A number of non‐noble catalysts are developed for hydrogen production via acidic water electrolysis. Nevertheless, for the more economical alkaline hydrogen generation, the restricted kinetics of the water dissociation Volmer step along with its following proton recombination Tafel step for these non‐noble electrocatalysts generally lead to sluggish hydrogen‐production process. Here, a facile method is designed to nest nanometric Ni₅P₄ clusters on NiCo₂O₄ (achieving Ni₅P₄@NiCo₂O₄) by a phosphating process of NiO clusters on NiCo₂O₄. Acting as a high‐efficiency electrode for alkaline water electrolysis, the Ni₅P₄@NiCo₂O₄ can efficiently and preferentially convert H₂O to H₂ with a low overpotential of 27 mV at 10 mA cm⁻² and the Tafel slope of 27 mV dec⁻¹, which are comparable to the results for platinum and superior than those of the state‐of‐the‐art platinum‐free electrocatalysts. Density functional theory calculations confirm that NiCo₂O₄ species exhibit a higher ability to electrolyze water into H* intermediate and then Ni₅P₄ clusters facilitate the subsequent desorption of the H₂ products. Profiting from the promoted kinetic steps, the Ni₅P₄@NiCo₂O₄ electrocatalyst is promising for scalable alkaline hydrogen production.

中文翻译：

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嵌套在NiCo2O4上的纳米Ni5P4团簇，可通过碱性水电解有效地制氢

已开发出许多用于通过酸性水电解制氢的非贵金属催化剂。然而，对于更经济的碱性氢生成，这些非贵金属电催化剂的水离解沃尔默步骤及其随后的质子重组塔菲尔步骤受限的动力学通常会导致氢生成过程缓慢。在这里，一个浅显的方法被设计为巢纳米的Ni ₅ P ₄簇上镍钴₂ ø ₄（达到的Ni ₅ P ₄ @NiCo ₂ ö ₄）通过的NiO簇的磷化工艺上镍钴₂ ö ₄。充当用于碱性电解水的高效率的电极，将Ni ₅ P ₄ @NiCo ₂ ø ₄能够高效且优先地转换ħ ₂到H 2 O ₂具有低的超电势27毫伏在10mA厘米^-2和塔菲尔斜率27 mV dec ^-1的电导率与铂的结果相当，并且优于最新的无铂电催化剂。密度泛函理论计算证实，NiCo ₂ O ₄种类具有更高的将水电解成H *中间体和Ni ₅ P _{4的能力。}团簇促进H ₂产物的随后解吸。Ni ₅ P ₄ @NiCo ₂ O ₄电催化剂得益于促进的动力学步骤，有望用于可扩展的碱性氢生产。