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

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
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,*

^aKey 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;
^bState Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China;
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-11-08 Accepted:2026-01-20
Contact: ^*E-mail: lizl@lzu.edu.cn (Z. Li), tangyu@lzu.edu.cn (Y. Tang).
Supported by:
National Key Research and Development Program of China (2021YFA1501101), the Gansu Provincial Major Science and Technology Special Project Plan (24ZDGA009), and the 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、产氢纯度优等技术优势, 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, 是制约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, 维持甚至提升催化剂的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, 镧的掺杂显著调控了催化反应路径, 使铱活性位点的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, 有效解决了低铱负载催化剂活性与稳定性难以兼顾的核心难题.
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, DOI: 10.1016/S1872-2067(26)65056-5.

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, DOI: 10.1016/S1872-2067(26)65056-5.

×
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/V/I/7

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, MA2019-02, 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.