Cationic Vacancy Modulates Co Spin State in CoP for pH-Universal and Seawater Hydrogen Evolution

IF 4.5 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters Pub Date : 2026-10-09 DOI:10.1021/acs.jpclett.6c02680

Beibei Shi,Guangyao Li,Mei Yang,Kai Tang,Liangjie Fu,Aidong Tang

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引用次数: 0

Abstract

Abstract Precisely controlling cationic vacancy concentration to tune the spin configuration of metal sites remains a challenge for designing high-performance hydrogen evolution reaction (HER) electrocatalysts. Here, we demonstrated a density functional theory-guided strategy to programmatically engineer cationic vacancies in cobalt phosphide (CoP), enabling targeted modulation of the Co spin state. Theoretical screening identified 8.33% cation vacancies as optimal, which rearranged the unpaired 3d electrons of adjacent Co atoms, lowered the Co magnetic moment to 0.944 μB, and achieved near-thermoneutral hydrogen adsorption free energy (ΔGH* = 0.027 eV). Guided by this prediction, we synthesized CoP-V-0.5 with experimentally determined vacancy concentrations of 10.1% (bulk, ICP-OES) and 7.07% (surface, XPS), which closely approximated the theoretical optimum (8.33%) and validated the DFT-guided design. The optimized catalysts exhibited outstanding HER activity, requiring only 94, 116, and 106 mV to achieve 100 mA cm–2 in 1.0 M KOH, 0.5 M H2SO4, and 1.0 M PBS, respectively, and operated stably for 50 h in alkaline seawater. This work established a theory-guided, spin-mediated paradigm for defect engineering in electrocatalysis.

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阳离子空位调节CoP中Co自旋态对ph - universal和海水析氢的影响

精确控制阳离子空位浓度以调整金属位的自旋构型仍然是设计高性能析氢反应（HER）电催化剂的挑战。在这里，我们展示了一种密度泛函理论指导的策略，可以编程地设计磷化钴（CoP）中的阳离子空位，从而实现Co自旋态的靶向调制。理论筛选发现8.33%的阳离子空位最优，使相邻Co原子未配对的三维电子重排，使Co磁矩降至0.944 μB，获得近热中性氢吸附自由能（ΔGH* = 0.027 eV）。在此预测的指导下，我们合成了co - v -0.5，实验确定的空位浓度为10.1%（体积，ICP-OES）和7.07%（表面，XPS），接近理论最优（8.33%），验证了dft指导设计。优化后的催化剂表现出优异的HER活性，在1.0 M KOH、0.5 M H2SO4和1.0 M PBS条件下，分别仅需94、116和106 mV即可达到100 mA cm-2，并在碱性海水中稳定运行50 h。这项工作为电催化缺陷工程建立了一个理论指导、自旋介导的范式。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

The Journal of Physical Chemistry Letters CHEMISTRY, PHYSICAL-NANOSCIENCE & NANOTECHNOLOGY

CiteScore

9.60

自引率

7.00%

发文量

1519

审稿时长

1.6 months

期刊介绍： The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.