Electrolyte-Guided Design Of Electroreductive Co Coupling On Copper Surfaces

Engineering the interfacial distribution of electrolytic ions can aid in modulating the electrocatalyst performance and efficiency. Using a hybrid quantum-classical modeling approach, we describe how predictive tuning of the solution microenvironment on copper can enhance the efficiency of CO2 reduction (CO2R) to C-2 products. We elucidate how competing electrolyte constituents in mixed electrolyte solutions stimulate restructuring of the electrochemical double layer (EDL) and stabilize the OCCO* dimer (* denotes surface adsorbed), with predictions validated in flow reactors using copper gas diffusion electrodes (Cu-GDEs). Our findings highlight how molecular-scale electrolyte engineering with informed models of the EDL can be leveraged to tailor CO2R activity and selectivity toward C-2 products.