Engineering Surface Oxophilicity of Copper for Electrochemical CO2 Reduction to Ethanol.

ABSTRACT

Copper-based materials are known for converting CO2 into deep reduction products via electrochemical reduction reaction (CO2 RR). As the major multicarbon products (C2+ ), ethanol (C2 H5 OH) and ethylene (C2 H4 ) are believed to share a common oxygenic intermediate according to theoretical studies, while the key factors that bifurcate C2 H5 OH and C2 H4 pathways on Cu-based catalysts are not fully understood. Here, a surface oxophilicity regulation strategy to enhance C2 H5 OH production in CO2 RR is proposed, demonstrated by a Cu-Sn bimetallic system. Compared with bare Cu catalyst, the Cu-Sn bimetallic catalysts show improved C2 H5 OH but suppressed C2 H4 selectivity. The experimental results and theoretical calculations demonstrate that the surface oxophilicity of Cu-Sn catalysts plays an important role in steering the protonation of the key oxygenic intermediate and guides the reaction pathways to C2 H5 OH. This study provides new insights into the electrocatalyst design for enhanced production of oxygenic products from CO2 RR by engineering the surface oxophilicity of copper-based catalysts.