铜表面原位卡宾聚合调控界面微环境促进选择性CO2电还原

doi:10.1016/S1872-2067(25)64918-7

催化学报 ›› 2026, Vol. 82: 153-160.DOI: 10.1016/S1872-2067(25)64918-7

铜表面原位卡宾聚合调控界面微环境促进选择性CO₂电还原

曹雨羊^a, 张婷婷^b, 杨华倩^a, 张文峰^a, 李非非^a^,^*(), 熊礼威^a, 王功伟^b^,^*()

^a武汉工程大学材料科学与工程学院, 等离子体化学与新材料湖北省重点实验室, 湖北武汉 430205
^b武汉大学化学与分子科学学院, 化学电源材料与技术湖北省重点实验室, 湖北武汉 430072

收稿日期:2025-07-28 接受日期:2025-10-15 出版日期:2026-03-18 发布日期:2026-03-05
通讯作者: * 电子信箱: feifeili1907@wit.edu.cn (李非非),gwwang@whu.edu.cn (王功伟).
基金资助:
国家自然科学基金(52203279);国家自然科学基金(22172115);湖北省自然科学基金(2022CFB637)

In-situ carbene polymerization on copper electrodes to modulate interface microenvironment for selective electrochemical CO₂ reduction

Yuyang Cao^a, Tingting Zhang^b, Huaqian Yang^a, Wenfeng Zhang^a, Feifei Li^a^,^*(), Liwei Xiong^a, Gongwei Wang^b^,^*()

^aSchool of Materials Science and Engineering, Hubei Key Laboratory of Plasma Chemistry and Advanced Materials, Wuhan Institute of Technology, Wuhan 430205, Hubei, China
^bCollege of Chemistry and Molecular Sciences, Hubei Key Lab of Electrochemical Power Sources, Wuhan University, Wuhan 430072, Hubei, China

Received:2025-07-28 Accepted:2025-10-15 Online:2026-03-18 Published:2026-03-05
Contact: * E-mail: feifeili1907@wit.edu.cn (F. Li),gwwang@whu.edu.cn (G. Wang).
Supported by:
National Natural Science Foundation of China(52203279);National Natural Science Foundation of China(22172115);Natural Science Foundation of Hubei Province(2022CFB637)

摘要/Abstract

摘要：

电化学CO₂还原反应作为实现碳中和的重要途径, 具有广阔的应用前景. Cu基催化剂具备将CO₂深度还原成C₂₊产物的能力, 但目前仍面临特定产物选择性差、稳定性不足等挑战. 为应对这些挑战, 研究者们采取了多种策略来提升Cu基电催化剂的CO₂还原性能. 一方面, 对其组分、形貌、缺陷、氧化态等进行调控; 另一方面, 除了调控Cu基催化剂自身结构, 在其表面构筑功能化微环境, 调控界面亲疏水性、局部pH及反应中间体含量等, 也能显著影响CO₂还原的反应机制与产物分布. 与小分子表面修饰相比, 功能性聚合物薄膜能提供更稳定的界面微环境, 在电催化条件下不易发生溶解或脱落流失. 然而, 目前普遍采用滴涂、喷涂等方法进行聚合物的表面修饰,存在聚合物在电极表面分布不均、膜层厚度可控性差等问题. 因此, 开发一种普适、有效的表面聚合物修饰策略来调控电极的界面微环境, 对于提升高价值产物的选择性以及深入理解电催化机理具有重要意义.

本研究基于金属Cu可直接催化重氮化合物裂解发生卡宾聚合反应这一原理, 采用Cu电极诱导重氮化合物分解释放N₂、并生成能够引发卡宾聚合的高反应性金属-卡宾自由基, 进而促进卡宾聚合. 通过该策略, 在Cu电极表面原位生长了一系列具有不同电子效应、不同亲疏水性的聚合物膜. 利用扫描电子显微镜、核磁共振波谱、电喷雾质谱、拉曼光谱、X射线光电子能谱等表征技术, 证实重氮化合物成功在Cu电极表面引发原位卡宾聚合, 构筑了均匀、稳固的聚合物修饰层. 系统探究了该修饰层对电化学CO₂还原反应的影响规律. 研究结果表明, 采用具有给电子效应的苯基重氮化合物卡宾聚合修饰的Cu电极, 能够显著促进电化学CO₂还原成乙烯(C₂H₄). 在H型池测试中, C₂H₄的法拉第效率达43%; 在流动池测试中, C₂H₄的选择性提升至50%, C₂₊产物的总法拉第效率超过70%. 这与空白Cu箔电极表面CO₂还原主要产物为甲烷(CH₄)形成鲜明对比. 为了阐明表面聚合物修饰对CO₂还原性能的影响机制, 结合电化学原位拉曼光谱分析, 研究聚合物修饰前后界面物种差异. 发现空白Cu电极表面以低*CO覆盖率和高含水量为特征, 有利于*CO加氢产生CH₄; 经甲氧基苯基重氮化合物卡宾聚合物修饰后, 在测试电势范围内观察到明显的*COOH信号和高强度的*CO信号, 同时界面水对应的ν(O-H)明显变弱, 表明含苯基的卡宾聚合物修饰显著降低了界面水含量, 抑制析氢副反应, 同时促进了关键中间物种*CO的产生, 从而促进C-C偶联生成C₂H₄.

综上, 本文发展的金属表面原位卡宾聚合策略, 为构筑稳定、功能化的金属电极-聚合物界面微环境提供了新方法. 同时, 该研究通过精准调控界面微环境, 显著提升了CO₂电还原制C₂H₄选择性, 为设计高效的电催化CO₂还原界面提供了新思路.

关键词: CO₂还原, 界面微环境, 表面修饰, 卡宾聚合, 乙烯

Abstract:

The development of functional interfacial microenvironments via polymer coating modification offers a promising strategy for enhancing electrocatalytic reactions. However, conventional polymer modification typically relies on physical approaches such as drop-coating or spraying, which often suffer from issues such as uneven distribution and limited controllability. In this study, we introduce a novel approach that leverages the direct metal-catalyzed cleavage of diazo compounds to initiate carbene polymerization, enabling the in-situ growth of functional polymers on the Cu surface. By employing this method with three different diazo monomers, we fabricated distinct carbene polymer (CP) modification layers on a Cu electrode surface and investigated their influence on the electrocatalytic CO₂ reduction reaction. Our findings demonstrate that Cu electrodes modified with CP derived from phenyl diazo compounds exhibit a substantial improvement in C₂₊ production (primarily ethylene). In-situ Raman spectroscopy analysis revealed that CP modification effectively reduced the interfacial H₂O content and increased the *CO intermediate coverage, thereby facilitating C-C coupling and enhancing ethylene production. This study highlights the potential of surface polymerization for constructing functional interfacial microenvironments to control electrocatalytic reactions.

Key words: CO₂ reduction, Interfacial microenvironment, Surface modification, Carbene polymerization, Ethylene

曹雨羊, 张婷婷, 杨华倩, 张文峰, 李非非, 熊礼威, 王功伟. 铜表面原位卡宾聚合调控界面微环境促进选择性CO₂电还原[J]. 催化学报, 2026, 82: 153-160.

Yuyang Cao, Tingting Zhang, Huaqian Yang, Wenfeng Zhang, Feifei Li, Liwei Xiong, Gongwei Wang. In-situ carbene polymerization on copper electrodes to modulate interface microenvironment for selective electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2026, 82: 153-160.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64918-7

https://www.cjcatal.com/CN/Y2026/V82/I3/153

图/表 4

Fig. 1. (a) Scheme of the carbene polymerization mechanism. (b) Schematic illustration of the in situ carbene polymerization on the Cu surface. SEM image (c), AFM image (d), and EDS elemental mapping images (e,f) of a representative Cu@CP(MeO-diazo) surface using p-methoxyphenyl diazonium tetrafluoroborate (MeO-diazo) as the polymerization monomer.

Fig. 2. ESI-MS spectra of the Cu@CP(MeO-diazo) in the m/z range of 100-500 (a) and 500-1400 (b). (c) Raman spectra of the blank Cu foil (black), Cu@CP(MeO-diazo) (purple), and MeO-diazo monomer (blue). (d) C 1s, N 1s, and Cu 2p XPS spectra of the blank Cu (black) and the Cu@CP(MeO-diazo) (red). Water CA measurements of the blank Cu (e) and Cu@CP(MeO-diazo) (f).

Fig. 3. CO2RR performance of the blank Cu (a) and Cu@CP(MeO-diazo) (b) electrode (60 min treatment) in the H-cell with CO2-saturated 0.1 mol L-1 KHCO3 electrolyte (pH = 6.8) and continuous CO2 supply at 5 mL min-1. (c) Potential-dependent C2H4 FEs for the blank Cu and Cu@CP(MeO-diazo) electrodes obtained via immersion treatment for 30, 45, 60 min, and 4 h. (d) CO2RR performance of the Cu@CP(MeO-diazo) GDE in the flow-cell with 0.5 mol L-1 KHCO3 electrolyte (pH = 7.2) and continuous CO2 supply at 20 mL min-1. The error bars represent the standard deviations (SD) of three independent tests.

Fig. 4. In-situ Raman spectra of CO2RR on the blank Cu foil electrode (a) and Cu@CP(MeO-diazo) electrode (b) under different cathodic potentials (vs. RHE). The electrochemical Raman cell comprised a Cu foil working electrode, a Pt wire counter electrode, an Ag wire reference electrode (calibrated against RHE), and a CO2-saturated 0.1 mol L-1 KHCO3 electrolyte (pH ~6.8). The gray-shaded ranges indicate the vibrations of the surface polymer CP(MeO-diazo).

参考文献

[1]	F. P. García de Arquer, C.-T. Dinh, A. Ozden, J. Wicks, C. McCallum, A. R. Kirmani, D.-H. Nam, C. Gabardo, A. Seifitokaldani, X. Wang, Y. C. Li, F. Li, J. Edwards, L. J. Richter, S. J. Thorpe, D. Sinton, E. H. Sargent, Science, 2020, 367, 661-666.
[2]	M. B. Ross, P. De Luna, Y. Li, C.-T. Dinh, D. Kim, P. Yang, E. H. Sargent, Nat. Catal., 2019, 2, 648-658.
[3]	M. Jiang, H. Wang, M. Zhu, X. Luo, Y. He, M. Wang, C. Wu, L. Zhang, X. Li, X. Liao, Z. Jiang, Z. Jin, Chem. Soc. Rev., 2024, 53, 5149-5189.
[4]	X. She, Y. Wang, H. Xu, S. Chi Edman Tsang, S. Ping Lau, Angew. Chem. Int. Ed., 2022, 61, e202211396.
[5]	H. Yang, S. Li, Q. Xu, Chin. J. Catal., 2023, 48, 32-65.
[6]	S. Li, G. Wu, J. Mao, A. Chen, X. Liu, J. Zeng, Y. Wei, J. Wang, H. Zhu, J. Xia, X. Wang, G. Li, Y. Song, X. Dong, W. Wei, W. Chen, Angew. Chem. Int. Ed., 2024, 63, e202407612.
[7]	F. Li, H. Tariq, H. Yang, Y. Cao, T. Zhou, G. Wang, ACS Catal., 2024, 14, 15088-15095.
[8]	Z. Liu, L. Song, X. Lv, M. Liu, Q. Wen, L. Qian, H. Wang, M. Wang, Q. Han, G. Zheng, J. Am. Chem. Soc., 2024, 146, 14260-14266.
[9]	H. Gao, G. Zhang, D. Cheng, Y. Wang, J. Zhao, X. Li, X. Du, Z.-J. Zhao, T. Wang, P. Zhang, J. Gong, Chin. J. Catal., 2023, 52, 187-195.
[10]	X. Tong, P. Zhang, P. Chen, Z. He, X. Kang, Y. Yin, Y. Cheng, M. Zhou, L. Jing, C. Wang, B. Xu, L. Zheng, X. Xing, Z. Wu, B. Han, Angew. Chem. Int. Ed., 2025, 64, e202413005.
[11]	S. Mu, L. Li, R. Zhao, H. Lu, H. Dong, C. Cui, ACS Appl. Mater. Interfaces, 2021, 13, 47619-47628.
[12]	J. Chen, H. Qiu, Y. Zhao, H. Yang, L. Fan, Z. Liu, S. Xi, G. Zheng, J. Chen, L. Chen, Y. Liu, L. Guo, L. Wang, Nat. Commun., 2024, 15, 5893.
[13]	C. Kim, J. C. Bui, X. Luo, J. K. Cooper, A. Kusoglu, A. Z. Weber, A. T. Bell, Nat. Energy, 2021, 6, 1026-1034.
[14]	H. Wang, J. Wang, F. Wei, Z. Mi, F. Li, L. Xiao, G. Wang, L. Zhuang, ACS Appl. Energy Mater., 2024, 7, 11154-11160.
[15]	A. Ozden, F. Li, F. P,. Garcı́a de Arquer, A. Rosas-Hernández, A. Thevenon, Y. Wang, S.-F. Hung, X. Wang, B. Chen, J. Li, J. Wicks, M. Luo, Z. Wang, T. Agapie, J. C. Peters, E. H. Sargent, D. Sinton, ACS Energy Lett., 2020, 5, 2811-2818.
[16]	A. Thevenon, A. Rosas-Hernández, J. C. Peters, T. Agapie, Angew. Chem. Int. Ed., 2019, 58, 16952-16958.
[17]	Y. Wang, Y. Cheng, S. Liu, Y. Yin, J. Yang, H. Wang, K. Li, M. Zhou, J. Jiao, P. Zhang, Q. Qian, Q. Zhu, X. Sun, Y. Xu, M. Luo, X. Kang, B. Han, Angew. Chem. Int. Ed., 2025, 64, e202420661.
[18]	C. Yan, D. Gao, J.-J. Velasco-Vélez, G. Wang, EES Catal., 2024, 2, 220-230.
[19]	S. Yu, S. Louisia, P. Yang, JACS Au, 2022, 2, 562-572.
[20]	J.-J. Lv, R. Yin, L. Zhou, J. Li, R. Kikas, T. Xu, Z.-J. Wang, H. Jin, X. Wang, S. Wang, Angew. Chem. Int. Ed., 2022, 61, e202207252.
[21]	X. Wei, Z. Yin, K. Lyu, Z. Li, J. Gong, G. Wang, L. Xiao, J. Lu, L. Zhuang, ACS Catal., 2020, 10, 4103-4111.
[22]	X. Kong, B. Liu, Z. Tong, R. Bao, J. Yi, S. Bu, Y. Liu, P. Wang, C.-S. Lee, W. Zhang, SmartMat, 2024, 5, e1262.
[23]	Z. Xing, L. Hu, D. S. Ripatti, X. Hu, X. Feng, Nat. Commun., 2021, 12, 136.
[24]	Y. Yao, T. Shi, W. Chen, J. Wu, Y. Fan, Y. Liu, L. Cao, Z. Chen, Nat. Commun., 2024, 15, 1257.
[25]	D. Wakerley, S. Lamaison, F. Ozanam, N. Menguy, D. Mercier, P. Marcus, M. Fontecave, V. Mougel, Nat. Mater., 2019, 18, 1222-1227.
[26]	B. Wang, X. Wang, B. Wu, P. Li, S. Chen, R. Lu, W. Lai, Y. Shen, Z. Zhuang, J. Zhu, Z. Wang, D. Wang, Y. Lum, Angew. Chem. Int. Ed., 2025, 64, e202417196.
[27]	W. Fu, Y. Li, J. Chen, J. Che n, S. Xi, J. Zhang, L. Wang, Angew. Chem. Int. Ed., 2024, 63, e202407992.
[28]	J. Li, F. Li, C. Liu, F. Wei, J. Gong, W. Li, L. Xue, J. Yin, L. Xiao, G. Wang, J. Lu, L. Zhuang, ACS Energy Lett., 2022, 7, 4045-4051.
[29]	N. B. Watkins, Y. Wu, W. Nie, J. C. Peters, T. Agapie, ACS Energy Lett., 2023, 8, 189-195.
[30]	T. Deng, S. Jia, C. Chen, J. Jiao, X. Chen, C. Xue, W. Xia, X. Xing, Q. Zhu, H. Wu, M. He, B. Han, Angew. Chem. Int. Ed., 2024, 63, e202313796.
[31]	J. Wang, T. Cheng, A. Q. Fenwick, T. N. Baroud, A. Rosas-Hernández, J. H. Ko, Q. Gan, W. A. Goddard, R. H. Grubbs, J. Am. Chem. Soc., 2021, 143, 2857-2865.
[32]	S. Jia, Q. Zhu, M. Chu, S. Han, R. Feng, J. Zhai, W. Xia, M. He, H. Wu, B. Han, Angew. Chem. Int. Ed., 2021, 60, 10977-10982.
[33]	X. Du, P. Zhang, G. Zhang, H. Gao, L. Zhang, M. Zhang, T. Wang, J. Gong, Natl. Sci. Rev., 2024, 11, nwad149.
[34]	J. Wang, Z. Zhang, W. Wu, Y. Liu, B. Dong, Y. Wang, Y. Wang, ACS Energy Lett., 2024, 9, 110-117.
[35]	R. Zhang, F. Chen, H. Jin, Y. Zhang, X. Hao, Y. Liu, T. Feng, X. Zhang, Z. Lu, W. Wang, F. Lu, H. Dong, H. Liu, H. Liu, Y. Cheng, Chem. Eng. J., 2023, 461, 142052.
[36]	H. Wu, L. Huang, J. Timoshenko, K. Qi, W. Wang, J. Liu, Y. Zhang, S. Yang, E. Petit, V. Flaud, J. Li, C. Salameh, P. Miele, L. Lajaunie, B. Roldán Cuenya, D. Rao, D. Voiry, Nat. Energy, 2024, 9, 422-433.
[37]	F. Li, L. Xiao, B. Li, X. Hu, L. Liu, Coord. Chem. Rev., 2022, 473, 214806.
[38]	D. Wang, M. K. Khan, M. G. Moloney, Tetrahedron Lett., 2020, 61, 151672.
[39]	X. Jia, Y. Li, L. Xiao, L. Liu, Polym. Chem., 2014, 5, 4781-4789.
[40]	H. Zhang, C. Gu, M. Fan, Z. Zhao, X. Kong, Z. Geng, Sci. China Chem., 2024, 67, 3925-3933.
[41]	Y. Zhao, X.-G. Zhang, N. Bodappa, W.-M. Yang, Q. Liang, P. M. Radjenovica, Y.-H. Wang, Y.-J. Zhang, J.-C. Dong, Z.-Q. Tian, J.-F. Li, Energy Environ. Sci., 2022, 15, 3968-3977.
[42]	T. Zhang, S. Xu, D.-L. Chen, T. Luo, J. Zhou, L. Kong, J. Feng, J.-Q. Lu, X. Weng, A.-J. Wang, Z. Li, Y. Su, F. Yang, Angew. Chem. Int. Ed., 2024, 63, e202407748.
[43]	J. Gong, J. Li, C. Liu, F. Wei, J. Yin, W. Li, L. Xiao, G. Wang, J. Lu, L. Zhuang, Chin. J. Catal., 2022, 43, 3101-3106.
[44]	S. Jiang, K. Klingan, C. Pasquini, H. Dau, J. Chem. Phys., 2019, 150, 041718.

铜表面原位卡宾聚合调控界面微环境促进选择性CO₂电还原

In-situ carbene polymerization on copper electrodes to modulate interface microenvironment for selective electrochemical CO₂ reduction

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