Monitoring the Structure Evolution of Titanium Oxide Photocatalysts: From the Molecular Form via the Amorphous State to the Crystalline Phase

Amorphous Ti_xO_y with high surface area has attracted significant interest as photocatalyst with higher activity in ultraviolet (UV) light-induced water splitting applications compared to commercial nanocrystalline TiO₂. Under photocatalytic operation conditions, the structure of the molecular titanium alkoxide precursor rearranges upon hydrolysis and leads to higher connectivity of the structure-building units. Structurally ordered domains with sizes smaller than 7 Å form larger aggregates. The experimental scattering data can be explained best with a structure model consisting of an anatase-like core and a distorted shell. Upon exposure to UV light, the white Ti_xO_y suspension turns dark corresponding to the reduction of Ti⁴⁺ to Ti³⁺ as confirmed by electron energy loss spectroscopy (EELS). Heat-induced crystallisation was followed by in situ temperature-dependent total scattering experiments. First, ordering in the Ti?O environment takes place upon to 350 °C. Above this temperature, the distorted anatase core starts to grow but the structure obtained at 400 °C is still not fully ordered.