Insight into the adsorption and dissociation of water over different CuO(111) surfaces: The effect of surface structures

First-principles analysis of the stability of water on oxidised and reduced CuO(111) surfaces

“…The effect on the water binding energies is relatively small for a change of U up to 7.0 eV and it would not bring any substantial qualitative change in the extrapolated adsorption-desorption. However what is most important is the effect of including the +U correction in the rst place (with a sufficiently large value of U)failure to account for the correlated nature of the Cu 2+ oxidation state in the thermodynamics analysis will lead to very different results, given the large difference in water binding energy between our calculations and those of Zhang et al 20 Aer these considerations we can conclude that water dissociation may occur only in the areas of the phase diagram where water adsorbed on the surface is stable. As seen in the last section, this would bring a gain in energy, which therefore indicates that the process is thermodynamically favourable.…”

“…Unlike other metal oxide surfaces such as (110) rutile and (101) anatase TiO 2 or CeO 2 (111), [17][18][19]35,36 little is known about the interaction of water with CuO surfaces. An attempt to study surface-water interactions has been presented by Zhang et al 20 They investigated the interaction of a single water molecule with perfect and defective CuO(111) surfaces using density functional theory within the GGA approximation, using the Perdew and Wang functional (PW91) for the exchange-correlation term where copper atoms were kept frozen and substituted by a DFT semi-core pseudopotential and other atoms are treated with an all-electron basis set. However, they neglected to include any consistent description of localized electron in the Cu-3d shell.…”

First-Principles Analysis of the Stability of Water on the Oxidised and Reduced CuO(111) Surface

“…Unlike other metal oxide surfaces such as TiO 2 (110) rutile and (101) anatase, or CeO 2 (111) [17][18][19] , little is known about the interaction of water with CuO surfaces. An attempt to study surface-water interactions has been presented by Zhang et al 20 They investigated the interaction of a single water molecule with perfect and defective CuO(111) surfaces by using Density Functional Theory (DFT) within the GGA-PBE approximation, thus neglecting to include any consistent description of the Cu 2+ oxidation state of CuO. These authors obtained adsorption energies and dissociation barriers, and conclude that the oxygen vacancy can exhibit a strong catalytic activity towards H 2 O dissociation.…”

Investigating metal oxides for C1 chemistry : a computational and experimental study

“…This H bonding configuration was also detected by FTIR analysis in our recent study. 127 Finally, the dissociation of H2O on CuO(111) is quite feasible 168 with the computed activation barrier of 5 kJ mol -1 (cf Fig. 3.10c),…”

“…Water and hydroxide species can be present on the CuO surface, either from the preparation method or via the adsorption from moisture in the atmosphere. 127,[168][169][170] However, the binding energy of water is within the magnitude of ~60 kJ mol -1 and therefore H2O can be considered to be physisorbed on CuO(111) (cf Fig. 3.10a).…”