XPS and NEXAFS study of fluorine modified TiO2 nano-ovoids reveals dependence of Ti3+ surface population on the modifying agent

Abstract

Crystalline titanium dioxide was synthesised under mild conditions by the thermal degradation of peroxotitanic acid in the presence of a number of fluoride-containing surface modifying agents (NH₄F, NH₄BF₄, NH₄PF₆, NBu₄F, NBu₄BF₄, NBu₄PF₆). The resulting materials were characterised by PXRD, SEM, HRTEM, XPS and NEXAFS. Particle phase, size, and surface area were noticeably affected by the choice of surface modifying agent. Both the cation and anion comprising the modifying agent affect the surface Ti³⁺ population of the materials, with two apparent trends observed: F⁻ > BF₄⁻ > PF₆⁻ and NBu₄⁺ > NH₄⁺. All materials displayed evidence of fluorine doping on their surfaces, although no evidence of bulk doping was observed.