Copper-based electrocatalysts demonstrate significant potential for electrochemical CO 2 reduction toward value-added chemicals. However, achieving selective synthesis of multi-carbon (C 2+ ) products on copper-based catalysts remains a substantial challenge. In this study, a Cu 2 O electrocatalyst (Mg 0.1 -Cu 2 O-SC) doped with magnesium (Mg) and surface-modified by sodium citrate (SC) was successfully synthesized via a simple wet chemical reduction method. The Mg 0.1 -Cu 2 O-SC achieves a Faradaic efficiency (FE) of 77.8% and a partial current density of 357.9 mA cm −2 for C 2+ products, which is 1.35 times higher than the FE of unmodified Cu 2 O. Mg 0.1 -Cu 2 O achieves an enhancement in the FE for CO, demonstrating that the Lewis-acidic Mg weakens the bond strength of Cu−*CO and enhances the local concentration of *CO by attracting electrons from Cu. In situ spectroscopic analysis reveals that the surface modification of SC facilitates the *CO to *CHO hydrogenation, which shifts the C−C coupling to a more favorable *CO−*CHO route with a lower-energy barrier and consequently improves the FE for C 2+ products. Theoretical calculations indicate that the electron-withdrawing effect of Mg induces a downward shift in the copper d-band center. Energy barrier analyses reveal that SC effectively lowers the energy barriers for both the water dissociation reaction and the *CO−*CHO coupling reaction. This work confirms that Mg effectively modulates the adsorption behavior of key intermediates and synergistically optimizes the reaction pathway in concert with SC.
Zhong et al. (Mon,) studied this question.
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