Surface and electronic structure of titanium dioxide photocatalysts

TiO2 films prepared by sol-gel route are active photocatalysts for the oxid ation of organics in photoelectrochemical cells. The as-grown films for pho tocatalysis applications and those exposed to Ar+ or H-2(+)-Ar+ ion bombard ment are characterized by different spectroscopic methods, such as X-ray di ffraction (XRD), atomic force microscopy (AFM), UV-vis transmittance, photo thermal deflection spectroscopy (PDS) and X-ray photoelectron spectroscopy (XPS), as well as by conductance. This material has defects associated with oxygen vacancies produced during the sample preparation which support nond issociative adsorption of Oz when films are exposed to air. Charge transfer from reduced Ti species to adsorbed dioxygen leads to Ti-O-2(-) surface co mplexes that are partially removed by heating at 200 degreesC, and fully re moved after 30 min ion bombardment. By comparison with the relatively well- understood structural defects of bombarded TiO2 we arise to a quite complet e structural model of the as grown material which corresponds to an amorpho us semiconductor possessing relative low disorder and density of states as compared with a pure amorphous material. These TiO2 films are modeled as lo w size crystalline domain embedded in an amorphous matrix whose electronic structure exhibit exponential band tails and a narrow band close to the con duction band. The latter is fully or partially occupied depending on the pr esence of adsorbed electron scavengers such as dioxygen.