Thick mesoporous TiO2 films through a sol–gel method involving a non-ionic surfactant: Characterization and enhanced performance for water photo-electrolysis

A method for the preparation of TiO2 thick films made of anatase nanocrystallites and featuring a mesoporous structure is described. Modification of a typical sol–gel synthesis that uses Titanium (IV) isopropoxide (TTIP) as precursor, through both the incorporation of a non-ionic surfactant (Tween 20) and the optimization of thermal treatments, allows to increase the thickness of each spin-coated layer, and to obtain by successive runs porous, transparent, homogeneous and crackless films with thickness up to 1.2 μm. The effect of the changing the Tween 20/TTIP ratio (R, ranging from 0.25 to 1.00) on the crystallographic, morphological and optical properties has been studied by X-ray Diffraction, N2 adsorption, UV–Visible Spectroscopy and Field Emission Scanning Electron Microscopy, in both powder and film form. The size of particles decreases slightly with increasing R, while the specific surface area increases somewhat. For all the R values, including R = 0, nanoparticles behave as direct semiconductors, in contrast with bulk anatase: changes in the band gap extent caused by the porous structure are negligible. Photo-electrochemical performance and carrier dynamics were studied using the films as anodes for the water photo-electrolysis reaction by means of Linear Sweep Voltammetry, Amperometry and Electrochemical Impedance Spectroscopy. Increasing R values improves the photo-catalytic performance of the TiO2 films and leads to a comprehensive faster charge transfer at the oxide–solution interface, so that those with R = 1 offer highest performance, due to the combination of both higher thickness and improved quality of the material.