Understanding Metal Oxide Surfaces at the Atomic Scale: STM Investigations of Bulk-defect Dependent Surface Processes

Abstract

AbstractSurface defects are important in oxide surface chemistry, because they change not only the surface geometric structure, but also affect the local electronic structure. Scanning Tunneling Microscopy (STM) images with atomic-scale resolution, in combination with area-averaging surface spectroscopies, is an ideal tool to study local surface defects and their relationship to surface reactivity. We report STM results onTiO2(110) surfaces which show the surprising influence of bulk defects on surface properties. Thereduced crystals used in this and other surface science studies contain Ti interstitials and oxygen vacancies. Re-oxidation at elevated temperatures results in the growth of additional TiO2 layers with Ti coming from the bulk of the crystal and O from the gas phase. This often result in partially incomplete surface structures with many undercoordinated atoms. The esorption behavior of elemental S, dosed at room temperature, depends on the reduction state of the sample. This is explained by a mechanism where desorption froma weaklybound precursor state competes with the availability of new adsorption sites in the form of oxygen vacancies which migrate from the bulk to the surface.