Carbene dual-function bridging of Ag-Cu sites enables *CO pooling for *COCHO coupling with > 80% C2+ selectivity in CO2 electroreduction

doi:10.1016/S1872-2067(25)64888-1

Abstract

Abstract:

The electrocatalytic CO₂ reduction reaction (CO₂RR) offers a promising sustainable route for producing high-value C₂₊ chemicals and fuels by using renewable electricity. However, boosting C₂₊ product yields has been significantly hindered by insufficient *CO intermediate generation in confined spaces and limited activity of sites for subsequent hydrogenation and C-C coupling processes. Herein, we introduce an efficient strategy that involves carbene dual-function bridging of Ag-Cu sites to enable *CO pooling and facilitate *COCHO coupling. As a result, a remarkable C₂₊ Faradaic efficiency of 80.3% at 400 mA cm^-2 was achieved. In-situ surface-enhanced Raman spectroscopy, in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy, and density functional theory calculations collectively uncover the underlying mechanism. Carbene facilitates CO spillover from Ag to Cu sites, modulates the electronic structure of Cu, stabilizes CO intermediates, and reduces the energy barrier for CO hydrogenation. These effects synergistically enhance C-C coupling, thereby improving the Faradaic efficiency for C₂₊ product formation.

Key words: Carbon dioxide, C₂₊ products, Electrolysis, Carbene modification, Dual-function bridging

Haoyu Zhang, Lujie Jin, Tanghong Zheng, Xinran Qiu, Yang Liu, Dongyun Chen, Qingfeng Xu, Youyong Li, Jianmei Lu. Carbene dual-function bridging of Ag-Cu sites enables *CO pooling for *COCHO coupling with > 80% C₂₊ selectivity in CO₂ electroreduction[J]. Chinese Journal of Catalysis, 2026, 82: 105-114.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64888-1

https://www.cjcatal.com/EN/Y2026/V82/I3/105

Figures/Tables 5

Fig. 1. (a) Schematic illustration of the synthesis of Ag-Cu2O-carbene. TEM (b), HRTEM (c) HAADF-STEM images and corresponding elemental mapping, (d) of Ag-Cu2O-carbene. High-resolution Ag 3d (e) and N 1s (f) XPS spectra, and FTIR spectra (g) of Cu2O, Ag-Cu2O, and Ag-Cu2O-carbene.

Fig. 2. (a) LSV curves of the different electrodes under Ar or CO2 atmosphere. Faradaic efficiency of C1 (b) and C2+ (c) products for the three electrodes at different current densities. Faradaic efficiencies of various products for the Cu2O (d), Ag-Cu2O (e) and Ag-Cu2O-carbene (f) electrode at different current densities. (g) Comparison of Ag-Cu2O-carbene with other reported electrocatalysts. (h) Long-term stability of the Ag-Cu2O-carbene electrode at a current density of 400 mA cm-2.

Fig. 3. In-situ SERS of the Cu2O electrode (a), the Ag-Cu2O electrode (b) and Ag-Cu2O-carbene electrode (c). (d) Schematic illustration of the *CO coverage and the “desorption-re-adsorption” process on the surfaces of the three materials.

Fig. 4. (a) In-situ ATR-SEIRAS of the Cu2O electrode. (b) In-situ ATR-SEIRAS of the Ag-Cu2O electrode. (c) In-situ ATR-SEIRAS of the Ag-Cu2O-carbene electrode. Integrated peak areas of the *CHO (d) and *COCHO (e) signals on the surfaces of the three materials.

Fig. 5. (a) Adsorption energies of *CO intermediates on the surfaces of Ag, Cu, and Cu-carbene. (b) The projected density of states of the d orbital of Cu and p orbital of C atom on Cu and Cu-carbene, respectively. (c) Gibbs free energy profiles for the *CO → *COCHO reaction pathway. (d) The pCOHP for *CO adsorption on pristine Cu surface and Cu surface with carbene, respectively. (e) Schematic illustration of carbene dual-function bridging of Ag-Cu sites for enhancing *CO spillover and *COCHO coupling.

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Carbene dual-function bridging of Ag-Cu sites enables CO pooling for COCHO coupling with > 80% C₂₊ selectivity in CO₂ electroreduction

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