Lattice O-O ligands in Fe-incorporated hydroxides enhance water oxidation electrocatalysis.

Journal: Nature chemistry
Published Date: Aug 18, 2025

Abstract

Understanding the structural dynamics of ligands and their interaction with catalytic centres under reaction conditions remains a fundamental challenge, yet it is essential for catalyst design. Here we reveal an in situ transformation of Ni-Fe hydroxide into a stable superoxo-hydroxide phase, which is accompanied by the formation of lattice O-O (O-O) ligands, as demonstrated using operando O-labelling spectroelectrochemistry and machine-learning-assisted global optimization. By correlating the intrinsic activity of Fe with the O-O concentration across a series of Fe-incorporated transition-metal hydroxides and oxides, we demonstrate that O-O triggers Fe activation for oxygen evolution electrocatalysis-a finding further supported by first-principles calculations. Oxygen production proceeds via an adsorbate evolution mechanism, and the enhanced reaction kinetics stem from the lowered activation energy at surface Fe sites in the newly formed superoxo-hydroxide structure. This work offers a strategic framework for designing high-performance Fe-incorporated electrocatalysts and underscores the pivotal role of ligand dynamics in activating catalytic centres.

Authors

  • Guoshuai Shi
    Department of Chemistry, State Key Laboratory of Porous Materials for Separation and Conversion, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
  • Jili Li
    West China School of Medicine, Sichuan University, Chengdu, China.
  • Tingyu Lu
    Department of Chemistry, State Key Laboratory of Porous Materials for Separation and Conversion, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
  • Chunlei Yang
    Department of Chemistry, State Key Laboratory of Porous Materials for Separation and Conversion, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
  • Qinshang Xu
    Department of Chemistry, State Key Laboratory of Porous Materials for Separation and Conversion, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
  • Huoliang Gu
    Department of Chemistry, State Key Laboratory of Porous Materials for Separation and Conversion, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
  • Haonan Tong
    Electrical and Computer Engineering Department, North Carolina State University, Raleigh, NC, U.S.A.
  • Siwen Zhao
    State Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing, 100193, China.
  • Chenyuan Zhu
    Department of Chemistry, State Key Laboratory of Porous Materials for Separation and Conversion, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
  • Yuluo Shen
    Department of Chemistry, State Key Laboratory of Porous Materials for Separation and Conversion, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China.
  • Jing Wu
    School of Pharmaceutical Science, Jiangnan University, Wuxi, 214122, Jiangsu, China.
  • Xianzhuo Lao
    College of Smart Materials and Future Energy, Fudan University, Shanghai, China.
  • Peng-Cheng Chen
    College of Smart Materials and Future Energy, Fudan University, Shanghai, China.
  • Jiong Li
    Ministry of Education-Shanghai Key Laboratory of Children's Environmental Health, Department of Pediatrics, Xinhua Hospital, Early Life Health Institute, Shanghai Jiao-Tong University School of Medicine, Kong-Jiang Road, Shanghai, 200092, China.
  • Shuo Zhang
    Ph.D. Program in Computer Science, The City University of New York, New York, NY, United States.
  • Jueli Shi
    State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
  • Kelvin H L Zhang
    State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
  • Ye-Fei Li
    State Key Laboratory of Porous Materials for Separation and Conversion, Collaborative Innovation Center of Chemistry for Energy Material, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Key Laboratory of Computational Physical Science, Department of Chemistry, Fudan University, Shanghai, 200433, China. yefeil@fudan.edu.cn.
  • Zhi-Pan Liu
    Collaborative Innovation Center of Chemistry for Energy Material, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Key Laboratory of Computational Physical Science, Department of Chemistry, Fudan University Shanghai 200433 China zpliu@fudan.edu.cn.
  • Liming Zhang
    Department of Gastroenterology, Peking University People's Hospital, Beijing, China.

Keywords

No keywords available for this article.

External Resources

Popular Topics
Recent Journals