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

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64918-7

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

Figures/Tables 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).

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

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