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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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Stabilizing Low-Valence Single Atoms by Constructing Metalloid Tungsten Carbide Supports for Efficient Hydrogen Oxidation and Evolution

Luqi Wang, Zipeng Xu, Chun-Han Kuo, Jian Peng, Feng Hu, Linlin Li, Han-Yi Chen, Jiazhao WangShengjie Peng
Angewandte Chemie - International Edition, 卷.62(42), e202311937
10/2023

摘要

Hydrogen Evolution Reaction Hydrogen Oxidation Reaction Low-Valence Metal Carbides Single-Atom Catalysts Catalysis Chemistry (all)
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-WC x , M=Ru, Ir, Pd) are rationally developed through a facile pyrolysis method. Benefiting from the metalloid properties of WC x , 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 WC x surface and improves the electronic orbital energy level distribution of the active sites. As expected, the representative Ru-WC x exhibits superior mass activities of 7.84 and 62.52 A mg Ru −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 H ad and OH ad , resulting in an energetically favorable Volmer step. This work offers new guidance for the precise construction of highly active SACs.

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https://doi.org/10.1002/anie.202311937檢視
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