催化学报

催化学报 ›› 2027, Vol. 92: 170-181.DOI: 10.1016/S1872-2067(26)65222-9

• 论文 • 上一篇    下一篇

异质原子掺杂与表面工程协同调控普鲁士蓝衍生物的电子结构为高效水裂解

刘玉婵a, 高文婧a,b, 黄沁彤a, 刘晓雄c,*, 欧阳慧欢a, 叶融凯a, 李旻鸶d,*, 胡建强a,*   

  1. a华南理工大学化学与化工学院, 广东省燃料电池技术重点实验室, 广东省功能分子工程重点实验室, 广东广州 510641;
    b河南省科学院智慧创制研究所, 河南郑州 451162;
    c南方科技大学理学院物理系, 广东深圳 518055;
    d宁波工程学院微纳研究院, 浙江宁波 315211
  • 收稿日期:2026-01-12 接受日期:2026-04-21 出版日期:2027-01-18 发布日期:2026-10-30
  • 通讯作者: *电子信箱: jqhusc@scut.edu.cn (胡建强), liuxx@sustech.edu.cn (刘晓雄), tjminsi@nbut.edu.cn (李旻鸶).
  • 基金资助:
    国家自然科学基金(22272058); 国家自然科学基金青年科学基金项目(52502271).

Heteroatom doping and surface engineering co-modulated electronic structure of prussian blue analogs for efficient overall water splitting

Yuchan Liua, Wenjing Gaoa,b, Qintong Huanga, Xiaoxiong Liuc,*, Huihuan Ouyanga, Rongkai Yea, Minsi Lid,*, Jianqiang Hua,*   

  1. aKey Laboratory of Fuel Cell Technology of Guangdong Province, Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, Guangdong, China;
    bInstitute of Intelligent Innovation, Henan Academy of Sciences, Zhengzhou 451162, Henan, China;
    cDepartment of Physics, Southern University of Science and Technology (SUSTech), Shenzhen 518055, Guangdong, China;
    dInstitute of Micro/Nano Materials and Devices, Ningbo University of Technology, Ningbo 315211, Zhejiang, China
  • Received:2026-01-12 Accepted:2026-04-21 Online:2027-01-18 Published:2026-10-30
  • Contact: *E-mail: jqhusc@scut.edu.cn (J. Hu), liuxx@sustech.edu.cn (X. Liu), tjminsi@nbut.edu.cn (M. Li).
  • Supported by:
    National Natural Science Foundation of China (22272058) and the Young Scientists Fund of the National Natural Science Foundation of China (52502271).

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摘要： 氢能作为清洁高效的能源载体, 是实现能源低碳转型的重要途径. 电解水制氢因原料丰富、产物纯度高且过程无碳排放而成为发展潜力大的制氢策略. 然而, 电解水析氢反应(HER)和析氧反应(OER)的动力学缓慢, 通常需高的过电位, 制约了其能量转换效率. 贵金属催化剂(如Pt/C和RuO2)在HER和OER中虽有优异的催化活性, 但其资源稀缺且成本高昂. 因此, 开发高效、稳定且低成本的非贵金属电催化剂具有重要的意义. 普鲁士蓝衍生物(PBAs)因其三维框架结构、可调构型、合成工艺简单以及在电催化分解水领域的应用而被广泛关注. 但其实际应用常受结构不稳和活性位点少等不足的限制.
本文采用杂原子掺杂与表面工程协同的策略, 通过两步水热法在泡沫镍(NF)上原位生长V掺杂的镍铁三金属PBAs前驱体(V-NiFe PBAs/NF), 再经低温磷化成功制备了具有优秀稳定性和催化性能的V-NiFeP PBAs/NF立方体纳米材料(NCs)预催化剂. 利用V, Fe和Ni三金属间的协同效应, 通过优化V-NiFeP PBAs/NF NCs的电子结构和重构其活性羟基氧化物, 该V-NiFeP PBAs/NF NCs预催化剂在碱性电解质溶液中表现出优异的双功能催化活性和稳定性. 在OER测试中, V-NiFeP PBAs/NF NCs预催化剂在100 mA·cm–2电流密度下, 仅需~257 mV的过电位, 比商业RuO2(~443 mV)降低约42%; 其Tafel斜率为~50.43 mV·dec–1, 表明V-NiFeP PBAs/NF NCs具有较快的反应动力学和较低的电荷转移阻力(约1.35 Ω); 其有相对较大的电化学活性面积(对应Cdl约为4.3 mF·cm–2)和暴露更多活性位点, 且在50 mA·cm–2下能稳定运行超500 h, 说明其有很强的电化学活性和高的稳定性. X-射线光电子能谱和X-射线吸收精细结构结果表明, V掺杂优化了V-NiFeP PBAs/NF NCs催化剂中的金属活性位点Ni和Fe的d带中心, 使反应过程中的决速步能垒降低, 从而提升了其OER催化活性. pH依赖实验和化学探针实验表明, V-NiFeP PBAs/NF NCs遵循晶格氧介导机制. 密度泛函理论计算进一步揭示, 与传统的吸附演化机制相比, V掺杂能够改善电化学重构后真实活性物种对含氧中间体的吸附能力, 明显降低速率控制步骤的能垒, 这也是其OER性能优异的原因. 此外, 得益于V-NiFeP PBAs/NF NCs催化剂的独特结构和组成, 该预催化剂在HER中也表现出良好的活性, 在20 mA·cm–2下过电位约为170 mV, 在全水裂解中在10 mA·cm–2电流密度下其可实现约1.59 V的驱动电压.
综上, 本文为理解多元金属磷化物的表面重构提供了实验依据, 揭示了V掺杂与预磷化协同策略可实现催化活性与稳定性兼顾. 该策略有望扩展至Co, Mn等非贵金属体系, 为开发高效稳定的双功能催化剂和高电流密度长寿命水分解催化剂提供设计依据.

关键词: 过渡金属磷化物, 钒掺杂, 表面重构, 氧析出反应, 全水裂解, 晶格氧机制

Abstract: Overall water splitting based on Prussian blue analogues (PBAs) electrocatalysts has attracted increasing attention due to its tunable structures, facile synthesis, reducing costs and promoting green energy applications. However, it is usually hindered by structural instability and limited active sites of electrocatalysts. Herein, we have constructed vanadium-doped and surface-phosphated NiFeP PBAs/Ni foam (V-NiFeP PBAs/NF) nanocubes (NCs) with excellent stability and catalytic performance by heteroatom doping and surface engineering strategy. Benefiting from optimized electronic structures and reconstructed active oxyhydroxides, the V-NiFeP PBAs/NF NCs as pre-catalysts exhibited exceptional oxygen evolution reaction (OER) activity in alkaline media (~257 mV at 100 mA·cm–2), which was ~42% lower than commercial RuO2 (~443 mV) and excellent stability (500 h at 50 mA·cm–2). Experimental and theoretical results indicated that the V-doping of the V-NiFeP PBAs/NF NCs could effectively modulate its electronic configuration by upward-shifting d-band center of Ni and Fe, thereby increasing its conductivity and active sites. The V-NiFeP PBAs/NF NCs had lower reaction energy barrier for lattice oxygen mechanism pathway than that for adsorption evolution mechanism pathway. The V-NiFeP PBAs/NF NCs had excellent hydrogen evolution (~170 mV at 20 mA·cm–2) and overall water splitting performance (~1.59 V at 10 mA·cm–2). This work provides a synthetic paradigm for in-situ growth of surface-engineered PBAs on conductive substrates and offers fundamental insights for designing high-performance OER catalysts.

Key words: Transition metal phosphide, V-doping, Surface reconstruction, Oxygen evolution reaction, Overall water splitting, Lattice oxygen mechanism