Electrochemical CO2 Reduction to Ethanol on Zn‐Coordinated Cu Sites Formed by Atmosphere‐Induced Surface Reconstruction

Abstract Electrochemical CO 2 reduction reaction (CO 2 RR) to produce chemicals and fuels is a promising strategy to achieve carbon neutrality. However, due to the slow C─C coupling kinetics and the fact that C 2 H 5 OH and C 2 H 4 products share the same *HCCOH intermediate, achieving high activity and selectivity for C 2 H 5 OH remains challenging. This paper describes an atmosphere‐induced reconstruction method to optimize the surface composition and coordination structure of the Cu x Zn y bimetallic alloy catalysts for C 2 H 5 OH production. Specifically, the Cu x Zn y alloy catalyst treated within CO atmosphere (CO‐Cu x Zn y ) enriches with low‐coordinated Cu sites, which are favorable for the adsorption of the *CO intermediates for promoted C 2 H 5 OH production. A C 2+ Faradaic efficiency (FE) of 85.1% and a C 2 H 5 OH FE of 59.5% are achieved by the CO‐Cu 84 Zn 16 at a current density of 300 mA cm −2 . In‐situ spectroscopic studies and DFT calculations demonstrate that the enhanced *CO adsorption promotes the C─C coupling process. At the same time, the hydrogenation of *HCCOH is more favorable on CO‐Cu 84 Zn 16 to inhibit the C 2 H 4 pathway, thus enhancing the generation of C 2 H 5 OH. This study provides an effective strategy to regulate the selectivity of CO 2 RR through the control of the surface coordination environment of the active sites.