Designing highly active and cost‐effective electrocatalysts for the alkaline hydrogen oxidation reaction (HOR) is critical for advancing anion‐exchange membrane fuel cells (AEMFCs). While dilute metal alloys have demonstrated substantial potential in enhancing alkaline HOR performance, there has been limited exploration in terms of rational design, controllable synthesis, and mechanism study. Herein, we developed a series of dilute Pd‐Ni alloys, denoted as x% Pd‐Ni, based on a trace‐Pd decorated Ni‐based coordination polymer through a facile low‐temperature pyrolysis approach. The x% Pd‐Ni alloys exhibit efficient electrocatalytic activity for HOR in alkaline media. Notably, the optimal 0.5% Pd‐Ni catalyst demonstrates high intrinsic activity with an exchange current density of 0.055 mA cm‐2, surpassing that of many other alkaline HOR catalysts. The mechanism study reveals that the strong synergy between Pd single atoms (SAs)/Pd dimer and Ni substrate can modulate the binding strength of proton (H)/hydroxyl (OH), thereby significantly reducing the activation energy barrier of a decisive reaction step. This work offers new insights into designing advanced dilute metal or single‐atom‐alloys (SAAs) for alkaline HOR and potentially other energy conversion processes.

中文翻译：

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低温热解稀释 Pd-Ni 合金增强电催化氢氧化


设计用于碱性氢氧化反应（HOR）的高活性且经济高效的电催化剂对于推进阴离子交换膜燃料电池（AEMFC）至关重要。虽然稀金属合金在增强碱性 HOR 性能方面表现出巨大潜力，但在合理设计、可控合成和机理研究方面的探索有限。在此，我们通过简便的低温热解方法，基于痕量钯装饰的镍基配位聚合物，开发了一系列稀钯镍合金，表示为 x% Pd-Ni。 x% Pd-Ni 合金在碱性介质中对 HOR 表现出高效的电催化活性。值得注意的是，最佳的 0.5% Pd-Ni 催化剂表现出高固有活性，交换电流密度为 0.055 mA cm-2，超过了许多其他碱性 HOR 催化剂。机理研究表明，Pd单原子（SAs）/Pd二聚体与Ni底物之间的强协同作用可以调节质子（H）/羟基（OH）的结合强度，从而显着降低关键反应步骤的活化能垒。这项工作为设计用于碱性 HOR 和其他潜在能量转换过程的先进稀金属或单原子合金 (SAA) 提供了新的见解。