title: Reduction of the (001) surface of gamma-V2O5 compared to alpha-V2O5.
abstract: The defect-free gamma-V(2)O(5)(001) surface and ordered structures of oxygen vacancies have been studied for a wide range of defect concentrations, Theta ((1)/(6) monolayer (ML) < or = Theta < or = 1 ML), combining density functional theory and statistical thermodynamics. The gamma polymorph of V(2)O(5) is characterized by two structurally different vanadium sites, V(A) and V(B). The V(A) sites having a weaker bond to an adjacent crystal layer are easier to reduce. Up to (1)/(2) ML, the V(A) defect structures with defects aligned along the [010] direction are increasingly more stable as in alpha-V(2)O(5)(001). At higher defect concentrations, the different coordination of the V(B) vanadium atoms at the gamma-V(2)O(5) surface causes an increase in the vacancy formation energy of approximately 0.8 eV/atom at Theta = 1.0 compared to Theta = (1)/(2). For alpha-V(2)O(5), this increase amounts to 0.2 eV/atom only. Under conditions (low oxygen partial pressures and high temperatures) at which the alpha-V(2)O(5)(001) surface would be fully reduced, the gamma-V(2)O(5)(001) surface is only partially reduced. The presence of surface vanadyl oxygen groups at V(B) sites may change the surface reactivity compared to that of alpha-V(2)O(5)(001).
authors.affiliation: Institut für Chemie, Arbeitsgruppe Quantenchemie, Humboldt Universität zu Berlin, Unter den Linden 6, D-10099 Berlin, Germany.
authors.forename: M Veronica
authors.initials: MV
authors.lastname: Ganduglia-Pirovano
authors.forename: Joachim
authors.initials: J
authors.lastname: Sauer