Intermediates Adsorption Engineering of CO2 Electroreduction Reaction in Highly Selective Heterostructure Cu‐Based Electrocatalysts for CO Production

Abstract The challenge in the artificial CO 2 reduction to fuel is achieving high selective electrocatalysts. Here, a highly selective Cu 2 O/CuO heterostructure electrocatalyst is developed for CO 2 electroreduction. The Cu 2 O/CuO nanowires modified by Ni nanoparticles exhibit superior catalytic performance with high faradic efficiency (95% for CO). Theoretical and experimental analyses show that the hybridization of Cu 2 O/CuO nanowires and Ni nanoparticles can not only adjust the d‐band center of electrocatalysts to enhance the intrinsic catalytic activity but also improve the adsorption of COOH* intermediates and suppress the hydrogen evolution reaction to promote the CO conversion efficiency during CO 2 reduction reaction. An in situ Raman spectroscopic study further confirms the existence of COOH* species and the engineering intermediates adsorption. This work offers new insights for facile designing of nonprecious transition metal compound heterostructure for CO 2 reduction reaction through adjusting the reaction pathway.