Binary alloys for electrocatalytic CO2 conversion to hydrocarbons and alcohols

[Display omitted] •Conversion of CO2 to hydrocarbons and alcohols catalyzed by binary alloys.•Regulating CO binding strength by both electronic and surface structures of catalysts.•Comprehensive kinetic study on competing CH, OH, and CC bond formations.•Simultaneously promotion of catalytic activity and selectivity of CO2RR. Bimetallic alloys are expected to create superior catalytic performance that cannot be achieved on monometallic catalysts by regulations of both electronic and surface structures. In this work, the reaction mechanism and catalytic kinetics of electrochemical CO2 conversion on nine ⅠB group metal binary alloys are studied by using DFT computations. Various reduction products, from CO to CO-beyond products and from C1 to C2 hydrocarbons and alcohols, can be produced on different bimetallic catalysts by controlling their reaction kinetics of competing OH bond formation, CH bond formation, and CC coupling. Among all the studied binary alloys, Au-Ag alloys show enhanced CO production ability with respect to elemental Au and Ag. Cu1/4Au3/4 gives the best performance to catalyze CO2 conversion to methane and methanol as a result of simultaneously promoting CORR activity and suppressing HER side reaction. By adjusting the CORR pathway through COH* intermediate, the CC coupling barriers are lowered on Cu3/4Ag1/4 and Cu3/4Au1/4 catalysts, which deliver potential capacity to catalyze CO2 transformation to C2 products.