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Stabilizing Low-Valence Single Atoms by Constructing Metalloid Tungsten Carbide Supports for Efficient Hydrogen Oxidation and Evolution |
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| Authors: | Luqi Wang Zipeng Xu Chun-Han Kuo Jian Peng Prof Feng Hu Prof Linlin Li Prof Han-Yi Chen Prof Jiazhao Wang Prof Shengjie Peng |
| Institution: | 1. College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016 China
Contribution: Conceptualization (lead), Data curation (lead), Writing - original draft (lead);2. College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016 China Contribution: Formal analysis (equal), Investigation (equal);3. Department of Materials Science and Engineering, National Tsing Hua University Hsinchu 30013 (Taiwan) Contribution: Formal analysis (supporting);4. Institute for Superconducting and Electronic Materials Australian Institute for Innovative Materials, University of Wollongong Innovation Campus, Squires Way, North Wollongong, NSW2522 Australia Contribution: Formal analysis (supporting);5. College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016 China Contribution: Funding acquisition (supporting);6. College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016 China Contribution: Funding acquisition (supporting), Investigation (supporting);7. Department of Materials Science and Engineering, National Tsing Hua University Hsinchu 30013 (Taiwan) Contribution: Project administration (supporting);8. Institute for Superconducting and Electronic Materials Australian Institute for Innovative Materials, University of Wollongong Innovation Campus, Squires Way, North Wollongong, NSW2522 Australia Contribution: Formal analysis (supporting), Writing - review & editing (supporting);9. College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016 China |
| Abstract: | Designing novel single-atom catalysts (SACs) supports to modulate the electronic structure is crucial to optimize the catalytic activity, but rather challenging. Herein, a general strategy is proposed to utilize the metalloid properties of supports to trap and stabilize single-atoms with low-valence states. A series of single-atoms supported on the surface of tungsten carbide (M-WCx, M=Ru, Ir, Pd) are rationally developed through a facile pyrolysis method. Benefiting from the metalloid properties of WCx, the single-atoms exhibit weak coordination with surface W and C atoms, resulting in the formation of low-valence active centers similar to metals. The unique metal-metal interaction effectively stabilizes the low-valence single atoms on the WCx surface and improves the electronic orbital energy level distribution of the active sites. As expected, the representative Ru-WCx exhibits superior mass activities of 7.84 and 62.52 A mgRu−1 for the hydrogen oxidation and evolution reactions (HOR/HER), respectively. In-depth mechanistic analysis demonstrates that an ideal dual-sites cooperative mechanism achieves a suitable adsorption balance of Had and OHad, resulting in an energetically favorable Volmer step. This work offers new guidance for the precise construction of highly active SACs. |
| Keywords: | Hydrogen Evolution Reaction Hydrogen Oxidation Reaction Low-Valence Metal Carbides Single-Atom Catalysts |