Experimental and Theoretical Characterization of Superoxide Complexes [W2O6(O2?)] and [W3O9?(O2?)]: Models for the Interaction of O2 with Reduced W Sites on Tungsten Oxide Surfaces

January 16, 2006

Journal Article

Experimental and Theoretical Characterization of Superoxide Complexes [W2O6(O2?)] and [W3O9?(O2?)]: Models for the Interaction of O2 with Reduced W Sites on Tungsten Oxide Surfaces

Abstract

Two O-rich tungsten oxide clusters, W2O8- and W3O11-, were produced and investigated by photoelectron spectroscopy and density functional theory calculations. The two anions are best considered as W2O6(O2-) and W3O9(O2-), respectively, each containing a side-on bound superoxide ligand, whereas the neutral clusters W2O8 and W3O11 are shown to involve O2 physisorbed to the W2O6 or W3O9 stoichiometric cluster. The current study indicates that the extra electron in W2O6- and W3O9- are capable of activating dioxygen by non-dissociative electron transfer (W 5d - O2 -*), and the two anionic clusters can be viewed as models for reduced defect sites on tungsten oxide surfaces for the chemisorption of O2.

Revised: March 8, 2006 | Published: January 16, 2006

Citation

Huang X., H.J. Zhai, T. Waters, J. Li, and L.S. Wang. 2006. Experimental and Theoretical Characterization of Superoxide Complexes [W2O6(O2?)] and [W3O9?(O2?)]: Models for the Interaction of O2 with Reduced W Sites on Tungsten Oxide Surfaces. Angewandte Chemie International Edition 45, no. 4:657-660. PNNL-SA-47289. doi:10.1002/anie.200503652