SIOC English
化学学报
高级检索

化学学报 上一篇    下一篇

研究论文

铜配位三维共价有机框架提升电催化硝酸盐还原制氨

王佳雨a,b†, 赵文娟a†, 贾宏宇a, 刘永博c, 张敏a, 董龙龙a, 张安杰*,a, 王锐*,d   

  1. a航天化学能源全国重点实验室 内蒙合成化工研究所, 内蒙古 呼和浩特 010010;
    b北京理工大学 化学化工学院,北京市 100081;
    c内蒙古大学 化学化工学院,内蒙古 呼和浩特 010010;
    d吉林大学 无机合成与制备国家重点实验室,吉林省长春市 130021
  • 投稿日期:2025-06-15
  • 作者简介:†在这项工作中做出来同样的贡献

Enhancing Electrocatalytic Nitrate Reduction to Ammonia via Copper-Coordinated Three-Dimensional Covalent Organic Frameworks

Jiayu Wanga,b†, Wenjuan Zhaoa†, Hongyu Jiaa, Yongbo Liuc, Min Zhanga, Longlong Donga, Anjie Zhanga,*, Rui Wangd,*   

  1. aNational Key Laboratory of Aerospace Chemical Power, Inner Mongolia Research Institute of Synthetic Chemical Industry, Hohhot, 010010, Inner Mongolia, China;
    bSchool of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, China;
    cCollege of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, China;
    dState Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, PR China
  • Received:2025-06-15

PDF

33

补充材料

1

电化学硝酸盐还原反应（NO₃RR）已成为处理硝酸盐污染废水和实现可持续氨合成的一种有前景的策略。然而,其实际应用仍受到催化活性低、选择性差和法拉第效率（FE）有限等问题的制约。在本研究中,我们通过精确调控多孔三维共价有机框架（3D COF）中的铜配位方式,有效优化了NO₃RR的电催化性能。所合成的Cu-8mgATZ-COF材料具有稳定的骨架结构和良好的化学稳定性。在3000 ppm的高浓度硝酸盐条件下,Cu-8mgATZ-COF的硝酸盐还原效率显著优于COF-300,实现了34%的氨产物法拉第效率和2284.5 μg·mg⁻¹·h⁻¹的氨产率。本研究首次报道了基于铜修饰的COF-300在高浓度NO3RR体系中的应用,为COF材料在硝酸盐电还原领域的高效电催化剂设计提供了新的思路。

关键词: 共价有机框架, 硝酸盐还原反应, 三维多孔材料, 氨合成, 环境电催化

Electrochemical nitrate reduction reaction (NO3RR) has gained significant attention as a dual-purpose strategy for sustainable wastewater treatment and value-added ammonia synthesis. However, the practical implementation of NO3RR is fundamentally constrained by the lack of efficient electrocatalysts capable of achieving high activity, superior ammonia selectivity, and satisfactory Faradaic efficiency simultaneously. To address these challenges, we herein report a molecular-level coordination engineering approach to optimize the NO3RR performance by incorporating precisely controlled copper active sites into a robust three-dimensional covalent organic framework (3D COF). The designed catalyst, denoted as Cu-8mgATZ-COF, was synthesized through a post-modification strategy that ensures uniform copper coordination while maintaining structural integrity. Extensive characterization confirms its highly porous architecture, exceptional stability, and well-dispersed metal sites. When evaluated as an electrocatalyst for nitrate reduction, Cu-8mgATZ-COF delivers outstanding performance under high nitrate concentration (3000 ppm), markedly surpassing the unmodified COF-300 benchmark. It achieves a notable ammonia Faradaic efficiency of 34% and a high ammonia yield rate of 2284.5 μg mg⁻¹cat h⁻¹, making it among the best-performing noble-metal-free COF catalysts reported for nitrate-to-ammonia conversion. Furthermore, the catalyst exhibits remarkable operational durability across multiple cycling tests. This study not only presents the first successful example of a copper-integrated 3D COF for high-concentration nitrate electroreduction but also offers new insights into the rational design of molecularly defined porous catalysts for sustainable electrochemical applications such as environmental remediation and energy-efficient ammonia production.

Key words: Covalent organic framework, Nitrate reduction reaction, 3D Porous Materials, Ammonia Synthesis, Environmental electrocatalysis