni/N-LC, 8Ni/N-LC, 10Ni/N-LC","matchedCharacterization":"6Ni/N-LC","role":"active catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Ni precursor dissolved in THF, mixed with N-LC support and stirred at 60 °C for 4 h; solvent removed by natural evaporation; treated at 350 °C in Ar flow to decompose acetate moieties.","phase":"Single-atom","surfaceStates":"Fresh state contains Ni2+ bonded to N (855.5 eV) and O (856.6 eV); reduced to metallic/Ni-N species.","structureLink":"Highest reaction rate and lowest apparent activation energy (95 kJ/mol), indicating superior activity of single-atom sites over nanoparticles.","reactionConditions":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","selectivity":"> 99% selectivity toward H2 production","stability":"Tested at 280 °C for > 50 h; conversion increased during first few hours, then stabilized (97.4% after breaks). Selectivity decreased from 99.2% to 95.7% after air exposure breaks.","deactivation":"XPS showed Ni content decrease (from 0.48 at.% to 0.27 at.%) and formation of Ni-Ni bonds, indicating metal agglomeration/migration.","whyPerformsWell":"Contains single-atom Ni sites coordinated with N and O atoms on a high surface area N-doped carbon support.","metricCount":"4"},{"paperId":"P226","catalystId":"P226_PERF_002","name":"8Ni/N-LC","support":"N-doped porous carbon (N-LC)","matchedSynthesis":"6Ni/N-LC, 8Ni/N-LC, 10Ni/N-LC","matchedCharacterization":"8Ni/N-LC","role":"active catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Ni precursor dissolved in THF, mixed with N-LC support and stirred at 60 °C for 4 h; solvent removed by natural evaporation; treated at 350 °C in Ar flow to decompose acetate moieties.","phase":"Single-atom (implied by activity and Ea)","surfaceStates":"Ni2+ bonded to N and O in fresh state.","structureLink":"Activity and activation energy (99 kJ/mol) are close to 6Ni/N-LC, suggesting similar electronic states of active Ni species.","reactionConditions":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","selectivity":"> 99% selectivity toward H2 production","whyPerformsWell":"High dispersion of Ni on N-doped carbon support.","metricCount":"3"},{"paperId":"P226","catalystId":"P226_PERF_003","name":"10Ni/N-LC","support":"N-doped porous carbon (N-LC)","matchedSynthesis":"6Ni/N-LC, 8Ni/N-LC, 10Ni/N-LC","matchedCharacterization":"10Ni/N-LC","role":"active catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Ni precursor dissolved in THF, mixed with N-LC support and stirred at 60 °C for 4 h; solvent removed by natural evaporation; treated at 350 °C in Ar flow to decompose acetate moieties.","phase":"Sub-nanosized particles","particleSize":"Average 0.84 ± 0.24 nm (range 0.2 to 1.6 nm)","surfaceStates":"Ni2+ bonded to N and O; presence of Ni-Ni bonds (853.0 eV in XPS) indicates particle formation.","structureLink":"Lower activity and higher activation energy (105 kJ/mol) compared to single-atom catalysts.","reactionConditions":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","selectivity":"> 99% selectivity toward H2 production","stability":"Tested at 280 °C for > 50 h; conversion increased during first few hours, then stabilized (85.4% after breaks). Selectivity decreased from 98.6% to 97.1% after air exposure breaks.","deactivation":"XPS showed Ni content decrease (from 0.81 at.% to 0.26 at.%) and slight increase in Ni-Ni bonding intensity, indicating lower mobility than single atoms.","whyPerformsWell":"Contains sub-nanosized nickel particles with an average size of 0.84 nm on N-doped carbon support.","metricCount":"3"},{"paperId":"P226","catalystId":"P226_PERF_004","name":"10Ni/LC","support":"Porous carbon (LC) and NH3-treated porous carbon (LCNH3)","matchedSynthesis":"10Ni/LC, 10Ni/LCNH3","matchedCharacterization":"10Ni/LC","role":"control catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Same technique as Ni/N-LC catalysts.","phase":"Nanoparticles","surfaceStates":"High fraction of Ni-Ni bonds","structureLink":"Highest activation energy (126 kJ/mol) and highest temperature for complete conversion (320 °C).","reactionConditions":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor","selectivity":"Lower selectivity than N-LC supported catalysts","whyPerformsWell":"Control catalyst with Ni in the form of surface-oxidized nanoparticles on nitrogen-free carbon.","metricCount":"3"},{"paperId":"P226","catalystId":"P226_PERF_005","name":"10Ni/LC_NH3","support":"Porous carbon (LC) and NH3-treated porous carbon (LCNH3)","matchedSynthesis":"10Ni/LC, 10Ni/LCNH3","matchedCharacterization":"10Ni/LCNH3","role":"control catalyst","composition":"Ni","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"wet_impregnation","synthesis":"Same technique as Ni/N-LC catalysts.","phase":"Nanoparticles","surfaceStates":"High fraction of Ni-Ni bonds","structureLink":"Activation energy (115 kJ/mol) and conversion temperature (340 °C) are higher than for N-LC supported catalysts.","reactionConditions":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor","selectivity":"Lower selectivity than N-LC supported catalysts","whyPerformsWell":"Control catalyst with Ni in the form of surface-oxidized nanoparticles on nitrogen-doped carbon (prepared without fluorination).","metricCount":"3"},{"paperId":"P227","catalystId":"P227_PERF_001","name":"Pd/NC800","support":"N-doped carbon (NC)","matchedSynthesis":"Pd/NC800","matchedCharacterization":"Pd/NC800","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Sunflower seed husks, ZnCl2, and melamine were dispersed in water, stirred for 24h, dried at 60°C, carbonized at 240°C (2h), and annealed at 800°C (2h) under N2. The support was cleaned with 3 M HCl. Pd was then deposited via impregnation of H2PdCl4 solution followed by NaBH4 reduction.","phase":"fcc Pd (plane spacing 0.224 nm corresponding to (1 1 1) plane)","particleSize":"XRD: 2.89 nm, TEM: 2.45 nm","surfaceStates":"Highest level of D3 carbon defects (amorphous carbon); high content of sp3 carbon defects; Pd2+/Pd0 ratio is 0.93.","structureLink":"Topological defects promote electron transfer from sp3 carbon to Pd, enhancing metal-support interaction, stabilizing smaller NPs, and shifting the d-band center downward to facilitate HCOO adsorption.","reactionConditions":"10 mL of 1 M FA/SF solution (10 mmol FA, 10 mmol sodium formate) at 30 °C in a 50 mL round-bottom flask with 40 mg catalyst.","stability":"Excellent stability; particle size increased from 2.45 to 2.91 nm over three cycles.","whyPerformsWell":"Topological defects (specifically the 5-8-5 defect induced by pyrrolic N) promote electron transfer at the Pd-carbon interface, enhancing metal-support interaction and modulating the electronic state of Pd NPs (downshifting the d-band center), which reinforces bonding to HCOO intermediates.","metricCount":"3"},{"paperId":"P227","catalystId":"P227_PERF_002","name":"Pd/NC700","support":"N-doped carbon (NC)","matchedSynthesis":"Pd/NC700","matchedCharacterization":"Pd/NC700","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Sunflower seed husks, ZnCl2, and melamine were dispersed in water, stirred for 24h, dried at 60°C, carbonized at 240°C (2h), and annealed at 700°C (2h) under N2. The support was cleaned with 3 M HCl. Pd was then deposited via impregnation of H2PdCl4 solution followed by NaBH4 reduction.","phase":"fcc Pd","particleSize":"XRD: 2.92 nm, TEM: 2.84 nm","surfaceStates":"Contains pyridinic N (7.23 wt%), pyrrolic N (4.99 wt%), and graphitic N (1.58 wt%); Pd2+/Pd0 ratio is 0.35.","structureLink":"Lower topological defect density compared to Pd/NC800 leads to lower catalytic activity.","reactionConditions":"10 mL of 1 M FA/SF solution (10 mmol FA, 10 mmol sodium formate) at 30 °C in a 50 mL round-bottom flask with 40 mg catalyst.","stability":"Activity decreased rapidly and almost deactivated in the third cycle.","metricCount":"2"},{"paperId":"P227","catalystId":"P227_PERF_003","name":"Pd/NC900","support":"N-doped carbon (NC)","matchedSynthesis":"Pd/NC900","matchedCharacterization":"Pd/NC900","role":"catalyst for formic acid dehydrogenation","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"Sunflower seed husks, ZnCl2, and melamine were dispersed in water, stirred for 24h, dried at 60°C, carbonized at 240°C (2h), and annealed at 900°C (2h) under N2. The support was cleaned with 3 M HCl. Pd was then deposited via impregnation of H2PdCl4 solution followed by NaBH4 reduction.","phase":"fcc Pd","particleSize":"XRD: 3.16 nm, TEM: 3.46 nm","surfaceStates":"Reduced carbon defects and N content due to high-temperature evaporation; Pd2+/Pd0 ratio is 0.62.","structureLink":"Decrease in topological defect content and N concentration leads to a sharp decline in TOF for formic acid dehydrogenation.","reactionConditions":"10 mL of 1 M FA/SF solution (10 mmol FA, 10 mmol sodium formate) at 30 °C in a 50 mL round-bottom flask with 40 mg catalyst.","stability":"Activity decreased rapidly and almost deactivated in the third cycle.","metricCount":"2"},{"paperId":"P228","catalystId":"P228_PERF_001","name":"Pd0.75Au0.25/NH2-SPP","support":"amino-grafted self-pillared pentasil (SPP) zeolite","matchedSynthesis":"Pd0.75Au0.25/NH2-SPP","matchedCharacterization":"Pd0.75Au0.25/NH2-SPP","role":"main catalyst","composition":"Pd:Au = 0.75:0.25 (molar ratio)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"SPP zeolite was synthesized and calcined, then amino-functionalized with APTES. Pd and Au precursors were added to a suspension of NH2-SPP in water, followed by liquid-phase reduction using sodium borohydride.","phase":"PdAu alloy nanoparticles (XRD peak at 39.2°; lattice spacings of 0.231 nm for (111) and 0.198 nm for (200); EDS line scan confirms uniform alloy without intraparticle segregation)","particleSize":"0.76 nm","surfaceStates":"Electron-rich surface resulting from electron donation from the NH2-SPP support and electron migration from Pd to Au due to electronegativity differences.","structureLink":"Ultrahigh dispersion and electronic synergy between Pd and Au optimize FA adsorption and C-H bond cleavage; hydrophobic surface promotes contact with FA molecules; amino groups act as proton scavengers promoting O-H bond dissociation.","reactionConditions":"298 K, aqueous FA-SF solution, nFA = 2.5 mmol, nSF = 2.5 mmol, nmetal/nFA = 0.04","selectivity":"100% hydrogen selectivity; no CO detected","stability":"Maintained performance for six consecutive runs; reaction time increased from approximately 5 min (1st run) to 8 min (6th run)","whyPerformsWell":"Ultrahigh dispersion of PdAu alloy nanoclusters (~0.76 nm); electronic synergy between Pd and Au creating electron-enriched Pd sites; amino groups acting as proton scavengers promoting O-H bond dissociation; hydrophobic surface enhancing contact with FA molecules","metricCount":"2"},{"paperId":"P228","catalystId":"P228_PERF_002","name":"Pd/NH2-SPP","matchedCharacterization":"Pd/NH2-SPP","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Metallic Pd (no XRD peaks observed due to high dispersion)","surfaceStates":"Pd0","structureLink":"Stronger adsorption toward HCOOH molecules compared to PdAu alloy, which is less conducive to forming the key HCOO* intermediate.","reactionConditions":"298 K, aqueous FA-SF solution, nFA = 2.5 mmol, nSF = 2.5 mmol, nmetal/nFA = 0.04","whyPerformsWell":"Presence of amino groups on SPP zeolite surface improves metal dispersion compared to Pd/SPP","metricCount":"2"},{"paperId":"P228","catalystId":"P228_PERF_003","name":"Pd/SPP","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"298 K, aqueous FA-SF solution, nFA = 2.5 mmol, nSF = 2.5 mmol, nmetal/nFA = 0.04","whyPerformsWell":"Remarkably low activity compared to amino-functionalized support","metricCount":"1"},{"paperId":"P229","catalystId":"P229_PERF_001","name":"Au0.3Pd0.7/A-M-β-CD","support":"amine-functionalized monochlorotriazinyl β-cyclodextrin (A-M-β-CD)","matchedSynthesis":"Au0.3Pd0.7/A-M-β-CD","matchedCharacterization":"Au0.3Pd0.7/A-M-β-CD","role":"main catalyst","composition":"Au:Pd = 0.3:0.7","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"M-β-CD was functionalized with APTES to form A-M-β-CD; Au and Pd precursors were added to the suspension, stirred for 3 h, and then reduced using NaBH4.","phase":"Alloy structure; HRTEM lattice spacing is 0.231 nm (between Au 0.235 nm and Pd 0.224 nm); XRD shows a broad diffraction peak for the (111) plane located between those of Au and Pd; HAADF-STEM mapping confirms co-distribution of Au and Pd.","particleSize":"~2.0 nm","surfaceStates":"Binding energies of Pd 3d and Au 4f are shifted to negative values relative to unsupported NPs, indicating electron transfer from the A-M-β-CD support to the AuPd NPs; charge transfer also occurs between Pd and Au within the alloy structure.","structureLink":"The combination of ultrafine particle size, excellent dispersion, and electron-rich active sites (via strong metal-support interaction) accelerates the rate-determining step for C–H cleavage of adsorbed HCOO* intermediates, resulting in a high TOF of 7352 h-1.","reactionConditions":"323 K, 1 M FA aqueous solution (5 mL), no additives, ambient atmosphere, magnetic stirring (600 rpm)","selectivity":"no CO detected at the level of detection limit of 10 ppm; gas composed of H2 and CO2","stability":"slight decay in catalytic activity after the 4th run","deactivation":"slightly increased particle size (by ~0.7 nm) after the 4th run","whyPerformsWell":"strong interaction between AuPd NPs and A-M-β-CD support endowing ultrafine size (~2.0 nm), excellent dispersion, and electron-rich active sites through electron transfer from support to NPs","metricCount":"1"},{"paperId":"P229","catalystId":"P229_PERF_002","name":"Au0.3Pd0.7 NP","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"323 K, 1 M FA aqueous solution (5 mL), no additives, ambient atmosphere","whyPerformsWell":"severe aggregation (average size ~9.5 nm)","metricCount":"1"},{"paperId":"P229","catalystId":"P229_PERF_003","name":"Au0.3Pd0.7/M-β-CD","matchedCharacterization":"Au0.3Pd0.7/M-β-CD","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","particleSize":"~5.2 nm","reactionConditions":"323 K, 1 M FA aqueous solution (5 mL), no additives, ambient atmosphere","whyPerformsWell":"obvious agglomeration (average size ~5.2 nm)","metricCount":"2"},{"paperId":"P229","catalystId":"P229_PERF_004","name":"Au0.3Pd0.7-A","support":"amine-functionalized monochlorotriazinyl β-cyclodextrin (A-M-β-CD)","matchedSynthesis":"Au0.3Pd0.7/A-M-β-CD","matchedCharacterization":"Au0.3Pd0.7-A","role":"main catalyst","composition":"Au:Pd = 0.3:0.7","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"M-β-CD was functionalized with APTES to form A-M-β-CD; Au and Pd precursors were added to the suspension, stirred for 3 h, and then reduced using NaBH4.","particleSize":"~3.4 nm","surfaceStates":"No obvious shift for Pd 3d and Au 4f XPS peaks compared to unsupported NPs, indicating no bond formed between AuPd and APTES amine groups.","reactionConditions":"323 K, 1 M FA aqueous solution (5 mL), no additives, ambient atmosphere","whyPerformsWell":"tinier particle size (average size ~3.4 nm) compared to other samples","metricCount":"2"},{"paperId":"P229","catalystId":"P229_PERF_005","name":"Au0.3Pd0.7/C","support":"Vulcan XC-72 carbon (C)","matchedSynthesis":"Au0.3Pd0.7/C","matchedCharacterization":"Au0.3Pd0.7/C","role":"comparison catalyst","composition":"Au:Pd = 0.3:0.7","activeMetals":"Au-Pd","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Synthesized by the same method as Au0.3Pd0.7/A-M-β-CD but using Vulcan XC-72 carbon support.","particleSize":"~4.8 nm","reactionConditions":"323 K, 1 M FA aqueous solution (5 mL), no additives, ambient atmosphere","whyPerformsWell":"larger average size (~4.8 nm) than Au0.3Pd0.7/A-M-β-CD","metricCount":"1"},{"paperId":"P230","catalystId":"P230_PERF_001","name":"Pd/NMC-400","support":"N-doped mesoporous carbon (NMC)","matchedSynthesis":"Pd/NMC","matchedCharacterization":"Pd/NMC","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF.","reactionConditions":"10 mL of 1.0 M FA solution, 30 mg catalyst, 25 °C, round-bottom flask, ambient atmosphere","selectivity":"close to 100% selectivity for H2; no CO detected","whyPerformsWell":"Enrichment of pyridinic N and metallic Pd sites facilitating deprotonation of FA and activation of C-H bonds.","metricCount":"3"},{"paperId":"P230","catalystId":"P230_PERF_002","name":"Pd/NMC-500","support":"N-doped mesoporous carbon (NMC)","matchedSynthesis":"Pd/NMC","matchedCharacterization":"Pd/NMC","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF.","reactionConditions":"10 mL of 1.0 M FA solution, 30 mg catalyst, 25 °C, round-bottom flask, ambient atmosphere","selectivity":"close to 100% selectivity for H2; no CO detected","metricCount":"2"},{"paperId":"P230","catalystId":"P230_PERF_003","name":"Pd/NMC-600","support":"N-doped mesoporous carbon (NMC)","matchedSynthesis":"Pd/NMC","matchedCharacterization":"Pd/NMC","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF.","reactionConditions":"10 mL of FA solution, 30 mg catalyst, round-bottom flask, ambient atmosphere","selectivity":"close to 100% selectivity for H2; no CO detected","stability":">95% retention efficiency within 4 cycles (8 h running)","whyPerformsWell":"Synergy of ultra-fine Pd particles (1.2 nm), pyridinic N species acting as activation sites for deprotonation and anchoring sites for stabilization, and ordered mesoporous structure providing confinement effects.","metricCount":"7"},{"paperId":"P230","catalystId":"P230_PERF_004","name":"Pd/NMC-700","support":"N-doped mesoporous carbon (NMC)","matchedSynthesis":"Pd/NMC","matchedCharacterization":"Pd/NMC","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF.","reactionConditions":"10 mL of 1.0 M FA solution, 30 mg catalyst, 25 °C, round-bottom flask, ambient atmosphere","selectivity":"close to 100% selectivity for H2; no CO detected","metricCount":"2"},{"paperId":"P230","catalystId":"P230_PERF_005","name":"Pd/NMC-800","support":"N-doped mesoporous carbon (NMC)","matchedSynthesis":"Pd/NMC","matchedCharacterization":"Pd/NMC","role":"active catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF.","reactionConditions":"10 mL of 1.0 M FA solution, 30 mg catalyst, 25 °C, round-bottom flask, ambient atmosphere","selectivity":"close to 100% selectivity for H2; no CO detected","metricCount":"2"},{"paperId":"P230","catalystId":"P230_PERF_006","name":"Pd/MC-600","support":"mesoporous carbon (MC)","matchedSynthesis":"Pd/MC","matchedCharacterization":"Pd/MC-600","role":"comparison catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"deposition_precipitation","synthesis":"MC support was synthesized via hard template method and carbonized at 600 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","phase":"Metallic Pd","particleSize":"8.1 ± 3.9 nm (range: 2.3-20.9 nm)","surfaceStates":"Predominantly metallic Pd due to weak interaction between Pd and carbon support.","structureLink":"Larger, nonuniform particle size and lack of N-doping result in significantly lower H2 production compared to Pd/NMC.","reactionConditions":"10 mL of 1.0 M FA solution, 30 mg catalyst, 25 °C, round-bottom flask, ambient atmosphere","selectivity":"close to 100% selectivity for H2; no CO detected","metricCount":"2"},{"paperId":"P231","catalystId":"P231_PERF_001","name":"Pd/NH2-CNT (also referred to as Pd/CNTs (Cit and APTES))","support":"Multiwalled carbon nanotubes (CNTs, MR99)","matchedSynthesis":"Pd/CNT","matchedCharacterization":"Pd/CNT","role":"control sample (no additives)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/NH2-CNT but without Cit or APTES.","phase":"Metallic Pd nanoparticles","particleSize":"13.9 nm (CO chemisorption)","structureLink":"Severely aggregated particles with a small number of active surface atoms result in negligible catalytic activity.","reactionConditions":"Semi-batch reactor, vigorous stirring at 1000 rpm, catalyst containing 11.75 µmol of Pd, reactant volume 9 mL.","selectivity":"No CO detected in product gases (detection limit 10 ppm).","stability":"Activity steadily reduced when regenerated by washing with water and drying overnight at 105 °C; completely deactivated without regeneration process after the second injection of FA.","deactivation":"Sintering of Pd particles (during regeneration); fouling of reactants/products or accumulation of CO adsorbed on Pd (without regeneration).","whyPerformsWell":"Minimized Pd size (1.76 nm), proton-scavenging effect of amine functional groups, absence of micropores in CNTs facilitating mass transport, and electronic effect of CNTs on Pd.","metricCount":"6"},{"paperId":"P231","catalystId":"P231_PERF_002","name":"Pd/CNT","support":"Multiwalled carbon nanotubes (CNTs, MR99)","matchedSynthesis":"Pd/CNT","matchedCharacterization":"Pd/CNT","role":"control sample (no additives)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/NH2-CNT but without Cit or APTES.","phase":"Metallic Pd nanoparticles","particleSize":"13.9 nm (CO chemisorption)","structureLink":"Severely aggregated particles with a small number of active surface atoms result in negligible catalytic activity.","whyPerformsWell":"Large Pd particles have small number of active surface atoms and high hydrogen desorption barrier.","metricCount":"1"},{"paperId":"P231","catalystId":"P231_PERF_003","name":"Pd/CNT (Cit)","support":"Multiwalled carbon nanotubes (CNTs, MR99)","matchedSynthesis":"Pd/CNT (Cit)","matchedCharacterization":"Pd/CNT (Cit)","role":"control sample (stabilizer only)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/NH2-CNT but using only Cit without APTES.","phase":"Metallic Pd nanoparticles","particleSize":"2.93 ± 0.63 nm (TEM), 2.4 nm (CO chemisorption)","structureLink":"Smaller particle size compared to Pd/CNT improves activity, but requires SF additive for noticeable performance.","metricCount":"1"},{"paperId":"P231","catalystId":"P231_PERF_004","name":"Pd/CNT (APTES)","support":"Multiwalled carbon nanotubes (CNTs, MR99)","matchedSynthesis":"Pd/CNT (APTES)","matchedCharacterization":"Pd/CNT (APTES)","role":"control sample (functionalization only)","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/NH2-CNT but using only APTES without Cit.","phase":"Metallic Pd nanoparticles","particleSize":"2.03 ± 0.37 nm (TEM), 2.0 nm (CO chemisorption)","surfaceStates":"Pd 0 peak shifted to higher binding energy due to interaction with amine functional groups; high proportion of Pd 2+.","structureLink":"Amine functional groups provide a proton-scavenging effect, enabling activity even in FA-only reactants.","whyPerformsWell":"Proton scavenging effect of amine functional groups.","metricCount":"1"},{"paperId":"P231","catalystId":"P231_PERF_005","name":"Pd/C (APTES)","support":"Activated carbon","matchedSynthesis":"Pd/C (APTES)","matchedCharacterization":"Pd/C (APTES)","role":"support comparison sample","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/CNT (APTES) but using activated carbon instead of CNTs.","phase":"Metallic Pd nanoparticles","particleSize":"2.09 nm (TEM)","structureLink":"Lower activity than Pd/NH2-CNT despite similar Pd size and amine groups, attributed to mass transport limitations caused by micropores in activated carbon.","whyPerformsWell":"Presence of amine functional groups and similar Pd size, but hampered by micropores in activated carbon limiting mass transport.","metricCount":"1"},{"paperId":"P232","catalystId":"P232_PERF_001","name":"Pd0.6Au0.4/VXC-72-NH2","support":"VXC-72 carbon black","matchedSynthesis":"Pd0.6Au0.4/VXC-72-NH2","matchedCharacterization":"Pd0.6Au0.4/VXC-72-NH2","role":"active catalyst","composition":"Pd:Au = 0.6:0.4 (molar ratio)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"VXC-72 was acid-treated with HNO3 and functionalized with APTES. Pd and Au precursors were added to the suspension, stirred for 1 h at 3°C, and then reduced using NaBH4 solution for 5 h at 3°C.","phase":"PdAu alloy (confirmed by XRD after annealing at 773 K in Ar)","particleSize":"1.5 nm","surfaceStates":"Metallic Au0 and Pd0; partial electron transfer from Pd to Au due to electronegativity differences; electron transfer from VXC-72-NH2 support to PdAu NPs increasing electron density of active centers.","structureLink":"Amine functionalization converts the hydrophobic carbon surface to hydrophilic, enabling ultra-fine particle size and high dispersion. The resulting electronic modulation increases electron density on PdAu, facilitating metal-formate formation and enhancing FA dehydrogenation rate.","reactionConditions":"Dehydrogenation of formic acid in a 25 mL flask under continuous magnetic stirring (600 rpm).","selectivity":"100% H2 selectivity; no CO detected","stability":"No significant decrease in catalytic activity after the 5th run.","deactivation":"no obvious loss of N, Au and Pd in recycled catalyst determined by ICP-AES","whyPerformsWell":"Hydrophilic VXC-72-NH2 support facilitates formation of ultra fine PdAu NPs; amine groups modulate electronic structure (increasing electron density) and act as proton scavengers to facilitate O-H bond dissociation and metal-formate formation.","metricCount":"6"},{"paperId":"P232","catalystId":"P232_PERF_002","name":"Pd0.6Au0.4/VXC-72","support":"VXC-72 carbon black","matchedSynthesis":"Pd0.6Au0.4/VXC-72","matchedCharacterization":"Pd0.6Au0.4/VXC-72","role":"comparison catalyst","composition":"Pd:Au = 0.6:0.4 (molar ratio)","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Prepared using a similar method to Pd0.6Au0.4/VXC-72-NH2 but without the addition of APTES.","phase":"PdAu alloy (XRD peak at 38.7°)","particleSize":"3.0 nm","surfaceStates":"Higher binding energies for Pd 3d and Au 4f compared to Pd0.6Au0.4/VXC-72-NH2","structureLink":"Lack of amine groups results in larger particle size and lower catalytic activity.","reactionConditions":"Dehydrogenation of formic acid in a 25 mL flask under continuous magnetic stirring (600 rpm).","whyPerformsWell":"Lower activity compared to amine-functionalized support due to larger particle size (3.0 nm vs 1.5 nm) and hydrophobic surface of VXC-72.","metricCount":"1"},{"paperId":"P232","catalystId":"P232_PERF_003","name":"Au/VXC-72-NH2","matchedCharacterization":"Au/VXC-72-NH2","activeMetals":"Au","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"metallic Au (XRD peak at 38.2°)","particleSize":"null","surfaceStates":"null","structureLink":"No activity for FA dehydrogenation without Pd.","reactionConditions":"Dehydrogenation of formic acid at 298 K.","whyPerformsWell":"No activity without Pd addition.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_001","name":"Pd3Co2/CeZrSBA-15-NH2","support":"CeZrSBA-15-NH2","matchedSynthesis":"Pd3Co2/CeZrSBA-15-NH2","matchedCharacterization":"Pd3Co2/CeZrSBA-15-NH2","role":"optimized catalyst","composition":"Pd:Co = 3:2 (molar ratio)","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Metal precursors and support were mixed in deionized water, ultrasonicated for 30 min, stirred, reduced with NaBH4 for 30 min, centrifuged, washed thrice with deionized water, and vacuum dried.","phase":"PdCo alloy; HRTEM lattice spacing of 0.223 nm (between Pd 0.23 nm and Co 0.21 nm).","particleSize":"1.6 nm","surfaceStates":"Electron-rich PdCo alloy NPs; XPS shows a shift to lower binding energy for Pd0 (335.6 eV) and higher for Co0 (781.1 eV), indicating electron transfer from Co to Pd and from the amine-functionalized support via metal-support interaction (MSI).","structureLink":"The combination of ultrafine size, high dispersion, short channels in the support facilitating mass transfer, electronic synergistic effects between Pd and Co, and MSI with CeZrSBA-15-NH2 enhances catalytic activity.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution with sodium formate (SF) additive.","selectivity":"100% H2 selectivity; no evidence of CO formation (substantiated by NaOH trap and GC analysis)","stability":"Robust stability and recyclability throughout six successive runs, with negligible alterations in initial TOF and total reaction completion time.","deactivation":"Recovered catalyst showed slightly increased particle size of 2.7 nm (from 1.6 nm) and partial reduction in amine functionalities.","whyPerformsWell":"Short channels facilitate efficient mass transfer; ultrafine PdCo NPs (1.6 nm) with high dispersion; synergistic electronic effects between Pd and Co; metal-support interaction (MSI); surface amine groups acting as proton scavengers to promote O-H bond dissociation.","metricCount":"7"},{"paperId":"P233","catalystId":"P233_PERF_002","name":"Pd/CeZrSBA-15-NH2","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_003","name":"Pd4Co1/CeZrSBA-15-NH2","support":"CeZrSBA-15-NH2","matchedSynthesis":"Pd4Co1/CeZrSBA-15-NH2","role":"comparative catalyst (molar ratio study)","composition":"Pd:Co = 4:1 (molar ratio)","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Analogous to Pd3Co2/CeZrSBA-15-NH2","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_004","name":"Pd2Co3/CeZrSBA-15-NH2","support":"CeZrSBA-15-NH2","matchedSynthesis":"Pd2Co3/CeZrSBA-15-NH2","role":"comparative catalyst (molar ratio study)","composition":"Pd:Co = 2:3 (molar ratio)","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Analogous to Pd3Co2/CeZrSBA-15-NH2","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_005","name":"Pd1Co4/CeZrSBA-15-NH2","support":"CeZrSBA-15-NH2","matchedSynthesis":"Pd1Co4/CeZrSBA-15-NH2","role":"comparative catalyst (molar ratio study)","composition":"Pd:Co = 1:4 (molar ratio)","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Analogous to Pd3Co2/CeZrSBA-15-NH2","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_006","name":"Co/CeZrSBA-15-NH2","activeMetals":"Co","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_007","name":"Pd3Co2/ZrSBA-15-NH2","matchedCharacterization":"Pd3Co2/ZrSBA-15-NH2","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdCo alloy","particleSize":"2.3 nm","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_008","name":"Pd3Co2/CeSBA-15-NH2","matchedCharacterization":"Pd3Co2/CeSBA-15-NH2","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdCo alloy","particleSize":"2.5 nm","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_009","name":"Pd3Co2/SBA-15-NH2","matchedCharacterization":"Pd3Co2/SBA-15-NH2","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"PdCo alloy","particleSize":"2.6 nm","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"1"},{"paperId":"P233","catalystId":"P233_PERF_010","name":"Pd3Co2/CeZrSBA-15","support":"CeZrSBA-15-NH2","matchedSynthesis":"Pd3Co2/CeZrSBA-15-NH2","matchedCharacterization":"Pd3Co2/CeZrSBA-15","role":"optimized catalyst","composition":"Pd:Co = 3:2 (molar ratio)","activeMetals":"Pd-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Metal precursors and support were mixed in deionized water, ultrasonicated for 30 min, stirred, reduced with NaBH4 for 30 min, centrifuged, washed thrice with deionized water, and vacuum dried.","phase":"PdCo alloy","particleSize":"5.1 nm","structureLink":"Lack of surface amine groups leads to larger particle size and negligible catalytic activity.","reactionConditions":"FA dehydrogenation, 323 K, FA/SF = 1:2, n_metal/n_FA = 0.04.","metricCount":"2"},{"paperId":"P234","catalystId":"P234_PERF_001","name":"Pd/DUT-67-PZDC(10)","support":"DUT-67-PZDC","matchedSynthesis":"Pd/DUT-67-PZDC(10)","matchedCharacterization":"Pd/DUT-67-PZDC(10)","role":"optimized catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Na2PdCl4 and DUT-67-PZDC were mixed in DI water, sonicated and stirred, then reduced with NaBH4.","phase":"fcc Pd (111) plane","particleSize":"1.7 nm","surfaceStates":"Electron deficient Pd NPs resulting from electron transfer from Pd to the N sites of the DUT-67-PZDC support (indicated by a shift in N 1s peak from 400.3 eV to 399.2 eV).","structureLink":"The ultrasmall size and high dispersion expose more catalytic active sites; the hierarchical microporous structure of the MOF stabilizes the NPs; and dual N sites on the support act as proton buffers to stimulate O-H bond cleavage in formic acid.","reactionConditions":"60 °C, n_metal/n_FA = 0.02","selectivity":"100% H2 selectivity; no detectable CO formation","stability":"Maintained good stability over five consecutive runs with only minimal decline in catalytic activity.","deactivation":"Recovered catalyst showed Pd NPs aggregation (size increased from 1.7 nm to 1.9 nm) and partial loss of Pd content.","whyPerformsWell":"Synergistic effect of hierarchical pore structure, metal-support interaction (MSI), ultrasmall size (1.7 nm) for high dispersion, and N sites on the support acting as proton buffers to stimulate O-H bond cleavage in FA.","metricCount":"5"},{"paperId":"P234","catalystId":"P234_PERF_002","name":"Pd/DUT-67-PZDC(5)","support":"DUT-67-PZDC","matchedSynthesis":"Pd/DUT-67-PZDC(5), Pd/DUT-67-PZDC(15), Pd/DUT-67-PZDC(20)","role":"comparative samples with varying metal loading","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Analogous to Pd/DUT-67-PZDC(10) but with varying quantities of DUT-67-PZDC support.","reactionConditions":"60 °C, n_metal/n_FA = 0.02, FA/SF ratio 1:2","metricCount":"2"},{"paperId":"P234","catalystId":"P234_PERF_003","name":"Pd/DUT-67-PZDC(15)","support":"DUT-67-PZDC","matchedSynthesis":"Pd/DUT-67-PZDC(5), Pd/DUT-67-PZDC(15), Pd/DUT-67-PZDC(20)","role":"comparative samples with varying metal loading","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Analogous to Pd/DUT-67-PZDC(10) but with varying quantities of DUT-67-PZDC support.","reactionConditions":"60 °C, n_metal/n_FA = 0.02, FA/SF ratio 1:2","metricCount":"2"},{"paperId":"P234","catalystId":"P234_PERF_004","name":"Pd/DUT-67-PZDC(20)","support":"DUT-67-PZDC","matchedSynthesis":"Pd/DUT-67-PZDC(5), Pd/DUT-67-PZDC(15), Pd/DUT-67-PZDC(20)","role":"comparative samples with varying metal loading","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Analogous to Pd/DUT-67-PZDC(10) but with varying quantities of DUT-67-PZDC support.","reactionConditions":"60 °C, n_metal/n_FA = 0.02, FA/SF ratio 1:2","metricCount":"2"},{"paperId":"P234","catalystId":"P234_PERF_005","name":"Pd/DUT-67-PZDC-CH3","support":"DUT-67-PZDC-CH3","matchedSynthesis":"Pd/DUT-67-PZDC-CH3","matchedCharacterization":"Pd/DUT-67-PZDC-CH3","role":"comparative catalyst to study N site functionality","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd/DUT-67-PZDC(10) but using DUT-67-PZDC-CH3 support.","particleSize":"2.6 nm","structureLink":"Introduction of methyl groups weakened the proton buffer ability and led to larger particle size and lower dispersion, reducing catalytic activity.","reactionConditions":"60 °C, n_metal/n_FA = 0.02","whyPerformsWell":"Introduction of methyl groups might weaken the ability of the proton buffer.","metricCount":"2"},{"paperId":"P234","catalystId":"P234_PERF_006","name":"Pd/C","support":"C","matchedSynthesis":"Pd/C","matchedCharacterization":"Pd/C","role":"comparative catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd/DUT-67-PZDC(10) but using carbon support.","structureLink":"Less active than Pd/DUT-67-PZDC(10), demonstrating the significance of the MOF support.","reactionConditions":"60 °C, n_metal/n_FA = 0.02","metricCount":"2"},{"paperId":"P235","catalystId":"P235_PERF_001","name":"Pd60Au40/HPC-NH2","support":"amine-functionalized hierarchically porous carbon (HPC-NH2)","matchedSynthesis":"Pd(100-x)Au_x/HPC-NH2 (optimal: Pd60Au40/HPC-NH2)","matchedCharacterization":"Pd60Au40/HPC-NH2","role":"main catalyst","composition":"Pd:Au molar ratios varied (x = 0, 20, 40, 50, 60, 80, 100); optimal is Pd60Au40","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"HPC was functionalized with APTMS; Pd and Au precursors were added to the HPC-NH2 mixture, followed by reduction using NaBH4.","phase":"PdAu alloy","particleSize":"~2 nm (specifically 2.04 nm)","surfaceStates":"Pd loses partial electrons to Au due to electronegativity differences (Au: 2.4, Pd: 2.2); strong interaction between metal and amine-modified support verified by N 1s XPS shift.","structureLink":"Synergistic effect of electronic properties (electron transfer from Pd to Au), geometric effects (dilution of Pd surface ensembles by Au), basic amine sites, and hierarchically porous structure for effective mass transport of bubbles.","reactionConditions":"1.0 M FA solution in water, n(noble metal)/n(FA) = 0.01, stirring speed 720 rpm, two-necked round bottom flask with condenser","selectivity":"~100% selectivity for FA dehydrogenation; CO content ~70 ppm","stability":"reused at least 6 times without apparent change in activity","whyPerformsWell":"Synergism of electronic effect of PdAu alloy clusters, introduced basic amine sites on the support, and hierarchically porous structure for effective mass transport.","metricCount":"3"},{"paperId":"P235","catalystId":"P235_PERF_002","name":"Pd50Au50/HPC-NH2","activeMetals":"Pd-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"1.0 M FA solution in water, n(noble metal)/n(FA) = 0.01, stirring speed 720 rpm","metricCount":"1"},{"paperId":"P236","catalystId":"P236_PERF_001","name":"Pd/C-0T","matchedCharacterization":"Pd/C-0T","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Metallic Pd","particleSize":"2.5 nm (TEM), 2.4 nm (CO chemisorption)","surfaceStates":"Pd(0): 24.3%, Pd(II): 75.7% (XPS)","structureLink":"Smallest size provides highest activity due to maximum active sites and lowest activation energy (44.9 kJ/mol).","reactionConditions":"Aqueous phase dehydrogenation of formic acid","selectivity":"absence of CO gas; almost 100% H2 selectivity","whyPerformsWell":"Smallest Pd size provides the largest number of active sites and lowest activation energy for H2 desorption.","metricCount":"3"},{"paperId":"P236","catalystId":"P236_PERF_002","name":"Pd/C-4T","matchedCharacterization":"Pd/C-4T","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"Metallic Pd","particleSize":"4.8 nm (TEM), 5.0 nm (CO chemisorption)","surfaceStates":"Pd(0): 60.0%, Pd(II): 40.0% (XPS)","structureLink":"Lowest activity due to fewest active sites and highest activation energy (63.9 kJ/mol).","reactionConditions":"Aqueous phase dehydrogenation of formic acid","selectivity":"absence of CO gas; almost 100% H2 selectivity","whyPerformsWell":"Performs worst among the series due to largest Pd size, which reduces active sites and increases activation energy for H2 desorption.","metricCount":"3"},{"paperId":"P237","catalystId":"P237_PERF_001","name":"Pd/UiO-67@NN","support":"UiO-67@NN","matchedSynthesis":"Pd/UiO-67@NN","matchedCharacterization":"Pd/UiO-67@NN","role":"optimized catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Support and Pd precursor were mixed in DI water, ultrasonicated, stirred, then reduced using sodium borohydride (NaBH4).","phase":"Face-centered cubic (fcc) Pd","particleSize":"2.1 nm","surfaceStates":"Electron-rich Pd0 active sites (Pd 3d5/2 at 335.1 eV) resulting from strong metal-support interaction (MSI) where bipyridyl sites donate electrons to Pd NPs.","structureLink":"Bipyridyl sites facilitate the formation of ultrasmall, highly dispersed Pd NPs and act as proton scavengers that promote O–H bond cleavage and store excess protons, reducing recombination of adsorbed HCOO- and H+ on active sites.","reactionConditions":"Aqueous FA/SF solution, nPd/nFA = 0.02","selectivity":"100% H2 selectivity; no CO formation detected over the whole catalytic process","stability":"Remarkable recyclability even after ten consecutive catalytic cycles, with initial TOF decreasing from 1443 h-1 (cycle 1) to 1009 h-1 (cycle 10)","deactivation":"Slight growth in Pd NP size from 2.1 nm to 3.5 nm after cycling; minor decrease in Pd content from 14.86 wt% to 13.67 wt%","whyPerformsWell":"Bipyridyl sites act as proton scavengers facilitating O-H bond cleavage and storing excess protons, reducing recombination of adsorbed HCOO- and H+; strong metal-support interaction (MSI) between Pd NPs and UiO-67@NN support; surface functional group effect leading to high dispersion of ultrasmall Pd NPs (2.1 nm)","metricCount":"19"},{"paperId":"P237","catalystId":"P237_PERF_002","name":"Pd/UiO-67@N","support":"UiO-67@N","matchedSynthesis":"Pd/UiO-67@N","matchedCharacterization":"Pd/UiO-67@N","role":"comparative catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd/UiO-67@NN using UiO-67@N support.","phase":"Face-centered cubic (fcc) Pd","particleSize":"2.5 nm","surfaceStates":"Electron-rich Pd0 active sites (Pd 3d5/2 at 335.2 eV), though with weaker MSI compared to Pd/UiO-67@NN.","structureLink":"Monopyridyl groups provide some stabilization and electron donation, but result in larger particles and lower activity than bipyridyl sites.","reactionConditions":"Aqueous FA/SF solution, nPd/nFA = 0.02","whyPerformsWell":"Endowed with monopyridyl groups","metricCount":"3"},{"paperId":"P237","catalystId":"P237_PERF_003","name":"Pd/UiO-67","support":"UiO-67","matchedSynthesis":"Pd/UiO-67","matchedCharacterization":"Pd/UiO-67","role":"comparative catalyst","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd/UiO-67@NN using UiO-67 support.","phase":"Face-centered cubic (fcc) Pd","particleSize":"2.7 nm","surfaceStates":"Metallic Pd0 active sites (Pd 3d5/2 at 335.3 eV).","structureLink":"Lack of pyridyl functionalities leads to larger Pd NPs, lower dispersion, and the lowest catalytic activity among the three MOF-supported catalysts.","reactionConditions":"Aqueous FA/SF solution, nPd/nFA = 0.02","whyPerformsWell":"Devoid of pyridyl functionalities","metricCount":"3"},{"paperId":"P238","catalystId":"P238_PERF_001","name":"Pd-sCeO2/C","support":"sCeO2/C","matchedSynthesis":"Pd-sCeO2/C","matchedCharacterization":"Pd-sCeO2/C","role":"active catalyst","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Hydrothermal synthesis of sCeO2, hydrothermal assembly with biomass carbon to form sCeO2/C, wet impregnation of Pd precursor, and NaBH4 reduction.","phase":"Face-centered cubic (FCC) structure for both Pd and CeO2; heterostructure formation.","particleSize":"2.6 nm","surfaceStates":"Preferential orientation of CeO2 (110) facet; highest Ce3+/Ce4+ ratio (0.36); highest oxygen vacancy ratio (Rb = 4.01); high hydrophilicity (contact angle 31.32°).","structureLink":"Synergism between the CeO2(110) facet and abundant oxygen vacancies creates electron-rich Pd centers, lowering activation energy to 20.41 kJ/mol and increasing TOF to 2691 h-1.","reactionConditions":"1 M FA aqueous solution, nPd/nFA = 0.2%, 30 °C","selectivity":"100% selectivity to hydrogen; no gaseous CO detected","stability":"good stability in the catalyst repeatability test","deactivation":"slight decrease is due to the loss of catalyst in the recovery process","whyPerformsWell":"Synergism between CeO2 (1 1 0) facet and more oxygen vacancies; biomass carbon promotes Pd dispersion and creates defects; high hydrophilicity of sCeO2 improves performance in liquid-phase FA dehydrogenation.","metricCount":"2"},{"paperId":"P238","catalystId":"P238_PERF_002","name":"Pd/C","matchedCharacterization":"Pd/C","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"unknown","phase":"FCC structure.","particleSize":"3.0 nm","surfaceStates":"Surface contains quinones, C-O, and O=C-O functional groups; contact angle 27.93°.","structureLink":"Activity is higher than Pd-sCeO2 but lower than heterostructures due to lack of metal-oxide synergistic effects.","reactionConditions":"1 M FA aqueous solution, nPd/nFA = 0.2%, 30 °C","whyPerformsWell":"large specific surface area and surface oxygenated functional groups are conducive to obtaining highly dispersed Pd nanoparticles","metricCount":"1"},{"paperId":"P238","catalystId":"P238_PERF_003","name":"Pd-sCeO2","support":"sCeO2/C","matchedSynthesis":"Pd-sCeO2/C","matchedCharacterization":"Pd-sCeO2","role":"active catalyst","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Hydrothermal synthesis of sCeO2, hydrothermal assembly with biomass carbon to form sCeO2/C, wet impregnation of Pd precursor, and NaBH4 reduction.","phase":"FCC structure; heterostructure.","particleSize":"3.6 nm","surfaceStates":"Preferential orientation of CeO2 (110) facet; lowest oxygen vacancy ratio among the listed catalysts (ID/IF2g = 0.48); contact angle 36.92°.","structureLink":"Poor activity due to Pd agglomeration and lower defect density compared to Pd-sCeO2/C.","reactionConditions":"1 M FA aqueous solution, nPd/nFA = 0.2%, 30 °C","metricCount":"2"},{"paperId":"P238","catalystId":"P238_PERF_004","name":"Pd-rCeO2/C","support":"rCeO2/C","matchedSynthesis":"Pd-rCeO2/C","matchedCharacterization":"Pd-rCeO2/C","role":"active catalyst","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Hydrothermal synthesis of rCeO2, hydrothermal assembly with biomass carbon to form rCeO2/C, wet impregnation of Pd precursor, and NaBH4 reduction.","phase":"FCC structure; heterostructure.","particleSize":"2.5 nm","surfaceStates":"Preferential orientation of CeO2 (200) facet; observed facets include (100) and (111); Ce3+/Ce4+ ratio = 0.29; oxygen vacancy ratio (Rb) = 3.28; contact angle 50.50°.","structureLink":"Lower activity than Pd-sCeO2/C due to different crystal facets and fewer oxygen vacancies.","reactionConditions":"1 M FA aqueous solution, nPd/nFA = 0.2%, 30 °C","metricCount":"0"},{"paperId":"P238","catalystId":"P238_PERF_005","name":"Pd-oCeO2/C","support":"oCeO2/C","matchedSynthesis":"Pd-oCeO2/C","matchedCharacterization":"Pd-oCeO2/C","role":"active catalyst","composition":"Pd","activeMetals":"Pd-Ce","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"wet_impregnation","synthesis":"Hydrothermal synthesis of oCeO2, hydrothermal assembly with biomass carbon to form oCeO2/C, wet impregnation of Pd precursor, and NaBH4 reduction.","phase":"FCC structure; heterostructure.","particleSize":"2.8 nm","surfaceStates":"Preferential orientation of CeO2 (111) facet; lowest Ce3+/Ce4+ ratio (0.25); lowest oxygen vacancy ratio among heterostructures (Rb = 2.98); most hydrophobic (contact angle 79.76°).","structureLink":"Lowest activity among Pd-CeO2/C catalysts due to the dominance of the (111) facet and lower defect concentration.","reactionConditions":"1 M FA aqueous solution, nPd/nFA = 0.2%, 30 °C","metricCount":"0"},{"paperId":"P239","catalystId":"P239_PERF_001","name":"Pd/AOP AN","support":"amidoxime polyacrylonitrile (AOP AN) beads","matchedSynthesis":"Pd/AOP AN","matchedCharacterization":"Pd/AOP AN","role":"catalyst for dehydrogenation of formic acid","composition":"Pd","activeMetals":"Pd","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Pd-only","pdBased":"True","method":"wet_impregnation","synthesis":"AOP AN beads were mixed with H2PdCl4 aqueous solution, stirred for 5h at room temperature, reduced with NaBH4 for 3h at room temperature, then filtered, washed and dried.","phase":"Single metal nanoparticles","particleSize":"7 nm to 40 nm","surfaceStates":"Pd 3d5/2 and Pd 3d3/2 binding energies at 335.8 eV and 341.2 eV correspond to Pd0.","structureLink":"Larger particle size compared to Pd/PAN results in lower catalytic activity; amidoxime groups stabilize nanoparticles against leaching or agglomeration.","reactionConditions":"FA aqueous solution (0.19 M) at 323 K, additive-free","metricCount":"1"},{"paperId":"P239","catalystId":"P239_PERF_002","name":"PdNi6/AOP AN","matchedCharacterization":"PdNi6/AOP AN","activeMetals":"Pd-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","phase":"Bimetallic alloy nanoparticles","particleSize":"4 nm to 16 nm","surfaceStates":"Predominantly Pd0, with weak signals at 336.6 eV and 342.3 eV assigned to Pd2+; Ni 2p region showed poor resolution.","structureLink":"Formation of PdNi alloy nanoparticles adjusts the electronic structure of Pd for improved formic acid activation; amidoxime and cyano groups provide a basic environment for synergetic activation (forming HCOO-).","reactionConditions":"FA aqueous solution (0.19 M) at 323 K, additive-free","stability":"catalytic activity remained unchanged after seven cycles of operation","deactivation":"strong coordination ability of amidoxime groups stabilize the Pd-based NPs against leaching or agglomeration","whyPerformsWell":"formation of PdNi alloy nanoparticles which adjust the electronic structure of Pd species; amidoxime and cyano groups provide a suitable basic environment for synergetic activation of formic acid to form HCOO-","metricCount":"1"},{"paperId":"P240","catalystId":"P240_PERF_001","name":"Ni0.8Mo0.2/ZIF-67@SiO2 yolk-shell","matchedCharacterization":"Ni0.8Mo0.2/ZIF-67@SiO2 yolk-shell","activeMetals":"Ni-Mo","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","phase":"Nano-patterned Ni–Mo solid solution/alloy.","particleSize":"5.22 nm (fresh), 4.44 nm (after 10 cycles)","surfaceStates":"Fresh: Ni2+ (856.60 eV, 870.57 eV), Mo3+ (229.02 eV), Mo4+ (231.81, 234.72 eV), Mo6+ (235.13 eV), and Co(II). Used: Ni3+, Mo4+, and Co3+ are dominant.","structureLink":"High activity attributed to the synergistic effect between NiMo NPs and ZIF-67@SiO2 supporter, ultra-fine dispersion of NPs, and electron transfer from the bi-support to the NiMo NPs which facilitates C–H cleavage of formic acid.","reactionConditions":"Formic acid (FA) dehydrogenation in aqueous solution at room temperature without additives.","selectivity":"approximately 100% H2 selectivity at 25 °C; CO concentration lower than GC/TCD detection limit (10 ppm)","stability":"99% activity after 10 cycles at 25 °C with 500 rpm stirring speed","deactivation":"marginally reduced catalytic activity attributed to mean size of NiMo NPs decreasing from 5.22 to 4.44 nm","whyPerformsWell":"uniform dispersion of fine metal nanoparticles; synergistic effect between NiMo NPs and ZIF-67@SiO2 supporter; MOF@SiO2 acts as Bronsted basic active sites influencing O-H dissociation; electron transfer from bi-support to NiMo NPs catalysts","metricCount":"5"},{"paperId":"P241","catalystId":"P241_PERF_001","name":"Pt3Ni8/TiB2 (calcined at 600 °C)","support":"TiB2","matchedSynthesis":"Pt3Ni8/TiB2","matchedCharacterization":"Pt3Ni8/TiB2","role":"catalyst for formic acid dehydrogenation","composition":"Pt:Ni = 3:8","activeMetals":"Pt-Ni","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"PtNi alloy nanoparticles were synthesized via solvothermal method in DMF at 150 °C for 32 h, then loaded onto TiB2 support using incipient-wetness impregnation with ethanol as solvent, followed by thermal treatment in nitrogen.","phase":"PtNi alloy exhibiting lattice contraction","particleSize":"12.5 nm for Pt3Ni8 NPs; TiB2 overlayer thickness of 1.7 nm at 600 °C (0.82 nm at 500 °C and 2.45 nm at 800 °C)","surfaceStates":"Encapsulated by TiB2 overlayers via SMSI; electronic state characterized by electron transfer from Ni to Pt and a net transfer of electrons from metal nanoparticles to the TiB2 support.","structureLink":"SMSI-induced encapsulation prevents nanoparticle aggregation and leaching while providing active sites on the TiB2 surface; lattice contraction and magnetic interaction enhance electron transfer and SMSI, improving FA dehydrogenation activity.","reactionConditions":"10.0 M aqueous FA solution, room temperature, N2 atmosphere, vigorous stirring","selectivity":"> 99.9% toward H2 and CO2; no CO detected by GC or DRIFTS","stability":"maintained approximately 89.7% of the initial H2 production rate after 5 cycles (each cycle = 3 h)","deactivation":"SMSI prevents aggregation and leaching; activity decrease attributed to reduction in TiB2 overlayer thickness from 1.71 nm to 0.98 nm","whyPerformsWell":"Synergistic effect of PtNi alloy (lattice contraction, magnetic interaction) and strong metal-support interaction (SMSI) where TiB2 encapsulates NPs and serves as the active site.","metricCount":"5"},{"paperId":"P241","catalystId":"P241_PERF_002","name":"Pt/TiB2","support":"TiB2","matchedSynthesis":"Pt/TiB2","matchedCharacterization":"Pt/TiB2","role":"monometallic comparison catalyst","composition":"Pt only","activeMetals":"Pt","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Pt NPs synthesized via solvothermal method in DMF, then loaded onto TiB2 via IWI and thermally treated","phase":"Monometallic Pt","structureLink":"Lower stability (56.3% initial activity) compared to the alloy catalyst.","reactionConditions":"10.0 M aqueous FA solution, 25 °C, N2 atmosphere","stability":"56.3% of the initial H2 production rate after 5 cycles","metricCount":"1"},{"paperId":"P241","catalystId":"P241_PERF_003","name":"Ni/TiB2","support":"TiB2","matchedSynthesis":"Ni/TiB2","matchedCharacterization":"Ni/TiB2","role":"monometallic comparison catalyst","composition":"Ni only","activeMetals":"Ni","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"incipient_wetness_impregnation","synthesis":"Ni NPs synthesized via solvothermal method in DMF, then loaded onto TiB2 via IWI and thermally treated","phase":"Monometallic Ni","structureLink":"Lower stability (51.9% initial activity) compared to the alloy catalyst.","reactionConditions":"10.0 M aqueous FA solution, 25 °C, N2 atmosphere","stability":"51.9% of the initial H2 production rate after 5 cycles","metricCount":"1"},{"paperId":"P241","catalystId":"P241_PERF_004","name":"unloaded TiB2","activeMetals":"Ti","activeMetalCount":"1","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"10.0 M aqueous FA solution, 25 °C, N2 atmosphere","metricCount":"1"},{"paperId":"P241","catalystId":"P241_PERF_005","name":"PtAu/TiB2","activeMetals":"Pt-Au","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"10.0 M aqueous FA solution, 25 °C, N2 atmosphere","metricCount":"1"},{"paperId":"P241","catalystId":"P241_PERF_006","name":"PtCo/TiB2","activeMetals":"Pt-Co","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Non-Pd or Pd-free","pdBased":"False","method":"unknown","reactionConditions":"10.0 M aqueous FA solution, 25 °C, N2 atmosphere","metricCount":"1"},{"paperId":"P241","catalystId":"P241_PERF_007","name":"PdRu/TiB2","activeMetals":"Pd-Ru","activeMetalCount":"2","activeMetalSource":"catalyst_name","metalClass":"Pd-based multimetal","pdBased":"True","method":"unknown","reactionConditions":"10.0 M aqueous FA solution, 25 °C, N2 atmosphere","metricCount":"1"}],"activities":[{"activityId":"P001_PERF_001_ACT_001","paperId":"P001","catalystId":"P001_PERF_001","catalyst":"Pt nanoclusters on 1D GaN nanowires","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"sol_immobilization","metric":"hydrogen production rate","value":"54.89","metricType":"rate","numericValue":"54.89","unit":"mmol · gcat-1 · h-1","reactionContext":"Formic acid decomposition in a commercial stainless-steel reactor (0.25 L) under atmospheric argon.","temperatureC":"30.0","solution":"liquid formic acid","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"liquid formic acid\", \"formic_acid_amount_or_concentration\": \"1 ml\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"0.24 mg · cm-2\", \"metal_amount_or_substrate_to_metal_ratio\": \"0.026 μmol · cm-2 Pt\", \"reactor_or_atmosphere\": \"stainless-steel reactor, atmospheric argon\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"1 h\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","definition":"Product yield per unit area of catalyst per hour (mol · cm-2 · h-1) / Mass of catalyst per unit area (g · cm-2)","selectivity":"nearly 100%","stability":"no great decrease in activity in the first 200 h","whyPerformsWell":"Synergistic effect between Pt nanoclusters and GaN reduces energy barrier for HCOO* formation (O-H dissociation) while increasing the energy barrier of HCOOH -> HCO* + *OH, improving both activity and selectivity.","temperatureReported":"30 °C","formicAcid":"1 ml","catalystAmount":"0.24 mg · cm-2","metalAmountOrRatio":"0.026 μmol · cm-2 Pt","reactorOrAtmosphere":"stainless-steel reactor, atmospheric argon","timeOrConversionBasis":"1 h"},{"activityId":"P001_PERF_001_ACT_002","paperId":"P001","catalystId":"P001_PERF_001","catalyst":"Pt nanoclusters on 1D GaN nanowires","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"sol_immobilization","metric":"TOF Pt","value":"505.7","metricType":"TOF","numericValue":"505.7","unit":"h-1","tof":"505.7","reactionContext":"Formic acid decomposition in a commercial stainless-steel reactor (0.25 L) under atmospheric argon.","temperatureC":"30.0","solution":"liquid formic acid","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"liquid formic acid\", \"formic_acid_amount_or_concentration\": \"1 ml\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"0.24 mg · cm-2\", \"metal_amount_or_substrate_to_metal_ratio\": \"0.026 μmol · cm-2 Pt\", \"reactor_or_atmosphere\": \"stainless-steel reactor, atmospheric argon\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"1 h\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pt","definition":"H2 production amount (μmol) / (Content of immobilized Pt nanoparticles (μmol) × Reaction time (h))","selectivity":"nearly 100%","stability":"no great decrease in activity in the first 200 h","whyPerformsWell":"Synergistic effect between Pt nanoclusters and GaN reduces energy barrier for HCOO* formation (O-H dissociation) while increasing the energy barrier of HCOOH -> HCO* + *OH, improving both activity and selectivity.","temperatureReported":"30 °C","formicAcid":"1 ml","catalystAmount":"0.24 mg · cm-2","metalAmountOrRatio":"0.026 μmol · cm-2 Pt","reactorOrAtmosphere":"stainless-steel reactor, atmospheric argon","timeOrConversionBasis":"1 h"},{"activityId":"P001_PERF_001_ACT_003","paperId":"P001","catalystId":"P001_PERF_001","catalyst":"Pt nanoclusters on 1D GaN nanowires","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"sol_immobilization","metric":"hydrogen production rate","value":"1592.1","metricType":"rate","numericValue":"1592.1","unit":"mmol · gcat-1 · h-1","reactionContext":"Formic acid decomposition in a commercial stainless-steel reactor (0.25 L) under atmospheric argon.","temperatureC":"150.0","solution":"liquid formic acid","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"150 °C\", \"reaction_solution\": \"liquid formic acid\", \"formic_acid_amount_or_concentration\": \"1 ml\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"0.24 mg · cm-2\", \"metal_amount_or_substrate_to_metal_ratio\": \"0.025 μmol Pt · cm-2\", \"reactor_or_atmosphere\": \"stainless-steel reactor, atmospheric argon\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"1 h\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","definition":"Product yield per unit area of catalyst per hour (mol · cm-2 · h-1) / Mass of catalyst per unit area (g · cm-2)","selectivity":"nearly 100%","stability":"no great decrease in activity in the first 200 h","whyPerformsWell":"Synergistic effect between Pt nanoclusters and GaN reduces energy barrier for HCOO* formation (O-H dissociation) while increasing the energy barrier of HCOOH -> HCO* + *OH, improving both activity and selectivity.","temperatureReported":"150 °C","formicAcid":"1 ml","catalystAmount":"0.24 mg · cm-2","metalAmountOrRatio":"0.025 μmol Pt · cm-2","reactorOrAtmosphere":"stainless-steel reactor, atmospheric argon","timeOrConversionBasis":"1 h"},{"activityId":"P001_PERF_001_ACT_004","paperId":"P001","catalystId":"P001_PERF_001","catalyst":"Pt nanoclusters on 1D GaN nanowires","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"sol_immobilization","metric":"TOF Pt","value":"14667.2","metricType":"TOF","numericValue":"14667.2","unit":"h-1","tof":"14667.2","reactionContext":"Formic acid decomposition in a commercial stainless-steel reactor (0.25 L) under atmospheric argon.","temperatureC":"150.0","solution":"liquid formic acid","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"150 °C\", \"reaction_solution\": \"liquid formic acid\", \"formic_acid_amount_or_concentration\": \"1 ml\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"0.24 mg · cm-2\", \"metal_amount_or_substrate_to_metal_ratio\": \"0.026 μmol · cm-2 Pt\", \"reactor_or_atmosphere\": \"stainless-steel reactor, atmospheric argon\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"1 h\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pt","definition":"H2 production amount (μmol) / (Content of immobilized Pt nanoparticles (μmol) × Reaction time (h))","selectivity":"nearly 100%","stability":"no great decrease in activity in the first 200 h","whyPerformsWell":"Synergistic effect between Pt nanoclusters and GaN reduces energy barrier for HCOO* formation (O-H dissociation) while increasing the energy barrier of HCOOH -> HCO* + *OH, improving both activity and selectivity.","temperatureReported":"150 °C","formicAcid":"1 ml","catalystAmount":"0.24 mg · cm-2","metalAmountOrRatio":"0.026 μmol · cm-2 Pt","reactorOrAtmosphere":"stainless-steel reactor, atmospheric argon","timeOrConversionBasis":"1 h"},{"activityId":"P001_PERF_001_ACT_005","paperId":"P001","catalystId":"P001_PERF_001","catalyst":"Pt nanoclusters on 1D GaN nanowires","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"sol_immobilization","metric":"TON Pt","value":"306981","metricType":"TON","numericValue":"306981.0","unit":"mol H2 per mole Pt","reactionContext":"Formic acid decomposition in a commercial stainless-steel reactor (0.25 L) under atmospheric argon.","temperatureC":"75.0","solution":"liquid formic acid","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"75 °C\", \"reaction_solution\": \"liquid formic acid\", \"formic_acid_amount_or_concentration\": \"1 ml\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"0.24 mg · cm-2\", \"metal_amount_or_substrate_to_metal_ratio\": \"0.026 μmol · cm-2 Pt\", \"reactor_or_atmosphere\": \"stainless-steel reactor, atmospheric argon\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"200 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\"water\", \"catalyst_amount\": \"~ 4 g\", \"metal_amount_or_substrate_to_metal_ratio\": \"5 wt% Pd\", \"reactor_or_atmosphere\": \"fixed-bed reactor; Helium carrier gas (17 NmL min-1)\", \"stirring_or_flow_condition\": \"continuous mode; liquid flow rate (QL) = 0.25 mL min-1; spatial time (τ) = 267 gCAT·h·L-1\", \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","definition":"XFA (%) = ((CFA,0 - CFA) / CFA,0) * 100","selectivity":"CO-free H2; H2 and CO2 were the unique species detected; H2/CO2 molar ratio ~ 1.2","stability":"Activity decreased from 1 h of operation, completely deactivated after 3 h on stream; activity restored after drying at 60 °C overnight (2nd use)","whyPerformsWell":"Presence of both Pd0 and Pd2+ species; robust structured catalyst conformation reduces pressure drop compared to powders","temperatureReported":"55 °C","formicAcid":"1 M","solvent":"water","catalystAmount":"~ 4 g","metalAmountOrRatio":"5 wt% 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\"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"~ 4 g\", \"metal_amount_or_substrate_to_metal_ratio\": \"5 wt% Pd\", \"reactor_or_atmosphere\": \"fixed-bed reactor; Helium carrier gas (17 NmL min-1)\", \"stirring_or_flow_condition\": \"continuous mode; liquid flow rate (QL) = 0.25 mL min-1; spatial time (τ) = 267 gCAT·h·L-1\", \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","selectivity":"CO-free H2; H2 and CO2 were the unique species detected; H2/CO2 molar ratio ~ 1.2","stability":"Activity decreased from 1 h of operation, completely deactivated after 3 h on stream; activity restored after drying at 60 °C overnight (2nd use)","whyPerformsWell":"Presence of both Pd0 and Pd2+ species; robust structured catalyst conformation reduces pressure drop compared to powders","temperatureReported":"55 °C","formicAcid":"1 M","solvent":"water","catalystAmount":"~ 4 g","metalAmountOrRatio":"5 wt% Pd","reactorOrAtmosphere":"fixed-bed reactor; Helium carrier gas (17 NmL min-1)","stirringOrFlow":"continuous mode; liquid flow rate (QL) = 0.25 mL min-1; spatial time (τ) = 267 gCAT·h·L-1","timeOrConversionBasis":"initial"},{"activityId":"P003_PERF_001_ACT_001","paperId":"P003","catalystId":"P003_PERF_001","catalyst":"3D Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"XFA (conversion)","value":"99","metricType":"conversion","numericValue":"99.0","unit":"%","reactionContext":"Fixed-bed reactor, continuous mode, spatial time (s) = 160 gCAT hL-1, carrier gas He at 17 N mL min-1, ambient pressure (1 atm), liquid flow rate (QL) = 0.25 mL min-1","temperatureC":"55.0","solution":"formic acid solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"55 °C\", \"reaction_solution\": \"formic acid solution\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"~2.5 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"fixed-bed reactor / He carrier gas\", \"stirring_or_flow_condition\": \"continuous mode, QL = 0.25 mL min-1\", \"time_point_or_conversion_basis\": \"maximum conversion (XFA max)\"}","basis":"unclear","basisRaw":"unclear","definition":"(CFA,0 - CFA) / CFA,0 * 100","selectivity":"100% selective for the dehydrogenation of FA; CO-free hydrogen produced","stability":"Good catalytic stability and recyclability. Activity could be totally recovered after 1st use via dry treatment at 60 °C. 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Activity could be totally recovered after 1st use via dry treatment at 60 °C. 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Activity could be totally recovered after 1st use via dry treatment at 60 °C. 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Activity could be totally recovered after 1st use via dry treatment at 60 °C. Irreversible deactivation observed from 4th use at 25 °C and 3rd use at 55 °C.","whyPerformsWell":"High porosity (86%), small Pd particle size (~2 nm), and high Pd2+/Pd0 ratio (1.4) in fresh catalyst.","temperatureReported":"25 °C","formicAcid":"unclear","solvent":"water","catalystAmount":"~2.5 g","reactorOrAtmosphere":"fixed-bed reactor / 1 atm","stirringOrFlow":"continuous mode, s = 160 gCAT hL-1","timeOrConversionBasis":"ambient conditions"},{"activityId":"P003_PERF_001_ACT_005","paperId":"P003","catalystId":"P003_PERF_001","catalyst":"3D Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"V*H2 (hydrogen volume per gram of catalyst)","value":"1.2-0.3","metricType":"other","numericValue":"1.2","unit":"L gCAT-1","reactionContext":"Fixed-bed reactor, continuous mode, spatial time (s) = 160 gCAT hL-1, carrier gas He at 17 N mL min-1, ambient pressure (1 atm), liquid flow rate (QL) = 0.25 mL min-1","temperatureC":"55.0","solution":"formic acid solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"55 °C\", \"reaction_solution\": \"formic acid solution\", \"formic_acid_amount_or_concentration\": \"1 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"~2.5 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"fixed-bed reactor / He carrier gas\", \"stirring_or_flow_condition\": \"continuous mode, QL = 0.25 mL min-1\", \"time_point_or_conversion_basis\": \"over 5 cycles\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","selectivity":"100% selective for the dehydrogenation of FA; CO-free hydrogen produced","stability":"Good catalytic stability and recyclability. Activity could be totally recovered after 1st use via dry treatment at 60 °C. 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Activity could be totally recovered after 1st use via dry treatment at 60 °C. Irreversible deactivation observed from 4th use at 25 °C and 3rd use at 55 °C.","whyPerformsWell":"High porosity (86%), small Pd particle size (~2 nm), and high Pd2+/Pd0 ratio (1.4) in fresh catalyst.","temperatureReported":"25 °C","formicAcid":"1 M","solvent":"water","catalystAmount":"~2.5 g","reactorOrAtmosphere":"fixed-bed reactor / He carrier gas","stirringOrFlow":"continuous mode, QL = 0.25 mL min-1","timeOrConversionBasis":"over 5 cycles"},{"activityId":"P004_PERF_001_ACT_001","paperId":"P004","catalystId":"P004_PERF_001","catalyst":"Pd0.8Au0.2/1'","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"TOF","value":"1854","metricType":"TOF","numericValue":"1854.0","unit":"h-1","tof":"1854.0","reactionContext":"Dehydrogenation of formic acid at 333 K","temperatureC":"59.85","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"333 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"total metal content 0.25 mmol g-1\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial; 100% conversion of FA (110 mL gas within 50 min)\"}","basis":"unclear","basisRaw":"unclear","definition":"derived from eqn (S3)","selectivity":"No CO detected; H2 and CO2 generated with a 1:1 volume ratio","stability":"Activity decreased after the fourth run at 333 K","whyPerformsWell":"High surface area (527 m2 g-1) for NP encapsulation; double-solvent method ensures tiny NPs; uncoordinated N atoms act as Lewis base sites promoting HCOO- generation and anchor PdAu NPs; alloying effect of PdAu modifies electronic structure of Pd","temperatureReported":"333 K","metalAmountOrRatio":"total metal content 0.25 mmol g-1","timeOrConversionBasis":"initial; 100% conversion of FA (110 mL gas within 50 min)"},{"activityId":"P004_PERF_001_ACT_002","paperId":"P004","catalystId":"P004_PERF_001","catalyst":"Pd0.8Au0.2/1'","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"activation energy (Ea)","value":"75.61","metricType":"activation_energy","numericValue":"75.61","unit":"kJ mol-1","reactionContext":"Dehydrogenation of formic acid at 333 K","temperatureC":"42.35","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"298 to 333 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius equation (eqn S2)","selectivity":"No CO detected; H2 and CO2 generated with a 1:1 volume ratio","stability":"Activity decreased after the fourth run at 333 K","whyPerformsWell":"High surface area (527 m2 g-1) for NP encapsulation; double-solvent method ensures tiny NPs; uncoordinated N atoms act as Lewis base sites promoting HCOO- generation and anchor PdAu NPs; alloying effect of PdAu modifies electronic structure of Pd","temperatureReported":"298 to 333 K"},{"activityId":"P005_PERF_001_ACT_001","paperId":"P005","catalystId":"P005_PERF_001","catalyst":"Pd/BPC (optimal: C:B ratio 1:5, calcined at 900 °C, reduced at 60 °C)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"Gas volume (H2 and CO2)","value":"105","metricType":"other","numericValue":"105.0","unit":"mL","reactionContext":"50 °C water bath, 30 mg catalyst, 10 mL deionized water, 1 mL sodium formate solution (5 mol/L), 90 min reaction time","temperatureC":"50.0","solution":"deionized water","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"deionized water\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"1 mL of 5 mol/L sodium formate solution\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass bottle reactor\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"90 min\"}","basis":"unclear","basisRaw":"unclear","definition":"volume of mixed H2 and CO2 collected via drainage method","selectivity":"no poisonous CO gas produced","stability":"excellent recyclability with no significant reduction after five consecutive cycles","whyPerformsWell":"Boron doping facilitates homogenous distribution of Pd nanoparticles and induces a stronger support-metal interaction, modifying electronic properties (reduction of electron density of Pd 3d orbitals) and preventing agglomeration/sintering. 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\"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"HCOONa\", \"solvent\": \"water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"U-tube under ambient atmosphere\", \"stirring_or_flow_condition\": \"agitated by reformed gases\", \"time_point_or_conversion_basis\": \"2 h\"}","basis":"unclear","basisRaw":"unclear","selectivity":"CO content in reformed gases was 17.18 mg/m3; decomposition mainly proceeded via HCOOH -> H2 + CO2","stability":"Reused for 3 cycles; activity reduced slightly in the 2nd and 3rd cycle but not changed obviously overall","whyPerformsWell":"Spongelike structure with larger nanopores providing more active sites that benefit O-H bond dissociation and subsequent C-H bond cleavage","temperatureReported":"25 °C","formicAcid":"6.64 mol/L","formate":"3.32 mol/L HCOONa","baseOrAdditive":"HCOONa","solvent":"water","catalystAmount":"10 mg","reactorOrAtmosphere":"U-tube under ambient 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null, \"reactor_or_atmosphere\": \"U-tube under ambient atmosphere\", \"stirring_or_flow_condition\": \"agitated by reformed gases\", \"time_point_or_conversion_basis\": \"2 h\"}","basis":"unclear","basisRaw":"unclear","selectivity":"CO content in reformed gases was 17.18 mg/m3; decomposition mainly proceeded via HCOOH -> H2 + CO2","stability":"Reused for 3 cycles; activity reduced slightly in the 2nd and 3rd cycle but not changed obviously overall","whyPerformsWell":"Spongelike structure with larger nanopores providing more active sites that benefit O-H bond dissociation and subsequent C-H bond cleavage","temperatureReported":"25 °C","formicAcid":"6.64 mol/L","formate":"3.32 mol/L HCOONa","baseOrAdditive":"HCOONa","solvent":"water","catalystAmount":"10 mg","reactorOrAtmosphere":"U-tube under ambient atmosphere","stirringOrFlow":"agitated by reformed gases","timeOrConversionBasis":"2 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\"stirring_or_flow_condition\": \"agitated by reformed gases\", \"time_point_or_conversion_basis\": \"10 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"CO content in reformed gases was 17.18 mg/m3; decomposition mainly proceeded via HCOOH -> H2 + CO2","stability":"Reused for 3 cycles; activity reduced slightly in the 2nd and 3rd cycle but not changed obviously overall","whyPerformsWell":"Spongelike structure with larger nanopores providing more active sites that benefit O-H bond dissociation and subsequent C-H bond cleavage","temperatureReported":"25 °C","formicAcid":"6.64 mol/L","formate":"3.32 mol/L HCOONa","baseOrAdditive":"HCOONa","solvent":"water","catalystAmount":"10 mg","reactorOrAtmosphere":"U-tube under ambient atmosphere","stirringOrFlow":"agitated by reformed gases","timeOrConversionBasis":"10 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\"formate_or_sodium_formate_amount_or_concentration\": \"7.5 mmol PF\", \"formic_acid_to_formate_ratio\": \"1:3\", \"base_or_additive\": \"potassium formate (PF)\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"25 mL round-bottom flask\", \"stirring_or_flow_condition\": \"stirred\", \"time_point_or_conversion_basis\": \"10% conversion of formic acid\"}","basis":"unclear","basisRaw":"unclear","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 82% of initial catalytic activity and provided 95% conversion after the fifth consecutive cycle/run.","whyPerformsWell":"MnOx nanoparticles act as CO-sponges enhancing catalytic activity and CO-resistivity; air activation maintains spherical morphology and provides more oxygen-containing functional groups.","temperatureReported":"50 °C","formicAcid":"2.5 mmol","formate":"7.5 mmol 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\"2.5 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"7.5 mmol PF\", \"formic_acid_to_formate_ratio\": \"1:3\", \"base_or_additive\": \"potassium formate (PF)\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"25 mL round-bottom flask\", \"stirring_or_flow_condition\": \"stirred\", \"time_point_or_conversion_basis\": \"100% conversion of formic acid\"}","basis":"unclear","basisRaw":"unclear","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 82% of initial catalytic activity and provided 95% conversion after the fifth consecutive cycle/run.","whyPerformsWell":"MnOx nanoparticles act as CO-sponges enhancing catalytic activity and CO-resistivity; air activation maintains spherical morphology and provides more oxygen-containing functional groups.","temperatureReported":"50 °C","formicAcid":"2.5 mmol","formate":"7.5 mmol 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\"formic_acid_amount_or_concentration\": \"0.19 mL (95%) in 10 mL water\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"0.055 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"100 mL Teflon-lined reactor, nitrogen purge for 30 min\", \"stirring_or_flow_condition\": \"without stirring\", \"time_point_or_conversion_basis\": \"20% of conversion\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"PV / (RT nPd t)","selectivity":"volumetric ratio of H2 to CO2 was 50.9:49.1; CO not detected (<10 ppm)","whyPerformsWell":"Trade-off pore structure between easy diffusion of molecules and confinement of active metal nanoparticles (Pd particle size 1.60 nm).","temperatureReported":"25 °C","formicAcid":"0.19 mL (95%) in 10 mL 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\"formic_acid_amount_or_concentration\": \"0.19 mL (95%) in 10 mL water\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"0.055 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"100 mL Teflon-lined reactor, nitrogen purge for 30 min\", \"stirring_or_flow_condition\": \"without stirring\", \"time_point_or_conversion_basis\": \"20% of conversion\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"PV / (RT nPd t)","whyPerformsWell":"Pore size did not provide easy diffusion of reactant and product molecules.","temperatureReported":"25 °C","formicAcid":"0.19 mL (95%) in 10 mL water","baseOrAdditive":"additive-free","solvent":"distilled water","catalystAmount":"0.055 g","reactorOrAtmosphere":"100 mL Teflon-lined reactor, nitrogen purge for 30 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\"base_or_additive\": \"additive-free\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"0.055 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"100 mL Teflon-lined reactor, nitrogen purge for 30 min\", \"stirring_or_flow_condition\": \"without stirring\", \"time_point_or_conversion_basis\": \"20% of conversion\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"PV / (RT nPd t)","whyPerformsWell":"Large pore size did not give the confinement effect of active metal nanoparticles, resulting in increased Pd nanoparticle size (2.58 nm) and aggregation.","temperatureReported":"25 °C","formicAcid":"0.19 mL (95%) in 10 mL water","baseOrAdditive":"additive-free","solvent":"distilled water","catalystAmount":"0.055 g","reactorOrAtmosphere":"100 mL Teflon-lined reactor, nitrogen purge for 30 min","stirringOrFlow":"without stirring","timeOrConversionBasis":"20% of 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tested at 100 °C. Lower bound TTON of >=7500 mol H2/mol catalyst.","whyPerformsWell":"Strong Metal-Molecular Support Interaction (SMMSI) due to free amine groups from APTS facilitating FA adsorption/storage and O-H bond cleavage; ALD-SiO2 layers protect against sintering and leaching; trimetallic alloy structure provides high CO poisoning resistivity.","temperatureReported":"room temperature","formicAcid":"0.175 M","formate":"0.175 M SF","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate (SF)","solvent":"water","reactorOrAtmosphere":"jacketed one-necked reaction flask","stirringOrFlow":"900 rpm","timeOrConversionBasis":"initial"},{"activityId":"P020_PERF_001_ACT_002","paperId":"P020","catalystId":"P020_PERF_001","catalyst":"Pd0.60Co0.18Ni0.22/TiO2-ALD-SiO2 (6 cycles)","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"3","method":"unknown","metric":"selectivity","value":">99","metricType":"selectivity","numericValue":"99.0","unit":"%","reactionContext":"Dehydrogenation of aqueous formic acid solution at room temperature","solution":"aqueous FA solution","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"room temperature\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"0.175 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.175 M SF\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": \"900 rpm\", \"time_point_or_conversion_basis\": \"almost complete conversion\"}","basis":"unclear","basisRaw":"unclear","selectivity":">99% dehydrogenation selectivity; CO below detection limit (<10 ppm)","stability":"Retains >=83% of initial catalytic activity and selectivity at >90% conversion even at the 20th reuse when tested at 100 °C. 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dehydrogenation, 1.0 M FA (5.0 mL), aqueous solution, without any additive","solution":"aqueous","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"1.0 M (5.0 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"37 min\"}","basis":"unclear","basisRaw":"unclear","whyPerformsWell":"Better activity than Au0.3Pd0.7/BN due to more ultrafine particle size (~4.1 nm) and higher active site concentration.","formicAcid":"1.0 M (5.0 mL)","baseOrAdditive":"none","solvent":"water","timeOrConversionBasis":"37 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\"252 min\"}","basis":"unclear","basisRaw":"unclear","formicAcid":"1.0 M (5.0 mL)","baseOrAdditive":"none","solvent":"water","timeOrConversionBasis":"252 min"},{"activityId":"P021_PERF_004_ACT_001","paperId":"P021","catalystId":"P021_PERF_004","catalyst":"Au0.3Pd0.7 NPs (free)","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"conversion","value":"27","metricType":"conversion","numericValue":"27.0","unit":"%","reactionContext":"Formic acid (FA) dehydrogenation, 1.0 M FA (5.0 mL), aqueous solution, without any additive","solution":"aqueous","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"1.0 M (5.0 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": null, 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\"formic_acid_amount_or_concentration\": \"2.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2.5 M\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-neck flask, ambient atmosphere\", \"stirring_or_flow_condition\": \"magnetic stirring\", \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","selectivity":"100% hydrogen generation and selectivity to CO2 and H2; CO-free","stability":"Productivity of hydrogen remained almost unchanged after two cycles; morphology and structure maintained after three cycles.","whyPerformsWell":"Coordinated effect from Au-Pd alloying and nitrogen-decorated carbon nanosheets; specifically, a high ratio of graphitic N to pyridinic N modifies electron density distribution and minimizes metal nanoparticle size (mean diameter ~1.82 nm).","temperatureReported":"25 °C","formicAcid":"2.5 M","formate":"2.5 M","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"100 mg","reactorOrAtmosphere":"two-neck flask, ambient atmosphere","stirringOrFlow":"magnetic stirring","timeOrConversionBasis":"initial"},{"activityId":"P022_PERF_001_ACT_002","paperId":"P022","catalystId":"P022_PERF_001","catalyst":"AuPd/n-CNS-Th-160","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"TOF","value":"1896","metricType":"TOF","numericValue":"1896.0","unit":"h-1","tof":"1896.0","reactionContext":"Dehydrogenation of FA/SF solution in deionized water under ambient atmosphere with magnetic stirring.","temperatureC":"60.0","solution":"FA/SF solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"FA/SF solution\", \"formic_acid_amount_or_concentration\": \"2.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2.5 M\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-neck flask, ambient atmosphere\", \"stirring_or_flow_condition\": \"magnetic stirring\", \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","selectivity":"100% hydrogen generation and selectivity to CO2 and H2; CO-free","stability":"Productivity of hydrogen remained almost unchanged after two cycles; morphology and structure maintained after three cycles.","whyPerformsWell":"Coordinated effect from Au-Pd alloying and nitrogen-decorated carbon nanosheets; specifically, a high ratio of graphitic N to pyridinic N modifies electron density distribution and minimizes metal nanoparticle size (mean diameter ~1.82 nm).","temperatureReported":"60 °C","formicAcid":"2.5 M","formate":"2.5 M","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"100 mg","reactorOrAtmosphere":"two-neck flask, ambient atmosphere","stirringOrFlow":"magnetic stirring","timeOrConversionBasis":"initial"},{"activityId":"P022_PERF_001_ACT_003","paperId":"P022","catalystId":"P022_PERF_001","catalyst":"AuPd/n-CNS-Th-160","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"gas released","value":"215","metricType":"other","numericValue":"215.0","unit":"mL","reactionContext":"Dehydrogenation of FA/SF solution in deionized water under ambient atmosphere with magnetic stirring.","temperatureC":"24.85","solution":"FA/SF solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"FA/SF solution\", \"formic_acid_amount_or_concentration\": \"2.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2.5 M\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-neck flask, ambient atmosphere\", \"stirring_or_flow_condition\": \"magnetic stirring\", \"time_point_or_conversion_basis\": \"10 min\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","selectivity":"100% hydrogen generation and selectivity to CO2 and H2; CO-free","stability":"Productivity of hydrogen remained almost unchanged after two cycles; morphology and structure maintained after three cycles.","whyPerformsWell":"Coordinated effect from Au-Pd alloying and nitrogen-decorated carbon nanosheets; specifically, a high ratio of graphitic N to pyridinic N modifies electron density distribution and minimizes metal nanoparticle size (mean diameter ~1.82 nm).","temperatureReported":"298 K","formicAcid":"2.5 M","formate":"2.5 M","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"100 mg","reactorOrAtmosphere":"two-neck flask, ambient atmosphere","stirringOrFlow":"magnetic stirring","timeOrConversionBasis":"10 min"},{"activityId":"P022_PERF_002_ACT_001","paperId":"P022","catalystId":"P022_PERF_002","catalyst":"AuPd/AC","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"initial TOF","value":"approx. 270","metricType":"TOF","numericValue":"270.0","unit":"h-1","tof":"270.0","reactionContext":"FA/SF solution (2.5 M/2.5 M, 2 mL) at 25 °C under ambient atmosphere.","temperatureC":"25.0","solution":"FA/SF solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"FA/SF solution\", \"formic_acid_amount_or_concentration\": \"2.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2.5 M\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"ambient atmosphere\", \"stirring_or_flow_condition\": \"magnetic stirring\", \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","definition":"Calculated as 1/1.7 of AuPd/n-CNS-Th-160 TOF","temperatureReported":"25 °C","formicAcid":"2.5 M","formate":"2.5 M","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"100 mg","reactorOrAtmosphere":"ambient atmosphere","stirringOrFlow":"magnetic stirring","timeOrConversionBasis":"initial"},{"activityId":"P022_PERF_003_ACT_001","paperId":"P022","catalystId":"P022_PERF_003","catalyst":"commercial 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\"initial\"}","basis":"unclear","basisRaw":"unclear","definition":"Calculated as 1/2.8 of AuPd/n-CNS-Th-160 TOF","temperatureReported":"25 °C","formicAcid":"2.5 M","formate":"2.5 M","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"100 mg","reactorOrAtmosphere":"ambient atmosphere","stirringOrFlow":"magnetic stirring","timeOrConversionBasis":"initial"},{"activityId":"P023_PERF_001_ACT_001","paperId":"P023","catalystId":"P023_PERF_001","catalyst":"Au-Pd-SBA-15-NH2-TD","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"TOF","value":"631","metricType":"TOF","numericValue":"631.0","unit":"hours^-1","tof":"2271600.0","reactionContext":"308 K, 100 mg catalyst, 5 mL H2O + 0.4 mL HCOOH (0.5 M) + 70 mg sodium formate, stirred in a water bath in a two-necked round-bottom flask","temperatureC":"24.85","solution":"5 mL H2O + 0.4 mL HCOOH (0.5 M) + 70 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water bath in a two-necked round-bottom flask","solution":"5 mL H2O + 0.4 mL HCOOH (0.5 M) + 70 mg sodium formate","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": \"5 mL H2O + 0.4 mL HCOOH (0.5 M) + 70 mg sodium formate\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"70 mg\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"H2O\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-necked round-bottom flask\", \"stirring_or_flow_condition\": \"stirred in a water bath\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"CO was not detected; high selectivity for H2 and CO2","stability":"Activity reduced by no more than 11% after three cycles","whyPerformsWell":"Synergistic effect between 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multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"TOF","value":"251","metricType":"TOF","numericValue":"251.0","unit":"h-1","tof":"251.0","reactionContext":"Formic acid dehydrogenation in a three-necked round-bottom flask placed in a thermostatic water bath.","temperatureC":"29.85","solution":"aqueous formic acid","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"303 K\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"5.3 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"DI water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"three-necked round-bottom flask\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"Hydrogen selectivity close to 100%; no carbon monoxide detected at the detection limit of 10 ppm.","stability":"Stable and active under five cycle performance tests at 50 °C with no significant attenuation in decomposition rate or amount of gas produced.","whyPerformsWell":"Formation of small (2.05 nm) and highly dispersed PdCr NPs due to amino groups; synergistic effect between bimetal and support; electron-donor amino groups modulate the electronic structure of catalytic sites, increasing electron cloud density and alkalinity.","temperatureReported":"303 K","formicAcid":"5.3 mmol","solvent":"DI water","reactorOrAtmosphere":"three-necked round-bottom flask"},{"activityId":"P027_PERF_001_ACT_003","paperId":"P027","catalystId":"P027_PERF_001","catalyst":"Pd0.6Cr0.4/OPDA-SmMn2O5","activeMetals":"Pd-Cr","metalClass":"Pd-based 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to 100%; no carbon monoxide detected at the detection limit of 10 ppm.","stability":"Stable and active under five cycle performance tests at 50 °C with no significant attenuation in decomposition rate or amount of gas produced.","whyPerformsWell":"Formation of small (2.05 nm) and highly dispersed PdCr NPs due to amino groups; synergistic effect between bimetal and support; electron-donor amino groups modulate the electronic structure of catalytic sites, increasing electron cloud density and alkalinity.","temperatureReported":"313 K","formicAcid":"5.3 mmol","solvent":"DI water","reactorOrAtmosphere":"three-necked round-bottom flask"},{"activityId":"P027_PERF_001_ACT_004","paperId":"P027","catalystId":"P027_PERF_001","catalyst":"Pd0.6Cr0.4/OPDA-SmMn2O5","activeMetals":"Pd-Cr","metalClass":"Pd-based 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close to 100%; no carbon monoxide detected at the detection limit of 10 ppm.","stability":"Stable and active under five cycle performance tests at 50 °C with no significant attenuation in decomposition rate or amount of gas produced.","whyPerformsWell":"Formation of small (2.05 nm) and highly dispersed PdCr NPs due to amino groups; synergistic effect between bimetal and support; electron-donor amino groups modulate the electronic structure of catalytic sites, increasing electron cloud density and alkalinity.","temperatureReported":"333 K","formicAcid":"5.3 mmol","solvent":"DI water","reactorOrAtmosphere":"three-necked round-bottom flask"},{"activityId":"P027_PERF_001_ACT_005","paperId":"P027","catalystId":"P027_PERF_001","catalyst":"Pd0.6Cr0.4/OPDA-SmMn2O5","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"activation energy (Ea)","value":"46.8","metricType":"activation_energy","numericValue":"46.8","unit":"kJ/mol","reactionContext":"Formic acid dehydrogenation in a three-necked round-bottom flask placed in a thermostatic water bath.","temperatureC":"44.85","solution":"aqueous formic acid","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"303-333 K\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"5.3 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"DI water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"three-necked round-bottom flask\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius relationship (ln TOF-T-1)","selectivity":"Hydrogen selectivity close to 100%; no carbon 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dehydrogenation in a three-necked round-bottom flask placed in a thermostatic water bath.","solution":"aqueous formic acid","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"5.3 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"DI water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"three-necked round-bottom flask\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"32 min\"}","basis":"unclear","basisRaw":"unclear","whyPerformsWell":"Lacks amino groups which are necessary for high dispersion and electronic modulation of PdCr NPs.","formicAcid":"5.3 mmol","solvent":"DI water","reactorOrAtmosphere":"three-necked round-bottom flask","timeOrConversionBasis":"32 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\"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.04\", \"reactor_or_atmosphere\": \"two-necked round-bottomed flask in a water bath\", \"stirring_or_flow_condition\": \"600 r/min\", \"time_point_or_conversion_basis\": \"converting 20% of FA\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Ag","definition":"TOF = (PV / RT) / (2 * n_metal * t)","selectivity":"100% selectivity to H2 (CO-free)","stability":"Hydrogen production rate was maintained well during three cycling tests","whyPerformsWell":"Hierarchical SPP zeolite allows easy encapsulation and well dispersion of metal clusters; SF additive promotes dehydrogenation by forming electronically enriched Pd via adsorption of formate anions","temperatureReported":"80 °C","formicAcid":"2.5 mmol","formate":"2.5 mmol","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate (SF)","solvent":"water","catalystAmount":"0.1 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\"formate_or_sodium_formate_amount_or_concentration\": \"2.5 mmol\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.04\", \"reactor_or_atmosphere\": \"two-necked round-bottomed flask in a water bath\", \"stirring_or_flow_condition\": \"600 r/min\", \"time_point_or_conversion_basis\": \"converting 20% of FA\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Ag","definition":"TOF = (PV / RT) / (2 * n_metal * t)","selectivity":"100% selectivity to H2 (CO-free)","stability":"Hydrogen production rate was maintained well during three cycling tests","whyPerformsWell":"Hierarchical SPP zeolite allows easy encapsulation and well dispersion of metal clusters; SF additive promotes dehydrogenation by forming electronically enriched Pd via adsorption of formate 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null, \"base_or_additive\": \"none\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 0.001\", \"reactor_or_atmosphere\": \"ambient atmosphere\", \"stirring_or_flow_condition\": \"shaking water bath\", \"time_point_or_conversion_basis\": \"20% conversion\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"PVH2 / (RT * nmetal * t)","selectivity":"1:1 volume ratio of H2 and CO2; no detectable CO","stability":"Conversion remains nearly unchanged after the fourth reaction and decreases slightly at the fifth test","whyPerformsWell":"Formation of highly dispersed PdAu alloy NPs, suitable electronic structure adjusted by alloy effect and metal-support interaction, and abundant amine groups promoting FA activation via HCOO- formation","temperatureReported":"333 K","formicAcid":"4 M (0.5 mL)","baseOrAdditive":"none","solvent":"deionized 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\"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 0.001\", \"reactor_or_atmosphere\": \"ambient atmosphere\", \"stirring_or_flow_condition\": \"shaking water bath\", \"time_point_or_conversion_basis\": \"20% conversion\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"PVH2 / (RT * nmetal * t)","selectivity":"1:1 volume ratio of H2 and CO2; no detectable CO","stability":"Conversion remains nearly unchanged after the fourth reaction and decreases slightly at the fifth test","whyPerformsWell":"Formation of highly dispersed PdAu alloy NPs, suitable electronic structure adjusted by alloy effect and metal-support interaction, and abundant amine groups promoting FA activation via HCOO- formation","temperatureReported":"298 K","formicAcid":"4 M (0.5 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\"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 0.001\", \"reactor_or_atmosphere\": \"ambient atmosphere\", \"stirring_or_flow_condition\": \"shaking water bath\", \"time_point_or_conversion_basis\": \"20% conversion\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"PVH2 / (RT * nmetal * t)","selectivity":"1:1 volume ratio of H2 and CO2; no detectable CO","stability":"Catalytic activity decreases obviously with increasing recycling numbers","temperatureReported":"333 K","formicAcid":"4 M (0.5 mL)","baseOrAdditive":"none","solvent":"deionized water","catalystAmount":"10 mg","metalAmountOrRatio":"nPd/nFA = 0.001","reactorOrAtmosphere":"ambient atmosphere","stirringOrFlow":"shaking water 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\"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 0.001\", \"reactor_or_atmosphere\": \"ambient atmosphere\", \"stirring_or_flow_condition\": \"shaking water bath\", \"time_point_or_conversion_basis\": \"5 h\"}","basis":"unclear","basisRaw":"unclear","selectivity":"1:1 volume ratio of H2 and CO2; no detectable CO","stability":"Catalytic activity decreases obviously with increasing recycling numbers","temperatureReported":"333 K","formicAcid":"4 M (0.5 mL)","baseOrAdditive":"none","solvent":"deionized water","catalystAmount":"10 mg","metalAmountOrRatio":"nPd/nFA = 0.001","reactorOrAtmosphere":"ambient atmosphere","stirringOrFlow":"shaking water bath","timeOrConversionBasis":"5 h"},{"activityId":"P030_PERF_001_ACT_001","paperId":"P030","catalystId":"P030_PERF_001","catalyst":"PdCo0.2/EDA-HPAN","activeMetals":"Pd-Co","metalClass":"Pd-based 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Surface amino and cyano groups act as basic sites to promote deprotonation of FA. 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magnetic stirring","timeOrConversionBasis":"initial 5 min"},{"activityId":"P044_PERF_001_ACT_002","paperId":"P044","catalystId":"P044_PERF_001","catalyst":"Pd/C-H2P","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"incipient_wetness_impregnation","metric":"total volume of generated gas (H2 and CO2)","value":"317","metricType":"rate","numericValue":"317.0","unit":"ml","reactionContext":"50 °C, deionized water, 4 M HCOOH and 4 M sodium formate (SF), magnetic stirring","temperatureC":"50.0","solution":"deionized water, 4 M HCOOH and 4 M SF","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"deionized water, 4 M HCOOH and 4 M SF\", \"formic_acid_amount_or_concentration\": \"2 ml of 4 M HCOOH\", \"formate_or_sodium_formate_amount_or_concentration\": \"8 ml of 4 M sodium formate (SF)\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"0.05 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-necked 60 ml distillation flask, rubber plug sealed\", \"stirring_or_flow_condition\": \"200 r/min magnetic stirring\", \"time_point_or_conversion_basis\": \"4 h\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","selectivity":"No CO was detected during the reaction.","whyPerformsWell":"High Pd/C atomic ratio (0.0229), high content of metallic Pd (50.8%), small average particle size (2.6 ± 1.0 nm), and strong metal-support interaction.","temperatureReported":"50 °C","formicAcid":"2 ml of 4 M HCOOH","formate":"8 ml of 4 M sodium formate (SF)","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"0.05 g","reactorOrAtmosphere":"two-necked 60 ml distillation flask, rubber plug sealed","stirringOrFlow":"200 r/min magnetic stirring","timeOrConversionBasis":"4 h"},{"activityId":"P044_PERF_002_ACT_001","paperId":"P044","catalystId":"P044_PERF_002","catalyst":"Pd/C-ArP","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"incipient_wetness_impregnation","metric":"total volume of generated gas (H2 and CO2)","value":"310","metricType":"rate","numericValue":"310.0","unit":"ml","reactionContext":"50 °C, deionized water, 4 M HCOOH and 4 M sodium formate (SF), magnetic stirring","temperatureC":"50.0","solution":"deionized water, 4 M HCOOH and 4 M SF","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"deionized water, 4 M HCOOH and 4 M SF\", \"formic_acid_amount_or_concentration\": \"2 ml of 4 M HCOOH\", \"formate_or_sodium_formate_amount_or_concentration\": \"8 ml of 4 M sodium formate (SF)\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"0.05 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-necked 60 ml distillation flask, rubber plug sealed\", \"stirring_or_flow_condition\": \"200 r/min magnetic stirring\", \"time_point_or_conversion_basis\": \"4 h\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","selectivity":"No CO was detected during the reaction.","whyPerformsWell":"Discharge in Ar plasma was mild and regulation effect not as strong as H2 plasma.","temperatureReported":"50 °C","formicAcid":"2 ml of 4 M HCOOH","formate":"8 ml of 4 M sodium formate (SF)","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"0.05 g","reactorOrAtmosphere":"two-necked 60 ml distillation flask, rubber plug sealed","stirringOrFlow":"200 r/min magnetic stirring","timeOrConversionBasis":"4 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PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"50 °C","formicAcid":"0.5 M","baseOrAdditive":"none","solvent":"water","catalystAmount":"150 mg","reactorOrAtmosphere":"Plug Flow Reactor (PFR), 5 bar back pressure","stirringOrFlow":"0.25 mL min-1","timeOrConversionBasis":"initial activity"},{"activityId":"P045_PERF_001_ACT_002","paperId":"P045","catalystId":"P045_PERF_001","catalyst":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"commercial","metric":"initial turnover frequency (TOF0)","value":"2360","metricType":"TOF","numericValue":"2360.0","unit":"h-1","tof":"2360.0","reactionContext":"Additive-free dehydrogenation of aqueous formic acid","temperatureC":"70.0","solution":"aqueous formic acid","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"70 °C\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"150 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Plug Flow Reactor (PFR), 5 bar back pressure\", \"stirring_or_flow_condition\": \"0.5 mL min-1\", \"time_point_or_conversion_basis\": \"initial activity\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"n_converted / (n_Pd * time)","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"70 °C","formicAcid":"0.5 M","baseOrAdditive":"none","solvent":"water","catalystAmount":"150 mg","reactorOrAtmosphere":"Plug Flow Reactor (PFR), 5 bar back pressure","stirringOrFlow":"0.5 mL min-1","timeOrConversionBasis":"initial activity"},{"activityId":"P045_PERF_001_ACT_003","paperId":"P045","catalystId":"P045_PERF_001","catalyst":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"commercial","metric":"initial turnover frequency (TOF0)","value":"3540","metricType":"TOF","numericValue":"3540.0","unit":"h-1","tof":"3540.0","reactionContext":"Additive-free dehydrogenation of aqueous formic acid","temperatureC":"90.0","solution":"aqueous formic acid","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"90 °C\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"150 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Plug Flow Reactor (PFR), 5 bar back pressure\", \"stirring_or_flow_condition\": \"0.5 mL min-1\", \"time_point_or_conversion_basis\": \"initial activity\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"n_converted / (n_Pd * time)","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"90 °C","formicAcid":"0.5 M","baseOrAdditive":"none","solvent":"water","catalystAmount":"150 mg","reactorOrAtmosphere":"Plug Flow Reactor (PFR), 5 bar back pressure","stirringOrFlow":"0.5 mL min-1","timeOrConversionBasis":"initial activity"},{"activityId":"P045_PERF_001_ACT_004","paperId":"P045","catalystId":"P045_PERF_001","catalyst":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"commercial","metric":"initial turnover frequency (TOF0)","value":"5860","metricType":"TOF","numericValue":"5860.0","unit":"h-1","tof":"5860.0","reactionContext":"Additive-free dehydrogenation of aqueous formic acid","temperatureC":"110.0","solution":"aqueous formic acid","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"110 °C\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"150 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Plug Flow Reactor (PFR), 5 bar back pressure\", \"stirring_or_flow_condition\": \"0.85 mL min-1\", \"time_point_or_conversion_basis\": \"initial activity\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"n_converted / (n_Pd * time)","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"110 °C","formicAcid":"0.5 M","baseOrAdditive":"none","solvent":"water","catalystAmount":"150 mg","reactorOrAtmosphere":"Plug Flow Reactor (PFR), 5 bar back pressure","stirringOrFlow":"0.85 mL min-1","timeOrConversionBasis":"initial activity"},{"activityId":"P045_PERF_001_ACT_005","paperId":"P045","catalystId":"P045_PERF_001","catalyst":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"commercial","metric":"rate of deactivation (kd)","value":"0.031","metricType":"rate","numericValue":"0.031","unit":"min-1","reactionContext":"Additive-free dehydrogenation of aqueous formic acid","temperatureC":"50.0","solution":"aqueous formic acid","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"150 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Plug Flow Reactor (PFR), 5 bar back pressure\", \"stirring_or_flow_condition\": \"0.25 mL min-1\", \"time_point_or_conversion_basis\": \"calculated from Levenspiel plot\"}","basis":"unclear","basisRaw":"unclear","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"50 °C","formicAcid":"0.5 M","baseOrAdditive":"none","solvent":"water","catalystAmount":"150 mg","reactorOrAtmosphere":"Plug Flow Reactor (PFR), 5 bar back pressure","stirringOrFlow":"0.25 mL min-1","timeOrConversionBasis":"calculated from Levenspiel plot"},{"activityId":"P045_PERF_001_ACT_006","paperId":"P045","catalystId":"P045_PERF_001","catalyst":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"commercial","metric":"rate of deactivation (kd)","value":"0.043","metricType":"rate","numericValue":"0.043","unit":"min-1","reactionContext":"Additive-free dehydrogenation of aqueous formic acid","temperatureC":"70.0","solution":"aqueous formic acid","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"70 °C\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"150 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Plug Flow Reactor (PFR), 5 bar back pressure\", \"stirring_or_flow_condition\": \"0.5 mL min-1\", \"time_point_or_conversion_basis\": \"calculated from Levenspiel plot\"}","basis":"unclear","basisRaw":"unclear","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"70 °C","formicAcid":"0.5 M","baseOrAdditive":"none","solvent":"water","catalystAmount":"150 mg","reactorOrAtmosphere":"Plug Flow Reactor (PFR), 5 bar back pressure","stirringOrFlow":"0.5 mL min-1","timeOrConversionBasis":"calculated from Levenspiel plot"},{"activityId":"P045_PERF_001_ACT_007","paperId":"P045","catalystId":"P045_PERF_001","catalyst":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"commercial","metric":"rate of deactivation (kd)","value":"0.059","metricType":"rate","numericValue":"0.059","unit":"min-1","reactionContext":"Additive-free dehydrogenation of aqueous formic acid","temperatureC":"90.0","solution":"aqueous formic acid","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"90 °C\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"150 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Plug Flow Reactor (PFR), 5 bar back pressure\", \"stirring_or_flow_condition\": \"0.5 mL min-1\", \"time_point_or_conversion_basis\": \"calculated from Levenspiel plot\"}","basis":"unclear","basisRaw":"unclear","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"90 °C","formicAcid":"0.5 M","baseOrAdditive":"none","solvent":"water","catalystAmount":"150 mg","reactorOrAtmosphere":"Plug Flow Reactor (PFR), 5 bar back pressure","stirringOrFlow":"0.5 mL min-1","timeOrConversionBasis":"calculated from Levenspiel plot"},{"activityId":"P045_PERF_001_ACT_008","paperId":"P045","catalystId":"P045_PERF_001","catalyst":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"commercial","metric":"rate of deactivation (kd)","value":"0.081","metricType":"rate","numericValue":"0.081","unit":"min-1","reactionContext":"Additive-free dehydrogenation of aqueous formic acid","temperatureC":"110.0","solution":"aqueous formic acid","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"110 °C\", \"reaction_solution\": \"aqueous formic acid\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"150 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Plug Flow Reactor (PFR), 5 bar back pressure\", \"stirring_or_flow_condition\": \"0.85 mL min-1\", \"time_point_or_conversion_basis\": \"calculated from Levenspiel plot\"}","basis":"unclear","basisRaw":"unclear","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"110 °C","formicAcid":"0.5 M","baseOrAdditive":"none","solvent":"water","catalystAmount":"150 mg","reactorOrAtmosphere":"Plug Flow Reactor (PFR), 5 bar back pressure","stirringOrFlow":"0.85 mL min-1","timeOrConversionBasis":"calculated from Levenspiel plot"},{"activityId":"P045_PERF_001_ACT_009","paperId":"P045","catalystId":"P045_PERF_001","catalyst":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"commercial","metric":"substrate turnover","value":">2500","metricType":"rate","numericValue":"2500.0","unit":"turnovers","reactionContext":"Additive-free dehydrogenation of aqueous formic acid","temperatureC":"50.0","solution":"pure formic acid in water","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"pure formic acid in water\", \"formic_acid_amount_or_concentration\": \"0.01 mL min-1 flow of pure FA into 60 mL water\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"45 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Continuous Stirred Tank Reactor (CSTR)\", \"stirring_or_flow_condition\": \"800 rpm\", \"time_point_or_conversion_basis\": \"continuous operation without loss of activity\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","selectivity":"High selectivity for dehydrogenation; CO/CO2 ratio of 1:100,000 detected at 50 °C","stability":"Batch tests showed <5% loss over 5 cycles. PFR shows significant deactivation correlating to substrate turnover. CSTR exhibits high stability with kd 35 times lower than in PFR mode.","whyPerformsWell":"CSTR performance is superior because it minimizes the steady state concentration of formic acid, mitigating substrate-induced poisoning and fouling.","temperatureReported":"50 °C","formicAcid":"0.01 mL min-1 flow of pure FA into 60 mL water","baseOrAdditive":"none","solvent":"water","catalystAmount":"45 mg","reactorOrAtmosphere":"Continuous Stirred Tank Reactor (CSTR)","stirringOrFlow":"800 rpm","timeOrConversionBasis":"continuous operation without loss of activity"},{"activityId":"P046_PERF_001_ACT_001","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"X_FA (conversion)","value":"15.33","metricType":"conversion","numericValue":"15.33","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:800\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"XFA = 0.5pVevolved / (RTninitial FA) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:800","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"24 h"},{"activityId":"P046_PERF_001_ACT_002","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF initial","value":"15.7","metricType":"TOF","numericValue":"15.7","unit":"h-1","tof":"15.7","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:800\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 2 min\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:800","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 2 min"},{"activityId":"P046_PERF_001_ACT_003","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF at XFA=4%","value":"35.6","metricType":"TOF","numericValue":"35.6","unit":"h-1","tof":"35.6","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:800\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"XFA=4%\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:800","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"XFA=4%"},{"activityId":"P046_PERF_001_ACT_004","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"X_FA (conversion)","value":"6.89","metricType":"conversion","numericValue":"6.89","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"1.0 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"1.0 M FA\", \"formic_acid_amount_or_concentration\": \"1.0 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:1600\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"XFA = 0.5pVevolved / (RTninitial FA) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"1.0 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:1600","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"24 h"},{"activityId":"P046_PERF_001_ACT_005","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF initial","value":"39.2","metricType":"TOF","numericValue":"39.2","unit":"h-1","tof":"39.2","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"1.0 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"1.0 M FA\", \"formic_acid_amount_or_concentration\": \"1.0 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:1600\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 2 min\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"1.0 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:1600","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 2 min"},{"activityId":"P046_PERF_001_ACT_006","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"X_FA (conversion)","value":"4.7","metricType":"conversion","numericValue":"4.7","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"2.0 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"2.0 M FA\", \"formic_acid_amount_or_concentration\": \"2.0 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:3200\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"XFA = 0.5pVevolved / (RTninitial FA) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"2.0 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:3200","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"24 h"},{"activityId":"P046_PERF_001_ACT_007","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF initial","value":"143.7","metricType":"TOF","numericValue":"143.7","unit":"h-1","tof":"143.7","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"2.0 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"2.0 M FA\", \"formic_acid_amount_or_concentration\": \"2.0 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:3200\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 2 min\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"2.0 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:3200","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 2 min"},{"activityId":"P046_PERF_001_ACT_008","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"X_FA (conversion)","value":"49.9","metricType":"conversion","numericValue":"49.9","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:270\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"6 h\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"XFA = 0.5pVevolved / (RTninitial FA) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:270","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"6 h"},{"activityId":"P046_PERF_001_ACT_009","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF initial","value":"65.3","metricType":"TOF","numericValue":"65.3","unit":"h-1","tof":"65.3","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:270\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 2 min\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:270","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 2 min"},{"activityId":"P046_PERF_001_ACT_010","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"X_FA (conversion)","value":"63.3","metricType":"conversion","numericValue":"63.3","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:270\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"XFA = 0.5pVevolved / (RTninitial FA) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:270","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"24 h"},{"activityId":"P046_PERF_001_ACT_011","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF 10 min","value":"32.7","metricType":"TOF","numericValue":"32.7","unit":"h-1","tof":"32.7","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:270\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 10 min (XFA < 10%)\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:270","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 10 min (XFA < 10%)"},{"activityId":"P046_PERF_001_ACT_012","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"X_FA (conversion)","value":"54.4","metricType":"conversion","numericValue":"54.4","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"40.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"40 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:270\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"XFA = 0.5pVevolved / (RTninitial FA) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"40 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:270","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"24 h"},{"activityId":"P046_PERF_001_ACT_013","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF 10 min","value":"67.9","metricType":"TOF","numericValue":"67.9","unit":"h-1","tof":"67.9","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"40.0","solution":"0.5 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"40 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:270\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 10 min (XFA < 10%)\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"40 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:270","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 10 min (XFA < 10%)"},{"activityId":"P046_PERF_001_ACT_014","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"X_FA (conversion)","value":"60.1","metricType":"conversion","numericValue":"60.1","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"60.0","solution":"0.5 M FA","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:270\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"XFA = 0.5pVevolved / (RTninitial FA) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"60 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:270","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"24 h"},{"activityId":"P046_PERF_001_ACT_015","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF 10 min","value":"218.8","metricType":"TOF","numericValue":"218.8","unit":"h-1","tof":"218.8","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"60.0","solution":"0.5 M FA","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"0.5 M FA\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:270\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 10 min (XFA < 10%)\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"60 °C","formicAcid":"0.5 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:270","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 10 min (XFA < 10%)"},{"activityId":"P046_PERF_001_ACT_016","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"X_FA (conversion)","value":"99","metricType":"conversion","numericValue":"99.0","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"2.0 M FA","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"2.0 M FA\", \"formic_acid_amount_or_concentration\": \"2.0 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd:FA = 1:2100\", \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"264 h (11 days)\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"XFA = 0.5pVevolved / (RTninitial FA) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"2.0 M","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"Pd:FA = 1:2100","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"264 h (11 days)"},{"activityId":"P046_PERF_001_ACT_017","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF 10 min","value":"64.0","metricType":"TOF","numericValue":"64.0","unit":"h-1","tof":"64.0","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"FA:SF = 3:1 mixture (total [FA]+[SF]=0.5 M)","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"FA:SF = 3:1 mixture (total [FA]+[SF]=0.5 M)\", \"formic_acid_amount_or_concentration\": \"0.375 M FA\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.125 M SF\", \"formic_acid_to_formate_ratio\": \"3:1\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 10 min\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.375 M FA","formate":"0.125 M SF","acidFormateRatio":"3:1","baseOrAdditive":"sodium formate (SF)","solvent":"water","catalystAmount":"20 mg","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 10 min"},{"activityId":"P046_PERF_001_ACT_018","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"H2 yield (Phi)","value":"48.1","metricType":"other","numericValue":"48.1","unit":"%","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"FA:SF = 3:1 mixture (total [FA]+[SF]=0.5 M)","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"FA:SF = 3:1 mixture (total [FA]+[SF]=0.5 M)\", \"formic_acid_amount_or_concentration\": \"0.375 M FA\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.125 M SF\", \"formic_acid_to_formate_ratio\": \"3:1\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"PhiH2 = (n formed H2 / (nFA + nSF)) * 100","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.375 M FA","formate":"0.125 M SF","acidFormateRatio":"3:1","baseOrAdditive":"sodium formate (SF)","solvent":"water","catalystAmount":"20 mg","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"24 h"},{"activityId":"P046_PERF_001_ACT_019","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF 10 min","value":"282.1","metricType":"TOF","numericValue":"282.1","unit":"h-1","tof":"282.1","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"25.0","solution":"0.5 M FA with added solid SF (FA:SF = 1:3)","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"0.5 M FA with added solid SF (FA:SF = 1:3)\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"15 mmol solid SF in 10 mL solution\", \"formic_acid_to_formate_ratio\": \"1:3\", \"base_or_additive\": \"solid sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 10 min\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"25 °C","formicAcid":"0.5 M","formate":"15 mmol solid SF in 10 mL solution","acidFormateRatio":"1:3","baseOrAdditive":"solid sodium formate (SF)","solvent":"water","catalystAmount":"20 mg","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 10 min"},{"activityId":"P046_PERF_001_ACT_020","paperId":"P046","catalystId":"P046_PERF_001","catalyst":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF initial","value":"535","metricType":"TOF","numericValue":"535.0","unit":"h-1","tof":"535.0","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution, ambient atmosphere of air, stirring at 1000 rpm.","temperatureC":"60.0","solution":"0.5 M FA with added solid SF (FA:SF = 3:1)","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"0.5 M FA with added solid SF (FA:SF = 3:1)\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"solid SF\", \"formic_acid_to_formate_ratio\": \"3:1\", \"base_or_additive\": \"solid sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round bottom flask, air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"t = 5 min\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = pVH2 / (RTnPdt)","selectivity":"CO-free decomposition; MS analysis revealed H2 and CO2 as constituent components with no detectable traces of CO.","stability":"Reused 10 times at 25 °C (0.5 M FA, Pd:FA = 1:270). Total evolved gas volume decreased after the first two runs; last two runs were practically identical (12.8 and 12.2 mL).","whyPerformsWell":"High surface area of templated carbon support and uniform distribution of small Pd nanoparticles (~2 nm and below) over the TC support.","temperatureReported":"60 °C","formicAcid":"0.5 M","formate":"solid SF","acidFormateRatio":"3:1","baseOrAdditive":"solid sodium formate (SF)","solvent":"water","catalystAmount":"20 mg","reactorOrAtmosphere":"round bottom flask, air","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"t = 5 min"},{"activityId":"P047_PERF_001_ACT_001","paperId":"P047","catalystId":"P047_PERF_001","catalyst":"AP-SiO2@NGO-PDA@Pd0.51Au0.49","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF","value":"16647","metricType":"TOF","numericValue":"16647.0","unit":"mol H2 molPd^-1 h^-1","tof":"16647.0","reactionContext":"Additive-free dehydrogenation of formic acid (FA) in aqueous solution at 50 °C","temperatureC":"49.85","solution":"aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"323 K\", \"reaction_solution\": \"aqueous solution\", \"formic_acid_amount_or_concentration\": \"1.06 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"water\", \"catalyst_amount\": \"0.08 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"double-neck round-bottom flask connected to a gas burette with water\", \"stirring_or_flow_condition\": \"stirring in a water bath\", \"time_point_or_conversion_basis\": \"when the volume of the generated gases reached 20% of total released gases\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = (Vgas * 22.4) / (Vs * CPd * t)","selectivity":"selective dehydrogenation","whyPerformsWell":"combination of the bimetallic synergistic effect and the carrier effect; 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\"formate_or_sodium_formate_amount_or_concentration\": \"0.68 g in 10 mL water\", \"formic_acid_to_formate_ratio\": \"nFA:nSF = 1:1.8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"Milli-Q water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"single flask with gas bag attached\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"180 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"nearly 100% (no CO signal detected)","temperatureReported":"298 K","formicAcid":"0.37 M (210 μL in 5 mL water)","formate":"0.68 g in 10 mL water","acidFormateRatio":"nFA:nSF = 1:1.8","baseOrAdditive":"sodium formate","solvent":"Milli-Q water","reactorOrAtmosphere":"single flask with gas bag attached","timeOrConversionBasis":"180 min"},{"activityId":"P069_PERF_002_ACT_002","paperId":"P069","catalystId":"P069_PERF_002","catalyst":"Pd4.6/C-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF","value":"275","metricType":"TOF","numericValue":"275.0","unit":"mol H2 mol Pd-1 h-1","tof":"275.0","reactionContext":"Room temperature, FA and sodium formate aqueous solution","temperatureC":"24.85","solution":"FA and sodium formate aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"FA and sodium formate aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.37 M (210 μL in 5 mL water)\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.68 g in 10 mL water\", \"formic_acid_to_formate_ratio\": \"nFA:nSF = 1:1.8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"Milli-Q water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"single flask with gas bag attached\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"20 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF(h-1) = (Patm * VH2) / (R * T * NPd * t)","selectivity":"nearly 100% (no CO signal detected)","temperatureReported":"298 K","formicAcid":"0.37 M (210 μL in 5 mL water)","formate":"0.68 g in 10 mL water","acidFormateRatio":"nFA:nSF = 1:1.8","baseOrAdditive":"sodium formate","solvent":"Milli-Q water","reactorOrAtmosphere":"single flask with gas bag attached","timeOrConversionBasis":"20 min"},{"activityId":"P069_PERF_003_ACT_001","paperId":"P069","catalystId":"P069_PERF_003","catalyst":"Pd9.2/C-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"gas volume","value":"260","metricType":"other","numericValue":"260.0","unit":"mL","reactionContext":"Room temperature to 333 K, FA and sodium formate aqueous solution","temperatureC":"24.85","solution":"FA and sodium formate aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"FA and sodium formate aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.37 M (210 μL in 5 mL water)\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.68 g in 10 mL water\", \"formic_acid_to_formate_ratio\": \"nFA:nSF = 1:1.8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"Milli-Q water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"single flask with gas bag attached\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"180 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"nearly 100% (no CO signal detected)","stability":"In the second run, produced 90% volume of H2 in 20 min and TOF decreased to 92.52%. 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In the third cycle, produced 65% volume of H2 in 20 min and TOF decayed by about 25% (to 74.95%).","whyPerformsWell":"Well-distributed ultrafine palladium nanoparticles (2.2-2.6 nm), proper metal-carrier interaction enhancing C-H bond cleavage, electron transfer from graphitic-N and pyridinic-N to Pd, and high specific surface area of the support.","temperatureReported":"298 K","formicAcid":"0.37 M (210 μL in 5 mL water)","formate":"0.68 g in 10 mL water","acidFormateRatio":"nFA:nSF = 1:1.8","baseOrAdditive":"sodium formate","solvent":"Milli-Q water","reactorOrAtmosphere":"single flask with gas bag attached","timeOrConversionBasis":"20 min"},{"activityId":"P069_PERF_003_ACT_003","paperId":"P069","catalystId":"P069_PERF_003","catalyst":"Pd9.2/C-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"initial TOF","value":"615","metricType":"TOF","numericValue":"615.0","unit":"mol H2 mol Pd-1 h-1","tof":"615.0","reactionContext":"Room temperature to 333 K, FA and sodium formate aqueous solution","solution":"FA and sodium formate aqueous solution","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"room temperature\", \"reaction_solution\": \"FA and sodium formate aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","selectivity":"nearly 100% (no CO signal detected)","stability":"In the second run, produced 90% volume of H2 in 20 min and TOF decreased to 92.52%. In the third cycle, produced 65% volume of H2 in 20 min and TOF decayed by about 25% (to 74.95%).","whyPerformsWell":"Well-distributed ultrafine palladium nanoparticles (2.2-2.6 nm), proper metal-carrier interaction enhancing C-H bond cleavage, electron transfer from graphitic-N and pyridinic-N to Pd, and high specific surface area of the support.","temperatureReported":"room temperature","baseOrAdditive":"sodium formate","solvent":"water","timeOrConversionBasis":"initial"},{"activityId":"P069_PERF_003_ACT_004","paperId":"P069","catalystId":"P069_PERF_003","catalyst":"Pd9.2/C-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"activation energy","value":"39.15","metricType":"activation_energy","numericValue":"39.15","unit":"kJ mol-1","reactionContext":"Room temperature to 333 K, FA and sodium formate aqueous solution","temperatureC":"59.85","solution":"FA and sodium formate aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"303, 313, 323, 333 K\", \"reaction_solution\": \"FA and sodium formate aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.37 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": \"nFA:nSF = 1:1.8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"Milli-Q water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial reaction stage\"}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius law: ln k = -Ea/RT + ln A","selectivity":"nearly 100% (no CO signal detected)","stability":"In the second run, produced 90% volume of H2 in 20 min and TOF decreased to 92.52%. In the third cycle, produced 65% volume of H2 in 20 min and TOF decayed by about 25% (to 74.95%).","whyPerformsWell":"Well-distributed ultrafine palladium nanoparticles (2.2-2.6 nm), proper metal-carrier interaction enhancing C-H bond cleavage, electron transfer from graphitic-N and pyridinic-N to Pd, and high specific surface area of the support.","temperatureReported":"303, 313, 323, 333 K","formicAcid":"0.37 M","acidFormateRatio":"nFA:nSF = 1:1.8","baseOrAdditive":"sodium formate","solvent":"Milli-Q water","timeOrConversionBasis":"initial reaction stage"},{"activityId":"P069_PERF_003_ACT_005","paperId":"P069","catalystId":"P069_PERF_003","catalyst":"Pd9.2/C-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF","value":"766, 997, 1297, 2593","metricType":"TOF","numericValue":"766.0","unit":"h-1","tof":"766.0","reactionContext":"Room temperature to 333 K, FA and sodium formate aqueous solution","temperatureC":"59.85","solution":"FA and sodium formate aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"303, 313, 323, 333 K\", \"reaction_solution\": \"FA and sodium formate aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.37 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": \"nFA:nSF = 1:1.8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"Milli-Q water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial reaction stage\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","selectivity":"nearly 100% (no CO signal detected)","stability":"In the second run, produced 90% volume of H2 in 20 min and TOF decreased to 92.52%. In the third cycle, produced 65% volume of H2 in 20 min and TOF decayed by about 25% (to 74.95%).","whyPerformsWell":"Well-distributed ultrafine palladium nanoparticles (2.2-2.6 nm), proper metal-carrier interaction enhancing C-H bond cleavage, electron transfer from graphitic-N and pyridinic-N to Pd, and high specific surface area of the support.","temperatureReported":"303, 313, 323, 333 K","formicAcid":"0.37 M","acidFormateRatio":"nFA:nSF = 1:1.8","baseOrAdditive":"sodium formate","solvent":"Milli-Q water","timeOrConversionBasis":"initial reaction stage"},{"activityId":"P069_PERF_004_ACT_001","paperId":"P069","catalystId":"P069_PERF_004","catalyst":"Pd18.4/C-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"gas volume","value":"328","metricType":"other","numericValue":"328.0","unit":"mL","reactionContext":"Room temperature, FA and sodium formate aqueous solution","temperatureC":"24.85","solution":"FA and sodium formate aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"FA and sodium formate aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.37 M (210 μL in 5 mL water)\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.68 g in 10 mL water\", \"formic_acid_to_formate_ratio\": \"nFA:nSF = 1:1.8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"Milli-Q water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"single flask with gas bag attached\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"180 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"nearly 100% (no CO signal detected)","temperatureReported":"298 K","formicAcid":"0.37 M (210 μL in 5 mL water)","formate":"0.68 g in 10 mL water","acidFormateRatio":"nFA:nSF = 1:1.8","baseOrAdditive":"sodium formate","solvent":"Milli-Q water","reactorOrAtmosphere":"single flask with gas bag attached","timeOrConversionBasis":"180 min"},{"activityId":"P069_PERF_004_ACT_002","paperId":"P069","catalystId":"P069_PERF_004","catalyst":"Pd18.4/C-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF","value":"128","metricType":"TOF","numericValue":"128.0","unit":"mol H2 mol Pd-1 h-1","tof":"128.0","reactionContext":"Room temperature, FA and sodium formate aqueous solution","temperatureC":"24.85","solution":"FA and sodium formate aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"FA and sodium formate aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.37 M (210 μL in 5 mL water)\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.68 g in 10 mL water\", \"formic_acid_to_formate_ratio\": \"nFA:nSF = 1:1.8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"Milli-Q water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"single flask with gas bag attached\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"20 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF(h-1) = (Patm * VH2) / (R * T * NPd * t)","selectivity":"nearly 100% (no CO signal detected)","temperatureReported":"298 K","formicAcid":"0.37 M (210 μL in 5 mL water)","formate":"0.68 g in 10 mL water","acidFormateRatio":"nFA:nSF = 1:1.8","baseOrAdditive":"sodium formate","solvent":"Milli-Q water","reactorOrAtmosphere":"single flask with gas bag attached","timeOrConversionBasis":"20 min"},{"activityId":"P069_PERF_005_ACT_001","paperId":"P069","catalystId":"P069_PERF_005","catalyst":"Pd23.1/C-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"gas volume","value":"268","metricType":"other","numericValue":"268.0","unit":"mL","reactionContext":"Room temperature, FA and sodium formate aqueous solution","temperatureC":"24.85","solution":"FA and sodium formate aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"FA and sodium formate aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.37 M (210 μL in 5 mL water)\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.68 g in 10 mL water\", \"formic_acid_to_formate_ratio\": \"nFA:nSF = 1:1.8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"Milli-Q water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"single flask with gas bag attached\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"180 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"nearly 100% (no CO signal detected)","temperatureReported":"298 K","formicAcid":"0.37 M (210 μL in 5 mL water)","formate":"0.68 g in 10 mL water","acidFormateRatio":"nFA:nSF = 1:1.8","baseOrAdditive":"sodium formate","solvent":"Milli-Q water","reactorOrAtmosphere":"single flask with gas bag attached","timeOrConversionBasis":"180 min"},{"activityId":"P070_PERF_001_ACT_001","paperId":"P070","catalystId":"P070_PERF_001","catalyst":"Pd@TU-PMO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF","value":"32","metricType":"TOF","numericValue":"32.0","tof":"32.0","reactionContext":"Catalytic dehydrogenation of formic acid in water","temperatureC":"80.0","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"within the first 30 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"almost 100% selectivity for formic acid dehydrogenation; CO was not detected","stability":"Excellent recyclability was observed.","whyPerformsWell":"stable immobilization of the Pd nanoparticles on the surface of the mesopores via interactions between the Pd and the thiourea functionalities","temperatureReported":"80 °C","solvent":"water","catalystAmount":"30 mg","timeOrConversionBasis":"within the first 30 min"},{"activityId":"P070_PERF_001_ACT_002","paperId":"P070","catalystId":"P070_PERF_001","catalyst":"Pd@TU-PMO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"apparent activation energy","value":"63","metricType":"activation_energy","numericValue":"63.0","unit":"kJ mol-1","reactionContext":"Catalytic dehydrogenation of formic acid in water","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"almost 100% selectivity for formic acid dehydrogenation; CO was not detected","stability":"Excellent recyclability was observed.","whyPerformsWell":"stable immobilization of the Pd nanoparticles on the surface of the mesopores via interactions between the Pd and the thiourea functionalities","solvent":"water","catalystAmount":"30 mg"},{"activityId":"P070_PERF_002_ACT_001","paperId":"P070","catalystId":"P070_PERF_002","catalyst":"Pd2+@TU-PMO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"rate of H2 generation","value":"lower than Pd@TU-PMO","metricType":"rate","reactionContext":"Catalytic dehydrogenation of formic acid in water","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","whyPerformsWell":"Pd2+ may consume part of the produced H2 to deposit metallic Pd","solvent":"water"},{"activityId":"P071_PERF_001_ACT_001","paperId":"P071","catalystId":"P071_PERF_001","catalyst":"Pd/HTNC-950","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF","value":"1631","metricType":"TOF","numericValue":"1631.0","unit":"h⁻¹","tof":"1631.0","reactionContext":"FA/SF aqueous solution, 30 °C","temperatureC":"30.0","solution":"FA/SF aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"FA/SF aqueous solution\", \"formic_acid_amount_or_concentration\": \"1 M (implied by total 2M and 1:1 ratio)\", \"formate_or_sodium_formate_amount_or_concentration\": \"1 M (implied by total 2M and 1:1 ratio)\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"Sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"nPd/nFA = 0.2%\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"gas burette\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": \"initial rate\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = pV / (nPdRTt)","selectivity":"no CO (< 1 ppm) detected","stability":"did not show an obvious loss of catalytic activity even after the fifth run","whyPerformsWell":"N species adjusted electronic properties of Pd (Pd2+ for formate adsorption and Pd0 for C-H bond activation) and promoted dispersion of small Pd NPs","temperatureReported":"30 °C","formicAcid":"1 M (implied by total 2M and 1:1 ratio)","formate":"1 M (implied by total 2M and 1:1 ratio)","acidFormateRatio":"1:1","baseOrAdditive":"Sodium formate (SF)","solvent":"water","catalystAmount":"nPd/nFA = 0.2%","reactorOrAtmosphere":"gas burette","stirringOrFlow":"stirring","timeOrConversionBasis":"initial rate"},{"activityId":"P071_PERF_001_ACT_002","paperId":"P071","catalystId":"P071_PERF_001","catalyst":"Pd/HTNC-950","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"time for 50% conversion","value":"18","metricType":"conversion","numericValue":"18.0","unit":"min","reactionContext":"FA/SF aqueous solution, 30 °C","temperatureC":"30.0","solution":"FA/SF aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"FA/SF aqueous solution\", \"formic_acid_amount_or_concentration\": \"1 M (implied by total 2M and 1:1 ratio)\", \"formate_or_sodium_formate_amount_or_concentration\": \"1 M (implied by total 2M and 1:1 ratio)\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"Sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"nPd/nFA = 0.2%\", 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(3.61 nm) and N-doped hierarchical porous carbon (NHPC-150); N-doping modifies electronic properties of Pd, facilitates C-H bond cleavage, lowers activation energy (21.39 kJ/mol), and stabilizes intermediates.","temperatureReported":"40 °C","formicAcid":"2.5 mmol","baseOrAdditive":"additive-free","solvent":"distilled water","catalystAmount":"10 mg","reactorOrAtmosphere":"two-necked round-bottom flask linked to a gas burette","timeOrConversionBasis":"20% FA conversion"},{"activityId":"P073_PERF_001_ACT_005","paperId":"P073","catalystId":"P073_PERF_001","catalyst":"8 wt.% Pd/NHPC-150","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"conversion","value":"100","metricType":"conversion","numericValue":"100.0","unit":"%","reactionContext":"Additive-free formic acid dehydrogenation (FAD) in distilled water at 25-40 °C.","temperatureC":"25.0","solution":"distilled water","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"distilled water\", \"formic_acid_amount_or_concentration\": \"2.5 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-necked round-bottom flask linked to a gas burette\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"100% selectivity for CO-free FAD; absence of CO confirmed at a detection limit of 10 ppm","stability":"Maintained 95% of initial activity after 8 successive reaction cycles; achieved 100% FAD even after 200 days of storage at room temperature.","whyPerformsWell":"Synergistic interface between small-sized Pd NPs (3.61 nm) and N-doped hierarchical porous 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\"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"0.150 g\", \"metal_amount_or_substrate_to_metal_ratio\": \"1 wt% Pd nominal loading\", \"reactor_or_atmosphere\": \"liquid phase\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"30 min\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","definition":"mLgas/gcat","stability":"good stability preserved after six consecutive reaction cycles","whyPerformsWell":"Nitrogen functional groups modify basicity favoring FA interaction and can be involved in deprotonation of FA.","temperatureReported":"75 °C","formicAcid":"1 M (final concentration)","formate":"1 M (final concentration)","acidFormateRatio":"9:1","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"0.150 g","metalAmountOrRatio":"1 wt% Pd nominal loading","reactorOrAtmosphere":"liquid phase","timeOrConversionBasis":"30 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\"reactor_or_atmosphere\": \"liquid phase\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"30 min (1st run)\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","definition":"mLgas/gcat","stability":"catalytic activity decay of ~43% after 6 cycles (745 to 425 mLgas/gcat)","whyPerformsWell":"Presence of Ag modifies electronic properties and size of nanoparticles, favoring electron-rich Pd species.","temperatureReported":"75 °C","formicAcid":"1 M (final concentration)","formate":"1 M (final concentration)","acidFormateRatio":"9:1","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"0.150 g","metalAmountOrRatio":"1 wt% Pd nominal loading, Pd/Ag molar ratio 1/0.5","reactorOrAtmosphere":"liquid phase","timeOrConversionBasis":"30 min (1st run)"},{"activityId":"P074_PERF_003_ACT_002","paperId":"P074","catalystId":"P074_PERF_003","catalyst":"PdAg/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based 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\"time_point_or_conversion_basis\": \"30 min (1st run)\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","definition":"mLgas/gcat","stability":"excellent stability; activity loss almost negligible (~3%) after 6 cycles (988 to 954 mLgas/gcat)","whyPerformsWell":"Synergistic effect of N and Ag; small well-dispersed nanoparticles (2.8 nm); basic character of support; presence of both metallic Pd and electron-deficient Pd species.","temperatureReported":"75 °C","formicAcid":"1 M (final concentration)","formate":"1 M (final concentration)","acidFormateRatio":"9:1","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"0.150 g","metalAmountOrRatio":"1 wt% Pd nominal loading, Pd/Ag molar ratio 1/0.5","reactorOrAtmosphere":"liquid phase","timeOrConversionBasis":"30 min (1st run)"},{"activityId":"P074_PERF_004_ACT_002","paperId":"P074","catalystId":"P074_PERF_004","catalyst":"PdAg/N-AS","activeMetals":"Pd-Ag","metalClass":"Pd-based 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\"water\", \"catalyst_amount\": \"0.150 g\", \"metal_amount_or_substrate_to_metal_ratio\": \"1 wt% Pd nominal loading\", \"reactor_or_atmosphere\": \"liquid phase\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"30 min\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","definition":"mLgas/gcat","stability":"better activity than pre-reduced Pd/N-AS","whyPerformsWell":"In-situ reduction with H2 produced in reaction; nitrogen atoms stabilize cationic Pd species and serve as anchoring sites.","temperatureReported":"75 °C","formicAcid":"1 M (final concentration)","formate":"1 M (final concentration)","acidFormateRatio":"9:1","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"0.150 g","metalAmountOrRatio":"1 wt% Pd nominal loading","reactorOrAtmosphere":"liquid phase","timeOrConversionBasis":"30 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\"metal_amount_or_substrate_to_metal_ratio\": \"n Pd/nFA = 0.0057\", \"reactor_or_atmosphere\": \"two-necked round-bottom flask, gas buret\", \"stirring_or_flow_condition\": \"magnetic stirrer\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"no generating of CO at the level of detection limit","stability":"reused for more than 5 times without significant activity lost; constantly in use for more than 2 h","whyPerformsWell":"N-doping increases proportion of Pd0 (54%) providing more active sites, and anchors noble metal via affinity of nitrogen to prevent aggregation.","temperatureReported":"60 °C","formicAcid":"4.5 mmol","formate":"4.5 mmol","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate (SF)","solvent":"deionized water","catalystAmount":"100 mg","metalAmountOrRatio":"n Pd/nFA = 0.0057","reactorOrAtmosphere":"two-necked round-bottom flask, gas buret","stirringOrFlow":"magnetic 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abundance of accessible active sites), and PdCo alloying (optimal electronic structure due to electron redistribution on Pd)","temperatureReported":"50 °C","formicAcid":"3 M","formate":"7.5 M","acidFormateRatio":"1:2.5","baseOrAdditive":"sodium formate (SF)","solvent":"H2O","reactorOrAtmosphere":"double-necked flask","timeOrConversionBasis":"time to generate 72 mL mixture gases (H2 + CO2)"},{"activityId":"P079_PERF_002_ACT_001","paperId":"P079","catalystId":"P079_PERF_002","catalyst":"Pd/CK-BN","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"TOF","value":"1808","metricType":"TOF","numericValue":"1808.0","unit":"h-1","tof":"1808.0","reactionContext":"Aqueous FA/SF solution","temperatureC":"50.0","solution":"aqueous FA/SF solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"aqueous FA/SF solution\", \"formic_acid_amount_or_concentration\": \"3 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"7.5 M\", \"formic_acid_to_formate_ratio\": \"1:2.5\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"H2O\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"double-necked flask\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"time to generate 72 mL mixture gases (H2 + CO2)\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = P0V / (2RTtnM)","whyPerformsWell":"Abundance of accessible active sites such as N and B species; rich defects from KCl etching","temperatureReported":"50 °C","formicAcid":"3 M","formate":"7.5 M","acidFormateRatio":"1:2.5","baseOrAdditive":"sodium formate (SF)","solvent":"H2O","reactorOrAtmosphere":"double-necked flask","timeOrConversionBasis":"time to generate 72 mL mixture gases (H2 + 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\"time_point_or_conversion_basis\": \"time to generate 72 mL mixture gases (H2 + CO2)\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = P0V / (2RTtnM)","whyPerformsWell":"B doping on carbon support regulates surface-interface property","temperatureReported":"50 °C","formicAcid":"3 M","formate":"7.5 M","acidFormateRatio":"1:2.5","baseOrAdditive":"sodium formate (SF)","solvent":"H2O","reactorOrAtmosphere":"double-necked flask","timeOrConversionBasis":"time to generate 72 mL mixture gases (H2 + CO2)"},{"activityId":"P079_PERF_004_ACT_001","paperId":"P079","catalystId":"P079_PERF_004","catalyst":"Pd/CK-N","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF","value":"572","metricType":"TOF","numericValue":"572.0","unit":"h-1","tof":"572.0","reactionContext":"Aqueous FA/SF solution","temperatureC":"50.0","solution":"aqueous FA/SF solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"aqueous FA/SF solution\", \"formic_acid_amount_or_concentration\": \"3 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"7.5 M\", \"formic_acid_to_formate_ratio\": \"1:2.5\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"H2O\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"double-necked flask\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"time to generate 72 mL mixture gases (H2 + CO2)\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd","definition":"TOF = P0V / (2RTtnM)","whyPerformsWell":"N doping on carbon support regulates surface-interface property","temperatureReported":"50 °C","formicAcid":"3 M","formate":"7.5 M","acidFormateRatio":"1:2.5","baseOrAdditive":"sodium formate (SF)","solvent":"H2O","reactorOrAtmosphere":"double-necked flask","timeOrConversionBasis":"time to generate 72 mL mixture gases (H2 + CO2)"},{"activityId":"P080_PERF_001_ACT_001","paperId":"P080","catalystId":"P080_PERF_001","catalyst":"Pd/DMSNs-1.0-NH2","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"initial TOF","value":"473.8","metricType":"TOF","numericValue":"473.8","unit":"h-1","tof":"473.8","reactionContext":"Formic acid dehydrogenation (FAD) in a 25 mL two-necked round-bottom flask with stirring; FA-SF mixed solution (2 mL, molar ratio FA:SF = 1:2, containing 2.5 mmol FA); catalyst dispersed in deionized water (3 mL).","temperatureC":"29.85","solution":"FA-SF mixed solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"303 K\", \"reaction_solution\": \"FA-SF mixed solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"molar ratio of FA to SF of 1:2\", \"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"deionized water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"5 wt% Pd\", \"reactor_or_atmosphere\": \"25 mL two-necked round-bottom flask\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": \"initial rate\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no detectable CO formation observed","stability":"Good recyclability across five consecutive tests: TOF values were 473.8, 468.5, 466.6, 462.5, and 460.3 h-1; total reaction times were 24.00, 24.30, 24.45, 24.48, and 24.55 min.","whyPerformsWell":"Dendritic center-radial 3D pore channels with high surface area, notable pore volume, and concentrative pore size distribution for modulated mass transfer; ultrasmall Pd NPs (1.6 nm) with high dispersion; suitable metal-support interaction (MSI) between 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solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"303 K\", \"reaction_solution\": \"FA-SF mixed solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"molar ratio of FA to SF of 1:2\", \"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"deionized water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"5 wt% Pd\", \"reactor_or_atmosphere\": \"25 mL two-necked round-bottom flask\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"100% H2 selectivity; no detectable CO formation observed","stability":"Good recyclability across five consecutive tests: TOF values were 473.8, 468.5, 466.6, 462.5, and 460.3 h-1; total reaction times were 24.00, 24.30, 24.45, 24.48, and 24.55 min.","whyPerformsWell":"Dendritic center-radial 3D pore channels with high surface area, notable pore volume, and concentrative pore size distribution for modulated mass transfer; ultrasmall Pd NPs (1.6 nm) with high dispersion; suitable metal-support interaction (MSI) between Pd NPs and DMSNs-1.0-NH2 support.","temperatureReported":"303 K","formicAcid":"2.5 mmol","formate":"molar ratio of FA to SF of 1:2","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","solvent":"deionized water","metalAmountOrRatio":"5 wt% Pd","reactorOrAtmosphere":"25 mL two-necked round-bottom flask","stirringOrFlow":"stirring"},{"activityId":"P080_PERF_001_ACT_003","paperId":"P080","catalystId":"P080_PERF_001","catalyst":"Pd/DMSNs-1.0-NH2","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"H2 selectivity","value":"100","metricType":"selectivity","numericValue":"100.0","unit":"%","reactionContext":"Formic acid dehydrogenation (FAD) in a 25 mL two-necked round-bottom flask with stirring; FA-SF mixed solution (2 mL, molar ratio FA:SF = 1:2, containing 2.5 mmol FA); catalyst dispersed in deionized water (3 mL).","temperatureC":"29.85","solution":"FA-SF mixed solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"303 K\", \"reaction_solution\": \"FA-SF mixed solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"molar ratio of FA to SF of 1:2\", \"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"deionized water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"5 wt% Pd\", \"reactor_or_atmosphere\": \"25 mL two-necked round-bottom flask\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"100% H2 selectivity; no detectable CO formation observed","stability":"Good recyclability across five consecutive tests: TOF values were 473.8, 468.5, 466.6, 462.5, and 460.3 h-1; total reaction times were 24.00, 24.30, 24.45, 24.48, and 24.55 min.","whyPerformsWell":"Dendritic center-radial 3D pore channels with high surface area, notable pore volume, and concentrative pore size distribution for modulated mass transfer; ultrasmall Pd NPs (1.6 nm) with high dispersion; suitable metal-support interaction (MSI) between Pd NPs and DMSNs-1.0-NH2 support.","temperatureReported":"303 K","formicAcid":"2.5 mmol","formate":"molar ratio of FA to SF of 1:2","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","solvent":"deionized water","metalAmountOrRatio":"5 wt% Pd","reactorOrAtmosphere":"25 mL two-necked round-bottom 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\"sodium formate (SF)\", \"solvent\": \"deionized water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"5 wt% Pd\", \"reactor_or_atmosphere\": \"25 mL two-necked round-bottom flask\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius equation","selectivity":"100% H2 selectivity; no detectable CO formation observed","stability":"Good recyclability across five consecutive tests: TOF values were 473.8, 468.5, 466.6, 462.5, and 460.3 h-1; total reaction times were 24.00, 24.30, 24.45, 24.48, and 24.55 min.","whyPerformsWell":"Dendritic center-radial 3D pore channels with high surface area, notable pore volume, and concentrative pore size distribution for modulated mass transfer; ultrasmall Pd NPs (1.6 nm) with high dispersion; suitable metal-support interaction (MSI) between Pd NPs and DMSNs-1.0-NH2 support.","temperatureReported":"various 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\"metal_amount_or_substrate_to_metal_ratio\": \"5 wt% Pd\", \"reactor_or_atmosphere\": \"25 mL two-necked round-bottom flask\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius equation","selectivity":"100% FA conversion","temperatureReported":"various temperatures","formicAcid":"2.5 mmol","formate":"molar ratio of FA to SF of 1:2","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","solvent":"deionized water","metalAmountOrRatio":"5 wt% Pd","reactorOrAtmosphere":"25 mL two-necked round-bottom flask","stirringOrFlow":"stirring"},{"activityId":"P080_PERF_004_ACT_001","paperId":"P080","catalystId":"P080_PERF_004","catalyst":"Pd/DMSNs-2.0-NH2","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF","value":"344.4","metricType":"TOF","numericValue":"344.4","unit":"h-1","tof":"344.4","reactionContext":"Same as 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\"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","temperatureReported":"298.15 K","solvent":"gas phase"},{"activityId":"P081_PERF_001_ACT_002","paperId":"P081","catalystId":"P081_PERF_001","catalyst":"C2N-Co","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"Density Functional Theory (DFT) calculations","metric":"rate-determining step barrier (high-spin state)","value":"0.93","metricType":"rate","numericValue":"0.93","unit":"eV","reactionContext":"HCOOH dehydrogenation","temperatureC":"25.0","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298.15 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"gas phase\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","temperatureReported":"298.15 K","solvent":"gas phase"},{"activityId":"P081_PERF_002_ACT_001","paperId":"P081","catalystId":"P081_PERF_002","catalyst":"C2N-Co-Sn","activeMetals":"Co-Sn","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"2","method":"Density Functional Theory (DFT) calculations","metric":"rate-determining step barrier (low-spin, 1,4 adsorption)","value":"0.79","metricType":"rate","numericValue":"0.79","unit":"eV","reactionContext":"HCOOH dehydrogenation","temperatureC":"25.0","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298.15 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"gas phase\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","stability":"nitrogen-doped porous-carbon-supported Co or Sn could maintain intact under 450−650 °C","whyPerformsWell":"Noncontact single atom promoter (Sn) manipulates the electronic state of Co via charge redistribution of C2N support, making high-spin and low-spin states almost degenerate. High-spin Co provides a lower reaction barrier due to increased charge transfer from HCOOH to Co and d-band center shifting closer to the Fermi level.","temperatureReported":"298.15 K","solvent":"gas phase"},{"activityId":"P081_PERF_002_ACT_002","paperId":"P081","catalystId":"P081_PERF_002","catalyst":"C2N-Co-Sn","activeMetals":"Co-Sn","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"2","method":"Density Functional Theory (DFT) calculations","metric":"rate-determining step barrier (low-spin, 1,3 adsorption)","value":"0.74","metricType":"rate","numericValue":"0.74","unit":"eV","reactionContext":"HCOOH dehydrogenation","temperatureC":"25.0","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298.15 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"gas phase\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","stability":"nitrogen-doped porous-carbon-supported Co or Sn could maintain intact under 450−650 °C","whyPerformsWell":"Noncontact single atom promoter (Sn) manipulates the electronic state of Co via charge redistribution of C2N support, making high-spin and low-spin states almost degenerate. 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High-spin Co provides a lower reaction barrier due to increased charge transfer from HCOOH to Co and d-band center shifting closer to the Fermi level.","temperatureReported":"298.15 K","solvent":"gas phase"},{"activityId":"P081_PERF_003_ACT_001","paperId":"P081","catalystId":"P081_PERF_003","catalyst":"C2N-Co-Ge","activeMetals":"Co-Ge","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"2","method":"Density Functional Theory (DFT) calculations","metric":"rate-determining step barrier (high-spin)","metricType":"rate","unit":"eV","reactionContext":"HCOOH dehydrogenation","temperatureC":"25.0","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298.15 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"gas phase\", \"catalyst_amount\": null, 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\"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"gas phase\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"lower than low-spin state and enhanced compared to C2N-Co","whyPerformsWell":"Similar to C2N-Co-Sn, Pb acts as a noncontact SAP manipulating the spin state of Co.","temperatureReported":"298.15 K","solvent":"gas phase"},{"activityId":"P082_PERF_001_ACT_001","paperId":"P082","catalystId":"P082_PERF_001","catalyst":"PdNi-WOx/KIT-6-NH2","activeMetals":"Pd-Ni-W","metalClass":"Pd-based 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\"formate_or_sodium_formate_amount_or_concentration\": \"none\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": null, \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.04\", \"reactor_or_atmosphere\": \"double-necked round-bottomed flask\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd; Ni","whyPerformsWell":"Poorer activity due to larger particle size (7.7 nm) and lack of amino groups","temperatureReported":"323 K","formicAcid":"2.5 mmol","formate":"none","baseOrAdditive":"none","metalAmountOrRatio":"n_metal/n_FA = 0.04","reactorOrAtmosphere":"double-necked round-bottomed 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initial catalysis activity and conversion of phenol to cyclohexanone with five recycled uses.","whyPerformsWell":"Ultra-fine Pd NPs (avg 2.8 nm) on N-doped porous biochar; phosphate-mediation ensures fine dispersion; reduced H poisoning and more exposed (100) surface/Pd-cluster-edge.","temperatureReported":"313 K","acidFormateRatio":"1/2.5","solvent":"water","timeOrConversionBasis":"1/10 of the dehydrogenation reaction"},{"activityId":"P088_PERF_001_ACT_003","paperId":"P088","catalystId":"P088_PERF_001","catalyst":"Pd@MC(2)-P","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOFg","value":"2735","metricType":"other","numericValue":"2735.0","unit":"h-1","reactionContext":"Formic acid (FA) dehydrogenation in FA/SF solution; In situ hydrogenation of phenol to cyclohexanone.","temperatureC":"49.85","solution":"FA/SF solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"323 K\", 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high initial catalysis activity and conversion of phenol to cyclohexanone with five recycled uses.","whyPerformsWell":"Ultra-fine Pd NPs (avg 2.8 nm) on N-doped porous biochar; phosphate-mediation ensures fine dispersion; reduced H poisoning and more exposed (100) surface/Pd-cluster-edge.","temperatureReported":"333 K","acidFormateRatio":"1/2.5","solvent":"water","timeOrConversionBasis":"1/10 of the dehydrogenation reaction"},{"activityId":"P088_PERF_001_ACT_005","paperId":"P088","catalystId":"P088_PERF_001","catalyst":"Pd@MC(2)-P","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOFs","value":"1597","metricType":"other","numericValue":"1597.0","unit":"h-1","reactionContext":"Formic acid (FA) dehydrogenation in FA/SF solution; In situ hydrogenation of phenol to cyclohexanone.","temperatureC":"29.85","solution":"FA/SF solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"303 K\", \"reaction_solution\": \"FA/SF solution\", \"formic_acid_to_formate_ratio\": \"1/2.5\", \"solvent\": \"water\", \"time_point_or_conversion_basis\": \"1/10 of the dehydrogenation reaction\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"PV / (RT * nPd,d * t)","selectivity":"High selectivity for cyclohexanone (>90%) in phenol hydrogenation.","stability":"Maintains high initial catalysis activity and conversion of phenol to cyclohexanone with five recycled uses.","whyPerformsWell":"Ultra-fine Pd NPs (avg 2.8 nm) on N-doped porous biochar; phosphate-mediation ensures fine dispersion; reduced H poisoning and more exposed (100) surface/Pd-cluster-edge.","temperatureReported":"303 K","acidFormateRatio":"1/2.5","solvent":"water","timeOrConversionBasis":"1/10 of the dehydrogenation 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dehydrogenation in FA/SF solution.","temperatureC":"59.85","solution":"FA/SF solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"333 K\", \"reaction_solution\": \"FA/SF solution\", \"formic_acid_to_formate_ratio\": \"1/2.5\", \"solvent\": \"water\", \"time_point_or_conversion_basis\": \"1/10 of the dehydrogenation reaction\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"PV / (RT * nPd,a * t)","whyPerformsWell":"Lowest activity due to severe agglomeration of Pd particles (avg 5.7 nm) and absence of phosphate-mediated dispersion.","temperatureReported":"333 K","acidFormateRatio":"1/2.5","solvent":"water","timeOrConversionBasis":"1/10 of the dehydrogenation 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dispersion.","temperatureReported":"303 K","acidFormateRatio":"1/2.5","solvent":"water","timeOrConversionBasis":"1/10 of the dehydrogenation reaction"},{"activityId":"P088_PERF_003_ACT_006","paperId":"P088","catalystId":"P088_PERF_003","catalyst":"Pd@MC(2)-0","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOFs","value":"419","metricType":"other","numericValue":"419.0","unit":"h-1","reactionContext":"Formic acid (FA) dehydrogenation in FA/SF solution.","temperatureC":"39.85","solution":"FA/SF solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"313 K\", \"reaction_solution\": \"FA/SF solution\", \"formic_acid_to_formate_ratio\": \"1/2.5\", \"solvent\": \"water\", \"time_point_or_conversion_basis\": \"1/10 of the dehydrogenation reaction\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"PV / (RT * nPd,d * 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null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"distilled water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"reaction tube connected to a gas burette\", \"stirring_or_flow_condition\": \"300 rpm\", \"time_point_or_conversion_basis\": \"5 min\"}","basis":"unclear","basisRaw":"unclear","definition":"n = PV/RT","whyPerformsWell":"Possesses fewer Pd hollow sites than catalyst 1.","temperatureReported":"50 °C","formicAcid":"10 mmol (370 μL in 9.7 mL distilled water)","solvent":"distilled water","catalystAmount":"50 mg","reactorOrAtmosphere":"reaction tube connected to a gas burette","stirringOrFlow":"300 rpm","timeOrConversionBasis":"5 min"},{"activityId":"P089_PERF_003_ACT_001","paperId":"P089","catalystId":"P089_PERF_003","catalyst":"PdAu/Al2O3–N2 (3)","activeMetals":"Pd-Au","metalClass":"Pd-based 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\"reaction_solution\": \"aqueous FA solution (~1.0 M)\", \"formic_acid_amount_or_concentration\": \"10 mmol (370 μL in 9.7 mL distilled water)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"distilled water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"reaction tube connected to a gas burette\", \"stirring_or_flow_condition\": \"300 rpm\", \"time_point_or_conversion_basis\": \"5 min\"}","basis":"unclear","basisRaw":"unclear","whyPerformsWell":"Lower H2-release activity compared to catalyst 1 despite higher quantity of 3-fold hollow Pd sites, indicating the importance of the ligand effect from Au sublayers.","temperatureReported":"50 °C","formicAcid":"10 mmol (370 μL in 9.7 mL distilled water)","solvent":"distilled water","catalystAmount":"50 mg","reactorOrAtmosphere":"reaction tube connected to a gas 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Initial reaction rates for cycles 1-6: 22.7, 20.5, 19.6, 20.0, 17.4, and 17.0 mL min-1.","whyPerformsWell":"Nitrogen functional groups in NAS support serve as anchoring sites for smaller, well-distributed bimetallic nanoparticles; increase surface basicity favoring HCOOH interaction; stabilize Pd2+ species which, along with Pd0, are needed for the dehydrogenation mechanism via formate intermediate. Ag incorporation modifies electronic properties of Pd.","temperatureReported":"75 °C","formicAcid":"2 M (part of mixture)","formate":"2 M (part of mixture)","acidFormateRatio":"9/1","baseOrAdditive":"sodium formate","solvent":"distilled water","catalystAmount":"0.15 g","reactorOrAtmosphere":"reactor purged with nitrogen gas connected to a burette system","timeOrConversionBasis":"first 3 minutes of reaction"},{"activityId":"P090_PERF_001_ACT_002","paperId":"P090","catalystId":"P090_PERF_001","catalyst":"Pd1Ag0.5/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"co_impregnation","metric":"total volume of gas generated","value":"218","metricType":"rate","numericValue":"218.0","unit":"mL","reactionContext":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g catalyst","temperatureC":"75.0","solution":"formic acid/sodium formate 2 M solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"75 °C\", \"reaction_solution\": \"formic acid/sodium formate 2 M solution\", \"formic_acid_amount_or_concentration\": \"2 M (part of mixture)\", \"formate_or_sodium_formate_amount_or_concentration\": \"2 M (part of mixture)\", \"formic_acid_to_formate_ratio\": \"9/1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"0.15 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"reactor purged with nitrogen gas connected to a burette system\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"30 min of reaction\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","stability":"Maintained substantial activity over 6 consecutive reaction cycles; loss of 25% of initial activity in the sixth cycle. Initial reaction rates for cycles 1-6: 22.7, 20.5, 19.6, 20.0, 17.4, and 17.0 mL min-1.","whyPerformsWell":"Nitrogen functional groups in NAS support serve as anchoring sites for smaller, well-distributed bimetallic nanoparticles; increase surface basicity favoring HCOOH interaction; stabilize Pd2+ species which, along with Pd0, are needed for the dehydrogenation mechanism via formate intermediate. 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Initial reaction rates for cycles 1-6: 23.5, 19.6, 17.9, 12.6, 12.2, and 10.0 mL min-1.","whyPerformsWell":"PdAg alloy formation modifies electronic properties compared to monometallic Pd.","temperatureReported":"75 °C","formicAcid":"2 M (part of mixture)","formate":"2 M (part of mixture)","acidFormateRatio":"9/1","baseOrAdditive":"sodium formate","solvent":"distilled water","catalystAmount":"0.15 g","reactorOrAtmosphere":"reactor purged with nitrogen gas connected to a burette system","timeOrConversionBasis":"30 min of reaction"},{"activityId":"P090_PERF_003_ACT_001","paperId":"P090","catalystId":"P090_PERF_003","catalyst":"Pd/AS","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"total volume of gas generated","value":"35","metricType":"rate","numericValue":"35.0","unit":"mL","reactionContext":"75 °C, 2 M formic acid/sodium formate solution (9:1 molar ratio) in distilled water, 0.15 g 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0.04","reactorOrAtmosphere":"water-filled graduated buret system","stirringOrFlow":"magnetic stirring (implied by fabrication and general setup)","timeOrConversionBasis":"initial"},{"activityId":"P095_PERF_001_ACT_002","paperId":"P095","catalystId":"P095_PERF_001","catalyst":"Pd−Cr(OH)3/NH2-rGO","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"sequential_impregnation","metric":"initial TOF","value":"3599.8","metricType":"TOF","numericValue":"3599.8","unit":"h−1","tof":"3599.8","reactionContext":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","temperatureC":"49.85","solution":"aqueous FA solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"323 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol (in 2 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, 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dissociation.","temperatureReported":"323 K","formicAcid":"2.5 mmol (in 2 mL)","baseOrAdditive":"none","solvent":"deionized water (3 mL)","metalAmountOrRatio":"nPd/nFA = 0.04","reactorOrAtmosphere":"water-filled graduated buret system","timeOrConversionBasis":"initial"},{"activityId":"P095_PERF_001_ACT_003","paperId":"P095","catalystId":"P095_PERF_001","catalyst":"Pd−Cr(OH)3/NH2-rGO","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"sequential_impregnation","metric":"apparent activation energy","value":"38.2","metricType":"activation_energy","numericValue":"38.2","unit":"kJ/mol","reactionContext":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","temperatureC":"54.85","solution":"aqueous FA solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"313 to 343 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol (in 2 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"deionized water (3 mL)\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 0.04\", \"reactor_or_atmosphere\": \"water-filled graduated buret system\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"calculated from Arrhenius curves","selectivity":"100% H2 selectivity; CO-free","stability":"Robust durability with no significant decline in activity and aggregation of metal NCs even after 10 cycles.","whyPerformsWell":"Well-distributed ultrafine Pd−Cr(OH)3 nanoclusters (1.6 nm), strong electronic coupling of Pd with Cr(OH)3 making Pd electron-rich, synergistic interaction of Pd−Cr(OH)3 with NH2-rGO, and the promotion effect of amino groups acting as Brønsted basic sites to accelerate O-H bond dissociation.","temperatureReported":"313 to 343 K","formicAcid":"2.5 mmol (in 2 mL)","baseOrAdditive":"none","solvent":"deionized water (3 mL)","metalAmountOrRatio":"nPd/nFA = 0.04","reactorOrAtmosphere":"water-filled graduated buret system"},{"activityId":"P095_PERF_002_ACT_001","paperId":"P095","catalystId":"P095_PERF_002","catalyst":"Pd/NH2-rGO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"sequential_impregnation","metric":"initial TOF","value":"1183.4","metricType":"TOF","numericValue":"1183.4","unit":"h−1","tof":"1183.4","reactionContext":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","temperatureC":"49.85","solution":"aqueous FA solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"323 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol (in 2 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"deionized water (3 mL)\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 0.04\", \"reactor_or_atmosphere\": \"water-filled graduated buret system\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","stability":"Good durability, but an obvious loss of activity was observed after the 9th and 10th runs.","whyPerformsWell":"Amino groups on NH2-rGO serve as anchoring sites for ultrafine metal NCs and act as Brønsted basic sites.","temperatureReported":"323 K","formicAcid":"2.5 mmol (in 2 mL)","baseOrAdditive":"none","solvent":"deionized water (3 mL)","metalAmountOrRatio":"nPd/nFA = 0.04","reactorOrAtmosphere":"water-filled graduated buret system","timeOrConversionBasis":"initial"},{"activityId":"P095_PERF_002_ACT_002","paperId":"P095","catalystId":"P095_PERF_002","catalyst":"Pd/NH2-rGO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"sequential_impregnation","metric":"apparent activation energy","value":"59.1","metricType":"activation_energy","numericValue":"59.1","unit":"kJ/mol","reactionContext":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","temperatureC":"54.85","solution":"aqueous FA solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"313 to 343 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol (in 2 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"deionized water (3 mL)\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 0.04\", \"reactor_or_atmosphere\": \"water-filled graduated buret system\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"calculated from Arrhenius curves","stability":"Good durability, but an obvious loss of activity was observed after the 9th and 10th runs.","whyPerformsWell":"Amino groups on NH2-rGO serve as anchoring sites for ultrafine metal NCs and act as Brønsted basic sites.","temperatureReported":"313 to 343 K","formicAcid":"2.5 mmol (in 2 mL)","baseOrAdditive":"none","solvent":"deionized water (3 mL)","metalAmountOrRatio":"nPd/nFA = 0.04","reactorOrAtmosphere":"water-filled graduated buret system"},{"activityId":"P095_PERF_003_ACT_001","paperId":"P095","catalystId":"P095_PERF_003","catalyst":"Pd−Cr(OH)3/rGO","activeMetals":"Pd-Cr","metalClass":"Pd-based 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\"initial\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","whyPerformsWell":"Integration of Cr(OH)3 significantly enhances the catalytic performance of Pd compared to Pd/rGO.","temperatureReported":"323 K","formicAcid":"2.5 mmol (in 2 mL)","baseOrAdditive":"none","solvent":"deionized water (3 mL)","metalAmountOrRatio":"nPd/nFA = 0.04","reactorOrAtmosphere":"water-filled graduated buret system","timeOrConversionBasis":"initial"},{"activityId":"P095_PERF_004_ACT_001","paperId":"P095","catalystId":"P095_PERF_004","catalyst":"Pd/rGO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"sequential_impregnation","metric":"initial TOF","value":"29.4","metricType":"TOF","numericValue":"29.4","unit":"h−1","tof":"29.4","reactionContext":"Additive-free formic acid dehydrogenation (FAD) in a water-filled graduated buret system.","temperatureC":"49.85","solution":"aqueous FA solution","temperatureBin":"40-60 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\"aqueous\", \"formic_acid_amount_or_concentration\": \"0.3 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"1 M\", \"formic_acid_to_formate_ratio\": \"0.3:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Schlenk tube\", \"stirring_or_flow_condition\": \"batch\", \"time_point_or_conversion_basis\": \"15 min\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Ag; Pd","definition":"TOF = (P0 * V) / (2 * R * T * n(Ag+Pd) * t)","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th cycle; no significant decrement in aldehyde hydrogenation activity after 6 consecutive cycles.","whyPerformsWell":"Ultrafine dispersion (2.2 nm), synergistic effects between Ag and Pd, strong metal-support 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hydrogenation.","temperatureC":"34.85","solution":"aqueous","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"308 K\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"0.3 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"1 M\", \"formic_acid_to_formate_ratio\": \"0.3:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Schlenk tube\", \"stirring_or_flow_condition\": \"batch\", \"time_point_or_conversion_basis\": null}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Ag; Pd","definition":"TOF = (P0 * V) / (2 * R * T * n(Ag+Pd) * t)","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th cycle; no significant decrement in 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Suzuki-Miyaura coupling, and aldehyde hydrogenation.","temperatureC":"44.85","solution":"aqueous","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"318 K\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"0.3 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"1 M\", \"formic_acid_to_formate_ratio\": \"0.3:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Schlenk tube\", \"stirring_or_flow_condition\": \"batch\", \"time_point_or_conversion_basis\": null}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Ag; Pd","definition":"TOF = (P0 * V) / (2 * R * T * n(Ag+Pd) * t)","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th 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formic acid dehydrogenation, Suzuki-Miyaura coupling, and aldehyde hydrogenation.","temperatureC":"54.85","solution":"aqueous","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"328 K\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"0.3 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"1 M\", \"formic_acid_to_formate_ratio\": \"0.3:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Schlenk tube\", \"stirring_or_flow_condition\": \"batch\", \"time_point_or_conversion_basis\": null}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Ag; Pd","definition":"TOF = (P0 * V) / (2 * R * T * n(Ag+Pd) * t)","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th cycle; no significant decrement in aldehyde hydrogenation activity after 6 consecutive cycles.","whyPerformsWell":"Ultrafine dispersion (2.2 nm), synergistic effects between Ag and Pd, strong metal-support interaction (SMSI) with PDA coating, strain effect from nanoalloying, and lower energy path for hydrogen desorption as shown by DFT calculations.","temperatureReported":"328 K","formicAcid":"0.3 M","formate":"1 M","acidFormateRatio":"0.3:1","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"10 mg","reactorOrAtmosphere":"Schlenk tube","stirringOrFlow":"batch"},{"activityId":"P096_PERF_001_ACT_006","paperId":"P096","catalystId":"P096_PERF_001","catalyst":"AgPd@MIL-125-NH2-PDA","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"yield","value":"98","metricType":"other","numericValue":"98.0","unit":"%","reactionContext":"Multifunctional catalysis including formic acid dehydrogenation, Suzuki-Miyaura coupling, and aldehyde hydrogenation.","temperatureC":"60.0","solution":"ethanol/water (1:1)","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"ethanol/water (1:1)\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"K2CO3 (1.5 mmol)\", \"solvent\": \"ethanol/water\", \"catalyst_amount\": \"15 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Schlenk tube, N2 purged\", \"stirring_or_flow_condition\": \"batch\", \"time_point_or_conversion_basis\": \"1.5 h\"}","basis":"unclear","basisRaw":"unclear","definition":"isolated yield","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th cycle; no 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Suzuki-Miyaura coupling, and aldehyde hydrogenation.","temperatureC":"85.0","solution":"2-propanol","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"85 °C\", \"reaction_solution\": \"2-propanol\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"KOH (0.2 mmol)\", \"solvent\": \"2-propanol\", \"catalyst_amount\": \"15 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"reflux\", \"stirring_or_flow_condition\": \"batch\", \"time_point_or_conversion_basis\": \"4-nitrobenzaldehyde model\"}","basis":"unclear","basisRaw":"unclear","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th cycle; no significant decrement in aldehyde hydrogenation activity after 6 consecutive cycles.","whyPerformsWell":"Ultrafine dispersion (2.2 nm), synergistic effects between Ag and Pd, strong metal-support interaction (SMSI) with PDA coating, strain effect from nanoalloying, and lower energy path for hydrogen desorption as shown by DFT calculations.","temperatureReported":"85 °C","baseOrAdditive":"KOH (0.2 mmol)","solvent":"2-propanol","catalystAmount":"15 mg","reactorOrAtmosphere":"reflux","stirringOrFlow":"batch","timeOrConversionBasis":"4-nitrobenzaldehyde model"},{"activityId":"P096_PERF_001_ACT_008","paperId":"P096","catalystId":"P096_PERF_001","catalyst":"AgPd@MIL-125-NH2-PDA","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"rate constant","value":"20 x 10^3","metricType":"rate","numericValue":"20.0","unit":"sec⁻¹","reactionContext":"Multifunctional catalysis including formic acid dehydrogenation, Suzuki-Miyaura coupling, and aldehyde hydrogenation.","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": \"nitrophenol reduction\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th cycle; no significant decrement in aldehyde hydrogenation activity after 6 consecutive cycles.","whyPerformsWell":"Ultrafine dispersion (2.2 nm), synergistic effects between Ag and Pd, strong metal-support interaction (SMSI) with PDA coating, strain effect from nanoalloying, and lower energy path for hydrogen desorption as shown by DFT calculations.","stirringOrFlow":"nitrophenol reduction"},{"activityId":"P096_PERF_001_ACT_009","paperId":"P096","catalystId":"P096_PERF_001","catalyst":"AgPd@MIL-125-NH2-PDA","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"TOF","value":"3200","metricType":"TOF","numericValue":"3200.0","unit":"h⁻¹","tof":"3200.0","reactionContext":"Multifunctional catalysis including formic acid dehydrogenation, Suzuki-Miyaura coupling, and aldehyde hydrogenation.","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": \"nitrophenol reduction\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","stability":"Highly stable; no apparent reduction in FA dehydrogenation performance till 5 cycles; >93% conversion achieved during each cycle of Suzuki coupling until 6th cycle; no significant decrement in aldehyde hydrogenation activity after 6 consecutive cycles.","whyPerformsWell":"Ultrafine dispersion (2.2 nm), synergistic effects between Ag and Pd, strong metal-support interaction (SMSI) with PDA coating, strain effect from nanoalloying, and lower energy path for hydrogen desorption as shown by DFT calculations.","stirringOrFlow":"nitrophenol 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\"Schlenk tube\", \"stirring_or_flow_condition\": \"batch\", \"time_point_or_conversion_basis\": null}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd","definition":"TOF = (P0 * V) / (2 * R * T * n(Ag+Pd) * t)","temperatureReported":"35 °C","formicAcid":"0.3 M","formate":"1 M","acidFormateRatio":"0.3:1","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"10 mg","reactorOrAtmosphere":"Schlenk tube","stirringOrFlow":"batch"},{"activityId":"P097_PERF_001_ACT_001","paperId":"P097","catalystId":"P097_PERF_001","catalyst":"Zn51.9Pd48.1","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"solid-vapor synthesis","metric":"activity (A)","value":"21","metricType":"other","numericValue":"21.0","unit":"mmolCOx mmolPd-1 h-1","reactionContext":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","temperatureC":"270.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"270 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"0.021 mL min-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)\", \"stirring_or_flow_condition\": \"flow\", \"time_point_or_conversion_basis\": \"1 h\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"A = COx_out / (nPd * t)","selectivity":"98.5-99.9% CO2 selectivity","stability":"Undergoes reversible oxidation/reduction during heating/cooling in formic acid; H2/CO2 ratio drops to ~0.8 above 240 °C","whyPerformsWell":"Oxidation of Zn and formation of zinc formate hinders the overall reaction rate compared to Pd-rich samples.","temperatureReported":"270 °C","formicAcid":"0.021 mL min-1","catalystAmount":"50 mg","reactorOrAtmosphere":"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)","stirringOrFlow":"flow","timeOrConversionBasis":"1 h"},{"activityId":"P097_PERF_001_ACT_002","paperId":"P097","catalystId":"P097_PERF_001","catalyst":"Zn51.9Pd48.1","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"solid-vapor synthesis","metric":"apparent activation energy","value":"34(3) / 45(2)","metricType":"activation_energy","numericValue":"34.0","unit":"kJ mol-1","reactionContext":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","temperatureC":"180.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"150-210 °C / 240-330 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"0.021 mL min-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)\", \"stirring_or_flow_condition\": \"flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"98.5-99.9% CO2 selectivity","stability":"Undergoes reversible oxidation/reduction during heating/cooling in formic acid; H2/CO2 ratio drops to ~0.8 above 240 °C","whyPerformsWell":"Oxidation of Zn and formation of zinc formate hinders the overall reaction rate compared to Pd-rich samples.","temperatureReported":"150-210 °C / 240-330 °C","formicAcid":"0.021 mL min-1","catalystAmount":"50 mg","reactorOrAtmosphere":"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)","stirringOrFlow":"flow"},{"activityId":"P097_PERF_002_ACT_001","paperId":"P097","catalystId":"P097_PERF_002","catalyst":"Zn49.8Pd50.2","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"solid-vapor synthesis","metric":"activity (A)","value":"25","metricType":"other","numericValue":"25.0","unit":"mmolCOx mmolPd-1 h-1","reactionContext":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","temperatureC":"270.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"270 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"0.021 mL min-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)\", \"stirring_or_flow_condition\": \"flow\", \"time_point_or_conversion_basis\": \"1 h\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"A = COx_out / (nPd * t)","selectivity":"Reversible decrease of CO2 selectivity down to 96% with increasing reaction temperature","stability":"Undergoes reversible oxidation/reduction during heating/cooling in formic acid; H2/CO2 ratio drops to ~0.9 above 240 °C","whyPerformsWell":"Oxidation of Zn and formation of zinc formate hinders the overall reaction rate compared to Pd-rich samples.","temperatureReported":"270 °C","formicAcid":"0.021 mL min-1","catalystAmount":"50 mg","reactorOrAtmosphere":"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)","stirringOrFlow":"flow","timeOrConversionBasis":"1 h"},{"activityId":"P097_PERF_002_ACT_002","paperId":"P097","catalystId":"P097_PERF_002","catalyst":"Zn49.8Pd50.2","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"solid-vapor synthesis","metric":"apparent activation energy","value":"32(3) / 47(3)","metricType":"activation_energy","numericValue":"32.0","unit":"kJ mol-1","reactionContext":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","temperatureC":"180.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"150-210 °C / 240-330 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"0.021 mL min-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)\", \"stirring_or_flow_condition\": \"flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"Reversible decrease of CO2 selectivity down to 96% with increasing reaction temperature","stability":"Undergoes reversible oxidation/reduction during heating/cooling in formic acid; H2/CO2 ratio drops to ~0.9 above 240 °C","whyPerformsWell":"Oxidation of Zn and formation of zinc formate hinders the overall reaction rate compared to Pd-rich samples.","temperatureReported":"150-210 °C / 240-330 °C","formicAcid":"0.021 mL min-1","catalystAmount":"50 mg","reactorOrAtmosphere":"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)","stirringOrFlow":"flow"},{"activityId":"P097_PERF_003_ACT_001","paperId":"P097","catalystId":"P097_PERF_003","catalyst":"Zn42.0Pd58.0","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"solid-vapor synthesis","metric":"activity (A)","value":"85","metricType":"other","numericValue":"85.0","unit":"mmolCOx mmolPd-1 h-1","reactionContext":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","temperatureC":"270.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"270 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"0.021 mL min-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)\", \"stirring_or_flow_condition\": \"flow\", \"time_point_or_conversion_basis\": \"1 h\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"A = COx_out / (nPd * t)","selectivity":"99.5-99.9% CO2 selectivity","stability":"More resistant against surface oxidation; H2/CO2 ratio remains approximately 1.0","whyPerformsWell":"Higher Pd content leads to higher stability against oxidation and prevents the formation of hindering zinc formate species.","temperatureReported":"270 °C","formicAcid":"0.021 mL min-1","catalystAmount":"50 mg","reactorOrAtmosphere":"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)","stirringOrFlow":"flow","timeOrConversionBasis":"1 h"},{"activityId":"P097_PERF_003_ACT_002","paperId":"P097","catalystId":"P097_PERF_003","catalyst":"Zn42.0Pd58.0","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"solid-vapor synthesis","metric":"apparent activation energy","value":"53(2)","metricType":"activation_energy","numericValue":"53.0","unit":"kJ mol-1","reactionContext":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: reduced in 100 vol.% H2 at 200 °C for 1h","temperatureC":"195.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"150-240 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"0.021 mL min-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)\", \"stirring_or_flow_condition\": \"flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"99.5-99.9% CO2 selectivity","stability":"More resistant against surface oxidation; H2/CO2 ratio remains approximately 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°C","evaluationConditions":"{\"reaction_temperature\": \"270 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"0.021 mL min-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)\", \"stirring_or_flow_condition\": \"flow\", \"time_point_or_conversion_basis\": \"1 h\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"A = COx_out / (nPd * t)","selectivity":"99.2-99.8% CO2 selectivity","stability":"H2/CO2 ratio change similar to Zn-rich bulk samples; reproducible and reversible upon second heating","whyPerformsWell":"Highest activity among tested materials due to the supported ZnPd nanoparticles on ZnO.","temperatureReported":"270 °C","formicAcid":"0.021 mL min-1","catalystAmount":"10 mg","reactorOrAtmosphere":"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)","stirringOrFlow":"flow","timeOrConversionBasis":"1 h"},{"activityId":"P097_PERF_004_ACT_002","paperId":"P097","catalystId":"P097_PERF_004","catalyst":"ZnPd/ZnO","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"incipient_wetness_impregnation","metric":"apparent activation energy","value":"32(3) / 28(3)","metricType":"activation_energy","numericValue":"32.0","unit":"kJ mol-1","reactionContext":"Plug-flow reactor; feed: 0.021 mL min-1 formic acid, 41 mL min-1 N2, 4 mL min-1 He; catalyst mixed with 200 mg graphite; pretreatment: calcined at 500 °C in synthetic air for 3h and reduced in 5 vol.% H2 at 500 °C for 2h","temperatureC":"180.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"150-210 °C / 240-330 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"0.021 mL min-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)\", \"stirring_or_flow_condition\": \"flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"99.2-99.8% CO2 selectivity","stability":"H2/CO2 ratio change similar to Zn-rich bulk samples; reproducible and reversible upon second heating","whyPerformsWell":"Highest activity among tested materials due to the supported ZnPd nanoparticles on ZnO.","temperatureReported":"150-210 °C / 240-330 °C","formicAcid":"0.021 mL min-1","catalystAmount":"10 mg","reactorOrAtmosphere":"plug-flow reactor; N2 (41 mL min-1) and He (4 mL min-1)","stirringOrFlow":"flow"},{"activityId":"P098_PERF_001_ACT_001","paperId":"P098","catalystId":"P098_PERF_001","catalyst":"Pd/C3N4","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF","value":"36.80","metricType":"TOF","numericValue":"36.8","unit":"h-1","tof":"36.8","reactionContext":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C, stirring at 1036 rpm; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","temperatureC":"60.0","solution":"1M formic acid aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"1M formic acid aqueous solution\", \"formic_acid_amount_or_concentration\": \"1M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"semi-batch reactor\", \"stirring_or_flow_condition\": \"1036 rpm\", \"time_point_or_conversion_basis\": \"120 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"mmol of H2 produced / (mmol of Pd * time)","selectivity":"Liquid-phase: complete selectivity towards dehydrogenation (no CO, CH4 detected). Gas-phase: negligible CO at low temperatures; CO production increased above 300 °C.","stability":"Stable performance for 30 h at 250 °C in gas phase, conversion > 90%.","whyPerformsWell":"Nitrogen species on C3N4 surface stabilize Pd particles and provide adsorption sites while reducing electron density on the Pd surface, allowing easier adsorption of reactives.","temperatureReported":"60 °C","formicAcid":"1M","solvent":"water","catalystAmount":"0.1 g","reactorOrAtmosphere":"semi-batch reactor","stirringOrFlow":"1036 rpm","timeOrConversionBasis":"120 min"},{"activityId":"P098_PERF_001_ACT_002","paperId":"P098","catalystId":"P098_PERF_001","catalyst":"Pd/C3N4","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TON","value":"73.59","metricType":"TON","numericValue":"73.59","reactionContext":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C, stirring at 1036 rpm; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","temperatureC":"60.0","solution":"1M formic acid aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"1M formic acid aqueous solution\", \"formic_acid_amount_or_concentration\": \"1M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"semi-batch reactor\", \"stirring_or_flow_condition\": \"1036 rpm\", \"time_point_or_conversion_basis\": \"120 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"mmol of H2 produced / mmol of Pd","selectivity":"Liquid-phase: complete selectivity towards dehydrogenation (no CO, CH4 detected). 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Gas-phase: CO produced at low temperatures (< 275 °C) via dehydration; above 275 °C, selectivity shifts to CH4 production via CO methanation.","stability":"Stable performance for 30 h at 250 °C in gas phase, conversion > 90%.","temperatureReported":"250 °C","formicAcid":"5% v/v formic acid","solvent":"25% v/v distilled water","catalystAmount":"0.5 mL","reactorOrAtmosphere":"fixed-bed stainless-steel reactor, 70% v/v N2","stirringOrFlow":"GHSV ≈ 18,000 h-1","timeOrConversionBasis":"30 h stability test"},{"activityId":"P098_PERF_003_ACT_001","paperId":"P098","catalystId":"P098_PERF_003","catalyst":"PdRu/C3N4","activeMetals":"Pd-Ru","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"TOF","value":"30.34","metricType":"TOF","numericValue":"30.34","unit":"h-1","tof":"30.34","reactionContext":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","temperatureC":"60.0","solution":"1M formic acid aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"1M formic acid aqueous solution\", \"formic_acid_amount_or_concentration\": \"1M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"semi-batch reactor\", \"stirring_or_flow_condition\": \"1036 rpm\", \"time_point_or_conversion_basis\": \"120 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"mmol of H2 produced / (mmol of Pd * time)","selectivity":"Liquid-phase: complete selectivity towards dehydrogenation. 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Bimetallic catalyst combines the action of both metals in gas phase (WGS at low T and methanation at high T).","temperatureReported":"60 °C","formicAcid":"1M","solvent":"water","catalystAmount":"0.1 g","reactorOrAtmosphere":"semi-batch reactor","stirringOrFlow":"1036 rpm","timeOrConversionBasis":"120 min"},{"activityId":"P098_PERF_003_ACT_002","paperId":"P098","catalystId":"P098_PERF_003","catalyst":"PdRu/C3N4","activeMetals":"Pd-Ru","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"TON","value":"60.68","metricType":"TON","numericValue":"60.68","reactionContext":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","temperatureC":"60.0","solution":"1M formic acid aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"1M formic acid aqueous solution\", \"formic_acid_amount_or_concentration\": \"1M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"semi-batch reactor\", \"stirring_or_flow_condition\": \"1036 rpm\", \"time_point_or_conversion_basis\": \"120 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"mmol of H2 produced / mmol of Pd","selectivity":"Liquid-phase: complete selectivity towards dehydrogenation. 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Bimetallic catalyst combines the action of both metals in gas phase (WGS at low T and methanation at high T).","temperatureReported":"60 °C","formicAcid":"1M","solvent":"water","catalystAmount":"0.1 g","reactorOrAtmosphere":"semi-batch reactor","stirringOrFlow":"1036 rpm","timeOrConversionBasis":"120 min"},{"activityId":"P098_PERF_003_ACT_003","paperId":"P098","catalystId":"P098_PERF_003","catalyst":"PdRu/C3N4","activeMetals":"Pd-Ru","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"TOF","value":"95.24","metricType":"TOF","numericValue":"95.24","unit":"h-1","tof":"95.24","reactionContext":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","temperatureC":"60.0","solution":"1M FA:AF (1:9 molar ratio) aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"1M FA:AF (1:9 molar ratio) aqueous solution\", \"formic_acid_amount_or_concentration\": \"1M\", \"formate_or_sodium_formate_amount_or_concentration\": \"ammonium formate\", \"formic_acid_to_formate_ratio\": \"1:9\", \"base_or_additive\": \"ammonium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"semi-batch reactor\", \"stirring_or_flow_condition\": \"1036 rpm\", \"time_point_or_conversion_basis\": \"120 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"mmol of H2 produced / (mmol of Pd * time)","selectivity":"Liquid-phase: complete selectivity towards dehydrogenation. 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Bimetallic catalyst combines the action of both metals in gas phase (WGS at low T and methanation at high T).","temperatureReported":"60 °C","formicAcid":"1M","formate":"ammonium formate","acidFormateRatio":"1:9","baseOrAdditive":"ammonium formate","solvent":"water","catalystAmount":"0.1 g","reactorOrAtmosphere":"semi-batch reactor","stirringOrFlow":"1036 rpm","timeOrConversionBasis":"120 min"},{"activityId":"P098_PERF_003_ACT_004","paperId":"P098","catalystId":"P098_PERF_003","catalyst":"PdRu/C3N4","activeMetals":"Pd-Ru","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"TON","value":"190.47","metricType":"TON","numericValue":"190.47","reactionContext":"Liquid-phase: 1M formic acid aqueous solution, T = 60 °C; Gas-phase: Fixed-bed reactor, feed flow 100 mL·min⁻¹ (5% v/v FA, 25% v/v distilled water, 70% v/v N2), GHSV ≈ 18,000 h⁻¹","temperatureC":"60.0","solution":"1M FA:AF (1:9 molar ratio) aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"1M FA:AF (1:9 molar ratio) aqueous solution\", \"formic_acid_amount_or_concentration\": \"1M\", \"formate_or_sodium_formate_amount_or_concentration\": \"ammonium formate\", \"formic_acid_to_formate_ratio\": \"1:9\", \"base_or_additive\": \"ammonium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"semi-batch reactor\", \"stirring_or_flow_condition\": \"1036 rpm\", \"time_point_or_conversion_basis\": \"120 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"mmol of H2 produced / mmol of Pd","selectivity":"Liquid-phase: complete selectivity towards dehydrogenation. 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Bimetallic catalyst combines the action of both metals in gas phase (WGS at low T and methanation at high T).","temperatureReported":"60 °C","formicAcid":"1M","formate":"ammonium formate","acidFormateRatio":"1:9","baseOrAdditive":"ammonium formate","solvent":"water","catalystAmount":"0.1 g","reactorOrAtmosphere":"semi-batch reactor","stirringOrFlow":"1036 rpm","timeOrConversionBasis":"120 min"},{"activityId":"P099_PERF_001_ACT_001","paperId":"P099","catalystId":"P099_PERF_001","catalyst":"Pd 5","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TON","value":"32.3","metricType":"TON","numericValue":"32.3","reactionContext":"FA 1 M, 60 °C, 100 mg catalyst, semi-batch reactor, N2 flow carrier","temperatureC":"60.0","solution":"1 M formic acid","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"1 M formic acid\", \"formic_acid_amount_or_concentration\": \"1 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"semi-batch reactor, N2 flow carrier\", \"stirring_or_flow_condition\": \"vigorous stirring\", \"time_point_or_conversion_basis\": \"10 min\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"TON = mmol H2 produced / (mmol Pd * D)","selectivity":"Only CO2 and H2 detected; no CO observed. H2/CO2 ratio close to 1.","stability":"Activity completely recovered after heating post-reacted samples at 150 °C in an oven for a few hours.","whyPerformsWell":"Addition of formates (especially ammonium formate) increases intermediate concentration and stabilizes monodentate adsorption, inhibiting bidentate deactivation.","temperatureReported":"60 °C","formicAcid":"1 M","solvent":"water","catalystAmount":"100 mg","reactorOrAtmosphere":"semi-batch reactor, N2 flow carrier","stirringOrFlow":"vigorous stirring","timeOrConversionBasis":"10 min"},{"activityId":"P099_PERF_001_ACT_002","paperId":"P099","catalystId":"P099_PERF_001","catalyst":"Pd 5","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF","value":"193.7","metricType":"TOF","numericValue":"193.7","unit":"h-1","tof":"193.7","reactionContext":"FA 1 M, 60 °C, 100 mg catalyst, semi-batch reactor, N2 flow carrier","temperatureC":"60.0","solution":"1 M formic acid","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"1 M formic acid\", \"formic_acid_amount_or_concentration\": \"1 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"semi-batch reactor, N2 flow carrier\", \"stirring_or_flow_condition\": \"vigorous stirring\", \"time_point_or_conversion_basis\": \"10 min\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"TOF = TON / t(h)","selectivity":"Only CO2 and H2 detected; no CO observed. 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\"time when the conversion rate reaches 20%\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = PatmVH2+CO2 / (2nmetalRT)","temperatureReported":"348 K","formicAcid":"2 mmol","acidFormateRatio":"1:8","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"50 mg","reactorOrAtmosphere":"three-neck round-bottom flask connected to a water-jacketed gas burette","stirringOrFlow":"magnetic stirrer","timeOrConversionBasis":"time when the conversion rate reaches 20%"},{"activityId":"P110_PERF_003_ACT_001","paperId":"P110","catalystId":"P110_PERF_003","catalyst":"Pd/CN-B1M","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"initial TOF","value":"654.2","metricType":"TOF","numericValue":"654.2","unit":"h-1","tof":"654.2","reactionContext":"Formic acid dehydrogenation in FA/SF mixture (n(FA):n(SF)= 1:8, total FA= 2 mmol) using 50 mg catalyst in 10 mL deionized water at 348 K.","temperatureC":"74.85","solution":"formic acid/sodium formate (FA/SF) mixture","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"348 K\", \"reaction_solution\": \"formic acid/sodium formate (FA/SF) mixture\", \"formic_acid_amount_or_concentration\": \"2 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": \"1:8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"three-neck round-bottom flask connected to a water-jacketed gas burette\", \"stirring_or_flow_condition\": \"magnetic stirrer\", \"time_point_or_conversion_basis\": \"time when the conversion rate reaches 20%\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = PatmVH2+CO2 / (2nmetalRT)","temperatureReported":"348 K","formicAcid":"2 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acid/sodium formate (FA/SF) mixture\", \"formic_acid_amount_or_concentration\": \"2 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": \"1:8\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"three-neck round-bottom flask connected to a water-jacketed gas burette\", \"stirring_or_flow_condition\": \"magnetic stirrer\", \"time_point_or_conversion_basis\": \"time when the conversion rate reaches 20%\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = PatmVH2+CO2 / (2nmetalRT)","temperatureReported":"348 K","formicAcid":"2 mmol","acidFormateRatio":"1:8","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"50 mg","reactorOrAtmosphere":"three-neck round-bottom flask connected to a water-jacketed gas 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\"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"three-neck round-bottom flask connected to a water-jacketed gas burette\", \"stirring_or_flow_condition\": \"magnetic stirrer\", \"time_point_or_conversion_basis\": \"time when the conversion rate reaches 20%\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = PatmVH2+CO2 / (2nmetalRT)","temperatureReported":"348 K","formicAcid":"2 mmol","acidFormateRatio":"1:8","baseOrAdditive":"sodium formate","solvent":"deionized water","catalystAmount":"50 mg","reactorOrAtmosphere":"three-neck round-bottom flask connected to a water-jacketed gas burette","stirringOrFlow":"magnetic stirrer","timeOrConversionBasis":"time when the conversion rate reaches 20%"},{"activityId":"P111_PERF_001_ACT_001","paperId":"P111","catalystId":"P111_PERF_001","catalyst":"Pd-Ag 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\"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"steady state after 10 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"volume rate divided by the total weight of Pd in the reactor","whyPerformsWell":"Attributed to the average activity of three facets: Pd-Ag{111}, Pd-Ag{100}, and Pd-Ag{hcp} at the edges.","uncertainty":"± 4870","temperatureReported":"90 °C","formicAcid":"5 M","formate":"2.5 M sodium formate","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"30 mg","reactorOrAtmosphere":"thermostat bath","timeOrConversionBasis":"steady state after 10 min"},{"activityId":"P111_PERF_001_ACT_002","paperId":"P111","catalystId":"P111_PERF_001","catalyst":"Pd-Ag nanoplate (nPd:nAg = 8.33 x 10^-4) supported on Vulcan XC-72 carbon black","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"TOF","value":"9170 ± 690","metricType":"TOF","numericValue":"9170.0","unit":"h-1","tof":"9170.0","reactionContext":"90 °C, 5 M formic acid, 2.5 M sodium formate, 30 mg catalyst in 5 mL solution","temperatureC":"90.0","solution":"aqueous","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"90 °C\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2.5 M sodium formate\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"thermostat bath\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"steady state after 10 min\"}","basis":"surface_active_sites","basisRaw":"surface active 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M formic acid, 2.5 M sodium formate, 30 mg catalyst in 5 mL solution","temperatureC":"90.0","solution":"aqueous","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"90 °C\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2.5 M sodium formate\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"thermostat bath\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"steady state after 10 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"volume rate divided by the total weight of Pd in the reactor","whyPerformsWell":"Attributed to the activity of the Pd-Ag{111} facet in the mid part of the nanoplate.","uncertainty":"± 40","temperatureReported":"90 °C","formicAcid":"5 M","formate":"2.5 M sodium formate","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"30 mg","reactorOrAtmosphere":"thermostat bath","timeOrConversionBasis":"steady state after 10 min"},{"activityId":"P111_PERF_002_ACT_002","paperId":"P111","catalystId":"P111_PERF_002","catalyst":"Pd-Ag nanoplate (nPd:nAg = 0.33) supported on Vulcan XC-72 carbon black","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"TOF","value":"6570 ± 60","metricType":"TOF","numericValue":"6570.0","unit":"h-1","tof":"6570.0","reactionContext":"90 °C, 5 M formic acid, 2.5 M sodium formate, 30 mg catalyst in 5 mL solution","temperatureC":"90.0","solution":"aqueous","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"90 °C\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2.5 M sodium formate\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"thermostat bath\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"steady state after 10 min\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"(number of produced hydrogen molecules) / (reaction time * number of Pd atoms on the surface)","whyPerformsWell":"Attributed to the activity of the Pd-Ag{111} facet in the mid part of the nanoplate.","uncertainty":"± 60","temperatureReported":"90 °C","formicAcid":"5 M","formate":"2.5 M sodium formate","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"30 mg","reactorOrAtmosphere":"thermostat bath","timeOrConversionBasis":"steady state after 10 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\"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"steady state after 10 min\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","whyPerformsWell":"Activity is dominated by the Pd-Ag{100} facet on the side wall.","uncertainty":"± 280","temperatureReported":"90 °C","formicAcid":"5 M","formate":"2.5 M sodium formate","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"30 mg","reactorOrAtmosphere":"thermostat bath","timeOrConversionBasis":"steady state after 10 min"},{"activityId":"P111_PERF_004_ACT_001","paperId":"P111","catalystId":"P111_PERF_004","catalyst":"Pd-Ag{hcp} nanofacet","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"TOF {hcp}","value":"19000 ± 1630","metricType":"TOF","numericValue":"19000.0","unit":"h-1","tof":"19000.0","reactionContext":"90 °C or 60 °C, 5 M formic acid, 2.5 M sodium 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k1) and comparable binding affinity of CO ad compared to Pd-Ag{100}.","uncertainty":"± 1630","temperatureReported":"90 °C","formicAcid":"5 M","formate":"2.5 M sodium formate","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"30 mg","reactorOrAtmosphere":"thermostat bath","timeOrConversionBasis":"steady state after 10 min"},{"activityId":"P111_PERF_004_ACT_002","paperId":"P111","catalystId":"P111_PERF_004","catalyst":"Pd-Ag{hcp} nanofacet","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"initial activity","value":"3.13 ± 0.19 x 10^6","metricType":"other","numericValue":"3.13","unit":"h-1","reactionContext":"90 °C or 60 °C, 5 M formic acid, 2.5 M sodium formate","temperatureC":"90.0","solution":"aqueous","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"90 °C\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2.5 M sodium formate\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"thermostat bath\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial rate from kinetics fitting\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"Derived from kinetic model fitting (Eq. 9)","selectivity":"k1/k2 = 2070","stability":"Activity can reach a plate after 15 min","whyPerformsWell":"Extremely active in activating the C-H bond (high k1) and comparable binding affinity of CO ad compared to Pd-Ag{100}.","uncertainty":"± 0.19 x 10^6","temperatureReported":"90 °C","formicAcid":"5 M","formate":"2.5 M sodium formate","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"30 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\"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"thermostat bath\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"steady state after 10 min\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","selectivity":"k1/k2 = 2070","stability":"Activity can reach a plate after 15 min","whyPerformsWell":"Extremely active in activating the C-H bond (high k1) and comparable binding affinity of CO ad compared to Pd-Ag{100}.","temperatureReported":"60 °C","formicAcid":"5 M","formate":"2.5 M sodium formate","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"30 mg","reactorOrAtmosphere":"thermostat bath","timeOrConversionBasis":"steady state after 10 min"},{"activityId":"P111_PERF_004_ACT_004","paperId":"P111","catalystId":"P111_PERF_004","catalyst":"Pd-Ag{hcp} nanofacet","activeMetals":"Pd-Ag","metalClass":"Pd-based 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\"base_or_additive\": \"additive-free\", \"solvent\": \"water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": \"magnetic stirring at ~850 rpm\", \"time_point_or_conversion_basis\": \"150 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"~100% selectivity toward FA dehydrogenation; no trace of CO detected","whyPerformsWell":"Lower activity compared to Pd/D201 due to larger Pd NP size (~5.6 nm) and lower metallic Pd0 content","temperatureReported":"50 °C","formicAcid":"0.25 M, 5 mL","baseOrAdditive":"additive-free","solvent":"water","catalystAmount":"50 mg","reactorOrAtmosphere":"atmospheric pressure","stirringOrFlow":"magnetic stirring at ~850 rpm","timeOrConversionBasis":"150 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(Ea)","value":"52.1","metricType":"activation_energy","numericValue":"52.1","unit":"kJ mol-1","reactionContext":"50 °C, 5 mL of 0.25 M FA solution, atmospheric pressure, magnetic stirring at ~850 rpm","temperatureC":"50.0","solution":"aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"30-70 °C\", \"reaction_solution\": \"aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.25 M, 5 mL\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": \"magnetic stirring at ~850 rpm\", \"time_point_or_conversion_basis\": \"TOF at 5 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"~100% selectivity toward FA dehydrogenation; no trace of CO detected","whyPerformsWell":"Lower activity compared to Pd/D201 due to larger Pd NP size (~5.6 nm) and lower metallic Pd0 content","temperatureReported":"30-70 °C","formicAcid":"0.25 M, 5 mL","baseOrAdditive":"additive-free","solvent":"water","catalystAmount":"50 mg","reactorOrAtmosphere":"atmospheric pressure","stirringOrFlow":"magnetic stirring at ~850 rpm","timeOrConversionBasis":"TOF at 5 min"},{"activityId":"P121_PERF_003_ACT_001","paperId":"P121","catalystId":"P121_PERF_003","catalyst":"Pd/D311","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"conversion","value":"27.2","metricType":"conversion","numericValue":"27.2","unit":"%","reactionContext":"50 °C, 5 mL of 0.25 M FA solution, atmospheric pressure, magnetic stirring at ~850 rpm","temperatureC":"50.0","solution":"aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"aqueous 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min"},{"activityId":"P121_PERF_003_ACT_002","paperId":"P121","catalystId":"P121_PERF_003","catalyst":"Pd/D311","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF initial","value":"445.3","metricType":"TOF","numericValue":"445.3","unit":"h-1","tof":"445.3","reactionContext":"50 °C, 5 mL of 0.25 M FA solution, atmospheric pressure, magnetic stirring at ~850 rpm","temperatureC":"50.0","solution":"aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.25 M, 5 mL\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": \"magnetic stirring at ~850 rpm\", \"time_point_or_conversion_basis\": \"after 5 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","selectivity":"~100% selectivity toward FA dehydrogenation; no trace of CO detected","whyPerformsWell":"Lower activity compared to Pd/D201 due to larger Pd NP size (~4.4 nm) and lower metallic Pd0 content","temperatureReported":"50 °C","formicAcid":"0.25 M, 5 mL","baseOrAdditive":"additive-free","solvent":"water","catalystAmount":"50 mg","reactorOrAtmosphere":"atmospheric pressure","stirringOrFlow":"magnetic stirring at ~850 rpm","timeOrConversionBasis":"after 5 min"},{"activityId":"P121_PERF_003_ACT_003","paperId":"P121","catalystId":"P121_PERF_003","catalyst":"Pd/D311","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"apparent activation energy (Ea)","value":"53.1","metricType":"activation_energy","numericValue":"53.1","unit":"kJ mol-1","reactionContext":"50 °C, 5 mL of 0.25 M FA solution, atmospheric pressure, magnetic stirring at ~850 rpm","temperatureC":"50.0","solution":"aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"30-70 °C\", \"reaction_solution\": \"aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.25 M, 5 mL\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"water\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": \"magnetic stirring at ~850 rpm\", \"time_point_or_conversion_basis\": \"TOF at 5 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"~100% selectivity toward FA dehydrogenation; no trace of CO detected","whyPerformsWell":"Lower activity compared to Pd/D201 due to larger Pd NP size (~4.4 nm) and lower metallic Pd0 content","temperatureReported":"30-70 °C","formicAcid":"0.25 M, 5 mL","baseOrAdditive":"additive-free","solvent":"water","catalystAmount":"50 mg","reactorOrAtmosphere":"atmospheric pressure","stirringOrFlow":"magnetic stirring at ~850 rpm","timeOrConversionBasis":"TOF at 5 min"},{"activityId":"P122_PERF_001_ACT_001","paperId":"P122","catalystId":"P122_PERF_001","catalyst":"AuNPs-PPO","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"78","metricType":"conversion","numericValue":"78.0","unit":"%","reactionContext":"Formic acid decomposition in aqueous or mixed solvent media, catalyst amount 100 mg (1 x 10^-5 mol Au), solvent volume 4 mL.","temperatureC":"100.0","solution":"aqueous","temperatureBin":"60-100 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\"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"deionized water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 1:50\", \"reactor_or_atmosphere\": \"two-necked round-bottom flask\", \"stirring_or_flow_condition\": \"vigorous stirring\", \"time_point_or_conversion_basis\": \"initial TOF (FA conversion reaches 20%)\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"normalizing H2 production rates to the number of surface Pd atoms","whyPerformsWell":"Lacks surface amine groups which are necessary for O-H bond dissociation and stabilizing ultrafine Pd NPs.","temperatureReported":"323 K","formicAcid":"2.5 mmol","formate":"nFA/nSF = 1:2","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","solvent":"deionized water","metalAmountOrRatio":"nPd/nFA = 1:50","reactorOrAtmosphere":"two-necked round-bottom 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TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"60 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02","timeOrConversionBasis":"initial"},{"activityId":"P136_PERF_001_ACT_002","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"FA conversion","value":"100","metricType":"conversion","numericValue":"100.0","unit":"%","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"60.0","solution":"FA/SF system","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"FA/SF system\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"60 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02"},{"activityId":"P136_PERF_001_ACT_003","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF (30 °C)","value":"663","metricType":"TOF","numericValue":"663.0","unit":"h-1","tof":"663.0","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"30.0","solution":"FA/SF system","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"FA/SF system\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"30 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02","timeOrConversionBasis":"initial"},{"activityId":"P136_PERF_001_ACT_004","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF (40 °C)","value":"1041","metricType":"TOF","numericValue":"1041.0","unit":"h-1","tof":"1041.0","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"40.0","solution":"FA/SF system","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"40 °C\", \"reaction_solution\": \"FA/SF system\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"40 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02","timeOrConversionBasis":"initial"},{"activityId":"P136_PERF_001_ACT_005","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF (50 °C)","value":"2197","metricType":"TOF","numericValue":"2197.0","unit":"h-1","tof":"2197.0","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"50.0","solution":"FA/SF system","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"FA/SF system\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"50 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02","timeOrConversionBasis":"initial"},{"activityId":"P136_PERF_001_ACT_006","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF (70 °C)","value":"5399","metricType":"TOF","numericValue":"5399.0","unit":"h-1","tof":"5399.0","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"70.0","solution":"FA/SF system","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"70 °C\", \"reaction_solution\": \"FA/SF system\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:2\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"70 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:2","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02","timeOrConversionBasis":"initial"},{"activityId":"P136_PERF_001_ACT_007","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF (FA/SF 1:0.5)","value":"2133","metricType":"TOF","numericValue":"2133.0","unit":"h-1","tof":"2133.0","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"60.0","solution":"FA/SF system","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"FA/SF system\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:0.5\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"60 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:0.5","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02","timeOrConversionBasis":"initial"},{"activityId":"P136_PERF_001_ACT_008","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF (FA/SF 1:1)","value":"2759","metricType":"TOF","numericValue":"2759.0","unit":"h-1","tof":"2759.0","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"60.0","solution":"FA/SF system","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"FA/SF system\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"60 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02","timeOrConversionBasis":"initial"},{"activityId":"P136_PERF_001_ACT_009","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF (FA/SF 1:3)","value":"1919","metricType":"TOF","numericValue":"1919.0","unit":"h-1","tof":"1919.0","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"60.0","solution":"FA/SF system","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"FA/SF system\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:3\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. TOF decreased from 3252 h-1 (1st cycle) to 2063 h-1 (6th cycle).","whyPerformsWell":"Highly dispersed ultrasmall Pd NPs (2.0 nm), strong metal-support interaction (MSI) effect, and modulated N sites acting as Bronsted basic sites for promoting O-H bond cleavage of FA molecules.","temperatureReported":"60 °C","formate":"sodium formate (SF)","acidFormateRatio":"1:3","baseOrAdditive":"sodium formate (SF)","catalystAmount":"15 wt% Pd loading","metalAmountOrRatio":"n_metal/n_FA = 0.02","timeOrConversionBasis":"initial"},{"activityId":"P136_PERF_001_ACT_010","paperId":"P136","catalystId":"P136_PERF_001","catalyst":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"TOF (Pure FA)","value":"1179","metricType":"TOF","numericValue":"1179.0","unit":"h-1","tof":"1179.0","reactionContext":"Formic acid (FA) dehydrogenation in the presence of sodium formate (SF) additive.","temperatureC":"60.0","solution":"pure FA solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"pure FA solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"none\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": null, \"catalyst_amount\": \"15 wt% Pd loading\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_metal/n_FA = 0.02\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","selectivity":"100% H2 selectivity; no CO detected","stability":"Maintained 100% FA conversion over six consecutive cycles. 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in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"80 °C","formate":"2.0 mol/L KHCO3","baseOrAdditive":"none","solvent":"water","metalAmountOrRatio":"(Pd+Au)/KHCO3 = 1.83 x 10^-2","reactorOrAtmosphere":"5 MPa H2","timeOrConversionBasis":"2 h"},{"activityId":"P143_PERF_001_ACT_007","paperId":"P143","catalystId":"P143_PERF_001","catalyst":"Pd0.50Au0.50/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"PF yield","value":"83","metricType":"other","numericValue":"83.0","unit":"%","reactionContext":"Hydrogenation of KHCO3 in aqueous solution; Dehydrogenation of PF or FA in aqueous solution.","temperatureC":"80.0","solution":"KHCO3 aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": \"KHCO3 aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"2.0 mol/L KHCO3\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"(Pd+Au)/KHCO3 = 1.83 x 10^-2\", \"reactor_or_atmosphere\": \"5 MPa H2\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"6 h\"}","basis":"unclear","basisRaw":"unclear","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"80 °C","formate":"2.0 mol/L KHCO3","baseOrAdditive":"none","solvent":"water","metalAmountOrRatio":"(Pd+Au)/KHCO3 = 1.83 x 10^-2","reactorOrAtmosphere":"5 MPa H2","timeOrConversionBasis":"6 h"},{"activityId":"P143_PERF_001_ACT_008","paperId":"P143","catalystId":"P143_PERF_001","catalyst":"Pd0.50Au0.50/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"initial TOF","value":"9.18 x 10^2","metricType":"TOF","numericValue":"9.18","unit":"h^-1","tof":"9.18","reactionContext":"Hydrogenation of KHCO3 in aqueous solution; Dehydrogenation of PF or FA in aqueous solution.","temperatureC":"80.0","solution":"PF aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": \"PF aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"2 mol/L PF\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"(Pd+Au) = 31.6 umol\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"20% PF conversion\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"based on the overall catalyst amount","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"80 °C","formate":"2 mol/L PF","baseOrAdditive":"none","solvent":"water","catalystAmount":"(Pd+Au) = 31.6 umol","reactorOrAtmosphere":"atmospheric pressure","timeOrConversionBasis":"20% PF conversion"},{"activityId":"P143_PERF_001_ACT_009","paperId":"P143","catalystId":"P143_PERF_001","catalyst":"Pd0.50Au0.50/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"initial TOF","value":"1.63 x 10^3","metricType":"TOF","numericValue":"1.63","unit":"h^-1","tof":"1.63","reactionContext":"Hydrogenation of KHCO3 in aqueous solution; Dehydrogenation of PF or FA in aqueous solution.","temperatureC":"80.0","solution":"PF aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": \"PF aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"6 mol/L PF\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"(Pd+Au) = 31.6 umol\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"20% PF conversion\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"based on the overall catalyst amount","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"80 °C","formate":"6 mol/L PF","baseOrAdditive":"none","solvent":"water","catalystAmount":"(Pd+Au) = 31.6 umol","reactorOrAtmosphere":"atmospheric pressure","timeOrConversionBasis":"20% PF conversion"},{"activityId":"P143_PERF_001_ACT_010","paperId":"P143","catalystId":"P143_PERF_001","catalyst":"Pd0.50Au0.50/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"initial TOF","value":"4.87 x 10^3","metricType":"TOF","numericValue":"4.87","unit":"h^-1","tof":"4.87","reactionContext":"Hydrogenation of KHCO3 in aqueous solution; Dehydrogenation of PF or FA in aqueous solution.","temperatureC":"80.0","solution":"FA aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": \"FA aqueous solution\", \"formic_acid_amount_or_concentration\": \"2 mol/L FA\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"(Pd+Au) = 31.6 umol\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial state\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"based on the overall catalyst amount","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"80 °C","formicAcid":"2 mol/L FA","baseOrAdditive":"none","solvent":"water","catalystAmount":"(Pd+Au) = 31.6 umol","reactorOrAtmosphere":"atmospheric pressure","timeOrConversionBasis":"initial state"},{"activityId":"P143_PERF_001_ACT_011","paperId":"P143","catalystId":"P143_PERF_001","catalyst":"Pd0.50Au0.50/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"initial TOF","value":"7.18 x 10^3","metricType":"TOF","numericValue":"7.18","unit":"h^-1","tof":"7.18","reactionContext":"Hydrogenation of KHCO3 in aqueous solution; Dehydrogenation of PF or FA in aqueous solution.","temperatureC":"80.0","solution":"FA aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": \"FA aqueous solution\", \"formic_acid_amount_or_concentration\": \"2 mol/L FA\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"n(Pd+Au)/nFA = 3.9 x 10^-3\", \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial state\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"based on the overall catalyst amount","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"80 °C","formicAcid":"2 mol/L FA","baseOrAdditive":"none","solvent":"water","metalAmountOrRatio":"n(Pd+Au)/nFA = 3.9 x 10^-3","reactorOrAtmosphere":"atmospheric pressure","timeOrConversionBasis":"initial state"},{"activityId":"P143_PERF_001_ACT_012","paperId":"P143","catalystId":"P143_PERF_001","catalyst":"Pd0.50Au0.50/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"initial TOF","value":"6.98 x 10^3","metricType":"TOF","numericValue":"6.98","unit":"h^-1","tof":"6.98","reactionContext":"Hydrogenation of KHCO3 in aqueous solution; Dehydrogenation of PF or FA in aqueous solution.","temperatureC":"80.0","solution":"FA aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": \"FA aqueous solution\", \"formic_acid_amount_or_concentration\": \"8 mol/L FA\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"n(Pd+Au)/nFA = 3.9 x 10^-3\", \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial state\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"based on the overall catalyst amount","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"80 °C","formicAcid":"8 mol/L 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\"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"n(Pd+Au)/nFA = 3.9 x 10^-3\", \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"final state\"}","basis":"unclear","basisRaw":"unclear","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"80 °C","formicAcid":"8 mol/L FA","baseOrAdditive":"none","solvent":"water","metalAmountOrRatio":"n(Pd+Au)/nFA = 3.9 x 10^-3","reactorOrAtmosphere":"atmospheric pressure","timeOrConversionBasis":"final 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\"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial state\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"based on the overall catalyst amount","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"50 °C","formicAcid":"2 mol/L FA","baseOrAdditive":"none","solvent":"water","metalAmountOrRatio":"n(Pd+Au)/nFA = 3.9 x 10^-3","reactorOrAtmosphere":"atmospheric pressure","timeOrConversionBasis":"initial 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\"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial state\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Au","definition":"based on the overall catalyst amount","selectivity":"No CO detected in all cases of PF and FA dehydrogenation.","stability":"PF yield decreased from 74% to 32% after two cycles (hydrogenation of 0.5 mol/L KHCO3 at 30 °C for 4 h).","whyPerformsWell":"Nanosized metal particles (1.8 ± 0.5 nm), amine group on support acting as proton scavenger, Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","temperatureReported":"25 °C","formicAcid":"2 mol/L FA","baseOrAdditive":"none","solvent":"water","metalAmountOrRatio":"n(Pd+Au)/nFA = 3.9 x 10^-3","reactorOrAtmosphere":"atmospheric pressure","timeOrConversionBasis":"initial 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null}","basis":"unclear","basisRaw":"unclear","stability":"No gas generation observed at 25 °C for FA dehydrogenation.","baseOrAdditive":"none","solvent":"water"},{"activityId":"P143_PERF_002_ACT_002","paperId":"P143","catalystId":"P143_PERF_002","catalyst":"Pd/PDA-rGO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"initial TOF","value":"2.46 x 10^3","metricType":"TOF","numericValue":"2.46","unit":"h^-1","tof":"2.46","reactionContext":"Hydrogenation of KHCO3; Dehydrogenation of FA.","temperatureC":"80.0","solution":"FA aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": \"FA aqueous solution\", \"formic_acid_amount_or_concentration\": \"2 mol/L FA\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial state\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd","definition":"based on the overall catalyst amount","stability":"No gas generation observed at 25 °C for FA dehydrogenation.","temperatureReported":"80 °C","formicAcid":"2 mol/L FA","baseOrAdditive":"none","solvent":"water","reactorOrAtmosphere":"atmospheric pressure","timeOrConversionBasis":"initial state"},{"activityId":"P143_PERF_003_ACT_001","paperId":"P143","catalystId":"P143_PERF_003","catalyst":"Au/PDA-rGO","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"PF yield","value":"8.1","metricType":"other","numericValue":"8.1","unit":"%","reactionContext":"Hydrogenation of KHCO3.","solution":"KHCO3 aqueous solution","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": \"KHCO3 aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","baseOrAdditive":"none","solvent":"water"},{"activityId":"P143_PERF_004_ACT_001","paperId":"P143","catalystId":"P143_PERF_004","catalyst":"Pd0.57(Low)Au0.43(Low)/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"PF 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\"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"Cs2CO3 (1.5 mmol)\", \"solvent\": \"DMF (5 mL)\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Phenylacetylene (1.0 mmol), CO2 (1.0 atm)\", \"reactor_or_atmosphere\": \"CO2 balloon\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"isolated product","basisRaw":"isolated product","selectivity":"15% alkyne dimerization yield","stability":"recycled five times with no loss of activity (Cr reduction)","whyPerformsWell":"MOF captures CO2 around catalytic centers; Lewis acidity of unsaturated chromium sites in MIL-101 enhances adsorption of aromatic substrates","temperatureReported":"25°C","baseOrAdditive":"Cs2CO3 (1.5 mmol)","solvent":"DMF (5 mL)","catalystAmount":"100 mg","metalAmountOrRatio":"Phenylacetylene (1.0 mmol), CO2 (1.0 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null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"Cs2CO3 (1.5 mmol)\", \"solvent\": \"DMF (5 mL)\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"Phenylacetylene (1.0 mmol), CO2 (1.0 atm)\", \"reactor_or_atmosphere\": \"CO2 balloon\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": \"24 h\"}","basis":"isolated product","basisRaw":"isolated product","selectivity":"25-45% alkyne dimerization yield","whyPerformsWell":"Bimetallic catalytic systems show higher activities than single-metal systems due to electron transfer across the metal-metal interface","temperatureReported":"25°C","baseOrAdditive":"Cs2CO3 (1.5 mmol)","solvent":"DMF (5 mL)","catalystAmount":"100 mg","metalAmountOrRatio":"Phenylacetylene (1.0 mmol), CO2 (1.0 atm)","reactorOrAtmosphere":"CO2 balloon","stirringOrFlow":"stirring","timeOrConversionBasis":"24 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42 mL serum vials (21 mL deionized water, 21 mL headspace) at 25 °C with rotary shaker (40 rpm)","temperatureC":"25.0","solution":"deionized water","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"deionized water\", \"formic_acid_amount_or_concentration\": \"1 g·L-1\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"deionized water\", \"catalyst_amount\": \"1 g·L-1\", \"metal_amount_or_substrate_to_metal_ratio\": \"TCE initial concentration: 10.6 mg·L-1\", \"reactor_or_atmosphere\": \"42 mL serum vials sealed with PTFE septa, 21 mL headspace\", \"stirring_or_flow_condition\": \"rotary shaker (40 rpm)\", \"time_point_or_conversion_basis\": \"after 1 h of reaction (all TCE degraded)\"}","basis":"unclear","basisRaw":"unclear","definition":"εH = nTCE / (nTCE + nH2) * 100%","selectivity":"Ethane was the primary 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2.6 mmol HCOOH in 10 mL deionized water, magnetic stirring, 30 mg catalyst","temperatureC":"80.0","solution":"HCOOH in deionized water","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"80 °C\", \"reaction_solution\": \"HCOOH in deionized water\", \"formic_acid_amount_or_concentration\": \"2.6 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"deionized water (10 mL)\", \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"three-neck flask\", \"stirring_or_flow_condition\": \"magnetic stirring\", \"time_point_or_conversion_basis\": \"initial 10 min\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","definition":"234 / 1.8","temperatureReported":"80 °C","formicAcid":"2.6 mmol","solvent":"deionized water (10 mL)","catalystAmount":"30 mg","reactorOrAtmosphere":"three-neck 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\"sodium formate\", \"solvent\": \"distilled water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"1.6 mM Pd\", \"reactor_or_atmosphere\": \"N2 filling and purging\", \"stirring_or_flow_condition\": \"1200 rpm\", \"time_point_or_conversion_basis\": \"initial rate\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd","definition":"mol gas.mol metal.-1 h-1","selectivity":"No carbon monoxide was detected; selectively promotes dehydrogenation over dehydration.","stability":"Provided only 50% conversion of FA in the second run.","whyPerformsWell":"Ascribed to the reducible nature of ceria (redox cycling between Ce4+ and Ce3+) during FA decomposition.","temperatureReported":"25.0 ± 0.1 °C","formicAcid":"0.06 mL","formate":"918 mg sodium formate","acidFormateRatio":"1/9","baseOrAdditive":"sodium formate","solvent":"distilled water","metalAmountOrRatio":"1.6 mM Pd","reactorOrAtmosphere":"N2 filling and 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AuPd particle size induced by the nanosheet morphology and higher graphitic N content.","temperatureReported":"25 °C","formicAcid":"3.0 M","formate":"7.5 M","solvent":"deionized water","catalystAmount":"10 mg","reactorOrAtmosphere":"atmospheric pressure","stirringOrFlow":"stirring","timeOrConversionBasis":"first 5 min"},{"activityId":"P158_PERF_004_ACT_001","paperId":"P158","catalystId":"P158_PERF_004","catalyst":"AuPd/g-C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"gas volume","value":"48","metricType":"other","numericValue":"48.0","unit":"mL","reactionContext":"Dehydrogenation of formic acid at 25 °C and atmospheric pressure.","temperatureC":"25.0","solution":"3.0 M formic acid and 7.5 M sodium formate","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"25 °C\", \"reaction_solution\": \"3.0 M formic acid and 7.5 M sodium formate\", \"formic_acid_amount_or_concentration\": \"3.0 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"7.5 M\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"deionized water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"atmospheric pressure\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": \"1 h\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","temperatureReported":"25 °C","formicAcid":"3.0 M","formate":"7.5 M","solvent":"deionized water","catalystAmount":"10 mg","reactorOrAtmosphere":"atmospheric pressure","stirringOrFlow":"stirring","timeOrConversionBasis":"1 h"},{"activityId":"P159_PERF_001_ACT_001","paperId":"P159","catalystId":"P159_PERF_001","catalyst":"Pd/AC–CP (250 W, 10 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\"formic_acid_amount_or_concentration\": \"25 mL\", \"formate_or_sodium_formate_amount_or_concentration\": \"10 mL of 0.5 g/mL sodium formate solution\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"0.1 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"100 mL round bottom flask\", \"stirring_or_flow_condition\": \"oil bath conditions\", \"time_point_or_conversion_basis\": \"5 h\"}","basis":"unclear","basisRaw":"unclear","stability":"Maintained high activity even at the fourth recycle","whyPerformsWell":"Distinctive interaction of Pd and PPy resulting from different valence ratios of Pd 3d","temperatureReported":"60 °C","formicAcid":"25 mL","formate":"10 mL of 0.5 g/mL sodium formate solution","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"0.1 g","reactorOrAtmosphere":"100 mL round bottom flask","stirringOrFlow":"oil bath 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round bottom flask\", \"stirring_or_flow_condition\": \"oil bath conditions\", \"time_point_or_conversion_basis\": \"5 h\"}","basis":"unclear","basisRaw":"unclear","stability":"Catalytic activity was slightly decreased after four cycles","temperatureReported":"60 °C","formicAcid":"25 mL","formate":"10 mL of 0.5 g/mL sodium formate solution","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"0.1 g","reactorOrAtmosphere":"100 mL round bottom flask","stirringOrFlow":"oil bath conditions","timeOrConversionBasis":"5 h"},{"activityId":"P166_PERF_001_ACT_001","paperId":"P166","catalystId":"P166_PERF_001","catalyst":"Pd/NMC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"69.7","metricType":"conversion","numericValue":"69.7","unit":"%","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"79.85","solution":"KHCO3 aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"353 K\", \"reaction_solution\": \"KHCO3 aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"4 mol L-1 KHCO3\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": \"P(CO2) = 0 MPa, P(H2) = 6 MPa\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"2 h\"}","basis":"unclear","basisRaw":"unclear","definition":"calculated with respect to KHCO3","selectivity":"No CO signal detected by gas-phase chromatography or TPD-MS during dehydrogenation of formate.","stability":"For hydrogenation: conversion decreases after first run then levels off; yield after 4th run remains superior to Pd/MC-8 and Pd/AC. For dehydrogenation at 353 K: activity slightly higher in second run, falling again in third run.","whyPerformsWell":"Nitrogen functionalities (especially pyridine N) interact with Pd precursors leading to well-dispersed, small nanoparticles (~2.4 nm). Electron donation from the support increases electron density of Pd NPs. Potential electrostatic interaction between nitrogen species and positively polarized carbon in reactants.","temperatureReported":"353 K","formate":"4 mol L-1 KHCO3","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd","reactorOrAtmosphere":"P(CO2) = 0 MPa, P(H2) = 6 MPa","timeOrConversionBasis":"2 h"},{"activityId":"P166_PERF_001_ACT_002","paperId":"P166","catalystId":"P166_PERF_001","catalyst":"Pd/NMC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"84.9","metricType":"conversion","numericValue":"84.9","unit":"%","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"59.85","solution":"KHCO3 aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"333 K\", \"reaction_solution\": \"KHCO3 aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"4 mol L-1 KHCO3\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": \"P(CO2) = 0 MPa, P(H2) = 6 MPa\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"3 h\"}","basis":"unclear","basisRaw":"unclear","definition":"calculated with respect to KHCO3","selectivity":"No CO signal detected by gas-phase chromatography or TPD-MS during dehydrogenation of formate.","stability":"For hydrogenation: conversion decreases after first run then levels off; yield after 4th run remains superior to Pd/MC-8 and Pd/AC. For dehydrogenation at 353 K: activity slightly higher in second run, falling again in third run.","whyPerformsWell":"Nitrogen functionalities (especially pyridine N) interact with Pd precursors leading to well-dispersed, small nanoparticles (~2.4 nm). Electron donation from the support increases electron density of Pd NPs. Potential electrostatic interaction between nitrogen species and positively polarized carbon in reactants.","temperatureReported":"333 K","formate":"4 mol L-1 KHCO3","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd","reactorOrAtmosphere":"P(CO2) = 0 MPa, P(H2) = 6 MPa","timeOrConversionBasis":"3 h"},{"activityId":"P166_PERF_001_ACT_003","paperId":"P166","catalystId":"P166_PERF_001","catalyst":"Pd/NMC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"83.3","metricType":"conversion","numericValue":"83.3","unit":"%","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"39.85","solution":"KHCO3 aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"313 K\", \"reaction_solution\": \"KHCO3 aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"4 mol L-1 KHCO3\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": \"P(CO2) = 0 MPa, P(H2) = 6 MPa\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"4 h\"}","basis":"unclear","basisRaw":"unclear","definition":"calculated with respect to KHCO3","selectivity":"No CO signal detected by gas-phase chromatography or TPD-MS during dehydrogenation of formate.","stability":"For hydrogenation: conversion decreases after first run then levels off; yield after 4th run remains superior to Pd/MC-8 and Pd/AC. For dehydrogenation at 353 K: activity slightly higher in second run, falling again in third run.","whyPerformsWell":"Nitrogen functionalities (especially pyridine N) interact with Pd precursors leading to well-dispersed, small nanoparticles (~2.4 nm). Electron donation from the support increases electron density of Pd NPs. Potential electrostatic interaction between nitrogen species and positively polarized carbon in reactants.","temperatureReported":"313 K","formate":"4 mol L-1 KHCO3","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd","reactorOrAtmosphere":"P(CO2) = 0 MPa, P(H2) = 6 MPa","timeOrConversionBasis":"4 h"},{"activityId":"P166_PERF_001_ACT_004","paperId":"P166","catalystId":"P166_PERF_001","catalyst":"Pd/NMC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"TON","value":"1598","metricType":"TON","numericValue":"1598.0","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"79.85","solution":"KHCO3 aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"353 K\", \"reaction_solution\": \"KHCO3 aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"4 mol L-1 KHCO3\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": \"P(CO2) = 0 MPa, P(H2) = 6 MPa\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"2 h\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","selectivity":"No CO signal detected by gas-phase chromatography or TPD-MS during dehydrogenation of formate.","stability":"For hydrogenation: conversion decreases after first run then levels off; yield after 4th run remains superior to Pd/MC-8 and Pd/AC. For dehydrogenation at 353 K: activity slightly higher in second run, falling again in third run.","whyPerformsWell":"Nitrogen functionalities (especially pyridine N) interact with Pd precursors leading to well-dispersed, small nanoparticles (~2.4 nm). Electron donation from the support increases electron density of Pd NPs. Potential electrostatic interaction between nitrogen species and positively polarized carbon in reactants.","temperatureReported":"353 K","formate":"4 mol L-1 KHCO3","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd","reactorOrAtmosphere":"P(CO2) = 0 MPa, P(H2) = 6 MPa","timeOrConversionBasis":"2 h"},{"activityId":"P166_PERF_001_ACT_005","paperId":"P166","catalystId":"P166_PERF_001","catalyst":"Pd/NMC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"TOF","value":"1118","metricType":"TOF","numericValue":"1118.0","unit":"h-1","tof":"1118.0","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"59.85","solution":"HCOOK aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"333 K\", \"reaction_solution\": \"HCOOK aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"2 mol L-1 HCOOK\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"first 10 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"calculated strictly according to the pure H2 produced after the absorption of CO2 with excess concentrated NaOH solution","selectivity":"No CO signal detected by gas-phase chromatography or TPD-MS during dehydrogenation of formate.","stability":"For hydrogenation: conversion decreases after first run then levels off; yield after 4th run remains superior to Pd/MC-8 and Pd/AC. For dehydrogenation at 353 K: activity slightly higher in second run, falling again in third run.","whyPerformsWell":"Nitrogen functionalities (especially pyridine N) interact with Pd precursors leading to well-dispersed, small nanoparticles (~2.4 nm). Electron donation from the support increases electron density of Pd NPs. Potential electrostatic interaction between nitrogen species and positively polarized carbon in reactants.","temperatureReported":"333 K","formate":"2 mol L-1 HCOOK","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd","timeOrConversionBasis":"first 10 min"},{"activityId":"P166_PERF_001_ACT_006","paperId":"P166","catalystId":"P166_PERF_001","catalyst":"Pd/NMC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"TOF","value":"2416","metricType":"TOF","numericValue":"2416.0","unit":"h-1","tof":"2416.0","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"79.85","solution":"HCOOK aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"353 K\", \"reaction_solution\": \"HCOOK aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"2 mol L-1 HCOOK\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"calculated strictly according to the pure H2 produced after the absorption of CO2 with excess concentrated NaOH solution","selectivity":"No CO signal detected by gas-phase chromatography or TPD-MS during dehydrogenation of formate.","stability":"For hydrogenation: conversion decreases after first run then levels off; yield after 4th run remains superior to Pd/MC-8 and Pd/AC. For dehydrogenation at 353 K: activity slightly higher in second run, falling again in third run.","whyPerformsWell":"Nitrogen functionalities (especially pyridine N) interact with Pd precursors leading to well-dispersed, small nanoparticles (~2.4 nm). Electron donation from the support increases electron density of Pd NPs. Potential electrostatic interaction between nitrogen species and positively polarized carbon in reactants.","temperatureReported":"353 K","formate":"2 mol L-1 HCOOK","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd"},{"activityId":"P166_PERF_002_ACT_001","paperId":"P166","catalystId":"P166_PERF_002","catalyst":"Pd/MC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"45.2","metricType":"conversion","numericValue":"45.2","unit":"%","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"79.85","solution":"KHCO3 aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"353 K\", \"reaction_solution\": \"KHCO3 aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"4 mol L-1 KHCO3\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": \"P(CO2) = 0 MPa, P(H2) = 6 MPa\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"2 h\"}","basis":"unclear","basisRaw":"unclear","definition":"calculated with respect to KHCO3","whyPerformsWell":"Poor dispersion and larger particle size (3.1 nm) compared to Pd/NMC-8.","temperatureReported":"353 K","formate":"4 mol L-1 KHCO3","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd","reactorOrAtmosphere":"P(CO2) = 0 MPa, P(H2) = 6 MPa","timeOrConversionBasis":"2 h"},{"activityId":"P166_PERF_002_ACT_002","paperId":"P166","catalystId":"P166_PERF_002","catalyst":"Pd/MC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"TOF","value":"243","metricType":"TOF","numericValue":"243.0","unit":"h-1","tof":"243.0","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"59.85","solution":"HCOOK aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"333 K\", \"reaction_solution\": \"HCOOK aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"2 mol L-1 HCOOK\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"first 10 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"calculated strictly according to the pure H2 produced after the absorption of CO2 with excess concentrated NaOH solution","whyPerformsWell":"Poor dispersion and larger particle size (3.1 nm) compared to Pd/NMC-8.","temperatureReported":"333 K","formate":"2 mol L-1 HCOOK","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd","timeOrConversionBasis":"first 10 min"},{"activityId":"P166_PERF_002_ACT_003","paperId":"P166","catalystId":"P166_PERF_002","catalyst":"Pd/MC-8","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"TOF","value":"1182","metricType":"TOF","numericValue":"1182.0","unit":"h-1","tof":"1182.0","reactionContext":"Hydrogenation of bicarbonate or dehydrogenation of formate in aqueous solution","temperatureC":"79.85","solution":"HCOOK aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"353 K\", \"reaction_solution\": \"HCOOK aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"2 mol L-1 HCOOK\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"calculated strictly according to the pure H2 produced after the absorption of CO2 with excess concentrated NaOH solution","whyPerformsWell":"Poor dispersion and larger particle size (3.1 nm) compared to Pd/NMC-8.","temperatureReported":"353 K","formate":"2 mol L-1 HCOOK","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd"},{"activityId":"P166_PERF_003_ACT_001","paperId":"P166","catalystId":"P166_PERF_003","catalyst":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"unknown","metric":"conversion","value":"43.2","metricType":"conversion","numericValue":"43.2","unit":"%","reactionContext":"Hydrogenation of bicarbonate in aqueous solution","temperatureC":"79.85","solution":"KHCO3 aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"353 K\", \"reaction_solution\": \"KHCO3 aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": \"4 mol L-1 KHCO3\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"8.7 mmol Pd\", \"reactor_or_atmosphere\": \"P(CO2) = 0 MPa, P(H2) = 6 MPa\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"2 h\"}","basis":"unclear","basisRaw":"unclear","definition":"calculated with respect to KHCO3","temperatureReported":"353 K","formate":"4 mol L-1 KHCO3","solvent":"water","catalystAmount":"20 mg","metalAmountOrRatio":"8.7 mmol Pd","reactorOrAtmosphere":"P(CO2) = 0 MPa, P(H2) = 6 MPa","timeOrConversionBasis":"2 h"},{"activityId":"P167_PERF_001_ACT_001","paperId":"P167","catalystId":"P167_PERF_001","catalyst":"Pd/BCNTs","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF","value":"3451","metricType":"TOF","numericValue":"3451.0","unit":"h-1","tof":"3451.0","reactionContext":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","temperatureC":"50.0","solution":"0.5 M FA + 2 M SF","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"0.5 M FA + 2 M SF\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2 M\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"SF\", \"solvent\": \"water\", \"catalyst_amount\": \"42 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Ar atmosphere\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"60 min\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"number of moles of H2 produced per mole of Pd within an h","selectivity":"product primarily comprises CO2 and H2 in a ratio of approximately 1:1","stability":"Regenerated catalyst reused three times showed an 11.69% decrease in catalytic activity.","whyPerformsWell":"High SBET (128.1273 m2 g-1), large Vmeso, highly dispersed PdNPs with smallest particle size (6.28 nm), and synergetic interaction between PdNPs and BCNTs involving electron transfer from B to Pd.","temperatureReported":"50 °C","formicAcid":"0.5 M","formate":"2 M","baseOrAdditive":"SF","solvent":"water","catalystAmount":"42 mg","reactorOrAtmosphere":"Ar atmosphere","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"60 min"},{"activityId":"P167_PERF_001_ACT_002","paperId":"P167","catalystId":"P167_PERF_001","catalyst":"Pd/BCNTs","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"gas yield","value":"84","metricType":"other","numericValue":"84.0","unit":"mL","reactionContext":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","temperatureC":"50.0","solution":"0.5 M FA + 2 M SF","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"0.5 M FA + 2 M SF\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2 M\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"SF\", \"solvent\": \"water\", \"catalyst_amount\": \"42 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Ar atmosphere\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": \"60 min\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","selectivity":"product primarily comprises CO2 and H2 in a ratio of approximately 1:1","stability":"Regenerated catalyst reused three times showed an 11.69% decrease in catalytic activity.","whyPerformsWell":"High SBET (128.1273 m2 g-1), large Vmeso, highly dispersed PdNPs with smallest particle size (6.28 nm), and synergetic interaction between PdNPs and BCNTs involving electron transfer from B to Pd.","temperatureReported":"50 °C","formicAcid":"0.5 M","formate":"2 M","baseOrAdditive":"SF","solvent":"water","catalystAmount":"42 mg","reactorOrAtmosphere":"Ar atmosphere","stirringOrFlow":"1000 rpm","timeOrConversionBasis":"60 min"},{"activityId":"P167_PERF_001_ACT_003","paperId":"P167","catalystId":"P167_PERF_001","catalyst":"Pd/BCNTs","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"FA conversion","value":"41.67","metricType":"conversion","numericValue":"41.67","unit":"%","reactionContext":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","temperatureC":"50.0","solution":"0.5 M FA + 2 M SF","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"50 °C\", \"reaction_solution\": \"0.5 M FA + 2 M SF\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2 M\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"SF\", \"solvent\": \"water\", \"catalyst_amount\": \"42 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Ar atmosphere\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"(mole of carbon contained in products / mole of FA fed) * 100%","selectivity":"product primarily comprises CO2 and H2 in a ratio of approximately 1:1","stability":"Regenerated catalyst reused three times showed an 11.69% decrease in catalytic activity.","whyPerformsWell":"High SBET (128.1273 m2 g-1), large Vmeso, highly dispersed PdNPs with smallest particle size (6.28 nm), and synergetic interaction between PdNPs and BCNTs involving electron transfer from B to Pd.","temperatureReported":"50 °C","formicAcid":"0.5 M","formate":"2 M","baseOrAdditive":"SF","solvent":"water","catalystAmount":"42 mg","reactorOrAtmosphere":"Ar atmosphere","stirringOrFlow":"1000 rpm"},{"activityId":"P167_PERF_001_ACT_004","paperId":"P167","catalystId":"P167_PERF_001","catalyst":"Pd/BCNTs","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF","value":"2300 - 8798","metricType":"TOF","numericValue":"2300.0","unit":"h-1","tof":"2300.0","reactionContext":"42 mg catalyst, 9 mL reactant solution, stirring at 1000 rpm, Ar atmosphere, condenser temperature 5 °C","temperatureC":"45.0","solution":"0.5 M FA + 2 M SF","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"30 - 60 °C\", \"reaction_solution\": \"0.5 M FA + 2 M SF\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"2 M\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"SF\", \"solvent\": \"water\", \"catalyst_amount\": \"42 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"Ar atmosphere\", 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\"stirring_or_flow_condition\": \"N2 carrier gas flow rate 193.5 mL·min−1\", \"time_point_or_conversion_basis\": \"steady state\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","temperatureReported":"300°C","formicAcid":"0.8 g·h−1 (3.2 mol% in N2)","reactorOrAtmosphere":"tubular quartz reactor","stirringOrFlow":"N2 carrier gas flow rate 193.5 mL·min−1","timeOrConversionBasis":"steady state"},{"activityId":"P182_PERF_001_ACT_001","paperId":"P182","catalystId":"P182_PERF_001","catalyst":"Pd(NO3)2","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"Volume of gases released (H2 + CO2)","value":"330","metricType":"other","numericValue":"330.0","unit":"mL","reactionContext":"60 °C, aqueous solution of formic acid and sodium formate","temperatureC":"60.0","solution":"aqueous","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"9 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"9 mmol sodium formate\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"94 μmol\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass tube purged by nitrogen\", \"stirring_or_flow_condition\": \"stirred vigorously\", \"time_point_or_conversion_basis\": \"3 h\"}","basis":"unclear","basisRaw":"unclear","definition":"Volume of the gases released (H2 + CO2)","selectivity":"selective for H2 and CO2","whyPerformsWell":"Highest activity among the complexes employed; coordinating ligands are important for FA decomposition kinetics.","temperatureReported":"60 °C","formicAcid":"9 mmol","formate":"9 mmol sodium formate","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"distilled water","catalystAmount":"94 μmol","reactorOrAtmosphere":"glass tube purged by nitrogen","stirringOrFlow":"stirred vigorously","timeOrConversionBasis":"3 h"},{"activityId":"P182_PERF_002_ACT_001","paperId":"P182","catalystId":"P182_PERF_002","catalyst":"PdCl2","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"Volume of gases released (H2 + CO2)","value":"< 50","metricType":"other","numericValue":"50.0","unit":"mL","reactionContext":"60 °C, aqueous solution of formic acid and sodium formate","temperatureC":"60.0","solution":"aqueous","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"9 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"9 mmol sodium formate\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"94 μmol\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass tube purged by nitrogen\", \"stirring_or_flow_condition\": \"stirred vigorously\", \"time_point_or_conversion_basis\": \"1 h\"}","basis":"unclear","basisRaw":"unclear","definition":"Volume of the gases released (H2 + CO2)","whyPerformsWell":"Showed nearly no activity; potentially due to rapid aggregation following reduction induced by weakening zeta-potential of initially formed Pd nanoparticles.","temperatureReported":"60 °C","formicAcid":"9 mmol","formate":"9 mmol sodium formate","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"distilled water","catalystAmount":"94 μmol","reactorOrAtmosphere":"glass tube purged by nitrogen","stirringOrFlow":"stirred vigorously","timeOrConversionBasis":"1 h"},{"activityId":"P182_PERF_003_ACT_001","paperId":"P182","catalystId":"P182_PERF_003","catalyst":"Na2PdCl4","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"Volume of gases released (H2 + CO2)","value":"< 50","metricType":"other","numericValue":"50.0","unit":"mL","reactionContext":"60 °C, aqueous solution of formic acid and sodium formate","temperatureC":"60.0","solution":"aqueous","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"9 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"9 mmol sodium formate\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"94 μmol\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass tube purged by nitrogen\", \"stirring_or_flow_condition\": \"stirred vigorously\", \"time_point_or_conversion_basis\": \"1 h\"}","basis":"unclear","basisRaw":"unclear","definition":"Volume of the gases released (H2 + CO2)","whyPerformsWell":"Showed nearly no activity.","temperatureReported":"60 °C","formicAcid":"9 mmol","formate":"9 mmol sodium formate","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"distilled water","catalystAmount":"94 μmol","reactorOrAtmosphere":"glass tube purged by nitrogen","stirringOrFlow":"stirred vigorously","timeOrConversionBasis":"1 h"},{"activityId":"P182_PERF_004_ACT_001","paperId":"P182","catalystId":"P182_PERF_004","catalyst":"Pd(NH3)4Cl2","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"Volume of gases released (H2 + CO2)","value":"< 50","metricType":"other","numericValue":"50.0","unit":"mL","reactionContext":"60 °C, aqueous solution of formic acid and sodium formate","temperatureC":"60.0","solution":"aqueous","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"60 °C\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"9 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"9 mmol sodium formate\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"distilled water\", \"catalyst_amount\": \"94 μmol\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass tube purged by nitrogen\", \"stirring_or_flow_condition\": \"stirred vigorously\", \"time_point_or_conversion_basis\": \"1 h\"}","basis":"unclear","basisRaw":"unclear","definition":"Volume of the gases released (H2 + CO2)","whyPerformsWell":"Showed nearly no activity.","temperatureReported":"60 °C","formicAcid":"9 mmol","formate":"9 mmol sodium formate","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"distilled 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water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"40 umol Pd\", \"reactor_or_atmosphere\": \"nitrogen filled reactor\", \"stirring_or_flow_condition\": \"750 rpm\", \"time_point_or_conversion_basis\": null}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = P0V / (2RT nPd t)","selectivity":"No CO was detected; CO2 to H2 molar ratio is about 1:1.","stability":"Consistent catalytic activity over 8th recycled use.","whyPerformsWell":"Synergistic effects and electronic modification between Pd NPs, Zr species, and amino groups; dual-support structure stabilizes small Pd NP size and dispersion.","temperatureReported":"313 K","formicAcid":"5 mmol","baseOrAdditive":"additive-free","solvent":"deionized water","metalAmountOrRatio":"40 umol Pd","reactorOrAtmosphere":"nitrogen filled reactor","stirringOrFlow":"750 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\"stirring_or_flow_condition\": \"750 rpm\", \"time_point_or_conversion_basis\": null}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = P0V / (2RT nPd t)","selectivity":"No CO was detected; CO2 to H2 molar ratio is about 1:1.","stability":"Consistent catalytic activity over 8th recycled use.","whyPerformsWell":"Synergistic effects and electronic modification between Pd NPs, Zr species, and amino groups; dual-support structure stabilizes small Pd NP size and dispersion.","temperatureReported":"323 K","formicAcid":"5 mmol","baseOrAdditive":"additive-free","solvent":"deionized water","metalAmountOrRatio":"40 umol Pd","reactorOrAtmosphere":"nitrogen filled reactor","stirringOrFlow":"750 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rpm"},{"activityId":"P183_PERF_001_ACT_005","paperId":"P183","catalystId":"P183_PERF_001","catalyst":"Pd@UIO-66/NH2-SEP","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"apparent activation energy","value":"49.72","metricType":"activation_energy","numericValue":"49.72","unit":"kJ/mol","reactionContext":"Dehydrogenation of formic acid (FA) in aqueous solution under ambient pressure.","temperatureC":"49.85","solution":"aqueous FA solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"303-343 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"deionized water\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius plot of ln(TOF) vs 1/T","selectivity":"No CO was detected; CO2 to H2 molar ratio is about 1:1.","stability":"Consistent catalytic activity over 8th recycled use.","whyPerformsWell":"Synergistic effects and electronic modification between Pd NPs, Zr species, and amino groups; dual-support structure stabilizes small Pd NP size and dispersion.","temperatureReported":"303-343 K","baseOrAdditive":"additive-free","solvent":"deionized water","catalystAmount":"100 mg"},{"activityId":"P183_PERF_002_ACT_001","paperId":"P183","catalystId":"P183_PERF_002","catalyst":"Pd@NH2-SEP","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"initial TOF","value":"reduced to almost half","metricType":"TOF","reactionContext":"Dehydrogenation of formic acid in aqueous solution.","solution":"additive-free FA aqueous solution","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": \"additive-free FA aqueous solution\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"after three cycles of use\"}","basis":"unclear","basisRaw":"unclear","stability":"Unsatisfactory reusability; initial TOF reduced to almost half after three cycles.","whyPerformsWell":"High initial activity attributed to amino groups on SEP surface modifying electronic states of Pd NPs, but lacks structural stability provided by 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catalytic activity; drops slightly at the eighth cycling","whyPerformsWell":"higher concentration of amino groups promotes formation of tinier AuPd NPs (below 1.1 nm), inhibits aggregation via stronger coordination, and provides more basic sites for FA activation","temperatureReported":"room temperature","baseOrAdditive":"additive-free","solvent":"aqueous solution","metalAmountOrRatio":"nPd/nFA = 0.001","timeOrConversionBasis":"initial TOF"},{"activityId":"P184_PERF_001_ACT_003","paperId":"P184","catalystId":"P184_PERF_001","catalyst":"Pd0.8Au0.2/UiO-66-(NH2)2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"conversion","value":"nearly 100%","metricType":"conversion","numericValue":"100.0","unit":"%","reactionContext":"Formic acid dehydrogenation in aqueous solution","temperatureC":"49.85","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"323 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"aqueous solution\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"nPd/nFA = 0.001\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"20 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"H2 and CO2 (1:1 volume ratio); no CO signal detected","stability":"recycled seven times without obvious loss in catalytic activity; drops slightly at the eighth cycling","whyPerformsWell":"higher concentration of amino groups promotes formation of tinier AuPd NPs (below 1.1 nm), inhibits aggregation via stronger coordination, and provides more basic sites for FA activation","temperatureReported":"323 K","baseOrAdditive":"additive-free","solvent":"aqueous 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\"reaction_solution\": \"aqueous FA\", \"formic_acid_amount_or_concentration\": \"1.0 mol·L⁻¹\", \"formate_or_sodium_formate_amount_or_concentration\": \"0\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"pure water\", \"catalyst_amount\": \"16.7 g·L⁻¹\", \"metal_amount_or_substrate_to_metal_ratio\": \"10 wt% Pd\", \"reactor_or_atmosphere\": \"round-bottom flask connected to gas buret\", \"stirring_or_flow_condition\": \"stirred\", \"time_point_or_conversion_basis\": null}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"pVgasRT / (nPd * D * t)","selectivity":"Composed totally of H2 and CO2 at 303 K; trace CO (0.018% by volume of CO2) detected at 323 K.","stability":"Reused for at least five runs: first run reached 95% conversion in 30 min; fifth run reached 70% conversion in 85 min.","whyPerformsWell":"Hierarchical pore structure (especially mesopores) facilitating mass 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min"},{"activityId":"P192_PERF_001_ACT_006","paperId":"P192","catalystId":"P192_PERF_001","catalyst":"Pd/rGO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"Ea","value":"24.4","metricType":"activation_energy","numericValue":"24.4","unit":"kJ mol-1","reactionContext":"Formic acid (FA) dehydrogenation in aqueous solution; catalyst amount 10 mg; volume 5 mL; magnetic stirring 1000 rpm; ambient air atmosphere.","temperatureC":"52.35","solution":"FA/SF aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"298-353 K\", \"reaction_solution\": \"FA/SF aqueous solution\", \"formic_acid_amount_or_concentration\": \"C_FA + C_SF = 0.25 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"C_FA + C_SF = 0.25 M\", \"formic_acid_to_formate_ratio\": \"3:1\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_Pd/n_FA = 0.010\", \"reactor_or_atmosphere\": \"ambient air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius plot of ln TOF vs. 1/T","selectivity":"No detectable traces of CO; generated gases are H2 and CO2.","stability":"Preserved initial activity even after 5 recycling runs at 313 K and 363 K.","temperatureReported":"298-353 K","formicAcid":"C_FA + C_SF = 0.25 M","formate":"C_FA + C_SF = 0.25 M","acidFormateRatio":"3:1","baseOrAdditive":"sodium formate (SF)","solvent":"water","catalystAmount":"10 mg","metalAmountOrRatio":"n_Pd/n_FA = 0.010","reactorOrAtmosphere":"ambient air","stirringOrFlow":"1000 rpm"},{"activityId":"P192_PERF_002_ACT_001","paperId":"P192","catalystId":"P192_PERF_002","catalyst":"PdAu/rGO","activeMetals":"Pd-Au","metalClass":"Pd-based 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\"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"No CO detected in the evolved gas (H2 + CO2).","whyPerformsWell":"Smaller particles, good dispersion and synergistic effect with reduced graphene oxide.","temperatureReported":"298-365 K","formicAcid":"C_FA + C_SF = 0.25 M","formate":"C_FA + C_SF = 0.25 M","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate (SF)","solvent":"water","catalystAmount":"11.25 mg","metalAmountOrRatio":"n_Pd-Au/n_FA = 0.015","reactorOrAtmosphere":"ambient air","stirringOrFlow":"1000 rpm"},{"activityId":"P192_PERF_002_ACT_002","paperId":"P192","catalystId":"P192_PERF_002","catalyst":"PdAu/rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"wet_impregnation","metric":"Ea","value":"13.4","metricType":"activation_energy","numericValue":"13.4","unit":"kJ mol-1","reactionContext":"Formic acid (FA) dehydrogenation in FA/SF aqueous solution; catalyst amount 11.25 mg; volume 5 mL; magnetic stirring 1000 rpm; ambient air atmosphere.","temperatureC":"52.35","solution":"FA/SF aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"298-353 K\", \"reaction_solution\": \"FA/SF aqueous solution\", \"formic_acid_amount_or_concentration\": \"C_FA + C_SF = 0.25 M\", \"formate_or_sodium_formate_amount_or_concentration\": \"C_FA + C_SF = 0.25 M\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate (SF)\", \"solvent\": \"water\", \"catalyst_amount\": \"11.25 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"n_Pd-Au/n_FA = 0.015\", \"reactor_or_atmosphere\": \"ambient air\", \"stirring_or_flow_condition\": \"1000 rpm\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius plot of ln(TOF) vs 1/T","selectivity":"No CO detected in the evolved gas (H2 + CO2).","whyPerformsWell":"Smaller particles, good dispersion and synergistic effect with reduced graphene oxide.","temperatureReported":"298-353 K","formicAcid":"C_FA + C_SF = 0.25 M","formate":"C_FA + C_SF = 0.25 M","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate (SF)","solvent":"water","catalystAmount":"11.25 mg","metalAmountOrRatio":"n_Pd-Au/n_FA = 0.015","reactorOrAtmosphere":"ambient air","stirringOrFlow":"1000 rpm"},{"activityId":"P193_PERF_001_ACT_001","paperId":"P193","catalystId":"P193_PERF_001","catalyst":"Pd0.90Ag0.10B/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"gas volume (CO2 + H2)","value":"220","metricType":"other","numericValue":"220.0","unit":"mL","reactionContext":"Dehydrogenation of FA/SF aqueous solution at 298 K under ambient atmosphere in a round-bottomed flask.","temperatureC":"24.85","solution":"aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"aqueous solution\", \"formic_acid_amount_or_concentration\": \"5.0 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"3.5 mmol\", \"formic_acid_to_formate_ratio\": \"10:7 (approx)\", \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round-bottomed flask, ambient atmosphere\", \"stirring_or_flow_condition\": \"magnetic stirring\", \"time_point_or_conversion_basis\": \"40 min\"}","basis":"unclear","basisRaw":"unclear","selectivity":"Excellent H2 selectivity; no CO detected (detection limit ≈10 ppm).","stability":"Little decrease in the second run; obvious activity loss observed in the third run.","whyPerformsWell":"Combination of engineered alloy nanostructure, electronic modification effect of boron species (creating electron-rich Pd active sites), and support effects of rGO providing uniform adhesion and modifying electronic structure.","temperatureReported":"298 K","formicAcid":"5.0 mmol","formate":"3.5 mmol","acidFormateRatio":"10:7 (approx)","solvent":"water","reactorOrAtmosphere":"round-bottomed flask, ambient atmosphere","stirringOrFlow":"magnetic stirring","timeOrConversionBasis":"40 min"},{"activityId":"P193_PERF_001_ACT_002","paperId":"P193","catalystId":"P193_PERF_001","catalyst":"Pd0.90Ag0.10B/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"TOF","value":"164","metricType":"TOF","numericValue":"164.0","unit":"h-1","tof":"164.0","reactionContext":"Dehydrogenation of FA/SF aqueous solution at 298 K under ambient atmosphere in a round-bottomed flask.","temperatureC":"24.85","solution":"aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"aqueous solution\", \"formic_acid_amount_or_concentration\": \"5.0 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"3.5 mmol\", \"formic_acid_to_formate_ratio\": \"10:7 (approx)\", \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round-bottomed flask, ambient atmosphere\", \"stirring_or_flow_condition\": \"magnetic stirring\", \"time_point_or_conversion_basis\": \"20% conversion of FA\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Pd; Ag","definition":"sum of the rate of the formation of H2 and CO2 molecules related to the total number of metal atoms in the samples","selectivity":"Excellent H2 selectivity; no CO detected (detection limit ≈10 ppm).","stability":"Little decrease in the second run; obvious activity loss observed in the third run.","whyPerformsWell":"Combination of engineered alloy nanostructure, electronic modification effect of boron species (creating electron-rich Pd active 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providing uniform adhesion and modifying electronic structure.","temperatureReported":"25 to 55 °C","formicAcid":"5.0 mmol","formate":"3.5 mmol","acidFormateRatio":"10:7 (approx)","solvent":"water","reactorOrAtmosphere":"round-bottomed flask, ambient atmosphere","stirringOrFlow":"magnetic stirring"},{"activityId":"P193_PERF_002_ACT_001","paperId":"P193","catalystId":"P193_PERF_002","catalyst":"Pd0.90Ag0.10/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"gas volume (CO2 + H2)","value":"122","metricType":"other","numericValue":"122.0","unit":"mL","reactionContext":"Dehydrogenation of FA/SF aqueous solution at 298 K under ambient atmosphere.","temperatureC":"24.85","solution":"aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"aqueous solution\", \"formic_acid_amount_or_concentration\": \"5.0 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"3.5 mmol\", \"formic_acid_to_formate_ratio\": \"10:7 (approx)\", \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round-bottomed flask, ambient atmosphere\", \"stirring_or_flow_condition\": \"magnetic stirring\", \"time_point_or_conversion_basis\": \"40 min\"}","basis":"unclear","basisRaw":"unclear","temperatureReported":"298 K","formicAcid":"5.0 mmol","formate":"3.5 mmol","acidFormateRatio":"10:7 (approx)","solvent":"water","reactorOrAtmosphere":"round-bottomed flask, ambient atmosphere","stirringOrFlow":"magnetic stirring","timeOrConversionBasis":"40 min"},{"activityId":"P193_PERF_003_ACT_001","paperId":"P193","catalystId":"P193_PERF_003","catalyst":"PdB/rGO","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"TOF","value":"15","metricType":"TOF","numericValue":"15.0","unit":"h-1","tof":"15.0","reactionContext":"Dehydrogenation of FA/SF aqueous solution at 298 K under ambient atmosphere.","temperatureC":"24.85","solution":"aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"aqueous solution\", \"formic_acid_amount_or_concentration\": \"5.0 mmol\", \"formate_or_sodium_formate_amount_or_concentration\": \"3.5 mmol\", \"formic_acid_to_formate_ratio\": \"10:7 (approx)\", \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round-bottomed flask, ambient atmosphere\", 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at 303 K using a mixture of formic acid and sodium formate.","temperatureC":"29.85","solution":"5 mL mixture of 1.1 mol/L formic acid and 0.8 mol/L sodium formate","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"303 K\", \"reaction_solution\": \"5 mL mixture of 1.1 mol/L formic acid and 0.8 mol/L sodium formate\", \"formic_acid_amount_or_concentration\": \"1.1 mol/L\", \"formate_or_sodium_formate_amount_or_concentration\": \"0.8 mol/L\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"sodium formate\", \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial 40 min (for intrinsic activity)\"}","basis":"surface_active_sites","basisRaw":"surface active sites","metalsInDenominator":"Pd","definition":"normalized by the number of surface sites titrated by 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Durability test showed TOF drop from 1408 h-1 to 131 h-1 by the fourth cycle.","whyPerformsWell":"Synergistic electronic effects of Pd and ZrO2, strong metal-support interaction (SMSI) between Pd-ZrO2 NPs and SBA-15-NH2 substrate, abundant basic sites from ZrO2 and -NH2 groups promoting C-H bond splitting and FA deprotonation, and high dispersion of ultrasmall nanoparticles.","temperatureReported":"298 K","formicAcid":"2.5 mmol (0.5 M, 5 mL)","baseOrAdditive":"additive-free","solvent":"H2O","metalAmountOrRatio":"(Pd + ZrO2)/FA = 0.04","reactorOrAtmosphere":"gas burette system","timeOrConversionBasis":"initial"},{"activityId":"P195_PERF_001_ACT_002","paperId":"P195","catalystId":"P195_PERF_001","catalyst":"Pd-ZrO2/SBA-15-NH2","activeMetals":"Pd-Zr","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"TOF","value":"623","metricType":"TOF","numericValue":"623.0","unit":"h-1","tof":"623.0","reactionContext":"Additive-free dehydrogenation of formic acid (FA) in H2O","temperatureC":"14.85","solution":"aqueous FA solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"288 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol (0.5 M, 5 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"H2O\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"(Pd + ZrO2)/FA = 0.04\", \"reactor_or_atmosphere\": \"gas burette system\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","selectivity":"100% hydrogen selectivity (CO-free)","stability":"Well retained after one cycle; slight decrease after five cycles; obvious decrease after ten cycles. Durability test showed TOF drop from 1408 h-1 to 131 h-1 by the fourth cycle.","whyPerformsWell":"Synergistic electronic effects of Pd and ZrO2, strong metal-support interaction (SMSI) between Pd-ZrO2 NPs and SBA-15-NH2 substrate, abundant basic sites from ZrO2 and -NH2 groups promoting C-H bond splitting and FA deprotonation, and high dispersion of ultrasmall nanoparticles.","temperatureReported":"288 K","formicAcid":"2.5 mmol (0.5 M, 5 mL)","baseOrAdditive":"additive-free","solvent":"H2O","metalAmountOrRatio":"(Pd + ZrO2)/FA = 0.04","reactorOrAtmosphere":"gas burette system","timeOrConversionBasis":"initial"},{"activityId":"P195_PERF_001_ACT_003","paperId":"P195","catalystId":"P195_PERF_001","catalyst":"Pd-ZrO2/SBA-15-NH2","activeMetals":"Pd-Zr","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"TOF","value":"2083","metricType":"TOF","numericValue":"2083.0","unit":"h-1","tof":"2083.0","reactionContext":"Additive-free dehydrogenation of formic acid (FA) in H2O","temperatureC":"34.85","solution":"aqueous FA solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"308 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol (0.5 M, 5 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"H2O\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"(Pd + ZrO2)/FA = 0.04\", \"reactor_or_atmosphere\": \"gas burette system\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","selectivity":"100% hydrogen selectivity (CO-free)","stability":"Well retained after one cycle; slight decrease after five cycles; obvious decrease after ten cycles. Durability test showed TOF drop from 1408 h-1 to 131 h-1 by the fourth cycle.","whyPerformsWell":"Synergistic electronic effects of Pd and ZrO2, strong metal-support interaction (SMSI) between Pd-ZrO2 NPs and SBA-15-NH2 substrate, abundant basic sites from ZrO2 and -NH2 groups promoting C-H bond splitting and FA deprotonation, and high dispersion of ultrasmall nanoparticles.","temperatureReported":"308 K","formicAcid":"2.5 mmol (0.5 M, 5 mL)","baseOrAdditive":"additive-free","solvent":"H2O","metalAmountOrRatio":"(Pd + ZrO2)/FA = 0.04","reactorOrAtmosphere":"gas burette system","timeOrConversionBasis":"initial"},{"activityId":"P195_PERF_001_ACT_004","paperId":"P195","catalystId":"P195_PERF_001","catalyst":"Pd-ZrO2/SBA-15-NH2","activeMetals":"Pd-Zr","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"TOF","value":"3571","metricType":"TOF","numericValue":"3571.0","unit":"h-1","tof":"3571.0","reactionContext":"Additive-free dehydrogenation of formic acid (FA) in H2O","temperatureC":"44.85","solution":"aqueous FA solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"318 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol (0.5 M, 5 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"H2O\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"(Pd + ZrO2)/FA = 0.04\", \"reactor_or_atmosphere\": \"gas burette system\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"unclear","basisRaw":"unclear","selectivity":"100% hydrogen selectivity (CO-free)","stability":"Well retained after one cycle; slight decrease after five cycles; obvious decrease after ten cycles. Durability test showed TOF drop from 1408 h-1 to 131 h-1 by the fourth cycle.","whyPerformsWell":"Synergistic electronic effects of Pd and ZrO2, strong metal-support interaction (SMSI) between Pd-ZrO2 NPs and SBA-15-NH2 substrate, abundant basic sites from ZrO2 and -NH2 groups promoting C-H bond splitting and FA deprotonation, and high dispersion of ultrasmall nanoparticles.","temperatureReported":"318 K","formicAcid":"2.5 mmol (0.5 M, 5 mL)","baseOrAdditive":"additive-free","solvent":"H2O","metalAmountOrRatio":"(Pd + ZrO2)/FA = 0.04","reactorOrAtmosphere":"gas burette system","timeOrConversionBasis":"initial"},{"activityId":"P195_PERF_001_ACT_005","paperId":"P195","catalystId":"P195_PERF_001","catalyst":"Pd-ZrO2/SBA-15-NH2","activeMetals":"Pd-Zr","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"chemical_reduction_loading","metric":"apparent activation energy (Ea)","value":"45.97","metricType":"activation_energy","numericValue":"45.97","unit":"kJ mol-1","reactionContext":"Additive-free dehydrogenation of formic acid (FA) in H2O","temperatureC":"29.85","solution":"aqueous FA solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"288-318 K\", \"reaction_solution\": \"aqueous FA solution\", \"formic_acid_amount_or_concentration\": \"2.5 mmol (0.5 M, 5 mL)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"additive-free\", \"solvent\": \"H2O\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"(Pd + ZrO2)/FA = 0.04\", \"reactor_or_atmosphere\": \"gas burette system\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"100% hydrogen selectivity (CO-free)","stability":"Well retained after one cycle; slight decrease after five cycles; obvious decrease after ten cycles. Durability test showed TOF drop from 1408 h-1 to 131 h-1 by the fourth cycle.","whyPerformsWell":"Synergistic electronic effects of Pd and ZrO2, strong metal-support interaction (SMSI) between Pd-ZrO2 NPs and SBA-15-NH2 substrate, abundant basic sites from ZrO2 and -NH2 groups promoting C-H bond splitting and FA deprotonation, and high dispersion of ultrasmall nanoparticles.","temperatureReported":"288-318 K","formicAcid":"2.5 mmol (0.5 M, 5 mL)","baseOrAdditive":"additive-free","solvent":"H2O","metalAmountOrRatio":"(Pd + ZrO2)/FA = 0.04","reactorOrAtmosphere":"gas burette system"},{"activityId":"P195_PERF_002_ACT_001","paperId":"P195","catalystId":"P195_PERF_002","catalyst":"Pd/SBA-15-NH2","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"apparent activation energy (Ea)","value":"53.01","metricType":"activation_energy","numericValue":"53.01","unit":"kJ mol-1","reactionContext":"Additive-free 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\"water\", \"catalyst_amount\": \"125 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"initial substrate concentration 21 mmol/L\", \"reactor_or_atmosphere\": \"high pressure autoclave, 20%O2/80%N2, 50 atm\", \"stirring_or_flow_condition\": \"1500 rpm\", \"time_point_or_conversion_basis\": \"3 h\"}","basis":"unclear","basisRaw":"unclear","temperatureReported":"160 °C","solvent":"water","catalystAmount":"125 mg","metalAmountOrRatio":"initial substrate concentration 21 mmol/L","reactorOrAtmosphere":"high pressure autoclave, 20%O2/80%N2, 50 atm","stirringOrFlow":"1500 rpm","timeOrConversionBasis":"3 h"},{"activityId":"P197_PERF_004_ACT_001","paperId":"P197","catalystId":"P197_PERF_004","catalyst":"Ru/4.8%N-CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"unknown","metric":"PhOH conversion","value":"94-97","metricType":"conversion","numericValue":"94.0","unit":"%","reactionContext":"CWAO of phenol: 160 °C, 50 atm, 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in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","temperatureC":"59.85","solution":"FA-SF (1:1) solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"333 K\", \"reaction_solution\": \"FA-SF (1:1) solution\", \"formic_acid_amount_or_concentration\": \"6 M, 0.5 mL\", \"formate_or_sodium_formate_amount_or_concentration\": \"sodium formate (SF)\", \"formic_acid_to_formate_ratio\": \"1:1\", \"base_or_additive\": \"sodium formate\", \"solvent\": \"deionized H2O\", \"catalyst_amount\": \"suitable amount\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd/FA = 0.006\", \"reactor_or_atmosphere\": \"two-necked flask in a water bath\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": \"when the conversion reached 20 %\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = (P * Vgas / (R * T)) / (2 * nPd * t)","selectivity":"no detectable 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dehydrogenation in a two-necked flask with stirring; Pd/FA molar ratio = 0.006; solvent: deionized H2O","temperatureC":"59.85","solution":"aqueous FA","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"333 K\", \"reaction_solution\": \"aqueous FA\", \"formic_acid_amount_or_concentration\": \"6 M, 0.5 mL\", \"formate_or_sodium_formate_amount_or_concentration\": \"none\", \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"without any additives\", \"solvent\": \"1.0 mL deionized H2O\", \"catalyst_amount\": \"suitable amount\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd/FA = 0.006\", \"reactor_or_atmosphere\": \"two-necked flask in a water bath\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": \"when the conversion reached 20 %\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = (P * Vgas / (R * T)) / (2 * nPd * t)","whyPerformsWell":"Bimetallic 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\"catalyst_amount\": \"suitable amount\", \"metal_amount_or_substrate_to_metal_ratio\": \"Pd/FA = 0.006\", \"reactor_or_atmosphere\": \"two-necked flask in a water bath\", \"stirring_or_flow_condition\": \"stirring\", \"time_point_or_conversion_basis\": \"when the conversion reached 20 %\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = (P * Vgas / (R * T)) / (2 * nPd * t)","whyPerformsWell":"Bimetallic effect","temperatureReported":"333 K","formicAcid":"6 M, 0.5 mL","formate":"none","baseOrAdditive":"without any additives","solvent":"1.0 mL deionized H2O","catalystAmount":"suitable amount","metalAmountOrRatio":"Pd/FA = 0.006","reactorOrAtmosphere":"two-necked flask in a water bath","stirringOrFlow":"stirring","timeOrConversionBasis":"when the conversion reached 20 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\"first 120 s\"}","basis":"unclear","basisRaw":"unclear","selectivity":"no CO but CO2 was detected during the reaction","stability":"activity remained unchanged even after six reaction cycles","whyPerformsWell":"Abundant oxygen-containing functional groups (OCGs) and -NH2 promote small-sized, highly dispersed Pd nanoparticles and enhance metal-support interaction; high Pd2+/Pd0 ratio regulates electronic structure to promote formation/adsorption of active intermediates (Pd-HCOO* and H*); OCGs increase hydrophilicity for better dispersion in aqueous solution.","temperatureReported":"333 K","solvent":"water","timeOrConversionBasis":"first 120 s"},{"activityId":"P211_PERF_001_ACT_002","paperId":"P211","catalystId":"P211_PERF_001","catalyst":"Pd/O-NCNTs-P","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"gas production 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\"time_point_or_conversion_basis\": \"2 h\"}","basis":"unclear","basisRaw":"unclear","whyPerformsWell":"Pd is the crucial active center","temperatureReported":"383 K","baseOrAdditive":"triethylamine (5 mL)","solvent":"ethanol (15 mL)","metalAmountOrRatio":"5 wt% metal loading","stirringOrFlow":"500 rpm","timeOrConversionBasis":"2 h"},{"activityId":"P217_PERF_002_ACT_001","paperId":"P217","catalystId":"P217_PERF_002","catalyst":"Pd-Au/AC","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"adsorption_or_loading","metric":"TOF","value":"81.3","metricType":"TOF","numericValue":"81.3","unit":"h-1","tof":"81.3","reactionContext":"CO2 hydrogenation to formate; ethanol solvent, triethylamine base, 383 K, 500 rpm stirring, 2 h reaction time","temperatureC":"109.85","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"383 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, 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Higher redox potential of Au makes it more durable in acidic FA solutions during dehydrogenation.","temperatureReported":"353 K","formicAcid":"1 mol/L (5 mmol)","baseOrAdditive":"triethylamine (0.5 mol/L, 2.5 mmol)","solvent":"water","metalAmountOrRatio":"5 wt% metal loading, Pd:Au mass ratio 1:1","reactorOrAtmosphere":"ambient pressure (1 atm)","stirringOrFlow":"750 rpm","timeOrConversionBasis":"at 10% FA conversion"},{"activityId":"P217_PERF_003_ACT_001","paperId":"P217","catalystId":"P217_PERF_003","catalyst":"Pd-Cu/AC","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"adsorption_or_loading","metric":"TOF","value":"100.3","metricType":"TOF","numericValue":"100.3","unit":"h-1","tof":"100.3","reactionContext":"CO2 hydrogenation to formate; ethanol solvent, triethylamine base, 383 K, 500 rpm stirring, 2 h reaction time","temperatureC":"109.85","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"383 K\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"triethylamine (5 mL)\", \"solvent\": \"ethanol (15 mL)\", \"catalyst_amount\": \"100 mg\", \"metal_amount_or_substrate_to_metal_ratio\": \"5 wt% metal loading, Pd:Cu mass ratio 1:1\", \"reactor_or_atmosphere\": \"7 MPa (Table 1) or 3.5/3.5 MPa CO2/H2 (Table 2)\", \"stirring_or_flow_condition\": \"500 rpm\", \"time_point_or_conversion_basis\": \"2 h\"}","basis":"unclear","basisRaw":"unclear","stability":"No prominent fluctuations in TOF up to five cycles for both CO2 hydrogenation and FA dehydrogenation","whyPerformsWell":"Synergistic effect between Pd and Cu; lower activation energy (27 kJ/mol) compared to Pd-Au/AC. Divalent Cu may act as assist active sites by attracting negatively charged HCO3-. 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Divalent Cu may act as assist active sites by attracting negatively charged HCO3-. 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Divalent Cu may act as assist active sites by attracting negatively charged HCO3-. 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\"time_point_or_conversion_basis\": \"3 h\"}","basis":"unclear","temperatureReported":"room temperature","formicAcid":"5%","baseOrAdditive":"none","solvent":"water","catalystAmount":"10 mg","reactorOrAtmosphere":"N2 gas","timeOrConversionBasis":"3 h"},{"activityId":"P219_PERF_005_ACT_001","paperId":"P219","catalystId":"P219_PERF_005","catalyst":"Cu(BDC)∙nDMF","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"unknown","metric":"catalytic activity","value":"almost catalytic inactive","metricType":"other","reactionContext":"Aqueous solution of FA (5%, 5 mL), room temperature, N2 atmosphere","solution":"aqueous solution of FA","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"room temperature\", \"reaction_solution\": \"aqueous solution of FA\", \"formic_acid_amount_or_concentration\": \"5%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water\", \"catalyst_amount\": \"10 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"N2 gas\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"3 h\"}","basis":"unclear","temperatureReported":"room temperature","formicAcid":"5%","baseOrAdditive":"none","solvent":"water","catalystAmount":"10 mg","reactorOrAtmosphere":"N2 gas","timeOrConversionBasis":"3 h"},{"activityId":"P220_PERF_001_ACT_001","paperId":"P220","catalystId":"P220_PERF_001","catalyst":"Pd90Rh10/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"Activity","value":"1793","metricType":"other","numericValue":"1793.0","unit":"h-1","reactionContext":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","temperatureC":"30.0","solution":"aqueous solution 0.5 M of HCOOH","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"aqueous solution 0.5 M of HCOOH\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"2000:1\", \"reactor_or_atmosphere\": \"two-necked 100 mL round-bottom flask with reflux condenser\", \"stirring_or_flow_condition\": \"1400 rpm\", \"time_point_or_conversion_basis\": \"after 5 min of reaction\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Rh","definition":"mol of formic acid reacted per total mol of metal per hour","selectivity":"CO under the detection limit of the instrument (5 ppm)","stability":"Deactivated during recycling tests; average particle size increased from 2.9 to 4.5 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condenser","stirringOrFlow":"1400 rpm","timeOrConversionBasis":"after 2 h of reaction"},{"activityId":"P220_PERF_002_ACT_001","paperId":"P220","catalystId":"P220_PERF_002","catalyst":"Pd69Rh31/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"Activity","value":"921","metricType":"other","numericValue":"921.0","unit":"h-1","reactionContext":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","temperatureC":"30.0","solution":"aqueous solution 0.5 M of HCOOH","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"aqueous solution 0.5 M of HCOOH\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"2000:1\", \"reactor_or_atmosphere\": \"two-necked 100 mL round-bottom flask with reflux condenser\", \"stirring_or_flow_condition\": \"1400 rpm\", \"time_point_or_conversion_basis\": \"after 5 min of reaction\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Rh","definition":"mol of formic acid reacted per total mol of metal per hour","selectivity":"CO under the detection limit of the instrument (5 ppm)","stability":"Good stability during 6 cycles; conversion was constant","whyPerformsWell":"High stability might be attributed to a catalyst with a Pd-Rh composition similar to the most active ones after leaching","temperatureReported":"30 °C","formicAcid":"0.5 M","solvent":"water","metalAmountOrRatio":"2000:1","reactorOrAtmosphere":"two-necked 100 mL round-bottom flask with reflux condenser","stirringOrFlow":"1400 rpm","timeOrConversionBasis":"after 5 min of reaction"},{"activityId":"P220_PERF_002_ACT_002","paperId":"P220","catalystId":"P220_PERF_002","catalyst":"Pd69Rh31/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"conversion","value":"54","metricType":"conversion","numericValue":"54.0","unit":"%","reactionContext":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","temperatureC":"30.0","solution":"aqueous solution 0.5 M of HCOOH","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"aqueous solution 0.5 M of HCOOH\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"2000:1\", \"reactor_or_atmosphere\": \"two-necked 100 mL round-bottom flask with reflux condenser\", \"stirring_or_flow_condition\": \"1400 rpm\", \"time_point_or_conversion_basis\": \"after 2 h of reaction\"}","basis":"unclear","basisRaw":"unclear","selectivity":"CO under the detection limit of the instrument (5 ppm)","stability":"Good stability during 6 cycles; conversion was constant","whyPerformsWell":"High stability might be attributed to a catalyst with a Pd-Rh composition similar to the most active ones after leaching","temperatureReported":"30 °C","formicAcid":"0.5 M","solvent":"water","metalAmountOrRatio":"2000:1","reactorOrAtmosphere":"two-necked 100 mL round-bottom flask with reflux condenser","stirringOrFlow":"1400 rpm","timeOrConversionBasis":"after 2 h of reaction"},{"activityId":"P220_PERF_003_ACT_001","paperId":"P220","catalystId":"P220_PERF_003","catalyst":"Pd/HHT","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"sol_immobilization","metric":"Activity","value":"979","metricType":"other","numericValue":"979.0","unit":"h-1","reactionContext":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","temperatureC":"30.0","solution":"aqueous solution 0.5 M of HCOOH","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"aqueous solution 0.5 M of HCOOH\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"2000:1\", \"reactor_or_atmosphere\": \"two-necked 100 mL round-bottom flask with reflux condenser\", \"stirring_or_flow_condition\": \"1400 rpm\", \"time_point_or_conversion_basis\": \"after 5 min of reaction\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd","definition":"mol of formic acid reacted per total mol of metal per hour","selectivity":"12 ppm CO","stability":"Rapidly deactivated after the first run","temperatureReported":"30 °C","formicAcid":"0.5 M","solvent":"water","metalAmountOrRatio":"2000:1","reactorOrAtmosphere":"two-necked 100 mL round-bottom flask with reflux condenser","stirringOrFlow":"1400 rpm","timeOrConversionBasis":"after 5 min of reaction"},{"activityId":"P220_PERF_003_ACT_002","paperId":"P220","catalystId":"P220_PERF_003","catalyst":"Pd/HHT","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"sol_immobilization","metric":"conversion","value":"28","metricType":"conversion","numericValue":"28.0","unit":"%","reactionContext":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","temperatureC":"30.0","solution":"aqueous solution 0.5 M of HCOOH","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"aqueous solution 0.5 M of HCOOH\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"2000:1\", \"reactor_or_atmosphere\": \"two-necked 100 mL round-bottom flask with reflux condenser\", \"stirring_or_flow_condition\": \"1400 rpm\", \"time_point_or_conversion_basis\": \"after 2 h of reaction\"}","basis":"unclear","basisRaw":"unclear","selectivity":"12 ppm CO","stability":"Rapidly deactivated after the first run","temperatureReported":"30 °C","formicAcid":"0.5 M","solvent":"water","metalAmountOrRatio":"2000:1","reactorOrAtmosphere":"two-necked 100 mL round-bottom flask with reflux condenser","stirringOrFlow":"1400 rpm","timeOrConversionBasis":"after 2 h of reaction"},{"activityId":"P220_PERF_004_ACT_001","paperId":"P220","catalystId":"P220_PERF_004","catalyst":"Pd40Rh60/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"Activity","value":"696","metricType":"other","numericValue":"696.0","unit":"h-1","reactionContext":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","temperatureC":"30.0","solution":"aqueous solution 0.5 M of HCOOH","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"aqueous solution 0.5 M of HCOOH\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"2000:1\", \"reactor_or_atmosphere\": \"two-necked 100 mL round-bottom flask with reflux condenser\", \"stirring_or_flow_condition\": \"1400 rpm\", \"time_point_or_conversion_basis\": \"after 5 min of reaction\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Rh","definition":"mol of formic acid reacted per total mol of metal per hour","selectivity":"CO under the detection limit (5 ppm)","temperatureReported":"30 °C","formicAcid":"0.5 M","solvent":"water","metalAmountOrRatio":"2000:1","reactorOrAtmosphere":"two-necked 100 mL round-bottom flask with reflux condenser","stirringOrFlow":"1400 rpm","timeOrConversionBasis":"after 5 min of reaction"},{"activityId":"P220_PERF_005_ACT_001","paperId":"P220","catalystId":"P220_PERF_005","catalyst":"Pd48Rh52/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","pdBased":"True","activeMetalCount":"2","method":"unknown","metric":"Activity","value":"341","metricType":"other","numericValue":"341.0","unit":"h-1","reactionContext":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","temperatureC":"30.0","solution":"aqueous solution 0.5 M of HCOOH","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"aqueous solution 0.5 M of HCOOH\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"2000:1\", \"reactor_or_atmosphere\": \"two-necked 100 mL round-bottom flask with reflux condenser\", \"stirring_or_flow_condition\": \"1400 rpm\", \"time_point_or_conversion_basis\": \"after 5 min of reaction\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Pd; Rh","definition":"mol of formic acid reacted per total mol of metal per hour","selectivity":"CO under the detection limit (5 ppm)","temperatureReported":"30 °C","formicAcid":"0.5 M","solvent":"water","metalAmountOrRatio":"2000:1","reactorOrAtmosphere":"two-necked 100 mL round-bottom flask with reflux condenser","stirringOrFlow":"1400 rpm","timeOrConversionBasis":"after 5 min of reaction"},{"activityId":"P220_PERF_006_ACT_001","paperId":"P220","catalystId":"P220_PERF_006","catalyst":"Rh/HHT","activeMetals":"Rh","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"sol_immobilization","metric":"Activity","value":"very low","metricType":"other","reactionContext":"Liquid-phase dehydrogenation of formic acid; 30 °C, 0.5 M HCOOH in water, stirring rate 1400 rpm, substrate/metal molar ratio 2000:1","temperatureC":"30.0","solution":"aqueous solution 0.5 M of HCOOH","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"30 °C\", \"reaction_solution\": \"aqueous solution 0.5 M of HCOOH\", \"formic_acid_amount_or_concentration\": \"0.5 M\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": \"2000:1\", \"reactor_or_atmosphere\": \"two-necked 100 mL round-bottom flask with reflux condenser\", \"stirring_or_flow_condition\": \"1400 rpm\", \"time_point_or_conversion_basis\": \"after 5 min of reaction\"}","basis":"total_noble_metal_amount","basisRaw":"total noble metal amount","metalsInDenominator":"Rh","definition":"mol of formic acid reacted per total mol of metal per hour","selectivity":"CO under the detection limit (5 ppm)","temperatureReported":"30 °C","formicAcid":"0.5 M","solvent":"water","metalAmountOrRatio":"2000:1","reactorOrAtmosphere":"two-necked 100 mL round-bottom flask with reflux condenser","stirringOrFlow":"1400 rpm","timeOrConversionBasis":"after 5 min of reaction"},{"activityId":"P221_PERF_001_ACT_001","paperId":"P221","catalystId":"P221_PERF_001","catalyst":"Au/N-SBA-15_K(9.5)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"full","metricType":"conversion","unit":"%","reactionContext":"Gas-phase dehydrogenation of formic acid, fixed-bed quartz tube (4 mm i.d.), 30 mg catalyst, N2 carrier gas at 5 mL min-1 through a saturator containing 98% formic acid, atmospheric pressure.","temperatureC":"115.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"115 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"98%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"fixed-bed quartz tube, atmospheric pressure\", \"stirring_or_flow_condition\": \"N2 carrier gas at 5 mL min-1\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"complete selectivity to hydrogen; no carbon monoxide formation detected","whyPerformsWell":"Smallest particle size (0.8 ± 0.2 nm) and amine-functionalized support which stabilizes particles and allows them to enter pores.","temperatureReported":"115 °C","formicAcid":"98%","catalystAmount":"30 mg","reactorOrAtmosphere":"fixed-bed quartz tube, atmospheric pressure","stirringOrFlow":"N2 carrier gas at 5 mL min-1"},{"activityId":"P221_PERF_002_ACT_001","paperId":"P221","catalystId":"P221_PERF_002","catalyst":"Au/N-SBA-15_K(11)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"full","metricType":"conversion","unit":"%","reactionContext":"Gas-phase dehydrogenation of formic acid, fixed-bed quartz tube (4 mm i.d.), 30 mg catalyst, N2 carrier gas at 5 mL min-1 through a saturator containing 98% formic acid, atmospheric pressure.","temperatureC":"115.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"115 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"98%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"fixed-bed quartz tube, atmospheric pressure\", \"stirring_or_flow_condition\": \"N2 carrier gas at 5 mL min-1\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"complete selectivity to hydrogen; no carbon monoxide formation detected","whyPerformsWell":"Small particle size (0.9 ± 0.2 nm) and amine-functionalized support.","temperatureReported":"115 °C","formicAcid":"98%","catalystAmount":"30 mg","reactorOrAtmosphere":"fixed-bed quartz tube, atmospheric pressure","stirringOrFlow":"N2 carrier gas at 5 mL min-1"},{"activityId":"P221_PERF_003_ACT_001","paperId":"P221","catalystId":"P221_PERF_003","catalyst":"Au/SBA-15","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"<100","metricType":"conversion","numericValue":"100.0","unit":"%","reactionContext":"Gas-phase dehydrogenation of formic acid, fixed-bed quartz tube (4 mm i.d.), 30 mg catalyst, N2 carrier gas at 5 mL min-1 through a saturator containing 98% formic acid, atmospheric pressure.","temperatureC":"350.0","temperatureBin":">100 °C","evaluationConditions":"{\"reaction_temperature\": \"350 °C\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"98%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": null, \"catalyst_amount\": \"30 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"fixed-bed quartz tube, atmospheric pressure\", \"stirring_or_flow_condition\": \"N2 carrier gas at 5 mL min-1\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"53% selectivity to hydrogen and 44% selectivity to carbon monoxide at 350 °C","whyPerformsWell":"Performs poorly due to large particle size (26 ± 18 nm).","temperatureReported":"350 °C","formicAcid":"98%","catalystAmount":"30 mg","reactorOrAtmosphere":"fixed-bed quartz tube, atmospheric pressure","stirringOrFlow":"N2 carrier gas at 5 mL min-1"},{"activityId":"P222_PERF_001_ACT_001","paperId":"P222","catalystId":"P222_PERF_001","catalyst":"Gly-Cu/Ag/MnO2","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"kobs","value":"0.5 to 5.5","metricType":"other","numericValue":"0.5","unit":"10^-4 s^-1","reactionContext":"Decomposition of formic acid in aqueous solution, monitored by water displacement method.","temperatureC":"39.85","solution":"aqueous","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"313 K\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"1.0 to 6.0 x 10^-3 mol/L\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"NaOH (0.1 to 0.8 mol/L)\", \"solvent\": \"water\", \"catalyst_amount\": \"0.01 to 0.04 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"round bottom three-necked reaction vessel\", \"stirring_or_flow_condition\": \"magnetic stirrer\", \"time_point_or_conversion_basis\": \"initial slope up to 80% completion\"}","basis":"unclear","basisRaw":"unclear","definition":"kobs = 1/t ln(Vα - V0)/(Vα - Vt)","selectivity":"H2:CO2 molar ratio = 1:1","stability":"Excellent for four consecutive cycles; performance slightly decreased in higher cyclic experiments.","whyPerformsWell":"Synergistic electronic effect and strong interactions between the three metals (Cu, Ag, Mn).","uncertainty":"± 3.0 to 5.0 x 10^-4 s^-1","temperatureReported":"313 K","formicAcid":"1.0 to 6.0 x 10^-3 mol/L","baseOrAdditive":"NaOH (0.1 to 0.8 mol/L)","solvent":"water","catalystAmount":"0.01 to 0.04 g","reactorOrAtmosphere":"round bottom three-necked reaction vessel","stirringOrFlow":"magnetic stirrer","timeOrConversionBasis":"initial slope up to 80% completion"},{"activityId":"P222_PERF_001_ACT_002","paperId":"P222","catalystId":"P222_PERF_001","catalyst":"Gly-Cu/Ag/MnO2","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"TOF","value":"146","metricType":"TOF","numericValue":"146.0","unit":"h^-1","tof":"146.0","reactionContext":"Decomposition of formic acid in aqueous solution, monitored by water displacement method.","temperatureC":"24.85","solution":"aqueous","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"0.032 g\", \"metal_amount_or_substrate_to_metal_ratio\": \"nCu+Ag+Mn = 1.38 x 10^-4 mol\", \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"time of half decomposition\"}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Cu; Ag; Mn","definition":"TOF = PV(CO2 + H2) / (RT * 2ncatalyst) * (1/t)","selectivity":"H2:CO2 molar ratio = 1:1","stability":"Excellent for four consecutive cycles; performance slightly decreased in higher cyclic experiments.","whyPerformsWell":"Synergistic electronic effect and strong interactions between the three metals (Cu, Ag, Mn).","temperatureReported":"298 K","solvent":"water","catalystAmount":"0.032 g","metalAmountOrRatio":"nCu+Ag+Mn = 1.38 x 10^-4 mol","timeOrConversionBasis":"time of half decomposition"},{"activityId":"P222_PERF_001_ACT_003","paperId":"P222","catalystId":"P222_PERF_001","catalyst":"Gly-Cu/Ag/MnO2","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"Ea","value":"56","metricType":"activation_energy","numericValue":"56.0","unit":"kJ/mol","reactionContext":"Decomposition of formic acid in aqueous solution, monitored by water displacement method.","temperatureC":"39.85","solution":"aqueous","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 to 328 K\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"5.0 x 10^-3 mol/L\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"0.032 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","definition":"Arrhenius equation: k0bs = Ae^(-Ea/RT)","selectivity":"H2:CO2 molar ratio = 1:1","stability":"Excellent for four consecutive cycles; performance slightly decreased in higher cyclic experiments.","whyPerformsWell":"Synergistic electronic effect and strong interactions between the three metals (Cu, Ag, Mn).","temperatureReported":"298 to 328 K","formicAcid":"5.0 x 10^-3 mol/L","solvent":"water","catalystAmount":"0.032 g"},{"activityId":"P222_PERF_001_ACT_004","paperId":"P222","catalystId":"P222_PERF_001","catalyst":"Gly-Cu/Ag/MnO2","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"chemical_reduction_loading","metric":"conversion","value":"22.3, 31.8, 54.2, 70.1","metricType":"conversion","numericValue":"22.3","unit":"%","reactionContext":"Decomposition of formic acid in aqueous solution, monitored by water displacement method.","temperatureC":"54.85","solution":"aqueous","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"298, 308, 318, 328 K\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": \"7.0 x 10^-3 mol/L\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"0.032 g\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": null, \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"20 min\"}","basis":"catalyst_mass","basisRaw":"catalyst mass","definition":"HCOOH conversion% = (nCO2 + H2) / (2nHCOOH) * 100%","selectivity":"H2:CO2 molar ratio = 1:1","stability":"Excellent for four consecutive cycles; performance slightly decreased in higher cyclic experiments.","whyPerformsWell":"Synergistic electronic effect and strong interactions between the three metals (Cu, Ag, Mn).","temperatureReported":"298, 308, 318, 328 K","formicAcid":"7.0 x 10^-3 mol/L","solvent":"water","catalystAmount":"0.032 g","timeOrConversionBasis":"20 min"},{"activityId":"P222_PERF_002_ACT_001","paperId":"P222","catalystId":"P222_PERF_002","catalyst":"Gly-Cu/Ag","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"other","metric":"TOF","value":"97","metricType":"TOF","numericValue":"97.0","unit":"h^-1","tof":"97.0","reactionContext":"Decomposition of formic acid in aqueous solution.","temperatureC":"24.85","solution":"aqueous","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"298 K\", \"reaction_solution\": \"aqueous\", \"formic_acid_amount_or_concentration\": null, \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"0.032 g\", 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This spatial separation leads to lower tandem reaction efficiency compared to cubic nanocrystals.","uncertainty":"15.7","temperatureReported":"323 K","formicAcid":"3 mol L-1","solvent":"H2O","catalystAmount":"0.2 mg","metalAmountOrRatio":"0.2 mmol styrene (1 mL), 3 mol L-1 HCOOH aqueous solution (1 mL)","reactorOrAtmosphere":"argon or air atmosphere","timeOrConversionBasis":"60 min"},{"activityId":"P224_PERF_003_ACT_001","paperId":"P224","catalystId":"P224_PERF_003","catalyst":"Pd tetrahedral nanocrystals","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"shape-controlled synthesis","metric":"TOF surface","value":"18.6","metricType":"TOF","numericValue":"18.6","unit":"h-1","tof":"18.6","reactionContext":"Varies by reaction","temperatureC":"91.85","solution":"aqueous solution","temperatureBin":"60-100 °C","evaluationConditions":"{\"reaction_temperature\": \"365 K\", \"reaction_solution\": \"aqueous solution\", 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295.0","metricType":"TOF","numericValue":"1554.1","unit":"h-1","tof":"1554.1","reactionContext":"Tandem hydrogen transfer reaction at 323 K, 1 h","temperatureC":"49.85","solution":"various substrates (alkenes, nitrobenzene)","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"323 K\", \"reaction_solution\": \"various substrates (alkenes, nitrobenzene)\", \"formic_acid_amount_or_concentration\": \"0.5 mmol (Entries 1-2), 3 mmol (Entries 3-5)\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"not specified\", \"catalyst_amount\": \"0.2 mg Pd usage\", \"metal_amount_or_substrate_to_metal_ratio\": \"0.2 mmol substrate (1 mL)\", \"reactor_or_atmosphere\": \"not specified\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"1 h\"}","basis":"unclear","basisRaw":"unclear","metalsInDenominator":"Pd","whyPerformsWell":"Ag modification accelerates the limiting step (HCOOH decomposition), forming Had not only at edge sites but also on planes, promoting overall tandem reactions.","uncertainty":"35.7, 24.5, 43.5, 37.8, 19.8","temperatureReported":"323 K","formicAcid":"0.5 mmol (Entries 1-2), 3 mmol (Entries 3-5)","solvent":"not specified","catalystAmount":"0.2 mg Pd usage","metalAmountOrRatio":"0.2 mmol substrate (1 mL)","reactorOrAtmosphere":"not specified","timeOrConversionBasis":"1 h"},{"activityId":"P225_PERF_001_ACT_001","paperId":"P225","catalystId":"P225_PERF_001","catalyst":"Pd/EDA-PAN","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF","value":"3989","metricType":"TOF","numericValue":"3989.0","unit":"h⁻¹","tof":"3989.0","reactionContext":"Dehydrogenation of formic acid (FA) aqueous solution without additives.","temperatureC":"59.85","solution":"FA aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"333 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amidinate and amino groups facilitate FA deprotonation.","temperatureReported":"333 K","formicAcid":"0.5 ml of 4 mol/L FA aqueous solution","baseOrAdditive":"none","solvent":"water (9.5 ml added to FA solution)","catalystAmount":"50 mg","reactorOrAtmosphere":"two-necked bottle","stirringOrFlow":"agitation","timeOrConversionBasis":"20% conversion of FA"},{"activityId":"P225_PERF_001_ACT_002","paperId":"P225","catalystId":"P225_PERF_001","catalyst":"Pd/EDA-PAN","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"TOF","value":"688","metricType":"TOF","numericValue":"688.0","unit":"h⁻¹","tof":"688.0","reactionContext":"Dehydrogenation of formic acid (FA) aqueous solution without additives.","temperatureC":"29.85","solution":"FA aqueous solution","temperatureBin":"≤40 °C","evaluationConditions":"{\"reaction_temperature\": \"303 K\", \"reaction_solution\": \"FA aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.5 ml of 4 mol/L FA aqueous solution\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water (9.5 ml added to FA solution)\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-necked bottle\", \"stirring_or_flow_condition\": \"agitation\", \"time_point_or_conversion_basis\": \"20% conversion of FA\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = P0V / (2RT nPd t)","selectivity":"Excellent selectivity; no CO signal detected by GC analysis.","stability":"High activity maintained after recycling five times.","whyPerformsWell":"Surface amination with EDA achieves high dispersion of ultra-small Pd NPs (~1.2 nm) and builds strong metal-support interaction; basic features of amidinate and amino groups facilitate FA deprotonation.","temperatureReported":"303 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\"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water (9.5 ml added to FA solution)\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-necked bottle\", \"stirring_or_flow_condition\": \"agitation\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"Excellent selectivity; no CO signal detected by GC analysis.","stability":"High activity maintained after recycling five times.","whyPerformsWell":"Surface amination with EDA achieves high dispersion of ultra-small Pd NPs (~1.2 nm) and builds strong metal-support interaction; basic features of amidinate and amino groups facilitate FA deprotonation.","temperatureReported":"303–353 K","formicAcid":"0.5 ml of 4 mol/L FA aqueous solution","baseOrAdditive":"none","solvent":"water (9.5 ml added to FA solution)","catalystAmount":"50 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\"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-necked bottle\", \"stirring_or_flow_condition\": \"agitation\", \"time_point_or_conversion_basis\": \"20% conversion of FA\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF = P0V / (2RT nPd t)","selectivity":"Excellent selectivity; no CO signal detected by GC analysis.","stability":"Slight decline in catalytic activity observed with increasing recycling numbers.","temperatureReported":"333 K","formicAcid":"0.5 ml of 4 mol/L FA aqueous solution","baseOrAdditive":"none","solvent":"water (9.5 ml added to FA solution)","catalystAmount":"50 mg","reactorOrAtmosphere":"two-necked bottle","stirringOrFlow":"agitation","timeOrConversionBasis":"20% conversion of FA"},{"activityId":"P225_PERF_002_ACT_002","paperId":"P225","catalystId":"P225_PERF_002","catalyst":"Pd/PAN","activeMetals":"Pd","metalClass":"Pd-only","pdBased":"True","activeMetalCount":"1","method":"wet_impregnation","metric":"activation energy","value":"38.0","metricType":"activation_energy","numericValue":"38.0","unit":"kJ/mol","reactionContext":"Dehydrogenation of formic acid (FA) aqueous solution without additives.","temperatureC":"54.85","solution":"FA aqueous solution","temperatureBin":"40-60 °C","evaluationConditions":"{\"reaction_temperature\": \"303–353 K\", \"reaction_solution\": \"FA aqueous solution\", \"formic_acid_amount_or_concentration\": \"0.5 ml of 4 mol/L FA aqueous solution\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": \"none\", \"solvent\": \"water (9.5 ml added to FA solution)\", \"catalyst_amount\": \"50 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"two-necked bottle\", \"stirring_or_flow_condition\": \"agitation\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"Excellent selectivity; no CO signal detected by GC analysis.","stability":"Slight decline in catalytic activity observed with increasing recycling numbers.","temperatureReported":"303–353 K","formicAcid":"0.5 ml of 4 mol/L FA aqueous solution","baseOrAdditive":"none","solvent":"water (9.5 ml added to FA solution)","catalystAmount":"50 mg","reactorOrAtmosphere":"two-necked bottle","stirringOrFlow":"agitation"},{"activityId":"P226_PERF_001_ACT_001","paperId":"P226","catalystId":"P226_PERF_001","catalyst":"6Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"conversion","value":"100","metricType":"conversion","numericValue":"100.0","unit":"%","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"280\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"> 99% selectivity toward H2 production","stability":"Tested at 280 °C for > 50 h; conversion increased during first few hours, then stabilized (97.4% after breaks). Selectivity decreased from 99.2% to 95.7% after air exposure breaks.","whyPerformsWell":"Contains single-atom Ni sites coordinated with N and O atoms on a high surface area N-doped carbon support.","temperatureReported":"280","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow"},{"activityId":"P226_PERF_001_ACT_002","paperId":"P226","catalystId":"P226_PERF_001","catalyst":"6Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"H2 selectivity","value":"99.6","metricType":"selectivity","numericValue":"99.6","unit":"%","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"280\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": \"100% conversion\"}","basis":"unclear","basisRaw":"unclear","selectivity":"> 99% selectivity toward H2 production","stability":"Tested at 280 °C for > 50 h; conversion increased during first few hours, then stabilized (97.4% after breaks). Selectivity decreased from 99.2% to 95.7% after air exposure breaks.","whyPerformsWell":"Contains single-atom Ni sites coordinated with N and O atoms on a high surface area N-doped carbon support.","temperatureReported":"280","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow","timeOrConversionBasis":"100% conversion"},{"activityId":"P226_PERF_001_ACT_003","paperId":"P226","catalystId":"P226_PERF_001","catalyst":"6Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"apparent activation energy (Ea)","value":"95","metricType":"activation_energy","numericValue":"95.0","unit":"kJ/mol","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"> 99% selectivity toward H2 production","stability":"Tested at 280 °C for > 50 h; conversion increased during first few hours, then stabilized (97.4% after breaks). Selectivity decreased from 99.2% to 95.7% after air exposure breaks.","whyPerformsWell":"Contains single-atom Ni sites coordinated with N and O atoms on a high surface area N-doped carbon support.","uncertainty":"4","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow"},{"activityId":"P226_PERF_001_ACT_004","paperId":"P226","catalystId":"P226_PERF_001","catalyst":"6Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"specific reaction rate","value":"1.4 times faster than 10Ni/N-LC at 200 °C; 1.2 times faster than 10Ni/N-LC at 240 °C","metricType":"rate","numericValue":"1.4","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"200 or 240\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"total_metal_amount","basisRaw":"total metal amount","metalsInDenominator":"Ni","definition":"calculated using the Ni content measured by ICP-AES","selectivity":"> 99% selectivity toward H2 production","stability":"Tested at 280 °C for > 50 h; conversion increased during first few hours, then stabilized (97.4% after breaks). Selectivity decreased from 99.2% to 95.7% after air exposure breaks.","whyPerformsWell":"Contains single-atom Ni sites coordinated with N and O atoms on a high surface area N-doped carbon support.","temperatureReported":"200 or 240","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow"},{"activityId":"P226_PERF_002_ACT_001","paperId":"P226","catalystId":"P226_PERF_002","catalyst":"8Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"conversion","value":"100","metricType":"conversion","numericValue":"100.0","unit":"%","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"280\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"> 99% selectivity toward H2 production","whyPerformsWell":"High dispersion of Ni on N-doped carbon support.","temperatureReported":"280","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow"},{"activityId":"P226_PERF_002_ACT_002","paperId":"P226","catalystId":"P226_PERF_002","catalyst":"8Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"H2 selectivity","value":"99.3","metricType":"selectivity","numericValue":"99.3","unit":"%","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"280\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": \"100% conversion\"}","basis":"unclear","basisRaw":"unclear","selectivity":"> 99% selectivity toward H2 production","whyPerformsWell":"High dispersion of Ni on N-doped carbon support.","temperatureReported":"280","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow","timeOrConversionBasis":"100% conversion"},{"activityId":"P226_PERF_002_ACT_003","paperId":"P226","catalystId":"P226_PERF_002","catalyst":"8Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"apparent activation energy (Ea)","value":"99","metricType":"activation_energy","numericValue":"99.0","unit":"kJ/mol","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"> 99% selectivity toward H2 production","whyPerformsWell":"High dispersion of Ni on N-doped carbon support.","uncertainty":"4","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow"},{"activityId":"P226_PERF_003_ACT_001","paperId":"P226","catalystId":"P226_PERF_003","catalyst":"10Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"conversion","value":"100","metricType":"conversion","numericValue":"100.0","unit":"%","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"280\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"> 99% selectivity toward H2 production","stability":"Tested at 280 °C for > 50 h; conversion increased during first few hours, then stabilized (85.4% after breaks). Selectivity decreased from 98.6% to 97.1% after air exposure breaks.","whyPerformsWell":"Contains sub-nanosized nickel particles with an average size of 0.84 nm on N-doped carbon support.","temperatureReported":"280","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow"},{"activityId":"P226_PERF_003_ACT_002","paperId":"P226","catalystId":"P226_PERF_003","catalyst":"10Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"H2 selectivity","value":"99.3","metricType":"selectivity","numericValue":"99.3","unit":"%","reactionContext":"2.5 vol% HCOOH in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor, pre-treated with HCOOH/Ar at 350 °C for 0.5 h","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": \"280\", \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": \"100% conversion\"}","basis":"unclear","basisRaw":"unclear","selectivity":"> 99% selectivity toward H2 production","stability":"Tested at 280 °C for > 50 h; conversion increased during first few hours, then stabilized (85.4% after breaks). 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null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"Lower selectivity than N-LC supported catalysts","whyPerformsWell":"Control catalyst with Ni in the form of surface-oxidized nanoparticles on nitrogen-free carbon.","temperatureReported":"320-340","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow"},{"activityId":"P226_PERF_004_ACT_002","paperId":"P226","catalystId":"P226_PERF_004","catalyst":"10Ni/LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"H2 selectivity","value":"92.2 (at 320 °C), 94.0 (at 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\"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"Lower selectivity than N-LC supported catalysts","whyPerformsWell":"Control catalyst with Ni in the form of surface-oxidized nanoparticles on nitrogen-free carbon.","uncertainty":"4","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed reactor","stirringOrFlow":"65 mL/min total flow"},{"activityId":"P226_PERF_005_ACT_001","paperId":"P226","catalystId":"P226_PERF_005","catalyst":"10Ni/LC_NH3","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","pdBased":"False","activeMetalCount":"1","method":"wet_impregnation","metric":"conversion","value":"100","metricType":"conversion","numericValue":"100.0","unit":"%","reactionContext":"2.5 vol% HCOOH in Ar, total gas 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in Ar, total gas flow rate 65 mL/min, glass fixed-bed reactor","temperatureBin":"temperature missing","evaluationConditions":"{\"reaction_temperature\": null, \"reaction_solution\": null, \"formic_acid_amount_or_concentration\": \"2.5 vol%\", \"formate_or_sodium_formate_amount_or_concentration\": null, \"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"Ar\", \"catalyst_amount\": null, \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"glass fixed-bed reactor\", \"stirring_or_flow_condition\": \"65 mL/min total flow\", \"time_point_or_conversion_basis\": null}","basis":"unclear","basisRaw":"unclear","selectivity":"Lower selectivity than N-LC supported catalysts","whyPerformsWell":"Control catalyst with Ni in the form of surface-oxidized nanoparticles on nitrogen-doped carbon (prepared without fluorination).","uncertainty":"4","formicAcid":"2.5 vol%","solvent":"Ar","reactorOrAtmosphere":"glass fixed-bed 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\"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"50 mL round-bottom flask\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": \"initial\"}","basis":"total_Pd_amount","basisRaw":"total Pd amount","metalsInDenominator":"Pd","definition":"TOF based on the total Pd content","stability":"Excellent stability; particle size increased from 2.45 to 2.91 nm over three cycles.","whyPerformsWell":"Topological defects (specifically the 5-8-5 defect induced by pyrrolic N) promote electron transfer at the Pd-carbon interface, enhancing metal-support interaction and modulating the electronic state of Pd NPs (downshifting the d-band center), which reinforces bonding to HCOO intermediates.","temperatureReported":"30 °C","formicAcid":"10 mmol","formate":"10 mmol sodium formate","acidFormateRatio":"1:1","baseOrAdditive":"sodium formate","solvent":"water","catalystAmount":"40 mg","reactorOrAtmosphere":"50 mL round-bottom 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\"formic_acid_to_formate_ratio\": null, \"base_or_additive\": null, \"solvent\": \"water\", \"catalyst_amount\": \"20 mg\", \"metal_amount_or_substrate_to_metal_ratio\": null, \"reactor_or_atmosphere\": \"N2\", \"stirring_or_flow_condition\": null, \"time_point_or_conversion_basis\": null}","basis":"catalyst_mass","basisRaw":"catalyst mass","temperatureReported":"25 °C","formicAcid":"10.0 M","solvent":"water","catalystAmount":"20 mg","reactorOrAtmosphere":"N2"}],"preparations":[{"paperId":"P001","catalystId":"P001_PERF_001","name":"Pt nanoclusters on 1D GaN nanowires","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"1D GaN nanowires on Si(111) wafer","method":"sol_immobilization","synthesis":"GaN nanowires were grown on a Si(111) substrate via MBE. Pt nanoclusters were then immobilized by placing the GaN/Si wafer in a sealed quartz chamber with a methanol-water precursor solution and irradiating it with a 300 W Xenon lamp for 30 min.","matchedSynthesis":"Pt nanoclusters on 1D GaN nanowires","composition":"Pt","role":"catalyst for formic acid decomposition"},{"paperId":"P001","catalystId":"P001_PERF_002","name":"bare GaN nanowires","activeMetals":"Ga","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P002","catalystId":"P002_PERF_001","name":"3D Pd/8YSZ","activeMetals":"Pd","metalClass":"Pd-only","support":"8 mol% yttria-stabilized cubic zirconia (8YSZ)","method":"deposition_precipitation","synthesis":"8YSZ scaffolds were robocast and sintered at 1200 °C, then doped with sulfate ions via (NH4)2SO4. Pd was deposited using a Na2CO3 solution followed by the addition of Na2PdCl4, heated to evaporate water, calcined, and reduced with NaBH4.","matchedSynthesis":"Pd/8YSZ","composition":"Pd","role":"hydrogen production from formic acid (FA) dehydrogenation"},{"paperId":"P003","catalystId":"P003_PERF_001","name":"3D Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon (AC) and alumina (Al2O3)","method":"wet_impregnation","synthesis":"3D AC supports were submerged in a PdCl2/HCl solution, evaporated at 95 °C, washed with Milli-Q water, dried at 60 °C, and reduced under H2/N2 stream.","matchedSynthesis":"3D Pd/AC","composition":"Pd","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P004","catalystId":"P004_PERF_001","name":"Pd0.8Au0.2/1'","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"MOF 1' ([(CH3)2NH2][Cd(L)])","method":"wet_impregnation","synthesis":"Impregnation of MOF 1' in n-hexane with aqueous metal precursors, followed by vacuum drying and liquid-phase reduction using NaBH4.","matchedSynthesis":"Pd0.8Au0.2/1'","composition":"Pd:Au = 0.8:0.2 (molar ratio)","role":"Catalyst for formic acid dehydrogenation"},{"paperId":"P005","catalystId":"P005_PERF_001","name":"Pd/BPC (optimal: C:B ratio 1:5, calcined at 900 °C, reduced at 60 °C)","activeMetals":"Pd","metalClass":"Pd-only","support":"Boron-Doped Porous Carbon (BPC)","method":"chemical_reduction_loading","synthesis":"Porous carbon (PC) was synthesized from petroleum asphalt using alpha-Fe2O3 as a template at 800 °C. BPC was prepared by calcining PC and boron acid (1:5 ratio) at 900 °C under N2. Pd nanoparticles were then loaded onto BPC via reduction of palladium acetate in methanol at 60 °C.","matchedSynthesis":"Pd/BPC","composition":"Pd; precursor to support ratio 1:9","role":"main catalyst"},{"paperId":"P005","catalystId":"P005_PERF_002","name":"Pd/PC","activeMetals":"Pd","metalClass":"Pd-only","support":"Porous Carbon (PC)","method":"chemical_reduction_loading","synthesis":"Similar to Pd/BPC but without the boron doping step for the support.","matchedSynthesis":"Pd/PC","composition":"Pd; precursor to support ratio 1:9","role":"control sample"},{"paperId":"P005","catalystId":"P005_PERF_003","name":"commercial Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P005","catalystId":"P005_PERF_004","name":"Pd/NPC","activeMetals":"Pd","metalClass":"Pd-only","support":"Nitrogen-Doped Porous Carbon (NPC)","method":"chemical_reduction_loading","synthesis":"Similar to Pd/BPC, but urea was used instead of boron acid for the support doping step.","matchedSynthesis":"Pd/NPC","composition":"Pd; precursor to support ratio 1:9","role":"comparison sample"},{"paperId":"P006","catalystId":"P006_PERF_001","name":"Pd/NMP-360-t","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P006","catalystId":"P006_PERF_002","name":"Pd1Au1/16-NMP-360-t","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P006","catalystId":"P006_PERF_003","name":"Pd1Au1/8-NMP-360-t","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P006","catalystId":"P006_PERF_004","name":"Pd1Au1/4-NMP-360-t (powder)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P006","catalystId":"P006_PERF_005","name":"Pd1Au1/2-NMP-360-t","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P006","catalystId":"P006_PERF_006","name":"monolithic Pd1Au1/4-NMP-360-t","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P007","catalystId":"P007_PERF_001","name":"Ag@Pd/N-GCNT aerogel (optimized as Ag1@Pd1)","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","support":"nitrogen-doped graphene carbon nanotube (N-GCNT) aerogel","method":"sequential_impregnation","synthesis":"N-GCNT aerogel and AgNO3 were dissolved in ethylene glycol and heated to 120 °C under N2 for 30 min; then a solution of PdCl2 in ethylene glycol was added and the mixture was heated to 90 °C for 2 h under N2.","matchedSynthesis":"Ag@Pd/N-GCNT aerogel","composition":"Ag:Pd molar ratios of 1:1, 1:2, and 2:1","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P007","catalystId":"P007_PERF_002","name":"support-free Ag@Pd nanoparticles","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P008","catalystId":"P008_PERF_001","name":"PdMg","activeMetals":"Pd","metalClass":"Pd-only","method":"chemical_reduction_loading","synthesis":"One-step replacement reaction where Mg powder is added to a Pd(NO3)2 solution at room temperature, followed by acid treatment to remove residual Mg.","matchedSynthesis":"PdMg","composition":"Pd","role":"catalyst for formic acid decomposition"},{"paperId":"P008","catalystId":"P008_PERF_002","name":"PdNaBH4","activeMetals":"Pd","metalClass":"Pd-only","method":"chemical_reduction_loading","synthesis":"One-step reduction of Pd(NO3)2 solution using NaBH4 at room temperature.","matchedSynthesis":"PdNaBH4","composition":"Pd","role":"catalyst for formic acid decomposition"},{"paperId":"P008","catalystId":"P008_PERF_003","name":"PdHCOONa","activeMetals":"Pd","metalClass":"Pd-only","method":"chemical_reduction_loading","synthesis":"One-step reduction of Pd(NO3)2 solution using HCOONa at room temperature.","matchedSynthesis":"PdHCOONa","composition":"Pd","role":"catalyst for formic acid decomposition"},{"paperId":"P009","catalystId":"P009_PERF_001","name":"Ag1Pd9–(MnOx)1.5/A-CS","activeMetals":"Ag-Pd-Mn","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P009","catalystId":"P009_PERF_002","name":"Ag1Pd9–(MnOx)1.5/K-CS","activeMetals":"Ag-Pd-Mn","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P009","catalystId":"P009_PERF_003","name":"Ag1Pd9/A-CS","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P010","catalystId":"P010_PERF_001","name":"Pd/NH2-KIE-11-k","activeMetals":"Pd","metalClass":"Pd-only","support":"NH2-functionalized mesoporous silica (NH2-KIE-11)","method":"wet_impregnation","synthesis":"KIE-11 support was functionalized with APTMS, impregnated with palladium(II) nitrate hydrate solution, and reduced using aqueous NaBH4.","matchedSynthesis":"Pd/NH2-KIE-11","composition":"Pd","role":"formic acid dehydrogenation catalyst"},{"paperId":"P010","catalystId":"P010_PERF_002","name":"Pd/NH2-KIE-11-c","activeMetals":"Pd","metalClass":"Pd-only","support":"NH2-functionalized mesoporous silica (NH2-KIE-11)","method":"wet_impregnation","synthesis":"KIE-11 support was functionalized with APTMS, impregnated with palladium(II) nitrate hydrate solution, and reduced using aqueous NaBH4.","matchedSynthesis":"Pd/NH2-KIE-11","composition":"Pd","role":"formic acid dehydrogenation catalyst"},{"paperId":"P010","catalystId":"P010_PERF_003","name":"Pd/NH2-KIE-11-l","activeMetals":"Pd","metalClass":"Pd-only","support":"NH2-functionalized mesoporous silica (NH2-KIE-11)","method":"wet_impregnation","synthesis":"KIE-11 support was functionalized with APTMS, impregnated with palladium(II) nitrate hydrate solution, and reduced using aqueous NaBH4.","matchedSynthesis":"Pd/NH2-KIE-11","composition":"Pd","role":"formic acid dehydrogenation catalyst"},{"paperId":"P011","catalystId":"P011_PERF_001","name":"Pd1Au2/AC-LA","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"active carbon (AC)","method":"chemical_reduction_loading","synthesis":"L-arginine was dissolved in water, followed by the addition of active carbon and sonication for 10 min. An aqueous solution of Na2PdCl4 and AuCl3 was slowly added to the mixture. After 1 hour, a fresh NaBH4 solution was rapidly added under magnetic stirring for 25 min. The product was centrifuged, washed with water, and vacuum dried.","matchedSynthesis":"Pd1Au2/AC-LA","composition":"Pd:Au = 1:2","role":"active catalyst for ambient hydrogen storage and release"},{"paperId":"P011","catalystId":"P011_PERF_002","name":"PdAu/AC-LA (various ratios)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P011","catalystId":"P011_PERF_003","name":"PdAu/AC","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P012","catalystId":"P012_PERF_001","name":"Pd-La(OH)3/N-PCB-NH2","activeMetals":"Pd-La","metalClass":"Pd-based multimetal","support":"amine-functionalized N-doped porous carbon bowl (N-PCB-NH2)","method":"wet_impregnation","synthesis":"N-PCB was functionalized with APTES, followed by the addition of Na2PdCl4 and La(NO3)3 precursors via sonication. Pd2+ was reduced to Pd0 using NaBH4, while La3+ was converted to La(OH)3 in situ by the alkali solution generated from NaBH4 hydrolysis.","matchedSynthesis":"Pd-La(OH)3/N-PCB-NH2","composition":"Pd and La; designed molar ratio of La(OH)3/Pd = 0.2 (actual measured ratio = 0.14)","role":"main catalyst"},{"paperId":"P012","catalystId":"P012_PERF_002","name":"Pd/N-PCB-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P012","catalystId":"P012_PERF_003","name":"Pd-La(OH)3 (support-free)","activeMetals":"Pd-La","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P012","catalystId":"P012_PERF_004","name":"Pd-La(OH)3/N-PCB (amine-free)","activeMetals":"Pd-La","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P013","catalystId":"P013_PERF_001","name":"Pd/HNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"Halloysite nanotubes (HNTs)","method":"wet_impregnation","synthesis":"HNTs dispersed in water, Pd precursor added and stirred for 12 h at room temperature; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","matchedSynthesis":"Pd/HNTs","composition":"Pd","role":"comparison sample"},{"paperId":"P013","catalystId":"P013_PERF_002","name":"Pd/HNTs (1.28 wt.% Pd)","activeMetals":"Pd","metalClass":"Pd-only","support":"Halloysite nanotubes (HNTs)","method":"wet_impregnation","synthesis":"HNTs dispersed in water, Pd precursor added and stirred for 12 h at room temperature; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","matchedSynthesis":"Pd/HNTs","composition":"Pd","role":"comparison sample"},{"paperId":"P013","catalystId":"P013_PERF_003","name":"Pd/NH2-HNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"Halloysite nanotubes (HNTs)","method":"wet_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd precursor added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","matchedSynthesis":"Pd/NH2-HNTs","composition":"Pd","role":"active catalyst"},{"paperId":"P013","catalystId":"P013_PERF_004","name":"Pd/NH2-HNTs (1.30 wt.% Pd)","activeMetals":"Pd","metalClass":"Pd-only","support":"Halloysite nanotubes (HNTs)","method":"wet_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd precursor added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","matchedSynthesis":"Pd/NH2-HNTs","composition":"Pd","role":"active catalyst"},{"paperId":"P013","catalystId":"P013_PERF_005","name":"PdAu/NH2-HNTs","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"Halloysite nanotubes (HNTs)","method":"co_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd and Au precursors added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","matchedSynthesis":"PdAu/NH2-HNTs","composition":"Pd:Au","role":"active catalyst"},{"paperId":"P013","catalystId":"P013_PERF_006","name":"PdAg/NH2-HNTs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Halloysite nanotubes (HNTs)","method":"co_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd and Ag precursors added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","matchedSynthesis":"PdAg/NH2-HNTs","composition":"Pd:Ag","role":"active catalyst"},{"paperId":"P013","catalystId":"P013_PERF_007","name":"Au/NH2-HNTs","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"Halloysite nanotubes (HNTs)","method":"co_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd and Au precursors added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","matchedSynthesis":"PdAu/NH2-HNTs","composition":"Pd:Au","role":"active catalyst"},{"paperId":"P013","catalystId":"P013_PERF_008","name":"Ag/NH2-HNTs","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","support":"Halloysite nanotubes (HNTs)","method":"co_impregnation","synthesis":"NH2-HNTs dispersed in water, Pd and Ag precursors added and stirred for 12 h at room temperature with vacuumizing/aerating cycles; solid dried at 80°C then reduced using NaBH4 in Na2CO3 solution.","matchedSynthesis":"PdAg/NH2-HNTs","composition":"Pd:Ag","role":"active catalyst"},{"paperId":"P014","catalystId":"P014_PERF_001","name":"AgPd-NH2-SBA-15","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"SBA-15 was modified with APMS to introduce amino and hydrido groups; subsequently, a mixture of PdCl2 and AgNO3 was introduced and reduced by the residual surface Si-H groups.","matchedSynthesis":"AgPd-NH2-SBA-15","composition":"Ag:Pd = 1.6 wt% : 0.8 wt%","role":"dehydrogenation catalyst for generation of H2 from formic acid"},{"paperId":"P014","catalystId":"P014_PERF_002","name":"Pd-NH2-SBA-15","activeMetals":"Pd","metalClass":"Pd-only","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"SBA-15 modified with APMS to create NH2-H-SBA-15, followed by introduction of PdCl2 for on-site reduction by surface Si-H groups.","matchedSynthesis":"Pd-NH2-SBA-15","composition":"Pd","role":"dehydrogenation catalyst for generation of H2 from formic acid"},{"paperId":"P014","catalystId":"P014_PERF_003","name":"Ag-NH2-SBA-15","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"SBA-15 modified with APMS to create NH2-H-SBA-15, followed by introduction of silver ions for on-site reduction by surface Si-H groups.","matchedSynthesis":"Ag-NH2-SBA-15","composition":"Ag","role":"comparison catalyst"},{"paperId":"P015","catalystId":"P015_PERF_001","name":"Arg-Pd/MSC-30","activeMetals":"Pd","metalClass":"Pd-only","support":"Maxsorb MSC-30 (Mesoporous Carbon)","method":"chemical_reduction_loading","synthesis":"Arginine was dispersed in deionized water and mixed with MSC-30; K2PdCl4 solution was added followed by sonication for 0.5 h. NaBH4 solution was then rapidly injected, and the mixture was stirred for 0.5 h at room temperature.","matchedSynthesis":"Arg-Pd/MSC-30","composition":"Pd","role":"active catalyst"},{"paperId":"P015","catalystId":"P015_PERF_002","name":"Pd/MSC-30","activeMetals":"Pd","metalClass":"Pd-only","support":"Maxsorb MSC-30 (Mesoporous Carbon)","method":"chemical_reduction_loading","synthesis":"Synthesized using the same procedure as Arg-Pd/MSC-30 but in the absence of amino acids.","matchedSynthesis":"Pd/MSC-30","composition":"Pd","role":"comparison catalyst"},{"paperId":"P016","catalystId":"P016_PERF_001","name":"PdNC/AC-NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"active carbon (AC)","method":"wet_impregnation","synthesis":"AC was modified with APTES, soaked in Na2PdCl4 solution, and then reduced using NaBH4.","matchedSynthesis":"PdNC/AC-NH2","composition":"Pd","role":"active catalyst"},{"paperId":"P016","catalystId":"P016_PERF_002","name":"Pd1/AC-NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"active carbon (AC)","method":"wet_impregnation","synthesis":"Similar to PdNC/AC-NH2 but with lower Pd precursor amount.","matchedSynthesis":"Pd1/AC-NH2","composition":"Pd","role":"benchmark catalyst (single atom)"},{"paperId":"P016","catalystId":"P016_PERF_003","name":"PdNP/AC-NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"active carbon (AC)","method":"wet_impregnation","synthesis":"Similar to PdNC/AC-NH2 but reduced by H2 gas instead of NaBH4.","matchedSynthesis":"PdNP/AC-NH2","composition":"Pd","role":"benchmark catalyst (nanoparticle)"},{"paperId":"P016","catalystId":"P016_PERF_004","name":"Pd/AC-NH2 (unreduced)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P016","catalystId":"P016_PERF_005","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P016","catalystId":"P016_PERF_006","name":"PdNC/SiO2-NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"silica (SiO2)","method":"wet_impregnation","synthesis":"SiO2 was first functionalized with APTES, then loaded with Na2PdCl4 and reduced with NaBH4.","matchedSynthesis":"PdNC/SiO2-NH2","composition":"Pd","role":"comparison sample (nonreducing carrier)"},{"paperId":"P017","catalystId":"P017_PERF_001","name":"Pd@KNDC(10-900)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P017","catalystId":"P017_PERF_002","name":"Pd@NDC(10-900)","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon (NDC)","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd@KNDC(10-900) but using non-etched NDC support.","matchedSynthesis":"Pd@NDC(10-900)","composition":"Pd","role":"reference catalyst"},{"paperId":"P018","catalystId":"P018_PERF_001","name":"Pd0.9Ag0.1/CDs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P019","catalystId":"P019_PERF_001","name":"PdAu/NH2-MIL-101","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"NH2-MIL-101","method":"wet_impregnation","synthesis":"NH2-MIL-101 was synthesized via a one-step hydrothermal method (453 K, 4 h). Pd and Au precursors were impregnated into the support suspension through sonication and stirring, followed by liquid-phase reduction using NaBH4.","matchedSynthesis":"PdAu/NH2-MIL-101","composition":"Pd:Au = 0.7:0.3 (molar ratio)","role":"main catalyst for formic acid dehydrogenation (FAD)"},{"paperId":"P019","catalystId":"P019_PERF_002","name":"Pd/NH2-MIL-101","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P019","catalystId":"P019_PERF_003","name":"PdAu/MIL-101","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P019","catalystId":"P019_PERF_004","name":"pure PdAu NPs","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P020","catalystId":"P020_PERF_001","name":"Pd0.60Co0.18Ni0.22/TiO2-ALD-SiO2 (6 cycles)","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P020","catalystId":"P020_PERF_002","name":"Pd0.60Co0.18Ni0.22/TiO2","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P021","catalystId":"P021_PERF_001","name":"Au0.3Pd0.7/CA-BN-NH2","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"citric acid-modified boron nitride with amino groups (CA-BN-NH2)","method":"wet_impregnation","synthesis":"Pristine h-BN was modified with citric acid to create defective sites, followed by APTES functionalization to introduce -NH2 groups. Aqueous solutions of HAuCl4 and Na2PdCl4 were impregnated into the CA-BN-NH2 suspension and subsequently reduced using NaBH4.","matchedSynthesis":"Au0.3Pd0.7/CA-BN-NH2","composition":"Au:Pd = 0.3:0.7 (atomic ratio)","role":"main catalyst"},{"paperId":"P021","catalystId":"P021_PERF_002","name":"Au0.3Pd0.7/BN-NH2","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P021","catalystId":"P021_PERF_003","name":"Au0.3Pd0.7/BN","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P021","catalystId":"P021_PERF_004","name":"Au0.3Pd0.7 NPs (free)","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P022","catalystId":"P022_PERF_001","name":"AuPd/n-CNS-Th-160","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"nitrogen-decorated carbon nanosheets (n-CNS)","method":"wet_impregnation","synthesis":"n-CNS support was prepared from g-C3N4 and glucose; Au and Pd precursors were added to the n-CNS suspension, stirred overnight, and reduced using NaBH4.","matchedSynthesis":"AuPd/n-CNS","composition":"AuPd (1:1 molar ratio based on precursor concentrations)","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P022","catalystId":"P022_PERF_002","name":"AuPd/AC","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P022","catalystId":"P022_PERF_003","name":"commercial Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P023","catalystId":"P023_PERF_001","name":"Au-Pd-SBA-15-NH2-TD","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"SBA-15 was first calcined and then functionalized with APTES in a toluene/DMF mixture. The resulting SBA-15-NH2 support was dispersed in water, mixed with Au and Pd precursors, and reduced using NaBH4.","matchedSynthesis":"Au-Pd-SBA-15-NH2-TD","composition":"Au and Pd (equal mass loading based on precursor volumes)","role":"active catalyst"},{"paperId":"P023","catalystId":"P023_PERF_002","name":"Au-Pd-SBA-15-NH2-T","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"SBA-15 was first calcined and then functionalized with APTES in pure toluene. The resulting SBA-15-NH2 support was dispersed in water, mixed with Au and Pd precursors, and reduced using NaBH4.","matchedSynthesis":"Au-Pd-SBA-15-NH2-T","composition":"Au and Pd (equal mass loading based on precursor volumes)","role":"active catalyst"},{"paperId":"P023","catalystId":"P023_PERF_003","name":"Au-Pd-SBA-15-NH2-D","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"SBA-15 was first calcined and then functionalized with APTES in pure DMF. The resulting SBA-15-NH2 support was dispersed in water, mixed with Au and Pd precursors, and reduced using NaBH4.","matchedSynthesis":"Au-Pd-SBA-15-NH2-D","composition":"Au and Pd (equal mass loading based on precursor volumes)","role":"active catalyst"},{"paperId":"P023","catalystId":"P023_PERF_004","name":"Au-Pd-SBA-15","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"SBA-15 was first calcined and then functionalized with APTES in a toluene/DMF mixture. The resulting SBA-15-NH2 support was dispersed in water, mixed with Au and Pd precursors, and reduced using NaBH4.","matchedSynthesis":"Au-Pd-SBA-15-NH2-TD","composition":"Au and Pd (equal mass loading based on precursor volumes)","role":"active catalyst"},{"paperId":"P024","catalystId":"P024_PERF_001","name":"Au1Pd3/rGO","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"reduced graphene oxide (rGO)","method":"sol_immobilization","synthesis":"Metal salts were reduced with NaBH4 in a PVA solution, acidified to pH 2 with sulfuric acid, and immobilized by adding rGO support under vigorous stirring for 2 h.","matchedSynthesis":"Au1Pd3/rGO","composition":"Au:Pd = 1:3 molar ratio","role":"catalyst"},{"paperId":"P024","catalystId":"P024_PERF_002","name":"Au1Pd1/rGO","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"reduced graphene oxide (rGO)","method":"sol_immobilization","synthesis":"Metal salts were reduced with NaBH4 in a PVA solution, acidified to pH 2 with sulfuric acid, and immobilized by adding rGO support under vigorous stirring for 2 h.","matchedSynthesis":"Au1Pd1/rGO","composition":"Au:Pd = 1:1 molar ratio","role":"catalyst"},{"paperId":"P024","catalystId":"P024_PERF_003","name":"Au3Pd1/rGO","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"reduced graphene oxide (rGO)","method":"sol_immobilization","synthesis":"Metal salts were reduced with NaBH4 in a PVA solution, acidified to pH 2 with sulfuric acid, and immobilized by adding rGO support under vigorous stirring for 2 h.","matchedSynthesis":"Au3Pd1/rGO","composition":"Au:Pd = 3:1 molar ratio","role":"catalyst"},{"paperId":"P025","catalystId":"P025_PERF_001","name":"Ag/AgPd CS-0.3","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P025","catalystId":"P025_PERF_002","name":"Ag/AgPd CS-0.6","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P025","catalystId":"P025_PERF_003","name":"Ag/AgPd CS-0.9","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P025","catalystId":"P025_PERF_004","name":"Ag/AgPd CS-1.2","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P026","catalystId":"P026_PERF_001","name":"Au1Pd3/BNNFs-A","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"porous boron nitride nanofibers (BNNFs)","method":"wet_impregnation","synthesis":"BNNFs were dispersed in an ethanol and deionized water mixed solution and treated with APTES. A combined solution of Na2PdCl4 and HAuCl4 was added under stirring, followed by reduction using aqueous NaBH4 in an ice-water bath.","matchedSynthesis":"Au1Pd3/BNNFs-A","composition":"Au:Pd = 1:3","role":"catalyst"},{"paperId":"P027","catalystId":"P027_PERF_001","name":"Pd0.6Cr0.4/OPDA-SmMn2O5","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P027","catalystId":"P027_PERF_002","name":"Pd0.6Cr0.4/SmMn2O5","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P028","catalystId":"P028_PERF_001","name":"Pd7Ag3/SPP","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P028","catalystId":"P028_PERF_002","name":"PdAg/SPP (various ratios)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"self-pillared pentasil (SPP) zeolite","method":"wet_impregnation","synthesis":"SPP support was suspended in DI water, impregnated with Pd and Ag nitrate solutions, and then reduced using sodium borohydride in a sodium carbonate solution.","matchedSynthesis":"PdAg/SPP","composition":"Pd:Ag molar ratios of 9:1, 7:3, 1:1, and 3:7","role":"catalyst"},{"paperId":"P028","catalystId":"P028_PERF_003","name":"Pd/SPP and Ag/SPP","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P029","catalystId":"P029_PERF_001","name":"Pd0.8Au0.2/UiO-66-D","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"NH2-UiO-66","method":"wet_impregnation","synthesis":"NH2-UiO-66 was suspended in n-hexane and sonicated; aqueous metal precursors were added dropwise and stirred. The product was dried, reduced with NaBH4 in an ice bath, washed, and dried again.","matchedSynthesis":"Pd0.8Au0.2/UiO-66-D","composition":"Pd:Au = 0.8:0.2","role":"active catalyst"},{"paperId":"P029","catalystId":"P029_PERF_002","name":"Pd0.8Au0.2/UiO-66-S","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"NH2-UiO-66","method":"wet_impregnation","synthesis":"Activated NH2-UiO-66 was dispersed in deionized water and sonicated; aqueous metal precursors were added and stirred, followed by NaBH4 reduction in an ice bath.","matchedSynthesis":"Pd0.8Au0.2/UiO-66-S","composition":"Pd:Au = 0.8:0.2","role":"comparison catalyst"},{"paperId":"P029","catalystId":"P029_PERF_003","name":"Pd0.8Au0.2/UiO-66-ref-D","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"UiO-66","method":"wet_impregnation","synthesis":"Same procedure as Pd0.8Au0.2/UiO-66-D using conventional UiO-66 support.","matchedSynthesis":"Pd0.8Au0.2/UiO-66-ref-D","composition":"Pd:Au = 0.8:0.2","role":"reference catalyst"},{"paperId":"P029","catalystId":"P029_PERF_004","name":"Pd0.8Au0.2/UiO-66-ref-S","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"UiO-66","method":"wet_impregnation","synthesis":"Same procedure as Pd0.8Au0.2/UiO-66-S using conventional UiO-66 support.","matchedSynthesis":"Pd0.8Au0.2/UiO-66-ref-S","composition":"Pd:Au = 0.8:0.2","role":"reference catalyst"},{"paperId":"P030","catalystId":"P030_PERF_001","name":"PdCo0.2/EDA-HPAN","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","support":"EDA-HPAN (amine modified polyacrylonitrile hollow spheres)","method":"wet_impregnation","synthesis":"EDA-HPAN was impregnated with Pd and Co precursors, dried, and then reduced using NaBH4.","matchedSynthesis":"PdCo0.2/EDA-HPAN","composition":"Pd:Co = 1:0.2 molar ratio","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P030","catalystId":"P030_PERF_002","name":"Pd/EDA-HPAN","activeMetals":"Pd","metalClass":"Pd-only","support":"EDA-HPAN (amine modified polyacrylonitrile hollow spheres)","method":"wet_impregnation","synthesis":"EDA-HPAN was impregnated with Pd precursor, dried, and then reduced using NaBH4.","matchedSynthesis":"Pd/EDA-HPAN","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P031","catalystId":"P031_PERF_001","name":"Pd0.7Cr0.3/NH2-MXene","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P031","catalystId":"P031_PERF_002","name":"Pd0.7Cr0.3/MXene","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P032","catalystId":"P032_PERF_001","name":"POLITAG-20-Pd(0)","activeMetals":"Pd","metalClass":"Pd-only","support":"macroreticular resin (POLITAG-20-L)","method":"wet_impregnation","synthesis":"Synthesis of macroreticular resin SP-20-Cl, functionalization with ligand 3,3-bis(1H-imidazol-1-yl)propan-1-ol and quaternization with iodomethane to form POLITAG-20-L; loading of Pd(II) using Na2PdCl4 in water to obtain POLITAG-20-Pd(II), followed by reduction to Pd(0) using NaBH4 in ethanol.","matchedSynthesis":"POLITAG-20-Pd(0)","composition":"Pd","role":"catalyst"},{"paperId":"P033","catalystId":"P033_PERF_001","name":"1Pd/C3Ny_650_4","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (g-C3N4)","method":"wet_impregnation","synthesis":"Melamine was thermally polycondensed at 650 °C for 4 h to create the C3N4 support. Palladium acetate dissolved in acetone was added dropwise to the support, followed by drying and reduction under a hydrogen/nitrogen flow.","matchedSynthesis":"1Pd/C3Ny_650_4","composition":"Pd","role":"active catalyst"},{"paperId":"P033","catalystId":"P033_PERF_002","name":"5Pd/C3Ny_650_4","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (g-C3N4)","method":"wet_impregnation","synthesis":"Melamine was thermally polycondensed at 650 °C for 4 h to create the C3N4 support. Palladium acetate dissolved in acetone was added dropwise to the support, followed by drying and reduction under a hydrogen/nitrogen flow.","matchedSynthesis":"5Pd/C3Ny_650_4","composition":"Pd","role":"active catalyst"},{"paperId":"P033","catalystId":"P033_PERF_003","name":"10Pd/C3Ny_650_4","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (g-C3N4)","method":"wet_impregnation","synthesis":"Melamine was thermally polycondensed at 650 °C for 4 h to create the C3N4 support. Palladium acetate dissolved in acetone was added dropwise to the support, followed by drying and reduction under a hydrogen/nitrogen flow.","matchedSynthesis":"10Pd/C3Ny_650_4","composition":"Pd","role":"active catalyst"},{"paperId":"P034","catalystId":"P034_PERF_001","name":"Pd/NC-Co1%","activeMetals":"Pd","metalClass":"Pd-only","support":"NC-Co1% (N-doped carbon decorated with Co)","method":"wet_impregnation","synthesis":"Urea calcined to C3N4; hydrothermal with glucose to form C3N4@G; Co salt added and heated under N2 to form NC-Co support; Pd immobilized via NaBH4 reduction.","matchedSynthesis":"Pd/NC-Co1%","composition":"Pd:Co (approx. 4:1 by weight based on ICP)","role":"active catalyst"},{"paperId":"P034","catalystId":"P034_PERF_002","name":"Pd/NC","activeMetals":"Pd","metalClass":"Pd-only","support":"NC (N-doped carbon)","method":"adsorption_or_loading","synthesis":"Urea calcined to C3N4; hydrothermal with glucose to form C3N4@G; Pd immobilized via NaBH4 reduction.","matchedSynthesis":"Pd/NC","composition":"Pd only","role":"control sample"},{"paperId":"P034","catalystId":"P034_PERF_003","name":"PdCo1%/NC","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P035","catalystId":"P035_PERF_001","name":"0.1Pt/MoC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"α-MoC","method":"arc discharge","synthesis":"One-step ultrahigh-temperature synthesis using an arc-discharge route. Mixed Pt and Mo powders were filled in a graphite anode tube with a graphite rod as the cathode. The chamber was vacuumized to 3 Pa, then filled with pure hydrogen to 0.08 MPa. Arc discharge was performed at 80 A for approximately 30 minutes.","matchedSynthesis":"0.1Pt/MoC","composition":"Pt:Mo (0.1 wt% Pt)","role":"catalyst"},{"paperId":"P035","catalystId":"P035_PERF_002","name":"0.2Pt/MoC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"α-MoC","method":"arc discharge","synthesis":"One-step ultrahigh-temperature synthesis using an arc-discharge route. Mixed Pt and Mo powders were filled in a graphite anode tube with a graphite rod as the cathode. The chamber was vacuumized to 3 Pa, then filled with pure hydrogen to 0.08 MPa. Arc discharge was performed at 80 A for approximately 30 minutes.","matchedSynthesis":"0.2Pt/MoC","composition":"Pt:Mo (0.2 wt% Pt)","role":"catalyst"},{"paperId":"P035","catalystId":"P035_PERF_003","name":"1Pt/MoC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"α-MoC","method":"arc discharge","synthesis":"One-step ultrahigh-temperature synthesis using an arc-discharge route. Mixed Pt and Mo powders were filled in a graphite anode tube with a graphite rod as the cathode. The chamber was vacuumized to 3 Pa, then filled with pure hydrogen to 0.08 MPa. Arc discharge was performed at 80 A for approximately 30 minutes.","matchedSynthesis":"1Pt/MoC","composition":"Pt:Mo (1 wt% Pt)","role":"catalyst"},{"paperId":"P035","catalystId":"P035_PERF_004","name":"2Pt/MoC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"α-MoC","method":"arc discharge","synthesis":"One-step ultrahigh-temperature synthesis using an arc-discharge route. Mixed Pt and Mo powders were filled in a graphite anode tube with a graphite rod as the cathode. The chamber was vacuumized to 3 Pa, then filled with pure hydrogen to 0.08 MPa. Arc discharge was performed at 80 A for approximately 30 minutes.","matchedSynthesis":"2Pt/MoC","composition":"Pt:Mo (2 wt% Pt)","role":"catalyst"},{"paperId":"P036","catalystId":"P036_PERF_001","name":"Ru4/AC","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"Vulcan XC72R carbon","method":"chemical_reduction_loading","synthesis":"Prepared on Vulcan XC72R without any nitrogen source by a chemical reduction method.","matchedSynthesis":"Ru4/AC","composition":"Ru","role":"catalyst"},{"paperId":"P036","catalystId":"P036_PERF_002","name":"Ru5/ACN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"Vulcan XC72R carbon","method":"pyrolysis_or_thermal_conversion","synthesis":"Prepared following the same synthesis procedure as Ru/CN but using Vulcan XC72R carbon as support and phenanthroline ligand.","matchedSynthesis":"Ru5/ACN","composition":"Ru","role":"catalyst"},{"paperId":"P036","catalystId":"P036_PERF_003","name":"Ru2/CN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"nitrogen-doped carbon","method":"pyrolysis_or_thermal_conversion","synthesis":"Pyrolysis of RuCl3·xH2O in the presence of 1,10-phenanthroline (Phen) on C3N4 support.","matchedSynthesis":"Ru2/CN","composition":"Ru","role":"catalyst"},{"paperId":"P036","catalystId":"P036_PERF_004","name":"Ru4/CN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"nitrogen-doped carbon","method":"pyrolysis_or_thermal_conversion","synthesis":"Pyrolysis of RuCl3·xH2O in the presence of 1,10-phenanthroline (Phen) on C3N4 support.","matchedSynthesis":"Ru4/CN","composition":"Ru","role":"catalyst"},{"paperId":"P036","catalystId":"P036_PERF_005","name":"Ru7/CN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"nitrogen-doped carbon","method":"pyrolysis_or_thermal_conversion","synthesis":"Pyrolysis of RuCl3·xH2O in the presence of 1,10-phenanthroline (Phen) on C3N4 support.","matchedSynthesis":"Ru7/CN","composition":"Ru","role":"optimal catalyst"},{"paperId":"P036","catalystId":"P036_PERF_006","name":"Ru14/CN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"nitrogen-doped carbon","method":"pyrolysis_or_thermal_conversion","synthesis":"Pyrolysis of RuCl3·xH2O in the presence of 1,10-phenanthroline (Phen) on C3N4 support.","matchedSynthesis":"Ru14/CN","composition":"Ru","role":"catalyst"},{"paperId":"P036","catalystId":"P036_PERF_007","name":"Ru5/C","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P036","catalystId":"P036_PERF_008","name":"Pd5/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P037","catalystId":"P037_PERF_001","name":"PdAu/ACB","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"amine-functionalized carbon bowls (ACB)","method":"chemical_reduction_loading","synthesis":"ACB was dispersed in DI water, metal precursors were added and stirred for 3 h, followed by reduction with NaBH4.","matchedSynthesis":"PdAu/ACB","composition":"Pd:Au = 3:2","role":"active catalyst"},{"paperId":"P037","catalystId":"P037_PERF_002","name":"PdAu/CB","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P037","catalystId":"P037_PERF_003","name":"Pd/ACB","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P037","catalystId":"P037_PERF_004","name":"Au/ACB","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"amine-functionalized carbon bowls (ACB)","method":"chemical_reduction_loading","synthesis":"ACB was dispersed in DI water, metal precursors were added and stirred for 3 h, followed by reduction with NaBH4.","matchedSynthesis":"PdAu/ACB","composition":"Pd:Au = 3:2","role":"active catalyst"},{"paperId":"P037","catalystId":"P037_PERF_005","name":"PdAu (support-free)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P038","catalystId":"P038_PERF_001","name":"Pd/SiO2@SC-1:3","activeMetals":"Pd","metalClass":"Pd-only","support":"commercial SiO2 nanoparticles","method":"wet_impregnation","synthesis":"Same procedure as Pd/SiO2@SC-1:x but using commercial SiO2 nanoparticles instead of the carbon-coated support.","matchedSynthesis":"Pd/SiO2","composition":"Pd","role":"comparison catalyst"},{"paperId":"P038","catalystId":"P038_PERF_002","name":"Pd/SiO2","activeMetals":"Pd","metalClass":"Pd-only","support":"commercial SiO2 nanoparticles","method":"wet_impregnation","synthesis":"Same procedure as Pd/SiO2@SC-1:x but using commercial SiO2 nanoparticles instead of the carbon-coated support.","matchedSynthesis":"Pd/SiO2","composition":"Pd","role":"comparison catalyst"},{"paperId":"P038","catalystId":"P038_PERF_003","name":"Pd/E-SiO2@SC-1:3","activeMetals":"Pd","metalClass":"Pd-only","support":"E-SiO2@SC-1:3","method":"wet_impregnation","synthesis":"SiO2 core was etched from SiO2@SC-1:3 using NaOH, followed by Pd loading via the same wet impregnation reduction procedure as Pd/SiO2@SC-1:x.","matchedSynthesis":"Pd/E-SiO2@SC-1:3","composition":"Pd","role":"control catalyst (etched support)"},{"paperId":"P039","catalystId":"P039_PERF_001","name":"Au1–Pd11/KIT-6","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"KIT-6","method":"wet_impregnation","synthesis":"Wet impregnation of KIT-6 with Pd and Au precursors in acidic solution, followed by stirring, solvent evaporation, and calcination.","matchedSynthesis":"Au1–Pd11/KIT-6","composition":"Au: 0.25 wt%, Pd: 2.80 wt%","role":"active catalyst"},{"paperId":"P039","catalystId":"P039_PERF_002","name":"Au1–Pd18/KIT-6","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"KIT-6","method":"wet_impregnation","synthesis":"Wet impregnation of KIT-6 with Pd and Au precursors in acidic solution, followed by stirring, solvent evaporation, and calcination.","matchedSynthesis":"Au1–Pd18/KIT-6","composition":"Au: 0.15 wt%, Pd: 2.70 wt%","role":"active catalyst"},{"paperId":"P039","catalystId":"P039_PERF_003","name":"Au1–Pd14/KIT-6","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"KIT-6","method":"wet_impregnation","synthesis":"Wet impregnation of KIT-6 with Pd and Au precursors in acidic solution, followed by stirring, solvent evaporation, and calcination.","matchedSynthesis":"Au1–Pd14/KIT-6","composition":"Au: 0.20 wt%, Pd: 2.70 wt%","role":"active catalyst"},{"paperId":"P039","catalystId":"P039_PERF_004","name":"Au1–Pd17/KIT-6","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"KIT-6","method":"wet_impregnation","synthesis":"Wet impregnation followed by calcination at 350 °C and subsequent activation under oxygen flow.","matchedSynthesis":"Au1–Pd17/KIT-6","composition":"Au: 0.10 wt%, Pd: 1.70 wt%","role":"activated catalyst"},{"paperId":"P039","catalystId":"P039_PERF_005","name":"Pd/KIT-6","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P040","catalystId":"P040_PERF_001","name":"LS-NH2/Pd","activeMetals":"Pd","metalClass":"Pd-only","support":"Amino-functionalized layered silicate (LS-NH2)","method":"wet_impregnation","synthesis":"LS-NH2 dispersed in ethanol was mixed with aqueous K2PdCl4, sonicated, stirred, and dried. The powder was redispersed in H2O:EtOH (1:1) and reduced by dropwise addition of methanolic NaBH4.","matchedSynthesis":"LS-NH2/Pd","composition":"Pd","role":"Catalyst for formic acid dehydrogenation"},{"paperId":"P040","catalystId":"P040_PERF_002","name":"LS-SH/Pd","activeMetals":"Pd","metalClass":"Pd-only","support":"Thio-functionalized layered silicate (LS-SH)","method":"wet_impregnation","synthesis":"LS-SH dispersed in ethanol was mixed with aqueous K2PdCl4, sonicated, stirred, and dried. The powder was redispersed in H2O:EtOH (1:1) and reduced by dropwise addition of methanolic NaBH4.","matchedSynthesis":"LS-SH/Pd","composition":"Pd","role":"Catalyst for formic acid dehydrogenation"},{"paperId":"P041","catalystId":"P041_PERF_001","name":"2 wt.% Pd/KCC-1-PDETA","activeMetals":"Pd","metalClass":"Pd-only","support":"KCC-1","method":"wet_impregnation","synthesis":"KCC-1 was functionalized with PDETA in toluene at 80 °C for 24 h, then impregnated with Na2PdCl4 solution and reduced using sodium borohydride.","matchedSynthesis":"2 wt.% Pd/KCC-1-PDETA","composition":"Pd","role":"catalyst for additive-free dehydrogenation of formic acid"},{"paperId":"P041","catalystId":"P041_PERF_002","name":"2 wt.% Pd/MSF-PDETA","activeMetals":"Pd","metalClass":"Pd-only","support":"MSF","method":"wet_impregnation","synthesis":"MSF support functionalized with PDETA, then impregnated with Na2PdCl4 solution and reduced using sodium borohydride.","matchedSynthesis":"2 wt.% Pd/MSF-PDETA","composition":"Pd","role":"comparison catalyst for support effect study"},{"paperId":"P041","catalystId":"P041_PERF_003","name":"2 wt.% Pd/KIT-6-PDETA","activeMetals":"Pd","metalClass":"Pd-only","support":"KIT-6","method":"wet_impregnation","synthesis":"KIT-6 support functionalized with PDETA, then impregnated with Na2PdCl4 solution and reduced using sodium borohydride.","matchedSynthesis":"2 wt.% Pd/KIT-6-PDETA","composition":"Pd","role":"comparison catalyst for support effect study"},{"paperId":"P041","catalystId":"P041_PERF_004","name":"5 wt.% Pd/KCC-1-PDETA","activeMetals":"Pd","metalClass":"Pd-only","support":"KCC-1","method":"wet_impregnation","synthesis":"Same as 2 wt.% Pd/KCC-1-PDETA with adjusted Na2PdCl4 amount.","matchedSynthesis":"5 wt.% Pd/KCC-1-PDETA","composition":"Pd","role":"catalyst for additive-free dehydrogenation of formic acid"},{"paperId":"P041","catalystId":"P041_PERF_005","name":"10 wt.% Pd/KCC-1-PDETA","activeMetals":"Pd","metalClass":"Pd-only","support":"KCC-1","method":"wet_impregnation","synthesis":"Same as 2 wt.% Pd/KCC-1-PDETA with adjusted Na2PdCl4 amount.","matchedSynthesis":"10 wt.% Pd/KCC-1-PDETA","composition":"Pd","role":"catalyst for additive-free dehydrogenation of formic acid"},{"paperId":"P042","catalystId":"P042_PERF_001","name":"2% Pd/Al2O3","activeMetals":"Pd","metalClass":"Pd-only","support":"Al2O3","method":"incipient_wetness_impregnation","synthesis":"Ex situ synthesis of PVP-stabilized Pd nanoparticles using 1-ascorbic acid as reducing agent at 368 K, followed by incipient wetness impregnation on Al2O3 support.","matchedSynthesis":"2% Pd/Al2O3","composition":"Pd (2%)","role":"comparison catalyst"},{"paperId":"P042","catalystId":"P042_PERF_002","name":"2% Pd/ZnO","activeMetals":"Pd","metalClass":"Pd-only","support":"ZnO","method":"incipient_wetness_impregnation","synthesis":"Ex situ synthesis of PVP-stabilized Pd nanoparticles using 1-ascorbic acid as reducing agent at 368 K, followed by incipient wetness impregnation on ZnO support.","matchedSynthesis":"2% Pd/ZnO","composition":"Pd (2%)","role":"main catalyst"},{"paperId":"P042","catalystId":"P042_PERF_003","name":"1% Pd/ZnO","activeMetals":"Pd","metalClass":"Pd-only","support":"ZnO","method":"wet_impregnation","synthesis":"Aqueous solution of PdCl2(HCl) added to ZnO suspension, stirred for 24 h at room temperature, filtered, washed and dried.","matchedSynthesis":"1% Pd/ZnO","composition":"Pd (1%)","role":"comparison catalyst (ionic precursor)"},{"paperId":"P042","catalystId":"P042_PERF_004","name":"1.2% Pt/ZnO","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"ZnO","method":"wet_impregnation","synthesis":"Aqueous solution of hexachloroplatinic acid added to ZnO suspension, stirred for 24 h at room temperature, filtered, washed and dried.","matchedSynthesis":"1.2% Pt/ZnO","composition":"Pt (1.2%)","role":"comparison catalyst (ionic precursor)"},{"paperId":"P042","catalystId":"P042_PERF_005","name":"ZnO support","activeMetals":"Zn","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P043","catalystId":"P043_PERF_001","name":"Au0.4Pd0.6Pt0.2/CNC-NH2","activeMetals":"Au-Pd-Pt","metalClass":"Pd-based multimetal","support":"amino-modified cellulose nanocrystals (CNC-NH2)","method":"chemical_reduction_loading","synthesis":"Metal precursors were added to a CNC-NH2 aqueous solution, stirred, and then reduced using sodium borohydride in an ice water bath.","matchedSynthesis":"Au0.4Pd0.6Pt0.2/CNC-NH2","composition":"Au:Pd:Pt = 0.4:0.6:0.2","role":"main catalyst"},{"paperId":"P044","catalystId":"P044_PERF_001","name":"Pd/C-H2P","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"incipient_wetness_impregnation","synthesis":"Pre-oxidized activated carbon was impregnated with PdCl2 solution, dried, calcined under H2, and then treated with H2 working gas in a dielectric barrier discharge (DBD) cold plasma reactor.","matchedSynthesis":"Pd/C-H2P","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P044","catalystId":"P044_PERF_002","name":"Pd/C-ArP","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"incipient_wetness_impregnation","synthesis":"Pre-oxidized activated carbon was impregnated with PdCl2 solution, dried, calcined under H2, and then treated with Ar working gas in a dielectric barrier discharge (DBD) cold plasma reactor.","matchedSynthesis":"Pd/C-ArP","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P044","catalystId":"P044_PERF_003","name":"Pd/C-AirP","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"incipient_wetness_impregnation","synthesis":"Pre-oxidized activated carbon was impregnated with PdCl2 solution, dried, calcined under H2, and then treated with compressed air working gas in a dielectric barrier discharge (DBD) cold plasma reactor.","matchedSynthesis":"Pd/C-AirP","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P044","catalystId":"P044_PERF_004","name":"Pd/C-O2P","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"incipient_wetness_impregnation","synthesis":"Pre-oxidized activated carbon was impregnated with PdCl2 solution, dried, calcined under H2, and then treated with O2 working gas in a dielectric barrier discharge (DBD) cold plasma reactor.","matchedSynthesis":"Pd/C-O2P","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P045","catalystId":"P045_PERF_001","name":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"commercial","synthesis":"Commercially available Pd/C was purchased from Merck-Sigma and used as received.","matchedSynthesis":"Pd/C","composition":"Pd","role":"main catalyst"},{"paperId":"P046","catalystId":"P046_PERF_001","name":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","support":"templated carbon","method":"wet_impregnation","synthesis":"Templated carbon was synthesized via CVD of acetylene on NaY zeolite and HF washing. Pd was deposited onto the TC support using wet impregnation from an aqueous PdCl2 solution, dried at room temperature, and reduced under H2 flow.","matchedSynthesis":"Pd/TC","composition":"Pd","role":"catalyst"},{"paperId":"P047","catalystId":"P047_PERF_001","name":"AP-SiO2@NGO-PDA@Pd0.51Au0.49","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P047","catalystId":"P047_PERF_002","name":"AP-SiO2@NGO-PDA@Au","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P047","catalystId":"P047_PERF_003","name":"AP-SiO2@NGO-PDA@Pd5Au5 (higher loading)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P048","catalystId":"P048_PERF_001","name":"Au0.28Pd0.47Co0.25/MIL-101-NH2","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","support":"MIL-101-NH2","method":"wet_impregnation","synthesis":"Metal precursors were dispersed in deionized water, followed by the addition of activated MIL-101-NH2 and stirring for 2 h. Reduction was then performed by adding NaBH4 solution and stirring under Ar atmosphere for 2 h.","matchedSynthesis":"Au0.28Pd0.47Co0.25/MIL-101-NH2","composition":"Au:Pd:Co = 0.283:0.467:0.250","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P048","catalystId":"P048_PERF_002","name":"Au0.28Pd0.47Fe0.25/MIL-101-NH2","activeMetals":"Au-Pd-Fe","metalClass":"Pd-based multimetal","support":"MIL-101-NH2","method":"wet_impregnation","synthesis":"Same process as Au0.28Pd0.47Co0.25/MIL-101-NH2 using Fe(NO3)2·6H2O instead of cobalt source.","matchedSynthesis":"Au0.28Pd0.47Fe0.25/MIL-101-NH2","composition":"Au:Pd:Fe = 0.281:0.473:0.246","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P048","catalystId":"P048_PERF_003","name":"Au0.28Pd0.47Ni0.25/MIL-101-NH2","activeMetals":"Au-Pd-Ni","metalClass":"Pd-based multimetal","support":"MIL-101-NH2","method":"wet_impregnation","synthesis":"Same process as Au0.28Pd0.47Co0.25/MIL-101-NH2 using Ni(NO3)2·6H2O instead of cobalt source.","matchedSynthesis":"Au0.28Pd0.47Ni0.25/MIL-101-NH2","composition":"Au:Pd:Ni = 0.284:0.475:0.241","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P048","catalystId":"P048_PERF_004","name":"Au0.28Pd0.47Co0.25/MIL-101-NO2","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P048","catalystId":"P048_PERF_005","name":"Au0.28Pd0.47Co0.25/MIL-101-SO3H","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P048","catalystId":"P048_PERF_006","name":"Au0.28Pd0.47Co0.25/MIL-101 (bare)","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P048","catalystId":"P048_PERF_007","name":"Au0.28Pd0.47Co0.25/SBA-15-NH2","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P048","catalystId":"P048_PERF_008","name":"Au0.28Pd0.47Co0.25/SBA-15","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P049","catalystId":"P049_PERF_001","name":"Co5Pd5/CTF-600","activeMetals":"Co-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P049","catalystId":"P049_PERF_002","name":"Co5Pd5/CTF-500","activeMetals":"Co-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P049","catalystId":"P049_PERF_003","name":"Co5Pd5/CTF-400","activeMetals":"Co-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P049","catalystId":"P049_PERF_004","name":"Co5Pd5/XC-72","activeMetals":"Co-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P050","catalystId":"P050_PERF_001","name":"Pd/a_MSC-30","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P051","catalystId":"P051_PERF_001","name":"Pd/a_MSC-30","activeMetals":"Pd","metalClass":"Pd-only","support":"MSC-30","method":"wet_impregnation","synthesis":"Porous carbon was treated with HNO3 at room temperature, washed, and dispersed in water; K2PdCl4 precursor was added and shaken for 1 hour, followed by reduction with sodium borohydride.","matchedSynthesis":"Pd/a_MSC-30","composition":"Pd","role":"benchmark catalyst"},{"paperId":"P051","catalystId":"P051_PERF_002","name":"Pd/MSC-30","activeMetals":"Pd","metalClass":"Pd-only","support":"MSC-30","method":"wet_impregnation","synthesis":"Prepared by the same procedure as Pd/a_MSC-30 but using pristine MSC-30 support.","matchedSynthesis":"Pd/MSC-30","composition":"Pd","role":"control experiment"},{"paperId":"P051","catalystId":"P051_PERF_003","name":"Pd/C_commercial","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P052","catalystId":"P052_PERF_001","name":"Pd6Cr4@NH2-MIL-101","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","support":"NH2-MIL-101","method":"co_impregnation","synthesis":"NH2-MIL-101 was dispersed in deionized water via ultrasonication; Cr and Pd precursors were added under stirring for 2 h, followed by liquid-phase reduction with NaBH4 solution.","matchedSynthesis":"Pd6Cr4@NH2-MIL-101","composition":"Pd:Cr = 6:4","role":"active catalyst"},{"paperId":"P053","catalystId":"P053_PERF_001","name":"1 wt% Pd/g-C3N4","activeMetals":"Pd","metalClass":"Pd-only","support":"graphitic carbon nitride (g-C3N4)","method":"chemical_reduction_loading","synthesis":"Metal precursor and support were sonicated for 30 min and stirred for 4 h; pH adjusted to 8-9 using 0.5M NaOH; reduced by droplet addition of NaBH4 solution; re-sonicated for 20 min and stirred for 1 h at 10°C; centrifuged, washed with ethanol and distilled water, and dried.","matchedSynthesis":"Pd/g-C3N4","composition":"Pd (1 wt%, 3 wt%, and 5 wt%)","role":"Catalyst"},{"paperId":"P053","catalystId":"P053_PERF_002","name":"3 wt% Pd/g-C3N4","activeMetals":"Pd","metalClass":"Pd-only","support":"graphitic carbon nitride (g-C3N4)","method":"chemical_reduction_loading","synthesis":"Metal precursor and support were sonicated for 30 min and stirred for 4 h; pH adjusted to 8-9 using 0.5M NaOH; reduced by droplet addition of NaBH4 solution; re-sonicated for 20 min and stirred for 1 h at 10°C; centrifuged, washed with ethanol and distilled water, and dried.","matchedSynthesis":"Pd/g-C3N4","composition":"Pd (1 wt%, 3 wt%, and 5 wt%)","role":"Catalyst"},{"paperId":"P053","catalystId":"P053_PERF_003","name":"5 wt% Pd/g-C3N4","activeMetals":"Pd","metalClass":"Pd-only","support":"graphitic carbon nitride (g-C3N4)","method":"chemical_reduction_loading","synthesis":"Metal precursor and support were sonicated for 30 min and stirred for 4 h; pH adjusted to 8-9 using 0.5M NaOH; reduced by droplet addition of NaBH4 solution; re-sonicated for 20 min and stirred for 1 h at 10°C; centrifuged, washed with ethanol and distilled water, and dried.","matchedSynthesis":"Pd/g-C3N4","composition":"Pd (1 wt%, 3 wt%, and 5 wt%)","role":"Catalyst"},{"paperId":"P053","catalystId":"P053_PERF_004","name":"5 wt% Cu/g-C3N4","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","support":"graphitic carbon nitride (g-C3N4)","method":"chemical_reduction_loading","synthesis":"Same method as Pd/g-C3N4: sonication, stirring, pH adjustment to 8-9 with NaOH, NaBH4 reduction, re-sonication and stirring at 10°C, centrifugation, washing, and drying.","matchedSynthesis":"Cu/g-C3N4","composition":"Cu (5 wt%)","role":"Catalyst"},{"paperId":"P053","catalystId":"P053_PERF_005","name":"5 wt% Zn/g-C3N4","activeMetals":"Zn","metalClass":"Non-Pd or Pd-free","support":"graphitic carbon nitride (g-C3N4)","method":"chemical_reduction_loading","synthesis":"Same method as Pd/g-C3N4: sonication, stirring, pH adjustment to 8-9 with NaOH, NaBH4 reduction, re-sonication and stirring at 10°C, centrifugation, washing, and drying.","matchedSynthesis":"Zn/g-C3N4","composition":"Zn (5 wt%)","role":"Catalyst"},{"paperId":"P054","catalystId":"P054_PERF_001","name":"5Ni–SiO2 (P123)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"SiO2","method":"one-pot synthesis","synthesis":"P123 mixed in HNO3 and water at 50 °C; Ni salt added, followed by dropwise addition of TEOS. Mixed for 24 h, then hydrothermally treated at 80 °C for 24 h, and evaporated at 80 °C.","matchedSynthesis":"5Ni–SiO2(P123)","composition":"Ni","role":"active catalyst"},{"paperId":"P054","catalystId":"P054_PERF_002","name":"2.5Ni–SiO2 (P123)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"SiO2","method":"one-pot synthesis","synthesis":"P123 mixed in HNO3 and water at 50 °C; Ni salt added, followed by dropwise addition of TEOS. Mixed for 24 h, then hydrothermally treated at 80 °C for 24 h, and evaporated at 80 °C.","matchedSynthesis":"2.5Ni–SiO2(P123)","composition":"Ni","role":"active catalyst"},{"paperId":"P054","catalystId":"P054_PERF_003","name":"5Ni–SiO2 (NH3-CA)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"SiO2","method":"one-pot synthesis","synthesis":"TEOS added to ethanol and mixed at 50 °C; ammonia solution added and stirred for 3 h. Citric acid added and stirred at RT for 30 min, then Ni salt added and mixed for 30 min.","matchedSynthesis":"5Ni–SiO2(NH3-CA)","composition":"Ni","role":"active catalyst"},{"paperId":"P054","catalystId":"P054_PERF_004","name":"5Ni–SiO2 (Tw80–NaF)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"SiO2","method":"one-pot synthesis","synthesis":"Tween-80 solution mixed with HCl (pH 2) at 65 °C for 2 h. Ni salt dissolved in water added dropwise, followed by TEOS addition. NaF added while stirring at 65 °C, then evaporated at 65 °C.","matchedSynthesis":"5Ni–SiO2(Tw80–NaF)","composition":"Ni","role":"active catalyst"},{"paperId":"P054","catalystId":"P054_PERF_005","name":"5Ni–SiO2 (Tw80)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"SiO2","method":"one-pot synthesis","synthesis":"Tween-80 added to HCl solution at 65 °C. Ni salt dissolved in water added dropwise, followed by TEOS addition. Stirred under reflux at 65 °C and evaporated at 65 °C.","matchedSynthesis":"5Ni–SiO2(Tw80)","composition":"Ni","role":"active catalyst"},{"paperId":"P055","catalystId":"P055_PERF_001","name":"Au@SiO2 2.8 ± 0.5 nm (Entry A)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P055","catalystId":"P055_PERF_002","name":"Au@SiO2 2.6 ± 0.3 nm (Entry B)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P055","catalystId":"P055_PERF_003","name":"Au@SiO2 2.2 ± 0.3 nm (Entry C)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P055","catalystId":"P055_PERF_004","name":"Au@SiO2 2.7 ± 0.4 nm (Entry D)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P056","catalystId":"P056_PERF_001","name":"Pd/rGO-SI","activeMetals":"Pd","metalClass":"Pd-only","support":"reduced graphene oxide (rGO)","method":"sol_immobilization","synthesis":"PdCl2 and PVA were mixed in water, reduced with NaBH4, acidified to pH 2 with sulfuric acid, then rGO was added under dynamic stirring for 1 h.","matchedSynthesis":"Pd/rGO-SI","composition":"Pd","role":"catalyst"},{"paperId":"P056","catalystId":"P056_PERF_002","name":"Pd/rGO-IMP","activeMetals":"Pd","metalClass":"Pd-only","support":"reduced graphene oxide (rGO)","method":"wet_impregnation","synthesis":"PdCl2 solution was added to rGO and stirred for 6 h, followed by reduction with aqueous NaBH4 and further stirring for 6 h.","matchedSynthesis":"Pd/rGO-IMP","composition":"Pd","role":"catalyst"},{"paperId":"P056","catalystId":"P056_PERF_003","name":"Pd/rGO-SI-Used","activeMetals":"Pd","metalClass":"Pd-only","support":"reduced graphene oxide (rGO)","method":"sol_immobilization","synthesis":"PdCl2 and PVA were mixed in water, reduced with NaBH4, acidified to pH 2 with sulfuric acid, then rGO was added under dynamic stirring for 1 h.","matchedSynthesis":"Pd/rGO-SI","composition":"Pd","role":"catalyst"},{"paperId":"P056","catalystId":"P056_PERF_004","name":"Pd/rGO-IMP-Used","activeMetals":"Pd","metalClass":"Pd-only","support":"reduced graphene oxide (rGO)","method":"wet_impregnation","synthesis":"PdCl2 solution was added to rGO and stirred for 6 h, followed by reduction with aqueous NaBH4 and further stirring for 6 h.","matchedSynthesis":"Pd/rGO-IMP","composition":"Pd","role":"catalyst"},{"paperId":"P057","catalystId":"P057_PERF_001","name":"Pd-ZrO2/RUB-15-NH2","activeMetals":"Pd-Zr","metalClass":"Pd-based multimetal","support":"RUB-15-NH2","method":"co_impregnation","synthesis":"Pd and Zr precursors were dissolved in HCl, added to a mixture of RUB-15 support, distilled water, and APTES, reduced using NaBH4, centrifuged, and dried.","matchedSynthesis":"Pd-ZrO2/RUB-15-NH2","composition":"Pd (1–4 wt%) and Zr (0.2–2 wt%); optimal ratio Pd: 2.5 wt%, Zr: 0.2 wt%","role":"hydrogen production from formic acid decomposition"},{"paperId":"P058","catalystId":"P058_PERF_001","name":"Bare Pd octahedrons","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P058","catalystId":"P058_PERF_002","name":"Bare Pd tetrahedrons","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P058","catalystId":"P058_PERF_003","name":"Bare Pd cuboctahedrons","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P058","catalystId":"P058_PERF_004","name":"Octahedrons-TiO2","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","support":"TiO2","method":"adsorption_or_loading","synthesis":"One-step synthesis of Pd nano-octahedrons using K2PdCl4, PVP, ascorbic acid (AA), and formaldehyde in aqueous media with a precursor feeding rate of 90 mL/h, followed by loading onto TiO2 via an in-situ growth protocol.","matchedSynthesis":"Pd octahedrons-TiO2","composition":"Pd","role":"catalyst"},{"paperId":"P058","catalystId":"P058_PERF_005","name":"Tetrahedrons-TiO2","activeMetals":"Te-Ti","metalClass":"Non-Pd or Pd-free","support":"TiO2","method":"adsorption_or_loading","synthesis":"One-step synthesis of Pd nano-tetrahedrons using K2PdCl4, PVP, ascorbic acid (AA), and formaldehyde in aqueous media with a precursor feeding rate of 5–45 mL/h, followed by loading onto TiO2 via an in-situ growth protocol.","matchedSynthesis":"Pd tetrahedrons-TiO2","composition":"Pd","role":"catalyst"},{"paperId":"P058","catalystId":"P058_PERF_006","name":"Cuboctahedrons-TiO2","activeMetals":"Cu-Ti","metalClass":"Non-Pd or Pd-free","support":"TiO2","method":"adsorption_or_loading","synthesis":"One-step synthesis of Pd cuboctahedron nanocrystals using K2PdCl4, PVP, ascorbic acid (AA), and formaldehyde in aqueous media with a precursor feeding rate of 360 mL/h, followed by loading onto TiO2 via an in-situ growth protocol.","matchedSynthesis":"Pd cuboctahedrons-TiO2","composition":"Pd","role":"catalyst"},{"paperId":"P058","catalystId":"P058_PERF_007","name":"Tetrahedrons-C","activeMetals":"Te","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P058","catalystId":"P058_PERF_008","name":"Tetrahedrons-Al2O3","activeMetals":"Te-Al","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P059","catalystId":"P059_PERF_001","name":"Pd-PCN-350R","activeMetals":"Pd","metalClass":"Pd-only","support":"polymeric carbon nitride (PCN)","method":"chemical_reduction_loading","synthesis":"Synthesized via stepwise annealing to form Pd-PCN, followed by reduction at 350 °C in an H2 atmosphere.","matchedSynthesis":"Pd-PCN-350R","composition":"Pd","role":"active catalyst"},{"paperId":"P059","catalystId":"P059_PERF_002","name":"Pd-PCN","activeMetals":"Pd","metalClass":"Pd-only","support":"polymeric carbon nitride (PCN)","method":"stepwise annealing","synthesis":"PCN support was prepared via calcination of melamine and cyanuric acid complex; Pd was loaded using a modified stepwise annealing approach.","matchedSynthesis":"Pd-PCN","composition":"Pd","role":"active catalyst"},{"paperId":"P059","catalystId":"P059_PERF_003","name":"Pd-PCN-500R","activeMetals":"Pd","metalClass":"Pd-only","support":"polymeric carbon nitride (PCN)","method":"chemical_reduction_loading","synthesis":"Synthesized via stepwise annealing to form Pd-PCN, followed by reduction at 500 °C in an H2 atmosphere.","matchedSynthesis":"Pd-PCN-500R","composition":"Pd","role":"active catalyst"},{"paperId":"P059","catalystId":"P059_PERF_004","name":"5 wt % Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P060","catalystId":"P060_PERF_001","name":"1%Pd@HHT","activeMetals":"Pd","metalClass":"Pd-only","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","method":"sol_immobilization","synthesis":"Precursor salt dissolved in water, PVA added as capping agent, reduced with NaBH4. HHT nanofibers added to the colloid and acidified to pH 2 using sulfuric acid.","matchedSynthesis":"1 %Pd@HHT","composition":"Pd only","role":"monometallic catalyst for formic acid decomposition"},{"paperId":"P060","catalystId":"P060_PERF_002","name":"1%Au@HHT","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","method":"sol_immobilization","synthesis":"Precursor salt dissolved in water, PVA added as capping agent, reduced with NaBH4. HHT nanofibers added to the colloid and acidified to pH 2 using sulfuric acid.","matchedSynthesis":"1 %Au@HHT","composition":"Au only","role":"monometallic catalyst for formic acid decomposition"},{"paperId":"P060","catalystId":"P060_PERF_003","name":"1%Pd8Au2@HHT","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","method":"sol_immobilization","synthesis":"Precursor salts were dissolved in water, PVA was added as a capping agent, and the solution was reduced with NaBH4. HHT nanofibers were then added to the colloidal solution, which was acidified to pH 2 using sulfuric acid to ensure nanoparticle immobilization.","matchedSynthesis":"1 %Pd8Au2@HHT, 1 %Pd6Au4@HHT, 1 %Pd4Au6@HHT, 1 %Pd2Au8@HHT","composition":"Pd:Au nominal molar ratios of 8:2, 6:4, 4:6, and 2:8","role":"bimetallic catalysts for formic acid decomposition"},{"paperId":"P060","catalystId":"P060_PERF_004","name":"1%Pd6Au4@HHT","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","method":"sol_immobilization","synthesis":"Precursor salts were dissolved in water, PVA was added as a capping agent, and the solution was reduced with NaBH4. HHT nanofibers were then added to the colloidal solution, which was acidified to pH 2 using sulfuric acid to ensure nanoparticle immobilization.","matchedSynthesis":"1 %Pd8Au2@HHT, 1 %Pd6Au4@HHT, 1 %Pd4Au6@HHT, 1 %Pd2Au8@HHT","composition":"Pd:Au nominal molar ratios of 8:2, 6:4, 4:6, and 2:8","role":"bimetallic catalysts for formic acid decomposition"},{"paperId":"P060","catalystId":"P060_PERF_005","name":"1%Pd4Au6@HHT","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","method":"sol_immobilization","synthesis":"Precursor salts were dissolved in water, PVA was added as a capping agent, and the solution was reduced with NaBH4. HHT nanofibers were then added to the colloidal solution, which was acidified to pH 2 using sulfuric acid to ensure nanoparticle immobilization.","matchedSynthesis":"1 %Pd8Au2@HHT, 1 %Pd6Au4@HHT, 1 %Pd4Au6@HHT, 1 %Pd2Au8@HHT","composition":"Pd:Au nominal molar ratios of 8:2, 6:4, 4:6, and 2:8","role":"bimetallic catalysts for formic acid decomposition"},{"paperId":"P060","catalystId":"P060_PERF_006","name":"1%Pd2Au8@HHT","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"High temperature heat-treated carbon nanofibers (HHT CNFs)","method":"sol_immobilization","synthesis":"Precursor salts were dissolved in water, PVA was added as a capping agent, and the solution was reduced with NaBH4. HHT nanofibers were then added to the colloidal solution, which was acidified to pH 2 using sulfuric acid to ensure nanoparticle immobilization.","matchedSynthesis":"1 %Pd8Au2@HHT, 1 %Pd6Au4@HHT, 1 %Pd4Au6@HHT, 1 %Pd2Au8@HHT","composition":"Pd:Au nominal molar ratios of 8:2, 6:4, 4:6, and 2:8","role":"bimetallic catalysts for formic acid decomposition"},{"paperId":"P061","catalystId":"P061_PERF_001","name":"Pd@CMK3","activeMetals":"Pd","metalClass":"Pd-only","support":"CMK3","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of CMK3 with K2PdCl4 aqueous solution, followed by NaBH4 reduction and drying.","matchedSynthesis":"Pd@CMK3","composition":"Pd","role":"active catalyst"},{"paperId":"P061","catalystId":"P061_PERF_002","name":"Pd@HHT","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P062","catalystId":"P062_PERF_001","name":"Pd@MHCP-2","activeMetals":"Pd","metalClass":"Pd-only","support":"MHCP-2 (m-phenylenediamine-based hypercrosslinked polymer)","method":"wet_impregnation","synthesis":"Synthesis of MHCP support via Friedel-Crafts alkylation, followed by Pd precursor impregnation and NaBH4 reduction.","matchedSynthesis":"Pd@MHCP-2","composition":"Pd-Fe bimetallic species (residual Fe from support synthesis)","role":"optimized catalyst for formic acid dehydrogenation"},{"paperId":"P062","catalystId":"P062_PERF_002","name":"Pd@MHCP-X (X=1, 3, 4)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P062","catalystId":"P062_PERF_003","name":"Pd@MHCP-2(s)","activeMetals":"Pd","metalClass":"Pd-only","support":"MHCP-2 (m-phenylenediamine-based hypercrosslinked polymer)","method":"wet_impregnation","synthesis":"Synthesis of MHCP support via Friedel-Crafts alkylation, followed by Pd precursor impregnation and NaBH4 reduction.","matchedSynthesis":"Pd@MHCP-2","composition":"Pd-Fe bimetallic species (residual Fe from support synthesis)","role":"optimized catalyst for formic acid dehydrogenation"},{"paperId":"P062","catalystId":"P062_PERF_004","name":"Fe@MHCP-2","activeMetals":"Fe","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P063","catalystId":"P063_PERF_001","name":"NiCu/rGO10","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"reduced graphene oxide (rGO10)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/rGO10","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_002","name":"NiCu/rGO325","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"reduced graphene oxide (rGO325)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/rGO325","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_003","name":"NiCu/SXC","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"spheres of xerogel carbons (SXC)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/SXC","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_004","name":"NiCu/MWCNT","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"multi-walled carbon nanotubes (MWCNT)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/MWCNT","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_005","name":"NiCu/SWCNT","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"single-walled carbon nanotubes (SWCNT)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/SWCNT","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_006","name":"NiCu/HSAG","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"high surface area graphite (HSAG)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/HSAG","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_007","name":"NiCu/NrGO10","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"N-doped reduced graphene oxide (NrGO10)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/NrGO10","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_008","name":"NiCu/NrGO325","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"N-doped reduced graphene oxide (NrGO325)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/NrGO325","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_009","name":"NiCu/NCNT","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"N-doped carbon nanotubes (NCNT)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/NCNT","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P063","catalystId":"P063_PERF_010","name":"NiCu/NSXC","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","support":"N-doped spheres of xerogel carbons (NSXC)","method":"incipient_wetness_impregnation","synthesis":"Metal precursors dissolved in water/ethanol and incorporated via incipient wetness impregnation, followed by drying and H2 reduction.","matchedSynthesis":"NiCu/NSXC","composition":"Ni:Cu = 1:1","role":"catalyst"},{"paperId":"P064","catalystId":"P064_PERF_001","name":"1% Pt/N-graphene (Pt(NO3)4)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"N-graphene","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","matchedSynthesis":"Pt/N-graphene (Pt(NO3)4)","composition":"Pt","role":"active catalyst"},{"paperId":"P064","catalystId":"P064_PERF_002","name":"0.2% Pt/N-graphene (Pt(NO3)4)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"N-graphene","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","matchedSynthesis":"Pt/N-graphene (Pt(NO3)4)","composition":"Pt","role":"active catalyst"},{"paperId":"P064","catalystId":"P064_PERF_003","name":"N-graphene","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"N-graphene","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","matchedSynthesis":"Pt/N-graphene (Pt(NO3)4)","composition":"Pt","role":"active catalyst"},{"paperId":"P064","catalystId":"P064_PERF_004","name":"1% Pt/N-graphene (H2PtCl6)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"N-graphene","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","matchedSynthesis":"Pt/N-graphene (H2PtCl6)","composition":"Pt","role":"active catalyst"},{"paperId":"P064","catalystId":"P064_PERF_005","name":"0.4% Pt/N-graphene (H2PtCl6)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"N-graphene","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","matchedSynthesis":"Pt/N-graphene (H2PtCl6)","composition":"Pt","role":"active catalyst"},{"paperId":"P064","catalystId":"P064_PERF_006","name":"0.2% Pt/N-graphene (H2PtCl6)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"N-graphene","method":"wet_impregnation","synthesis":"Platinum was deposited from an aqueous precursor solution onto the carbon support under continuous mixing, followed by water evaporation, heating in a muffle furnace, and reduction in H2-Ar flow.","matchedSynthesis":"Pt/N-graphene (H2PtCl6)","composition":"Pt","role":"active catalyst"},{"paperId":"P065","catalystId":"P065_PERF_001","name":"Pd/rutile","activeMetals":"Pd","metalClass":"Pd-only","support":"rutile TiO2","method":"wet_impregnation","synthesis":"Impregnation of Pd onto rutile TiO2 support, followed by drying, calcination, and reduction.","matchedSynthesis":"Pd/rutile","composition":"Pd","role":"catalyst"},{"paperId":"P065","catalystId":"P065_PERF_002","name":"Pd/anatase","activeMetals":"Pd","metalClass":"Pd-only","support":"anatase TiO2","method":"wet_impregnation","synthesis":"Impregnation of Pd onto anatase TiO2 support, followed by drying, calcination, and reduction.","matchedSynthesis":"Pd/anatase","composition":"Pd","role":"catalyst"},{"paperId":"P065","catalystId":"P065_PERF_003","name":"Pd/brookite","activeMetals":"Pd","metalClass":"Pd-only","support":"brookite TiO2","method":"wet_impregnation","synthesis":"Impregnation of Pd onto brookite TiO2 support, followed by drying, calcination, and reduction.","matchedSynthesis":"Pd/brookite","composition":"Pd","role":"catalyst"},{"paperId":"P065","catalystId":"P065_PERF_004","name":"Pd/TiO2(B)","activeMetals":"Pd","metalClass":"Pd-only","support":"TiO2(B)","method":"wet_impregnation","synthesis":"Impregnation of Pd onto TiO2(B) support, followed by drying, calcination, and reduction.","matchedSynthesis":"Pd/TiO2(B)","composition":"Pd","role":"catalyst"},{"paperId":"P066","catalystId":"P066_PERF_001","name":"Pd/c-Al2O3","activeMetals":"Pd","metalClass":"Pd-only","support":"c-Al2O3","method":"wet_impregnation","synthesis":"Support was calcined, suspended in water at pH 9, impregnated with Pd precursor, dried via rotary evaporation, calcined in air, and reduced under H2/N2.","matchedSynthesis":"Pd/c-Al2O3","composition":"Pd","role":"active catalyst"},{"paperId":"P067","catalystId":"P067_PERF_001","name":"Pt–PVP","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","method":"chemical_reduction_loading","synthesis":"Colloidal platinum nanoparticles were prepared via the chemical reduction of chloroplatinic acid in the presence of polyvinylpyrrolidone (PVP) as a dispersant to maintain nanoscale particle size.","matchedSynthesis":"Pt–PVP","composition":"Pt","role":"catalyst for formic acid decomposition"},{"paperId":"P068","catalystId":"P068_PERF_001","name":"Au/NdZrO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"NdZrO2","method":"adsorption_or_loading","synthesis":"ZrO2 was doped with Nd3+ by partial substitution of Zr4+ to form a solid solution support, followed by the loading of Au nanoparticles.","matchedSynthesis":"Au/NdZrO2","composition":"Au","role":"catalyst"},{"paperId":"P068","catalystId":"P068_PERF_002","name":"Au/CeZrO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"CeZrO2","method":"adsorption_or_loading","synthesis":"ZrO2 was doped with Ce3+ by partial substitution of Zr4+ to form a solid solution support, followed by the loading of Au nanoparticles.","matchedSynthesis":"Au/CeZrO2","composition":"Au","role":"catalyst"},{"paperId":"P068","catalystId":"P068_PERF_003","name":"Au/SmZrO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"SmZrO2","method":"adsorption_or_loading","synthesis":"ZrO2 was doped with Sm3+ by partial substitution of Zr4+ to form a solid solution support, followed by the loading of Au nanoparticles.","matchedSynthesis":"Au/SmZrO2","composition":"Au","role":"catalyst"},{"paperId":"P068","catalystId":"P068_PERF_004","name":"Au/ZrO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"ZrO2","method":"other","synthesis":"Gold nanoparticles were supported on a ZrO2 support.","matchedSynthesis":"Au/ZrO2","composition":"Au","role":"catalyst"},{"paperId":"P069","catalystId":"P069_PERF_001","name":"Pd2.3/C-N","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P069","catalystId":"P069_PERF_002","name":"Pd4.6/C-N","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P069","catalystId":"P069_PERF_003","name":"Pd9.2/C-N","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P069","catalystId":"P069_PERF_004","name":"Pd18.4/C-N","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P069","catalystId":"P069_PERF_005","name":"Pd23.1/C-N","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P070","catalystId":"P070_PERF_001","name":"Pd@TU-PMO","activeMetals":"Pd","metalClass":"Pd-only","support":"TU-PMO","method":"wet_impregnation","synthesis":"TU-PMO was dispersed in a tetrachloropalladate solution to incorporate Pd2+ into the pore channels, followed by reduction with sodium borohydride.","matchedSynthesis":"Pd@TU-PMO","composition":"Pd","role":"catalyst for the catalytic dehydrogenation of formic acid in water"},{"paperId":"P070","catalystId":"P070_PERF_002","name":"Pd2+@TU-PMO","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P071","catalystId":"P071_PERF_001","name":"Pd/HTNC-950","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P071","catalystId":"P071_PERF_002","name":"Pd/HTNC-O","activeMetals":"Pd","metalClass":"Pd-only","support":"Activated carbon (AC)","method":"wet_impregnation","synthesis":"Parental AC sonicated in deionized water, mixed with H2PdCl4 solution at room temperature, reduced using NaBH4 after pH adjustment, then centrifuged, washed, and dried.","matchedSynthesis":"Pd/HTNC-O","composition":"Pd","role":"Control catalyst (parental AC support)"},{"paperId":"P071","catalystId":"P071_PERF_003","name":"Pd/AC-950","activeMetals":"Pd","metalClass":"Pd-only","support":"Activated carbon (AC)","method":"wet_impregnation","synthesis":"AC treated with N2 at 950 °C, then Pd deposited via the same impregnation and NaBH4 reduction method as Pd/HTNC.","matchedSynthesis":"Pd/AC-950","composition":"Pd","role":"Control catalyst (non-nitrogen doped high temp AC)"},{"paperId":"P072","catalystId":"P072_PERF_001","name":"Ag16Pd1/C","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","support":"carbon","method":"deposition_precipitation","synthesis":"Commercial Pd/C was mixed with an aqueous solution of Ag salt at an atomic Ag/Pd ratio of 16, followed by reduction using sodium borohydride at 30 °C.","matchedSynthesis":"Ag16Pd1/C","composition":"Ag:Pd = 16:1","role":"catalyst for sodium formate decomposition"},{"paperId":"P072","catalystId":"P072_PERF_002","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P072","catalystId":"P072_PERF_003","name":"Cu16Pd1/C","activeMetals":"Cu-Pd","metalClass":"Pd-based multimetal","support":"carbon","method":"deposition_precipitation","synthesis":"Commercial Pd/C was mixed with an aqueous solution of Cu salt at an atomic Cu/Pd ratio of 16, followed by reduction using sodium borohydride at 30 °C.","matchedSynthesis":"Cu16Pd1/C","composition":"Cu:Pd = 16:1","role":"catalyst for sodium formate decomposition"},{"paperId":"P072","catalystId":"P072_PERF_004","name":"Ag/C","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P073","catalystId":"P073_PERF_001","name":"8 wt.% Pd/NHPC-150","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped hierarchical porous carbon (NHPC-150)","method":"wet_impregnation","synthesis":"Support dispersed in ethylene glycol (EG) and H2O (2:3 ml ratio) via ultrasonication; PdCl2/NaOH solution added under ultrasonication, followed by reduction with NaBH4 aqueous solution.","matchedSynthesis":"Pd/NHPC-150","composition":"Pd","role":"active catalyst"},{"paperId":"P074","catalystId":"P074_PERF_001","name":"Pd/AS","activeMetals":"Pd","metalClass":"Pd-only","support":"biomass-derived activated carbon (AS)","method":"wet_impregnation","synthesis":"Impregnation of AS support with Pd precursor followed by reduction with NaBH4.","matchedSynthesis":"Pd/AS","composition":"Pd","role":"catalyst"},{"paperId":"P074","catalystId":"P074_PERF_002","name":"Pd/N-AS","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped biomass-derived activated carbon (N-AS)","method":"wet_impregnation","synthesis":"Impregnation of N-AS support with Pd precursor followed by reduction with NaBH4.","matchedSynthesis":"Pd/N-AS","composition":"Pd","role":"catalyst"},{"paperId":"P074","catalystId":"P074_PERF_003","name":"PdAg/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"biomass-derived activated carbon (AS)","method":"wet_impregnation","synthesis":"Impregnation of AS support with Pd and Ag precursors followed by reduction with NaBH4.","matchedSynthesis":"PdAg/AS","composition":"Pd/Ag molar ratio = 1/0.5","role":"catalyst"},{"paperId":"P074","catalystId":"P074_PERF_004","name":"PdAg/N-AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"N-doped biomass-derived activated carbon (N-AS)","method":"wet_impregnation","synthesis":"Impregnation of N-AS support with Pd and Ag precursors followed by reduction with NaBH4.","matchedSynthesis":"PdAg/N-AS","composition":"Pd/Ag molar ratio = 1/0.5","role":"catalyst"},{"paperId":"P074","catalystId":"P074_PERF_005","name":"Pd/AS(n.r.)","activeMetals":"Pd","metalClass":"Pd-only","support":"biomass-derived activated carbon (AS)","method":"wet_impregnation","synthesis":"Impregnation of AS support with Pd precursor followed by reduction with NaBH4.","matchedSynthesis":"Pd/AS","composition":"Pd","role":"catalyst"},{"paperId":"P074","catalystId":"P074_PERF_006","name":"Pd/N-AS(n.r.)","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped biomass-derived activated carbon (N-AS)","method":"wet_impregnation","synthesis":"Impregnation of N-AS support with Pd precursor followed by reduction with NaBH4.","matchedSynthesis":"Pd/N-AS","composition":"Pd","role":"catalyst"},{"paperId":"P074","catalystId":"P074_PERF_007","name":"PdAg/AS(n.r.)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"biomass-derived activated carbon (AS)","method":"wet_impregnation","synthesis":"Impregnation of AS support with Pd and Ag precursors followed by reduction with NaBH4.","matchedSynthesis":"PdAg/AS","composition":"Pd/Ag molar ratio = 1/0.5","role":"catalyst"},{"paperId":"P074","catalystId":"P074_PERF_008","name":"PdAg/N-AS(n.r.)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"N-doped biomass-derived activated carbon (N-AS)","method":"wet_impregnation","synthesis":"Impregnation of N-AS support with Pd and Ag precursors followed by reduction with NaBH4.","matchedSynthesis":"PdAg/N-AS","composition":"Pd/Ag molar ratio = 1/0.5","role":"catalyst"},{"paperId":"P075","catalystId":"P075_PERF_001","name":"Pd/NHPC-AC","activeMetals":"Pd","metalClass":"Pd-only","support":"NHPC-AC (N-doped porous carbon)","method":"chemical_reduction_loading","synthesis":"NHPC-AC dispersed in water, PdCl2 added, pH adjusted to 8 with Na2CO3, stirred for 2 h, heated to 60 °C, reduced by dropwise addition of HCOOH, pH adjusted to 9-10 with Na2CO3, stirred for 1 h, filtered, washed and dried.","matchedSynthesis":"Pd/NHPC-AC","composition":"Pd","role":"main catalyst"},{"paperId":"P075","catalystId":"P075_PERF_002","name":"Pd/HPC-AC","activeMetals":"Pd","metalClass":"Pd-only","support":"HPC-AC (porous carbon)","method":"chemical_reduction_loading","synthesis":"Same methodology as Pd/NHPC-AC using HPC-AC support.","matchedSynthesis":"Pd/HPC-AC","composition":"Pd","role":"comparison catalyst"},{"paperId":"P075","catalystId":"P075_PERF_003","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","support":"AC (activated carbon)","method":"chemical_reduction_loading","synthesis":"Same methodology as Pd/NHPC-AC using AC support.","matchedSynthesis":"Pd/AC","composition":"Pd","role":"comparison catalyst"},{"paperId":"P076","catalystId":"P076_PERF_001","name":"PdAg/CNT (various Pd:Ag molar ratios including Pd/CNT, Ag/CNT, Pd9Ag1/CNT, Pd8Ag2/CNT, Pd7Ag3/CNT, Pd6Ag4/CNT)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P077","catalystId":"P077_PERF_001","name":"PdMn0.6@S-1","activeMetals":"Pd-Mn","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P077","catalystId":"P077_PERF_002","name":"Pd@S-1","activeMetals":"Pd","metalClass":"Pd-only","support":"silicalite-1 (S-1) zeolite","method":"incipient_wetness_impregnation","synthesis":"Prepared by incipient wetness impregnation method.","matchedSynthesis":"Pd/S-1-im","composition":"Pd","role":"control sample"},{"paperId":"P077","catalystId":"P077_PERF_003","name":"Pd/Al2O3","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P077","catalystId":"P077_PERF_004","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P077","catalystId":"P077_PERF_005","name":"Mn@S-1","activeMetals":"Mn","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P078","catalystId":"P078_PERF_001","name":"Co&CoN-0.5","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P078","catalystId":"P078_PERF_002","name":"Co SAC","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"carbon derived from ZIFs-2","method":"pyrolysis_or_thermal_conversion","synthesis":"ZIFs-2 precursor synthesized from Co/Zn nitrates and 2-methylimidazole in methanol, then pyrolyzed at 800 °C under argon.","matchedSynthesis":"Co SAC","composition":"Co and Zn (Zn/Co = 2)","role":"comparison catalyst"},{"paperId":"P078","catalystId":"P078_PERF_003","name":"Co&CoN-2","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P078","catalystId":"P078_PERF_004","name":"Co&CoN-0","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P078","catalystId":"P078_PERF_005","name":"Co NPs","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"carbon black","method":"wet_impregnation","synthesis":"Co nitrate solution was poured into a carbon black methanol slurry, stirred for 6 h, centrifuged, washed, dried, and then reduced under H2 gas.","matchedSynthesis":"Co NPs","composition":"Co","role":"comparison catalyst"},{"paperId":"P079","catalystId":"P079_PERF_001","name":"Pd0.95Co0.05/CK-BN","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","support":"CK-BN","method":"chemical_reduction_loading","synthesis":"CK-BN support was mixed with Pd and Co precursor solutions in water, stirred for 1 h, then reduced by adding NaBH4 solution and stirring for 90 min.","matchedSynthesis":"Pd0.95Co0.05/CK-BN","composition":"Pd:Co = 0.95:0.05 (atomic ratio)","role":"optimal catalyst"},{"paperId":"P079","catalystId":"P079_PERF_002","name":"Pd/CK-BN","activeMetals":"Pd","metalClass":"Pd-only","support":"CK-BN","method":"chemical_reduction_loading","synthesis":"Similar to Pd0.95Co0.05/CK-BN but without Co precursor.","matchedSynthesis":"Pd/CK-BN","composition":"Pd only","role":"comparison catalyst"},{"paperId":"P079","catalystId":"P079_PERF_003","name":"Pd/CK-B","activeMetals":"Pd","metalClass":"Pd-only","support":"CK-BN","method":"chemical_reduction_loading","synthesis":"Similar to Pd0.95Co0.05/CK-BN but without Co precursor.","matchedSynthesis":"Pd/CK-BN","composition":"Pd only","role":"comparison catalyst"},{"paperId":"P079","catalystId":"P079_PERF_004","name":"Pd/CK-N","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P080","catalystId":"P080_PERF_001","name":"Pd/DMSNs-1.0-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P080","catalystId":"P080_PERF_002","name":"Pd/DMSNs-0.25-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P080","catalystId":"P080_PERF_003","name":"Pd/DMSNs-0.5-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P080","catalystId":"P080_PERF_004","name":"Pd/DMSNs-2.0-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P080","catalystId":"P080_PERF_005","name":"Pd/DMSNs-3.0-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P081","catalystId":"P081_PERF_001","name":"C2N-Co","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"C2N","method":"Density Functional Theory (DFT) calculations","synthesis":"Theoretical construction of C2N cluster models by anchoring one Co atom and one Sn atom in the same cavity.","matchedSynthesis":"C2N-Co-Sn","composition":"Co:Sn = 1:1 (per cavity)","role":"theoretical catalyst model"},{"paperId":"P081","catalystId":"P081_PERF_002","name":"C2N-Co-Sn","activeMetals":"Co-Sn","metalClass":"Non-Pd or Pd-free","support":"C2N","method":"Density Functional Theory (DFT) calculations","synthesis":"Theoretical construction of C2N cluster models by anchoring one Co atom and one Sn atom in the same cavity.","matchedSynthesis":"C2N-Co-Sn","composition":"Co:Sn = 1:1 (per cavity)","role":"theoretical catalyst model"},{"paperId":"P081","catalystId":"P081_PERF_003","name":"C2N-Co-Ge","activeMetals":"Co-Ge","metalClass":"Non-Pd or Pd-free","support":"C2N","method":"Density Functional Theory (DFT) calculations","synthesis":"Theoretical construction of C2N cluster models by anchoring one Co atom and one Ge atom in the same cavity.","matchedSynthesis":"C2N-Co-Ge","composition":"Co:Ge = 1:1 (per cavity)","role":"theoretical catalyst model"},{"paperId":"P081","catalystId":"P081_PERF_004","name":"C2N-Co-Pb","activeMetals":"Co-Pb","metalClass":"Non-Pd or Pd-free","support":"C2N","method":"Density Functional Theory (DFT) calculations","synthesis":"Theoretical construction of C2N cluster models by anchoring one Co atom and one Pb atom in the same cavity.","matchedSynthesis":"C2N-Co-Pb","composition":"Co:Pb = 1:1 (per cavity)","role":"theoretical catalyst model"},{"paperId":"P082","catalystId":"P082_PERF_001","name":"PdNi-WOx/KIT-6-NH2","activeMetals":"Pd-Ni-W","metalClass":"Pd-based multimetal","support":"KIT-6-NH2","method":"chemical_reduction_loading","synthesis":"Aqueous solutions of Pd, Ni, and W precursors were added to KIT-6-NH2 support under magnetic stirring and subsequently reduced with NaBH4 at room temperature.","matchedSynthesis":"PdNi-WOx/KIT-6-NH2","composition":"Pd:Ni = 8:2","role":"active catalyst"},{"paperId":"P082","catalystId":"P082_PERF_002","name":"PdNi/KIT-6-NH2","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","support":"KIT-6-NH2","method":"chemical_reduction_loading","synthesis":"Prepared according to the same experimental conditions as PdNi-WOx/KIT-6-NH2.","matchedSynthesis":"Pd/KIT-6-NH2, Pd-WOx/KIT-6-NH2, PdNi/KIT-6-NH2","role":"comparative catalysts"},{"paperId":"P082","catalystId":"P082_PERF_003","name":"Pd-WOx/KIT-6-NH2","activeMetals":"Pd-W","metalClass":"Pd-based multimetal","support":"KIT-6-NH2","method":"chemical_reduction_loading","synthesis":"Prepared according to the same experimental conditions as PdNi-WOx/KIT-6-NH2.","matchedSynthesis":"Pd/KIT-6-NH2, Pd-WOx/KIT-6-NH2, PdNi/KIT-6-NH2","role":"comparative catalysts"},{"paperId":"P082","catalystId":"P082_PERF_004","name":"Pd/KIT-6-NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"KIT-6-NH2","method":"chemical_reduction_loading","synthesis":"Prepared according to the same experimental conditions as PdNi-WOx/KIT-6-NH2.","matchedSynthesis":"Pd/KIT-6-NH2, Pd-WOx/KIT-6-NH2, PdNi/KIT-6-NH2","role":"comparative catalysts"},{"paperId":"P082","catalystId":"P082_PERF_005","name":"PdNi-WOx/KIT-6","activeMetals":"Pd-Ni-W","metalClass":"Pd-based multimetal","support":"KIT-6-NH2","method":"chemical_reduction_loading","synthesis":"Aqueous solutions of Pd, Ni, and W precursors were added to KIT-6-NH2 support under magnetic stirring and subsequently reduced with NaBH4 at room temperature.","matchedSynthesis":"PdNi-WOx/KIT-6-NH2","composition":"Pd:Ni = 8:2","role":"active catalyst"},{"paperId":"P083","catalystId":"P083_PERF_001","name":"Pd/Al2O3-HS","activeMetals":"Pd","metalClass":"Pd-only","support":"Al2O3 hollow spheres (HS)","method":"deposition_precipitation","synthesis":"Al2O3-HS support dispersed in deionized water, PdCl2/NaCl mixture added, pH adjusted to 10.8 with NaOH, filtered, washed, dried, and reduced.","matchedSynthesis":"Pd/Al2O3-HS","composition":"Pd","role":"catalyst"},{"paperId":"P083","catalystId":"P083_PERF_002","name":"Pd/Al2O3-NB","activeMetals":"Pd","metalClass":"Pd-only","support":"Al2O3 nanobelts (NB)","method":"deposition_precipitation","synthesis":"Al2O3-NB support dispersed in deionized water, PdCl2/NaCl mixture added, pH adjusted to 10.8 with NaOH, filtered, washed, dried, and reduced.","matchedSynthesis":"Pd/Al2O3-NB","composition":"Pd","role":"catalyst"},{"paperId":"P083","catalystId":"P083_PERF_003","name":"Pd/Al2O3-NP","activeMetals":"Pd","metalClass":"Pd-only","support":"Al2O3 nanoparticles (NP)","method":"deposition_precipitation","synthesis":"Al2O3-NP support dispersed in deionized water, PdCl2/NaCl mixture added, pH adjusted to 10.8 with NaOH, filtered, washed, dried, and reduced.","matchedSynthesis":"Pd/Al2O3-NP","composition":"Pd","role":"catalyst"},{"paperId":"P084","catalystId":"P084_PERF_001","name":"Pd/ZrO2@C","activeMetals":"Pd","metalClass":"Pd-only","support":"ZrO2@C (t-ZrO2 embedded in amorphous carbon)","method":"wet_impregnation","synthesis":"ZrO2@C support was synthesized via pyrolysis of UiO-66. Pd was loaded using wet impregnation with K2PdCl4, followed by NaOH addition and NaBH4 reduction.","matchedSynthesis":"Pd/ZrO2@C","composition":"Pd","role":"main catalyst"},{"paperId":"P084","catalystId":"P084_PERF_002","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon (AC)","method":"wet_impregnation","synthesis":"Prepared using the same method as Pd/ZrO2@C (impregnation with K2PdCl4 and NaBH4 reduction).","matchedSynthesis":"Pd/AC","composition":"Pd","role":"comparison catalyst"},{"paperId":"P084","catalystId":"P084_PERF_003","name":"Pd/ZrO2","activeMetals":"Pd","metalClass":"Pd-only","support":"ZrO2","method":"wet_impregnation","synthesis":"Prepared using the same method as Pd/ZrO2@C on a ZrO2 support derived from thermal decomposition of ZrO2@C.","matchedSynthesis":"Pd/ZrO2","composition":"Pd","role":"comparison catalyst"},{"paperId":"P084","catalystId":"P084_PERF_004","name":"Pd/UiO-66","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P085","catalystId":"P085_PERF_001","name":"PVPI-capped networked Pd5Ag5 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P085","catalystId":"P085_PERF_002","name":"PVP-capped networked Pd5Ag5 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P086","catalystId":"P086_PERF_001","name":"1 wt%Pd@O-HHT","activeMetals":"Pd","metalClass":"Pd-only","support":"Oxygen Functionalised High Heat Treated carbon nanofibers (O-HHT)","method":"sol_immobilization","synthesis":"Pd precursor salt was mixed with PVA capping agent and reduced by NaBH4. The resulting colloidal solution was added to O-HHT nanofibers, acidified to pH 2 using sulphuric acid, filtered, washed, and dried.","matchedSynthesis":"1 wt%Pd@O-HHT","composition":"Pd, 1 wt%","role":"active catalyst"},{"paperId":"P086","catalystId":"P086_PERF_002","name":"1 wt%Pd@P-HHT","activeMetals":"Pd","metalClass":"Pd-only","support":"Phosphorous Functionalised High Heat Treated carbon nanofibers (P-HHT)","method":"sol_immobilization","synthesis":"Pd precursor salt was mixed with PVA capping agent and reduced by NaBH4. The resulting colloidal solution was added to P-HHT nanofibers, acidified to pH 2 using sulphuric acid, filtered, washed, and dried.","matchedSynthesis":"1 wt%Pd@P-HHT","composition":"Pd, 1 wt%","role":"active catalyst"},{"paperId":"P086","catalystId":"P086_PERF_003","name":"1 wt%Pd@HHT","activeMetals":"Pd","metalClass":"Pd-only","support":"High Heat Treated carbon nanofibers (HHT)","method":"sol_immobilization","synthesis":"Pd precursor salt was mixed with PVA capping agent and reduced by NaBH4. The resulting colloidal solution was added to HHT nanofibers, acidified to pH 2 using sulphuric acid, filtered, washed, and dried.","matchedSynthesis":"1 wt%Pd@HHT","composition":"Pd, 1 wt%","role":"reference catalyst"},{"paperId":"P087","catalystId":"P087_PERF_001","name":"Cr0.4Pd0.6/M-β-CD-A","activeMetals":"Cr-Pd","metalClass":"Pd-based multimetal","support":"3-aminopropyl triethoxysilane functionalized monochlortriazinyl β-cyclodextrin (M-β-CD-A)","method":"chemical_reduction_loading","synthesis":"M-β-CD was functionalized with APTES via ultrasonication; Cr and Pd precursors were added to the suspension and stirred, followed by reduction with NaBH4.","matchedSynthesis":"Cr0.4Pd0.6/M-β-CD-A","composition":"Cr:Pd = 0.4:0.6 (molar ratio)","role":"main catalyst"},{"paperId":"P087","catalystId":"P087_PERF_002","name":"Cr0.4Pd0.6 NPs (free)","activeMetals":"Cr-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P087","catalystId":"P087_PERF_003","name":"Cr0.4Pd0.6/M-β-CD","activeMetals":"Cr-Pd","metalClass":"Pd-based multimetal","support":"3-aminopropyl triethoxysilane functionalized monochlortriazinyl β-cyclodextrin (M-β-CD-A)","method":"chemical_reduction_loading","synthesis":"M-β-CD was functionalized with APTES via ultrasonication; Cr and Pd precursors were added to the suspension and stirred, followed by reduction with NaBH4.","matchedSynthesis":"Cr0.4Pd0.6/M-β-CD-A","composition":"Cr:Pd = 0.4:0.6 (molar ratio)","role":"main catalyst"},{"paperId":"P087","catalystId":"P087_PERF_004","name":"Cr0.4Pd0.6-A","activeMetals":"Cr-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P088","catalystId":"P088_PERF_001","name":"Pd@MC(2)-P","activeMetals":"Pd","metalClass":"Pd-only","support":"MC(2)-P","method":"wet_impregnation","synthesis":"CMC, NaHCO3, and (NH4)2C2O4 were calcined at 973 K to form MC(2). MC(2) was then hydrothermally treated with concentrated H3PO4 at 403 K for 12 h to produce MC(2)-P. Pd precursor solution was added to the support dispersion, followed by reduction with NaBH4 in NaOH solution.","matchedSynthesis":"Pd@MC(2)-P","composition":"Pd","role":"active catalyst"},{"paperId":"P088","catalystId":"P088_PERF_002","name":"Pd@MC(0)-P","activeMetals":"Pd","metalClass":"Pd-only","support":"MC(0)-P","method":"wet_impregnation","synthesis":"Same procedure as Pd@MC(2)-P, but using MC(0)-P support (CMC calcined without NaHCO3 and (NH4)2C2O4, then treated with H3PO4).","matchedSynthesis":"Pd@MC(0)-P","composition":"Pd","role":"control catalyst"},{"paperId":"P088","catalystId":"P088_PERF_003","name":"Pd@MC(2)-0","activeMetals":"Pd","metalClass":"Pd-only","support":"MC(2)-0","method":"wet_impregnation","synthesis":"Same procedure as Pd@MC(2)-P, but using MC(2)-0 support (CMC calcined with foaming agents, without H3PO4 hydrothermal treatment).","matchedSynthesis":"Pd@MC(2)-0","composition":"Pd","role":"control catalyst"},{"paperId":"P089","catalystId":"P089_PERF_001","name":"PdAu/Al2O3–CO (1)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"g-Al2O3","method":"incipient_wetness_impregnation","synthesis":"Impregnation of g-Al2O3 with Pd and Au precursors, drying, calcination, reduction under H2, followed by heat treatment under CO.","matchedSynthesis":"PdAu/Al2O3–CO (1)","composition":"Pd:Au = 1:1","role":"active catalyst"},{"paperId":"P089","catalystId":"P089_PERF_002","name":"PdAu/Al2O3–H2 (2)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"g-Al2O3","method":"incipient_wetness_impregnation","synthesis":"Impregnation of g-Al2O3 with Pd and Au precursors, drying, calcination, and reduction under H2.","matchedSynthesis":"PdAu/Al2O3–H2 (2)","composition":"Pd:Au = 1:1","role":"active catalyst"},{"paperId":"P089","catalystId":"P089_PERF_003","name":"PdAu/Al2O3–N2 (3)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"g-Al2O3","method":"incipient_wetness_impregnation","synthesis":"Impregnation of g-Al2O3 with Pd and Au precursors, drying, calcination, reduction under H2, followed by heat treatment under N2.","matchedSynthesis":"PdAu/Al2O3–N2 (3)","composition":"Pd:Au = 1:1","role":"active catalyst"},{"paperId":"P089","catalystId":"P089_PERF_004","name":"Pd/Al2O3 (4)","activeMetals":"Pd","metalClass":"Pd-only","support":"g-Al2O3","method":"wet_impregnation","synthesis":"Prepared for comparison; specific steps not detailed but implied to follow similar protocol as PdAu catalysts.","matchedSynthesis":"Pd/Al2O3 (4)","composition":"Pd only","role":"comparison sample"},{"paperId":"P090","catalystId":"P090_PERF_001","name":"Pd1Ag0.5/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","matchedSynthesis":"Pd1Ag0.5/NAS","composition":"Pd:Ag = 1:0.5","role":"bimetallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_002","name":"Pd1Ag0.5/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Almond shell-derived activated carbon (AS)","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","matchedSynthesis":"Pd1Ag0.5/AS","composition":"Pd:Ag = 1:0.5","role":"bimetallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_003","name":"Pd/AS","activeMetals":"Pd","metalClass":"Pd-only","support":"Almond shell-derived activated carbon (AS)","method":"wet_impregnation","synthesis":"Standard impregnation followed by reduction with NaBH4.","matchedSynthesis":"Pd/AS","composition":"Pd","role":"monometallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_004","name":"Pd1Ag0.3/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Almond shell-derived activated carbon (AS)","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","matchedSynthesis":"Pd1Ag0.3/AS","composition":"Pd:Ag = 1:0.3","role":"bimetallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_005","name":"Pd1Ag0.7/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Almond shell-derived activated carbon (AS)","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","matchedSynthesis":"Pd1Ag0.7/AS","composition":"Pd:Ag = 1:0.7","role":"bimetallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_006","name":"Pd1Ag1/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Almond shell-derived activated carbon (AS)","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","matchedSynthesis":"Pd1Ag1/AS","composition":"Pd:Ag = 1:1","role":"bimetallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_007","name":"Pd/NAS","activeMetals":"Pd","metalClass":"Pd-only","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","method":"wet_impregnation","synthesis":"Standard impregnation followed by reduction with NaBH4.","matchedSynthesis":"Pd/NAS","composition":"Pd","role":"monometallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_008","name":"Pd1Ag0.3/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","matchedSynthesis":"Pd1Ag0.3/NAS","composition":"Pd:Ag = 1:0.3","role":"bimetallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_009","name":"Pd1Ag0.7/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","matchedSynthesis":"Pd1Ag0.7/NAS","composition":"Pd:Ag = 1:0.7","role":"bimetallic catalyst"},{"paperId":"P090","catalystId":"P090_PERF_010","name":"Pd1Ag1/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Nitrogen-doped almond shell-derived activated carbon (NAS)","method":"co_impregnation","synthesis":"Co-impregnation of metal precursors followed by reduction with NaBH4.","matchedSynthesis":"Pd1Ag1/NAS","composition":"Pd:Ag = 1:1","role":"bimetallic catalyst"},{"paperId":"P091","catalystId":"P091_PERF_001","name":"Pd/CMS-ZnCl2","activeMetals":"Pd","metalClass":"Pd-only","support":"CMS-ZnCl2","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3 and ZnCl2, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","matchedSynthesis":"Pd/CMS-ZnCl2","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P091","catalystId":"P091_PERF_002","name":"Pd/CPS-ZnCl2","activeMetals":"Pd","metalClass":"Pd-only","support":"CPS-ZnCl2","method":"incipient_wetness_impregnation","synthesis":"Peanut seed shell was pretreated with HNO3 and ZnCl2, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","matchedSynthesis":"Pd/CPS-ZnCl2","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P091","catalystId":"P091_PERF_003","name":"Pd/CMS","activeMetals":"Pd","metalClass":"Pd-only","support":"CMS","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","matchedSynthesis":"Pd/CMS","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P091","catalystId":"P091_PERF_004","name":"Pd/CPS","activeMetals":"Pd","metalClass":"Pd-only","support":"CPS","method":"incipient_wetness_impregnation","synthesis":"Peanut seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","matchedSynthesis":"Pd/CPS","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P091","catalystId":"P091_PERF_005","name":"Pd/CMS-2gZnCl2","activeMetals":"Pd","metalClass":"Pd-only","support":"CMS","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","matchedSynthesis":"Pd/CMS","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P091","catalystId":"P091_PERF_006","name":"Pd/CMS-6gZnCl2","activeMetals":"Pd","metalClass":"Pd-only","support":"CMS","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","matchedSynthesis":"Pd/CMS","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P091","catalystId":"P091_PERF_007","name":"Pd/CMS-ZnCl2 (carbonized at 500 °C)","activeMetals":"Pd","metalClass":"Pd-only","support":"CMS","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","matchedSynthesis":"Pd/CMS","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P091","catalystId":"P091_PERF_008","name":"Pd/CMS-900","activeMetals":"Pd","metalClass":"Pd-only","support":"CMS","method":"incipient_wetness_impregnation","synthesis":"Melon seed shell was pretreated with HNO3, pyrolyzed at 800°C under N2 for 2 h, washed with HCl; Pd was then loaded via incipient wetness and reduced with NaBH4.","matchedSynthesis":"Pd/CMS","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P092","catalystId":"P092_PERF_001","name":"AuPd/TiO2 nanosheets-400","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"TiO2 nanosheets","method":"wet_impregnation","synthesis":"TiO2 nanosheets were first synthesized and calcined; then Au and Pd precursors were impregnated onto the support followed by liquid-phase reduction with NaBH4.","matchedSynthesis":"AuPd/TiO2 nanosheets","composition":"Au:Pd = 1:1 molar ratio in precursor solution","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P092","catalystId":"P092_PERF_002","name":"AuPd","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"TiO2 nanosheets","method":"wet_impregnation","synthesis":"TiO2 nanosheets were first synthesized and calcined; then Au and Pd precursors were impregnated onto the support followed by liquid-phase reduction with NaBH4.","matchedSynthesis":"AuPd/TiO2 nanosheets","composition":"Au:Pd = 1:1 molar ratio in precursor solution","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P092","catalystId":"P092_PERF_003","name":"Pd/TiO2 nanosheets-400","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P092","catalystId":"P092_PERF_004","name":"Au/TiO2 nanosheets-400","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P092","catalystId":"P092_PERF_005","name":"AuPd/TiO2 nanotubes-250","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P092","catalystId":"P092_PERF_006","name":"AuPd/TiO2 nanoparticles-N","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P093","catalystId":"P093_PERF_001","name":"Au2Pd8/SBA-15-Amine","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P094","catalystId":"P094_PERF_001","name":"Pd@CN900K","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped hierarchically porous carbon (CN900K)","method":"adsorption_or_loading","synthesis":"Al-MIL-101-NH2 was carbonized at 900 °C in argon to form CN900, which was then etched with aq KOH via ultrasonication to produce the hierarchically porous support CN900K. Pd nanoparticles were subsequently immobilized on this support using a wet chemical reduction process with NaBH4.","matchedSynthesis":"Pd@CN900K","composition":"Pd","role":"active catalyst"},{"paperId":"P094","catalystId":"P094_PERF_002","name":"Pd@CN600K","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P094","catalystId":"P094_PERF_003","name":"Pd@CN700K","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P094","catalystId":"P094_PERF_004","name":"Pd@CN800K","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P094","catalystId":"P094_PERF_005","name":"Pd@CN1000K","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P095","catalystId":"P095_PERF_001","name":"Pd−Cr(OH)3/NH2-rGO","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","support":"amino-modified reduced graphene oxide (NH2-rGO)","method":"sequential_impregnation","synthesis":"GO was modified with APTMS to form NH2-rGO, followed by the addition of Pd and Cr precursors under stirring, and finally reduced using NaBH4.","matchedSynthesis":"Pd-Cr(OH)3/NH2-rGO","composition":"Pd/Cr molar ratio = 0.1/0.06","role":"active catalyst"},{"paperId":"P095","catalystId":"P095_PERF_002","name":"Pd/NH2-rGO","activeMetals":"Pd","metalClass":"Pd-only","support":"amino-modified reduced graphene oxide (NH2-rGO)","method":"sequential_impregnation","synthesis":"Prepared using the same method as Pd-Cr(OH)3/NH2-rGO but without Cr precursor.","matchedSynthesis":"Pd/NH2-rGO","composition":"Pd only","role":"comparative catalyst"},{"paperId":"P095","catalystId":"P095_PERF_003","name":"Pd−Cr(OH)3/rGO","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","support":"reduced graphene oxide (rGO)","method":"sequential_impregnation","synthesis":"Prepared using the same method as Pd-Cr(OH)3/NH2-rGO but without APTMS modification of GO.","matchedSynthesis":"Pd-Cr(OH)3/rGO","composition":"Pd/Cr = 0.1/0.06","role":"comparative catalyst"},{"paperId":"P095","catalystId":"P095_PERF_004","name":"Pd/rGO","activeMetals":"Pd","metalClass":"Pd-only","support":"reduced graphene oxide (rGO)","method":"sequential_impregnation","synthesis":"Prepared using the same method as Pd-Cr(OH)3/NH2-rGO but without APTMS and Cr precursor.","matchedSynthesis":"Pd/rGO","composition":"Pd only","role":"comparative catalyst"},{"paperId":"P095","catalystId":"P095_PERF_005","name":"Cr(OH)3/NH2-rGO","activeMetals":"Cr","metalClass":"Non-Pd or Pd-free","support":"amino-modified reduced graphene oxide (NH2-rGO)","method":"sequential_impregnation","synthesis":"GO was modified with APTMS to form NH2-rGO, followed by the addition of Pd and Cr precursors under stirring, and finally reduced using NaBH4.","matchedSynthesis":"Pd-Cr(OH)3/NH2-rGO","composition":"Pd/Cr molar ratio = 0.1/0.06","role":"active catalyst"},{"paperId":"P096","catalystId":"P096_PERF_001","name":"AgPd@MIL-125-NH2-PDA","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","support":"MIL-125-NH2 modified with polydopamine (PDA)","method":"chemical_reduction_loading","synthesis":"MIL-125-NH2 was synthesized solvothermally and then coated with PDA. Ag and Pd precursors were adsorbed onto the MOF-PDA surface followed by NaBH4 induced reduction.","matchedSynthesis":"AgPd@MIL-125-NH2-PDA","composition":"Ag and Pd; atomic ratio 0.283:0.717","role":"active catalyst"},{"paperId":"P096","catalystId":"P096_PERF_002","name":"Pd@MIL-125-NH2-PDA","activeMetals":"Pd","metalClass":"Pd-only","support":"MIL-125-NH2 modified with polydopamine (PDA)","method":"chemical_reduction_loading","synthesis":"Similar approach to AgPd@MIL-125-NH2-PDA using only palladium precursor.","matchedSynthesis":"Pd@MIL-125-NH2-PDA","composition":"Pd","role":"control sample"},{"paperId":"P097","catalystId":"P097_PERF_001","name":"Zn51.9Pd48.1","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","method":"solid-vapor synthesis","synthesis":"Reactants placed in a quartz glass ampoule with a neck to avoid direct contact; heated at 60 °C/min to 500 °C, annealed for 1 day, then raised to 900 °C and held for 10 days, followed by water quenching.","matchedSynthesis":"Zn51.9Pd48.1","composition":"Zn: 51.9 at.%, Pd: 48.1 at.%","role":"bulk catalyst"},{"paperId":"P097","catalystId":"P097_PERF_002","name":"Zn49.8Pd50.2","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","method":"solid-vapor synthesis","synthesis":"Reactants placed in a quartz glass ampoule with a neck to avoid direct contact; heated at 60 °C/min to 500 °C, annealed for 1 day, then raised to 900 °C and held for 10 days, followed by water quenching.","matchedSynthesis":"Zn49.8Pd50.2","composition":"Zn: 49.8 at.%, Pd: 50.2 at.%","role":"bulk catalyst"},{"paperId":"P097","catalystId":"P097_PERF_003","name":"Zn42.0Pd58.0","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","method":"solid-vapor synthesis","synthesis":"Reactants placed in a quartz glass ampoule with a neck to avoid direct contact; heated at 60 °C/min to 500 °C, annealed for 1 day, then raised to 900 °C and held for 10 days, followed by water quenching.","matchedSynthesis":"Zn42.0Pd58.0","composition":"Zn: 42.0 at.%, Pd: 58.0 at.%","role":"bulk catalyst"},{"paperId":"P097","catalystId":"P097_PERF_004","name":"ZnPd/ZnO","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","support":"ZnO","method":"incipient_wetness_impregnation","synthesis":"Standard incipient wetness impregnation of Pd nitrate on ZnO, followed by calcination and reduction to induce reactive metal-support interaction (RMSI) for ZnPd formation.","matchedSynthesis":"ZnPd/ZnO","composition":"nominal Pd loading of 9.7 at.% (ICP-OES: 7.8(3) at.%)","role":"supported catalyst"},{"paperId":"P098","catalystId":"P098_PERF_001","name":"Pd/C3N4","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"C3N4 support was prepared by melamine calcination. Pd was deposited via wetness impregnation, followed by thermal treatment in N2 and reduction in N2/H2.","matchedSynthesis":"Pd/C3N4","composition":"Pd","role":"catalyst"},{"paperId":"P098","catalystId":"P098_PERF_002","name":"Ru/C3N4","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"C3N4 support was prepared by melamine calcination. Ru was deposited via wetness impregnation, followed by thermal treatment in N2 and reduction in N2/H2.","matchedSynthesis":"Ru/C3N4","composition":"Ru","role":"catalyst"},{"paperId":"P098","catalystId":"P098_PERF_003","name":"PdRu/C3N4","activeMetals":"Pd-Ru","metalClass":"Pd-based multimetal","support":"carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"C3N4 support was prepared by melamine calcination. Pd and Ru were deposited via wetness impregnation, followed by thermal treatment in N2 and reduction in N2/H2.","matchedSynthesis":"PdRu/C3N4","composition":"Pd:Ru = 1:1 molar ratio","role":"catalyst"},{"paperId":"P099","catalystId":"P099_PERF_001","name":"Pd 5","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon (AC) DARCO G-60","method":"wet_impregnation","synthesis":"Precursor dissolved in acetone, mixed with support, solvent evaporated via rotary evaporator, dried at 100 °C, and reduced under N2:H2 flow at 350 °C.","matchedSynthesis":"Pd 5","composition":"Pd","role":"active catalyst"},{"paperId":"P099","catalystId":"P099_PERF_002","name":"Pd 10","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon (AC) DARCO G-60","method":"wet_impregnation","synthesis":"Precursor dissolved in acetone, mixed with support, solvent evaporated via rotary evaporator, dried at 100 °C, and reduced under N2:H2 flow at 350 °C.","matchedSynthesis":"Pd 10","composition":"Pd","role":"active catalyst"},{"paperId":"P099","catalystId":"P099_PERF_003","name":"PdCo 3:1","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P099","catalystId":"P099_PERF_004","name":"PdCo 2:1","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P099","catalystId":"P099_PERF_005","name":"PdCo 1:1","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P099","catalystId":"P099_PERF_006","name":"PdCo 1:3","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P099","catalystId":"P099_PERF_007","name":"Co 5","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"activated carbon (AC) DARCO G-60","method":"wet_impregnation","synthesis":"Precursor dissolved in acetone, mixed with support, solvent evaporated via rotary evaporator, dried at 100 °C, and reduced under N2:H2 flow at 350 °C.","matchedSynthesis":"Co 5","composition":"Co","role":"reference catalyst"},{"paperId":"P100","catalystId":"P100_PERF_001","name":"1 wt.% Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"C","method":"commercial","synthesis":"Supplied by Sigma-Aldrich","matchedSynthesis":"1 wt.% Pd/C","composition":"Pd","role":"unpromoted catalyst"},{"paperId":"P100","catalystId":"P100_PERF_002","name":"10:1 K–Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"C","method":"incipient_wetness_impregnation","synthesis":"Potassium carbonate was deposited on commercial 1.0 wt.% Pd/C via incipient wetness impregnation.","matchedSynthesis":"10:1 K–Pd/C","composition":"K:Pd = 10:1 (weight ratio)","role":"promoted catalyst"},{"paperId":"P100","catalystId":"P100_PERF_003","name":"1 wt.% Pd/SiO2","activeMetals":"Pd","metalClass":"Pd-only","support":"SiO2","method":"commercial","synthesis":"Supplied by Johnson Matthey","matchedSynthesis":"1 wt.% Pd/SiO2","composition":"Pd","role":"unpromoted catalyst"},{"paperId":"P100","catalystId":"P100_PERF_004","name":"4:1 K–Pd/SiO2","activeMetals":"Pd","metalClass":"Pd-only","support":"SiO2","method":"incipient_wetness_impregnation","synthesis":"Potassium carbonate was deposited on commercial 1.0 wt.% Pd/SiO2 via incipient wetness impregnation.","matchedSynthesis":"4:1 K–Pd/SiO2","composition":"K:Pd = 4:1 (weight ratio)","role":"promoted catalyst"},{"paperId":"P100","catalystId":"P100_PERF_005","name":"1 wt.% Pd/Al2O3","activeMetals":"Pd","metalClass":"Pd-only","support":"Al2O3","method":"commercial","synthesis":"Supplied by Johnson Matthey","matchedSynthesis":"1 wt.% Pd/Al2O3","composition":"Pd","role":"unpromoted catalyst"},{"paperId":"P100","catalystId":"P100_PERF_006","name":"2:1 K–Pd/Al2O3","activeMetals":"Pd","metalClass":"Pd-only","support":"Al2O3","method":"incipient_wetness_impregnation","synthesis":"Potassium carbonate was deposited on commercial 1.0 wt.% Pd/Al2O3 via incipient wetness impregnation.","matchedSynthesis":"2:1 K–Pd/Al2O3","composition":"K:Pd = 2:1 (weight ratio)","role":"promoted catalyst"},{"paperId":"P101","catalystId":"P101_PERF_001","name":"Pd–CeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"CeO2","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd precursor mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","matchedSynthesis":"Pd–CeO2","composition":"Pd","role":"monometallic catalyst"},{"paperId":"P101","catalystId":"P101_PERF_002","name":"0.5 PdAg–CeO2","activeMetals":"Pd-Ag-Ce","metalClass":"Pd-based multimetal","support":"CeO2","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd and Ag precursors mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","matchedSynthesis":"0.5 PdAg–CeO2","composition":"Pd:Ag = 0.5 (atomic ratio)","role":"alloy catalyst"},{"paperId":"P101","catalystId":"P101_PERF_003","name":"Pd–TiO2","activeMetals":"Pd-Ti","metalClass":"Pd-based multimetal","support":"TiO2","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd precursor mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","matchedSynthesis":"Pd–TiO2","composition":"Pd","role":"monometallic catalyst"},{"paperId":"P101","catalystId":"P101_PERF_004","name":"0.5 PdAg–TiO2","activeMetals":"Pd-Ag-Ti","metalClass":"Pd-based multimetal","support":"TiO2","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd and Ag precursors mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","matchedSynthesis":"0.5 PdAg–TiO2","composition":"Pd:Ag = 0.5 (atomic ratio)","role":"alloy catalyst"},{"paperId":"P101","catalystId":"P101_PERF_005","name":"Pd–Al2O3","activeMetals":"Pd-Al","metalClass":"Pd-based multimetal","support":"Al2O3","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd precursor mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","matchedSynthesis":"Pd–Al2O3","composition":"Pd","role":"monometallic catalyst"},{"paperId":"P101","catalystId":"P101_PERF_006","name":"0.5 PdAg–Al2O3","activeMetals":"Pd-Ag-Al","metalClass":"Pd-based multimetal","support":"Al2O3","method":"incipient_wetness_impregnation","synthesis":"Aqueous Pd and Ag precursors mixed with support at 400 rpm; heated to 338 K (0.5 h), then 363 K until evaporation, and maintained at 383 K overnight; finally reduced in a tubular furnace.","matchedSynthesis":"0.5 PdAg–Al2O3","composition":"Pd:Ag = 0.5 (atomic ratio)","role":"alloy catalyst"},{"paperId":"P102","catalystId":"P102_PERF_001","name":"5Pd-M1U3-600","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","support":"graphitic carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine/urea mixture; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","matchedSynthesis":"5Pd-M1U3-600","composition":"Pd","role":"active catalyst"},{"paperId":"P102","catalystId":"P102_PERF_002","name":"5Pd-M1U3-550","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","support":"graphitic carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine/urea mixture; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","matchedSynthesis":"5Pd-M1U3-550","composition":"Pd","role":"active catalyst"},{"paperId":"P102","catalystId":"P102_PERF_003","name":"5Pd-M-600","activeMetals":"Pd","metalClass":"Pd-only","support":"graphitic carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","matchedSynthesis":"5Pd-M-600","composition":"Pd","role":"active catalyst"},{"paperId":"P102","catalystId":"P102_PERF_004","name":"5Pd-M-550","activeMetals":"Pd","metalClass":"Pd-only","support":"graphitic carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","matchedSynthesis":"5Pd-M-550","composition":"Pd","role":"active catalyst"},{"paperId":"P102","catalystId":"P102_PERF_005","name":"5Pd-M3U1-600","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","support":"graphitic carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine/urea mixture; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","matchedSynthesis":"5Pd-M3U1-600","composition":"Pd","role":"active catalyst"},{"paperId":"P102","catalystId":"P102_PERF_006","name":"5Pd-M3U1-550","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","support":"graphitic carbon nitride (C3N4)","method":"wet_impregnation","synthesis":"Support synthesized via thermal condensation of melamine/urea mixture; Pd loaded by aqueous impregnation of palladium nitrate, followed by drying and H2/N2 reduction.","matchedSynthesis":"5Pd-M3U1-550","composition":"Pd","role":"active catalyst"},{"paperId":"P102","catalystId":"P102_PERF_007","name":"5Pd-U-600","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P102","catalystId":"P102_PERF_008","name":"5Pd-U-550","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P103","catalystId":"P103_PERF_001","name":"Pd/MWCNT","activeMetals":"Pd","metalClass":"Pd-only","support":"MWCNT","method":"wet_impregnation","synthesis":"Prepared using the same experimental procedure as Pd/MWCNT-C3N4 catalysts.","matchedSynthesis":"Pd/MWCNT","composition":"Pd","role":"reference catalyst"},{"paperId":"P103","catalystId":"P103_PERF_002","name":"Pd/C3N4","activeMetals":"Pd","metalClass":"Pd-only","support":"g-C3N4","method":"wet_impregnation","synthesis":"Prepared using the same experimental procedure as Pd/MWCNT-C3N4 catalysts.","matchedSynthesis":"Pd/C3N4","composition":"Pd","role":"reference catalyst"},{"paperId":"P103","catalystId":"P103_PERF_003","name":"Pd/MWCNT-C3N4(63)","activeMetals":"Pd","metalClass":"Pd-only","support":"MWCNT","method":"wet_impregnation","synthesis":"Prepared using the same experimental procedure as Pd/MWCNT-C3N4 catalysts.","matchedSynthesis":"Pd/MWCNT","composition":"Pd","role":"reference catalyst"},{"paperId":"P103","catalystId":"P103_PERF_004","name":"Pd/MWCNT-C3N4(38)","activeMetals":"Pd","metalClass":"Pd-only","support":"MWCNT","method":"wet_impregnation","synthesis":"Prepared using the same experimental procedure as Pd/MWCNT-C3N4 catalysts.","matchedSynthesis":"Pd/MWCNT","composition":"Pd","role":"reference catalyst"},{"paperId":"P104","catalystId":"P104_PERF_001","name":"Pd/N–C","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped carbon (N–C)","method":"wet_impregnation","synthesis":"Same procedure as Pd1Nix/N–C using only the Pd precursor.","matchedSynthesis":"Pd/N–C","composition":"Pd only","role":"comparison catalyst"},{"paperId":"P104","catalystId":"P104_PERF_002","name":"Pd1Ni0.37/N–C","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P104","catalystId":"P104_PERF_003","name":"Pd1Ni1.3/N–C","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P104","catalystId":"P104_PERF_004","name":"Pd1Ni3.6/N–C","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P104","catalystId":"P104_PERF_005","name":"Ni/N–C","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"nitrogen-doped carbon (N–C)","method":"wet_impregnation","synthesis":"Same procedure as Pd1Nix/N–C using only the Ni precursor.","matchedSynthesis":"Ni/N–C","composition":"Ni only","role":"comparison catalyst"},{"paperId":"P104","catalystId":"P104_PERF_006","name":"Pd1Ni1.3/C","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","support":"commercial carbon (Ketjen)","method":"wet_impregnation","synthesis":"Same procedure as Pd1Nix/N–C but using commercial Ketjen carbon instead of N-doped carbon.","matchedSynthesis":"Pd1Ni1.3/C","composition":"Pd:Ni = 1:1.3","role":"comparison catalyst"},{"paperId":"P104","catalystId":"P104_PERF_007","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P105","catalystId":"P105_PERF_001","name":"Pd0.5Au0.5/AC","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P105","catalystId":"P105_PERF_002","name":"Pd NPs/AC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P106","catalystId":"P106_PERF_001","name":"10 wt% Pd/AC (commercial Noblyst® P1070)","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"commercial","synthesis":"Commercial catalyst (Noblyst ® P1070) supplied by Evonik in powder form.","matchedSynthesis":"Pd/AC","composition":"Pd"},{"paperId":"P107","catalystId":"P107_PERF_001","name":"Pd/Cdarco","activeMetals":"Pd","metalClass":"Pd-only","support":"Cdarco","method":"wet_impregnation","synthesis":"Wetness impregnation of Pd(II) acetate in acetone onto commercial activated carbon, followed by drying and reduction.","matchedSynthesis":"Pd/Cdarco","composition":"Pd","role":"catalyst"},{"paperId":"P107","catalystId":"P107_PERF_002","name":"Pd/Ccel","activeMetals":"Pd","metalClass":"Pd-only","support":"Ccel","method":"wet_impregnation","synthesis":"Support prepared via CO2 pyrolysis of cellulose, followed by wetness impregnation of Pd(II) acetate in acetone, drying, and reduction.","matchedSynthesis":"Pd/Ccel","composition":"Pd","role":"catalyst"},{"paperId":"P107","catalystId":"P107_PERF_003","name":"Pd/CcelZnCl2","activeMetals":"Pd","metalClass":"Pd-only","support":"CcelZnCl2","method":"wet_impregnation","synthesis":"Support prepared via ZnCl2 chemical activation and CO2 pyrolysis of cellulose, followed by wetness impregnation of Pd(II) acetate in acetone, drying, and reduction.","matchedSynthesis":"Pd/CcelZnCl2","composition":"Pd","role":"catalyst"},{"paperId":"P107","catalystId":"P107_PERF_004","name":"Pd/Cvin","activeMetals":"Pd","metalClass":"Pd-only","support":"Cvin","method":"wet_impregnation","synthesis":"Support prepared via HNO3 demineralization and CO2 pyrolysis of vine shoots, followed by wetness impregnation of Pd(II) acetate in acetone, drying, and reduction.","matchedSynthesis":"Pd/Cvin","composition":"Pd","role":"catalyst"},{"paperId":"P107","catalystId":"P107_PERF_005","name":"Pd/CvinZnCl2","activeMetals":"Pd","metalClass":"Pd-only","support":"CvinZnCl2","method":"wet_impregnation","synthesis":"Support prepared via HNO3 demineralization, ZnCl2 chemical activation and CO2 pyrolysis of vine shoots, followed by wetness impregnation of Pd(II) acetate in acetone, drying, and reduction.","matchedSynthesis":"Pd/CvinZnCl2","composition":"Pd","role":"catalyst"},{"paperId":"P108","catalystId":"P108_PERF_001","name":"Pd/MWCNTs-AP","activeMetals":"Pd","metalClass":"Pd-only","support":"MWCNTs","method":"plasma synthesis","synthesis":"MWCNTs were amino-modified with APTES to obtain MWCNTs-A; H2PdCl4 solution was added to MWCNTs-A in a quartz reactor and treated with surface dielectric barrier discharge (DBD) plasma using an Ar/H2 working gas mixture, followed by drying.","matchedSynthesis":"Pd/MWCNTs-AP","composition":"Pd","role":"active catalyst"},{"paperId":"P108","catalystId":"P108_PERF_002","name":"Sigma-Aldrich Pd/C","activeMetals":"Al-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P108","catalystId":"P108_PERF_003","name":"Pd/MWCNTs-P","activeMetals":"Pd","metalClass":"Pd-only","support":"MWCNTs","method":"plasma synthesis","synthesis":"Prepared via the same plasma-assisted method as Pd/MWCNTs-AP but without APTES amino-modification of the MWCNTs support.","matchedSynthesis":"Pd/MWCNTs-P","composition":"Pd","role":"comparison sample"},{"paperId":"P108","catalystId":"P108_PERF_004","name":"Pd/MWCNTs-AH","activeMetals":"Pd","metalClass":"Pd-only","support":"MWCNTs","method":"wet_impregnation","synthesis":"MWCNTs were amino-modified with APTES; H2PdCl4 was supported on MWCNTs-A via equivalent volume impregnation, followed by hydrogen thermal reduction.","matchedSynthesis":"Pd/MWCNTs-AH","composition":"Pd","role":"comparison sample"},{"paperId":"P109","catalystId":"P109_PERF_001","name":"Pd/BC","activeMetals":"Pd","metalClass":"Pd-only","support":"BC","method":"wet_impregnation","synthesis":"The carbon support was dispersed in acetone, and an aqueous solution of 0.01 M Pd(OAc)2 was added; the mixture was stirred at room temperature, washed with distilled water, and dried.","matchedSynthesis":"Pd/BC","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P109","catalystId":"P109_PERF_002","name":"Pd/BC_TT","activeMetals":"Pd","metalClass":"Pd-only","support":"BC_TT","method":"wet_impregnation","synthesis":"The carbon support was dispersed in acetone, and an aqueous solution of 0.01 M Pd(OAc)2 was added; the mixture was stirred at room temperature, washed with distilled water, and dried.","matchedSynthesis":"Pd/BC_TT","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P109","catalystId":"P109_PERF_003","name":"Pd/N-BC","activeMetals":"Pd","metalClass":"Pd-only","support":"N-BC","method":"wet_impregnation","synthesis":"The carbon support was dispersed in acetone, and an aqueous solution of 0.01 M Pd(OAc)2 was added; the mixture was stirred at room temperature, washed with distilled water, and dried.","matchedSynthesis":"Pd/N-BC","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P109","catalystId":"P109_PERF_004","name":"Pd/N-BC_TT","activeMetals":"Pd","metalClass":"Pd-only","support":"N-BC_TT","method":"wet_impregnation","synthesis":"The carbon support was dispersed in acetone, and an aqueous solution of 0.01 M Pd(OAc)2 was added; the mixture was stirred at room temperature, washed with distilled water, and dried.","matchedSynthesis":"Pd/N-BC_TT","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P110","catalystId":"P110_PERF_001","name":"Pd/CN-B1.5M","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P110","catalystId":"P110_PERF_002","name":"Pd/CN-M","activeMetals":"Pd","metalClass":"Pd-only","support":"Nanotubular carbon nitride (CN)","method":"wet_impregnation","synthesis":"Nanotubular CN was synthesized by dispersing melamine and barbituric acid in DI water, hydrothermal treatment, drying at 353 K, and annealing at 823 K. Pd nanoparticles were then loaded by dispersing the support in DI water, adding palladium acetate, stirring for 1 h, and reducing with NaBH4 solution.","matchedSynthesis":"Pd/CN-BxM (x = 1, 1.5, 2), Pd/CN-M, Pd/CN-B","composition":"Pd","role":"Catalyst for hydrogen production from formic acid dehydrogenation"},{"paperId":"P110","catalystId":"P110_PERF_003","name":"Pd/CN-B1M","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P110","catalystId":"P110_PERF_004","name":"Pd/CN-B2M","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P110","catalystId":"P110_PERF_005","name":"Pd/CN-B","activeMetals":"Pd","metalClass":"Pd-only","support":"Nanotubular carbon nitride (CN)","method":"wet_impregnation","synthesis":"Nanotubular CN was synthesized by dispersing melamine and barbituric acid in DI water, hydrothermal treatment, drying at 353 K, and annealing at 823 K. Pd nanoparticles were then loaded by dispersing the support in DI water, adding palladium acetate, stirring for 1 h, and reducing with NaBH4 solution.","matchedSynthesis":"Pd/CN-BxM (x = 1, 1.5, 2), Pd/CN-M, Pd/CN-B","composition":"Pd","role":"Catalyst for hydrogen production from formic acid dehydrogenation"},{"paperId":"P111","catalystId":"P111_PERF_001","name":"Pd-Ag nanoplate (nPd:nAg = 8.33 x 10^-4) supported on Vulcan XC-72 carbon black","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Vulcan XC-72 carbon black","method":"chemical_reduction_loading","synthesis":"Ag nanoplates were synthesized by adding AgNO3 and trisodium citrate to water, followed by rapid injection of NaBH4 and dropwise addition of H2O2 at room temperature. Pd was then deposited onto the Ag nanoplates by injecting PdCl2 and ascorbic acid into the nanoplate solution and heating at 40 °C for 2 h. The resulting nanoparticles were supported on Vulcan XC-72 carbon black.","matchedSynthesis":"Pd-Ag nanoplate catalyst","composition":"nPd:nAg from 4.17 x 10^-4 to 1.0","role":"active catalyst"},{"paperId":"P111","catalystId":"P111_PERF_002","name":"Pd-Ag nanoplate (nPd:nAg = 0.33) supported on Vulcan XC-72 carbon black","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Vulcan XC-72 carbon black","method":"chemical_reduction_loading","synthesis":"Ag nanoplates were synthesized by adding AgNO3 and trisodium citrate to water, followed by rapid injection of NaBH4 and dropwise addition of H2O2 at room temperature. Pd was then deposited onto the Ag nanoplates by injecting PdCl2 and ascorbic acid into the nanoplate solution and heating at 40 °C for 2 h. The resulting nanoparticles were supported on Vulcan XC-72 carbon black.","matchedSynthesis":"Pd-Ag nanoplate catalyst","composition":"nPd:nAg from 4.17 x 10^-4 to 1.0","role":"active catalyst"},{"paperId":"P111","catalystId":"P111_PERF_003","name":"Pd-Ag nanowire (nPd:nAg = 8.33 x 10^-3)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Vulcan XC-72 carbon black","method":"polyol_reduction","synthesis":"Ag nanowires were synthesized by adding NaCl and PVP to ethylene glycol, followed by dropwise addition of AgNO3 and heating at 160 °C for 6 h in an autoclave. Pd was deposited onto the Ag nanowires using ascorbic acid and PdCl2 at 40 °C for 2 h, then supported on Vulcan XC-72 carbon black.","matchedSynthesis":"Pd-Ag nanowire catalyst","composition":"nPd:nAg varied (e.g., 8.33 x 10^-3)","role":"comparison catalyst"},{"paperId":"P111","catalystId":"P111_PERF_004","name":"Pd-Ag{hcp} nanofacet","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P111","catalystId":"P111_PERF_005","name":"quasi-spherical Pd-Ag alloy nanocatalyst","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P112","catalystId":"P112_PERF_001","name":"Pd/C650","activeMetals":"Pd","metalClass":"Pd-only","support":"Vulcan XC-72 carbon black","method":"wet_impregnation","synthesis":"Similar to Pd0.9Co0.1/C650 but without the addition of cobalt acetate.","matchedSynthesis":"Pd/C650","composition":"Pd only","role":"control catalyst"},{"paperId":"P112","catalystId":"P112_PERF_002","name":"Pd0.9Co0.1/C650","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","support":"Vulcan XC-72 carbon black","method":"wet_impregnation","synthesis":"Pretreated Vulcan XC-72 was mixed with water and APTS, followed by the addition of Pd and Co precursors. The mixture was reduced using NaOH and NaBH4, then centrifuged and vacuum dried.","matchedSynthesis":"Pd0.9Co0.1/C650","composition":"Pd:Co = 9:1","role":"active catalyst"},{"paperId":"P113","catalystId":"P113_PERF_001","name":"PdCe0.2/SP-S-1","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"self-pillared silicalite-1 (SP-S-1) zeolite nanosheets","method":"incipient_wetness_impregnation","synthesis":"SP-S-1 zeolite nanosheets were synthesized hydrothermally and calcinated. Pd and Ce precursors were dissolved in deionized water, co-impregnated into the support, and then reduced under H2.","matchedSynthesis":"PdCe0.2/SP-S-1","composition":"Pd and Ce (molar ratio Ce/Pd = 0.2)","role":"optimized catalyst"},{"paperId":"P113","catalystId":"P113_PERF_002","name":"Pd/SP-S-1","activeMetals":"Pd","metalClass":"Pd-only","support":"self-pillared silicalite-1 (SP-S-1) zeolite nanosheets","method":"direct hydrothermal synthesis","synthesis":"Prepared under direct hydrothermal conditions using [Pd(NH2CH2CH2NH2)2]Cl2 as metal precursor and TBAOH as template.","matchedSynthesis":"Pd@SP-S-1","composition":"Pd","role":"comparison catalyst"},{"paperId":"P113","catalystId":"P113_PERF_003","name":"Pd/Con-S-1","activeMetals":"Pd","metalClass":"Pd-only","support":"conventional silicalite-1 (Con-S-1)","method":"incipient_wetness_impregnation","synthesis":"Pd precursor dissolved in deionized water, impregnated into Con-S-1 zeolites, followed by H2 reduction.","matchedSynthesis":"Pd/Con-S-1","composition":"Pd","role":"comparison catalyst"},{"paperId":"P113","catalystId":"P113_PERF_004","name":"Pd@SP-S-1","activeMetals":"Pd","metalClass":"Pd-only","support":"self-pillared silicalite-1 (SP-S-1) zeolite nanosheets","method":"direct hydrothermal synthesis","synthesis":"Prepared under direct hydrothermal conditions using [Pd(NH2CH2CH2NH2)2]Cl2 as metal precursor and TBAOH as template.","matchedSynthesis":"Pd@SP-S-1","composition":"Pd","role":"comparison catalyst"},{"paperId":"P114","catalystId":"P114_PERF_001","name":"PdP/NC","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon (NC)","method":"other","synthesis":"NC support was first prepared via soft-nitriding. H2PdCl4 solution was mixed with dispersed NC and dried under vacuum filtration. NaH2PO2 solution was then injected to grow PdP alloy nanoclusters in situ.","matchedSynthesis":"PdP/NC","composition":"Pd/P = 86:14 (molar ratio)","role":"active nanocatalyst"},{"paperId":"P114","catalystId":"P114_PERF_002","name":"Pd/NC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P114","catalystId":"P114_PERF_003","name":"PdP/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P114","catalystId":"P114_PERF_004","name":"commercial Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P115","catalystId":"P115_PERF_001","name":"Pd/NH2-P-GC","activeMetals":"Pd","metalClass":"Pd-only","support":"NH2-functionalized phosphorous-doped glucose-based porous carbon (NH2-P-GC)","method":"wet_impregnation","synthesis":"P-GC support synthesized by heating glucose, MgO template, and sodium hypophosphite at 120 °C followed by annealing at 800 °C under N2; MgO removed via HCl washing. Support then grafted with APTES. Pd precursor was impregnated onto the modified support and reduced using NaBH4.","matchedSynthesis":"Pd/NH2-P-GC","composition":"Pd","role":"main catalyst"},{"paperId":"P115","catalystId":"P115_PERF_002","name":"Pd/NH2-GC","activeMetals":"Pd","metalClass":"Pd-only","support":"NH2-functionalized glucose-based porous carbon (NH2-GC)","method":"wet_impregnation","synthesis":"Similar to Pd/NH2-P-GC but without sodium hypophosphite during support synthesis.","matchedSynthesis":"Pd/NH2-GC","composition":"Pd","role":"comparison sample"},{"paperId":"P115","catalystId":"P115_PERF_003","name":"Pd/GC","activeMetals":"Pd","metalClass":"Pd-only","support":"glucose-based porous carbon (GC)","method":"wet_impregnation","synthesis":"Similar to Pd/NH2-P-GC but without sodium hypophosphite and APTES.","matchedSynthesis":"Pd/GC","composition":"Pd","role":"comparison sample"},{"paperId":"P115","catalystId":"P115_PERF_004","name":"Pd/P-GC","activeMetals":"Pd","metalClass":"Pd-only","support":"phosphorous-doped glucose-based porous carbon (P-GC)","method":"wet_impregnation","synthesis":"Similar to Pd/NH2-P-GC but without APTES functionalization.","matchedSynthesis":"Pd/P-GC","composition":"Pd","role":"comparison sample"},{"paperId":"P116","catalystId":"P116_PERF_001","name":"0.2 wt % Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"N-CNTs","method":"incipient_wetness_impregnation","synthesis":"Palladium was deposited onto N-CNT supports via incipient wetness impregnation using an acetone solution of palladium acetate.","matchedSynthesis":"Pd/N-CNTs","composition":"Pd","role":"catalyst"},{"paperId":"P116","catalystId":"P116_PERF_002","name":"2 wt % Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"N-CNTs","method":"incipient_wetness_impregnation","synthesis":"Palladium was deposited onto N-CNT supports via incipient wetness impregnation using an acetone solution of palladium acetate.","matchedSynthesis":"Pd/N-CNTs","composition":"Pd","role":"catalyst"},{"paperId":"P116","catalystId":"P116_PERF_003","name":"2 wt % Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"CNTs","method":"incipient_wetness_impregnation","synthesis":"Palladium was deposited onto CNT supports via incipient wetness impregnation using an acetone solution of palladium acetate.","matchedSynthesis":"Pd/CNTs","composition":"Pd","role":"catalyst"},{"paperId":"P116","catalystId":"P116_PERF_004","name":"0.2 wt % Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"CNTs","method":"incipient_wetness_impregnation","synthesis":"Palladium was deposited onto CNT supports via incipient wetness impregnation using an acetone solution of palladium acetate.","matchedSynthesis":"Pd/CNTs","composition":"Pd","role":"catalyst"},{"paperId":"P117","catalystId":"P117_PERF_001","name":"Pd/CN-U1W5","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (CN)","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P117","catalystId":"P117_PERF_002","name":"Pd/CN-U","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (CN)","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P117","catalystId":"P117_PERF_003","name":"Pd/CN-U1W3","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (CN)","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P117","catalystId":"P117_PERF_004","name":"Pd/CN-U1W1","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (CN)","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P117","catalystId":"P117_PERF_005","name":"Pd/CN-U1W7","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nitride (CN)","method":"wet_impregnation","synthesis":"Ultrathin carbon nitride nanosheets were synthesized by calcining a mixture of urea and water. Palladium nanoparticles were then supported on these CN nanosheets and reduced using sodium borohydride.","matchedSynthesis":"Pd/CN-U1Wx (including Pd/CN-U, Pd/CN-U1W1, Pd/CN-U1W3, Pd/CN-U1W5, Pd/CN-U1W7)","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P118","catalystId":"P118_PERF_001","name":"Pd@S-1-H","activeMetals":"Pd","metalClass":"Pd-only","support":"silicalite-1 (S-1) zeolite","method":"chemical_reduction_loading","synthesis":"Synthesized via hydrothermal method at 170 °C for 3 days using a reaction gel, followed by direct reduction in H2 flow.","matchedSynthesis":"Pd@S-1-H","composition":"Pd","role":"active catalyst"},{"paperId":"P118","catalystId":"P118_PERF_002","name":"Pd@S-1-C","activeMetals":"Pd","metalClass":"Pd-only","support":"silicalite-1 (S-1) zeolite","method":"chemical_reduction_loading","synthesis":"Synthesized via hydrothermal method at 170 °C for 3 days, then calcinated and reduced.","matchedSynthesis":"Pd@S-1-C","composition":"Pd","role":"comparison catalyst"},{"paperId":"P118","catalystId":"P118_PERF_003","name":"Pd/S-1-im","activeMetals":"Pd","metalClass":"Pd-only","support":"silicalite-1 (S-1) zeolite","method":"incipient_wetness_impregnation","synthesis":"Prepared by incipient wetness impregnation with the same metal loading as Pd@S-1.","matchedSynthesis":"Pd/S-1-im","composition":"Pd","role":"comparison catalyst"},{"paperId":"P118","catalystId":"P118_PERF_004","name":"0.8Pd0.2Ni(OH)2@S-1-H","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","support":"silicalite-1 (S-1) zeolite","method":"chemical_reduction_loading","synthesis":"Synthesized via hydrothermal method at 170 °C for 3 days using a reaction gel, followed by direct reduction in H2 flow.","matchedSynthesis":"0.8Pd0.2Ni(OH)2@S-1-H","composition":"Pd/Ni = 0.8/0.2 (molar ratio)","role":"optimized bimetallic catalyst"},{"paperId":"P119","catalystId":"P119_PERF_001","name":"Pd/BNC","activeMetals":"Pd","metalClass":"Pd-only","support":"B, N co-doped carbon (BNC)","method":"deposition_precipitation","synthesis":"BNC support was synthesized by physical grinding of EDTA-2Na and H3BO3 followed by pyrolysis at 800 C in N2. Pd was loaded via deposition-precipitation using an H2PdCl4 solution, pH adjusted to 10 with NaOH, then reduced under H2/N2 flow.","matchedSynthesis":"Pd/BNC","composition":"Pd","role":"main catalyst"},{"paperId":"P119","catalystId":"P119_PERF_002","name":"Pd/NC","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon (NC)","method":"deposition_precipitation","synthesis":"NC support prepared by pyrolysis of EDTA-2Na at 800 C in N2. Pd loaded and reduced using the same route as Pd/BNC.","matchedSynthesis":"Pd/NC","composition":"Pd","role":"comparison catalyst"},{"paperId":"P119","catalystId":"P119_PERF_003","name":"BNC","activeMetals":"Pd","metalClass":"Pd-only","support":"B, N co-doped carbon (BNC)","method":"deposition_precipitation","synthesis":"BNC support was synthesized by physical grinding of EDTA-2Na and H3BO3 followed by pyrolysis at 800 C in N2. Pd was loaded via deposition-precipitation using an H2PdCl4 solution, pH adjusted to 10 with NaOH, then reduced under H2/N2 flow.","matchedSynthesis":"Pd/BNC","composition":"Pd","role":"main catalyst"},{"paperId":"P119","catalystId":"P119_PERF_004","name":"Pd/BNC-700","activeMetals":"Pd","metalClass":"Pd-only","support":"B, N co-doped carbon (BNC-700)","method":"deposition_precipitation","synthesis":"Same route as Pd/BNC but support pyrolysis temperature changed to 700 C.","matchedSynthesis":"Pd/BNC-700","composition":"Pd","role":"comparison catalyst (temperature effect)"},{"paperId":"P119","catalystId":"P119_PERF_005","name":"Pd/BNC-900","activeMetals":"Pd","metalClass":"Pd-only","support":"B, N co-doped carbon (BNC-900)","method":"deposition_precipitation","synthesis":"Same route as Pd/BNC but support pyrolysis temperature changed to 900 C.","matchedSynthesis":"Pd/BNC-900","composition":"Pd","role":"comparison catalyst (temperature effect)"},{"paperId":"P120","catalystId":"P120_PERF_001","name":"Pd1Ag1-NH2/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"pristine carbon supports","method":"chemical_reduction_loading","synthesis":"L-histidine was dissolved in Na2PdCl4 aqueous solution to form a Pd-based complex, followed by the addition of AgNO3 and subsequent co-reduction using NaBH4 on carbon support at room temperature.","matchedSynthesis":"Pd1Ag1-NH2/C","composition":"Pd:Ag = 1:1 (molar ratio of precursors)","role":"active catalyst"},{"paperId":"P120","catalystId":"P120_PERF_002","name":"Pd1Ag1/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"pristine carbon supports","method":"chemical_reduction_loading","synthesis":"Co-reduction of Na2PdCl4 and AgNO3 using NaBH4 on carbon support without L-histidine.","matchedSynthesis":"Pd1Ag1/C","composition":"Pd:Ag = 1:1 (molar ratio of precursors)","role":"control sample"},{"paperId":"P120","catalystId":"P120_PERF_003","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"pristine carbon supports","method":"chemical_reduction_loading","synthesis":"Reduction of Na2PdCl4 using NaBH4 on carbon support without L-histidine or Ag precursor.","matchedSynthesis":"Pd/C","composition":"Pd only","role":"control sample"},{"paperId":"P120","catalystId":"P120_PERF_004","name":"Pd-NH2/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P120","catalystId":"P120_PERF_005","name":"Pd1Ag2-NH2/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P120","catalystId":"P120_PERF_006","name":"Pd2Ag1-NH2/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P120","catalystId":"P120_PERF_007","name":"Pd1Ag1/C-NH2","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"carbon blacks","method":"chemical_reduction_loading","synthesis":"Bare Pd1Ag1 nanoparticles were loaded onto L-histidine modified carbon blacks.","matchedSynthesis":"Pd1Ag1/C-NH2","composition":"Pd:Ag = 1:1","role":"control sample"},{"paperId":"P121","catalystId":"P121_PERF_001","name":"Pd/D201","activeMetals":"Pd","metalClass":"Pd-only","support":"D201 resin","method":"wet_impregnation","synthesis":"Resin pretreatment -> impregnation with PdCl2 solution at room temperature for 24 h -> filtration/washing -> liquid-phase reduction with NaBH4 -> vacuum drying","matchedSynthesis":"Pd/D201","composition":"Pd","role":"FA dehydrogenation catalyst"},{"paperId":"P121","catalystId":"P121_PERF_002","name":"Pd/D301","activeMetals":"Pd","metalClass":"Pd-only","support":"D301 resin","method":"wet_impregnation","synthesis":"Resin pretreatment -> impregnation with PdCl2 solution at room temperature for 24 h -> filtration/washing -> liquid-phase reduction with NaBH4 -> vacuum drying","matchedSynthesis":"Pd/D301","composition":"Pd","role":"FA dehydrogenation catalyst"},{"paperId":"P121","catalystId":"P121_PERF_003","name":"Pd/D311","activeMetals":"Pd","metalClass":"Pd-only","support":"D311 resin","method":"wet_impregnation","synthesis":"Resin pretreatment -> impregnation with PdCl2 solution at room temperature for 24 h -> filtration/washing -> liquid-phase reduction with NaBH4 -> vacuum drying","matchedSynthesis":"Pd/D311","composition":"Pd","role":"FA dehydrogenation catalyst"},{"paperId":"P122","catalystId":"P122_PERF_001","name":"AuNPs-PPO","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)","method":"chemical_reduction_loading","synthesis":"PPO was swollen in anhydrous THF, followed by the addition of HAuCl4·3H2O and reduction with sodium triethylborohydride. The resulting catalyst was precipitated in methanol, filtered, washed with methanol, and dried under vacuum.","matchedSynthesis":"AuNPs-PPO","composition":"Au","role":"catalyst for formic acid decomposition (FAD)"},{"paperId":"P123","catalystId":"P123_PERF_001","name":"3Ni@KIT-6","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"KIT-6","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Ni precursor solution was added dropwise and stirred until dry, followed by calcination and H2 reduction.","matchedSynthesis":"3Ni@KIT-6","composition":"Ni: 3 wt.%","role":"catalyst"},{"paperId":"P123","catalystId":"P123_PERF_002","name":"5Ni@KIT-6","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"KIT-6","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Ni precursor solution was added dropwise and stirred until dry, followed by calcination and H2 reduction.","matchedSynthesis":"5Ni@KIT-6","composition":"Ni: 5 wt.%","role":"catalyst"},{"paperId":"P123","catalystId":"P123_PERF_003","name":"3Co@KIT-6","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"KIT-6","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Co precursor solution was added dropwise and stirred until dry, followed by calcination and H2 reduction.","matchedSynthesis":"3Co@KIT-6","composition":"Co: 3 wt.%","role":"catalyst"},{"paperId":"P123","catalystId":"P123_PERF_004","name":"5Co@KIT-6","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"KIT-6","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Co precursor solution was added dropwise and stirred until dry, followed by calcination and H2 reduction.","matchedSynthesis":"5Co@KIT-6","composition":"Co: 5 wt.%","role":"catalyst"},{"paperId":"P123","catalystId":"P123_PERF_005","name":"4Ni1Co@KIT-6","activeMetals":"Ni-Co","metalClass":"Non-Pd or Pd-free","support":"KIT-6","method":"wet_impregnation","synthesis":"KIT-6 support was mixed with deionized water to form a slurry at 40 °C; Ni and Co precursor solutions were added dropwise and stirred until dry, followed by calcination and H2 reduction.","matchedSynthesis":"4Ni1Co@KIT-6","composition":"Ni: 4 wt.%, Co: 1 wt.%","role":"catalyst"},{"paperId":"P124","catalystId":"P124_PERF_001","name":"Au/C","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"N-free porous carbon","method":"adsorption_or_loading","synthesis":"Carbon support was placed in HAuCl4 water solution, interacted for 1 h at 343 K, centrifuged, and treated with a 10 wt% NH3-water solution at 333 K for 1 h.","matchedSynthesis":"Au/C","composition":"Au","role":"catalyst for hydrogen production from formic acid"},{"paperId":"P124","catalystId":"P124_PERF_002","name":"Au/N-C","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"N-doped porous carbon","method":"adsorption_or_loading","synthesis":"Carbon support was placed in HAuCl4 water solution, interacted for 1 h at 343 K, centrifuged, and treated with a 10 wt% NH3-water solution at 333 K for 1 h.","matchedSynthesis":"Au/N-C","composition":"Au","role":"catalyst for hydrogen production from formic acid"},{"paperId":"P124","catalystId":"P124_PERF_003","name":"Au/Al2O3","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"Al2O3","method":"adsorption_or_loading","synthesis":"Support mixed with HAuCl4 solution, stirred at 343 K for 2 h, treated with 4 M ammonia solution, stirred again for 1 h at 343 K, filtered and washed.","matchedSynthesis":"Au/Al2O3","composition":"Au","role":"catalyst for hydrogen production from formic acid"},{"paperId":"P124","catalystId":"P124_PERF_004","name":"Au/SiO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"SiO2","method":"adsorption_or_loading","synthesis":"Support mixed with HAuCl4 solution, stirred at 343 K for 2 h, treated with 4 M ammonia solution, stirred again for 1 h at 343 K, filtered and washed.","matchedSynthesis":"Au/SiO2","composition":"Au","role":"catalyst for hydrogen production from formic acid"},{"paperId":"P125","catalystId":"P125_PERF_001","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"Vulcan XC72 carbon","method":"wet_impregnation","synthesis":"Pd was impregnated on carbon using deposition-precipitation with Na2CO3 and reduced with NaBH4.","matchedSynthesis":"Pd/C","composition":"Pd only","role":"Control catalyst"},{"paperId":"P125","catalystId":"P125_PERF_002","name":"Pd/Ceria0.4/C","activeMetals":"Pd","metalClass":"Pd-only","support":"Vulcan XC72 carbon","method":"wet_impregnation","synthesis":"Pd was impregnated on carbon using deposition-precipitation with Na2CO3 and reduced with NaBH4.","matchedSynthesis":"Pd/C","composition":"Pd only","role":"Control catalyst"},{"paperId":"P125","catalystId":"P125_PERF_003","name":"Physical mixture of Pd/C and Ceria0.4/C","activeMetals":"Pd","metalClass":"Pd-only","support":"Vulcan XC72 carbon","method":"wet_impregnation","synthesis":"Pd was impregnated on carbon using deposition-precipitation with Na2CO3 and reduced with NaBH4.","matchedSynthesis":"Pd/C","composition":"Pd only","role":"Control catalyst"},{"paperId":"P125","catalystId":"P125_PERF_004","name":"Pd/C with added Ce precursors","activeMetals":"Pd","metalClass":"Pd-only","support":"Vulcan XC72 carbon","method":"wet_impregnation","synthesis":"Pd was impregnated on carbon using deposition-precipitation with Na2CO3 and reduced with NaBH4.","matchedSynthesis":"Pd/C","composition":"Pd only","role":"Control catalyst"},{"paperId":"P126","catalystId":"P126_PERF_001","name":"Pd/200-8-1.5","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P126","catalystId":"P126_PERF_002","name":"Pd1Ni2/200-8-1.5","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P127","catalystId":"P127_PERF_001","name":"Ag3Pd12/MOF-5-C-900","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","support":"MOF-5 derived porous carbon (MOF-5-C)","method":"wet_impregnation","synthesis":"MOF-5 was carbonized to create the support, then impregnated with Ag and Pd salts, followed by NaBH4 reduction.","matchedSynthesis":"Ag3Pd12/MOF-5-C-900","composition":"Ag:Pd = 1:4 (mass ratio)","role":"active catalyst"},{"paperId":"P127","catalystId":"P127_PERF_002","name":"Pd15/MOF-5-C-900","activeMetals":"Pd","metalClass":"Pd-only","support":"MOF-5 derived porous carbon (MOF-5-C)","method":"wet_impregnation","synthesis":"Same procedure as Ag3Pd12/MOF-5-C-900 but with only Pd precursor.","matchedSynthesis":"Pd15/MOF-5-C-900","composition":"Ag:Pd = 0:5 (mass ratio)","role":"active catalyst"},{"paperId":"P127","catalystId":"P127_PERF_003","name":"physical mixture of Ag15/MOF-5-C-900 and Pd15/MOF-5-C-900 (m ratio 1:4)","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","support":"MOF-5 derived porous carbon (MOF-5-C)","method":"wet_impregnation","synthesis":"Same procedure as Ag3Pd12/MOF-5-C-900 but with only Pd precursor.","matchedSynthesis":"Pd15/MOF-5-C-900","composition":"Ag:Pd = 0:5 (mass ratio)","role":"active catalyst"},{"paperId":"P127","catalystId":"P127_PERF_004","name":"Ag3/Pd12/MOF-5-C-900","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","support":"MOF-5 derived porous carbon (MOF-5-C)","method":"wet_impregnation","synthesis":"MOF-5 was carbonized to create the support, then impregnated with Ag and Pd salts, followed by NaBH4 reduction.","matchedSynthesis":"Ag3Pd12/MOF-5-C-900","composition":"Ag:Pd = 1:4 (mass ratio)","role":"active catalyst"},{"paperId":"P127","catalystId":"P127_PERF_005","name":"Ag3Pd12/XC-72","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","support":"Vulcan XC-72 Carbon","method":"wet_impregnation","synthesis":"Same procedure as Ag3Pd12/MOF-5-C-900 but using Vulcan XC-72 Carbon support.","matchedSynthesis":"Ag3Pd12/XC-72","composition":"Ag:Pd = 1:4 (mass ratio)","role":"active catalyst"},{"paperId":"P127","catalystId":"P127_PERF_006","name":"Ag3Pd12/MOF-5","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","support":"MOF-5 derived porous carbon (MOF-5-C)","method":"wet_impregnation","synthesis":"MOF-5 was carbonized to create the support, then impregnated with Ag and Pd salts, followed by NaBH4 reduction.","matchedSynthesis":"Ag3Pd12/MOF-5-C-900","composition":"Ag:Pd = 1:4 (mass ratio)","role":"active catalyst"},{"paperId":"P127","catalystId":"P127_PERF_007","name":"Ag15/MOF-5-C-900","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","support":"MOF-5 derived porous carbon (MOF-5-C)","method":"wet_impregnation","synthesis":"Same procedure as Ag3Pd12/MOF-5-C-900 but with only Ag precursor.","matchedSynthesis":"Ag15/MOF-5-C-900","composition":"Ag:Pd = 5:0 (mass ratio)","role":"active catalyst"},{"paperId":"P127","catalystId":"P127_PERF_008","name":"AgPd alloy (m Ag:mPd = 1:4)","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P128","catalystId":"P128_PERF_001","name":"Pt/AC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"activated carbon","method":"incipient_wetness_impregnation","synthesis":"H2PtCl6 solution was added dropwise to activated carbon, dried in an oven and then in a flow reactor, followed by heating under nitrogen flow to 500 °C.","matchedSynthesis":"Pt/AC","composition":"Pt","role":"comparison catalyst"},{"paperId":"P128","catalystId":"P128_PERF_002","name":"Pt@C 500 °C","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"carbon derived from WA-30 resin","method":"ion-exchange resin method","synthesis":"WA-30 resin was dispersed in HCl; H2PtCl6 solution was added dropwise and stirred for 24 h at room temperature. The resulting Pt@WA-30 was filtered, air dried, and then carbonized in a nitrogen stream.","matchedSynthesis":"Pt@C","composition":"Pt","role":"active catalyst"},{"paperId":"P128","catalystId":"P128_PERF_003","name":"Pt@C 700 °C","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"carbon derived from WA-30 resin","method":"ion-exchange resin method","synthesis":"WA-30 resin was dispersed in HCl; H2PtCl6 solution was added dropwise and stirred for 24 h at room temperature. The resulting Pt@WA-30 was filtered, air dried, and then carbonized in a nitrogen stream.","matchedSynthesis":"Pt@C","composition":"Pt","role":"active catalyst"},{"paperId":"P128","catalystId":"P128_PERF_004","name":"Pt@C 900 °C","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"carbon derived from WA-30 resin","method":"ion-exchange resin method","synthesis":"WA-30 resin was dispersed in HCl; H2PtCl6 solution was added dropwise and stirred for 24 h at room temperature. The resulting Pt@WA-30 was filtered, air dried, and then carbonized in a nitrogen stream.","matchedSynthesis":"Pt@C","composition":"Pt","role":"active catalyst"},{"paperId":"P129","catalystId":"P129_PERF_001","name":"NP","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"adsorption_or_loading","synthesis":"Colloidal Pd nanoparticles were synthesized via polyol method using PVP and ethylene glycol, purified with acetone, redispersed in methanol, and then adsorbed onto activated carbon.","matchedSynthesis":"NP","composition":"Pd","role":"active catalyst"},{"paperId":"P129","catalystId":"P129_PERF_002","name":"AR","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"wet_impregnation","synthesis":"Metal precursor was adsorbed onto activated carbon suspended in deionized water, followed by hydrogen reduction.","matchedSynthesis":"AR","composition":"Pd","role":"active catalyst"},{"paperId":"P129","catalystId":"P129_PERF_003","name":"ADR","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"wet_impregnation","synthesis":"Pd precursor was adsorbed on activated carbon, heated to 393 K, treated with NaOH to form Pd(OH)2, and then reduced with H2.","matchedSynthesis":"ADR","composition":"Pd","role":"active catalyst"},{"paperId":"P129","catalystId":"P129_PERF_004","name":"IR","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"chemical_reduction_loading","synthesis":"Activated carbon was suspended in sodium carbonate solution, mixed with Pd precursor, and reduced with H2.","matchedSynthesis":"IR","composition":"Pd","role":"active catalyst"},{"paperId":"P129","catalystId":"P129_PERF_005","name":"IDR","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"chemical_reduction_loading","synthesis":"Similar to IR, but included a deposition step using NaOH to adjust pH to 12 before H2 reduction.","matchedSynthesis":"IDR","composition":"Pd","role":"active catalyst"},{"paperId":"P129","catalystId":"P129_PERF_006","name":"SR","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"sol_immobilization","synthesis":"In-situ colloidal Pd sols were formed by adding Na2CO3 to the metal precursor, adsorbed on activated carbon, and reduced with H2.","matchedSynthesis":"SR","composition":"Pd","role":"active catalyst"},{"paperId":"P129","catalystId":"P129_PERF_007","name":"SDR","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"wet_impregnation","synthesis":"Similar to SR, but pH was adjusted to 12 using NaOH after impregnation and before H2 reduction.","matchedSynthesis":"SDR","composition":"Pd","role":"active catalyst"},{"paperId":"P129","catalystId":"P129_PERF_008","name":"Pd2+/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P129","catalystId":"P129_PERF_009","name":"Pd(OH)2/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P129","catalystId":"P129_PERF_010","name":"Pd/C (untreated support)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P129","catalystId":"P129_PERF_011","name":"Pd/C (1 wt% HNO3 treated support)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P129","catalystId":"P129_PERF_012","name":"Pd/C (10 wt% HNO3 treated support)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P129","catalystId":"P129_PERF_013","name":"Pd/C (10 wt% HNO3 + 10 wt% H2O2 treated support)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P130","catalystId":"P130_PERF_001","name":"Pd/NMC1","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped mesoporous carbon (NMC1)","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","matchedSynthesis":"Pd/NMC1","composition":"Pd","role":"catalyst"},{"paperId":"P130","catalystId":"P130_PERF_002","name":"Pd/NMC2","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped mesoporous carbon (NMC2)","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","matchedSynthesis":"Pd/NMC2","composition":"Pd","role":"catalyst"},{"paperId":"P130","catalystId":"P130_PERF_003","name":"Pd/NMC3","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped mesoporous carbon (NMC3)","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","matchedSynthesis":"Pd/NMC3","composition":"Pd","role":"catalyst"},{"paperId":"P130","catalystId":"P130_PERF_004","name":"Pd/NMC4","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped mesoporous carbon (NMC4)","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","matchedSynthesis":"Pd/NMC4","composition":"Pd","role":"catalyst"},{"paperId":"P130","catalystId":"P130_PERF_005","name":"Pd/NMC5","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped mesoporous carbon (NMC5)","method":"deposition_precipitation","synthesis":"NMC support prepared by carbonizing glucose/urea mixture with colloidal silica at 300°C and 700°C under N2, followed by NaOH etching. Pd was loaded via deposition-precipitation using Na2PdCl4 in Na2CO3 solution and reduced with NaBH4.","matchedSynthesis":"Pd/NMC5","composition":"Pd","role":"catalyst"},{"paperId":"P131","catalystId":"P131_PERF_001","name":"30 sc% Pd-on-Au/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"activated carbon (Darco-G60)","method":"adsorption_or_loading","synthesis":"Pd-on-Au nanoparticles were synthesized via previously reported protocols and then immobilized onto activated carbon.","matchedSynthesis":"30 sc% Pd-on-Au/C","composition":"Pd: 1 wt%, Au: 13.5 wt%","role":"catalyst"},{"paperId":"P131","catalystId":"P131_PERF_002","name":"60 sc% Pd-on-Au/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"activated carbon (Darco-G60)","method":"adsorption_or_loading","synthesis":"Pd-on-Au nanoparticles were synthesized via previously reported protocols and then immobilized onto activated carbon.","matchedSynthesis":"60 sc% Pd-on-Au/C","composition":"Pd: 1 wt%, Au: 6.8 wt%","role":"catalyst"},{"paperId":"P131","catalystId":"P131_PERF_003","name":"150 sc% Pd-on-Au/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"activated carbon (Darco-G60)","method":"adsorption_or_loading","synthesis":"Pd-on-Au nanoparticles were synthesized via previously reported protocols and then immobilized onto activated carbon.","matchedSynthesis":"150 sc% Pd-on-Au/C","composition":"Pd: 1 wt%, Au: 2.5 wt%","role":"catalyst"},{"paperId":"P131","catalystId":"P131_PERF_004","name":"300 sc% Pd-on-Au/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"activated carbon (Darco-G60)","method":"adsorption_or_loading","synthesis":"Pd-on-Au nanoparticles were synthesized via previously reported protocols and then immobilized onto activated carbon.","matchedSynthesis":"300 sc% Pd-on-Au/C","composition":"Pd: 1 wt%, Au: 1.4 wt%","role":"catalyst"},{"paperId":"P131","catalystId":"P131_PERF_005","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon (Darco-G60)","method":"adsorption_or_loading","synthesis":"Pd nanoparticles were immobilized onto activated carbon.","matchedSynthesis":"Pd/C","composition":"Pd: 1 wt%","role":"control catalyst"},{"paperId":"P131","catalystId":"P131_PERF_006","name":"Au/C","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"activated carbon (Darco-G60)","method":"adsorption_or_loading","synthesis":"Au nanoparticles were immobilized onto activated carbon.","matchedSynthesis":"Au/C","composition":"Au: 1 wt%","role":"control catalyst"},{"paperId":"P132","catalystId":"P132_PERF_001","name":"Pd/NCZIF-8-25","activeMetals":"Pd","metalClass":"Pd-only","support":"NCZIF-8","method":"wet_impregnation","synthesis":"ZIF-L was synthesized using Zn(NO3)2, 2-dimethylimidazole, and CTAB; ZIF-L underwent phase transition to ZIF-8 at 70 °C in DMF/ethanol for 48 h; ZIF-8 was calcined at 900 °C in N2 for 2 h to form NCZIF-8; Pd was deposited via impregnation of H2PdCl4 followed by NaBH4 reduction.","matchedSynthesis":"Pd/NCZIF-8","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P132","catalystId":"P132_PERF_002","name":"Pd/NCZIF-8-35","activeMetals":"Pd","metalClass":"Pd-only","support":"NCZIF-8","method":"wet_impregnation","synthesis":"ZIF-L was synthesized using Zn(NO3)2, 2-dimethylimidazole, and CTAB; ZIF-L underwent phase transition to ZIF-8 at 70 °C in DMF/ethanol for 48 h; ZIF-8 was calcined at 900 °C in N2 for 2 h to form NCZIF-8; Pd was deposited via impregnation of H2PdCl4 followed by NaBH4 reduction.","matchedSynthesis":"Pd/NCZIF-8","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P133","catalystId":"P133_PERF_001","name":"Pd0.8Ag0.2/NH2-MIL-101(Cr)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"NH2-MIL-101(Cr)","method":"chemical_reduction_loading","synthesis":"NH2-MIL-101(Cr) was dispersed in water and sonicated; an aqueous solution of Pd and Ag precursors was added and stirred, followed by reduction with NaBH4, centrifugation, and vacuum drying.","matchedSynthesis":"Pd0.8Ag0.2/NH2-MIL-101(Cr)","composition":"Pd:Ag = 0.8:0.2 (nominal); Pd:Ag = 0.78:0.22 (actual)","role":"catalyst"},{"paperId":"P134","catalystId":"P134_PERF_001","name":"Pd@CN","activeMetals":"Pd","metalClass":"Pd-only","support":"Nitrogen-doped carbon (CN)","method":"adsorption_or_loading","synthesis":"TAT monomer was polymerized to PTAT. Pd NPs were formed by reducing Pd(OAc)2 in diethylene glycol at 130 °C in the presence of PTAT for adsorption (forming Pd/PTAT). The resulting complex was pyrolyzed at 450 °C under N2 to produce Pd@CN.","matchedSynthesis":"Pd@CN","composition":"Pd","role":"target catalyst"},{"paperId":"P134","catalystId":"P134_PERF_002","name":"Pd/PTAT","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P134","catalystId":"P134_PERF_003","name":"Pd/pre-CN","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P135","catalystId":"P135_PERF_001","name":"Pd/YSMSNs-NH2(10-3)","activeMetals":"Pd","metalClass":"Pd-only","support":"yolk-shell mesoporous silica nanospheres (YSMSNs)","method":"adsorption_or_loading","synthesis":"YSMSNs were functionalized with APTES in anhydrous toluene at 80 °C for 24 h, then Pd was immobilized via ultrasonic treatment and reduction using NaBH4 in deionized water.","matchedSynthesis":"Pd/YSMSNs-NH2(10-3)","composition":"Pd","role":"optimized catalyst"},{"paperId":"P135","catalystId":"P135_PERF_002","name":"Pd/YSMSNs","activeMetals":"Pd","metalClass":"Pd-only","support":"yolk-shell mesoporous silica nanospheres (YSMSNs)","method":"adsorption_or_loading","synthesis":"YSMSNs were functionalized with APTES in anhydrous toluene at 80 °C for 24 h, then Pd was immobilized via ultrasonic treatment and reduction using NaBH4 in deionized water.","matchedSynthesis":"Pd/YSMSNs-NH2(10-3)","composition":"Pd","role":"optimized catalyst"},{"paperId":"P135","catalystId":"P135_PERF_003","name":"Pd/SBA-15-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P136","catalystId":"P136_PERF_001","name":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P136","catalystId":"P136_PERF_002","name":"Pd@PNCNCs-700","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P136","catalystId":"P136_PERF_003","name":"Pd@PNCNCs-800","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P136","catalystId":"P136_PERF_004","name":"Pd@PNCNCs-1000","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P137","catalystId":"P137_PERF_001","name":"Pd/OB-C1","activeMetals":"Pd","metalClass":"Pd-only","support":"OB-C1","method":"adsorption_or_loading","synthesis":"Support synthesized via one-step coannealing of XC-72R and boric acid at 800 °C; Pd immobilized by NaOH-assisted NaBH4 reduction.","matchedSynthesis":"Pd/OB-C1","composition":"Pd","role":"active catalyst"},{"paperId":"P137","catalystId":"P137_PERF_002","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"XC-72R","method":"wet_impregnation","synthesis":"Immobilization of Pd nanoparticles on pristine XC-72R via wet chemical impregnation and NaBH4 reduction.","matchedSynthesis":"Pd/C","composition":"Pd","role":"reference catalyst"},{"paperId":"P137","catalystId":"P137_PERF_003","name":"Pd/OB-C-N1","activeMetals":"Pd","metalClass":"Pd-only","support":"OB-C-N1","method":"adsorption_or_loading","synthesis":"Support synthesized via coannealing of XC-72R, boric acid, and melamine at 800 °C; Pd immobilized by NaOH-assisted NaBH4 reduction.","matchedSynthesis":"Pd/OB-C-N1","composition":"Pd","role":"active catalyst"},{"paperId":"P138","catalystId":"P138_PERF_001","name":"Au0.3Pd0.7/NH2–N-HMCS","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"NH2–N-HMCS (amino and nitrogen functionalized mesoporous hollow carbon spheres)","method":"wet_impregnation","synthesis":"HMCS was synthesized via a template method, oxidized using APS/H2SO4, and functionalized with APTMS. Au and Pd precursors were added to the support suspension, followed by liquid-phase reduction with NaBH4.","matchedSynthesis":"Au0.3Pd0.7/NH2–N-HMCS","composition":"Au:Pd = 0.3:0.7 (molar ratio)","role":"main catalyst"},{"paperId":"P138","catalystId":"P138_PERF_002","name":"Au xPd1/C0x/NH2–N-HMCS","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P138","catalystId":"P138_PERF_003","name":"Au0.3Pd0.7/N-HMCS","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"N-HMCS (nitrogen-doped hollow mesoporous carbon spheres)","method":"wet_impregnation","synthesis":"N-HMCS support was prepared by hydrothermal treatment, then Au and Pd precursors were added followed by NaBH4 reduction.","matchedSynthesis":"Au0.3Pd0.7/N-HMCS","composition":"Au:Pd = 0.3:0.7 (molar ratio)","role":"comparison catalyst"},{"paperId":"P138","catalystId":"P138_PERF_004","name":"Au0.3Pd0.7/HMCS","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"HMCS (non-modified hollow mesoporous carbon spheres)","method":"wet_impregnation","synthesis":"Synthesized using a method similar to Au0.3Pd0.7/NH2–N-HMCS but without support functionalization.","matchedSynthesis":"Au0.3Pd0.7/HMCS","composition":"Au:Pd = 0.3:0.7 (molar ratio)","role":"comparison catalyst"},{"paperId":"P138","catalystId":"P138_PERF_005","name":"unsupported Au0.3Pd0.7","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P139","catalystId":"P139_PERF_001","name":"Pd/TBT/rGO","activeMetals":"Pd","metalClass":"Pd-only","support":"TBT/rGO","method":"chemical_reduction_loading","synthesis":"TBT/rGO was dispersed in DI water, H2PdCl4 was added and stirred for 3 h, pH adjusted to 11 with NaOH, then reduced using NaH2PO2 solution.","matchedSynthesis":"Pd/TBT/rGO","composition":"Pd","role":"active catalyst"},{"paperId":"P139","catalystId":"P139_PERF_002","name":"Pd/rGO(3.6)","activeMetals":"Pd","metalClass":"Pd-only","support":"rGO","method":"chemical_reduction_loading","synthesis":"Prepared by the same method as Pd/TBT/rGO using rGO as support.","matchedSynthesis":"Pd/rGO","composition":"Pd","role":"control catalyst"},{"paperId":"P139","catalystId":"P139_PERF_003","name":"Pd/TBT","activeMetals":"Pd","metalClass":"Pd-only","support":"TBT","method":"chemical_reduction_loading","synthesis":"Prepared by the same method as Pd/TBT/rGO using TBT as support.","matchedSynthesis":"Pd/TBT","composition":"Pd","role":"control catalyst"},{"paperId":"P139","catalystId":"P139_PERF_004","name":"Pd/rGO","activeMetals":"Pd","metalClass":"Pd-only","support":"rGO","method":"chemical_reduction_loading","synthesis":"Prepared by the same method as Pd/TBT/rGO using rGO as support.","matchedSynthesis":"Pd/rGO","composition":"Pd","role":"control catalyst"},{"paperId":"P139","catalystId":"P139_PERF_005","name":"TBT/rGO","activeMetals":"Pd","metalClass":"Pd-only","support":"TBT/rGO","method":"chemical_reduction_loading","synthesis":"TBT/rGO was dispersed in DI water, H2PdCl4 was added and stirred for 3 h, pH adjusted to 11 with NaOH, then reduced using NaH2PO2 solution.","matchedSynthesis":"Pd/TBT/rGO","composition":"Pd","role":"active catalyst"},{"paperId":"P140","catalystId":"P140_PERF_001","name":"Pd/C–SiO2","activeMetals":"Pd","metalClass":"Pd-only","support":"C–SiO2","method":"incipient_wetness_impregnation","synthesis":"C–SiO2 was dispersed in distilled water via ultrasound; H2PdCl4 precursor was added and stirred at room temperature, followed by reduction with NaBH4 and vacuum drying.","matchedSynthesis":"Pd/C–SiO2","composition":"Pd","role":"active catalyst"},{"paperId":"P140","catalystId":"P140_PERF_002","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"C","method":"incipient_wetness_impregnation","synthesis":"Prepared according to the same experimental operation as Pd/C–SiO2.","matchedSynthesis":"Pd/C","composition":"Pd","role":"comparison sample"},{"paperId":"P140","catalystId":"P140_PERF_003","name":"Pd/SiO2","activeMetals":"Pd","metalClass":"Pd-only","support":"SiO2","method":"incipient_wetness_impregnation","synthesis":"Prepared according to the same experimental operation as Pd/C–SiO2.","matchedSynthesis":"Pd/SiO2","composition":"Pd","role":"comparison sample"},{"paperId":"P141","catalystId":"P141_PERF_001","name":"Pd/TiO2","activeMetals":"Pd","metalClass":"Pd-only","support":"TiO2","method":"wet_impregnation","synthesis":"PdCl2 and HCl aqueous solution were added dropwise to dried TiO2 powders, placed statically overnight, dried, calcined, and then reduced.","matchedSynthesis":"Pd/TiO2","composition":"Pd","role":"catalyst"},{"paperId":"P141","catalystId":"P141_PERF_002","name":"Zn-Pd/TiO2","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","support":"TiO2","method":"wet_impregnation","synthesis":"ZnCl2 was added to the PdCl2 and HCl aqueous solution, followed by the same steps as Pd/TiO2: dropwise addition to TiO2, static overnight, drying, calcination, and reduction.","matchedSynthesis":"Zn-Pd/TiO2","composition":"Zn/Pd molar ratio of 1","role":"catalyst"},{"paperId":"P142","catalystId":"P142_PERF_001","name":"Pd/4N-CX-meso","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P142","catalystId":"P142_PERF_002","name":"Pd/CX-meso","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P142","catalystId":"P142_PERF_003","name":"Pd/4N-CX-macro","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P142","catalystId":"P142_PERF_004","name":"Pd/8N-CX-macro","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P142","catalystId":"P142_PERF_005","name":"Pd/2N-CX-meso","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped carbon xerogels (N-CXs) or N-free carbon xerogel (CX-meso)","method":"wet_impregnation","synthesis":"CX support was dispersed in acetone, Pd(OAc)2 solution was added and stirred for 4 h at room temperature, solvent was evaporated under vacuum at 55 °C, followed by reduction under H2 flow.","matchedSynthesis":"Pd/CX-meso, Pd/2N-CX-meso, Pd/4N-CX-meso, Pd/4N-CX-macro, Pd/8N-CX-macro","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P143","catalystId":"P143_PERF_001","name":"Pd0.50Au0.50/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"phenylenediamine-alkalized reduced graphene oxide (PDA-rGO)","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","matchedSynthesis":"Pd0.50Au0.50/PDA-rGO","composition":"Pd:Au = 1:1 molar ratio","role":"main catalyst"},{"paperId":"P143","catalystId":"P143_PERF_002","name":"Pd/PDA-rGO","activeMetals":"Pd","metalClass":"Pd-only","support":"phenylenediamine-alkalized reduced graphene oxide (PDA-rGO)","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","matchedSynthesis":"Pd/PDA-rGO","composition":"Pd only","role":"monometallic comparison catalyst"},{"paperId":"P143","catalystId":"P143_PERF_003","name":"Au/PDA-rGO","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"phenylenediamine-alkalized reduced graphene oxide (PDA-rGO)","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","matchedSynthesis":"Au/PDA-rGO","composition":"Au only","role":"monometallic comparison catalyst"},{"paperId":"P143","catalystId":"P143_PERF_004","name":"Pd0.57(Low)Au0.43(Low)/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"phenylenediamine-alkalized reduced graphene oxide (PDA-rGO)","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","matchedSynthesis":"Pd0.57(Low)Au0.43(Low)/PDA-rGO","composition":"Pd:Au = 0.57:0.43 molar ratio","role":"low loading comparison catalyst"},{"paperId":"P143","catalystId":"P143_PERF_005","name":"Pd0.49Au0.51/rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"reduced graphene oxide (rGO)","method":"wet_impregnation","synthesis":"Simple wetness impregnation followed by reduction.","matchedSynthesis":"Pd0.49Au0.51/rGO","composition":"Pd:Au = 0.49:0.51 molar ratio","role":"support comparison catalyst (without PDA)"},{"paperId":"P144","catalystId":"P144_PERF_001","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P144","catalystId":"P144_PERF_002","name":"Pd1NiO1.3/C (co)","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P144","catalystId":"P144_PERF_003","name":"Pd1/NiOx/C (seq)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P145","catalystId":"P145_PERF_001","name":"Cp*Ir-HMDAbpy@PAA","activeMetals":"Ir","metalClass":"Non-Pd or Pd-free","support":"cross-linked polyacrylic acid (PAA)","method":"sequential_impregnation","synthesis":"Synthesis of cross-linked PAA support followed by immobilization of 4-hmdabpy ligand, and subsequent coordination of the iridium precursor.","matchedSynthesis":"Cp*Ir-HMDAbpy@PAA","composition":"Ir","role":"release-and-catch catalyst for continuous formic acid dehydrogenation"},{"paperId":"P145","catalystId":"P145_PERF_002","name":"free Cp*Ir-HMDAbpy ([Cp*Ir(HMDAbpy)(H2O)]SO4)","activeMetals":"Ir","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P145","catalystId":"P145_PERF_003","name":"pre-Cp*Ir-HMDAbpy@PAA","activeMetals":"Ir","metalClass":"Non-Pd or Pd-free","support":"cross-linked polyacrylic acid (PAA)","method":"adsorption_or_loading","synthesis":"[Cp*Ir(4HMDAbpy)(H2O)]SO4 was prepared before immobilization on cross-linked PAA.","matchedSynthesis":"pre-Cp*Ir-HMDAbpy@PAA","composition":"Ir","role":"comparison catalyst"},{"paperId":"P146","catalystId":"P146_PERF_001","name":"PdAu-VOx/NHMS","activeMetals":"Pd-Au-V","metalClass":"Pd-based multimetal","support":"amino-functionalized hollow mesoporous carbon sphere (NHMS)","method":"wet_impregnation","synthesis":"VOx species were first deposited onto HMS via impregnation of aqueous VCl3 followed by calcination. Subsequently, (3-aminopropyl) triethoxysilane (APTS), Na2PdCl4, and HAuCl4·3H2O were introduced in succession, and the Pd and Au cations were reduced using NaBH4.","matchedSynthesis":"PdAu-VOx/NHMS","composition":"Pd: 0.60 wt.%, Au: 1.11 wt.%, V: 0.92 wt.%","role":"best catalyst"},{"paperId":"P146","catalystId":"P146_PERF_002","name":"PdAu/NHMS","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P146","catalystId":"P146_PERF_003","name":"Pd/NHMS","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P146","catalystId":"P146_PERF_004","name":"PdAu-VOx/HMS","activeMetals":"Pd-Au-V","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P147","catalystId":"P147_PERF_001","name":"Co(1)/phen(2)/C","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P147","catalystId":"P147_PERF_002","name":"Co@NC-W","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of carbon with Co(II) complex with 1,10-phenanthroline followed by pyrolysis.","matchedSynthesis":"Co@NC-W","composition":"Co1/L1 = 1:2","role":"reference catalyst"},{"paperId":"P147","catalystId":"P147_PERF_003","name":"Co@NC-ZIF","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"pyrolysis_or_thermal_conversion","synthesis":"Carbonization of ZIF-67 metal-organic framework.","matchedSynthesis":"Co@NC-ZIF","composition":"Co2/L2 = 1:40","role":"reference catalyst"},{"paperId":"P147","catalystId":"P147_PERF_004","name":"Co@NC-Gr1","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","matchedSynthesis":"Co@NC-Gr1","composition":"Co1/L1 = 1:2","role":"active catalyst"},{"paperId":"P147","catalystId":"P147_PERF_005","name":"Co@NC-Gr2","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","matchedSynthesis":"Co@NC-Gr2","composition":"Co1/L1 = 1:2","role":"active catalyst"},{"paperId":"P147","catalystId":"P147_PERF_006","name":"Co@NC-Gr3","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","matchedSynthesis":"Co@NC-Gr3","composition":"Co1/L1 = 1:2.5","role":"active catalyst"},{"paperId":"P147","catalystId":"P147_PERF_007","name":"Co@NC-Gr4","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","matchedSynthesis":"Co@NC-Gr4","composition":"Co2/L2 = 1:2","role":"active catalyst"},{"paperId":"P147","catalystId":"P147_PERF_008","name":"Co@NC-Gr5","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","matchedSynthesis":"Co@NC-Gr5","composition":"Co2/L2 = 1:5","role":"active catalyst"},{"paperId":"P147","catalystId":"P147_PERF_009","name":"Co@NC-Gr6","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"pyrolysis_or_thermal_conversion","synthesis":"Physical mixing of cobalt salt and carbon, addition of N-ligand, grinding to paste, drying, and pyrolysis.","matchedSynthesis":"Co@NC-Gr6","composition":"Co1/L2 = 1:5","role":"active catalyst"},{"paperId":"P147","catalystId":"P147_PERF_010","name":"Co@NC-WSA","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"acid leaching","synthesis":"Treatment of Co@NC-W with sulfuric acid to dissolve cobalt nanoparticles.","matchedSynthesis":"Co@NC-WSA","role":"acid-treated catalyst"},{"paperId":"P147","catalystId":"P147_PERF_011","name":"Co@NC-Gr1SA","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"VulcanXC72R carbon powder","method":"acid leaching","synthesis":"Treatment of Co@NC-Gr1 with sulfuric acid to dissolve cobalt nanoparticles.","matchedSynthesis":"Co@NC-Gr1SA","role":"acid-treated catalyst"},{"paperId":"P148","catalystId":"P148_PERF_001","name":"Pd/AC (Commercial 10 wt% Pd/AC)","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon","method":"commercial purchase","synthesis":"Commercial catalyst purchased from Sigma Aldrich, dried and activated in a reducing atmosphere.","matchedSynthesis":"Pd/AC","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P149","catalystId":"P149_PERF_001","name":"Pd/CB","activeMetals":"Pd","metalClass":"Pd-only","support":"CD-6008 carbon black (CB)","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto carbon black support.","matchedSynthesis":"Pd/CB","composition":"Pd","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P149","catalystId":"P149_PERF_002","name":"Pd/Vulcan","activeMetals":"Pd","metalClass":"Pd-only","support":"XC-72F Vulcan carbon black (Vulcan)","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto Vulcan carbon black support.","matchedSynthesis":"Pd/Vulcan","composition":"Pd","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P149","catalystId":"P149_PERF_003","name":"Pd/MWCNT","activeMetals":"Pd","metalClass":"Pd-only","support":"multiwall carbon nanotubes (MWCNT)","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto MWCNT support.","matchedSynthesis":"Pd/MWCNT","composition":"Pd","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P149","catalystId":"P149_PERF_004","name":"Pd/CB(t)","activeMetals":"Pd","metalClass":"Pd-only","support":"CD-6008 carbon black (CB)","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto carbon black support.","matchedSynthesis":"Pd/CB","composition":"Pd","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P149","catalystId":"P149_PERF_005","name":"Pd/Vulcan(t)","activeMetals":"Pd","metalClass":"Pd-only","support":"XC-72F Vulcan carbon black (Vulcan)","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto Vulcan carbon black support.","matchedSynthesis":"Pd/Vulcan","composition":"Pd","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P149","catalystId":"P149_PERF_006","name":"Pd/MWCNT(t)","activeMetals":"Pd","metalClass":"Pd-only","support":"multiwall carbon nanotubes (MWCNT)","method":"wet_impregnation","synthesis":"PVP-capped Pd nanoparticles were synthesized via the polyol method using ethylene glycol as solvent and reducing agent at 100 °C, then impregnated onto MWCNT support.","matchedSynthesis":"Pd/MWCNT","composition":"Pd","role":"catalyst for the dehydrogenation of formic acid"},{"paperId":"P151","catalystId":"P151_PERF_001","name":"AuT-MA","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"titania from metatitanic acid","method":"wet_impregnation","synthesis":"Titania was synthesized using metatitanic acid as precursor, calcined, and then impregnated with gold.","matchedSynthesis":"AuT-MA","composition":"Au","role":"reference catalyst"},{"paperId":"P151","catalystId":"P151_PERF_002","name":"Au2.3LT-CP","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P151","catalystId":"P151_PERF_003","name":"Au15LT-CP","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P151","catalystId":"P151_PERF_004","name":"AuXLT-WI","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"La-modified titania","method":"wet_impregnation","synthesis":"Lanthana was wet-impregnated onto anatase titania, dried and calcined to form the support; subsequently, gold was impregnated via pore volume method, aged, washed, and calcined.","matchedSynthesis":"AuXLT-WI","composition":"Au and La (X wt% lanthana)","role":"catalyst for formic acid decomposition"},{"paperId":"P152","catalystId":"P152_PERF_001","name":"Pd0.6Ag0.4@ZrO2/C/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P152","catalystId":"P152_PERF_002","name":"Pd0.6Ag0.4@C/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P152","catalystId":"P152_PERF_003","name":"Pd0.6Ag0.4@ZrO2/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P152","catalystId":"P152_PERF_004","name":"Pd0.6Ag0.4@UiO-66/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P152","catalystId":"P152_PERF_005","name":"Pd0.6Ag0.4@rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P152","catalystId":"P152_PERF_006","name":"Pd0.6Ag0.4@UiO-66","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P153","catalystId":"P153_PERF_001","name":"Pd 0.5 Cu 0.5 / MIL-101","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P153","catalystId":"P153_PERF_002","name":"Pd 0.2 Cu 0.8 / MIL-101","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P153","catalystId":"P153_PERF_003","name":"Pd 0.3 Cu 0.7 / MIL-101","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P153","catalystId":"P153_PERF_004","name":"Pd 0.7 Cu 0.3 / MIL-101","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P153","catalystId":"P153_PERF_005","name":"Pd 0.8 Cu 0.2 / MIL-101","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P153","catalystId":"P153_PERF_006","name":"Pd-Cu NCs (various ratios)","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P154","catalystId":"P154_PERF_001","name":"Fe@C-Pd","activeMetals":"Fe","metalClass":"Non-Pd or Pd-free","support":"Fe@C","method":"chemical_reduction_loading","synthesis":"Reduction of Pd2+ in Fe@C suspension using ethylene glycol.","matchedSynthesis":"Fe@C-Pd","composition":"Pd","role":"unmodified catalyst"},{"paperId":"P154","catalystId":"P154_PERF_002","name":"Fe@C-Pd-B","activeMetals":"Fe","metalClass":"Non-Pd or Pd-free","support":"Fe@C","method":"chemical_reduction_loading","synthesis":"Liquid-phase reduction in ice-water using Fe@C, DMAB, and Pd(NO3)2 as precursors.","matchedSynthesis":"Fe@C-Pd-B","composition":"Pd-B","role":"modified catalyst"},{"paperId":"P154","catalystId":"P154_PERF_003","name":"Fe@C-Pd-Ag","activeMetals":"Fe","metalClass":"Non-Pd or Pd-free","support":"Fe@C","method":"chemical_reduction_loading","synthesis":"Liquid-phase reduction using Fe@C, Pd(NO3)2, and AgNO3 as precursors.","matchedSynthesis":"Fe@C-Pd-Ag","composition":"Pd-Ag","role":"modified catalyst"},{"paperId":"P155","catalystId":"P155_PERF_001","name":"Au0.4Pd0.6/PEI-PDA@CNCs","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"PEI-PDA@CNC","method":"chemical_reduction_loading","synthesis":"Metal precursors were added to the modified CNC suspension, stirred at room temperature and in an ice bath, followed by reduction with NaBH4.","matchedSynthesis":"Au0.4Pd0.6/PEI-PDA@CNC","composition":"Au:Pd = 0.4:0.6","role":"optimized catalyst"},{"paperId":"P155","catalystId":"P155_PERF_002","name":"Au/PEI-PDA@CNC","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P155","catalystId":"P155_PERF_003","name":"Pd/PEI-PDA@CNC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P155","catalystId":"P155_PERF_004","name":"carrier-free Au0.4Pd0.6","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P155","catalystId":"P155_PERF_005","name":"unmodified Au0.4Pd0.6/CNC","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P156","catalystId":"P156_PERF_001","name":"Ti3C2Tx-250","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"Etching and thermal treatment","synthesis":"Ti3C2Tx-25 was treated in a muffle furnace with air at 250 °C for 1 h.","matchedSynthesis":"Ti3C2Tx-250","composition":"Ti","role":"catalyst"},{"paperId":"P156","catalystId":"P156_PERF_002","name":"Ti3C2Tx-25","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"Etching","synthesis":"Commercial Ti3AlC2 powder was immersed in 40% HF for 72 h at room temperature, washed with ethanol and water to pH 6.0, centrifuged, dried, and ultrasonicated in water for 24 h.","matchedSynthesis":"Ti3C2Tx-25","composition":"Ti","role":"catalyst"},{"paperId":"P156","catalystId":"P156_PERF_003","name":"Ti3C2Tx-150","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"Etching and thermal treatment","synthesis":"Ti3C2Tx-25 was treated in a muffle furnace with air at 150 °C for 1 h.","matchedSynthesis":"Ti3C2Tx-150","composition":"Ti","role":"catalyst"},{"paperId":"P156","catalystId":"P156_PERF_004","name":"Ti3C2Tx-350","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"Etching and thermal treatment","synthesis":"Ti3C2Tx-25 was treated in a muffle furnace with air at 350 °C for 1 h.","matchedSynthesis":"Ti3C2Tx-350","composition":"Ti","role":"catalyst"},{"paperId":"P156","catalystId":"P156_PERF_005","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P156","catalystId":"P156_PERF_006","name":"Pt/C","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P156","catalystId":"P156_PERF_007","name":"Ti2CTx-250","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"Etching and thermal treatment","synthesis":"Ti2CTx-25 was treated in a muffle furnace with air at 250 °C for 1 h.","matchedSynthesis":"Ti2CTx-250","composition":"Ti","role":"catalyst"},{"paperId":"P156","catalystId":"P156_PERF_008","name":"Ti2CTx-25","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"Etching","synthesis":"Commercial Ti2AlC powder was immersed in 16% HF for 72 h at room temperature, washed with ethanol and water to pH 6.0, centrifuged, dried, and ultrasonicated in water for 24 h.","matchedSynthesis":"Ti2CTx-25","composition":"Ti","role":"catalyst"},{"paperId":"P156","catalystId":"P156_PERF_009","name":"Ti2CTx-150","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"Etching and thermal treatment","synthesis":"Ti2CTx-25 was treated in a muffle furnace with air at 150 °C for 1 h.","matchedSynthesis":"Ti2CTx-150","composition":"Ti","role":"catalyst"},{"paperId":"P156","catalystId":"P156_PERF_010","name":"Ti2CTx-350","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"Etching and thermal treatment","synthesis":"Ti2CTx-25 was treated in a muffle furnace with air at 350 °C for 1 h.","matchedSynthesis":"Ti2CTx-350","composition":"Ti","role":"catalyst"},{"paperId":"P157","catalystId":"P157_PERF_001","name":"Pd0/CeO2","activeMetals":"Pd","metalClass":"Pd-only","support":"nanoceria (CeO2)","method":"wet_impregnation","synthesis":"Ceria was stirred in an aqueous solution of palladium(II) nitrate for 18 h, followed by dropwise addition of NaBH4 at room temperature. The resulting catalyst was isolated via centrifugation, washed with distilled water, and vacuum dried.","matchedSynthesis":"Pd0/CeO2","composition":"Pd","role":"main catalyst"},{"paperId":"P157","catalystId":"P157_PERF_002","name":"Pd0/SiO2, Pd0/Al2O3, Pd0/TiO2, Pd0/ZrO2, Pd0/HfO2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P158","catalystId":"P158_PERF_001","name":"AuPd/T-g-C3N4","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"T-g-C3N4","method":"wet_impregnation","synthesis":"Precursors dissolved in deionized water, support added, reduced with NaBH4 at room temperature for 12 h.","matchedSynthesis":"AuPd/T-g-C3N4","composition":"AuPd (molar ratio Au/Pd = 1/3)","role":"catalyst"},{"paperId":"P158","catalystId":"P158_PERF_002","name":"AuPd/S-g-C3N4","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"S-g-C3N4","method":"wet_impregnation","synthesis":"Precursors dissolved in deionized water, support added, reduced with NaBH4 at room temperature for 12 h.","matchedSynthesis":"AuPd/S-g-C3N4","composition":"AuPd (molar ratio Au/Pd = 1/3)","role":"catalyst"},{"paperId":"P158","catalystId":"P158_PERF_003","name":"AuPd/B-g-C3N4","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"B-g-C3N4","method":"wet_impregnation","synthesis":"Precursors dissolved in deionized water, support added, reduced with NaBH4 at room temperature for 12 h.","matchedSynthesis":"AuPd/B-g-C3N4","composition":"AuPd (molar ratio Au/Pd = 1/3)","role":"catalyst"},{"paperId":"P158","catalystId":"P158_PERF_004","name":"AuPd/g-C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"graphene nanoplatelets","method":"wet_impregnation","synthesis":"Precursors dissolved in deionized water, support added, reduced with NaBH4 at room temperature for 12 h.","matchedSynthesis":"AuPd/g-C","composition":"AuPd (molar ratio Au/Pd = 1/3)","role":"catalyst"},{"paperId":"P159","catalystId":"P159_PERF_001","name":"Pd/AC–CP (250 W, 10 min)","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon (AC)","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation followed by vacuum drying, H2 thermal reduction, and N2 RF cold plasma treatment.","matchedSynthesis":"Pd/AC-CP (250 W, 10 min)","composition":"Pd","role":"active catalyst"},{"paperId":"P159","catalystId":"P159_PERF_002","name":"Pd/AC–C","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon (AC)","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation, vacuum drying, and H2 thermal reduction.","matchedSynthesis":"Pd/AC-C","composition":"Pd","role":"comparison catalyst"},{"paperId":"P159","catalystId":"P159_PERF_003","name":"Pd/AC-P (250 W, 10 min)","activeMetals":"Pd","metalClass":"Pd-only","support":"activated carbon (AC)","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation, vacuum drying, and N2 RF cold plasma treatment without thermal reduction.","matchedSynthesis":"Pd/AC-P (250 W, 10 min)","composition":"Pd","role":"comparison catalyst"},{"paperId":"P160","catalystId":"P160_PERF_001","name":"Ni0.4@Pd0.6/NH2-Fe3O4","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P161","catalystId":"P161_PERF_001","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P161","catalystId":"P161_PERF_002","name":"Pd0.90Au0.10/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P161","catalystId":"P161_PERF_003","name":"Pd0.82Au0.18/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P161","catalystId":"P161_PERF_004","name":"Pd0.75Au0.25/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P161","catalystId":"P161_PERF_005","name":"Pd0.69Au0.31/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P161","catalystId":"P161_PERF_006","name":"Pd0.64Au0.36/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P161","catalystId":"P161_PERF_007","name":"Au/C","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"carbon powder","method":"chemical_reduction_loading","synthesis":"PdAu/C alloyed catalysts were synthesized via a modified coprecipitation-reduction method using carbon powder as support and Pd(H2PdCl4) and Au(HAuCl4) precursors.","matchedSynthesis":"PdAu/C","composition":"Pd and Au; atomic ratios of Au varied from 0 to 0.36 (samples: Pd/C, Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","role":"catalyst for room-temperature formic acid decomposition (FAD)"},{"paperId":"P162","catalystId":"P162_PERF_001","name":"PdAu/NH2-W18O49","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P162","catalystId":"P162_PERF_002","name":"Pd/NH2-W18O49","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P162","catalystId":"P162_PERF_003","name":"PdAu/NH2-WO3","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P162","catalystId":"P162_PERF_004","name":"PdAu/W18O49","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P162","catalystId":"P162_PERF_005","name":"Au/NH2-W18O49","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P162","catalystId":"P162_PERF_006","name":"bare W18O49","activeMetals":"W","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P163","catalystId":"P163_PERF_001","name":"PdCuCr/resin (Pd1Cu0.5Cr0.5/resin)","activeMetals":"Pd-Cu-Cr","metalClass":"Pd-based multimetal","support":"IRA96SB resin","method":"wet_impregnation","synthesis":"Resin was crushed, mixed with an aqueous solution of metal precursors, stirred at room temperature for 1 hour, evaporated under vacuum, dried overnight, and then prereduced with NaBH4.","matchedSynthesis":"PdCuCr/resin","composition":"Pd/Cu/Cr = 1:0.5:0.5","role":"ternary catalyst"},{"paperId":"P163","catalystId":"P163_PERF_002","name":"PdCu/resin (Pd1Cu0.5/resin)","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P163","catalystId":"P163_PERF_003","name":"Pd/resin","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P164","catalystId":"P164_PERF_001","name":"Pd/CS","activeMetals":"Pd","metalClass":"Pd-only","support":"Chitosan (CS)","method":"wet_impregnation","synthesis":"CS beads were impregnated with Pd precursor, converted to alcogels via ethanol exchange, reduced with NaBH4 in ethanol, and dried using supercritical CO2.","matchedSynthesis":"Pd/CS","composition":"Pd","role":"Catalyst for hydrogen generation from formate"},{"paperId":"P164","catalystId":"P164_PERF_002","name":"Pd/CS-GO2","activeMetals":"Pd","metalClass":"Pd-only","support":"Chitosan-Graphene Oxide (CS-GO)","method":"wet_impregnation","synthesis":"CS-GO beads were impregnated with Pd precursor, converted to alcogels via ethanol exchange, reduced with NaBH4 in ethanol, and dried using supercritical CO2.","matchedSynthesis":"Pd/CS-GO2","composition":"Pd","role":"Catalyst for hydrogen generation from formate"},{"paperId":"P164","catalystId":"P164_PERF_003","name":"10% Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P164","catalystId":"P164_PERF_004","name":"Pd/CS-GO1","activeMetals":"Pd","metalClass":"Pd-only","support":"Chitosan-Graphene Oxide (CS-GO)","method":"wet_impregnation","synthesis":"CS-GO beads were impregnated with Pd precursor, converted to alcogels via ethanol exchange, reduced with NaBH4 in ethanol, and dried using supercritical CO2.","matchedSynthesis":"Pd/CS-GO1","composition":"Pd","role":"Catalyst for hydrogen generation from formate"},{"paperId":"P164","catalystId":"P164_PERF_005","name":"Pd/CS-GO3","activeMetals":"Pd","metalClass":"Pd-only","support":"Chitosan-Graphene Oxide (CS-GO)","method":"wet_impregnation","synthesis":"CS-GO beads were impregnated with Pd precursor, converted to alcogels via ethanol exchange, reduced with NaBH4 in ethanol, and dried using supercritical CO2.","matchedSynthesis":"Pd/CS-GO3","composition":"Pd","role":"Catalyst for hydrogen generation from formate"},{"paperId":"P165","catalystId":"P165_PERF_001","name":"Pd/PPy-S1","activeMetals":"Pd","metalClass":"Pd-only","support":"polypyrrole (PPy)","method":"wet_impregnation","synthesis":"PPy-S1 was dispersed in deionized water, followed by dropwise addition of H2PdCl4 solution. After stirring for 30 min, sodium formate (HCOONa) solution was added as a reducing agent and stirred at room temperature for 5 hours.","matchedSynthesis":"Pd/PPy-S1","composition":"Pd","role":"catalyst for hydrogen production from formic acid"},{"paperId":"P165","catalystId":"P165_PERF_002","name":"Pd/PPy-S2","activeMetals":"Pd","metalClass":"Pd-only","support":"polypyrrole (PPy)","method":"wet_impregnation","synthesis":"Commercial PPy-S2 was dispersed in deionized water, followed by dropwise addition of H2PdCl4 solution. After stirring for 30 min, sodium formate (HCOONa) solution was added as a reducing agent and stirred at room temperature for 5 hours.","matchedSynthesis":"Pd/PPy-S2","composition":"Pd","role":"comparison catalyst for hydrogen production from formic acid"},{"paperId":"P166","catalystId":"P166_PERF_001","name":"Pd/NMC-8","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped mesoporous carbon (NMC-8)","method":"chemical_reduction_loading","synthesis":"Support fabricated by hard templating with Zr-SBA-15, template removed via HF washing, and nitridated under ammonia flow at 873 K. Palladium was then loaded using wet-chemical reduction.","matchedSynthesis":"Pd/NMC-8","composition":"Pd","role":"bifunctional catalyst for formate-based hydrogen storage"},{"paperId":"P166","catalystId":"P166_PERF_002","name":"Pd/MC-8","activeMetals":"Pd","metalClass":"Pd-only","support":"mesoporous carbon (MC-8)","method":"chemical_reduction_loading","synthesis":"Support fabricated by hard templating with Zr-SBA-15, template removed via HF washing, and carbonized under nitrogen flow at 873 K. Palladium was then loaded using wet-chemical reduction.","matchedSynthesis":"Pd/MC-8","composition":"Pd","role":"reference catalyst"},{"paperId":"P166","catalystId":"P166_PERF_003","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P166","catalystId":"P166_PERF_004","name":"Pd/NMC-9","activeMetals":"Pd","metalClass":"Pd-only","support":"nitrogen-doped mesoporous carbon (NMC-9)","method":"chemical_reduction_loading","synthesis":"Support fabricated by hard templating with Zr-SBA-15, template removed via HF washing, and nitridated under ammonia flow at 973 K. Palladium was then loaded using wet-chemical reduction.","matchedSynthesis":"Pd/NMC-9","composition":"Pd","role":"bifunctional catalyst for formate-based hydrogen storage"},{"paperId":"P167","catalystId":"P167_PERF_001","name":"Pd/BCNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"BCNTs","method":"wet_impregnation","synthesis":"Acidification of CNTs, hydrothermal treatment with boric acid to form BCNTs, followed by impregnation with H2PdCl4 and NaBH4 reduction.","matchedSynthesis":"Pd/BCNTs","composition":"Pd","role":"catalyst for formic acid hydrogen production"},{"paperId":"P167","catalystId":"P167_PERF_002","name":"Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"CNTs","method":"wet_impregnation","synthesis":"Impregnation of unmodified CNTs with H2PdCl4 followed by NaBH4 reduction.","matchedSynthesis":"Pd/CNTs","composition":"Pd","role":"catalyst for formic acid hydrogen production"},{"paperId":"P167","catalystId":"P167_PERF_003","name":"Pd/NCNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"NCNTs","method":"wet_impregnation","synthesis":"Acidification of CNTs, hydrothermal treatment with urea to form NCNTs, followed by impregnation with H2PdCl4 and NaBH4 reduction.","matchedSynthesis":"Pd/NCNTs","composition":"Pd","role":"catalyst for formic acid hydrogen production"},{"paperId":"P167","catalystId":"P167_PERF_004","name":"Pd/OCNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"OCNTs","method":"wet_impregnation","synthesis":"Acidification of CNTs to form OCNTs, followed by impregnation with H2PdCl4 and NaBH4 reduction.","matchedSynthesis":"Pd/OCNTs","composition":"Pd","role":"catalyst for formic acid hydrogen production"},{"paperId":"P168","catalystId":"P168_PERF_001","name":"KCC-1/IL/PbS","activeMetals":"Pb","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"adsorption_or_loading","synthesis":"KCC-1/IL NPs were dispersed in lead dichloride solution for 0.5 h to adsorb Pb2+ ions, washed, then dispersed in thioacetamide solution and heated at 45 °C for 1 h.","matchedSynthesis":"KCC-1/IL/PbS","composition":"PbS","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_002","name":"KCC-1/IL/ZnS","activeMetals":"Zn","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"adsorption_or_loading","synthesis":"Similar to KCC-1/IL/PbS synthesis using Zn2+ and thioacetamide.","matchedSynthesis":"KCC-1/IL/ZnS","composition":"ZnS","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_003","name":"KCC-1/IL/HgS","activeMetals":"Hg","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"adsorption_or_loading","synthesis":"Similar to KCC-1/IL/PbS synthesis using Hg2+ and thioacetamide.","matchedSynthesis":"KCC-1/IL/HgS","composition":"HgS","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_004","name":"KCC-1/IL/Au","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"chemical_reduction_loading","synthesis":"KCC-1/IL suspension was stirred with HAuCl4.3H2O for 1 h at room temperature, followed by dropwise addition of ice-cold NaBH4.","matchedSynthesis":"KCC-1/IL/Au","composition":"Au","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_005","name":"KCC-1/IL/Cu","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"adsorption_or_loading","synthesis":"KCC-1/IL was dispersed in water, Cu(NO3)2.3H2O added and sonicated for 2 h, then stirred at room temperature for 24 h.","matchedSynthesis":"KCC-1/IL/Cu","composition":"Cu","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_006","name":"KCC-1/IL/Pd","activeMetals":"Pd","metalClass":"Pd-only","support":"KCC-1/IL","method":"adsorption_or_loading","synthesis":"KCC-1/IL was dispersed in water, PdCl2 added and sonicated for 2 h, then stirred at room temperature for 24 h.","matchedSynthesis":"KCC-1/IL/Pd","composition":"Pd","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_007","name":"KCC-1/IL/Ag","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"chemical_reduction_loading","synthesis":"KCC-1/IL was dispersed in water, AgNO3 added and stirred for 30 min, then NaBH4 solution added dropwise.","matchedSynthesis":"KCC-1/IL/Ag","composition":"Ag","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_008","name":"KCC-1/IL/Pt","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"chemical_reduction_loading","synthesis":"KCC-1/IL was dispersed in water, H2PtCl6 added and stirred for 30 min, then NaBH4 solution added dropwise.","matchedSynthesis":"KCC-1/IL/Pt","composition":"Pt","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_009","name":"KCC-1/IL/Mn","activeMetals":"Mn","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"adsorption_or_loading","synthesis":"KCC-1/IL was dispersed in water, Mn(NO3)2 added and sonicated for 2 h, then stirred at room temperature for 24 h.","matchedSynthesis":"KCC-1/IL/Mn","composition":"Mn","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_010","name":"KCC-1/IL/Ni","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"adsorption_or_loading","synthesis":"KCC-1/IL was dispersed in water, Ni(NO3)2 added and sonicated for 2 h, then stirred at room temperature for 24 h.","matchedSynthesis":"KCC-1/IL/Ni","composition":"Ni","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_011","name":"KCC-1/IL/Zn","activeMetals":"Zn","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"adsorption_or_loading","synthesis":"Similar to KCC-1/IL/PbS synthesis using Zn2+ and thioacetamide.","matchedSynthesis":"KCC-1/IL/ZnS","composition":"ZnS","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P168","catalystId":"P168_PERF_012","name":"KCC-1/IL/Co","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"KCC-1/IL","method":"chemical_reduction_loading","synthesis":"KCC-1/IL was dispersed in water, CoCl2 added and stirred for 1 h at room temperature, then ice-cold NH4Cl solution (0.1 mmol) delivered dropwise.","matchedSynthesis":"KCC-1/IL/Co","composition":"Co","role":"heterogeneous catalyst for the dehydrogenation of formic acid"},{"paperId":"P169","catalystId":"P169_PERF_001","name":"Pd/hatnCTF","activeMetals":"Pd","metalClass":"Pd-only","support":"hatnCTF","method":"wet_impregnation","synthesis":"The hatnCTF support was synthesized using the corresponding linker and ZnCl2 at 773 K, followed by impregnation with a Pd(acac)2 solution in acetone and final pretreatment.","matchedSynthesis":"Pd/hatnCTF","composition":"Pd","role":"catalyst"},{"paperId":"P169","catalystId":"P169_PERF_002","name":"Pd/acacCTF","activeMetals":"Pd","metalClass":"Pd-only","support":"acacCTF","method":"wet_impregnation","synthesis":"The acacCTF support was synthesized using the corresponding linker and ZnCl2 at 773 K, followed by impregnation with a Pd(acac)2 solution in acetone and final pretreatment.","matchedSynthesis":"Pd/acacCTF","composition":"Pd","role":"catalyst"},{"paperId":"P169","catalystId":"P169_PERF_003","name":"Pd/g-C3N4","activeMetals":"Pd","metalClass":"Pd-only","support":"g-C3N4","method":"wet_impregnation","synthesis":"g-C3N4 was synthesized via heat treatment of dicyandiamide and chemical exfoliation in H2SO4, followed by impregnation with Pd(acac)2 in acetone and final pretreatment.","matchedSynthesis":"Pd/g-C3N4","composition":"Pd","role":"comparison catalyst"},{"paperId":"P170","catalystId":"P170_PERF_001","name":"Pd/AC_C3N4(19)","activeMetals":"Pd","metalClass":"Pd-only","support":"AC","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","matchedSynthesis":"Pd/AC","composition":"Pd","role":"reference"},{"paperId":"P170","catalystId":"P170_PERF_002","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","support":"AC","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","matchedSynthesis":"Pd/AC","composition":"Pd","role":"reference"},{"paperId":"P170","catalystId":"P170_PERF_003","name":"Pd/C3N4","activeMetals":"Pd","metalClass":"Pd-only","support":"g-C3N4","method":"wet_impregnation","synthesis":"Standard impregnation of g-C3N4 with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","matchedSynthesis":"Pd/C3N4","composition":"Pd","role":"reference"},{"paperId":"P170","catalystId":"P170_PERF_004","name":"Pd/AC_C3N4(3)","activeMetals":"Pd","metalClass":"Pd-only","support":"AC","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","matchedSynthesis":"Pd/AC","composition":"Pd","role":"reference"},{"paperId":"P170","catalystId":"P170_PERF_005","name":"Pd/AC_C3N4(10)","activeMetals":"Pd","metalClass":"Pd-only","support":"AC","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","matchedSynthesis":"Pd/AC","composition":"Pd","role":"reference"},{"paperId":"P170","catalystId":"P170_PERF_006","name":"Pd/AC_C3N4(22)","activeMetals":"Pd","metalClass":"Pd-only","support":"AC","method":"wet_impregnation","synthesis":"Standard impregnation of AC with Pd(OAc)2 in acetone, followed by stirring, filtering, washing, and drying. No ex situ reduction performed.","matchedSynthesis":"Pd/AC","composition":"Pd","role":"reference"},{"paperId":"P171","catalystId":"P171_PERF_001","name":"0.2% Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"bamboo-like nitrogen-doped carbon nanotubes (N-CNTs)","method":"incipient_wetness_impregnation","synthesis":"N-CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","matchedSynthesis":"Pd/N-CNTs","composition":"Pd","role":"hydrogen production via gas phase formic acid decomposition"},{"paperId":"P171","catalystId":"P171_PERF_002","name":"0.5% Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"bamboo-like nitrogen-doped carbon nanotubes (N-CNTs)","method":"incipient_wetness_impregnation","synthesis":"N-CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","matchedSynthesis":"Pd/N-CNTs","composition":"Pd","role":"hydrogen production via gas phase formic acid decomposition"},{"paperId":"P171","catalystId":"P171_PERF_003","name":"1% Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"bamboo-like nitrogen-doped carbon nanotubes (N-CNTs)","method":"incipient_wetness_impregnation","synthesis":"N-CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","matchedSynthesis":"Pd/N-CNTs","composition":"Pd","role":"hydrogen production via gas phase formic acid decomposition"},{"paperId":"P171","catalystId":"P171_PERF_004","name":"2% Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"bamboo-like nitrogen-doped carbon nanotubes (N-CNTs)","method":"incipient_wetness_impregnation","synthesis":"N-CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","matchedSynthesis":"Pd/N-CNTs","composition":"Pd","role":"hydrogen production via gas phase formic acid decomposition"},{"paperId":"P171","catalystId":"P171_PERF_005","name":"0.2% Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nanotubes (CNTs)","method":"incipient_wetness_impregnation","synthesis":"CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","matchedSynthesis":"Pd/CNTs","composition":"Pd","role":"comparison catalysts for hydrogen production via gas phase formic acid decomposition"},{"paperId":"P171","catalystId":"P171_PERF_006","name":"2% Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nanotubes (CNTs)","method":"incipient_wetness_impregnation","synthesis":"CNTs were pre-dried in Ar at 170 °C, impregnated with Pd acetate–acetone solution, dried in air at 105 °C for 8 h, and reduced in H2/Ar flow at 200 °C for 1 h.","matchedSynthesis":"Pd/CNTs","composition":"Pd","role":"comparison catalysts for hydrogen production via gas phase formic acid decomposition"},{"paperId":"P172","catalystId":"P172_PERF_001","name":"Pd/BN_{C,O}-1-A","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P172","catalystId":"P172_PERF_002","name":"Pd/BN_{C,O}-3","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P172","catalystId":"P172_PERF_003","name":"Pd/BN_{C,O}-0","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P173","catalystId":"P173_PERF_001","name":"Pd/PNCC","activeMetals":"Pd","metalClass":"Pd-only","support":"porous nitrogen-doped carbon cages (PNCC)","method":"wet_impregnation","synthesis":"ZIF-8@ZIF-67 was mixed with KCl and pyrolyzed at 750 °C under N2 to form PNCC after HF etching. Pd nanoparticles were then immobilized via sonication of K2PdCl4 followed by NaBH4 reduction.","matchedSynthesis":"Pd/PNCC","composition":"Pd","role":"active catalyst"},{"paperId":"P173","catalystId":"P173_PERF_002","name":"Pd/ZIF-8@ZIF-67","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P173","catalystId":"P173_PERF_003","name":"Pd/KB","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P173","catalystId":"P173_PERF_004","name":"Pd/GO","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P173","catalystId":"P173_PERF_005","name":"Pd/super P","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P173","catalystId":"P173_PERF_006","name":"Pd/CNT","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P173","catalystId":"P173_PERF_007","name":"Pd/NCC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P173","catalystId":"P173_PERF_008","name":"Pd and PNCC mixture","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P174","catalystId":"P174_PERF_001","name":"Pd/CNT-base-4","activeMetals":"Pd","metalClass":"Pd-only","support":"Carbon Nanotubes (CNTs)","method":"wet_impregnation","synthesis":"CNTs were dispersed in water, Na2PdCl4 solution was added, pH adjusted to 1 using NaOH, stirred, dried, and reduced under H2/Ar.","matchedSynthesis":"Pd/CNT","composition":"Pd","role":"Catalyst for formic acid dehydrogenation"},{"paperId":"P174","catalystId":"P174_PERF_002","name":"Pd/CNT-acid","activeMetals":"Pd","metalClass":"Pd-only","support":"Carbon Nanotubes (CNTs)","method":"wet_impregnation","synthesis":"CNTs were pretreated with HNO3 reflux. The resulting support was dispersed in water, Na2PdCl4 solution was added, pH adjusted to 1 using NaOH, stirred, dried, and reduced under H2/Ar.","matchedSynthesis":"Pd/CNT-acid","composition":"Pd","role":"Catalyst for formic acid dehydrogenation"},{"paperId":"P174","catalystId":"P174_PERF_003","name":"Pd/CNT","activeMetals":"Pd","metalClass":"Pd-only","support":"Carbon Nanotubes (CNTs)","method":"wet_impregnation","synthesis":"CNTs were dispersed in water, Na2PdCl4 solution was added, pH adjusted to 1 using NaOH, stirred, dried, and reduced under H2/Ar.","matchedSynthesis":"Pd/CNT","composition":"Pd","role":"Catalyst for formic acid dehydrogenation"},{"paperId":"P175","catalystId":"P175_PERF_001","name":"Pd/N,P-C","activeMetals":"Pd","metalClass":"Pd-only","support":"N,P-co-doped carbon (N,P-C)","method":"wet_impregnation","synthesis":"N,P-C support was synthesized by pyrolyzing a mixture of 1,10-phenanthroline (PAH) and triphenylphosphine (TPP) with an MgO template. Pd was loaded via impregnation of PdCl2 in HCl, followed by pH adjustment to ~10 and reduction with NaBH4.","matchedSynthesis":"Pd/N,P-C","composition":"Pd","role":"Catalyst for reversible formate-based chemical hydrogen storage"},{"paperId":"P175","catalystId":"P175_PERF_002","name":"Pd/NC","activeMetals":"Pd","metalClass":"Pd-only","support":"Nitrogen-doped porous carbon (NC)","method":"wet_impregnation","synthesis":"Support synthesized using PAH via the same method as N,P-C; metal loading followed the same procedure as Pd/N,P-C.","matchedSynthesis":"Pd/NC","composition":"Pd","role":"Comparison catalyst"},{"paperId":"P175","catalystId":"P175_PERF_003","name":"Pd/PC","activeMetals":"Pd","metalClass":"Pd-only","support":"Phosphorus-doped porous carbon (PC)","method":"wet_impregnation","synthesis":"Support synthesized using TPP via the same method as N,P-C; metal loading followed the same procedure as Pd/N,P-C.","matchedSynthesis":"Pd/PC","composition":"Pd","role":"Comparison catalyst"},{"paperId":"P175","catalystId":"P175_PERF_004","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","support":"Activated carbon (AC)","method":"wet_impregnation","synthesis":"Metal loading followed the same procedure as Pd/N,P-C.","matchedSynthesis":"Pd/AC","composition":"Pd","role":"Comparison catalyst"},{"paperId":"P176","catalystId":"P176_PERF_001","name":"Pd/NHPC-NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"amino-functionalized hierarchically porous carbon (NHPC-NH2)","method":"chemical_reduction_loading","synthesis":"NHPC was functionalized with APTMS to form NHPC-NH2; PdCl2 aqueous solution was then added under magnetic stirring, followed by reduction using NaBH4.","matchedSynthesis":"Pd/NHPC-NH2","composition":"Pd","role":"active catalyst"},{"paperId":"P176","catalystId":"P176_PERF_002","name":"Pd/NHPC","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped hierarchically porous carbon (NHPC)","method":"chemical_reduction_loading","synthesis":"Similar to Pd/NHPC-NH2 but without APTMS functionalization of the support.","matchedSynthesis":"Pd/NHPC","composition":"Pd","role":"control catalyst"},{"paperId":"P176","catalystId":"P176_PERF_003","name":"Pd/NHPC H2","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped hierarchically porous carbon (NHPC)","method":"chemical_reduction_loading","synthesis":"Pd deposited on NHPC and reduced using hydrogen gas.","matchedSynthesis":"Pd/NHPC H2","composition":"Pd","role":"comparison catalyst (particle size effect)"},{"paperId":"P177","catalystId":"P177_PERF_001","name":"Pd/HNDC (20 wt% Pd)","activeMetals":"Pd","metalClass":"Pd-only","support":"HF-etched N-doped carbon (HNDC)","method":"chemical_reduction_loading","synthesis":"HNDC support and Na2PdCl4 were dispersed in DI water via ultrasonication, stirred for 3 h, reduced with NaBH4, centrifuged, washed, and dried.","matchedSynthesis":"Pd/HNDC","composition":"Pd","role":"optimized catalyst"},{"paperId":"P177","catalystId":"P177_PERF_002","name":"Pd/HNDC (10 wt% Pd)","activeMetals":"Pd","metalClass":"Pd-only","support":"HF-etched N-doped carbon (HNDC)","method":"chemical_reduction_loading","synthesis":"HNDC support and Na2PdCl4 were dispersed in DI water via ultrasonication, stirred for 3 h, reduced with NaBH4, centrifuged, washed, and dried.","matchedSynthesis":"Pd/HNDC","composition":"Pd","role":"optimized catalyst"},{"paperId":"P177","catalystId":"P177_PERF_003","name":"Pd/HNDC (15 wt% Pd)","activeMetals":"Pd","metalClass":"Pd-only","support":"HF-etched N-doped carbon (HNDC)","method":"chemical_reduction_loading","synthesis":"HNDC support and Na2PdCl4 were dispersed in DI water via ultrasonication, stirred for 3 h, reduced with NaBH4, centrifuged, washed, and dried.","matchedSynthesis":"Pd/HNDC","composition":"Pd","role":"optimized catalyst"},{"paperId":"P177","catalystId":"P177_PERF_004","name":"Pd/HNDC (25 wt% Pd)","activeMetals":"Pd","metalClass":"Pd-only","support":"HF-etched N-doped carbon (HNDC)","method":"chemical_reduction_loading","synthesis":"HNDC support and Na2PdCl4 were dispersed in DI water via ultrasonication, stirred for 3 h, reduced with NaBH4, centrifuged, washed, and dried.","matchedSynthesis":"Pd/HNDC","composition":"Pd","role":"optimized catalyst"},{"paperId":"P177","catalystId":"P177_PERF_005","name":"Pd/ZrO2/NDC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P178","catalystId":"P178_PERF_001","name":"Pd/MCTP-1","activeMetals":"Pd","metalClass":"Pd-only","support":"MCTP-1","method":"chemical_reduction_loading","synthesis":"MCTP-1 support was synthesized via Friedel-Crafts reaction. Pd nanoparticles were loaded using a deposition-reduction method where the anionic palladium precursor was deposited, followed by the addition of a strong base to form Pd(OH)2 before reduction.","matchedSynthesis":"Pd/MCTP-1","composition":"Pd","role":"catalyst for H2 production via formic acid decomposition"},{"paperId":"P178","catalystId":"P178_PERF_002","name":"Pd/MIL-101-DETA","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P178","catalystId":"P178_PERF_003","name":"Pd/UiO-66-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P179","catalystId":"P179_PERF_001","name":"Pd/BCNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"BCNTs","method":"wet_impregnation","synthesis":"Acidification of CNTs, B-doping via hydrothermal treatment with boric acid, followed by impregnation with H2PdCl4 and NaBH4 reduction.","matchedSynthesis":"Pd/BCNTs","composition":"Pd","role":"catalyst for formic acid hydrogen production"},{"paperId":"P179","catalystId":"P179_PERF_002","name":"Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"CNTs","method":"wet_impregnation","synthesis":"Impregnation of unmodified CNTs with H2PdCl4 followed by NaBH4 reduction at ambient temperature.","matchedSynthesis":"Pd/CNTs","composition":"Pd","role":"catalyst for formic acid hydrogen production"},{"paperId":"P179","catalystId":"P179_PERF_003","name":"Pd/NCNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"NCNTs","method":"wet_impregnation","synthesis":"Acidification of CNTs, N-doping via hydrothermal treatment with urea, followed by impregnation with H2PdCl4 and NaBH4 reduction.","matchedSynthesis":"Pd/NCNTs","composition":"Pd","role":"catalyst for formic acid hydrogen production"},{"paperId":"P179","catalystId":"P179_PERF_004","name":"Pd/OCNTs","activeMetals":"Pd","metalClass":"Pd-only","support":"OCNTs","method":"wet_impregnation","synthesis":"Acidification of CNTs to form OCNTs, followed by impregnation with H2PdCl4 and NaBH4 reduction at ambient temperature.","matchedSynthesis":"Pd/OCNTs","composition":"Pd","role":"catalyst for formic acid hydrogen production"},{"paperId":"P180","catalystId":"P180_PERF_001","name":"10 wt% Pd*CeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"CeO2 nanospheres","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","matchedSynthesis":"Pd*CeO2","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P180","catalystId":"P180_PERF_002","name":"0.5 wt% Pd*CeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"CeO2 nanospheres","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","matchedSynthesis":"Pd*CeO2","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P180","catalystId":"P180_PERF_003","name":"1 wt% Pd*CeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"CeO2 nanospheres","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","matchedSynthesis":"Pd*CeO2","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P180","catalystId":"P180_PERF_004","name":"3 wt% Pd*CeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"CeO2 nanospheres","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","matchedSynthesis":"Pd*CeO2","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P180","catalystId":"P180_PERF_005","name":"5 wt% Pd*CeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"CeO2 nanospheres","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","matchedSynthesis":"Pd*CeO2","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P180","catalystId":"P180_PERF_006","name":"CeO2","activeMetals":"Ce","metalClass":"Non-Pd or Pd-free","support":"CeO2 nanospheres","method":"deposition_precipitation","synthesis":"CeO2 nanospheres were first synthesized via a hydrothermal method. Pd was then loaded onto the support using a deposition-precipitation method at pH 9, followed by drying and calcination.","matchedSynthesis":"Pd*CeO2","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P181","catalystId":"P181_PERF_001","name":"7C","activeMetals":"Pd","metalClass":"Pd-only","support":"SiC monolith foam / silicon wafer","method":"Magnetron sputtering","synthesis":"One-step co-deposition using a single magnetron with a homemade target (C target with 5 Pd strips) under Ar process gas (10-2 mbar working pressure) and bias voltage (150–220 V).","matchedSynthesis":"7C","composition":"Pd:C = 93:7 (at%)","role":"catalyst for formic acid decomposition"},{"paperId":"P181","catalystId":"P181_PERF_002","name":"12C","activeMetals":"Pd","metalClass":"Pd-only","support":"SiC monolith foam / silicon wafer","method":"Magnetron sputtering","synthesis":"One-step co-deposition using a single magnetron with a homemade target (C target with 5 Pd strips) under Ar process gas (10-2 mbar working pressure) and bias voltage (150–220 V).","matchedSynthesis":"12C","composition":"Pd:C = 88:12 (at%)","role":"catalyst for formic acid decomposition"},{"paperId":"P181","catalystId":"P181_PERF_003","name":"65C","activeMetals":"Pd","metalClass":"Pd-only","support":"SiC monolith foam / silicon wafer","method":"Magnetron sputtering","synthesis":"One-step co-deposition using a two-magnetron configuration under Ar process gas (10-2 mbar working pressure) and bias voltage (150–220 V). Magnetron 1 used a homemade target (C with 2 Pd strips); Magnetron 2 used a single carbon target.","matchedSynthesis":"65C","composition":"Pd:C = 35:65 (at%)","role":"catalyst for formic acid decomposition"},{"paperId":"P181","catalystId":"P181_PERF_004","name":"Pd particles supported on carbon (Norit)","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P182","catalystId":"P182_PERF_001","name":"Pd(NO3)2","activeMetals":"Pd","metalClass":"Pd-only","method":"chemical_reduction_loading","synthesis":"Pd(NO3)2 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","matchedSynthesis":"Pd(NO3)2","composition":"Pd","role":"Catalyst precursor"},{"paperId":"P182","catalystId":"P182_PERF_002","name":"PdCl2","activeMetals":"Pd","metalClass":"Pd-only","method":"chemical_reduction_loading","synthesis":"PdCl2 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","matchedSynthesis":"PdCl2","composition":"Pd","role":"Catalyst precursor"},{"paperId":"P182","catalystId":"P182_PERF_003","name":"Na2PdCl4","activeMetals":"Pd","metalClass":"Pd-only","method":"chemical_reduction_loading","synthesis":"Na2PdCl4 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","matchedSynthesis":"Na2PdCl4","composition":"Pd","role":"Catalyst precursor"},{"paperId":"P182","catalystId":"P182_PERF_004","name":"Pd(NH3)4Cl2","activeMetals":"Pd","metalClass":"Pd-only","method":"chemical_reduction_loading","synthesis":"Pd(NH3)4Cl2 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","matchedSynthesis":"Pd(NH3)4Cl2","composition":"Pd","role":"Catalyst precursor"},{"paperId":"P182","catalystId":"P182_PERF_005","name":"Pd(OAc)2","activeMetals":"Pd","metalClass":"Pd-only","method":"chemical_reduction_loading","synthesis":"Pd(OAc)2 was dissolved in distilled water, purged with nitrogen, and heated to 60 °C. An aqueous mixture of formic acid and sodium formate was then injected into the reactor.","matchedSynthesis":"Pd(OAc)2","composition":"Pd","role":"Catalyst precursor"},{"paperId":"P183","catalystId":"P183_PERF_001","name":"Pd@UIO-66/NH2-SEP","activeMetals":"Pd","metalClass":"Pd-only","support":"UIO-66/NH2-SEP","method":"wet_impregnation","synthesis":"UIO-66 was synthesized on NH2-SEP via hydrothermal method (393 K, 48 h). Pd nanoparticles were then loaded onto the dual support using an anionic exchange method followed by chemical reduction with NaBH4.","matchedSynthesis":"Pd@UIO-66/NH2-SEP","composition":"Pd","role":"main catalyst"},{"paperId":"P183","catalystId":"P183_PERF_002","name":"Pd@NH2-SEP","activeMetals":"Pd","metalClass":"Pd-only","support":"NH2-SEP","method":"wet_impregnation","synthesis":"Synthesized using the same anionic exchange and chemical reduction process as Pd@UIO-66/NH2-SEP, replacing the support with NH2-SEP.","matchedSynthesis":"Pd@NH2-SEP","composition":"Pd","role":"comparison catalyst"},{"paperId":"P183","catalystId":"P183_PERF_003","name":"Pd@UIO-66","activeMetals":"Pd","metalClass":"Pd-only","support":"UIO-66","method":"wet_impregnation","synthesis":"Synthesized using the same anionic exchange and chemical reduction process as Pd@UIO-66/NH2-SEP, replacing the support with UIO-66.","matchedSynthesis":"Pd@UIO-66","composition":"Pd","role":"comparison catalyst"},{"paperId":"P184","catalystId":"P184_PERF_001","name":"Pd0.8Au0.2/UiO-66-(NH2)2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"UiO-66-(NH2)2","method":"wet_impregnation","synthesis":"UiO-66-(NH2)2 was suspended in n-hexane, followed by dropwise addition of aqueous Pd and Au precursors, drying, and reduction with NaBH4.","matchedSynthesis":"Pd0.8Au0.2/UiO-66-(NH2)2","composition":"Pd:Au = 4:1","role":"active catalyst"},{"paperId":"P184","catalystId":"P184_PERF_002","name":"Pd0.8Au0.2/UiO-66-NH2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"UiO-66-(NH2)2","method":"wet_impregnation","synthesis":"UiO-66-(NH2)2 was suspended in n-hexane, followed by dropwise addition of aqueous Pd and Au precursors, drying, and reduction with NaBH4.","matchedSynthesis":"Pd0.8Au0.2/UiO-66-(NH2)2","composition":"Pd:Au = 4:1","role":"active catalyst"},{"paperId":"P185","catalystId":"P185_PERF_001","name":"Pd60Au40/ZrSBA-15-AP","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"ZrSBA-15","method":"incipient_wetness_impregnation","synthesis":"Pristine ZrSBA-15 was impregnated with an aqueous solution of Pd and Au precursors, followed by liquid-phase reduction using NaBH4.","matchedSynthesis":"Pd60Au40/ZrSBA-15","composition":"Pd:Au = 60:40","role":"control catalyst (pristine support)"},{"paperId":"P185","catalystId":"P185_PERF_002","name":"Pd60Au40/ZrSBA-15","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"ZrSBA-15","method":"incipient_wetness_impregnation","synthesis":"Pristine ZrSBA-15 was impregnated with an aqueous solution of Pd and Au precursors, followed by liquid-phase reduction using NaBH4.","matchedSynthesis":"Pd60Au40/ZrSBA-15","composition":"Pd:Au = 60:40","role":"control catalyst (pristine support)"},{"paperId":"P185","catalystId":"P185_PERF_003","name":"Pd60Au40/ZrSBA-15-MAP, Pd60Au40/ZrSBA-15-AEAEAP, Pd60Au40/ZrSBA-15-AEAP, Pd60Au40/ZrSBA-15-DMAP","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"ZrSBA-15","method":"incipient_wetness_impregnation","synthesis":"Amine-modified ZrSBA-15 was impregnated with an aqueous solution of Pd and Au precursors, followed by liquid-phase reduction using NaBH4.","matchedSynthesis":"Pd60Au40/ZrSBA-15-AEAP","composition":"Pd:Au = 60:40","role":"active catalyst"},{"paperId":"P186","catalystId":"P186_PERF_001","name":"1Pd-SS","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P186","catalystId":"P186_PERF_002","name":"5Pd-SS","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P186","catalystId":"P186_PERF_003","name":"15Pd-SS","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P186","catalystId":"P186_PERF_004","name":"35Pd-SD","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P186","catalystId":"P186_PERF_005","name":"15Pd-SD","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P186","catalystId":"P186_PERF_006","name":"5Pd-Lean","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P187","catalystId":"P187_PERF_001","name":"Pd/ZrO2-F","activeMetals":"Pd","metalClass":"Pd-only","support":"ZrO2 (hollow nanoframes)","method":"wet_impregnation","synthesis":"ZrO2-F support was prepared via hydrothermal method and calcined; Pd was loaded via impregnation of H2PdCl4, reduced with NaBH4, and vacuum dried.","matchedSynthesis":"Pd/ZrO2-F","composition":"Pd","role":"catalyst"},{"paperId":"P187","catalystId":"P187_PERF_002","name":"Pd/ZrO2-S","activeMetals":"Pd","metalClass":"Pd-only","support":"ZrO2 (hollow spheres)","method":"wet_impregnation","synthesis":"ZrO2-S support was prepared via hydrothermal method and calcined; Pd was loaded via impregnation of H2PdCl4, reduced with NaBH4, and vacuum dried.","matchedSynthesis":"Pd/ZrO2-S","composition":"Pd","role":"catalyst"},{"paperId":"P187","catalystId":"P187_PERF_003","name":"Pd/ZrO2-P","activeMetals":"Pd","metalClass":"Pd-only","support":"ZrO2 (irregular particles)","method":"wet_impregnation","synthesis":"ZrO2-P support was prepared via precipitation and calcined; Pd was loaded via impregnation of H2PdCl4, reduced with NaBH4, and vacuum dried.","matchedSynthesis":"Pd/ZrO2-P","composition":"Pd","role":"catalyst"},{"paperId":"P188","catalystId":"P188_PERF_001","name":"Au2Pd3@(P)N-C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"nitrogen (N)-doped porous carbon","method":"phosphate-mediation approach","synthesis":"ZIF-8 was carbonized at 1000 °C and acid etched to produce N-doped porous carbon (N-C). N-C underwent a hydrothermal process with H3PO4 at 130 °C for 12 h to form phosphate-anchored carbon (PN-C). Au and Pd precursors were then anchored onto PN-C and reduced in an alkaline solution, which simultaneously removed the phosphate species.","matchedSynthesis":"Au2Pd3@(P)N-C","composition":"Au:Pd = 2:3","role":"main catalyst"},{"paperId":"P188","catalystId":"P188_PERF_002","name":"Au2Pd3@N-C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P188","catalystId":"P188_PERF_003","name":"Au2Pd3/N-C-hydrogen phosphate","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P188","catalystId":"P188_PERF_004","name":"AuPd/ZIF-8","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P189","catalystId":"P189_PERF_001","name":"Pd/PAN","activeMetals":"Pd","metalClass":"Pd-only","support":"Polyacrylonitrile (PAN) beads","method":"wet_impregnation","synthesis":"PAN beads were impregnated with an aqueous Pd precursor solution, followed by reduction with NaBH4.","matchedSynthesis":"Pd/PAN","composition":"Pd","role":"catalyst for dehydrogenation of formic acid and reduction of organic dyes"},{"paperId":"P189","catalystId":"P189_PERF_002","name":"PdCo0.6/PAN","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P189","catalystId":"P189_PERF_003","name":"PdFe0.9/PAN","activeMetals":"Pd-Fe","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P190","catalystId":"P190_PERF_001","name":"Pd@M1/20NB","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P190","catalystId":"P190_PERF_002","name":"Pd@U1/20NB","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P190","catalystId":"P190_PERF_003","name":"Pd@WBA","activeMetals":"Pd","metalClass":"Pd-only","support":"Undoped porous carbon (WBA)","method":"wet_impregnation","synthesis":"Undoped woodchar was coactivated with NaHCO3 and air at 700 °C for 3 h in air/N2 flow, followed by Pd loading via K2PdCl4 impregnation and NaBH4 reduction.","matchedSynthesis":"Pd@WBA","composition":"Pd","role":"Control catalyst (undoped support)"},{"paperId":"P191","catalystId":"P191_PERF_001","name":"Pd/C in situ reduction","activeMetals":"Pd","metalClass":"Pd-only","support":"Vulcan carbon powder XC-72","method":"chemical_reduction_loading","synthesis":"Precursor prepared by precipitation: Pd precursor added to support slurry, stirred 4h, pH adjusted to 10.9 with NaOH, stirred 4h for nucleation/maturation, filtered and dried; catalyst then prepared by reducing the precursor with sodium formate.","matchedSynthesis":"Pd/C in situ reduction","composition":"Pd","role":"main catalyst"},{"paperId":"P191","catalystId":"P191_PERF_002","name":"Pd/C-EG reduction","activeMetals":"Pd","metalClass":"Pd-only","support":"Vulcan carbon powder XC-72","method":"polyol_reduction","synthesis":"Support mixed with ethylene glycol, Pd precursor added and stirred 3h, pH adjusted to 10.8 with NaOH, microwave treatment applied, followed by 8h stirring/ripening, filtration, washing, and drying.","matchedSynthesis":"Pd/C-EG reduction","composition":"Pd","role":"comparison catalyst"},{"paperId":"P191","catalystId":"P191_PERF_003","name":"Pd/C-30% commercial","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P192","catalystId":"P192_PERF_001","name":"Pd/rGO","activeMetals":"Pd","metalClass":"Pd-only","support":"reduced graphene oxide (rGO)","method":"wet_impregnation","synthesis":"GO was impregnated with PdCl2 solution, dried at room temperature, thermally reduced in Ar, and then treated in a H2+Ar mixture.","matchedSynthesis":"Pd/rGO","composition":"Pd","role":"catalyst"},{"paperId":"P192","catalystId":"P192_PERF_002","name":"PdAu/rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"reduced graphene oxide (rGO)","method":"wet_impregnation","synthesis":"GO was impregnated with a mixture of PdCl2 and HAuCl4 aqueous solutions, dried at room temperature, and thermally treated in a H2+Ar mixture.","matchedSynthesis":"PdAu/rGO","composition":"Pd:Au = 7.5:2.5 wt%","role":"catalyst"},{"paperId":"P193","catalystId":"P193_PERF_001","name":"Pd0.90Ag0.10B/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"reduced graphene oxide (rGO)","method":"chemical_reduction_loading","synthesis":"Co-reduction of metal ions deposited on GO using NaBH4 as the reducing agent and boron source.","matchedSynthesis":"Pd0.90Ag0.10B/rGO","composition":"Pd:Ag = 0.90:0.10 (molar ratio)","role":"active"},{"paperId":"P193","catalystId":"P193_PERF_002","name":"Pd0.90Ag0.10/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"reduced graphene oxide (rGO)","method":"chemical_reduction_loading","synthesis":"Co-reduction of metal ions deposited on GO using N2H4·H2O as the reducing agent.","matchedSynthesis":"Pd0.90Ag0.10/rGO","composition":"Pd:Ag = 0.90:0.10 (molar ratio)","role":"comparison"},{"paperId":"P193","catalystId":"P193_PERF_003","name":"PdB/rGO","activeMetals":"Pd","metalClass":"Pd-only","support":"reduced graphene oxide (rGO)","method":"chemical_reduction_loading","synthesis":"Reduction of Pd ions on GO using NaBH4.","matchedSynthesis":"PdB/rGO","composition":"Pd only","role":"comparison"},{"paperId":"P194","catalystId":"P194_PERF_001","name":"Pd/C-Li, Pd/C-Na, Pd/C-Ca, Pd/C-Ba","activeMetals":"Pd","metalClass":"Pd-only","support":"Vulcan XC-72","method":"chemical_reduction_loading","synthesis":"Synthesized via the cation dipole adjustment method using microwave-assisted reduction in ethylene glycol (EG) with LiOH as the pH-adjustment agent.","matchedSynthesis":"Pd/C-Li","composition":"Pd","role":"catalyst for formic acid decomposition"},{"paperId":"P195","catalystId":"P195_PERF_001","name":"Pd-ZrO2/SBA-15-NH2","activeMetals":"Pd-Zr","metalClass":"Pd-based multimetal","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"One-step coreduction strategy at ambient conditions using NaBH4.","matchedSynthesis":"Pd-ZrO2/SBA-15-NH2","composition":"Pd/ZrO2 molar ratio = 0.9/0.1","role":"main catalyst"},{"paperId":"P195","catalystId":"P195_PERF_002","name":"Pd/SBA-15-NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"Similar to Pd-ZrO2/SBA-15-NH2 but omitting Zr precursor.","matchedSynthesis":"Pd/SBA-15-NH2","composition":"Pd only","role":"comparative catalyst"},{"paperId":"P196","catalystId":"P196_PERF_001","name":"Pd6Ir4/KIT-6-NH2","activeMetals":"Pd-Ir","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P196","catalystId":"P196_PERF_002","name":"Pd/KIT-6-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P196","catalystId":"P196_PERF_003","name":"PdIr/KIT-6 (bare)","activeMetals":"Pd-Ir","metalClass":"Pd-based multimetal","support":"KIT-6","method":"wet_impregnation","synthesis":"Pd and Ir loaded onto bare KIT-6 via impregnation-reduction.","matchedSynthesis":"PdIr/KIT-6","composition":"Pd and Ir","role":"comparative sample (bare support)"},{"paperId":"P196","catalystId":"P196_PERF_004","name":"Pd6Ir4/SBA-NH2","activeMetals":"Pd-Ir","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P197","catalystId":"P197_PERF_001","name":"Ru/CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"Carbon nanotubes (CNTs)","method":"incipient_wetness_impregnation","synthesis":"Ru(NO)(NO3)3 aqueous solution added to dried CNTs, stirred, stored in a closed vessel for 30 min, dried in air, and reduced under hydrogen flow.","matchedSynthesis":"Ru/CNTs","composition":"Ru","role":"Catalyst"},{"paperId":"P197","catalystId":"P197_PERF_002","name":"Ru/1.9%N-CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P197","catalystId":"P197_PERF_003","name":"Ru/3.0%N-CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P197","catalystId":"P197_PERF_004","name":"Ru/4.8%N-CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P198","catalystId":"P198_PERF_001","name":"Pd0.6Co0.2Ni0.2/CNSC","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","support":"Schiff base conjugated carbon nitride (CNSC)","method":"chemical_reduction_loading","synthesis":"CNSC support was prepared by urea/terephthalaldehyde pyrolysis. Metal precursors were added to a CNSC aqueous suspension, pH adjusted to 9.8, and reduced using NaBH4.","matchedSynthesis":"Pd0.6Co0.2Ni0.2/CNSC","composition":"Pd:Co:Ni = 0.6:0.2:0.2","role":"optimized catalyst"},{"paperId":"P198","catalystId":"P198_PERF_002","name":"Pd0.6Co0.2Ni0.2/g-C3N4","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","support":"graphitic carbon nitride (g-C3N4)","method":"chemical_reduction_loading","synthesis":"Similar to PdCoNi/CNSC but using g-C3N4 support.","matchedSynthesis":"Pd0.6Co0.2Ni0.2/g-C3N4","composition":"Pd:Co:Ni = 0.6:0.2:0.2","role":"comparison catalyst"},{"paperId":"P198","catalystId":"P198_PERF_003","name":"Pd/CNSC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P198","catalystId":"P198_PERF_004","name":"Pd0.8Co0.1Ni0.1/CNSC","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P198","catalystId":"P198_PERF_005","name":"Pd0.4Co0.3Ni0.3/CNSC","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P198","catalystId":"P198_PERF_006","name":"Pd0.2Co0.4Ni0.4/CNSC","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P198","catalystId":"P198_PERF_007","name":"Pd0.6Co0.4/CNSC","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P198","catalystId":"P198_PERF_008","name":"Pd0.6Ni0.4/CNSC","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P199","catalystId":"P199_PERF_001","name":"γ-Mo2N/ 0.2 NK-C","activeMetals":"Mo","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P200","catalystId":"P200_PERF_001","name":"Pd-NPs@TA-COP","activeMetals":"Pd","metalClass":"Pd-only","support":"TA-COP (Triazine-based covalent organic polymer)","method":"wet_impregnation","synthesis":"PdCl2 was sonicated in methanol, added to a dispersion of TA-COP in ethanol, stirred, and then reduced using NaBH4.","matchedSynthesis":"Pd-NPs@TA-COP","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P201","catalystId":"P201_PERF_001","name":"PdAg/CA-5","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P201","catalystId":"P201_PERF_002","name":"PdAg/CA-1","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P201","catalystId":"P201_PERF_003","name":"PdAg/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","support":"Amine-functionalized carbon (CA-x)","method":"chemical_reduction_loading","synthesis":"CA-x support was dispersed in an aqueous solution of Pd(NH3)4Cl2 and AgNO3, stirred at RT for 1 h, followed by the injection of aqueous NaBH4 for reduction.","matchedSynthesis":"PdAg/CA-x (x=1-5)","composition":"Pd:Ag = 1:1","role":"catalyst"},{"paperId":"P201","catalystId":"P201_PERF_004","name":"Pd/CA-5","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P201","catalystId":"P201_PERF_005","name":"unsupported PdAg NPs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P202","catalystId":"P202_PERF_001","name":"Pd/CDs-III","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon dots (CDs-III)","method":"chemical_reduction_loading","synthesis":"CDs dissolved in water, Pd precursor added via ultrasonication, reduced with NaBH4, dried, and annealed under Ar.","matchedSynthesis":"Pd/CDs-III","composition":"Pd","role":"active catalyst"},{"paperId":"P202","catalystId":"P202_PERF_002","name":"Pd/CDs-II","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon dots (CDs-II)","method":"chemical_reduction_loading","synthesis":"CDs dissolved in water, Pd precursor added via ultrasonication, reduced with NaBH4, dried, and annealed under Ar.","matchedSynthesis":"Pd/CDs-II","composition":"Pd","role":"active catalyst"},{"paperId":"P202","catalystId":"P202_PERF_003","name":"Pd/CDs-I","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon dots (CDs-I)","method":"chemical_reduction_loading","synthesis":"CDs dissolved in water, Pd precursor added via ultrasonication, reduced with NaBH4, dried, and annealed under Ar.","matchedSynthesis":"Pd/CDs-I","composition":"Pd","role":"active catalyst"},{"paperId":"P202","catalystId":"P202_PERF_004","name":"Pd/XC-72","activeMetals":"Pd","metalClass":"Pd-only","support":"commercial active carbon (XC-72)","method":"chemical_reduction_loading","synthesis":"Synthesized using the same method as Pd/CDs catalysts.","matchedSynthesis":"Pd/XC-72","composition":"Pd","role":"comparison catalyst"},{"paperId":"P203","catalystId":"P203_PERF_001","name":"Pd-loaded Tp-Azo-COF/SiO2","activeMetals":"Pd","metalClass":"Pd-only","support":"Tp-Azo-COF/SiO2","method":"adsorption_or_loading","synthesis":"Pd(II) was adsorbed onto the Tp-Azo-COF/SiO2 composite via batch adsorption, then reduced to metallic Pd using sodium borohydride (NaBH4).","matchedSynthesis":"Pd-loaded Tp-Azo-COF/SiO2","composition":"Pd","role":"Catalyst for formic acid decomposition (hydrogen production)"},{"paperId":"P204","catalystId":"P204_PERF_001","name":"Pd@NaA30700","activeMetals":"Pd","metalClass":"Pd-only","support":"biochar-derived hierarchically porous carbon (HPC)","method":"chemical_reduction_loading","synthesis":"Pd(II) salt was added dropwise to an aqueous dispersion of HPC at pH 8.5, followed by magnetic agitation and liquid-phase reduction using NaBH4.","matchedSynthesis":"Pd@NaA30700","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P204","catalystId":"P204_PERF_002","name":"Pd@KA30700","activeMetals":"Pd","metalClass":"Pd-only","support":"biochar-derived hierarchically porous carbon (HPC)","method":"chemical_reduction_loading","synthesis":"Pd(II) salt was added dropwise to an aqueous dispersion of HPC at pH 8.5, followed by magnetic agitation and liquid-phase reduction using NaBH4.","matchedSynthesis":"Pd@KA30700","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P205","catalystId":"P205_PERF_001","name":"0.3Pt/N-CNFs","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"N-doped carbon nanofibers (N-CNFs)","method":"chemical_reduction_loading","synthesis":"Homogeneous precipitation of Pt from H2PtCl6 using NaOH as a precipitant, followed by drying and reduction.","matchedSynthesis":"0.3Pt/N-CNFs","composition":"Pt","role":"active catalyst"},{"paperId":"P205","catalystId":"P205_PERF_002","name":"1Pt/N-CNFs","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"N-doped carbon nanofibers (N-CNFs)","method":"chemical_reduction_loading","synthesis":"Homogeneous precipitation of Pt from H2PtCl6 using NaOH as a precipitant, followed by drying and reduction.","matchedSynthesis":"1Pt/N-CNFs","composition":"Pt","role":"active catalyst"},{"paperId":"P205","catalystId":"P205_PERF_003","name":"1Pt/CNFs","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"Carbon nanofibers (CNFs)","method":"chemical_reduction_loading","synthesis":"Homogeneous precipitation of Pt from H2PtCl6 using NaOH as a precipitant, followed by drying and reduction.","matchedSynthesis":"1Pt/CNFs","composition":"Pt","role":"active catalyst"},{"paperId":"P205","catalystId":"P205_PERF_004","name":"1Pd/N-CNFs","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon nanofibers (N-CNFs)","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of Pd precursor onto N-CNFs followed by reduction.","matchedSynthesis":"1Pd/N-CNFs","composition":"Pd","role":"active catalyst"},{"paperId":"P205","catalystId":"P205_PERF_005","name":"1Pd/CNFs","activeMetals":"Pd","metalClass":"Pd-only","support":"Carbon nanofibers (CNFs)","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of Pd precursor onto CNFs followed by reduction.","matchedSynthesis":"1Pd/CNFs","composition":"Pd","role":"active catalyst"},{"paperId":"P205","catalystId":"P205_PERF_006","name":"1Ru/N-CNFs","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"N-doped carbon nanofibers (N-CNFs)","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of Ru precursor onto N-CNFs followed by reduction.","matchedSynthesis":"1Ru/N-CNFs","composition":"Ru","role":"active catalyst"},{"paperId":"P205","catalystId":"P205_PERF_007","name":"1Ru/CNFs","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","support":"Carbon nanofibers (CNFs)","method":"incipient_wetness_impregnation","synthesis":"Incipient wetness impregnation of Ru precursor onto CNFs followed by reduction.","matchedSynthesis":"1Ru/CNFs","composition":"Ru","role":"active catalyst"},{"paperId":"P205","catalystId":"P205_PERF_008","name":"unsupported Pt powder","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P205","catalystId":"P205_PERF_009","name":"unsupported Pd powder","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P206","catalystId":"P206_PERF_001","name":"Pd/CTF-1","activeMetals":"Pd","metalClass":"Pd-only","support":"CTF-1","method":"wet_impregnation","synthesis":"Support impregnated with Pd acetylacetonate in acetone, stirred, dried, and then treated under a formic acid/Ar flow to remove ligands and stabilize Pd.","matchedSynthesis":"Pd/CTF-1","composition":"Pd","role":"active catalyst"},{"paperId":"P206","catalystId":"P206_PERF_002","name":"Pd/pyCTF","activeMetals":"Pd","metalClass":"Pd-only","support":"pyCTF","method":"wet_impregnation","synthesis":"Support impregnated with Pd acetylacetonate in acetone, stirred, dried, and then treated under a formic acid/Ar flow to remove ligands and stabilize Pd.","matchedSynthesis":"Pd/pyCTF","composition":"Pd","role":"active catalyst"},{"paperId":"P206","catalystId":"P206_PERF_003","name":"Pd/bipyCTF","activeMetals":"Pd","metalClass":"Pd-only","support":"bipyCTF","method":"wet_impregnation","synthesis":"Support impregnated with Pd acetylacetonate in acetone, stirred, dried, and then treated under a formic acid/Ar flow to remove ligands and stabilize Pd.","matchedSynthesis":"Pd/bipyCTF","composition":"Pd","role":"active catalyst"},{"paperId":"P206","catalystId":"P206_PERF_004","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"mesoporous Sibunit-type graphitic carbon","method":"unknown","matchedSynthesis":"Pd/C","composition":"Pd nanoparticles (~2.3 nm)","role":"reference catalyst"},{"paperId":"P207","catalystId":"P207_PERF_001","name":"Pd(6 wt %)/KIE-8-d","activeMetals":"Pd","metalClass":"Pd-only","support":"KIE-8","method":"wet_impregnation","synthesis":"KIE-8 was added to H2PdCl4 solution, stirred, pH adjusted to 9.5 with NaOH, further stirred at room temperature, then reduced using NaBH4.","matchedSynthesis":"Pd(6 wt %)/KIE-8","composition":"Pd","role":"active catalyst"},{"paperId":"P207","catalystId":"P207_PERF_002","name":"Pd(6 wt %)/KIE-8-e","activeMetals":"Pd","metalClass":"Pd-only","support":"KIE-8","method":"wet_impregnation","synthesis":"KIE-8 was added to H2PdCl4 solution, stirred, pH adjusted to 9.5 with NaOH, further stirred at room temperature, then reduced using NaBH4.","matchedSynthesis":"Pd(6 wt %)/KIE-8","composition":"Pd","role":"active catalyst"},{"paperId":"P207","catalystId":"P207_PERF_003","name":"Pd(6 wt %)/KIE-8-f","activeMetals":"Pd","metalClass":"Pd-only","support":"KIE-8","method":"wet_impregnation","synthesis":"KIE-8 was added to H2PdCl4 solution, stirred, pH adjusted to 9.5 with NaOH, further stirred at room temperature, then reduced using NaBH4.","matchedSynthesis":"Pd(6 wt %)/KIE-8","composition":"Pd","role":"active catalyst"},{"paperId":"P207","catalystId":"P207_PERF_004","name":"Pd(6 wt %)/KIE-8-g","activeMetals":"Pd","metalClass":"Pd-only","support":"KIE-8","method":"wet_impregnation","synthesis":"KIE-8 was added to H2PdCl4 solution, stirred, pH adjusted to 9.5 with NaOH, further stirred at room temperature, then reduced using NaBH4.","matchedSynthesis":"Pd(6 wt %)/KIE-8","composition":"Pd","role":"active catalyst"},{"paperId":"P207","catalystId":"P207_PERF_005","name":"Pd(6 wt %)/N-charcoal","activeMetals":"Pd","metalClass":"Pd-only","support":"N-charcoal","method":"wet_impregnation","synthesis":"Same deposition method as used for Pd/KIE-8.","matchedSynthesis":"Pd(6 wt %)/N-charcoal","composition":"Pd","role":"comparison catalyst"},{"paperId":"P208","catalystId":"P208_PERF_001","name":"Pt/TiB2-600","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"TiB2","method":"incipient_wetness_impregnation","synthesis":"TiB2 support was synthesized via molten-salt assisted borothermal reduction. Pt nanoparticles were loaded onto the TiB2 surface using IWI, followed by calcination in flowing N2.","matchedSynthesis":"Pt/TiB2","composition":"Pt","role":"catalyst"},{"paperId":"P208","catalystId":"P208_PERF_002","name":"Pt/TiB2-300","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"TiB2","method":"incipient_wetness_impregnation","synthesis":"TiB2 support was synthesized via molten-salt assisted borothermal reduction. Pt nanoparticles were loaded onto the TiB2 surface using IWI, followed by calcination in flowing N2.","matchedSynthesis":"Pt/TiB2","composition":"Pt","role":"catalyst"},{"paperId":"P208","catalystId":"P208_PERF_003","name":"bare TiB2","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P209","catalystId":"P209_PERF_001","name":"PdAcet. Acet./Cdarco","activeMetals":"Pd","metalClass":"Pd-only","support":"DARCO G-60 activated carbon","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in acetone, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","matchedSynthesis":"PdAcet. Acet./Cdarco","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P209","catalystId":"P209_PERF_002","name":"PdCl2 W./Cdarco","activeMetals":"Pd-W","metalClass":"Pd-based multimetal","support":"DARCO G-60 activated carbon","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in water, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","matchedSynthesis":"PdCl2 W./Cdarco","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P209","catalystId":"P209_PERF_003","name":"Pd(NO3)2 Acet./Cdarco","activeMetals":"Pd","metalClass":"Pd-only","support":"DARCO G-60 activated carbon","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in acetone, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","matchedSynthesis":"Pd(NO3)2 Acet./Cdarco","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P209","catalystId":"P209_PERF_004","name":"Pd(NO3)2 W./Cdarco","activeMetals":"Pd-W","metalClass":"Pd-based multimetal","support":"DARCO G-60 activated carbon","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in water, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","matchedSynthesis":"Pd(NO3)2 W./Cdarco","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P209","catalystId":"P209_PERF_005","name":"PdAcet. W./Cdarco","activeMetals":"Pd-W","metalClass":"Pd-based multimetal","support":"DARCO G-60 activated carbon","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in water, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","matchedSynthesis":"PdAcet. W./Cdarco","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P209","catalystId":"P209_PERF_006","name":"PdCl2 Acet./Cdarco","activeMetals":"Pd","metalClass":"Pd-only","support":"DARCO G-60 activated carbon","method":"wet_impregnation","synthesis":"Palladium precursor dissolved in acetone, added dropwise to dried activated carbon, dried at 100 °C, and reduced under N2/H2 flow at 300 °C.","matchedSynthesis":"PdCl2 Acet./Cdarco","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P210","catalystId":"P210_PERF_001","name":"PdMn0.25@S-1-0.005NH2","activeMetals":"Pd-Mn","metalClass":"Pd-based multimetal","support":"Silicalite-1 (S-1) zeolite","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating metal complexes and silane coupling agents, followed by freeze-drying and direct H2 reduction.","matchedSynthesis":"PdMny@S-1-xNH2 (e.g., PdMn0.25@S-1-0.005NH2)","composition":"Pd and Mn; molar ratio Mn/Pd = y (optimized at 0.25)","role":"Optimized bimetallic catalyst"},{"paperId":"P210","catalystId":"P210_PERF_002","name":"Pd@S-1","activeMetals":"Pd","metalClass":"Pd-only","support":"Silicalite-1 (S-1) zeolite","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating Pd complex, followed by freeze-drying and direct H2 reduction.","matchedSynthesis":"Pd@S-1","composition":"Pd","role":"Control catalyst (non-functionalized)"},{"paperId":"P210","catalystId":"P210_PERF_003","name":"Pd@S-1-0.005NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"Silicalite-1 (S-1) zeolite","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating Pd complex, followed by freeze-drying and direct H2 reduction.","matchedSynthesis":"Pd@S-1","composition":"Pd","role":"Control catalyst (non-functionalized)"},{"paperId":"P210","catalystId":"P210_PERF_004","name":"Pd@S-1-0.01NH2","activeMetals":"Pd","metalClass":"Pd-only","support":"Silicalite-1 (S-1) zeolite","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating Pd complex, followed by freeze-drying and direct H2 reduction.","matchedSynthesis":"Pd@S-1","composition":"Pd","role":"Control catalyst (non-functionalized)"},{"paperId":"P210","catalystId":"P210_PERF_005","name":"Pd@S-1-0.005CH3","activeMetals":"Pd","metalClass":"Pd-only","support":"Silicalite-1 (S-1) zeolite","method":"chemical_reduction_loading","synthesis":"One-pot hydrothermal synthesis of S-1 zeolite incorporating Pd complex, followed by freeze-drying and direct H2 reduction.","matchedSynthesis":"Pd@S-1","composition":"Pd","role":"Control catalyst (non-functionalized)"},{"paperId":"P210","catalystId":"P210_PERF_006","name":"PdMn0.5@S-1-0.005NH2","activeMetals":"Pd-Mn","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P210","catalystId":"P210_PERF_007","name":"PdFe@S-1-0.005NH2","activeMetals":"Pd-Fe","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P210","catalystId":"P210_PERF_008","name":"PdCo@S-1-0.005NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P210","catalystId":"P210_PERF_009","name":"PdNi@S-1-0.005NH2","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P211","catalystId":"P211_PERF_001","name":"Pd/O-NCNTs-P","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nanotubes (CNTs)","method":"chemical_reduction_loading","synthesis":"CNTs were treated with oxygen plasma to generate O-CNTs, which were then modified with APTES to prepare O-NCNTs. A mixture of O-NCNTs and H2PdCl4 solution was subsequently treated by H2/Ar surface DBD plasma.","matchedSynthesis":"Pd/O-NCNTs-P","composition":"Pd","role":"formic acid dehydrogenation catalyst"},{"paperId":"P211","catalystId":"P211_PERF_002","name":"Pd/NCNTs-P","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nanotubes (CNTs)","method":"chemical_reduction_loading","synthesis":"CNTs were modified with APTES to prepare NCNTs, then a mixture of NCNTs and H2PdCl4 solution was treated by surface DBD plasma.","matchedSynthesis":"Pd/NCNTs-P","composition":"Pd","role":"comparison catalyst (without oxygen plasma pretreatment)"},{"paperId":"P211","catalystId":"P211_PERF_003","name":"Pd/O-NCNTs-C","activeMetals":"Pd","metalClass":"Pd-only","support":"carbon nanotubes (CNTs)","method":"chemical_reduction_loading","synthesis":"CNTs were treated with oxygen plasma and modified with APTES to form O-NCNTs. The mixture of H2PdCl4 solution and O-NCNTs was then reduced using NaBH4.","matchedSynthesis":"Pd/O-NCNTs-C","composition":"Pd","role":"comparison catalyst"},{"paperId":"P211","catalystId":"P211_PERF_004","name":"Sigma-Aldrich Pd/C","activeMetals":"Al-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P212","catalystId":"P212_PERF_001","name":"Pd-tetrahedron–TiO2","activeMetals":"Pd-Ti","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P212","catalystId":"P212_PERF_002","name":"Pd@Ag5%-tetrahedron–TiO2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P212","catalystId":"P212_PERF_003","name":"Pd@Cu5%-tetrahedron–TiO2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P212","catalystId":"P212_PERF_004","name":"Pd@Au5%-tetrahedron–TiO2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P212","catalystId":"P212_PERF_005","name":"Pd@Pt5%-tetrahedron–TiO2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P212","catalystId":"P212_PERF_006","name":"Pd@Pb-tetrahedron–TiO2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P213","catalystId":"P213_PERF_001","name":"D-Pd5Ag5 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P213","catalystId":"P213_PERF_002","name":"D-Pd3Ag7 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P213","catalystId":"P213_PERF_003","name":"D-Pd7Ag3 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P213","catalystId":"P213_PERF_004","name":"C-Pd5Ag5 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","method":"chemical_reduction_loading","synthesis":"Prepared by co-reduction methods.","matchedSynthesis":"C-Pd5Ag5 NWs","composition":"Pd:Ag (5:5)","role":"comparison catalyst"},{"paperId":"P214","catalystId":"P214_PERF_001","name":"Pd/APC","activeMetals":"Pd","metalClass":"Pd-only","support":"amine-implanted porous carbon (APC)","method":"chemical_reduction_loading","synthesis":"PPC was functionalized via hydrothermal treatment with ammonium hydroxide to create APC; Pd precursor was then loaded onto the support and reduced using NaBH4 in a NaOH solution.","matchedSynthesis":"Pd/APC","composition":"Pd","role":"catalyst"},{"paperId":"P214","catalystId":"P214_PERF_002","name":"Pd/PPC","activeMetals":"Pd","metalClass":"Pd-only","support":"pristine porous carbon (PPC)","method":"chemical_reduction_loading","synthesis":"PPC was used as support; Pd precursor was loaded and reduced using NaBH4 in a NaOH solution.","matchedSynthesis":"Pd/PPC","composition":"Pd","role":"control catalyst"},{"paperId":"P214","catalystId":"P214_PERF_003","name":"Pd/APC*","activeMetals":"Pd","metalClass":"Pd-only","support":"amine-implanted porous carbon (APC)","method":"chemical_reduction_loading","synthesis":"PPC was functionalized via hydrothermal treatment with ammonium hydroxide to create APC; Pd precursor was then loaded onto the support and reduced using NaBH4 in a NaOH solution.","matchedSynthesis":"Pd/APC","composition":"Pd","role":"catalyst"},{"paperId":"P215","catalystId":"P215_PERF_001","name":"Pd-Cu/TiO2-NSs (3:7)","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","support":"TiO2 nanosheets (TiO2-NSs)","method":"co_impregnation","synthesis":"TiO2-NSs were co-impregnated with Pd and Cu precursors, stirred and ultrasonicated at room temperature, then reduced using aqueous NaBH4.","matchedSynthesis":"Pd-Cu/TiO2-NSs","composition":"Pd:Cu atomic ratios of 10:0, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 0:10","role":"catalyst"},{"paperId":"P215","catalystId":"P215_PERF_002","name":"Pd-Cu/TiO2-NSs series (ratios 10:0 to 0:10)","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","support":"TiO2 nanosheets (TiO2-NSs)","method":"co_impregnation","synthesis":"TiO2-NSs were co-impregnated with Pd and Cu precursors, stirred and ultrasonicated at room temperature, then reduced using aqueous NaBH4.","matchedSynthesis":"Pd-Cu/TiO2-NSs","composition":"Pd:Cu atomic ratios of 10:0, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 0:10","role":"catalyst"},{"paperId":"P216","catalystId":"P216_PERF_001","name":"Ni0.2Co0.8–Soy","activeMetals":"Ni-Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P216","catalystId":"P216_PERF_002","name":"Ni-Soy","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P216","catalystId":"P216_PERF_003","name":"Co-Soy","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P217","catalystId":"P217_PERF_001","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P217","catalystId":"P217_PERF_002","name":"Pd-Au/AC","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"activated carbon (AC)","method":"adsorption_or_loading","synthesis":"Pretreated AC was dispersed in DI water with metal salts, stirred at 363 K for 1 h, then reduced by adding Cacumen Platycladi (CP) leaf extract and stirring for another 1 h.","matchedSynthesis":"Pd-Au/AC","composition":"Pd:Au = 1:1 mass ratio","role":"catalyst for CO2 hydrogenation and FA dehydrogenation"},{"paperId":"P217","catalystId":"P217_PERF_003","name":"Pd-Cu/AC","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","support":"activated carbon (AC)","method":"adsorption_or_loading","synthesis":"Pretreated AC was immersed in an aqueous solution of metal salts, stirred at 363 K for 1 h, then reduced by adding Cacumen Platycladi (CP) leaf extract and stirring for another 1 h.","matchedSynthesis":"Pd-Cu/AC","composition":"Pd:Cu = 1:1 mass ratio","role":"catalyst for CO2 hydrogenation and FA dehydrogenation"},{"paperId":"P218","catalystId":"P218_PERF_001","name":"Co@Cr(OH)3/ZrO2","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"Cr(OH)3/ZrO2","method":"chemical_reduction_loading","synthesis":"UiO-66 MOF was synthesized using ZrCl4 and PET-derived 1,4-benzenedicarboxylic acid (BDC), then annealed under N2 to produce ZrO2. Co and Cr precursors were added to the ZrO2 support in a water/ethylene glycol mixture and reduced with NaBH4 via sonication.","matchedSynthesis":"Co@Cr(OH)3/ZrO2","composition":"Co and Cr; optimal Co loading is 5.0 wt%","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P218","catalystId":"P218_PERF_002","name":"Co/ZrO2","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P218","catalystId":"P218_PERF_003","name":"Co@Cr(OH)3","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"Cr(OH)3/ZrO2","method":"chemical_reduction_loading","synthesis":"UiO-66 MOF was synthesized using ZrCl4 and PET-derived 1,4-benzenedicarboxylic acid (BDC), then annealed under N2 to produce ZrO2. Co and Cr precursors were added to the ZrO2 support in a water/ethylene glycol mixture and reduced with NaBH4 via sonication.","matchedSynthesis":"Co@Cr(OH)3/ZrO2","composition":"Co and Cr; optimal Co loading is 5.0 wt%","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P218","catalystId":"P218_PERF_004","name":"Co@Cr(OH)3/ZrO2-Air","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","support":"Cr(OH)3/ZrO2","method":"chemical_reduction_loading","synthesis":"UiO-66 MOF was synthesized using ZrCl4 and PET-derived 1,4-benzenedicarboxylic acid (BDC), then annealed under N2 to produce ZrO2. Co and Cr precursors were added to the ZrO2 support in a water/ethylene glycol mixture and reduced with NaBH4 via sonication.","matchedSynthesis":"Co@Cr(OH)3/ZrO2","composition":"Co and Cr; optimal Co loading is 5.0 wt%","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P219","catalystId":"P219_PERF_001","name":"4-PySI-Pd@Cu(BDC)","activeMetals":"Pd","metalClass":"Pd-only","support":"OMS-Cu(BDC)","method":"post-synthetic modification","synthesis":"Synthesis of Cu(BDC)∙nDMF -> thermal/vacuum activation to OMS-Cu(BDC) -> coordination with 4-PySI ligand -> post-synthetic metalation with PdCl2","matchedSynthesis":"4-PySI-Pd@Cu(BDC)","composition":"Pd and Cu","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P219","catalystId":"P219_PERF_002","name":"2-PySI-Pd@Cu(BDC)","activeMetals":"Pd","metalClass":"Pd-only","support":"OMS-Cu(BDC)","method":"post-synthetic modification","synthesis":"Synthesis of Cu(BDC)∙nDMF -> thermal/vacuum activation to OMS-Cu(BDC) -> coordination with 2-PySI ligand -> post-synthetic metalation with PdCl2","matchedSynthesis":"2-PySI-Pd@Cu(BDC)","composition":"Pd and Cu","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P219","catalystId":"P219_PERF_003","name":"4-PySI@Cu(BDC)","activeMetals":"unknown","metalClass":"Unknown/unclear","method":"unknown"},{"paperId":"P219","catalystId":"P219_PERF_004","name":"OMS-Cu(BDC)","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P219","catalystId":"P219_PERF_005","name":"Cu(BDC)∙nDMF","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P220","catalystId":"P220_PERF_001","name":"Pd90Rh10/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P220","catalystId":"P220_PERF_002","name":"Pd69Rh31/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P220","catalystId":"P220_PERF_003","name":"Pd/HHT","activeMetals":"Pd","metalClass":"Pd-only","support":"HHT CNFs (High Heat Treated carbon nanofibers)","method":"sol_immobilization","synthesis":"Metal precursor and PVA were dissolved in H2O/EtOH, reduced by NaBH4 to form a colloid, immobilized on HHT CNFs, acidified to pH 2 with sulfuric acid, stirred for 30 min, filtered, washed, and dried.","matchedSynthesis":"Pd/HHT","composition":"Pd:100","role":"monometallic catalyst for formic acid dehydrogenation"},{"paperId":"P220","catalystId":"P220_PERF_004","name":"Pd40Rh60/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P220","catalystId":"P220_PERF_005","name":"Pd48Rh52/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P220","catalystId":"P220_PERF_006","name":"Rh/HHT","activeMetals":"Rh","metalClass":"Non-Pd or Pd-free","support":"HHT CNFs (High Heat Treated carbon nanofibers)","method":"sol_immobilization","synthesis":"Metal precursor and PVA were dissolved in H2O/EtOH, reduced by NaBH4 to form a colloid, immobilized on HHT CNFs, acidified to pH 2 with sulfuric acid, stirred for 30 min, filtered, washed, and dried.","matchedSynthesis":"Rh/HHT","composition":"Rh:100","role":"monometallic catalyst for formic acid dehydrogenation"},{"paperId":"P221","catalystId":"P221_PERF_001","name":"Au/N-SBA-15_K(9.5)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"N-SBA-15","method":"chemical_reduction_loading","synthesis":"Support suspended in distilled water, pH adjusted to 9.5 with K2CO3, HAuCl4 added and stirred for 60 min, sodium citrate added (Na citrate:Au = 20), then stirred at 80 °C for 30 min","matchedSynthesis":"Au/N-SBA-15_K(9.5)","composition":"Au","role":"catalyst"},{"paperId":"P221","catalystId":"P221_PERF_002","name":"Au/N-SBA-15_K(11)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"N-SBA-15","method":"chemical_reduction_loading","synthesis":"Support suspended in distilled water, pH adjusted to 11 with K2CO3, HAuCl4 added and stirred for 60 min, sodium citrate added (Na citrate:Au = 20), then stirred at 80 °C for 30 min","matchedSynthesis":"Au/N-SBA-15_K(11)","composition":"Au","role":"catalyst"},{"paperId":"P221","catalystId":"P221_PERF_003","name":"Au/SBA-15","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","support":"SBA-15","method":"chemical_reduction_loading","synthesis":"Support suspended in distilled water, no pH adjustment, HAuCl4 added and stirred for 60 min, sodium citrate added (Na citrate:Au = 20), then stirred at 80 °C for 30 min","matchedSynthesis":"Au/SBA-15","composition":"Au","role":"catalyst"},{"paperId":"P222","catalystId":"P222_PERF_001","name":"Gly-Cu/Ag/MnO2","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","method":"chemical_reduction_loading","synthesis":"MnO2 was prepared by reacting KMnO4 with Na2S2O3 in the presence of CTAB at room temperature. Gly-Cu/Ag (10 ml, 5.0 x 10^-3 mol/L) was mixed with MnO2 suspension (10 ml, 5.0 x 10^-4 mol/L), stirred overnight, and treated with NaBH4.","matchedSynthesis":"Gly-Cu/Ag/MnO2","composition":"Cu:Ag:Mn (bulk mole ratio 1:1:1)","role":"catalyst for hydrogen generation from formic acid decomposition"},{"paperId":"P222","catalystId":"P222_PERF_002","name":"Gly-Cu/Ag","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","method":"other","synthesis":"Gly-Cu nanoparticles were treated with AgNO3 solution in the presence of CTAB to deposit Ag onto the Cu surface via metal displacement.","matchedSynthesis":"Gly-Cu/Ag","composition":"Cu/Ag","role":"catalyst for hydrogen generation from formic acid decomposition"},{"paperId":"P222","catalystId":"P222_PERF_003","name":"Gly-Cu","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","method":"chemical_reduction_loading","synthesis":"Glycine solution was mixed with copper nitrate and equilibrated at room temperature for 30 min to form Cu(glycine)2 complex, followed by dropwise addition of NaBH4 solution.","matchedSynthesis":"Gly-Cu","composition":"Cu","role":"catalyst for hydrogen generation from formic acid decomposition"},{"paperId":"P222","catalystId":"P222_PERF_004","name":"Gly-Ag","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P223","catalystId":"P223_PERF_001","name":"Pd/N-MSC-30-two-175","activeMetals":"Pd","metalClass":"Pd-only","support":"N-MSC-30-two-175","method":"wet_impregnation","synthesis":"N-functionalized MSC-30 was prepared via tandem urea heat treatment. Pd nanoclusters were immobilized by dispersing the support in water, adding K2PdCl4 solution, and reducing with NaBH4 in a NaOH solution.","matchedSynthesis":"Pd/N-MSC-30-two-175","composition":"Pd","role":"catalyst"},{"paperId":"P223","catalystId":"P223_PERF_002","name":"Pd/N-MSC-30-one","activeMetals":"Pd","metalClass":"Pd-only","support":"N-MSC-30-one","method":"wet_impregnation","synthesis":"Identical metal loading and reduction process as Pd/N-MSC-30-two-175, using a one-step N-functionalized support.","matchedSynthesis":"Pd/N-MSC-30-one","composition":"Pd","role":"catalyst"},{"paperId":"P223","catalystId":"P223_PERF_003","name":"Pd/MSC-30","activeMetals":"Pd","metalClass":"Pd-only","support":"MSC-30","method":"wet_impregnation","synthesis":"Identical metal loading and reduction process as Pd/N-MSC-30-two-175, using non-functionalized MSC-30.","matchedSynthesis":"Pd/MSC-30","composition":"Pd","role":"catalyst"},{"paperId":"P224","catalystId":"P224_PERF_001","name":"Pd cubic nanocrystals","activeMetals":"Pd","metalClass":"Pd-only","method":"shape-controlled synthesis","synthesis":"Synthesis of Pd nanocrystals enclosed by {100} facets; surface ligands (PVP) were removed via centrifugation and washing at least 6 times.","matchedSynthesis":"Pd cubic nanocrystals","composition":"Pd","role":"model catalyst"},{"paperId":"P224","catalystId":"P224_PERF_002","name":"Pd octahedral nanocrystals","activeMetals":"Pd","metalClass":"Pd-only","method":"shape-controlled synthesis","synthesis":"Synthesis of Pd nanocrystals enclosed by {111} facets; surface ligands (PVP) were removed via centrifugation and washing at least 6 times.","matchedSynthesis":"Pd octahedral nanocrystals","composition":"Pd","role":"model catalyst"},{"paperId":"P224","catalystId":"P224_PERF_003","name":"Pd tetrahedral nanocrystals","activeMetals":"Pd","metalClass":"Pd-only","method":"shape-controlled synthesis","synthesis":"Synthesis of Pd nanocrystals enclosed by {111} facets; surface ligands (PVP) were removed via centrifugation and washing at least 6 times.","matchedSynthesis":"Pd tetrahedral nanocrystals","composition":"Pd","role":"model catalyst"},{"paperId":"P224","catalystId":"P224_PERF_004","name":"Pd@Ag nanocubes","activeMetals":"Pd","metalClass":"Pd-only","method":"selective overgrowth","synthesis":"Selective overgrowth of Ag atoms starting at the edges of Pd nanocubes, enabled by Br- capping of {100} facets; Ag subsequently spills over from edges to plane sites.","matchedSynthesis":"Pd@Ag nanocubes","composition":"Pd-Ag","role":"modified catalyst for enhanced HCOOH decomposition"},{"paperId":"P225","catalystId":"P225_PERF_001","name":"Pd/EDA-PAN","activeMetals":"Pd","metalClass":"Pd-only","support":"EDA-PAN","method":"wet_impregnation","synthesis":"EDA-PAN was dispersed in water, H2PdCl4 was added and stirred for 8 h; the resulting Pd2+/EDA-PAN was dried and then reduced by injecting NaBH4 solution into an aqueous dispersion under strong stirring for 6 h.","matchedSynthesis":"Pd/EDA-PAN","composition":"Pd","role":"active catalyst"},{"paperId":"P225","catalystId":"P225_PERF_002","name":"Pd/PAN","activeMetals":"Pd","metalClass":"Pd-only","support":"PAN","method":"wet_impregnation","synthesis":"PAN was dispersed in water, H2PdCl4 was added and stirred for 8 h; the resulting Pd2+/PAN was dried and then reduced by injecting NaBH4 solution into an aqueous dispersion under strong stirring for 6 h.","matchedSynthesis":"Pd/PAN","composition":"Pd","role":"reference sample"},{"paperId":"P226","catalystId":"P226_PERF_001","name":"6Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"N-doped porous carbon (N-LC)","method":"wet_impregnation","synthesis":"Ni precursor dissolved in THF, mixed with N-LC support and stirred at 60 °C for 4 h; solvent removed by natural evaporation; treated at 350 °C in Ar flow to decompose acetate moieties.","matchedSynthesis":"6Ni/N-LC, 8Ni/N-LC, 10Ni/N-LC","composition":"Ni","role":"active catalyst"},{"paperId":"P226","catalystId":"P226_PERF_002","name":"8Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"N-doped porous carbon (N-LC)","method":"wet_impregnation","synthesis":"Ni precursor dissolved in THF, mixed with N-LC support and stirred at 60 °C for 4 h; solvent removed by natural evaporation; treated at 350 °C in Ar flow to decompose acetate moieties.","matchedSynthesis":"6Ni/N-LC, 8Ni/N-LC, 10Ni/N-LC","composition":"Ni","role":"active catalyst"},{"paperId":"P226","catalystId":"P226_PERF_003","name":"10Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"N-doped porous carbon (N-LC)","method":"wet_impregnation","synthesis":"Ni precursor dissolved in THF, mixed with N-LC support and stirred at 60 °C for 4 h; solvent removed by natural evaporation; treated at 350 °C in Ar flow to decompose acetate moieties.","matchedSynthesis":"6Ni/N-LC, 8Ni/N-LC, 10Ni/N-LC","composition":"Ni","role":"active catalyst"},{"paperId":"P226","catalystId":"P226_PERF_004","name":"10Ni/LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"Porous carbon (LC) and NH3-treated porous carbon (LCNH3)","method":"wet_impregnation","synthesis":"Same technique as Ni/N-LC catalysts.","matchedSynthesis":"10Ni/LC, 10Ni/LCNH3","composition":"Ni","role":"control catalyst"},{"paperId":"P226","catalystId":"P226_PERF_005","name":"10Ni/LC_NH3","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"Porous carbon (LC) and NH3-treated porous carbon (LCNH3)","method":"wet_impregnation","synthesis":"Same technique as Ni/N-LC catalysts.","matchedSynthesis":"10Ni/LC, 10Ni/LCNH3","composition":"Ni","role":"control catalyst"},{"paperId":"P227","catalystId":"P227_PERF_001","name":"Pd/NC800","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon (NC)","method":"wet_impregnation","synthesis":"Sunflower seed husks, ZnCl2, and melamine were dispersed in water, stirred for 24h, dried at 60°C, carbonized at 240°C (2h), and annealed at 800°C (2h) under N2. The support was cleaned with 3 M HCl. Pd was then deposited via impregnation of H2PdCl4 solution followed by NaBH4 reduction.","matchedSynthesis":"Pd/NC800","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P227","catalystId":"P227_PERF_002","name":"Pd/NC700","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon (NC)","method":"wet_impregnation","synthesis":"Sunflower seed husks, ZnCl2, and melamine were dispersed in water, stirred for 24h, dried at 60°C, carbonized at 240°C (2h), and annealed at 700°C (2h) under N2. The support was cleaned with 3 M HCl. Pd was then deposited via impregnation of H2PdCl4 solution followed by NaBH4 reduction.","matchedSynthesis":"Pd/NC700","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P227","catalystId":"P227_PERF_003","name":"Pd/NC900","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped carbon (NC)","method":"wet_impregnation","synthesis":"Sunflower seed husks, ZnCl2, and melamine were dispersed in water, stirred for 24h, dried at 60°C, carbonized at 240°C (2h), and annealed at 900°C (2h) under N2. The support was cleaned with 3 M HCl. Pd was then deposited via impregnation of H2PdCl4 solution followed by NaBH4 reduction.","matchedSynthesis":"Pd/NC900","composition":"Pd","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P228","catalystId":"P228_PERF_001","name":"Pd0.75Au0.25/NH2-SPP","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"amino-grafted self-pillared pentasil (SPP) zeolite","method":"wet_impregnation","synthesis":"SPP zeolite was synthesized and calcined, then amino-functionalized with APTES. Pd and Au precursors were added to a suspension of NH2-SPP in water, followed by liquid-phase reduction using sodium borohydride.","matchedSynthesis":"Pd0.75Au0.25/NH2-SPP","composition":"Pd:Au = 0.75:0.25 (molar ratio)","role":"main catalyst"},{"paperId":"P228","catalystId":"P228_PERF_002","name":"Pd/NH2-SPP","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P228","catalystId":"P228_PERF_003","name":"Pd/SPP","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P229","catalystId":"P229_PERF_001","name":"Au0.3Pd0.7/A-M-β-CD","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"amine-functionalized monochlorotriazinyl β-cyclodextrin (A-M-β-CD)","method":"wet_impregnation","synthesis":"M-β-CD was functionalized with APTES to form A-M-β-CD; Au and Pd precursors were added to the suspension, stirred for 3 h, and then reduced using NaBH4.","matchedSynthesis":"Au0.3Pd0.7/A-M-β-CD","composition":"Au:Pd = 0.3:0.7","role":"main catalyst"},{"paperId":"P229","catalystId":"P229_PERF_002","name":"Au0.3Pd0.7 NP","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P229","catalystId":"P229_PERF_003","name":"Au0.3Pd0.7/M-β-CD","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P229","catalystId":"P229_PERF_004","name":"Au0.3Pd0.7-A","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"amine-functionalized monochlorotriazinyl β-cyclodextrin (A-M-β-CD)","method":"wet_impregnation","synthesis":"M-β-CD was functionalized with APTES to form A-M-β-CD; Au and Pd precursors were added to the suspension, stirred for 3 h, and then reduced using NaBH4.","matchedSynthesis":"Au0.3Pd0.7/A-M-β-CD","composition":"Au:Pd = 0.3:0.7","role":"main catalyst"},{"paperId":"P229","catalystId":"P229_PERF_005","name":"Au0.3Pd0.7/C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","support":"Vulcan XC-72 carbon (C)","method":"wet_impregnation","synthesis":"Synthesized by the same method as Au0.3Pd0.7/A-M-β-CD but using Vulcan XC-72 carbon support.","matchedSynthesis":"Au0.3Pd0.7/C","composition":"Au:Pd = 0.3:0.7","role":"comparison catalyst"},{"paperId":"P230","catalystId":"P230_PERF_001","name":"Pd/NMC-400","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped mesoporous carbon (NMC)","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","matchedSynthesis":"Pd/NMC","composition":"Pd","role":"active catalyst"},{"paperId":"P230","catalystId":"P230_PERF_002","name":"Pd/NMC-500","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped mesoporous carbon (NMC)","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","matchedSynthesis":"Pd/NMC","composition":"Pd","role":"active catalyst"},{"paperId":"P230","catalystId":"P230_PERF_003","name":"Pd/NMC-600","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped mesoporous carbon (NMC)","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","matchedSynthesis":"Pd/NMC","composition":"Pd","role":"active catalyst"},{"paperId":"P230","catalystId":"P230_PERF_004","name":"Pd/NMC-700","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped mesoporous carbon (NMC)","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","matchedSynthesis":"Pd/NMC","composition":"Pd","role":"active catalyst"},{"paperId":"P230","catalystId":"P230_PERF_005","name":"Pd/NMC-800","activeMetals":"Pd","metalClass":"Pd-only","support":"N-doped mesoporous carbon (NMC)","method":"deposition_precipitation","synthesis":"NMC support was synthesized via hard template method and carbonized at 400, 500, 600, 700, or 800 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","matchedSynthesis":"Pd/NMC","composition":"Pd","role":"active catalyst"},{"paperId":"P230","catalystId":"P230_PERF_006","name":"Pd/MC-600","activeMetals":"Pd","metalClass":"Pd-only","support":"mesoporous carbon (MC)","method":"deposition_precipitation","synthesis":"MC support was synthesized via hard template method and carbonized at 600 °C. Pd was loaded using deposition-precipitation with pH adjustment to 10.5, followed by drying and H2 reduction.","matchedSynthesis":"Pd/MC","composition":"Pd","role":"comparison catalyst"},{"paperId":"P231","catalystId":"P231_PERF_001","name":"Pd/NH2-CNT (also referred to as Pd/CNTs (Cit and APTES))","activeMetals":"Pd","metalClass":"Pd-only","support":"Multiwalled carbon nanotubes (CNTs, MR99)","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/NH2-CNT but without Cit or APTES.","matchedSynthesis":"Pd/CNT","composition":"Pd","role":"control sample (no additives)"},{"paperId":"P231","catalystId":"P231_PERF_002","name":"Pd/CNT","activeMetals":"Pd","metalClass":"Pd-only","support":"Multiwalled carbon nanotubes (CNTs, MR99)","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/NH2-CNT but without Cit or APTES.","matchedSynthesis":"Pd/CNT","composition":"Pd","role":"control sample (no additives)"},{"paperId":"P231","catalystId":"P231_PERF_003","name":"Pd/CNT (Cit)","activeMetals":"Pd","metalClass":"Pd-only","support":"Multiwalled carbon nanotubes (CNTs, MR99)","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/NH2-CNT but using only Cit without APTES.","matchedSynthesis":"Pd/CNT (Cit)","composition":"Pd","role":"control sample (stabilizer only)"},{"paperId":"P231","catalystId":"P231_PERF_004","name":"Pd/CNT (APTES)","activeMetals":"Pd","metalClass":"Pd-only","support":"Multiwalled carbon nanotubes (CNTs, MR99)","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/NH2-CNT but using only APTES without Cit.","matchedSynthesis":"Pd/CNT (APTES)","composition":"Pd","role":"control sample (functionalization only)"},{"paperId":"P231","catalystId":"P231_PERF_005","name":"Pd/C (APTES)","activeMetals":"Pd","metalClass":"Pd-only","support":"Activated carbon","method":"chemical_reduction_loading","synthesis":"Prepared in the same manner as Pd/CNT (APTES) but using activated carbon instead of CNTs.","matchedSynthesis":"Pd/C (APTES)","composition":"Pd","role":"support comparison sample"},{"paperId":"P232","catalystId":"P232_PERF_001","name":"Pd0.6Au0.4/VXC-72-NH2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"VXC-72 carbon black","method":"chemical_reduction_loading","synthesis":"VXC-72 was acid-treated with HNO3 and functionalized with APTES. Pd and Au precursors were added to the suspension, stirred for 1 h at 3°C, and then reduced using NaBH4 solution for 5 h at 3°C.","matchedSynthesis":"Pd0.6Au0.4/VXC-72-NH2","composition":"Pd:Au = 0.6:0.4 (molar ratio)","role":"active catalyst"},{"paperId":"P232","catalystId":"P232_PERF_002","name":"Pd0.6Au0.4/VXC-72","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"VXC-72 carbon black","method":"chemical_reduction_loading","synthesis":"Prepared using a similar method to Pd0.6Au0.4/VXC-72-NH2 but without the addition of APTES.","matchedSynthesis":"Pd0.6Au0.4/VXC-72","composition":"Pd:Au = 0.6:0.4 (molar ratio)","role":"comparison catalyst"},{"paperId":"P232","catalystId":"P232_PERF_003","name":"Au/VXC-72-NH2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P233","catalystId":"P233_PERF_001","name":"Pd3Co2/CeZrSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","support":"CeZrSBA-15-NH2","method":"chemical_reduction_loading","synthesis":"Metal precursors and support were mixed in deionized water, ultrasonicated for 30 min, stirred, reduced with NaBH4 for 30 min, centrifuged, washed thrice with deionized water, and vacuum dried.","matchedSynthesis":"Pd3Co2/CeZrSBA-15-NH2","composition":"Pd:Co = 3:2 (molar ratio)","role":"optimized catalyst"},{"paperId":"P233","catalystId":"P233_PERF_002","name":"Pd/CeZrSBA-15-NH2","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P233","catalystId":"P233_PERF_003","name":"Pd4Co1/CeZrSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","support":"CeZrSBA-15-NH2","method":"chemical_reduction_loading","synthesis":"Analogous to Pd3Co2/CeZrSBA-15-NH2","matchedSynthesis":"Pd4Co1/CeZrSBA-15-NH2","composition":"Pd:Co = 4:1 (molar ratio)","role":"comparative catalyst (molar ratio study)"},{"paperId":"P233","catalystId":"P233_PERF_004","name":"Pd2Co3/CeZrSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","support":"CeZrSBA-15-NH2","method":"chemical_reduction_loading","synthesis":"Analogous to Pd3Co2/CeZrSBA-15-NH2","matchedSynthesis":"Pd2Co3/CeZrSBA-15-NH2","composition":"Pd:Co = 2:3 (molar ratio)","role":"comparative catalyst (molar ratio study)"},{"paperId":"P233","catalystId":"P233_PERF_005","name":"Pd1Co4/CeZrSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","support":"CeZrSBA-15-NH2","method":"chemical_reduction_loading","synthesis":"Analogous to Pd3Co2/CeZrSBA-15-NH2","matchedSynthesis":"Pd1Co4/CeZrSBA-15-NH2","composition":"Pd:Co = 1:4 (molar ratio)","role":"comparative catalyst (molar ratio study)"},{"paperId":"P233","catalystId":"P233_PERF_006","name":"Co/CeZrSBA-15-NH2","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P233","catalystId":"P233_PERF_007","name":"Pd3Co2/ZrSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P233","catalystId":"P233_PERF_008","name":"Pd3Co2/CeSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P233","catalystId":"P233_PERF_009","name":"Pd3Co2/SBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P233","catalystId":"P233_PERF_010","name":"Pd3Co2/CeZrSBA-15","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","support":"CeZrSBA-15-NH2","method":"chemical_reduction_loading","synthesis":"Metal precursors and support were mixed in deionized water, ultrasonicated for 30 min, stirred, reduced with NaBH4 for 30 min, centrifuged, washed thrice with deionized water, and vacuum dried.","matchedSynthesis":"Pd3Co2/CeZrSBA-15-NH2","composition":"Pd:Co = 3:2 (molar ratio)","role":"optimized catalyst"},{"paperId":"P234","catalystId":"P234_PERF_001","name":"Pd/DUT-67-PZDC(10)","activeMetals":"Pd","metalClass":"Pd-only","support":"DUT-67-PZDC","method":"chemical_reduction_loading","synthesis":"Na2PdCl4 and DUT-67-PZDC were mixed in DI water, sonicated and stirred, then reduced with NaBH4.","matchedSynthesis":"Pd/DUT-67-PZDC(10)","composition":"Pd","role":"optimized catalyst"},{"paperId":"P234","catalystId":"P234_PERF_002","name":"Pd/DUT-67-PZDC(5)","activeMetals":"Pd","metalClass":"Pd-only","support":"DUT-67-PZDC","method":"chemical_reduction_loading","synthesis":"Analogous to Pd/DUT-67-PZDC(10) but with varying quantities of DUT-67-PZDC support.","matchedSynthesis":"Pd/DUT-67-PZDC(5), Pd/DUT-67-PZDC(15), Pd/DUT-67-PZDC(20)","composition":"Pd","role":"comparative samples with varying metal loading"},{"paperId":"P234","catalystId":"P234_PERF_003","name":"Pd/DUT-67-PZDC(15)","activeMetals":"Pd","metalClass":"Pd-only","support":"DUT-67-PZDC","method":"chemical_reduction_loading","synthesis":"Analogous to Pd/DUT-67-PZDC(10) but with varying quantities of DUT-67-PZDC support.","matchedSynthesis":"Pd/DUT-67-PZDC(5), Pd/DUT-67-PZDC(15), Pd/DUT-67-PZDC(20)","composition":"Pd","role":"comparative samples with varying metal loading"},{"paperId":"P234","catalystId":"P234_PERF_004","name":"Pd/DUT-67-PZDC(20)","activeMetals":"Pd","metalClass":"Pd-only","support":"DUT-67-PZDC","method":"chemical_reduction_loading","synthesis":"Analogous to Pd/DUT-67-PZDC(10) but with varying quantities of DUT-67-PZDC support.","matchedSynthesis":"Pd/DUT-67-PZDC(5), Pd/DUT-67-PZDC(15), Pd/DUT-67-PZDC(20)","composition":"Pd","role":"comparative samples with varying metal loading"},{"paperId":"P234","catalystId":"P234_PERF_005","name":"Pd/DUT-67-PZDC-CH3","activeMetals":"Pd","metalClass":"Pd-only","support":"DUT-67-PZDC-CH3","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd/DUT-67-PZDC(10) but using DUT-67-PZDC-CH3 support.","matchedSynthesis":"Pd/DUT-67-PZDC-CH3","composition":"Pd","role":"comparative catalyst to study N site functionality"},{"paperId":"P234","catalystId":"P234_PERF_006","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","support":"C","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd/DUT-67-PZDC(10) but using carbon support.","matchedSynthesis":"Pd/C","composition":"Pd","role":"comparative catalyst"},{"paperId":"P235","catalystId":"P235_PERF_001","name":"Pd60Au40/HPC-NH2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","support":"amine-functionalized hierarchically porous carbon (HPC-NH2)","method":"wet_impregnation","synthesis":"HPC was functionalized with APTMS; Pd and Au precursors were added to the HPC-NH2 mixture, followed by reduction using NaBH4.","matchedSynthesis":"Pd(100-x)Au_x/HPC-NH2 (optimal: Pd60Au40/HPC-NH2)","composition":"Pd:Au molar ratios varied (x = 0, 20, 40, 50, 60, 80, 100); optimal is Pd60Au40","role":"main catalyst"},{"paperId":"P235","catalystId":"P235_PERF_002","name":"Pd50Au50/HPC-NH2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P236","catalystId":"P236_PERF_001","name":"Pd/C-0T","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P236","catalystId":"P236_PERF_002","name":"Pd/C-4T","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P237","catalystId":"P237_PERF_001","name":"Pd/UiO-67@NN","activeMetals":"Pd","metalClass":"Pd-only","support":"UiO-67@NN","method":"chemical_reduction_loading","synthesis":"Support and Pd precursor were mixed in DI water, ultrasonicated, stirred, then reduced using sodium borohydride (NaBH4).","matchedSynthesis":"Pd/UiO-67@NN","composition":"Pd","role":"optimized catalyst"},{"paperId":"P237","catalystId":"P237_PERF_002","name":"Pd/UiO-67@N","activeMetals":"Pd","metalClass":"Pd-only","support":"UiO-67@N","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd/UiO-67@NN using UiO-67@N support.","matchedSynthesis":"Pd/UiO-67@N","composition":"Pd","role":"comparative catalyst"},{"paperId":"P237","catalystId":"P237_PERF_003","name":"Pd/UiO-67","activeMetals":"Pd","metalClass":"Pd-only","support":"UiO-67","method":"chemical_reduction_loading","synthesis":"Same procedure as Pd/UiO-67@NN using UiO-67 support.","matchedSynthesis":"Pd/UiO-67","composition":"Pd","role":"comparative catalyst"},{"paperId":"P238","catalystId":"P238_PERF_001","name":"Pd-sCeO2/C","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"sCeO2/C","method":"wet_impregnation","synthesis":"Hydrothermal synthesis of sCeO2, hydrothermal assembly with biomass carbon to form sCeO2/C, wet impregnation of Pd precursor, and NaBH4 reduction.","matchedSynthesis":"Pd-sCeO2/C","composition":"Pd","role":"active catalyst"},{"paperId":"P238","catalystId":"P238_PERF_002","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","method":"unknown"},{"paperId":"P238","catalystId":"P238_PERF_003","name":"Pd-sCeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"sCeO2/C","method":"wet_impregnation","synthesis":"Hydrothermal synthesis of sCeO2, hydrothermal assembly with biomass carbon to form sCeO2/C, wet impregnation of Pd precursor, and NaBH4 reduction.","matchedSynthesis":"Pd-sCeO2/C","composition":"Pd","role":"active catalyst"},{"paperId":"P238","catalystId":"P238_PERF_004","name":"Pd-rCeO2/C","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"rCeO2/C","method":"wet_impregnation","synthesis":"Hydrothermal synthesis of rCeO2, hydrothermal assembly with biomass carbon to form rCeO2/C, wet impregnation of Pd precursor, and NaBH4 reduction.","matchedSynthesis":"Pd-rCeO2/C","composition":"Pd","role":"active catalyst"},{"paperId":"P238","catalystId":"P238_PERF_005","name":"Pd-oCeO2/C","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","support":"oCeO2/C","method":"wet_impregnation","synthesis":"Hydrothermal synthesis of oCeO2, hydrothermal assembly with biomass carbon to form oCeO2/C, wet impregnation of Pd precursor, and NaBH4 reduction.","matchedSynthesis":"Pd-oCeO2/C","composition":"Pd","role":"active catalyst"},{"paperId":"P239","catalystId":"P239_PERF_001","name":"Pd/AOP AN","activeMetals":"Pd","metalClass":"Pd-only","support":"amidoxime polyacrylonitrile (AOP AN) beads","method":"wet_impregnation","synthesis":"AOP AN beads were mixed with H2PdCl4 aqueous solution, stirred for 5h at room temperature, reduced with NaBH4 for 3h at room temperature, then filtered, washed and dried.","matchedSynthesis":"Pd/AOP AN","composition":"Pd","role":"catalyst for dehydrogenation of formic acid"},{"paperId":"P239","catalystId":"P239_PERF_002","name":"PdNi6/AOP AN","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","method":"unknown"},{"paperId":"P240","catalystId":"P240_PERF_001","name":"Ni0.8Mo0.2/ZIF-67@SiO2 yolk-shell","activeMetals":"Ni-Mo","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P241","catalystId":"P241_PERF_001","name":"Pt3Ni8/TiB2 (calcined at 600 °C)","activeMetals":"Pt-Ni","metalClass":"Non-Pd or Pd-free","support":"TiB2","method":"incipient_wetness_impregnation","synthesis":"PtNi alloy nanoparticles were synthesized via solvothermal method in DMF at 150 °C for 32 h, then loaded onto TiB2 support using incipient-wetness impregnation with ethanol as solvent, followed by thermal treatment in nitrogen.","matchedSynthesis":"Pt3Ni8/TiB2","composition":"Pt:Ni = 3:8","role":"catalyst for formic acid dehydrogenation"},{"paperId":"P241","catalystId":"P241_PERF_002","name":"Pt/TiB2","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","support":"TiB2","method":"incipient_wetness_impregnation","synthesis":"Pt NPs synthesized via solvothermal method in DMF, then loaded onto TiB2 via IWI and thermally treated","matchedSynthesis":"Pt/TiB2","composition":"Pt only","role":"monometallic comparison catalyst"},{"paperId":"P241","catalystId":"P241_PERF_003","name":"Ni/TiB2","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","support":"TiB2","method":"incipient_wetness_impregnation","synthesis":"Ni NPs synthesized via solvothermal method in DMF, then loaded onto TiB2 via IWI and thermally treated","matchedSynthesis":"Ni/TiB2","composition":"Ni only","role":"monometallic comparison catalyst"},{"paperId":"P241","catalystId":"P241_PERF_004","name":"unloaded TiB2","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P241","catalystId":"P241_PERF_005","name":"PtAu/TiB2","activeMetals":"Pt-Au","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P241","catalystId":"P241_PERF_006","name":"PtCo/TiB2","activeMetals":"Pt-Co","metalClass":"Non-Pd or Pd-free","method":"unknown"},{"paperId":"P241","catalystId":"P241_PERF_007","name":"PdRu/TiB2","activeMetals":"Pd-Ru","metalClass":"Pd-based multimetal","method":"unknown"}],"characterization":[{"paperId":"P001","catalystId":"P001_PERF_001","name":"Pt nanoclusters on 1D GaN nanowires","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","deactivation":"activity showed an evident reduction after 200 h, attributed to severe coking reaction"},{"paperId":"P002","catalystId":"P002_PERF_001","name":"3D Pd/8YSZ","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/8YSZ","phase":"Cubic zirconia support phase; metallic Pd nanoparticles.","particleSize":"5.2 ± 1.2 nm (fresh); 5.9 ± 0.9 nm (used)","surfaceStates":"Pd0 and Pd2+ species identified; both are noted as required to activate the catalytic reaction.","structureLink":"Sintering at 1200 °C provided an optimal balance between high porosity (86%) for anchoring Pd nanoparticles and compressive strength (3.7 MPa) for stability in a fixed-bed reactor.","deactivation":"Fouling of Pd active sites by water and FA (or HCOO- species); slight loss of Pd loading from 5.0 to 4.5 wt%"},{"paperId":"P003","catalystId":"P003_PERF_001","name":"3D Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"3D Pd/AC","phase":"Pd0 and PdO","particleSize":"1.9 ± 0.4 nm (fresh); increased to 2.8 nm after 5th use at 25 °C and 4.4 nm after 5th use at 55 °C.","surfaceStates":"Pd0 (335.9 and 341.1 eV) and Pd2+ (337.6 and 342.8 eV, ascribed to PdO); fresh catalyst Pd2+/Pd0 ratio was ~1.4.","structureLink":"The progressive reduction of Pd2+ species into Pd0 with time-on-stream is identified as the main factor responsible for permanent loss of activity; particle agglomeration occurred but had less impact on performance than the change in oxidation state.","deactivation":"No Pd leaching detected in aqueous effluent. Deactivation caused by progressive reduction of Pd2+ species into Pd0 with time-on-stream and agglomeration of Pd nanoparticles (particle size increased from 1.9 nm to 2.8-4.4 nm)."},{"paperId":"P004","catalystId":"P004_PERF_001","name":"Pd0.8Au0.2/1'","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.8Au0.2/1'","phase":"Fresh catalyst shows no distinct alloy peaks due to high dispersion; spent catalyst exhibits an alloy structure signal at 39.1° (between Au and Pd characteristic peaks).","particleSize":"0.8 nm to 2.3 nm (fresh); 2.2 nm to 6.8 nm (spent)","surfaceStates":"Electron transfer from support to metal NPs indicated by shift in N 1s XPS binding energy from 398.75 eV (pristine 1') to 400.30 eV.","structureLink":"High activity is attributed to the high surface area of the MOF support, ultra-small particle size, alloying effect of Au on Pd electronic structure, and Lewis basic N sites promoting FA activation.","deactivation":"Aggregation of metal NPs (size increased from 2.2 nm to 6.8 nm)"},{"paperId":"P005","catalystId":"P005_PERF_001","name":"Pd/BPC (optimal: C:B ratio 1:5, calcined at 900 °C, reduced at 60 °C)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BPC","phase":"Pd crystal planes (111), (200), and (220) identified by XRD (JCPDS No. 88-2335).","particleSize":"3.6 nm","surfaceStates":"XPS shows C-B bonds at 283.8 eV. Pd 3d XPS peaks at 335.7/341.0 eV (Pd(0)) and 337.2/342.5 eV (Pd2+). DFT indicates strong charge transfer between B and C atoms regulates metal-support interaction, reducing electron density of Pd 3d orbitals.","structureLink":"Boron doping induces a stronger support-metal interaction (adsorption energy -1.10 eV) compared to undoped or N-doped carbon, optimizing the electronic density of Pd and facilitating homogeneous nanoparticle distribution for enhanced formic acid dehydrogenation.","deactivation":"slight reduction in performance due to catalyst loss during filtration recovery"},{"paperId":"P005","catalystId":"P005_PERF_002","name":"Pd/PC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PC","phase":"Pd crystal planes (111), (200), and (220) identified by XRD.","particleSize":"Larger than Pd/BPC","structureLink":"Lack of boron doping results in larger particle size and weaker metal-support interaction, leading to lower catalytic activity than Pd/BPC."},{"paperId":"P005","catalystId":"P005_PERF_004","name":"Pd/NPC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NPC","surfaceStates":"DFT suggests N-doping increases charge density on surrounding C atoms, promoting electronic interaction between Pd and C.","structureLink":"N-doping improves performance over Pd/PC but is less effective than B-doping due to lower adsorption energy (-0.49 eV vs -1.10 eV)."},{"paperId":"P006","catalystId":"P006_PERF_001","name":"Pd/NMP-360-t","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMP-360","phase":"Monometallic Pd","particleSize":"2.3 ± 0.5 nm"},{"paperId":"P006","catalystId":"P006_PERF_004","name":"Pd1Au1/4-NMP-360-t (powder)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Au1/4/NMP-360","phase":"Alloy phase; XRD shows a broad symmetric diffraction peak between Pd and Au peaks; HRTEM interplanar spacing is 0.23 nm (larger than Pd(111) at 0.22 nm).","particleSize":"2.5 ± 0.5 nm","surfaceStates":"XPS shows negative shifts in binding energy for both Au 4f and Pd 3d levels, indicating electron transfer between Pd and Au (Pd gains d electrons).","structureLink":"Enhanced catalytic performance in formic acid dehydrogenation compared to monometallic analogues is attributed to the electronic interaction/synergistic effect between Pd and Au."},{"paperId":"P006","catalystId":"P006_PERF_006","name":"monolithic Pd1Au1/4-NMP-360-t","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Au1/4/NMP-360","phase":"Alloy phase; XRD shows a broad symmetric diffraction peak between Pd and Au peaks; HRTEM interplanar spacing is 0.23 nm (larger than Pd(111) at 0.22 nm).","particleSize":"2.5 ± 0.5 nm","surfaceStates":"XPS shows negative shifts in binding energy for both Au 4f and Pd 3d levels, indicating electron transfer between Pd and Au (Pd gains d electrons).","structureLink":"Enhanced catalytic performance in formic acid dehydrogenation compared to monometallic analogues is attributed to the electronic interaction/synergistic effect between Pd and Au."},{"paperId":"P007","catalystId":"P007_PERF_001","name":"Ag@Pd/N-GCNT aerogel (optimized as Ag1@Pd1)","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ag@Pd/N-GCNT aerogel","phase":"Ag core Pd shell structure with face-centered cubic (fcc) phase; XRD pattern is described as Pd-like.","particleSize":"3–12 nm","surfaceStates":"Metallic Pd (Pd 3d5/2 at 335.2 eV, Pd 3d3/2 at 340.0 eV) and metallic Ag (Ag 3d5/2 at 367.6 eV, Ag 3d3/2 at 374.1 eV).","structureLink":"The N-GCNT aerogel support enhances activity by inhibiting aggregation through strong metal-support interactions and providing anchoring points via nitrogen doping. A synergistic effect exists between Ag and Pd due to electronic promotion and charge transfer from Ag to Pd.","deactivation":"Heterogeneous nature confirmed; Ag and Pd contents in filtrate were below the detection limit of AAS"},{"paperId":"P008","catalystId":"P008_PERF_001","name":"PdMg","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdMg","phase":"Face-centered-cubic (fcc) palladium","particleSize":"5 nm to 20 nm; primary nanoparticles fused into larger particles in the range of 10-20 nm","surfaceStates":"Presence of steps, corners, kinks, and edges with lower coordination atoms; specific surface area of 36.0 m2/g","structureLink":"The larger nanopores compared to PdHCOONa provide a larger surface area and more active sites that benefit O-H bond dissociation.","deactivation":"Reduced catalytic activity may be attributed to Pd active sites being poisoned during the initial run"},{"paperId":"P008","catalystId":"P008_PERF_002","name":"PdNaBH4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdNaBH4","phase":"Face-centered-cubic (fcc) palladium","particleSize":"5 nm to 20 nm; contains small nano-sized grains","surfaceStates":"Presence of steps, corners, kinks, and edges; interplanar fringes of 0.225 nm corresponding to (111) planes","structureLink":"Larger nanopores compared to PdHCOONa may lead to larger surface areas and more active sites for O-H bond dissociation."},{"paperId":"P008","catalystId":"P008_PERF_003","name":"PdHCOONa","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdHCOONa","phase":"Face-centered-cubic (fcc) palladium","particleSize":"5 nm to 20 nm; nanoparticles are relatively big and dense compared to PdNaBH4","surfaceStates":"Presence of steps, corners, kinks, and edges; interplanar fringes of 0.225 nm corresponding to (111) planes","structureLink":"Smaller nanopores and denser nanoparticles result in lower catalytic activity compared to PdMg and PdNaBH4.","deactivation":"Distinct deactivation effect after 20 min, possibly due to formation of poisoning intermediates on the catalyst surface"},{"paperId":"P009","catalystId":"P009_PERF_001","name":"Ag1Pd9–(MnOx)1.5/A-CS","activeMetals":"Ag-Pd-Mn","metalClass":"Pd-based multimetal","matchedCharacterization":"Ag1Pd9–(MnOx)1.5/A-CS","phase":"AgPd alloy (fcc structure confirmed by XRD diffraction peak between Ag(111) and Pd(111), and HRTEM lattice spacing of 0.23 nm)","particleSize":"< 5 nm","surfaceStates":"Ag: Ag0 (3d5/2 at 367.75 eV); Pd: Pd0 (3d5/2 at 335.78 eV) and Pd2+ (3d5/2 at 337.78 eV); Mn: Mn2+ (2p3/2 at 640.3 eV), Mn3+ (2p3/2 at 641.6 eV), and Mn4+ (2p3/2 at 642.8 eV). Negative binding energy shifts for Ag 3d and Pd 3d indicate electron transfer from Ag to Pd.","structureLink":"MnOx acts as a CO-sponge enhancing activity and CO-resistivity; alloy formation and ultrafine particle size (< 5 nm) are critical for high catalytic activity; air activation preserves spherical morphology and oxygen-containing functional groups which benefit performance.","deactivation":"No leaching of metals into the solution (determined by ICP-AES)."},{"paperId":"P010","catalystId":"P010_PERF_001","name":"Pd/NH2-KIE-11-k","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-KIE-11-k","phase":"Pd nanoparticles","particleSize":"1.60 nm","structureLink":"Highest catalytic activity (TOF: 860.7 mol H2 mol Pd-1 h-1) due to a trade-off pore structure providing both easy diffusion of molecules and confinement of active metal nanoparticles to suppress aggregation"},{"paperId":"P010","catalystId":"P010_PERF_002","name":"Pd/NH2-KIE-11-c","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-KIE-11-c","phase":"Pd nanoparticles","particleSize":"1.75 nm","structureLink":"Lower catalytic activity compared to Pd/NH2-KIE-11-k due to small pore size restricting easy diffusion of reactant and product molecules"},{"paperId":"P010","catalystId":"P010_PERF_003","name":"Pd/NH2-KIE-11-l","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-KIE-11-l","phase":"Pd nanoparticles","particleSize":"2.58 nm","structureLink":"Lowest catalytic activity due to increased Pd nanoparticle size and aggregation resulting from lack of confinement in the large pores of KIE-11-l"},{"paperId":"P011","catalystId":"P011_PERF_001","name":"Pd1Au2/AC-LA","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Au2/AC-LA","phase":"Uniform PdAu alloy","particleSize":"5.2 nm","surfaceStates":"Pd and Au peaks shift to lower binding energies compared to monometallic catalysts, indicating electron transfer from the support and L-arginine (LA) to PdAu NPs; Pd becomes more electron-rich as Au content increases.","structureLink":"Synergistic effect between PdAu alloy and basic LA regulates reactant adsorption. Lewis acidity of Au adsorbs lone-pair electrons of bicarbonate intermediate, while electron-rich Pd facilitates nucleophilic attack on the positive C atom of bicarbonate. The guanidine group of LA enhances CO2 capture and activation.","deactivation":"No obvious loss of Pd (before: 1.96 wt %, after: 1.87 wt %) and Au (before: 6.38 wt %, after: 6.07 wt %)"},{"paperId":"P012","catalystId":"P012_PERF_001","name":"Pd-La(OH)3/N-PCB-NH2","activeMetals":"Pd-La","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-La(OH)3/N-PCB-NH2","phase":"Low crystallinity; HRTEM shows a plane distance of 0.222 nm assigned to the Pd(111) planes.","particleSize":"1.6 nm","surfaceStates":"Pd 3d binding energies (335.9 and 341.2 eV) shifted to higher values compared to support-free Pd-La(OH)3, indicating strong metal-support interaction (SMSI). La exists as La3+ in the form of La(OH)3 (La 3d5/2 at 836.1 eV).","structureLink":"The high catalytic activity is attributed to the ultrafine particle size, the strong metal-support interaction (SMSI), and the abundance of surface basic sites provided by La(OH)3 and amine groups which facilitate O-H bond dissociation of formic acid.","deactivation":"Pd leaching: 0.21% (single reaction), 0.23% (durability test); La leaching: 0.20% (single reaction), 0.30% (durability test); particle size increased from 1.6 to 2.4 nm"},{"paperId":"P013","catalystId":"P013_PERF_001","name":"Pd/HNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HNTs","phase":"Metallic Pd nanoparticles supported on natural halloysite nanotubes","particleSize":"3.5 nm (chemisorption); >4.3 nm to 25 nm (TEM)","surfaceStates":"Pd0 and Pd2+","structureLink":"Larger particle size and aggregation lead to significantly lower catalytic activity compared to the amino-functionalized support."},{"paperId":"P013","catalystId":"P013_PERF_002","name":"Pd/HNTs (1.28 wt.% Pd)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HNTs","phase":"Metallic Pd nanoparticles supported on natural halloysite nanotubes","particleSize":"3.5 nm (chemisorption); >4.3 nm to 25 nm (TEM)","surfaceStates":"Pd0 and Pd2+","structureLink":"Larger particle size and aggregation lead to significantly lower catalytic activity compared to the amino-functionalized support."},{"paperId":"P013","catalystId":"P013_PERF_003","name":"Pd/NH2-HNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-HNTs","phase":"Metallic Pd nanoparticles supported on amino-functionalized halloysite nanotubes","particleSize":"1.2 nm (chemisorption); 1.8 ± 0.4 nm (TEM)","surfaceStates":"Pd0 and Pd2+; Pd 3d peaks shifted toward higher binding energies compared to Pd/HNTs due to interaction with -NH2 groups (electron migration from Pd to N)","structureLink":"The -NH2 groups facilitate high dispersion of ultra-fine particles and act as basic sites for formate ion formation; the electronic interaction between Pd and N enhances the combination of active centers with formate ions.","deactivation":"Pd NP size increased after the fifth catalytic reaction cycle."},{"paperId":"P013","catalystId":"P013_PERF_004","name":"Pd/NH2-HNTs (1.30 wt.% Pd)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-HNTs","phase":"Metallic Pd nanoparticles supported on amino-functionalized halloysite nanotubes","particleSize":"1.2 nm (chemisorption); 1.8 ± 0.4 nm (TEM)","surfaceStates":"Pd0 and Pd2+; Pd 3d peaks shifted toward higher binding energies compared to Pd/HNTs due to interaction with -NH2 groups (electron migration from Pd to N)","structureLink":"The -NH2 groups facilitate high dispersion of ultra-fine particles and act as basic sites for formate ion formation; the electronic interaction between Pd and N enhances the combination of active centers with formate ions."},{"paperId":"P013","catalystId":"P013_PERF_005","name":"PdAu/NH2-HNTs","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/NH2-HNTs","phase":"Bimetallic PdAu nanoparticles","surfaceStates":"Shift in Pd 3d binding energies relative to Pd/NH2-HNTs due to differences in work functions between Pd and Au, causing electron migration","structureLink":"Synergistic electronic effects between Pd and Au and the support significantly enhance catalytic performance for DFA."},{"paperId":"P013","catalystId":"P013_PERF_006","name":"PdAg/NH2-HNTs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAg/NH2-HNTs","phase":"Bimetallic PdAg nanoparticles","surfaceStates":"Shift in Pd 3d binding energies relative to Pd/NH2-HNTs due to work function differences between Pd and Ag","structureLink":"Electronic effects modify the electron density of Pd0, influencing the activity which is lower than that of PdAu/NH2-HNTs."},{"paperId":"P013","catalystId":"P013_PERF_007","name":"Au/NH2-HNTs","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"PdAu/NH2-HNTs","phase":"Bimetallic PdAu nanoparticles","surfaceStates":"Shift in Pd 3d binding energies relative to Pd/NH2-HNTs due to differences in work functions between Pd and Au, causing electron migration","structureLink":"Synergistic electronic effects between Pd and Au and the support significantly enhance catalytic performance for DFA."},{"paperId":"P013","catalystId":"P013_PERF_008","name":"Ag/NH2-HNTs","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"PdAg/NH2-HNTs","phase":"Bimetallic PdAg nanoparticles","surfaceStates":"Shift in Pd 3d binding energies relative to Pd/NH2-HNTs due to work function differences between Pd and Ag","structureLink":"Electronic effects modify the electron density of Pd0, influencing the activity which is lower than that of PdAu/NH2-HNTs."},{"paperId":"P014","catalystId":"P014_PERF_001","name":"AgPd-NH2-SBA-15","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AgPd-NH2-SBA-15","phase":"Ag-doped Pd nanoparticles","particleSize":"<1 nm (ultrasmall NPs); >20 nm (outer surface Ag NPs); single metal atoms","surfaceStates":"Ag: Ag+ (367.5, 373.5 eV, likely AgCl) and Ag0 (368.2, 374.2 eV); Pd: Pd0 (334.8, 340.2 eV) and Pd2+ (336.9, 342.3 eV, unreacted PdCl2)","structureLink":"High activity attributed to the synergy between amino groups (acting as Brønsted basic sites for FA deprotonation) and single metal atoms/ultrasmall Ag-doped Pd NPs (distorted crystal lattice)."},{"paperId":"P014","catalystId":"P014_PERF_002","name":"Pd-NH2-SBA-15","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd-NH2-SBA-15","particleSize":"ca. 1 nm (ultrasmall NPs); ca. 10 nm (outer surface NPs)"},{"paperId":"P014","catalystId":"P014_PERF_003","name":"Ag-NH2-SBA-15","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ag-NH2-SBA-15","particleSize":"<6 nm (average ca. 3 nm)"},{"paperId":"P015","catalystId":"P015_PERF_001","name":"Arg-Pd/MSC-30","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Arg-Pd/MSC-30","phase":"Metallic Pd; PXRD shows a weak broad diffraction peak at ~40° corresponding to the (111) plane.","particleSize":"1.9 ± 0.3 nm","surfaceStates":"Surface oxidation to Pd(II); presence of amine groups from arginine (N 1s at 400.5 eV).","structureLink":"Superior activity is attributed to smaller particle size (more active sites) and a synergetic effect where arginine provides an alkalized environment facilitating FA deprotonation; MSC-30 pores provide spatial confinement preventing aggregation."},{"paperId":"P015","catalystId":"P015_PERF_002","name":"Pd/MSC-30","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MSC-30","phase":"Metallic Pd; distinct characteristic diffraction peaks observed in PXRD.","particleSize":"3.9 ± 0.5 nm","surfaceStates":"Surface oxidation of ultrafine Pd NPs to Pd(II).","structureLink":"Larger particle size and lack of amino acid synergy resulted in significantly lower catalytic activity for FA dehydrogenation."},{"paperId":"P016","catalystId":"P016_PERF_001","name":"PdNC/AC-NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdNC/AC-NH2","phase":"Nanoclusters","particleSize":"2.20 nm","surfaceStates":"Intermediate electronic state between single atoms and nanoparticles","structureLink":"Highest activity (TOF 40856 h-1 at 328 K) due to an optimal balance of the Pd0/Pd2+ synergistic electronic effect for C-H cleavage and a robust hydrogen spillover effect for H2 desorption."},{"paperId":"P016","catalystId":"P016_PERF_002","name":"Pd1/AC-NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd1/AC-NH2","phase":"Single atoms","particleSize":"Isolated atoms","surfaceStates":"Lowest electronic state among the three Pd species (highest binding energy in XPS)","structureLink":"Highest hydrogen spillover capacity but lower activity than nanoclusters due to lack of optimal balance between electronic properties and spillover."},{"paperId":"P016","catalystId":"P016_PERF_003","name":"PdNP/AC-NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdNP/AC-NH2","phase":"Metallic Pd (XRD peaks at 41.12° and 46.66°, JCPDS: 46-1043)","particleSize":"5.42 nm","surfaceStates":"Richest electronic state (lowest binding energy in XPS)","structureLink":"Lowest activity among the three due to the lowest hydrogen spillover capacity, despite having the richest Pd0 electronic state."},{"paperId":"P016","catalystId":"P016_PERF_006","name":"PdNC/SiO2-NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdNC/SiO2-NH2","phase":"Nanoclusters","particleSize":"2.15 nm","surfaceStates":"Similar electronic properties to PdNC/AC-NH2","structureLink":"No activity for FA dehydrogenation, underscoring the critical role of the support's hydrogen spillover effect (SiO2 is a nonreducing carrier with mild spillover)."},{"paperId":"P017","catalystId":"P017_PERF_001","name":"Pd@KNDC(10-900)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@KNDC(10-900)","phase":"Metallic Pd (PDF no. 89-4897) with identified planes (1 1 1), (2 0 0), and (2 2 0).","particleSize":"4.1 nm","surfaceStates":"Mainly metallic Pd0 (Pd 3d5/2 at 335.1 eV, Pd 3d3/2 at 340.3 eV) with minor surface Pd2+.","structureLink":"The superior catalytic performance is attributed to the robust synergistic interactions between Pd NPs and N sites on the KNDC(900) support (metal-support interaction, MSI), as well as the ultrafine size and high dispersion of the active Pd NPs.","deactivation":"increased mean size from 4.1 nm to 4.3 nm for recovered catalyst; partial loss of Pd content found"},{"paperId":"P018","catalystId":"P018_PERF_001","name":"Pd0.9Ag0.1/CDs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.9Ag0.1/CDs","phase":"PdAg alloy; crystal plane spacing of 0.227 nm (between fcc Pd 0.224 nm and Ag 0.235 nm); XRD shows shift of Pd peaks to lower 2 theta values with increasing Ag content.","particleSize":"1.14 nm (freshly prepared); increased to approximately 1.45 nm after five cycles.","surfaceStates":"XPS shows negative shift in Pd 3d binding energy (electron-enriched Pd) and positive shift in Ag 3d binding energy (electron-depleted Ag); N 1s spectrum shifted positively by 0.11 eV compared to Pd/CDs.","structureLink":"High activity is attributed to electron transfer from Ag to Pd, strong electronic interactions between the PdAg alloy and N-doped CDs support, and the restrictive effect of CDs preventing nanoparticle aggregation.","deactivation":"Decrease in durability is due to the increase in particle size of the PdAg alloys and the erosion of the catalyst by the reactants."},{"paperId":"P019","catalystId":"P019_PERF_001","name":"PdAu/NH2-MIL-101","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/NH2-MIL-101","phase":"Pd-Au alloy structure (verified by HRTEM lattice spacing of 0.232 nm and XRD shift of the Pd(111) peak to a lower angle)","particleSize":"1.2 nm (increased to 1.9 nm after durability tests)","surfaceStates":"Electron migration from Pd to Au; Pd0 shifted to higher binding energies (341.3 eV and 336.1 eV) and Au0 shifted to lower binding energies (87.7 eV and 84.0 eV)","structureLink":"Synergy between amino groups (acting as anchor sites and proton scavengers), electronic coupling between Pd and Au, and strong metal-support interaction (SMSI) promotes the formation of reactive ultrafine NCs and reduces activation energy to 36.3 kJ/mol","deactivation":"H2 generation rate decreases slightly after cycle test; slight size increase of PdAu NCs to 1.9 nm"},{"paperId":"P019","catalystId":"P019_PERF_002","name":"Pd/NH2-MIL-101","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-MIL-101","phase":"Monometallic Pd","surfaceStates":"Pd0 3d3/2 at 341.2 eV and Pd0 3d5/2 at 335.9 eV","structureLink":"Mild catalytic activity with a higher activation energy (37.7 kJ/mol) than the PdAu alloy catalyst","deactivation":"null"},{"paperId":"P019","catalystId":"P019_PERF_003","name":"PdAu/MIL-101","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/MIL-101","particleSize":"3.1 nm","structureLink":"Poor activity compared to PdAu/NH2-MIL-101 due to the absence of amino groups which are necessary for stabilizing NCs and promoting FA deprotonation","deactivation":"null"},{"paperId":"P019","catalystId":"P019_PERF_004","name":"pure PdAu NPs","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","deactivation":"null"},{"paperId":"P020","catalystId":"P020_PERF_001","name":"Pd0.60Co0.18Ni0.22/TiO2-ALD-SiO2 (6 cycles)","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","deactivation":"No Pd, Co, or Ni detected in reaction solutions after 5th, 10th, and 20th reuse (no leaching). Minimal sintering observed: mean particle size increased from 3.52 to 3.75 nm."},{"paperId":"P020","catalystId":"P020_PERF_002","name":"Pd0.60Co0.18Ni0.22/TiO2","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","deactivation":"Highly agglomerated as a result of sintering on the surface of TiO2 under forcing conditions (100 °C)."},{"paperId":"P021","catalystId":"P021_PERF_001","name":"Au0.3Pd0.7/CA-BN-NH2","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/CA-BN-NH2","phase":"Au0.3Pd0.7 alloy (confirmed by XRD broad peaks between Pd and Au; HRTEM lattice spacing of 0.230 nm indicates lattice expansion of fcc Pd)","particleSize":"~3.6 nm","surfaceStates":"Electron-rich Pd active sites resulting from strong metal-support interaction (electron transfer from CA-BN-NH2 to AuPd) and ligand effect (charge transfer between Pd and Au)","structureLink":"Ultrafine particle size, excellent dispersion, and electronic modification (electron-rich Pd promoting C-H dissociation and weak H atom adsorption boosting H2 desorption) lead to extraordinary catalytic activity.","deactivation":"Metal loading amount of AuPd NPs decreased after the fifth run"},{"paperId":"P021","catalystId":"P021_PERF_002","name":"Au0.3Pd0.7/BN-NH2","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/BN-NH2","phase":"Au0.3Pd0.7 alloy","particleSize":"~4.1 nm","surfaceStates":"No significant shift in Pd 3d and Au 4f peaks compared to Au0.3Pd0.7/BN, indicating that amine groups from APTES alone do not significantly modify the electronic structure.","structureLink":"Higher activity than Au0.3Pd0.7/BN due to smaller particle size (higher active site concentration), but lower than Au0.3Pd0.7/CA-BN-NH2 due to lack of support-induced electronic modification."},{"paperId":"P021","catalystId":"P021_PERF_003","name":"Au0.3Pd0.7/BN","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/BN","phase":"Au0.3Pd0.7 alloy","particleSize":"~10.4 nm","surfaceStates":"Higher binding energies for Pd 3d and Au 4f compared to CA-BN-NH2 supported catalyst, indicating weaker electron density on the metal NPs.","structureLink":"Larger particle size and poor dispersion result in significantly lower catalytic activity."},{"paperId":"P022","catalystId":"P022_PERF_001","name":"AuPd/n-CNS-Th-160","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AuPd/n-CNS-Th-160","phase":"fcc alloy structure","particleSize":"1.82 nm","surfaceStates":"Electron transfer from the support to Pd and Au, evidenced by XPS binding energy shifts to lower values (Pd 3d shift ~0.2 eV; Au 4f shift ~0.3 eV) compared to pure metals.","structureLink":"The high ratio of graphitic N to pyridinic N in the support modifies electron density distribution and minimizes nanoparticle size, which greatly enhances catalytic activity for formic acid dehydrogenation.","deactivation":"Possible losses of supported catalyst, nanoparticle detachment from support, or trapping of byproducts/intermediates in porous catalyst."},{"paperId":"P023","catalystId":"P023_PERF_001","name":"Au-Pd-SBA-15-NH2-TD","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au-Pd-SBA-15-NH2-TD","phase":"Au-Pd bimetal alloy (HRTEM lattice fringe of 0.230 nm, between Pd(111) and Au(111))","particleSize":"3.2 nm (distribution 2.8-3.6 nm)","surfaceStates":"Metallic Au, Pd0, positively charged Pd, -NH2 groups, and protonated amine groups (NH3+).","structureLink":"Smallest nanoparticle size and highest surface amine density lead to strong metal-metal and metal-support interactions, resulting in the best catalytic performance."},{"paperId":"P023","catalystId":"P023_PERF_002","name":"Au-Pd-SBA-15-NH2-T","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au-Pd-SBA-15-NH2-T","phase":"Poorly formed bimetal; line scanning and mapping primarily show Au species with difficult-to-observe Pd.","particleSize":"6.2 nm","surfaceStates":"Metallic Au and Pd species.","structureLink":"Largest bimetal nanoparticle size and poorly formed bimetallic structure lead to the worst catalytic performance."},{"paperId":"P023","catalystId":"P023_PERF_003","name":"Au-Pd-SBA-15-NH2-D","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au-Pd-SBA-15-NH2-D","phase":"Au-Pd bimetal","particleSize":"4.0 nm","surfaceStates":"Metallic Au and Pd species.","structureLink":"Larger metal particle size and lower amine content compared to the TD sample result in lower catalytic activity."},{"paperId":"P023","catalystId":"P023_PERF_004","name":"Au-Pd-SBA-15","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au-Pd-SBA-15-NH2-TD","phase":"Au-Pd bimetal alloy (HRTEM lattice fringe of 0.230 nm, between Pd(111) and Au(111))","particleSize":"3.2 nm (distribution 2.8-3.6 nm)","surfaceStates":"Metallic Au, Pd0, positively charged Pd, -NH2 groups, and protonated amine groups (NH3+).","structureLink":"Smallest nanoparticle size and highest surface amine density lead to strong metal-metal and metal-support interactions, resulting in the best catalytic performance."},{"paperId":"P024","catalystId":"P024_PERF_001","name":"Au1Pd3/rGO","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","deactivation":"Negligible leaching (Au < 0.04%; Pd < 0.05%). Deactivation attributed to agglomeration of Au-Pd particles (mean size increased from 3.5 nm to 6.8 nm), strong absorption of FA on rGO, and CO poisoning."},{"paperId":"P025","catalystId":"P025_PERF_003","name":"Ag/AgPd CS-0.9","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","deactivation":"no obvious changes in Ag/Pd composition or network-like morphology after 4 runs"},{"paperId":"P026","catalystId":"P026_PERF_001","name":"Au1Pd3/BNNFs-A","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au1Pd3/BNNFs-A","phase":"AuPd alloy (confirmed by XRD peaks between metallic Au and Pd, HRTEM lattice spacing of ~0.228 nm, and EDS elemental mapping)","particleSize":"~2.2 nm","surfaceStates":"Partial transfer of electrons from Pd to Au; electron transfer from Au1Pd3 nanoparticles to the BNNFs-A carrier.","structureLink":"High activity is attributed to small particle size, high dispersion, modified Pd electronic structure via synergistic effect with Au, and the role of amine groups on BN surfaces as proton scavengers.","deactivation":"Slight increase in nanoparticle size from 2.2 to 3.3 nm after cycling test."},{"paperId":"P027","catalystId":"P027_PERF_001","name":"Pd0.6Cr0.4/OPDA-SmMn2O5","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.6Cr0.4/OPDA-SmMn2O5","phase":"Bimetallic PdCr NPs exist in an alloyed state, characterized by lattice contraction (lattice spacing 0.188 nm) compared to pure Pd (0.193 nm).","particleSize":"2.05 nm","surfaceStates":"XPS confirms metallic Pd0 (Pd 3d: 340.4, 335.2 eV) and Cr0 (Cr 2p: 584.3, 574.5 eV). The amino-modified support creates electron-rich PdCr NPs by modulating the electronic structure.","structureLink":"The formation of ultrafine, highly dispersed alloyed nanoparticles and the electronic modulation provided by the amino groups (OPDA) significantly enhance catalytic activity for formic acid dehydrogenation.","deactivation":"No significant agglomeration after reaction confirmed by TEM."},{"paperId":"P028","catalystId":"P028_PERF_001","name":"Pd7Ag3/SPP","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd7Ag3/SPP","phase":"PdAg alloy","surfaceStates":"Formation of electronically enriched Pd by adsorption of formate anions","structureLink":"The hierarchical SPP zeolite carrier is more advantageous than bulky zeolites for making highly active catalysts; the optimized Pd/Ag ratio was found to be 7:3.","deactivation":"Slight increase in reaction time after three cycles may be due to the loss of catalyst during cycling"},{"paperId":"P028","catalystId":"P028_PERF_002","name":"PdAg/SPP (various ratios)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Ag/SPP","phase":"Metallic silver","structureLink":"Exhibited low activity for formic acid dehydrogenation."},{"paperId":"P028","catalystId":"P028_PERF_003","name":"Pd/SPP and Ag/SPP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/SPP","phase":"Metallic palladium","structureLink":"Pd plays a decisive role in formic acid dehydrogenation compared to Ag."},{"paperId":"P029","catalystId":"P029_PERF_001","name":"Pd0.8Au0.2/UiO-66-D","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.8Au0.2/UiO-66-D","phase":"PdAu alloy","particleSize":"1.4 nm","surfaceStates":"Pd0 (3d5/2: 335.44 eV) and Au0 (4f7/2: 84.46 eV); partial electron transfer from Pd to Au due to electronegativity differences","structureLink":"High activity attributed to highly dispersed PdAu alloy NPs, electronic structure adjusted by the alloy effect and metal-support interaction, and basic amine groups promoting formic acid activation.","deactivation":"Slight aggregation of PdAu NPs (average size increased to about 2 nm) over time"},{"paperId":"P029","catalystId":"P029_PERF_002","name":"Pd0.8Au0.2/UiO-66-S","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.8Au0.2/UiO-66-S","phase":"PdAu alloy","particleSize":"5.6 nm","surfaceStates":"Pd0 (3d5/2: 335.64 eV) and Au0 (4f7/2: 84.74 eV)","structureLink":"Lower activity and stability compared to -D sample due to larger particle size and distribution on the external surface, leading to easier aggregation.","deactivation":"Obvious aggregation of PdAu NPs (about 10.2 nm) in spent catalyst"},{"paperId":"P029","catalystId":"P029_PERF_003","name":"Pd0.8Au0.2/UiO-66-ref-D","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.8Au0.2/UiO-66-ref-D","phase":"PdAu alloy","particleSize":"> 5 nm","structureLink":"Nearly inactive for formic acid decomposition, indicating that NH2 groups are crucial for activity."},{"paperId":"P029","catalystId":"P029_PERF_004","name":"Pd0.8Au0.2/UiO-66-ref-S","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.8Au0.2/UiO-66-ref-S","phase":"PdAu alloy","particleSize":"> 5 nm","structureLink":"Nearly inactive for formic acid decomposition."},{"paperId":"P030","catalystId":"P030_PERF_001","name":"PdCo0.2/EDA-HPAN","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"PdCo0.2/EDA-HPAN","phase":"Bimetallic alloy","particleSize":"0.81 nm","surfaceStates":"Pd0 signals shift toward lower binding energies compared to Pd/EDA-HPAN due to electron transfer from Co to Pd. Co 2p XPS peaks at 781.1 and 797.3 eV.","structureLink":"The alloy effect adjusts the electronic state of Pd, decreasing particle size and improving dehydrogenation activity compared to single metal Pd.","deactivation":"Strong capability against aggregation; spent catalyst particle size around 0.9 nm"},{"paperId":"P030","catalystId":"P030_PERF_002","name":"Pd/EDA-HPAN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/EDA-HPAN","phase":"Single metal nanoparticles","particleSize":"0.88 nm","surfaceStates":"Pd 3d XPS peaks: Pd2+ (342.8, 337.8 eV) and Pd0 (341.1, 335.9 eV).","structureLink":"Ultra-small particle size and high dispersion on the aminated hollow support contribute to catalytic activity.","deactivation":"Strong capability against aggregation; spent catalyst particle size around 1.0 nm"},{"paperId":"P031","catalystId":"P031_PERF_001","name":"Pd0.7Cr0.3/NH2-MXene","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.7Cr0.3/NH2-MXene","phase":"Bimetallic PdCr nanoparticles; HRTEM shows a lattice spacing of 0.230 nm, indicating lattice contraction relative to the Pd(111) plane (0.231 nm) due to Cr incorporation.","particleSize":"1.2-1.8 nm","surfaceStates":"Electron-rich metal sites; XPS reveals negative shifts in binding energies for both Pd and Cr compared to the non-amine functionalized support, indicating electron transfer from amine groups to the nanoparticles. Specific peaks: Pd 3d5/2 at 335.1 eV (Pd0), Cr 2p3/2 at 574.9 eV (Cr0) and 577.0 eV (Cr3+).","structureLink":"Amine groups act as anchors to prevent aggregation and donate electrons to the PdCr sites, accelerating O-H bond cleavage in formic acid. Cr incorporation modulates the electronic structure, local strain, and atomic coordination number of Pd active sites."},{"paperId":"P031","catalystId":"P031_PERF_002","name":"Pd0.7Cr0.3/MXene","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.7Cr0.3/MXene","particleSize":"Seriously aggregated compared to Pd0.7Cr0.3/NH2-MXene","surfaceStates":"Higher binding energies for Pd and Cr compared to the amine-functionalized version, indicating a lack of electron transfer from the support.","structureLink":"Lack of amine anchors leads to nanoparticle aggregation and less electron-rich active sites, resulting in significantly lower catalytic activity (17.6 times lower TOF)."},{"paperId":"P032","catalystId":"P032_PERF_001","name":"POLITAG-20-Pd(0)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"POLITAG-20-Pd(0)","phase":"Pd nanoparticles","surfaceStates":"Pd(0) stabilized by pincer-type bis-imidazolium ionic tags on a macroreticular resin support.","structureLink":"The macroreticular polymeric matrix provides a stable and durable porous structure suitable for aqueous media. The use of pincer-type ionic tags to stabilize Pd(0) and the operation in an alkaline environment (pH 9) were linked to enhanced dehydrogenation rates and total selectivity, inhibiting the dehydration pathway.","deactivation":"TEM analysis confirmed preservation of Pd nanoparticle morphology and dimensions in the recycled catalyst."},{"paperId":"P033","catalystId":"P033_PERF_001","name":"1Pd/C3Ny_650_4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1Pd/C3Ny_650_4","phase":"Metallic Pd","particleSize":"2.8 nm","structureLink":"Lowest activity among the series due to smallest particle size and lowest metal loading.","deactivation":"minimal Pd leaching; drop in rate ascribed to formation of intermediate species (COH and CHOO) blocking the active phase"},{"paperId":"P033","catalystId":"P033_PERF_002","name":"5Pd/C3Ny_650_4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"5Pd/C3Ny_650_4","phase":"fcc Pd0","particleSize":"4.6 nm (TEM), 4.5 nm (XRD)","surfaceStates":"Preferential orientation of the (111) facet","structureLink":"Optimal particle size (~4.6 nm) for maximum specific rate in formic acid decomposition, following a volcano relationship.","deactivation":"minimal Pd leaching; drop in rate ascribed to formation of intermediate species (COH and CHOO) blocking the active phase"},{"paperId":"P033","catalystId":"P033_PERF_003","name":"10Pd/C3Ny_650_4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"10Pd/C3Ny_650_4","phase":"Coexistence of metallic palladium (Pd0) and palladium hydride (PdHx)","particleSize":"10.2 nm (TEM), 11.1 nm (XRD)","surfaceStates":"Preferential orientation of the (111) facet; expanded Pd lattice (3.9123 Å vs bulk 3.8910 Å)","structureLink":"Highest TOF and cumulative H2 production; larger, thermodynamically stable single-crystalline nanoparticles are more resistant to deactivation than smaller clusters.","deactivation":"minimal Pd leaching; drop in rate ascribed to formation of intermediate species (COH and CHOO) blocking the active phase"},{"paperId":"P034","catalystId":"P034_PERF_001","name":"Pd/NC-Co1%","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NC-Co1%","phase":"Pd nanoparticles immobilized on a support (not an alloy).","particleSize":"1.86 nm","surfaceStates":"Pd 3d peak at 336.2 eV with an increased area for Pd2+ compared to Pd/NC, indicating strong interaction between Co and Pd NPs. Co is present as Co2+-N species. N 1s spectra show pyridinic N (398.5 eV), pyrrolic N (400.5 eV), graphitic N (401 eV), and N-Co species (399.5 eV).","structureLink":"Atomically dispersed Co atoms on the support increase carbon defects, provide additional active sites for Pd dispersion, and regulate the nucleation/growth of Pd NPs to reduce their size, resulting in enhanced catalytic activity for FA dehydrogenation."},{"paperId":"P034","catalystId":"P034_PERF_002","name":"Pd/NC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NC","phase":"Pd nanoparticles","surfaceStates":"Pd 3d peak at 336.2 eV.","structureLink":"Lower activity than Pd/NC-Co1%, demonstrating the promotional effect of Co doping on the support."},{"paperId":"P034","catalystId":"P034_PERF_003","name":"PdCo1%/NC","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"PdCo1%/NC","phase":"PdCo alloy","particleSize":"2.41 nm","surfaceStates":"Binding energy of Co is 0.2 eV lower than in NC-Co1% and Pd/NC-Co1%; Pd 3d peak is 0.25 eV higher than in Pd/NC and Pd/NC-Co1%.","structureLink":"Lower catalytic activity compared to Pd/NC-Co1%, suggesting that atomically dispersed Co on the support is more effective for performance enhancement than alloying Co into the nanoparticles."},{"paperId":"P035","catalystId":"P035_PERF_001","name":"0.1Pt/MoC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"0.1Pt/MoC","phase":"Single-crystal FCC α-MoC support with Pt single atoms (SAs)","particleSize":"Single atom","surfaceStates":"Pt exists as Ptδ+ species (positive charge); Mo exists in Mo2+ and Mo4+ states","structureLink":"SAs maximize FA dehydrogenation and CO2 hydrogenation efficiency due to strong Pt-MoC interactions and high adsorption energies for FA (-2.84 eV) and CO2 (-1.42 eV), but exhibit low CO oxidation activity due to CO poisoning (adsorption energy -2.35 eV).","deactivation":"ICP-AES analysis shows Pt and Mo contents in the filtrate are below detection limit."},{"paperId":"P035","catalystId":"P035_PERF_002","name":"0.2Pt/MoC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"0.2Pt/MoC","phase":"α-MoC support with Pt nanoclusters (NCs) and small amount of nanoparticles (NPs)","particleSize":"ca. 1.1 nm (average size of NCs)","surfaceStates":"Coexistence of metallic Pt and positively charged Ptδ+ species","structureLink":"Displays the highest performance for room-temperature CO oxidation."},{"paperId":"P035","catalystId":"P035_PERF_003","name":"1Pt/MoC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"1Pt/MoC","phase":"α-MoC support with co-existing NCs and NPs","particleSize":"ca. 2.2 nm","structureLink":"Lower activity for FA dehydrogenation and CO2 hydrogenation compared to SAs."},{"paperId":"P035","catalystId":"P035_PERF_004","name":"2Pt/MoC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"2Pt/MoC","phase":"α-MoC support with co-existing NCs and NPs","particleSize":"ca. 3.1 nm","surfaceStates":"Dominating metallic Pt state","structureLink":"Lowest activity for FA dehydrogenation and CO2 hydrogenation among the series."},{"paperId":"P036","catalystId":"P036_PERF_001","name":"Ru4/AC","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru4/AC","phase":"Hexagonal-close-packed (hcp) structure of metallic Ru.","particleSize":"3–5 nm","surfaceStates":"Strong interaction between Ru nanoparticles and CO, leading to easy poisoning.","structureLink":"Lack of nitrogen coordination results in strong CO adsorption, which poisons active sites and inhibits activity.","deactivation":"poisoned by generated CO"},{"paperId":"P036","catalystId":"P036_PERF_003","name":"Ru2/CN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru2/CN, Ru4/CN, Ru14/CN","phase":"Metallic Ru species on nitrogen-doped carbon; XRD peak intensity at 43.4° increases with higher Ru content.","particleSize":"2–3 nm","surfaceStates":"Electron-deficient state due to Ru-N interaction.","structureLink":"Activity increases with Ru content up to 7 wt%, then stabilizes."},{"paperId":"P036","catalystId":"P036_PERF_004","name":"Ru4/CN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru2/CN, Ru4/CN, Ru14/CN","phase":"Metallic Ru species on nitrogen-doped carbon; XRD peak intensity at 43.4° increases with higher Ru content.","particleSize":"2–3 nm","surfaceStates":"Electron-deficient state due to Ru-N interaction.","structureLink":"Activity increases with Ru content up to 7 wt%, then stabilizes."},{"paperId":"P036","catalystId":"P036_PERF_005","name":"Ru7/CN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru7/CN","phase":"Metallic Ru species supported on nitrogen-doped carbon; broad XRD peaks suggest an amorphous structure or ultra-small size.","particleSize":"2–3 nm","surfaceStates":"Electron-deficient state caused by strong electronic interaction between Ru and nitrogen doping on the support.","structureLink":"Nitrogen coordination weakens CO adsorption strength via electron depletion on Ru, increasing CO tolerance and suppressing CO2 dissociation into CO."},{"paperId":"P036","catalystId":"P036_PERF_006","name":"Ru14/CN","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru2/CN, Ru4/CN, Ru14/CN","phase":"Metallic Ru species on nitrogen-doped carbon; XRD peak intensity at 43.4° increases with higher Ru content.","particleSize":"2–3 nm","surfaceStates":"Electron-deficient state due to Ru-N interaction.","structureLink":"Activity increases with Ru content up to 7 wt%, then stabilizes."},{"paperId":"P036","catalystId":"P036_PERF_007","name":"Ru5/C","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru5/C","surfaceStates":"High surface oxidation.","structureLink":"Surface oxidation leads to significantly lower TOF compared to Ru7/CN."},{"paperId":"P036","catalystId":"P036_PERF_008","name":"Pd5/C","activeMetals":"Pd","metalClass":"Pd-only","deactivation":"almost completely poisoned by the generated CO"},{"paperId":"P037","catalystId":"P037_PERF_001","name":"PdAu/ACB","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/ACB","phase":"PdAu alloy (lattice spacing 0.232 nm; XRD Pd(111) peak shifted to lower angle)","particleSize":"0.9 nm","surfaceStates":"Electron-rich PdAu clusters; partial electron transfer from Pd to Au (due to electronegativity difference) and from ACB support to PdAu clusters via electronic metal-support interaction.","structureLink":"Subnanometric size provides abundant active sites; electron-rich nature facilitates rate-determining C-H activation in FAD; surface amine groups act as Brønsted basic sites (proton scavengers) boosting O-H bond cleavage in FA.","deactivation":"slightly increased particle size of PdAu clusters is responsible for the decreased activity"},{"paperId":"P037","catalystId":"P037_PERF_002","name":"PdAu/CB","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/CB","phase":"PdAu alloy","particleSize":"4.9 nm","structureLink":"Lack of amine groups on CB leads to cluster aggregation and lower catalytic activity compared to PdAu/ACB."},{"paperId":"P037","catalystId":"P037_PERF_003","name":"Pd/ACB","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/ACB","phase":"monometallic Pd","particleSize":"1.1 nm"},{"paperId":"P037","catalystId":"P037_PERF_004","name":"Au/ACB","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"PdAu/ACB","phase":"PdAu alloy (lattice spacing 0.232 nm; XRD Pd(111) peak shifted to lower angle)","particleSize":"0.9 nm","surfaceStates":"Electron-rich PdAu clusters; partial electron transfer from Pd to Au (due to electronegativity difference) and from ACB support to PdAu clusters via electronic metal-support interaction.","structureLink":"Subnanometric size provides abundant active sites; electron-rich nature facilitates rate-determining C-H activation in FAD; surface amine groups act as Brønsted basic sites (proton scavengers) boosting O-H bond cleavage in FA."},{"paperId":"P038","catalystId":"P038_PERF_001","name":"Pd/SiO2@SC-1:3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/SiO2@SC-1:3","phase":"Metallic Pd and PdO","particleSize":"3.26 nm","surfaceStates":"Electron-deficient state of Pd0 (B.E. = 336 eV)","structureLink":"The electron-deficient state and optimal Pd0/PdO ratio weaken the Pd-H bond, accelerating hydrogen desorption (the rate-determining step), resulting in a TOF of 1138 h^-1 and Ea of 28.6 kJ/mol.","deactivation":"Carbon layer is destroyed, particles are agglomerated, and PdO is consumed."},{"paperId":"P038","catalystId":"P038_PERF_002","name":"Pd/SiO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/SiO2","phase":"PdO","particleSize":"20-30 nm","surfaceStates":"Pd loses electrons to SiO2 (B.E. shift)"},{"paperId":"P038","catalystId":"P038_PERF_003","name":"Pd/E-SiO2@SC-1:3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/E-SiO2@SC-1:3","phase":"Metallic Pd","surfaceStates":"Electron-deficient state is weakened compared to Pd/SiO2@SC-1:3; B.E. of Pd0 decreases.","structureLink":"Dramatic decrease in dehydrogenation performance due to the loss of the electron-deficient state induced by SiO2."},{"paperId":"P039","catalystId":"P039_PERF_004","name":"Au1–Pd17/KIT-6","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","deactivation":"decrease in catalytic activity over four runs"},{"paperId":"P039","catalystId":"P039_PERF_005","name":"Pd/KIT-6","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Au–Pd/KIT-6","phase":"Formation of a Pd–Au alloy was indicated by XRD peaks appearing at intermediate values between metallic Pd and Au. Recycled catalysts showed face-centered cubic (fcc) Pd, while those calcined at 550 °C exhibited fcc PdO.","surfaceStates":"Oxygen treatment inhibits the diffusion of Pd atoms into Au sublayers, maintaining more Pd on the surface. At higher temperatures, Au nanoparticles tend to migrate to the catalyst surface.","structureLink":"Catalysts calcined at 350 °C exhibited higher activity than those calcined at 550 °C. The transition from a non-crystalline state (at 350 °C) to PdO crystal formation via oxygen treatment significantly increased gas release from 62 mL to 142 mL."},{"paperId":"P040","catalystId":"P040_PERF_001","name":"LS-NH2/Pd","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"LS-NH2/Pd","phase":"Pd nanoclusters","particleSize":"Average lateral size 1.1-1.3 nm; thickness < 0.5 nm","surfaceStates":"XPS Pd 3d5/2 main peak at 336.0 eV and shoulder at 338.2 eV; exhibits weaker binding with the amine-functionalized surface and retains more metallic characteristics due to minimal hybridization between Pd 4d and N 2p states.","structureLink":"Higher catalytic activity (TOF = 246 h-1 at 70 °C) is attributed to weaker Pd-N covalency, which preserves the structural integrity of the nanoclusters and maintains more available metallic 4d electrons for catalysis.","deactivation":"agglomeration"},{"paperId":"P040","catalystId":"P040_PERF_002","name":"LS-SH/Pd","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"LS-SH/Pd","phase":"Pd nanoclusters","particleSize":"Average lateral size 1.1-1.3 nm; thickness < 1.1 nm","surfaceStates":"XPS Pd 3d5/2 peak at 337.3 eV (higher BE than LS-NH2/Pd); UV-vis absorption band at 390 nm indicates ligand-to-metal-charge-transfer (LMCT) and strong Pd 4d-S 3p hybridization.","structureLink":"Lower catalytic activity (TOF = 9 h-1 at 70 °C) is attributed to strong Pd-S covalency causing charge transfer from Pd to S, and structural deformation into a flatter, quasi-two-dimensional structure that reduces the overall surface area and number of active sites."},{"paperId":"P041","catalystId":"P041_PERF_001","name":"2 wt.% Pd/KCC-1-PDETA","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"2 wt.% Pd/KCC-1-PDETA","phase":"Pd nanoparticles","particleSize":"2.8 nm (mean diameter; 90% in range 2–4 nm)","surfaceStates":"Pd(0) peaks at 339.9 and 334.6 eV; Pd(2+) peaks at 337.5 and 342.8 eV","structureLink":"The unique fibrous morphology of KCC-1 and presence of amine groups reduced particle size and improved reactant access to active sites, resulting in the highest TOF (332 h-1).","deactivation":"No Pd leaching detected (limit: ~0.01 ppm); Pd particle size grew from 2.8 nm to 3.3 nm after reuse"},{"paperId":"P041","catalystId":"P041_PERF_002","name":"2 wt.% Pd/MSF-PDETA","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"2 wt.% Pd/MSF-PDETA","phase":"Pd nanoparticles","particleSize":"4.9 nm","surfaceStates":"Higher fraction of Pd(2+) than 2 wt.% Pd/KCC-1-PDETA","structureLink":"Larger particle size and lower nitrogen content compared to KCC-1 resulted in lower catalytic activity (TOF 147 h-1)."},{"paperId":"P041","catalystId":"P041_PERF_003","name":"2 wt.% Pd/KIT-6-PDETA","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"2 wt.% Pd/KIT-6-PDETA","phase":"Pd nanoparticles","particleSize":"14.5 nm","surfaceStates":"Higher fraction of Pd(2+) than 2 wt.% Pd/KCC-1-PDETA","structureLink":"Significantly larger particle size compared to KCC-1 resulted in the lowest catalytic activity (TOF 97 h-1)."},{"paperId":"P041","catalystId":"P041_PERF_004","name":"5 wt.% Pd/KCC-1-PDETA","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"5 wt.% Pd/KCC-1-PDETA","phase":"Pd nanoparticles (characteristic Pd(111) peak at 39.1° in XRD)","particleSize":"5.6 nm","surfaceStates":"Higher portion of unreduced Pd(2+) compared to 2 wt.% loading","structureLink":"Increased particle size and agglomeration, along with a higher fraction of unreduced Pd(2+), contributed to lower catalytic activity (TOF 242 h-1)."},{"paperId":"P041","catalystId":"P041_PERF_005","name":"10 wt.% Pd/KCC-1-PDETA","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"10 wt.% Pd/KCC-1-PDETA","phase":"Pd nanoparticles (characteristic Pd(111) peak at 39.1° in XRD)","particleSize":"8.0 nm","surfaceStates":"Highest portion of unreduced Pd(2+) among KCC-1 samples","structureLink":"Largest particle size and highest fraction of unreduced Pd(2+) led to the lowest activity among KCC-1 catalysts (TOF 222 h-1)."},{"paperId":"P042","catalystId":"P042_PERF_001","name":"2% Pd/Al2O3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"2% Pd/Al2O3","phase":"Pure Pd nanoparticles","particleSize":"8.2 ± 3.3 nm","surfaceStates":"Single Pd atoms on edges (weak band at 2060 cm-1), hollow Pd sites (<1920 cm-1), and double coordinated Pd sites (>1920 cm-1).","structureLink":"Lower hydrogen selectivity (91.1%) compared to Pd/ZnO, attributed to the absence of PdZn alloy and higher activity for the reverse water-gas shift reaction."},{"paperId":"P042","catalystId":"P042_PERF_002","name":"2% Pd/ZnO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"2% Pd/ZnO","phase":"PdZn alloy","particleSize":"9.8 ± 4.1 nm (reduced at 573 K)","surfaceStates":"High concentration of single Pd sites surrounded by Zn atoms (DRIFTS band at ~2080 cm-1) and double coordinated Pd sites due to dilution of surface Pd with Zn.","structureLink":"Formation of PdZn alloy directs formic acid decomposition toward dehydrogenation, resulting in high hydrogen selectivity (up to 99.3%) and reducing the reverse water-gas shift reaction compared to pure Pd."},{"paperId":"P042","catalystId":"P042_PERF_003","name":"1% Pd/ZnO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1% Pd/ZnO","phase":"PdZn alloy","particleSize":"6.5 ± 2.2 nm (at 573 K); 11.6 ± 4.1 nm (at 773 K)","structureLink":"Catalytic activity is independent of the reduction temperature and resulting particle size, suggesting the ZnO support plays a key role in the rate-determining step."},{"paperId":"P042","catalystId":"P042_PERF_004","name":"1.2% Pt/ZnO","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"1.2% Pt/ZnO","phase":"PtZn alloy (for reduced samples); pure Pt nanoparticles (for air-treated sample)","particleSize":"2.3 ± 0.5 nm (at 573 K); 5.9 ± 2.0 nm (at 773 K); 5.0 ± 1.7 nm (air treated)","structureLink":"Hydrogen selectivity increases with reduction temperature (from 95.3% to 96.3%)."},{"paperId":"P043","catalystId":"P043_PERF_001","name":"Au0.4Pd0.6Pt0.2/CNC-NH2","activeMetals":"Au-Pd-Pt","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.4Pd0.6Pt0.2/CNC-NH2","phase":"Ternary alloy (confirmed by lattice spacing of 0.23 nm, XRD after heat treatment, and absence of Au nanoparticles in UV-vis spectra)","particleSize":"Average size 2.28 nm","surfaceStates":"Binding energy shifts observed via XPS: Pt 4f increased (71.0 to 72.6 eV), Au 4f decreased (83.8 to 82.9 eV), and Pd 3d decreased (335.2 to 334.5 eV) upon loading on CNC-NH2.","structureLink":"The optimized local electron environment facilitates O-H bond cleavage (the rate-determining step) and reduces the binding energy barrier between H*; ultrafine size and high dispersion further enhance catalytic activity.","deactivation":"Degradation attributed to poor dispersion stability leading to particle aggregation and loss of metal particles that fail to bind to carrier during centrifugation/washing cycles."},{"paperId":"P044","catalystId":"P044_PERF_001","name":"Pd/C-H2P","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C-H2P","phase":"Metallic Pd (fcc)","particleSize":"2.6 ± 1.0 nm (TEM)","surfaceStates":"Pd0: 50.8%, PdII: 29.2%, PdIV: 20.0%; presence of Pd-C bonds at 282.5 eV indicating strong metal-support interaction.","structureLink":"Small particle size, high metallic Pd content, and high Pd/C atomic ratio (0.0229) contribute to the highest HCOOH dehydrogenation activity."},{"paperId":"P044","catalystId":"P044_PERF_002","name":"Pd/C-ArP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C-ArP","phase":"Metallic Pd (fcc)","particleSize":"3.2 ± 1.1 nm (TEM)","surfaceStates":"Pd0: 46.3%, PdII: 28.5%, PdIV: 25.2%; Pd/C atomic ratio: 0.0141","structureLink":"Activity is inferior to Pd/C-H2P due to milder discharge and weaker regulation effect of Ar plasma."},{"paperId":"P044","catalystId":"P044_PERF_003","name":"Pd/C-AirP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C-AirP","phase":"Metallic Pd (fcc)","particleSize":"5.2 ± 1.8 nm (TEM); 4.9 nm (XRD crystallite size)","surfaceStates":"Pd0: 50.1%, PdII: 24.6%, PdIV: 25.3%; presence of adsorbed [NOy]s at 405.9 eV; Pd/C atomic ratio: 0.0087","structureLink":"Poor activity due to large particle size (> 4 nm) and harmful adsorbed NOx species."},{"paperId":"P044","catalystId":"P044_PERF_004","name":"Pd/C-O2P","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C-O2P","phase":"Metallic Pd (fcc)","particleSize":"7.0 ± 2.4 nm (TEM); 8.0 nm (XRD crystallite size)","surfaceStates":"Pd0: 46.6%, PdII: 26.7%, PdIV: 26.7%; Pd/C atomic ratio: 0.0115","structureLink":"Poor activity due to large particle size (approx. 2.7 times that of Pd/C-H2P) exceeding the optimal range for HCOOH dehydrogenation."},{"paperId":"P045","catalystId":"P045_PERF_001","name":"Pd/C (5 wt % Pd)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd nanoparticles on activated carbon","particleSize":"3.2 nm","surfaceStates":"Fresh: 78% Pd0, 22% PdII; Used/Regenerated: 100% Pd0","structureLink":"Deactivation is attributed to pore fouling (92% loss of micropore area) and active site poisoning by formate ions rather than changes in particle size or oxidation state. Metallic Pd was found to be the most active species.","deactivation":"No Pd leaching observed via ICP-MS. Deactivation attributed to pore fouling and poisoning by formate ions; CO is an effective poison but not the primary cause during standard operation."},{"paperId":"P046","catalystId":"P046_PERF_001","name":"Pd/TC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/TC (Pd/templated carbon)","phase":"Small Pd particles (evidenced by a broad and low amplitude XRD peak at 39.9°)","particleSize":"Around 2 nm and below","structureLink":"The high surface area (965 m2/g) and uniformly dispersed small Pd nanoparticles on the nanostructured templated carbon are linked to superior activity in FA decomposition at room temperature. TGA showed that Pd nanoparticles significantly decreased the combustion temperature of the TC support from 500-600 °C down to 290 °C.","deactivation":"Activity decrease observed during reuse cycles."},{"paperId":"P048","catalystId":"P048_PERF_001","name":"Au0.28Pd0.47Co0.25/MIL-101-NH2","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.28Pd0.47Co0.25/MIL-101-NH2","phase":"Homogeneous AuPdCo alloy with a face-centered cubic (fcc) structure similar to metallic Au; lattice spacing of 0.230 nm.","particleSize":"2.3 ± 0.4 nm","surfaceStates":"XPS shows binding energies for Pd 3d and Au 4f shifted to lower values and Co 2p shifted to higher values compared to monometallic counterparts, indicating electron transfer from Co to Au and Pd.","structureLink":"The NH2 group effectively immobilizes metal ions via coordination or electrostatic interactions, inducing small particle size and high dispersion; the H2N-Co complex acts as a proton scavenger facilitating FA decomposition.","deactivation":"Aggregations of AuPdCo NPs; acidic catalytic environment of FA-SF aqueous solution weakened interaction force between AuPdCo NPs and MIL-101-NH2"},{"paperId":"P048","catalystId":"P048_PERF_002","name":"Au0.28Pd0.47Fe0.25/MIL-101-NH2","activeMetals":"Au-Pd-Fe","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.28Pd0.47Fe0.25/MIL-101-NH2","phase":"AuPdFe alloy nanoparticles","particleSize":"5.2 ± 0.5 nm","surfaceStates":"Fe in oxidation state"},{"paperId":"P048","catalystId":"P048_PERF_003","name":"Au0.28Pd0.47Ni0.25/MIL-101-NH2","activeMetals":"Au-Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.28Pd0.47Ni0.25/MIL-101-NH2","phase":"AuPdNi alloy nanoparticles","particleSize":"4.2 ± 0.5 nm","surfaceStates":"Ni in oxidation state"},{"paperId":"P048","catalystId":"P048_PERF_004","name":"Au0.28Pd0.47Co0.25/MIL-101-NO2","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.28Pd0.47Co0.25/MIL-101-NO2","particleSize":"2.6 ± 0.3 nm","surfaceStates":"Co in oxidation state","structureLink":"Electron-accepting NO2 group leads to stronger bonding of intermediates (CO2 and H2) on the surface, hindering desorption and reducing activity."},{"paperId":"P048","catalystId":"P048_PERF_005","name":"Au0.28Pd0.47Co0.25/MIL-101-SO3H","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.28Pd0.47Co0.25/MIL-101-SO3H","particleSize":"5.3 ± 0.5 nm","surfaceStates":"Co in oxidation state"},{"paperId":"P048","catalystId":"P048_PERF_006","name":"Au0.28Pd0.47Co0.25/MIL-101 (bare)","activeMetals":"Au-Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.28Pd0.47Co0.25/MIL-101","particleSize":"3.6 ± 0.5 nm"},{"paperId":"P049","catalystId":"P049_PERF_001","name":"Co5Pd5/CTF-600","activeMetals":"Co-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Co5Pd5/CTF-600","phase":"Amorphous or ultrafine nanoparticles (no characteristic XRD peaks for Co or Pd); synergistic bimetallic effect observed between Co and Pd.","particleSize":"approximately 2 nm","surfaceStates":"Pd exists as both Pd0 (335.75, 340.95 eV) and Pd2+ (338.1, 343.35 eV); Co exists as Co2+ (781.4, 797.2 eV). Positive shift in N 1s binding energy indicates electron transfer between metal NPs and the CTF support.","structureLink":"High catalytic activity is attributed to the ultrafine particle size (~2 nm), the synergistic effect between Co and Pd, and the nitrogen-rich CTF support (specifically pyridinic-N) which enhances electron transfer and provides coordination sites for metal anchoring."},{"paperId":"P049","catalystId":"P049_PERF_002","name":"Co5Pd5/CTF-500","activeMetals":"Co-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Co5Pd5/CTF-500","particleSize":"3.86 nm","structureLink":"Activity is higher than CTF-400 but lower than CTF-600 due to particle size and support pore volume differences."},{"paperId":"P049","catalystId":"P049_PERF_003","name":"Co5Pd5/CTF-400","activeMetals":"Co-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Co5Pd5/CTF-400","particleSize":"4.51 nm","structureLink":"Lower activity than CTF-600 due to larger particle size and inferior dispersion."},{"paperId":"P049","catalystId":"P049_PERF_004","name":"Co5Pd5/XC-72","activeMetals":"Co-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Co5Pd5/XC-72","structureLink":"Exhibited torpid catalytic activity compared to CTF-supported catalysts, highlighting the role of nitrogen doping in the support."},{"paperId":"P050","catalystId":"P050_PERF_001","name":"Pd/a_MSC-30","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/a_MSC-30","phase":"Pd nanoparticles","structureLink":"Acid activation of the MSC-30 carbon support improves catalytic activity for formic acid dehydrogenation compared to non-activated supports."},{"paperId":"P051","catalystId":"P051_PERF_001","name":"Pd/a_MSC-30","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/a_MSC-30","phase":"Metallic palladium (Pd^0)","particleSize":"~2.4 nm","surfaceStates":"Pd 3d binding energies at 335.5 and 340.8 eV; stabilized by oxygen-containing functional groups introduced via HNO3 treatment.","structureLink":"Ultrafine feature and high dispersibility lead to a record-high TOF of 13333 h^-1 for formic acid dehydrogenation.","deactivation":"slight increase in particle size of Pd NPs"},{"paperId":"P051","catalystId":"P051_PERF_002","name":"Pd/MSC-30","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MSC-30","phase":"Metallic palladium","particleSize":"Much larger than Pd/a_MSC-30","structureLink":"Lower catalytic activity (TOF) compared to the ultrafine Pd/a_MSC-30 due to larger particle size."},{"paperId":"P052","catalystId":"P052_PERF_001","name":"Pd6Cr4@NH2-MIL-101","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd6Cr4@NH2-MIL-101","phase":"Bimetallic nanoparticles with crystalline nature; lattice spacing of 0.294 nm (close to the (101) crystal plane of Cr)","particleSize":"0.29 nm","surfaceStates":"Strong interaction between Pd nanoparticles and NH2-MIL-101, evidenced by a shift in the binding energy of Pd 3d compared to Pd6Cr4@MIL-101; weak interaction between Cr nanoparticles and NH2-MIL-101","structureLink":"Catalyst deactivation (decrease in TOF) is attributed to the agglomeration of Pd and Cr atoms on the outer surface, with particle sizes increasing from 0.29 nm to approximately 300 nm after two cycles and up to 800 nm after four cycles.","deactivation":"Deactivation is caused by agglomeration of Pd and Cr atoms on the outer surface of the catalyst; ICP-OES analysis confirmed that leaching of active metals into the liquid was very low."},{"paperId":"P053","catalystId":"P053_PERF_001","name":"1 wt% Pd/g-C3N4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/g-C3N4","phase":"Metallic phase (Pd0)","particleSize":"8.14 nm (1 wt%), 11.14 nm (3 wt%), 17.63 nm (5 wt%)","surfaceStates":"Nitrogen atoms in g-C3N4 support transfer electrons to Pd NPs, increasing electron cloud density.","structureLink":"Higher Pd loading increases active sites but leads to particle agglomeration and lower activity at high temperatures due to possible passive layer formation (PdCO or Pd formate)."},{"paperId":"P053","catalystId":"P053_PERF_002","name":"3 wt% Pd/g-C3N4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/g-C3N4","phase":"Metallic phase (Pd0)","particleSize":"8.14 nm (1 wt%), 11.14 nm (3 wt%), 17.63 nm (5 wt%)","surfaceStates":"Nitrogen atoms in g-C3N4 support transfer electrons to Pd NPs, increasing electron cloud density.","structureLink":"Higher Pd loading increases active sites but leads to particle agglomeration and lower activity at high temperatures due to possible passive layer formation (PdCO or Pd formate)."},{"paperId":"P053","catalystId":"P053_PERF_003","name":"5 wt% Pd/g-C3N4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/g-C3N4","phase":"Metallic phase (Pd0)","particleSize":"8.14 nm (1 wt%), 11.14 nm (3 wt%), 17.63 nm (5 wt%)","surfaceStates":"Nitrogen atoms in g-C3N4 support transfer electrons to Pd NPs, increasing electron cloud density.","structureLink":"Higher Pd loading increases active sites but leads to particle agglomeration and lower activity at high temperatures due to possible passive layer formation (PdCO or Pd formate).","deactivation":"At higher temperature (70 °C), total gas decreased for 5 wt% Pd/g-C3N4 compared to lower loadings; attributed to early dehydration reaction producing PdCO or Pd formate causing inhibition"},{"paperId":"P053","catalystId":"P053_PERF_004","name":"5 wt% Cu/g-C3N4","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Cu/g-C3N4","phase":"Oxide phase (CuO)","particleSize":"20.39 nm","surfaceStates":"Presence of CuO promotes passive layer formation on the catalyst surface.","structureLink":"Low catalytic activity attributed to high metal oxide (CuO) content and small amount of metallic Cu."},{"paperId":"P053","catalystId":"P053_PERF_005","name":"5 wt% Zn/g-C3N4","activeMetals":"Zn","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Zn/g-C3N4","phase":"Oxide phase (ZnO)","particleSize":"25.24 nm","surfaceStates":"Presence of ZnO promotes passive layer formation on the catalyst surface.","structureLink":"Low catalytic activity attributed to high metal oxide (ZnO) content and larger crystal size leading to poor dispersion."},{"paperId":"P054","catalystId":"P054_PERF_001","name":"5Ni–SiO2 (P123)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"5Ni–SiO2(P123)","phase":"Metallic Ni (111) plane","particleSize":"22.6 nm","surfaceStates":"Lewis acid sites; lower intensity peaks in terms of acidity compared to other catalysts.","structureLink":"Highest H2 concentration and selectivity among 5 wt% Ni catalysts."},{"paperId":"P054","catalystId":"P054_PERF_002","name":"2.5Ni–SiO2 (P123)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"2.5Ni–SiO2(P123)","phase":"Metallic Ni (111) plane","particleSize":"18.4 nm","surfaceStates":"Highest Lewis acidity among the catalysts.","structureLink":"Lower H2 distribution and selectivity compared to 5Ni–SiO2(P123) due to reduced nickel content."},{"paperId":"P054","catalystId":"P054_PERF_003","name":"5Ni–SiO2 (NH3-CA)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"5Ni–SiO2(NH3-CA)","phase":"Metallic Ni dispersed as small crystals in the SiO2 lattice structure","surfaceStates":"Lewis and Brønsted acid sites.","structureLink":"Highest total pore volume; H2 selectivity of 0.69."},{"paperId":"P054","catalystId":"P054_PERF_004","name":"5Ni–SiO2 (Tw80–NaF)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"5Ni–SiO2(Tw80–NaF)","phase":"Metallic Ni (111) plane","particleSize":"15.4 nm","surfaceStates":"Lewis acid sites.","structureLink":"Lowest surface area and pore volume; H2 selectivity of 0.56."},{"paperId":"P054","catalystId":"P054_PERF_005","name":"5Ni–SiO2 (Tw80)","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"5Ni–SiO2(Tw80)","phase":"Metallic Ni (111) plane","particleSize":"34.8 nm","surfaceStates":"Lewis and Brønsted acid sites.","structureLink":"Highest Ni crystallite size; H2 selectivity of 0.55."},{"paperId":"P055","catalystId":"P055_PERF_001","name":"Au@SiO2 2.8 ± 0.5 nm (Entry A)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","deactivation":"Partial chemical deactivation attributed to irreversible formation of amide species between grafted amines and formic acid (substrate poisoning)"},{"paperId":"P055","catalystId":"P055_PERF_002","name":"Au@SiO2 2.6 ± 0.3 nm (Entry B)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","deactivation":"Partial chemical deactivation attributed to irreversible formation of amide species between grafted amines and formic acid (substrate poisoning)"},{"paperId":"P055","catalystId":"P055_PERF_003","name":"Au@SiO2 2.2 ± 0.3 nm (Entry C)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","deactivation":"Partial chemical deactivation attributed to irreversible formation of amide species between grafted amines and formic acid (substrate poisoning)"},{"paperId":"P055","catalystId":"P055_PERF_004","name":"Au@SiO2 2.7 ± 0.4 nm (Entry D)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","deactivation":"Partial chemical deactivation attributed to irreversible formation of amide species between grafted amines and formic acid (substrate poisoning)"},{"paperId":"P056","catalystId":"P056_PERF_001","name":"Pd/rGO-SI","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rGO-SI","phase":"fcc Pd","particleSize":"2.51 ± 0.3 nm (fresh), 3.11 ± 0.3 nm (used)","surfaceStates":"Higher metallic Pd content and higher atomic percentage of Pd (0.93%) compared to IMP","structureLink":"Smaller particle size, higher dispersion, and higher metallic Pd content lead to superior catalytic activity (TOF = 910-911 h⁻¹)."},{"paperId":"P056","catalystId":"P056_PERF_002","name":"Pd/rGO-IMP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rGO-IMP","phase":"fcc Pd","particleSize":"12.81 ± 0.5 nm (fresh), 13.29 ± 0.5 nm (used)","surfaceStates":"Contains Pd0 and PdII; atomic percentage of Pd is 0.65%","structureLink":"Larger particle size, lower metallic content, and lower dispersion result in lower catalytic activity (TOF = 503-506 h⁻¹)."},{"paperId":"P056","catalystId":"P056_PERF_003","name":"Pd/rGO-SI-Used","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rGO-SI","phase":"fcc Pd","particleSize":"2.51 ± 0.3 nm (fresh), 3.11 ± 0.3 nm (used)","surfaceStates":"Higher metallic Pd content and higher atomic percentage of Pd (0.93%) compared to IMP","structureLink":"Smaller particle size, higher dispersion, and higher metallic Pd content lead to superior catalytic activity (TOF = 910-911 h⁻¹)."},{"paperId":"P056","catalystId":"P056_PERF_004","name":"Pd/rGO-IMP-Used","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rGO-IMP","phase":"fcc Pd","particleSize":"12.81 ± 0.5 nm (fresh), 13.29 ± 0.5 nm (used)","surfaceStates":"Contains Pd0 and PdII; atomic percentage of Pd is 0.65%","structureLink":"Larger particle size, lower metallic content, and lower dispersion result in lower catalytic activity (TOF = 503-506 h⁻¹)."},{"paperId":"P057","catalystId":"P057_PERF_001","name":"Pd-ZrO2/RUB-15-NH2","activeMetals":"Pd-Zr","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-ZrO2/RUB-15-NH2","phase":"Pd-ZrO2 nanoparticles","particleSize":"3.75 nm","surfaceStates":"Functionalized with amine groups (-NH2) via APTES, which provide strong adsorption capacity for Pd2+ and Zr4+ ions","structureLink":"The confinement of ultrasmall Pd-ZrO2 NPs within the layered RUB-15-NH2 structure provides numerous and accessible active sites for formic acid molecules"},{"paperId":"P058","catalystId":"P058_PERF_004","name":"Octahedrons-TiO2","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pd octahedrons-TiO2","phase":"Single-crystal nano-octahedrons covered by {111} facets","particleSize":"8 nm (average edge length)","surfaceStates":"Electron accumulation on the Pd side due to interfacial polarization with TiO2; Schottky junction formed under light traps photoexcited electrons on Pd.","structureLink":"Enhanced activity compared to bare Pd due to interface polarization, but lower than tetrahedrons due to a smaller interface angle (70.5°) increasing steric effects."},{"paperId":"P058","catalystId":"P058_PERF_005","name":"Tetrahedrons-TiO2","activeMetals":"Te-Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pd tetrahedrons-TiO2","phase":"Single-crystal nano-tetrahedrons covered by {111} facets","particleSize":"8 nm (average edge length)","surfaceStates":"Electron accumulation on the Pd side due to interfacial polarization with TiO2; Schottky junction formed under light traps photoexcited electrons on Pd.","structureLink":"Highest activity in FA dehydrogenation attributed to a large interface angle (109.5°) which reduces steric effects during molecular bond whirligig/wrench processes, combined with electronic polarization from the TiO2 interface."},{"paperId":"P058","catalystId":"P058_PERF_006","name":"Cuboctahedrons-TiO2","activeMetals":"Cu-Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pd cuboctahedrons-TiO2","phase":"Nanocrystals enclosed by a mix of {111} and {100} facets","particleSize":"about 5 nm","surfaceStates":"Electron accumulation on the Pd side due to interfacial polarization with TiO2.","structureLink":"Lower catalytic activity than octahedrons-TiO2 attributed to a small interface angle (54.7°) which hinders the catalytic reaction via steric effects."},{"paperId":"P059","catalystId":"P059_PERF_001","name":"Pd-PCN-350R","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd-PCN-350R","phase":"Pd nanoparticles and single atoms on PCN","particleSize":"ca. 2-3 nm (specifically 2.4 nm)","surfaceStates":"Average charge QPd = 2.6; metallic Pd fingerprint at 335.3 eV","structureLink":"Optimal activity associated with a moderate average charge (QPd = 2.6) and ultrafine particle size","deactivation":"Leaching of Pd was excluded by analyzing the metal content in the recovered solvent. Average particle size slightly increased from 2.5 to 3.0 nm."},{"paperId":"P059","catalystId":"P059_PERF_002","name":"Pd-PCN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd-PCN","phase":"Pd nanoparticles and single atoms on polymeric carbon nitride (PCN)","particleSize":"ca. 4-5 nm","surfaceStates":"Average charge QPd = 3.4; XPS peaks at 338.3 eV (Pd4+) and 336.6 eV (Pd2+)","structureLink":"Lower activity compared to Pd-PCN-350R due to higher average charge"},{"paperId":"P059","catalystId":"P059_PERF_003","name":"Pd-PCN-500R","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd-PCN-500R","phase":"Pd nanoparticles on PCN","particleSize":"slightly below 6 nm","surfaceStates":"Average charge QPd = 1.1; metallic Pd (335.3 eV) is the main contribution","structureLink":"Lower activity compared to Pd-PCN-350R, following a volcano relationship with average charge"},{"paperId":"P060","catalystId":"P060_PERF_001","name":"1%Pd@HHT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1 %Pd@HHT","phase":"Monometallic","particleSize":"3.9 ± 1.2 nm","surfaceStates":"Pd0 (B.E. 336.70 eV) and PdII (B.E. 337.80 eV)","structureLink":"Rapidly deactivates due to coalescence, agglomeration (size increase from 3.0 to 4.7 nm), and CO-poisoning","deactivation":"coalescence and agglomeration of particles (average size increase from 3.0 to 4.7 nm) and CO poisoning"},{"paperId":"P060","catalystId":"P060_PERF_002","name":"1%Au@HHT","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"1 %Au@HHT","phase":"Monometallic","particleSize":"3.4 ± 1.2 nm","surfaceStates":"Au0 (B.E. 84.22 eV) and Auδ+ (B.E. 85.60 eV)","structureLink":"Extremely low activity in formic acid decomposition"},{"paperId":"P060","catalystId":"P060_PERF_003","name":"1%Pd8Au2@HHT","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"1 %Pd8Au2@HHT","phase":"Au-Pd alloy; surface enrichment of Pd atoms","particleSize":"3.5 ± 0.9 nm (fresh), 3.9 ± 1.1 nm (used)","surfaceStates":"Pd0, PdII, Au0, Auδ+; decrease in Pd0 binding energy (~1.1-1.2 eV) relative to monometallic Pd","structureLink":"High stability over 6 cycles with minimal morphology changes","deactivation":"no significant modifications of catalyst morphology; mean particle size increase from 3.5 nm to 3.9 nm"},{"paperId":"P060","catalystId":"P060_PERF_004","name":"1%Pd6Au4@HHT","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"1 %Pd6Au4@HHT","phase":"Au-Pd alloy; surface enrichment of Pd atoms","particleSize":"2.9 ± 0.7 nm (fresh), 3.1 ± 0.8 nm (used)","surfaceStates":"Pd0, PdII, Au0, Auδ+; decrease in Pd0 binding energy (~1.1-1.2 eV) relative to monometallic Pd","structureLink":"Highest initial activity (3539 h-1) and high selectivity (>99% H2); DFT suggests optimal balance between lattice and ligand effects and stronger interaction with support for superior stability","deactivation":"no significant modifications of catalyst morphology; mean particle size increase from 2.9 nm to 3.1 nm"},{"paperId":"P060","catalystId":"P060_PERF_005","name":"1%Pd4Au6@HHT","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"1 %Pd4Au6@HHT","phase":"Au-Pd alloy; surface enrichment of Pd atoms","particleSize":"4.0 ± 0.8 nm","surfaceStates":"Pd0, PdII, Au0, Auδ+; decrease in Pd0 binding energy (~1.1-1.2 eV) relative to monometallic Pd","structureLink":"High initial activity (1983 h-1)"},{"paperId":"P060","catalystId":"P060_PERF_006","name":"1%Pd2Au8@HHT","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"1 %Pd2Au8@HHT","phase":"Au-Pd alloy; surface enrichment of Pd atoms","particleSize":"3.1 ± 0.6 nm","surfaceStates":"Pd0, PdII, Au0, Auδ+; decrease in Pd0 binding energy (~1.1-1.2 eV) relative to monometallic Pd","structureLink":"Lower activity compared to other bimetallics (878 h-1)"},{"paperId":"P061","catalystId":"P061_PERF_001","name":"Pd@CMK3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@CMK3","phase":"Monometallic Pd nanoparticles","particleSize":"Fresh: average 2.7 nm; Used (batch and fixed bed): average 3.3 nm, with some particles > 5 nm.","surfaceStates":"Adsorption of poison species such as CO","structureLink":"Confinement effects within CMK3 mesopores provide higher stability and activity compared to Pd@HHT (where NPs are only on external surfaces). Fixed bed reactors exhibit more severe metal leaching and faster deactivation than batch reactors due to the continuous flow of reactants removing leached species.","deactivation":"Severe leaching of Pd (59 wt% loss) in fixed bed reactor. In batch reactor, 23 wt% Pd was lost with significant redeposition and aggregation on the external surface. Deactivation also attributed to CO poisoning."},{"paperId":"P062","catalystId":"P062_PERF_001","name":"Pd@MHCP-2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@MHCP-2","phase":"Bimetallic Pd-Fe species; low-crystallinity ultrafine Pd nanoparticles embedded in HCP pores.","particleSize":"1.21 ± 0.35 nm","surfaceStates":"XPS shows electron transfer between Fe and Pd atoms (decrease in Fe 2p binding energy) and interaction between amino groups and Pd NPs (N 1s shift).","structureLink":"Ultrafine particle size and bimetallic synergistic effect with oxidized Fe lower the O-H bond dissociation barrier to 0.040 eV (vs 0.06 eV for pure Pd), resulting in a TOF of 1486 h^-1.","deactivation":"Particle agglomeration observed (some particles > 3 nm) as internal Pd nanoparticles escape from pores and attach to external amino groups."},{"paperId":"P062","catalystId":"P062_PERF_003","name":"Pd@MHCP-2(s)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@MHCP-2","phase":"Bimetallic Pd-Fe species; low-crystallinity ultrafine Pd nanoparticles embedded in HCP pores.","particleSize":"1.21 ± 0.35 nm","surfaceStates":"XPS shows electron transfer between Fe and Pd atoms (decrease in Fe 2p binding energy) and interaction between amino groups and Pd NPs (N 1s shift).","structureLink":"Ultrafine particle size and bimetallic synergistic effect with oxidized Fe lower the O-H bond dissociation barrier to 0.040 eV (vs 0.06 eV for pure Pd), resulting in a TOF of 1486 h^-1."},{"paperId":"P063","catalystId":"P063_PERF_001","name":"NiCu/rGO10","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/rGO10","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"7 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 showed only Cu0/+ species (no Cu2+).","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites."},{"paperId":"P063","catalystId":"P063_PERF_002","name":"NiCu/rGO325","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/rGO325","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"8 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites."},{"paperId":"P063","catalystId":"P063_PERF_003","name":"NiCu/SXC","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/SXC","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"8 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 binding energy at 932.99 eV (reduced copper species).","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites."},{"paperId":"P063","catalystId":"P063_PERF_004","name":"NiCu/MWCNT","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/MWCNT","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"7 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites."},{"paperId":"P063","catalystId":"P063_PERF_005","name":"NiCu/SWCNT","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/SWCNT","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"7 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites."},{"paperId":"P063","catalystId":"P063_PERF_006","name":"NiCu/HSAG","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/HSAG","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"High CO2 selectivity attributed to particle size > 5 nm providing a high ratio of terrace sites."},{"paperId":"P063","catalystId":"P063_PERF_007","name":"NiCu/NrGO10","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/NrGO10","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 showed a shift to lower binding energy (0.2 eV) compared to undoped counterpart; contains Cu0/+ and Cu2+.","structureLink":"Lower activity attributed to metal particles located on pyridinic N atoms, making them less positively charged and less capable of stabilizing formate species."},{"paperId":"P063","catalystId":"P063_PERF_008","name":"NiCu/NrGO325","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/NrGO325","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"Contains Cu0/+ and Cu2+ species.","structureLink":"Lower activity attributed to metal particles located on pyridinic N atoms, making them less positively charged and less capable of stabilizing formate species."},{"paperId":"P063","catalystId":"P063_PERF_009","name":"NiCu/NCNT","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/NCNT","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 atomic ratio of Cu0/+ to Cu2+ is close to 1.","structureLink":"Most active catalyst; attributed to metal nanoparticles located on defect sites rather than N atoms, and the presence of pyrrolic nitrogen acting as activation sites for formic acid."},{"paperId":"P063","catalystId":"P063_PERF_010","name":"NiCu/NSXC","activeMetals":"Ni-Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"NiCu/NSXC","phase":"fcc phase; bimetallic NiCu particles suggested by XRD (200) plane shift to 50.2-50.9°.","particleSize":"6 ± 1 nm","surfaceStates":"XPS Cu 2p3/2 binding energy at 932.47 eV (reduced copper species).","structureLink":"Lower activity attributed to metal particles located on pyridinic N atoms, making them less positively charged and less capable of stabilizing formate species."},{"paperId":"P064","catalystId":"P064_PERF_001","name":"1% Pt/N-graphene (Pt(NO3)4)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/N-graphene (Pt(NO3)4)","phase":"nanocrystals","particleSize":"10-16 nm","structureLink":"lower catalytic activity and selectivity compared to catalysts prepared with H2PtCl6 due to lower dispersion"},{"paperId":"P064","catalystId":"P064_PERF_002","name":"0.2% Pt/N-graphene (Pt(NO3)4)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/N-graphene (Pt(NO3)4)","phase":"nanocrystals","particleSize":"10-16 nm","structureLink":"lower catalytic activity and selectivity compared to catalysts prepared with H2PtCl6 due to lower dispersion"},{"paperId":"P064","catalystId":"P064_PERF_003","name":"N-graphene","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/N-graphene (Pt(NO3)4)","phase":"nanocrystals","particleSize":"10-16 nm","structureLink":"lower catalytic activity and selectivity compared to catalysts prepared with H2PtCl6 due to lower dispersion"},{"paperId":"P064","catalystId":"P064_PERF_004","name":"1% Pt/N-graphene (H2PtCl6)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/N-graphene (H2PtCl6)","phase":"atomically dispersed platinum","particleSize":"2 ± 0.5 Å","surfaceStates":"Pt2+ (72.4 eV) and Pt4+ (73.5 eV); predominantly Pt2+ after reduction","structureLink":"Atomically dispersed state leads to higher catalytic activity and selectivity (up to 100% for H2/CO2) compared to nanocrystalline form; atomically dispersed platinum is unable to adsorb CO"},{"paperId":"P064","catalystId":"P064_PERF_005","name":"0.4% Pt/N-graphene (H2PtCl6)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/N-graphene (H2PtCl6)","phase":"atomically dispersed platinum","particleSize":"2 ± 0.5 Å","surfaceStates":"Pt2+ (72.4 eV) and Pt4+ (73.5 eV); predominantly Pt2+ after reduction","structureLink":"Atomically dispersed state leads to higher catalytic activity and selectivity (up to 100% for H2/CO2) compared to nanocrystalline form; atomically dispersed platinum is unable to adsorb CO"},{"paperId":"P064","catalystId":"P064_PERF_006","name":"0.2% Pt/N-graphene (H2PtCl6)","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/N-graphene (H2PtCl6)","phase":"atomically dispersed platinum","particleSize":"2 ± 0.5 Å","surfaceStates":"Pt2+ (72.4 eV) and Pt4+ (73.5 eV); predominantly Pt2+ after reduction","structureLink":"Atomically dispersed state leads to higher catalytic activity and selectivity (up to 100% for H2/CO2) compared to nanocrystalline form; atomically dispersed platinum is unable to adsorb CO"},{"paperId":"P065","catalystId":"P065_PERF_001","name":"Pd/rutile","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rutile","phase":"Metallic Pd nanoparticles on rutile TiO2 support","particleSize":"3.0 nm","surfaceStates":"Higher proportion of Pd(111) crystal plane; linear adsorption of CO on corner and edge Pd atoms.","structureLink":"Highest catalytic performance due to smallest particle size, high metallic Pd content, and easier transformation of bidentate formate to monodentate formate, resulting in the lowest activation energy (21.1 kJ/mol)."},{"paperId":"P065","catalystId":"P065_PERF_002","name":"Pd/anatase","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/anatase","phase":"Metallic Pd nanoparticles on anatase TiO2 support","particleSize":"3.3 nm","surfaceStates":"Higher proportion of Pd(111) crystal plane; linear adsorption of CO on corner and edge Pd atoms.","structureLink":"High catalytic performance linked to relatively small particle size and high metallic Pd content (Ea = 37.2 kJ/mol)."},{"paperId":"P065","catalystId":"P065_PERF_003","name":"Pd/brookite","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/brookite","phase":"Metallic Pd nanoparticles on brookite TiO2 support","particleSize":"4.7 nm","surfaceStates":"Higher proportion of Pd(100) crystal plane.","structureLink":"Highest selectivity for HCOOH dehydration to CO due to higher proportion of Pd(100) planes, which inhibits dehydrogenation and increases activation energy (65.9 kJ/mol).","deactivation":"By-product CO can be strongly absorbed on the Pd surface to inhibit the absorption and reaction of HCOOH"},{"paperId":"P065","catalystId":"P065_PERF_004","name":"Pd/TiO2(B)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/TiO2(B)","phase":"Metallic Pd nanoparticles on TiO2(B) support","particleSize":"4.5 nm","surfaceStates":"Higher proportion of Pd(100) crystal plane.","structureLink":"Lowest catalytic performance attributed to the lowest metallic Pd content, poor dispersion state, and preference for HCOOH dehydration over dehydrogenation."},{"paperId":"P066","catalystId":"P066_PERF_001","name":"Pd/c-Al2O3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/c-Al2O3","particleSize":"2.8 nm","surfaceStates":"Pd0/Pd2+ ratio of 2.3; ATR-IR detected linear bonded (2110 cm-1) and bridged bonded (1830 cm-1) CO on the Pd surface.","structureLink":"Small Pd particles oxidize easily in air. Catalyst deactivation is caused by the strong adsorption of CO on the Pd surface, which can be suppressed by trace oxygen via oxidation of adsorbed CO to CO2.","deactivation":"Deactivation is caused by CO poisoning; adsorbed CO on Pd surface was confirmed via ATR-IR and pretreatment with CO led to complete deactivation."},{"paperId":"P067","catalystId":"P067_PERF_001","name":"Pt–PVP","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt–PVP (colloidal platinum nanoparticles dispersed in polyvinylpyrrolidone)","phase":"colloidal platinum nanoparticles","particleSize":"2.3 nm","structureLink":"The catalytic activity of platinum nanoparticles is controlled by the dispersing agent.","deactivation":"Deactivation of the catalyst due to the adsorption of simultaneously produced CO2 onto Pt-PVP"},{"paperId":"P068","catalystId":"P068_PERF_001","name":"Au/NdZrO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/NdZrO2","phase":"Tetragonal phase ZrO2 solid solution; lattice expansion induced by Nd3+ incorporation.","particleSize":"< 1.0 nm","surfaceStates":"Au 4f peak shifted to lower binding energy (83.4 eV), indicating electron-enrichment due to oxygen vacancies in support.","structureLink":"Stronger metal-support interaction and charge transfer from support to Au enhance catalytic activity for FA dehydrogenation, resulting in the highest TOF (2452.5 h-1) and lowest Ea (35.6 kJ mol-1).","deactivation":"Slight Au leaching determined by ICP"},{"paperId":"P068","catalystId":"P068_PERF_002","name":"Au/CeZrO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/CeZrO2","phase":"Tetragonal phase ZrO2 solid solution; lattice expansion induced by Ce3+ incorporation.","particleSize":"< 1.0 nm","surfaceStates":"Au 4f peak shifted to lower binding energy (83.5 eV), indicating electron-enrichment due to oxygen vacancies in support.","structureLink":"Enhanced metal-support interaction via oxygen vacancy formation promotes charge transfer to Au, improving activity over Au/ZrO2."},{"paperId":"P068","catalystId":"P068_PERF_003","name":"Au/SmZrO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/SmZrO2","phase":"Tetragonal phase ZrO2 solid solution; lattice expansion induced by Sm3+ incorporation.","particleSize":"< 1.0 nm","surfaceStates":"Au 4f peak shifted to lower binding energy (83.6 eV), indicating electron-enrichment due to oxygen vacancies in support.","structureLink":"Enhanced metal-support interaction via oxygen vacancy formation promotes charge transfer to Au, improving activity over Au/ZrO2."},{"paperId":"P068","catalystId":"P068_PERF_004","name":"Au/ZrO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/ZrO2","phase":"Support exhibits mixed monoclinic and tetragonal phases (tetragonal is main phase).","particleSize":"< 1.0 nm","surfaceStates":"Au 4f peak located at 83.8 eV.","structureLink":"Baseline catalyst with lowest TOF (1524.9 h-1) and highest activation energy (45.5 kJ mol-1)."},{"paperId":"P069","catalystId":"P069_PERF_003","name":"Pd9.2/C-N","activeMetals":"Pd","metalClass":"Pd-only","deactivation":"Deactivation attributed to destruction of N active sites on support surface (N content decreased from 4.13% to 2.29%), contamination with other components, and agglomeration of Pd particles."},{"paperId":"P070","catalystId":"P070_PERF_001","name":"Pd@TU-PMO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@TU-PMO","phase":"metallic palladium","particleSize":"ca. 2.3 nm","surfaceStates":"XPS peaks at 337.16 and 342.51 eV assigned to metallic palladium.","structureLink":"High activity is attributed to small, highly dispersed Pd nanoparticles resulting from strong interactions between the Pd precursors and thiourea groups; metallic Pd is more active than Pd2+ ions.","deactivation":"no significant leaching from support into the reaction media (verified by hot-filtration test)"},{"paperId":"P070","catalystId":"P070_PERF_002","name":"Pd2+@TU-PMO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd2+@TU-PMO","phase":"ionic Pd2+","surfaceStates":"XPS peaks at 337.90 and 343.14 eV assigned to ionic species (Pd2+).","structureLink":"Lower rate of H2 generation compared to metallic Pd; may consume produced H2 to deposit metallic Pd."},{"paperId":"P071","catalystId":"P071_PERF_001","name":"Pd/HTNC-950","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HTNC-950","particleSize":"2.8 ± 0.1 nm (fresh); 3.3 nm (after 5 runs)","surfaceStates":"Pd0 binding energy at 335.8 eV and Pd2+ at 337.8 eV; electronic enrichment of Pd0 due to interaction with N species.","structureLink":"High TOF (1631 h-1) attributed to well-dispersed NPs and the synergy between Pd2+ sites for formate ion adsorption and Pd0 sites for C-H bond activation.","deactivation":"particle size increased from 2.8 nm to 3.3 nm after five runs"},{"paperId":"P071","catalystId":"P071_PERF_002","name":"Pd/HTNC-O","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HTNC-O","particleSize":"5.8 nm (fresh); 6.4 nm (after 5 runs)","structureLink":"Lower activity and stability compared to Pd/HTNC-950 due to larger particle size and poor dispersion.","deactivation":"particle size increased from 5.8 nm to 6.4 nm after five runs"},{"paperId":"P071","catalystId":"P071_PERF_003","name":"Pd/AC-950","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC-950","particleSize":"4.3 nm","structureLink":"Lower activity than Pd/HTNC-950 indicates that high surface area of the support is not the decisive factor for catalytic performance."},{"paperId":"P072","catalystId":"P072_PERF_001","name":"Ag16Pd1/C","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Ag16Pd1/C","phase":"PdAg alloy (confirmed by HRTEM lattice fringe distance of 0.238 nm for PdAg (111) and EDX mapping/line scanning)","particleSize":"3.36 nm (increased to 3.61 nm after 5 reuses)","surfaceStates":"Metallic Ag0 (Ag 3d 5/2 at 368.42 eV) and Pd0 (Pd 3d 5/2 at 335.98 eV)","structureLink":"The formation of the PdAg alloy significantly enhances catalytic activity for sodium formate decomposition compared to commercial Pd/C.","deactivation":"Particle size slightly increased from 3.36 nm to 3.61 nm after 5th reuse"},{"paperId":"P072","catalystId":"P072_PERF_002","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C (commercial)","particleSize":"3.08 nm","structureLink":"Less active than Ag16Pd1/C for SF decomposition."},{"paperId":"P072","catalystId":"P072_PERF_003","name":"Cu16Pd1/C","activeMetals":"Cu-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Cu16Pd1/C","phase":"Alloyed onto the surface of Pd/C","particleSize":"3.43 nm","structureLink":"Catalytically inactive for SF decomposition."},{"paperId":"P073","catalystId":"P073_PERF_001","name":"8 wt.% Pd/NHPC-150","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NHPC-150","phase":"Face-centered cubic (FCC) structure","particleSize":"3.61 ± 0.24 nm","surfaceStates":"Pd 3d binding energy is 0.6 eV higher than metallic Pd, indicating strong interaction between Pd particles and N functional groups of NHPC-150.","structureLink":"The synergistic interface between Pd NPs and NHPC-150 sites, combined with the small particle size effect and N-doping, modifies the electronic environment of Pd atoms, facilitating C-H bond cleavage and lowering activation energy (21.39 kJ/mol).","deactivation":"Outstanding durability to leaching; average Pd NP size grew marginally from 3.54 nm (after 8th run) to 3.99 nm (after 10th cycle)."},{"paperId":"P074","catalystId":"P074_PERF_001","name":"Pd/AS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AS","phase":"Monometallic Pd","particleSize":"3.8 ± 2.1 nm (fresh), 4.4 ± 1.9 nm (used)","surfaceStates":"Pd0 main species; Pd2+ content is 17% (fresh) and 11% (used)"},{"paperId":"P074","catalystId":"P074_PERF_002","name":"Pd/N-AS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-AS","phase":"Monometallic Pd","particleSize":"3.2 ± 0.9 nm (fresh), 3.6 ± 1.0 nm (used)","surfaceStates":"Higher Pd2+ content than Pd/AS: 46% (fresh) and 21% (used)","structureLink":"Nitrogen functional groups serve as anchoring sites to maintain smaller nanoparticle size compared to N-free support."},{"paperId":"P074","catalystId":"P074_PERF_003","name":"PdAg/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAg/AS","phase":"Bimetallic PdAg alloy","particleSize":"5.0 ± 2.0 nm (fresh), 6.6 ± 2.6 nm (used)","surfaceStates":"Only Pd0 present; electronic enrichment of Pd surface atoms due to alloying with Ag","structureLink":"Poor stability and activity in non-reduced version attributed to formation of Ag-rich surface nanoparticles.","deactivation":"slight increase in average nanoparticle size from 5.0 ± 2.0 nm to 6.6 ± 2.6 nm"},{"paperId":"P074","catalystId":"P074_PERF_004","name":"PdAg/N-AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAg/N-AS","phase":"Bimetallic PdAg alloy","particleSize":"2.8 ± 0.5 nm (fresh), 4.0 ± 0.7 nm (used)","surfaceStates":"Presence of Pd2+ due to strong Pd2+-N interaction: 52% (fresh) and 11% (used)","structureLink":"Superior performance attributed to the smallest nanoparticle size, high dispersion, and coexistence of metallic Pd0 and electron-deficient Pd species.","deactivation":"small increase in particle size from 2.8 ± 0.5 nm to 4.0 ± 0.7 nm"},{"paperId":"P074","catalystId":"P074_PERF_005","name":"Pd/AS(n.r.)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AS","phase":"Monometallic Pd","particleSize":"3.8 ± 2.1 nm (fresh), 4.4 ± 1.9 nm (used)","surfaceStates":"Pd0 main species; Pd2+ content is 17% (fresh) and 11% (used)"},{"paperId":"P074","catalystId":"P074_PERF_006","name":"Pd/N-AS(n.r.)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-AS","phase":"Monometallic Pd","particleSize":"3.2 ± 0.9 nm (fresh), 3.6 ± 1.0 nm (used)","surfaceStates":"Higher Pd2+ content than Pd/AS: 46% (fresh) and 21% (used)","structureLink":"Nitrogen functional groups serve as anchoring sites to maintain smaller nanoparticle size compared to N-free support."},{"paperId":"P074","catalystId":"P074_PERF_007","name":"PdAg/AS(n.r.)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAg/AS","phase":"Bimetallic PdAg alloy","particleSize":"5.0 ± 2.0 nm (fresh), 6.6 ± 2.6 nm (used)","surfaceStates":"Only Pd0 present; electronic enrichment of Pd surface atoms due to alloying with Ag","structureLink":"Poor stability and activity in non-reduced version attributed to formation of Ag-rich surface nanoparticles."},{"paperId":"P074","catalystId":"P074_PERF_008","name":"PdAg/N-AS(n.r.)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAg/N-AS","phase":"Bimetallic PdAg alloy","particleSize":"2.8 ± 0.5 nm (fresh), 4.0 ± 0.7 nm (used)","surfaceStates":"Presence of Pd2+ due to strong Pd2+-N interaction: 52% (fresh) and 11% (used)","structureLink":"Superior performance attributed to the smallest nanoparticle size, high dispersion, and coexistence of metallic Pd0 and electron-deficient Pd species."},{"paperId":"P075","catalystId":"P075_PERF_001","name":"Pd/NHPC-AC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NHPC-AC","phase":"Metallic Pd (111 plane)","particleSize":"1.88 ± 0.48 nm","surfaceStates":"Pd0 (54%) and Pd2+","structureLink":"Nitrogen doping prevents nanoparticle aggregation, increases metal dispersion, and enhances the proportion of active Pd0 sites via electron effects, resulting in higher TOF.","deactivation":"nitrogen doping prevents Pd nanoparticles from aggregation and leaching from the support surface"},{"paperId":"P075","catalystId":"P075_PERF_002","name":"Pd/HPC-AC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HPC-AC","phase":"Metallic Pd (111 and 200 planes)","particleSize":"2.56 nm","surfaceStates":"Pd0 (41%) and Pd2+","structureLink":"Lower nitrogen-free support leads to larger particle size, lower dispersion, and fewer active Pd0 sites compared to Pd/NHPC-AC."},{"paperId":"P075","catalystId":"P075_PERF_003","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC","phase":"Metallic Pd (111 and 200 planes)","particleSize":"3.31 nm","surfaceStates":"Pd0 (39%) and Pd2+","structureLink":"Lack of nitrogen doping results in the largest particle size, lowest dispersion, and lowest proportion of active Pd0 sites."},{"paperId":"P076","catalystId":"P076_PERF_001","name":"PdAg/CNT (various Pd:Ag molar ratios including Pd/CNT, Ag/CNT, Pd9Ag1/CNT, Pd8Ag2/CNT, Pd7Ag3/CNT, Pd6Ag4/CNT)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAg/CNT","phase":"PdAg alloy; XRD showed a shift of the combined Pd-Ag peak from 40° (metallic Pd) toward 38° (metallic Ag) as the Ag/Pd molar ratio increased.","particleSize":"Average particle sizes were 3.0 nm for Pd/CNT and 3.1 nm for Pd7Ag3/CNT.","surfaceStates":"Electronic modification of Pd by Ag; XPS revealed a red shift (lower binding energy) in Pd 3d spectra with increasing Ag content, peaking at a Pd:Ag ratio of 7:3.","structureLink":"The electronic modification of Pd (maximized at Pd7Ag3/CNT) correlates with the highest TOF calculated based on surface Pd sites. KIE experiments suggest this effect weakens the C-H bond of adsorbed formate, facilitating its cleavage and enhancing overall activity.","deactivation":"Absence of micropores in CNT excludes fouling as a deactivation cause."},{"paperId":"P077","catalystId":"P077_PERF_001","name":"PdMn0.6@S-1","activeMetals":"Pd-Mn","metalClass":"Pd-based multimetal","matchedCharacterization":"PdMn0.6@S-1","phase":"Pd-Mn alloy structures.","particleSize":"< 0.7 nm","surfaceStates":"Electron-enriched Pd surfaces (indicated by CO-DRIFTS shift to 2076–2082 cm-1 and lower XANES white-line intensity).","structureLink":"Synergistic effect between Pd and Mn creates electron-enriched Pd surfaces that enhance bicarbonate hydrogenation and prevent overly strong binding of HCOO* and H* intermediates during FA dehydrogenation."},{"paperId":"P077","catalystId":"P077_PERF_002","name":"Pd@S-1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@S-1","phase":"Monometallic sub-nanometer clusters.","particleSize":"< 0.7 nm","surfaceStates":"Linear-adsorbed CO peak at 2089 cm-1.","structureLink":"Sub-nanometer size increases the number of accessible active sites compared to larger nanoparticles, though TOF is similar to bulk Pd."},{"paperId":"P077","catalystId":"P077_PERF_005","name":"Mn@S-1","activeMetals":"Mn","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Mn@S-1","phase":"Monometallic clusters.","particleSize":"Sub-nanometer","surfaceStates":"No CO adsorption observed via DRIFTS.","structureLink":"Inactive for both CO2 hydrogenation and FA dehydrogenation without Pd."},{"paperId":"P078","catalystId":"P078_PERF_001","name":"Co&CoN-0.5","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co&CoN-0.5","phase":"Metallic Co phase (diffraction peaks at 2θ = 44°, 53°, and 76° corresponding to (111), (211), and (311) planes) coexisting with single atomic Co-N-C sites.","particleSize":"Mean size of ~10 nm for nanoparticles; some clusters < 3 nm observed.","surfaceStates":"Co0 and Co2+ coexist; high concentration of metal Co-N bonds identified via XPS N 1s spectra.","structureLink":"The hybrid core-shell structure optimizes the adsorption energy of intermediates, lowering the dehydrogenation energy barrier (81.48 kJ/mol) and increasing the dehydration energy barrier (227.54 kJ/mol), thereby enhancing activity and suppressing CO formation.","deactivation":"high antiacid leaching stability; no metal found in reaction solution via ICP-MS; only neat formic acid resulted in a 10% loss of Co"},{"paperId":"P078","catalystId":"P078_PERF_002","name":"Co SAC","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co SAC","phase":"Single atomic Co sites coordinated with N atoms (Co-N-C).","particleSize":"No metal particles observed.","surfaceStates":"Co2+ valence state; pyridinic N accounts for > 50% of total N.","structureLink":"Single atomic Co sites facilitate the dehydration reaction, leading to high CO concentration (1644 ppm) compared to hybrid structures.","deactivation":"null"},{"paperId":"P078","catalystId":"P078_PERF_003","name":"Co&CoN-2","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co&CoN-2","phase":"Single atomic Co sites; no metal Co peaks observed in XRD.","particleSize":"No nanoparticles present (high dispersion).","surfaceStates":"Co exists in Co2+ valence state; pyridinic N accounts for > 50% of total N.","structureLink":"Despite higher Co load than Co SAC, mass activity is similar because many single atomic sites are wrapped inside and inaccessible to reactants.","deactivation":"null"},{"paperId":"P078","catalystId":"P078_PERF_004","name":"Co&CoN-0","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co&CoN-0.5","phase":"Metallic Co phase (diffraction peaks at 2θ = 44°, 53°, and 76° corresponding to (111), (211), and (311) planes) coexisting with single atomic Co-N-C sites.","particleSize":"Mean size of ~10 nm for nanoparticles; some clusters < 3 nm observed.","surfaceStates":"Co0 and Co2+ coexist; high concentration of metal Co-N bonds identified via XPS N 1s spectra.","structureLink":"The hybrid core-shell structure optimizes the adsorption energy of intermediates, lowering the dehydrogenation energy barrier (81.48 kJ/mol) and increasing the dehydration energy barrier (227.54 kJ/mol), thereby enhancing activity and suppressing CO formation.","deactivation":"null"},{"paperId":"P078","catalystId":"P078_PERF_005","name":"Co NPs","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co NPs","phase":"Metallic cobalt nanoparticles on nitrogen-free active carbon support.","particleSize":"~10 nm","surfaceStates":"Co0 and Co2+ coexist.","structureLink":"Low mass activity due to particle aggregation, low metal load, and lack of single atomic sites.","deactivation":"acid leaching stability is intractable for supported Co nanoparticle catalysts"},{"paperId":"P079","catalystId":"P079_PERF_001","name":"Pd0.95Co0.05/CK-BN","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.95Co0.05/CK-BN","phase":"PdCo alloy nanoparticles","particleSize":"2.34 nm","surfaceStates":"Pd0 binding energy is 0.25 eV higher than in Pd/CK-BN due to interaction with Co; support contains pyridine N (398.5 eV), pyrrole N (400.5 eV), BC2O (191.2 eV), and BCO2 (192.4 eV).","structureLink":"Alloying Pd with Co modulates the electronic structure of Pd, increasing TOF to 3123 h-1; KCl etching and B,N co-doping increase surface area, defects, and hydrophilicity, facilitating NP immobilization.","deactivation":"Decreased activity attributed to surface and structure change of alloy NPs (agglomeration) and weakening signal of Co"},{"paperId":"P079","catalystId":"P079_PERF_002","name":"Pd/CK-BN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CK-BN","phase":"Pd nanoparticles","surfaceStates":"Pd0 peak at 336.1 eV.","structureLink":"B and N co-doping improves support hydrophilicity and provides accessible active sites, resulting in a TOF of 1808 h-1."},{"paperId":"P079","catalystId":"P079_PERF_003","name":"Pd/CK-B","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CK-BN","phase":"Pd nanoparticles","surfaceStates":"Pd0 peak at 336.1 eV.","structureLink":"B and N co-doping improves support hydrophilicity and provides accessible active sites, resulting in a TOF of 1808 h-1."},{"paperId":"P079","catalystId":"P079_PERF_004","name":"Pd/CK-N","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Pd nanoparticles on carbon","structureLink":"Lower catalytic activity compared to Pd/CK-BN due to the absence of alkaline etching and heteroatom doping in the support."},{"paperId":"P080","catalystId":"P080_PERF_001","name":"Pd/DMSNs-1.0-NH2","activeMetals":"Pd","metalClass":"Pd-only","deactivation":"Minor decrease in catalytic performance attributed to an increase in Pd NP size from 1.6 nm to 2.8 nm after five cycles."},{"paperId":"P081","catalystId":"P081_PERF_001","name":"C2N-Co","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"C2N-Co","phase":"Single atom catalyst","particleSize":"single atom","surfaceStates":"low-spin (S = 1/2) and high-spin ground state","structureLink":"Low-spin state is active for HCOOH dehydrogenation but higher in energy than the high-spin ground state."},{"paperId":"P081","catalystId":"P081_PERF_002","name":"C2N-Co-Sn","activeMetals":"Co-Sn","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"C2N-Co-Sn","phase":"Single atom catalyst with noncontact single atom promoter","particleSize":"single atom","surfaceStates":"Degenerate low-spin (S = 1/2) and high-spin (S = 3/2) states; d-band center closer to Fermi level at high-spin (-3.02 eV)","structureLink":"The noncontact Sn promoter facilitates spin manipulation, where the high-spin state of Co remarkably lowers the reaction barrier for HCOOH dehydrogenation compared to C2N-Co."},{"paperId":"P081","catalystId":"P081_PERF_003","name":"C2N-Co-Ge","activeMetals":"Co-Ge","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"C2N-Co","phase":"Single atom catalyst","particleSize":"single atom","surfaceStates":"low-spin (S = 1/2) and high-spin ground state","structureLink":"Low-spin state is active for HCOOH dehydrogenation but higher in energy than the high-spin ground state."},{"paperId":"P081","catalystId":"P081_PERF_004","name":"C2N-Co-Pb","activeMetals":"Co-Pb","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"C2N-Co","phase":"Single atom catalyst","particleSize":"single atom","surfaceStates":"low-spin (S = 1/2) and high-spin ground state","structureLink":"Low-spin state is active for HCOOH dehydrogenation but higher in energy than the high-spin ground state."},{"paperId":"P082","catalystId":"P082_PERF_001","name":"PdNi-WOx/KIT-6-NH2","activeMetals":"Pd-Ni-W","metalClass":"Pd-based multimetal","matchedCharacterization":"PdNi-WOx/KIT-6-NH2","phase":"fcc PdNi alloy (XRD peak at 40.9°; HRTEM lattice spacing 0.216 nm)","particleSize":"1.4 nm","surfaceStates":"Electron-rich Pd active sites resulting from: 1) electronic coupling (electron transfer from WOx to PdNi), 2) electronic metal-support interaction (EMSI, electron transfer from KIT-6-NH2 to PdNi-WOx), and 3) alloying effect (partial electron transfer from Ni to Pd).","structureLink":"Ultrafine size increases exposed active sites; electron-rich Pd surface favors C-H bond cleavage of the Pd-formate intermediate. WOx stabilizes low-coordination surface Pd atoms, improving stability.","deactivation":"Leaching percentages after durability test: Pd (0.12 wt%), Ni (0.43 wt%), W (0.10 wt%). Particle size increased from 1.4 to 2.3 nm."},{"paperId":"P082","catalystId":"P082_PERF_002","name":"PdNi/KIT-6-NH2","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"PdNi/KIT-6-NH2","phase":"fcc PdNi alloy","particleSize":"2.2 nm","deactivation":"Leaching percentages: Pd (0.52 wt%), Ni (0.99 wt%)"},{"paperId":"P082","catalystId":"P082_PERF_003","name":"Pd-WOx/KIT-6-NH2","activeMetals":"Pd-W","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-WOx/KIT-6-NH2","particleSize":"2.3 nm"},{"paperId":"P082","catalystId":"P082_PERF_004","name":"Pd/KIT-6-NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/KIT-6-NH2","particleSize":"2.6 nm"},{"paperId":"P082","catalystId":"P082_PERF_005","name":"PdNi-WOx/KIT-6","activeMetals":"Pd-Ni-W","metalClass":"Pd-based multimetal","matchedCharacterization":"PdNi-WOx/KIT-6","particleSize":"7.7 nm","structureLink":"Larger particle size leads to poorer catalytic activity compared to the amino-modified support version."},{"paperId":"P083","catalystId":"P083_PERF_001","name":"Pd/Al2O3-HS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Al2O3-HS","phase":"gamma-Al2O3 support with Pd nanoparticles/PdO","particleSize":"3.1 nm (fresh), 4.5 nm (spent)","surfaceStates":"High density of weak (<300 °C) and moderate (300-450 °C) basic sites on the support; Pd exists as PdO in fresh state (CN Pd-O = 4.0, Pd-Pd = 0.7).","structureLink":"High density of engineered basic sites promotes formic acid dissociation into formate ions and facilitates the formation of reactive Pd-HCOO* intermediates, leading to superior TOF (4606 h-1).","deactivation":"pronounced activity decline after the fifth cycle, attributed to possible Pd leaching and/or nanoparticle aggregation"},{"paperId":"P083","catalystId":"P083_PERF_002","name":"Pd/Al2O3-NB","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Al2O3-NB","phase":"gamma-Al2O3 support with Pd nanoparticles/PdO","particleSize":"2.8 nm (fresh), 3.9 nm (spent)","surfaceStates":"Intermediate basicity with a complete distribution of weak, moderate, and strong (>450 °C) basic sites.","structureLink":"Moderate density of basic sites results in lower activity compared to Pd/Al2O3-HS but higher than Pd/Al2O3-NP."},{"paperId":"P083","catalystId":"P083_PERF_003","name":"Pd/Al2O3-NP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Al2O3-NP","phase":"gamma-Al2O3 support with Pd nanoparticles/PdO","particleSize":"3.0 nm (fresh), 4.1 nm (spent)","surfaceStates":"Lowest concentration of surface basicity, exhibiting only weak basic sites.","structureLink":"Low content of weak basic sites correlates with the lowest catalytic performance (TOF = 1842 h-1)."},{"paperId":"P084","catalystId":"P084_PERF_001","name":"Pd/ZrO2@C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/ZrO2@C","phase":"fcc Pd; tetragonal ZrO2 embedded in amorphous carbon.","particleSize":"2.5 ± 0.3 nm","surfaceStates":"Electron-rich Pd surfaces indicated by negative shift in XPS binding energies compared to Pd/AC.","structureLink":"Uniform dispersion of smaller nanoparticles and electron-rich surfaces promote the dissociation of O-H bonds in formic acid and favor the formation of Pd-formate intermediates, enhancing catalytic activity.","deactivation":"slight aggregation of the catalyst"},{"paperId":"P084","catalystId":"P084_PERF_002","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC","particleSize":"Similar to Pd/ZrO2@C (~2.5 nm)","surfaceStates":"Less electron-rich than Pd/ZrO2@C.","structureLink":"Higher fraction of oxidized Pd species and less electron-rich surface lead to lower activity compared to Pd/ZrO2@C despite similar particle size."},{"paperId":"P084","catalystId":"P084_PERF_003","name":"Pd/ZrO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/ZrO2","structureLink":"Lowest activity attributed to the lowest BET surface area and poor Pd NP dispersion."},{"paperId":"P085","catalystId":"P085_PERF_001","name":"PVPI-capped networked Pd5Ag5 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"PVPI-capped networked Pd5Ag5 NWs","phase":"Homogeneously alloyed fcc PdAg; polycrystalline structure with (111) facet lattice fringe distance of 0.23 nm","surfaceStates":"High density of low coordination atoms; extensive defects around kinks and steps; electron-rich Pd centers due to interfacial electron transfer from PVPI imino groups","structureLink":"Electron donation from PVPI imino groups increases electron density of Pd active centers, facilitating O-H cleavage and strengthening formate adsorption; the imino group also acts as a proton scavenger promoting b-hydride elimination"},{"paperId":"P086","catalystId":"P086_PERF_001","name":"1 wt%Pd@O-HHT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1 wt%Pd@O-HHT","phase":"Pd nanoparticles","particleSize":"2.3 nm","surfaceStates":"Surface Pd exposure of 1.14%; preferential deposition on O functionalities","structureLink":"Smaller particle size, higher dispersion, and electronic interaction between Pd and oxygen functional groups enhance activity, stability, and selectivity for the dehydrogenation pathway.","deactivation":"Avoids leaching of Pd; no signs of deactivation observed during 2h kinetic profiles"},{"paperId":"P086","catalystId":"P086_PERF_002","name":"1 wt%Pd@P-HHT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1 wt%Pd@P-HHT","phase":"Pd nanoparticles","particleSize":"2.3 nm","surfaceStates":"Surface Pd exposure of 1.57%; preferential deposition on P functionalities (confirmed by STEM-EDS)","structureLink":"Smaller particle size, higher dispersion, and electronic interaction between Pd and phosphorous functional groups enhance stability and activity compared to non-functionalized HHT.","deactivation":"Avoids leaching of Pd; no signs of deactivation observed during 2h kinetic profiles"},{"paperId":"P086","catalystId":"P086_PERF_003","name":"1 wt%Pd@HHT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1 wt%Pd@HHT","phase":"Pd nanoparticles","particleSize":"3 nm","surfaceStates":"Surface Pd exposure of 0.77%","structureLink":"Larger particle size and lower dispersion compared to functionalized supports result in lower activity and stability.","deactivation":"Sintering (average particle size increased from 3.0 to 4.7 nm during 9 h), CO poisoning of NPs, and leaching of Pd"},{"paperId":"P087","catalystId":"P087_PERF_001","name":"Cr0.4Pd0.6/M-β-CD-A","activeMetals":"Cr-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Cr0.4Pd0.6/M-β-CD-A","phase":"Alloy structure; HRTEM shows lattice spacing of 0.222 nm (smaller than Pd(111) at 0.224 nm); XRD shows a broad diffraction peak between characteristic peaks of Pd and Cr.","particleSize":"~2.8 nm","surfaceStates":"Binding energies of Pd 3d 5/2 and Cr 2p 3/2 are shifted to lower values compared to free NPs, indicating electron transfer from the M-β-CD-A support to CrPd NPs; charge transfer occurs between Pd and Cr due to alloying, resulting in an electron-rich Pd surface.","structureLink":"Strong metal/organic interfacial interactions control particle size and distribution while modifying the electronic structure of Pd active centers, which promotes the rate-determining C–H dissociation of the Pd-formate intermediate."},{"paperId":"P087","catalystId":"P087_PERF_002","name":"Cr0.4Pd0.6 NPs (free)","activeMetals":"Cr-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Cr0.4Pd0.6 NPs (free)","particleSize":"~4.8 nm"},{"paperId":"P087","catalystId":"P087_PERF_003","name":"Cr0.4Pd0.6/M-β-CD","activeMetals":"Cr-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Cr0.4Pd0.6/M-β-CD","particleSize":"~3.8 nm"},{"paperId":"P087","catalystId":"P087_PERF_004","name":"Cr0.4Pd0.6-A","activeMetals":"Cr-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Cr0.4Pd0.6-A","particleSize":"3.1 nm"},{"paperId":"P088","catalystId":"P088_PERF_001","name":"Pd@MC(2)-P","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@MC(2)-P","phase":"Metallic Pd nanoparticles","particleSize":"2.8 nm","surfaceStates":"Pd0 peaks at 339.9 and 334.7 eV; Pd2+ peaks at 341.6 and 335.9 eV. A distinct downshift of Pd0 peaks indicates stronger interaction with the N-doped carbon support compared to control samples.","structureLink":"Ultra-fine particle size, high dispersion, and exposure of active Pd-cluster-edge (edges of Pd-cluster-100 and Pd-cluster-111 surfaces) reduce H poisoning and lower energy barriers for formic acid dehydrogenation."},{"paperId":"P088","catalystId":"P088_PERF_002","name":"Pd@MC(0)-P","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@MC(0)-P","phase":"Metallic Pd nanoparticles","particleSize":"4.8 nm","surfaceStates":"Pd0 peaks at 340.4 and 335.3 eV."},{"paperId":"P088","catalystId":"P088_PERF_003","name":"Pd@MC(2)-0","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@MC(2)-0","phase":"Metallic Pd nanoparticles","particleSize":"5.7 nm","surfaceStates":"Pd0 peaks at 342.5 and 335.9 eV."},{"paperId":"P089","catalystId":"P089_PERF_001","name":"PdAu/Al2O3–CO (1)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/Al2O3–CO (1)","phase":"PdAu alloy (verified by XPS shift of Pd 3d 5/2 peak from 335.2 eV to 335.4 eV)","particleSize":"1.2–1.3 nm","surfaceStates":"High population of Pd 3-fold hollow sites (1800–1900 cm-1 in DRIFT) compared to H2 or N2 treated samples.","structureLink":"Highest activity for FA dehydrogenation due to the synergistic effect of a high density of Pd hollow sites (ensemble effect) and electronic perturbation from Au sublayers (ligand effect)."},{"paperId":"P089","catalystId":"P089_PERF_002","name":"PdAu/Al2O3–H2 (2)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/Al2O3–H2 (2)","phase":"PdAu alloy (verified by XPS shift of Pd 3d 5/2 peak from 335.2 eV to 335.4 eV)","particleSize":"1.2–1.3 nm","surfaceStates":"Moderate population of Pd hollow sites (2.8 times greater than catalyst 3).","structureLink":"Moderate activity for FA dehydrogenation, correlating with the intermediate density of Pd hollow sites."},{"paperId":"P089","catalystId":"P089_PERF_003","name":"PdAu/Al2O3–N2 (3)","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/Al2O3–N2 (3)","phase":"PdAu alloy (verified by XPS shift of Pd 3d 5/2 peak from 335.2 eV to 335.4 eV)","particleSize":"1.2–1.3 nm","surfaceStates":"Negligible intensity of CO vibration at Pd hollow sites (1800–1900 cm-1).","structureLink":"Lowest activity for FA dehydrogenation due to low surface Pd coverage and lack of Pd hollow sites."},{"paperId":"P089","catalystId":"P089_PERF_004","name":"Pd/Al2O3 (4)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Al2O3 (4)","phase":"Pure Pd","surfaceStates":"High quantity of 3-fold hollow sites, but lower relative ratio than catalyst 1 because CO adsorption on bridge sites is more favorable at high coverage.","structureLink":"Lower activity compared to Catalyst 1 despite higher total hollow site count, demonstrating the positive ligand effect provided by Au sublayers in PdAu alloys."},{"paperId":"P090","catalystId":"P090_PERF_001","name":"Pd1Ag0.5/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag0.5/NAS","phase":"Fresh: Ag crystalline facets (38°, 44°, 64°, 77°) and incomplete alloy; Used: PdAg alloy (XRD signals at 38.4° and 44.4°)","particleSize":"2.8 ± 1.1 nm","surfaceStates":"Highest relative proportion of Pd2+/Pd0 among all catalysts; Ag species electronic charge redistribution","structureLink":"Outstanding performance (TOF 1716 h-1) linked to the highest Pd2+/Pd0 ratio and small particle size.","deactivation":"No Pd leaching observed via ICP-OES. Deactivation attributed to sintering (average nanoparticle size increased by 39%) and reduction of Pd2+ species to Pd0 under reaction conditions."},{"paperId":"P090","catalystId":"P090_PERF_002","name":"Pd1Ag0.5/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag0.5/AS","phase":"PdAg alloy (XRD signals at 38.4° and 44.4°)","particleSize":"4.0 ± 1.3 nm","surfaceStates":"Predominantly Pd0; Ag species enriched in electronic charge","structureLink":"Optimal bimetallic composition for AS support, showing maximum gas volume among AS-supported catalysts.","deactivation":"No Pd leaching observed via ICP-OES. Deactivation attributed to sintering (average nanoparticle size increased by 55%) and complete reduction of Pd species to Pd0."},{"paperId":"P090","catalystId":"P090_PERF_003","name":"Pd/AS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AS","phase":"Monometallic Pd","particleSize":"3.8 ± 2.1 nm","surfaceStates":"Pd0 and Pd2+; Pd0 3d5/2 at 335.6 eV, Pd2+ 3d5/2 at 337.5 eV","structureLink":"Lower activity compared to bimetallic and NAS-supported counterparts due to larger particle size and lower Pd2+/Pd0 ratio."},{"paperId":"P090","catalystId":"P090_PERF_004","name":"Pd1Ag0.3/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag0.3/AS","phase":"PdAg alloy","particleSize":"4.5 ± 0.9 nm","surfaceStates":"Pd0 and Pd2+; Ag species enriched in electronic charge (shift of ~0.4 eV towards lower binding energies)","structureLink":"Increased activity compared to monometallic Pd/AS due to alloy formation."},{"paperId":"P090","catalystId":"P090_PERF_005","name":"Pd1Ag0.7/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag0.7/AS","phase":"PdAg alloy","particleSize":"4.1 ± 1.2 nm","surfaceStates":"Pd0 and Pd2+; Ag species enriched in electronic charge","structureLink":"Activity lower than Pd1Ag0.5/AS, following a volcano-type relationship with Ag content."},{"paperId":"P090","catalystId":"P090_PERF_006","name":"Pd1Ag1/AS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag1/AS","phase":"PdAg alloy","particleSize":"5.0 ± 2.0 nm","surfaceStates":"Purely Pd0; Ag species enriched in electronic charge","structureLink":"Lower activity than Pd1Ag0.5/AS due to larger particle size and absence of Pd2+."},{"paperId":"P090","catalystId":"P090_PERF_007","name":"Pd/NAS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NAS","phase":"Monometallic Pd","particleSize":"3.2 ± 0.9 nm","surfaceStates":"Pd0 and Pd2+; shift towards higher binding energies (Pd0 3d5/2 at 336.0 eV, Pd2+ 3d5/2 at 338.0 eV) due to N-groups","structureLink":"Enhanced activity over Pd/AS attributed to smaller particle size and higher concentration of Pd2+ species."},{"paperId":"P090","catalystId":"P090_PERF_008","name":"Pd1Ag0.3/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag0.3/NAS","phase":"PdAg alloy","particleSize":"2.7 ± 0.7 nm","surfaceStates":"Pd0 and Pd2+; Ag species electronic charge redistribution influenced by electronegative N-groups","structureLink":"Higher activity than Pd1Ag0.3/AS due to smaller particle size and higher Pd2+ content."},{"paperId":"P090","catalystId":"P090_PERF_009","name":"Pd1Ag0.7/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag0.7/NAS","phase":"PdAg alloy","particleSize":"2.7 ± 0.6 nm","surfaceStates":"Pd0 and Pd2+; Ag species electronic charge redistribution","structureLink":"High activity but lower than Pd1Ag0.5/NAS, correlating with a lower Pd2+/Pd0 ratio."},{"paperId":"P090","catalystId":"P090_PERF_010","name":"Pd1Ag1/NAS","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag1/NAS","phase":"PdAg alloy","particleSize":"2.8 ± 0.5 nm","surfaceStates":"Pd0 and Pd2+; Ag species electronic charge redistribution","structureLink":"Activity lower than Pd1Ag0.5/NAS, following the volcano trend with Ag content."},{"paperId":"P091","catalystId":"P091_PERF_001","name":"Pd/CMS-ZnCl2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CMS-ZnCl2","phase":"Metallic Pd (weak diffraction peaks due to small particle size)","particleSize":"XRD: 2.8 nm; TEM: 2.9 ± 0.5 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Smallest particle size, high specific surface area (1081 m2/g), and uniform honeycomb morphology led to the highest TON value due to more active sites and uncapped surfaces.","deactivation":"Average Pd particle size increased from 2.9 nm to 3.2 nm; content of Pd0 decreased"},{"paperId":"P091","catalystId":"P091_PERF_002","name":"Pd/CPS-ZnCl2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CPS-ZnCl2","phase":"Metallic Pd (weak diffraction peaks due to small particle size)","particleSize":"XRD: 3.8 nm; TEM: 3.6 ± 0.6 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"ZnCl2 activation increased surface O content, providing nucleation points that reduced particle size and improved dispersion, increasing activity."},{"paperId":"P091","catalystId":"P091_PERF_003","name":"Pd/CMS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CMS","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites."},{"paperId":"P091","catalystId":"P091_PERF_004","name":"Pd/CPS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CPS","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 7.2 nm; TEM: 6.7 ± 0.6 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites."},{"paperId":"P091","catalystId":"P091_PERF_005","name":"Pd/CMS-2gZnCl2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CMS","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites."},{"paperId":"P091","catalystId":"P091_PERF_006","name":"Pd/CMS-6gZnCl2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CMS","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites."},{"paperId":"P091","catalystId":"P091_PERF_007","name":"Pd/CMS-ZnCl2 (carbonized at 500 °C)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CMS","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites."},{"paperId":"P091","catalystId":"P091_PERF_008","name":"Pd/CMS-900","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CMS","phase":"Metallic Pd (planes (111), (200), and (220); PDF#01-1310)","particleSize":"XRD: 6.8 nm; TEM: 6.4 ± 0.4 nm","surfaceStates":"Pd0 (335.8 eV) and Pd2+ (337.8 eV)","structureLink":"Larger particle size correlated with lower TON value due to fewer active sites."},{"paperId":"P092","catalystId":"P092_PERF_001","name":"AuPd/TiO2 nanosheets-400","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AuPd/TiO2 nanosheets-400","phase":"AuPd alloy with face-centered cubic (fcc) structure; HRTEM lattice fringe distance of 0.231 nm is between fcc Pd (0.224 nm) and Au (0.235 nm).","particleSize":"2.8 nm","surfaceStates":"XPS shows binding energies of Au 4f and Pd 3d shifted to lower values compared to pure metals (reduced by approximately 1.8 eV and 1.1 eV, respectively), indicating electron transfer from the TiO2 support to the metal nanoparticles.","structureLink":"Superior activity is attributed to the alloy structure of AuPd centers, the low crystallinity anatase phase of the TiO2 nanosheets, and strong electron transfer interaction between the AuPd nanoparticles and the TiO2 substrate.","deactivation":"little deactivation observed over two cycles"},{"paperId":"P092","catalystId":"P092_PERF_002","name":"AuPd","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AuPd/TiO2 nanosheets-400","phase":"AuPd alloy with face-centered cubic (fcc) structure; HRTEM lattice fringe distance of 0.231 nm is between fcc Pd (0.224 nm) and Au (0.235 nm).","particleSize":"2.8 nm","surfaceStates":"XPS shows binding energies of Au 4f and Pd 3d shifted to lower values compared to pure metals (reduced by approximately 1.8 eV and 1.1 eV, respectively), indicating electron transfer from the TiO2 support to the metal nanoparticles.","structureLink":"Superior activity is attributed to the alloy structure of AuPd centers, the low crystallinity anatase phase of the TiO2 nanosheets, and strong electron transfer interaction between the AuPd nanoparticles and the TiO2 substrate.","deactivation":"aggregate severely without the support"},{"paperId":"P092","catalystId":"P092_PERF_003","name":"Pd/TiO2 nanosheets-400","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"AuPd/TiO2 nanosheets-400","phase":"AuPd alloy with face-centered cubic (fcc) structure; HRTEM lattice fringe distance of 0.231 nm is between fcc Pd (0.224 nm) and Au (0.235 nm).","particleSize":"2.8 nm","surfaceStates":"XPS shows binding energies of Au 4f and Pd 3d shifted to lower values compared to pure metals (reduced by approximately 1.8 eV and 1.1 eV, respectively), indicating electron transfer from the TiO2 support to the metal nanoparticles.","structureLink":"Superior activity is attributed to the alloy structure of AuPd centers, the low crystallinity anatase phase of the TiO2 nanosheets, and strong electron transfer interaction between the AuPd nanoparticles and the TiO2 substrate."},{"paperId":"P093","catalystId":"P093_PERF_001","name":"Au2Pd8/SBA-15-Amine","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au2Pd8/SBA-15-Amine","phase":"Au-Pd alloy structure","particleSize":"4.5 ± 0.5 nm","surfaceStates":"Metallic Au0 and Pd0; XPS shows binding energy shifts (Au shifted to lower values: 83.5, 87.1 eV; Pd shifted to higher values: 336.1, 341.5 eV) compared to monometallic counterparts, indicating alloying.","structureLink":"Alloy formation between Au and Pd exerts a positive synergistic effect on the dehydrogenation of formic acid."},{"paperId":"P094","catalystId":"P094_PERF_001","name":"Pd@CN900K","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@CN900K","phase":"Metallic Pd0 phase (JCPDS: 46-1043)","particleSize":"1.1 ± 0.2 nm","surfaceStates":"Pd exists as Pd0 and Pd2+; the carbon support contains pyridinic, pyrrolic, and graphitic nitrogen species, as well as C=O and C-OH groups.","structureLink":"Smaller particle size compared to other samples provides more accessible active sites. Rich mesoporosity facilitates effective mass transport. N-doping stabilizes Pd NPs against aggregation and exerts an electronic effect that facilitates the rate-determining step (C-H bond cleavage)."},{"paperId":"P095","catalystId":"P095_PERF_001","name":"Pd−Cr(OH)3/NH2-rGO","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-Cr(OH)3/NH2-rGO","phase":"Non-alloyed nanoclusters with strong electronic coupling between Pd and Cr(OH)3","particleSize":"1.6 nm","surfaceStates":"Electron-rich Pd0 (Pd0/(Pd0+Pd2+) = 0.76); partial electron transfer from Cr(OH)3 to Pd and from NH2-rGO to the nanoclusters.","structureLink":"Ultrafine size increases exposed active sites; electron-rich Pd NCs facilitate C-H bond dissociation (RDS); basic amino groups and Cr(OH)3 promote O-H bond dissociation of FA molecules."},{"paperId":"P095","catalystId":"P095_PERF_002","name":"Pd/NH2-rGO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-rGO","particleSize":"1.8 nm","surfaceStates":"Pd0/(Pd0+Pd2+) = 0.71"},{"paperId":"P095","catalystId":"P095_PERF_003","name":"Pd−Cr(OH)3/rGO","activeMetals":"Pd-Cr","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-Cr(OH)3/rGO","particleSize":"2.3 nm"},{"paperId":"P095","catalystId":"P095_PERF_004","name":"Pd/rGO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rGO","particleSize":"4.8 nm"},{"paperId":"P095","catalystId":"P095_PERF_005","name":"Cr(OH)3/NH2-rGO","activeMetals":"Cr","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pd-Cr(OH)3/NH2-rGO","phase":"Non-alloyed nanoclusters with strong electronic coupling between Pd and Cr(OH)3","particleSize":"1.6 nm","surfaceStates":"Electron-rich Pd0 (Pd0/(Pd0+Pd2+) = 0.76); partial electron transfer from Cr(OH)3 to Pd and from NH2-rGO to the nanoclusters.","structureLink":"Ultrafine size increases exposed active sites; electron-rich Pd NCs facilitate C-H bond dissociation (RDS); basic amino groups and Cr(OH)3 promote O-H bond dissociation of FA molecules."},{"paperId":"P096","catalystId":"P096_PERF_001","name":"AgPd@MIL-125-NH2-PDA","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AgPd@MIL-125-NH2-PDA","phase":"Bimetallic nanoalloy confirmed by d-spacing of 0.23 nm (between FCC Pd 0.22 nm and FCC Ag 0.24 nm), XPS binding energy shifts (Ag0 downshifted to 373.7 eV, Pd0 upshifted to 341.1 eV), and the complete disappearance of the Ag plasmon resonance peak in UV-Vis spectroscopy.","particleSize":"2.2 ± 0.3 nm","surfaceStates":"Pd is electronically promoted due to nanoalloying with Ag; strong metal-support interaction (SMSI) between the bimetallic nanoparticles and the PDA-coated MOF support.","structureLink":"The thin PDA layer provides abundant catechol and amino groups that act as nucleation sites, preventing nanoparticle agglomeration and leaching. DFT calculations indicate that alloying Ag with Pd lowers the energy barrier for hydrogen desorption (0.76 eV vs 0.94 eV for pure Pd), which is the rate-determining step in formic acid dehydrogenation.","deactivation":"ICP-MS analysis of filtrate showed less than 0.001 ppb Ag and 0.0015 ppb Pd, confirming negligible leaching."},{"paperId":"P096","catalystId":"P096_PERF_002","name":"Pd@MIL-125-NH2-PDA","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"AgPd@MIL-125-NH2-PDA","phase":"Bimetallic nanoalloy confirmed by d-spacing of 0.23 nm (between FCC Pd 0.22 nm and FCC Ag 0.24 nm), XPS binding energy shifts (Ag0 downshifted to 373.7 eV, Pd0 upshifted to 341.1 eV), and the complete disappearance of the Ag plasmon resonance peak in UV-Vis spectroscopy.","particleSize":"2.2 ± 0.3 nm","surfaceStates":"Pd is electronically promoted due to nanoalloying with Ag; strong metal-support interaction (SMSI) between the bimetallic nanoparticles and the PDA-coated MOF support.","structureLink":"The thin PDA layer provides abundant catechol and amino groups that act as nucleation sites, preventing nanoparticle agglomeration and leaching. DFT calculations indicate that alloying Ag with Pd lowers the energy barrier for hydrogen desorption (0.76 eV vs 0.94 eV for pure Pd), which is the rate-determining step in formic acid dehydrogenation."},{"paperId":"P097","catalystId":"P097_PERF_001","name":"Zn51.9Pd48.1","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Bulk Zn51.9Pd48.1 / Zn49.8Pd50.2 (Zn-rich)","phase":"Single-phase intermetallic compound ZnPd","surfaceStates":"Surface consists of a layer of oxidized Zn species (Zn 3d5/2 at 10.5 eV) and intermetallic Zn (Zn 3d5/2 at 9.65 or 9.49 eV); formate carbon detected at 289.2 eV during reaction.","structureLink":"Surface oxidation to ZnO and subsequent zinc formate formation hinders the overall reaction rate compared to Pd-rich samples."},{"paperId":"P097","catalystId":"P097_PERF_002","name":"Zn49.8Pd50.2","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Bulk Zn51.9Pd48.1 / Zn49.8Pd50.2 (Zn-rich)","phase":"Single-phase intermetallic compound ZnPd","surfaceStates":"Surface consists of a layer of oxidized Zn species (Zn 3d5/2 at 10.5 eV) and intermetallic Zn (Zn 3d5/2 at 9.65 or 9.49 eV); formate carbon detected at 289.2 eV during reaction.","structureLink":"Surface oxidation to ZnO and subsequent zinc formate formation hinders the overall reaction rate compared to Pd-rich samples."},{"paperId":"P097","catalystId":"P097_PERF_003","name":"Zn42.0Pd58.0","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Bulk Zn42.0Pd58.0 (Pd-rich)","phase":"Single-phase intermetallic compound ZnPd","surfaceStates":"Predominantly intermetallic Zn (Zn 3d5/2 at 9.30 eV).","structureLink":"Higher stability against oxidation correlates with higher catalytic activity in formic acid decomposition."},{"paperId":"P097","catalystId":"P097_PERF_004","name":"ZnPd/ZnO","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"ZnPd/ZnO (Supported)","phase":"Intermetallic compound ZnPd nanoparticles supported on ZnO","surfaceStates":"Dynamic formation and decomposition of zinc formate species during catalysis.","structureLink":"Significantly higher activity than bulk ZnPd; performance is linked to the modification of ZnO crystallinity through the zinc formate cycle.","deactivation":"Modification of ZnO support observed via SEM (fine pores, less compact morphology) attributed to zinc formate formation/decomposition"},{"paperId":"P098","catalystId":"P098_PERF_001","name":"Pd/C3N4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C3N4","phase":"Face-centered cubic Pd0 and H-loaded Pd species (PdHx)","particleSize":"2.8 nm (TEM), 17.2 nm (XRD crystallite size)","surfaceStates":"Hydrogen atoms diffused into the Pd lattice; nitrogen species on C3N4 support reduce electron density on the Pd surface","structureLink":"Nitrogen species stabilize Pd particles and provide adsorption sites, facilitating reactant adsorption.","deactivation":"No signs of catalytic deactivation; cumulative H2 volume increased linearly."},{"paperId":"P098","catalystId":"P098_PERF_002","name":"Ru/C3N4","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru/C3N4","phase":"Hexagonal Ru crystal structure","particleSize":"4.2 nm (TEM), 15.3 nm (XRD crystallite size)","structureLink":"Inactive in liquid-phase FAD due to competitive absorption of water and surface hydroxylation.","deactivation":"No signs of catalytic deactivation; cumulative H2 volume increased linearly."},{"paperId":"P098","catalystId":"P098_PERF_003","name":"PdRu/C3N4","activeMetals":"Pd-Ru","metalClass":"Pd-based multimetal","matchedCharacterization":"PdRu/C3N4","phase":"Hexagonal Ru crystal structure; no alloy formation detected","particleSize":"3.6 nm (TEM), 9.8 nm (XRD crystallite size for Ru)","structureLink":"Presence of Ru facilitates carboxyl formation on Pd sites; presence of Pd diminishes Ru particle size.","deactivation":"No signs of catalytic deactivation; cumulative H2 volume increased linearly."},{"paperId":"P099","catalystId":"P099_PERF_001","name":"Pd 5","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd 5","phase":"Metallic Pd","particleSize":"1.64 nm","structureLink":"Higher surface availability compared to Pd 10 leads to higher initial hydrogen production velocity.","deactivation":"Surface progressively covered by reaction intermediates, leading to decrease in gas flow; bidentate formate adsorption is responsible for deactivation."},{"paperId":"P099","catalystId":"P099_PERF_002","name":"Pd 10","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd 10","phase":"Metallic Pd","particleSize":"5.62 nm","structureLink":"Larger average particle size indicates lower Pd surface availability, resulting in lower initial hydrogen production velocity compared to Pd 5."},{"paperId":"P099","catalystId":"P099_PERF_007","name":"Co 5","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co 5","phase":"Metallic Co / Co3O4","particleSize":"28 nm","structureLink":"Inactive in FAD conditions."},{"paperId":"P100","catalystId":"P100_PERF_001","name":"1 wt.% Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1 wt.% Pd/C","particleSize":"3.6 ± 1.7 nm"},{"paperId":"P100","catalystId":"P100_PERF_002","name":"10:1 K–Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"10:1 K–Pd/C","particleSize":"3.7 ± 1.3 nm","structureLink":"K-promotion increases TOF and hydrogen selectivity via formation of a buffer solution of potassium formate and formic acid in pores"},{"paperId":"P100","catalystId":"P100_PERF_003","name":"1 wt.% Pd/SiO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1 wt.% Pd/SiO2","particleSize":"7.4 ± 2.4 nm","surfaceStates":"Condensed HCOOH on SiO2; very small concentrations of formate species (1578 cm-1)"},{"paperId":"P100","catalystId":"P100_PERF_004","name":"4:1 K–Pd/SiO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"4:1 K–Pd/SiO2","surfaceStates":"Formate anions in solution (1586 cm-1) and bulk potassium formate (crystalline or molten KHCOO, 1606 cm-1)","structureLink":"Presence of mobile formate ions stabilized by K ions in a buffer-like solution is an essential factor in promoting activity"},{"paperId":"P100","catalystId":"P100_PERF_005","name":"1 wt.% Pd/Al2O3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"1 wt.% Pd/Al2O3","particleSize":"4.2 ± 1.0 nm"},{"paperId":"P100","catalystId":"P100_PERF_006","name":"2:1 K–Pd/Al2O3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"2:1 K–Pd/Al2O3","structureLink":"Promotion by K increases TOF and hydrogen selectivity"},{"paperId":"P101","catalystId":"P101_PERF_001","name":"Pd–CeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd–CeO2","phase":"Monometallic Pd nanoparticles","particleSize":"~7 nm","surfaceStates":"High surface coverage of atomic oxygen under ambient conditions.","structureLink":"Surface atomic oxygen promotes H2O formation and decreases H2 selectivity; apparent activation barrier is 25 ± 3 kJ mol−1."},{"paperId":"P101","catalystId":"P101_PERF_002","name":"0.5 PdAg–CeO2","activeMetals":"Pd-Ag-Ce","metalClass":"Pd-based multimetal","matchedCharacterization":"0.5 PdAg–CeO2","phase":"Alloyed PdAg nanoparticles (confirmed by HR-TEM elemental detection)","particleSize":"~7 nm","surfaceStates":"Increased surface coverage of reduced Pd0 compared to monometallic Pd; decreased atomic oxygen coverage.","structureLink":"Alloying increases Pd0 coverage and reduces atomic oxygen, suppressing oxidative dehydrogenation and decreasing the apparent activation barrier to 8 ± 4 kJ mol−1, increasing H2 TOF and selectivity.","deactivation":"Surface intermediates, such as formate ions, possibly lead to deactivation during the FA reaction."},{"paperId":"P101","catalystId":"P101_PERF_003","name":"Pd–TiO2","activeMetals":"Pd-Ti","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd–TiO2","phase":"Monometallic Pd nanoparticles","particleSize":"~7 nm","structureLink":"Low H2 TOF (5 h−1) and selectivity (3%) compared to alloyed version."},{"paperId":"P101","catalystId":"P101_PERF_004","name":"0.5 PdAg–TiO2","activeMetals":"Pd-Ag-Ti","metalClass":"Pd-based multimetal","matchedCharacterization":"0.5 PdAg–TiO2","phase":"Alloyed PdAg nanoparticles","particleSize":"~7 nm","structureLink":"Higher H2 TOF (115 h−1) and selectivity (26%) than Pd–TiO2; performance comparable to 0.5 PdAg–CeO2 due to similar support basicity (PZC)."},{"paperId":"P101","catalystId":"P101_PERF_005","name":"Pd–Al2O3","activeMetals":"Pd-Al","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd–Al2O3","phase":"Monometallic Pd nanoparticles","particleSize":"~12 nm","surfaceStates":"Adsorbed atomic oxygen present on surface.","structureLink":"H2 TOF of 113 h−1 and selectivity of 17%; apparent activation energy is 25 ± 3 kJ mol−1."},{"paperId":"P101","catalystId":"P101_PERF_006","name":"0.5 PdAg–Al2O3","activeMetals":"Pd-Ag-Al","metalClass":"Pd-based multimetal","matchedCharacterization":"0.5 PdAg–Al2O3","phase":"Alloyed PdAg nanoparticles","particleSize":"~12 nm","surfaceStates":"CO binds stronger in bridging mode compared to Pd–Al2O3; strongly adsorbed atomic oxygen.","structureLink":"Lower H2 TOF (5 h−1) and selectivity (8%) than Pd–Al2O3; higher apparent activation energy (42 ± 5 kJ mol−1) due to stronger adsorption of intermediates like HCOO* and H*."},{"paperId":"P102","catalystId":"P102_PERF_001","name":"5Pd-M1U3-600","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","matchedCharacterization":"5Pd-M1U3-600","phase":"fcc cubic metallic Pd","particleSize":"2.8 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm; presence of cyano defects enhances N-to-Pd transfer.","structureLink":"Highest BET surface area (94 m2/g) and smallest particle size result in almost complete FA conversion (98%) and highest 2,5-DMF yield in HDO by suppressing humins formation."},{"paperId":"P102","catalystId":"P102_PERF_002","name":"5Pd-M1U3-550","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","matchedCharacterization":"5Pd-M1U3-550","phase":"fcc cubic metallic Pd","particleSize":"3.6 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm","structureLink":"High dispersion and small particle size contribute to high FA conversion (96%)."},{"paperId":"P102","catalystId":"P102_PERF_003","name":"5Pd-M-600","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"5Pd-M-600","phase":"fcc cubic metallic Pd","particleSize":"9.1 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm; higher aromaticity (lower C/H ratio) increases electron density on Pd.","structureLink":"Higher specific activity compared to 5Pd-M-550 attributed to increased support surface area and decreased C/H ratio."},{"paperId":"P102","catalystId":"P102_PERF_004","name":"5Pd-M-550","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"5Pd-M-550","phase":"fcc cubic metallic Pd","particleSize":"6.7 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm","structureLink":"Lower BET surface area (12 m2/g) and larger particle size compared to M1U3 series correlate with lower FA conversion."},{"paperId":"P102","catalystId":"P102_PERF_005","name":"5Pd-M3U1-600","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","matchedCharacterization":"5Pd-M3U1-600","phase":"fcc cubic metallic Pd","particleSize":"9.1 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm","structureLink":"Moderate performance; lower gas pressure in HDO compared to M1U3 series."},{"paperId":"P102","catalystId":"P102_PERF_006","name":"5Pd-M3U1-550","activeMetals":"Pd-U","metalClass":"Pd-based multimetal","matchedCharacterization":"5Pd-M3U1-550","phase":"fcc cubic metallic Pd","particleSize":"15.4 nm","surfaceStates":"N-to-Pd electron transfer suggested by UV-Vis band at 220 nm","structureLink":"Poor FA conversion despite high metal loading (11 wt%) due to largest particle size and lowest dispersion."},{"paperId":"P103","catalystId":"P103_PERF_001","name":"Pd/MWCNT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MWCNTs","phase":"Metallic Pd","particleSize":"4 ± 4 nm","surfaceStates":"Metallic state and Pd2+","structureLink":"Poor activity compared to composite supports."},{"paperId":"P103","catalystId":"P103_PERF_002","name":"Pd/C3N4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C3N4","phase":"Metallic Pd","particleSize":"6 ± 2 nm","surfaceStates":"Mainly Pd2+","structureLink":"Moderate activity; low surface area and layer stacking limit available N ligand sites."},{"paperId":"P103","catalystId":"P103_PERF_003","name":"Pd/MWCNT-C3N4(63)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MWCNT-C3N4(63)","phase":"Metallic Pd","particleSize":"2.4 ± 0.8 nm","surfaceStates":"Metallic state, Pd2+, electron-deficient species (~338.7 eV), and electron-rich Pd species (Pdδ-) at 334.3 eV.","structureLink":"Highest activity attributed to the presence of both electron-deficient species (for formate adsorption) and electron-rich species (for C-H bond cleavage)."},{"paperId":"P103","catalystId":"P103_PERF_004","name":"Pd/MWCNT-C3N4(38)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MWCNT-C3N4(38)","phase":"Metallic Pd","particleSize":"2.2 ± 0.4 nm","surfaceStates":"Metallic state, Pd2+, and electron-deficient species (~338.7 eV).","structureLink":"Improved Pd-N interaction due to efficient distribution of C3N4 layers on MWCNTs."},{"paperId":"P104","catalystId":"P104_PERF_001","name":"Pd/N–C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N–C","phase":"Crystalline Pd nanoparticles","surfaceStates":"Baseline Pd 3d binding energies for comparison with alloys","structureLink":"Lower activity than PdNi alloys due to lack of synergistic electronic/geometric effects from Ni"},{"paperId":"P104","catalystId":"P104_PERF_002","name":"Pd1Ni0.37/N–C","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ni0.37/N–C","phase":"PdNi isomorphous alloy with face-centered cubic (fcc) structure","particleSize":"3.0 nm","surfaceStates":"Increased Pd 3d binding energies relative to Pd/N–C indicating electronic interactions between Pd and Ni","structureLink":"Ni alloying perturbs the Pd electronic structure, facilitating H2 release from aqueous FA solution"},{"paperId":"P104","catalystId":"P104_PERF_003","name":"Pd1Ni1.3/N–C","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ni1.3/N–C","phase":"PdNi isomorphous alloy with face-centered cubic (fcc) structure","particleSize":"3.1 nm","surfaceStates":"Increased Pd 3d binding energies relative to Pd/N–C indicating electronic interactions between Pd and Ni","structureLink":"Highest activity attributed to optimum Ni content, synergistic interaction between Pd and Ni atoms creating new active sites, and compressive strain weakening H* adsorption facilitating desorption"},{"paperId":"P104","catalystId":"P104_PERF_004","name":"Pd1Ni3.6/N–C","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ni3.6/N–C","phase":"PdNi isomorphous alloy with face-centered cubic (fcc) structure","particleSize":"2.5 nm","surfaceStates":"Increased Pd 3d binding energies relative to Pd/N–C indicating electronic interactions between Pd and Ni","structureLink":"Ni alloying perturbs the Pd electronic structure, facilitating H2 release from aqueous FA solution"},{"paperId":"P104","catalystId":"P104_PERF_005","name":"Ni/N–C","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ni/N–C","phase":"Ni nanoparticles","structureLink":"Negligible FA dehydrogenation activity compared to Pd-based catalysts"},{"paperId":"P104","catalystId":"P104_PERF_006","name":"Pd1Ni1.3/C","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ni1.3/C","phase":"PdNi alloy","particleSize":"7.9 nm","structureLink":"Larger particle size and lower dispersion on commercial carbon support result in lower activity than N-doped carbon support"},{"paperId":"P106","catalystId":"P106_PERF_001","name":"10 wt% Pd/AC (commercial Noblyst® P1070)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"10 wt% Pd/AC","phase":"Metallic Pd and PdO","particleSize":"Fresh: 1.6 ± 0.2 nm; Used (55 °C): 3.7 nm; Used (85 °C): 4.8 nm","surfaceStates":"Pd0 and Pd2+ species; Fresh Pd2+/Pd0 ratio is ~2.4, which decreases to 0.88 (at 55 °C) and 0.79 (at 85 °C) after the 3rd use.","structureLink":"Irreversible deactivation at T > 55 °C is primarily caused by CO2 chemisorption on Pd active sites; loss of Pd2+ species and Pd-PdO interfaces also contributes to quicker deactivation, while sintering of Pd nanoparticles does not significantly affect activity.","deactivation":"No Pd leaching detected. Deactivation caused by fouling of active sites and chemisorption of CO2 on Pd nanoparticles at T > 55-65 °C; sintering of Pd particles (1.6 to 4.8 nm) occurs but does not significantly affect activity."},{"paperId":"P107","catalystId":"P107_PERF_001","name":"Pd/Cdarco","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Cdarco","phase":"Cubic palladium metal phase","particleSize":"4.6 nm (XRD), 5 nm (TEM)","structureLink":"Intermediate external surface area and intermediate catalytic activity."},{"paperId":"P107","catalystId":"P107_PERF_002","name":"Pd/Ccel","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Ccel","phase":"Cubic palladium metal phase","particleSize":"18.4 nm (XRD), 20 nm (TEM)","structureLink":"High microporosity leads to higher particle size and poor catalytic performance due to palladium being inaccessible within pores."},{"paperId":"P107","catalystId":"P107_PERF_003","name":"Pd/CcelZnCl2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CcelZnCl2","phase":"Cubic palladium metal phase","particleSize":"2.3 nm (XRD), 2.7 nm (TEM)","structureLink":"ZnCl2 treatment enhances meso-macroporosity and surface area, facilitating high metal dispersion and improving catalytic activity.","deactivation":"Specific speed drops sharply after six hours of reaction; partial and continuous deactivation observed over repeated cycles"},{"paperId":"P107","catalystId":"P107_PERF_004","name":"Pd/Cvin","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Cvin","phase":"Cubic palladium metal phase","particleSize":"30.4 nm (XRD), 24 nm (TEM)","structureLink":"High microporosity leads to higher particle size and poor catalytic performance."},{"paperId":"P107","catalystId":"P107_PERF_005","name":"Pd/CvinZnCl2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CvinZnCl2","phase":"Cubic palladium metal phase","particleSize":"2.3 nm (XRD), 2.4 nm (TEM)","structureLink":"ZnCl2 treatment increases pore volume and surface area, leading to the highest dispersion and high catalytic activity."},{"paperId":"P108","catalystId":"P108_PERF_001","name":"Pd/MWCNTs-AP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MWCNTs-AP","phase":"Face-centered cubic (fcc) Pd; HRTEM shows lattice spacing of 0.220 nm corresponding to the Pd(111) crystal plane.","particleSize":"2.9 ± 0.8 nm (TEM); 2.9 nm (CO pulse chemisorption)","surfaceStates":"Metallic Pd0 with higher binding energy than Pd/MWCNTs-AH, suggesting electron transfer from Pd to MWCNTs; nitrogen mainly exists as pyridinic N (53.1%) and pyrrolic N (27.3%).","structureLink":"Ultrasmall particle size, high surface Pd concentration (high Pd/C ratio), abundant -OH groups, and highly active pyridinic N facilitate formic acid adsorption and the breakage of C-H and O-H bonds.","deactivation":"Slight agglomeration of Pd nanoparticles observed by XRD after 6 cycles; no loss of active components (Pd mass fraction remained within error range: 4.6 to 4.8 wt%)"},{"paperId":"P108","catalystId":"P108_PERF_003","name":"Pd/MWCNTs-P","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MWCNTs-P","phase":"Face-centered cubic (fcc) Pd; XRD peaks at 40.1, 46.7, 68.1, and 82.1 degrees corresponding to (111), (200), (220), and (311) planes.","particleSize":"8.6 ± 1.3 nm (TEM); 8.6 nm (CO pulse chemisorption)","surfaceStates":"Metallic Pd0, Pd2+, and Pd4+; negligible nitrogen content compared to amino-modified samples.","structureLink":"Large particle size and poor dispersion lead to lower catalytic activity compared to Pd/MWCNTs-AP."},{"paperId":"P108","catalystId":"P108_PERF_004","name":"Pd/MWCNTs-AH","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MWCNTs-AH","phase":"Face-centered cubic (fcc) Pd; HRTEM shows lattice spacing of 0.220 nm corresponding to the Pd(111) crystal plane.","particleSize":"3.0 ± 0.5 nm (TEM); 3.0 nm (CO pulse chemisorption)","surfaceStates":"Metallic Pd0, Pd2+, and Pd4+; lower N/C ratio (0.028) compared to Pd/MWCNTs-AP.","structureLink":"Despite small particle size, the high-temperature reduction process caused significant damage to support functional groups (-OH, -NH2), resulting in poor catalytic activity."},{"paperId":"P109","catalystId":"P109_PERF_001","name":"Pd/BC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BC","phase":"Pd nanoparticles","particleSize":"3.6 ± 1.8 nm (spent)","surfaceStates":"Fresh: Pd2+; Spent: Pd0 and Pd2+","deactivation":"No significant leaching of Pd after six reaction runs; no significant sintering"},{"paperId":"P109","catalystId":"P109_PERF_002","name":"Pd/BC_TT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BC_TT","phase":"Pd nanoparticles","particleSize":"3.7 ± 1.3 nm (spent)","surfaceStates":"Fresh: Pd2+; Spent: Pd0 and Pd2+","structureLink":"Small Pd clusters in the fresh catalyst are highly active in FA decomposition; thermal treatment reduced surface acidity, favoring interaction with FA molecules.","deactivation":"No significant leaching of Pd after six reaction runs; no significant sintering"},{"paperId":"P109","catalystId":"P109_PERF_003","name":"Pd/N-BC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-BC","phase":"Pd nanoparticles","particleSize":"3.5 ± 2.2 nm (spent)","surfaceStates":"Fresh: Pd2+; Spent: Pd0 and Pd2+. XPS shows a shift towards higher binding energies attributed to Pd-N interaction.","structureLink":"Nitrogen functionalization helps in attaining promising catalysts with outstanding stability during reaction cycles.","deactivation":"No significant leaching of Pd after six reaction runs; no significant sintering"},{"paperId":"P109","catalystId":"P109_PERF_004","name":"Pd/N-BC_TT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-BC_TT","phase":"Pd nanoparticles","particleSize":"2.6 ± 0.9 nm (spent)","surfaceStates":"Fresh: Pd2+; Spent: Pd0 and Pd2+. XPS shows a shift towards higher binding energies attributed to Pd-N interaction.","structureLink":"Lowest average particle size and narrowest distribution among samples, contributing to preserved activity over multiple cycles.","deactivation":"No significant leaching of Pd after six reaction runs; no significant sintering"},{"paperId":"P110","catalystId":"P110_PERF_001","name":"Pd/CN-B1.5M","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-B1.5M","phase":"Face-centered cubic (fcc) palladium","particleSize":"1.8 nm","surfaceStates":"High Pd2+/Pd0 ratio (0.590); strong metal-support interaction via Pd-N coordination with high pyrrolic N content (0.406).","structureLink":"Synergistic effect of Pd and pyrrolic N interactions induces electron transfer from Pd to N, creating electron-deficient Pd sites that strengthen interactions with formic acid and accelerate activation; small particle size and high dispersion further enhance activity.","deactivation":"increase in Pd nanoparticle size observed after three cycles; reduction in both Pd2+ species and pyrrolic nitrogen content"},{"paperId":"P110","catalystId":"P110_PERF_002","name":"Pd/CN-M","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-M","phase":"fcc palladium","particleSize":"Larger than Pd/CN-B1.5M (indicated by sharper XRD peaks)","surfaceStates":"Lower Pd2+/Pd0 ratio (0.298) compared to B1.5M."},{"paperId":"P110","catalystId":"P110_PERF_003","name":"Pd/CN-B1M","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-B1M","phase":"fcc palladium","surfaceStates":"Pd2+/Pd0 ratio of 0.475."},{"paperId":"P110","catalystId":"P110_PERF_004","name":"Pd/CN-B2M","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-B2M","phase":"fcc palladium","particleSize":"Increased particle size due to aggregation (indicated by sharpening/intensification of Pd(111) XRD peak)","surfaceStates":"Pd2+/Pd0 ratio of 0.433.","structureLink":"Excessive barbituric acid promotes Pd particle growth and disrupts uniform active-site distribution, diminishing catalytic activity."},{"paperId":"P110","catalystId":"P110_PERF_005","name":"Pd/CN-B","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-B","phase":"fcc palladium","surfaceStates":"Pd2+/Pd0 ratio of 0.300.","structureLink":"Poor maintenance of carbon nitride structure when pure barbiturate is used as precursor leads to lower activity."},{"paperId":"P111","catalystId":"P111_PERF_005","name":"quasi-spherical Pd-Ag alloy nanocatalyst","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"quasi-spherical Pd-Ag alloy nanocatalyst","phase":"Pd-Ag alloy","structureLink":"Significantly lower activity (TOF = 22 h^-1 at 92 °C) compared to nanofacet catalysts."},{"paperId":"P112","catalystId":"P112_PERF_001","name":"Pd/C650","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C650","phase":"Pure Pd phase (JCPDS: 65-2867)","particleSize":"13.50 nm","surfaceStates":"Pd0 and Pd2+; Pd2+/Pd0 ratio of 1.2","structureLink":"Larger particle size and lower Pd2+ content result in lower catalytic activity (TOF = 7257 h-1) compared to the Co-doped catalyst."},{"paperId":"P112","catalystId":"P112_PERF_002","name":"Pd0.9Co0.1/C650","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.9Co0.1/C650","phase":"Pd-Co alloy (lattice spacing 0.222 nm)","particleSize":"3.41 nm","surfaceStates":"Pd0, Pd2+, and Co0; Pd2+/Pd0 ratio of 5.43; Pd2+ binding energy shifted to 337.5 eV due to Co presence","structureLink":"Formation of Pd-Co alloy reduces particle size and increases the amount of Pd2+, which promotes O-H fracture and enhances formic acid decomposition (TOF = 8117 h-1).","deactivation":"particle size increased after 10 cycles; Pd2+ to Pd0 ratio decreased significantly"},{"paperId":"P113","catalystId":"P113_PERF_001","name":"PdCe0.2/SP-S-1","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","matchedCharacterization":"PdCe0.2/SP-S-1","phase":"Bimetallic nanoparticles with a heterojunction interface; no metal peaks in PXRD indicate high dispersion.","particleSize":"Average size of 2.0 nm; maintains 2.4–2.7 nm after thermal treatment at 700 °C in H2.","surfaceStates":"Electron-enriched state compared to Pd/SP-S-1 due to electron transfer from Ce to Pd atoms.","structureLink":"The interfacial effect between Pd and cerium oxide clusters reduces activation barriers for both FA dehydrogenation and CO2 hydrogenation, enhancing catalytic performance.","deactivation":"decrease of catalytic performance in FA dehydrogenation may be related to the oxidation of some Pd species in air during drying"},{"paperId":"P113","catalystId":"P113_PERF_002","name":"Pd/SP-S-1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/SP-S-1","phase":"Metallic Pd nanoparticles; no metal peaks in PXRD indicate high dispersion.","particleSize":"Average size of 2.0 nm; maintains 2.4–2.7 nm after thermal treatment at 700 °C in H2.","surfaceStates":"Positively charged Pdδ+ species.","structureLink":"Small particle size and high dispersion on the hydrophilic SP-S-1 surface provide more exposed active sites compared to Con-S-1 support."},{"paperId":"P113","catalystId":"P113_PERF_003","name":"Pd/Con-S-1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Con-S-1","phase":"Large-sized metal species; PXRD shows a weak diffraction peak assigned to Pd foil.","particleSize":"Mean size of 12.5 nm; increases significantly to 26.0 nm after thermal treatment at 700 °C in H2.","structureLink":"Larger particle size and lower dispersion lead to inferior catalytic activity compared to SP-S-1 supported catalysts.","deactivation":"activity for nitrobenzene hydrogenation decreased by approximately 38% after treatment at 700 °C"},{"paperId":"P113","catalystId":"P113_PERF_004","name":"Pd@SP-S-1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/SP-S-1","phase":"Metallic Pd nanoparticles; no metal peaks in PXRD indicate high dispersion.","particleSize":"Average size of 2.0 nm; maintains 2.4–2.7 nm after thermal treatment at 700 °C in H2.","surfaceStates":"Positively charged Pdδ+ species.","structureLink":"Small particle size and high dispersion on the hydrophilic SP-S-1 surface provide more exposed active sites compared to Con-S-1 support."},{"paperId":"P114","catalystId":"P114_PERF_001","name":"PdP/NC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdP/NC","phase":"fcc PdP alloy; XRD shows a shift toward higher angle in the (111) plane compared to Pd/NC, indicating decreased interplanar spacing due to amorphous P alloying.","particleSize":"1.59 ± 0.24 nm","surfaceStates":"Pd 3d5/2 binding energy at 336.3 eV; P exists as elemental P0 (131.4 eV) and oxidized P5+ (134.0 eV); NC support contains quaternary N (14.82%), amine/amide groups (71.44%), and pyridine N (13.74%).","structureLink":"Synergistic effect of alloyed P and doped N modifies Pd electronic states to optimize FA adsorption energy, weaken CO poisoning, and strengthen HCOO* intermediate adsorption; optimal particle size (1.59 nm) and P content follow the Sabatier principle for maximum TOF.","deactivation":"Phosphorus content decreased from 14 to 1 at. % over four cycles; particle diameter increased during recycling."},{"paperId":"P114","catalystId":"P114_PERF_002","name":"Pd/NC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NC","phase":"fcc Pd","surfaceStates":"Pd 3d5/2 binding energy at 336.5 eV.","structureLink":"Lower activity than PdP/NC due to lack of P-alloying electronic modification.","deactivation":"Gradually increased particle diameters"},{"paperId":"P114","catalystId":"P114_PERF_004","name":"commercial Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"commercial Pd/C","surfaceStates":"Pd 3d5/2 binding energy at 335.6 eV.","structureLink":"Lowest activity and highest reduction temperature; susceptible to CO poisoning.","deactivation":"Gradually increased particle diameters; low-coverage COads accumulation on Pd surface especially at higher temperatures"},{"paperId":"P115","catalystId":"P115_PERF_001","name":"Pd/NH2-P-GC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-P-GC","phase":"Metallic Pd nanoparticles; HRTEM/IFFT shows lattice fringes of 0.229 nm corresponding to Pd {111} planes.","particleSize":"1.47 nm (increased to 1.86 nm after use)","surfaceStates":"Electron-deficient Pd species, indicated by a positive shift in XPS binding energies (336.6 and 338.9 eV) compared to Pd/NH2-GC.","structureLink":"High activity is attributed to the small particle size, high dispersion, SMSI from amine groups, and P doping which acts as an electronic promoter creating electron-deficient active centers; amine groups also act as Brønsted basic sites for proton scavenging.","deactivation":"minor activity attenuation due to small loss of surface amine functional groups and slight increase in Pd particle size from 1.47 nm to 1.86 nm"},{"paperId":"P115","catalystId":"P115_PERF_002","name":"Pd/NH2-GC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-GC","phase":"Metallic Pd nanoparticles.","particleSize":"2.54 nm","surfaceStates":"Less electron-deficient than Pd/NH2-P-GC (XPS binding energies at 336.2 and 338.0 eV).","structureLink":"Inferior catalytic activity compared to Pd/NH2-P-GC due to larger particle size and absence of P doping."},{"paperId":"P115","catalystId":"P115_PERF_003","name":"Pd/GC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/GC","phase":"Metallic Pd nanoparticles.","structureLink":"Nearly inactive for FA dehydrogenation due to the absence of both amine groups and P doping."},{"paperId":"P115","catalystId":"P115_PERF_004","name":"Pd/P-GC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/P-GC","phase":"Metallic Pd nanoparticles.","surfaceStates":"XPS shows binding energies for zero-valent Pd 3d shifted towards higher values compared to Pd/NH2-GC.","structureLink":"Nearly inactive for FA dehydrogenation due to the absence of amine groups acting as proton scavengers."},{"paperId":"P116","catalystId":"P116_PERF_001","name":"0.2 wt % Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-CNTs","phase":"Single-atom isolated ions at low loading; nanoparticles at high loading.","particleSize":"Not visible for <1 wt%; 1.2–1.4 nm for 1–2 wt%.","surfaceStates":"Isolated Pd2+ ions coordinated by pyridinic nitrogen sites.","structureLink":"Single-atom ionic Pd sites provide maximum TOF and higher selectivity to hydrogen in formic acid decomposition compared to nanoparticles."},{"paperId":"P116","catalystId":"P116_PERF_002","name":"2 wt % Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-CNTs","phase":"Single-atom isolated ions at low loading; nanoparticles at high loading.","particleSize":"Not visible for <1 wt%; 1.2–1.4 nm for 1–2 wt%.","surfaceStates":"Isolated Pd2+ ions coordinated by pyridinic nitrogen sites.","structureLink":"Single-atom ionic Pd sites provide maximum TOF and higher selectivity to hydrogen in formic acid decomposition compared to nanoparticles."},{"paperId":"P116","catalystId":"P116_PERF_003","name":"2 wt % Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNTs","phase":"Metallic palladium nanoparticles","particleSize":"1.2–2.3 nm","surfaceStates":"Surface oxidized PdO","structureLink":"Less active in formic acid decomposition compared to N-doped counterparts."},{"paperId":"P116","catalystId":"P116_PERF_004","name":"0.2 wt % Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNTs","phase":"Metallic palladium nanoparticles","particleSize":"1.2–2.3 nm","surfaceStates":"Surface oxidized PdO","structureLink":"Less active in formic acid decomposition compared to N-doped counterparts."},{"paperId":"P117","catalystId":"P117_PERF_001","name":"Pd/CN-U1W5","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-U1W5","phase":"fcc Pd(111)","particleSize":"2.4 nm","surfaceStates":"Electron-deficient palladium with a higher percentage of cationic Pd (Pd2+ = 46.2%, Pd0 = 53.8%) compared to Pd/CN-U; electronic properties regulated by pyridinic N via Pd-N covalent bonds causing electron transfer from Pd to N.","structureLink":"High catalytic activity is attributed to the high amount of pyridinic N, small particle size (2.4 nm), and high dispersion, which increases the surface Pd2+/Pd0 ratio.","deactivation":"decrease in catalytic activity attributed to decrease in Pd2+ and pyridinic N content in recovered catalyst"},{"paperId":"P117","catalystId":"P117_PERF_002","name":"Pd/CN-U","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-U","phase":"fcc Pd(111)","particleSize":"3.0 nm","surfaceStates":"Pd0 (64.8%) and Pd2+ (35.2%)"},{"paperId":"P117","catalystId":"P117_PERF_003","name":"Pd/CN-U1W3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-U","phase":"fcc Pd(111)","particleSize":"3.0 nm","surfaceStates":"Pd0 (64.8%) and Pd2+ (35.2%)"},{"paperId":"P117","catalystId":"P117_PERF_004","name":"Pd/CN-U1W1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-U","phase":"fcc Pd(111)","particleSize":"3.0 nm","surfaceStates":"Pd0 (64.8%) and Pd2+ (35.2%)"},{"paperId":"P117","catalystId":"P117_PERF_005","name":"Pd/CN-U1W7","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CN-U","phase":"fcc Pd(111)","particleSize":"3.0 nm","surfaceStates":"Pd0 (64.8%) and Pd2+ (35.2%)"},{"paperId":"P118","catalystId":"P118_PERF_001","name":"Pd@S-1-H","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@S-1-H","phase":"Single and pseudo-single atoms; atomically dispersed.","particleSize":"Subnanometer","surfaceStates":"Pd valence state of +1.83; higher oxidation state than Pd foil and Pd@S-1-C.","structureLink":"Decreased size and increased dispersion expose more accessible active sites (especially corner sites), resulting in superior methane combustion activity (complete combustion temperature of 390 °C)."},{"paperId":"P118","catalystId":"P118_PERF_002","name":"Pd@S-1-C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@S-1-C","phase":"Subnanometer Pd clusters; Pd-Pd metallic bonds observed.","particleSize":"Subnanometer (larger than Pd@S-1-H)","surfaceStates":"Pd valence state of +1.67.","structureLink":"Larger metal size compared to Pd@S-1-H leads to lower methane combustion activity (complete combustion temperature of 416 °C)."},{"paperId":"P118","catalystId":"P118_PERF_003","name":"Pd/S-1-im","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/S-1-im","phase":"Pd nanoparticles (NPs)","particleSize":"4–5 nm","structureLink":"Large particle size and aggregation lead to poor methane combustion activity (complete combustion temperature of 513 °C)."},{"paperId":"P118","catalystId":"P118_PERF_004","name":"0.8Pd0.2Ni(OH)2@S-1-H","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"0.8Pd0.2Ni(OH)2@S-1-H","phase":"Partial formation of Pd–Ni alloy structure (Pd–Ni metallic bond CN = 0.13); Pd is dimer- or single-atomic dispersion (Pd–Pd CN = 0.9).","particleSize":"Subnanometer / pseudo-single atoms; remains small (1.6 nm) after calcination at 700 °C under N2.","surfaceStates":"Pd valence state of +1.17; electron-enriched Pd surfaces due to electron transfer from Ni to Pd.","structureLink":"Synergistic effect of the bimetallic Pd–Ni(OH)2 interface and electron-rich Pd surface lowers the energy barrier for FA dehydrogenation, affording a TOF up to 9308 h⁻¹."},{"paperId":"P119","catalystId":"P119_PERF_001","name":"Pd/BNC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BNC","phase":"Highly dispersed Pd nanoparticles; no XRD signals for Pd nanocrystals observed","particleSize":"1.3 nm","surfaceStates":"Strong interaction between Pd and pyridinic-N as well as BC2O species","structureLink":"B and N co-doping provides more anchor sites (BC2O, pyridinic-N), resulting in smaller Pd particle size and optimized electronic properties (Pd2+/Pd0 ratio), which lowers the activation barrier to 31.84 kJ/mol and increases TOF."},{"paperId":"P119","catalystId":"P119_PERF_002","name":"Pd/NC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NC","phase":"Highly dispersed Pd nanoparticles; no XRD signals for Pd nanocrystals observed","particleSize":"2.3 nm","surfaceStates":"Pd0 and Pd2+ states present with weaker support interaction compared to Pd/BNC","structureLink":"Larger particle size and less optimized electronic properties lead to lower activity (TOF = 747 h-1) and higher activation energy (50.88 kJ/mol)."},{"paperId":"P119","catalystId":"P119_PERF_003","name":"BNC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BNC","phase":"Highly dispersed Pd nanoparticles; no XRD signals for Pd nanocrystals observed","particleSize":"1.3 nm","surfaceStates":"Strong interaction between Pd and pyridinic-N as well as BC2O species","structureLink":"B and N co-doping provides more anchor sites (BC2O, pyridinic-N), resulting in smaller Pd particle size and optimized electronic properties (Pd2+/Pd0 ratio), which lowers the activation barrier to 31.84 kJ/mol and increases TOF."},{"paperId":"P119","catalystId":"P119_PERF_004","name":"Pd/BNC-700","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BNC-700","particleSize":"1.0 nm","surfaceStates":"Excessively strong interaction between carrier and Pd NPs","structureLink":"Too high a Pd2+/Pd0 ratio hinders the reaction compared to Pd/BNC."},{"paperId":"P119","catalystId":"P119_PERF_005","name":"Pd/BNC-900","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BNC-900","particleSize":"1.8 nm","structureLink":"Larger Pd size compared to Pd/BNC provides fewer active sites, reducing performance."},{"paperId":"P120","catalystId":"P120_PERF_001","name":"Pd1Ag1-NH2/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag1-NH2/C","phase":"PdAg alloy (confirmed by XRD peaks located between pristine Ag and Pd, and HRTEM lattice spacing of 0.229 nm)","particleSize":"4.03 ± 0.08 nm (fresh); 5.2 ± 0.35 nm (after cycling)","surfaceStates":"L-histidine coordinated at the metal surface; electron density transferred from metal nanoparticles to L-histidine/complexes (indicated by positive shifts in Pd0 and Ag0 XPS signals); presence of -NH2 groups (N1s peak at 400.5 eV).","structureLink":"L-histidine acts as a 'transfer station' for protons, promoting formic acid deprotonation via acid-base interactions and reducing energy barriers for the rate-determining steps (bi-HCOO to mo-HCOO isomerization and H-H coupling) through optimized electronic structure.","deactivation":"Slight coarsening of nanoparticles (average size increased to 5.2 ± 0.35 nm) responsible for decreased TOF during stability test"},{"paperId":"P120","catalystId":"P120_PERF_002","name":"Pd1Ag1/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag1/C","phase":"PdAg alloy (confirmed by XRD)","particleSize":"7.8 ± 0.3 nm","surfaceStates":"Binding energy of Pd0 is negatively shifted by 0.25 eV compared to Pd/C due to electron transfer from Ag to Pd.","deactivation":"Catalyst poisoning by CO generated as a side product"},{"paperId":"P120","catalystId":"P120_PERF_003","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Pure Pd nanoparticles","particleSize":"4.8 ± 0.06 nm","deactivation":"Irreversible poisoning by CO generated as a side product (via dehydration)"},{"paperId":"P120","catalystId":"P120_PERF_007","name":"Pd1Ag1/C-NH2","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1Ag1/C-NH2","phase":"PdAg alloy (confirmed by EDS mapping)","particleSize":"4.33 ± 0.05 nm","structureLink":"Lower activity compared to Pd1Ag1-NH2/C due to the larger distance between resulting H species (protonated -NH2 at carbon vs. metal surface), retarding H-H coupling."},{"paperId":"P121","catalystId":"P121_PERF_001","name":"Pd/D201","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/D201","phase":"Monometallic Pd nanoparticles","particleSize":"2.3 nm","surfaceStates":"Pd 0, Pd 2+","structureLink":"The optimized particle size (~2.3 nm) and higher content of metallic Pd 0 are beneficial for superior catalytic performance in FA dehydrogenation."},{"paperId":"P121","catalystId":"P121_PERF_002","name":"Pd/D301","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/D301","phase":"Monometallic Pd nanoparticles","particleSize":"5.6 nm","surfaceStates":"Pd 0, Pd 2+","structureLink":"Larger particle size (~5.6 nm) and lower metallic Pd 0 content compared to Pd/D201 correlate with poorer catalytic activity."},{"paperId":"P121","catalystId":"P121_PERF_003","name":"Pd/D311","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/D311","phase":"Monometallic Pd nanoparticles","particleSize":"4.4 nm","surfaceStates":"Pd 0, Pd 2+","structureLink":"Larger particle size (~4.4 nm) and lowest metallic Pd 0 content correlate with poor catalytic performance."},{"paperId":"P122","catalystId":"P122_PERF_001","name":"AuNPs-PPO","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"AuNPs-PPO","phase":"face-centered cubic (fcc) gold","particleSize":"4-6 nm","surfaceStates":"Cubic morphology with exposed <220> planes of fcc gold.","structureLink":"The cubic geometry and <220> crystalline facets are attributed to high catalytic activity due to the low coordination number of the metal atoms."},{"paperId":"P123","catalystId":"P123_PERF_001","name":"3Ni@KIT-6","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"3Ni@KIT-6","phase":"Metallic Ni","particleSize":"9.9 nm (crystallite size)","surfaceStates":"Lewis acid sites present; lower Lewis acidity compared to Co-based catalysts.","structureLink":"Highest H2 selectivity linked to relatively higher surface area (851 m2/g), pore volume (1.35 cm3/g), and smaller crystallite size compared to 5Ni@KIT-6."},{"paperId":"P123","catalystId":"P123_PERF_002","name":"5Ni@KIT-6","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"5Ni@KIT-6","phase":"Metallic Ni","particleSize":"10.6 nm (crystallite size)","surfaceStates":"Lewis acid sites present; slight increase in Lewis acidity compared to 3Ni@KIT-6.","structureLink":"Lower H2 selectivity than 3Ni@KIT-6 attributed to larger crystallite size and lower surface area/pore volume.","deactivation":"Coke accumulation weight loss of about 7.1% (TG analysis)"},{"paperId":"P123","catalystId":"P123_PERF_003","name":"3Co@KIT-6","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"3Co@KIT-6","phase":"Metallic Co","particleSize":"4.5 nm (crystallite size)","surfaceStates":"Lewis acid sites present; higher Lewis acidity than Ni-based catalysts.","structureLink":"Higher H2 selectivity compared to 5Co@KIT-6 linked to lower metal loading and associated surface properties."},{"paperId":"P123","catalystId":"P123_PERF_004","name":"5Co@KIT-6","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"5Co@KIT-6","phase":"Metallic Co","particleSize":"6.5 nm (crystallite size)","surfaceStates":"Lewis acid sites present; slight increase in Lewis acidity compared to 3Co@KIT-6.","structureLink":"Lower catalytic activity associated with increased coke formation (9.6% weight loss in TG analysis).","deactivation":"Coke accumulation weight loss of 9.6% (TG analysis)"},{"paperId":"P123","catalystId":"P123_PERF_005","name":"4Ni1Co@KIT-6","activeMetals":"Ni-Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"4Ni1Co@KIT-6","phase":"Bimetallic (Ni-Co)","particleSize":"10.1 nm (crystallite size)","surfaceStates":"Lewis acid sites present.","structureLink":"Decreased H2 selectivity and increased CO production compared to monometallic Ni, attributed to the active role of Co in coke formation."},{"paperId":"P124","catalystId":"P124_PERF_001","name":"Au/C","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/C","phase":"Metallic nanoparticles and single atoms","particleSize":"10 ± 6 nm","surfaceStates":"Metallic state (Au 4f7/2 ~ 84.1 eV); narrower XPS lines attributed to larger particle size","structureLink":"Lower activity compared to Au/N-C due to significantly lower dispersion and larger particle size"},{"paperId":"P124","catalystId":"P124_PERF_002","name":"Au/N-C","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/N-C","phase":"Metallic nanoparticles and single atoms","particleSize":"2.2 ± 0.9 nm","surfaceStates":"Metallic state (Au 4f7/2 ~ 83.9 eV); support contains pyridinic N (30 at%), pyrrolic N (49 at%), graphitic N (15 at%), and pyridine-N-oxide (6 at%)","structureLink":"High activity attributed to high Au dispersion and the presence of pyridinic nitrogen which activates formic acid via protonation to form pyridinium formate species that interact with Au"},{"paperId":"P124","catalystId":"P124_PERF_003","name":"Au/Al2O3","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/Al2O3","phase":"Metallic nanoparticles","particleSize":"2.2 ± 1.0 nm","surfaceStates":"Metallic state (Au 4f7/2 ~ 83.9 eV)"},{"paperId":"P124","catalystId":"P124_PERF_004","name":"Au/SiO2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/SiO2","phase":"Metallic nanoparticles","particleSize":"1.6 ± 0.8 nm","surfaceStates":"Metallic state (Au 4f7/2 ~ 84.1 eV)"},{"paperId":"P125","catalystId":"P125_PERF_001","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd","particleSize":"2.5 nm","surfaceStates":"XPS shows 25.1% Pd0 and 74.9% Pd2+"},{"paperId":"P125","catalystId":"P125_PERF_002","name":"Pd/Ceria0.4/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd","particleSize":"2.5 nm","surfaceStates":"XPS shows 25.1% Pd0 and 74.9% Pd2+","deactivation":"Ceria was dissolved by the acidic formic acid solution (Ce content decreased from 3.5 wt % to 0.1 wt % after reaction)"},{"paperId":"P125","catalystId":"P125_PERF_003","name":"Physical mixture of Pd/C and Ceria0.4/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd","particleSize":"2.5 nm","surfaceStates":"XPS shows 25.1% Pd0 and 74.9% Pd2+"},{"paperId":"P125","catalystId":"P125_PERF_004","name":"Pd/C with added Ce precursors","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd","particleSize":"2.5 nm","surfaceStates":"XPS shows 25.1% Pd0 and 74.9% Pd2+"},{"paperId":"P126","catalystId":"P126_PERF_001","name":"Pd/200-8-1.5","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MIL-88 (Pd/200-8-1.5)","phase":"Highly dispersed Pd on MIL-88 support","surfaceStates":"Pd 3d5/2 peaks at 335.3 eV (Pd(0)) and 336.6 eV (Pd(II))","structureLink":"The rod-like MIL-88 crystal structure provides better hydrogen production performance than the octahedral MIL-101; Pd(II) species strengthen the dispersion of active sites and enhance formate ion adsorption."},{"paperId":"P126","catalystId":"P126_PERF_002","name":"Pd1Ni2/200-8-1.5","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-Ni/MIL-88 (Pd1Ni2/200-8-1.5)","phase":"Pd-Ni alloy confirmed by HRTEM lattice fringes (d = 0.223 nm and 0.205 nm, between Pd(111) and Ni(111))","particleSize":"Highly dispersed fine particles","surfaceStates":"Electron transfer from Ni to Pd; binding energies of Pd(0) and Pd(II) are lower than in Pd/MIL-88, while the Ni(0) peak is higher than nickel metal.","structureLink":"Pd-Ni alloying creates electron-rich Pd active sites that facilitate C-H bond activation in the Pd-formate intermediate, resulting in a TOF of 863.6 h-1 and lower activation energy (42.47 kJ/mol)."},{"paperId":"P127","catalystId":"P127_PERF_001","name":"Ag3Pd12/MOF-5-C-900","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Ag3Pd12/MOF-5-C-900","phase":"Co-existence of AgPd bimetallic alloy, Ag0, and Pd0; HRTEM lattice spacings (0.22, 0.23, 0.24 nm) and XRD patterns confirm the presence of fcc Pd(111), AgPd alloy(111), and Ag(111). UV-Vis DRS shows a red-shift of the Ag surface plasmon absorption peak from 406 nm to 414 nm, confirming alloy formation.","particleSize":"approximately 4 nm","surfaceStates":"Metallic Pd0 and Ag0","structureLink":"Enhanced catalytic performance is attributed to the special composition (Pd0, Ag0, and AgPd alloy), small particle size, and high dispersion on the MOF-5-C support."},{"paperId":"P127","catalystId":"P127_PERF_004","name":"Ag3/Pd12/MOF-5-C-900","activeMetals":"Ag","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ag3Pd12/MOF-5-C-900","phase":"Co-existence of AgPd bimetallic alloy, Ag0, and Pd0; HRTEM lattice spacings (0.22, 0.23, 0.24 nm) and XRD patterns confirm the presence of fcc Pd(111), AgPd alloy(111), and Ag(111). UV-Vis DRS shows a red-shift of the Ag surface plasmon absorption peak from 406 nm to 414 nm, confirming alloy formation.","particleSize":"approximately 4 nm","surfaceStates":"Metallic Pd0 and Ag0","structureLink":"Enhanced catalytic performance is attributed to the special composition (Pd0, Ag0, and AgPd alloy), small particle size, and high dispersion on the MOF-5-C support."},{"paperId":"P127","catalystId":"P127_PERF_006","name":"Ag3Pd12/MOF-5","activeMetals":"Ag-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Ag3Pd12/MOF-5-C-900","phase":"Co-existence of AgPd bimetallic alloy, Ag0, and Pd0; HRTEM lattice spacings (0.22, 0.23, 0.24 nm) and XRD patterns confirm the presence of fcc Pd(111), AgPd alloy(111), and Ag(111). UV-Vis DRS shows a red-shift of the Ag surface plasmon absorption peak from 406 nm to 414 nm, confirming alloy formation.","particleSize":"approximately 4 nm","surfaceStates":"Metallic Pd0 and Ag0","structureLink":"Enhanced catalytic performance is attributed to the special composition (Pd0, Ag0, and AgPd alloy), small particle size, and high dispersion on the MOF-5-C support.","deactivation":"Low activity ascribed to moisture sensitivity of MOF-5 material; crystal structure can decompose in moist atmosphere/FA-SF solution."},{"paperId":"P128","catalystId":"P128_PERF_001","name":"Pt/AC","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/AC","phase":"Platinum metal","particleSize":"dXRD: 2.66 nm; dTEM: 5.00 nm","surfaceStates":"Active Pt surface area of 14.6 m2/g-Pt; metal accessibility of 26.1%.","structureLink":"Lower activity compared to Pt@C catalysts due to larger particle size and nonuniform dispersion; hydrogen adsorption on the Pt surface may inhibit reaction.","deactivation":"Pt particle size increased slightly after reaction; hydrogen adsorption may inhibit the reaction particularly at the initial stage"},{"paperId":"P128","catalystId":"P128_PERF_002","name":"Pt@C 500 °C","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt@C500°C","phase":"Platinum metal","particleSize":"dXRD: 1.76 nm; dTEM: 2.91 nm","surfaceStates":"Active Pt surface area of 26.3 m2/g-Pt; metal accessibility of 27.3%.","structureLink":"High activity attributed to small particle size and uniform dispersion achieved via the ion-exchange resin method.","deactivation":"decrease in hydrogen production rate during initial 150 min ascribed to gaseous products stuck inside the pores of the carbon support"},{"paperId":"P128","catalystId":"P128_PERF_003","name":"Pt@C 700 °C","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt@C700°C","phase":"Platinum metal","particleSize":"dXRD: 1.69 nm; dTEM: 2.61 nm","surfaceStates":"Active Pt surface area of 20.6 m2/g-Pt; metal accessibility of 19.2%.","structureLink":"High activity due to small particle size and uniform dispersion; exhibits good durability over 24 h.","deactivation":"initial decrease in hydrogen production rate during first 150 min attributed to product retention in micropores; deactivation less pronounced at higher FA concentrations (e.g., 100 wt%)"},{"paperId":"P128","catalystId":"P128_PERF_004","name":"Pt@C 900 °C","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt@C900°C","phase":"Platinum metal","particleSize":"dXRD: 2.62 nm; dTEM: 3.24 nm","surfaceStates":"Active Pt surface area of 5.90 m2/g-Pt; metal accessibility of 6.83%.","structureLink":"Lowest activity among Pt@C catalysts due to increased particle size and decreased metal accessibility (platinum particles become more embedded in the carbon support at higher carbonization temperatures)."},{"paperId":"P129","catalystId":"P129_PERF_001","name":"NP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"NP","phase":"FCC Pd, [111]/[200] ratio = 21.9","particleSize":"3.4 ± 0.9 nm","surfaceStates":"Pd0 and Pd2+","structureLink":"Moderate catalytic performance; part of a volcano-type relationship with particle size."},{"paperId":"P129","catalystId":"P129_PERF_002","name":"AR","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"AR","phase":"FCC Pd, [111]/[200] ratio = 2.9","particleSize":"9.4 ± 1.4 nm","surfaceStates":"Pd0 and Pd2+","structureLink":"Poor activity attributed to larger particle size."},{"paperId":"P129","catalystId":"P129_PERF_003","name":"ADR","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"ADR","phase":"FCC Pd, [111]/[200] ratio = 12.9","particleSize":"4.4 ± 0.7 nm","surfaceStates":"Pd0, Pd2+, and PdO species","structureLink":"Activity improved over AR due to smaller particle size."},{"paperId":"P129","catalystId":"P129_PERF_004","name":"IR","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"IR","phase":"FCC Pd, [111]/[200] ratio = 4.4","surfaceStates":"Pd0 and Pd2+","structureLink":"Best performance (TOF = 87 h-1); attributed to higher [200] phase content."},{"paperId":"P129","catalystId":"P129_PERF_005","name":"IDR","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"IDR","phase":"FCC Pd, [111]/[200] ratio = 9.7","surfaceStates":"Pd0, Pd2+, and PdO species","structureLink":"Lower activity than IR; attributed to higher [111]/[200] ratio."},{"paperId":"P129","catalystId":"P129_PERF_006","name":"SR","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"SR","phase":"FCC Pd, [111]/[200] ratio = 13.4","surfaceStates":"Pd0 and Pd2+","structureLink":"Higher activity than SDR; attributed to higher [200] phase content."},{"paperId":"P129","catalystId":"P129_PERF_007","name":"SDR","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"SDR","phase":"FCC Pd, [111]/[200] ratio = 43.9","surfaceStates":"Pd0, Pd2+, and PdO species","structureLink":"Lower activity than SR; attributed to higher [111]/[200] ratio."},{"paperId":"P129","catalystId":"P129_PERF_011","name":"Pd/C (1 wt% HNO3 treated support)","activeMetals":"Pd","metalClass":"Pd-only","deactivation":"activity can be almost fully recovered by drying at an elevated temperature (383 K)"},{"paperId":"P130","catalystId":"P130_PERF_001","name":"Pd/NMC1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC1","phase":"Metallic Pd","particleSize":"4.2 nm (TEM), 4.8 nm (CO chemisorption)","surfaceStates":"Pd0: 52.4%, Pd2+: 47.6%; highest binding energy for both species compared to N-doped samples.","structureLink":"Largest particle size and lack of nitrogen dopant result in the lowest catalytic activity and highest activation energy."},{"paperId":"P130","catalystId":"P130_PERF_002","name":"Pd/NMC2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC2","phase":"Metallic Pd","particleSize":"3.8 nm (TEM), 4.1 nm (CO chemisorption)","surfaceStates":"Pd0: 45.2%, Pd2+: 54.8%; binding energy shifted lower by 0.11-0.18 eV relative to Pd/NMC1 due to electron transfer from N dopants.","structureLink":"Low TOF attributed to difficulty in C-H bond cleavage and high activation barrier despite some nitrogen doping."},{"paperId":"P130","catalystId":"P130_PERF_003","name":"Pd/NMC3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC3","phase":"Metallic Pd","particleSize":"3.3 nm (TEM), 3.3 nm (CO chemisorption)","surfaceStates":"Pd0: 40.9%, Pd2+: 59.1%; binding energy shifted lower relative to Pd/NMC1.","structureLink":"Optimum nitrogen doping and small particle size result in the lowest activation barrier for hydrogen desorption, enhancing activity."},{"paperId":"P130","catalystId":"P130_PERF_004","name":"Pd/NMC4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC4","phase":"Metallic Pd","particleSize":"3.6 nm (TEM), 3.7 nm (CO chemisorption)","surfaceStates":"Pd0: 43.9%, Pd2+: 56.1%; binding energy shifted lower relative to Pd/NMC1.","structureLink":"Lower activation energy than Pd/NMC2 attributed to higher nitrogen content despite similar particle size."},{"paperId":"P130","catalystId":"P130_PERF_005","name":"Pd/NMC5","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC5","phase":"Metallic Pd","particleSize":"2.9 nm (TEM), 2.9 nm (CO chemisorption)","surfaceStates":"Pd0: 28.7%, Pd2+: 71.3%; binding energy shifted lower relative to Pd/NMC1; highest proportion of Pd2+ correlated with smallest particle size.","structureLink":"Excessive nitrogen interaction raises the activation barrier for hydrogen desorption, offsetting the benefit of the smallest particle size."},{"paperId":"P131","catalystId":"P131_PERF_001","name":"30 sc% Pd-on-Au/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"30 sc% Pd-on-Au/C","phase":"Core-shell (Au core, Pd shell)","surfaceStates":"Small Pd ensembles","structureLink":"Low activity due to linear binding of formate on small Pd ensembles favoring dehydration and CO poisoning.","deactivation":"in situ CO poisoning of the Pd atoms"},{"paperId":"P131","catalystId":"P131_PERF_002","name":"60 sc% Pd-on-Au/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"60 sc% Pd-on-Au/C","phase":"Core-shell (Au core, Pd shell)","surfaceStates":"Partially oxidized","structureLink":"Low activity; small Pd ensembles favor dehydration pathway.","deactivation":"correlated to the dehydration pathway (due to CO formation)"},{"paperId":"P131","catalystId":"P131_PERF_003","name":"150 sc% Pd-on-Au/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"150 sc% Pd-on-Au/C","phase":"Core-shell (Au core, Pd shell)","surfaceStates":"Partially oxidized ex situ; reduced in situ","structureLink":"Moderate activity; increased ensemble size reduces CO formation.","deactivation":"correlated to the dehydration pathway (due to CO formation)"},{"paperId":"P131","catalystId":"P131_PERF_004","name":"300 sc% Pd-on-Au/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"300 sc% Pd-on-Au/C","phase":"Core-shell (Au core, Pd shell)","surfaceStates":"Partially oxidized ex situ; reduced in situ","structureLink":"Highest activity and selectivity for dehydrogenation due to large Pd ensembles favoring bridging binding of formate."},{"paperId":"P131","catalystId":"P131_PERF_005","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Monometallic Pd nanoparticles","particleSize":"2-3 nm (in situ); 3-4 nm (after H2 treatment at 200 °C)","surfaceStates":"Partially oxidized ex situ; reduced in situ","structureLink":"Slightly active; prone to CO formation and deactivation."},{"paperId":"P131","catalystId":"P131_PERF_006","name":"Au/C","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/C","phase":"Monometallic Au nanoparticles","particleSize":"~4.3 nm","surfaceStates":"Metallic","structureLink":"Inactive for formic acid decomposition."},{"paperId":"P132","catalystId":"P132_PERF_001","name":"Pd/NCZIF-8-25","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NCZIF-8","phase":"HRTEM identified an interplanar spacing of 0.224 nm, corresponding to the Pd(111) facet.","particleSize":"Average Pd NP size varied with CTAB dosage: 2.85 nm (0 mg), 1.84 nm (25 mg), and 2.32 nm (35 mg).","surfaceStates":"XPS showed electron-rich Pd NPs with binding energy shifting from 335.46 to 334.81 eV as CTAB increased. Surface contains pyridinic N (enriched by CTAB), pyrrolic N, graphitic N, and hydrophilic oxygen-containing groups (carboxyl and hydroxyl).","structureLink":"The combination of ultrafine Pd NPs (minimized in Pd/NCZIF-8-25), high hydrophilicity (contact angle reduced to 15.7° for Pd/NCZIF-8-25), and a hierarchical pore structure significantly enhanced the TOF (1925 h-1) by improving mass transfer and metal-support interaction."},{"paperId":"P132","catalystId":"P132_PERF_002","name":"Pd/NCZIF-8-35","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NCZIF-8","phase":"HRTEM identified an interplanar spacing of 0.224 nm, corresponding to the Pd(111) facet.","particleSize":"Average Pd NP size varied with CTAB dosage: 2.85 nm (0 mg), 1.84 nm (25 mg), and 2.32 nm (35 mg).","surfaceStates":"XPS showed electron-rich Pd NPs with binding energy shifting from 335.46 to 334.81 eV as CTAB increased. Surface contains pyridinic N (enriched by CTAB), pyrrolic N, graphitic N, and hydrophilic oxygen-containing groups (carboxyl and hydroxyl).","structureLink":"The combination of ultrafine Pd NPs (minimized in Pd/NCZIF-8-25), high hydrophilicity (contact angle reduced to 15.7° for Pd/NCZIF-8-25), and a hierarchical pore structure significantly enhanced the TOF (1925 h-1) by improving mass transfer and metal-support interaction."},{"paperId":"P133","catalystId":"P133_PERF_001","name":"Pd0.8Ag0.2/NH2-MIL-101(Cr)","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.8Ag0.2/NH2-MIL-101(Cr)","phase":"Alloy; HRTEM shows a lattice spacing of 2.3 Å, which differs from pure Pd (2.25 Å) and Ag (2.35 Å), indicating lattice contraction induced by alloying.","particleSize":"2.2 nm","surfaceStates":"Electron-rich PdAg catalytic sites formed via electron transfer from the amine groups of the support, evidenced by negatively shifted binding energies in XPS compared to Pd0.8Ag0.2/MIL-101.","structureLink":"Excellent kinetics are attributed to ultrafine size and high dispersion of PdAg NPs, synergistic electronic effects between Pd and Ag (modulating atomic coordination and local strain), and the presence of amine groups acting as Brønsted basic sites to facilitate O-H bond dissociation of formic acid.","deactivation":"no apparent aggregation was observed"},{"paperId":"P134","catalystId":"P134_PERF_001","name":"Pd@CN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@CN","phase":"Face centered cubic crystal phases of Pd NPs ((111), (200), and (220)); HR-TEM confirms (111) lattice spacing of 0.212 nm for Pd0","particleSize":"6–8 nm","surfaceStates":"Negatively charged Pd NPs induced by strong electronic coupling with pyridinic-N; XPS shows coexistence of Pd0 and Pd2+.","structureLink":"Superior activity is attributed to electronically modulated Pd NPs (via pyridinic-N), an accessible mesoporous structure, and an optimal particle size of 6–8 nm which improves reactant binding energy compared to smaller particles.","deactivation":"No obvious leaching of Pd species (recovered Pd content 2.36%, almost unchanged)."},{"paperId":"P134","catalystId":"P134_PERF_002","name":"Pd/PTAT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PTAT","particleSize":"3–4 nm","surfaceStates":"Pd0 state (XPS binding energy peaks at 340.1 and 334.7 eV)"},{"paperId":"P135","catalystId":"P135_PERF_001","name":"Pd/YSMSNs-NH2(10-3)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/YSMSNs-NH2(10-3)","phase":"Face-centered cubic (fcc) Pd (111) plane","particleSize":"1.5 nm (average); increased to 2.2 nm after recovery","surfaceStates":"Electron-rich surface on Pd NPs due to metal-support interaction (MSI) where YSMSNs-NH2 acts as an electron donor. XPS peaks for Pd0 shifted to lower binding energies: 335.7 eV (Pd0 3d5/2) and 340.9 eV (Pd0 3d3/2).","structureLink":"The combination of ultrafine Pd NPs, high dispersion, electron-rich surface via MSI, and radially oriented mesoporous channels for rapid mass transfer enhances FA dehydrogenation activity. Amine groups act as Brønsted basic sites promoting O-H bond cleavage.","deactivation":"Recovered catalyst showed increased particle size (1.5 nm to 2.2 nm) due to Pd NPs aggregation and partial reduction in grafted amine groups."},{"paperId":"P135","catalystId":"P135_PERF_002","name":"Pd/YSMSNs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/YSMSNs","particleSize":"2.9 nm","surfaceStates":"Pd0 peaks located at 336.0 eV (Pd0 3d5/2) and 341.2 eV (Pd0 3d3/2).","structureLink":"Larger particle size and lack of MSI from amine groups result in nearly negligible catalytic activity."},{"paperId":"P136","catalystId":"P136_PERF_001","name":"Pd@PNCNCs-900","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@PNCNCs-900","phase":"Metallic Pd phase; XRD peaks at 40.12°, 46.66°, and 68.12° correspond to (111), (200), and (220) planes of Pd (PDF no. 87-0641). HRTEM shows a lattice fringe of 0.222 nm corresponding to the Pd(111) crystal plane.","particleSize":"2.0 nm","surfaceStates":"XPS N 1s reveals pyridinic N, pyrrolic N, graphitic N, and oxidized N. Pyridinic N acts as an electron donor to the Pd NPs, creating electron-rich active sites. CO2-TPD confirms strong basic properties.","structureLink":"The high degree of graphitization and defects in PNCNCs-900 enhances electrical conductivity for FA adsorption and electron migration. Strong metal-support interaction (MSI) via electron transfer from pyridinic N to Pd creates electron-rich active sites. Bronsted basic N sites promote the cleavage of O-H bonds in formic acid molecules.","deactivation":"Slight decline in activity attributed to the increase of Pd NP size from 2.0 nm to 2.9 nm after consecutive tests."},{"paperId":"P136","catalystId":"P136_PERF_002","name":"Pd@PNCNCs-700","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@PNCNCs-700","particleSize":"2.4 nm"},{"paperId":"P136","catalystId":"P136_PERF_003","name":"Pd@PNCNCs-800","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@PNCNCs-800","particleSize":"2.2 nm"},{"paperId":"P136","catalystId":"P136_PERF_004","name":"Pd@PNCNCs-1000","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@PNCNCs-1000","particleSize":"2.3 nm"},{"paperId":"P137","catalystId":"P137_PERF_001","name":"Pd/OB-C1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/OB-C1","phase":"Metallic Pd (JCPDS 46-1043)","particleSize":"~ 1.7 nm","surfaceStates":"Pd0 and Pd2+; binding energy shift observed compared to Pd/C due to charge transfer caused by B doping.","structureLink":"Strong interaction between B species and Pd NPs leads to small particle size and uniform dispersion, improving catalytic activity for FA dehydrogenation."},{"paperId":"P137","catalystId":"P137_PERF_002","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd (JCPDS 46-1043)","particleSize":"~ 3.1 nm","surfaceStates":"Pd0 (340.1 and 334.7 eV) and Pd2+ (342.2 and 336.5 eV)"},{"paperId":"P137","catalystId":"P137_PERF_003","name":"Pd/OB-C-N1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/OB-C-N1","phase":"Metallic Pd","particleSize":"~ 1.4 nm","surfaceStates":"Pd0 and Pd2+; presence of O-B-C (BCO2, BC2O) and N-C (pyridinic, pyrrolic, graphitic-N) species on support.","structureLink":"Ultrafine Pd particle size combined with high levels of B-O and N functionalities enhances activity; B-O species strengthen support-metal interaction while N dopants provide basic sites facilitating FA deprotonation."},{"paperId":"P138","catalystId":"P138_PERF_001","name":"Au0.3Pd0.7/NH2–N-HMCS","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/NH2–N-HMCS","phase":"AuPd alloy (confirmed by XRD broad diffraction peak between Au and Pd peaks and HRTEM lattice spacing of 0.234 nm).","particleSize":"2.2 nm","surfaceStates":"Pd is in an electron depletion state caused by metal-support interactions (electron transfer to NH2–N-HMCS) and synergistic effects with Au.","structureLink":"The combination of hollow mesoporous structure, ultra-fine particle size, high dispersion, and the electron-depleted state of Pd accelerates C-H cleavage in adsorbed formate, leading to superior H2 evolution activity.","deactivation":"Particle size increased from 2.2 to 2.7 nm after the 4th run."},{"paperId":"P138","catalystId":"P138_PERF_003","name":"Au0.3Pd0.7/N-HMCS","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/N-HMCS","phase":"Alloy","particleSize":"Contains a mixture of various large-sized nanoparticles","structureLink":"Lower activity compared to NH2-functionalized support due to larger particle sizes and lack of amino groups to facilitate FA adsorption/O-H cleavage."},{"paperId":"P138","catalystId":"P138_PERF_004","name":"Au0.3Pd0.7/HMCS","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/HMCS","structureLink":"Poor catalytic performance attributed to low metal dispersion."},{"paperId":"P139","catalystId":"P139_PERF_001","name":"Pd/TBT/rGO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/TBT/rGO","phase":"Metallic Pd on tetragonal-phase barium titanate (TBT) and reduced graphene oxide (rGO)","particleSize":"4.6 nm","surfaceStates":"Electron-rich Pd (Pd 3d binding energy shifted to 335.3 eV) due to metal-support interaction (MSI) where BaTiO3 acts as a strong electron donor.","structureLink":"Small particle size improves mass activity; electron-rich Pd facilitates C-H bond cleavage in HCOO*; internal electric field from TBT promotes hydrogen desorption on Pd(111); rGO enhances interfacial charge transport capacity.","deactivation":"Mass loss (reduced from 50 to 25 mg after three tests), Pd nanoparticle agglomeration, and TBT completely separated from rGO."},{"paperId":"P139","catalystId":"P139_PERF_002","name":"Pd/rGO(3.6)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rGO","phase":"Metallic Pd on reduced graphene oxide (rGO)","particleSize":"35.8 nm","surfaceStates":"Electron-deficient compared to TBT-supported catalysts (Pd 3d binding energy of 335.8 eV).","structureLink":"Larger particle size and lack of internal electric field/electron-donating support lead to lower catalytic activity for FAD."},{"paperId":"P139","catalystId":"P139_PERF_003","name":"Pd/TBT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/TBT","phase":"Metallic Pd on tetragonal-phase barium titanate (TBT)","particleSize":"4.0 nm","surfaceStates":"Electron-rich Pd (Pd 3d binding energy shifted to 335.3 eV) due to MSI with BaTiO3.","structureLink":"Small particle size and electron-rich state facilitate activity, but lacks the charge transfer enhancement provided by rGO."},{"paperId":"P139","catalystId":"P139_PERF_004","name":"Pd/rGO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rGO","phase":"Metallic Pd on reduced graphene oxide (rGO)","particleSize":"35.8 nm","surfaceStates":"Electron-deficient compared to TBT-supported catalysts (Pd 3d binding energy of 335.8 eV).","structureLink":"Larger particle size and lack of internal electric field/electron-donating support lead to lower catalytic activity for FAD."},{"paperId":"P139","catalystId":"P139_PERF_005","name":"TBT/rGO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/TBT/rGO","phase":"Metallic Pd on tetragonal-phase barium titanate (TBT) and reduced graphene oxide (rGO)","particleSize":"4.6 nm","surfaceStates":"Electron-rich Pd (Pd 3d binding energy shifted to 335.3 eV) due to metal-support interaction (MSI) where BaTiO3 acts as a strong electron donor.","structureLink":"Small particle size improves mass activity; electron-rich Pd facilitates C-H bond cleavage in HCOO*; internal electric field from TBT promotes hydrogen desorption on Pd(111); rGO enhances interfacial charge transport capacity."},{"paperId":"P140","catalystId":"P140_PERF_001","name":"Pd/C–SiO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C–SiO2","phase":"Metallic Pd (111) plane","particleSize":"1.8 nm (TEM); 2.5 nm (XRD)","surfaceStates":"Electron-rich Pd catalytic sites formed by electron transfer from the C–SiO2 support to Pd (indicated by negative shift in Pd 3d binding energy).","structureLink":"Small particle size, high dispersion, and electron-rich surface enhance FA dehydrogenation activity; oxygen-rich species provided by SiO2 limit CO adsorption on the Pd surface; Pd–O–Si coordination stabilizes NPs against agglomeration.","deactivation":"No loss of Pd (ICP-OES showed 4.9% after 5 cycles); particle size increased slightly from 1.8 to 2.0 nm"},{"paperId":"P140","catalystId":"P140_PERF_002","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd (111) plane","particleSize":"3.7 nm (TEM); 5.0 nm (XRD)","structureLink":"Larger particle size and lower Pd0/Pd2+ ratio compared to Pd/C–SiO2 result in lower catalytic activity."},{"paperId":"P140","catalystId":"P140_PERF_003","name":"Pd/SiO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/SiO2","phase":"Metallic Pd (111) plane","particleSize":"3.1 nm (TEM); 3.8 nm (XRD)","structureLink":"Lower specific surface area and larger particle size compared to Pd/C–SiO2 lead to the lowest FA conversion rate."},{"paperId":"P141","catalystId":"P141_PERF_001","name":"Pd/TiO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/TiO2","phase":"Highly dispersed Pd species on anatase and rutile TiO2 support","particleSize":"Slight increase observed after reaction (not statistically significant)","surfaceStates":"Pristine catalyst contains 93.1% Pd0, which decreases slightly after reaction; CO-DRIFTS shows linear, bridge, and tri-coordination adsorption of CO on Pd","structureLink":"Rapid deactivation is attributed to the accumulation of formate species on the surface (HCOOH -> HCOO + H), which blocks active sites from interacting with reactants","deactivation":"Reversible deactivation caused by accumulation of formate on the catalyst surface, which hinders contact between active sites and reactants. No significant Pd leaching observed via ICP-MS."},{"paperId":"P141","catalystId":"P141_PERF_002","name":"Zn-Pd/TiO2","activeMetals":"Zn-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Zn-Pd/TiO2","phase":"Zn-Pd alloy structure; HAADF-STEM mapping shows Zn elements distributed on Pd nanoparticles","particleSize":"Approximately 2.8 nm (remains essentially constant across reaction cycles)","surfaceStates":"Pristine catalyst contains 57.9% Pd0, increasing to 63.3% after reaction; CO-DRIFTS confirms presence of multi-atomic Pd ensembles","structureLink":"The alloy structure facilitates an alternative HCOOH decomposition pathway (HCOOH -> COOH + H -> CO2 + 2H), preventing formate accumulation and maintaining high catalytic stability","deactivation":"No significant metal leaching. Minimal decline in activity attributed to unavoidable catalyst loss during recycling process."},{"paperId":"P142","catalystId":"P142_PERF_001","name":"Pd/4N-CX-meso","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/4N-CX-meso","phase":"Metallic Pd","particleSize":"2.3 nm","surfaceStates":"Electron deficient Pd (XPS shift to higher binding energy)","structureLink":"Optimal nitrogen content (4 wt%) and micro-mesoporous texture lead to high TOF (2014 h-1)."},{"paperId":"P142","catalystId":"P142_PERF_002","name":"Pd/CX-meso","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CX-meso","phase":"Metallic Pd","particleSize":"3.4 nm","surfaceStates":"Metallic state","structureLink":"Poor catalytic ability compared to N-doped counterparts.","deactivation":"reaction ceased after 5 min"},{"paperId":"P142","catalystId":"P142_PERF_003","name":"Pd/4N-CX-macro","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/4N-CX-macro","phase":"Metallic Pd","particleSize":"2.2 nm","surfaceStates":"Electron deficient Pd (XPS shift to higher binding energy)","structureLink":"Lower activity than the meso-porous counterpart due to micro-macroporous texture impacting accessibility.","deactivation":"reaction was dramatically sluggish after 5 min"},{"paperId":"P142","catalystId":"P142_PERF_004","name":"Pd/8N-CX-macro","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/8N-CX-macro","phase":"Metallic Pd","particleSize":"8.3 ± 5.2 nm","surfaceStates":"Less important Pd-N interaction compared to low/moderate N catalysts","structureLink":"High nitrogen content (8 wt%) and lower surface area lead to Pd aggregation and poor catalytic activity.","deactivation":"behavior very similar to that of the N-free sample"},{"paperId":"P142","catalystId":"P142_PERF_005","name":"Pd/2N-CX-meso","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/2N-CX-meso","phase":"Metallic Pd","particleSize":"2.7 nm","surfaceStates":"Electron deficient Pd (XPS shift to higher binding energy)","structureLink":"Small particle size and electron deficiency enhance catalytic activity."},{"paperId":"P143","catalystId":"P143_PERF_001","name":"Pd0.50Au0.50/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.50Au0.50/PDA-rGO","phase":"Bimetallic PdAu nanoparticles; XRD peaks at 38.14° and 44.50° are slightly shifted from Au reference peaks, and TEM-EDS confirms bimetallic composition with no monometallic particles.","particleSize":"Two populations: smaller nanoparticles (1.8 ± 0.5 nm) and larger nanoparticles (ca. 5-8 nm).","surfaceStates":"Amine groups on the PDA-rGO support act as proton scavengers; XPS shows Au and Pd(0) signals shifted to lower energy compared to monometallic counterparts, indicating electronic interaction/alloying.","structureLink":"High activity is attributed to nanosized particles, amine groups acting as proton scavengers for O-H cleavage, and the Au component prohibiting CO formation and enhancing durability in high concentration FA/formate solutions.","deactivation":"PDA in the support was transformed and removed during reaction under high pressure H2 conditions."},{"paperId":"P143","catalystId":"P143_PERF_002","name":"Pd/PDA-rGO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PDA-rGO","phase":"Monometallic Pd","particleSize":"2.3 ± 0.5 nm"},{"paperId":"P143","catalystId":"P143_PERF_004","name":"Pd0.57(Low)Au0.43(Low)/PDA-rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.57(Low)Au0.43(Low)/PDA-rGO","phase":"Bimetallic PdAu","particleSize":"1.7 ± 0.5 nm"},{"paperId":"P143","catalystId":"P143_PERF_005","name":"Pd0.49Au0.51/rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.49Au0.51/rGO","phase":"Bimetallic PdAu","particleSize":"2.7 ± 0.8 nm","structureLink":"Larger particle size compared to PDA-supported catalysts suggests PDA acts as a stabilizer during synthesis."},{"paperId":"P144","catalystId":"P144_PERF_001","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd","particleSize":"4.6 nm","surfaceStates":"Binding energy of Pd 3d5/2 is 336.13 eV; contains 0.402 mmol g-1 of Pd2+ species (49.2 mol%)"},{"paperId":"P144","catalystId":"P144_PERF_002","name":"Pd1NiO1.3/C (co)","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd1NiO1.3/C (co)","phase":"Metallic Pd phase; interacts directly with neighboring Ni atoms","particleSize":"3.6 nm","surfaceStates":"Binding energy of Pd 3d5/2 is 335.80 eV (more negative than Pd/C); contains 0.276 mmol g-1 of Pd2+ species (32.2 mol%)","structureLink":"More negative Pd cannot interact well with negatively charged intermediates, which counteracts the promoting effect of its smaller particle size compared to Pd/C."},{"paperId":"P144","catalystId":"P144_PERF_003","name":"Pd1/NiOx/C (seq)","activeMetals":"Pd","metalClass":"Pd-only","deactivation":"Loss of Ni metal (6.2 wt% to 0.5 wt%) and Pd particle agglomeration"},{"paperId":"P145","catalystId":"P145_PERF_001","name":"Cp*Ir-HMDAbpy@PAA","activeMetals":"Ir","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Cp*Ir-HMDAbpy@PAA","particleSize":"10 μm to several hundred μm","surfaceStates":"XPS analysis after reaction showed no peak shifts compared to the homogeneous Cp*Ir(HMDAbpy) complex, indicating minimal degradation.","structureLink":"The release-and-catch mechanism allows the catalyst to function as a homogeneous species during FA dehydrogenation (high TOF) and be recaptured by PAA carboxylic acid groups via electrostatic or coordination interactions for recovery. Optimal activity was linked to a ligand content of 212 μmol g−1 and Ir loading of 1.16 wt%.","deactivation":"Ir remaining in solution < 0.1 ppm after batch cycles; below ICP-AES detection limit after flow recycles. Ir recovery rate between 99.39% and 99.98%."},{"paperId":"P145","catalystId":"P145_PERF_003","name":"pre-Cp*Ir-HMDAbpy@PAA","activeMetals":"Ir","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Cp*Ir-HMDAbpy@PAA","particleSize":"10 μm to several hundred μm","surfaceStates":"XPS analysis after reaction showed no peak shifts compared to the homogeneous Cp*Ir(HMDAbpy) complex, indicating minimal degradation.","structureLink":"The release-and-catch mechanism allows the catalyst to function as a homogeneous species during FA dehydrogenation (high TOF) and be recaptured by PAA carboxylic acid groups via electrostatic or coordination interactions for recovery. Optimal activity was linked to a ligand content of 212 μmol g−1 and Ir loading of 1.16 wt%.","deactivation":"Lower elution of complex (34% compared to Cp*Ir-HMDAbpy@PAA) leads to lower activity."},{"paperId":"P146","catalystId":"P146_PERF_001","name":"PdAu-VOx/NHMS","activeMetals":"Pd-Au-V","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu-VOx/NHMS","phase":"Binary PdAu nanoclusters","particleSize":"1.94 nm","surfaceStates":"XPS shows Pd (Pd0 main, Pd2+), Au (Au0 main, Au3+), and V (V5+, V4+, V2+). V5+ exhibits a positive shift of 0.25 eV compared to VOx/NHMS, indicating electron transfer from V to PdAu. Amino groups act as Brønsted base sites; V atoms act as Lewis acid sites.","structureLink":"Synergy between Lewis acidic VOx (facilitates HCOO* adsorption and C-H bond activation), PdAu clusters, and Brønsted basic amino groups (promotes O-H bond cleavage) reduces activation energy to 31.2 kJ/mol.","deactivation":"Slight decrease in activity due to aggregation of nanoparticles (mean size increased from 1.94 nm to 2.07 nm) and valence change of metal species; trace amounts of CO may adsorb on Pd sites"},{"paperId":"P146","catalystId":"P146_PERF_002","name":"PdAu/NHMS","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/NHMS","phase":"PdAu nanoclusters","particleSize":"1.88 nm","surfaceStates":"Contains Pd0, Pd2+, Au0, and Au3+ species.","structureLink":"Lower activity than PdAu-VOx/NHMS due to lack of VOx Lewis acid sites; higher activation energy (33.2 kJ/mol)."},{"paperId":"P146","catalystId":"P146_PERF_004","name":"PdAu-VOx/HMS","activeMetals":"Pd-Au-V","metalClass":"Pd-based multimetal","matchedCharacterization":"VOx/HMS","phase":"VOx species","particleSize":"~1 nm","surfaceStates":"Contains V5+, V4+, and V2+ species."},{"paperId":"P147","catalystId":"P147_PERF_002","name":"Co@NC-W","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co@NC (including Co@NC-W, Co@NC-ZIF, and Co@NC-Gr series)","phase":"Cubic metallic Co","particleSize":"20 ± 10 nm","surfaceStates":"Co2+ (XPS peaks at 781 and 797 eV) and metallic Co (778 eV). Nitrogen species include pyridinic (398.9 eV), pyrrolic/graphitic (400.8 eV), and NOx (402.5, 405.4 eV).","structureLink":"Cobalt nanoparticles do not play a significant role in FA dehydrogenation; activity is attributed to sub-nanosized cobalt species or CoNx centers.","deactivation":"Cobalt leaching upon corrosive action of FA; lost about 12% of Co after 20 h of reaction, gas production rate decreased by ~7%"},{"paperId":"P147","catalystId":"P147_PERF_003","name":"Co@NC-ZIF","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co@NC (including Co@NC-W, Co@NC-ZIF, and Co@NC-Gr series)","phase":"Cubic metallic Co","particleSize":"20 ± 10 nm","surfaceStates":"Co2+ (XPS peaks at 781 and 797 eV) and metallic Co (778 eV). Nitrogen species include pyridinic (398.9 eV), pyrrolic/graphitic (400.8 eV), and NOx (402.5, 405.4 eV).","structureLink":"Cobalt nanoparticles do not play a significant role in FA dehydrogenation; activity is attributed to sub-nanosized cobalt species or CoNx centers."},{"paperId":"P147","catalystId":"P147_PERF_004","name":"Co@NC-Gr1","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co@NC-WSA and Co@NC-Gr1SA","phase":"Single atomic Co species","particleSize":"Sub-nanosized / single atom","structureLink":"Retention of considerable catalytic activity after nanoparticle removal confirms that sub-nanosized/single atomic cobalt species are the primary active sites.","deactivation":"Gas production rate showed a gradual and slowing drop-off to around 90% of the initial value over 8h; attributed to hydrogen accumulation, formate species accumulation, or slow formation of cobalt salts"},{"paperId":"P147","catalystId":"P147_PERF_010","name":"Co@NC-WSA","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co@NC-WSA and Co@NC-Gr1SA","phase":"Single atomic Co species","particleSize":"Sub-nanosized / single atom","structureLink":"Retention of considerable catalytic activity after nanoparticle removal confirms that sub-nanosized/single atomic cobalt species are the primary active sites."},{"paperId":"P147","catalystId":"P147_PERF_011","name":"Co@NC-Gr1SA","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co@NC-WSA and Co@NC-Gr1SA","phase":"Single atomic Co species","particleSize":"Sub-nanosized / single atom","structureLink":"Retention of considerable catalytic activity after nanoparticle removal confirms that sub-nanosized/single atomic cobalt species are the primary active sites."},{"paperId":"P149","catalystId":"P149_PERF_001","name":"Pd/CB","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CB","phase":"Metallic and oxidized Pd species","particleSize":"3.3 ± 0.9 nm","surfaceStates":"43% Pd(0), 57% Pdδ+","structureLink":"PVP capping provides N-containing groups and increases hydrophilicity, enhancing interface contact with formic acid."},{"paperId":"P149","catalystId":"P149_PERF_002","name":"Pd/Vulcan","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Vulcan","phase":"Metallic and oxidized Pd species","particleSize":"2.6 ± 0.7 nm","surfaceStates":"57% Pd(0), 43% Pdδ+","structureLink":"PVP capping provides N-containing groups and increases hydrophilicity, enhancing interface contact with formic acid."},{"paperId":"P149","catalystId":"P149_PERF_003","name":"Pd/MWCNT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MWCNT","phase":"Metallic and oxidized Pd species","particleSize":"2.5 ± 0.9 nm","surfaceStates":"60% Pd(0), 40% Pdδ+","structureLink":"MWCNT's 1D structure and high available external surface area, combined with PVP capping, result in the highest TOF."},{"paperId":"P149","catalystId":"P149_PERF_004","name":"Pd/CB(t)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CB(t)","phase":"Metallic and oxidized Pd species","particleSize":"3.3 ± 0.8 nm","surfaceStates":"81% Pd(0), 19% Pdδ+","structureLink":"Removal of PVP leads to a significant decay in catalytic performance."},{"paperId":"P149","catalystId":"P149_PERF_005","name":"Pd/Vulcan(t)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/Vulcan(t)","phase":"Metallic and oxidized Pd species","particleSize":"3.5 ± 1.6 nm","surfaceStates":"82% Pd(0), 18% Pdδ+","structureLink":"Removal of PVP leads to a significant decay in catalytic performance."},{"paperId":"P149","catalystId":"P149_PERF_006","name":"Pd/MWCNT(t)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MWCNT(t)","phase":"Metallic and oxidized Pd species","particleSize":"4.0 ± 1.9 nm","surfaceStates":"78% Pd(0), 22% Pdδ+","structureLink":"Removal of PVP decreases initial activity compared to the as-synthesized counterpart."},{"paperId":"P151","catalystId":"P151_PERF_001","name":"AuT-MA","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"AuT / AuT-MA","phase":"Anatase phase","particleSize":"Gold particles: 5-7 nm; Anatase crystallite size: ~15 nm (for AuT-MA)","structureLink":"Baseline activity for formic acid decomposition."},{"paperId":"P151","catalystId":"P151_PERF_004","name":"AuXLT-WI","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"AuXLT-WI (Wet Impregnated)","phase":"Anatase phase; lanthanum phases are amorphous and/or well-dispersed","particleSize":"Gold particles: 2-3 nm (for Au5LT-WI and Au15LT-WI); Anatase crystallite size: reduced from 25 nm to ~18 nm (at 2.3 wt% La) and stabilized at ~14 nm (at 29 wt% La)","surfaceStates":"Higher density and coverage of formates compared to coprecipitated catalysts due to high surface basicity","structureLink":"Lower activity than CP counterparts because excessive lanthana surface coverage blocks active sites for hydroperoxy species (OOH*) formation and impedes Au-Ti synergy."},{"paperId":"P152","catalystId":"P152_PERF_001","name":"Pd0.6Ag0.4@ZrO2/C/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.6Ag0.4@ZrO2/C/rGO","phase":"Bimetallic PdAg nanoparticles","particleSize":"2.5 ± 0.03 nm","surfaceStates":"Electron-rich PdAg NP surface resulting from electron transfer from ZrO2 to the metal nanoparticles.","structureLink":"Ultrafine particle size provides more active sites; the electron-rich surface (induced by ZrO2) facilitates O–H bond dissociation of formic acid and favors the formation of the PdAg-formate intermediate."},{"paperId":"P152","catalystId":"P152_PERF_002","name":"Pd0.6Ag0.4@C/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.6Ag0.4@C/rGO","phase":"Bimetallic PdAg nanoparticles","particleSize":"2.4 ± 0.04 nm","surfaceStates":"Less electron-rich than Pd0.6Ag0.4@ZrO2/C/rGO, evidenced by a positive shift in binding energies of Pd 3d and Ag 3d in XPS.","structureLink":"Lower activity compared to ZrO2-supported catalyst despite similar particle size and larger surface area (862 m2 g-1), highlighting the electronic role of ZrO2."},{"paperId":"P152","catalystId":"P152_PERF_003","name":"Pd0.6Ag0.4@ZrO2/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.6Ag0.4@ZrO2/C/rGO","phase":"Bimetallic PdAg nanoparticles","particleSize":"2.5 ± 0.03 nm","surfaceStates":"Electron-rich PdAg NP surface resulting from electron transfer from ZrO2 to the metal nanoparticles.","structureLink":"Ultrafine particle size provides more active sites; the electron-rich surface (induced by ZrO2) facilitates O–H bond dissociation of formic acid and favors the formation of the PdAg-formate intermediate."},{"paperId":"P154","catalystId":"P154_PERF_001","name":"Fe@C-Pd","activeMetals":"Fe","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Fe@C-Pd","phase":"Monometallic Pd nanoparticles","particleSize":"5-10 nm","surfaceStates":"Pd 3d peaks correspond to majority Pd0; CO-DRIFT showed susceptibility to CO poisoning.","structureLink":"Low activity for FA dehydrogenation and high susceptibility to CO poisoning compared to modified versions."},{"paperId":"P154","catalystId":"P154_PERF_002","name":"Fe@C-Pd-B","activeMetals":"Fe","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Fe@C-Pd-B","phase":"B atoms penetrated into the Pd lattice, causing expansion and lattice defects.","particleSize":"5-10 nm","surfaceStates":"Pd 3d peak shifted to lower binding energies, indicating electron transfer from B to Pd d orbitals; increased corrosion current (Icorr) compared to Fe@C-Pd.","structureLink":"Expanded lattice spacing (0.239 and 0.237 nm) and electronic effects induced by work function discrepancy enhance electron transfer, promoting FA dehydrogenation and TCE dechlorination stability."},{"paperId":"P154","catalystId":"P154_PERF_003","name":"Fe@C-Pd-Ag","activeMetals":"Fe","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Fe@C-Pd-Ag","phase":"Pd-Ag alloy structure","particleSize":"5-10 nm","surfaceStates":"Pronounced shift of Pd 3d peak to lower binding energies (larger than B modification), indicating significant electron transfer from Ag to Pd; highest Icorr among catalysts.","structureLink":"Lattice expansion (0.230 and 0.235 nm) and large work function discrepancy facilitate H*ads formation and spillover, leading to the highest initial TCE dechlorination rate but poor stability due to Ag leaching.","deactivation":"Leaching of Ag atoms from Pd-Ag NPs induced by accumulated Cl- during TCE dechlorination, destroying the alloy structure"},{"paperId":"P155","catalystId":"P155_PERF_001","name":"Au0.4Pd0.6/PEI-PDA@CNCs","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.4Pd0.6/PEI-PDA@CNC","phase":"AuPd alloy; confirmed by XRD (post-heating peaks between Au and Pd), HRTEM lattice spacing of 0.229 nm, absence of Au plasma resonance peak at 516 nm in UV-Vis, and EDS mapping showing co-localization of Au and Pd.","particleSize":"2.18 ± 0.4 nm","surfaceStates":"Electron transfer from Pd to Au (Au 4f shifted to lower binding energy 83.0 eV, Pd 3d shifted to higher binding energy 336.3 eV); strong metal-support interaction (SMSI) between the alloy and PEI-PDA@CNC carrier.","structureLink":"The optimized local electronic structure promotes bi-HCOO* rearrangement and lowers the energy barrier for H* binding; high dispersion increases metal utilization rates.","deactivation":"Slight increase in particle size from ~2 nm to 2.29 nm after 5 cycles"},{"paperId":"P155","catalystId":"P155_PERF_002","name":"Au/PEI-PDA@CNC","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/PEI-PDA@CNC","phase":"Monometallic Au","particleSize":"Relatively large nanoparticles compared to Pd/PEI-PDA@CNC","surfaceStates":"Au 4f binding energy at 83.3 eV","structureLink":"Low catalytic activity for FA dehydrogenation due to weak adsorption of H."},{"paperId":"P155","catalystId":"P155_PERF_003","name":"Pd/PEI-PDA@CNC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PEI-PDA@CNC","phase":"Monometallic Pd","particleSize":"Smallest average size among the tested catalysts","surfaceStates":"Pd 3d binding energy at 335.3 eV","structureLink":"Poor activity due to high surface energy of tiny particles increasing the energy required for hydrogen desorption."},{"paperId":"P155","catalystId":"P155_PERF_005","name":"unmodified Au0.4Pd0.6/CNC","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.4Pd0.6/CNC","structureLink":"Poor catalytic activity attributed to metal particle aggregation."},{"paperId":"P156","catalystId":"P156_PERF_001","name":"Ti3C2Tx-250","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ti3C2Tx-250","phase":"Ti3C2Tx MXene phase","particleSize":"Lattice spacing of 2.6 Å corresponding to (0110) crystal plane","surfaceStates":"High surface oxygen coverage: Surface O-Ti species (26.5% relative proportion), surface OH groups, and surface-adsorbed oxygen.","structureLink":"Increased oxygen coverage promotes the conversion from HCOO* to CO2* by lowering the energy barrier and weakens the adsorption energy of CO2 and H2; active sites are identified as surface [O-Ti-C] species."},{"paperId":"P156","catalystId":"P156_PERF_002","name":"Ti3C2Tx-25","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ti3C2Tx-25","phase":"Ti3C2Tx MXene phase","surfaceStates":"Surface O-Ti species (3.4% relative proportion)","structureLink":"Low oxygen coverage results in lower catalytic activity for HCOOH dehydrogenation compared to Ti3C2Tx-250."},{"paperId":"P156","catalystId":"P156_PERF_003","name":"Ti3C2Tx-150","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ti3C2Tx-150","phase":"Ti3C2Tx MXene phase","surfaceStates":"Surface O-Ti species (7.3% relative proportion)","structureLink":"Moderate increase in oxygen coverage slightly improves activity over Ti3C2Tx-25."},{"paperId":"P156","catalystId":"P156_PERF_004","name":"Ti3C2Tx-350","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ti3C2Tx-350","phase":"MXene/TiO2 mixture","surfaceStates":"Dominated by lattice oxygen in TiO2; negligible Ti-C and Ti-F peaks in XPS.","structureLink":"Excessive oxidation to TiO2 phase leads to a decrease in catalytic activity compared to Ti3C2Tx-250."},{"paperId":"P156","catalystId":"P156_PERF_007","name":"Ti2CTx-250","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ti2CTx series (Ti2CTx-25, Ti2CTx-150, Ti2CTx-250, Ti2CTx-350)","phase":"Ti2CTx MXene","surfaceStates":"Oxygen coverage modulated by thermal treatment","structureLink":"Catalytic activity is modulated by surface oxygen coverage, with Ti2CTx-250 exhibiting the highest activity among the series."},{"paperId":"P156","catalystId":"P156_PERF_008","name":"Ti2CTx-25","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ti2CTx series (Ti2CTx-25, Ti2CTx-150, Ti2CTx-250, Ti2CTx-350)","phase":"Ti2CTx MXene","surfaceStates":"Oxygen coverage modulated by thermal treatment","structureLink":"Catalytic activity is modulated by surface oxygen coverage, with Ti2CTx-250 exhibiting the highest activity among the series."},{"paperId":"P156","catalystId":"P156_PERF_009","name":"Ti2CTx-150","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ti2CTx series (Ti2CTx-25, Ti2CTx-150, Ti2CTx-250, Ti2CTx-350)","phase":"Ti2CTx MXene","surfaceStates":"Oxygen coverage modulated by thermal treatment","structureLink":"Catalytic activity is modulated by surface oxygen coverage, with Ti2CTx-250 exhibiting the highest activity among the series."},{"paperId":"P156","catalystId":"P156_PERF_010","name":"Ti2CTx-350","activeMetals":"Ti","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ti2CTx series (Ti2CTx-25, Ti2CTx-150, Ti2CTx-250, Ti2CTx-350)","phase":"Ti2CTx MXene","surfaceStates":"Oxygen coverage modulated by thermal treatment","structureLink":"Catalytic activity is modulated by surface oxygen coverage, with Ti2CTx-250 exhibiting the highest activity among the series."},{"paperId":"P157","catalystId":"P157_PERF_001","name":"Pd0/CeO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd0/CeO2","phase":"Monometallic Pd(0) nanoparticles supported on nanoceria; XRD showed no observable peaks for Pd due to low loading and small particle size.","particleSize":"1.6–4.0 nm (mean diameter: 1.9 ± 0.4 nm) for 2.27% wt Pd; mean diameter 2.5 ± 0.6 nm for 4.73% wt Pd.","surfaceStates":"Pd(0) identified by XPS peaks at 335.3 eV (3d5/2) and 340.6 eV (3d3/2).","structureLink":"The higher catalytic activity of the 2.27% wt Pd sample compared to the 4.73% wt Pd sample is attributed to its smaller mean particle size (1.9 nm vs 2.5 nm). The overall superb activity is ascribed to the reducible nature of ceria and the redox cycling between Ce4+ and Ce3+.","deactivation":"No leaching of palladium into solution. Deactivation attributed to agglomeration of nanoparticles on ceria surface and deposition of sodium formate species."},{"paperId":"P158","catalystId":"P158_PERF_001","name":"AuPd/T-g-C3N4","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AuPd/T-g-C3N4","phase":"Alloy particles","particleSize":"5.4 nm","surfaceStates":"Electron transfer from g-C3N4 support to Au.","structureLink":"Highest catalytic activity attributed to the confinement effect of the one-dimensional nanotubular geometry, which increases reactant concentration inside the nanoreactor.","deactivation":"Slight decrease in activity during the third cycle due to by-products and intermediates trapped on AuPd surface and support pores."},{"paperId":"P158","catalystId":"P158_PERF_002","name":"AuPd/S-g-C3N4","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AuPd/S-g-C3N4","phase":"Alloy particles","particleSize":"2.7 nm","surfaceStates":"Electron transfer from g-C3N4 support to Au; highest graphitic N content helps modify electron density for smaller particle size.","structureLink":"Higher activity than bulk B-g-C3N4 attributed to smaller nanoparticle size and higher surface area."},{"paperId":"P158","catalystId":"P158_PERF_003","name":"AuPd/B-g-C3N4","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AuPd/B-g-C3N4","phase":"Alloy particles","particleSize":"4.6 nm","surfaceStates":"Electron transfer from g-C3N4 support to Au (lower binding energies in XPS)","structureLink":"Higher activity than AuPd/g-C due to nitrogen anchoring and electron donation effects."},{"paperId":"P158","catalystId":"P158_PERF_004","name":"AuPd/g-C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"AuPd/g-C","phase":"Alloy particles","particleSize":"5.5 nm","structureLink":"Lowest activity among the tested catalysts; rapid deactivation possibly due to adsorption of reactants or intermediates.","deactivation":"Deactivated rapidly, possibly due to the adsorption of reactants or intermediates on the metal surface."},{"paperId":"P159","catalystId":"P159_PERF_001","name":"Pd/AC–CP (250 W, 10 min)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC–CP (250 W, 10 min)","phase":"Face-centered cubic metallic Pd(111)","particleSize":"1.9 ± 0.4 nm","surfaceStates":"Pd0 (336.0 eV) and Pd2+ (337.8 eV); shifted to lower binding energies compared to Pd/AC–C, indicating electron transfer from N species to Pd.","structureLink":"Smallest particle size, highest specific surface area (877.6 m2/g), high pyridine nitrogen content (39.8%), and electron-rich Pd0 sites lead to the lowest activation energy (29.67 kJ/mol) and highest TOF."},{"paperId":"P159","catalystId":"P159_PERF_002","name":"Pd/AC–C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC–C","phase":"Face-centered cubic metallic Pd(111) and (200)","particleSize":"2.1 ± 0.5 nm","surfaceStates":"Pd0 (336.2 eV) and Pd2+ (338.0 eV)","structureLink":"Small size and uniform dispersion anchored by oxygen-rich functional groups on AC support contribute to high catalytic performance."},{"paperId":"P159","catalystId":"P159_PERF_003","name":"Pd/AC-P (250 W, 10 min)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC-P (250 W, 10 min)","phase":"Face-centered cubic metallic Pd","particleSize":"5.4 ± 1.9 nm","surfaceStates":"Pd0 (336.2 eV) and Pd2+ (338.0 eV)","structureLink":"Poor activity attributed to larger particle size, lower reduction degree, and reduced specific surface area (733.9 m2/g)."},{"paperId":"P161","catalystId":"P161_PERF_001","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Pure Pd NPs (fcc)","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II)","structureLink":"Lowest FAD activity despite having the highest ECSA (323 m2 g-1)."},{"paperId":"P161","catalystId":"P161_PERF_002","name":"Pd0.90Au0.10/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content."},{"paperId":"P161","catalystId":"P161_PERF_003","name":"Pd0.82Au0.18/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content."},{"paperId":"P161","catalystId":"P161_PERF_004","name":"Pd0.75Au0.25/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content."},{"paperId":"P161","catalystId":"P161_PERF_005","name":"Pd0.69Au0.31/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content."},{"paperId":"P161","catalystId":"P161_PERF_006","name":"Pd0.64Au0.36/C","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/C alloyed catalysts (series: Pd0.90Au0.10/C, Pd0.82Au0.18/C, Pd0.75Au0.25/C, Pd0.69Au0.31/C, Pd0.64Au0.36/C)","phase":"Alloyed PdAu NPs with face-centered cubic (fcc) structure; lattice expansion observed as Au content increases (lattice parameters 0.6365 to 0.6431 nm).","particleSize":"3.5 - 5.5 nm","surfaceStates":"Pd(0) and Pd(II); Au(0). The Pd(II)/Pd(0) ratio increases with Au content up to a ratio of 0.31, then decreases.","structureLink":"Activity (TOF) is directly related to the surface PdO:Pd ratio. At low Au ratios (≤0.31), lattice strain dominates and promotes dissociative adsorption of O2 to form active PdO. At high Au ratios (>0.31), the ligand effect (charge transfer from Au to Pd) dominates, weakening O2 adsorption and decreasing PdO content."},{"paperId":"P161","catalystId":"P161_PERF_007","name":"Au/C","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/C","phase":"Pure Au NPs","structureLink":"No detectable gas generated during FAD."},{"paperId":"P162","catalystId":"P162_PERF_001","name":"PdAu/NH2-W18O49","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/NH2-W18O49","phase":"fcc PdAu alloy","particleSize":"~2.9 nm","surfaceStates":"Electron-rich Pd sites (negative XPS binding energy shift); surface modified with -NH2 groups (Lewis base sites); abundant oxygen vacancies (W5+ species in XPS and EPR signal at g = 2.004).","structureLink":"The O_v-rich W18O49 support enables a highly efficient hydrogen spillover effect, facilitating the storage of dissociated H atoms and desorption of adsorbates, which reduces activation energy for FA dehydrogenation (21.8 kJ/mol) and CO2 hydrogenation (11.8 kJ/mol).","deactivation":"Slight decrease in FA dehydrogenation rate and loss of active sites in long-term CO2 hydrogenation (up to 36 h) attributed to PdAu NP agglomeration and possible CO poisoning"},{"paperId":"P162","catalystId":"P162_PERF_004","name":"PdAu/W18O49","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","deactivation":"Dramatic activity decline for CO2 hydrogenation due to aggregated PdAu NPs and lack of -NH2 groups"},{"paperId":"P162","catalystId":"P162_PERF_005","name":"Au/NH2-W18O49","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"PdAu/NH2-W18O49","phase":"fcc PdAu alloy","particleSize":"~2.9 nm","surfaceStates":"Electron-rich Pd sites (negative XPS binding energy shift); surface modified with -NH2 groups (Lewis base sites); abundant oxygen vacancies (W5+ species in XPS and EPR signal at g = 2.004).","structureLink":"The O_v-rich W18O49 support enables a highly efficient hydrogen spillover effect, facilitating the storage of dissociated H atoms and desorption of adsorbates, which reduces activation energy for FA dehydrogenation (21.8 kJ/mol) and CO2 hydrogenation (11.8 kJ/mol)."},{"paperId":"P163","catalystId":"P163_PERF_001","name":"PdCuCr/resin (Pd1Cu0.5Cr0.5/resin)","activeMetals":"Pd-Cu-Cr","metalClass":"Pd-based multimetal","matchedCharacterization":"PdCuCr/resin","phase":"Random ternary alloy structure with Pd, Cu, and Cr distributed homogeneously throughout the NPs, though Cr specifically constitutes surface clusters.","particleSize":"8.1 nm (fresh/pretreated); 2.3 nm (isolated after induction period/reaction)","surfaceStates":"Electron-rich Pd species (XPS binding energy shifted to 335.4 eV compared to 335.8 eV for monometallic Pd).","structureLink":"In situ construction of highly dispersed NPs and the synergistic alloying effect of Cr boost C-H bond dissociation (KIE = 1.37). Surface Cr clusters act as anchors to inhibit agglomeration, enhancing durability. Electron-rich Pd stabilizes bridging formate intermediates, suppressing CO production.","deactivation":"No metal leaching observed by ICP-OES"},{"paperId":"P163","catalystId":"P163_PERF_002","name":"PdCu/resin (Pd1Cu0.5/resin)","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","matchedCharacterization":"PdCu/resin","phase":"Bimetallic alloy","particleSize":"2.0 nm (initial); 3.7 nm (after reaction)","surfaceStates":"Electron-rich Pd species (XPS binding energy of 335.4 eV).","structureLink":"Suppresses CO production (2.0 ppm) better than monometallic Pd but exhibits more agglomeration and lower activity than the ternary PdCuCr system."},{"paperId":"P163","catalystId":"P163_PERF_003","name":"Pd/resin","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/resin","phase":"Monometallic","particleSize":"2.4 nm (initial); 4.6 nm (after reaction)","surfaceStates":"XPS binding energy of 335.8 eV.","structureLink":"Prone to significant agglomeration and higher CO poisoning (7.0 ppm) compared to alloyed systems.","deactivation":"Durability decreased due to CO poisoning"},{"paperId":"P164","catalystId":"P164_PERF_001","name":"Pd/CS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CS","phase":"Pd nanoparticles","particleSize":"1.7 ± 0.5 nm (fresh); grew to 3.67–6.17 nm after reaction","structureLink":"Gradual deactivation attributed to Pd NP agglomeration and increase in average particle size.","deactivation":"Pd NP size increased from 1.7 nm to 3.67–6.17 nm after reaction"},{"paperId":"P164","catalystId":"P164_PERF_002","name":"Pd/CS-GO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CS-GO2","phase":"Pd nanoparticles","particleSize":"1.8 ± 0.8 nm (fresh); grew to 3.67 nm after reuse","surfaceStates":"Pd(0) at 336.05 eV and PdO (Pd2+) at 338.21 eV; Pd(0)/Pd2+ ratio of 1.35","structureLink":"Deactivation caused by agglomeration of Pd NPs; optimal particle size for activity suggested to be ~2 nm.","deactivation":"Pd leached was <0.006% of initial total Pd content; average particle size increased from 1.7 nm to 3.67 nm upon reuse"},{"paperId":"P164","catalystId":"P164_PERF_004","name":"Pd/CS-GO1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CS-GO1","phase":"Pd nanoparticles","particleSize":"1.6 ± 0.9 nm"},{"paperId":"P164","catalystId":"P164_PERF_005","name":"Pd/CS-GO3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CS-GO3","phase":"Pd nanoparticles","particleSize":"1.7 ± 0.5 nm"},{"paperId":"P165","catalystId":"P165_PERF_001","name":"Pd/PPy-S1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PPy-S1","phase":"Pd nanoparticles (low crystallinity/fine particles)","particleSize":"5-30 nm","surfaceStates":"XPS Pd 3d peaks: Pd(0) at 335.4 eV and 340.6 eV; Pd(II) at 338.0 eV and 343.4 eV","structureLink":"Higher catalytic activity compared to Pd/PPy-S2 despite smaller specific surface area (7.8 m2/g), attributed to different valence ratios of Pd 3d and distinctive interaction between Pd and the in situ polymerized PPy support."},{"paperId":"P165","catalystId":"P165_PERF_002","name":"Pd/PPy-S2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PPy-S2","phase":"Pd nanoparticles (good crystal shape and larger particles; XRD peaks at 2 theta = 40, 46, 68)","particleSize":"5-30 nm","surfaceStates":"XPS Pd 3d peaks: Pd(0) at 336.2 eV and 341.6 eV; Pd(II) at 338.6 eV and 344.0 eV","structureLink":"Lower catalytic activity than Pd/PPy-S1 despite larger specific surface area (384.3 m2/g) and better dispersion, attributed to different valence ratios of Pd 3d.","deactivation":"Pd particles were slightly grown (indicated by XRD)"},{"paperId":"P166","catalystId":"P166_PERF_001","name":"Pd/NMC-8","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC-8","phase":"Pd0 (111) crystal plane","particleSize":"2.4 ± 0.5 nm","surfaceStates":"Electron-enriched metallic palladium; binding energy is 0.4 eV lower than Pd/MC-8 due to electron donation from nitrogen species (pyridine, nitrile, pyrrole, and quaternary N).","structureLink":"High activity is attributed to the good dispersion and small size of Pd NPs resulting from interactions between palladium and nitrogen functional groups in the support.","deactivation":"Deactivation tentatively attributed to adsorption of reaction product HCO3- blocking active sites; can be circumvented by washing with deionized water and drying in vacuum at 333–353 K."},{"paperId":"P166","catalystId":"P166_PERF_002","name":"Pd/MC-8","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MC-8","phase":"Pd0 (111) crystal plane","particleSize":"3.1 ± 0.8 nm","surfaceStates":"Metallic palladium binding energy is higher than that of Pd/NMC-8 by 0.4 eV.","structureLink":"Lower activity compared to Pd/NMC-8 due to larger particle size and poorer dispersion."},{"paperId":"P166","catalystId":"P166_PERF_004","name":"Pd/NMC-9","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC-9","particleSize":"2.2 ± 0.5 nm","structureLink":"Highest activity among the NMC series due to highest nitrogen content facilitating better dispersion and smallest particle size."},{"paperId":"P167","catalystId":"P167_PERF_001","name":"Pd/BCNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BCNTs","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"6.28 nm","surfaceStates":"Pd0 core-level binding energy is slightly upshifted compared to Pd/CNTs, suggesting effective electron transfer from B to Pd.","structureLink":"Highest performance attributed to the largest specific surface area (128.1273 m2/g), large mesopore volume (0.894 cm3/g), smallest particle size, and synergetic interaction between PdNPs and BCNTs.","deactivation":"Long-term stability test without regeneration showed reduction of 52.92% in second injection and complete deactivation by fourth injection; attributed to CO poisoning, fouling of reactants/products on Pd surface, and agglomeration of PdNPs."},{"paperId":"P167","catalystId":"P167_PERF_002","name":"Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNTs","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"7.25 nm","surfaceStates":"Pd0 (3d5/2 ~ 335.3 eV), PdO (~ 337.2 eV), and PdO2 (~ 333.8 eV).","structureLink":"Lowest catalytic performance attributed to aggregation of Pd particles, leading to fewer accessible active sites.","deactivation":"Aggregation of Pd particles leading to fewer accessible exposed active sites"},{"paperId":"P167","catalystId":"P167_PERF_003","name":"Pd/NCNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NCNTs","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"8.31 nm","surfaceStates":"Negative shift in Pd0 core-level binding energy due to electron-donating effects of N, increasing stability of Pd0.","structureLink":"Moderate performance; electronic properties modified by N enhance the stability of Pd0 and prevent agglomeration."},{"paperId":"P167","catalystId":"P167_PERF_004","name":"Pd/OCNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/OCNTs","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"8.95 nm","surfaceStates":"Strong interaction between Pd and surface O-containing functionalities facilitates electron transfer from metallic Pd nanoparticles to the CNTs support.","structureLink":"Higher Pd loading compared to Pd/CNTs but inferior catalytic performance relative to B/N doped versions despite strong anchoring."},{"paperId":"P168","catalystId":"P168_PERF_001","name":"KCC-1/IL/PbS","activeMetals":"Pb","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"KCC-1/IL/PbS","phase":"cubic phase of PbS (JCPDS card No. 05-0592)","particleSize":"about 250 nm","surfaceStates":"XPS confirmed presence of Si, O, C, N, S, Cl and Pb; FT-IR confirmed imidazolium IL introduction via C=N (1635 cm-1) and CH2 (2905 cm-1) stretching vibrations","structureLink":"The dendritic fibrous morphology of KCC-1 makes active sites accessible, while the ionic liquid units prevent agglomeration of PbS nanoparticles, maintaining high catalytic activity.","deactivation":"PbS leaching after ten repeated recycling was 1.3%."},{"paperId":"P169","catalystId":"P169_PERF_001","name":"Pd/hatnCTF","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/hatnCTF","phase":"Single atoms and dimers","particleSize":"Nanoparticles are rarely seen","surfaceStates":"Pd 3d5/2 components at 338.2 eV (Pd2+ stabilized by N) and 336.8 eV (attributed to Pd2+ in PdO or small clusters); surface Pd2+/Pdtotal ratio is 0.77","structureLink":"High activity attributed to the prevalence of single-atom Pd2+−C1N3 sites; high tolerance to CO poisoning due to weak adsorption on Pd2+ sites.","deactivation":"High tolerance to CO poisoning as Pd2+ sites do not adsorb CO as strongly as metallic Pd."},{"paperId":"P169","catalystId":"P169_PERF_002","name":"Pd/acacCTF","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/acacCTF","phase":"Metallic Pd nanoparticles and isolated Pd2+ atoms","particleSize":"5.2 ± 0.6 nm","surfaceStates":"Pd 3d5/2 components at 336.0 eV (metallic Pd) and 338.0 eV (isolated Pd2+ attached to O-atoms); surface Pd2+/Pdtotal ratio is 0.54","structureLink":"Lower activity than Pd/hatnCTF; metallic nanoparticles are relatively large and low active, while Pd2+−O4 sites may have negligible activity.","deactivation":"High tolerance of single-atom Pd2+-O4 sites with respect to CO."},{"paperId":"P169","catalystId":"P169_PERF_003","name":"Pd/g-C3N4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/g-C3N4","phase":"Metallic Pd nanoparticles","particleSize":"3.0 ± 1.2 nm","surfaceStates":"Pd 3d5/2 components at 335.0 eV (metallic Pd) and 337.4 eV (isolated Pd2+); surface Pd2+/Pdtotal ratio is 0.31","structureLink":"Poor performance in formic acid decomposition compared to Pd/hatnCTF due to the prevalence of metallic sites."},{"paperId":"P170","catalystId":"P170_PERF_001","name":"Pd/AC_C3N4(19)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC_C3N4(19)","phase":"Pd nanoparticles","particleSize":"2.3 ± 0.6 nm","surfaceStates":"Electron-deficient Pd species stabilized by high nitrogen content (signals shifted to higher binding energies).","structureLink":"Combination of small particle size, modified electronic properties (Pd2+ favoring formate adsorption), and high surface area leads to highest TOF (2893 h-1) and high stability.","deactivation":"low Pd loss (fresh 0.7 wt% to used 0.6 wt%)"},{"paperId":"P170","catalystId":"P170_PERF_002","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC","phase":"Pd nanoparticles","surfaceStates":"Reduced Pd species (Pd0)","structureLink":"Poor performance compared to C3N4-modified catalysts due to lack of nitrogen functional groups and poor dispersion.","deactivation":"Pd loss from 0.9 wt% (fresh) to 0.7 wt% (used)"},{"paperId":"P170","catalystId":"P170_PERF_003","name":"Pd/C3N4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C3N4","phase":"Pd nanoparticles","particleSize":"4.2 ± 2.0 nm","surfaceStates":"Reduced species (334.8 eV) and electron-deficient species (336.5, 337.9 eV)","deactivation":"Pd content remained at 0.3 wt%"},{"paperId":"P170","catalystId":"P170_PERF_004","name":"Pd/AC_C3N4(3)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC_C3N4(3)","phase":"Pd nanoparticles","particleSize":"4.8 ± 2.0 nm","surfaceStates":"Electronic properties dependent on support composition; lower N content results in signals shifted to lower binding energies compared to Pd/AC_C3N4(19) and (22).","deactivation":"Pd loss from 0.8 wt% (fresh) to 0.7 wt% (used)"},{"paperId":"P170","catalystId":"P170_PERF_005","name":"Pd/AC_C3N4(10)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC_C3N4(10)","phase":"Pd nanoparticles","particleSize":"3.8 ± 1.4 nm","surfaceStates":"Electronic properties dependent on support composition; lower N content results in signals shifted to lower binding energies compared to Pd/AC_C3N4(19) and (22).","deactivation":"Pd content remained at 0.7 wt%"},{"paperId":"P170","catalystId":"P170_PERF_006","name":"Pd/AC_C3N4(22)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC_C3N4(22)","phase":"Pd nanoparticles","particleSize":"3.5 ± 1.2 nm","surfaceStates":"Electron-deficient Pd species stabilized by high nitrogen content (signals shifted to higher binding energies).","structureLink":"Decay in activity compared to Pd/AC_C3N4(19) likely due to significant blockage of AC porosity and C3N4 stacking.","deactivation":"Pd loss from 0.7 wt% (fresh) to 0.5 wt% (used)"},{"paperId":"P171","catalystId":"P171_PERF_001","name":"0.2% Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"0.2% Pd/N-CNTs","phase":"Isolated palladium ions","particleSize":"not detectable","surfaceStates":"Pd2+-NPy (BE Pd 3d = 337.7 eV)","structureLink":"Maximum activity observed for this catalyst as isolated palladium ions are more active than metallic nanoparticles."},{"paperId":"P171","catalystId":"P171_PERF_004","name":"2% Pd/N-CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"0.2% Pd/N-CNTs","phase":"Isolated palladium ions","particleSize":"not detectable","surfaceStates":"Pd2+-NPy (BE Pd 3d = 337.7 eV)","structureLink":"Maximum activity observed for this catalyst as isolated palladium ions are more active than metallic nanoparticles."},{"paperId":"P171","catalystId":"P171_PERF_006","name":"2% Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"0.2-2% Pd/CNTs","phase":"Metallic Pd","particleSize":"1.2 nm (for 0.2% Pd), 2.3 nm (for 2% Pd)","surfaceStates":"Pd0 (BE Pd 3d = 335.6 eV)","structureLink":"Lower activity and selectivity compared to Pd/N-CNTs; TOF decreases as particle size increases from 1.2 nm to 2.3 nm."},{"paperId":"P172","catalystId":"P172_PERF_001","name":"Pd/BN_{C,O}-1-A","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BN_{C,O}-1-A","phase":"Cubic-phase Pd; XRD shows primarily (111) diffraction peaks around 2θ = 40.1°.","particleSize":"~2.1 nm","surfaceStates":"Strong metal-support interaction enhanced by combined effect of -NH2 functionalization and C/O doping, resulting in electron transfer from Pd to BN_{C,O}-1-A.","structureLink":"Synergistic effect of heteroatom doping and -NH2 groups (acting as proton scavengers) leads to the smallest particle size, strongest metal-support interaction, lowest activation energy (23.6 kJ/mol), and highest TOF (522.0 h-1 at 298 K).","deactivation":"agglomeration of Pd nanoparticles (size increased from ~2.1 to ~2.6 nm); possible CO poison accumulation; mass loss of catalyst"},{"paperId":"P172","catalystId":"P172_PERF_002","name":"Pd/BN_{C,O}-3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BN_{C,O}-3","phase":"Cubic-phase Pd (PDF #46-1043)","particleSize":"~2.6 nm","surfaceStates":"Strong metal-support interaction characterized by electron transfer from Pd to the BN_{C,O}-3 support (Pd0 peak shifted 0.67-0.7 eV higher than pure Pd).","structureLink":"C and O doping introduces defects in BN, facilitating smaller particle size and better dispersion compared to unmodified BN, which lowers activation energy (32.9 kJ/mol) and increases TOF."},{"paperId":"P172","catalystId":"P172_PERF_003","name":"Pd/BN_{C,O}-0","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BN_{C,O}-0","phase":"Cubic-phase Pd (PDF #46-1043)","particleSize":"~9.9 nm","surfaceStates":"Lower binding energy for Pd2+ compared to Pd/BN_{C,O}-3, indicating weaker metal-support interaction.","structureLink":"Larger particle size and poor dispersion result in higher activation energy (41.4 kJ/mol) and significantly lower catalytic activity."},{"paperId":"P173","catalystId":"P173_PERF_001","name":"Pd/PNCC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PNCC","phase":"Metallic Pd with a lattice spacing of 0.232 nm corresponding to the (110) crystal face.","particleSize":"2.5 nm","surfaceStates":"Electron-rich Pd sites characterized by a negative shift in XPS signals compared to pure Pd NPs, indicating electron transfer from the PNCC support to Pd.","structureLink":"The strong electronic metal–support interaction (EMSI) optimizes the electron configuration of Pd active sites to accelerate O-H bond cleavage. The hierarchical porous structure improves mass transfer and accessibility of FA molecules to the catalytic sites."},{"paperId":"P174","catalystId":"P174_PERF_001","name":"Pd/CNT-base-4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNT-base-4","phase":"Metallic Pd (fcc), characteristic peak at 40° corresponding to the (111) crystal plane.","particleSize":"5.4 nm","surfaceStates":"Predominantly electron-deficient Pdδ+ (up to 81% of sample); XPS shows a shift in Pd0 3d5/2 binding energy to 335.0 eV (+0.4 eV) due to electron transfer from Pd to carbonyl C=O groups.","structureLink":"The formation of the Pd0-Pdδ+ interface and Pd-PdO interfaces reduces the activation energy for formic acid dehydrogenation (27.1 kJ/mol) and increases TOF (1702 h-1)."},{"paperId":"P174","catalystId":"P174_PERF_002","name":"Pd/CNT-acid","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNT-acid","phase":"Metallic Pd","particleSize":"4.1 nm","surfaceStates":"Contains both Pd0 and Pd2+ states.","structureLink":"Higher activity than Pd/CNT due to higher metal dispersion, but lower activity than Pd/CNT-base-4 because it lacks the specific electronic modulation provided by carbonyl groups."},{"paperId":"P174","catalystId":"P174_PERF_003","name":"Pd/CNT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNT","phase":"Metallic Pd (fcc), characteristic peak at 40° corresponding to the (111) crystal plane.","particleSize":"6.7 nm","surfaceStates":"Predominantly zerovalent metallic Pd (Pd0 3d5/2 binding energy at 334.6 eV).","structureLink":"Highest activation energy (33.3 kJ/mol) and lowest TOF (425.1 h-1) due to lack of support-induced electronic modulation."},{"paperId":"P175","catalystId":"P175_PERF_001","name":"Pd/N,P-C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N,P-C","phase":"Metallic Pd {111} crystal plane (lattice fringe 2.20 Å).","particleSize":"2.2 nm","surfaceStates":"Electron-enriched Pd0 active sites due to charge transfer from the N,P-co-doped carbon support, evidenced by a shift in Pd 3d5/2 XPS peaks to lower binding energies compared to Pd/AC.","structureLink":"Synergistic effects of N and P co-dopants modulate the electronic state of Pd via metal-support interactions, enhancing activity for formate dehydrogenation (TOF 3248 h-1) and bicarbonate hydrogenation; a correlation exists between TON and Pd 3d5/2 binding energy."},{"paperId":"P175","catalystId":"P175_PERF_002","name":"Pd/NC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NC","particleSize":"Similar to Pd/N,P-C (~2 nm)","surfaceStates":"Pd0 peaks shifted to lower binding energies compared to Pd/AC, but less so than Pd/N,P-C."},{"paperId":"P175","catalystId":"P175_PERF_003","name":"Pd/PC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PC","particleSize":"Similar to Pd/N,P-C (~2 nm)","surfaceStates":"Pd0 peaks shifted to lower binding energies compared to Pd/AC, but less so than Pd/N,P-C."},{"paperId":"P175","catalystId":"P175_PERF_004","name":"Pd/AC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AC","particleSize":"Similar to Pd/N,P-C (~2 nm)","surfaceStates":"Reference binding energy for Pd0; lacks the electron enrichment seen in doped carbon supports."},{"paperId":"P176","catalystId":"P176_PERF_001","name":"Pd/NHPC-NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NHPC-NH2","phase":"fcc Pd (lattice fringe distance 0.224 nm)","particleSize":"2.5 nm","surfaceStates":"Zero-valent Pd (Pd 3d 3/2 at 341.4 eV, Pd 3d 5/2 at 336.1 eV) shifted to higher binding energies due to strong metal-support interaction (SMSI); positively charged Pd surface.","structureLink":"Synergy between amino groups (acting as proton scavengers for O-H bond dissociation) and positively charged Pd (promoting HCOO- adsorption) enables additive-free FA dehydrogenation at room temperature."},{"paperId":"P176","catalystId":"P176_PERF_002","name":"Pd/NHPC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NHPC","phase":"fcc Pd (planes 111, 200, 220)","particleSize":"6.7 nm","surfaceStates":"Zero-valent Pd (Pd 3d 3/2 at 341.2 eV, Pd 3d 5/2 at 335.9 eV)","structureLink":"Inert under test conditions due to relatively weak alkalinity of doped nitrogen and larger particle size."},{"paperId":"P176","catalystId":"P176_PERF_003","name":"Pd/NHPC H2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NHPC H2","particleSize":"1.75 nm","surfaceStates":"Lower Pd 3d binding energy compared to Pd/NHPC-NH2","structureLink":"Negligible catalytic activity despite small particle size, indicating that particle size alone is not the key factor for performance."},{"paperId":"P177","catalystId":"P177_PERF_001","name":"Pd/HNDC (20 wt% Pd)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HNDC","phase":"fcc Pd (111)","particleSize":"3.0 nm","surfaceStates":"Electron-rich active Pd centers induced by graphitic N and pyridinic N from the HNDC support; XPS identified graphitic N (401.3 eV), pyrrolic N (399.7 eV), and pyridinic N (398.5 eV).","structureLink":"The high surface area and hierarchical pore characteristics of HNDC facilitate mass transfer, while the strong synergistic interaction between Pd NPs and N sites on HNDC, along with ultrasmall size and high dispersion, enhance catalytic activity.","deactivation":"Partial loss of Pd content in recycled catalyst; average Pd NP size increased from 3.0 nm to 3.3 nm due to aggregation."},{"paperId":"P177","catalystId":"P177_PERF_002","name":"Pd/HNDC (10 wt% Pd)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HNDC","phase":"fcc Pd (111)","particleSize":"3.0 nm","surfaceStates":"Electron-rich active Pd centers induced by graphitic N and pyridinic N from the HNDC support; XPS identified graphitic N (401.3 eV), pyrrolic N (399.7 eV), and pyridinic N (398.5 eV).","structureLink":"The high surface area and hierarchical pore characteristics of HNDC facilitate mass transfer, while the strong synergistic interaction between Pd NPs and N sites on HNDC, along with ultrasmall size and high dispersion, enhance catalytic activity."},{"paperId":"P177","catalystId":"P177_PERF_003","name":"Pd/HNDC (15 wt% Pd)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HNDC","phase":"fcc Pd (111)","particleSize":"3.0 nm","surfaceStates":"Electron-rich active Pd centers induced by graphitic N and pyridinic N from the HNDC support; XPS identified graphitic N (401.3 eV), pyrrolic N (399.7 eV), and pyridinic N (398.5 eV).","structureLink":"The high surface area and hierarchical pore characteristics of HNDC facilitate mass transfer, while the strong synergistic interaction between Pd NPs and N sites on HNDC, along with ultrasmall size and high dispersion, enhance catalytic activity."},{"paperId":"P177","catalystId":"P177_PERF_004","name":"Pd/HNDC (25 wt% Pd)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HNDC","phase":"fcc Pd (111)","particleSize":"3.0 nm","surfaceStates":"Electron-rich active Pd centers induced by graphitic N and pyridinic N from the HNDC support; XPS identified graphitic N (401.3 eV), pyrrolic N (399.7 eV), and pyridinic N (398.5 eV).","structureLink":"The high surface area and hierarchical pore characteristics of HNDC facilitate mass transfer, while the strong synergistic interaction between Pd NPs and N sites on HNDC, along with ultrasmall size and high dispersion, enhance catalytic activity."},{"paperId":"P178","catalystId":"P178_PERF_001","name":"Pd/MCTP-1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MCTP-1","phase":"Pd nanoparticles","particleSize":"2.4 ± 0.5 nm","surfaceStates":"Triazine groups regularly distributed on the MCTP-1 structure offer selective adsorption sites for anionic palladium precursors.","structureLink":"Superior activity is attributed to the formation of the smallest Pd NPs and the maintenance of a neutral reaction pH provided by triazine groups."},{"paperId":"P178","catalystId":"P178_PERF_002","name":"Pd/MIL-101-DETA","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MIL-101-DETA","phase":"Pd nanoparticles","particleSize":"3.5-5 nm","surfaceStates":"Basic amine groups provide selective adsorption for anionic palladium precursors, suppressing agglomeration during reduction.","structureLink":"Improved activity due to smaller Pd NPs and a pH shift toward neutral values via basic amine groups."},{"paperId":"P178","catalystId":"P178_PERF_003","name":"Pd/UiO-66-NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/UiO-66-NH2","phase":"Pd nanoparticles","particleSize":"3.5-5 nm","surfaceStates":"Basic amine groups provide selective adsorption for anionic palladium precursors, suppressing agglomeration during reduction.","structureLink":"Improved activity due to smaller Pd NPs and a pH shift toward neutral values via basic amine groups."},{"paperId":"P179","catalystId":"P179_PERF_001","name":"Pd/BCNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/BCNTs","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"6.28 nm","surfaceStates":"Pd0 core-level binding energy is slightly upshifted compared to Pd/CNTs, suggesting effective electron transfer from B to Pd.","structureLink":"Highest performance attributed to largest specific surface area (128.1273 m2/g), large mesopore volume (0.894 cm3/g), smallest particle size, and synergetic interaction between PdNPs and BCNTs.","deactivation":"Long-term stability test without regeneration showed reduction of 52.92% in second injection and complete deactivation by fourth injection; attributed to CO poisoning, fouling of reactants/products on Pd surface, and agglomeration of PdNPs."},{"paperId":"P179","catalystId":"P179_PERF_002","name":"Pd/CNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNTs","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"7.25 nm","surfaceStates":"Pd0 (3d5/2 ~ 335.3 eV), PdO (~ 337.2 eV), and PdO2 (~ 333.8 eV).","structureLink":"Lowest catalytic performance attributed to aggregation of Pd particles, leading to fewer accessible active sites.","deactivation":"Aggregation of Pd particles leads to fewer accessible exposed active sites."},{"paperId":"P179","catalystId":"P179_PERF_003","name":"Pd/NCNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NCNTs","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"8.31 nm","surfaceStates":"Negative shift in Pd0 core-level binding energy due to electron-donating effects of N, increasing stability of Pd0.","structureLink":"Moderate performance; electronic properties modified by N-doping enhance Pd0 stability and prevent agglomeration."},{"paperId":"P179","catalystId":"P179_PERF_004","name":"Pd/OCNTs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/OCNTs","phase":"Face-centered cubic Pd structure (JCPDS card NO. 46-1043)","particleSize":"8.95 nm","surfaceStates":"Strong interaction between Pd and surface O-containing functionalities facilitates electron transfer from metallic Pd nanoparticles to the CNTs support.","structureLink":"Higher Pd loading achieved via anchor points, but performance is moderate/poor compared to doped versions."},{"paperId":"P180","catalystId":"P180_PERF_006","name":"CeO2","activeMetals":"Ce","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"CeO2 nanospheres","phase":"Fluorite structure with face centered cubic (FCC) lattice","particleSize":"80-200 nm (nanosphere size); 14.1 nm (crystallite size)","surfaceStates":"Ce3+/Ce4+ ratio of 0.161; Oads/Olatt ratio of 0.597","structureLink":"Low catalytic activity due to lack of active Pd species"},{"paperId":"P181","catalystId":"P181_PERF_001","name":"7C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"7C","phase":"PdCx phase (x < 0.13)","particleSize":"13.8 nm (crystal size)","structureLink":"Lower carbon content resulted in larger column width and lower surface roughness compared to 12C and 65C, correlating with the lowest activity."},{"paperId":"P181","catalystId":"P181_PERF_002","name":"12C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"12C","phase":"PdCx phase (x = 0.13–0.15)","particleSize":"32.5 nm (crystal size)","surfaceStates":"Pd0 (93%) and PdII (7%)","structureLink":"Intermediate carbon content led to intermediate column width and surface roughness, resulting in moderate activity."},{"paperId":"P181","catalystId":"P181_PERF_003","name":"65C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"65C","phase":"PdCx phase (x = 0.13–0.15)","particleSize":"10.2 nm (crystal size)","surfaceStates":"Pd0 (87%) and PdII (13%)","structureLink":"Highest carbon content led to the smallest column width, highest surface roughness and dispersion, and formation of PdCx phase, resulting in the highest activity but reduced CO2 selectivity.","deactivation":"Pd sintering due to elimination of carbon and/or segregation and agglomeration of Pd (crystal size increased from 10.2 nm to 58 nm)."},{"paperId":"P182","catalystId":"P182_PERF_001","name":"Pd(NO3)2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd(NO3)2","phase":"metallic Pd0","structureLink":"The activity is highly dependent on the coordinating ligands; nitrate ligands facilitate ligand exchange with formate more effectively than chloride or bipyridine ligands, promoting both Pd2+ reduction and FA decomposition.","deactivation":"Pd2+ was in situ reduced to Pd0 species (black particles)"},{"paperId":"P182","catalystId":"P182_PERF_002","name":"PdCl2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd chloride complexes (PdCl2, Na2PdCl4, Pd(NH3)4Cl2)","phase":"metallic Pd0","structureLink":"Chloride ligands resulted in nearly no activity over 1 hour, possibly due to rapid nanoparticle aggregation induced by weakened zeta-potential."},{"paperId":"P182","catalystId":"P182_PERF_003","name":"Na2PdCl4","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd chloride complexes (PdCl2, Na2PdCl4, Pd(NH3)4Cl2)","phase":"metallic Pd0","structureLink":"Chloride ligands resulted in nearly no activity over 1 hour, possibly due to rapid nanoparticle aggregation induced by weakened zeta-potential."},{"paperId":"P182","catalystId":"P182_PERF_004","name":"Pd(NH3)4Cl2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd chloride complexes (PdCl2, Na2PdCl4, Pd(NH3)4Cl2)","phase":"metallic Pd0","structureLink":"Chloride ligands resulted in nearly no activity over 1 hour, possibly due to rapid nanoparticle aggregation induced by weakened zeta-potential."},{"paperId":"P182","catalystId":"P182_PERF_005","name":"Pd(OAc)2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd(OAc)2","phase":"metallic Pd0","structureLink":"Showed significantly improved dehydrogenation kinetics compared to chloride-based complexes."},{"paperId":"P183","catalystId":"P183_PERF_001","name":"Pd@UIO-66/NH2-SEP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@UIO-66/NH2-SEP","phase":"Pd nanoparticles supported on a composite of sepiolite (SEP) and UIO-66; XRD identifies monoclinic (m-ZrO2) and tetragonal (t-ZrO2) phases of zirconia characteristic of the UIO-66 structure.","particleSize":"2.3 nm","surfaceStates":"Electronic states of Pd NPs are modified by the surface MOF framework and amino functionalities on SEP; synergistic effects exist between Pd NPs, Zr species, and amino groups.","structureLink":"The UIO-66 framework exerts a sacrificial effect, preventing the agglomeration of Pd nanoparticles on the fibrous NH2-SEP structure, which maintains high catalytic activity and reusability over 8 cycles.","deactivation":"UIO-66 framework prevents agglomeration of Pd nanoparticles on NH2-SEP through a sacrificial effect."},{"paperId":"P183","catalystId":"P183_PERF_002","name":"Pd@NH2-SEP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@NH2-SEP","particleSize":"2.0 nm (fresh); increases to over 3.6 nm after 3 cycles due to serious aggregation.","surfaceStates":"Amino groups on SEP modify the electronic states of Pd NPs.","structureLink":"Lack of MOF framework leads to rapid particle aggregation and poor reusability after 3 cycles.","deactivation":"Serious aggregation of Pd particles observed (average size increased from 2.0 nm to over 3.6 nm) after three repeated cycles."},{"paperId":"P183","catalystId":"P183_PERF_003","name":"Pd@UIO-66","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@UIO-66","phase":"Pd nanoparticles on UIO-66; XRD matches simulated pure UIO-66 crystal structure.","structureLink":"The single MOF support is less stable than the dual-support system, leading to structural changes and poor reusability.","deactivation":"Lamellar structure becomes evidently thinner after 3 uses and particle agglomeration is very obvious."},{"paperId":"P184","catalystId":"P184_PERF_001","name":"Pd0.8Au0.2/UiO-66-(NH2)2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.8Au0.2/UiO-66-(NH2)2","phase":"Alloy; HRTEM lattice spacing of ~0.229 nm is between Pd(111) (0.224 nm) and Au(111) (0.235 nm).","particleSize":"0.5 - 1.1 nm","surfaceStates":"XPS shows Pd 0 (340.51 and 334.77 eV) and Au 0 (86.37 and 84.23 eV); N 1s binding energy shift from 399.46 eV to 400.47 eV indicates interaction between NPs and amino groups.","structureLink":"The higher concentration of amino groups in the diamine support increases hydrophilicity and coordination ability, resulting in tinier nanoparticles (<1.1 nm) and better stability against aggregation compared to monoamine supports, which leads to a higher TOF (3660 h-1).","deactivation":"no obvious loss of noble metal ingredients ((Au+Pd)/Zr molar ratio 0.060 fresh vs 0.059 spent); BET surface area decreased from 745 to 522 m2/g and pore volume from 0.61 to 0.49 cm3/g, suggesting some cavities were blocked"},{"paperId":"P184","catalystId":"P184_PERF_002","name":"Pd0.8Au0.2/UiO-66-NH2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.8Au0.2/UiO-66-(NH2)2","phase":"Alloy; HRTEM lattice spacing of ~0.229 nm is between Pd(111) (0.224 nm) and Au(111) (0.235 nm).","particleSize":"0.5 - 1.1 nm","surfaceStates":"XPS shows Pd 0 (340.51 and 334.77 eV) and Au 0 (86.37 and 84.23 eV); N 1s binding energy shift from 399.46 eV to 400.47 eV indicates interaction between NPs and amino groups.","structureLink":"The higher concentration of amino groups in the diamine support increases hydrophilicity and coordination ability, resulting in tinier nanoparticles (<1.1 nm) and better stability against aggregation compared to monoamine supports, which leads to a higher TOF (3660 h-1).","deactivation":"AuPd NPs aggregated to a mean size of 2.4 nm"},{"paperId":"P185","catalystId":"P185_PERF_001","name":"Pd60Au40/ZrSBA-15-AP","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd60Au40/ZrSBA-15-AP","phase":"PdAu alloy NPs","particleSize":"Below 2 nm","surfaceStates":"Partial electron transfer from Au to Pd, evidenced by XPS binding energy shifts (Pd 3d shifted to lower values; Au 4f shifted to higher values)","structureLink":"The coexistence of small PdAu alloy NPs and suitable amino groups provides highly efficient bifunctional sites for synergistic activation of formic acid molecules."},{"paperId":"P185","catalystId":"P185_PERF_002","name":"Pd60Au40/ZrSBA-15","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd60Au40/ZrSBA-15","phase":"PdAu alloy NPs","particleSize":"7 nm","structureLink":"Inactive under test conditions due to larger particle size and lack of amino groups."},{"paperId":"P185","catalystId":"P185_PERF_003","name":"Pd60Au40/ZrSBA-15-MAP, Pd60Au40/ZrSBA-15-AEAEAP, Pd60Au40/ZrSBA-15-AEAP, Pd60Au40/ZrSBA-15-DMAP","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd60Au40/ZrSBA-15","phase":"PdAu alloy NPs","particleSize":"7 nm","structureLink":"Inactive under test conditions due to larger particle size and lack of amino groups."},{"paperId":"P186","catalystId":"P186_PERF_001","name":"1Pd-SS","activeMetals":"Pd","metalClass":"Pd-only","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition"},{"paperId":"P186","catalystId":"P186_PERF_002","name":"5Pd-SS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"15Pd-SS","phase":"Pd/TiO2 (anatase/rutile mixture)","particleSize":"< 2 nm","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"Higher activation energy (Ea = 34.5 kJ/mol) compared to SD-FSP counterparts due to lower PdO:Pd0 ratio.","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition"},{"paperId":"P186","catalystId":"P186_PERF_003","name":"15Pd-SS","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"15Pd-SS","phase":"Pd/TiO2 (anatase/rutile mixture)","particleSize":"< 2 nm","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"Higher activation energy (Ea = 34.5 kJ/mol) compared to SD-FSP counterparts due to lower PdO:Pd0 ratio.","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition"},{"paperId":"P186","catalystId":"P186_PERF_004","name":"35Pd-SD","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"35Pd-SD","phase":"Tetragonal crystalline PdO phase (confirmed by XRD and Raman); TiO2 support","particleSize":"Aggregated particles; low SSA (49.3 m2/g)","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"Lowest activation energy (Ea = 23.2 kJ/mol) due to highest [PdO:Pd0] ratio, but lower overall rate than 15Pd-SD due to low SSA.","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition"},{"paperId":"P186","catalystId":"P186_PERF_005","name":"15Pd-SD","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"15Pd-SD","phase":"Tetragonal crystalline PdO; TiO2 support","particleSize":"Aggregated formations on TiO2 surface","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"High [PdO:Pd0] ratio leads to high H2 production rate (534 mmol/g Pd/min) and lower activation energy (Ea = 26.5 kJ/mol).","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition"},{"paperId":"P186","catalystId":"P186_PERF_006","name":"5Pd-Lean","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"5Pd-Lean","phase":"Pd/TiO2 (predominantly rutile phase TiO2)","particleSize":"Large rutile TiO2 particles (~29.7 nm); tendency to form large Pd particles","surfaceStates":"Pd0, Pd1+, Pd2+","structureLink":"Lowest [PdO:Pd0] ratio correlates with the highest activation energy (Ea = 55.1 kJ/mol) and lowest efficiency.","deactivation":"reduction of surficial PdO to Pd0 by produced H2; secondary effect from carbonate deposition"},{"paperId":"P187","catalystId":"P187_PERF_001","name":"Pd/ZrO2-F","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/ZrO2-F","phase":"Metallic Pd nanoparticles on ZrO2 support.","particleSize":"Support particle size approximately 200 nm.","surfaceStates":"Dominantly zerovalent Pd (Pd0) with minor oxidized states (Pd2+); oxygen vacancy content is 15.98%.","structureLink":"Synergistic effect of m-ZrO2 and t-ZrO2 phases promotes FA dehydrogenation, achieving the highest TOF (1348 h-1) due to balanced dissociation and recombination steps."},{"paperId":"P187","catalystId":"P187_PERF_002","name":"Pd/ZrO2-S","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/ZrO2-S","phase":"Metallic Pd nanoparticles on ZrO2 support.","particleSize":"Hollow sphere structure with diameter of 100 nm; total particle size range 100-200 nm.","surfaceStates":"Dominantly zerovalent Pd (Pd0); electron-rich state due to interaction with m-ZrO2; oxygen vacancy content is 11.38%.","structureLink":"High specific surface area (194.8 m2/g) and electron-rich Pd sites facilitate FA dissociation but lack the synergistic recombination advantage of mixed phases."},{"paperId":"P187","catalystId":"P187_PERF_003","name":"Pd/ZrO2-P","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/ZrO2-P","phase":"Metallic Pd nanoparticles on ZrO2 support.","particleSize":"Irregular particles with size approximately 20 nm.","surfaceStates":"Dominantly zerovalent Pd (Pd0); electron-deficient state due to interaction with t-ZrO2; highest oxygen vacancy content at 21.65%.","structureLink":"Strong metal-support interaction and electron-deficient Pd sites facilitate H recombination but inhibit the rate-determining FA dissociation step, leading to lower TOF (577 h-1)."},{"paperId":"P188","catalystId":"P188_PERF_001","name":"Au2Pd3@(P)N-C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au2Pd3@(P)N-C","phase":"AuPd alloy","particleSize":"1.5 ± 0.4 nm","surfaceStates":"Surface contains pyridinic, pyrrolic, and graphitic N; Au 4f and Pd 3d doublets shift to lower binding energies compared to monometallic counterparts; addition of Au decreases the oxidation of Pd.","structureLink":"The phosphate-mediation approach ensures a uniform distribution of ultrafine AuPd NPs, which results in significantly higher catalytic activity (TOF of 5400 h−1 at 30 °C) compared to catalysts prepared without phosphate mediation (Au2Pd3@N-C)."},{"paperId":"P188","catalystId":"P188_PERF_002","name":"Au2Pd3@N-C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au2Pd3@N-C","particleSize":"2.1 ± 0.6 nm","structureLink":"Larger particle size and poor dispersion lead to much lower catalytic activity (TOF of 1350 h−1 at 30 °C) compared to the phosphate-mediated catalyst."},{"paperId":"P188","catalystId":"P188_PERF_003","name":"Au2Pd3/N-C-hydrogen phosphate","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au2Pd3@N-C","particleSize":"2.1 ± 0.6 nm","structureLink":"Larger particle size and poor dispersion lead to much lower catalytic activity (TOF of 1350 h−1 at 30 °C) compared to the phosphate-mediated catalyst."},{"paperId":"P188","catalystId":"P188_PERF_004","name":"AuPd/ZIF-8","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","deactivation":"ZIF-8 is totally decomposed in the FA/SF system (pH = 5)"},{"paperId":"P189","catalystId":"P189_PERF_001","name":"Pd/PAN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PAN","phase":"Pd nanoparticles","particleSize":"9 nm","surfaceStates":"Metallic Pd(0) (binding energies at 335.1 and 340.7 eV)"},{"paperId":"P189","catalystId":"P189_PERF_002","name":"PdCo0.6/PAN","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"PdCo0.6/PAN","phase":"Bimetallic alloy NPs","particleSize":"1.6 nm","surfaceStates":"Predominantly metallic Pd(0) and Co (778.3 eV), with minor oxidized species (Pd 2+ at 336.3/341.6 eV, Co at 782.0 eV)","structureLink":"Addition of Co reduces particle size and influences chemical states or forms novel basic sites to enhance FA activation; eCN groups stabilize NPs against aggregation or leaching.","deactivation":"Strong chemical affinity of eCN groups stabilizes Pd NPs against aggregation or leaching"},{"paperId":"P189","catalystId":"P189_PERF_003","name":"PdFe0.9/PAN","activeMetals":"Pd-Fe","metalClass":"Pd-based multimetal","matchedCharacterization":"PdFe0.9/PAN","phase":"Bimetallic alloy NPs","particleSize":"2.5 nm","surfaceStates":"Predominantly metallic Pd(0) and Fe (707.3 eV), with minor oxidized species (Pd 2+ at 336.3/341.6 eV, Fe at 711.5 eV)","structureLink":"Addition of Fe reduces particle size and influences chemical states or forms novel basic sites to enhance FA activation; eCN groups stabilize NPs against aggregation or leaching."},{"paperId":"P190","catalystId":"P190_PERF_001","name":"Pd@M1/20NB","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@M1/20NB","phase":"Cubic Pd (XRD peaks attenuated due to small particle size)","particleSize":"Mean size 0.762 nm (range 0.4-1.4 nm)","surfaceStates":"Pd0 and PdII species present","structureLink":"Ultrafine particles, high dispersion, and hierarchical pore structure (1-3 nm) of the NPC support facilitate fast mass transfer and provide more surface sites, leading to a TOF of 446 h-1. Pyridinic N in the support modulates electronic properties of Pd.","deactivation":"Gradual deactivation attributed to agglomeration of Pd particles (size increased from ~0.762 nm to 1.67 nm after first run and 2.21 nm after second run)."},{"paperId":"P190","catalystId":"P190_PERF_002","name":"Pd@U1/20NB","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@U1/20NB","phase":"Cubic Pd (XRD peaks attenuated)","particleSize":"Mean size 1.06 nm","surfaceStates":"Pd0 and PdII species present","structureLink":"Smaller particle size and higher dispersion compared to Pd@WBA result in enhanced activity (TOF = 307 h-1)."},{"paperId":"P190","catalystId":"P190_PERF_003","name":"Pd@WBA","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@WBA","phase":"Cubic Pd (sharp XRD peaks at 2θ = 40.3° and 46.7°)","particleSize":"Larger than Pd@NPC catalysts","surfaceStates":"Pd0 and PdII species present","structureLink":"Lower dispersion and larger particle size result in the lowest activity (TOF = 156 h-1)."},{"paperId":"P191","catalystId":"P191_PERF_001","name":"Pd/C in situ reduction","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C in situ reduction","phase":"Pd crystal, specifically the Pd(111) plane (lattice spacing 0.22–0.23 nm).","particleSize":"1.86 nm","surfaceStates":"Pd(II) to Pd(0) ratio of 0.49:0.51 (approximately 1:1).","structureLink":"The optimum valence composition (1:1 Pd(0)/Pd(II)) and ultra-small size result in high mass-specific activity (8.94 mol H2/(gPd·h)) and low activation energy (33.1 kJ/mol). Pd(0) sites facilitate adsorption while Pd(II) promotes desorption of formic acid and inhibits CO production.","deactivation":"Did not fully deactivate before complete decomposition of formic acid; decrease in rate attributed to dilute formic acid rather than activity loss"},{"paperId":"P191","catalystId":"P191_PERF_002","name":"Pd/C-EG reduction","activeMetals":"Pd","metalClass":"Pd-only","deactivation":"Deactivated by CO poisoning"},{"paperId":"P191","catalystId":"P191_PERF_003","name":"Pd/C-30% commercial","activeMetals":"Pd","metalClass":"Pd-only","deactivation":"Deactivated by CO poisoning"},{"paperId":"P192","catalystId":"P192_PERF_001","name":"Pd/rGO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/rGO","phase":"Pd","particleSize":"3.7 nm (TEM), 5 nm (XRD)","structureLink":"Activation energy for FA dehydrogenation is 28.5 kJ/mol without SF and 24.4 kJ/mol with SF promoter."},{"paperId":"P192","catalystId":"P192_PERF_002","name":"PdAu/rGO","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAu/rGO","phase":"PdAu alloy","particleSize":"2.9 nm (TEM), 3.5 nm (XRD)","surfaceStates":"STEM-EDX suggests segregation with gold concentrated on the surface and palladium in the core.","structureLink":"Smaller particles, good dispersion, and synergistic effect lead to superior activity and a significantly lower activation energy of 13.4 kJ/mol."},{"paperId":"P193","catalystId":"P193_PERF_001","name":"Pd0.90Ag0.10B/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.90Ag0.10B/rGO","phase":"Low crystallinity PdAgB alloy; exhibits lattice expansion with a (1 1 1) spacing of 0.233 nm; HAADF-STEM indicates an alloy structure rather than core-shell.","surfaceStates":"Electron-rich Pd active sites (Pd 3d binding energies: 341.0 eV and 335.8 eV) resulting from electron transfer from Ag, B, and rGO to Pd atoms.","structureLink":"The combination of engineered alloy nanostructure and electronic modification by boron promotes C–H scission in the absorbed HCOO* intermediate, which is the rate-determining step for formic acid dehydrogenation.","deactivation":"Activity loss possibly attributed to the aggregation of rGO during the reaction process."},{"paperId":"P193","catalystId":"P193_PERF_002","name":"Pd0.90Ag0.10/rGO","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.90Ag0.10/rGO","phase":"PdAg alloy with face-centered cubic (fcc) structure; lattice spacing of (1 1 1) is 0.230 nm.","particleSize":"3.47 nm","surfaceStates":"Pd 3d binding energies are higher than those of Pd0.90Ag0.10B/rGO.","structureLink":"Displays lower activity compared to the boron-doped version despite smaller particle size, highlighting the promotional effect of B."},{"paperId":"P193","catalystId":"P193_PERF_003","name":"PdB/rGO","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdB/rGO","phase":"Low crystallinity PdB alloy; XRD shows diffraction peaks shifted toward lower 2θ values, indicating enlargement of Pd–Pd interatomic distance due to B incorporation.","particleSize":"9.45 nm","surfaceStates":"Pd 3d binding energies: 341.25 eV and 336.05 eV.","structureLink":"Relatively low activity attributed to uneven dispersion and large mean particle size."},{"paperId":"P194","catalystId":"P194_PERF_001","name":"Pd/C-Li, Pd/C-Na, Pd/C-Ca, Pd/C-Ba","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C-Li","phase":"fcc Pd crystal","particleSize":"3.0-6.5 nm (range for series)","surfaceStates":"Pd(0) (67% ± 1%) and Pd(II) (33% ± 1%)","structureLink":"Small particle size inhibits formic acid dehydration and extends catalyst life by reducing adjacent Pd(0) face sites.","deactivation":"Deactivation occurs via the formic acid dehydration pathway (CO formation); deactivation rate increases with increasing particle size."},{"paperId":"P195","catalystId":"P195_PERF_001","name":"Pd-ZrO2/SBA-15-NH2","activeMetals":"Pd-Zr","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-ZrO2/SBA-15-NH2","phase":"Pd(111) phase identified; ZrO2 present but not detected by wide-angle XRD due to low content","particleSize":"1.5 nm (increased to 1.9 nm after reusability test)","surfaceStates":"Electron-rich metallic Pd surface due to electron donation from ZrO2; strong metal-support interaction (SMSI) between NPs and SBA-15-NH2 substrate indicated by positive shift in N 1s XPS peak; abundant basic sites from ZrO2 and -NH2 groups","structureLink":"Synergistic electronic effects of Pd and ZrO2, SMSI with the support, and high density of surface basic sites promote C-H bond splitting and FA deprotonation, leading to a TOF of 1408 h-1 and 100% H2 selectivity","deactivation":"Mean particle size increased from 1.5 to 1.9 nm after reusability tests; possible catalyst loss during recycle process and adsorption of impurities on surface."},{"paperId":"P195","catalystId":"P195_PERF_002","name":"Pd/SBA-15-NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/SBA-15-NH2","particleSize":"1.7 nm","structureLink":"Lower activity and selectivity compared to Pd-ZrO2/SBA-15-NH2 due to lack of ZrO2 promoter"},{"paperId":"P196","catalystId":"P196_PERF_001","name":"Pd6Ir4/KIT-6-NH2","activeMetals":"Pd-Ir","metalClass":"Pd-based multimetal","deactivation":"Slight increase in the size of PdIr NPs and small decrease of amino-groups amounts"},{"paperId":"P196","catalystId":"P196_PERF_003","name":"PdIr/KIT-6 (bare)","activeMetals":"Pd-Ir","metalClass":"Pd-based multimetal","matchedCharacterization":"PdIr/KIT-6","phase":"PdIr alloy","particleSize":"7.4 nm","structureLink":"Almost no catalytic activity compared to amino-modified support due to larger particle size and lack of amino-group promotion."},{"paperId":"P197","catalystId":"P197_PERF_001","name":"Ru/CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru/CNTs","phase":"Metallic Ru nanoparticles","particleSize":"2.3 ± 0.6 nm","surfaceStates":"Metallic Ru0 (XPS Ru3p3/2 main maximum at 462.6–462.9 eV)"},{"paperId":"P197","catalystId":"P197_PERF_002","name":"Ru/1.9%N-CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru/1.9%N-CNTs","phase":"Metallic Ru nanoparticles","particleSize":"1.7 ± 0.3 nm","surfaceStates":"Positively charged small metal particles (Ruδ+); XPS Ru3p3/2 main peak shifted toward higher binding energies by 0.2–0.3 eV compared to Ru/CNTs due to interaction with pyridinic nitrogen centers (Ruδ+–NPy)"},{"paperId":"P197","catalystId":"P197_PERF_003","name":"Ru/3.0%N-CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru/3.0%N-CNTs","phase":"Metallic Ru nanoparticles","particleSize":"1.6 ± 0.3 nm","surfaceStates":"Positively charged small metal particles (Ruδ+); XPS Ru3p3/2 main peak shifted toward higher binding energies by 0.2–0.3 eV compared to Ru/CNTs due to interaction with pyridinic nitrogen centers (Ruδ+–NPy)"},{"paperId":"P197","catalystId":"P197_PERF_004","name":"Ru/4.8%N-CNTs (3 wt.%)","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru/4.8%N-CNTs","phase":"Metallic Ru nanoparticles and single atoms","particleSize":"1.5 ± 0.3 nm","surfaceStates":"Positively charged small metal particles (Ruδ+) and single atoms stabilized by pyridinic nitrogen centers (Ruδ+–NPy); HAADF-STEM confirms coexistence of nanoparticles and single Ru atoms","structureLink":"Presence of sub-nanoparticles and single atoms increases catalytic activity and selectivity in formic acid decomposition (FAD) but has no effect on catalytic wet air oxidation (CWAO) of phenol.","deactivation":"In CWAO: partial oxidation/destruction of N-CNTs leading to carbonaceous deposits blocking Ru surface; iron leaching (3 wt.%) and minor ruthenium loss (0.05 wt.%) observed"},{"paperId":"P198","catalystId":"P198_PERF_001","name":"Pd0.6Co0.2Ni0.2/CNSC","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.6Co0.2Ni0.2/CNSC","phase":"Trimetallic alloy phase; lattice spacing of 0.216 nm (between fcc Pd, Co, and Ni).","particleSize":"1.70 nm","surfaceStates":"Electron-rich Pd species resulting from electron transfer from Co and Ni (due to electronegativity differences) and from the CNSC support to the metal NPs.","structureLink":"The Schiff base conjugation enhances affinity between the support and metals, leading to smaller, well-dispersed nanoparticles and increased electron density on Pd active sites, which promotes FA dehydrogenation activity.","deactivation":"Slight degradation attributed to agglomeration of metal nanoparticles; ICP-AES ruled out metal leaching"},{"paperId":"P198","catalystId":"P198_PERF_002","name":"Pd0.6Co0.2Ni0.2/g-C3N4","activeMetals":"Pd-Co-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.6Co0.2Ni0.2/g-C3N4","phase":"Trimetallic phase","particleSize":"2.00 nm","surfaceStates":"Lower electron density on Pd active sites compared to the CNSC-supported catalyst.","structureLink":"Larger particle size and lower electron density on Pd lead to significantly lower catalytic activity (TOF = 33 h-1) compared to Pd0.6Co0.2Ni0.2/CNSC."},{"paperId":"P199","catalystId":"P199_PERF_001","name":"γ-Mo2N/ 0.2 NK-C","activeMetals":"Mo","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"γ-Mo2N/x NK-C (specifically γ-Mo2N/0.2 NK-C)","phase":"γ-Mo2N (cubic phase, PDF #25-1366)","particleSize":"2.1 nm","surfaceStates":"Surface contains Moδ+ (nitride), Mo6+ (oxide), K+, pyridinic-N, and pyrrolic-N. Acid-base properties include Brønsted and Lewis acid sites (B/L ratio 0.17) and three distinct basic sites (desorption temperatures at 174, 268, and 402 °C).","structureLink":"γ-Mo2N nanoparticles are responsible for the rate-limiting H-C bond cleavage of adsorbed HCOO-. K-containing sites promote HCOO- generation and adsorption; N-doped sites act as Lewis base sites for H+ adsorption. Water molecules occupy Brønsted acid sites, inhibiting FA dehydration to CO.","deactivation":"Significant K leaching (80.6%) occurred after the stability test; Mo leaching was negligible (2.5 mg/L). Air oxidation at 400 °C caused remarkable deactivation."},{"paperId":"P200","catalystId":"P200_PERF_001","name":"Pd-NPs@TA-COP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd-NPs@TA-COP","phase":"Metallic Pd (XRD peaks at 2θ = 38.32°, 44.55°, 64.73°, 77.81°, and 81.92° corresponding to planes 111, 200, 220, 311, and 222)","particleSize":"2.52 nm","surfaceStates":"Pd(0)","structureLink":"Synergistic effects between the nitrogen-rich TA-COP support and Pd nanoparticles enhance catalytic activity; the N-rich support prevents nanoparticle aggregation.","deactivation":"Lack of Pd NPs aggregations after six runs verified by TEM image."},{"paperId":"P201","catalystId":"P201_PERF_003","name":"PdAg/C","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAg/CA-x (x=1-5)","phase":"PdAg alloy nanoparticles; confirmed by Pd and Ag K-edge EXAFS showing Pd-Ag bonds with longer interatomic distances than pure Pd-Pd or Ag-Ag bonds.","particleSize":"5.6 nm for PdAg/CA-5; 4.5-6.5 nm for other PdAg/CA-x specimens.","surfaceStates":"XPS shows Pd 3d and Ag 3d peaks shifted to higher binding energies in amine-functionalized supports compared to PdAg/C, indicating altered electronic states due to surface amine groups.","structureLink":"D2 selectivity correlates with the basicity of grafted amine groups (measured by FA adsorption energy Ead); alloying with Ag promotes C-H bond dissociation; surface amine groups promote O-H bond dissociation and govern isotope selectivity."},{"paperId":"P201","catalystId":"P201_PERF_005","name":"unsupported PdAg NPs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","deactivation":"aggregation into larger particles under the catalytic reaction conditions"},{"paperId":"P202","catalystId":"P202_PERF_001","name":"Pd/CDs-III","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CDs-III","phase":"Cubic Pd (JCPDS: 46-1043)","particleSize":"1.94 nm","surfaceStates":"Pd0 binding energy of 335.10 eV; presence of N-Pd coordination (XPS peak at 398.3 eV)","structureLink":"Highest pyridine nitrogen content (34.7%) leads to the smallest particle size and highest electron density on Pd, facilitating C-H bond rupture; Pd2+ promotes HCOO* adsorption via Coulomb interaction.","deactivation":"Slight decrease in activity due to growth of Pd particles and decrease in N content leading to decrease in electron density of metal Pd"},{"paperId":"P202","catalystId":"P202_PERF_002","name":"Pd/CDs-II","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CDs-II","phase":"Cubic Pd (JCPDS: 46-1043)","particleSize":"2.28 nm","surfaceStates":"Pd0 binding energy of 335.32 eV","structureLink":"Pyridine nitrogen content (23.9%) correlates with reduced particle size and increased electron density on Pd."},{"paperId":"P202","catalystId":"P202_PERF_003","name":"Pd/CDs-I","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CDs-I","phase":"Cubic Pd (JCPDS: 46-1043)","particleSize":"2.65 nm","surfaceStates":"Pd0 binding energy of 335.58 eV","structureLink":"Pyridine nitrogen content (13.5%) influences Pd nanoparticle size and electron density."},{"paperId":"P202","catalystId":"P202_PERF_004","name":"Pd/XC-72","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/XC-72","phase":"Cubic Pd","surfaceStates":"Pd0 binding energy is approximately 0.8 eV higher than that of Pd/CDs-III","structureLink":"Lacks the electron-donating effect of pyridine nitrogen found in CD supports, resulting in lower catalytic activity."},{"paperId":"P203","catalystId":"P203_PERF_001","name":"Pd-loaded Tp-Azo-COF/SiO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd-loaded Tp-Azo-COF/SiO2","phase":"Pd(1 1 1) facet","particleSize":"nanoscale (referred to as Pd nanoclusters)","surfaceStates":"XPS analysis indicated the presence of two valence states: a dominant Pd0 state and some remaining adsorbed Pd2+.","structureLink":"C-NH containing carriers facilitate the decomposition of formic acid roots; Pd nanoclusters capture H+ ions from solution, where mutual collision on the Pd nanoscale surface catalyzes the formation of H2.","deactivation":"H2, CO2 and HCOO intermediates generated by the decomposition of formic acid occupy active sites and deactivate the catalyst"},{"paperId":"P204","catalystId":"P204_PERF_001","name":"Pd@NaA30700","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@NaA30700","phase":"Cubic Pd","particleSize":"3.61 nm","surfaceStates":"Pd0 and PdII","structureLink":"Hierarchical pores enhanced Pd nanoparticle dispersion and provided fast channels for reactants; the high mesopore surface area made active sites readily accessible and facilitated gas product diffusion, resulting in a TOF of 156 h-1.","deactivation":"Decline related to block of pores; recycled catalyst showed decreased surface area (SA BET = 645 m2 g-1, SA meso = 113 m2 g-1)"},{"paperId":"P204","catalystId":"P204_PERF_002","name":"Pd@KA30700","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@KA30700","phase":"Cubic Pd","particleSize":"1.31 nm","surfaceStates":"Pd0 and PdII","structureLink":"Hierarchical pores improved nanoparticle distribution, but lower mesopore surface area compared to Pd@NaA30700 led to lower catalytic activity (TOF = 83.0 h-1)."},{"paperId":"P205","catalystId":"P205_PERF_001","name":"0.3Pt/N-CNFs","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/N-CNFs","phase":"Single atoms and clusters (monolayer to few layers thick)","particleSize":"1.0 nm (mean size from conventional TEM for 1 wt% sample)","surfaceStates":"Ionic/electron-deficient state (Pt2+); XPS Pt 4f 7/2 binding energy ~72.1 eV (1.0 eV higher than bulk Pt powder).","structureLink":"Single Pt atoms stabilized by a pair of pyridinic nitrogen atoms at graphene edges provide high activity for formic acid decomposition and nearly 100% selectivity to H2."},{"paperId":"P205","catalystId":"P205_PERF_002","name":"1Pt/N-CNFs","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/N-CNFs","phase":"Single atoms and clusters (monolayer to few layers thick)","particleSize":"1.0 nm (mean size from conventional TEM for 1 wt% sample)","surfaceStates":"Ionic/electron-deficient state (Pt2+); XPS Pt 4f 7/2 binding energy ~72.1 eV (1.0 eV higher than bulk Pt powder).","structureLink":"Single Pt atoms stabilized by a pair of pyridinic nitrogen atoms at graphene edges provide high activity for formic acid decomposition and nearly 100% selectivity to H2."},{"paperId":"P205","catalystId":"P205_PERF_004","name":"1Pd/N-CNFs","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-CNFs","phase":"Single atoms and nanoparticles","particleSize":"2.3 nm (mean size from conventional TEM for 1 wt% sample)","surfaceStates":"Coexistence of metallic Pd0 (335.7 eV) and ionic Pd2+ (337.6 eV); ionic content is significantly higher in N-doped samples.","structureLink":"Unreducible Pd2+ species attached to pyridinic nitrogen are identified as the active sites for formic acid decomposition."},{"paperId":"P205","catalystId":"P205_PERF_006","name":"1Ru/N-CNFs","activeMetals":"Ru","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ru/N-CNFs","phase":"Nanoparticles","particleSize":"1.5 nm (mean size from conventional TEM for 1 wt% sample)","surfaceStates":"Electron-deficient Ru species; XPS Ru 3d 5/2 binding energy of 280.3 eV (0.3 eV higher than bulk Ru metal).","structureLink":"Ru interacts more strongly with the support than Pt or Pd, which correlates with lower catalytic activity for formic acid decomposition."},{"paperId":"P206","catalystId":"P206_PERF_001","name":"Pd/CTF-1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CTF-1","phase":"Single-atom catalyst; EXAFS/wavelet transform indicated a low content of small Pd clusters with Pd-Pd distance of 2.74 Å.","particleSize":"Single atoms (observed as individual bright dots in HAADF/STEM)","surfaceStates":"Pd2+ state; best EXAFS model corresponds to Pd-C2N2 sites (Pd-C: 2.05 Å, Pd-N: 2.09 Å).","structureLink":"The highest catalytic activity was associated with the presence of Pd2+-C2N2 sites."},{"paperId":"P206","catalystId":"P206_PERF_002","name":"Pd/pyCTF","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/pyCTF","phase":"Single-atom catalyst; EXAFS indicated a low content of small Pd clusters with Pd-Pd distances of 2.71-2.72 Å.","particleSize":"Single atoms (observed as individual bright dots in HAADF/STEM)","surfaceStates":"Pd2+ state; EXAFS showed strong peak corresponding to Pd-N4 sites (~2.04 Å).","structureLink":"Lower catalytic activity compared to Pd/CTF-1, associated with the formation of Pd2+-N4 sites."},{"paperId":"P206","catalystId":"P206_PERF_003","name":"Pd/bipyCTF","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/bipyCTF","phase":"Single-atom catalyst; EXAFS indicated a low content of small Pd clusters with Pd-Pd distances of 2.71-2.72 Å.","particleSize":"Single atoms (observed as individual bright dots in HAADF/STEM)","surfaceStates":"Pd2+ state; EXAFS showed strong peak corresponding to Pd-N4 sites (~2.04 Å).","structureLink":"Lower catalytic activity compared to Pd/CTF-1, associated with the formation of Pd2+-N4 sites."},{"paperId":"P206","catalystId":"P206_PERF_004","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"Metallic Pd nanoparticles with surface oxide layer.","particleSize":"2.3 ± 0.3 nm","surfaceStates":"Mixed oxidation states: Pd0 (335.5 eV) and Pd2+ in Pd oxide (336.8 eV).","structureLink":"Active sites involve the surface of Pd metal nanoparticles; less stable and selective than single-atom CTF catalysts.","deactivation":"notable deactivation"},{"paperId":"P207","catalystId":"P207_PERF_001","name":"Pd(6 wt %)/KIE-8-d","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd(6 wt %)/KIE-8","phase":"nanoparticles","particleSize":"5.8 nm (KIE-8-f), 6.8 nm (KIE-8-g), 9.7 nm (KIE-8-e), 16.3 nm (KIE-8-d)","surfaceStates":"Electronic structure of Pd nanoparticles depends on the intensity ratio of graphitic nitrogen to pyridinic nitrogen in the support.","structureLink":"Catalytic activity for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content, pore structure (higher surface area and pore volume), and resulting Pd nanoparticle size and dispersion. Higher graphitic nitrogen content improves TOF."},{"paperId":"P207","catalystId":"P207_PERF_002","name":"Pd(6 wt %)/KIE-8-e","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd(6 wt %)/KIE-8","phase":"nanoparticles","particleSize":"5.8 nm (KIE-8-f), 6.8 nm (KIE-8-g), 9.7 nm (KIE-8-e), 16.3 nm (KIE-8-d)","surfaceStates":"Electronic structure of Pd nanoparticles depends on the intensity ratio of graphitic nitrogen to pyridinic nitrogen in the support.","structureLink":"Catalytic activity for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content, pore structure (higher surface area and pore volume), and resulting Pd nanoparticle size and dispersion. Higher graphitic nitrogen content improves TOF."},{"paperId":"P207","catalystId":"P207_PERF_003","name":"Pd(6 wt %)/KIE-8-f","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd(6 wt %)/KIE-8","phase":"nanoparticles","particleSize":"5.8 nm (KIE-8-f), 6.8 nm (KIE-8-g), 9.7 nm (KIE-8-e), 16.3 nm (KIE-8-d)","surfaceStates":"Electronic structure of Pd nanoparticles depends on the intensity ratio of graphitic nitrogen to pyridinic nitrogen in the support.","structureLink":"Catalytic activity for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content, pore structure (higher surface area and pore volume), and resulting Pd nanoparticle size and dispersion. Higher graphitic nitrogen content improves TOF."},{"paperId":"P207","catalystId":"P207_PERF_004","name":"Pd(6 wt %)/KIE-8-g","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd(6 wt %)/KIE-8","phase":"nanoparticles","particleSize":"5.8 nm (KIE-8-f), 6.8 nm (KIE-8-g), 9.7 nm (KIE-8-e), 16.3 nm (KIE-8-d)","surfaceStates":"Electronic structure of Pd nanoparticles depends on the intensity ratio of graphitic nitrogen to pyridinic nitrogen in the support.","structureLink":"Catalytic activity for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content, pore structure (higher surface area and pore volume), and resulting Pd nanoparticle size and dispersion. Higher graphitic nitrogen content improves TOF."},{"paperId":"P207","catalystId":"P207_PERF_005","name":"Pd(6 wt %)/N-charcoal","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd(6 wt %)/N-charcoal","structureLink":"Lower catalytic activity compared to Pd/KIE-8 is attributed to the microporous structure of the activated charcoal support.","deactivation":"Lower catalytic activity compared to Pd/KIE-8 is attributed to the microporous structure of activated charcoal."},{"paperId":"P208","catalystId":"P208_PERF_001","name":"Pt/TiB2-600","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/TiB2","phase":"Core-shell nanostructure consisting of a Pt core encapsulated by a TiB2 overlayer with distinctive Pt-B bonds at the interface.","particleSize":"Average size below 3 nm (Pt/TiB2-500: 2.28 ± 0.1 nm; Pt/TiB2-600: 2.37 ± 0.1 nm; Pt/TiB2-800: 2.43 ± 0.1 nm).","surfaceStates":"TiO x-terminated TiB2 overlayers serve as active sites; charge transfer occurs from TiB2 to Pt, evidenced by a negative shift in Pt 4f XPS binding energy.","structureLink":"Maximum HCOOH dehydrogenation activity is achieved with Pt/TiB2-600, where Pt nanoparticles are completely encapsulated by a thin layer of TiB2. The encapsulated Pt acts as an electronic modulator for the active TiO x-terminated TiB2 overlayers."},{"paperId":"P208","catalystId":"P208_PERF_002","name":"Pt/TiB2-300","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/TiB2","phase":"Core-shell nanostructure consisting of a Pt core encapsulated by a TiB2 overlayer with distinctive Pt-B bonds at the interface.","particleSize":"Average size below 3 nm (Pt/TiB2-500: 2.28 ± 0.1 nm; Pt/TiB2-600: 2.37 ± 0.1 nm; Pt/TiB2-800: 2.43 ± 0.1 nm).","surfaceStates":"TiO x-terminated TiB2 overlayers serve as active sites; charge transfer occurs from TiB2 to Pt, evidenced by a negative shift in Pt 4f XPS binding energy.","structureLink":"Maximum HCOOH dehydrogenation activity is achieved with Pt/TiB2-600, where Pt nanoparticles are completely encapsulated by a thin layer of TiB2. The encapsulated Pt acts as an electronic modulator for the active TiO x-terminated TiB2 overlayers."},{"paperId":"P209","catalystId":"P209_PERF_001","name":"PdAcet. Acet./Cdarco","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdAcet. Acet./Cdarco","phase":"cubic palladium metal","particleSize":"2.8 nm (TEM), 3 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase"},{"paperId":"P209","catalystId":"P209_PERF_002","name":"PdCl2 W./Cdarco","activeMetals":"Pd-W","metalClass":"Pd-based multimetal","matchedCharacterization":"PdCl2 W./Cdarco","phase":"cubic palladium metal","particleSize":"6.5 nm (TEM), 47 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase"},{"paperId":"P209","catalystId":"P209_PERF_003","name":"Pd(NO3)2 Acet./Cdarco","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd(NO3)2 Acet./Cdarco","phase":"cubic palladium metal","particleSize":"8.8 nm (TEM), 13 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase"},{"paperId":"P209","catalystId":"P209_PERF_004","name":"Pd(NO3)2 W./Cdarco","activeMetals":"Pd-W","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd(NO3)2 W./Cdarco","phase":"cubic palladium metal","particleSize":"12 nm (TEM), 25 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase"},{"paperId":"P209","catalystId":"P209_PERF_005","name":"PdAcet. W./Cdarco","activeMetals":"Pd-W","metalClass":"Pd-based multimetal","matchedCharacterization":"PdAcet. W./Cdarco","phase":"cubic palladium metal","particleSize":"17 nm (TEM), 98 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase"},{"paperId":"P209","catalystId":"P209_PERF_006","name":"PdCl2 Acet./Cdarco","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"PdCl2 Acet./Cdarco","phase":"cubic palladium metal","particleSize":"58 nm (TEM), 180 nm (XRD)","surfaceStates":"Low coordination (LC, edges and corners) and high coordination (HC, terraces)","structureLink":"Activity is more strongly influenced by low coordinated sites than total surface atoms; volcano-type relationship with optimal size around 4-5 nm.","deactivation":"activity drop assigned to the formation of intermediate species such as COH or CHOO that block the active phase"},{"paperId":"P210","catalystId":"P210_PERF_002","name":"Pd@S-1","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@S-1","phase":"Monometallic Pd clusters","particleSize":"Subnanometric/ultrasmall","surfaceStates":"Pd anchored on silanol defects of zeolite framework."},{"paperId":"P210","catalystId":"P210_PERF_003","name":"Pd@S-1-0.005NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@S-1","phase":"Monometallic Pd clusters","particleSize":"Subnanometric/ultrasmall","surfaceStates":"Pd anchored on silanol defects of zeolite framework."},{"paperId":"P210","catalystId":"P210_PERF_004","name":"Pd@S-1-0.01NH2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@S-1","phase":"Monometallic Pd clusters","particleSize":"Subnanometric/ultrasmall","surfaceStates":"Pd anchored on silanol defects of zeolite framework."},{"paperId":"P210","catalystId":"P210_PERF_005","name":"Pd@S-1-0.005CH3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@S-1","phase":"Monometallic Pd clusters","particleSize":"Subnanometric/ultrasmall","surfaceStates":"Pd anchored on silanol defects of zeolite framework."},{"paperId":"P211","catalystId":"P211_PERF_001","name":"Pd/O-NCNTs-P","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/O-NCNTs-P","phase":"Metallic Pd (lattice fringes ~0.220 nm corresponding to (111) plane)","particleSize":"3.5 ± 1.1 nm (fresh); 3.8 ± 0.7 nm (after 6 cycles)","surfaceStates":"Pd2+ (73.2%) and Pd0 (26.8%); electron-deficient Pd2+ with a 0.5 eV positive shift in binding energy compared to Pd/NCNTs-P","structureLink":"High Pd2+/Pd0 ratio regulates electronic structure to promote formation of active intermediates (Pd-HCOO* and H*); charge repulsion among Pd2+ species prevents agglomeration; OCGs and -NH2 enhance metal-support interaction for high stability.","deactivation":"no leaching of Pd species was observed"},{"paperId":"P211","catalystId":"P211_PERF_002","name":"Pd/NCNTs-P","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NCNTs-P","structureLink":"Lack of oxygen plasma pretreatment results in fewer anchoring sites (OCGs), leading to poor Pd nanoparticle dispersion and lower catalytic activity."},{"paperId":"P211","catalystId":"P211_PERF_003","name":"Pd/O-NCNTs-C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/O-NCNTs-C","phase":"Metallic Pd (lattice fringes ~0.220 nm); after 6 cycles, XRD shows peaks for Pd (111), (200), and (220) facets","particleSize":"3.8 ± 0.6 nm (fresh); 6.2 ± 1.0 nm (after 6 cycles)","surfaceStates":"Pd2+ (37.4%) and Pd0 (62.6%); Pd2+ content decreased to 18.9% after 6 cycles","structureLink":"Excess NaBH4 reduces OCGs and -NH2 groups, weakening metal-support interaction and leading to lower Pd2+ content, which results in nanoparticle agglomeration and poor stability.","deactivation":"small amount of leaching of Pd species; agglomeration of Pd species observed via XRD (peaks at 40, 47, and 68 degrees)"},{"paperId":"P212","catalystId":"P212_PERF_001","name":"Pd-tetrahedron–TiO2","activeMetals":"Pd-Ti","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-tetrahedron–TiO2","phase":"Pd tetrahedrons","particleSize":"6.3 nm","surfaceStates":"covered by {111} facets","structureLink":"Mott–Schottky junction allows photoexcited electrons in TiO2 to transfer to Pd, increasing electron density and promoting HCOOH dehydrogenation under UV light."},{"paperId":"P212","catalystId":"P212_PERF_006","name":"Pd@Pb-tetrahedron–TiO2","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@Pb-tetrahedron–TiO2","phase":"Pd@Pb alloy surface","surfaceStates":"Low work function but large atomic radius","structureLink":"Catalytic activity is suppressed by surface poisoning due to the large atomic radius of Pb.","deactivation":"suppressed by surface poisoning due to large atomic radius of Pb"},{"paperId":"P213","catalystId":"P213_PERF_001","name":"D-Pd5Ag5 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"D-Pd5Ag5 NWs","phase":"fcc PdAg alloy; polycrystalline structure confirmed by SAED and XRD peaks located between pure Pd and Ag","particleSize":"Seed Ag NPs diameter: 3.6 nm","surfaceStates":"Pd-rich surface; XPS shows binding energies of Ag 3d shifted to higher values and Pd 3d shifted to lower values compared to C-Pd5Ag5 NWs, indicating efficient electron transfer from Ag to Pd","structureLink":"Enhanced activity for FA dehydrogenation and ADN hydrogenation attributed to the Pd-rich surface, more efficient Ag-to-Pd electron transfer, high density of low coordination atoms/defects on kink surfaces, and a larger active surface area (0.40 cm2 mg-1)","deactivation":"No Pd in liquid phase; no obvious changes in Ag/Pd composition or morphology after 8 cycles"},{"paperId":"P213","catalystId":"P213_PERF_004","name":"C-Pd5Ag5 NWs","activeMetals":"Pd-Ag","metalClass":"Pd-based multimetal","matchedCharacterization":"C-Pd5Ag5 NWs","phase":"PdAg alloy","surfaceStates":"Less efficient electron transfer from Ag to Pd compared to D-Pd5Ag5 NWs (confirmed by XPS)","structureLink":"Lower catalytic activity and smaller active surface area (0.10 cm2 mg-1) compared to D-Pd5Ag5 NWs"},{"paperId":"P214","catalystId":"P214_PERF_001","name":"Pd/APC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/APC","phase":"Pd0 crystalline phase","particleSize":"about 2.3 nm","surfaceStates":"Amine groups (-NH-, -NH2) identified by N 1s signal at 399.9 eV; surface Pd atoms are partially oxidized (Pd2+).","structureLink":"Amine species promote the anchoring and dispersion of ultrafine Pd NPs, while providing an alkaline, electron-donating environment that facilitates formic acid deprotonation.","deactivation":"Low tolerance to CO (activity decreased sharply upon exposure); no leaching of Pd observed (4.62 wt.% initial vs 4.58 wt.% recycled)."},{"paperId":"P214","catalystId":"P214_PERF_002","name":"Pd/PPC","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PPC","phase":"Pd0 crystalline phase","particleSize":"3.2 nm","structureLink":"Larger particle size and inferior dispersion result in lower catalytic activity relative to the amine-functionalized support."},{"paperId":"P214","catalystId":"P214_PERF_003","name":"Pd/APC*","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/APC","phase":"Pd0 crystalline phase","particleSize":"about 2.3 nm","surfaceStates":"Amine groups (-NH-, -NH2) identified by N 1s signal at 399.9 eV; surface Pd atoms are partially oxidized (Pd2+).","structureLink":"Amine species promote the anchoring and dispersion of ultrafine Pd NPs, while providing an alkaline, electron-donating environment that facilitates formic acid deprotonation."},{"paperId":"P215","catalystId":"P215_PERF_001","name":"Pd-Cu/TiO2-NSs (3:7)","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-Cu/TiO2-NSs (3:7)","phase":"Face-centered cubic (fcc) Pd-Cu alloy; XRD peaks are positioned between pure fcc Pd and pure fcc Cu with a lattice spacing of 0.217 nm for the (111) plane.","particleSize":"4.44 ± 0.08 nm","surfaceStates":"Pd 3d5/2 peaks at 334.7 eV (Pd0) and 335.9 eV (Pd2+); Cu 2p3/2 signal at approximately 932 eV; Ti exists primarily as Ti4+ with a mixed-valence Ti3+/Ti4+ state observed upon co-catalyst addition.","structureLink":"Synergistic electronic interactions, d-band center shift, and strong metal-support interaction (SMSI) lower the activation energy for O-H bond cleavage to 15 kJ/mol. Electron transfer from TiO2 support to PdCu alloy and from Cu to Pd increases electron density on Pd, enhancing catalytic activity."},{"paperId":"P216","catalystId":"P216_PERF_001","name":"Ni0.2Co0.8–Soy","activeMetals":"Ni-Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ni0.2Co0.8–Soy","phase":"Co-rich fcc Ni–Co solid solution/alloy (lattice spacing 0.2043 nm).","particleSize":"4.8 ± 1.2 nm","surfaceStates":"Surface contains pyridinic N, pyrrolic N, graphitic N; pentavalent phosphorus (P5+) and P–O bonds; and K+ species that impart surface basicity.","structureLink":"The Ni-Co alloy structure promotes the dehydrogenation pathway and suppresses CO formation. K-derived basic sites enhance formic acid adsorption and initial decomposition, while small particle size increases active site density.","deactivation":"Slight decrease in K content from 4.99 wt% to 4.69 wt% after cycling; slight decline in conversion observed over cycles."},{"paperId":"P216","catalystId":"P216_PERF_002","name":"Ni-Soy","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ni-Soy","phase":"fcc Ni (PDF#87–0712)","surfaceStates":"Contains N, P, and K species from soybean precursor.","structureLink":"High conversion efficiency but poor CO2 selectivity due to dominant dehydration pathway leading to CO formation."},{"paperId":"P216","catalystId":"P216_PERF_003","name":"Co-Soy","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co-Soy","phase":"fcc Co (PDF#15–0806)","surfaceStates":"Contains N, P, and K species from soybean precursor.","structureLink":"Higher CO2 selectivity but lower conversion efficiency than Ni-based counterparts."},{"paperId":"P217","catalystId":"P217_PERF_002","name":"Pd-Au/AC","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-Au/AC","phase":"Bimetallic alloy structure; XRD shows a broad band at 2θ = 38.4° between Au(111) and Pd(111); HRTEM d-spacing is 2.29 Å.","particleSize":"6.83 nm","surfaceStates":"Electron-enriched Pd due to electron transfer from Au; XPS shows a downshift in Pd 0 3d binding energy (Pd 0 3d5/2 at 335.73 eV vs 335.92 eV for Pd/AC) and a positive shift in Au 4f peaks.","structureLink":"Electron-enriched Pd favors adsorption of active intermediate species during CO2 hydrogenation to FA and facilitates the formation of metal-formate composites during dehydrogenation."},{"paperId":"P217","catalystId":"P217_PERF_003","name":"Pd-Cu/AC","activeMetals":"Pd-Cu","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-Cu/AC","phase":"Bimetallic alloy structure; XRD peak for (111) plane at 2θ = 40.78° (between Pd/AC and Cu/AC); HRTEM d-spacing is 2.17 Å.","particleSize":"6.12 nm","surfaceStates":"Electron-enriched Pd; XPS shows a downshift in Pd 0 3d binding energy (Pd 0 3d5/2 at 335.86 eV vs 335.92 eV for Pd/AC).","structureLink":"Smaller particle size compared to Pd-Au/AC and the presence of positively charged Cu sites (Cu2+) increase contact efficiency between reactants and active centers, enhancing hydrogenation activity."},{"paperId":"P218","catalystId":"P218_PERF_001","name":"Co@Cr(OH)3/ZrO2","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co@Cr(OH)3/ZrO2","phase":"Tetragonal phase of ZrO2 (confirmed by XRD and SAED); Co present as nanoparticles.","particleSize":"3.75 nm (fresh), 4.19 ± 0.42 nm (used)","surfaceStates":"Cr exists in the 3+ state (XPS Cr 2p peaks at 577.9 and 587.8 eV). ZrO2 is tetragonal with lattice fringes d-spacing of 0.288 nm corresponding to the (111) plane.","structureLink":"High catalytic activity (TOF 7685 h-1) is attributed to the small size and uniform dispersion of Co NPs, synergistic interactions between Co NPs, Cr(OH)3 atoms, and ZrO2 sites, and a mesoporous structure with a pore size of 8.24 nm that improves mass transfer.","deactivation":"Slight decrease in activity in 5th cycle attributed to increase in Co NP size from 3.75 ± 0.24 nm (fresh) to 4.19 ± 0.42 nm (used)"},{"paperId":"P218","catalystId":"P218_PERF_003","name":"Co@Cr(OH)3","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co@Cr(OH)3/ZrO2","phase":"Tetragonal phase of ZrO2 (confirmed by XRD and SAED); Co present as nanoparticles.","particleSize":"3.75 nm (fresh), 4.19 ± 0.42 nm (used)","surfaceStates":"Cr exists in the 3+ state (XPS Cr 2p peaks at 577.9 and 587.8 eV). ZrO2 is tetragonal with lattice fringes d-spacing of 0.288 nm corresponding to the (111) plane.","structureLink":"High catalytic activity (TOF 7685 h-1) is attributed to the small size and uniform dispersion of Co NPs, synergistic interactions between Co NPs, Cr(OH)3 atoms, and ZrO2 sites, and a mesoporous structure with a pore size of 8.24 nm that improves mass transfer."},{"paperId":"P218","catalystId":"P218_PERF_004","name":"Co@Cr(OH)3/ZrO2-Air","activeMetals":"Co","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Co@Cr(OH)3/ZrO2","phase":"Tetragonal phase of ZrO2 (confirmed by XRD and SAED); Co present as nanoparticles.","particleSize":"3.75 nm (fresh), 4.19 ± 0.42 nm (used)","surfaceStates":"Cr exists in the 3+ state (XPS Cr 2p peaks at 577.9 and 587.8 eV). ZrO2 is tetragonal with lattice fringes d-spacing of 0.288 nm corresponding to the (111) plane.","structureLink":"High catalytic activity (TOF 7685 h-1) is attributed to the small size and uniform dispersion of Co NPs, synergistic interactions between Co NPs, Cr(OH)3 atoms, and ZrO2 sites, and a mesoporous structure with a pore size of 8.24 nm that improves mass transfer."},{"paperId":"P219","catalystId":"P219_PERF_001","name":"4-PySI-Pd@Cu(BDC)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"4-PySI-Pd@Cu(BDC)","phase":"Single-site Pd grafted on Schiff-base decorated OMS-Cu(BDC) pore cage","surfaceStates":"Initial state is Pd(II); reduced to Pd(0) during reaction.","structureLink":"The para position of the coordination bond in 4-PySI provides a more open active site compared to 2-PySI, resulting in higher catalytic activity (TOF = 412 h⁻¹). Synergistic effects between Pd and the Schiff-base group enhance dehydrogenation.","deactivation":"No significant activity loss during reuse; XPS indicates reduction of Pd(II) to Pd(0) during reaction"},{"paperId":"P219","catalystId":"P219_PERF_002","name":"2-PySI-Pd@Cu(BDC)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"2-PySI-Pd@Cu(BDC)","phase":"Single-site Pd grafted on Schiff-base decorated OMS-Cu(BDC) pore cage","structureLink":"Lower activity (TOF = 315 h⁻¹) compared to 4-PySI-Pd@Cu(BDC) due to a less open active site resulting from the ortho position of the coordination bond."},{"paperId":"P220","catalystId":"P220_PERF_001","name":"Pd90Rh10/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","deactivation":"Partial leaching of Rh in the reaction solution; coalescence of particles"},{"paperId":"P220","catalystId":"P220_PERF_002","name":"Pd69Rh31/HHT","activeMetals":"Pd-Rh","metalClass":"Pd-based multimetal","deactivation":"Leaching of Rh in the solution; limited growing of average particle size from 2.5 to 3.0 nm"},{"paperId":"P220","catalystId":"P220_PERF_003","name":"Pd/HHT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/HHT","phase":"Monometallic","particleSize":"3.2 ± 0.8 nm (fresh); 4.5 ± 1.3 nm (used)","structureLink":"Rapid deactivation attributed to particle coalescence and CO poisoning.","deactivation":"Leaching of 5% of Pd; agglomeration and coalescence (particle size increased from 3.0 to 4.7 nm); poisoning by CO"},{"paperId":"P220","catalystId":"P220_PERF_006","name":"Rh/HHT","activeMetals":"Rh","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Rh/HHT","phase":"Monometallic","particleSize":"3.5 ± 1.1 nm","structureLink":"Showed very low activity in formic acid dehydrogenation."},{"paperId":"P221","catalystId":"P221_PERF_001","name":"Au/N-SBA-15_K(9.5)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/N-SBA-15_K(9.5)","particleSize":"0.8 ± 0.2 nm","structureLink":"Smallest particle size correlated with highest productivity, reaching full conversion of formic acid at 115 °C."},{"paperId":"P221","catalystId":"P221_PERF_002","name":"Au/N-SBA-15_K(11)","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/N-SBA-15_K(11)","particleSize":"0.9 ± 0.2 nm","structureLink":"Second smallest particle size correlated with high productivity, reaching full conversion of formic acid at 115 °C."},{"paperId":"P221","catalystId":"P221_PERF_003","name":"Au/SBA-15","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/SBA-15","particleSize":"26 ± 18 nm","structureLink":"Largest particles did not reach full conversion at 350 °C and showed lower selectivity to hydrogen (53%) with higher CO formation (44%)."},{"paperId":"P222","catalystId":"P222_PERF_001","name":"Gly-Cu/Ag/MnO2","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Gly-Cu/Ag/MnO2","phase":"Ternary nanocomposite","particleSize":"Crystallite size ca. 30 nm; spherical NPs 10-50 nm; overall chain/rod structures up to 100 nm","surfaceStates":"Glycine-capped; MnO2-doped Gly-Cu/Ag","structureLink":"Highest catalytic activity (TOF = 146 h-1, Ea = 56 kJ/mol) attributed to strong metal-metal interactions and synergistic electronic effects between Cu, Ag, and MnO2.","deactivation":"Stability decreased due to the release of MnO2 from the surface by formic acid."},{"paperId":"P222","catalystId":"P222_PERF_002","name":"Gly-Cu/Ag","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Gly-Cu/Ag","phase":"Cu/Ag core-shell","particleSize":"15 nm","surfaceStates":"Glycine-capped","structureLink":"Higher catalytic activity than Gly-Cu due to the incorporation of Ag."},{"paperId":"P222","catalystId":"P222_PERF_003","name":"Gly-Cu","activeMetals":"Cu","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Gly-Cu","particleSize":"40 nm","surfaceStates":"Glycine-capped","structureLink":"Shows no effect on the decomposition of formic acid compared to multi-metal systems."},{"paperId":"P223","catalystId":"P223_PERF_001","name":"Pd/N-MSC-30-two-175","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-MSC-30-two-175","phase":"Metallic palladium (111 reflection)","particleSize":"1.4 nm","surfaceStates":"Pd 3d 5/2 peaks at 335.9 eV (Pd 0) and 337.5 eV (Pd 2+); N 1s peaks at 400.0 eV (amine/amide groups) and 398.7 eV (pyridinic N).","structureLink":"The ultrasmall size, high specific surface area, and synergistic effect between Pd NCs and N-functional groups (acting as base sites for FA deprotonation) result in a high TOF of 8414 h-1. Pore confinement prevents aggregation."},{"paperId":"P223","catalystId":"P223_PERF_002","name":"Pd/N-MSC-30-one","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/N-MSC-30-one","phase":"Pd phase (distinct diffraction peaks)","particleSize":"Contains some large particles due to aggregation","surfaceStates":"N 1s peaks at 400.0 eV and 398.7 eV.","structureLink":"Lower TOF (5408 h-1) compared to Pd/N-MSC-30-two-175 due to poorer dispersity of Pd NCs."},{"paperId":"P223","catalystId":"P223_PERF_003","name":"Pd/MSC-30","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MSC-30","phase":"Pd phase (distinct diffraction peaks)","particleSize":"2.6 nm","structureLink":"Poor catalytic performance relative to the N-functionalized counterpart due to larger particle size."},{"paperId":"P224","catalystId":"P224_PERF_004","name":"Pd@Ag nanocubes","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd@Ag nanocubes","phase":"Bimetallic (Ag-modified Pd)","particleSize":"14.4 nm","surfaceStates":"Ag atoms modified at both edge and plane sites of the Pd nanocube","structureLink":"Ag modification accelerates HCOOH decomposition (the limiting step), promoting overall tandem reaction TOF by generating Had not only at edges but also on planes."},{"paperId":"P225","catalystId":"P225_PERF_001","name":"Pd/EDA-PAN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/EDA-PAN","phase":"Pd nanoparticles","particleSize":"1.2 nm","surfaceStates":"Fresh catalyst contains both Pd0 and Pd2+, with Pd2+ as the dominant species; spent catalyst remains consistent with fresh state.","structureLink":"The coexistence of Pd0 and Pd2+ and the ultra-small particle size (1.2 nm) are linked to improved catalytic activity for formic acid dehydrogenation. Strong metal-support interaction provided by amino groups enhances chemical stability.","deactivation":"Particle size of Pd NPs increased slightly after five recycling experiments, but structural stability is excellent."},{"paperId":"P225","catalystId":"P225_PERF_002","name":"Pd/PAN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/PAN","phase":"Pd nanoparticles","particleSize":"1.6 nm","surfaceStates":"Fresh catalyst consists primarily of Pd0 (binding energies 336.0 and 341.2 eV); spent catalyst shows formation of Pd2+ (338.1 and 343.2 eV).","deactivation":"Particle size of Pd NPs increased slightly after five recycling experiments."},{"paperId":"P226","catalystId":"P226_PERF_001","name":"6Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"6Ni/N-LC","phase":"Single-atom","surfaceStates":"Fresh state contains Ni2+ bonded to N (855.5 eV) and O (856.6 eV); reduced to metallic/Ni-N species.","structureLink":"Highest reaction rate and lowest apparent activation energy (95 kJ/mol), indicating superior activity of single-atom sites over nanoparticles.","deactivation":"XPS showed Ni content decrease (from 0.48 at.% to 0.27 at.%) and formation of Ni-Ni bonds, indicating metal agglomeration/migration."},{"paperId":"P226","catalystId":"P226_PERF_002","name":"8Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"8Ni/N-LC","phase":"Single-atom (implied by activity and Ea)","surfaceStates":"Ni2+ bonded to N and O in fresh state.","structureLink":"Activity and activation energy (99 kJ/mol) are close to 6Ni/N-LC, suggesting similar electronic states of active Ni species."},{"paperId":"P226","catalystId":"P226_PERF_003","name":"10Ni/N-LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"10Ni/N-LC","phase":"Sub-nanosized particles","particleSize":"Average 0.84 ± 0.24 nm (range 0.2 to 1.6 nm)","surfaceStates":"Ni2+ bonded to N and O; presence of Ni-Ni bonds (853.0 eV in XPS) indicates particle formation.","structureLink":"Lower activity and higher activation energy (105 kJ/mol) compared to single-atom catalysts.","deactivation":"XPS showed Ni content decrease (from 0.81 at.% to 0.26 at.%) and slight increase in Ni-Ni bonding intensity, indicating lower mobility than single atoms."},{"paperId":"P226","catalystId":"P226_PERF_004","name":"10Ni/LC","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"10Ni/LC","phase":"Nanoparticles","surfaceStates":"High fraction of Ni-Ni bonds","structureLink":"Highest activation energy (126 kJ/mol) and highest temperature for complete conversion (320 °C)."},{"paperId":"P226","catalystId":"P226_PERF_005","name":"10Ni/LC_NH3","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"10Ni/LCNH3","phase":"Nanoparticles","surfaceStates":"High fraction of Ni-Ni bonds","structureLink":"Activation energy (115 kJ/mol) and conversion temperature (340 °C) are higher than for N-LC supported catalysts."},{"paperId":"P227","catalystId":"P227_PERF_001","name":"Pd/NC800","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NC800","phase":"fcc Pd (plane spacing 0.224 nm corresponding to (1 1 1) plane)","particleSize":"XRD: 2.89 nm, TEM: 2.45 nm","surfaceStates":"Highest level of D3 carbon defects (amorphous carbon); high content of sp3 carbon defects; Pd2+/Pd0 ratio is 0.93.","structureLink":"Topological defects promote electron transfer from sp3 carbon to Pd, enhancing metal-support interaction, stabilizing smaller NPs, and shifting the d-band center downward to facilitate HCOO adsorption."},{"paperId":"P227","catalystId":"P227_PERF_002","name":"Pd/NC700","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NC700","phase":"fcc Pd","particleSize":"XRD: 2.92 nm, TEM: 2.84 nm","surfaceStates":"Contains pyridinic N (7.23 wt%), pyrrolic N (4.99 wt%), and graphitic N (1.58 wt%); Pd2+/Pd0 ratio is 0.35.","structureLink":"Lower topological defect density compared to Pd/NC800 leads to lower catalytic activity."},{"paperId":"P227","catalystId":"P227_PERF_003","name":"Pd/NC900","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NC900","phase":"fcc Pd","particleSize":"XRD: 3.16 nm, TEM: 3.46 nm","surfaceStates":"Reduced carbon defects and N content due to high-temperature evaporation; Pd2+/Pd0 ratio is 0.62.","structureLink":"Decrease in topological defect content and N concentration leads to a sharp decline in TOF for formic acid dehydrogenation."},{"paperId":"P228","catalystId":"P228_PERF_001","name":"Pd0.75Au0.25/NH2-SPP","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.75Au0.25/NH2-SPP","phase":"PdAu alloy nanoparticles (XRD peak at 39.2°; lattice spacings of 0.231 nm for (111) and 0.198 nm for (200); EDS line scan confirms uniform alloy without intraparticle segregation)","particleSize":"0.76 nm","surfaceStates":"Electron-rich surface resulting from electron donation from the NH2-SPP support and electron migration from Pd to Au due to electronegativity differences.","structureLink":"Ultrahigh dispersion and electronic synergy between Pd and Au optimize FA adsorption and C-H bond cleavage; hydrophobic surface promotes contact with FA molecules; amino groups act as proton scavengers promoting O-H bond dissociation."},{"paperId":"P228","catalystId":"P228_PERF_002","name":"Pd/NH2-SPP","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NH2-SPP","phase":"Metallic Pd (no XRD peaks observed due to high dispersion)","surfaceStates":"Pd0","structureLink":"Stronger adsorption toward HCOOH molecules compared to PdAu alloy, which is less conducive to forming the key HCOO* intermediate."},{"paperId":"P229","catalystId":"P229_PERF_001","name":"Au0.3Pd0.7/A-M-β-CD","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/A-M-β-CD","phase":"Alloy structure; HRTEM lattice spacing is 0.231 nm (between Au 0.235 nm and Pd 0.224 nm); XRD shows a broad diffraction peak for the (111) plane located between those of Au and Pd; HAADF-STEM mapping confirms co-distribution of Au and Pd.","particleSize":"~2.0 nm","surfaceStates":"Binding energies of Pd 3d and Au 4f are shifted to negative values relative to unsupported NPs, indicating electron transfer from the A-M-β-CD support to the AuPd NPs; charge transfer also occurs between Pd and Au within the alloy structure.","structureLink":"The combination of ultrafine particle size, excellent dispersion, and electron-rich active sites (via strong metal-support interaction) accelerates the rate-determining step for C–H cleavage of adsorbed HCOO* intermediates, resulting in a high TOF of 7352 h-1.","deactivation":"slightly increased particle size (by ~0.7 nm) after the 4th run"},{"paperId":"P229","catalystId":"P229_PERF_003","name":"Au0.3Pd0.7/M-β-CD","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/M-β-CD","particleSize":"~5.2 nm"},{"paperId":"P229","catalystId":"P229_PERF_004","name":"Au0.3Pd0.7-A","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7-A","particleSize":"~3.4 nm","surfaceStates":"No obvious shift for Pd 3d and Au 4f XPS peaks compared to unsupported NPs, indicating no bond formed between AuPd and APTES amine groups."},{"paperId":"P229","catalystId":"P229_PERF_005","name":"Au0.3Pd0.7/C","activeMetals":"Au-Pd","metalClass":"Pd-based multimetal","matchedCharacterization":"Au0.3Pd0.7/C","particleSize":"~4.8 nm"},{"paperId":"P230","catalystId":"P230_PERF_001","name":"Pd/NMC-400","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF."},{"paperId":"P230","catalystId":"P230_PERF_002","name":"Pd/NMC-500","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF."},{"paperId":"P230","catalystId":"P230_PERF_003","name":"Pd/NMC-600","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF."},{"paperId":"P230","catalystId":"P230_PERF_004","name":"Pd/NMC-700","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF."},{"paperId":"P230","catalystId":"P230_PERF_005","name":"Pd/NMC-800","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/NMC","phase":"Metallic Pd","particleSize":"1.2-1.4 nm (for carbonization temperatures >= 500 °C); 2.7 ± 0.6 nm (for Pd/NMC-400)","surfaceStates":"Pd exists as metallic and bivalent states; strong metal-support interaction via Pd-N covalent bonds, particularly with pyridinic N.","structureLink":"Ultrasmall particle size and high dispersion expose more active sites. Pyridinic N facilitates FA deprotonation, while metallic Pd sites facilitate C-H bond activation; a trade-off between these two determines the TOF."},{"paperId":"P230","catalystId":"P230_PERF_006","name":"Pd/MC-600","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/MC-600","phase":"Metallic Pd","particleSize":"8.1 ± 3.9 nm (range: 2.3-20.9 nm)","surfaceStates":"Predominantly metallic Pd due to weak interaction between Pd and carbon support.","structureLink":"Larger, nonuniform particle size and lack of N-doping result in significantly lower H2 production compared to Pd/NMC."},{"paperId":"P231","catalystId":"P231_PERF_001","name":"Pd/NH2-CNT (also referred to as Pd/CNTs (Cit and APTES))","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNT","phase":"Metallic Pd nanoparticles","particleSize":"13.9 nm (CO chemisorption)","structureLink":"Severely aggregated particles with a small number of active surface atoms result in negligible catalytic activity.","deactivation":"Sintering of Pd particles (during regeneration); fouling of reactants/products or accumulation of CO adsorbed on Pd (without regeneration)."},{"paperId":"P231","catalystId":"P231_PERF_002","name":"Pd/CNT","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNT","phase":"Metallic Pd nanoparticles","particleSize":"13.9 nm (CO chemisorption)","structureLink":"Severely aggregated particles with a small number of active surface atoms result in negligible catalytic activity."},{"paperId":"P231","catalystId":"P231_PERF_003","name":"Pd/CNT (Cit)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNT (Cit)","phase":"Metallic Pd nanoparticles","particleSize":"2.93 ± 0.63 nm (TEM), 2.4 nm (CO chemisorption)","structureLink":"Smaller particle size compared to Pd/CNT improves activity, but requires SF additive for noticeable performance."},{"paperId":"P231","catalystId":"P231_PERF_004","name":"Pd/CNT (APTES)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/CNT (APTES)","phase":"Metallic Pd nanoparticles","particleSize":"2.03 ± 0.37 nm (TEM), 2.0 nm (CO chemisorption)","surfaceStates":"Pd 0 peak shifted to higher binding energy due to interaction with amine functional groups; high proportion of Pd 2+.","structureLink":"Amine functional groups provide a proton-scavenging effect, enabling activity even in FA-only reactants."},{"paperId":"P231","catalystId":"P231_PERF_005","name":"Pd/C (APTES)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C (APTES)","phase":"Metallic Pd nanoparticles","particleSize":"2.09 nm (TEM)","structureLink":"Lower activity than Pd/NH2-CNT despite similar Pd size and amine groups, attributed to mass transport limitations caused by micropores in activated carbon."},{"paperId":"P232","catalystId":"P232_PERF_001","name":"Pd0.6Au0.4/VXC-72-NH2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.6Au0.4/VXC-72-NH2","phase":"PdAu alloy (confirmed by XRD after annealing at 773 K in Ar)","particleSize":"1.5 nm","surfaceStates":"Metallic Au0 and Pd0; partial electron transfer from Pd to Au due to electronegativity differences; electron transfer from VXC-72-NH2 support to PdAu NPs increasing electron density of active centers.","structureLink":"Amine functionalization converts the hydrophobic carbon surface to hydrophilic, enabling ultra-fine particle size and high dispersion. The resulting electronic modulation increases electron density on PdAu, facilitating metal-formate formation and enhancing FA dehydrogenation rate.","deactivation":"no obvious loss of N, Au and Pd in recycled catalyst determined by ICP-AES"},{"paperId":"P232","catalystId":"P232_PERF_002","name":"Pd0.6Au0.4/VXC-72","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd0.6Au0.4/VXC-72","phase":"PdAu alloy (XRD peak at 38.7°)","particleSize":"3.0 nm","surfaceStates":"Higher binding energies for Pd 3d and Au 4f compared to Pd0.6Au0.4/VXC-72-NH2","structureLink":"Lack of amine groups results in larger particle size and lower catalytic activity."},{"paperId":"P232","catalystId":"P232_PERF_003","name":"Au/VXC-72-NH2","activeMetals":"Au","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Au/VXC-72-NH2","phase":"metallic Au (XRD peak at 38.2°)","particleSize":"null","surfaceStates":"null","structureLink":"No activity for FA dehydrogenation without Pd."},{"paperId":"P233","catalystId":"P233_PERF_001","name":"Pd3Co2/CeZrSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd3Co2/CeZrSBA-15-NH2","phase":"PdCo alloy; HRTEM lattice spacing of 0.223 nm (between Pd 0.23 nm and Co 0.21 nm).","particleSize":"1.6 nm","surfaceStates":"Electron-rich PdCo alloy NPs; XPS shows a shift to lower binding energy for Pd0 (335.6 eV) and higher for Co0 (781.1 eV), indicating electron transfer from Co to Pd and from the amine-functionalized support via metal-support interaction (MSI).","structureLink":"The combination of ultrafine size, high dispersion, short channels in the support facilitating mass transfer, electronic synergistic effects between Pd and Co, and MSI with CeZrSBA-15-NH2 enhances catalytic activity.","deactivation":"Recovered catalyst showed slightly increased particle size of 2.7 nm (from 1.6 nm) and partial reduction in amine functionalities."},{"paperId":"P233","catalystId":"P233_PERF_007","name":"Pd3Co2/ZrSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd3Co2/ZrSBA-15-NH2","phase":"PdCo alloy","particleSize":"2.3 nm"},{"paperId":"P233","catalystId":"P233_PERF_008","name":"Pd3Co2/CeSBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd3Co2/CeSBA-15-NH2","phase":"PdCo alloy","particleSize":"2.5 nm"},{"paperId":"P233","catalystId":"P233_PERF_009","name":"Pd3Co2/SBA-15-NH2","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd3Co2/SBA-15-NH2","phase":"PdCo alloy","particleSize":"2.6 nm"},{"paperId":"P233","catalystId":"P233_PERF_010","name":"Pd3Co2/CeZrSBA-15","activeMetals":"Pd-Co","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd3Co2/CeZrSBA-15","phase":"PdCo alloy","particleSize":"5.1 nm","structureLink":"Lack of surface amine groups leads to larger particle size and negligible catalytic activity."},{"paperId":"P234","catalystId":"P234_PERF_001","name":"Pd/DUT-67-PZDC(10)","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/DUT-67-PZDC(10)","phase":"fcc Pd (111) plane","particleSize":"1.7 nm","surfaceStates":"Electron deficient Pd NPs resulting from electron transfer from Pd to the N sites of the DUT-67-PZDC support (indicated by a shift in N 1s peak from 400.3 eV to 399.2 eV).","structureLink":"The ultrasmall size and high dispersion expose more catalytic active sites; the hierarchical microporous structure of the MOF stabilizes the NPs; and dual N sites on the support act as proton buffers to stimulate O-H bond cleavage in formic acid.","deactivation":"Recovered catalyst showed Pd NPs aggregation (size increased from 1.7 nm to 1.9 nm) and partial loss of Pd content."},{"paperId":"P234","catalystId":"P234_PERF_005","name":"Pd/DUT-67-PZDC-CH3","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/DUT-67-PZDC-CH3","particleSize":"2.6 nm","structureLink":"Introduction of methyl groups weakened the proton buffer ability and led to larger particle size and lower dispersion, reducing catalytic activity."},{"paperId":"P234","catalystId":"P234_PERF_006","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","structureLink":"Less active than Pd/DUT-67-PZDC(10), demonstrating the significance of the MOF support."},{"paperId":"P235","catalystId":"P235_PERF_001","name":"Pd60Au40/HPC-NH2","activeMetals":"Pd-Au","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd60Au40/HPC-NH2","phase":"PdAu alloy","particleSize":"~2 nm (specifically 2.04 nm)","surfaceStates":"Pd loses partial electrons to Au due to electronegativity differences (Au: 2.4, Pd: 2.2); strong interaction between metal and amine-modified support verified by N 1s XPS shift.","structureLink":"Synergistic effect of electronic properties (electron transfer from Pd to Au), geometric effects (dilution of Pd surface ensembles by Au), basic amine sites, and hierarchically porous structure for effective mass transport of bubbles."},{"paperId":"P236","catalystId":"P236_PERF_001","name":"Pd/C-0T","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C-0T","phase":"Metallic Pd","particleSize":"2.5 nm (TEM), 2.4 nm (CO chemisorption)","surfaceStates":"Pd(0): 24.3%, Pd(II): 75.7% (XPS)","structureLink":"Smallest size provides highest activity due to maximum active sites and lowest activation energy (44.9 kJ/mol)."},{"paperId":"P236","catalystId":"P236_PERF_002","name":"Pd/C-4T","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C-4T","phase":"Metallic Pd","particleSize":"4.8 nm (TEM), 5.0 nm (CO chemisorption)","surfaceStates":"Pd(0): 60.0%, Pd(II): 40.0% (XPS)","structureLink":"Lowest activity due to fewest active sites and highest activation energy (63.9 kJ/mol)."},{"paperId":"P237","catalystId":"P237_PERF_001","name":"Pd/UiO-67@NN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/UiO-67@NN","phase":"Face-centered cubic (fcc) Pd","particleSize":"2.1 nm","surfaceStates":"Electron-rich Pd0 active sites (Pd 3d5/2 at 335.1 eV) resulting from strong metal-support interaction (MSI) where bipyridyl sites donate electrons to Pd NPs.","structureLink":"Bipyridyl sites facilitate the formation of ultrasmall, highly dispersed Pd NPs and act as proton scavengers that promote O–H bond cleavage and store excess protons, reducing recombination of adsorbed HCOO- and H+ on active sites.","deactivation":"Slight growth in Pd NP size from 2.1 nm to 3.5 nm after cycling; minor decrease in Pd content from 14.86 wt% to 13.67 wt%"},{"paperId":"P237","catalystId":"P237_PERF_002","name":"Pd/UiO-67@N","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/UiO-67@N","phase":"Face-centered cubic (fcc) Pd","particleSize":"2.5 nm","surfaceStates":"Electron-rich Pd0 active sites (Pd 3d5/2 at 335.2 eV), though with weaker MSI compared to Pd/UiO-67@NN.","structureLink":"Monopyridyl groups provide some stabilization and electron donation, but result in larger particles and lower activity than bipyridyl sites."},{"paperId":"P237","catalystId":"P237_PERF_003","name":"Pd/UiO-67","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/UiO-67","phase":"Face-centered cubic (fcc) Pd","particleSize":"2.7 nm","surfaceStates":"Metallic Pd0 active sites (Pd 3d5/2 at 335.3 eV).","structureLink":"Lack of pyridyl functionalities leads to larger Pd NPs, lower dispersion, and the lowest catalytic activity among the three MOF-supported catalysts."},{"paperId":"P238","catalystId":"P238_PERF_001","name":"Pd-sCeO2/C","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-sCeO2/C","phase":"Face-centered cubic (FCC) structure for both Pd and CeO2; heterostructure formation.","particleSize":"2.6 nm","surfaceStates":"Preferential orientation of CeO2 (110) facet; highest Ce3+/Ce4+ ratio (0.36); highest oxygen vacancy ratio (Rb = 4.01); high hydrophilicity (contact angle 31.32°).","structureLink":"Synergism between the CeO2(110) facet and abundant oxygen vacancies creates electron-rich Pd centers, lowering activation energy to 20.41 kJ/mol and increasing TOF to 2691 h-1.","deactivation":"slight decrease is due to the loss of catalyst in the recovery process"},{"paperId":"P238","catalystId":"P238_PERF_002","name":"Pd/C","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/C","phase":"FCC structure.","particleSize":"3.0 nm","surfaceStates":"Surface contains quinones, C-O, and O=C-O functional groups; contact angle 27.93°.","structureLink":"Activity is higher than Pd-sCeO2 but lower than heterostructures due to lack of metal-oxide synergistic effects."},{"paperId":"P238","catalystId":"P238_PERF_003","name":"Pd-sCeO2","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-sCeO2","phase":"FCC structure; heterostructure.","particleSize":"3.6 nm","surfaceStates":"Preferential orientation of CeO2 (110) facet; lowest oxygen vacancy ratio among the listed catalysts (ID/IF2g = 0.48); contact angle 36.92°.","structureLink":"Poor activity due to Pd agglomeration and lower defect density compared to Pd-sCeO2/C."},{"paperId":"P238","catalystId":"P238_PERF_004","name":"Pd-rCeO2/C","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-rCeO2/C","phase":"FCC structure; heterostructure.","particleSize":"2.5 nm","surfaceStates":"Preferential orientation of CeO2 (200) facet; observed facets include (100) and (111); Ce3+/Ce4+ ratio = 0.29; oxygen vacancy ratio (Rb) = 3.28; contact angle 50.50°.","structureLink":"Lower activity than Pd-sCeO2/C due to different crystal facets and fewer oxygen vacancies."},{"paperId":"P238","catalystId":"P238_PERF_005","name":"Pd-oCeO2/C","activeMetals":"Pd-Ce","metalClass":"Pd-based multimetal","matchedCharacterization":"Pd-oCeO2/C","phase":"FCC structure; heterostructure.","particleSize":"2.8 nm","surfaceStates":"Preferential orientation of CeO2 (111) facet; lowest Ce3+/Ce4+ ratio (0.25); lowest oxygen vacancy ratio among heterostructures (Rb = 2.98); most hydrophobic (contact angle 79.76°).","structureLink":"Lowest activity among Pd-CeO2/C catalysts due to the dominance of the (111) facet and lower defect concentration."},{"paperId":"P239","catalystId":"P239_PERF_001","name":"Pd/AOP AN","activeMetals":"Pd","metalClass":"Pd-only","matchedCharacterization":"Pd/AOP AN","phase":"Single metal nanoparticles","particleSize":"7 nm to 40 nm","surfaceStates":"Pd 3d5/2 and Pd 3d3/2 binding energies at 335.8 eV and 341.2 eV correspond to Pd0.","structureLink":"Larger particle size compared to Pd/PAN results in lower catalytic activity; amidoxime groups stabilize nanoparticles against leaching or agglomeration."},{"paperId":"P239","catalystId":"P239_PERF_002","name":"PdNi6/AOP AN","activeMetals":"Pd-Ni","metalClass":"Pd-based multimetal","matchedCharacterization":"PdNi6/AOP AN","phase":"Bimetallic alloy nanoparticles","particleSize":"4 nm to 16 nm","surfaceStates":"Predominantly Pd0, with weak signals at 336.6 eV and 342.3 eV assigned to Pd2+; Ni 2p region showed poor resolution.","structureLink":"Formation of PdNi alloy nanoparticles adjusts the electronic structure of Pd for improved formic acid activation; amidoxime and cyano groups provide a basic environment for synergetic activation (forming HCOO-).","deactivation":"strong coordination ability of amidoxime groups stabilize the Pd-based NPs against leaching or agglomeration"},{"paperId":"P240","catalystId":"P240_PERF_001","name":"Ni0.8Mo0.2/ZIF-67@SiO2 yolk-shell","activeMetals":"Ni-Mo","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ni0.8Mo0.2/ZIF-67@SiO2 yolk-shell","phase":"Nano-patterned Ni–Mo solid solution/alloy.","particleSize":"5.22 nm (fresh), 4.44 nm (after 10 cycles)","surfaceStates":"Fresh: Ni2+ (856.60 eV, 870.57 eV), Mo3+ (229.02 eV), Mo4+ (231.81, 234.72 eV), Mo6+ (235.13 eV), and Co(II). Used: Ni3+, Mo4+, and Co3+ are dominant.","structureLink":"High activity attributed to the synergistic effect between NiMo NPs and ZIF-67@SiO2 supporter, ultra-fine dispersion of NPs, and electron transfer from the bi-support to the NiMo NPs which facilitates C–H cleavage of formic acid.","deactivation":"marginally reduced catalytic activity attributed to mean size of NiMo NPs decreasing from 5.22 to 4.44 nm"},{"paperId":"P241","catalystId":"P241_PERF_001","name":"Pt3Ni8/TiB2 (calcined at 600 °C)","activeMetals":"Pt-Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt3Ni8/TiB2","phase":"PtNi alloy exhibiting lattice contraction","particleSize":"12.5 nm for Pt3Ni8 NPs; TiB2 overlayer thickness of 1.7 nm at 600 °C (0.82 nm at 500 °C and 2.45 nm at 800 °C)","surfaceStates":"Encapsulated by TiB2 overlayers via SMSI; electronic state characterized by electron transfer from Ni to Pt and a net transfer of electrons from metal nanoparticles to the TiB2 support.","structureLink":"SMSI-induced encapsulation prevents nanoparticle aggregation and leaching while providing active sites on the TiB2 surface; lattice contraction and magnetic interaction enhance electron transfer and SMSI, improving FA dehydrogenation activity.","deactivation":"SMSI prevents aggregation and leaching; activity decrease attributed to reduction in TiB2 overlayer thickness from 1.71 nm to 0.98 nm"},{"paperId":"P241","catalystId":"P241_PERF_002","name":"Pt/TiB2","activeMetals":"Pt","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Pt/TiB2","phase":"Monometallic Pt","structureLink":"Lower stability (56.3% initial activity) compared to the alloy catalyst."},{"paperId":"P241","catalystId":"P241_PERF_003","name":"Ni/TiB2","activeMetals":"Ni","metalClass":"Non-Pd or Pd-free","matchedCharacterization":"Ni/TiB2","phase":"Monometallic Ni","structureLink":"Lower stability (51.9% initial activity) compared to the alloy catalyst."}],"insights":[{"paperId":"P001","section":"characterization","insight":"The 1D morphology of GaN NWs (length 500-700 nm, diameter 50-80 nm) maximizes catalytic site density."},{"paperId":"P001","section":"characterization","insight":"H2 desorption temperature is lowered from 312°C on bare GaN to 301°C upon Pt incorporation."},{"paperId":"P001","section":"characterization","insight":"In situ DRIFTS and EPR confirm the formation of HCOO* as a key intermediate on the Pt/GaN interface, whereas bare GaN favors HCO* and OH* intermediates."},{"paperId":"P001","section":"performance","insight":"The hydrogen evolution rate follows the order Pt > Pd > Rh > Ru > Au when supported on 1D GaN."},{"paperId":"P001","section":"performance","insight":"Incorporation of Pt reduces the apparent activation energy from 1.34 eV (bare GaN) to 0.66 eV."},{"paperId":"P002","section":"synthesis","insight":"The support was manufactured via robocasting from a pseudoplastic aqueous ink containing 38 vol% solids (8YSZ) and organic additives (H-PEI, L-PEI, MC, APA)."},{"paperId":"P002","section":"synthesis","insight":"Sintering temperature of the zirconia scaffold significantly affects porosity and compressive strength; 1200 °C was chosen as an optimal balance for catalytic support."},{"paperId":"P002","section":"characterization","insight":"Sintering temperature of 8YSZ scaffolds (1000–1400 °C) allows precise control over total porosity (88% to 75%), rod porosity (61% to 14%), grain size (200 nm to 2 μm), and compressive strength (0.6 to 6.9 MPa)."},{"paperId":"P002","section":"characterization","insight":"Ionic conductivity of the 3D scaffolds is strongly dependent on sintering temperature; scaffolds sintered at 1400 °C exhibit ionic conductivity values (~5 S m-1 at 800 °C) comparable to dense pellets."},{"paperId":"P002","section":"characterization","insight":"The deactivation of the Pd/8YSZ catalyst was attributed to fouling by reaction media species (water and formic acid) rather than changes in Pd oxidation state or particle size."},{"paperId":"P002","section":"performance","insight":"The 3D Pd/8YSZ catalyst demonstrates the feasibility of using a structured reactor for continuous hydrogen production from formic acid, avoiding the high pressure drops associated with powder catalysts."},{"paperId":"P003","section":"synthesis","insight":"The use of boehmite gel in the 3D printing ink allows for the creation of robust AC/Al2O3 supports after sintering at high temperatures (1300 °C)."},{"paperId":"P003","section":"characterization","insight":"The Pd2+/Pd0 ratio is critical for the dehydrogenation of formic acid, with electrodeficient Pd species being the active sites."},{"paperId":"P003","section":"characterization","insight":"Higher reaction temperatures accelerate both the agglomeration of Pd nanoparticles and the reduction of Pd2+ to Pd0."},{"paperId":"P003","section":"performance","insight":"Reaction at 25 °C is recommended because the longer catalyst lifetime offsets the lower hydrogen flow rate compared to 55 °C."},{"paperId":"P003","section":"performance","insight":"The use of a 3D-printed structured support provides similar H2 production per gram of Pd as powdered Pd/AC, but shows different FA disappearance behavior due to adsorption differences."},{"paperId":"P004","section":"synthesis","insight":"The double-solvent method (n-hexane as hydrophobic solvent and water as hydrophilic solvent) was used to inhibit metal deposition on the outer surface and promote incorporation into MOF cages."},{"paperId":"P004","section":"synthesis","insight":"Uncoordinated pyridine N atoms in the MOF framework act as Lewis basic sites that help disperse PdAu NPs and facilitate formic acid protonation."},{"paperId":"P004","section":"characterization","insight":"The uncoordinated pyridine N atoms in the MOF framework act as effective ligands to anchor and disperse noble metal nanoparticles."},{"paperId":"P004","section":"characterization","insight":"The double-solvent method (n-hexane/water) effectively incorporates metal cations into the MOF cages via capillary force, inhibiting surface deposition."},{"paperId":"P004","section":"performance","insight":"The catalytic activity depends strongly on the Pd/Au ratio, with Pd0.8Au0.2/1' showing the highest activity."},{"paperId":"P004","section":"performance","insight":"Pd is identified as the true active center; small amounts of Au significantly improve performance, but excessive Au decreases it."},{"paperId":"P005","section":"synthesis","insight":"Optimal carbon-to-boron ratio for support is 1:5."},{"paperId":"P005","section":"synthesis","insight":"Optimal boron doping calcination temperature is 900 °C; lower temperatures (800 °C) hinder B incorporation, while higher temperatures (1000 °C) cause decomposition."},{"paperId":"P005","section":"synthesis","insight":"Anhydrous methanol acts as a mild reducing agent for Pd2+; optimal reduction temperature is 60 °C. Temperatures above the boiling point of methanol (64.7 °C) lead to instability and ineffective support."},{"paperId":"P005","section":"characterization","insight":"Boron doping of porous carbon preserves the mesoporous structure (pore diameter ~26.3 nm) while significantly increasing the adsorption energy of Pd atoms (-1.10 eV)."},{"paperId":"P005","section":"characterization","insight":"The optimal catalyst preparation involves a C:B ratio of 1:5, calcination at 900 °C, and reduction in methanol at 60 °C."},{"paperId":"P005","section":"characterization","insight":"Stronger metal-support interaction induced by boron doping prevents sintering and agglomeration of Pd nanoparticles during cycling."},{"paperId":"P005","section":"performance","insight":"Boron doping significantly enhances the catalytic activity of Pd/C catalysts for formic acid dehydrogenation compared to nitrogen-doped or undoped porous carbon supports."},{"paperId":"P005","section":"performance","insight":"The optimal catalyst preparation involves a C:B ratio of 1:5, calcination at 900 °C, and reduction with methanol at 60 °C."},{"paperId":"P006","section":"synthesis","insight":"The nanoreactor strategy is applicable to other Pd-based bimetallics including PdRu, PdCo, PdNi, PdZn, PdAg and PdCu."},{"paperId":"P006","section":"synthesis","insight":"Coordination between 3-aminophenol (3-AP) and [PdCl4]2- is critical for forming highly dispersed Pd nanoclusters as seeds in the NMP-precursor."},{"paperId":"P006","section":"characterization","insight":"The coordination between 3-aminophenol (3-AP) and [PdCl4]2- is critical for forming highly dispersed Pd nanocluster seeds in the NMP-precursor."},{"paperId":"P006","section":"characterization","insight":"Ozone-air flow treatment at 180 °C followed by H2 reduction at 300 °C effectively cleans the surfaces of polymer-supported BNPs without altering their size, composition, or bimetallic structure."},{"paperId":"P006","section":"characterization","insight":"The nanoreactor strategy allows for scalable synthesis of ultra-fine bimetallic nanoparticles with narrow size distributions by separating nucleation (Pd seeds) and growth (second metal)."},{"paperId":"P006","section":"performance","insight":"The Pd1Au1/4 composition showed the highest catalytic activity for FA dehydrogenation among tested ratios."},{"paperId":"P006","section":"performance","insight":"Bimetallic PdAu catalysts exhibited significantly higher TOF than monometallic Pd, attributed to electronic interactions between Pd and Au."},{"paperId":"P006","section":"performance","insight":"Ozone-air flow treatment followed by H2 reduction effectively cleaned catalyst surfaces and enhanced activity without altering bimetallic structure."},{"paperId":"P007","section":"synthesis","insight":"The use of ethylene glycol serves as both the solvent and the reducing agent for the Ag and Pd precursors."},{"paperId":"P007","section":"synthesis","insight":"Sequential heating (120 °C then 90 °C) was used to facilitate the core-shell structure formation."},{"paperId":"P007","section":"characterization","insight":"The N-GCNT aerogel support exhibits a BET surface area of 381.8 m2/g and an average mesopore size of 15.4 nm."},{"paperId":"P007","section":"characterization","insight":"XPS confirms successful nitrogen doping (2.8 at%) with pyridinic, pyrrolic, quaternary, and oxidized N species."},{"paperId":"P007","section":"performance","insight":"The Ag1@Pd1 molar ratio was found to be the optimal metal composition for FA dehydrogenation."},{"paperId":"P007","section":"performance","insight":"Nitrogen-doped graphene carbon nanotube aerogel significantly enhances activity compared to support-free nanoparticles by inhibiting aggregation and providing electronic promotion."},{"paperId":"P008","section":"synthesis","insight":"The catalysts are described as agglomerated nano-porous/spongelike structures prepared without stabilizers."},{"paperId":"P008","section":"synthesis","insight":"Stronger reductants (NaBH4) lead to larger nanopores compared to weaker reductants (HCOONa)."},{"paperId":"P008","section":"synthesis","insight":"PdMg catalyst showed the highest activity and was synthesized via a displacement reaction."},{"paperId":"P008","section":"characterization","insight":"The use of different reductants (Mg, NaBH4, HCOONa) significantly influences the nanopore size and nanoparticle density within the resulting spongelike Pd agglomerates."},{"paperId":"P008","section":"characterization","insight":"Stronger reducibility (e.g., NaBH4 vs HCOONa) leads to more vigorous hydrogen evolution during synthesis, creating larger pores and smaller grains."},{"paperId":"P008","section":"performance","insight":"PdMg catalyst exhibited the highest catalytic activity among the tested agglomerated Pd catalysts for formic acid decomposition at room temperature."},{"paperId":"P008","section":"performance","insight":"The spongelike morphology and nanopore size significantly influence the catalytic performance, with larger pores facilitating better activity."},{"paperId":"P009","section":"synthesis","insight":"Air-activation of carbon nanospheres maintains the spherical morphology and provides more oxygen-containing functional groups compared to KOH activation, leading to higher catalytic activity."},{"paperId":"P009","section":"characterization","insight":"The addition of Ag to the Pd catalyst increases the dispersion of Pd active species."},{"paperId":"P009","section":"characterization","insight":"Air activation of carbon nanospheres is superior to KOH activation for maintaining morphology and surface oxygen groups, leading to higher catalytic activity."},{"paperId":"P009","section":"performance","insight":"The addition of potassium formate (PF) is more effective than sodium formate (SF) for facilitating H2 generation from FA."},{"paperId":"P009","section":"performance","insight":"An Ag:Pd molar ratio of 1:9 provides the highest catalytic activity among tested bimetallic compositions."},{"paperId":"P009","section":"performance","insight":"Air-assisted activation of carbon nanospheres is superior to KOH activation for supporting these catalysts."},{"paperId":"P010","section":"synthesis","insight":"The support KIE-11 is synthesized using a deep eutectic solvent (DES) of choline chloride/urea as both template and solvent, avoiding alcohol and water except for TEOS hydrolysis."},{"paperId":"P010","section":"synthesis","insight":"Pore size of the silica support can be tailored by changing DES content or aging conditions (furnace vs autoclave)."},{"paperId":"P010","section":"synthesis","insight":"Aging in an autoclave at 100-180 °C produces ultralarge pores (up to 24.5 nm) due to dissolution and recondensation of silica nanoparticles under hydrothermal conditions."},{"paperId":"P010","section":"characterization","insight":"Pd nanoparticle size is determined by the pore structure of the KIE-11 support."},{"paperId":"P010","section":"characterization","insight":"Catalytic activity for additive-free formic acid dehydrogenation increases as Pd nanoparticle size decreases."},{"paperId":"P010","section":"characterization","insight":"The optimal catalyst support requires a balance between large enough pores for molecular diffusion and small enough pores to provide confinement and prevent metal aggregation."},{"paperId":"P010","section":"performance","insight":"The pore structure of KIE-11 support is a significant factor in determining catalytic activity for additive-free formic acid dehydrogenation at room temperature, as it influences both the diffusion of molecules and the Pd nanoparticle size."},{"paperId":"P011","section":"synthesis","insight":"The catalyst was optimized by varying the Pd/Au molar ratio (0:1 to 1:2.5) and L-arginine content (0 to 200 mg per 100 mg AC)."},{"paperId":"P011","section":"synthesis","insight":"L-arginine is tethered to the active carbon support through covalent amide bonds and non-covalent interactions (hydrogen bonding, hydrophobic, and cation-pi interactions)."},{"paperId":"P011","section":"characterization","insight":"L-arginine (LA) is tethered to the active carbon (AC) support through covalent amide bonds and non-covalent interactions including hydrogen bonding, hydrophobic interactions, and cation-pi interactions."},{"paperId":"P011","section":"characterization","insight":"The addition of LA significantly enhances the hydrophilicity of the catalyst and its CO2 adsorption capacity due to the strong alkalinity of the guanidine group."},{"paperId":"P011","section":"characterization","insight":"Increasing the Au/Pd ratio in PdAu/AC-LA catalysts leads to an increase in nanoparticle size (from 4.17 to 5.61 nm)."},{"paperId":"P011","section":"performance","insight":"The Pd1Au2/AC-LA catalyst shows a synergistic effect between the PdAu alloy and L-arginine (LA), which enhances both CO2 hydrogenation to formate under alkaline conditions and FA dehydrogenation under acidic conditions."},{"paperId":"P011","section":"performance","insight":"L-arginine's guanidine group is critical for capturing and activating CO2, with activity following the order LA > LS (L-lysine) > GY (glycine)."},{"paperId":"P011","section":"performance","insight":"The Au:Pd ratio of 2:1 was found to be optimal for CO2 hydrogenation."},{"paperId":"P012","section":"synthesis","insight":"The use of amine groups (via APTES) on the N-PCB support is critical for stabilizing ultrafine Pd-La(OH)3 nanoparticles and preventing aggregation."},{"paperId":"P012","section":"synthesis","insight":"La(OH)3 is formed in situ during the reduction step due to the hydrolysis of NaBH4, which creates an alkaline environment."},{"paperId":"P012","section":"characterization","insight":"The introduction of La(OH)3 contributes to the formation of smaller Pd nanoparticles (1.6 nm for Pd-La(OH)3 vs 2.0 nm for Pd alone)."},{"paperId":"P012","section":"characterization","insight":"CO2-TPD confirms that La(OH)3 significantly increases the concentration of medium basic sites (~300 °C), boosting O-H bond dissociation."},{"paperId":"P012","section":"characterization","insight":"XPS N 1s spectra show a shift toward lower binding energies after loading Pd-La(OH)3, indicating electron transfer from Pd to N and confirming strong metal-support interactions."},{"paperId":"P012","section":"performance","insight":"The introduction of La(OH)3 increases the concentration of basic sites on the catalyst surface, which facilitates O-H bond dissociation and reduces activation energy (40.4 kJ/mol for Pd-La(OH)3/N-PCB-NH2 vs 43.4 kJ/mol for Pd/N-PCB-NH2)."},{"paperId":"P012","section":"performance","insight":"The bowl-like structure of N-PCB-NH2 provides a better support than the hollow carbon sphere (N-HCS), as evidenced by lower activation energy."},{"paperId":"P012","section":"performance","insight":"C-H bond cleavage is identified as the rate-determining step via kinetic isotope effect measurements."},{"paperId":"P013","section":"synthesis","insight":"Amino-functionalization of HNTs with APTES provides basic sites (-NH2) that facilitate the electrostatic attraction and anchoring of PdCl4(2-) ions, leading to higher metal loading and smaller nanoparticle size (1.2 nm vs 3.5 nm for unmodified HNTs)."},{"paperId":"P013","section":"synthesis","insight":"The use of Na2CO3 during the NaBH4 reduction step prevents rapid hydrolysis of NaBH4 and helps in growing uniform nanoparticles."},{"paperId":"P013","section":"characterization","insight":"Amino-functionalization of HNTs with APTES creates -NH2 groups that act as anchoring sites via electrostatic attraction to PdCl4 2- and Lewis base interactions, preventing metal nanoparticle aggregation."},{"paperId":"P013","section":"characterization","insight":"The electron density of the Pd active center is modulated by both the amino-functionalized support (electron migration from Pd to N) and the addition of second metals (Au or Ag) based on their respective work functions."},{"paperId":"P013","section":"characterization","insight":"Reducing the electron density on the surface of Pd nanoparticles is beneficial for the combination of catalytic active centers with formate ions, thereby enhancing activity."},{"paperId":"P013","section":"performance","insight":"Pd is the essential active center for DFA; catalysts without Pd showed no activity."},{"paperId":"P013","section":"performance","insight":"Amino-functionalization of HNTs significantly enhances catalytic activity by improving metal dispersion and providing basic sites that facilitate formate ion formation."},{"paperId":"P013","section":"performance","insight":"The addition of Au to Pd/NH2-HNTs creates a synergistic electronic effect, resulting in the highest observed TOF (701.6 h-1)."},{"paperId":"P013","section":"performance","insight":"Sodium formate acts as a promoter for the reaction, with an optimal FA/SF molar ratio around 50% SF."},{"paperId":"P014","section":"synthesis","insight":"The use of a dihydrosilane precursor (3-aminopropylmethylsilane) allows for the simultaneous introduction of amino groups and reducing hydrido groups on silica surfaces."},{"paperId":"P014","section":"synthesis","insight":"On-site reduction by surface Si-H groups, combined with spatial hindrance from mesopores and coordination effects from 3-aminopropyl groups, enables the formation of ultrasmall nanoparticles (<1 nm) and single metal atoms."},{"paperId":"P014","section":"characterization","insight":"Surface hydrido groups (Si-H) on NH2-H-SBA-15 act as effective reducing agents for noble metal ions."},{"paperId":"P014","section":"characterization","insight":"Nanoparticle size is controlled by the limited number of Si-H groups, spatial hindrance from cylindrical mesopores, and coordination effects from 3-aminopropyl groups."},{"paperId":"P014","section":"characterization","insight":"The incorporation of Ag into Pd nanoparticles distorts the Pd lattice, enhancing catalytic activity."},{"paperId":"P014","section":"performance","insight":"The AgPd-NH2-SBA-15 catalyst exhibits superior activity due to the synergistic effect of amino groups and ultrasmall Ag-doped Pd nanoparticles/single atoms."},{"paperId":"P014","section":"performance","insight":"Catalytic activity for FA dehydrogenation can be enhanced after recycling, possibly due to in situ reduction of surface PdO or generation of new Pd0 sites from unreacted PdCl2."},{"paperId":"P015","section":"synthesis","insight":"Arginine acts as a dispersing agent to control nucleation and growth of Pd nanoparticles via metal-amino acid complex intermediates, resulting in smaller particle size (1.9 nm vs 3.9 nm for the non-assisted sample)."},{"paperId":"P015","section":"synthesis","insight":"The presence of arginine reduces the total Pd loading compared to the non-assisted catalyst due to the occupancy of carbon mesopores by residual amino acids."},{"paperId":"P015","section":"characterization","insight":"Amino acids act as effective dispersing agents to downsize metal nanoparticles and prevent aggregation during reduction."},{"paperId":"P015","section":"characterization","insight":"The use of amino acids can significantly reduce the BET surface area of carbon supports due to occupancy or blockage of mesopores by residual organic molecules."},{"paperId":"P015","section":"performance","insight":"The addition of sodium formate (SF) as a promoter improves catalytic activity by increasing the contact chance of formate ions with active sites."},{"paperId":"P015","section":"performance","insight":"Amino acid-assisted growth results in smaller Pd nanoparticles and an alkalized surface environment, both contributing to superior TOF values compared to catalysts without amino acids."},{"paperId":"P016","section":"synthesis","insight":"The size of Pd species (single atoms vs nanoclusters vs nanoparticles) was controlled by varying the precursor amount and the reduction method (NaBH4 for smaller clusters/atoms, H2 for larger particles)."},{"paperId":"P016","section":"synthesis","insight":"Amine functionalization using APTES is used to anchor Pd and act as a proton scavenger during catalysis."},{"paperId":"P016","section":"characterization","insight":"Hydrogen spillover capacity is inversely related to Pd particle size: Pd1 > PdNC > PdNP."},{"paperId":"P016","section":"characterization","insight":"The electronic state (richness of Pd0) increases with particle size, evidenced by a shift to lower binding energy in XPS from Pd1 to PdNP."},{"paperId":"P016","section":"characterization","insight":"Optimal catalytic activity for FA dehydrogenation requires a balance between an electron-rich state (facilitating C-H cleavage) and high hydrogen spillover capacity (facilitating H2 desorption)."},{"paperId":"P016","section":"characterization","insight":"The coexistence of Pd0 and Pd2+ is crucial, where Pd2+ promotes HCOO- adsorption and Pd0 facilitates the rate-determining C-H bond cleavage."},{"paperId":"P016","section":"performance","insight":"Pd nanoclusters (PdNC) exhibit superior FA dehydrogenation activity compared to single atoms (Pd1) and nanoparticles (PdNP)."},{"paperId":"P016","section":"performance","insight":"The synergistic effect between PdNC and amine groups (-NH2), where -NH2 acts as a proton scavenger, significantly boosts activity."},{"paperId":"P016","section":"performance","insight":"A balance of electronic properties (Pd0/Pd2+ ratio) and hydrogen spillover capacity is essential for high TOF."},{"paperId":"P016","section":"performance","insight":"Sodium formate additive lowers the apparent activation energy from 60.7 to 41.8 kJ mol-1."},{"paperId":"P017","section":"synthesis","insight":"KOH etching of the MOF-derived NDC support creates new mesoporous pores (approx 3.8 nm) which facilitate high dispersion and smaller size of Pd nanoparticles."},{"paperId":"P017","section":"synthesis","insight":"Carbonization temperature of the support significantly affects the metal-support interaction (MSI) and resulting Pd nanoparticle size, with 900 °C being optimal for minimizing particle size (4.1 nm)."},{"paperId":"P017","section":"characterization","insight":"KOH etching of the MOF-303-derived NDC support creates new mesoporous pores (approx. 3.8 nm) that facilitate high dispersion of Pd NPs."},{"paperId":"P017","section":"characterization","insight":"The N-doped carbon support acts as an electron donor to regulate the electronic structure of Pd NPs via metal-support interaction (MSI)."},{"paperId":"P017","section":"characterization","insight":"Reusability tests showed a slight increase in Pd particle size from 4.1 nm to 4.3 nm after five cycles, indicating minor aggregation."},{"paperId":"P017","section":"performance","insight":"The addition of sodium formate (SF) as a promoter significantly facilitates the rate of hydrogen production and is necessary to achieve 100% FA conversion."},{"paperId":"P017","section":"performance","insight":"Optimal catalyst performance was achieved with Pd loading of 10 wt% and KNDC support carbonization temperature of 900 °C, resulting in ultrasmall Pd NPs (4.1 nm)."},{"paperId":"P017","section":"performance","insight":"The reaction follows zero-order kinetics with respect to FA concentration and near first-order kinetics with respect to catalyst concentration."},{"paperId":"P017","section":"performance","insight":"Activation energy for Pd@KNDC(10-900) is 41.4 kJ/mol."},{"paperId":"P018","section":"synthesis","insight":"The use of N-doped CDs as a support prevents the aggregation of PdAg nanoparticles and enhances electronic interaction."},{"paperId":"P018","section":"synthesis","insight":"Alloying Pd with Ag modifies the electronic structure of the Pd active center, optimizing catalytic activity for formic acid dehydrogenation."},{"paperId":"P018","section":"characterization","insight":"The alloying effect between Pd and Ag regulates the outer electron cloud density of Pd, enhancing formic acid dehydrogenation activity."},{"paperId":"P018","section":"characterization","insight":"N-doped carbon dots (CDs) effectively immobilize ultra-fine PdAg alloys and prevent their aggregation during reaction."},{"paperId":"P018","section":"performance","insight":"The Pd0.9Ag0.1/CDs catalyst showed a volcanic-type trend in TOF with respect to Ag content, peaking at 619 h-1."},{"paperId":"P018","section":"performance","insight":"N-doped carbon dots (CDs) provided superior support compared to TiO2, Al2O3, C3N4, CNT, and XC-72."},{"paperId":"P019","section":"synthesis","insight":"The amino groups in NH2-MIL-101 serve as anchor sites to stabilize ultrafine PdAu nanoclusters (1.2 nm) and prevent aggregation."},{"paperId":"P019","section":"synthesis","insight":"Direct synthesis of NH2-MIL-101 via atomic-level ligand design is more effective for FAD than post-synthetic modification of MIL-101."},{"paperId":"P019","section":"characterization","insight":"Amino groups in NH2-MIL-101 effectively stabilize PdAu nanoclusters and prevent aggregation into larger nanoparticles (1.2 nm vs 3.1 nm)."},{"paperId":"P019","section":"characterization","insight":"Electronic coupling between Pd and Au induces electron migration from Pd to Au, optimizing the electronic structure for enhanced catalytic performance."},{"paperId":"P019","section":"characterization","insight":"The strong metal-support interaction (SMSI) between PdAu NCs and the aminated MOF is critical for achieving high turnover frequencies."},{"paperId":"P019","section":"performance","insight":"The Pd/Au molar ratio of 0.7/0.3 is optimal for FAD activity."},{"paperId":"P019","section":"performance","insight":"A metal loading of 20 wt% PdAu on NH2-MIL-101 provides the fastest H2 production efficiency."},{"paperId":"P019","section":"performance","insight":"FAD reaction over PdAu/NH2-MIL-101 is nearly zero-order relative to initial FA concentration and nearly first-order relative to catalyst concentration."},{"paperId":"P020","section":"synthesis","insight":"The use of oleylamine as a blocking agent prevents the growth of SiO2 layers directly on PdCoNi nanoparticles during ALD."},{"paperId":"P020","section":"synthesis","insight":"Amine groups from the APTS precursor enhance catalytic activity via Strong Metal-Molecular Support Interaction (SMMSI)."},{"paperId":"P020","section":"synthesis","insight":"ALD-SiO2 coating provides significant stability against sintering and leaching compared to unprotected PdCoNi/TiO2."},{"paperId":"P020","section":"characterization","insight":"Trimetallic alloying of Pd with Co and Ni significantly reduces CO poisoning compared to monometallic Pd or bimetallic Pd-Co/Pd-Ni systems."},{"paperId":"P020","section":"characterization","insight":"Atomic layer deposition (ALD) of SiO2 allows for precise control over protective layer thickness, preventing nanoparticle sintering and leaching while maintaining catalytic activity."},{"paperId":"P020","section":"characterization","insight":"The introduction of amine groups via APTS during ALD enhances the turnover frequency (TOF) through SMMSI effects."},{"paperId":"P020","section":"performance","insight":"Trimetallic PdCoNi alloy nanoparticles exhibit higher activity and CO poisoning resistivity than monometallic (Pd/TiO2) or bimetallic (PdCo/TiO2, PdNi/TiO2) counterparts."},{"paperId":"P020","section":"performance","insight":"ALD-SiO2 coating significantly enhances the stability of supported metal NPs against sintering and leaching without blocking active sites if thickness is optimized (6 cycles)."},{"paperId":"P020","section":"performance","insight":"The presence of amine groups from APTS in the ALD process creates a Strong Metal-Molecular Support Interaction (SMMSI) that increases TOF."},{"paperId":"P021","section":"synthesis","insight":"Treatment of h-BN with molten citric acid breaks B-N bonds and increases defective sites, facilitating the grafting of -NH2 groups from APTES."},{"paperId":"P021","section":"synthesis","insight":"The amino groups on CA-BN-NH2 act as nucleation sites for Pd2+ and Au3+ ions via charge interactions, which controls the growth kinetics during NaBH4 reduction to produce ultrafine nanoparticles (~3.6 nm)."},{"paperId":"P021","section":"characterization","insight":"Citric acid treatment of h-BN breaks B-N bonds and creates defective sites that facilitate the grafting of -NH2 groups from APTES."},{"paperId":"P021","section":"characterization","insight":"-NH2 groups on CA-BN-NH2 act as nucleation sites for Pd2+ and Au3+ ions via charge interactions, controlling growth kinetics to produce ultrafine nanoparticles."},{"paperId":"P021","section":"characterization","insight":"The combination of a strong metal-support interaction (electron transfer from support to alloy) and the ligand effect between Au and Pd creates electron-rich Pd active sites."},{"paperId":"P021","section":"characterization","insight":"DFT calculations confirm that CA-BN-NH2 reduces H atom adsorption energy (3.24 eV vs 3.91 eV for BN), facilitating hydrogen desorption."},{"paperId":"P021","section":"performance","insight":"The Au0.3Pd0.7/CA-BN-NH2 catalyst exhibits an unprecedented initial TOF of 7046 mol H2 mol catalyst-1 h-1 without additives, outperforming most reported noble metal catalysts."},{"paperId":"P021","section":"performance","insight":"Alloying Pd with Au (specifically at x=0.3) significantly enhances activity due to the ligand effect modulating the electronic structure of Pd active centers."},{"paperId":"P021","section":"performance","insight":"The modification of BN with citric acid and APTES is critical for achieving ultrafine particle size, high dispersion, and hydrophilicity."},{"paperId":"P022","section":"synthesis","insight":"The support n-CNS was synthesized by immobilizing carbonized glucose onto g-C3N4 via hydrothermal process followed by high-temperature calcination, where g-C3N4 acts as the nitrogen precursor and glucose as the carbon source."},{"paperId":"P022","section":"synthesis","insight":"Catalytic activity is strongly influenced by the ratio of graphitic N to pyridinic N in the n-CNS support, with higher ratios leading to smaller metal nanoparticle sizes and enhanced performance."},{"paperId":"P022","section":"characterization","insight":"The ratio of graphitic N to pyridinic N in the nitrogen-decorated carbon nanosheets is a key factor for catalytic activity, more so than total nitrogen content."},{"paperId":"P022","section":"characterization","insight":"A higher graphitic N/pyridinic N ratio facilitates electron transfer from the support to the AuPd alloy nanoparticles and minimizes nanoparticle size."},{"paperId":"P022","section":"characterization","insight":"The formation of an fcc AuPd alloy structure is confirmed by XRD (peaks between pure Pd and Au) and STEM-EDX mapping."},{"paperId":"P022","section":"performance","insight":"The catalytic activity for FA dehydrogenation depends on the ratio of graphitic N to pyridinic N in the carbon support; a higher ratio correlates with better performance."},{"paperId":"P022","section":"performance","insight":"Higher ratios of graphitic N to pyridinic N facilitate electron transfer from the support to the AuPd nanoparticles and minimize nanoparticle size, enhancing activity."},{"paperId":"P022","section":"performance","insight":"Au-Pd alloying is essential for high hydrogen release rates, as pure Au shows no activity."},{"paperId":"P023","section":"synthesis","insight":"The volume ratio of toluene to DMF during APTES functionalization of SBA-15 significantly affects the surface amine content, with a 3:2 ratio maximizing amine density."},{"paperId":"P023","section":"synthesis","insight":"Higher surface amine content leads to smaller Au-Pd bimetal nanoparticle size and improved catalytic activity for formic acid decomposition."},{"paperId":"P023","section":"characterization","insight":"The volume ratio of toluene to DMF (3:2) during amine functionalization maximizes the surface content of -NH2 and NH3+ groups on SBA-15."},{"paperId":"P023","section":"characterization","insight":"Amine groups serve as coordination sites for metal ions, which facilitates high dispersion and smaller particle sizes of Au-Pd nanoparticles."},{"paperId":"P023","section":"characterization","insight":"XRD patterns showed no obvious diffraction peaks for Au or Pd, indicating non-crystalline phases or very high dispersion."},{"paperId":"P023","section":"characterization","insight":"The interaction between the amine-functionalized support and the bimetal (metal-support interaction) combined with metal-metal interactions is responsible for enhanced formic acid dehydrogenation."},{"paperId":"P023","section":"performance","insight":"The hydrogen production efficiency over Au-Pd-SBA-15-NH2 catalysts increases with the increase in surface amine content."},{"paperId":"P023","section":"performance","insight":"A toluene/DMF volume ratio of 3:2 during functionalization maximizes amine group density, leading to smaller bimetal nanoparticles and higher activity."},{"paperId":"P023","section":"performance","insight":"Amine groups facilitate O-H bond dissociation and serve as proton scavengers, while protonated amines (NH3+) assist in the rate-limiting C-H bond cleavage step."},{"paperId":"P024","section":"synthesis","insight":"The sol-immobilization method using PVA as a binder allows for accurate control over nanoparticle size and distribution."},{"paperId":"P024","section":"synthesis","insight":"Co-reduction of Au and Pd leads to smaller mean particle sizes compared to monometallic catalysts."},{"paperId":"P024","section":"synthesis","insight":"Secondary reduction with H2 gas at 250 °C increases the metallic content by converting remaining metal ions on the surface into nanoparticles."},{"paperId":"P024","section":"characterization","insight":"Bimetallic Au-Pd nanoparticles exhibit smaller average sizes (3.3–3.8 nm) compared to monometallic counterparts (4.0–4.5 nm)."},{"paperId":"P024","section":"characterization","insight":"Alloying results in a shift of binding energies for both Au and Pd toward lower values."},{"paperId":"P024","section":"characterization","insight":"H2 treatment increases the metallic content by reducing remaining metal ions on the catalyst surface."},{"paperId":"P024","section":"performance","insight":"Bimetallic Au-Pd catalysts supported on rGO exhibit higher activity and selectivity than monometallic Au/rGO and Pd/rGO."},{"paperId":"P024","section":"performance","insight":"Catalytic activity is highly composition-dependent, with the Au1Pd3 ratio being the most active."},{"paperId":"P024","section":"performance","insight":"The apparent activation energy for Au1Pd3/rGO was found to be 28.76 kJ mol-1."},{"paperId":"P025","section":"synthesis","insight":"The shell thickness of the Ag/AgPd CS-NWs is readily tunable by adjusting the molar amount of Pd(NO3)2 and AgNO3 precursors."},{"paperId":"P025","section":"synthesis","insight":"The formation mechanism involves burst nucleation of core/shell nanoparticles, followed by collision, oriented attachment into short nanowires, and finally interweaving into a networked structure."},{"paperId":"P025","section":"characterization","insight":"The core/shell architecture of Ag/AgPd CS-NWs creates a distinct electronic environment that enhances electron transfer to Pd, which is critical for bifunctional catalytic activity."},{"paperId":"P025","section":"characterization","insight":"Surface plasmon resonance (SPR) effects observed in UV-Vis spectra (330–550 nm) were used to verify the presence of the Ag core."},{"paperId":"P025","section":"performance","insight":"The core-shell structure with 0.9 nm AgPd shell thickness is the most active for FA dehydrogenation among tested thicknesses."},{"paperId":"P025","section":"performance","insight":"Ag/AgPd CS-0.9 can achieve H2 production from high concentration (up to 10 M) FA solutions without additives."},{"paperId":"P026","section":"characterization","insight":"Amine functionalization of BNNFs via APTES effectively immobilizes Pd2+ and Au3+ through coordination interactions, preventing agglomeration and ensuring smaller nanoparticle size."},{"paperId":"P026","section":"characterization","insight":"Strong metal-support interaction (SMSI) is evidenced by electron transfer from the alloy nanoparticles to the BNNFs-A carrier."},{"paperId":"P026","section":"characterization","insight":"The incorporation of Au into Pd modifies the electronic structure of Pd, creating a synergistic effect that enhances catalytic dehydrogenation of formic acid."},{"paperId":"P026","section":"performance","insight":"The catalytic activity follows a volcano-type behavior with respect to Au content in the AuPd alloy, peaking at an Au:Pd ratio of approximately 1:3."},{"paperId":"P026","section":"performance","insight":"Increasing the loading amount of Au1Pd3 on BNNFs increases activity up to 20.5 wt%, beyond which activity decreases due to nanoparticle aggregation."},{"paperId":"P027","section":"synthesis","insight":"The mullite-type SmMn2O5 support was synthesized via coprecipitation using Mn(CH3COO)2.4H2O and Sm(NO3)3.6H2O, followed by roasting at 500 °C and 800 °C."},{"paperId":"P027","section":"synthesis","insight":"Amine functionalization with o-phenylenediamine (OPDA) is critical for achieving high dispersion of PdCr nanoparticles and modulating the electronic structure of the catalytic sites."},{"paperId":"P027","section":"synthesis","insight":"The incorporation of Cr induces lattice contraction, facilitating the formation of ultrafine bimetallic nanoparticles (~2.05 nm)."},{"paperId":"P027","section":"characterization","insight":"The introduction of amino groups (OPDA) on the SmMn2O5 support prevents nanoparticle agglomeration and facilitates the growth of ultrafine PdCr NPs."},{"paperId":"P027","section":"characterization","insight":"Lattice contraction induced by replacing Pd with smaller Cr atoms is favorable for forming ultrafine particles."},{"paperId":"P027","section":"characterization","insight":"Amino groups act as electron donors, increasing the electron cloud density of the metallic sites and enhancing the alkalinity of the system."},{"paperId":"P027","section":"performance","insight":"The addition of o-phenylenediamine (OPDA) to the SmMn2O5 support increases the TOF by a factor of 23.8 compared to the unmodified support."},{"paperId":"P027","section":"performance","insight":"Bimetallic PdCr NPs with a molar ratio of x = 0.4 (Pd0.6Cr0.4) exhibit the best catalytic activity among tested ratios."},{"paperId":"P028","section":"characterization","insight":"XRD confirmed the formation of PdAg alloys by observing broad diffraction peaks between those of pure Pd and Ag."},{"paperId":"P028","section":"characterization","insight":"The use of hierarchical self-pillared pentasil (SPP) zeolite allows for easier encapsulation of metal precursors and better dispersion compared to microporous zeolites."},{"paperId":"P028","section":"performance","insight":"The use of hierarchical SPP zeolite as a carrier is more advantageous than bulky zeolites for FA dehydrogenation due to better metal dispersion."},{"paperId":"P028","section":"performance","insight":"Sodium formate (SF) acts as an effective additive that increases the concentration of HCOO- ions, favoring contact with active centers and electronically enriching Pd."},{"paperId":"P028","section":"performance","insight":"Reaction rate increases with temperature from 25 °C to 80 °C; activation energy for Pd7Ag3/SPP is estimated at 26.2 kJ/mol."},{"paperId":"P028","section":"performance","insight":"Increasing FA concentration from 0.5 M to 1.0 M increases the reaction rate, but concentrations above 1.0 M (up to 7.0 M) have little influence."},{"paperId":"P029","section":"synthesis","insight":"The double-solvent method (n-hexane/water) effectively encapsulates ultra-small PdAu nanoparticles (~1.4 nm) within the MOF cavities compared to conventional single-solvent impregnation (~5.6 nm)."},{"paperId":"P029","section":"synthesis","insight":"Amine groups in NH2-UiO-66 facilitate the uniform distribution of metal cations and inhibit nanoparticle aggregation during reduction."},{"paperId":"P029","section":"synthesis","insight":"The hydrophilic nature of the inner pore surface of Zr-MOFs drives the aqueous precursors into the cages when a hydrophobic solvent (n-hexane) is used as the bulk medium."},{"paperId":"P029","section":"characterization","insight":"The double-solvent method effectively encapsulates ultra-small PdAu alloy NPs (1.4 nm) within MOF cavities, whereas the single-solvent method results in larger particles (5.6 nm) on the external surface."},{"paperId":"P029","section":"characterization","insight":"Amine groups (-NH2) in NH2-UiO-66 are critical for both achieving high metal dispersion during synthesis and enhancing catalytic activity through synergistic activation of formic acid."},{"paperId":"P029","section":"characterization","insight":"XPS binding energy shifts confirm electron transfer from Pd to Au, verifying alloy formation."},{"paperId":"P029","section":"performance","insight":"The double-solvent method produces smaller, more dispersed PdAu alloy NPs encapsulated within MOF cavities compared to the single-solvent method."},{"paperId":"P029","section":"performance","insight":"Amine groups (-NH2) in NH2-UiO-66 are crucial for both stabilizing ultra-small nanoparticles and promoting FA activation by forming HCOO- intermediates."},{"paperId":"P029","section":"performance","insight":"Optimizing the Pd/(Pd+Au) ratio is essential; Pd0.8Au0.2/UiO-66-D showed superior activity."},{"paperId":"P030","section":"synthesis","insight":"The hollow structure and rough surface of HPAN provide higher specific surface area compared to coral-like PAN."},{"paperId":"P030","section":"synthesis","insight":"Surface amino groups from EDA modification coordinate with Pd2+ and Co2+ cations, inhibiting nanoparticle aggregation during NaBH4 reduction."},{"paperId":"P030","section":"characterization","insight":"The hollow structure and rough surface of HPAN, combined with amino groups from EDA modification, facilitate the nucleation of ultra-small Pd-based nanoparticles (< 1 nm) and inhibit aggregation during NaBH4 reduction."},{"paperId":"P030","section":"characterization","insight":"Strong electron interaction between Pd and Co in bimetallic NPs modifies the electronic state of palladium, enhancing catalytic performance."},{"paperId":"P030","section":"performance","insight":"Bimetallic PdCo nanoparticles exhibit higher activity than monometallic Pd nanoparticles on the EDA-HPAN support."},{"paperId":"P030","section":"performance","insight":"Optimizing the Co/Pd molar ratio (best at 0.2) improves catalytic performance by adjusting electron density of Pd and dispersion state of NPs."},{"paperId":"P031","section":"synthesis","insight":"Amine groups on the MXene support act as anchors to coordinate Pd2+ and Cr3+ ions, controlling nucleation and growth kinetics to produce ultrafine nanoparticles (1.2-1.8 nm) and preventing aggregation."},{"paperId":"P031","section":"characterization","insight":"Amine functionalization of MXene provides a 'confine effect' that anchors metal ions during synthesis, preventing nanoparticle aggregation and ensuring ultra-fine particle sizes."},{"paperId":"P031","section":"characterization","insight":"The amine groups serve as electron donors, shifting the electronic structure of the bimetallic PdCr nanoparticles to be more electron-rich, which facilitates the rate-determining O-H bond cleavage step in formic acid dehydrogenation."},{"paperId":"P031","section":"performance","insight":"The introduction of Cr into Pd nanoparticles creates a volcano-type relationship with optimal activity at Pd0.7Cr0.3."},{"paperId":"P031","section":"performance","insight":"Amine functionalization of MXene support significantly enhances catalytic activity by controlling NP size and modulating electronic properties."},{"paperId":"P032","section":"characterization","insight":"TEM analysis was used to confirm the preservation of Pd nanoparticle morphology and dimensions after five consecutive recycling runs, indicating high catalyst stability."},{"paperId":"P032","section":"performance","insight":"The catalyst shows a negative mass transfer effect at high loadings, with activity improving when reducing loading from 3 mol% to 1.2 mol%."},{"paperId":"P032","section":"performance","insight":"High formic acid concentration (2.5 M) is more efficient for H2 productivity compared to highly diluted concentrations common in literature."},{"paperId":"P032","section":"performance","insight":"Alkaline pH values are critical for inhibiting the dehydration pathway and promoting dehydrogenation."},{"paperId":"P033","section":"synthesis","insight":"The degree of polycondensation and C/N ratio of the carbon nitride support are highly dependent on the thermal treatment temperature and time."},{"paperId":"P033","section":"synthesis","insight":"A synthesis temperature of 650 °C for 4 h was found to provide an optimal balance between structural integrity, composition (lowest hydrogen content), and yield."},{"paperId":"P033","section":"characterization","insight":"C3N4 support properties (crystallinity, C/N ratio, and bandgap) are highly dependent on melamine decomposition temperature and time; 650 °C for 4 h provides the most condensed structure with lowest hydrogen content."},{"paperId":"P033","section":"characterization","insight":"Increasing Pd loading increases the BET surface area and microporosity of the catalysts compared to the bare support, likely due to H2 reduction removing functional groups."},{"paperId":"P033","section":"characterization","insight":"Operando DRIFTS-MS reveals that CO2 hydrogenation on Pd/C3N4 proceeds via initial CO2 dissociation into adsorbed CO* species, followed by hydrogenation to CHxO intermediates and then formates."},{"paperId":"P033","section":"characterization","insight":"The disappearance of the PdHx phase after reaction suggests that hydrogen initially incorporated into the Pd lattice contributes to H2 production."},{"paperId":"P033","section":"performance","insight":"The catalytic activity for formic acid dehydrogenation shows a palladium size dependence, where specific rate exhibits a volcano relationship with particle size (optimum around 4-5 nm), while TOF increases with larger Pd particles in this study."},{"paperId":"P033","section":"performance","insight":"Aqueous environment effectively inhibits the dehydration pathway to CO, ensuring high selectivity toward H2 and CO2."},{"paperId":"P034","section":"synthesis","insight":"The support is synthesized via a two-step process: urea calcination to C3N4 followed by hydrothermal treatment with glucose."},{"paperId":"P034","section":"synthesis","insight":"Transition metal atoms (Co, Fe, Ni) are anchored on the N-doped carbon through grinding and heat treatment under N2 atmosphere."},{"paperId":"P034","section":"synthesis","insight":"Pd nanoparticles are immobilized using a wet reduction method with NaBH4 as the reducing agent."},{"paperId":"P034","section":"synthesis","insight":"Sintering temperature of the Co-doped support significantly affects performance, with 900 °C identified as optimal."},{"paperId":"P034","section":"characterization","insight":"Co doping increases the BET surface area (311.9 m2/g for NC-Co1% vs 215.1 m2/g for NC) and porosity of the carbon support."},{"paperId":"P034","section":"characterization","insight":"Co doping induces a higher density of defects in the N-doped carbon, as evidenced by an increase in the Raman ID/IG ratio (3.92 for NC-Co1% vs 2.98 for NC)."},{"paperId":"P034","section":"characterization","insight":"Acid etching experiments confirmed that Co nanoparticles contribute little to catalytic performance; the enhancement originates from atomically dispersed Co atoms anchored on the N-doped carbon."},{"paperId":"P034","section":"characterization","insight":"Transition metal doping (Co, Fe, Ni) on carbon supports generally improves the dispersion and activity of immobilized Pd nanocatalysts."},{"paperId":"P034","section":"performance","insight":"Anchoring highly dispersed transition metal atoms (Co, Fe, Ni) on N-doped carbon supports significantly enhances the catalytic activity of immobilized Pd NPs for FA dehydrogenation."},{"paperId":"P034","section":"performance","insight":"Among Co, Fe, and Ni, Co-decorated catalysts showed the best performance."},{"paperId":"P034","section":"performance","insight":"The activation energy (Ea) for FA dehydrogenation over Pd/NC-Co1% is approximately 57.20 kJ mol-1."},{"paperId":"P035","section":"synthesis","insight":"The arc-discharge method allows for a one-step synthesis that avoids multi-step procedures and significantly shortens preparation time to tens of minutes."},{"paperId":"P035","section":"synthesis","insight":"Ultrahigh temperatures (up to 4000°C) facilitate strong Pt-MoC interactions and the formation of high-dispersion species ranging from single atoms to nanoparticles depending on loading."},{"paperId":"P035","section":"characterization","insight":"Arc-discharge synthesis allows precise tuning of Pt dispersion from single atoms to nanoclusters and nanoparticles by varying metal loading."},{"paperId":"P035","section":"characterization","insight":"Strong electronic interaction exists between Pt and the α-MoC substrate, with electron transfer occurring from MoC to Pt species, increasing surface electron density."},{"paperId":"P035","section":"characterization","insight":"A reaction-dependent particle size effect is observed: SAs are optimal for FA dehydrogenation and CO2 hydrogenation, while NCs (~1.1 nm) are most effective for CO oxidation."},{"paperId":"P035","section":"performance","insight":"FA dehydrogenation and CO2 hydrogenation are size-dependent reactions where Pt single atoms (SAs) maximize activity."},{"paperId":"P035","section":"performance","insight":"CO oxidation exhibits an opposite trend, where SAs show limited efficiency due to strong CO adsorption causing poisoning, while nanoclusters (NCs) of ca. 1.1 nm exhibit the highest performance."},{"paperId":"P035","section":"performance","insight":"The apparent activation energy for FA dehydrogenation over 0.1Pt/MoC is 47.5 kJ mol-1."},{"paperId":"P036","section":"synthesis","insight":"The use of C3N4 as a template results in 3D hierarchical hollow morphologies for the Ru/CN catalysts."},{"paperId":"P036","section":"synthesis","insight":"Nitrogen coordination (via Phen and N-doped support) is used to stabilize small Ru nanoparticles (2-3 nm) and enhance CO tolerance."},{"paperId":"P036","section":"characterization","insight":"Nitrogen doping of the carbon support induces an electron-deficient state in Ru nanoparticles, which weakens the back-bonding effect and reduces CO adsorption strength."},{"paperId":"P036","section":"characterization","insight":"The 3D hierarchical hollow morphology inherited from the C3N4 precursor facilitates the dispersion of Ru NPs."},{"paperId":"P036","section":"characterization","insight":"Defect-rich characteristics of the carbon matrix (indicated by Raman ID/IG ratios) help stabilize small-size Ru nanoparticles."},{"paperId":"P036","section":"characterization","insight":"In situ DRIFT and KIE experiments identify the dehydrogenation of formate species (HCOO*) as the rate-determining step."},{"paperId":"P036","section":"performance","insight":"Nitrogen-doped carbon supports enhance Ru catalyst activity and selectivity for FA dehydrogenation while significantly increasing CO tolerance."},{"paperId":"P036","section":"performance","insight":"The optimal catalyst Ru7/CN shows a TOF > 1300 h-1 at 140 °C, which is more than an order of magnitude higher than commercial Ru5/C."},{"paperId":"P036","section":"performance","insight":"N-doping suppresses the dissociation of CO2 into CO and weakens the adsorption strength of CO on the Ru surface."},{"paperId":"P037","section":"synthesis","insight":"Amine groups on ACB are critical for the formation of subnanometric PdAu clusters (~0.9 nm) by strongly interacting with metal ions."},{"paperId":"P037","section":"synthesis","insight":"The dosage of APTES during ACB synthesis impacts catalytic activity, with 1.5 mL being optimized."},{"paperId":"P037","section":"characterization","insight":"Amine groups on the carbon bowl support are critical for anchoring subnanometric clusters and preventing aggregation."},{"paperId":"P037","section":"characterization","insight":"Electronic metal-support interaction between ACB and PdAu clusters creates electron-rich active sites that enhance C-H activation during formic acid dehydrogenation."},{"paperId":"P037","section":"performance","insight":"The PdAu/ACB catalyst exhibits superior activity for additive-free FA dehydrogenation and Cr(VI) reduction due to the synergistic effect of subnanometric alloy clusters, amine-functionalized support (acting as Brønsted basic sites), and electronic metal-support interaction."},{"paperId":"P037","section":"performance","insight":"FAD catalyzed by PdAu/ACB follows zero-order kinetics with respect to FA concentration and first-order kinetics with respect to catalyst concentration."},{"paperId":"P038","section":"synthesis","insight":"The thickness of the carbon layer (controlled by sucrose ratio) regulates the Pd particle size and the Pd0/PdO ratio."},{"paperId":"P038","section":"synthesis","insight":"The SiO2 core induces an electron-deficient state in Pd through strong metal-support interaction (SMSI)."},{"paperId":"P038","section":"characterization","insight":"The SiO2 core induces an electron-deficient state in Pd0 via strong metal support interaction (SMSI)."},{"paperId":"P038","section":"characterization","insight":"A carbon shell provides anchoring sites that maintain small Pd particle sizes (<5 nm) and regulates the ratio of metallic Pd to PdO."},{"paperId":"P038","section":"characterization","insight":"Electron deficiency and optimal Pd0/PdO ratios lower the energy barrier for hydrogen desorption, which is the rate-determining step in formic acid decomposition."},{"paperId":"P038","section":"performance","insight":"The strong metal support interaction (SMSI) between Pd/PdO and the SiO2@SC support creates an electron-deficient state of Pd0, which is beneficial for FAD."},{"paperId":"P038","section":"performance","insight":"The thickness of the carbon layer regulates the ratio of Pd0 to PdO; an optimal ratio enhances anti-poisoning ability and hydrogen desorption kinetics."},{"paperId":"P038","section":"performance","insight":"Hydrogen desorption (H* + H* -> H2) is identified as the rate determining step (RDS), and its energy barrier is reduced by the electron-deficient state of Pd0."},{"paperId":"P039","section":"synthesis","insight":"Calcination temperature is a critical parameter; catalysts calcined at 350 °C showed higher activity than those calcined at 550 °C."},{"paperId":"P039","section":"synthesis","insight":"Exposure of the Au1-Pd14/KIT-6 catalyst to oxygen flow at 220 °C for 5 h (forming Au1-Pd17/KIT-6) significantly enhanced hydrogen production by promoting PdO crystal formation and preventing Pd diffusion into Au sublayers."},{"paperId":"P039","section":"characterization","insight":"Calcination temperature is a critical parameter affecting the oxidation state, crystallinity, and resulting catalytic activity of Au-Pd bimetallic catalysts."},{"paperId":"P039","section":"characterization","insight":"The synergy between Au and Pd, combined with the high surface area of the 3D-mesoporous KIT-6 support, facilitates formic acid dehydrogenation."},{"paperId":"P039","section":"characterization","insight":"Oxygen activation at moderate temperatures (220 °C) optimizes the surface composition by promoting active PdO species."},{"paperId":"P039","section":"performance","insight":"Calcination temperature is critical; catalysts calcined at 350 °C are more effective than those calcined at 550 °C."},{"paperId":"P039","section":"performance","insight":"Bimetallic Au-Pd catalysts show higher activity than monometallic Pd/KIT-6 or Au/KIT-6."},{"paperId":"P039","section":"performance","insight":"Oxygen treatment of the catalyst significantly enhances hydrogen production by increasing surface Pd availability."},{"paperId":"P039","section":"performance","insight":"Sodium formate is a more effective base for promoting FA decomposition compared to diethylamine and triethylamine."},{"paperId":"P040","section":"synthesis","insight":"The use of different ligands (amine vs thiol) on the layered silicate support significantly affects the electronic structure and morphology of Pd nanoclusters, with thiol groups causing structural deformation into a flatter, quasi-two-dimensional structure."},{"paperId":"P040","section":"characterization","insight":"The choice of functional group (amine vs. thiol) regulates the trade-off between structural stability and catalytic activity; thiol groups provide stronger anchoring but diminish activity through electronic charge transfer and morphological flattening."},{"paperId":"P040","section":"characterization","insight":"XPS binding energy shifts correlate with the strength of Pd-ligand interactions, where higher BE in LS-SH/Pd indicates stronger hybridization compared to LS-NH2/Pd."},{"paperId":"P040","section":"performance","insight":"Catalytic activity of Pd NCs on amino-functionalized LS is ~27-fold higher than those on thio-functionalized LS at 70 °C."},{"paperId":"P040","section":"performance","insight":"There is a trade-off between structural stability (higher for thiol) and catalytic activity/morphology (higher for amine)."},{"paperId":"P041","section":"synthesis","insight":"The use of PDETA as a tethering ligand helps bind Pd nanoparticles with high dispersion and uniform particle size."},{"paperId":"P041","section":"synthesis","insight":"KCC-1's unique fibrous morphology and open pore structure minimize Pd particle size compared to MSF and KIT-6 supports."},{"paperId":"P041","section":"characterization","insight":"The fibrous morphology of KCC-1 is more effective at minimizing Pd particle size than MSF or KIT-6 due to its highly accessible surface area."},{"paperId":"P041","section":"characterization","insight":"PDETA acts as a tethering ligand that binds Pd nanoparticles, improving dispersion and limiting agglomeration."},{"paperId":"P041","section":"characterization","insight":"Increasing Pd loading on the amine-functionalized support leads to larger nanoparticle sizes and an increase in the fraction of unreduced Pd(2+), both of which negatively impact catalytic activity."},{"paperId":"P041","section":"performance","insight":"The fibrous morphology of KCC-1 provides better accessibility for formic acid to the active Pd sites compared to MSF and KIT-6 supports."},{"paperId":"P041","section":"performance","insight":"Lower Pd loading (2 wt.%) on KCC-1-PDETA results in smaller nanoparticles, which enhances catalytic activity compared to higher loadings (5 and 10 wt.%)."},{"paperId":"P041","section":"performance","insight":"The presence of amine groups (PDETA) helps in reducing the Pd particle size and stabilizing them."},{"paperId":"P042","section":"synthesis","insight":"PVP-stabilized Pd nanoparticles were synthesized ex situ to control particle size independently of the support."},{"paperId":"P042","section":"synthesis","insight":"The formation of a PdZn alloy occurs during reductive pre-treatment, with higher reduction temperatures (773 K vs 573 K) increasing nanoparticle size but also improving hydrogen selectivity."},{"paperId":"P042","section":"characterization","insight":"The formation of PdZn alloy is critical for achieving high hydrogen selectivity in formic acid decomposition."},{"paperId":"P042","section":"characterization","insight":"Increasing the reduction temperature from 573 K to 773 K increases the mean nanoparticle size of PdZn and PtZn alloys but does not significantly affect catalytic activity, while it does increase hydrogen selectivity."},{"paperId":"P042","section":"characterization","insight":"The independence of reaction rate on metal particle size suggests that the ZnO support is involved in the rate-determining step (decomposition of formate species)."},{"paperId":"P042","section":"characterization","insight":"In situ DRIFTS indicates that formic acid interacts with the ZnO support to form bulk Zn formate."},{"paperId":"P042","section":"performance","insight":"Pd/ZnO catalysts show higher selectivity to hydrogen than Pd/Al2O3 and Pt/ZnO due to the formation of a PdZn alloy."},{"paperId":"P042","section":"performance","insight":"The activity (conversion) of Pd/ZnO and Pt/ZnO is independent of the reduction temperature, despite changes in nanoparticle size, suggesting the reaction may be structure-insensitive or limited by the ZnO support."},{"paperId":"P042","section":"performance","insight":"Hydrogen selectivity increases with higher catalyst reduction temperatures for both Pd/ZnO and Pt/ZnO catalysts."},{"paperId":"P043","section":"synthesis","insight":"Amine-functionalization of CNC using PEI and PDA provides stable local environments and alkaline active sites that facilitate HCOOH dissociation."},{"paperId":"P043","section":"synthesis","insight":"The use of an ice water bath during NaBH4 reduction helps in achieving ultrafine nanoclusters (~2nm)."},{"paperId":"P043","section":"characterization","insight":"The use of amino-modified cellulose nanocrystals (CNC-NH2) as a support results in ultrafine, highly dispersed metal clusters due to strong metal-support interaction (SMSI)."},{"paperId":"P043","section":"characterization","insight":"Ternary alloy formation can be verified by the absence of individual metal characteristic peaks in UV-vis and the presence of intermediate lattice spacing between the constituent fcc metals."},{"paperId":"P043","section":"performance","insight":"The introduction of Pt as a third metal to the AuPd alloy enhances catalytic activity by optimizing the local electron environment and facilitating O-H bond cleavage."},{"paperId":"P043","section":"performance","insight":"Amine-functionalized CNC supports are effective in stabilizing ultrafine ternary alloy nanoclusters, improving their dispersion and performance."},{"paperId":"P044","section":"synthesis","insight":"The use of H2 as a cold plasma working gas facilitates the migration of Pd species from pores to the outer surface and provides strong reduction effects, resulting in smaller nanoparticles (2.6 nm) and higher metallic Pd content compared to Ar, O2, or air."},{"paperId":"P044","section":"synthesis","insight":"Oxygen-containing working gases (O2 and air) cause severe ablation of the carbon support, leading to agglomeration of Pd nanoparticles (5.2–7.0 nm) and an increase in actual metal loading due to carbon combustion."},{"paperId":"P044","section":"characterization","insight":"Cold plasma working gas significantly influences Pd nanoparticle size, oxidation state, and distribution on carbon supports."},{"paperId":"P044","section":"characterization","insight":"H2 plasma promotes the migration of Pd species from pores to the surface via strong Coulomb repulsion without causing support ablation."},{"paperId":"P044","section":"characterization","insight":"Oxygen-containing gases (Air, O2) cause severe ablation of the activated carbon support, leading to Pd nanoparticle agglomeration and larger particle sizes."},{"paperId":"P044","section":"characterization","insight":"Strong metal-support interaction in Pd/C-H2P is evidenced by XPS (Pd-C bonds) and higher TPR reduction temperatures."},{"paperId":"P044","section":"performance","insight":"The catalytic activity for HCOOH dehydrogenation follows the order: Pd/C-H2P > Pd/C-ArP > Pd/C-AirP ≈ Pd/C-O2P."},{"paperId":"P044","section":"performance","insight":"Hydrogen plasma treatment is superior in enhancing activity by facilitating the migration of Pd species to the surface, maintaining small nanoparticle size (2.6 nm), and increasing metallic Pd content."},{"paperId":"P045","section":"characterization","insight":"Deactivation correlates with substrate turnover and is more severe at the front of the catalyst bed, indicating poisoning by the reactant (formic acid/formate) rather than products."},{"paperId":"P045","section":"characterization","insight":"Thermal regeneration at 180 °C in air removes carbonaceous residues, as evidenced by CO2 evolution in TPO-MS."},{"paperId":"P045","section":"characterization","insight":"Washing with water restores microporosity and activity, though not linearly, suggesting multiple deactivation mechanisms (fouling and poisoning)."},{"paperId":"P045","section":"performance","insight":"Deactivation in PFR correlates better with total substrate turnover than with temperature or time on stream."},{"paperId":"P045","section":"performance","insight":"Catalyst activity can be fully restored by thermal treatment (180 °C) or washing with water, indicating reversible deactivation."},{"paperId":"P046","section":"performance","insight":"The H2 generation rate increases with increasing temperature, while the H2 yield increases with decreasing FA concentration."},{"paperId":"P046","section":"performance","insight":"Sodium formate (SF) significantly enhances the initial hydrogen generation rate but can decrease the final H2 yield depending on whether it is added as a solution or solid."},{"paperId":"P047","section":"characterization","insight":"The incorporation of Au into Pd nanoclusters promotes the reduction of Pd and increases electron density on surface Pd atoms."},{"paperId":"P047","section":"characterization","insight":"Electron transfer occurs primarily between the support/Au and Pd species, rather than directly between the support and Au."},{"paperId":"P047","section":"characterization","insight":"Smaller particle sizes (1.9 nm vs 2.5 nm) correlate with significantly higher turnover frequencies."},{"paperId":"P047","section":"performance","insight":"The catalytic activity of AP-SiO2@NGO-PDA@PdxAuy follows a volcano-type relationship with the Pd/Au mole ratio, peaking near 1:1."},{"paperId":"P047","section":"performance","insight":"Increasing reaction temperature and increasing FA concentration (up to 2 M) both improve catalyst activity."},{"paperId":"P047","section":"performance","insight":"Electron transfer from Au or the support to Pd increases the electron density of surface Pd in the alloy, optimizing its ability to bond with H2."},{"paperId":"P048","section":"synthesis","insight":"The use of electron-donating NH2 groups in the MOF support (MIL-101-NH2) effectively immobilizes metal ions, leading to smaller nanoparticle sizes and higher catalytic activity compared to bare or electron-accepting functionalized supports."},{"paperId":"P048","section":"characterization","insight":"Electron-donating groups (NH2) in MOF supports facilitate the formation of smaller, more highly dispersed trimetallic nanoparticles compared to electron-accepting groups or bare supports."},{"paperId":"P048","section":"characterization","insight":"Trimetallic AuPdM alloys form a single fcc phase where Pd and Co are incorporated into the Au lattice due to similar atomic radii."},{"paperId":"P048","section":"characterization","insight":"Electronegativity differences drive electron transfer from non-precious transition metals (Co) to noble metals (Au, Pd) within the alloy nanoparticles."},{"paperId":"P048","section":"performance","insight":"The electron-donating NH2 group in the MOF support is crucial for enhancing both activity and H2 selectivity in FA dehydrogenation."},{"paperId":"P048","section":"performance","insight":"Trimetallic AuPdCo catalysts exhibit higher activity than bimetallic or monometallic counterparts, indicating synergistic effects between noble and non-precious metals."},{"paperId":"P048","section":"performance","insight":"The optimal molar ratio of Co/(Au+Pd+Co) was found to be 0.25 for maintaining high activity while reducing noble metal content."},{"paperId":"P049","section":"synthesis","insight":"The synthesis temperature of the CTF support (400, 500, or 600 °C) significantly affects the pore volume and surface area, which in turn influences the dispersion and size of the CoPd nanoparticles."},{"paperId":"P049","section":"synthesis","insight":"CTF-600 provided the best performance due to higher pore volume and pore size, facilitating metal nanoparticle entry into the channels."},{"paperId":"P049","section":"characterization","insight":"The synthesis temperature of the CTF support significantly impacts the resulting metal nanoparticle size and dispersion, with 600 °C yielding the smallest (2 nm) and best-dispersed particles."},{"paperId":"P049","section":"characterization","insight":"Nitrogen functionalities in the CTF framework act as coordination sites to anchor active metal nanoparticles and prevent agglomeration."},{"paperId":"P049","section":"characterization","insight":"The presence of cobalt oxide is suggested to promote the catalytic activity of palladium."},{"paperId":"P049","section":"performance","insight":"The catalytic activity of CoPd/CTF is strongly dependent on the metal composition; Co5Pd5/CTF-600 showed the highest activity, while monometallic Co10/CTF-600 was inactive."},{"paperId":"P049","section":"performance","insight":"A synergistic effect exists between Co and Pd, as well as between the bimetallic nanoparticles and the nitrogen-rich CTF support."},{"paperId":"P049","section":"performance","insight":"Increasing synthesis temperature of CTF to 600 °C improves pore volume and size, enhancing metal dispersion and reaction transmission."},{"paperId":"P049","section":"performance","insight":"The addition of potassium formate promotes FA dehydrogenation, with an optimal FA:formate molar ratio of 1:4."},{"paperId":"P050","section":"characterization","insight":"The use of NaBH4 as a reducing agent converts Pd2+ precursors to metallic Pd nanoparticles."},{"paperId":"P050","section":"characterization","insight":"N2 adsorption/desorption isotherms indicate that loading Pd nanoparticles leads to a decrease in the BET specific surface area and pore volume of the activated carbon supports (a_MSC-30, a_MSP-20X, a_APDC)."},{"paperId":"P050","section":"characterization","insight":"Acid activation of porous carbon supports using HNO3, HCl, H3PO4, or H2SO4 is employed to modify the support for improved Pd nanoparticle immobilization and catalytic activity."},{"paperId":"P051","section":"synthesis","insight":"Room-temperature HNO3 treatment (RTHTA) of carbon supports introduces oxygen-containing functional groups that stabilize Pd precursors and prevent direct reduction by the carbon support, leading to ultrafine Pd nanoparticles (~2.4 nm for Pd/a_MSC-30)."},{"paperId":"P051","section":"synthesis","insight":"Acid treatment with HNO3 is specifically necessary; other acids like HCl, H3PO4, and H2SO4 did not prevent the formation of larger Pd particles as evidenced by XRD."},{"paperId":"P051","section":"characterization","insight":"Room-temperature HNO3 treatment (RTHTA) of porous carbon introduces oxygen-containing functional groups that act as ligands to stabilize Pd precursors and prevent direct reduction by the carbon support, enabling the formation of ultrafine nanoparticles."},{"paperId":"P051","section":"characterization","insight":"HNO3 is specifically required for this stabilization effect; treatments with HCl, H3PO4, or H2SO4 result in sharp XRD peaks indicating larger Pd particles."},{"paperId":"P051","section":"characterization","insight":"The high surface area of a_MSC-30 (3065 m^2/g) decreases slightly upon Pd loading to 2755 m^2/g as nanopores are partially occupied by the metal species."},{"paperId":"P051","section":"performance","insight":"The RTHTA method allows for the immobilization of ultrafine Pd nanoparticles on various porous carbons (MSC-30, MSP-20X, APDC), significantly enhancing catalytic activity for FA dehydrogenation."},{"paperId":"P051","section":"performance","insight":"Pd/a_MSC-30 achieved a record-high TOF of 13333 h^-1 at 60 °C in an aqueous FA-SF system."},{"paperId":"P052","section":"characterization","insight":"The modification of MIL-101 with NH2 groups enhances the interaction between the support and Pd nanoparticles, affecting their electronic structure."},{"paperId":"P052","section":"characterization","insight":"ICP-OES analysis confirmed that active metal loss (leaching) into the reaction liquid is negligible, confirming that agglomeration is the primary deactivation mechanism."},{"paperId":"P052","section":"performance","insight":"The catalyst activity (TOF) decreases significantly with increasing recycling times due to metal agglomeration rather than loss of active components."},{"paperId":"P053","section":"characterization","insight":"g-C3N4 tri-s-triazine groups serve as anchoring points for metal precursors to produce small and well-dispersed nanoparticles."},{"paperId":"P053","section":"characterization","insight":"Higher metal loadings of Pd decrease the BET surface area of the catalyst."},{"paperId":"P053","section":"performance","insight":"Pd/g-C3N4 catalysts are significantly more active than Cu or Zn based counterparts for formic acid decomposition."},{"paperId":"P053","section":"performance","insight":"Increasing Pd loading generally increases gas production at low temperatures, but higher loadings (5 wt%) may show decreased activity at 70 °C due to catalyst inhibition by PdCO or Pd formate."},{"paperId":"P053","section":"performance","insight":"The optimum conditions identified were 98% FA concentration and a reaction temperature of 70 °C."},{"paperId":"P054","section":"synthesis","insight":"The use of P123 surfactant resulted in the highest surface area catalysts."},{"paperId":"P054","section":"synthesis","insight":"Addition of NaF during synthesis led to structural deterioration and very low surface area (41 m2/g) compared to Tween-80 without NaF (516 m2/g)."},{"paperId":"P054","section":"synthesis","insight":"Surfactant-free one-pot method using citric acid resulted in macroporous structures."},{"paperId":"P054","section":"characterization","insight":"The acidic-basic property (specifically Lewis acidity) was found to be more dominant than pore properties, surface area, or Ni crystallite size in determining catalytic activity for gas-phase hydrogen production from formic acid."},{"paperId":"P054","section":"characterization","insight":"Catalysts with higher Lewis acidity exhibited lower catalytic activity."},{"paperId":"P054","section":"performance","insight":"All tested Ni-SiO2 catalysts achieved complete formic acid conversion at 350 °C."},{"paperId":"P054","section":"performance","insight":"The catalyst synthesized with P123 surfactant and 5 wt% Ni exhibited the highest H2 concentration and selectivity (1.07), suggesting a water-gas shift reaction occurred."},{"paperId":"P054","section":"performance","insight":"Reducing nickel content from 5 to 2.5 wt% in P123 catalysts decreased hydrogen distribution to 29.5% and selectivity to 0.44."},{"paperId":"P054","section":"performance","insight":"Lewis acidity was found to be inversely related to catalytic activity: the catalyst with higher Lewis acidity showed lower catalytic activity."},{"paperId":"P054","section":"performance","insight":"Acidic-basic properties of the catalyst were determined to be more dominant than pore properties, surface area, or Ni crystallite size in gas-phase hydrogen production from formic acid."},{"paperId":"P055","section":"synthesis","insight":"The reverse micelle system using Brij C10 in cyclohexane allows for precise control over Au nanoparticle size and SiO2 shell thickness."},{"paperId":"P055","section":"synthesis","insight":"APTMS is used to functionalize the silica shell with amine groups, which are proposed as active sites facilitating OH bond cleavage."},{"paperId":"P055","section":"characterization","insight":"TEM and XRD confirm Au nanoparticles are uniformly encapsulated in amorphous SiO2 shells."},{"paperId":"P055","section":"characterization","insight":"N2 physisorption shows a total surface area of 203 m2/g, pore volume of 0.57 cm3/g, and average pore size of 11 nm (inter-particle voids)."},{"paperId":"P055","section":"characterization","insight":"In situ ATR-FTIR identifies the presence of silane grafted propylamine and demonstrates that formic acid is deprotonated to form ammonium formate species on the catalyst surface."},{"paperId":"P055","section":"characterization","insight":"ATR-FTIR reveals a side reaction forming inactive amide species between grafted amines and formic acid, leading to partial chemical deactivation."},{"paperId":"P055","section":"performance","insight":"Au nanoparticle size has a significant impact on intrinsic activity; the smallest particles (2.2 nm) are most active."},{"paperId":"P055","section":"performance","insight":"SiO2 shell thickness affects catalytic activity, with thicker shells potentially limiting reactant diffusion."},{"paperId":"P055","section":"performance","insight":"Amine functionalization is critical for facilitating OH bond cleavage and forming Au-formate species."},{"paperId":"P055","section":"performance","insight":"Deactivation occurs via an off-cycle reaction between the amine sites and formic acid to form inactive amide species."},{"paperId":"P056","section":"synthesis","insight":"Sol-immobilisation resulted in smaller Pd particle sizes (4–6 nm) compared to impregnation (10–15 nm)."},{"paperId":"P056","section":"synthesis","insight":"PVA ligand in the sol-immobilisation method inhibited metallic Pd surface oxidation."},{"paperId":"P056","section":"characterization","insight":"Sol-immobilisation produces smaller Pd nanoparticles with higher dispersion and metallic content compared to the impregnation method."},{"paperId":"P056","section":"characterization","insight":"The use of PVA ligand during sol-immobilisation inhibits the oxidation of the metallic Pd surface in ambient air."},{"paperId":"P056","section":"performance","insight":"Sol-immobilisation technique produces smaller Pd nanoparticles and higher metallic Pd content compared to impregnation, leading to significantly higher catalytic activity (TOF 910 h⁻¹ vs 506 h⁻¹)."},{"paperId":"P056","section":"performance","insight":"Reduced graphene oxide (rGO) is a more effective support for Pd than carbon black, graphite, or graphene oxide."},{"paperId":"P057","section":"synthesis","insight":"The support RUB-15 was synthesized using TMAOH and TEOS (SiO2:TMAOH = 1:1) at 140 °C for 7 days in a Teflon-lined autoclave."},{"paperId":"P057","section":"synthesis","insight":"Amine functionalization of the support via APTES provides strong adsorption capacity for Pd2+ and Zr4+ ions, preventing nanoparticle aggregation."},{"paperId":"P057","section":"characterization","insight":"XRD confirmed the highly crystalline layered structure of RUB-15 with a d-spacing of 1.4 nm."},{"paperId":"P057","section":"characterization","insight":"BET analysis showed that loading Pd-ZrO2 NPs reduced the specific surface area from 58.79 to 42.07 m2/g and pore volume from 0.0419 to 0.0299 cm3/g."},{"paperId":"P057","section":"characterization","insight":"FT-IR confirmed successful amine functionalization of RUB-15 with peaks at 1153 and 1630 cm-1."},{"paperId":"P057","section":"performance","insight":"The activation energy for formic acid decomposition over the 2.5%Pd-0.2%ZrO2/RUB-15-NH2 catalyst was calculated to be 17.9 kJ mol^-1."},{"paperId":"P057","section":"performance","insight":"Central Composite Design (CCD) optimization identified optimal conditions as 18 mL water, 2.5 wt% Pd, 0.2 wt% Zr, and a temperature of 60 °C."},{"paperId":"P058","section":"synthesis","insight":"The morphology of Pd nanocrystals is controlled by the feeding rate of the precursor (5-45 mL/h for tetrahedrons, 90 mL/h for octahedrons, and 360 mL/h for cuboctahedrons)."},{"paperId":"P058","section":"synthesis","insight":"PVP removal via water steam treatment was necessary to ensure surface cleanliness for catalytic evaluation."},{"paperId":"P058","section":"characterization","insight":"Interfacial polarization between Pd and TiO2 leads to electron accumulation on the Pd surface, which promotes formic acid decomposition."},{"paperId":"P058","section":"characterization","insight":"The interface angle of the metal-support hybrid structure significantly influences catalytic activity through steric effects; larger angles (e.g., 109.5° for tetrahedrons) provide more space for reaction intermediates."},{"paperId":"P058","section":"characterization","insight":"A Schottky junction between Pd and TiO2 can further enhance activity by trapping photoexcited electrons on the Pd surface under incident light."},{"paperId":"P058","section":"performance","insight":"Interfacial polarization between Pd and TiO2 enhances catalytic activity by increasing electron density on the Pd surface."},{"paperId":"P058","section":"performance","insight":"The interface angle significantly affects performance due to steric effects; a larger angle (109.5° for tetrahedrons) provides more space for molecular bond movements during FA decomposition compared to smaller angles (70.5° for octahedrons, 54.7° for cuboctahedrons)."},{"paperId":"P058","section":"performance","insight":"Incident light further improves activity of Pd{111}-TiO2 via the Schottky junction trapping photoexcited electrons on Pd."},{"paperId":"P059","section":"synthesis","insight":"The reduction step (350 °C or 500 °C) increases the specific surface area of the catalyst and modulates the average charge of Pd."},{"paperId":"P059","section":"synthesis","insight":"Higher reduction temperatures lead to the disappearance of single palladium atoms and the formation of larger nanoparticles."},{"paperId":"P059","section":"characterization","insight":"A volcano-type relationship exists between the average charge of Pd (QPd) and the catalytic activity for formic acid dehydrogenation."},{"paperId":"P059","section":"characterization","insight":"Stepwise annealing followed by H2 reduction allows tuning of Pd particle size, dispersion (single atoms vs nanoparticles), and electronic properties."},{"paperId":"P059","section":"characterization","insight":"Reduction at higher temperatures (500 °C) promotes the migration and agglomeration of Pd atoms into larger nanoparticles while eliminating single-atom species."},{"paperId":"P059","section":"performance","insight":"A volcano-type relationship was observed between the average charge of Pd (QPd) and catalytic activity."},{"paperId":"P059","section":"performance","insight":"The dehydrogenation reaction process occurs via a formate anion dehydrogenation pathway, as evidenced by the significant rate increase upon addition of sodium formate."},{"paperId":"P060","section":"synthesis","insight":"The sol immobilization method with PVA as a capping agent and NaBH4 as a reducing agent was used to produce small and homogeneously dispersed nanoparticles."},{"paperId":"P060","section":"synthesis","insight":"Acidification of the suspension to pH 2 using sulfuric acid is critical for ensuring full immobilization of the preformed nanoparticles on the carbon nanofiber support."},{"paperId":"P060","section":"characterization","insight":"Bimetallic PdAu catalysts exhibit a surface enrichment of Pd atoms compared to the bulk composition."},{"paperId":"P060","section":"characterization","insight":"Electronic interaction between Au and Pd involves electron donation from gold to palladium, which is evidenced by a decrease in the binding energy of the Pd0 peak in XPS."},{"paperId":"P060","section":"characterization","insight":"DFT calculations indicate that bimetallic clusters (e.g., Pd9Au6) have a stronger interaction with the carbon support than monometallic clusters, contributing to enhanced stability against sintering."},{"paperId":"P060","section":"characterization","insight":"The catalytic activity follows a volcano trend relative to the Pd:Au ratio, peaking at approximately 6:4."},{"paperId":"P060","section":"performance","insight":"Bimetallic Pd-Au catalysts show enhanced activity, stability, and selectivity compared to monometallic counterparts."},{"paperId":"P060","section":"performance","insight":"The initial activity follows a volcano trend with respect to the Pd:Au ratio, peaking at 1%Pd6Au4@HHT."},{"paperId":"P060","section":"performance","insight":"Alloying Au with Pd suppresses the dehydration pathway (CO formation), leading to high H2 selectivity (>99%)."},{"paperId":"P060","section":"performance","insight":"Bimetallic catalysts exhibit superior stability against sintering and CO poisoning compared to monometallic Pd/C."},{"paperId":"P060","section":"performance","insight":"DFT calculations suggest that bimetallic clusters stabilize FA more effectively than pure Pd clusters through a stronger interaction with the support."},{"paperId":"P061","section":"characterization","insight":"Electron tomography revealed that leached Pd species preferentially redeposit on the external surface of the support in both batch and fixed bed reactors."},{"paperId":"P061","section":"characterization","insight":"The confinement effect of mesopores limits the growth of internal particles, reducing the formation of large aggregates compared to the external surface."},{"paperId":"P061","section":"performance","insight":"Catalytic performance and stability differ significantly between batch and fixed bed reactors due to differences in metal leaching and redeposition behavior."},{"paperId":"P061","section":"performance","insight":"In batch reactors, a dynamic equilibrium of local leaching and redeposition occurs, which helps maintain activity."},{"paperId":"P061","section":"performance","insight":"In fixed bed reactors, continuous flow transports leached active metal species away from the support, leading to severe Pd loss and rapid deactivation."},{"paperId":"P062","section":"synthesis","insight":"A dual optimization strategy was used to modulate the amount of residual Fe3+ in the HCP support to balance nitrogen exposure and bimetallic synergistic effects."},{"paperId":"P062","section":"synthesis","insight":"Excessive FeCl3 leads to excessive coordination with amino groups, reducing BET surface area and N-exposure, which increases Pd nanoparticle size."},{"paperId":"P062","section":"characterization","insight":"Dual optimization of Fe3+ content modulates the balance between Friedel-Crafts alkylation and amino group coordination, maximizing BET surface area and nitrogen exposure."},{"paperId":"P062","section":"characterization","insight":"Increased amino group exposure enhances surface hydrophilicity (water contact angle ~4° for MHCP-2 vs 68° for MHCP-4), facilitating Pd species dispersion."},{"paperId":"P062","section":"characterization","insight":"Bimetallic synergistic effects between Pd and oxidized Fe species significantly lower the energy barrier for the rate-determining O-H bond scission step in formic acid dehydrogenation."},{"paperId":"P062","section":"performance","insight":"The apparent activation energy (Ea) of Pd@MHCP-2 was determined to be 45.8 kJ mol⁻¹."},{"paperId":"P062","section":"performance","insight":"Polymer-based heterogeneous catalysts like Pd@MHCP-2 can mobilize ultrafine nanoparticles and exhibit high performance without additives, whereas other carbon supports often require HCOO- additives."},{"paperId":"P063","section":"synthesis","insight":"N-doping generally increases the reduction temperature of NiCu nanoparticles compared to undoped supports due to stronger metal-support interactions."},{"paperId":"P063","section":"synthesis","insight":"The use of N-doped supports (except NCNT) resulted in lower catalytic activity, which is attributed to electronic changes where Cu becomes more negatively charged on pyridinic nitrogen sites."},{"paperId":"P063","section":"characterization","insight":"N-doping generally increases the reduction temperature of NiCu particles due to stronger metal-support interactions, except in NCNT where interaction is weaker."},{"paperId":"P063","section":"characterization","insight":"Nitrogen doping (especially in rGO) acts as nucleation sites, improving metal dispersion and reducing average particle size from 7-8 nm to 6 nm."},{"paperId":"P063","section":"characterization","insight":"XPS analysis indicates that Cu becomes more negatively charged on pyridinic N-doped supports, which correlates with decreased catalytic activity for formic acid decomposition."},{"paperId":"P063","section":"characterization","insight":"The high selectivity to CO2 (94-98%) across all catalysts is linked to particle sizes > 5 nm, ensuring a sufficient ratio of terrace sites for bridged adsorption of FA."},{"paperId":"P063","section":"performance","insight":"N-doped catalysts are generally less active than undoped counterparts, except for NiCu/NCNT."},{"paperId":"P063","section":"performance","insight":"The high activity of NiCu/NCNT is ascribed to the presence of pyrrolic nitrogen which may act as activation sites for formic acid."},{"paperId":"P063","section":"performance","insight":"Pyridinic nitrogen in other N-doped supports (NrGO and NSXC) leads to more negatively charged metal particles, hindering the stabilization of intermediate formate species."},{"paperId":"P064","section":"synthesis","insight":"The choice of platinum precursor significantly affects the metal state: Pt(NO3)4 leads to nanocrystals (>10 nm), while H2PtCl6 results in atomically dispersed platinum stabilized on nitrogen sites."},{"paperId":"P064","section":"synthesis","insight":"Nitrogen-doped graphene (N-graphene) with 5.0 wt.% N content provides stabilization sites for atomic platinum, specifically defects surrounded by four nitrogen atoms."},{"paperId":"P064","section":"characterization","insight":"The choice of platinum precursor substantially affects the metal state: Pt(NO3)4 yields nanocrystals, while H2PtCl6 leads to atomically dispersed platinum."},{"paperId":"P064","section":"characterization","insight":"EXAFS data for Pt/N-graphene (H2PtCl6) shows a Pt-N distance of 2.12–2.14 Å with a coordination number of 3.7–3.9, suggesting a square planar nitrogen environment."},{"paperId":"P064","section":"characterization","insight":"No bulk metal Pt0 was detected in the H2PtCl6-prepared catalysts via EXAFS (absence of peak at R ≈ 2.76 Å)."},{"paperId":"P064","section":"characterization","insight":"N-graphene support contains pyridine-like, pyrrole/amino, graphite-like, and oxidized nitrogen species (5.0 wt.% N total)."},{"paperId":"P064","section":"performance","insight":"The choice of platinum precursor substantially affects the state of the metal and catalytic activity: H2PtCl6 leads to atomically dispersed Pt, while Pt(NO3)4 results in nanocrystals."},{"paperId":"P064","section":"performance","insight":"Catalysts prepared using H2PtCl6 are more active (lower T50%) and more selective towards H2 and CO2 than those prepared with Pt(NO3)4."},{"paperId":"P064","section":"performance","insight":"Increasing platinum concentration generally increases catalytic activity and selectivity to the dehydrogenation pathway."},{"paperId":"P065","section":"synthesis","insight":"The crystal phase of the TiO2 support significantly influences Pd nanoparticle size, dispersion, and chemical valence state."},{"paperId":"P065","section":"characterization","insight":"The TiO2 crystal phase significantly influences the Pd nanoparticle size, oxidation state, and exposed crystal planes (Pd(111) vs Pd(100))."},{"paperId":"P065","section":"characterization","insight":"Smaller Pd particles on rutile and anatase supports correlate with higher intrinsic catalytic activity for transfer hydrogenation."},{"paperId":"P065","section":"characterization","insight":"Metal-support interaction strength varies by TiO2 phase, as evidenced by the different H2-TPR reduction temperatures of the TiO2 surface (Rutile < Brookite < Anatase < TiO2(B))."},{"paperId":"P065","section":"characterization","insight":"Pd(111) planes favor the dehydrogenation pathway (HCOOH to CO2), while Pd(100) planes promote the dehydration pathway (HCOOH to CO)."},{"paperId":"P065","section":"performance","insight":"The TiO2 crystal phase significantly affects the transfer hydrogenation performance of Pd/TiO2 catalysts in the order: Pd/rutile > Pd/anatase > Pd/brookite > Pd/TiO2(B)."},{"paperId":"P065","section":"performance","insight":"Pd/rutile's superior activity is attributed to its lowest activation energy and more efficient transformation of bidentate formate into monodentate formate."},{"paperId":"P065","section":"performance","insight":"The reaction pathway differs by crystal phase: rutile and anatase favor dehydrogenation, while brookite and TiO2(B) show higher selectivity for HCOOH dehydration (forming CO)."},{"paperId":"P066","section":"characterization","insight":"In-situ ATR-IR is necessary to detect adsorbed CO on Pd during formic acid decomposition, as ex-situ IR fails due to oxidation of CO in air."},{"paperId":"P066","section":"characterization","insight":"The presence of trace oxygen (below 0.1 vol%) maintains catalyst activity by removing poisoning CO species from the Pd surface."},{"paperId":"P066","section":"performance","insight":"Oxygen concentrations below 0.1 vol% enhance H2 production by preventing CO poisoning without significantly promoting H2 oxidation."},{"paperId":"P066","section":"performance","insight":"Increasing oxygen concentration above 0.1 vol% increases the overall formic acid conversion rate but decreases hydrogen yield due to dominating oxidation pathways."},{"paperId":"P067","section":"synthesis","insight":"The Pt-PVP catalyst was purchased commercially from TANAKA HOLDINGS Company Limited."},{"paperId":"P067","section":"characterization","insight":"Catalyst deactivation is attributed to the adsorption of simultaneously produced CO2 onto Pt–PVP."},{"paperId":"P067","section":"performance","insight":"The isobaric process system significantly improves the amount of H2 produced compared to an isochoric system by maintaining internal pressure at atmospheric level, preventing premature saturation due to equilibrium pressure."},{"paperId":"P067","section":"performance","insight":"Catalytic activity for Pt-PVP in formic acid decomposition is strongly pH-dependent, reaching a maximum around the pKa of formic acid (3.75)."},{"paperId":"P068","section":"synthesis","insight":"Doping rare earth metals (Nd, Ce, Sm) into the zirconia lattice stabilizes the tetragonal phase and generates oxygen vacancies."},{"paperId":"P068","section":"synthesis","insight":"The resulting oxygen vacancies enhance metal-support interaction by promoting charge transfer from the support to Au nanoclusters."},{"paperId":"P068","section":"characterization","insight":"Rare earth metal doping (Nd3+, Ce3+, Sm3+) stabilizes the tetragonal phase of ZrO2 and prevents sintering during calcination, reducing crystallite size from 12.7 nm to 6.3-7.2 nm."},{"paperId":"P068","section":"characterization","insight":"Doping with low-valence rare earth metals generates oxygen vacancies in the zirconia lattice, which is confirmed by XPS O 1s analysis (higher O II/O I ratio)."},{"paperId":"P068","section":"characterization","insight":"Oxygen vacancies facilitate electron transfer from the ReZrO2 support to Au nanoclusters, as evidenced by the negative shift in Au 4f binding energies and increased H2-TPR reduction temperatures."},{"paperId":"P068","section":"characterization","insight":"The enhanced metal-support interaction resulting from rare earth doping lowers the activation energy for formic acid dehydrogenation."},{"paperId":"P068","section":"performance","insight":"Rare earth metal doping (Nd, Ce, Sm) in ZrO2 stabilizes the tetragonal phase and creates oxygen vacancies."},{"paperId":"P068","section":"performance","insight":"Oxygen vacancies facilitate electron transfer from the support to Au nanoclusters, enhancing the metal-support interaction."},{"paperId":"P068","section":"performance","insight":"The enhanced metal-support interaction decreases the activation energy barrier for FA decomposition, thereby increasing the reaction rate."},{"paperId":"P069","section":"synthesis","insight":"Potassium carbonate (K2CO3) acted as a chemical activator to create a large specific surface area (2029.66 m2/g) in the chitosan-derived carbon support."},{"paperId":"P069","section":"synthesis","insight":"Pd loading above 9.2 wt % led to nanoparticle agglomeration and reduction of specific surface area."},{"paperId":"P069","section":"characterization","insight":"The chitosan-derived N-doped carbon support is microporous (pore sizes 1.72-1.85 nm) with a high specific surface area of 2029.66 m2/g."},{"paperId":"P069","section":"characterization","insight":"Nitrogen doping in the support consists of graphitic, pyrrolic, and pyridinic N; pyridinic N (40.49% in Pd9.2/C-N) is identified as particularly favorable for catalytic performance."},{"paperId":"P069","section":"characterization","insight":"Excessive Pd loading (>9.2 wt%) leads to particle agglomeration which blocks support pores and reduces the overall specific surface area."},{"paperId":"P069","section":"performance","insight":"The catalytic activity increases with Pd loading up to 18.4 wt%, but decreases at 23.1 wt% due to palladium aggregation."},{"paperId":"P069","section":"performance","insight":"Sodium formate acts as a positive facilitator for formic acid dehydrogenation reactions."},{"paperId":"P069","section":"performance","insight":"Nitrogen-doped carbon supports derived from chitosan provide better dispersion and electronic effects compared to N-free cellulose-based carbons."},{"paperId":"P070","section":"synthesis","insight":"The high dispersion and small size (ca. 2.3 nm) of Pd nanoparticles are attributed to strong interactions between the Pd precursors and the thiourea groups in the PMO walls."},{"paperId":"P070","section":"characterization","insight":"Strong interactions between the Pd precursors and thiourea groups in the PMO framework facilitate the formation of extremely small, highly dispersed nanoparticles."},{"paperId":"P070","section":"performance","insight":"Metallic Pd is more active than Pd2+ ions during catalysis."},{"paperId":"P070","section":"performance","insight":"H2 production rate increases with increasing temperature."},{"paperId":"P071","section":"synthesis","insight":"High-temperature amination of AC in NH3 flow introduces pyridinic, pyrrole, and graphitic N species, which promote Pd dispersion and modify its electronic state."},{"paperId":"P071","section":"synthesis","insight":"Amination temperature significantly affects nitrogen content and pore structure, with 950 °C being optimal for both surface area (1145 m2/g) and total nitrogen content (4.12%)."},{"paperId":"P071","section":"synthesis","insight":"The interaction between Pd and N-doped carbon prevents nanoparticle agglomeration during synthesis and catalytic recycling."},{"paperId":"P071","section":"characterization","insight":"N-doping of activated carbon (HTNC) promotes the dispersion of Pd nanoparticles and modifies their electronic properties."},{"paperId":"P071","section":"characterization","insight":"A positive linear correlation exists between graphitic N content and the Pd2+/Pd0 ratio."},{"paperId":"P071","section":"characterization","insight":"Strong interaction between Pd and nitrogen-doped AC decreases the mobility of Pd NPs, preventing agglomeration during reaction."},{"paperId":"P071","section":"performance","insight":"The addition of sodium formate (SF) promotes FA decomposition by providing formate ions, bypassing the O-H cleavage step and eliminating HCO3- accumulation."},{"paperId":"P071","section":"performance","insight":"Apparent activation energy for Pd/HTNC-950 was 33.67 kJ mol⁻¹."},{"paperId":"P072","section":"characterization","insight":"The addition of Ag to Pd/C creates a bimetallic alloy that significantly enhances the TOF and H2 yield for sodium formate decomposition in the presence of acetic acid."},{"paperId":"P072","section":"characterization","insight":"HRTEM and EDX mapping confirm that Ag is embedded into Pd nanoparticles, forming a uniform PdAg alloy phase."},{"paperId":"P072","section":"performance","insight":"The order of catalytic performance for SF decomposition is Ag16Pd1/C > Co16Pd1/C > Pd/C > Fe16Pd1/C > Ni16Pd1/C > Cu16Pd1/C."},{"paperId":"P072","section":"performance","insight":"H2 production rate is positively correlated with the concentration of initial SF and catalyst amount, but H2 yield decreases as SF concentration increases."},{"paperId":"P072","section":"performance","insight":"The activity depends on the acidity of the added organic acid: CH3COOH (highest) > C2H5COOH > C3H7COOH > C4H9COOH."},{"paperId":"P072","section":"performance","insight":"Strong inorganic acids (H2SO4, HNO3, HCl) inhibit SF decomposition due to excessive Pd surface protonation."},{"paperId":"P073","section":"synthesis","insight":"N-doping of the carbon support via urea calcination at 300 °C provides anchoring sites that result in smaller and more evenly distributed Pd nanoparticles compared to undoped HPC."},{"paperId":"P073","section":"synthesis","insight":"The use of NaBH4 as a reducing agent is critical, but excess amounts must be suppressed to avoid poisoning or blocking active sites on the nanoparticle surface."},{"paperId":"P073","section":"characterization","insight":"N-doping in the biomass-derived porous carbon support provides critical anchoring sites that stabilize Pd nanoparticles and prevent aggregation."},{"paperId":"P073","section":"characterization","insight":"The interaction between N atoms and Pd NPs modifies the electronic properties of the metal, which is essential for enhancing the rate-determining step (C-H bond breakdown) in formic acid dehydrogenation."},{"paperId":"P073","section":"characterization","insight":"BET analysis shows a significant reduction in surface area from HPC-150 (2854 m2/g) to Pd/NHPC-150 (1594 m2/g), attributed to partial cavity occupation by the deposited Pd NPs."},{"paperId":"P073","section":"performance","insight":"The use of N-doped hierarchical porous carbon derived from bamboo chopsticks as a support significantly enhances the TOF and stability of Pd nanoparticles for additive-free formic acid dehydrogenation compared to non-nitrogen-doped supports."},{"paperId":"P073","section":"performance","insight":"Optimal catalytic activity was observed at 8 wt.% Pd loading; lower loadings may block active sites with excess NHPC, while higher loadings lead to larger Pd NP sizes."},{"paperId":"P074","section":"synthesis","insight":"In-situ reduction of monometallic Pd species using H2 evolved from the reaction provided better performance than pre-reduction with NaBH4."},{"paperId":"P074","section":"synthesis","insight":"Pre-reduction with NaBH4 was mandatory for bimetallic PdAg catalysts to achieve high activity, as in-situ reduced PdAg samples showed poor activity and larger particle sizes."},{"paperId":"P074","section":"characterization","insight":"Nitrogen functional groups in the biomass-derived carbon support act as anchoring points, significantly reducing nanoparticle size and increasing dispersion."},{"paperId":"P074","section":"characterization","insight":"Alloying Pd with Ag results in electron-rich Pd species (Pd0), while N-doping of the support stabilizes electron-deficient Pd species (Pd2+)."},{"paperId":"P074","section":"characterization","insight":"The combination of metallic Pd0 and electron-deficient Pd species is identified as necessary for efficient formic acid dehydrogenation."},{"paperId":"P074","section":"characterization","insight":"Pre-reduction with NaBH4 is critical for bimetallic PdAg catalysts to avoid Ag-rich surface segregation that occurs during in-situ reduction."},{"paperId":"P074","section":"performance","insight":"The combination of nitrogen functional groups in the support and Ag in the metal phase (PdAg/N-AS) provides a synergistic effect, resulting in the highest activity and stability."},{"paperId":"P074","section":"performance","insight":"Pre-reduction is mandatory for bimetallic PdAg catalysts to achieve high activity, whereas monometallic Pd catalysts perform better when reduced in-situ during the reaction."},{"paperId":"P074","section":"performance","insight":"Nitrogen functional groups serve as anchoring sites that maintain small nanoparticle size and increase catalyst basicity, boosting FA dehydrogenation."},{"paperId":"P075","section":"synthesis","insight":"The 'leavening' strategy using NaHCO3 and NH4HCO3 significantly increases the BET surface area of activated carbon."},{"paperId":"P075","section":"synthesis","insight":"Nitrogen doping (via NH4HCO3) prevents Pd nanoparticle aggregation, resulting in smaller particle sizes (1.88 nm for Pd/NHPC-AC vs 2.56 nm for Pd/HPC-AC and 3.31 nm for Pd/AC)."},{"paperId":"P075","section":"synthesis","insight":"pH mediation using Na2CO3 is used to facilitate the adsorption of Pd2+ cations on the carbon surface before reduction."},{"paperId":"P075","section":"characterization","insight":"Nitrogen doping in carbon supports (pyridinic, pyrrolic, and graphitic N) improves the anchoring of Pd nanoparticles through nitrogen affinity."},{"paperId":"P075","section":"characterization","insight":"The 'leavening' strategy significantly increases the BET surface area of activated carbon."},{"paperId":"P075","section":"performance","insight":"N-doping of the carbon support prevents Pd nanoparticle aggregation and leaching, enhancing stability."},{"paperId":"P075","section":"performance","insight":"The presence of nitrogen increases the proportion of metallic Pd0 (54% for Pd/NHPC-AC), which provides more active sites compared to non-nitrogen doped supports."},{"paperId":"P075","section":"performance","insight":"Sodium formate acts as a catalytic promoter by forming metal-formate species that enrich the surface electronically."},{"paperId":"P076","section":"synthesis","insight":"The use of Na3Cit and APTES as stabilizing agents was optimized to maximize catalytic activity and control particle size (~3.0-3.1 nm)."},{"paperId":"P076","section":"synthesis","insight":"Synthesis at low temperature (ice bath) resulted in higher activity compared to room temperature synthesis."},{"paperId":"P076","section":"characterization","insight":"The use of CO chemisorption to quantify surface Pd atoms revealed that the optimal Pd:Ag ratio for specific activity (TOF) is 7:3, regardless of the reactant composition (FA-only vs FA-SF mixture)."},{"paperId":"P076","section":"characterization","insight":"BET surface area increased slightly from 22 m2/g (pristine CNT) to 27-30 m2/g for PdAg/CNT catalysts due to the addition of metal nanoparticles on a non-porous support."},{"paperId":"P076","section":"performance","insight":"The optimal catalyst for formic acid dehydrogenation based on surface active sites is Pd7Ag3/CNT, regardless of the FA:SF ratio in the reactant solution."},{"paperId":"P076","section":"performance","insight":"TOF calculated by total metal atoms shows a dependency on the FA:SF ratio (max at 9:1 for FA-only and 8:2 for FA-SF), whereas TOF based on surface Pd sites is independent of this ratio."},{"paperId":"P077","section":"synthesis","insight":"The ligand-protected method under direct hydrothermal conditions ensures the encapsulation of sub-nanometer metal clusters within the zeolite matrix, preventing aggregation and improving thermal stability compared to incipient wetness impregnation."},{"paperId":"P077","section":"characterization","insight":"Zeolite encapsulation in S-1 prevents metal aggregation and provides high thermal stability up to 700 C."},{"paperId":"P077","section":"characterization","insight":"Charge transfer from Mn to Pd creates electron-enriched Pd surfaces, which is critical for enhancing catalytic activity in CO2 hydrogenation and FA dehydrogenation."},{"paperId":"P077","section":"characterization","insight":"The combination of STEM-HAADF, XANES, and EXAFS confirms the formation of sub-nanometer bimetallic clusters (< 0.7 nm) confined within zeolite channels."},{"paperId":"P077","section":"performance","insight":"The introduction of Mn into zeolite-encaged Pd clusters significantly enhances both CO2 hydrogenation to formate and FA dehydrogenation to H2."},{"paperId":"P077","section":"performance","insight":"Electron-enriched Pd surfaces, induced by charge transfer from Mn to Pd, are key to the improved activity in bicarbonate hydrogenation."},{"paperId":"P077","section":"performance","insight":"Zeolite encapsulation provides high thermal stability and prevents metal aggregation compared to impregnation methods."},{"paperId":"P078","section":"synthesis","insight":"The use of a CN sacrifice template increases the Co loading in final catalysts compared to bare ZIF precursors."},{"paperId":"P078","section":"synthesis","insight":"Controlling the Zn/Co ratio in the ZIF precursor allows for regulation of active sites from single atoms (high Zn/Co) to nanoparticles (low Zn/Co)."},{"paperId":"P078","section":"synthesis","insight":"The interaction between CN and ZIFs during pyrolysis leads to a hybrid core-shell structure consisting of Co nanoparticle cores and carbon shell layers anchored with single atomic Co sites."},{"paperId":"P078","section":"characterization","insight":"The use of a CN sacrifice template allows for high Co loading while maintaining the ability to form single-atom sites through interaction during pyrolysis."},{"paperId":"P078","section":"characterization","insight":"A Zn/Co ratio of 2 in ZIF precursors is sufficient to prevent metal agglomeration, whereas lower ratios lead to nanoparticles and clusters."},{"paperId":"P078","section":"characterization","insight":"Hybrid core-shell structures (single atoms on a shell surrounding an NP core) exhibit superior synergy for formic acid dehydrogenation compared to pure SACs or NPs."},{"paperId":"P078","section":"performance","insight":"The hybrid core-shell structure (Co&CoN-0.5) significantly enhances mass activity and suppresses CO formation compared to single atomic Co sites or bare Co nanoparticles."},{"paperId":"P078","section":"performance","insight":"Optimal formic acid concentration for Co&CoN-0.5 is 1.6 M, but it remains active for pure formic acid (26 M)."},{"paperId":"P078","section":"performance","insight":"Mass activity of Co&CoN-0.5 increases 3-fold when temperature is raised from 90 to 110 °C."},{"paperId":"P079","section":"synthesis","insight":"The ECoDH strategy involves alkaline ion etching (KCl) to increase pore volume and defect sites, followed by B and N co-doping using boric acid and urea to improve hydrophilicity and metal dispersion."},{"paperId":"P079","section":"synthesis","insight":"Alloying Pd with a small amount of Co (5 at%) optimizes the electronic structure for formic acid dehydrogenation."},{"paperId":"P079","section":"characterization","insight":"KCl etching of carbon nanospheres increases the specific surface area (from 400 to 453 m2/g) and pore volume (from 0.2 to 0.22 cm3/g)."},{"paperId":"P079","section":"characterization","insight":"B and N co-doping enhances the hydrophilicity of the carbon support, evidenced by an O-H stretching vibration peak at 3470 cm-1 in FT-IR."},{"paperId":"P079","section":"characterization","insight":"Raman spectroscopy (ID/IG ratio) indicates that KCl etching and B,N co-doping increase the number of surface defects, which provide more sites for metal NP dispersion."},{"paperId":"P079","section":"characterization","insight":"The formation of PdCo alloys is confirmed by a decrease in XRD peak intensity for Pd and a positive shift in the Pd 3d binding energy in XPS."},{"paperId":"P079","section":"performance","insight":"The combination of KCl etching and B, N co-doping significantly improves the catalytic activity for FA dehydrogenation compared to non-etched/non-doped Pd/C."},{"paperId":"P079","section":"performance","insight":"Alloying Pd with a small amount (5%) of Co further enhances TOF by modulating the electronic structure of Pd NPs."},{"paperId":"P079","section":"performance","insight":"The activation energy (Ea) for the reaction over Pd0.95Co0.05/CK-BN was calculated to be 50.30 kJ mol-1."},{"paperId":"P080","section":"synthesis","insight":"The molar ratio of CTAB/NaSal (0.25 to 3.0) regulates the particle size and surface area of the DMSNs support, which directly influences the resulting Pd nanoparticle size and catalytic activity."},{"paperId":"P080","section":"synthesis","insight":"Amine functionalization using APTES provides anchoring sites that prohibit the clustering of Pd NPs, leading to ultrasmall particles (1.6 nm for Pd/DMSNs-1.0-NH2)."},{"paperId":"P080","section":"synthesis","insight":"The optimized support ratio CTAB/NaSal = 1.0 provides the highest surface area and most concentrated pore size distribution among the series."},{"paperId":"P080","section":"characterization","insight":"Amine functionalization of the silica support effectively prohibits the clustering of Pd NPs, resulting in significantly smaller particle sizes (1.6 nm) compared to non-functionalized supports (3.9 nm)."},{"paperId":"P080","section":"characterization","insight":"The molar ratio of CTAB/NaSal during support synthesis regulates the size of the DMSNs nanospheres and subsequently influences the dispersion and size of the loaded Pd nanoparticles."},{"paperId":"P080","section":"performance","insight":"The catalytic activity of Pd/DMSNs-x-NH2 catalysts is significantly influenced by the particle size and pore structural properties of the dendritic mesoporous silica supports."},{"paperId":"P080","section":"performance","insight":"Optimal performance was achieved with a 5 wt% Pd loading on DMSNs-1.0-NH2, where an APTES grafting volume of 3 mL provided the best results."},{"paperId":"P080","section":"performance","insight":"The rate-determining step (RDS) for FAD over these catalysts is the breaking of C-H bonds."},{"paperId":"P081","section":"synthesis","insight":"The study is entirely theoretical (DFT); however, the authors suggest that simultaneous deposition of Co and Sn atoms onto a C2N platform could experimentally realize the design due to high adsorption energy (8.02 eV) for the dual-atom configuration compared to homometallic pairs."},{"paperId":"P081","section":"characterization","insight":"The study is based on first-principle calculations (DFT) using the M06-L functional; no experimental characterization was performed in this work."},{"paperId":"P081","section":"characterization","insight":"Theoretical characterization tools used include electron density difference, Projected Density of States (PDOS), and Overlap Density of States (OPDOS)."},{"paperId":"P081","section":"characterization","insight":"The noncontact promoter (Sn, Ge, or Pb) modulates the electronic state of the Co active site via charge redistribution through the C2N support network rather than direct bonding."},{"paperId":"P081","section":"performance","insight":"Noncontact single atom promoters (SAP) like Sn, Ge, and Pb can modulate the electronic/spin states of a Co SAC on C2N support without changing its coordination environment."},{"paperId":"P081","section":"performance","insight":"The high-spin state of Co is significantly more active for HCOOH dehydrogenation than the low-spin state."},{"paperId":"P081","section":"performance","insight":"C2N-Co-Sn exhibits reaction barriers (0.55 eV) comparable to or lower than commercial Pt or Pd catalysts (0.65-0.88 eV)."},{"paperId":"P082","section":"synthesis","insight":"Amino groups on the KIT-6 support strongly adsorb metal ions, leading to smaller nanoparticle sizes during reduction."},{"paperId":"P082","section":"synthesis","insight":"WOx acts as a barrier to inhibit the growth of PdNi alloy nanoclusters, resulting in an ultrasmall size of 1.4 nm."},{"paperId":"P082","section":"characterization","insight":"Amino groups on KIT-6 strongly adsorb metal ions, leading to smaller NPs during reduction."},{"paperId":"P082","section":"characterization","insight":"WOx acts as a structural barrier that inhibits the growth of PdNi nanoclusters."},{"paperId":"P082","section":"characterization","insight":"The synergistic effect of alloying (PdNi) and promotion (WOx) significantly lowers the activation energy for formic acid dehydrogenation from 48.5 kJ/mol (Pd/KIT-6-NH2) to 34.6 kJ/mol (PdNi-WOx/KIT-6-NH2)."},{"paperId":"P082","section":"performance","insight":"The Pd8Ni2-WOx/KIT-6-NH2 catalyst exhibits the lowest activation energy (34.6 kJ mol-1) among investigated catalysts."},{"paperId":"P082","section":"performance","insight":"C-H bond cleavage is identified as the rate-determining step for FDR over PdNi-WOx/KIT-6-NH2."},{"paperId":"P082","section":"performance","insight":"The reaction order with respect to initial FA concentration is almost zero, while it is close to second-order with respect to catalyst amount."},{"paperId":"P083","section":"synthesis","insight":"The support morphology (hollow spheres vs nanobelts vs nanoparticles) was used to modulate the density and strength of surface basic sites."},{"paperId":"P083","section":"synthesis","insight":"Deposition-precipitation with pH control (pH 10.8) was employed for Pd loading."},{"paperId":"P083","section":"characterization","insight":"Support morphology regulates the density and strength of surface basic sites on alumina."},{"paperId":"P083","section":"characterization","insight":"Basic sites facilitate the deprotonation of formic acid to formate (HCOO-), which promotes the formation of Pd-HCOO* intermediates."},{"paperId":"P083","section":"characterization","insight":"Metallic Pd0 is identified as the primary active species for formic acid dehydrogenation after H2 reduction."},{"paperId":"P083","section":"performance","insight":"The catalytic efficiency for formic acid dehydrogenation is strongly correlated with the density and strength of basic sites on the alumina support."},{"paperId":"P083","section":"performance","insight":"Basic surfaces preferentially favor the dehydrogenation route over dehydration, suppressing CO formation."},{"paperId":"P083","section":"performance","insight":"Sodium formate (HCOONa) acts as a promoter by enhancing the reaction rate through the facilitation of HCOO* intermediates."},{"paperId":"P084","section":"synthesis","insight":"The addition of NaOH during synthesis regulates the Pd NP nucleation rate and growth process by inducing ligand exchange (forming [PdCl3(OH)]2- and [PdCl2(OH)2]2-), resulting in smaller particle sizes and higher dispersion."},{"paperId":"P084","section":"synthesis","insight":"ZrO2@C support is derived from MOF pyrolysis, providing a synergistic effect between the metal NPs and the support."},{"paperId":"P084","section":"characterization","insight":"NaOH addition during preparation regulates the nucleation rate and growth of Pd NPs, inhibiting rapid growth and resulting in smaller, more highly dispersed particles."},{"paperId":"P084","section":"characterization","insight":"The ZrO2 support modifies the electronic structure of Pd NPs via electron transfer, creating an electron-rich surface that facilitates formic acid decomposition."},{"paperId":"P084","section":"performance","insight":"The addition of NaOH during catalyst preparation regulates the Pd NP nucleation rate and growth, leading to smaller particle sizes and greater dispersion."},{"paperId":"P084","section":"performance","insight":"ZrO2 support modifies the electronic structure of Pd NPs via electron transfer, creating more electron-rich surfaces that promote FA decomposition."},{"paperId":"P084","section":"performance","insight":"Sodium formate (SF) acts as a promoter by increasing the concentration of HCOO- ions and their contact with metal catalytic sites."},{"paperId":"P085","section":"synthesis","insight":"The use of PVPI as a capping ligand induces an interfacial electron transfer from the imino group to the PdAg NW surface, enhancing catalytic activity."},{"paperId":"P085","section":"synthesis","insight":"Pd5Ag5 composition was found to be the most active for formic acid dehydrogenation."},{"paperId":"P085","section":"characterization","insight":"XPS and FTIR confirm electron transfer from the PVPI ligand to the PdAg nanowire surface, specifically increasing the electron density of Pd atoms."},{"paperId":"P085","section":"characterization","insight":"XRD patterns show diffraction peaks between those of pure Pd NWs and Ag NPs, confirming alloy formation."},{"paperId":"P085","section":"characterization","insight":"STEM-EDS mapping and linear scan analysis verify atomic-level homogeneous alloying of Pd and Ag."},{"paperId":"P085","section":"performance","insight":"The PVPI-capped networked Pd5Ag5 NWs exhibit the highest activity among various PdAg compositions (Pd3Ag7, Pd7Ag3) and pure Pd NWs."},{"paperId":"P085","section":"performance","insight":"Light irradiation at 365 nm enhances the catalytic activity of PVPI-capped catalysts via ligand-to-metal electron transfer."},{"paperId":"P085","section":"performance","insight":"The addition of sodium formate does not increase performance for PVPI-capped Pd5Ag5 NWs, suggesting that the imino group effectively handles O-H bond dissociation."},{"paperId":"P086","section":"synthesis","insight":"The use of PVA as a capping agent requires desorption (observed during initial reaction cycles) to fully expose active sites."},{"paperId":"P086","section":"synthesis","insight":"Acidification to pH 2 using H2SO4 is used to ensure full immobilisation of Pd nanoparticles on the carbon support."},{"paperId":"P086","section":"characterization","insight":"Support functionalization with O and P reduces Pd nanoparticle size from 3 nm to 2.3 nm and increases dispersion from 36% to 42%."},{"paperId":"P086","section":"characterization","insight":"XPS indicates that Pd is preferentially deposited on the oxygen and phosphorous functional groups of the carbon nanofibers."},{"paperId":"P086","section":"characterization","insight":"DFT simulations show that adhesion energy (EADH) for Pd clusters is more negative (more stable) on functionalized surfaces (G_CO, G_COOH, G_OH, G_PO3H) than on pristine graphene, with oxygen groups providing the strongest interaction."},{"paperId":"P086","section":"performance","insight":"Support functionalization with oxygen or phosphorous enhances the stability and selectivity of Pd catalysts for formic acid decomposition by strengthening metal-support interactions."},{"paperId":"P086","section":"performance","insight":"Oxygenated supports (Pd@O-HHT) showed higher activity and stability compared to phosphorous-functionalized (Pd@P-HHT) and non-functionalized (Pd@HHT) catalysts."},{"paperId":"P086","section":"performance","insight":"Functionalization leads to smaller Pd nanoparticles, higher dispersion, and increased metal exposure on the surface."},{"paperId":"P087","section":"synthesis","insight":"The use of APTES functionalization creates negatively-charged -NH2 groups that act as nucleation sites for Pd2+ and Cr3+ ions, preventing aggregation."},{"paperId":"P087","section":"synthesis","insight":"Synthesis was performed under ambient atmosphere and room temperature."},{"paperId":"P087","section":"characterization","insight":"The M-β-CD-A support uses negatively-charged -NH2 groups to anchor Pd2+ and Cr3+ ions, preventing nanoparticle aggregation."},{"paperId":"P087","section":"characterization","insight":"Metal/organic interfaces are more effective at enhancing formic acid dehydrogenation activity than metal/carbon or metal/oxide interfaces."},{"paperId":"P087","section":"characterization","insight":"Alloying Pd with Cr reduces the crystal lattice and modulates the electronic structure of Pd active centers."},{"paperId":"P087","section":"performance","insight":"The Cr0.4Pd0.6/M-β-CD-A catalyst shows a maximum initial TOF at x = 0.4 in the series CrxPd1-x/M-β-CD-A."},{"paperId":"P087","section":"performance","insight":"Activation energy (Ea) for Cr0.4Pd0.6/M-β-CD-A is calculated to be 49.4 kJ/mol."},{"paperId":"P088","section":"synthesis","insight":"The use of NaHCO3 and (NH4)2C2O4 as foaming agents creates a porous structure and introduces nitrogen doping into the biochar."},{"paperId":"P088","section":"synthesis","insight":"H3PO4 acts as both an impurity scavenger for alkaline residues in the support and a dispersing agent to prevent Pd nanoparticle aggregation, resulting in ultra-fine particles (~2.8 nm)."},{"paperId":"P088","section":"synthesis","insight":"The optimal calcination temperature for CMC to form the desired pore structure was found to be 973 K."},{"paperId":"P088","section":"characterization","insight":"Phosphate-mediation using H3PO4 acts as both a dispersing agent to prevent Pd aggregation and an impurity scavenger for the biochar support."},{"paperId":"P088","section":"characterization","insight":"N-doping of the biochar (via ammonium oxalate) modifies the electronic density of Pd NPs, facilitating higher catalytic activity."},{"paperId":"P088","section":"characterization","insight":"The use of foaming agents (NaHCO3 and (NH4)2C2O4) is critical for creating a porous structure that supports high metal loading and fine dispersion."},{"paperId":"P088","section":"characterization","insight":"DFT calculations and H2-TPD suggest that the Pd-cluster-edge sites on ultra-fine particles alleviate hydrogen poisoning compared to traditional lattice surfaces."},{"paperId":"P088","section":"performance","insight":"The use of a foaming agent ((NH4)2C2O4 and NaHCO3) creates an N-doped porous biochar support that enhances Pd dispersion and activity."},{"paperId":"P088","section":"performance","insight":"Phosphate-mediation (H3PO4 treatment) is critical for synthesizing ultra-fine Pd nanoparticles by acting as a dispersing agent and impurity scavenger."},{"paperId":"P088","section":"performance","insight":"DFT calculations indicate that the Pd-cluster-edge and Pd(100) surfaces are more active than Pd(111) due to lower energy barriers for H2 formation and reduced hydrogen poisoning."},{"paperId":"P089","section":"synthesis","insight":"Heat treatment under CO at 250 °C increases the surface Pd concentration and the number of 3-fold hollow sites compared to H2 or N2 treatments."},{"paperId":"P089","section":"characterization","insight":"CO treatment effectively increases the surface Pd concentration and the density of 3-fold hollow sites in PdAu alloys."},{"paperId":"P089","section":"characterization","insight":"The ensemble effect is characterized by the presence of triangular shaped Pd trimers (hollow sites) which stabilize reaction intermediates and lower kinetic barriers for FA dehydrogenation."},{"paperId":"P089","section":"characterization","insight":"The ligand effect involves charge transfer from subsurface Au to surface Pd, reducing the d-electron density near the Fermi level and decreasing the binding energy of HCOO compared to pure Pd(111)."},{"paperId":"P089","section":"characterization","insight":"DRIFT spectroscopy identifies three CO binding modes on Pd: atop (~2080 cm-1), bridge (1900–2050 cm-1), and hollow (1800–1900 cm-1)."},{"paperId":"P089","section":"performance","insight":"Triangular shaped Pd trimers (3-fold hollow sites) on the PdAu surface are critical for stabilizing reaction intermediates and reducing kinetic barriers for FA dehydrogenation."},{"paperId":"P089","section":"performance","insight":"Both ensemble effects (surface atomic arrangement) and ligand effects (electronic interaction between surface and subsurface layers) synergistically enhance catalytic activity."},{"paperId":"P089","section":"performance","insight":"The presence of Au in the subsurface layer modifies the d-states of surface Pd atoms, reducing the binding energy of HCOO and facilitating decomposition."},{"paperId":"P090","section":"synthesis","insight":"Nitrogen functional groups in the NAS support act as anchoring sites for Pd and Ag species, resulting in smaller and better-distributed bimetallic nanoparticles compared to N-free AS supports."},{"paperId":"P090","section":"synthesis","insight":"The use of a co-impregnation method followed by liquid-phase reduction with NaBH4 was employed to synthesize the PdAg alloys."},{"paperId":"P090","section":"characterization","insight":"Nitrogen functional groups in the NAS support act as anchoring sites for Pd and Ag, significantly reducing nanoparticle size (up to 44% reduction compared to AS) and enhancing sintering resistance."},{"paperId":"P090","section":"characterization","insight":"The presence of both electron-deficient (Pd2+) and electron-rich (Pd0) species is essential for the dehydrogenation of formic acid via a formate intermediate mechanism."},{"paperId":"P090","section":"characterization","insight":"Alloying Pd with Ag results in charge redistribution where Ag becomes enriched in electronic charge, as evidenced by XPS binding energy shifts (~0.4 eV lower)."},{"paperId":"P090","section":"characterization","insight":"N-doping increases surface basicity, which favors the interaction and local concentration of acidic HCOOH molecules near active sites."},{"paperId":"P090","section":"characterization","insight":"In NAS-supported catalysts, initial alloy formation may be hindered by strong Pd-N interactions (stabilizing Pd2+), with full PdAg alloy formation occurring during reaction as Pd2+ is reduced to Pd0."},{"paperId":"P090","section":"performance","insight":"A volcano-type relationship exists between the total volume of gas produced and Ag content, with a maximum at Pd/Ag molar ratio of 1/0.5."},{"paperId":"P090","section":"performance","insight":"Nitrogen doping in the carbon support (NAS) significantly enhances catalytic activity and stability compared to N-free supports (AS)."},{"paperId":"P090","section":"performance","insight":"The presence of both electron-deficient (Pd2+) and electron-rich (Pd0) species is critical for the dehydrogenation mechanism via formate intermediate."},{"paperId":"P091","section":"synthesis","insight":"ZnCl2 activation significantly increases the specific surface area and micropore rate of biomass-derived carbons."},{"paperId":"P091","section":"synthesis","insight":"The use of melon seed shell as a precursor results in higher hydrophilicity and a uniform honeycomb morphology compared to peanut shells."},{"paperId":"P091","section":"synthesis","insight":"ZnCl2 activation promotes smaller Pd nanoparticle sizes by increasing surface oxygen content, which acts as nucleation points."},{"paperId":"P091","section":"characterization","insight":"ZnCl2 activation of biomass carbon increases specific surface area, micropore volume, and oxygen content."},{"paperId":"P091","section":"characterization","insight":"Surface oxygen-containing functional groups act as nucleation points for Pd particles, promoting the formation of smaller nanoparticles."},{"paperId":"P091","section":"characterization","insight":"Pd particle size is negatively correlated with turnover number (TON), where smaller particles provide more active edge/corner atoms."},{"paperId":"P091","section":"characterization","insight":"Melon seed shell precursors yield supports with higher hydrophilicity and a uniform cylindrical honeycomb structure compared to peanut shells."},{"paperId":"P091","section":"characterization","insight":"Post-reaction TEM showed Pd particle growth from 2.9 nm to 3.2 nm, and XPS indicated a decrease in Pd0 content, contributing to activity decline."},{"paperId":"P091","section":"performance","insight":"The catalytic activity is negatively correlated with Pd particle size; smaller particles provide more active sites and cleaner surfaces."},{"paperId":"P091","section":"performance","insight":"ZnCl2 activation increases specific surface area and oxygen-containing functional groups, which improves Pd dispersion and reduces support acidity."},{"paperId":"P091","section":"performance","insight":"Melon seed shell precursors yield catalysts with higher surface areas, better hydrophilicity, and a uniform honeycomb morphology compared to peanut shells."},{"paperId":"P092","section":"synthesis","insight":"The catalytic activity of AuPd/TiO2 nanosheets is strongly dependent on the calcination temperature of the TiO2 support, with 400 °C providing optimal performance due to low crystallinity anatase phase."},{"paperId":"P092","section":"synthesis","insight":"Anatase-type TiO2 promotes electron transfer from the support to Pd and Au centers."},{"paperId":"P092","section":"characterization","insight":"Calcination temperature of TiO2 nanosheets affects the phase and crystallinity; anatase phase is present at 400 °C, while rutile phase appears after 700 °C."},{"paperId":"P092","section":"characterization","insight":"Low crystallinity anatase-type TiO2 improves catalytic activity for formic acid dehydrogenation."},{"paperId":"P092","section":"characterization","insight":"Metal particle size increases with increasing calcination temperature (from 2.4 nm for non-calcined to 5.0 nm at 900 °C), but particle size is not the primary driver of catalytic performance."},{"paperId":"P092","section":"characterization","insight":"BET surface area generally decreases as calcination temperature increases, though TiO2 nanosheets-400 maintains a relatively high surface area (117 m2 g-1)."},{"paperId":"P092","section":"performance","insight":"The catalytic activity of AuPd/TiO2 nanosheets shows a volcano-shaped relationship with the calcination temperature, peaking at 400 °C."},{"paperId":"P092","section":"performance","insight":"Low crystallinity anatase-type TiO2 is identified as the most crucial factor for high catalytic activity across different support morphologies (nanosheets, nanotubes, nanoparticles)."},{"paperId":"P092","section":"performance","insight":"The alloying effect of Au and Pd significantly enhances activity compared to monometallic catalysts; Pd is the essential active site."},{"paperId":"P092","section":"performance","insight":"Electron transfer from the anatase TiO2 nanosheets-400 support to the AuPd alloy NPs promotes catalytic performance."},{"paperId":"P092","section":"performance","insight":"UV-vis light has no significant effect on the catalytic performance of AuPd/TiO2 nanosheets-400."},{"paperId":"P093","section":"synthesis","insight":"The use of amine-functionalized SBA-15 provides interaction sites for anchoring metal ions and acts as deprotonation sites during the dehydrogenation of formic acid."},{"paperId":"P093","section":"characterization","insight":"XRD confirmed that the ordered two-dimensional hexagonal structure of SBA-15 was maintained during catalyst synthesis."},{"paperId":"P093","section":"characterization","insight":"HRTEM lattice spacing of 0.230 nm for Au2Pd8/SBA-15-Amine (between fcc Pd 0.224 nm and fcc Au 0.235 nm) confirms the alloy structure."},{"paperId":"P093","section":"performance","insight":"SF concentration > 0.5 mol L-1 allows sodium formate to partially participate in the dehydrogenation reaction."},{"paperId":"P093","section":"performance","insight":"At SF concentrations <= 0.5 mol L-1 (FA-SF molar ratio 3:1), FA completely reacts while SF is not involved in dehydrogenation."},{"paperId":"P093","section":"performance","insight":"The activation energy (Ea) for Au2Pd8/SBA-15-Amine was found to be 47.6 kJ mol-1."},{"paperId":"P094","section":"synthesis","insight":"The use of Al-MIL-101-NH2 as a sacrificial template followed by KOH activation creates a hierarchically porous carbon support with both micro- and mesoporosity, which helps stabilize ultra-fine Pd nanoparticles (1.1 ± 0.2 nm) likely immobilized within the micropores."},{"paperId":"P094","section":"synthesis","insight":"Carbonization temperature of the MOF precursor significantly affects the BET surface area and pore size distribution of the resulting N-doped carbon support, with 900 °C providing optimal hierarchical porosity."},{"paperId":"P094","section":"characterization","insight":"The use of Al-MIL-101-NH2 as a sacrificial template followed by KOH activation creates a hierarchically porous carbon (CN900K) with high surface area (1382 m2/g) and both micro- and mesoporosity."},{"paperId":"P094","section":"characterization","insight":"Micropores (~1.4 nm) serve as anchor sites to stabilize ultra-fine Pd nanoparticles, preventing aggregation."},{"paperId":"P094","section":"performance","insight":"The reaction exhibits close to first-order dependence on Pd concentration, half-order dependence on SF concentration, and zero-order dependence on FA concentration."},{"paperId":"P095","section":"synthesis","insight":"The addition of Cr(OH)3 is conducive to reducing the size of Pd nanoclusters."},{"paperId":"P095","section":"synthesis","insight":"Amino groups on NH2-rGO act as anchoring sites for metal cations, facilitating the formation and dispersion of ultrafine metal NCs."},{"paperId":"P095","section":"synthesis","insight":"NaBH4 serves a dual purpose: it reduces Pd2+ to Pd0 and creates an alkaline environment that transforms Cr3+ into Cr(OH)3."},{"paperId":"P095","section":"characterization","insight":"Amino groups on NH2-rGO act as anchoring sites for metal cations, significantly reducing particle size compared to rGO."},{"paperId":"P095","section":"characterization","insight":"Cr(OH)3 acts as a promoter that further reduces Pd NC size and serves as an electron donor to create electron-rich Pd active centers."},{"paperId":"P095","section":"characterization","insight":"The synergy between the basicity of amino groups/Cr(OH)3 and the electronic state of Pd optimizes the dehydrogenation pathway by facilitating O-H and C-H bond cleavage."},{"paperId":"P095","section":"performance","insight":"The catalytic activity follows the order: Pd/rGO < Pd−Cr(OH)3/rGO < Pd/NH2-rGO < Pd−Cr(OH)3/NH2-rGO, which is inversely proportional to the particle size."},{"paperId":"P095","section":"performance","insight":"Amino groups on NH2-rGO are critical for promoting FAD by providing anchoring sites for ultrafine NCs and acting as Brønsted basic sites."},{"paperId":"P096","section":"synthesis","insight":"The polydopamine layer provides nucleation and strong binding sites for metal nanoparticles, preventing agglomeration and leaching."},{"paperId":"P096","section":"synthesis","insight":"A double solvent approach was employed to synthesize the AgPd nanoalloy on the MOF support."},{"paperId":"P096","section":"characterization","insight":"Polydopamine (PDA) modification of MIL-125-NH2 creates a functional interface that significantly improves the adhesion and stability of ultrafine bimetallic nanoparticles compared to unmodified MOF supports."},{"paperId":"P096","section":"characterization","insight":"The disappearance of the Ag surface plasmon resonance band in UV-Vis spectra is used as evidence for the molecular binding of Pd to Ag, confirming alloy formation."},{"paperId":"P096","section":"performance","insight":"The bimetallic AgPd catalyst on PDA-modified MOF exhibits significantly higher activity than monometallic Pd or Ag catalysts due to synergistic electronic effects and improved hydrogen desorption kinetics."},{"paperId":"P096","section":"performance","insight":"PDA coating prevents nanoparticle agglomeration and leaching while providing functional groups (amino and catechol) that enhance reactant adsorption."},{"paperId":"P097","section":"synthesis","insight":"The solid-vapor synthesis method was used to obtain dense bulk samples and avoid direct contact between Zn and Pd initially."},{"paperId":"P097","section":"synthesis","insight":"ZnPd particles on ZnO were formed via Reactive Metal-Support Interaction (RMSI) where palladium oxide is reduced, subsequently reducing nearby ZnO to elemental zinc which diffuses into the palladium."},{"paperId":"P097","section":"characterization","insight":"The dehydrogenation of formate intermediates occurs preferentially on the intermetallic ZnPd phase rather than the ZnO oxide phase."},{"paperId":"P097","section":"characterization","insight":"Compositional shifts in bulk ZnPd significantly affect oxidative stability, with Pd-rich compositions being more resistant to surface oxidation."},{"paperId":"P097","section":"characterization","insight":"Operando XPS and DTA/TG confirm a reversible transition between zinc oxide and zinc formate during formic acid decomposition on Zn-rich surfaces."},{"paperId":"P097","section":"performance","insight":"Pd-rich bulk ZnPd (Zn42.0Pd58.0) is more active and stable against surface oxidation than Zn-rich samples in formic acid decomposition."},{"paperId":"P097","section":"performance","insight":"The formation of zinc formate on Zn-rich ZnPd surfaces hinders the overall reaction rate, suggesting that dehydrogenation occurs preferentially on the intermetallic compound phase."},{"paperId":"P097","section":"performance","insight":"ZnO-supported ZnPd exhibits significantly higher activity than bulk counterparts."},{"paperId":"P097","section":"performance","insight":"Apparent activation energies for MSR on ZnPd are approximately twice as high as those for formic acid decomposition, indicating that formate dehydrogenation is not the rate-limiting step in MSR."},{"paperId":"P098","section":"synthesis","insight":"The final atomic composition of the C3N4 support after melamine thermal treatment was determined to be C3N4.37H1.85."},{"paperId":"P098","section":"characterization","insight":"The C3N4 support has an atomic composition of C3N4.37H1.85."},{"paperId":"P098","section":"characterization","insight":"XRD analysis confirms that Pd and Ru species are not inserted into the interlayer of the graphitic carbon nitride structure."},{"paperId":"P098","section":"performance","insight":"Pd is identified as the primary active phase for liquid-phase FAD over C3N4 support."},{"paperId":"P098","section":"performance","insight":"The addition of ammonium formate (FA:AF 1:9) enhances hydrogen production more than threefold in liquid phase due to electron-donation ability and presence of NH3."},{"paperId":"P098","section":"performance","insight":"In gas phase, all catalysts achieved high conversion (>90%) at 250 °C, but selectivity varied significantly with temperature and metal composition."},{"paperId":"P098","section":"performance","insight":"Ru/C3N4 is inactive in the liquid phase due to competitive water absorption and surface hydroxylation."},{"paperId":"P099","section":"synthesis","insight":"The use of acetone as a solvent and rotary evaporation for removal allows for controlled impregnation on activated carbon."},{"paperId":"P099","section":"synthesis","insight":"Reduction at 350 °C under H2/N2 is used to activate the Pd and Co precursors."},{"paperId":"P099","section":"characterization","insight":"Bimetallic Pd:Co catalysts exhibit a bimodal particle size distribution consisting of small Pd-rich particles (< 7 nm) and larger Co/Co3O4 aggregates (> 7 nm)."},{"paperId":"P099","section":"characterization","insight":"XRD shifts in Pd:Co (3:1) and (2:1) samples suggest the formation of an intermetallic Pd2Co phase."},{"paperId":"P099","section":"characterization","insight":"Increasing cobalt fraction generally leads to a decrease in Pd particle size as suggested by XRD."},{"paperId":"P099","section":"characterization","insight":"The presence of Co/CoOx or ordered Pd2Co structures is linked to increased hydrogen production per mol of Pd and reduced dependence on formate intermediates."},{"paperId":"P099","section":"performance","insight":"Hydrogen production increases with Pd loading up to a certain value; however, very high loadings (Pd 10) show lower initial velocity due to larger particle size and reduced surface availability."},{"paperId":"P099","section":"performance","insight":"Bimetallic catalysts PdCo 2:1 and PdCo 1:3 exhibit synergy, achieving higher TOF/TON for low Pd content compared to monometallic Pd 5."},{"paperId":"P099","section":"performance","insight":"The addition of formates (AF or SF) significantly increases hydrogen production by promoting monodentate adsorption and inhibiting bidentate formate deactivation; ammonium formate is more effective than sodium formate."},{"paperId":"P099","section":"performance","insight":"Catalyst activity can be recovered by heating post-reacted samples at 150 °C."},{"paperId":"P100","section":"synthesis","insight":"K-doping was performed using incipient wetness impregnation of K2CO3 onto pre-existing Pd/support catalysts."},{"paperId":"P100","section":"synthesis","insight":"The weight ratio of K to Pd was varied based on the BET surface area of the support (10:1 for C, 4:1 for SiO2, and 2:1 for Al2O3) to ensure even dispersion."},{"paperId":"P100","section":"characterization","insight":"K-doping promotes formic acid decomposition across different supports (C, SiO2, Al2O3) by creating a buffer-like solution of formate anions and K+ ions in condensed HCOOH within the pores."},{"paperId":"P100","section":"characterization","insight":"DRIFTS analysis on Pd/SiO2 reveals that K-promotion facilitates the dissociation of HCOOH into mobile formate anions, which are more reactive than bulk potassium formate."},{"paperId":"P100","section":"performance","insight":"Introduction of potassium carbonate into Pd/Al2O3, Pd/SiO2 and Pd/C catalysts promoted both catalytic activities and hydrogen selectivities for vapor-phase formic acid decomposition."},{"paperId":"P100","section":"performance","insight":"K-doped catalysts showed TOF values at 343 K that were 8–33 times higher than undoped samples."},{"paperId":"P100","section":"performance","insight":"The promotional effect is attributed to the formation of a buffer-like solution in catalyst pores consisting of potassium formate and formic acid, providing mobile formate ions."},{"paperId":"P101","section":"synthesis","insight":"Pre-oxidized Pd–CeO2 was specifically prepared by heating as-synthesized catalyst to 573 K at 10 K min-1 and holding for 3 h under air flow."},{"paperId":"P101","section":"characterization","insight":"Alloying Pd with Ag on CeO2 increases the surface coverage of reduced Pd0 and decreases atomic oxygen coverage, which enhances H2 selectivity by suppressing oxidative dehydrogenation."},{"paperId":"P101","section":"characterization","insight":"Support basicity (measured via PZC) is a key factor; TiO2 and CeO2 show comparable affinity for protons, resulting in similar performance for PdAg catalysts on these supports."},{"paperId":"P101","section":"characterization","insight":"Metal particle size significantly influences the effect of alloying: smaller particles (~7 nm on CeO2/TiO2) benefit from Ag alloying, while larger particles (~12 nm on Al2O3) exhibit decreased H2 TOF and selectivity upon alloying."},{"paperId":"P101","section":"performance","insight":"Alloying Pd with Ag on CeO2 or TiO2 supports increases H2 TOF and selectivity by reducing surface atomic oxygen coverage and increasing reduced Pd (Pd0) species."},{"paperId":"P101","section":"performance","insight":"The identity of the support affects performance through basicity; CeO2 and TiO2 provide comparable results due to similar PZC values, while Al2O3 leads to different behavior."},{"paperId":"P101","section":"performance","insight":"Particle size is critical: larger 0.5 PdAg nanoparticles on Al2O3 (12 nm) show lower activity than smaller ones on CeO2/TiO2 (7 nm)."},{"paperId":"P101","section":"performance","insight":"Surface adsorbed oxygen under ambient conditions promotes H2O formation over H2 production."},{"paperId":"P102","section":"synthesis","insight":"The use of urea as a co-precursor with melamine increases the specific surface area and pore volume of the C3N4 support."},{"paperId":"P102","section":"synthesis","insight":"Higher calcination temperatures (600 °C vs 550 °C) generally improve formic acid dehydrogenation activity by increasing aromaticity (lower C/H ratio)."},{"paperId":"P102","section":"synthesis","insight":"The use of palladium nitrate as a precursor can lead to partial oxidation and loss of the carbon nitride support during reduction, resulting in actual Pd loadings higher than the theoretical 5 wt%."},{"paperId":"P102","section":"characterization","insight":"The addition of urea to melamine during support synthesis creates cyano defects and increases BET surface area, which facilitates higher Pd dispersion."},{"paperId":"P102","section":"characterization","insight":"UV-Vis spectroscopy identified a band at 220 nm as evidence of electron transfer from nitrogen sites in the C3N4 support to the Pd nanoparticles."},{"paperId":"P102","section":"characterization","insight":"Catalytic activity for formic acid dehydrogenation is more sensitive to Pd particle size and dispersion than to total metal loading."},{"paperId":"P102","section":"characterization","insight":"Higher specific surface area and the presence of cyano moieties suppress humin formation during HMF hydrodeoxygenation, orienting the reaction toward 2,5-DMF."},{"paperId":"P102","section":"performance","insight":"Higher BET surface area and smaller Pd particle size are the primary drivers for high formic acid conversion."},{"paperId":"P102","section":"performance","insight":"The use of urea as a precursor introduces cyano defects that enhance electron transfer from nitrogen to palladium, improving catalytic activity."},{"paperId":"P102","section":"performance","insight":"In HDO of 5-HMF, catalysts with higher specific surface areas suppress humin formation and orient the reaction toward utile products like 2,5-DMF via the 5-methylfuran (5-MF) pathway."},{"paperId":"P103","section":"synthesis","insight":"The composition of the MWCNT-C3N4 support (wt% C3N4) modulates the average size and electronic properties of Pd nanoparticles."},{"paperId":"P103","section":"synthesis","insight":"High dicyandiamide content in the composite preparation may impede cyclization, potentially leading to amorphous CN structures instead of g-C3N4 (observed for Pd/MWCNT-C3N4(63))."},{"paperId":"P103","section":"characterization","insight":"The use of MWCNT-C3N4 composite supports results in significantly smaller and better distributed Pd nanoparticles (~2 nm) compared to pure MWCNT or C3N4 supports."},{"paperId":"P103","section":"characterization","insight":"Nitrogen functional groups on the C3N4 domains wrapping the MWCNTs serve as efficient anchoring sites for Pd NPs."},{"paperId":"P103","section":"characterization","insight":"The electronic environment of Pd is modulated by the support composition, introducing electron-deficient (Pd2+-N) and electron-rich (Pdδ-) species that facilitate different steps of the formic acid dehydrogenation mechanism."},{"paperId":"P103","section":"performance","insight":"The composition of the MWCNT-C3N4 support modulates catalytic performance by controlling Pd nanoparticle size and electronic properties."},{"paperId":"P103","section":"performance","insight":"Composite supports (MWCNT-C3N4) significantly enhance activity compared to pure MWCNT or C3N4 supports, with activity increasing as C3N4 content increases."},{"paperId":"P104","section":"synthesis","insight":"The N-doped carbon support helps form relatively small PdNi nanoparticles in a well-dispersed manner compared to commercial carbon supports."},{"paperId":"P104","section":"characterization","insight":"N-doped carbon support promotes smaller particle size and higher dispersion of PdNi nanoparticles compared to commercial carbon."},{"paperId":"P104","section":"characterization","insight":"XRD peak shifts for the (111) plane from 39.1° (Pd) to 40.0° (Pd1Ni3.6) confirm the incorporation of Ni into the Pd lattice, forming an fcc isomorphous alloy."},{"paperId":"P104","section":"characterization","insight":"XPS analysis reveals that alloying Pd with Ni increases Pd 3d binding energies and indicates electronic interactions between the two metals."},{"paperId":"P104","section":"characterization","insight":"DFT calculations suggest a synergistic effect where electronic properties (via d-band center shifts) stabilize O-containing intermediates and geometric properties (compressive strain) weaken H* adsorption to facilitate H2 release."},{"paperId":"P104","section":"performance","insight":"Pd-Ni alloying exhibits a volcano-type activity relationship with the Pd/Ni ratio, where Pd1Ni1.3/N–C shows the highest activity."},{"paperId":"P104","section":"performance","insight":"The HCOO pathway is energetically favored over the COOH pathway for FA dehydrogenation on both Pd and PdNi surfaces."},{"paperId":"P104","section":"performance","insight":"Alloying Pd with Ni lowers the activation energy for FA dehydrogenation by stabilizing O-containing intermediates (electronic effect) and weakening H* adsorption to facilitate H2 release (geometric effect)."},{"paperId":"P105","section":"characterization","insight":"The slow synthesis methodology successfully overcomes the large gap in reduction potentials between Pd and Au to form a homogeneous solid solution alloy."},{"paperId":"P105","section":"characterization","insight":"Lattice constants of the alloys decrease linearly with increasing palladium content due to the smaller ionic radius of Pd compared to Au."},{"paperId":"P105","section":"performance","insight":"Pd0.5Au0.5 exhibited the highest activity among PdxAu1-x alloys (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1)."},{"paperId":"P105","section":"performance","insight":"The optimal FA/SF molar ratio for Pd0.5Au0.5 is 1:3 at 313 K."},{"paperId":"P105","section":"performance","insight":"The optimum metal loading of PdAu on AC is 5 wt.%."},{"paperId":"P106","section":"characterization","insight":"CO2 produced during formic acid decomposition chemisorbs on Pd active sites at high reaction temperatures (above 55 °C), leading to catalyst poisoning."},{"paperId":"P106","section":"characterization","insight":"The presence of crystalline PdO and the resulting Pd-PdO interface are identified as desirable species for high efficiency and selectivity."},{"paperId":"P106","section":"performance","insight":"The catalyst suffers from irreversible deactivation at temperatures above 55-65 °C due to CO2 chemisorption on Pd active sites."},{"paperId":"P106","section":"performance","insight":"Sodium formate (SF) significantly increases the initial reaction rate, especially at ambient temperature."},{"paperId":"P107","section":"synthesis","insight":"ZnCl2 chemical activation significantly increases biochar porosity and volume compared to physical CO2 activation alone."},{"paperId":"P107","section":"synthesis","insight":"The use of meso-macroporous supports facilitates better Pd dispersion (lower particle size) and higher catalytic activity for formic acid dehydrogenation."},{"paperId":"P107","section":"characterization","insight":"Higher pore volumes and specific surface areas facilitate metal dispersion."},{"paperId":"P107","section":"characterization","insight":"Meso-macroporosity is critical for stabilizing high palladium dispersion and improving mass transfer of formic acid dimers to active sites."},{"paperId":"P107","section":"characterization","insight":"Surface acidity (isoelectric point) influences metal anchoring; more acidic surfaces may negatively affect anchoring, leading to particle sintering and lower dispersion."},{"paperId":"P107","section":"characterization","insight":"Nitrogen groups in biochars act as anchorage centers for metallic nanoparticles, enhancing interaction and dispersion."},{"paperId":"P107","section":"performance","insight":"The presence of prevailing mesoporous character appeared to be the most important parameter influencing formic acid dehydrogenation and overall hydrogen production."},{"paperId":"P107","section":"performance","insight":"Higher specific surface area, particularly external area, leads to an almost exponential increase in TOF."},{"paperId":"P107","section":"performance","insight":"Catalytic activity is maximized when the isoelectric point of the catalyst is close to neutral pH values, which facilitates formate groups surface adsorption."},{"paperId":"P108","section":"synthesis","insight":"Amino-modification of MWCNTs using APTES prevents Pd nanoparticle agglomeration and increases the N/C atomic ratio."},{"paperId":"P108","section":"synthesis","insight":"Plasma synthesis is described as a mild, low-temperature (< 45 °C), and fast (6 min) alternative to traditional thermal reduction, preserving more surface functional groups (-OH) and support structure."},{"paperId":"P108","section":"characterization","insight":"Amino modification with APTES prevents Pd agglomeration and increases the N/C ratio, specifically enhancing pyridinic N content."},{"paperId":"P108","section":"characterization","insight":"Plasma synthesis is a milder method than thermal reduction, preserving support functional groups (-OH) and resulting in higher surface dispersion of Pd (higher Pd/C ratio)."},{"paperId":"P108","section":"characterization","insight":"The synergy between small Pd particles, pyridinic N, and amino groups promotes the breaking of O-H bonds via formate-amine intermediates."},{"paperId":"P108","section":"performance","insight":"Pd/MWCNTs-AP showed the highest activity among tested catalysts (Pd/MWCNTs-AP > Sigma-Aldrich Pd/C > Pd/MWCNTs-P > Pd/MWCNTs-AH)."},{"paperId":"P108","section":"performance","insight":"Plasma synthesis in solution is a milder method than hydrogen thermal reduction, preserving more surface functional groups and resulting in better Pd dispersion."},{"paperId":"P108","section":"performance","insight":"Amino modification of MWCNTs prevents Pd agglomeration and provides proton scavenging sites that accelerate the O-H bond cleavage step."},{"paperId":"P109","section":"synthesis","insight":"The synthesis methodology suppresses the use of reducing additives like NaBH4, relying instead on in situ reduction during the catalytic reaction."},{"paperId":"P109","section":"synthesis","insight":"Thermal treatment at 900 °C reduces surface acidity and oxygen functional groups, which enhances initial activity for Pd/BC_TT."},{"paperId":"P109","section":"characterization","insight":"N-atoms in the carbon support stabilize Pd2+ species, leading to an induction period during the initial stages of the reaction as the metal is reduced in situ."},{"paperId":"P109","section":"characterization","insight":"Thermal treatment (900°C) of the biomass-derived carbon reduces surface oxygen groups and acidity, which enhances catalytic activity and increases the reducibility of the supported Pd."},{"paperId":"P109","section":"characterization","insight":"The coexistence of electron-deficient (Pd2+) and electron-rich (Pd0) species is considered important for the dehydrogenation mechanism: Pd2+ favors formate adsorption, while Pd0 boosts C-H bond cleavage."},{"paperId":"P109","section":"performance","insight":"Thermal treatment of carbon supports significantly enhances initial reaction rates and total gas production by reducing surface acidity (increasing pHPZC)."},{"paperId":"P109","section":"performance","insight":"Nitrogen functionalization improves stability and activity, likely due to the basic character of N-groups and their ability to stabilize Pd species."},{"paperId":"P109","section":"performance","insight":"The combination of thermal treatment and nitrogen doping provides a strategy for tailoring catalyst performance and achieving high stability over multiple cycles."},{"paperId":"P110","section":"synthesis","insight":"The morphology and nitrogen species (specifically pyrrolic N content) of the nanotubular carbon nitride support were tailored by adjusting the melamine to barbituric acid molar ratio, hydrothermal temperature, and reaction time."},{"paperId":"P110","section":"synthesis","insight":"A molar ratio of 1.5 for barbituric acid to melamine (Pd/CN-B1.5M) was found optimal for maximizing pyrrolic N content and catalytic activity."},{"paperId":"P110","section":"characterization","insight":"The molar ratio of melamine to barbituric acid modulates the morphology of carbon nitride from nanotubes (optimal at 1.5:1) to solid nanorods."},{"paperId":"P110","section":"characterization","insight":"Pyrrolic nitrogen groups serve as critical metal anchor sites, facilitating high Pd dispersion and modulating the electronic state of Pd via electron transfer from Pd to N."},{"paperId":"P110","section":"characterization","insight":"The catalytic activity follows a volcanic trend relative to pyrrolic N content and the surface Pd2+/Pd0 ratio, peaking at the Pd/CN-B1.5M composition."},{"paperId":"P110","section":"performance","insight":"The Pd/CN-B1.5M catalyst showed the highest activity due to an optimal ratio of barbituric acid to melamine, which maximized pyrrolic N content and created electron-deficient Pd sites."},{"paperId":"P110","section":"performance","insight":"A binary FA/SF system (molar ratio 1:8) enhanced TOF by 8.77-fold compared to pure formic acid, highlighting the role of formate anions in the mechanism."},{"paperId":"P110","section":"performance","insight":"The apparent activation energy for FA decomposition over Pd/CN-B1.5M was approximately 63.14 kJ mol-1."},{"paperId":"P111","section":"synthesis","insight":"Pd preferentially deposits on the edges of Ag nanoplates at low nPd:nAg ratios (< 0.0417) and covers the entire surface at higher ratios."},{"paperId":"P111","section":"characterization","insight":"The formation of a Pd-Ag alloy is confirmed by the shift of the XRD {111} peak to a position between pure Ag and pure Pd."},{"paperId":"P111","section":"characterization","insight":"HRTEM identifies that Ag nanoplates possess a unique fcc/hcp/fcc three-layer structure, where the hcp layer is defect-induced."},{"paperId":"P111","section":"characterization","insight":"XPS analysis indicates that metallic Pd(0) is the primary active species for formic acid dehydrogenation."},{"paperId":"P111","section":"characterization","insight":"The crystal phase (hcp vs fcc) strongly influences catalytic activity, with the hcp phase providing superior C-H bond activation."},{"paperId":"P111","section":"performance","insight":"The activity order of Pd-decorated Ag nanofacets is Pd-Ag{hcp} > Pd-Ag{111} > Pd-Ag{100}."},{"paperId":"P111","section":"performance","insight":"Pd-Ag{hcp} facet dominates the high catalytic activity due to its superior ability in activating the C-H bond (rate-determining step)."},{"paperId":"P111","section":"performance","insight":"The synergetic effect between metallic state Pd and Ag is crucial for the high activity."},{"paperId":"P112","section":"synthesis","insight":"The addition of Co reduces the Pd particle size from 13.50 nm to 3.41 nm."},{"paperId":"P112","section":"synthesis","insight":"APTS (3-aminopropyl)triethoxysilane is used as an additive to improve catalyst activity."},{"paperId":"P112","section":"characterization","insight":"Calcination of the XC-72 carrier at 650 °C increases its BET specific surface area from 430.65 to 474.25 m2/g and introduces oxygen elements on the surface."},{"paperId":"P112","section":"characterization","insight":"The addition of Co significantly reduces Pd particle size from 13.50 nm to 3.41 nm."},{"paperId":"P112","section":"characterization","insight":"Co doping increases the Pd2+/Pd0 ratio, which is linked to improved catalytic activity for formic acid dehydrogenation."},{"paperId":"P112","section":"performance","insight":"Introducing nonprecious cobalt metal reduces precious palladium usage, decreases particle size, and increases the Pd2+/Pd0 ratio, leading to higher TOF and better cyclic stability compared to monometallic Pd/C650."},{"paperId":"P113","section":"synthesis","insight":"Zeolite nanosheets (SP-S-1) provide higher specific surface area and more isolated silanol groups compared to conventional S-1, which helps immobilize metal species and inhibit aggregation during high-temperature reduction."},{"paperId":"P113","section":"synthesis","insight":"Direct hydrothermal synthesis of Pd@SP-S-1 led to phase separation and large bulk Pd nanoparticles due to precursor decomposition in alkaline conditions."},{"paperId":"P113","section":"characterization","insight":"SP-S-1 zeolite nanosheets possess a higher specific surface area (556 m2/g) and significantly more isolated silanol groups (8.1% Si(OSi)3OH via MAS NMR) than conventional Con-S-1 zeolites."},{"paperId":"P113","section":"characterization","insight":"Isolated silanol groups on SP-S-1 are responsible for immobilizing metal species, inhibiting aggregation and sintering during high-temperature reduction."},{"paperId":"P113","section":"characterization","insight":"The synergistic effect of Pd and CeO2 is characterized by electron transfer from Ce to Pd, which modulates the electronic state of Pd and lowers activation barriers for C-H bond scission."},{"paperId":"P113","section":"performance","insight":"The use of self-pillared silicalite-1 (SP-S-1) zeolite nanosheets significantly improves metal dispersion and thermal stability compared to conventional S-1 zeolites."},{"paperId":"P113","section":"performance","insight":"Bimetallic Pd-Ce catalysts exhibit a synergistic effect where Ce acts as an electron donor, modulating the electronic state of Pd and lowering activation barriers for both FA dehydrogenation and CO2 hydrogenation."},{"paperId":"P113","section":"performance","insight":"Potassium formate (PF) is the most effective additive for enhancing FA dehydrogenation rates, while potassium bicarbonate (KHCO3) is optimal for CO2 hydrogenation to formate."},{"paperId":"P114","section":"synthesis","insight":"The diameter of PdP nanoclusters is positively correlated with the concentration of H2PdCl4."},{"paperId":"P114","section":"synthesis","insight":"The P content in binary PdP nanoclusters can be tuned by changing the molar ratio of NaH2PO2/H2PdCl4."},{"paperId":"P114","section":"synthesis","insight":"NC support is essential for maintaining small nanocluster size; without it, large nanoparticles are formed."},{"paperId":"P114","section":"characterization","insight":"The introduction of P into the Pd lattice and N into the carbon support synergistically shifts the electronic state of Pd, reducing the activation energy for FA dehydrogenation from 40.0 kJ/mol (Pd/NC) to 27.2 kJ/mol (PdP/NC)."},{"paperId":"P114","section":"characterization","insight":"A volcanic relationship exists between catalytic activity (TOF) and both the particle size of PdP nanoclusters and the P content, with an optimal diameter around 1.59 nm."},{"paperId":"P114","section":"characterization","insight":"N-doped carbon serves as a critical anchor to prevent nanoparticle sintering and maintain high dispersion."},{"paperId":"P114","section":"performance","insight":"The dehydrogenation reaction of FA over PdP/NC shows zero-order dependence on FA concentration (0.25 to 1 M), half-order dependence on SF concentration, and first-order dependence on Pd concentration."},{"paperId":"P114","section":"performance","insight":"Activation energy for PdP/NC is 27.2 kJ mol-1, significantly lower than that of Pd/NC (40.0 kJ mol-1)."},{"paperId":"P114","section":"performance","insight":"Catalytic activity follows a volcanic trend with respect to both the diameter of PdP nanoclusters (optimal at 1.59 nm) and phosphorus content."},{"paperId":"P115","section":"synthesis","insight":"Phosphorus doping in the carbon support acts as an anchoring site for metal precursors, leading to smaller and more well-distributed Pd nanoparticles (1.47 nm vs 2.54 nm for non-P doped)."},{"paperId":"P115","section":"synthesis","insight":"Amine groups from APTES serve as Brønsted basic sites that promote formic acid deprotonation and stabilize Pd2+ species via strong metal-support interactions."},{"paperId":"P115","section":"characterization","insight":"Phosphorus doping in the carbon support serves as both a pore expander and an electronic promoter, facilitating the formation of electron-deficient Pd species."},{"paperId":"P115","section":"characterization","insight":"Amine functionalization provides Brønsted basic sites that act as proton scavengers to accelerate FA deprotonation."},{"paperId":"P115","section":"characterization","insight":"Strong metal-support interactions (SMSI) between Pd and the N/NH2-functionalized support stabilize Pd2+ species even after strong reduction with NaBH4."},{"paperId":"P115","section":"characterization","insight":"The hierarchical micro-/mesoporous structure of the carbon support is conducive to mass transfer during catalysis."},{"paperId":"P115","section":"performance","insight":"The introduction of NH2 groups on the support acts as an immobilized amine-additive for FA dehydrogenation."},{"paperId":"P115","section":"performance","insight":"Phosphorus doping serves as an electronic promoter to keep Pd in an electron-deficient state and enlarges the aperture size of the carbon support."},{"paperId":"P115","section":"performance","insight":"The reaction follows a formate path, as evidenced by the activity of Pd/P-GC when FA is mixed with formate (1:1 ratio)."},{"paperId":"P115","section":"performance","insight":"Mass transport was identified as the restricting factor for performance based on activation energy values in the 20-30 kJ/mol range."},{"paperId":"P116","section":"synthesis","insight":"Low palladium concentrations (0.2–0.5 wt %) on N-CNTs result in isolated Pd2+ ions, whereas higher loadings lead to the formation of metallic nanoparticles."},{"paperId":"P116","section":"characterization","insight":"N-doping of CNTs stabilizes single-atom Pd2+ ions through coordination with pyridinic nitrogen fragments."},{"paperId":"P116","section":"characterization","insight":"The ionic capacity of N-CNTs for palladium is estimated at 0.8 wt%."},{"paperId":"P116","section":"characterization","insight":"Increasing Pd content beyond the ionic capacity leads to metal agglomeration and formation of nanoparticles (~1 nm)."},{"paperId":"P116","section":"performance","insight":"N-doping of CNT supports stabilizes ionic Pd2+ sites, which exhibit higher activity and selectivity for gas-phase formic acid decomposition compared to metallic Pd nanoparticles."},{"paperId":"P116","section":"performance","insight":"The stability of the single-atom catalyst is maintained up to 500 °C in a hydrogen atmosphere due to coordination by nitrogen-containing fragments of graphene layers."},{"paperId":"P117","section":"synthesis","insight":"The ratio of urea to water during the synthesis of the carbon nitride support regulates the type and content of nitrogen-containing functional groups (specifically pyridinic N), which in turn affects Pd nanoparticle size, dispersion, and electronic properties."},{"paperId":"P117","section":"characterization","insight":"The addition of water during the synthesis of carbon nitride (CN) acts as a stripping agent, creating ultrathin nanosheets that improve the immobilization and dispersion of Pd nanoparticles."},{"paperId":"P117","section":"characterization","insight":"Pyridinic N in the CN support interacts with Pd to form covalent bonds, transferring electrons from Pd to N and resulting in electron-deficient palladium sites."},{"paperId":"P117","section":"characterization","insight":"A linear relationship exists between the turnover frequency (TOF) and the surface pyridinic N/Pd molar ratio."},{"paperId":"P117","section":"characterization","insight":"XRD analysis of the supports shows that increasing the water-to-urea ratio leads to broader and weaker (002) peaks, indicating successful exfoliation into ultrathin nanosheets."},{"paperId":"P117","section":"performance","insight":"The catalytic activity of Pd/CN-UW catalysts exhibited a volcano-shaped relationship as a function of the urea/water ratio, with Pd/CN-U1W5 showing the highest activity."},{"paperId":"P117","section":"performance","insight":"There is an almost linear relationship between TOF and the surface pyridinic N/Pd molar ratio."},{"paperId":"P117","section":"performance","insight":"The apparent activation energy (Ea) for FA decomposition using Pd/CN-U1W5 was calculated to be approximately 29.7 kJ mol-1."},{"paperId":"P118","section":"synthesis","insight":"Direct H2 reduction of the hydrothermal gel prevents metal aggregation by producing ammonia gas during hydrolysis, which acts as a protective agent to maintain single/pseudo-single atom dispersion."},{"paperId":"P118","section":"synthesis","insight":"The direct H2 reduction method is more energy-efficient and results in smaller metal sizes compared to the conventional calcination-reduction process."},{"paperId":"P118","section":"characterization","insight":"Direct H2 reduction is more effective than calcination-reduction for achieving pseudo-single atom dispersion in zeolites because the simultaneous hydrolysis of organic templates produces ammonia, which acts as a protective agent against metal aggregation."},{"paperId":"P118","section":"characterization","insight":"The confinement effect of S-1 zeolite intersectional channels stabilizes ultra-small Pd species and prevents sintering even at high temperatures (up to 700 °C)."},{"paperId":"P118","section":"characterization","insight":"Bimetallic interaction between Pd and Ni(OH)2 creates electron-rich Pd sites, which significantly enhances the catalytic activity for formic acid dehydrogenation compared to monometallic Pd."},{"paperId":"P118","section":"performance","insight":"Zeolite-encaged pseudo-single atom catalysts exhibit superior activity and stability compared to impregnation-derived counterparts due to high metal dispersion and confinement effects."},{"paperId":"P118","section":"performance","insight":"The bimetallic Pd–Ni(OH)2 interface significantly enhances FA dehydrogenation rates through synergistic electronic effects."},{"paperId":"P119","section":"synthesis","insight":"Boric acid acts as a hard template during pyrolysis to create larger mesoporous and macroporous structures compared to NC."},{"paperId":"P119","section":"synthesis","insight":"The introduction of B increases the N content in the carbon support and regulates the type of nitrogen, specifically increasing the proportion of pyridinic-N (from 15.1% in Pd/NC to 45.3% in Pd/BNC)."},{"paperId":"P119","section":"synthesis","insight":"Pyridinic-N and BC2O species serve as anchor sites for Pd nanoparticles, leading to higher dispersion and smaller particle size (1.3 nm for Pd/BNC vs 2.3 nm for Pd/NC)."},{"paperId":"P119","section":"characterization","insight":"The introduction of B into N-doped carbon increases the content of pyridinic-N (from 15.1% in Pd/NC to 45.3% in Pd/BNC), which serves as a primary adsorption site for Pd NPs."},{"paperId":"P119","section":"characterization","insight":"BC2O species act as additional anchor sites for Pd, contributing to higher dispersion and smaller particle size."},{"paperId":"P119","section":"characterization","insight":"The catalytic activity of FA dehydrogenation is optimized by a balance of Pd0 (conducive to C-H bond dissociation) and Pd2+ (conducive to FA deprotonation)."},{"paperId":"P119","section":"performance","insight":"B, N co-doping of carbon supports increases the proportion of pyridinic-N and creates B-O species (BC2O), both acting as anchor sites for Pd nanoparticles."},{"paperId":"P119","section":"performance","insight":"The balance between Pd2+ (conducive to FA deprotonation) and Pd0 (conducive to C-H bond dissociation) is critical; too high a ratio (as seen in Pd/BNC-700) hinders activity."},{"paperId":"P120","section":"synthesis","insight":"The use of a Pd-based complex with L-histidine is essential to preserve the ligand at the metal surface and improve nanoparticle dispersion."},{"paperId":"P120","section":"synthesis","insight":"Coordination mode was identified as Pd-N^N (binding via amino group and imidazolic N)."},{"paperId":"P120","section":"synthesis","insight":"Liquid-phase co-reduction using NaBH4 effectively produces alloyed nanoparticles."},{"paperId":"P120","section":"characterization","insight":"L-histidine coordination during synthesis is essential for reducing particle size and improving dispersion of PdAg nanoparticles on carbon."},{"paperId":"P120","section":"characterization","insight":"Zeta potential measurements confirm that L-histidine binds to the metal via two amine moieties while the carboxylate entity points outwards, stabilizing the particles."},{"paperId":"P120","section":"characterization","insight":"The electronic interaction between PdAg and L-histidine involves electron transfer from the metal to the ligand, which modifies the catalyst's reactivity."},{"paperId":"P120","section":"performance","insight":"L-histidine modification directly on metal sites is significantly more effective than modifying the carbon support with amino groups for FAD."},{"paperId":"P120","section":"performance","insight":"The optimal FA:SF molar ratio for Pd1Ag1-NH2/C was found to be 1:3, balancing HCOO- coverage and proton availability."},{"paperId":"P121","section":"synthesis","insight":"The use of different weakly basic resin functional groups (-N+(CH3)3, -N(CH3)2, and -NH2) significantly affects the Pd nanoparticle size and the ratio of metallic Pd0 to Pd2+, with D201 providing the smallest particle size (~2.3 nm) and highest Pd0 content."},{"paperId":"P121","section":"characterization","insight":"The presence of quaternary amine groups (-N+(CH3)3) in D201 is more beneficial for the reduction of Pd 2+ to metallic Pd 0 compared to tertiary (-N(CH3)2) or primary (-NH2) amines."},{"paperId":"P121","section":"characterization","insight":"Optimal particle size for FA dehydrogenation on these supports was identified as being within the range of 1.8-3.5 nm, with particles >4 nm showing poor performance."},{"paperId":"P121","section":"performance","insight":"The catalytic activity of the resin-supported Pd catalysts follows the order: Pd/D201 > Pd/D301 > Pd/D311."},{"paperId":"P121","section":"performance","insight":"Pd NP size is a key factor; an optimized range of 1.8-3.5 nm was suggested, and Pd/D201 (~2.3 nm) fell within this range while others were larger."},{"paperId":"P121","section":"performance","insight":"The quaternary amine group (-N+(CH3)3) in D201 promotes the reduction of Pd2+ to metallic Pd0 and enhances HCOO- concentration via electrostatic interaction."},{"paperId":"P122","section":"characterization","insight":"The PPO support is amorphous and nanoporous, allowing rapid diffusion of formic acid (reaction order 0.81) without limiting reactivity."},{"paperId":"P122","section":"characterization","insight":"WAXD analysis before and after five catalytic cycles showed identical patterns, indicating that the AuNPs do not undergo coalescence or significant structural changes during reuse."},{"paperId":"P122","section":"performance","insight":"The AuNPs-PPO catalyst achieves high TOF (up to 600 h^-1) without the need for additional bases or modified supports, which is competitive with literature values that typically require base additives."},{"paperId":"P122","section":"performance","insight":"Reaction order of 0.81 ± 0.04 w.r.t FA concentration indicates diffusion within the polymer matrix does not limit reactivity but still plays a role."},{"paperId":"P123","section":"synthesis","insight":"KIT-6 support was synthesized using Pluronic P123 as template, 1-butanol as co-surfactant, and TEOS as silica source via a hydrothermal method (90 °C for 24 h) followed by calcination at 550 °C."},{"paperId":"P123","section":"characterization","insight":"KIT-6 support exhibits a well-ordered 3D mesoporous structure (Type IV isotherm, H1 hysteresis) with high surface area (~850 m2/g)."},{"paperId":"P123","section":"characterization","insight":"Metal loading preserves the mesoporous structure of KIT-6 but causes slight pore blockage and broadening of pore size distribution."},{"paperId":"P123","section":"characterization","insight":"Co-based catalysts generally exhibit smaller crystallite sizes than Ni-based catalysts on the KIT-6 support."},{"paperId":"P123","section":"characterization","insight":"DRIFT analysis confirms that all catalysts possess Lewis acid sites, with Co-based catalysts showing higher acidity than Ni-based ones."},{"paperId":"P123","section":"characterization","insight":"TG analysis reveals that Co metal promotes significantly more coke formation compared to Ni metal during formic acid decomposition."},{"paperId":"P123","section":"performance","insight":"Ni-based catalysts showed higher H2 selectivity than Co-based catalysts."},{"paperId":"P123","section":"performance","insight":"Co-based catalysts exhibited lower activity due to increased coke formation and carbon deposition on the surface."},{"paperId":"P123","section":"performance","insight":"The addition of Co to Ni@KIT-6 decreased H2 selectivity and increased CO production."},{"paperId":"P123","section":"performance","insight":"A high fraction of argon (FA/Ar 1/2 vs 1/1) had a positive effect on catalytic activity by removing water and carbon from the catalyst surface."},{"paperId":"P124","section":"characterization","insight":"N-doping of carbon supports significantly improves Au dispersion (from 12% in Au/C to 53% in Au/N-C) and reduces mean particle size from ~10 nm to ~2.2 nm."},{"paperId":"P124","section":"characterization","insight":"XPS confirms that the electronic state of Au remains metallic across all different supports after reaction, suggesting support nature affects activity primarily through dispersion and specific surface site interactions rather than changing the oxidation state of gold."},{"paperId":"P124","section":"characterization","insight":"HAADF/STEM reveals that both carbon-supported catalysts contain a mixture of nanoparticles and single Au atoms, with no chlorine stabilization present."},{"paperId":"P124","section":"performance","insight":"The activity trend at 448 K was Au/N-C > Au/SiO2 > Au/C, Au/Al2O3."},{"paperId":"P124","section":"performance","insight":"Selectivity to H2 followed the trend: Au/C (99.5%) > Au/Al2O3 (98.0%) > Au/N-C (96.3%) > Au/SiO2 (83.0%)."},{"paperId":"P124","section":"performance","insight":"N-doping of carbon support significantly improved gold dispersion compared to N-free carbon, leading to higher mass-based activity."},{"paperId":"P125","section":"synthesis","insight":"The deposition-precipitation method was used to maintain a uniform small Pd particle size (2.4-2.5 nm) regardless of ceria content."},{"paperId":"P125","section":"synthesis","insight":"Thermal treatment of the carbon support at 450 °C under N2 did not significantly alter its surface area or properties."},{"paperId":"P125","section":"characterization","insight":"The use of deposition-precipitation allowed for uniform Pd particle size (2.4-2.5 nm) regardless of ceria loading, isolating the promoter effect from the particle size effect."},{"paperId":"P125","section":"characterization","insight":"XPS and XANES confirmed that adding ceria does not significantly change the electronic state or oxidation ratio of Pd."},{"paperId":"P125","section":"characterization","insight":"Post-reaction ICP-AES analysis revealed significant dissolution of ceria (e.g., 3.5 wt% to 0.1 wt% for Pd/Ceria 0.4/C), indicating the promoter acts as a soluble species during reaction."},{"paperId":"P125","section":"performance","insight":"Ceria promotes Pd/C activity by producing formate anions upon dissolution and through interaction between dissolved Ce cations and formate anions, which reduces the activation barrier for C-H bond cleavage."},{"paperId":"P125","section":"performance","insight":"The promoting effect of ceria is independent of Pd particle size or electronic state changes in Pd."},{"paperId":"P125","section":"performance","insight":"Reducible oxides (CeO2, TiO2) improve activity compared to non-reducible oxides (Al2O3, ZrO2)."},{"paperId":"P126","section":"synthesis","insight":"The morphology of the MIL-MOF support (MIL-101 vs MIL-88) is controlled by hydrothermal temperature, reaction time, and HF amount; spindle rod-like MIL-88 was obtained at 200 °C for 8 h with an HF-to-Cr mole ratio of 1.5."},{"paperId":"P126","section":"synthesis","insight":"The use of NaBH4 reduction in an ice water bath facilitates the formation of Pd-Ni alloys on the MOF surface."},{"paperId":"P126","section":"characterization","insight":"The morphology of the Cr-based MOF support can be tuned from octahedral (MIL-101) to spindle rod-like (MIL-88) by adjusting HF amount, hydrothermal temperature, and reaction time."},{"paperId":"P126","section":"characterization","insight":"Bimetallic Pd-Ni alloying on MIL-88 enhances catalytic activity through electronic modulation (electron transfer from Ni to Pd), which optimizes the activation of formate intermediates."},{"paperId":"P126","section":"performance","insight":"The rod-like MIL-88 support provides better catalytic performance for formate hydrolysis than the octahedral MIL-101 structure."},{"paperId":"P126","section":"performance","insight":"Introduction of Ni to Pd/MIL-88 significantly increases TOF (by 250.8% at 60 °C) due to electronic modulation and alloying effects."},{"paperId":"P127","section":"synthesis","insight":"The carbonization temperature of the MOF-5 support significantly affects catalytic activity, with 900 °C being optimal."},{"paperId":"P127","section":"synthesis","insight":"Washing the MOF-5 derived carbon with HCl solution improves hydrogen production rates."},{"paperId":"P127","section":"characterization","insight":"The use of MOF-5 derived porous carbon (MOF-5-C) as a support facilitates high dispersion and small particle size of AgPd bimetallic nanoparticles."},{"paperId":"P127","section":"characterization","insight":"The catalyst consists of a mixture of metallic silver, metallic palladium, and an AgPd alloy phase rather than a single pure alloy phase."},{"paperId":"P127","section":"performance","insight":"The addition of sodium formate (SF) as a promoter significantly accelerates the kinetics of FA decomposition."},{"paperId":"P127","section":"performance","insight":"A molar ratio of 1:3 for FA/SF exhibits the highest hydrogen generation efficiency."},{"paperId":"P127","section":"performance","insight":"The catalyst Ag3Pd12/MOF-5-C-900 shows a volcano-shaped relationship between TOFtotal and FA concentration, with the peak at 1.25 mol L-1."},{"paperId":"P128","section":"synthesis","insight":"The ion-exchange resin method allows for higher Pt loading (26-28 wt%) and smaller particle sizes (2-3 nm) compared to the incipient wetness impregnation method."},{"paperId":"P128","section":"synthesis","insight":"Carbonization temperature affects pore size, metal accessibility, and Pt particle size."},{"paperId":"P128","section":"characterization","insight":"The ion-exchange resin method enables high Pt loadings (26–28 wt%) while maintaining small, uniformly dispersed nanoparticles (2–5 nm) compared to the impregnation method."},{"paperId":"P128","section":"characterization","insight":"Carbonization temperature affects catalyst properties: higher temperatures lead to thermal shrinkage of pores and increased carbon coverage on platinum particles, reducing metal accessibility."},{"paperId":"P128","section":"performance","insight":"Catalysts prepared from ion-exchange resins (Pt@C) exhibit higher activity and stability than those prepared by impregnation (Pt/AC) due to smaller, more uniformly dispersed Pt nanoparticles."},{"paperId":"P128","section":"performance","insight":"Hydrogen production rate shows a volcano-type dependency on formic acid concentration, peaking around 10 wt%; at concentrations above 30 wt%, the rate declines as adsorbed HCOO species occupy vacant active sites."},{"paperId":"P128","section":"performance","insight":"The carbonization temperature affects activity by altering pore size and metal accessibility; higher temperatures lead to smaller exposed Pt surface areas and lower activity."},{"paperId":"P128","section":"performance","insight":"Initial deactivation in Pt@C catalysts is attributed to product gases being trapped within the micropores of the carbon support, an effect that is mitigated at higher formic acid concentrations."},{"paperId":"P129","section":"synthesis","insight":"Acid treatment of activated carbon (1 wt% HNO3, 10 wt% HNO3, or 10 wt% HNO3/10 wt% H2O2) for 6 h was used to modify surface oxygen-containing groups."},{"paperId":"P129","section":"synthesis","insight":"Reduction at high pH (~12) using NaOH resulted in smaller and more monodisperse Pd nanoparticles compared to reduction of PdCl4(2-) ions."},{"paperId":"P129","section":"synthesis","insight":"The IR method (ion exchange - reduction) showed the highest catalytic performance among the tested deposition methods."},{"paperId":"P129","section":"characterization","insight":"Volcano-type relationship observed between Pd nanoparticle size and TOF, with an optimal size around 5.5 nm for acid-treated catalysts."},{"paperId":"P129","section":"characterization","insight":"Reduction at high pH (>10) via mononuclear Pd(OH)2 is more effective for producing smaller, monodisperse nanoparticles than reduction of PdCl4(2-) or polynuclear complexes."},{"paperId":"P129","section":"characterization","insight":"The [100] phase (associated with lower [111]/[200] ratios) is more active for formic acid dehydrogenation than the [111] phase."},{"paperId":"P129","section":"characterization","insight":"Electronic states significantly impact activity: Pd0 or a Pd0/Pd(OH)2 mixture is highly active, whereas Pd2+ is ineffective."},{"paperId":"P129","section":"characterization","insight":"Pd(OH)2 species may act as Lewis acid sites to accelerate formate ion adsorption."},{"paperId":"P129","section":"performance","insight":"Catalytic activity shows a volcano-type dependence on Pd particle size and reaction solution pH."},{"paperId":"P129","section":"performance","insight":"A neutral reaction solution is preferred to maximize performance; acidic solutions promote formate recombination, while basic solutions cause competitive adsorption between formate and hydroxyl ions."},{"paperId":"P129","section":"performance","insight":"Pd0 or a mixture of Pd0/Pd(OH)2 is significantly more active than Pd2+."},{"paperId":"P129","section":"performance","insight":"Surface structure affects activity, with the [100] phase (lower [111]/[200] ratio) being more active."},{"paperId":"P130","section":"synthesis","insight":"The nitrogen content of the NMC support was controlled by varying the initial amount of urea (0 to 3.0g) during synthesis."},{"paperId":"P130","section":"synthesis","insight":"Colloidal silica (Ludox HS-40) was used as a template to introduce mesoporosity, which was subsequently removed using NaOH."},{"paperId":"P130","section":"characterization","insight":"Nitrogen dopants (specifically pyridinic-N) donate electrons to Pd, shifting XPS binding energies lower by 0.11-0.18 eV."},{"paperId":"P130","section":"characterization","insight":"Pd particle size decreases as nitrogen content in the mesoporous carbon support increases."},{"paperId":"P130","section":"characterization","insight":"XANES and EXAFS confirm that oxidation is limited to the surface of Pd particles (Pd-O), while the bulk remains metallic (Pd-Pd)."},{"paperId":"P130","section":"characterization","insight":"The ratio of Pd2+/Pd0 is primarily determined by particle size; smaller particles exhibit a higher proportion of oxidized surface species."},{"paperId":"P130","section":"performance","insight":"Optimum nitrogen doping is required to efficiently improve catalytic activity for hydrogen production from formic acid by lowering the activation barrier of the rate-determining step (hydrogen desorption)."},{"paperId":"P130","section":"performance","insight":"Excessive nitrogen interaction can raise the activation barrier, potentially degrading performance."},{"paperId":"P130","section":"performance","insight":"The addition of sodium formate as an additive significantly increases the reaction rate by increasing the concentration of HCOO-, which is the main reactant."},{"paperId":"P131","section":"synthesis","insight":"The Pd loading was kept constant at 1 wt% across all bimetallic samples to isolate the effect of Au content (surface coverage)."},{"paperId":"P131","section":"synthesis","insight":"Immobilization on carbon involved a long stirring period (~24 h) followed by centrifugation and vacuum drying."},{"paperId":"P131","section":"characterization","insight":"H2 treatment at 200 °C fully reduces oxidized Pd in Pd-on-Au NPs without inducing alloying or changing the metal-on-metal structure."},{"paperId":"P131","section":"characterization","insight":"The Au core stabilizes surface Pd from oxidation compared to monometallic Pd/C."},{"paperId":"P131","section":"characterization","insight":"Catalytic activity and selectivity for FA dehydrogenation correlate with Pd ensemble size: large 3D ensembles (high sc%) favor bridging binding and H2 production, while isolated atoms or small 2D ensembles (low sc%) favor linear binding and CO formation."},{"paperId":"P131","section":"characterization","insight":"Electronic interaction between Au and Pd contributes to enhanced activity beyond simple geometric effects."},{"paperId":"P131","section":"performance","insight":"Catalytic activity for formic acid decomposition follows the order: 30 sc% < 60 sc% < 150 sc% < 300 sc% Pd-on-Au/C."},{"paperId":"P131","section":"performance","insight":"Higher Pd surface coverage correlates with higher activity and lower CO formation (higher dehydrogenation selectivity)."},{"paperId":"P131","section":"performance","insight":"Large 3D Pd ensembles favor the bridging binding of formate, promoting the dehydrogenation pathway, while single atoms or small 2D ensembles favor linear binding and the dehydration pathway leading to CO poisoning."},{"paperId":"P132","section":"synthesis","insight":"The introduction of CTAB (0, 10, 25, and 35 mg) during ZIF-L synthesis regulates the morphology from leaf-like to nanorods and enhances the hydrophilicity of the resulting carbon support."},{"paperId":"P132","section":"synthesis","insight":"Lowering the reduction temperature for Pd NPs (e.g., to 273 K) promotes smaller particle size and higher metal dispersion."},{"paperId":"P132","section":"characterization","insight":"CTAB modulation of ZIF-L transforms morphology from leaf-like to nanorods, resulting in hollow NCZIF-8 supports."},{"paperId":"P132","section":"characterization","insight":"Increased CTAB dosage increases the relative content of pyridinic N and carbon defect density (ID/IG ratio), which enhances catalyst hydrophilicity and Pd dispersion."},{"paperId":"P132","section":"characterization","insight":"The presence of Pd NPs further reduces the contact angle of the support, promoting super-hydrophilic behavior."},{"paperId":"P132","section":"characterization","insight":"In situ DRIFTS and isotopic tracing indicate that H2O molecules directly participate in the reaction via a hydrogen-bonding network that facilitates proton shuttling through the Grotthuss mechanism."},{"paperId":"P132","section":"performance","insight":"The introduction of CTAB surfactant modulates the morphology and chemical composition (pyridinic N, carbon defects) of MOF-derived carbon, significantly increasing catalyst hydrophilicity."},{"paperId":"P132","section":"performance","insight":"Water molecules act as active participants in the reaction rather than just a solvent, forming an FA-H2O hydrogen-bonding network that lowers the activation energy for proton transfer."},{"paperId":"P133","section":"synthesis","insight":"The amine groups on the NH2-MIL-101(Cr) support act as anchoring sites for Pd2+ and Ag+ ions and help stabilize the resulting ultrafine nanoparticles (average size 2.2 nm)."},{"paperId":"P133","section":"characterization","insight":"The amine functional groups in NH2-MIL-101(Cr) serve a dual purpose: anchoring and stabilizing ultrafine PdAg nanoparticles to prevent aggregation and acting as Brønsted basic sites to enhance the kinetics of formic acid decomposition."},{"paperId":"P133","section":"characterization","insight":"Bimetallic synergy between Pd and Ag modulates the electronic states, improving catalytic performance compared to monometallic counterparts."},{"paperId":"P133","section":"performance","insight":"The catalytic activity for FA decomposition follows the order: Pd0.8Ag0.2/NH2-MIL-101(Cr) > Pd0.8Ag0.2/MNCTs > Pd0.8Ag0.2/XC-72R > Pd0.8Ag0.2."},{"paperId":"P133","section":"performance","insight":"The amine functional group in the MOF support modulates the electronic structure of bimetallic PdAg NPs, creating electron-rich catalytic sites."},{"paperId":"P134","section":"synthesis","insight":"The PTAT polymer acts as an ideal precursor due to high N density and BET surface area, facilitating strong adsorption of Pd NPs."},{"paperId":"P134","section":"synthesis","insight":"Pyrolysis converts the organic PTAT framework into a nitrogen-doped carbon support while enhancing the Pd-support interaction."},{"paperId":"P134","section":"characterization","insight":"Pyrolysis of the PTAT polymer framework leads to a skeleton rearrangement into a layered graphene-like structure with increased mesoporosity (10–40 nm)."},{"paperId":"P134","section":"characterization","insight":"Pyridinic-N in the N-doped carbon support is identified as the primary contributor to electronic interaction and electron transfer to Pd NPs."},{"paperId":"P134","section":"characterization","insight":"The transition from Pd/PTAT to Pd@CN involves partial sintering of Pd nanoparticles, increasing average size from 3–4 nm to 6–8 nm."},{"paperId":"P134","section":"performance","insight":"Pyrolysis of Pd/PTAT to form Pd@CN significantly enhances catalytic activity and stability for both FA dehydrogenation and alkene hydrogenation."},{"paperId":"P134","section":"performance","insight":"The electronic interaction between pyridinic-N in the N-doped carbon support and Pd nanoparticles is a key driver for the improved performance."},{"paperId":"P135","section":"synthesis","insight":"Amine functionalization of YSMSNs using APTES prevents Pd nanoparticle aggregation and creates a basic environment that promotes O-H bond cleavage in formic acid."},{"paperId":"P135","section":"synthesis","insight":"The radial oriented pore structure of YSMSNs facilitates faster mass transfer compared to conventional porous silica like SBA-15."},{"paperId":"P135","section":"characterization","insight":"Radially oriented mesoporous channels in YSMSNs provide faster mass transfer of FA molecules compared to conventional uniform porous structures like SBA-15."},{"paperId":"P135","section":"characterization","insight":"Amine functionalization on silica supports serves a dual purpose: anchoring Pd NPs to prevent aggregation and acting as proton scavengers for O-H bond cleavage."},{"paperId":"P135","section":"performance","insight":"The optimized Pd/YSMSNs-NH2(10-3) catalyst shows superior activity due to the synergy of radially oriented mesoporous channels, amine functionalization (acting as Brønsted basic sites), and strong metal-support interaction."},{"paperId":"P135","section":"performance","insight":"Sodium formate acts as a potent promoter for FA dehydrogenation, significantly increasing the TOF from 1336 h-1 to 2783 h-1 at 323 K."},{"paperId":"P136","section":"synthesis","insight":"The carbonization temperature of the MOF-derived support significantly influences the graphitization degree and metal-support interaction (MSI), with 900 °C being optimal for Pd dispersion and activity."},{"paperId":"P136","section":"synthesis","insight":"Pd loading was optimized at 15 wt%; lower loadings limited active sites, while higher loadings (20 wt%) led to nanoparticle aggregation."},{"paperId":"P136","section":"characterization","insight":"Carbonization temperature of the MET-6 precursor significantly influences the graphitization degree, defect density, and basicity of the PNCNCs support."},{"paperId":"P136","section":"characterization","insight":"The optimal carbonization temperature (900°C) maximizes electron transfer from pyridinic N sites to Pd nanoparticles, enhancing catalytic activity via a strong metal-support interaction (MSI)."},{"paperId":"P136","section":"characterization","insight":"A higher I D/I G ratio in Raman spectra for other samples compared to Pd@PNCNCs-900 indicates that 900°C provides the best balance of graphitization and defect creation."},{"paperId":"P136","section":"performance","insight":"The optimal catalyst Pd@PNCNCs-900 (15 wt% Pd) exhibits the highest activity with an initial TOF of 3253 h-1 at 60 °C in a FA/SF system (1:2)."},{"paperId":"P136","section":"performance","insight":"Sodium formate (SF) acts as a potent promoter, significantly increasing the H2 production rate compared to pure formic acid."},{"paperId":"P136","section":"performance","insight":"The activation energy for Pd@PNCNCs-900 was calculated to be 45.97 kJ/mol."},{"paperId":"P136","section":"performance","insight":"KIE results indicate that O-H bond dissociation occurs prior to C-H bond cleavage during FA dehydrogenation over the catalyst."},{"paperId":"P137","section":"synthesis","insight":"The addition of melamine during the support coannealing process significantly increases boron incorporation (ca. 34 times higher in OB-C-N than OB-C)."},{"paperId":"P137","section":"synthesis","insight":"B-O functionalities on the carbon support act as anchoring sites for PdCl4(2-) precursors, leading to smaller and more uniform Pd nanoparticles."},{"paperId":"P137","section":"synthesis","insight":"NaOH-assisted NaBH4 reduction is used specifically to achieve well-dispersed ultrafine Pd NPs."},{"paperId":"P137","section":"characterization","insight":"B-O functionalization of carbon nanospheres effectively anchors ultrafine Pd nanoparticles and prevents aggregation."},{"paperId":"P137","section":"characterization","insight":"The addition of melamine during the synthesis of OB-C-N significantly increases boron content (ca. 34 times higher than OB-C), which further reduces Pd particle size to ~1.4 nm."},{"paperId":"P137","section":"characterization","insight":"Charge transfer from B doping induces a binding energy shift in the Pd 3d XPS spectra."},{"paperId":"P137","section":"performance","insight":"The addition of melamine to the precursor mixture significantly increases boron content in the carbon support, leading to smaller Pd particle sizes and higher catalytic activity."},{"paperId":"P137","section":"performance","insight":"Catalytic activity for FA dehydrogenation improves with increasing sodium formate (SF) molar percentage up to 71.4%."},{"paperId":"P138","section":"synthesis","insight":"The introduction of -NH2 groups via APTMS improves the wettability of carbon supports and facilitates the formation of ultra-fine AuPd nanoparticles (approx 2.2 nm)."},{"paperId":"P138","section":"synthesis","insight":"Support functionalization with amino groups acts as a proton scavenger to promote O-H cleavage in formic acid."},{"paperId":"P138","section":"characterization","insight":"The introduction of -NH2 groups and N-doping on the hollow mesoporous carbon spheres (HMCS) effectively anchors AuPd nanoparticles, preventing aggregation and resulting in ultra-fine particles (2.2 nm)."},{"paperId":"P138","section":"characterization","insight":"XPS analysis reveals a synergistic electronic effect where Pd binding energy is shifted by both the support interaction and the presence of Au, creating an electron-depleted state that optimizes C-H bond cleavage."},{"paperId":"P138","section":"characterization","insight":"The hollow mesoporous structure provides a confinement effect and facilitates mass diffusion of reactants."},{"paperId":"P138","section":"performance","insight":"The introduction of amine groups on N-doped hollow mesoporous carbon spheres significantly improves the wettability and dispersion of AuPd nanoparticles, leading to superior catalytic activity for formic acid dehydrogenation without additives."},{"paperId":"P138","section":"performance","insight":"A synergistic effect between Au and Pd modulates the electronic structure of Pd (increasing electron depletion), which accelerates the rate-determining C-H cleavage step."},{"paperId":"P139","section":"synthesis","insight":"The far-infrared radiation properties of barium titanate (TBT) reduce the surface tension of the reaction medium by breaking hydrogen bonds, which enhances the dispersion of [PdCl4]2- and leads to significantly smaller Pd nanoparticle sizes compared to rGO supports."},{"paperId":"P139","section":"characterization","insight":"Tetragonal-phase barium titanate (TBT) generates an internal electric field verified by P-E hysteresis loops and remanent polarization (Pr)."},{"paperId":"P139","section":"characterization","insight":"The far-infrared radiation properties of BaTiO3 are credited with reducing the particle size of Pd nanoparticles by decreasing solution surface tension during synthesis."},{"paperId":"P139","section":"characterization","insight":"Metal-support interaction between BaTiO3 and Pd results in electron transfer from the support to the metal, creating electron-rich Pd sites."},{"paperId":"P139","section":"characterization","insight":"rGO improves the electrical conductivity and interfacial charge-transfer rate of the TBT-based catalyst."},{"paperId":"P139","section":"performance","insight":"The apparent activation energy (Ea) of FAD catalyzed by Pd/TBT/rGO is 36.33 kJ/mol."},{"paperId":"P139","section":"performance","insight":"Introduction of TBT reduces the particle size of Pd nanoparticles and creates electron-rich Pd, which enhances catalytic activity."},{"paperId":"P140","section":"synthesis","insight":"The combination of carbon and SiO2 in the C-SiO2 support promotes smaller Pd nanoparticle size (1.8 nm) compared to single supports."},{"paperId":"P140","section":"synthesis","insight":"Surface Si-OH groups on SiO2 act as interaction sites for anchoring Pd nanoparticles."},{"paperId":"P140","section":"characterization","insight":"The combination of carbon and SiO2 (C–SiO2) increases the graphitization degree (IG/ID = 1.03), which facilitates electron transfer to Pd NPs."},{"paperId":"P140","section":"characterization","insight":"Hydrophilicity, enhanced by O2 (ethers or phenolic hydroxyl) and O3 (lactone or carboxyl) functional groups (92.6% of total O in Pd/C–SiO2), improves liquid-phase catalytic performance."},{"paperId":"P140","section":"characterization","insight":"The synergistic effect of the bi-carrier C–SiO2 promotes the formation of smaller, more highly dispersed Pd nanoparticles compared to single carriers."},{"paperId":"P140","section":"performance","insight":"The composite C-SiO2 carrier reduces Pd nanoparticle size (1.8 nm) compared to single carriers."},{"paperId":"P140","section":"performance","insight":"Synergistic effect of carbon and SiO2 enhances electron transfer to Pd, creating electron-rich active sites."},{"paperId":"P140","section":"performance","insight":"High graphitization degree in Pd/C-SiO2 facilitates electron transfer and increases H2 production rate."},{"paperId":"P140","section":"performance","insight":"Oxygen-containing functional groups (O2, O3) on the composite carrier improve hydrophilicity and act as proton scavengers."},{"paperId":"P141","section":"synthesis","insight":"The incorporation of Zn as a promoter into the Pd/TiO2 catalyst alters the HCOOH decomposition pathway to avoid formate accumulation."},{"paperId":"P141","section":"characterization","insight":"The deactivation of Pd/TiO2 is reversible and can be mitigated by washing with alkaline ammonia aqueous solution to remove accumulated formate."},{"paperId":"P141","section":"characterization","insight":"Pore structure (BET), metal loading (ICP-OES), and overall morphology (SEM/TEM) remain stable for both catalysts across reaction cycles, ruling them out as causes for deactivation."},{"paperId":"P141","section":"performance","insight":"The deactivation of Pd/TiO2 is reversible and can be restored by washing with alkaline ammonia aqueous solution, confirming that formate accumulation is the primary cause of activity loss."},{"paperId":"P141","section":"performance","insight":"Zn-Pd alloy nanoparticles facilitate a different dehydrogenation pathway for HCOOH compared to pure Pd, which avoids the rate-limiting step of formate decomposition."},{"paperId":"P142","section":"synthesis","insight":"Nitrogen doping in carbon xerogels (specifically at 4 wt.%) helps stabilize smaller Pd nanoparticles by acting as basic coordination sites, preventing aggregation during H2 reduction."},{"paperId":"P142","section":"synthesis","insight":"The pore texture of the support (micro-mesoporous vs micro-macroporous) significantly impacts catalytic activity for liquid-phase formic acid dehydrogenation."},{"paperId":"P142","section":"characterization","insight":"Nitrogen doping at 2-4 wt% acts as basic coordination sites that stabilize small Pd nanoparticles and prevent aggregation during reduction."},{"paperId":"P142","section":"characterization","insight":"XPS shifts to higher binding energies in N-doped catalysts indicate electron deficient Pd species, which are hypothesized to interact better with formate intermediates."},{"paperId":"P142","section":"characterization","insight":"Micro-mesoporous carbon xerogels provide better accessibility for formic acid molecules compared to micro-macroporous structures."},{"paperId":"P142","section":"characterization","insight":"EXAFS identifies a specific Pd-O(N) bond at 1.5 Å in catalysts with low to moderate nitrogen content, which is absent in the high-nitrogen (8 wt%) sample."},{"paperId":"P142","section":"performance","insight":"Nitrogen doping at 4 wt.% is optimal for achieving high Pd dispersion and catalytic activity."},{"paperId":"P142","section":"performance","insight":"Micro-mesoporous carbon xerogels are more effective than micro-macroporous ones for liquid phase formic acid dehydrogenation due to better accessibility of reactants to active sites."},{"paperId":"P142","section":"performance","insight":"N-doping modifies the electronic properties of Pd, creating electron deficient species that enhance interaction with formate ions."},{"paperId":"P143","section":"synthesis","insight":"PDA can act as a stabilizer to reduce the size of the nanoparticles during the synthesis process."},{"paperId":"P143","section":"characterization","insight":"PDA in the support acts as a stabilizer to reduce nanoparticle size during synthesis."},{"paperId":"P143","section":"characterization","insight":"The addition of Au modifies the electron state of Pd and prevents CO poisoning of the catalyst surface."},{"paperId":"P143","section":"characterization","insight":"PDA structure is unstable under high pressure H2 conditions, leading to its transformation/removal and subsequent loss of catalytic activity over cycles."},{"paperId":"P143","section":"performance","insight":"The PdAu bimetallic catalyst supported on PDA-rGO is highly efficient for both bicarbonate hydrogenation and FA/PF dehydrogenation without additives."},{"paperId":"P143","section":"performance","insight":"High concentration FA (8 mol/L) can be decomposed with 96% conversion, which is significant for increasing hydrogen capacity in practical applications."},{"paperId":"P143","section":"performance","insight":"The addition of Au to Pd enhances activity for FA dehydrogenation and prevents CO poisoning."},{"paperId":"P143","section":"performance","insight":"PDA acts as a stabilizer during synthesis but is unstable under high-pressure H2 conditions."},{"paperId":"P144","section":"synthesis","insight":"Sequential impregnation results in smaller Pd particle size and more positively charged Pd species compared to co-impregnation."},{"paperId":"P144","section":"synthesis","insight":"The optimal Ni/Pd molar ratio for the sequential impregnation method was found to be 1.3."},{"paperId":"P144","section":"characterization","insight":"Sequential impregnation is more effective than co-impregnation in constraining the growth of Pd nanoparticles."},{"paperId":"P144","section":"characterization","insight":"There is a positive linear correlation between the mol% of Pd2+ species (determined by H2-TPR) and the TOF for the formic acid dehydrogenation reaction."},{"paperId":"P144","section":"characterization","insight":"The electronic state of Pd is highly dependent on the impregnation order: co-impregnation leads to electron transfer from Ni to Pd (more negative), while sequential impregnation results in Pd interacting with oxygen sites of NiO (more positive)."},{"paperId":"P144","section":"characterization","insight":"Pd particle size follows a volcanic trend relative to the Ni/Pd molar ratio in sequentially impregnated catalysts, reaching a minimum at ratios between 1.3 and 1.6."},{"paperId":"P144","section":"performance","insight":"The sequential impregnation method produces catalysts with higher activity than co-impregnation for the same Ni/Pd ratio."},{"paperId":"P144","section":"performance","insight":"Catalytic activity follows a volcanic trend with respect to the Ni/Pd molar ratio, peaking at x = 1.3."},{"paperId":"P144","section":"performance","insight":"A positive linear correlation exists between the amount of Pd2+ species (determined by H2-TPR) and the initial TOF."},{"paperId":"P145","section":"synthesis","insight":"The release-and-catch mechanism is driven by the electrostatic or coordination interactions between the carboxylic acid groups of PAA and the Ir complex, which are disrupted by acids stronger than PAA (e.g., formic acid or sulfuric acid)."},{"paperId":"P145","section":"synthesis","insight":"Optimal catalytic activity was achieved with a ligand content of 212 μmol/g of 4-hmdabpy and an Ir loading of 1.16 wt% (approximately 30% relative to the ligand content)."},{"paperId":"P145","section":"characterization","insight":"The catalyst's structure was confirmed using FT-IR (shift of ring stretching vibration from 1590 to 1620 cm−1), 13C CPMAS NMR, and 1H solid-state NMR."},{"paperId":"P145","section":"characterization","insight":"UV-vis spectroscopy was used to monitor the release (dissolution) and catch (re-adsorption) cycles of the Ir complex in response to pH changes and FA concentration."},{"paperId":"P145","section":"performance","insight":"The release-and-catch system allows the catalyst to operate with homogeneous-like activity while maintaining easy recovery via filtration or flow columns."},{"paperId":"P145","section":"performance","insight":"Catalytic activity is optimized by adjusting ligand (4-hmdabpy) and Ir loading on PAA; optimal ratio was approximately 0.3 mol Ir per 1 mol ligand."},{"paperId":"P145","section":"performance","insight":"The release of the catalyst from PAA is triggered by acids stronger than the carboxylic acid groups of PAA, such as formic acid or sulfuric acid."},{"paperId":"P146","section":"characterization","insight":"The introduction of VOx increases the proportion of PdAu with strong metal-support interaction (evidenced by H2-TPR peak beta)."},{"paperId":"P146","section":"characterization","insight":"EPR confirms higher oxygen vacancy concentration in PdAu-VOx/NHMS (1.181 x 10^13 spins g-1) compared to PdAu/NHMS, correlating with increased Lewis acid sites."},{"paperId":"P146","section":"characterization","insight":"In situ ATR-IR and Raman spectroscopy identify HCOO* as the primary intermediate in the FA dehydrogenation pathway."},{"paperId":"P146","section":"characterization","insight":"DFT calculations indicate that V atoms are electron-deficient (Mulliken charge 0.75 e), confirming their role as Lewis acids."},{"paperId":"P146","section":"performance","insight":"The introduction of VOx species significantly enhances catalytic activity by providing Lewis acid sites that regulate HCOO* adsorption and facilitate C-H bond activation."},{"paperId":"P146","section":"performance","insight":"Amino groups on the support act as Brønsted base sites to promote O-H bond cleavage in formic acid."},{"paperId":"P146","section":"performance","insight":"Reaction rate is first-order with respect to catalyst amount (PdAu concentration) and quasi-zero-order with respect to FA concentration in a certain range (0.25 to 1.00 M)."},{"paperId":"P146","section":"performance","insight":"Catalytic performance decreases at high FA concentrations (above 15 M), possibly due to wetting difficulties, deactivation under lower pH, or CO generation via dehydration."},{"paperId":"P147","section":"synthesis","insight":"Solid-state grinding of cobalt salts, N-ligands and carbon support is a solvent-free, simplified alternative to incipient wetness impregnation or MOF carbonization for producing Co@NC materials."},{"paperId":"P147","section":"synthesis","insight":"Acid treatment with H2SO4 removes metallic cobalt nanoparticles while leaving single-atomic Co species intact."},{"paperId":"P147","section":"characterization","insight":"High temperature co-graphitization of carbon with Co(II) salts and N-heteroarenes leads to similar structural characteristics regardless of the initial deposition method."},{"paperId":"P147","section":"characterization","insight":"The catalytic activity for FA dehydrogenation is driven by highly dispersed atomic Co or CoNx centers rather than visible cobalt nanoparticles."},{"paperId":"P147","section":"characterization","insight":"Acid treatment removes metallic nanoparticles but leaves single-atomic species intact, which maintain a significant portion of the catalyst's activity."},{"paperId":"P147","section":"performance","insight":"The catalytic activity of Co@NC materials is primarily provided by highly dispersed single atomic cobalt species or CoNx centers incorporated in graphitic carbon, rather than cobalt nanoparticles."},{"paperId":"P147","section":"performance","insight":"Gas-phase decomposition provides a more acceptable quantitative assessment of catalytic activity as it avoids solvent effects that can distort results for catalysts with different cobalt contents."},{"paperId":"P147","section":"performance","insight":"In liquid phase, the rate of FA decomposition is highly dependent on the auxiliary solvent; o-xylene, propylene carbonate, 1,4-dioxane and toluene provide better results than water or tert-butanol."},{"paperId":"P147","section":"performance","insight":"Increasing the concentration of formic acid (decreasing the FA/solvent ratio) negatively impacts H2 production rates."},{"paperId":"P148","section":"characterization","insight":"The catalyst exhibits a type II N2 physisorption isotherm characteristic of micro/mesoporous solids with a BET surface area of 850 m2/g and an average pore diameter of 3.2 nm."},{"paperId":"P148","section":"performance","insight":"The catalytic activity follows the order: NH4OH > KOH > NaOH > LiOH, which is inversely proportional to the hydrated cationic radii of the alkali metals used for pH control."},{"paperId":"P148","section":"performance","insight":"A volcano-type dependence of TOF on reaction pH was observed, with an optimum around pH 3.5."},{"paperId":"P148","section":"performance","insight":"Alkaline pH allows for CO2 retention in the solution as bicarbonate/carbonate, resulting in a cleaner H2 stream (higher H2/CO2 ratio)."},{"paperId":"P149","section":"synthesis","insight":"The polyol method used a PVP/Pd molar ratio of 10/1."},{"paperId":"P149","section":"synthesis","insight":"PVP acts as both a capping agent and provides N-containing groups that enhance catalytic activity by increasing hydrophilicity and interaction with formic acid."},{"paperId":"P149","section":"characterization","insight":"PVP molecules exert an electron withdrawal effect on Pd nanoparticles via the carbonyl group, creating electron-deficient states (Pdδ+)."},{"paperId":"P149","section":"characterization","insight":"Heat treatment at 450 °C effectively removes PVP, which is evidenced by a ~10 wt% mass loss in TGA and an increase in metallic Pd(0) content observed via XPS."},{"paperId":"P149","section":"characterization","insight":"The use of MWCNTs as a support minimizes micropore contribution compared to carbon black (CB), reducing diffusion problems and enhancing catalytic performance."},{"paperId":"P149","section":"characterization","insight":"PVP capping increases the hydrophilicity of the catalysts, favoring dispersion in the reaction medium."},{"paperId":"P149","section":"performance","insight":"The presence of PVP as a capping agent enhances catalytic activity by introducing basic N-containing groups and increasing hydrophilicity, which improves the interface contact between reactants and active sites."},{"paperId":"P149","section":"performance","insight":"MWCNT is the most effective support among those tested due to its 1D structure, high available external surface area, and low microporosity, which reduces diffusion limitations."},{"paperId":"P151","section":"synthesis","insight":"Coprecipitation provides more intimate contact between lanthana and titania compared to wet impregnation."},{"paperId":"P151","section":"synthesis","insight":"Wet-impregnation leads to higher surface enrichment of lanthanum than coprecipitation at the same nominal loading."},{"paperId":"P151","section":"synthesis","insight":"Lanthana modification reduces gold particle size, likely due to increased density of surface hydroxyls facilitating precursor dispersion."},{"paperId":"P151","section":"characterization","insight":"Lanthana modification induces a red-shift of the nu(CH) band (by 25 cm-1), indicating weakening of the C-H bond in bidentate formates."},{"paperId":"P151","section":"characterization","insight":"Coprecipitation results in significantly smaller anatase crystallite sizes and higher specific surface areas compared to wet impregnation."},{"paperId":"P151","section":"characterization","insight":"High lanthana loading (>70 wt%) leads to phase segregation and the formation of rod-like morphologies consisting of lanthanum hydroxide and lanthana."},{"paperId":"P151","section":"characterization","insight":"Lanthana addition suppresses the formation of monodentate formates, which are precursors to carbon monoxide production."},{"paperId":"P151","section":"performance","insight":"Coprecipitation is the preferred method for preparing highly active catalysts for oxidative formic acid decomposition under SCR conditions compared to wet impregnation."},{"paperId":"P151","section":"performance","insight":"Lanthana modification steers selectivity towards CO2 by suppressing monodentate formates, which are precursors to CO."},{"paperId":"P151","section":"performance","insight":"An optimum lanthana loading exists (15 wt% for CP) beyond which activity declines due to surface area reduction and phase segregation of lanthana."},{"paperId":"P151","section":"performance","insight":"The reaction follows a hydroperoxy-mediated C-H bond cleavage mechanism where basicity promotes the rate-determining step."},{"paperId":"P152","section":"synthesis","insight":"The optimum mass ratio of UiO-66/GO is 10%."},{"paperId":"P152","section":"synthesis","insight":"Homogeneous dispersion of ZrO2/C on rGO facilitates the formation of ultrafine PdAg NPs (average size ~2.5 nm)."},{"paperId":"P152","section":"characterization","insight":"XRD confirmed the transformation of UiO-66/GO to ZrO2/C/rGO after calcination at 1073 K."},{"paperId":"P152","section":"characterization","insight":"Nitrogen sorption showed a decrease in specific surface area from 1088 m2 g-1 (UiO-66/GO) to 141 m2 g-1 (ZrO2/C/rGO)."},{"paperId":"P152","section":"characterization","insight":"The synergistic interaction between Pd and Ag is critical for enhancing the dehydrogenation of formic acid."},{"paperId":"P152","section":"performance","insight":"The molar ratio of Pd/Ag is critical; the maximum activity was observed at x = 0.6 (Pd0.6Ag0.4)."},{"paperId":"P152","section":"performance","insight":"Support composition significantly impacts performance, with ZrO2/C/rGO being superior to C/rGO, ZrO2/C, UiO-66/rGO, rGO, and UiO-66."},{"paperId":"P152","section":"performance","insight":"The activation energy (Ea) for FA dehydrogenation over Pd0.6Ag0.4@ZrO2/C/rGO was estimated to be 50.1 kJ mol-1."},{"paperId":"P153","section":"synthesis","insight":"The double solvents method was used to avoid deposition of metal precursors on the outer surface of the MOF framework."},{"paperId":"P153","section":"synthesis","insight":"Pd-Cu NC composition was controlled by adjusting the molar ratio of Cu precursor while keeping Pd precursor constant at 0.066 mmol."},{"paperId":"P153","section":"characterization","insight":"PXRD confirmed the formation of Pd-Cu alloys and the maintenance of the MIL-101 framework structure."},{"paperId":"P153","section":"characterization","insight":"N2 adsorption/desorption isotherms showed a decrease in pore volume and N2 adsorption for Pd-Cu/MIL-101 compared to pure MIL-101, indicating that nanocrystals occupy or block the host cavities."},{"paperId":"P153","section":"characterization","insight":"EDX and ICP-MS confirmed that the Pd:Cu atomic ratios were consistent with the precursor ratios."},{"paperId":"P153","section":"performance","insight":"Pd-Cu/MIL-101 nanocomposites are 3-5 times faster than Pd-Cu nanocrystals for Cr(VI) reduction."},{"paperId":"P153","section":"performance","insight":"For the carboxylation of terminal alkynes, the activity order is Pd 0.2 Cu 0.8 / MIL-101 > Pd 0.3 Cu 0.7 / MIL-101 > Pd 0.5 Cu 0.5 / MIL-101 > Pd 0.7 Cu 0.3 / MIL-101 > Pd 0.8 Cu 0.2 / MIL-101."},{"paperId":"P153","section":"performance","insight":"DMF is the superior solvent for alkyne carboxylation compared to CH3CN, NMP, and DMSO due to better solubility of Cs2CO3 and CO2."},{"paperId":"P154","section":"synthesis","insight":"The Fe@C support is magnetic and prepared via hydrothermal synthesis of Fe3O4 NPs with glucose followed by calcination, which reduces iron oxide to alpha-Fe0."},{"paperId":"P154","section":"characterization","insight":"The work function discrepancy between Pd and the incorporated element (B or Ag) is a more critical driver for FA dehydrogenation and TCE dechlorination than lattice expansion alone."},{"paperId":"P154","section":"characterization","insight":"Incorporation of low work function elements induces charge redistribution, increasing electron density on Pd atoms and lowering reduction onset potentials for H*ads formation."},{"paperId":"P154","section":"characterization","insight":"Ag incorporation promotes selective hydrogenation of alkynes to alkenes (ethene) due to decreased adsorption energy of ethene compared to monometallic Pd."},{"paperId":"P154","section":"performance","insight":"Incorporation of low work function elements (B or Ag) into Pd NPs enhances FA dehydrogenation and TCE dechlorination by inducing charge redistribution and increasing electron density on Pd atoms."},{"paperId":"P154","section":"performance","insight":"The work function discrepancy between the incorporated element and Pd is more crucial for catalytic activity than the enlargement of lattice spacing."},{"paperId":"P154","section":"performance","insight":"Ag incorporation provides higher initial activity and H utilization efficiency but suffers from poor stability due to Ag leaching in the presence of chloride ions."},{"paperId":"P154","section":"performance","insight":"B incorporation maintains high stability over multiple cycles while significantly improving performance compared to unmodified Pd."},{"paperId":"P155","section":"synthesis","insight":"The use of PEI and PDA modification on CNC creates a positively charged surface that immobilizes AuCl4- and PdCl4(2-) via electrostatic attraction, preventing nanoparticle aggregation."},{"paperId":"P155","section":"synthesis","insight":"A post-heating treatment at 573 K under Ar for 2 h was used specifically for XRD characterization to confirm the alloy structure, but not as a standard synthesis step."},{"paperId":"P155","section":"characterization","insight":"Amine functionalization (PEI) and PDA modification of CNC improve metal-support interaction, preventing nanoparticle aggregation and enhancing dispersion."},{"paperId":"P155","section":"characterization","insight":"Electron transfer from Pd to Au is driven by the difference in work functions (Au: 5.54 eV, Pd: 5.67 eV)."},{"paperId":"P155","section":"characterization","insight":"The optimal catalytic activity for formic acid dehydrogenation was found at an Au:Pd molar ratio of 4:6."},{"paperId":"P155","section":"performance","insight":"The optimal Au:Pd ratio for FA dehydrogenation was found to be 4:6."},{"paperId":"P155","section":"performance","insight":"Amine-functionalization of CNC using PDA and PEI effectively prevents metal nanoparticle aggregation, improving dispersion and metal utilization."},{"paperId":"P155","section":"performance","insight":"A volcano relationship exists between Pd particle size and activity; ~2 nm is optimal."},{"paperId":"P156","section":"synthesis","insight":"Oxygen coverage on Ti3C2Tx and Ti2CTx MXenes can be modulated by thermal treatment in air below 350 °C without altering the crystalline structure (up to 250 °C)."},{"paperId":"P156","section":"synthesis","insight":"Selective etching of Al from MAX phases using HF is used to synthesize the base MXene powders."},{"paperId":"P156","section":"characterization","insight":"Surface oxygen coverage on Ti3C2Tx MXenes can be modulated by thermal treatment in air below 250 °C without altering the crystalline structure."},{"paperId":"P156","section":"characterization","insight":"XPS O 1s spectra distinguish between surface-adsorbed oxygen, surface O-Ti species, surface OH groups, and lattice oxygen in TiO2."},{"paperId":"P156","section":"characterization","insight":"The coordination number (CN) for Ti-C/O shell increases from 4.5 to 4.9 as treatment temperature increases from 25 °C to 250 °C, then drops to 2.9 at 350 °C due to TiO2 formation."},{"paperId":"P156","section":"characterization","insight":"Linear correlation exists between the percentage of surface O-Ti species and HCOOH dehydrogenation activity."},{"paperId":"P156","section":"performance","insight":"Modulating oxygen coverage on Ti3C2Tx MXenes significantly boosts catalytic activity for HCOOH dehydrogenation."},{"paperId":"P156","section":"performance","insight":"Ti3C2Tx-250 exhibits higher mass activity than commercial Pd/C and Pt/C catalysts."},{"paperId":"P156","section":"performance","insight":"The rate-determining step is the dissociation of H/DCOO* to form COO* over Ti3C2Tx-250."},{"paperId":"P157","section":"synthesis","insight":"Catalysts were prepared without any pre-treatment by acid-base or other additives."},{"paperId":"P157","section":"synthesis","insight":"Liquid-phase reduction using NaBH4 at room temperature was used to generate Pd(0) nanoparticles."},{"paperId":"P157","section":"characterization","insight":"The reducible nature of the ceria support (Ce4+/Ce3+ fluctuation) is identified as a key factor in enhancing the catalytic activity of supported palladium nanoparticles for formic acid dehydrogenation."},{"paperId":"P157","section":"performance","insight":"The dehydrogenation of FA is first order with respect to the FA concentration when considering the equilibrium between FA and formate ion."},{"paperId":"P157","section":"performance","insight":"Ceria support significantly enhances Pd activity compared to other oxides (SiO2, Al2O3, TiO2, ZrO2, HfO2)."},{"paperId":"P157","section":"performance","insight":"Optimal Pd loading for Pd0/CeO2 was found to be 2.27% wt."},{"paperId":"P158","section":"synthesis","insight":"The nanotubular geometry of T-g-C3N4 provides a confinement effect that enhances catalytic activity despite having the lowest surface area among the carbon nitride supports."},{"paperId":"P158","section":"synthesis","insight":"Nitrogen atoms in g-C3N4 act as anchoring points for AuPd particles, leading to better dispersion compared to nitrogen-free graphene."},{"paperId":"P158","section":"characterization","insight":"Nitrogen atoms in g-C3N4 act as anchoring points and electron donors to AuPd particles, improving dispersion and activity compared to graphene."},{"paperId":"P158","section":"characterization","insight":"Graphitic N content correlates with smaller nanoparticle size (S-g-C3N4 > B-g-C3N4 > T-g-C3N4)."},{"paperId":"P158","section":"characterization","insight":"The nanotubular structure of T-g-C3N4 provides a confinement effect that outweighs the benefit of smaller particle sizes seen in S-g-C3N4."},{"paperId":"P158","section":"performance","insight":"The activity order for different supports was AuPd/T-g-C3N4 > AuPd/S-g-C3N4 > AuPd/B-g-C3N4 > AuPd/g-C."},{"paperId":"P158","section":"performance","insight":"Nitrogen-doped carbon nitride supports provide better dispersion and higher activity than nitrogen-free graphene due to anchoring and electron donation effects."},{"paperId":"P158","section":"performance","insight":"The nanotubular geometry of T-g-C3N4 provides a confinement effect that enhances catalytic reactivity despite having the lowest surface area among g-C3N4 supports."},{"paperId":"P159","section":"synthesis","insight":"Plasma treatment of thermally reduced Pd/AC promotes redispersion and migration of Pd NPs to the support surface."},{"paperId":"P159","section":"synthesis","insight":"N2 RF plasma enhances N-doping of the AC support, specifically increasing pyridine nitrogen content."},{"paperId":"P159","section":"synthesis","insight":"The combination of thermal reduction followed by plasma treatment (Pd/AC-CP) is more effective than plasma alone (Pd/AC-P) for achieving small Pd particle size and high activity."},{"paperId":"P159","section":"characterization","insight":"RF cold plasma treatment of thermally reduced Pd/AC catalysts achieves redispersion of Pd NPs, surface enrichment via etching and electric fields, and enhanced N-doping (specifically pyridine nitrogen)."},{"paperId":"P159","section":"characterization","insight":"H2-TPR negative peaks near 70 °C are inversely proportional to Pd NP size."},{"paperId":"P159","section":"characterization","insight":"Strong metal-support interaction in plasma-treated samples is evidenced by weak H2-TPR reduction peaks at approximately 200 °C."},{"paperId":"P159","section":"performance","insight":"RF plasma treatment of thermally reduced Pd/AC catalysts promotes redispersion and migration of Pd NPs to the surface, increases specific surface area, and enhances N-doping (especially pyridine nitrogen), which collectively lower the apparent activation energy from 34.93 to 29.67 kJ·mol-1."},{"paperId":"P159","section":"performance","insight":"The optimal plasma treatment conditions were identified as an input power of 250 W and a discharge time of 10 min."},{"paperId":"P160","section":"synthesis","insight":"The use of APTES provides NH2 groups that facilitate the dispersion of ultra-fine Ni@Pd core-shell nanoparticles on the magnetic Fe3O4 support."},{"paperId":"P160","section":"characterization","insight":"The use of APTES for amine functionalization of Fe3O4 nanoparticles is critical for the uniform dispersion and immobilization of the Ni@Pd core-shell nanoparticles."},{"paperId":"P160","section":"characterization","insight":"Lattice expansion in both Ni and Pd phases suggests significant electronic or structural interaction between the two metals and the magnetic support."},{"paperId":"P160","section":"performance","insight":"The catalyst Ni0.4@Pd0.6/NH2-Fe3O4 showed the highest activity among various tested compositions (Ni:Pd ratios of 0.6:0.4, 1:1, and 0.4:0.6) and single metal supported catalysts."},{"paperId":"P161","section":"characterization","insight":"Lattice strain increases linearly with the feed ratio of Au (0.0061 to 0.0103), leading to lattice expansion and an upshift of the Pd d-band center."},{"paperId":"P161","section":"characterization","insight":"The ligand effect involves electron transfer from Au to Pd, evidenced by a decrease in Pd 3d 3/2 binding energy and an increase in Au 4f 5/2 binding energy as Au ratio increases (up to 0.25)."},{"paperId":"P161","section":"characterization","insight":"Optimal catalytic activity for room-temperature formic acid decomposition is achieved at a Pd:Au atomic ratio of 0.69:0.31, balancing lattice strain and ligand effects to maximize surface PdO content."},{"paperId":"P161","section":"performance","insight":"The activity of PdAu/C catalysts towards room-temperature FAD is primarily related to the PdO:Pd ratio on the catalyst surface."},{"paperId":"P161","section":"performance","insight":"At low Au ratios (<=0.31), lattice strain dominates, promoting dissociative adsorption of O2 and increasing surface active species (PdO)."},{"paperId":"P161","section":"performance","insight":"At high Au ratios (>0.31), the ligand effect (electron transfer from Au to Pd) becomes dominant, decreasing the capability of Pd towards dissociative adsorption of O2."},{"paperId":"P162","section":"synthesis","insight":"The use of APTES modification is critical for coordinating metal ions and stabilizing ultrafine PdAu nanoparticles, preventing aggregation."},{"paperId":"P162","section":"synthesis","insight":"W18O49 support provides abundant oxygen vacancies which enhance the hydrogen spillover effect compared to WO3 or nonreducible supports like SiO2 and Carbon."},{"paperId":"P162","section":"characterization","insight":"NH2 modification is critical for stabilizing ultrafine PdAu NPs (~2.9 nm) and preventing aggregation (which increases size to ~4.5 nm in the absence of NH2)."},{"paperId":"P162","section":"characterization","insight":"The hydrogen spillover capacity is significantly higher on W18O49 than on WO3, as evidenced by H_upd-derived ECSA measurements and lower energy barriers for H migration in DFT calculations."},{"paperId":"P162","section":"characterization","insight":"Electron transfer occurs from the NH2-W18O49 support to the metal nanoparticles, creating electron-rich Pd sites that promote reactant activation."},{"paperId":"P162","section":"performance","insight":"The PdAu/NH2-W18O49 catalyst demonstrates superior activity for both FA dehydrogenation and CO2 hydrogenation compared to monometallic or non-modified counterparts."},{"paperId":"P162","section":"performance","insight":"Oxygen vacancies in the W18O49 support significantly lower the activation energy (Ea) for both reactions by enhancing the hydrogen spillover effect."},{"paperId":"P162","section":"performance","insight":"-NH2 modification is critical for stabilizing ultrafine PdAu NPs and promoting reactant/intermediate enrichment on the catalyst surface."},{"paperId":"P163","section":"synthesis","insight":"The active PdCuCr ternary nanoparticles are constructed in situ during the initial catalytic reaction, transforming from larger agglomerated particles formed by NaBH4 reduction into highly dispersed NPs."},{"paperId":"P163","section":"characterization","insight":"The active species in the PdCuCr/resin catalyst is constructed in situ during a ~2 minute induction period, transforming agglomerated particles (~8.1 nm) into highly dispersed NPs (~2.3 nm)."},{"paperId":"P163","section":"characterization","insight":"Charge transfer from Cr and Cu to Pd (based on ionization potentials) creates electron-rich Pd centers that facilitate the dehydrogenation pathway over the dehydration pathway."},{"paperId":"P163","section":"characterization","insight":"Cr doping provides a stabilization effect that prevents nanoparticle agglomeration during reaction, maintaining particle size at 2.3 nm."},{"paperId":"P163","section":"performance","insight":"The PdCuCr ternary catalyst exhibits significantly higher activity and durability than bimetallic PdCu, PdCr, or monometallic Pd catalysts."},{"paperId":"P163","section":"performance","insight":"Ternary nanoparticles are constructed in situ during an induction period of approximately 2 minutes."},{"paperId":"P163","section":"performance","insight":"The weakly basic @N(CH3)2 groups of the resin support act as a cocatalyst to accelerate O-H bond cleavage and stabilize formate intermediates."},{"paperId":"P163","section":"performance","insight":"Cr doping facilitates C-H bond dissociation (lower kH/kD = 1.37 compared to PdCu 1.59 and Pd 1.73) and prevents NP agglomeration."},{"paperId":"P164","section":"synthesis","insight":"Graphene oxide acts as a crosslinker for chitosan fibrils, enhancing the mechanical stability of the support beads."},{"paperId":"P164","section":"synthesis","insight":"Supercritical CO2 drying is used to maintain high surface area and macroporosity in the resulting aerogels."},{"paperId":"P164","section":"characterization","insight":"Graphene oxide (GO) acts as a crosslinker for chitosan fibrils, increasing the mechanical stability of the support and enhancing specific surface area (up to 430 m2/g) and pore volume."},{"paperId":"P164","section":"characterization","insight":"The presence of GO attenuates Pd NP agglomeration compared to pure CS supports by improving metal-support interaction."},{"paperId":"P164","section":"performance","insight":"Catalytic activity for H2 generation from ammonium formate in methanol increased with GO content of the support (3 to 12%)."},{"paperId":"P164","section":"performance","insight":"Pd/CS-GO2 showed higher activity in methanol than in water at both 25 and 60 °C."},{"paperId":"P164","section":"performance","insight":"Ammonia formed during decomposition may deactivate Pd catalysts by competing with formate for active sites."},{"paperId":"P165","section":"synthesis","insight":"The support synthesis method (in situ polymerization vs. commercial) significantly impacts the catalytic activity and Pd valence state despite similar Pd particle sizes (5-30 nm)."},{"paperId":"P165","section":"synthesis","insight":"Sodium formate serves as both a reducing agent during catalyst synthesis and an additive to enhance hydrogen production during the reaction."},{"paperId":"P165","section":"characterization","insight":"The catalytic activity for formic acid dehydrogenation is primarily influenced by the valence state of Pd and its interaction with the PPy support rather than the specific surface area or Pd particle size."},{"paperId":"P165","section":"characterization","insight":"Pd/PPy-S2 showed slight growth in Pd particles after reaction, leading to a decrease in catalytic activity."},{"paperId":"P165","section":"performance","insight":"The catalytic activity of dehydrogenation from formic acid can be enhanced by adding sodium formate."},{"paperId":"P165","section":"performance","insight":"Higher reaction temperature and the presence of sodium formate are beneficial to hydrogen production from formic acid using Pd/PPy catalysts."},{"paperId":"P166","section":"synthesis","insight":"Nitrogen doping of the carbon support was achieved by tuning the nitridation temperature (873, 973, and 1073 K) under ammonia flow."},{"paperId":"P166","section":"synthesis","insight":"The nitrogen-doped support interacts with Pd2+ precursors via electron-rich nitrogen atoms, leading to better dispersion and smaller palladium nanoparticle size compared to non-doped carbon supports."},{"paperId":"P166","section":"characterization","insight":"Nitrogen functionalities, particularly pyridinic nitrogen with high electron density, act as Lewis base sites that interact with Pd2+ precursors to prevent aggregation and increase the electron density of resulting Pd nanoparticles."},{"paperId":"P166","section":"characterization","insight":"The electronic enrichment of supported palladium is evidenced by a 0.4 eV decrease in XPS binding energy when using N-doped carbon compared to non-doped mesoporous carbon."},{"paperId":"P166","section":"characterization","insight":"Strong interactions between Pd and nitrogen dopants lead to lower reducibility, maintaining a portion of the metal in the Pd2+ state."},{"paperId":"P166","section":"performance","insight":"Nitrogen-doped mesoporous carbon supports enhance both the hydrogenation of bicarbonate and dehydrogenation of formate by improving Pd dispersion and increasing electron density on Pd nanoparticles."},{"paperId":"P166","section":"performance","insight":"The reaction is a reversible redox equilibrium between potassium formate and bicarbonate."},{"paperId":"P167","section":"synthesis","insight":"Support modification (acidification and B/N doping) significantly affects the specific surface area, Pd nanoparticle size, and electronic properties of the resulting catalysts."},{"paperId":"P167","section":"synthesis","insight":"B-doping resulted in the highest BET surface area (128.1 m2/g) and smallest Pd particle size (6.28 nm)."},{"paperId":"P167","section":"synthesis","insight":"Acidification provides chemical anchoring sites (-OH, -COOH), while subsequent B/N doping reduces these sites but modifies electronic properties to enhance catalytic activity."},{"paperId":"P167","section":"characterization","insight":"Acidification of CNTs increases specific surface area and introduces -OH and -COOH groups that act as anchoring sites for PdNPs, increasing loading but also particle size."},{"paperId":"P167","section":"characterization","insight":"Heteroatom doping (B or N) reduces the number of chemical anchoring sites compared to OCNTs, which leads to smaller PdNP sizes than in Pd/OCNTs."},{"paperId":"P167","section":"characterization","insight":"Boron doping induces electron transfer from B to Pd (upshifted BE), while Nitrogen doping provides an electron-donating effect to Pd (downshifted BE)."},{"paperId":"P167","section":"characterization","insight":"The specific surface area increases in the order: Pd/CNTs < Pd/OCNTs < Pd/NCNTs < Pd/BCNTs."},{"paperId":"P167","section":"performance","insight":"Pd/BCNTs exhibited superior performance due to high surface area, small particle size, and electronic effects from boron doping."},{"paperId":"P167","section":"performance","insight":"The addition of sodium formate (SF) enhances the reaction by increasing HCOO- concentration and promoting an 'H-down' adsorption configuration."},{"paperId":"P167","section":"performance","insight":"Increasing temperature and FA concentration positively impacts gas production rates."},{"paperId":"P168","section":"synthesis","insight":"The KCC-1 support is synthesized via a hydrothermal method using TEOS and CPB/urea as templates, followed by calcination at 550 °C."},{"paperId":"P168","section":"synthesis","insight":"Ionic liquid (IL) functionalization of the silica fibers prevents aggregation of PbS nanoparticles and increases loading capacity."},{"paperId":"P168","section":"characterization","insight":"The use of KCC-1 as a support preserves mesoporous texture (Type-IV isotherms) while providing high surface area for the immobilization of ionic liquid and PbS nanoparticles."},{"paperId":"P168","section":"characterization","insight":"ICP analysis determined a PbS loading of 1.8 wt% with low leaching (1.3%) after ten recycling cycles."},{"paperId":"P168","section":"performance","insight":"The catalytic activity of various nanoparticles followed the order: PbS > ZnS > HgS > Au > Cu > Pd > Ag > Pt > Mn > Ni > Zn > Co."},{"paperId":"P168","section":"performance","insight":"The addition of HCOONa as a base significantly improved the yield from 71% (KCC-1/IL/PbS alone) to 97%."},{"paperId":"P168","section":"performance","insight":"Reaction activity is sensitive to temperature, with 40 °C being identified as the optimal temperature."},{"paperId":"P169","section":"synthesis","insight":"The use of a higher synthesis temperature (773 K) for CTF supports was chosen to achieve higher surface areas."},{"paperId":"P169","section":"synthesis","insight":"Chemical exfoliation of g-C3N4 using concentrated sulfuric acid significantly increased its BET surface area from 12 m2/g to 85 m2/g."},{"paperId":"P169","section":"characterization","insight":"The nature of Pd active sites (single atoms vs nanoparticles) is strongly dependent on the CTF support chemistry: N-rich hatnCTF stabilizes single-atom Pd2+−C1N3, while O-rich acacCTF leads to a mixture of Pd2+−O4 and metallic nanoparticles."},{"paperId":"P169","section":"characterization","insight":"Single-atom Pd2+ sites exhibit higher tolerance to CO poisoning compared to metallic Pd nanoparticles."},{"paperId":"P169","section":"performance","insight":"Pd/hatnCTF showed the highest activity, exceeding Pd/acacCTF and Pd/g-C3N4 by factors of 5.6 and 8.6 at 453 K, respectively."},{"paperId":"P169","section":"performance","insight":"The high performance of Pd/hatnCTF is attributed to single-atom Pd2+-C1N3 sites."},{"paperId":"P169","section":"performance","insight":"Single-atom Pd2+ sites (both C1N3 and O4) exhibit higher tolerance to CO poisoning compared to metallic Pd nanoparticles."},{"paperId":"P170","section":"synthesis","insight":"The synthesis avoids ex situ reduction of the Pd precursor, relying on in situ reduction by H2 generated during the first reaction cycle (conditioning step)."},{"paperId":"P170","section":"synthesis","insight":"Nitrogen content in the support is controlled by varying the amount of dicyandiamide precursor used during composite support preparation."},{"paperId":"P170","section":"characterization","insight":"In situ reduction of Pd(OAc)2 to Pd0 occurs during the first catalytic cycle using H2 generated from formic acid decomposition, acting as a conditioning step."},{"paperId":"P170","section":"characterization","insight":"Nitrogen functional groups from C3N4 stabilize electron-deficient Pd2+ species, which are critical for formate ion adsorption and overall catalytic performance."},{"paperId":"P170","section":"characterization","insight":"The combination of activated carbon's high surface area and C3N4's nitrogen content prevents nanoparticle aggregation and improves leaching resistance."},{"paperId":"P170","section":"performance","insight":"Initial TOF values for Pd/AC_C3N4 catalysts increased with C3N4 content up to the Pd/AC_C3N4(19) sample, after which activity decayed."},{"paperId":"P170","section":"performance","insight":"A first reaction cycle is required as a conditioning step to partially reduce Pd2+ species to Pd0 using generated H2 to attain optimum activity."},{"paperId":"P170","section":"performance","insight":"The combination of AC (high surface area) and C3N4 (nitrogen functional groups/basicity) significantly enhances performance compared to either support alone."},{"paperId":"P171","section":"synthesis","insight":"The high acetone capacity of N-CNTs (6–7 cm3/g) compared to CNTs (3 cm3/g) is attributed to the bulk filling of inner channels, which may allow metals to be anchored both on the external surface and in the inner channels."},{"paperId":"P171","section":"characterization","insight":"Palladium preferentially interacts with pyridinic nitrogen (NPy) centers of N-CNTs over graphitic nitrogen (NQ) centers to form isolated ions."},{"paperId":"P171","section":"characterization","insight":"The high acetone capacity of bamboo-like N-CNTs facilitates uniform palladium distribution and allows metal anchoring in inner channels."},{"paperId":"P171","section":"characterization","insight":"Nitrogen doping stabilizes both isolated Pd ions and metallic nanoparticles, enhancing catalyst stability compared to N-free CNTs."},{"paperId":"P171","section":"performance","insight":"Isolated palladium ions (Pd2+-NPy) are more active than metallic palladium nanoparticles for formic acid decomposition."},{"paperId":"P171","section":"performance","insight":"Nitrogen-doped carbon nanotubes increase both activity and selectivity compared to nitrogen-free CNTs."},{"paperId":"P171","section":"performance","insight":"The presence of pyridinic nitrogen centers stabilizes isolated Pd ions, leading to higher TOF values at low metal loadings."},{"paperId":"P172","section":"synthesis","insight":"The addition of glucose during BN synthesis introduces C and O heteroatoms, creating defects that improve Pd dispersion."},{"paperId":"P172","section":"synthesis","insight":"Amine functionalization using APTES further reduces Pd nanoparticle size (to ~2.1 nm) and enhances metal-support interaction through electron transfer from Pd to the support."},{"paperId":"P172","section":"characterization","insight":"C and O co-doping of BN increases specific surface area and introduces defects that facilitate the nucleation of smaller Pd nanoparticles."},{"paperId":"P172","section":"characterization","insight":"Amine functionalization via APTES further reduces Pd particle size (~2.1 nm) and strengthens metal-support interactions through electron transfer from Pd to the support."},{"paperId":"P172","section":"characterization","insight":"The coexistence of Pd0 (C-H bond breaking) and Pd2+ (FA ion adsorption) is critical for FA dehydrogenation activity."},{"paperId":"P172","section":"characterization","insight":"-NH2 groups on the support act as proton scavengers, promoting O-H bond cleavage in formic acid."},{"paperId":"P172","section":"performance","insight":"C and O co-doping of BN support increases specific surface area and introduces defects that facilitate the dispersion of ultrafine Pd nanoparticles."},{"paperId":"P172","section":"performance","insight":"Amine functionalization (-NH2) further enhances activity by acting as proton scavengers to promote O-H bond cleavage in formic acid."},{"paperId":"P172","section":"performance","insight":"Strong metal-support interaction (SMSI), evidenced by XPS binding energy shifts, is critical for improving catalytic performance."},{"paperId":"P173","section":"synthesis","insight":"KCl acts as a confining template to prevent nitrogen loss, promote graphitization, and generate a mesoporous structure."},{"paperId":"P173","section":"synthesis","insight":"The support is derived from a core-shell ZIF-8@ZIF-67 precursor synthesized via seed epitaxial growth."},{"paperId":"P173","section":"characterization","insight":"The PNCC support (derived from ZIF-8@ZIF-67 with a KCl template) provides a high surface area (972.6 m2/g for pure PNCC) and uniform nanopores (0.7 to 2.0 nm), which facilitates the anchoring of ultrafine Pd nanoparticles."},{"paperId":"P173","section":"characterization","insight":"Nitrogen doping in the carbon cage consists of pyridine-N, pyrrole-N, and graphitic-N in a molar ratio of approximately 8.9:4.2:1."},{"paperId":"P173","section":"performance","insight":"The Pd/PNCC catalyst shows significantly higher activity than other supported Pd catalysts (Pd/KB, Pd/GO, Pd/super P, Pd/CNT) and a physical mixture of Pd and PNCC."},{"paperId":"P173","section":"performance","insight":"Activity is strongly temperature-dependent, with TOF increasing from 1587 h⁻¹ at 313 K to 6295 h⁻¹ at 343 K."},{"paperId":"P173","section":"performance","insight":"The optimal FA/SF molar ratio was found to be 1:2.5; excess sodium formate leads to a decay in activity due to active site poisoning."},{"paperId":"P174","section":"synthesis","insight":"High-temperature alkali etching of CNTs increases the proportion of carbonyl (C=O) groups and creates mesopores."},{"paperId":"P174","section":"synthesis","insight":"The presence of C=O groups on the support facilitates electron transfer from Pd to the carrier, creating electron-deficient Pd(delta+) species and Pd-PdO interfaces."},{"paperId":"P174","section":"characterization","insight":"High-temperature alkali etching increases the proportion of carbonyl C=O groups on CNTs, which facilitates electron transfer from Pd nanoparticles to the support."},{"paperId":"P174","section":"characterization","insight":"The interaction between Pd and carbonyl groups creates an electron-deficient Pdδ+ state and a Pd-PdO interface, both of which are identified as active sites for formic acid dehydrogenation."},{"paperId":"P174","section":"characterization","insight":"DFT calculations confirm that functional groups containing C=O bonds (aldehydes, carbonyls, quinones, anhydrides) promote stronger charge transfer from the Pd cluster to the carrier compared to those with C-O bonds."},{"paperId":"P174","section":"performance","insight":"The dehydrogenation rate of Pd/CNT-base-X catalysts follows a volcanic trend with increasing alkali concentration during carrier pretreatment, peaking at Pd/CNT-base-4."},{"paperId":"P174","section":"performance","insight":"Carbonyl groups on the CNT surface are more effective than carboxyl groups in modulating the electronic structure of Pd nanoparticles to create active Pdδ+ sites."},{"paperId":"P175","section":"synthesis","insight":"The use of MgO as a template allows for the creation of a laminated hexagonal morphology with high surface area (1485 m2/g for N,P-C)."},{"paperId":"P175","section":"synthesis","insight":"Co-doping with both N and P creates synergistic electronic effects that enhance Pd nanoparticle dispersion and catalytic activity compared to single-doped supports."},{"paperId":"P175","section":"characterization","insight":"DFT calculations indicate that N,P-co-doping shifts the Fermi level into the valence band and creates a hybridized N and P band crossing the Fermi level, increasing electron transport ability."},{"paperId":"P175","section":"characterization","insight":"CO pulse adsorption results suggest that higher metal dispersion values in Pd/NC, Pd/PC, and Pd/AC compared to Pd/N,P-C are due to stronger electron transfer from N,P-doped carbon to the Pd 4d band, creating a closed shell with lower affinity for CO."},{"paperId":"P175","section":"performance","insight":"Co-doping of carbon with N and P creates a synergistic effect that enhances the catalytic activity of Pd nanoparticles for both formate dehydrogenation and bicarbonate hydrogenation compared to single-doped or undoped supports."},{"paperId":"P175","section":"performance","insight":"Bicarbonate hydrogenation is exothermic, as evidenced by the decrease in formate yield when temperature was increased from 80 °C to 100 °C."},{"paperId":"P176","section":"synthesis","insight":"The introduction of amino groups via APTMS allows for the preparation of smaller and more well-dispersed Pd nanoparticles (~2.5 nm) compared to non-functionalized NHPC (~6.7 nm)."},{"paperId":"P176","section":"synthesis","insight":"Strong metal-support interaction (SMSI) between Pd and amino groups is identified as a key factor for catalytic activity, rather than just particle size or N-doping."},{"paperId":"P176","section":"characterization","insight":"The shift in Pd 3d binding energy for Pd/NHPC-NH2 is attributed to strong metal-support interaction (SMSI) rather than particle size effects."},{"paperId":"P176","section":"characterization","insight":"Amino groups on the support act as proton scavengers, providing a basic environment that promotes O-H bond dissociation of formic acid."},{"paperId":"P176","section":"performance","insight":"The apparent activation energy for FA dehydrogenation over Pd/NHPC-NH2 was measured to be 46.3 kJ mol^-1."},{"paperId":"P177","section":"synthesis","insight":"The HNDC support is derived from a Zr-based MOF (DUT-67-PZDC) using 3,5-pyrazoledicarboxylic acid monohydrate as the ligand."},{"paperId":"P177","section":"synthesis","insight":"HF etching removes ZrO2 from the carbonized MOF to create a hierarchically porous N-doped carbon structure."},{"paperId":"P177","section":"characterization","insight":"The 20 wt% Pd loading is optimal for achieving the smallest particle size (3.0 nm) and highest dispersion compared to 10 wt% (3.9 nm), 15 wt% (3.2 nm), and 25 wt% (3.6 nm)."},{"paperId":"P177","section":"characterization","insight":"HNDC support possesses a hierarchically porous structure with an average pore size of 2.28 nm, which is maintained after Pd loading."},{"paperId":"P177","section":"characterization","insight":"Recovered Pd/HNDC showed a slight increase in particle size to 3.3 nm and partial loss of Pd content."},{"paperId":"P177","section":"performance","insight":"The addition of sodium formate (SF) significantly improves the hydrogen production rate by increasing HCOO- concentration."},{"paperId":"P177","section":"performance","insight":"An optimal Pd loading of 20 wt% is favorable for high dispersion and ultrasmall particle size (3.0 nm), leading to regulated metal-support interaction (MSI)."},{"paperId":"P177","section":"performance","insight":"The reaction follows zero-order kinetics with respect to FA concentration and first-order kinetics with respect to catalyst concentration."},{"paperId":"P177","section":"performance","insight":"C-H bond dissociation of the formic acid molecule is identified as the rate-determining step (RDS)."},{"paperId":"P178","section":"synthesis","insight":"The triazine groups on MCTP-1 provide selective adsorption sites for the anionic palladium precursor, resulting in monodisperse and very small Pd nanoparticles (2.4 ± 0.5 nm)."},{"paperId":"P178","section":"synthesis","insight":"Most Pd NPs are located on the external surface due to the small pore size of the MCTP-1 support."},{"paperId":"P178","section":"characterization","insight":"Pd loading was consistent across all catalysts (1.7–2.0 wt%)."},{"paperId":"P178","section":"characterization","insight":"Catalytic activity for formic acid decomposition is strongly dependent on both Pd nanoparticle size (smaller is better) and the pH of the reaction medium (neutral is optimal)."},{"paperId":"P178","section":"characterization","insight":"Basic functional groups (amines, triazines) on supports help reduce Pd particle size by providing selective adsorption sites for anionic precursors."},{"paperId":"P178","section":"performance","insight":"Catalytic activity for formic acid decomposition is significantly affected by both Pd nanoparticle size (smaller is better) and the pH of the reaction medium (neutral is optimal)."},{"paperId":"P178","section":"performance","insight":"Acidic supports lead to larger Pd NPs and lower solution pH, resulting in poorer performance."},{"paperId":"P178","section":"performance","insight":"Basic media are unfavorable due to competitive adsorption between formate and hydroxyl ions."},{"paperId":"P179","section":"synthesis","insight":"Acidification of CNTs introduces hydroxyl and carboxyl groups that act as anchoring sites for PdNPs, increasing loading compared to unmodified CNTs."},{"paperId":"P179","section":"synthesis","insight":"Heteroatom doping (B or N) via hydrothermal treatment reduces the number of chemical anchoring sites but modifies electronic properties and increases specific surface area, particularly for B-doping."},{"paperId":"P179","section":"characterization","insight":"Acidification of CNTs increases specific surface area and introduces -OH and -COOH groups that act as anchoring sites for PdNPs."},{"paperId":"P179","section":"characterization","insight":"Heteroatom doping (B, N) modifies the electronic properties of Pd; B-doping leads to electron transfer from B to Pd (upshift in BE), while N-doping provides an electron-donating effect (downshift in BE)."},{"paperId":"P179","section":"characterization","insight":"The presence of Graphitic-N improves conductivity, and Pyridinic-N enhances H atom capture."},{"paperId":"P179","section":"characterization","insight":"B-doped CNTs provide the highest surface area and smallest Pd particle size among the tested supports."},{"paperId":"P179","section":"performance","insight":"Pd/BCNTs exhibited the best performance among tested catalysts due to high surface area, small particle size, and electronic effects from B-doping."},{"paperId":"P179","section":"performance","insight":"The addition of sodium formate (SF) enhances FAD by increasing HCOO- concentration, promoting an 'H-down' adsorption configuration."},{"paperId":"P179","section":"performance","insight":"Regeneration via filtration, rinsing, vacuum drying, and reduction is necessary to maintain activity and counteract CO poisoning/fouling."},{"paperId":"P180","section":"characterization","insight":"The incorporation of Pd ions into the ceria lattice is evidenced by a decrease in the lattice constant of CeO2, suggesting the formation of solid solutions."},{"paperId":"P180","section":"characterization","insight":"SMSI between Pd and CeO2 leads to a shift in Pd 3d binding energies toward lower values for the 10 wt% catalyst."},{"paperId":"P180","section":"characterization","insight":"The presence of Pd promotes the reduction of Ce4+ to Ce3+ and increases the concentration of active adsorbed oxygen species on the surface."},{"paperId":"P180","section":"performance","insight":"Catalytic efficiency increases with the increase of Pd loading on CeO2 nanospheres."},{"paperId":"P180","section":"performance","insight":"The 10 wt% Pd*CeO2 catalyst exhibited the highest activity among all tested samples."},{"paperId":"P181","section":"synthesis","insight":"Magnetron sputtering allows one-step preparation of Pd-C thin films with controlled nanostructure and composition."},{"paperId":"P181","section":"synthesis","insight":"Increasing carbon content leads to decreased column width, higher surface roughness, and improved catalyst dispersion."},{"paperId":"P181","section":"synthesis","insight":"The formation of a PdCx phase was identified via XRD and correlated with increased activity but decreased CO2 selectivity."},{"paperId":"P181","section":"characterization","insight":"Increasing carbon content during magnetron sputtering decreases column width and increases surface roughness and catalyst dispersion."},{"paperId":"P181","section":"characterization","insight":"XRD shifts indicate the presence of interstitial carbon forming PdCx phases, which are linked to increased activity but decreased selectivity for dehydrogenation."},{"paperId":"P181","section":"characterization","insight":"Deactivation of the 65C catalyst upon cycling is attributed to Pd sintering/aggregation (crystal size increasing from 10.2 nm to 58 nm) caused by Pd segregation and/or loss of carbon at high temperatures."},{"paperId":"P181","section":"characterization","insight":"Extended pre-reduction time (3 h vs 1.5 h) leads to decreased activity due to synergistic effects of high temperature, carbon loss, and Pd segregation causing aggregation."},{"paperId":"P181","section":"performance","insight":"Increasing carbon content in Pd-C thin films leads to decreased column width and increased surface roughness/dispersion, which correlates with higher catalytic activity."},{"paperId":"P181","section":"performance","insight":"The formation of a PdCx phase is associated with increased activity but reduced selectivity toward CO2 (dehydrogenation) compared to low-carbon samples."},{"paperId":"P181","section":"performance","insight":"Pd-C thin films are unstable at high temperatures due to Pd sintering and carbon loss."},{"paperId":"P182","section":"synthesis","insight":"The activity for FA decomposition is highly dependent on the coordinating ligands of the Pd(II) precursor; nitrate and acetate salts were significantly more active than chloride-based complexes."},{"paperId":"P182","section":"synthesis","insight":"Pd(II) species are reduced in situ to metallic Pd(0) particles by the mixture of formic acid and sodium formate during the reaction."},{"paperId":"P182","section":"characterization","insight":"The reduction of Pd2+ to Pd0 is monitored in situ via UV-Vis spectroscopy by observing the decrease in absorbance at 345 nm."},{"paperId":"P182","section":"characterization","insight":"DFT calculations indicate that C-H bond activation of formate on a Pd2+ center is a critical step for both FA decomposition and subsequent Pd2+ reduction."},{"paperId":"P182","section":"characterization","insight":"Strongly coordinating ligands like 2,2'-bipyridine hinder ligand exchange with formate, thereby retarding the reduction process and catalytic activity."},{"paperId":"P182","section":"performance","insight":"The rates of H2-release are highly dependent on the kind of Pd2+ compound, with nitrate and acetate ligands being more effective than chloride ligands."},{"paperId":"P182","section":"performance","insight":"Pd2+ complexes were in situ reduced to metallic Pd0 species during the reaction in the presence of formic acid and sodium formate."},{"paperId":"P182","section":"performance","insight":"Strongly coordinating ligands like 2,2'-bipyridine hinder ligand exchange between the metal center and formate, thereby suppressing activity."},{"paperId":"P183","section":"synthesis","insight":"Hydrothermal synthesis was found to be the most effective preparation method for MOF frameworks compared to co-precipitation and wet impregnation."},{"paperId":"P183","section":"synthesis","insight":"The pH of the impregnation environment significantly affects Pd loading; a weakly acidic environment (pH 3.0) was noted as optimal for high TON and TOF in some systems, although the specific synthesis described used Na2CO3 to reach pH 7.6."},{"paperId":"P183","section":"characterization","insight":"The dual-support system (UIO-66 and NH2-SEP) provides superior stability compared to single supports by combining the protective 'sacrificial' effect of the MOF with the electronic modification provided by amino-functionalized sepiolite."},{"paperId":"P183","section":"characterization","insight":"XPS analysis indicates that the dual support effectively stabilizes Pd in the zero-valence state, reducing its susceptibility to air oxidation."},{"paperId":"P183","section":"performance","insight":"The dual-support Pd@UIO-66/NH2-SEP exhibits significantly higher reusability (over 8 cycles) compared to single-supported catalysts."},{"paperId":"P183","section":"performance","insight":"A sacrificial effect of the UIO-66 framework protects active sites on NH2-SEP and prevents Pd nanoparticle aggregation."},{"paperId":"P183","section":"performance","insight":"Amino groups on SEP are critical for initial activity by facilitating O-H bond cleavage, but excessive amino grafting can cause steric hindrance."},{"paperId":"P184","section":"synthesis","insight":"The double-solvent strategy (H2O/hexane) utilizes capillary forces to drive hydrophilic metal precursors into the MOF cavities."},{"paperId":"P184","section":"synthesis","insight":"Increased amino group concentration in UiO-66-(NH2)2 compared to monoamine UiO-66-NH2 enhances hydrophilicity and coordination ability, leading to smaller nanoparticles (< 1.1 nm)."},{"paperId":"P184","section":"characterization","insight":"The double-solvent strategy (H2O/hexane) effectively confines metal precursors within MOF cavities via capillary forces."},{"paperId":"P184","section":"characterization","insight":"Diamine-containing Zr-MOFs provide superior stabilization and dispersion of PdAu NPs compared to monoamine-containing versions due to enhanced coordination with metal species."},{"paperId":"P184","section":"performance","insight":"Increasing the concentration of amino groups in the UiO-66 framework (from monoamine to diamine) significantly enhances both the catalytic activity and stability for formic acid dehydrogenation by reducing nanoparticle size and preventing aggregation."},{"paperId":"P185","section":"synthesis","insight":"The type of organic amine used for support modification significantly influences the dispersion and particle size of PdAu nanoparticles."},{"paperId":"P185","section":"synthesis","insight":"DMAP-modified supports lead to larger Au particles due to easier reduction of Au3+-DMAP complexes compared to other amines."},{"paperId":"P185","section":"synthesis","insight":"ZrSBA-15 provides a higher surface area and shorter channels than conventional SBA-15, facilitating better anchoring of amino groups and metal NPs."},{"paperId":"P185","section":"characterization","insight":"Organic amine modification of ZrSBA-15 significantly improves the dispersity and reduces the particle size of PdAu nanoparticles."},{"paperId":"P185","section":"characterization","insight":"The type of organic amine influences the stability and redox properties of noble metal-amine complexes, which determines whether alloy NPs or separated larger Au particles form."},{"paperId":"P185","section":"characterization","insight":"Electron transfer occurs from Au to Pd in the bimetallic alloy system due to differences in work functions."},{"paperId":"P185","section":"characterization","insight":"Alloy formation is critical for activity; a physical mixture of Pd and Au nanoparticles exhibits significantly lower catalytic performance than the PdAu alloy."},{"paperId":"P185","section":"performance","insight":"The Pd:Au molar ratio of 60:40 on ZrSBA-15-AP provides the highest catalytic activity for FA dehydrogenation."},{"paperId":"P185","section":"performance","insight":"PdAu alloy NPs are significantly more active than a physical mixture of Pd and Au NPs."},{"paperId":"P185","section":"performance","insight":"Amine modification of the support is essential for activity in additive-free aqueous FA solutions."},{"paperId":"P185","section":"performance","insight":"The catalyst exhibits excellent low-temperature activity, remaining functional at 275 K."},{"paperId":"P186","section":"synthesis","insight":"SD-FSP allows for higher PdO:Pd0 ratios (up to 79% PdO) compared to SS-FSP because the O2 is not consumed by TiO2 formation during the metal deposition step."},{"paperId":"P186","section":"synthesis","insight":"Oxygen-lean FSP using N2 sheath gas significantly reduces the PdO content (PdO/Pd0 ratio = 0.35)."},{"paperId":"P186","section":"synthesis","insight":"The SD-FSP method decouples support synthesis from metal particle formation, enabling higher palladium oxide loadings not feasible by liquid methods."},{"paperId":"P186","section":"characterization","insight":"The PdO:Pd0 ratio is a critical factor for FA dehydrogenation; maximizing this ratio significantly lowers the activation energy barrier."},{"paperId":"P186","section":"characterization","insight":"Sequential-Deposition FSP (SD-FSP) allows for much higher PdO content compared to Single-Step FSP by decoupling TiO2 formation from Pd deposition, reducing O2 competition."},{"paperId":"P186","section":"characterization","insight":"Catalyst deactivation is primarily driven by the reduction of surface PdO species to metallic Pd0 by produced H2 gas."},{"paperId":"P186","section":"characterization","insight":"Strong metal-support interactions (SMSIs) are indicated by Raman peak shifts and distorted TiO2 phases in high-Pd SD-FSP materials."},{"paperId":"P186","section":"performance","insight":"The presence of a high PdO:Pd0 ratio on TiO2 support significantly enhances H2 production rates and lowers the activation energy barrier Ea."},{"paperId":"P186","section":"performance","insight":"Sequential-deposition FSP (SD-FSP) allows for higher PdO content compared to single-step FSP, leading to superior catalytic performance."},{"paperId":"P186","section":"performance","insight":"The primary deactivation mechanism is the reduction of surficial PdO species to metallic Pd0 by the produced H2 gas."},{"paperId":"P186","section":"performance","insight":"PdO exhibits a higher affinity for hydride than Pd0 and is less prone to CO poisoning, facilitating the dehydrogenation pathway."},{"paperId":"P187","section":"synthesis","insight":"The crystal phase of ZrO2 (monoclinic vs tetragonal) was controlled by the introduction of ammonia and hydrothermal conditions, which significantly influenced Pd-support interaction and catalytic activity."},{"paperId":"P187","section":"characterization","insight":"The crystal phase of ZrO2 support modulates the electronic state of Pd: m-ZrO2 induces electron-rich Pd, while t-ZrO2 induces electron-deficient Pd."},{"paperId":"P187","section":"characterization","insight":"t-ZrO2 increases the metal-support interaction (MSI) and inhibits Pd aggregation compared to m-ZrO2."},{"paperId":"P187","section":"characterization","insight":"A synergistic effect exists where m-ZrO2 facets facilitate FA dissociation and HCOO- decomposition, while t-ZrO2 facets lower the energy barrier for hydrogen recombination."},{"paperId":"P187","section":"performance","insight":"The coexistence of m-ZrO2 and t-ZrO2 phases in Pd/ZrO2-F creates a synergistic effect that enhances catalytic activity compared to catalysts dominated by a single phase."},{"paperId":"P187","section":"performance","insight":"t-ZrO2 promotes strong metal-support interaction (MSI) and facilitates hydrogen recombination, while m-ZrO2 is more conducive to the dissociation of formic acid."},{"paperId":"P188","section":"synthesis","insight":"Phosphate-mediation (using H3PO4, NH4H2PO4, or (NH4)2HPO4) enhances the dispersion and absorption of both Au and Pd ions on N-doped carbon compared to N-doping alone."},{"paperId":"P188","section":"synthesis","insight":"The phosphate species act as a mediator for metal ion dispersion and are removed during the alkaline reduction process."},{"paperId":"P188","section":"synthesis","insight":"ZIF-8 derived N-doped porous carbon provides high surface area and hierarchical porosity, which is essential for catalytic activity."},{"paperId":"P188","section":"characterization","insight":"Phosphate anchoring on N-doped carbon (PN-C) enhances the absorption and dispersion of both Au and Pd ions."},{"paperId":"P188","section":"characterization","insight":"The phosphate species (-PO4 and -PO3) act as a mediation layer that is removed during the alkaline reduction process to leave ultrafine bimetallic NPs in close contact with the carbon support."},{"paperId":"P188","section":"characterization","insight":"A synergetic effect between N-doping and the phosphate-mediation approach results in the smallest nanoparticle size and highest catalytic performance."},{"paperId":"P188","section":"performance","insight":"The phosphate-mediation approach combined with N-doping of carbon supports results in the smallest AuPd NPs and the highest catalytic activity for FA dehydrogenation at low temperatures."},{"paperId":"P188","section":"performance","insight":"Sodium formate (SF) acts as a promoter, significantly increasing the TOF compared to reactions without SF."},{"paperId":"P189","section":"synthesis","insight":"The use of PAN beads with rough internal surfaces and abundant pores helps immobilize Pd-based nanoparticles more effectively than smooth PAN fibers."},{"paperId":"P189","section":"synthesis","insight":"Cyano (eCN) groups on the PAN surface act as anchoring sites to stabilize NPs against aggregation or leaching."},{"paperId":"P189","section":"characterization","insight":"The use of PAN beads provides a three-dimensional network of fibrils with an interconnected porous structure and rough internal surface, enhancing the accessibility of eCN groups for immobilizing nanoparticles."},{"paperId":"P189","section":"characterization","insight":"Doping Pd NPs with transition metals (Co or Fe) significantly reduces the nanoparticle size compared to monometallic Pd/PAN."},{"paperId":"P189","section":"characterization","insight":"The cyano (eCN) groups on PAN beads act as anchoring sites that stabilize metal nanoparticles against leaching and aggregation, while also potentially acting as proton scavengers during formic acid dehydrogenation."},{"paperId":"P189","section":"performance","insight":"Doping with Co or Fe enhances the catalytic activity for FA dehydrogenation compared to monometallic Pd/PAN."},{"paperId":"P189","section":"performance","insight":"The eCN groups of PAN beads serve as proton scavengers, eliminating the need for basic additives."},{"paperId":"P189","section":"performance","insight":"In-situ generated active hydrogen species from FA decomposition are responsible for dye reduction rather than H2 molecules."},{"paperId":"P190","section":"synthesis","insight":"Alkali/air coactivation using NaHCO3 is a milder and more economical method for expanding pores in N-doped carbon compared to KOH activation."},{"paperId":"P190","section":"synthesis","insight":"The optimized support (M1/20NB) was produced with an alkali/char ratio of 1:1, air percentage of 30%, and HTT of 700 °C, resulting in a BET surface area of 956 m2·g-1."},{"paperId":"P190","section":"characterization","insight":"N-doping of the carbon support (especially pyridinic N) anchors Pd nanoparticles, preventing agglomeration and resulting in ultrafine particles."},{"paperId":"P190","section":"characterization","insight":"The hierarchical pore structure (1-3 nm) of the NPC support helps confine Pd particle size and provides fast mass transfer channels for reactants and products."},{"paperId":"P190","section":"characterization","insight":"A higher ratio of PdII to Pd0 is associated with increased Pd-PdO interfaces, which is beneficial for formic acid dehydrogenation activity."},{"paperId":"P190","section":"performance","insight":"N-doping of biomass-derived carbon enhances the activity of Pd catalysts for FA dehydrogenation by modulating electronic properties (via pyridinic N) and improving Pd dispersion."},{"paperId":"P190","section":"performance","insight":"Pore expansion, particularly increasing mesopore surface area through alkali/air coactivation, is crucial to prevent mass transfer limitations and maximize catalyst potential."},{"paperId":"P190","section":"performance","insight":"The addition of sodium formate significantly accelerates the reaction rate, suggesting a formate anion dehydrogenation pathway."},{"paperId":"P191","section":"synthesis","insight":"Pre-nucleation via pH adjustment (alkalization) to remove coordinated Cl- allows for ultra-small particle size control without surfactants."},{"paperId":"P191","section":"synthesis","insight":"In situ reduction using formate/formic acid is used specifically to tune the surface electronic structure, targeting a Pd(0)-Pd(II) ratio of approximately 1:1."},{"paperId":"P191","section":"characterization","insight":"A 1:1 ratio of Pd(0) to Pd(II) is identified as the optimum valence composition for high-performance formic acid decomposition."},{"paperId":"P191","section":"characterization","insight":"The pre-nucleation strategy effectively decouples particle size control from electronic structure adjustment, enabling the synthesis of ultra-fine nanoparticles without surfactants."},{"paperId":"P191","section":"characterization","insight":"Pd(0)-Pd(0) sites are considered the primary sites for the undesirable dehydration pathway (CO production), whereas Pd(0)-Pd(II) interface sites favor selective dehydrogenation."},{"paperId":"P191","section":"performance","insight":"The coupling of pre-nucleation and in situ reduction allows for simultaneous control of ultra-small particle size (1.86 nm) and an optimized Pd(0)-Pd(II) surface electronic structure (~1:1 ratio)."},{"paperId":"P191","section":"performance","insight":"A high density of Pd(0)-Pd(II) interface sites is critical for reducing activation energy and increasing mass-specific activity while suppressing the dehydration pathway that produces CO."},{"paperId":"P192","section":"synthesis","insight":"Wet impregnation was performed on GO rather than rGO to leverage better hydrophilicity and functional group anchoring points for more homogeneous metal dispersion."},{"paperId":"P192","section":"characterization","insight":"The presence of Au favors the formation of smaller nanoparticles and prevents agglomeration compared to monometallic Pd."},{"paperId":"P192","section":"characterization","insight":"TGA results show that bimetallic PdAu NPs induce a greater decrease in carbon oxidation temperature (447 °C) than Pd NPs (517 °C), correlating with higher catalytic activity."},{"paperId":"P192","section":"performance","insight":"The addition of sodium formate (SF) as a promoter significantly accelerates the kinetics of FA decomposition for both catalysts."},{"paperId":"P192","section":"performance","insight":"PdAu/rGO exhibits lower activation energy (13.4 kJ mol-1) compared to Pd/rGO (28.5 kJ mol-1 in water, 24.4 kJ mol-1 with SF), indicating superior catalytic activity."},{"paperId":"P193","section":"synthesis","insight":"NaBH4 serves as both the reducing agent and the boron source for doping into the PdAg alloy."},{"paperId":"P193","section":"synthesis","insight":"The use of NaBH4 instead of hydrazine hydrate (N2H4·H2O) results in higher catalytic activity despite larger particle sizes, attributed to B-doping."},{"paperId":"P193","section":"characterization","insight":"Boron doping induces lattice expansion in PdAg alloys, as evidenced by XRD shifts and HRTEM spacing measurements."},{"paperId":"P193","section":"characterization","insight":"Synergistic electron transfer from Ag, B, and the rGO support to Pd creates electron-rich active sites that enhance catalytic activity for formic acid dehydrogenation."},{"paperId":"P193","section":"characterization","insight":"Surface boron atoms on these alloy nanoparticles are prone to oxidation, forming BxOy species."},{"paperId":"P193","section":"characterization","insight":"rGO provides superior adhesion sites and electronic modification compared to carbon black or CNT supports."},{"paperId":"P193","section":"performance","insight":"The catalytic activity of PdAgB/rGO catalysts is positively proportional to the content of Pd."},{"paperId":"P193","section":"performance","insight":"Boron-doping significantly promotes catalytic performance regardless of particle size compared to non-boron doped counterparts."},{"paperId":"P193","section":"performance","insight":"Support material (rGO) provides superior performance over carbon black and CNT by providing more uniform adhesion sites and modifying the electronic structure of NPs."},{"paperId":"P193","section":"performance","insight":"The optimal molar ratio of FA to SF for Pd0.90Ag0.10B/rGO is 10:7."},{"paperId":"P194","section":"synthesis","insight":"The cation dipole adjustment method allows tuning of Pd nanoparticle size (3.0-6.5 nm) without altering the surface valence states (Pd(0) and Pd(II) ratios remained constant at approximately 67% and 33%)."},{"paperId":"P194","section":"synthesis","insight":"Smaller cation radius and larger charge density in pH-adjustment agents lead to smaller particle sizes due to stronger affinity between cations and nanoparticles."},{"paperId":"P194","section":"characterization","insight":"Cation dipole adjustment allows for tuning Pd nanoparticle size (3.0-6.5 nm) without altering the surface valence state ratio of Pd(0)/Pd(II)."},{"paperId":"P194","section":"characterization","insight":"Intrinsic activity for formic acid dehydrogenation is primarily driven by Pd surface valence states and is not sensitive to particle size or facet orientation within the 3.0-6.5 nm range."},{"paperId":"P194","section":"characterization","insight":"Formic acid dehydration (the deactivation pathway) is size-dependent, with larger particles exhibiting faster dehydration due to a higher abundance of adjacent Pd(0) sites on face facets."},{"paperId":"P194","section":"characterization","insight":"Small nanoparticles are more stable against deactivation because they possess a higher proportion of corner and edge sites."},{"paperId":"P194","section":"performance","insight":"The intrinsic activity of FAD is not sensitive to Pd nanoparticle size (3.0-6.5 nm) or facet orientation when surface valence states are constant."},{"paperId":"P194","section":"performance","insight":"Site intrinsic activity for H2 production is primarily affected by Pd surface valence states."},{"paperId":"P194","section":"performance","insight":"Formic acid dehydration is sensitive to particle size, where larger particles lead to faster deactivation."},{"paperId":"P195","section":"synthesis","insight":"Amine groups on SBA-15 act as strong adsorption sites for Pd2+ and Zr4+ ions, preventing aggregation and resulting in ultrasmall nanoparticles (1.5 nm)."},{"paperId":"P195","section":"synthesis","insight":"The one-step coreduction strategy at ambient conditions is used to fabricate the metal-oxide/support system."},{"paperId":"P195","section":"characterization","insight":"Amine groups (-NH2) on SBA-15 serve as strong adsorption sites for Pd2+ and Zr4+ ions, preventing nanoparticle aggregation during synthesis."},{"paperId":"P195","section":"characterization","insight":"ZrO2 acts as an electronic promoter that donates electrons to metallic Pd, creating an electron-rich surface that facilitates the cleavage of the C-H bond in formic acid."},{"paperId":"P195","section":"characterization","insight":"The combination of basic sites from both ZrO2 and amine groups enhances the deprotonation process of FA molecules."},{"paperId":"P195","section":"performance","insight":"The addition of ZrO2 as a promoter to Pd/SBA-15-NH2 significantly increases TOF and hydrogen selectivity while lowering the activation energy."},{"paperId":"P195","section":"performance","insight":"Amine groups on SBA-15 are critical for stabilizing ultrasmall nanoparticles (1.5 nm) and providing Brønsted basic sites that accelerate FA deprotonation."},{"paperId":"P196","section":"synthesis","insight":"Amino-groups on KIT-6-NH2 act as anchoring sites that prevent nanoparticle aggregation, resulting in smaller PdIr alloy nanoparticles (1.8 nm) compared to those on bare KIT-6 (7.4 nm)."},{"paperId":"P196","section":"synthesis","insight":"APTES was identified as an effective organic amine for functionalizing the support via the reflux method."},{"paperId":"P196","section":"characterization","insight":"Amino-modification of KIT-6 provides anchoring sites that effectively prevent metal nanoparticle aggregation, reducing size from 7.4 nm (bare) to 1.8 nm (modified)."},{"paperId":"P196","section":"characterization","insight":"The electronic structure of the PdIr alloy is modified by both the bimetallic interaction and the electron donation from the support's amino groups."},{"paperId":"P196","section":"characterization","insight":"3D cubic structure of KIT-6 provides better mass transfer compared to 2D hexagonal SBA-15."},{"paperId":"P196","section":"performance","insight":"The addition of sodium formate (SF) significantly accelerates the hydrogen production rate, with an optimal FA/SF ratio of 1/2."},{"paperId":"P196","section":"performance","insight":"Amino-groups on KIT-6 serve as both anchoring sites for ultra-fine NPs and Brønsted basic sites to promote O-H bond dissociation."},{"paperId":"P197","section":"synthesis","insight":"The use of N-CNTs as a support afforded ultra-fine Ru particles (<2 nm) and allowed a portion of Ru to be stabilized in an atomic state."},{"paperId":"P197","section":"synthesis","insight":"Nitrogen doping (from 0 to 4.8 at.%) influenced the particle size, with higher nitrogen content leading to smaller nanoparticles (1.5 nm for 4.8%N-CNTs vs 2.3 nm for N-free CNTs)."},{"paperId":"P197","section":"characterization","insight":"N-doping of carbon nanotubes leads to a bamboo-like structure and stabilizes ultra-fine Ru nanoparticles (<2 nm) and single atoms."},{"paperId":"P197","section":"characterization","insight":"Increasing nitrogen content in N-CNTs monotonically decreases the mean Ru particle size from 2.3 nm (N-free) to 1.5 nm (4.8% N)."},{"paperId":"P197","section":"characterization","insight":"A discrepancy between TEM dispersion and CO chemisorption dispersion in N-doped catalysts is attributed to positive charging of Ru species, which weakens the metal-CO bond."},{"paperId":"P197","section":"characterization","insight":"In CWAO of phenol, catalyst deactivation occurs due to partial oxidation of bamboo-like N-CNTs and formation of carbonaceous deposits that block Ru nanoparticles, while particle size remains constant."},{"paperId":"P197","section":"performance","insight":"Ru catalysts on N-doped carbon nanotubes (N-CNTs) exhibit higher activity and selectivity in formic acid decomposition (FAD) compared to Ru/CNTs, attributed to the stabilization of single atoms."},{"paperId":"P197","section":"performance","insight":"In CWAO of phenol, all 3% Ru catalysts showed similar high conversion (~100%), suggesting that atomic Ru species do not significantly accelerate this reaction."},{"paperId":"P197","section":"performance","insight":"Bamboo-like N-CNTs are stable in reducing environments (FAD) but unstable in oxidizing environments (CWAO), where they undergo partial oxidative destruction and surface blocking by carbonaceous deposits."},{"paperId":"P198","section":"synthesis","insight":"The addition of terephthalaldehyde to urea during pyrolysis creates a Schiff base conjugated structure (CNSC) that enhances metal dispersion and reduces nanoparticle size compared to pristine g-C3N4."},{"paperId":"P198","section":"synthesis","insight":"pH adjustment to 9.8 is used prior to NaBH4 reduction to stabilize precursors on the support."},{"paperId":"P198","section":"characterization","insight":"The introduction of Schiff base groups on the carbon nitride support (CNSC) increases the BET specific surface area from 18 m2/g to 108 m2/g."},{"paperId":"P198","section":"characterization","insight":"Electron transfer occurs in a dual manner: from non-noble metals (Co, Ni) to Pd and from the CNSC support to the trimetallic nanoparticles."},{"paperId":"P198","section":"characterization","insight":"Trimetallic alloying of Pd, Co, and Ni is more effective for FA dehydrogenation than monometallic or bimetallic combinations."},{"paperId":"P198","section":"performance","insight":"The trimetallic PdCoNi alloy supported on Schiff base conjugated carbon nitride (CNSC) exhibits superior activity compared to monometallic and bimetallic counterparts."},{"paperId":"P198","section":"performance","insight":"Grafting Schiff base onto the support enhances metal dispersion, reduces nanoparticle size (to 1.70 nm), and increases electron density of Pd active sites through synergistic effects with Co and Ni."},{"paperId":"P198","section":"performance","insight":"The Schiff base groups act as proton scavengers to facilitate O-H bond dissociation in formic acid."},{"paperId":"P199","section":"synthesis","insight":"The soybean-based protein powder serves as a simultaneous source of carbon, nitrogen, and potassium."},{"paperId":"P199","section":"synthesis","insight":"The addition of ammonium molybdate increases the BET surface area (from 8.25 to 37.01 m2/g) due to a hole-opening effect."},{"paperId":"P199","section":"characterization","insight":"The addition of Mo during synthesis increases the BET surface area from 8.25 m2/g (support) to 37.01 m2/g due to a hole-opening effect."},{"paperId":"P199","section":"characterization","insight":"K leaching occurs significantly during stability tests, with 80.6% of K leached into the FA solution as potassium formate, which enhances HCOO- production."},{"paperId":"P199","section":"performance","insight":"The dehydrogenation activity of γ-Mo2N/ x NK-C catalysts increases with the AHM/protein mass ratio up to 0.2, after which further increase in molybdenum does not improve activity."},{"paperId":"P199","section":"performance","insight":"Water effectively inhibits the dehydration pathway (CO production) by occupying Brønsted acidic sites on the catalyst surface."},{"paperId":"P200","section":"synthesis","insight":"The TA-COP support was synthesized via Schiff base condensation and purified with ethyl acetate, THF, acetone, and chloroform before vacuum drying at 343 K for 12 h."},{"paperId":"P200","section":"characterization","insight":"The incorporation of Pd nanoparticles into the TA-COP framework increased its thermal stability, shifting decomposition from 200 °C to 355 °C."},{"paperId":"P200","section":"characterization","insight":"Pd loading resulted in a decrease in BET surface area (from 44.29 to 34.23 m2/g) and pore volume (from 0.53 to 0.27 cm3/g), attributed to the accommodation of nanoparticles within the pores."},{"paperId":"P200","section":"performance","insight":"The catalyst showed higher efficiency at 0.02 g compared to higher dosages in terms of TOF."},{"paperId":"P200","section":"performance","insight":"Water was found to be the most efficient solvent among H2O, ethanol, and DMF."},{"paperId":"P200","section":"performance","insight":"Ultrasound irradiation significantly accelerated the reaction, reducing the time to achieve 10 mL gas evolution from 40 min to 20 min."},{"paperId":"P201","section":"synthesis","insight":"The basicity of the grafted amine groups on the carbon support governs the selectivity between D2 and HD production."},{"paperId":"P201","section":"synthesis","insight":"Ketjen Black was found to be superior to Shirasagi and Vulcan X supports due to its combined mesoporous and microporous structure."},{"paperId":"P201","section":"characterization","insight":"The basicity of the grafted amine moieties on the periphery of active centers determines hydrogen isotope gas selectivity rather than the intrinsic catalytic ability or size of the PdAg nanoparticles."},{"paperId":"P201","section":"characterization","insight":"Ketjen Black support provides better activity than Shirasagi or Vulcan X due to its combination of mesoporous channels and uniform microporous structure."},{"paperId":"P201","section":"performance","insight":"D2 selectivity increases as the basicity of grafted amine groups decreases (higher Ead for FA corresponds to lower D2 selectivity)."},{"paperId":"P201","section":"performance","insight":"Alloying Pd with Ag promotes C-H bond dissociation during formic acid dehydrogenation."},{"paperId":"P201","section":"performance","insight":"Surface amine groups are crucial for promoting O-H bond dissociation and determining hydrogen isotope selectivity."},{"paperId":"P201","section":"performance","insight":"Amine-functionalized carbon supports provide higher activity than mesoporous silica (SBA-15) counterparts."},{"paperId":"P202","section":"synthesis","insight":"The molar ratio of citric acid to ethylenediamine controls the nitrogen doping level and particle size of the carbon dots."},{"paperId":"P202","section":"synthesis","insight":"Pyridine nitrogen is identified as crucial for stabilizing Pd precursors and increasing electron transfer from support to metal."},{"paperId":"P202","section":"characterization","insight":"Pyridine nitrogen acts as an electron donor, increasing the electron density of Pd0 and facilitating C-H bond rupture in formic acid dehydrogenation."},{"paperId":"P202","section":"characterization","insight":"The amount of pyridine nitrogen is inversely proportional to the Pd nanoparticle size."},{"paperId":"P202","section":"characterization","insight":"Strong metal-support interaction (N-Pd coordination) stabilizes ultra-fine Pd nanoparticles and prevents aggregation."},{"paperId":"P202","section":"performance","insight":"The catalytic activity of Pd/CD catalysts increases with the N-doping amount in the carbon dot support."},{"paperId":"P202","section":"performance","insight":"Pyridine nitrogen is identified as a key factor in enhancing performance by increasing electron density on Pd and facilitating HCOO* adsorption."},{"paperId":"P203","section":"synthesis","insight":"The catalyst is prepared by a two-step process: first synthesizing a COF/silica composite as an adsorbent and then performing in situ reduction of the adsorbed metal ions."},{"paperId":"P203","section":"characterization","insight":"The adsorbent Tp-Azo-COF/SiO2 maintains a regular spherical morphology and high crystallinity (XRD peaks at 3.2° and 5.5°) even after Pd(II) adsorption under high acidity (1–5 M HNO3)."},{"paperId":"P203","section":"characterization","insight":"Pd(II) adsorption occurs primarily on C-NH sites via soft acid-soft base interactions, with NO3- involved in coordination for charge balance."},{"paperId":"P203","section":"characterization","insight":"The composite exhibits good thermal stability up to 320°C and radiation stability up to 600 kGy."},{"paperId":"P203","section":"performance","insight":"Pd-loaded Tp-Azo-COF/SiO2 demonstrated better catalytic effect for formic acid decomposition than commercial Pd/C catalyst."},{"paperId":"P204","section":"synthesis","insight":"Simultaneous alkali/air activation using NaHCO3 at 700 °C in a mixed air/nitrogen flow (30% air) was more effective for mesopore development than KOH activation."},{"paperId":"P204","section":"synthesis","insight":"The use of air during alkali activation significantly enlarged the specific surface area and mesopore volume compared to pure nitrogen atmospheres."},{"paperId":"P204","section":"characterization","insight":"The Pd-PdO interface is identified as the active site for formic acid dehydrogenation."},{"paperId":"P204","section":"characterization","insight":"Hierarchical pore structure in carbon carriers (specifically mesopores) is critical for enhancing the accessibility of active sites and mass transfer of reactants and products."},{"paperId":"P204","section":"characterization","insight":"XPS analysis of recycled catalysts showed an increase in Pd0, correlating with a decline in activity and confirming the necessity of the Pd-PdO interface."},{"paperId":"P204","section":"performance","insight":"The simultaneous alkali/air activation method using NaHCO3 produced a hierarchically porous carbon (NaA30700) that served as a superior Pd catalyst carrier due to its high mesopore surface area."},{"paperId":"P204","section":"performance","insight":"Addition of sodium formate (SF) dramatically enhanced the reaction rate by favoring the formation of metal-formate intermediates."},{"paperId":"P205","section":"synthesis","insight":"Supports (CNFs and N-CNFs) were synthesized by decomposition of ethylene (and ammonia for N-doped) on a Ni/Cu/Al2O3 catalyst at 823 K."},{"paperId":"P205","section":"synthesis","insight":"N-doping in the carbon support stabilizes single Pt atoms, preventing sintering and enhancing activity for formic acid decomposition."},{"paperId":"P205","section":"characterization","insight":"N-doped carbon nanofibers (N-CNFs) act as macro-ligands that anchor single Pt-group metal atoms via pyridinic nitrogen at the edges of graphene sheets."},{"paperId":"P205","section":"characterization","insight":"The ionic/electron-deficient state of stabilized single atoms prevents sintering and weakens the back-donation to CO, resulting in low or undetectable CO chemisorption compared to metallic nanoparticles."},{"paperId":"P205","section":"characterization","insight":"Catalytic activity for formic acid decomposition is inversely related to CO chemisorption capacity, indicating that electron-deficient single sites are the primary active centers rather than nanoparticle surfaces."},{"paperId":"P205","section":"performance","insight":"The decomposition of formic acid proceeds more rapidly on single metal atoms (by up to 1 order of magnitude) compared to nanoparticles."},{"paperId":"P205","section":"performance","insight":"N-doping of the carbon support strongly promotes activity and selectivity for H2 production, particularly for Pt catalysts."},{"paperId":"P205","section":"performance","insight":"Catalytic activity in formic acid decomposition is inversely related to CO chemisorption capacity; sites that decompose FA are different from those that irreversibly chemisorb CO."},{"paperId":"P206","section":"synthesis","insight":"Higher synthesis temperature (773 K) for CTFs was used to provide higher surface area and pore volume compared to 673 K, though it leads to lower nitrogen content and amorphization."},{"paperId":"P206","section":"synthesis","insight":"Treatment in formic acid/Ar flow at 573 K is critical for removing acetylacetonate ligands and stabilizing single-atom Pd sites."},{"paperId":"P206","section":"characterization","insight":"CTF-based supports synthesized at 773 K are mostly amorphous N-doped carbon materials."},{"paperId":"P206","section":"characterization","insight":"The coordination environment of Pd in CTFs varies by support: Pd-C2N2 for CTF-1 and Pd-N4 for pyCTF/bipyCTF."},{"paperId":"P206","section":"characterization","insight":"Single-atom Pd catalysts on CTFs exhibit higher stability than nanoparticle-based Pd/C due to stronger binding energies (approx. 6 eV vs 4 eV)."},{"paperId":"P206","section":"performance","insight":"The catalytic activity order was Pd/CTF-1 > Pd/C > Pd/pyCTF >= Pd/bipyCTF."},{"paperId":"P206","section":"performance","insight":"Selectivity trend at temperatures above 500 K: Pd/bipyCTF > Pd/pyCTF > Pd/CTF-1 > Pd/C."},{"paperId":"P206","section":"performance","insight":"Increase in nitrogen content in CTF-based supports leads to a decrease in reaction rates but an increase in selectivity."},{"paperId":"P207","section":"synthesis","insight":"KIE-8 support synthesis involves dissolving chitosan and urea in 5.2 wt % acetic acid aqueous solution followed by addition of 3.8 wt % KOH aqueous solution."},{"paperId":"P207","section":"synthesis","insight":"The carbonization temperature of KIE-8 (700-1000 °C) significantly affects the nitrogen content, graphitization degree, and resulting catalytic activity of Pd nanoparticles."},{"paperId":"P207","section":"characterization","insight":"The carbonization temperature of KIE-8 (700-1000 °C) controls the transition from pyridinic nitrogen to graphitic nitrogen and the evolution of pore structure from nanosheets to agglomerated nano flakes."},{"paperId":"P207","section":"characterization","insight":"KOH activation in the presence of urea creates a hierarchically porous structure consisting of micropores (< 2 nm), small mesopores (~3.9 nm), and large mesopores (~27.2 nm)."},{"paperId":"P207","section":"characterization","insight":"Graphitic nitrogen content in the carbon support is a key driver for improving Pd nanoparticle dispersion and overall catalytic activity."},{"paperId":"P207","section":"performance","insight":"The catalytic activity of Pd/KIE-8 catalysts for formic acid dehydrogenation is significantly dependent on the graphitic nitrogen content in the nitrogen-doped porous carbon supports."},{"paperId":"P207","section":"performance","insight":"Higher surface area, pore volume, and graphitic nitrogen content lead to better catalytic activity by influencing the electronic structure, particle size, and dispersion of deposited Pd nanoparticles."},{"paperId":"P208","section":"synthesis","insight":"Pure-phase TiB2 supports require a reduction temperature of 1000 °C; temperatures below this result in TiO2, Ti2O3, or TiBO3 impurities."},{"paperId":"P208","section":"synthesis","insight":"The thickness and coverage of the boride overlayer (SMSI effect) are tuned by controlling the calcination temperature (e.g., partial coverage at 500 °C, monolayer encapsulation at 600 °C, and multilayer core-shell structure at 800 °C)."},{"paperId":"P208","section":"synthesis","insight":"TiB2-based SMSI is only attained after thermal treatment in inert (N2) or reducing (H2/Ar) environments; oxidation in air transforms TiB2 to TiO2."},{"paperId":"P208","section":"characterization","insight":"SMSI between noble metals and 2D TiB2 supports is driven by a combination of electrostatic and covalent interactions, with adhesion energy following the trend Pt ≈ Pd > Ag ≈ Au."},{"paperId":"P208","section":"characterization","insight":"The extent of SMSI (overlayer thickness and coverage) can be precisely tuned by controlling the calcination temperature in nonoxidizing environments."},{"paperId":"P208","section":"characterization","insight":"TiB2-based SMSI provides superior sintering resistance compared to conventional TiO2-based SMSI."},{"paperId":"P208","section":"characterization","insight":"Charge transfer occurs from the TiB2 support to Pt, Pd, and Ag, but is negligible for Au."},{"paperId":"P208","section":"characterization","insight":"The active sites for formic acid dehydrogenation are identified as the TiO x-terminated surfaces of the TiB2 overlayers."},{"paperId":"P208","section":"performance","insight":"The extent of SMSI (controlled by calcination temperature) significantly affects activity, with a thin continuous overlayer (Pt/TiB2-600) being optimal."},{"paperId":"P208","section":"performance","insight":"Noble metal nanoparticles in Pt/TiB2-600 are completely encapsulated and do not directly participate in the reaction; instead, they act as electronic modulators for the active TiO x-terminated TiB2 surfaces."},{"paperId":"P208","section":"performance","insight":"TiB2 is superior to other MBenes (ZrB2, HfB2, Cr2B) and transition metal oxides (TiO2) for formic acid dehydrogenation."},{"paperId":"P209","section":"synthesis","insight":"Catalysts prepared in acetone solutions generally resulted in smaller particles than water-mediated routes, except for the palladium chloride precursor."},{"paperId":"P209","section":"synthesis","insight":"PdAcet. Acet./Cdarco showed the smallest Pd particle size (2.8 nm), attributed to high solubility of acetate in acetone and better interaction with the support surface."},{"paperId":"P209","section":"characterization","insight":"Precursor and solvent choice significantly impact Pd particle size; acetone generally produced smaller particles than water, except for the PdCl2 precursor."},{"paperId":"P209","section":"characterization","insight":"A volcano-type relationship between TOF and particle size was observed, with an optimal activity peak around 4-5 nm."},{"paperId":"P209","section":"characterization","insight":"Catalytic activity is dominated by low coordination sites (edges and corners) rather than high coordination terrace sites or total surface area."},{"paperId":"P209","section":"characterization","insight":"Pd nanoparticles were modeled as regular truncated cuboctahedra."},{"paperId":"P209","section":"performance","insight":"A volcano-type relationship between TOF and Pd particle size was observed, with maximum specific activity situated around 4-5 nm."},{"paperId":"P209","section":"performance","insight":"Catalytic activity is influenced more strongly by low coordination sites (edges and corners) than by the total number of available surface atoms."},{"paperId":"P210","section":"synthesis","insight":"The use of ligand-protected precursors (Pd(en)2Cl2 and Mn-EDTA) combined with in-situ hydrothermal synthesis ensures subnanometric metal clusters are encapsulated within the zeolite channels."},{"paperId":"P210","section":"synthesis","insight":"Amino-functionalization via 3-aminopropyltriethoxysilane increases both alkalinity and hydrophilicity, which enhances formic acid dehydrogenation activity compared to methyl-functionalized or non-functionalized supports."},{"paperId":"P210","section":"characterization","insight":"Amino-functionalization of S-1 zeolite increases hydrophilicity and alkalinity, which synergistically works with encapsulated metal clusters to improve FA dehydrogenation."},{"paperId":"P210","section":"characterization","insight":"The introduction of Mn into Pd clusters creates electron-enriched Pd species and improves Pd dispersion (up to 92.5%)."},{"paperId":"P210","section":"characterization","insight":"EXAFS coordination numbers (Pd-M = 1.1 for monometallic, 2.1 for bimetallic) confirm the subnanometric nature of the encapsulated clusters."},{"paperId":"P210","section":"characterization","insight":"XPS and CO-DRIFTS provide evidence of electronic modification of Pd by both Mn co-catalysts and amino-functionalized supports."},{"paperId":"P210","section":"performance","insight":"The incorporation of Mn as a co-catalyst significantly enhances the TOF compared to other non-noble metals (Fe, Co, Ni)."},{"paperId":"P210","section":"performance","insight":"Amino-functionalization improves both hydrophilicity and basicity, which synergistically accelerates FA dehydrogenation."},{"paperId":"P210","section":"performance","insight":"Bimetallic Pd-Mn clusters create electron-enriched Pd sites that facilitate C-H bond cleavage of the formate intermediate."},{"paperId":"P211","section":"synthesis","insight":"Surface DBD plasma reduction is significantly faster (6 min) than chemical reduction with NaBH4 (3 h)."},{"paperId":"P211","section":"synthesis","insight":"Oxygen plasma pretreatment increases oxygen-containing functional groups (OCGs), which enhances the anchoring of amino groups from APTES and subsequently improves Pd dispersion and metal-support interaction."},{"paperId":"P211","section":"synthesis","insight":"The surface DBD plasma method preserves OCGs and amino groups better than chemical reduction, leading to a higher Pd2+/Pd0 ratio and greater stability against leaching and agglomeration."},{"paperId":"P211","section":"characterization","insight":"Oxygen plasma pretreatment increases oxygen-containing functional groups (OCGs), which facilitate amino modification via APTES and provide anchoring sites for Pd precursors."},{"paperId":"P211","section":"characterization","insight":"Surface DBD plasma is a milder reduction method than NaBH4, effectively preserving OCGs and -NH2 groups on the support."},{"paperId":"P211","section":"characterization","insight":"The synergistic effect between Pd0 (dehydrogenation of formic acid) and Pd2+ (extraction of hydrogen from intermediates) is critical for activity."},{"paperId":"P211","section":"characterization","insight":"Charge repulsion among electron-deficient Pd2+ species prevents the agglomeration of high-surface-energy nanoparticles, enhancing structural stability."},{"paperId":"P211","section":"performance","insight":"Surface DBD plasma preparation preserves more OCGs and -NH2 groups compared to chemical reduction with NaBH4, leading to higher Pd2+ content (73.2% vs 37.4%) and stronger metal-support interaction."},{"paperId":"P211","section":"performance","insight":"The synergistic effect between Pd0 and Pd2+ species, combined with high dispersion of nanoparticles, significantly enhances both the activity and stability of the Pd/O-NCNTs-P catalyst."},{"paperId":"P212","section":"synthesis","insight":"The use of nucleation concentration control allows for the creation of a PdM alloy surface layer rather than separate metal clusters."},{"paperId":"P212","section":"synthesis","insight":"Low temperature (< 160 °C) is critical to prevent the diffusion of modified atoms into the bulk of the Pd nanocrystal."},{"paperId":"P212","section":"characterization","insight":"Surface modification with foreign atoms allows precise control of the electronic state (charge density) of Pd surface atoms through a charge polarization mechanism driven by work function differences."},{"paperId":"P212","section":"characterization","insight":"The combination of a Mott-Schottky junction (TiO2-Pd) and surface alloy modification synergistically enhances HCOOH dehydrogenation under UV light."},{"paperId":"P212","section":"characterization","insight":"Depth-dependent synchrotron XPS confirms that foreign metal atoms are concentrated in the near-surface region rather than forming separate clusters."},{"paperId":"P212","section":"performance","insight":"The catalytic activity for HCOOH decomposition follows the order: Pd@Ag > Pd@Cu > Pd@Au > bare Pd > Pd@Pt."},{"paperId":"P212","section":"performance","insight":"Increased electron density of Pd sites, tuned by charge polarization from foreign atoms with lower work functions (Ag < Cu < Au < Pd < Pt), promotes HCOOH dehydrogenation."},{"paperId":"P212","section":"performance","insight":"The Mott-Schottky junction between TiO2 and Pd enhances activity under UV light up to 4.5 mW cm-2; beyond this intensity, plasmonic hot electron injection into TiO2 reduces the electron density of Pd and lowers activity."},{"paperId":"P213","section":"synthesis","insight":"The composition of D-PdAg NWs is tuned by controlling the amounts of precursors."},{"paperId":"P213","section":"synthesis","insight":"A diffusion strategy was used to create a Pd-rich surface on the nanowires."},{"paperId":"P213","section":"characterization","insight":"The diffusion strategy (D-PdAg) results in a Pd-rich surface and more efficient electron transfer from Ag to Pd compared to the co-reduction method (C-PdAg), significantly enhancing catalytic activity for formic acid dehydrogenation and adiponitrile hydrogenation."},{"paperId":"P213","section":"performance","insight":"D-Pd5Ag5 NWs exhibit the highest activity for FA dehydrogenation among D-PdAg compositions."},{"paperId":"P213","section":"performance","insight":"The diffusion strategy (D-series) results in a larger active surface area and more efficient electron transfer from Ag to Pd compared to co-reduction methods (C-series), enhancing catalytic performance."},{"paperId":"P214","section":"synthesis","insight":"The surface-amine-implanting approach (SAIA) using ammonium hydroxide hydrothermal treatment helps in dispersing ultrafine Pd NPs and preventing aggregation."},{"paperId":"P214","section":"synthesis","insight":"Amine groups on the carbon support act as proton scavengers and provide an alkaline environment that promotes formic acid deprotonation."},{"paperId":"P214","section":"characterization","insight":"Surface-amine-implanting approach (SAIA) effectively reduces metal nanoparticle size and prevents aggregation by enhancing interactions between the metal and electron-rich supports."},{"paperId":"P214","section":"characterization","insight":"BET surface area decreases upon Pd loading, indicating that nanoparticles are embedded within the pores of the carbon framework."},{"paperId":"P214","section":"characterization","insight":"Amine groups on the support act as proton scavengers, creating a local alkaline environment that promotes O-H bond dissociation in formic acid."},{"paperId":"P214","section":"performance","insight":"The best molar ratio of FA/SF for hydrogen generation over Pd/APC is 1:1."},{"paperId":"P214","section":"performance","insight":"Catalytic activity of Pd/APC depends strongly on temperature, with reaction completion times decreasing from 10.3 min at 30 °C to 3.3 min at 55 °C."},{"paperId":"P215","section":"characterization","insight":"TiO2 nanosheets exhibit an anatase phase structure rich in oxygen vacancies (VOs), which act as strong Lewis bases to enhance adsorption of CO2 and H2O."},{"paperId":"P215","section":"characterization","insight":"The Pd-Cu alloy's (111) facet is identified as the primary active crystal plane for formic acid dissociation."},{"paperId":"P215","section":"characterization","insight":"Electronic charge transfer occurs from the TiO2 support to the PdCu alloy, and further from Cu atoms to Pd atoms due to differences in ionization potentials (Cu: 7.72 eV, Pd: 8.34 eV)."},{"paperId":"P215","section":"performance","insight":"The Pd-Cu/TiO2-NSs (3:7) catalyst exhibits the highest activity among all tested atomic ratios."},{"paperId":"P215","section":"performance","insight":"Catalytic activity increases with increasing reaction temperature from 303 K to 343 K."},{"paperId":"P215","section":"performance","insight":"Formic acid dehydrogenation is a first-order reaction in terms of HCOOH concentration and zero order for catalyst quantity."},{"paperId":"P216","section":"synthesis","insight":"The use of soybean as a carbon source intrinsically introduces N, P, and K heteroatoms which aid in anchoring metal nanoparticles and providing basic sites."},{"paperId":"P216","section":"characterization","insight":"The Ni/Co ratio regulates the evolution of K species on the carbon surface, influencing the density and strength of Lewis basic sites."},{"paperId":"P216","section":"characterization","insight":"Endogenous heteroatoms (N, P) from soybean provide anchoring sites for alloy nanoparticles and modulate electronic structures."},{"paperId":"P216","section":"characterization","insight":"Electronic interaction between Ni and Co involves electron transfer from Ni to Co, which stabilizes the active phase at high temperatures."},{"paperId":"P216","section":"performance","insight":"The optimized Ni0.2Co0.8–Soy catalyst outperforms monometallic counterparts by combining high conversion and selectivity."},{"paperId":"P216","section":"performance","insight":"A Co-rich fcc Ni-Co solid solution reduces particle size (avg 4.8 nm), increasing active site density."},{"paperId":"P216","section":"performance","insight":"Endogenous K species from soybean provide basic sites that facilitate the initial dissociation of formic acid into formate intermediates."},{"paperId":"P217","section":"synthesis","insight":"Cacumen Platycladi leaf extract acts as both a reductant and stabilizer."},{"paperId":"P217","section":"synthesis","insight":"Nitric acid pretreatment of AC introduces oxygen functional groups (C=O, -COOH, C-O) to make the surface hydrophilic and facilitate metal anchoring."},{"paperId":"P217","section":"characterization","insight":"Biomass reduction using Cacumen Platycladi leaf extract acts as both a reductant and stabilizer, leaving residual biomass molecules on the catalyst surface (confirmed by FTIR and TG)."},{"paperId":"P217","section":"characterization","insight":"Nitric acid pretreatment of activated carbon introduces oxygen functional groups (C=O, -COOH, C-O) that increase hydrophilicity and provide anchoring sites for metal nanoparticles."},{"paperId":"P217","section":"characterization","insight":"Bimetallic Pd-based catalysts exhibit a mesoporous nanostructure (Type IV isotherm with H4 hysteresis loop), with specific surface area and pore volume slightly decreasing upon the addition of the second metal."},{"paperId":"P217","section":"characterization","insight":"The synergistic effect in bimetallic systems is driven by electronic modification where additive metals (Au, Cu) donate electrons to Pd."},{"paperId":"P217","section":"performance","insight":"Bimetallic Pd-based catalysts (Pd-Au/AC and Pd-Cu/AC) exhibit significantly higher activity for CO2 hydrogenation to formate than monometallic Pd/AC."},{"paperId":"P217","section":"performance","insight":"The optimal reaction temperature for CO2 hydrogenation is 383 K; temperatures above this lead to decreased TOF due to reduced gas solubility and thermal decomposition of products."},{"paperId":"P217","section":"performance","insight":"For FA dehydrogenation, the addition of triethylamine (NEt3) as a proton carrier drastically increases the H2 generation rate and TOF compared to additive-free systems."},{"paperId":"P217","section":"performance","insight":"Pd-Cu/AC is superior for CO2 hydrogenation due to lower activation energy and electronic effects of Cu, while Pd-Au/AC is more active for FA dehydrogenation likely due to the higher redox potential of Au in acidic conditions."},{"paperId":"P218","section":"synthesis","insight":"The organic ligand (BDC) for the MOF was sustainably sourced from waste PET bottles via alkaline hydrolysis at 180 °C."},{"paperId":"P218","section":"synthesis","insight":"Pyrolysis temperature and atmosphere significantly affect catalytic activity, with N2-annealed ZrO2-600 providing superior performance compared to air-annealed samples."},{"paperId":"P218","section":"characterization","insight":"The carbonization of PET-derived UiO-66 MOF results in a tetragonal ZrO2 phase, whereas annealing in air at 700°C leads to a monoclinic phase."},{"paperId":"P218","section":"characterization","insight":"The transition from the parent MOF (UiO-66) to the final catalyst increases the pore size from 3.33 nm to 8.24 nm, facilitating better mass transfer for formic acid dehydrogenation."},{"paperId":"P218","section":"performance","insight":"The Co@Cr(OH)3/ZrO2 catalyst pyrolyzed in N2 atmosphere is significantly more active than the one pyrolyzed in air (TOF 7685 vs 1726 h-1)."},{"paperId":"P218","section":"performance","insight":"Activation energy (Ea) for Co@Cr(OH)3/ZrO2 was determined to be 26.98 kJ mol-1."},{"paperId":"P218","section":"performance","insight":"Smaller particle size of Co NPs correlates with greater effect on FA dehydrogenation."},{"paperId":"P218","section":"performance","insight":"Optimal loading of Co NPs for the catalyst is 5.0 wt%."},{"paperId":"P219","section":"synthesis","insight":"The use of open metal site (OMS) Cu-MOFs allows for the grafting of Schiff-base ligands, which subsequently stabilize Pd ions."},{"paperId":"P219","section":"synthesis","insight":"Pd(II) is reduced to Pd(0) in situ during the formic acid decomposition process."},{"paperId":"P219","section":"characterization","insight":"OMS-Cu(BDC) serves as a stable, high-surface-area support for post-synthetic modification with Schiff-base ligands and Pd metalation."},{"paperId":"P219","section":"characterization","insight":"The immobilization of the Pd complex inside the MOF pore cage is confirmed by a decrease in micropore surface area from 340 cm³/g to 210 cm³/g."},{"paperId":"P219","section":"characterization","insight":"XPS analysis confirms that the active species for formic acid dehydrogenation involves the reduction of grafted Pd(II) to metallic Pd(0)."},{"paperId":"P219","section":"performance","insight":"The 4-PySI ligand is more effective than the 2-PySI ligand in stabilizing Pd and maintaining an open active state due to the para position of the coordination bond."},{"paperId":"P219","section":"performance","insight":"There is a synergistic effect between the Pd metal and the Schiff-base group that improves FA dehydrogenation compared to using only the MOF support or the ligand-modified MOF without Pd."},{"paperId":"P219","section":"performance","insight":"Increasing catalyst amount from 1 mg to 10 mg increases TOF (from 290 to 412 h-1), suggesting cooperative effects among active sites."},{"paperId":"P220","section":"synthesis","insight":"A mixture of ethanol and water was used as solvent due to the low solubility of rhodium(II) acetate in pure water."},{"paperId":"P220","section":"synthesis","insight":"The use of sol immobilization with PVA capping agent allowed for the synthesis of random-alloyed Pd-Rh nanoparticles at low temperature."},{"paperId":"P220","section":"characterization","insight":"Bimetallic Pd-Rh random alloys were successfully synthesized at low temperature using sol immobilization with PVA and NaBH4."},{"paperId":"P220","section":"characterization","insight":"A consistent discrepancy was observed between nominal and calculated Pd:Rh ratios, with actual catalysts being enriched in Pd due to unsuccessful quantitative immobilization of Rh (confirmed by ICP-OES)."},{"paperId":"P220","section":"characterization","insight":"STEM-XEDS line profiles indicated a relatively homogeneous distribution of metals within individual nanoparticles, ruling out core-shell structures."},{"paperId":"P220","section":"characterization","insight":"Reaction stability is linked to the leaching of Rh from the alloy structure, which leads to an increase in Pd content in the remaining particles."},{"paperId":"P220","section":"performance","insight":"Pd-rich bimetallic catalysts (especially Pd90Rh10) showed the highest initial activity for formic acid dehydrogenation."},{"paperId":"P220","section":"performance","insight":"Bimetallic Pd-Rh catalysts are more selective towards H2 and CO2, keeping CO levels below 10 ppm, which is critical for fuel cell applications."},{"paperId":"P220","section":"performance","insight":"Pd69Rh31 exhibited superior stability over multiple cycles compared to monometallic Pd and the more active Pd90Rh10."},{"paperId":"P220","section":"performance","insight":"In muconic acid hydrogenation using formic acid as a hydrogen donor, bimetallic catalysts were necessary to convert mono-unsaturated intermediates into adipic acid, with Pd69Rh31 performing best."},{"paperId":"P221","section":"synthesis","insight":"Amine-functionalization of SBA-15 (N-SBA-15) allows for the synthesis of sub-nanometer gold particles (0.8 nm) by promoting precursor entry into pores and stabilizing small clusters."},{"paperId":"P221","section":"synthesis","insight":"The use of basic pH (9.5 or 11) during deposition is critical for achieving smaller particle sizes on functionalized silica."},{"paperId":"P221","section":"synthesis","insight":"High pH conditions can lead to partial dissolution of the silica support, which may artificially increase measured metal loading."},{"paperId":"P221","section":"characterization","insight":"Amine-functionalization of SBA-15 (N-SBA-15) promotes the formation and stabilization of sub-nanometer gold particles within the pores."},{"paperId":"P221","section":"characterization","insight":"A direct correlation was observed between gold cluster size and catalytic activity/selectivity in formic acid dehydrogenation, with smaller clusters being more active and selective toward H2."},{"paperId":"P221","section":"characterization","insight":"The use of ammonia at pH 11 can achieve small particle sizes on both functionalized and non-functionalized SBA-15, suggesting a stabilizing effect of amine groups."},{"paperId":"P221","section":"characterization","insight":"Small-angle XRD confirmed that the characteristic diffraction maxima of SBA-15 were conserved after gold deposition."},{"paperId":"P221","section":"performance","insight":"A direct correlation between gold cluster size and catalytic performance was observed, with smaller particles showing higher productivity and better selectivity to hydrogen."},{"paperId":"P221","section":"performance","insight":"Amine-functionalization of SBA-15 promotes the formation of sub-nanometer gold particles within the pores and stabilizes them against growth."},{"paperId":"P222","section":"synthesis","insight":"Glycine acts as a complexing agent and capping ligand for Cu2+ ions."},{"paperId":"P222","section":"synthesis","insight":"CTAB is used as a shape controlling agent during the synthesis of Ag and MnO2 components."},{"paperId":"P222","section":"synthesis","insight":"The ternary catalyst Gly-Cu/Ag/MnO2 shows higher activity than binary or mono-metallic versions due to synergistic effects."},{"paperId":"P222","section":"characterization","insight":"The incorporation of additional metals (Ag and MnO2) into the Gly-Cu matrix systematically increases catalytic efficiency for formic acid decomposition."},{"paperId":"P222","section":"characterization","insight":"UV-Vis spectra indicate that the optical properties of Gly-Cu/Ag are dominated by the outer metallic silver shell, while the addition of MnO2 results in a featureless spectrum with an optical band gap of 2.75 eV."},{"paperId":"P222","section":"characterization","insight":"XRD confirms the crystalline nature of the ternary catalyst, showing characteristic peaks for both metallic phases (Cu, Ag) and the oxide phase (MnO2)."},{"paperId":"P222","section":"performance","insight":"Catalytic activity increases with an increasing number of incorporated metals: Gly-Cu/Ag/MnO2 > Gly-Cu/Ag > Gly-Cu or Gly-Ag."},{"paperId":"P222","section":"performance","insight":"Sodium formate (SF) acts as a promoter, enhancing the reactivity and adsorption of formic acid."},{"paperId":"P222","section":"performance","insight":"Hydrogen generation follows first-order kinetics with respect to catalyst amount."},{"paperId":"P223","section":"synthesis","insight":"Tandem heat-treatment of MSC-30 with urea provides more stable N-functional groups than a one-step process, leading to better dispersion and smaller Pd nanoclusters (1.4 nm)."},{"paperId":"P223","section":"synthesis","insight":"The use of NaOH/NaBH4 during the synthesis removes bulk thermolysis products of urea (e.g., cyanuric acid, ammelide, ammeline), which significantly increases the BET surface area of the N-functionalized support."},{"paperId":"P223","section":"characterization","insight":"Tandem heat-treatment of the carbon support creates more stable N-functional groups that better anchor Pd nanoclusters, preventing aggregation."},{"paperId":"P223","section":"characterization","insight":"Treatment with NaOH/NaBH4 during synthesis significantly increases the BET surface area of N-functionalized MSC-30 by removing urea thermolysis products (cyanuric acid, ammelide, ammeline)."},{"paperId":"P223","section":"characterization","insight":"The catalyst maintains its crystalline structure, electronic states, and particle size distribution after 15 cycles of formic acid dehydrogenation."},{"paperId":"P223","section":"performance","insight":"Tandem heat-treatment of MSC-30 with urea provides a more robust N-functionalized support than one-step treatment, leading to better Pd NC dispersion and higher activity."},{"paperId":"P223","section":"performance","insight":"The catalytic activity for FA decomposition improves as the molar percentage of SF in the FA-SF solution increases up to a ratio of 1:2.5."},{"paperId":"P224","section":"synthesis","insight":"Capping of {100} facets with Br- allows for selective Ag overgrowth at the edges of Pd nanocubes."},{"paperId":"P224","section":"synthesis","insight":"PVP ligands can be effectively removed by repeated centrifugation and washing, providing a surface comparable to water steam treatment."},{"paperId":"P224","section":"characterization","insight":"The tandem reaction efficiency is governed by the spatial proximity of active sites for each step; cubic Pd nanocrystals are superior because their edge sites catalyze both HCOOH decomposition and hydrogenation."},{"paperId":"P224","section":"characterization","insight":"HCOOH decomposition is identified as the limiting step in the tandem hydrogen transfer process."},{"paperId":"P224","section":"characterization","insight":"Surface ligands (PVP) were confirmed to be removed via centrifugation, washing, and steam treatment using FTIR."},{"paperId":"P224","section":"performance","insight":"The spatial integration of active sites is critical for catalytic efficiency in tandem reactions; cubic Pd nanocrystals outperform octahedral/tetrahedral ones because their edge sites are active for both HCOOH decomposition and substrate hydrogenation."},{"paperId":"P224","section":"performance","insight":"HCOOH decomposition is the limiting step in the tandem hydrogen transfer reaction."},{"paperId":"P224","section":"performance","insight":"Tandem reactions can undergo direct hydrogen transfer without forming and dissociating molecular H2, leading to higher TOFs than individual step reactions using molecular H2."},{"paperId":"P225","section":"synthesis","insight":"Surface amination of PAN with EDA significantly increases the Pd loading capacity (from 0.45 wt% to 3.01 wt%) and reduces Pd nanoparticle size to approximately 1.2 nm."},{"paperId":"P225","section":"synthesis","insight":"The coordination between amino groups on the support and Pd species is critical for achieving high dispersion and stability."},{"paperId":"P225","section":"characterization","insight":"Surface amination of PAN with ethylenediamine (EDA) increases the adsorption and coordination capacity for Pd species, leading to higher Pd loading (3.01 wt% vs 0.45 wt% for untreated PAN)."},{"paperId":"P225","section":"characterization","insight":"The absence of characteristic Pd peaks in XRD patterns for both catalysts suggests very high dispersion and small particle sizes."},{"paperId":"P225","section":"characterization","insight":"FTIR spectra indicate that the amination of PAN occurs via a reaction between cyano groups in PAN and amino groups in EDA, forming bridging amidinate structures."},{"paperId":"P225","section":"performance","insight":"Surface amination of PAN with EDA significantly enhances the catalytic activity for FA dehydrogenation by reducing Pd NP size to ~1.2 nm and providing basic sites (amino/amidinate) that facilitate FA deprotonation."},{"paperId":"P225","section":"performance","insight":"There is a volcano-shaped relationship between the concentration of EDA used during support preparation and the resulting TOF of the catalyst."},{"paperId":"P226","section":"synthesis","insight":"Fluorination of porous carbon with BrF3/Br2 at room temperature allows for high nitrogen doping (up to 4.8 at.% total N) when subsequently treated with NH3, specifically increasing pyridinic nitrogen content."},{"paperId":"P226","section":"synthesis","insight":"The use of a highly porous N-doped support enables the stabilization of Ni single atoms up to ~4.9 wt.% loading via simple impregnation."},{"paperId":"P226","section":"characterization","insight":"The use of N-doped porous carbon (N-LC) with high pyridinic nitrogen content allows for the stabilization of Ni single atoms up to 4.9 wt.% via simple impregnation."},{"paperId":"P226","section":"characterization","insight":"Increasing Ni loading beyond a certain threshold (~6.2 wt.%) leads to the aggregation of single atoms into sub-nanosized particles (< 1 nm)."},{"paperId":"P226","section":"characterization","insight":"Single-atom Ni sites coordinated with N and O exhibit higher catalytic activity for formic acid dehydrogenation than sub-nanosized Ni particles."},{"paperId":"P226","section":"characterization","insight":"Long-term stability tests indicate that single-atom Ni sites are more mobile and prone to agglomeration (forming Ni-Ni bonds) under reaction conditions compared to sub-nanosized particles."},{"paperId":"P226","section":"performance","insight":"Single-atom Ni catalysts (6Ni/N-LC) exhibit higher reaction rates and lower apparent activation energy compared to sub-nanosized Ni particles (10Ni/N-LC)."},{"paperId":"P226","section":"performance","insight":"The use of N-doped carbon supports synthesized via fluorination/NH3-defluorination allows for high metal loadings (up to 4.9 wt.% as single atoms) while maintaining high H2 selectivity (> 99%)."},{"paperId":"P226","section":"performance","insight":"Single-atom Ni sites show higher mobility and a greater tendency toward agglomeration during long-term testing compared to sub-nanosized particles."},{"paperId":"P226","section":"performance","insight":"The apparent activation energy increases in the order: N-LC supported catalysts < 10Ni/LC_NH3 < 10Ni/LC, which correlates with the fraction of Ni-Ni bonds."},{"paperId":"P227","section":"synthesis","insight":"N incorporation-evaporation strategy (using melamine) is used to induce topological carbon defects."},{"paperId":"P227","section":"synthesis","insight":"Annealing temperature significantly affects the type and density of carbon defects, with 800°C being optimal for inducing D3 defects."},{"paperId":"P227","section":"characterization","insight":"N incorporation-evaporation strategy induces topological carbon defects (specifically 5-8-5 defects induced by pyrrolic N) that enhance metal-support interaction."},{"paperId":"P227","section":"characterization","insight":"A volcanic trend is observed for amorphous carbon (D3 defects) relative to annealing temperature, peaking at 800°C."},{"paperId":"P227","section":"characterization","insight":"Electron transfer occurs between sp3 carbon defects and Pd nanoparticles, modulating the electronic state of Pd."},{"paperId":"P227","section":"characterization","insight":"The downshift of the Pd d-band center induced by topological defects reinforces bonding to HCOO intermediates, reducing the reaction barrier."},{"paperId":"P227","section":"performance","insight":"The Pd/NC800 catalyst exhibits the highest activity due to a high density of topological defects (D3 carbon defects) induced by N incorporation-evaporation at 800 °C."},{"paperId":"P227","section":"performance","insight":"There is a positive correlation between TOFtotal and the I D3/I G ratio, indicating that topological defects enhance metal-support interaction and Pd dispersion."},{"paperId":"P227","section":"performance","insight":"The apparent activation energy for Pd/NC800 was determined to be 31.90 kJ/mol."},{"paperId":"P228","section":"synthesis","insight":"The use of amino-functionalization (APTES) on the SPP zeolite provides electrostatic attraction for negatively charged PdCl4(2-) and AuCl4(-) complexes, promoting high dispersion of sub-nanometer alloy clusters."},{"paperId":"P228","section":"synthesis","insight":"Amino groups act as anchoring sites that prevent metal particles from entering the 10-MR channels of the MFI framework, confining them to mesopore walls and external surfaces."},{"paperId":"P228","section":"characterization","insight":"Amino-functionalization of SPP zeolite via APTES creates positively charged sites that electrostatically attract PdCl4(2-) and AuCl4(-) complexes, promoting the formation of ultrafine alloy nanoclusters."},{"paperId":"P228","section":"characterization","insight":"Amination prevents metal anchoring within the 10-MR channels of the MFI framework, confining active sites to mesopore walls and external surfaces to reduce mass transfer limitations."},{"paperId":"P228","section":"characterization","insight":"Alloying Pd with Au induces electron migration from Pd to Au, optimizing the electronic state of Pd sites for improved FA dehydrogenation."},{"paperId":"P228","section":"performance","insight":"The addition of sodium formate (SF) promotes FA dehydrogenation at an optimal SF/FA molar ratio of 1, likely by inducing a favorable adsorption orientation and increasing electron density on the PdAu surface."},{"paperId":"P228","section":"performance","insight":"Increasing the APTES liquid-solid ratio from 3:1 to 7.5:1 improves performance due to higher amino group density; however, further increase to 10:1 reduces activity due to steric hindrance."},{"paperId":"P228","section":"performance","insight":"Metal loading optimization shows that initial TOF increases as loading rises from 2.5 wt% to 10 wt%, but decreases at 12 wt% due to cluster aggregation."},{"paperId":"P228","section":"performance","insight":"Alloy composition follows the activity order: Pd0.75Au0.25/NH2-SPP > Pd0.9Au0.1/NH2-SPP > Pd0.6Au0.4/NH2-SPP > Pd0.5Au0.5/NH2-SPP."},{"paperId":"P228","section":"performance","insight":"Among various transition metal alloys (Ir, Au, Ag, Mn, Zn, Ni), the Pd0.75Au0.25/NH2-SPP catalyst exhibited the highest activity."},{"paperId":"P229","section":"synthesis","insight":"The use of APTES to functionalize M-β-CD provides amine groups that act as anchoring sites for AuPd NPs, resulting in ultrafine particle sizes (~2.0 nm) and high dispersion."},{"paperId":"P229","section":"synthesis","insight":"Strong metal-support interaction between AuPd NPs and A-M-β-CD leads to electron transfer from the support to the nanoparticles."},{"paperId":"P229","section":"characterization","insight":"The amine-functionalized M-β-CD (A-M-β-CD) support is significantly more effective at controlling the size and dispersion of AuPd nanoparticles than unmodified M-β-CD, carbon, or no support."},{"paperId":"P229","section":"characterization","insight":"Strong metal-support interaction between AuPd NPs and A-M-β-CD leads to electron transfer from the support to the metals, enhancing catalytic activity for formic acid dehydrogenation."},{"paperId":"P229","section":"performance","insight":"The catalyst Au0.3Pd0.7/A-M-β-CD exhibits an unprecedented initial TOF of 7352 mol H2 per mol catalyst h-1 at 323 K without additives."},{"paperId":"P229","section":"performance","insight":"Activation energy (Ea) for Au0.3Pd0.7/A-M-β-CD is calculated to be 39.5 kJ mol-1."},{"paperId":"P229","section":"performance","insight":"The optimal molar ratio of Au:Pd was found to be 0.3:0.7."},{"paperId":"P230","section":"synthesis","insight":"The carbonization temperature of NMC significantly influences the type and content of N species (particularly pyridinic N), which in turn affects Pd particle size, distribution, and dispersion through metal-support interactions."},{"paperId":"P230","section":"characterization","insight":"N-containing functionalities (especially pyridinic N) stabilize ultra-fine Pd particles and enhance metal dispersion through the formation of Pd-N covalent bonds."},{"paperId":"P230","section":"characterization","insight":"Ordered mesoporous structure provides confinement effects that prevent Pd particle growth."},{"paperId":"P230","section":"characterization","insight":"Carbonization temperature of NMC influences the type and content of N species, which in turn affects Pd particle size, distribution, and oxidation state."},{"paperId":"P230","section":"performance","insight":"The catalytic activity of Pd/NMC catalysts is significantly higher than that of Pd/MC-600 due to the synergy between ultra-fine Pd particles and N-doping."},{"paperId":"P230","section":"performance","insight":"Pyridinic N species play a critical role in adsorbing and activating FA, while metallic Pd sites facilitate C-H bond cleavage."},{"paperId":"P230","section":"performance","insight":"There is a trade-off between the amount of pyridinic N (which decreases with increasing carbonization temperature) and the proportion of metallic Pd (which increases), influencing the TOF."},{"paperId":"P231","section":"synthesis","insight":"Low synthesis temperature (~2 °C) was critical to limit Pd particle growth and achieve ultrafine nanoparticles (1.76 nm)."},{"paperId":"P231","section":"synthesis","insight":"APTES serves a dual purpose: it overcomes the hydrophobicity of CNTs via amine functionalization and acts as a stabilizing agent during Pd impregnation."},{"paperId":"P231","section":"synthesis","insight":"Trisodium citrate (Cit) further prevents agglomeration by stabilizing Pd precursors and reducing surface instability of nucleated particles."},{"paperId":"P231","section":"characterization","insight":"The use of APTES overcomes the hydrophobicity of CNTs and introduces amine functional groups that act as proton scavengers to generate formate anions."},{"paperId":"P231","section":"characterization","insight":"Low synthesis temperature (~2 °C) limits particle growth, resulting in ultrafine Pd nanoparticles."},{"paperId":"P231","section":"characterization","insight":"Small Pd particles exhibit a higher proportion of readily oxidized surface atoms (Pd 2+), evidenced by XPS and EXAFS (reduced Pd-Pd peak at 2.5 Å)."},{"paperId":"P231","section":"characterization","insight":"The absence of micropores in CNTs facilitates mass transport compared to activated carbon supports."},{"paperId":"P231","section":"performance","insight":"The catalytic activity for FAD is significantly enhanced by minimizing Pd particle size (1.76 nm), introducing amine functional groups for proton scavenging, and using a support without micropores (CNTs) to facilitate mass transport."},{"paperId":"P231","section":"performance","insight":"Amine functional groups allow the catalyst to be active even in FA-only solutions by generating formate anions near the Pd particles."},{"paperId":"P231","section":"performance","insight":"The absence of micropores in CNTs provides a mass transport advantage over activated carbon supports."},{"paperId":"P231","section":"performance","insight":"Regeneration via washing and drying is necessary for repeated use, as catalysts otherwise deactivate due to fouling or CO accumulation."},{"paperId":"P232","section":"synthesis","insight":"Amine functionalization of the carbon black support via APTES is critical for achieving ultra-fine PdAu nanoparticles (~1.5 nm) and high dispersion."},{"paperId":"P232","section":"synthesis","insight":"The use of a low temperature (3°C) during the reduction process with NaBH4 helps maintain small particle size."},{"paperId":"P232","section":"characterization","insight":"Amine functionalization of carbon black (VXC-72) is critical for achieving ultra-fine PdAu nanoparticles (~1.5 nm) and high dispersion by increasing support hydrophilicity."},{"paperId":"P232","section":"characterization","insight":"Electronic interaction exists between the amine-functionalized support and the metal NPs, where electrons are transferred from VXC-72-NH2 to the PdAu particles."},{"paperId":"P232","section":"characterization","insight":"Alloy formation is evidenced by XRD peak shifts (between Au and Pd standards) and XPS binding energy shifts indicating electron transfer from Pd to Au."},{"paperId":"P232","section":"performance","insight":"Amine functionalization of carbon black converts the surface from hydrophobic to hydrophilic, enabling the synthesis of ultra-fine (1.5 nm) and highly dispersed PdAu nanoparticles."},{"paperId":"P232","section":"performance","insight":"The amine groups act as proton scavengers facilitating O-H bond dissociation and modulate the electronic structure of PdAu NPs to enhance metal-formate formation."},{"paperId":"P233","section":"synthesis","insight":"The use of amine-functionalized CeZrSBA-15 with short channels facilitates the formation of ultrafine PdCo nanoparticles (average size 1.6 nm) and prevents aggregation."},{"paperId":"P233","section":"synthesis","insight":"Surface amine groups act as anchoring sites for metal species and proton scavengers during catalysis."},{"paperId":"P233","section":"characterization","insight":"Amine functionalization of the support is critical for anchoring PdCo nanoparticles and preventing aggregation."},{"paperId":"P233","section":"characterization","insight":"The CeZrSBA-15-NH2 support with short channels provides superior mass transfer and better dispersion (1.6 nm) compared to ZrSBA-15, CeSBA-15, or SBA-15 supports."},{"paperId":"P233","section":"characterization","insight":"Electronic synergy is observed where Co donates electrons to Pd, and the amine groups of the support further donate electrons to the alloy NPs via MSI."},{"paperId":"P233","section":"performance","insight":"The Pd3Co2/CeZrSBA-15-NH2 catalyst exhibits superior activity due to the combination of short channels in the support for mass transfer and ultrafine (1.6 nm) highly dispersed nanoparticles."},{"paperId":"P233","section":"performance","insight":"Surface amine groups on the CeZrSBA-15-NH2 support act as proton scavengers, facilitating O-H bond cleavage in formic acid."},{"paperId":"P233","section":"performance","insight":"The synergistic electronic effect between Pd and Co, along with metal-support interaction (MSI), enhances catalytic performance."},{"paperId":"P234","section":"synthesis","insight":"The hierarchically microporous structure of the DUT-67-PZDC support is beneficial for the stabilization of ultrasmall Pd NPs (1.7 nm)."},{"paperId":"P234","section":"synthesis","insight":"Dual N sites on the DUT-67-PZDC support act as proton buffers to stimulate O-H bond cleavage in formic acid."},{"paperId":"P234","section":"characterization","insight":"The dual N sites (C-NH and C-N) in the DUT-67-PZDC MOF act as effective proton buffers for formic acid dehydrogenation."},{"paperId":"P234","section":"characterization","insight":"Strong metal-support interaction (MSI) is evidenced by electron transfer from Pd NPs to the nitrogen sites of the support, creating electron-deficient active sites."},{"paperId":"P234","section":"characterization","insight":"The hierarchical microporous structure of DUT-67-PZDC is critical for stabilizing ultrasmall Pd nanoparticles and preventing aggregation."},{"paperId":"P234","section":"performance","insight":"The addition of sodium formate (SF) significantly enhances the catalytic activity of Pd/DUT-67-PZDC(10), with an optimal FA/SF molar ratio of 1:2."},{"paperId":"P234","section":"performance","insight":"N sites on the DUT-67-PZDC support act as proton buffers, facilitating O-H bond cleavage in formic acid."},{"paperId":"P234","section":"performance","insight":"The rate determining step (RDS) for FAD over Pd/DUT-67-PZDC(10) is the cleavage of the C-H bond in FA molecules."},{"paperId":"P235","section":"synthesis","insight":"Amine groups from APTMS act as weak capping agents to regulate nucleation and inhibit aggregation of PdAu nanoparticles, maintaining a size of ~2 nm."},{"paperId":"P235","section":"synthesis","insight":"The hierarchically porous structure of the support is critical for mass transport in bubble-generating reactions like formic acid dehydrogenation."},{"paperId":"P235","section":"characterization","insight":"Amino groups on the HPC support act as weak capping agents that regulate nucleation and inhibit aggregation of PdAu nanoparticles."},{"paperId":"P235","section":"characterization","insight":"The hierarchically porous structure (macropores ~170 nm) is essential for mass transport in bubble-generating reactions, whereas microporous (AC) or mesoporous (SBA-15) supports constrain performance due to diffusion barriers."},{"paperId":"P235","section":"characterization","insight":"Alloying Pd with Au induces an electronic effect where Pd loses electrons to Au and a geometric effect where Pd surface ensembles are diluted."},{"paperId":"P235","section":"performance","insight":"The hierarchically porous structure of the support is critical for mass transport in bubble-generating reactions like FA dehydrogenation; catalysts on microporous (AC) or mesoporous (SBA-15) supports are constrained by internal diffusion."},{"paperId":"P235","section":"performance","insight":"Amine functionalization of the carbon support serves as a weak capping agent to regulate nucleation and inhibit aggregation of PdAu nanoparticles, while also providing basic sites that enhance activity."},{"paperId":"P236","section":"synthesis","insight":"The number of NaBH4 treatments was the primary factor controlling Pd particle size (from 2.5 nm to 4.8 nm), while concentration, reaction time, and temperature had little influence."},{"paperId":"P236","section":"characterization","insight":"Pd particle size was controlled from 2.5 nm to 4.8 nm by varying the number of NaBH4 treatments."},{"paperId":"P236","section":"characterization","insight":"The proportion of Pd(II) surface species decreases as the Pd particle size increases."},{"paperId":"P236","section":"characterization","insight":"No noticeable D-band shift was identified via XPS for Pd sizes between 2.5 and 4.8 nm."},{"paperId":"P236","section":"characterization","insight":"TPHD analysis indicates that larger Pd particles require higher energy/temperature to desorb hydrogen (PdHx decomposition temperature increased from 50 °C to 55 °C with size)."},{"paperId":"P236","section":"characterization","insight":"H2 desorption is proposed as the rate-determining step for formic acid dehydrogenation, explaining why activation energy increases with particle size."},{"paperId":"P236","section":"performance","insight":"Catalytic activity of Pd/C catalysts for formic acid dehydrogenation declines as Pd particle size increases from 2.5 nm to 4.8 nm."},{"paperId":"P236","section":"performance","insight":"The decrease in activity is attributed to both a reduction in the number of active sites and a thermodynamic effect (increase in activation energy)."},{"paperId":"P236","section":"performance","insight":"Activation energy increases linearly with Pd size (from 44.9 to 63.9 kJ/mol), suggesting that H2 desorption is the rate-determining step."},{"paperId":"P236","section":"performance","insight":"The intrinsic activity difference (TOF surface) between small and large Pd particles vanishes at higher reaction temperatures (>50 °C)."},{"paperId":"P237","section":"synthesis","insight":"The bipyridyl sites in UiO-67@NN act as nucleation centers for Pd2+ cations, leading to smaller (2.1 nm) and more highly dispersed nanoparticles compared to monopyridyl or non-pyridyl supports."},{"paperId":"P237","section":"characterization","insight":"The bipyridyl sites in UiO-67@NN exhibit stronger coordination interaction with Pd2+ cations than monopyridyl or non-functionalized sites, serving as nucleation centers for ultrasmall NPs."},{"paperId":"P237","section":"characterization","insight":"XPS N 1s binding energy shifts (from 398.8 eV to 399.7 eV) confirm electron transfer from the MOF support to the Pd nanoparticles."},{"paperId":"P237","section":"characterization","insight":"The presence of bipyridyl moieties significantly lowers the activation energy for O-H bond dissociation in formic acid (0.60 eV vs 1.28 eV for non-functionalized UiO-67)."},{"paperId":"P237","section":"performance","insight":"The bipyridyl sites in UiO-67@NN act as proton scavengers, reducing the activation energy (Ea) from 64.0 kJ/mol to 39.4 kJ/mol when sodium formate is added."},{"paperId":"P237","section":"performance","insight":"Optimal Pd loading for Pd/UiO-67@NN was found to be 15 wt%, balancing active site availability and preventing nanoparticle agglomeration."},{"paperId":"P237","section":"performance","insight":"The optimal FA/SF molar ratio is 1:2, as excess SF can occupy active Pd centers and hinder the catalytic cycle."},{"paperId":"P238","section":"synthesis","insight":"The use of biomass carbon promotes Pd dispersion due to its large specific surface area and introduces more defects into the Pd-CeO2/C heterostructure."},{"paperId":"P238","section":"synthesis","insight":"Different CeO2 morphologies (spheres, rods, octahedrons) result in different preferential crystal facets ((1 1 0), (1 0 0), and (1 1 1) respectively), which significantly impact catalytic activity and hydrophilicity."},{"paperId":"P238","section":"characterization","insight":"The introduction of biomass carbon promotes Pd dispersion and increases the concentration of oxygen vacancies in Pd-CeO2 heterostructures."},{"paperId":"P238","section":"characterization","insight":"CeO2 morphology significantly influences the exposed crystal facets: sCeO2 (110), rCeO2 (100)/(111), and oCeO2 (111)."},{"paperId":"P238","section":"characterization","insight":"The CeO2(110) facet combined with high oxygen vacancy concentration facilitates electron transfer to Pd, creating electron-rich active sites that promote C-H bond cleavage of formate intermediates."},{"paperId":"P238","section":"characterization","insight":"Hydrophilicity is facet-dependent, with the (110) facet being more hydrophilic than the (111) facet, enhancing performance in liquid-phase formic acid dehydrogenation."},{"paperId":"P238","section":"performance","insight":"The morphology of CeO2 significantly affects the FA dehydrogenation performance, with sCeO2 (spheres) providing the best activity due to its preferential orientation of the (1 1 0) facet and higher concentration of oxygen vacancies."},{"paperId":"P238","section":"performance","insight":"Combining Pd-CeO2 heterostructures with biomass carbon improves Pd dispersion and increases defect density, leading to lower activation energy and higher TOF compared to Pd/C or Pd-CeO2 alone."},{"paperId":"P238","section":"performance","insight":"The reaction follows a formate pathway (HCOOH -> HCOO* -> CO2 + H2) over the Pd-sCeO2/C catalyst."},{"paperId":"P239","section":"synthesis","insight":"The amidoxime and cyano groups on the AOP AN beads are critical for stabilizing and distributing Pd-based nanoparticles."},{"paperId":"P239","section":"synthesis","insight":"Introduction of Ni inhibits the agglomeration of Pd particles, reducing particle size from 7-40 nm (Pd/AOP AN) to 4-16 nm (PdNi6/AOP AN)."},{"paperId":"P239","section":"characterization","insight":"The introduction of Ni effectively inhibits the agglomeration of Pd particles, reducing their size from 7-40 nm to 4-16 nm."},{"paperId":"P239","section":"characterization","insight":"FTIR spectra indicate a strong interaction between amidoxime groups and Pd-based NPs, evidenced by shifts in C=N (to 1678 cm-1) and N-O (to 939 cm-1) bands."},{"paperId":"P239","section":"characterization","insight":"The lack of distinct metal peaks in XRD patterns suggests that the nanoparticles are very small and highly dispersed on the polymer support."},{"paperId":"P239","section":"performance","insight":"The addition of Ni significantly enhances the TOF, with an optimal Pd:Ni ratio of 1:6."},{"paperId":"P239","section":"performance","insight":"AOP AN beads provide a basic environment and strong coordination sites that stabilize nanoparticles and promote FA activation."},{"paperId":"P240","section":"characterization","insight":"The ZIF-67 crystallinity is preserved after the combination with NiMo NPs and SiO2 spheres."},{"paperId":"P240","section":"characterization","insight":"BET analysis shows that the surface area of NiMo/ZIF-67@SiO2 (917 m2/g) is lower than pristine ZIF-67 (1,451 m2/g) due to coverage by NiMo NPs and SiO2."},{"paperId":"P240","section":"characterization","insight":"TGA indicates MOF skeleton breakdown occurs between 500 and 600 °C."},{"paperId":"P240","section":"performance","insight":"The catalytic activity of NixMo1/C0x/ZIF-67@SiO2 yolk-shell increased with the Ni addition ratio, peaking at a Ni/Mo molar ratio of 0.8/0.2."},{"paperId":"P240","section":"performance","insight":"The apparent activation energy (Ea) for FA dehydrogenation over Ni0.8Mo0.2/ZIF-67@SiO2 was estimated to be 32.67 kJ/mol."},{"paperId":"P241","section":"synthesis","insight":"The use of a solvothermal method with DMF as both solvent and reductant allows for the synthesis of PtNi alloy nanoparticles before loading onto the support."},{"paperId":"P241","section":"synthesis","insight":"Strong metal-support interaction (SMSI) is induced by thermal treatment in nitrogen, specifically at 600 °C, leading to TiB2 overlayers encapsulating the PtNi NPs."},{"paperId":"P241","section":"characterization","insight":"Strong metal-support interaction (SMSI) is induced by thermal treatment in N2, leading to the encapsulation of PtNi nanoparticles by a TiB2 overlayer."},{"paperId":"P241","section":"characterization","insight":"The active sites for formic acid dehydrogenation are located on the TiB2 surfaces of the encapsulating layer rather than directly on the metal sites."},{"paperId":"P241","section":"characterization","insight":"Alloying Pt with Ni induces lattice contraction and magnetic interactions that enhance electron transfer and strengthen the SMSI effect."},{"paperId":"P241","section":"characterization","insight":"Optimal calcination temperature for maximizing catalytic activity is 600 °C; higher temperatures (800 °C) lead to nanoparticle agglomeration and excessive overlayer thickness, reducing active sites."},{"paperId":"P241","section":"performance","insight":"The Pt3Ni8/TiB2 catalyst exhibits a synergistic effect between the alloy and the TiB2 support via SMSI, where TiB2 overlayers encapsulate the nanoparticles and act as active sites."},{"paperId":"P241","section":"performance","insight":"Lattice contraction in the Pt3Ni8 alloy enhances electron transfer and strengthens the SMSI effect."},{"paperId":"P241","section":"performance","insight":"The optimal calcination temperature for maximizing activity is 600 °C; higher temperatures lead to nanoparticle agglomeration and excessive encapsulation layer thickness, reducing active sites."}],"missingInfo":[{"paperId":"P001","catalystId":"P001_PERF_001","catalyst":"Pt nanoclusters on 1D GaN nanowires","category":"missing_synthesis_info","missingItem":"drying temperature"},{"paperId":"P001","catalystId":"P001_PERF_001","catalyst":"Pt nanoclusters on 1D GaN nanowires","category":"missing_synthesis_info","missingItem":"drying duration"},{"paperId":"P002","catalystId":"P002_PERF_001","catalyst":"3D 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