TiO₂ Processed by pressurized hot solvents as a novel photocatalyst for photocatalytic reduction of carbon dioxide

Highlights: • Synthesis of anatase-brookite TiO₂ photocatalysts has been described. • The materials photocatalyze carbon dioxide reduction to methane. • The photoactivity of the synthesized composites has been compared with the activity of anatase-rutile material (P25). • The influence of electronic structure on photocatalytic activity has been discussed. - Abstract: Anatase-brookite TiO₂ photocatalysts were prepared by the sol-gel process controlled within reverse micelles and processing by pressurized hot solvents–water/methanol/water (TiO₂(M)) and water/ethanol/water (TiO₂(E)), as an unconventional alternative to common calcination. The main goal of this work was to prepare anatase-brookite mixtures by processing by two different alcohols (methanol and ethanol) and evaluate the influence of the alcohol on the photocatalytic activity. Prepared photocatalysts were characterized by organic elemental analysis, nitrogen physisorption, XRD, UV–vis, photoelectrochemical and spectroelectrochemical measurements and XPS. The prepared photocatalysts efficiency was tested on the photocatalytic reduction of carbon dioxide and compared with commercial TiO₂ Evonik P25. Both prepared nanocomposites were more efficient towards methane production but Evonik P25 was the most efficient towards hydrogen generated through water splitting. The higher performance of anatase-brookite mixture towards methane production can be explained by (i) a higher photocatalytic activity of brookite than rutile; (ii) a large surface area of anatase-brookite composites enabling better carbon dioxide adsorption; (iii) the photoinduced electron transfer from the brookite conduction band to the anatase conduction band. On the other hand, a higher production of hydrogen in the presence of Evonik P25 is caused by a better charge separation in anatase-rutile than anatase-brookite phase compositions. TiO₂(M) appeared more active than TiO₂(E) in the photocatalytic reduction of carbon dioxide due to a lower density of defects created in the crystal lattice.