铜配位三维共价有机框架提升电催化硝酸盐还原制氨

doi:10.6023/A25060221

化学学报 ›› 2025, Vol. 83 ›› Issue (12): 1507-1513.DOI: 10.6023/A25060221 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^,^*()

^a 内蒙合成化工研究所航天化学能源全国重点实验室内蒙古呼和浩特 010010
^b 北京理工大学化学化工学院化学化工学院北京 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无机合成与制备国家重点实验室吉林省长春市 130012

投稿日期:2025-06-15 发布日期:2025-09-26
基金资助:
航天化学能源全国重点实验室和内蒙古自然科学基金(2021BS05014)

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

Jiayu Wang^a^,^b, Wenjuan Zhao^a, Hongyu Jia^a, Yongbo Liu^c, Min Zhang^a, Longlong Dong^a, Anjie Zhang^a^,^*(), Rui Wang^d^,^*()

^a National Key Laboratory of Aerospace Chemical Power, Inner Mongolia Research Institute of Synthetic Chemical Industry, Hohhot 010010, Inner Mongolia, China
^b School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
^c College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010010, China
^d State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, China

Received:2025-06-15 Published:2025-09-26
Contact: * E-mail: z14747392769@163.com;rwang19@mails.jlu.edu.cn
About author:
^†These authors contributed equally to this work.
Supported by:
National Key Laboratory of Aerospace Chemical Power and Natural Science Foundation of Inner Mongolia Autonomous Region(2021BS05014)

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1. Supporting Information-A25060221.pdf(705KB)

摘要/Abstract

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0.3%(质量分数)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 (mass fraction 0.3%), 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_cat⁻¹•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

引用此文

王佳雨, 赵文娟, 贾宏宇, 刘永博, 张敏, 董龙龙, 张安杰, 王锐. 铜配位三维共价有机框架提升电催化硝酸盐还原制氨[J]. 化学学报, 2025, 83(12): 1507-1513.

Jiayu Wang, Wenjuan Zhao, Hongyu Jia, Yongbo Liu, Min Zhang, Longlong Dong, Anjie Zhang, Rui Wang. Enhancing Electrocatalytic Nitrate Reduction to Ammonia via Copper-Coordinated Three-Dimensional Covalent Organic Frameworks[J]. Acta Chimica Sinica, 2025, 83(12): 1507-1513.

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图/表 4

图1. (a) Cu-ATZ-COF合成过程的示意图; (b) COF-300的PXRD图谱, 包含实验图(黑色)、Pawley拟合图(黑色)、差值曲线(橙色)与衍射峰位置(绿色); (c)各样品的傅里叶变换红外光谱(FT-IR): 包括COF-300、4mgATZ-COF、8mgATZ-COF、Cu-4mgATZ-COF、Cu-8mgATZ-COF及ATZ单体; (d)各样品在77 K下的氮气吸附-脱附等温线图

Figure 1. (a) schematic diagram of the synthesis of Cu-ATZ-COF. (b) PXRD patterns of COF-300. Observed (black), Pawley-refined (black), difference between observed and refined profiles (orange) and brag (green). (c) FT-IR spectra of COF-300, 4mgATZ-COF, 8mgATZ-COF, Cu-4mgATZ-COF, Cu-8mgATZ-COF and ATZ. (d) N2 adsorption-desorption isotherm of COF-300, 4mgATZ-COF, 8mgATZ-COF, Cu-4mgATZ-COF and Cu-8mgATZ-COF at 77 K

图2. (a, c) Cu-4mgATZ-COF和Cu-8mgATZ-COF的N 1s高分辨XPS谱图; (b, d) Cu-4mgATZ-COF和Cu-8mgATZ-COF的Cu 2p高分辨XPS谱图

Figure 2. (a, c) N 1s high-resolution XPS spectra of Cu-4mgATZ-COF and Cu-8mgATZ-COF; (b, d) Cu 2p high-resolution XPS spectra of Cu-4mgATZ-COF and Cu-8mgATZ-COF

图3. (a)各催化剂在$N{\text{O}}_{3}^{-}$电解液中的线性扫描伏安曲线(LSV); (b)在－0.75 V至－1.25 V (vs. RHE)电位区间内, 不同催化剂的氨产率对比; (c)在相同电位范围内, 各催化剂的法拉第效率对比; (d) Cu-4mgATZ-COF和Cu-8mgATZ-COF的时间-电位稳定性测试曲线; (e)各样品的双电层电容(Cdl)测试结果; (f)各催化剂的电化学阻抗谱(EIS), 插图为拟合的等效电路模型

Figure 3. (a) LSV curves of COF-300, 4mgATZ-COF, 8mg ATZ-COF, Cu-4mgATZ-COF and Cu-8mgATZ-COF. (b) The NH3 yield of all catalysts at －0.75 V to －1.25 V (vs. RHE). (c) The FE distribution comparison of all catalysts at －0.75 V to －1.25 V (vs. RHE). (d) Time-dependent potential curves for Cu-4mgATZ-COF and Cu-8mgATZ-COF. (e) Double-layer capacitance (Cdl) measurements of COF-300, 4mgATZ-COF, 8mgATZ-COF, Cu-4mgATZ-COF and Cu-8mgATZ-COF. (f) The impedance for COF-300, 4mgATZ-COF, 8mgATZ-COF, Cu-4mgATZ-COF and Cu-8mgATZ-COF. Inset: the equivalent electric circuit

图4. 在质量分数0.3%高浓度硝酸盐条件下, (a) Cu-4mgATZ-COF与(b) Cu-8mgATZ-COF的氨产率与法拉第效率对比, 测试电位范围为－0.75 V至－1.25 V (vs. RHE)

Figure 4. The NH3 yield and the FE distribution comparison of (a) Cu-4mgATZ-COF and (b) Cu-8mgATZ-COF at －0.75 V to －1.25 V (vs. RHE)

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铜配位三维共价有机框架提升电催化硝酸盐还原制氨

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

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