Ab initio study of surface structural changes during methanol synthesis over Zn/Cu(111)

We have studied the adsorption state of formate on clean and Zn-deposited Cu(111) surfaces by using a DFT–GGA–pseudopotential method. We show that, although the deposited Zn alone is substitutionally adsorbed on the Cu(111) surface, the formate stabilizes the Zn atom sitting on the Cu surface and forms a tilted bidentate formate bound to the Zn and Cu atoms. Our results suggest that the adsorption state of Zn changes from the substitutional to on-surface adsorption by co-adsorption with the formate.