LAUSR

Abstract This work reports a novel and effective method for the preparation of the copper-indium bimetallic electrocatalysts by the in situ growth of indium-based metal organic frameworks on oxidized copper foils as the precursor. Compared with the oxide-derived copper and the copper-based carbon material derivative grown in situ on oxidized copper foils, the as-prepared copper-indium electrocatalyst with a self-supporting structure, high roughness factor and rich lattice defects exhibits a superior CO Faradaic efficiency of 95% and good stability for the 36-h potentiostatic test at −0.6 V versus a reversible hydrogen electrode. Density functional theory calculations indicated that the indium atoms occupying the surface copper vacancy defects show lower free energy needed for the formation of *COOH and more difficult desorption of *H than indium atoms, supported on the perfect copper surface. Thereby, the copper-indium catalyst promotes CO2 electroreduction to CO and strongly inhibits hydrogen evolution.