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

Abstract Electrochemical CO₂ reduction reaction (CO₂RR) 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 C₂H₅OH and C₂H₄ products share the same *HCCOH intermediate, achieving high activity and selectivity for C₂H₅OH remains challenging. This paper describes an atmosphere‐induced reconstruction method to optimize the surface composition and coordination structure of the Cu_xZn_y bimetallic alloy catalysts for C₂H₅OH production. Specifically, the Cu_xZn_y alloy catalyst treated within CO atmosphere (CO‐Cu_xZn_y) enriches with low‐coordinated Cu sites, which are favorable for the adsorption of the *CO intermediates for promoted C₂H₅OH production. A C₂₊ Faradaic efficiency (FE) of 85.1% and a C₂H₅OH FE of 59.5% are achieved by the CO‐Cu₈₄Zn₁₆ 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‐Cu₈₄Zn₁₆ to inhibit the C₂H₄ pathway, thus enhancing the generation of C₂H₅OH. This study provides an effective strategy to regulate the selectivity of CO₂RR through the control of the surface coordination environment of the active sites.