CO2 and CH2 Adsorption on Copper-Decorated Graphene: Predictions from First Principle Calculations

Single-layer graphene decorated with monodisperse copper nanoparticles can support the size and mass-dependent catalysis of the selective electrochemical reduction of CO2 to ethylene (C2H2). In this study, various active adsorption sites of nanostructured Cu-decorated graphene have been calculated by using density functional theory to provide insight into its catalytic activity toward carbon dioxide electroreduction. Based on the results of our calculations, an enhanced adsorption of the CO2 molecule and CH2 counterpart placed atop of Cu-decorated graphene compared to adsorption at pristine Cu metal surfaces was predicted. This approach explains experimental observations for carbon-based catalysts that were found to be promising for the two-electron reduction reaction of CO2 to CO and, further, to ethylene. Active adsorption sites that lead to a better catalytic activity of Cu-decorated graphene, with respect to general copper catalysts, were identified. The atomic configuration of the most selective CO2 toward the reduction reaction nanostructured catalyst is suggested.