Chemical Research in Chinese Universities ›› 2025, Vol. 41 ›› Issue (6): 1485-1503.doi: 10.1007/s40242-025-5232-4

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Electrocatalytic Nitrate Reduction Promoted by Atomically Precise Metal Nanoclusters

ZHANG Min1,2, YANG Fan1,2,4, ZHU Moshuqi3,4, YAO Qiaofeng1,2   

  1. 1. State Key Laboratory of Advanced Materials for Intelligent Sensing & Key Laboratory of Organic Integrated Circuits, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, P. R. China;
    2. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China;
    3. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China;
    4. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, P. R. China
  • Received:2025-09-30 Accepted:2025-11-07 Online:2025-12-01 Published:2025-12-05
  • Contact: ZHU Moshuqi,E-mail:zhumoshuqi@tju.edu.cn;YAO Qiaofeng,E-mail:qfyao@tju.edu.cn E-mail:zhumoshuqi@tju.edu.cn;qfyao@tju.edu.cn
  • Supported by:
    This work was supported by the National Natural Science Foundation of China (No. 22371204), the Fundamental Research Funds for the Central Universities, China, the Emerging Frontiers Cultivation Program of Tianjin University Interdisciplinary Center (China), and the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation (No. GZC20231910).

Abstract: The massive discharge of nitrate (NO3-) represents a major challenge to the sustainability of both human society and ecosystems. Electrochemical reduction of NO3- to NH3 offers a “turning waste into treasure” solution, enabling the conversion of renewable electricity into chemical energy stored in NH3. In recent years, atomically precise metal nanoclusters (NCs) have attracted extensive research interest. Their protein-like hierarchical structures, from the metal core to the protecting layers, allow for multi-level design and synthesis, which not only offers a good means to tailor cluster structure at the atomic level for effective NO3- reduction, but also affords a paradigm for correlating cluster structure and catalytic performance. In this review, we summarize recent advances in atomically precise synthesis and electrocatalytic applications of metal NCs in NO3- reduction reactions. We first outline plausible mechanisms for the electrocatalytic NO3- reduction reactions, and then discuss the application of NCs in NO3- reduction based on their hierarchical architecture. We decipher design and synthesis strategies for metal NCs from four perspectives: metal core size, heteroatom doping, ligand engineering, and support engineering. Regarding the electrocatalytic applications of metal NCs, we aim to reveal the fundamentals governing the catalytic activity and selectivity for conversion of NO3- to NH3. The fundamental and methodological advances systemized in this review should add to the acceptance of metal NCs in the electrocatalytic reduction of NO3-.

Key words: Metal nanocluster, Electrocatalytic nitrate reduction, Model catalysis, Structure-performance relationship