Recent studies have shown that the microenvironment in the electrolyte adjacent to an electrocatalyst strongly influence the catalyst activity and selectivity. This talk will illustrate how knowledge of the intrinsic kinetics of electrochemical reduction of CO2 can be used to suggest ways in which the microenvironment near the catalyst surface should be changed to enhance catalyst activity and selectivity, particularly for the formation of C2+ products. We will show how catalyst performance is affected by the local concentrations of CO2 and H2O, the pH, and the composition and concentration of electrolyte cations and anions. The way in which pulsed electrolysis can be used to access transient microenvironments not attainable under conditions of static electrolysis will be illustrated as well. This presentation will also show how theoretical analysis can be used to understand the phenomena observed experimentally.
