Structural and Electronic Properties of a W₃O₉Cluster Supported on the TiO₂(110) Surface

Abstract

The stoichiometric tritungsten oxide cluster (W3O9) deposited on the TiO2(110) surface has been investigated using first-principles density functional theory calculations. Various possible configurations mainly derived from molecular dynamics simulations have been considered. On the basis of the comparisons of thermodynamic stability and STM images, two isoenergetic structures with chirality relationship between the geometries of W3O9 clusters can be tentatively assigned to be the most likely configurations under the experimental conditions, in which five new bonds including three Ti−O and two W−O bonds are formed at the interface. Due to the loss of three WO groups, the low chemical reactivity of the W3O9 cluster can be expected. After deposition of W3O9, the TiO2(110) surface still retains the semiconducting character and the charge transfer occurring between the cluster and the substrate is small. The variation of surface dipole moment is sensitive to the orientation of the six-membered ring structure of W3O9. In addition, our results indicate that the properties of the TiO2(110) surface may be adjusted by deposition of nonstoichiometric tungsten oxides.

Ultrasmall MoOx Clusters as a Novel Cocatalyst for Photocatalytic Hydrogen Evolution

“…To support the hypothesis, first-principle theoretical calculations are performed to provide fundamental insights into the electronic structures of CdS NWs before and after the decoration of MoO x clusters. [47] The partial charge density maps of VB from −1.0 eV to Fermi level and CB from 0 to 1.0 eV are also calculated ( Figure S17, Supporting Information). [44] The valence charge density difference (Δρ) changes from slightly negative to positive at the CdS(001)/MoO x interface (z = 9.0-12.5 Å) and reaches a maximum at about 11.8 Å.…”

Reactivity of sub 1 nm supported clusters: (TiO2)n clusters supported on rutile TiO2 (110)

“…(WO 3 ) 3 nanocluster on TiO 2 has been studied for catalytic dehydrogenation of propanol 5,18 and a structure of the 50 supported cluster has been proposed. A later first principles density functional theory study has examined a number of models of this system to assign the most likely adsorption structure 28 . The application of supported oxide nanoclusters in catalysis is 55 a very active field.…”

A DFT study of (WO3)3nanoclusters adsorption on defective MgO ultrathin films on Ag(001)

“…Finally, further structural optimizations were carried out to determine the most stable adsorption congurations using more accurate settings (see above). The results of previous studies 34,57,58 demonstrate that adopting the method of ab initio molecular dynamics combining with quantum mechanics to determine the conguration of complex systems is feasible.…”