Highly selective CO2 electroreduction to ethylene on long alkyl chains-functionalized copper nanowires

doi:10.1016/S1872-2067(25)64711-5

Abstract

Abstract:

Electrochemical reduction of carbon dioxide (CO₂RR) is a promising approach to complete the carbon cycle and potentially convert CO₂ into valuable chemicals and fuels. Cu is unique among transition metals in its ability to catalyze the CO₂RR and produce multi-carbon products. However, achieving high selectivity for C₂₊ products is challenging for copper-based catalysts, as C-C coupling reactions proceed slowly. Herein, a surface modification strategy involving grafting long alkyl chains onto copper nanowires (Cu NWs) has been proposed to regulate the electronic structure of Cu surface, which facilitates *CO-*CO coupling in the CO₂RR. The hydrophobicity of the catalysts increases greatly after the introduction of long alkyl chains, therefore the hydrogen evolution reaction (HER) has been inhibited effectively. Such surface modification approach proves to be highly efficient and universal, with the Faradaic efficiency (FE) of C₂H₄ up to 53% for the optimized Cu-SH catalyst, representing a significant enhancement compared to the pristine Cu NWs (30%). In-situ characterizations and theoretical calculations demonstrate that the different terminal groups of the grafted octadecyl chains can effectively regulate the charge density of Cu NWs interface and change the adsorption configuration of *CO intermediate. The top-adsorbed *CO intermediates (*CO_top) on Cu-SH catalytic interface endow Cu-SH with the highest charge density, which effectively lowers the reaction energy barrier for *CO-*CO coupling, promoting the formation of the *OCCO intermediate, thereby enhancing the selectivity towards C₂H₄. This study provides a promising method for designing efficient Cu-based catalysts with high catalytic activity and selectivity towards C₂H₄.

Key words: CO₂ electroreduction, Copper nanowires, Alkyl chain modification, Top-adsorption of *CO, Ethylene

Xiao-Han Li, Bo-Wen Zhang, Wan-Feng Xiong, Ze Li, Xiao-Yu Xiang, Si-Ying Zhang, Duan-Hui Si, Hong-Fang Li, Rong Cao. Highly selective CO₂ electroreduction to ethylene on long alkyl chains-functionalized copper nanowires[J]. Chinese Journal of Catalysis, 2025, 73: 196-204.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64711-5

https://www.cjcatal.com/EN/Y2025/V73/I6/196

Figures/Tables 4

Fig. 1. The preparation and characterizations of Cu NWs and Cu-SH. (a) Schematic illustration of the preparation of Cu NWs and Cu-RH (R = N, O, S). (b) SEM image, (c) TEM image, (d) HRTEM image and (e) the HAADF-STEM and corresponding EDS elemental mapping images of Cu-SH.

Fig. 2. Structure and composition characterization of Cu and Cu-RH. (a) XRD patterns. (b) The XPS of Cu 2p for Cu-RH and Cu NWs. (c) Cu LMM Auger spectra of Cu-RH and Cu NWs. (d) Normalized Cu K-edge XANES spectra of Cu-RH and Cu-based standard. (e) Deriv Normalized Cu K-edge XANES spectra of Cu-RH and Cu-based standard. (f) Cu K-edge wavelet transform EXAFS 2D plots of Cu foil standard and Cu-RH. (g) Cu K-edge Fourier transform (FT) EXAFS spectra of Cu-RH and Cu-based standard. (h) Fitting curves of Fourier transformation of EXAFS spectra for Cu-SH.

Fig. 3. (a) The C2+ Faradaic efficiency of Cu-RH and Cu NWs at different current. (b) The current density of C2+ for Cu-RH and Cu NWs after ECSA normalization. (c) Faradaic efficiency of Cu NWs at different current density. (d) The Faradaic efficiency of Cu-SH at different current density. (e) The C2H4 Faradaic efficiency of Cu-RH and Cu NWs at 400 mA/cm2. (f) The catalytic durability of Cu-SH at 400 mA/cm2 for 10 h.

Fig. 4. (a) In-situ ATR-FTIR spectra of Cu-SH recorded at -1.1 V vs. RHE over 700 s. (b) The detailed spectra of *OCCO intermediates over Cu-RH and Cu NWs at 400 s. (c) The detailed spectra of *COtop intermediates over Cu-RH and Cu NWs at 400 s. (d) The free energy of the C2H4 pathway from *CO-*CO on Cu-RH. (e) The charge density difference of *CO adsorbed on the surface of Cu-RH.

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Highly selective CO₂ electroreduction to ethylene on long alkyl chains-functionalized copper nanowires

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