Mirror‐Symmetric Nanoarray Networks of Atomic Ni‐Incorporated Tungsten Oxynitride for Efficient and Robust Alkaline Hydrogen Evolution

作者：Hongchuan Fu, Yucheng Wu, Li Wang, Ze Qin, Liyu Chen, Yingwei Li, Kui Shen · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202518043 · 被引用次数：14 · 研究领域：Electrocatalysts for Energy Conversion、Ammonia Synthesis and Nitrogen Reduction、Metalloenzymes and iron-sulfur proteins

Abstract The development of alkali‐efficient hydrogen evolution reaction (HER) electrocatalysts is essential for future deployment of anion‐exchange membrane water electrolysis technology. Herein, we report a novel heteroatom‐induced strategy to construct the mirror‐symmetric nanoarray networks of Ni‐doped WO 3 on carbon cloth and design a corresponding new type of atomic Ni‐incorporated tungsten oxynitride (Ni‐WNO) electrocatalyst for alkaline HER. Impressively, the Ni‐WNO shows high activity (−35 mV at −10 mA cm −2 ), small Tafel slope (32 mV dec −1 ) and excellent stability (>1200 h at −1.0 A cm −2 ), representing the best‐performing W‐based electrocatalyst for alkaline HER. Multiple spectroscopy characterizations reveal that Ni‐WNO is highly active for adsorbing aggressive OH − /H 2 O groups, resulting in the in situ formation of lattice hydroxyl (i.e., W−OH) species with Brønsted acidity, which, we disclose for the first time, can serve as a mediator to alter the generation of metal−H intermediates from a conventional sequential to a concerted proton−electron transfer (CPET) pathway, thus breaking the pH‐dependent limitations in proton‐deficient alkalies. Further isotope experiments demonstrate that the surface‐mediated H−H coupling can be feasibly accelerated on atomic W−Ni units, thereby enabling Ni‐WNO catalyzing alkaline HER via a new kinetically fast CPET–Tafel pathway.