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

doi:10.6023/A25060221

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (12): 1507-1513.DOI: 10.6023/A25060221 Previous Articles Next Articles

Article

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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Abstract

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

Cite this article

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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Fig. & Tab. 4

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

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

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

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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