Molecular and dissociative adsorption of water at a defective Cu(110) surface

Abstract

We performed a density functional theory (DFT) investigation of the molecular and dissociative adsorption of water at the perfect Cu(110) and at a defective Cu surface that provides a broad spectrum of adsorption sites in terms of coordination of Cu atoms, with the aim of understanding the role of surface defects in the dissociation of water molecules. The molecular adsorption of water is spontaneous at both surfaces but at the defective surface we found two stable molecular adsorption structures that differ slightly in the disposition of the O-atoms of H2O on the surface plane but differ considerably on the orientation of their H-atoms. Additionally we studied the dissociative adsorption of water accompanied with formation of H2(g). At the defective surface, starting from 1ML of molecularly adsorbed H2O, the dissociation of 0.22ML of H2O leading to 0.22ML of HO, 0.78ML H2O and H2(g) is exergonic but the dissociation of 0.44ML or more H2O molecules is endergonic. These findings are discussed in terms of the two main factors that affect the adsorption energies: the existence of exposed adatoms provides an environment that facilitates the interaction with small adsorbates leading to stronger bonds between the surface and such adsorbates; and at the same time, the limited polarizability of the defect sites causes high coverages of adsorbates that drag electron density from the surface to be unfavorable. The overall effect is that at the defective Cu(110) formation of low coverages of HO groups is more favorable than at the perfect Cu(110) while forming coverages higher than 0.44ML of HO is less favorable than at the perfect Cu(110). These effects have their origin in the extent of the polarization of the Cu–O bonds.