Surface oxides of the oxygen–copper system: Precursors to the bulk oxide phase?

To gain an initial understanding of the copper-based catalysts in commercially important chemical reactions such as the oxygen-assisted water–gas shift reaction, we performed density-functional theory calculations, investigating the interaction of oxygen and copper, focusing on the relative stability of surface oxides and oxide surfaces of the O/Cu system. By employing the technique of “ab initio atomistic thermodynamics”, we show that surface oxides are only metastable at relevant pressures and temperatures of technical catalysis, with no stable chemisorption phase observed even at very low coverage. Although exhibiting only metastability, these surface oxides resemble the bulk oxide material both geometrically and electronically, and may serve as a precursor phase before onset of the bulk oxide phase. Having identified the bulk oxide as the most stable phase under realistic catalytic conditions, we show that a Cu2O(1 1 1) surface with Cu vacancies has a lower free energy than the stoichiometric surface for the considered range of oxygen chemical potential and could be catalytically relevant.