镧介导的铱单原子分散及酸性析氧反应中的动态氧补充

doi:10.1016/S1872-2067(26)65056-5

催化学报 ›› 2026, Vol. 86: 236-243.DOI: 10.1016/S1872-2067(26)65056-5

镧介导的铱单原子分散及酸性析氧反应中的动态氧补充

曹晨^a^,^b^,^c, 崔诗锐^a, 石峰^b^,^c, 李彦琴^a, 赵春阳^a, 胡伟^a, 李泽龙^a^,^*(), 唐瑜^a^,^*()

^a 兰州大学化学化工学院, 甘肃省先进催化重点实验室, 天然产物化学全国重点实验室, 甘肃省有色金属化学与资源利用重点实验室, 甘肃兰州 730000
^b 中国科学院兰州化学物理研究所, 低碳催化与二氧化碳利用国家重点实验室, 甘肃兰州 730000
^c 中国科学院大学, 北京 100049

收稿日期:2025-11-08 接受日期:2026-01-20 出版日期:2026-07-05 发布日期:2026-06-12
通讯作者: ^*电子信箱: lizl@lzu.edu.cn (李泽龙),
tangyu@lzu.edu.cn (唐瑜).
基金资助:
国家重点研发计划(2021YFA1501101);甘肃省重大科技专项计划(24ZDGA009);甘肃省科技创新人才计划(24RCKA001)

Lanthanum-mediated single-atom dispersion of Ir and Dynamic oxygen replenishment in acidic water oxidation

Chen Cao^a^,^b^,^c, Shirui Cui^a, Feng Shi^b^,^c, Yanqin Li^a, Chunyang Zhao^a, Wei Hu^a, Zelong Li^a^,^*(), Yu Tang^a^,^*()

^a Key Laboratory of Advanced Catalysis, Gansu Province, State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China
^b State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
^c University of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-11-08 Accepted:2026-01-20 Online:2026-07-05 Published:2026-06-12
Supported by:
National Key Research and Development Program of China(2021YFA1501101);Gansu Provincial Major Science and Technology Special Project Plan(24ZDGA009);Science and Technology Innovation Talent Project of Gansu Province(24RCKA001)

摘要/Abstract

摘要：

氢作为极具应用前景的清洁能源载体, 是消纳转化风能、太阳能等间歇性可再生能源的理想储能介质. 质子交换膜水电解技术(PEMWE)凭借能量效率高、欧姆损耗低、产氢纯度高等优势, 成为可再生能源制氢的重要技术路线. 目前, 析氧反应(OER)动力学缓慢, 且电催化剂在酸性高电位工况下易发生腐蚀降解, 这些问题成为制约PEMWE产业化应用的核心瓶颈. 铱基催化剂凭借优异的本征催化活性与酸性环境下优越的稳定性, 成为当前PEMWE体系中性能最优的OER电催化剂. 但铱元素储量稀缺、原料成本高昂, 难以满足大规模工业化应用需求. 因此, 开发新型催化策略, 在降低铱负载量的同时, 同步提升催化剂的OER活性与长效稳定性, 已成为该领域的关键研究方向.

本研究通过引入镧(La)元素对钴尖晶石(Co₃O₄)载体进行改性, 成功实现了铱活性组分在载体表面的原子级分散, 构建出高效稳定的Ir/CoLaO_x催化剂体系. 更为关键的是, 镧的掺杂显著调控Ir位点电子结构与反应路径, 使OER反应机制从传统的吸附氧机理(AEM)转变为晶格氧机理(LOM), 为提升催化性能与稳定性提供了核心驱动力. 从机理层面分析, 镧元素具有极强的亲氧特性, 引入后不仅可精准调控铱活性位点的局域电子结构, 优化活性中心与反应中间体的相互作用强度, 还能显著加速界面水的解离过程, 为OER反应提供充足的活性氧源. 此外, 镧位点的亲氧性可保障LOM机理中消耗的晶格氧得到实时、高效补充, 这一动态氧补充过程有效抑制了催化剂因晶格氧流失导致的结构坍塌与活性位点降解, 从本质上提升了催化剂的结构与性能稳定性. 电化学测试结果充分验证了该催化剂的优异性能: 在酸性电解质环境中, 当电流密度达到10 mA cm^-2时, Ir/CoLaO_x催化剂的析氧过电位仅为215 mV, 远低于商业IrO₂催化剂及未掺杂镧的Ir/Co₃O₄催化剂, 展现出卓越的本征催化活性; 在模拟PEMWE实际运行工况的200 mA cm^-2高电流密度下, 该催化剂可稳定运行300 h, 期间电流密度无明显衰减, 极化曲线无显著正移, 表现出优异的长效稳定性. 这一性能优势源于La掺杂带来的原子级分散Ir位点、优化的电子结构及动态氧补充机制的协同作用, 有效解决了低铱催化剂活性与稳定性难以平衡的问题.

综上, 本文为通过动态氧补充策略稳定LOM催化过程提供了清晰的机理框架, 填补了晶格氧催化稳定性调控机制的研究空白, 还为低铱负载酸性OER催化剂的设计提供了切实可行的技术策略, 为推动铱单原子催化剂在PEMWE中的实际应用奠定了理论与实验基础.

关键词: 析氧反应, 单原子, 质子交换膜水电解, 制氢, 电催化

Abstract:

High-performance single-atom iridium (Ir) catalysts offer ultrahigh atomic utilization and can lower proton exchange membrane water electrolysis costs, but their improved oxygen evolution reaction (OER) activity often sacrifices stability. Here, incorporation of lanthanum (La) enables atomic dispersion of Ir on cobalt spinel (Co₃O₄) surface and shifts the Ir active-site OER pathway from the conventional adsorbate evolution mechanism to a lattice oxygen-mediated mechanism (LOM). The strongly oxophilic La sites tune the local electronic structure of Ir and accelerate interfacial water dissociation, enabling real-time replenishment of lattice oxygen consumed during LOM that a key process mitigates catalyst degradation. Consequently, Ir/CoLaO_x shows an overpotential of 215 mV at 10 mA cm^-2 in acid and sustains 200 mA cm^-2 operation for 300 h in a full proton exchange membrane water electrolysis. This work provides a mechanistic framework for dynamic oxygen replenishment to stabilize lattice-oxygen catalysis and offers a strategy for designing atomically dispersed Ir catalysts for efficient, durable acidic OER.

Key words: Oxygen evolution reaction, Single atom, Proton exchange membrane water, electrolysis, Hydrogen production, Electrocatalysis

曹晨, 崔诗锐, 石峰, 李彦琴, 赵春阳, 胡伟, 李泽龙, 唐瑜. 镧介导的铱单原子分散及酸性析氧反应中的动态氧补充[J]. 催化学报, 2026, 86: 236-243.

Chen Cao, Shirui Cui, Feng Shi, Yanqin Li, Chunyang Zhao, Wei Hu, Zelong Li, Yu Tang. Lanthanum-mediated single-atom dispersion of Ir and Dynamic oxygen replenishment in acidic water oxidation[J]. Chinese Journal of Catalysis, 2026, 86: 236-243.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65056-5

https://www.cjcatal.com/CN/Y2026/V86/I7/236

图/表 3

Fig. 1. Structureal characterizations of the Ir/CoLaOx catalyst. (a) XRD patterns for Co3O4, CoLaOx, IrO2, Ir/Co3O4, Ir/CoLaOx. AC-HADDF-STEM image of Ir/CoLaOx with scale bar of 2 nm (b) and 5 nm (c). (d) Analysis of the atomic intensity for the white circle region of (b). (e) EDS elemental mappings of Ir/CoLaOx. (f) Raman spectra of the Co3O4, CoLaOx, IrO2, Ir/Co3O4 and Ir/CoLaOx. Ir L3-edge (g) and Co K-edge (h) XANES spectra of different catalysts. Ir L3-edge (i) and Co K-edge (j) FT-EXAFS spectra of different catalysts. (k) XPS spectra of Ir 4f for Ir/CoLaOx and Ir/Co3O4.

Fig. 2. OER performance. (a) LSV curves of Co3O4, CoLaOx, IrO2, Ir/Co3O4 and Ir/CoLaOx. (b) Tafel plots of different catalysts. (c) The EIS Nyquist plots of different catalysts. (d) Chronopotentiometry curves of Co3O4, CoLaOx, IrO2, Ir/Co3O4 and Ir/CoLaOx at 100 mA cm-2. (e) The dissolved Ir and Co ion concentrations measured for Ir/Co3O4 and Ir/CoLaOx in the electrolyte by ICP-OES. (f) Steady-state polarization curves of PEMWE using IrCoLaOx as anode catalysts. (g) V-t curve of the PEM cell for Ir/CoLaOx, operating at 200 mA cm-2, 80 °C, and ambient pressure.

Fig. 3. OER mechanism. In-situ ATR-IR spectra for Ir/Co3O4 (a) and Ir/CoLaOx (b), (c) DEMS signals of O2 products for Ir/Co3O4 and Ir/CoLaOx. (d) LSV curves for Ir/CoLaOx in 0.5 mol L-1 H2SO4 with and without TMA+ (e) KIE values for Ir/Co3O4 and Ir/CoLaOx at 1.55, 1.60, 1.65, 1.70, and 1.75 V. (f) LSV curves for Ir/Co3O4 and Ir/CoLaOx in 0.5 mol L-1 H2SO4 with and without methanol (0.1 mol L-1).

参考文献

[1]	W. Shi, T. Shen, C. Xing, K. Sun, Q. Yan, W. Niu, X. Yang, J. Li, C. Wei, R. Wang, S. Fu, Y. Yang, L. Xue, J. Chen, S. Cui, X. Hu, K. Xie, X. Xu, S. Duan, Y. Xu, B. Zhang, Science, 2025, 387, 791-796.
[2]	L. Wang, R. Du, Z. Zhao, M. Na, X. Li, X. Zhao, X. Wang, Y. A. Wu, S. Jana, Y. Zou, H. Chen, X. Zou, Angew. Chem. Int. Ed., 2025, 64, e202501744.
[3]	H. Hu, S. Liu, H. Sun, W. Sun, J. Tang, L. Wei, X. Chen, Q. Chen, Y. Lin, Z. Tian, J. Su, Small, 2025, 21, 2412096.
[4]	A. Zagalskaya, V. Alexandrov, ACS Catal., 2020, 10, 3650-3657.
[5]	Y. Wang, Y. Qin, S. Liu, Y. Zhao, L. Liu, D. Zhang, S. Zhao, J. Liu, J. Wang, Y. Liu, H. Wu, B. Jia, X. Qu, H. Li, M. Qin, J. Am. Chem. Soc., 2025, 147, 13345-13355.
[6]	G. Li, A. Priyadarsini, Z. Xie, S. Kang, Y. Liu, X. Chen, S. Kattel, J. G. Chen, J. Am. Chem. Soc., 2025, 147, 7008-7016.
[7]	J. Shan, C. Ye, S. Chen, T. Sun, Y. Jiao, L. Liu, C. Zhu, L. Song, Y. Han, M. Jaroniec, Y. Zhu, Y. Zheng, S.-Z. Qiao, J. Am. Chem. Soc., 2021, 143, 5201-5211.
[8]	Z. Wei, Y. Ding, W. Shi, F. Zhang, Y. Song, X. Cui, Y. Guo, L. Sun, Q. Jiang, B. Zhang, Nat. Commun., 2025, 16, 8145.
[9]	T. Priamushko, E. Franz, A. Logar, L. Bijelić, P. Guggenberger, D. Escalera-López, M. Zlatar, J. Libuda, F. Kleitz, N. Hodnik, O. Brummel, S. Cherevko, J. Am. Chem. Soc., 2025, 147, 3517-3528.
[10]	R. Ram, L. Xia, H. Benzidi, A. Guha, V. Golovanova, A. Garzón Manjón, D. Llorens Rauret, P. Sanz Berman, M. Dimitropoulos, B. Mundet, E. Pastor, V. Celorrio, C. A. Mesa, A. M. Das, A. Pinilla-Sánchez, S. Giménez, J. Arbiol, N. López, F. P. García de Arquer, Science, 2024, 384, 1373-1380.
[11]	J. Huang, C. N. Borca, T. Huthwelker, N. S. Yüzbasi, D. Baster, M. El Kazzi, C. W. Schneider, T. J. Schmidt, E. Fabbri, Nat. Commun., 2024, 15, 3067.
[12]	J. Huang, Z. Zhang, C. Spezzati, A. H. Clark, N. Hales, N. S. Genz, N. Daffé, R. Skoupy, L. Gubler, I. E. Castelli, T. J. Schmidt, E. Fabbri, Nat. Commun., 2025, 16, 7518.
[13]	L. Chong, G. Gao, J. Wen, H. Li, H. Xu, Z. Green, J. D. Sugar, A. J. Kropf, W. Xu, X.-M. Lin, H. Xu, L.-W. Wang, D.-J. Liu, Science, 2023, 380, 609-616.
[14]	A. C. Hartnett, R. J. Evenson, A. E. Thorarinsdottir, S. S. Veroneau, D. G. Nocera, J. Am. Chem. Soc., 2025, 147, 1123-1133.
[15]	S. Li, S. Zhao, S.-F. Hung, L. Deng, L. Wang, F. Shi, A. Dong, Y. Zhang, T.-Y. Chen, F. Hu, L. Li, S. Ramakrishna, Y. Wu, S. Peng, J. Am. Chem. Soc., 2025, 147, 33770-33779.
[16]	C. Fan, X. Wang, X. Wu, Y. Chen, Z. Wang, M. Li, D. Sun, Y. Tang, G. Fu, Adv. Energy Mater., 2023, 13, 2203244.
[17]	C.-H. Li, C.-Z. Yuan, C.-L. Zhou, X. Yang, R. Xu, F.-L. Wu, L. Xin, L.-X. Wang, X. Zhang, K. N. Hui, Y. Chen, ACS Catal., 2025, 15, 7403-7413.
[18]	Z. Wang, J. Huang, Z. Guo, X. Dong, Y. Liu, Y. Wang, Y. Xia, Joule, 2019, 3, 1289-1300.
[19]	A. Li, S. Kong, K. Adachi, H. Ooka, K. Fushimi, Q. Jiang, H. Ofuchi, S. Hamamoto, M. Oura, K. Higashi, T. Kaneko, T. Uruga, N. Kawamura, D. Hashizume, R. Nakamura, Science, 2024, 384, 666-670.
[20]	L. Wang, S.-F. Hung, S. Zhao, Y. Wang, S. Bi, S. Li, J.-J. Ma, C. Zhang, Y. Zhang, L. Li, T.-Y. Chen, H.-Y. Chen, F. Hu, Y. Wu, S. Peng, Nat. Commun., 2025, 16, 3502.
[21]	Z. Shi, J. Li, Y. Wang, S. Liu, J. Zhu, J. Yang, X. Wang, J. Ni, Z. Jiang, L. Zhang, Y. Wang, C. Liu, W. Xing, J. Ge, Nat. Commun., 2023, 14, 843.
[22]	W. Hu, B. Huang, M. Sun, J. Du, Y. Hai, W. Yin, X. Wang, W. Gao, C. Zhao, Y. Yue, Z. Li, C. Li, Adv. Mater., 2025, 37, 2411709.
[23]	S. Zhao, S.-F. Hung, Y. Wang, S. Li, J. Yang, W.-J. Zeng, Y. Zhang, H.-H. Chang, H.-Y. Chen, F. Hu, L. Li, S. Peng, J. Am. Chem. Soc., 2025, 147, 7993-8003.
[24]	C. Liang, R. R. Rao, K. L. Svane, J. H. L. Hadden, B. Moss, S. B. Scott, M. Sachs, J. Murawski, A. M. Frandsen, D. J. Riley, M. P. Ryan, J. Rossmeisl, J. R. Durrant, I. E. L. Stephens, Nat. Catal., 2024, 7, 763-775.
[25]	N. Wang, P. Ou, R.-K. Miao, Y. Chang, Z. Wang, S.-F. Hung, J. Abed, A. Ozden, H.-Y. Chen, H.-L. Wu, J. E. Huang, D. Zhou, W. Ni, L. Fan, Y. Yan, T. Peng, D. Sinton, Y. Liu, H. Liang, E. H. Sargent, J. Am. Chem. Soc., 2023, 145, 7829-7836.
[26]	Y. Mu, J. Fan, T. Gao, L. Wang, L. Zhang, X. Zou, W. Zheng, Y.-W. Zhang, Z.-G. Yu, X. Cui, Angew. Chem. Int. Ed., 2025, 64, e202504876.
[27]	H. Yu, Y. Ji, C. Li, W. Zhu, Y. Wang, Z. Hu, J. Zhou, C.-W. Pao, W.-H. Huang, Y. Li, X. Huang, Q. Shao, J. Am. Chem. Soc., 2024, 146, 20251-20262.
[28]	N. Yao, H. Jia, J. Zhu, Z. Shi, H. Cong, J. Ge, W. Luo, Chem, 2023, 9, 1882-1896.
[29]	Y. Zhang, H. Zhang, H. Ji, W. Ma, C. Chen, J. Zhao, J. Am. Chem. Soc., 2016, 138, 2705-2711.
[30]	E. M. Simmons, J. F. Hartwig, Angew. Chem. Int. Ed., 2012, 51, 3066-3072.
[31]	H. Tao, Y. Xu, X. Huang, J. G. Chen, B. Liu, Meet. Abstr., 2019, MA 2019-02, 1744.
[32]	B. Zhou, X. Liu, L. Li, M. Liu, H. Liao, Y. Yu, F. Liu, P. Tan, J. Pan, Chem. Eng. J., 2025, 521, 166886.

镧介导的铱单原子分散及酸性析氧反应中的动态氧补充

Lanthanum-mediated single-atom dispersion of Ir and Dynamic oxygen replenishment in acidic water oxidation

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 3

参考文献

相关文章 15

编辑推荐

Metrics

[1]	卜辰宇, 卢卓然, 夏忠诚, 樊赟, 王才荣, 黄雨桐, 王双印, 邹雨芹. 界面双位点协同增效近中性介质中的生物质电氧化反应[J]. 催化学报, 2026, 86(7): 160-170.
[2]	王超, 冯坤, 唐梁书语, 章伍军, 周沐宇, 李佳璐, 邵天雨, 沈炎宾, 钟俊, 苏韧. 水系电催化氨氧化反应中MOFs活性位点的原位演变[J]. 催化学报, 2026, 86(7): 171-180.
[3]	王德志, 杨松华, 杨刘熠懿, 彭需发, 刘芳洋, 费浩, 吴壮志. 高效电催化固氮: 基于轨道耦合差异化响应解耦竞争反应[J]. 催化学报, 2026, 86(7): 181-190.
[4]	刘小虎, 李守杰, 毛佳宁, 陈奥辉, 董笑, 韦懿恒, 夏嘉雨, 朱桓毅, 王晓童, 徐子然, 李桂花, 宋艳芳, 魏伟, 陈为. 透散电极原位重构AgZn₃用于安培级CO₂电还原[J]. 催化学报, 2026, 86(7): 201-211.
[5]	代玲玉, 周本基, 徐能能, 彭芦苇, 刘鹤鸣, 郭正晓, 乔锦丽. 三相铋基异质界面调控实现1650 h循环寿命的高功率锌-空气电池[J]. 催化学报, 2026, 86(7): 315-326.
[6]	张权, 马鹤津, 韩若冰, 杨统林, 陈真会, 祝淼洋, 时佳维, 蔡卫卫, 杨方麒, 杨泽惠. 镧掺杂诱导晶格膨胀NiSe催化剂用于高效尿素氧化辅助电解水制氢[J]. 催化学报, 2026, 86(7): 254-264.
[7]	王湫溶, 李仁坤, 方燕, 谭明务, 李彤彤, 李仁宏. 铬驱动的高熵氧化物晶格氧活化用于高效析氧反应[J]. 催化学报, 2026, 86(7): 277-289.
[8]	柯俊, 张嘉熙, 张龙海, 钟承志, 宋慧宇, 杜丽, 张玉微, 崔志明. 通过界面电荷操控强化氢键连通性以加速析氧反应[J]. 催化学报, 2026, 86(7): 290-301.
[9]	王文搏, 龚善和, 阚二军, 朱国兴, 霍鹏伟, 关锦彤, 吕晓萌. 原子铋替代稳定的4H/fcc多相界面AgBi单原子合金用于高效CO₂还原[J]. 催化学报, 2026, 86(7): 212-224.
[10]	翟庆喜, 田轶棋, 王浩, 唐诗思, 原强, 刘旭, 丁维平, 田凡, 祝艳. Ni₆(SR)₁₂团簇电催化环己酮氧化制备己二酸[J]. 催化学报, 2026, 86(7): 225-235.
[11]	吴立清, 黄文霞, 赵冰冰, 蔡苹, 罗威. 钌氧化物表面阴离子介导的动态界面自由水富集微环境助力高效酸性氧析出反应[J]. 催化学报, 2026, 85(6): 237-246.
[12]	陈兰兰, 圣利, 周亚男, 罗其全, 李震宇, 张文华, 杨金龙. Ni₁-MoS₂单原子催化剂用于CO₂加氢制甲醇的优越性: 密度泛函理论与微观动力学研究[J]. 催化学报, 2026, 85(6): 143-152.
[13]	王翔, 周敏, 廖小彬, 韩旭, 省聪聪, Bes René, Huotari Simo, Arbiol Jordi, Cabot Andreu. MOFs衍生的磷掺杂Co₉S₈增强氧析出和还原反应: 迈向高性能锌空气电池[J]. 催化学报, 2026, 85(6): 204-215.
[14]	李昱伟, 何语馨, 郭宗瑶, 张静怡, 吴义志, 蒋铭坤, 陈诗语, 吴丹. 双位点CuS-Co₉S₈异质结实现高效选择性甘油电催化氧化[J]. 催化学报, 2026, 85(6): 272-285.
[15]	何邢晨, 邵俊辉, 李娜君, 陈冬赟, 李华, 徐庆锋, 王浩志, 路建美. 压电增强氢键网络调控氟化氮化碳实现CO₂还原的100% CO选择性[J]. 催化学报, 2026, 85(6): 130-142.