A computational study on water adsorption on Cu2O(111) surfaces: The effects of coverage and oxygen defect

Water adsorption on the clean and defective Cu2O(111) surfaces with different coverages was investigated using spin-polarized density functional theory. •Only molecular H2O chemisorption is preferred on clean Cu2O(111) surface.•Ordered surface layer structures are observed at 1–2 ML H2O adsorption.•The defect surface with oxygen vacancy favors dissociative H2O adsorption.•The adsorption mechanism was analyzed on the basis of the density of states. The interaction of water with solid surfaces plays an important role in many chemical reactions. The present work investigates water adsorption on the clean and defective Cu2O(111) surfaces using spin-polarized density functional theory. The results show that at low water coverage, only molecular H2O chemisorption is preferred on clean Cu2O(111) surface, and the water adsorption results in surface reconstruction. Up to 1 monolayer (ML), the adsorbed H2O molecules interact with the coordinatively unsaturated Cu atoms as well as the coordinatively unsaturated surface oxygen atoms via H-bonding. Up to 2 ML, the adsorbed H2O molecules interact with the coordinatively unsaturated surface oxygen atoms and the first layer adsorbed H2O molecules via H-bonding. Ordered surface layer structures are observed at 1 and 2 ML H2O adsorption. In contrast to the clean surface, the defect surface with oxygen vacancy favors dissociative H2O adsorption with the dissociated OH group bridging the surface Cu atoms and the H atom on the coordinatively saturated third layer O atom. The adsorption mechanisms are analyzed on the basis of the total density of states. It is found that wet electron states on the clean and H2O adsorbed Cu2O(111) surfaces might be important for their photocatalytic properties. Water adsorption on Cu2O surface is stronger than on MgO, Fe3O4, Fe2O3 and CeO2, while weaker than on Al2O3. The different H2O adsorption mechanisms on different metal oxides may benefit for new H2O-splitting metal oxides catalyst designing.