Enhancing the reaction selectivity for multicarbon products (C2+) is an important goal for the electrochemical CO(2) reduction (ECO(2)R) process. Cuprous compounds have demonstrated promising C2+ selectivity in the ECO(2)R process, but further investigation is necessary to thoroughly elucidate their catalytic behavior toward C2+ oxygenate production. In this study, copper nitride-based materials with varying reduction rates were employed as precatalysts. Consequently, a relationship between the selectivity toward C2+ oxygenates and the Cu oxidation state during the ECOR process is established. Results of theoretical and experimental analyses reveal that the Cu0/Cu+ interface plays a key role in enhancing *CO adsorption while lowering the formation energy of *CH2CO, thereby promoting acetate production. This work highlights the significance of the Cu0/Cu+ interface in the regulation of C2+ oxygenate production and paves the way for the development of highly selective catalysts in the future.
Keywords: CO reduction; CO2 reduction; acetate production; copper nitride; electrocatalysis; oxidation state.