催化学报

催化学报 ›› 2027, Vol. 92: 87-114.DOI: 10.1016/S1872-2067(26)65269-2

• 综述 • 上一篇    下一篇

金属有机框架基电催化剂在硝酸根电化学还原制氨中的最新进展

张博a, 焦玉烨b, 成慧杰b,*, 侯军刚b,*   

  1. a湖南科技学院化学与生物工程学院, 湖南永州 425199;
    b大连理工大学化工学院, 智能材料化工前沿科学中心, 精细化工国家重点实验室, 辽宁大连 116024
  • 收稿日期:2026-05-09 接受日期:2026-06-29 出版日期:2027-01-18 发布日期:2026-10-30
  • 通讯作者: *电子信箱: hjcheng@dlut.edu.cn (成慧杰),jhou@dlut.edu.cn (侯军刚).
  • 基金资助:
    国家自然科学基金(22508109, 22525201, 22372021, 224B2202, 225B2202); 湖南省教育厅科学研究基金(24B0761); 辽宁滨海实验室(LBLD-2025-05); 中央高校基础研究基金(DUT22LAB602, DUT24BK061, DUTZD25231, DUT25Z2779, DUT25Z3208, DUT25Z2734); 辽宁技术研发联合项目(2024JH2/102600047).

Recent advances in metal-organic framework-based electrocatalysts for electrochemical reduction of nitrate to ammonia

Bo Zhanga, Yuye Jiaob, Huijie Chengb,*, Jungang Houb,*   

  1. aCollege of Chemistry and Bioengineering, Hunan Institute of Science and Engineering, Yongzhou 425199, Hunan, China;
    bState Key Laboratory of Fine Chemical, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
  • Received:2026-05-09 Accepted:2026-06-29 Online:2027-01-18 Published:2026-10-30
  • Contact: *E-mail: hjcheng@dlut.edu.cn (H. Cheng),jhou@dlut.edu.cn (J. Hou).
  • About author:Jungang Hou (School of Chemical Engineering, Dalian University of Technology) received his PhD degree from Tianjin University in 2010. He joined the faculty of University of Science and Technology Beijing and was promoted to associate professor in 2013. He worked in Tohoku University as a fellow of Japan Society for the Promotion of Science (JSPS) from 2014 to 2015. Since 2015, he became a full professor in Dalian University of Technology. His research interests focus on photo(electro)catalytic and electrolytic water splitting and CO2 conversion using renewable energy.
  • Supported by:
    National Natural Science Foundation of China (22508109, 22525201, 22372021, 224B2202, 225B2202), the Scientific Research Fund of Hunan Provincial Education Department (24B0761), the Liaoning Binhai Laboratory (LBLD-2025-05), the Fundamental Research Funds for the Central Universities (DUT22LAB602, DUT24BK061, DUTZD25231, DUT25Z2779, DUT25Z3208, DUT25Z2734), and the Liaoning Joint Project for Technology Research and Development (2024JH2/102600047).

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摘要： 电催化硝酸根(NO3‒)还原合成氨(NH3)不仅为破解水体硝酸盐污染问题提供了绿色解决方案, 同时实现了污染物向高值化学品的资源化转化, 有望成为传统高能耗Haber‑Bosch工艺的可持续替代路线. 金属有机框架(MOF)材料凭借其高孔隙率、均匀的活性位点以及可调变的有机配体结构, 在电催化领域展现出独特优势. 然而, MOF材料本征导电性差、结构稳定性不足等瓶颈制约其实际应用. 近年来, 通过精细调控MOF材料微观结构, 构建复合材料以及衍生功能材料, 显著提升了NO3‒电还原制氨的催化效率. 因此, 系统梳理MOF材料在该领域的研究进展, 对于揭示MOF结构与催化性能的构效关系、指导高活性电催化剂的设计具有重要价值.
本文系统综述了MOF基电催化剂在NO3‒电还原制氨中的最新研究进展. 首先, 将MOF基催化剂划分为四大类: 单金属MOF、双金属MOF、MOF基复合材料和MOF衍生材料(金属纳米颗粒、金属化合物、单原子/双原子催化剂及多元复合材料), 分别阐述各类材料的结构特征、活性来源及性能差异, 并通过对比汇总典型催化剂的NH3产率、法拉第效率及稳定性, 揭示金属种类、配位环境与催化性能之间的关联. 随后, 重点归纳了提升催化性能的主要调控策略: (1) 形貌结构调控(二维纳米片、三维多孔骨架及模板法构筑大孔结构), 以暴露更多活性位点并加速传质. (2) 串联活性位点构建, 利用双金属或异质组分协同分工, 将NO3‒→NO2‒及NO2‒→NH3两步反应在空间上耦合, 打破单一活性位点的线性比例关系. (3) 有机配体修饰, 通过引入大π共轭配体、调控配位原子种类、缺陷工程及小分子功能化, 优化金属中心的d带中心和电荷分布. (4) 电子结构优化, 基于d带中心理论、晶体场理论和积分晶体轨道哈密顿布居分析, 阐明界面电荷转移、轨道占据及晶界对吸附活化NO3‒和H2O分子解离的影响. 在此基础上, 深入剖析了NO3‒电还原的间接自催化与直接电还原两条路径, 并着重介绍了原位电子顺磁共振、原位傅里叶变换红外光谱、原位拉曼光谱、差分电化学质谱及同步辐射X射线吸收光谱等先进表征技术在捕捉关键中间体(NO3*, NO2*, NO*, NH2*, NHOH*等)、解析反应路径和监测催化剂动态结构演化中的关键作用. 最后, 提出了MOF基催化剂在NO3‒电还原领域中的现状、挑战及未来发展方向.
展望未来, 该领域亟需攻克大电流密度(≥300 mA cm‒2)下的传质与稳定性问题, 发展流动电解槽和膜电极组件; 评价体系应逐步拓展至真实工业废水场景; 同时应降低全电解能耗, 耦合热力学更优的阳极反应; 借助人工智能和机器学习加速高熵MOF等新型催化材料的筛选. 本综述为高性能MOF基NO3‒电还原催化剂的设计提供了系统的理论指导和实验依据, 对推动绿色NH3合成及水污染治理具有重要参考价值.

关键词: 金属有机框架, 反应路径, 电化学还原, 合成氨

Abstract: Electrocatalytic conversion of nitrate (NO3–) to ammonia (NH3) represents a compelling strategy for mitigating the problem of nitrogen pollution while simultaneously enabling waste valorization, thereby offering a sustainable alternative to the energy-intensive Haber-Bosch process for NH3 synthesis. Metal-organic frameworks (MOFs), a class of porous materials composed of metal nodes and organic linkers, exhibit periodically extended network structures. Their inherent advantages, including high porosity, well-defined and uniform active sites, and tunable organic functionalities, position them as promising candidates in the field of energy and catalysis. Therefore, a systematic summary of the characteristics and recent research progress of MOF-based materials for the electroreduction reaction of NO3– holds significant importance. This review first introduces the current application of pristine MOF materials, MOF-based composites, and MOF-derived materials in the field of NO3– electroreduction reaction. It elaborates on the structural characteristics and performance differences of various types of catalysts, revealing the relationship between the catalytic activity and the composition. Subsequently, we highlight and discuss the key strategies for enhancing the performance of NO3– electroreduction reaction, thus offering theoretical insights to rationally design the catalysts with high activity and long-term stability. Furthermore, to achieve an in-depth understanding of the mechanism, this review delineates the state-of-the-art techniques employed to probe the structure of catalyst, as well as provide a reliable basis for understanding the reaction pathways of NO3– electroreduction reaction. Finally, the significance of MOF-based materials for NO3– electroreduction is summarized, and perspectives on their future development are provided.

Key words: Metal-organic frameworks, Reaction pathways, Electrochemical reduction, Ammonia synthesis