Acta Chimica Sinica Previous Articles    

Review

基于金属有机框架的中性介质硝酸盐电催化还原制氨:设计策略与机理研究

何乾龙, 胡洁颖, 钟礼匡*, 何军*   

  1. 轻工化工学院, 广东工业大学, 广州 510006, 广东省, 中国
  • 投稿日期:2026-01-31
  • 作者简介:框架材料化学”专辑

Metal-Organic Framework-Based Electrocatalysts for Neutral Nitrate-to-Ammonia Conversion: Design Strategies and Mechanistic Insights

He Qianlong, Hu Jieying, Chung Lai-Hon*, He Jun*   

  1. School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guang-dong, P. R. China
  • Received:2026-01-31
  • Contact: * E-mail: laihonchung@gdut.edu.cn; junhe@gdut.edu.cn
  • Supported by:
    National Natural Science Foundation of China (No. 22371054, 22301045), the Foundation of Basic and Applied Basic Research of Guangdong Province (No. 2024A1515012801, 2024B1515120009) and the Postdoctoral Fellowship Program of CPSF (GZC20240311).

With the continuous development of agriculture and industry, nitrate (NO3-) pollution in water bodies worldwide remains a serious issue, characterized by decentralized distribution across multiple sites. The electrocatalytic nitrate reduction reaction (eNO3RR) technology enables the reduction of NO3- waste into ammonia (NH3)—a substance useful to humans—under ambient temperature and pressure. However, under near-neutral pH conditions that mimic actual aquatic environments, eNO3RR faces multiple bottlenecks, including limited proton supply, competition from hydrogen evolution side reactions, risks of nitrite (NO2-) accumulation, and insufficient catalyst lifespan. Metal-organic framework (MOF) materials, which have attracted significant attention recently, hold tremendous potential. Their tunable porous structures and well-defined active sites are conducive to improving NO3- reduction efficiency and selectivity. Remarkable progress has been made in this field: advanced MOF-based materials have achieved an NH3 Faraday efficiency (FE) of nearly 99%, suppressed NO2- accumulation, and pushed the NH3 yield to >23000 μg h⁻1 mgcat1. By constructing conductive composite structures and employing derivatization strategies, MOF-based materials can maintain a FE of >90% and remain stable for over 10 hours at industrial-level current densities (>950 mA cm⁻2). This review focuses on MOF-based electrocatalysts and systematically analyzes the mechanism of neutral eNO3RR. Leveraging the atomic-level designability of MOFs, strategies such as single-atom/cluster regulation, multi-metal synergy, conductive composites, and derivatization can precisely overcome the bottlenecks of proton supply, hydrogen evolution competition, and stability in neutral eNO3RR, enabling efficient conversion of pollutants to NH3. Nevertheless, several challenges remain before this goal is fully achieved: the dynamic identification of active centers during catalysis is not sufficiently clear and accurate, long-term stability in real water bodies needs verification, and issues such as large-scale synthesis urgently require solutions.

Key words: Metal-organic frameworks, MOF derivatives, electrocatalytic nitrate reduction reaction, ammonia synthesis, neutral conditions