催化学报

催化学报 ›› 2026, Vol. 84: 130-143.DOI: 10.1016/S1872-2067(26)65000-0

• 论文 • 上一篇    下一篇

空间限制与含氮缺陷锚定协同增强钌纳米颗粒催化剂在工业电流密度下的析氢性能

万自杰a,1, 杨矞琦b,c,1(), 王振权b, 武林睿b, 张海鹏b,c, 时晴芳b, 刘翔b, 杨翰林a, 康博晗a, 徐泉e, 罗佳庆a(), 刘坚a,d()   

  1. a 中国石油大学(北京)重质油国家重点实验室, 油气光学探测技术北京市重点实验室, 北京 102249
    b 中国石油大学(北京)克拉玛依校区重油实验室, 新疆克拉玛依 834000
    c 克拉玛依氢能实验室, 新疆克拉玛依 834000
    d 辽宁石油化工大学石油化工学院, 辽宁抚顺 113001
    e 中国石油大学(北京), 北京 102249
  • 收稿日期:2025-09-05 接受日期:2025-11-16 出版日期:2026-05-18 发布日期:2026-04-16
  • 通讯作者: *电子信箱: yuqiyang@cupk.edu.cn (杨矞琦),
    luojiaqing@cupk.edu.cn (罗佳庆),
    liujian@cup.edu.cn (刘坚).
  • 作者简介:1共同第一作者.
  • 基金资助:
    新疆维吾尔自治区天山英才项目(2022TSYCCX0057);新疆维吾尔自治区重大科技专项(2024A01001-1);中国石油科技创新基金(2024DQ02-0148);新疆维吾尔自治区“一事一议”引进战略人才研究团队项目(XZT3-3);新疆天山创新团队项目(2022TSYCTD0002);新疆维吾尔自治区重点研发计划项目(2022B01058-2);国家自然科学基金面上项目(52574069)

Spatial confinement and nitrogenous defect anchoring synergistically enhance Ru nanoparticles catalyst performance for industrial current densities hydrogen evolution

Zijie Wana,1, Yuqi Yangb,c,1(), Zhenquan Wangb, Linrui Wub, Haipeng Zhangb,c, Qingfang Shib, Xiang Liub, Hanlin Yanga, Bohan Kanga, Quan Xue, Jiaqing Luoa(), Jian Liua,d()   

  1. a State Key Laboratory of Heavy Oil and Beijing Key Lab of Oil &Gas Optical Detection Technology, China University of Petroleum, Beijing 102249, China
    b Laboratory of Heavy Oil at Karamay, China University of Petroleum-Beijing at Karamay, Karamay 834000, Xinjiang, China
    c Karamay Hydrogen Energy Laboratory, Karamay 834000, Xinjiang, China
    d School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, Liaoning, China
    e China University of Petroleum, Beijing 102249, China
  • Received:2025-09-05 Accepted:2025-11-16 Online:2026-05-18 Published:2026-04-16
  • Contact: *E-mail: yuqiyang@cupk.edu.cn (Y. Yang),
    luojiaqing@cupk.edu.cn (J. Luo),
    liujian@cup.edu.cn (J. Liu).
  • About author:1Contributed equally to this work.
  • Supported by:
    Xinjiang Uygur Autonomous Region Tianshan Talents(2022TSYCCX0057);Major Science and Technology Projects of Xinjiang Uygur Autonomous Region(2024A01001-1);China Petroleum Science and Technology Innovation Fund(2024DQ02-0148);Research Team Program for Strategic Talents Recruitment through Case-by-Case Review(XZT3-3);Xinjiang Uygur Autonomous Region;Tianshan Innovation Team Program, Xinjiang Uygur Autonomous Region(2022TSYCTD0002);Key R&D Program of the Xinjiang Uygur Autonomous Region(2022B01058-2);National Natural Science Foundation of China(52574069)

RichHTML

4

PDF

12

摘要：

在全球碳中和战略推动下, 电解水制氢已成为实现大规模绿氢制备的重要途径. 阴离子交换膜水电解槽(AEMWE)技术因兼具碱性电解(ALK)的低成本优势与质子交换膜电解(PEMWE)的高效率特性, 被视为是下一代绿色制氢的重要技术方向. 然而, 碱性介质中析氢反应(HER)常受水分子解离步骤的动力学限制, 导致阴极过电位升高, 从而制约了AEMWE的整体能效和规模化应用. 传统Pt基催化剂虽具有接近理想的氢吸附自由能, 但其高成本以及在碱性条件下水解离能力不足, 严重限制了其在AEMWE系统中的大规模应用. 相比之下, Ru具有接近Pt的氢结合能与更优的水分子活化能力, 是极具潜力的替代金属. 但Ru往往存在的Ru-H结合过强以及纳米颗粒在高电流密度运行中易迁移/团聚等问题, 限制了催化活性与稳定性. 为此, 发展兼具高活性、高耐久性与低贵金属负载的Ru基HER催化剂, 对实现AEMWE的高效、低成本制氢具有重要科学意义与工程价值.

本研究提出了一种空间限域、氮缺陷锚定与电子结构调控的三重协同设计策略: 通过构建三维球形多孔氮掺杂碳载体(3DSPNC), 实现了Ru纳米颗粒(Ru NPs)的高效稳定负载与电子结构的精确调控. 该载体体系具有三项关键结构特征: (1)微孔-介孔分级孔道提供有效的空间限域作用; (2)高密度表面含氮缺陷通过强Ru-N配位作用实现对超细Ru NPs (1.3 ± 0.2 nm)的锚定, 提升金属分散性与结构稳定性; (3)内部石墨化网络有助于快速电荷传递. 上述结构特征的协同作用赋予催化体系优异的金属-载体界面耦合与电子调控能力, 从而在催化过程中有效保持Ru/3DSPNC的高稳定性与催化活性. 得益于三重协同效应, 所构建的Ru/3DSPNC催化剂在1.0 mol/L KOH溶液中表现出卓越的碱性HER性能: 低过电位(η10 = 11.2 mV)、小Tafel斜率(34.3 mV/dec)及优异的长期稳定性. 当该催化剂作为阴极应用于AEMWE电解槽时, 体系在30 °C下即可在1.9 V电压下实现1 A/cm²的工业级电流密度, 且在310 h连续运行中电压衰减仅为5.6%, 综合性能显著优于商业Pt/C (1.97 V@1 A/cm²)及多数已报道的Ru基催化剂. 性能提升的根本原因在于精确调控的载体微结构与界面电子特性: 介孔空腔的空间限域效应有效抑制了高电流密度下的颗粒团聚, 氮掺杂则强化了金属-载体相互作用并促进界面电荷重分布. 密度泛函理论计算进一步揭示, 氮掺杂诱导的电子调控诱导形成缺电子Ruδ+位点, 能够削弱Ru‒H键结合强度并促进水分子解离, 加速析氢反应的速率决定步骤. 与此同时, 增强的Ru与载体间的结合能有效提高了催化剂的稳定性, 该结论亦得到了分子动力学模拟的验证.

综上, 本研究通过三重协同策略成功构建了兼具稳定性与催化活性的Ru/3DSPNC催化体系, 为实现低贵金属负载、高效率、长寿命的碱性析氢催化剂提供了新的设计范式. 未来, 该空间限域与缺陷协同机制可推广至其他过渡金属及其复合体系, 为高电流密度电解水催化剂的设计与规模化应用奠定重要基础.

关键词: 碱性析氢反应, 氮掺杂碳, 空间限域, 含氮缺陷锚定, 阴离子交换膜水电解装置, 长期稳定性

Abstract:

ABSTRACT：Anion exchange membrane water electrolyzers (AEMWEs) are emerging as a sustainable platform for efficient hydrogen production. However, the sluggish hydrogen evolution reaction (HER) in alkaline media remains a major challenge, primarily due to the lack of highly active and durable non-Pt catalysts. Herein, development of a high-performance alkaline HER catalyst is achieved through a triple-synergy strategy that combines spatial confinement, nitrogenous defect anchoring, and electronic modulation. The catalyst consists of ultrafine ruthenium nanoparticles supported on a three-dimensional spherical porous N-doped carbon framework (Ru/3DSPNC), synthesized through a soft-template method followed by stepwise pyrolysis. The optimized Ru/3DSPNC exhibits an ultralow overpotential of 11.2 mV at 10 mA/cm2 in 1.0 mol/L KOH. When applied as the cathode in an AEMWE at 30 °C, it delivers a cell voltage of 1.9 V at 1 A/cm2, with less than 5.6% voltage degradation over 310 h, outperforming commercial Pt/C. The excellent catalytic activity and long-term durability could be attributed to that the micropore-mesopore hierarchical architecture and nitrogenous defect provide effective spatial confinement and strong chemical anchoring for highly homogeneously dispersion Ru nanoparticles, and substrate nitrogen doping induces favorable orientation of interfacial H2O for HER and generation of Ruδ+ site possessing optimized ΔGH*. This work presents a rational design strategy for advanced catalysts for the alkaline HER.

Key words: Alkaline hydrogen evolution reaction, Nitrogen-doped carbon, Spatial confinement, Nitrogenous defect anchoring, Anion exchange membrane water electrolysis device, Long-term durability