Moderate Surface Segregation Promotes Selective Ethanol Production in CO2Hydrogenation Reaction over CoCu Catalysts

Abstract Cobalt‐copper (CoCu) catalysts have industrial potential in CO/CO 2 hydrogenation reactions, and CoCu alloy has been elucidated as a major active phase during reactions. However, due to elemental surface segregation and dealloying phenomena, the actual surface morphology of CoCu alloy is still unclear. Combining theory and experiment, the dual effect of surface segregation and varied CO coverage over the CoCu(111) surface on the reactivity in CO 2 hydrogenation reactions is explored. The relationship between C−O bond scission and further hydrogenation of intermediate *CH 2 O was discovered to be a key step to promote ethanol production. The theoretical investigation suggests that moderate Co segregation provides a suitable surface Co ensemble with lateral interactions of co‐adsorbed *CO, leading to promoted selectivity to ethanol, in agreement with theory‐inspired experiments.