催化学报

催化学报

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镍位点局域原子环境调控用于工业级海水制氢

武鹏飞a, 娄志昊a, 马元硕a, 王鹏飞a, 薛达a, 马方怡a, 崔学晶a, 刘光波a,*, 周新b,c,*, 王二东d, 姜鲁华a,*   

  1. a青岛科技大学材料科学与工程学院, 山东青岛 266042;
    b辽宁师范大学化学与生物学交叉研究中心, 辽宁大连 116029;
    c大连大学环境与化学工程学院, 辽宁大连 116622;
    d中国科学院大连化学物理研究所, 大连清洁能源国家实验室, 辽宁大连 116023
  • 收稿日期:2025-12-02 接受日期:2025-12-02
  • 通讯作者: *电子信箱: liugb@qust.edu.cn (刘光波), xzhou@lnnu.edu.cn (周新), luhuajiang@qust.edu.cn (姜鲁华).
  • 基金资助:
    国家自然科学基金(22279069, 22478211, 22372017).

Local-atomic environment engineering of Ni-sites for industrial hydrogen production from seawater

Pengfei Wua, Zhihao Loua, Yuanshuo Maa, Pengfei Wanga, Da Xuea, Fangyi Maa, Xuejing Cuia, Guangbo Liua,*, Xin Zhoub,c,*, Erdong Wangd, Luhua Jianga,*   

  1. aCollege of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China;
    bInterdisciplinary Research Center for Biology and Chemistry, Liaoning Normal University, Dalian 116029, Liaoning, China;
    cCollege of Environment and Chemical Engineering, Dalian University, Dalian 116622, Liaoning, China;
    dDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
  • Received:2025-12-02 Accepted:2025-12-02
  • Contact: *E-mail: liugb@qust.edu.cn (G. Liu), xzhou@lnnu.edu.cn (X. Zhou), luhuajiang@qust.edu.cn (L. Jiang).
  • Supported by:
    Natural Science Foundation of China (22279069, 22478211, 22372017).

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摘要： 氢能是未来清洁能源体系中的关键载体, 对实现碳中和目标具有重要意义. 海水电解与可再生能源相结合, 是绿色可持续的制氢途径, 但其实际应用严重受限于低成本、高活性和可扩展电极的缺乏. 镍基催化剂是碱性/中性析氢反应(HER)的潜力材料, 但其活性受到强氢吸附与缓慢水解离动力学的限制. 研究表明, 构建异质结构界面可通过调控Ni的原子与电子结构来提升其HER活性. 然而, Ni位点的局部原子环境与其催化性能之间的构效关系尚不明确. 因此, 有必要通过精确设计具有不同Ni位点微环境的催化剂, 从原子层面阐明其内在的结构-活性关联, 以推动实际应用.
本文设计合成了多种Ni/VOx催化剂, 利用不同价态的V实现了对Ni局部环境的调控, 从而助于阐明Ni位点局域环境与HER活性之间的相关性. 结果表明, Ni价态与氢吸附自由能(∆GH*)和零电荷电势(PZC)之间存在火山型关系, 其中∆GH*和PZC均与HER活性呈线性相关. 原位傅里变换红外光谱(FTIR)证实, 较低的PZC有利于电极表面附近更多自由水分子的形成, 从而促进了HER过程. 理论研究结果表明, V2O3修饰可降低H*的强吸附能, 同时增强中间体OH*的稳定性, 从而加速水解离, 提高Ni的HER活性. 此外, V2O3的引入在Ni位点附件形成高OH‒覆盖度, 进而有效阻止Cl‒腐蚀, 增强长期耐久性. 实验结果显示, Ni/V2O3电极具有最优的Ni位点局部原子环境(Ni-O配位数0.6, Ni价态+0.21)使其在碱性海水中表现出优异的HER活性, 在283/361 mV的过电位下, 达到500/1000 mAcm‒2的电流密度. 同时, 该Ni/V2O3电极面积可扩大至50 cm2, 以此组装的千瓦级碱性海水电解槽能够在25 A的超高电流下连续运行长达880 h, 衰减率只有34.1 μV h-1, 展现出极佳的工业应用潜力. 此外, 经济性分析表明, 该电解槽的能耗仅有48.67 kWh kg-1 H2, 对应每公斤氢气的生产成本仅为2.48美元, 低于欧盟委员会制定的2030年产氢成本目标(2.50美元).
综上, 本文提出了一种合理设计非贵金属Ni基催化剂的方法, 明确了其HER反应机理, 并开展了面向工业制氢的探索性实验. 结果表明, 该方法具备良好的工业应用潜力, 实现了从基础研究向实际应用的有效推进. 这不仅为满足日益增长的氢气需求提供了新的可能, 也为后续高效催化剂的设计与应用提供了有益借鉴.

关键词: 局部原子环境, 镍位点, 析氢反应, 界面水, 零电荷电位

Abstract: Seawater electrolysis integrated with renewable energy sources represents a green and sustainable pathway for hydrogen production, yet its practical application is severely constrained by the lack of cost-effective, highly active, and scalable electrodes. Herein, we report the construction of a high-performance hydrogen evolution reaction (HER) electrode by engineering the local-atomic environment of Ni sites through vanadium oxide modification. This optimized electrode delivers current densities of 500/1000 mA cm-2 at only 283/361 mV in alkaline seawater. Impressively, a kW-scale alkaline seawater electrolyzer achieves continuous operation at an industrial-level current up to 25 A for over 880 h with an ultra-low degradation rate of 34.1 μV h-1. Combined experimental and theoretical investigations reveal a volcano-type relationship between the chemical state of Ni and the adsorption energy of the key intermediate H* (∆GH*), as well as the potential of zero charge (PZC) of the electrode. Furthermore, in-situ Fourier-transform infrared spectroscopy confirms that a lower PZC promotes the formation of more free water molecules near the electrode surface, thereby facilitating the HER process. This work uncovers atomic environment-governed HER mechanisms and develops a scalable, industrially stable seawater electrolysis electrode, bridging lab-innovation to practical hydrogen production.

Key words: Local-atomic environment, Ni-sites, Hydrogen evolution, Interfacial water, Potential of zero charge