物理化学学报

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磷化钴电子结构调控以增强其酸性析氢反应活性与稳定性

王子昊1,2, 张诗清1,2, 马绍凯1,2, 曹子航1,2, 刘芳1,2, 李英1, 徐学文1,2, 马原辉1,2, 唐成春1,2, 薛彦明1,2, 张军1,2   

  1. 1 河北工业大学材料科学与工程学院, 天津 300130;
    2 河北省微纳氮化硼材料重点实验室, 天津 300130
  • 收稿日期:2026-05-06 修回日期:2026-06-21 录用日期:2026-07-08
  • 通讯作者: 张军, 唐成春 E-mail:zhang.jun@hebut.edu.cn;tangcc@hebut.edu.cn
  • 基金资助:
    该项目得到了河北省自然科学基金(E2024202067和E2021202121)、河北省青年拔尖人才计划以及河北省科技计划(22567602H)的支持

Electronic structure modification of CoP for enhanced acidic hydrogen evolution activity and stability

Zihao Wang1,2, Shiqing Zhang1,2, Shaokai Ma1,2, Zihang Cao1,2, Fang Liu1,2, Ying Li1, Xuewen Xu1,2, Yuanhui Ma1,2, Chengchun Tang1,2, Yanming Xue1,2, Jun Zhang1,2   

  1. 1 School of Material Science and Engineering, Hebei University of Technology, Tianjin 300130, China;
    2 Hebei Key Laboratory of Boron Nitride Micro and Nano Materials, Tianjin 300130, China
  • Received:2026-05-06 Revised:2026-06-21 Accepted:2026-07-08
  • Contact: Jun Zhang, Chengchun Tang E-mail:zhang.jun@hebut.edu.cn;tangcc@hebut.edu.cn

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摘要： 全球能源体系正逐步向可持续能源转型，开发适用于酸性环境、高效且长寿命的析氢反应(HER)电催化剂，是实现规模化制氢的关键。尽管铂基催化剂具有优异的析氢反应活性，但其稀缺性和高昂成本严重限制了其在质子交换膜(PEM)水电解制氢中的大规模应用。因此，近年来大量研究致力于开发储量丰富的替代型催化剂。其中，磷化钴(CoP)凭借其良好的电子导电性和较高的本征催化活性，已成为最具潜力的非贵金属催化剂之一。然而，在酸性介质中实现高活性与长期稳定性的协同提升仍面临巨大挑战。特别是，CoP较弱的氢吸附能力限制了反应动力学过程，而苛刻的酸性环境以及强还原性的工作条件会导致活性金属中心发生过度还原和结构退化，从而引起显著的活性-稳定性权衡问题。因此，开发有效策略调控CoP的电子结构并克服这一根本性限制，对于推动基础科学研究和实际技术应用均具有重要意义。本文采用铋(Bi)掺杂策略对磷化钴进行电子结构调控，以此提升其酸性析氢性能。最优组分的Bi-CoP/CC催化剂析氢活性大幅提升：在电流密度为10 mAcm-2时，过电位仅为83 mV，塔菲尔斜率低至33 mV dec-1，性能优于纯相磷化钴。同时该催化剂的稳定性也得到显著改善，连续运行140 h后，性能衰减仅4 mV。实验表征结合密度泛函理论(DFT)计算结果表明：铋掺杂会提升钴的价态、降低磷的价态，进而强化d-p轨道杂化效应，优化氢吸附动力学过程，并增强金属-配体键合作用，最终实现催化活性与稳定性的同步提升。以Bi-CoP/CC为阴极、负载二氧化铱的铂钛毡为阳极，组装质子交换膜电解槽进行测试：在电流密度500 mA cm-2、温度60℃条件下，槽电压为1.683 V，且可稳定运行超过140 h。这些结果表明，Bi工程化策略在接近工业实际运行条件下具有良好的应用潜力。更重要的是，本工作建立了电子结构调控与催化活性及耐久性协同提升之间的明确关联。本研究为解决酸性体系下磷化钴基析氢催化剂活性-稳定性制衡难题提供了新思路，该改性策略同样可拓展至其他非贵金属过渡金属化合物，为研发高性能质子交换膜电解槽提供了普适性参考。

关键词: d-p轨道杂化, 磷化钴, 掺杂, 酸性析氢反应, 活性与稳定性

Abstract: With the global transition toward sustainable energy, the development of efficient and durable electrocatalysts for the hydrogen evolution reaction (HER) under acidic conditions is essential for practical hydrogen production. Although platinum-based catalysts exhibit outstanding HER activity, their scarcity and high cost severely hinder large-scale deployment in proton exchange membrane (PEM) water electrolysis. As a result, considerable efforts have been devoted to developing earth-abundant alternatives. Among them, cobalt phosphide (CoP) has emerged as one of the most promising non-noble-metal catalysts owing to its favorable electrical conductivity and intrinsic catalytic activity. However, achieving simultaneously high activity and long-term durability in acidic media remains a major challenge. In particular, the insufficient hydrogen adsorption capability of CoP limits reaction kinetics, while the harsh acidic and strongly reductive operating environment can induce excessive reduction and structural degradation of active metal centers, resulting in a pronounced activity-stability trade-off. Therefore, developing effective strategies to regulate the electronic structure of CoP and overcome this fundamental limitation is of great scientific and technological significance. Herein, bismuth (Bi) doping is selectively introduced as an effective strategy to modulate the electronic structure of CoP for enhanced acidic hydrogen evolution. The resulting optimal Bi-CoP/CC catalyst exhibits significantly improved HER activity, delivering an overpotential of 83 mV at 10 mA cm-2 and a small Tafel slope of 33 mV dec-1, outperforming pristine CoP. Moreover, it exhibits remarkably improved catalytic stability, with only a 4 mV loss in performance after 140 h of continuous operation. Experimental results and further density functional theory (DFT) calculations reveal that Bi doping increases the Co oxidation state while decreasing the P valence, which strengthens Co-P d-p orbital hybridization, optimizes hydrogen adsorption kinetics, and reinforces metal-ligand bonding, thereby accounting for the enhanced activity and stability. Furthermore, a proton exchange membrane water (PEM) electrolyzer assembled with Bi-CoP/CC as the cathode and IrO2 supported on Pt-Ti felt as the anode exhibits a cell voltage of 1.683 V at 500 mA cm-2 and maintains stable operation for over 140 h at 60 ℃. These results demonstrate the practical applicability of the Bi-engineering strategy under industrially relevant operating conditions. More importantly, this work establishes a clear correlation between electronic structure regulation and the simultaneous enhancement of catalytic activity and durability. Our findings provide valuable guidance for overcoming the activity-stability trade-off in acidic CoP HER electrocatalysts and can be extended to other non-precious transition-metal compounds, offering a general strategy for the development of high-performance PEM electrolyzers.

Key words: d-p orbital hybridization, Cobalt phosphide, Doping, Acidic hydrogen evolution reaction, Activity and stability