Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels.

An electrode's performance for catalytic CO2 conversion to fuels is a complex convolution of surface structure and transport effects. Using well-defined mesostructured silver inverse opal (Ag-IO) electrodes, it is demonstrated that mesostructure-induced transport limitations alone serve to increase the turnover frequency for CO2 activation per unit area, while simultaneously improving reaction selectivity. The specific activity for catalyzed CO evolution systematically rises by three-fold and the specific activity for catalyzed H2 evolution systematically declines by ten-fold with increasing mesostructural roughness of Ag-IOs. By exploiting the compounding influence of both of these effects, we demonstrate that mesostructure, rather than surface structure, can be used to tune CO evolution selectivity from less than 5 % to more than 80 %. These results establish electrode mesostructuring as a powerful complementary tool for tuning both catalyst selectivity and efficiency for CO2 conversion into fuels.