Surface and Electronic Structure of Titanium Dioxide Photocatalysts

TiO 2 films prepared by sol−gel route are active photocatalysts for the oxidation of organics in photoelectrochemical cells. The as-grown films for photocatalysis applications and those exposed to Ar + or H 2 + +Ar + ion bombardment are characterized by different spectroscopic methods, such as X-ray diffraction (XRD), atomic force microscopy (AFM), UV−vis transmittance, photothermal 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 nondissociative adsorption of O 2 when films are exposed to air. Charge transfer from reduced Ti species to adsorbed dioxygen leads to Ti−O 2 - surface complexes that are partially removed by heating at 200 °C, and fully removed after 30 min ion bombardment. By comparison with the relatively well-understood structural defects of bombarded TiO 2 we arise to a quite complete structural model of the as grown material which corresponds to an amorphous semiconductor possessing relative low disorder and density of states as compared with a pure amorphous material. These TiO 2 films are modeled as low size crystalline domain embedded in an amorphous matrix whose electronic structure exhibit exponential band tails and a narrow band close to the conduction band. The latter is fully or partially occupied depending on the presence of adsorbed electron scavengers such as dioxygen.