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Feeble Single-Atom Pd Catalysts for H2 Production from Formic Acid.
Esmail Doustkhah1,2,3, Nao Tsunoji4, Shinya Mine5
1Research Center for Materials Nanoarchitechtonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
ACS Applied Materials & Interfaces
|January 19, 2024
Summary
Single palladium atoms (PdSA) on amine-functionalized silica show high activity for H2 generation from formic acid, but their aggregation enhances yield. Loose Pd-N binding boosts catalysis, unlike strong Pd-S binding in thiol-based catalysts.
Area of Science:
- Heterogeneous Catalysis
- Materials Science
- Surface Chemistry
Background:
- Single-atom catalysts (SACs) represent a frontier in catalysis, but their efficacy requires rigorous validation for specific reactions.
- Formic acid is a promising hydrogen carrier for H2 generation, necessitating efficient catalytic systems.
Purpose of the Study:
- To investigate the catalytic performance and stability of single palladium atoms (PdSA) supported on different silica substrates for H2 generation from formic acid.
- To elucidate the structure-activity relationships governing PdSA catalysis on amine- and thiol-functionalized silica.
Main Methods:
- Synthesis of PdSA catalysts on mesoporous silica functionalized with amine, thiol, and dithiocarbamate groups.
- Evaluation of catalytic activity and stability for H2 generation from formic acid.
- Characterization using density functional theory (DFT) calculations to probe electronic structure and binding interactions.
Main Results:
- PdSA on amino-functionalized silica (SiO2-NH2/PdSA) exhibited significantly higher catalytic activity compared to thiol-based catalysts (SiO2-S-PdSA and SiO2-NHCS2-PdSA).
- SiO2-NH2/PdSA showed the lowest single-atom stability, with Pd aggregation paradoxically boosting the reaction yield.
- DFT calculations revealed loose Pd-N binding in SiO2-NH2/PdSA, preserving labile Pd 4d electrons near the Fermi level, while strong Pd-S binding in thiol-based catalysts lowered catalytic activity.
Conclusions:
- The catalytic activity of PdSA is strongly dependent on the nature of the support's functional groups.
- Loose binding interactions, as observed with amine groups, can enhance catalytic activity but compromise single-atom stability, leading to aggregation-induced yield improvements.
- Understanding these binding effects is crucial for designing highly active and stable single-atom catalysts.
Keywords:
Pd DOSPd nanoclustercatalyst reconstructiondensity functional theory (DFT)ligand−metal charge transfermetal−support interactionsilica-supported Pdsingle-atom catalysis (SAC)More Related Videos
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