Anion‐exchange membrane fuel cells provide the possibility to use platinum group metal‐free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel‐tungsten (Ni‐W) alloy catalysts, we show that the Ni:W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen‐bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state‐of‐the‐art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next‐generation catalysts for fuel cells.

中文翻译：

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揭示镍钨合金在碱性电解质中高效氢氧化催化的化学计量效应

阴离子交换膜燃料电池提供了使用无铂族金属催化剂的可能性，但阳极氢氧化反应（HOR）动力学缓慢，其来源仍存在争议。在这里，通过镍钨 (Ni-W) 合金催化剂，我们发现 Ni:W 比例极大地影响了碱性电解液中的 HOR 性能。实验和理论研究表明，与 W 形成合金可以调节 Ni 中的不成对电子，调整零电荷电位和催化表面以有利于羟基吸附 (OHad)。 OHad 物种与钾 (K+) 离子协同相互作用，打破 K+ 溶剂化鞘层，留下自由水分子，从而改善氢键网络的连通性。因此，最佳的 Ni17W3 合金表现出优于最先进的铂碳 (Pt/C) 催化剂的碱性 HOR 活性，并且在 10,000 次循环后稳定运行，衰减可忽略不计。我们的研究结果提供了对合金 HOR 催化剂的新认识，并将指导下一代燃料电池催化剂的合理设计。