The first-principles calculation to predict electroreduction of CO2 to ethanol over Al/Cu(111) bimetallic catalyst.

• In the present paper, we highlight the role of oxophilic Al atom in the Cu(111) surface for the CO 2 adsorption and in the subsequent reduction reactions. • Our periodic density functional theory (DFT) calculations show that introduction of the oxophilic Al atom into the Cu(111) surface effectively improves the CO 2 adsorption ability via formation of a Alδ+- (Cu6)δ- configuration on the Al/Cu(111) surface. • The adsorbed CO2 was easily reduced to CO via a unique dissociated adsorption process induced by the oxophilic Al center. Our energy calculations show that introduction of the Al atom into the Cu(111) surface is both thermodynamically and kinetically favorable for CO dimerization when compared with the pristine Cu(111) surface. And the Al center acts as an electron-transfer medium for the coupling of two CO molecules over Al/Cu(111) surface. Inspired by the work of Sargent et al. (Nature , 2020, 581 , 178–183), the oxophilic Al atom was introduced into the Cu(111) surface to design a Al/Cu(111) bimetallic catalysts for implementing electrochemical CO 2 reduction reaction based on the first-principles calculations. The results indicate that introduction of the oxophilic Al atom into the Cu(111) surface effectively improves the CO 2 adsorption ability via formation of a Alδ+- (Cu 6)δ− configuration on the Al/Cu(111) surface. And the adsorbed CO 2 was easily reduced to CO via a unique dissociated adsorption process induced by the oxophilic Al center. Our energy calculations show that introduction of the Al atom into the Cu(111) surface is both thermodynamically and kinetically favorable for CO dimerization when compared with the pristine Cu(111) surface. And the Al center acts as an electron-transfer medium for the coupling of two CO molecules over Al/Cu(111) surface. Finally, our mechanism investigation shows that the presence of oxophilic Al atom in the Cu(111) surface effectively improves the selectivity of ethanol product via the formation of the Al-O bond along the hydrogenation path. [Display omitted] [ABSTRACT FROM AUTHOR]