用于高效催化碱性析氢的银掺杂Ni4Mo/MoO2异质结构催化剂

doi:10.1016/j.actphy.2026.100413

摘要/Abstract

摘要： 开发高效且稳定的电催化剂是碱性析氢反应(HER)面临的关键挑战。本研究提出了一种Ag掺杂的Ni₄Mo/MoO₂异质结构，旨在实现高效催化碱性HER。金属Ag会诱导强烈的电子调控，从而引起Ni和Mo位点的价电子云偏移及局部电子密度的重新分布。密度泛函理论(DFT)计算证实，Ag的掺入有效降低了金属活性位点的d带中心。d带中心的降低削弱了金属位点与界面水分子之间的p-d轨道杂化，从而增加了弱氢键K⁺水合水(K·H₂O)的比例。此外，Ni位点上的电子密度调控优化了氢中间体的吸附强度。因此，Ag-Ni₄Mo/MoO_2-x表现出优异的HER活性，在1.0 mol L^-1 KOH溶液中仅需138 mV的过电位即可达到1 A cm^-2的电流密度。我们进一步构建了尿素氧化辅助水电解装置，工作电解质为1.0 mol L^-1 KOH+0.33 mol L^-1尿素，其中HER和尿素氧化反应(UOR)均采用相同的Ag-Ni₄Mo/MoO_2-x电极。该集成电解槽在1.62 V低槽压下实现了1 A cm^-2的电流密度。这种通过金属掺杂实现电子调控策略，为制备用于节能制氢的双功能异质结构电催化剂提供了一条有效途径。

关键词: 分子水吸附, 析氢反应, 掺杂效应, 异质结构, 原位表征

Abstract: Developing efficient and robust electrocatalysts is a key challenge for alkaline hydrogen evolution reaction (HER). This work presents Ag-doped Ni₄Mo/MoO₂ heterostructure toward highperformance alkaline HER. Metallic Ag induces strong electronic modulation, triggering valence electron cloud shift and local electron density redistribution at Ni and Mo sites. Density functional theory (DFT) calculations confirm that Ag incorporation effectively downshifts the d-band center of metallic active sites. The lowered d-band weakens the p-d orbital hybridization between metal sites and interfacial water, thereby increasing the proportion of weakly hydrogen-bond K⁺ hydrated water (K·H₂O). In addition, the tuned electron density of Ni optimizes the adsorption strength of hydrogen intermediates. Accordingly, the AgNi₄Mo/MoO_2-x delivers superior HER activity, requiring only a 138 mV overpotential to reach a current density of 1 A cm^-2 in 1.0 mol L^-1 KOH. We further construct a urea-assisted water electrolysis device with identical Ag-Ni₄Mo/MoO_2-x electrode for both HER and urea oxidation reaction (UOR) in 1.0 mol L^-1 KOH + 0.33 mol L^-1 urea electrolyte. The integrated electrolyzer achieves 1 A cm^-2 at a low cell voltage of 1.62 V. This electronic modulation strategy via metal doping offers a facile route to fabricate bifunctional heterostructure electrocatalysts toward energy-saving hydrogen generation.

Key words: Molecular water adsorption, Hydrogen evolution reaction, Doping effect, Heterostructure, In situ characterization

陈飞龙, 刘淑杰, 孙天宇, 任阿静, 王鸣魁, 申燕. 用于高效催化碱性析氢的银掺杂Ni₄Mo/MoO₂异质结构催化剂[J]. 物理化学学报 2026, (), 100413. doi: 10.1016/j.actphy.2026.100413

Feilong Chen, Shujie Liu, Tianyu Sun, Ajing Ren, Mingkui Wang, Yan Shen. Silver-doped Ni₄Mo/MoO₂ heterostructure as high-performance electrocatalysts toward alkaline hydrogen evolution reaction[J]. Acta Phys. -Chim. Sin. 2026, (), 100413. doi: 10.1016/j.actphy.2026.100413

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2026.100413

https://www.whxb.pku.edu.cn/CN/Y2026/V/I/100413

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用于高效催化碱性析氢的银掺杂Ni₄Mo/MoO₂异质结构催化剂

Silver-doped Ni₄Mo/MoO₂ heterostructure as high-performance electrocatalysts toward alkaline hydrogen evolution reaction

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