Redox Replacement of Silver on MOF-Derived Cu/C Nanoparticles on Gas Diffusion Electrodes for Electrocatalytic CO2 Reduction

Bimetallic tandem catalysts have emerged as a promising strategy to locally increase the CO flux during electrochemical CO2 reduction, so as to maximize the rate of conversion to C-C-coupled products. Considering this, a novel Cu/C-Ag nanostructured catalyst has been prepared by a redox replacement process, in which the ratio of the two metals can be tuned by the replacement time. An optimum Cu/Ag composition with similarly sized particles showed the highest CO2 conversion to C2+ products compared to non-Ag-modified gas-diffusion electrodes. Gas chromatography and in-situ Raman measurements in a CO2 gas diffusion cell suggest the formation of top-bound linear adsorbed *CO followed by consumption of CO in the successive cascade steps, as evidenced by the increasing nu C-H bands. These findings suggest that two mechanisms operate simultaneously towards the production of HCO2H and C-C-coupled products on the Cu/Ag bimetallic surface.