Solid-Gas Phase Photo-Catalytic Behaviour of Rutile and TiO_n (1 < n < 2) Sub-Oxide Phases for Self-Cleaning Applications

The solid-gas phase photo-catalytic activities of rutile TiO₂ and TiO_n (1 < n < 2) sub-oxide phases have been evaluated. Varying concentrations of Ti³⁺ defects were introduced into the rutile polymorph of titanium dioxide through carbo-thermal reduction at temperatures ranging from 350 °C to 1300 °C. The resulting sub-oxides formed were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, impedance spectroscopy and UV-visible diffuse reflectance spectroscopy. The presence of Ti³⁺ in rutile exposed to high reduction temperatures was confirmed by X-ray diffraction. In addition, a Ti³⁺-Ti⁴⁺ system was demonstrated to enhance the photo-catalytic properties of rutile for the degradation of the air pollutants NO₂ and CO₂ under UV irradiation of wavelengths (λ) 376⁻387 nm and 381⁻392 nm. The optimum reduction temperature for photo-catalytic activity was within the range 350⁻400 °C and attributed to improved charge-separation. The materials that were subject to carbo-thermal reduction at temperatures of 350 °C and 400 °C exhibited electrical conductivities over one hundred times higher compared to the non-reduced rutile. The results highlight that sub-oxide phases form an important alternative approach to doping with other elements to improve the photo-catalytic performance of TiO₂. Such materials are important for applications such as self-cleaning where particles can be incorporated into surface coatings.