TOWARDS THE PHOTOCATALYTIC PRODUCTION OF SOLAR FUELS - NANOSTRUCTURED TITANIUM DIOXIDE FOR PHOTOCATALYSIS & PHOTO-ELECTROCHEMISTRY

In spite of many efforts given during the last decades to find new alternative photocatalytic materials, titanium dioxide (TiO2) still represents the most widely employed semiconductor for photocatalytic applications, being photoactive, cheap, easily available, non-toxic, inert and, most of all, chemically stable. However, although exhibiting a powerful combination of extraordinary and attractive physico-chemical properties, it suffers from some issues, common to all semiconductors, related to the dynamic of the charge carriers. Precisely, trapping and recombination of valence band holes and conduction band electrons occur at a certain extent, anyway resulting in a drop of the process efficiency. Therefore, in view of limiting these detrimental phenomena, the charge transfer and the electric conductivity of a semiconductor can be enhanced, thus leading to an overall improvement of the photocatalyst performance. In the first part of the work, homemade and commercial TiO2 powders were studied as photocatalysts for different applications, including the liquid-phase photocatalytic oxidation of ammonia and formic acid, and the H2 production through photocatalytic reforming of water-methanol vapors. In this context, a dopant (NH4F) was used during the sol-gel synthesis of the semiconductor to stabilize the formation of the TiO2 anatase phase (typically more active than rutile TiO2 because of its higher electron mobility), especially when crystallization of the amorphous oxides was performed at high temperature (700 ˚C). Furthermore, the effects induced by noble metal nanoparticles deposition on TiO2 anatase powders were also investigated. In situ electron spin resonance spectroscopy was employed to determine the amount of electrons and holes trapping centers formed under irradiation, in the absence and in the presence of noble metal co-catalysts at the surface of TiO2, hence assessing also the ability of Au and Pt nanoparticles in trapping conduction band electrons. The results were of great usefulness not only to interpret the different H2 production rates but also to understand some mechanistic aspects concerning the selectivity towards the different oxidation products in the methanol photo-steam reforming reaction. In the second part of the work, the nanostructuring of the semiconductor was explored by fabricating TiO2 nanotube arrays through electrochemical anodization. The anodic oxides were employed for both photocatalytic and photo-electrochemical H2 production. In view of large-scale application, the anodization approach was studied on wide Ti substrate surfaces, in order to assess the feasibility of the scale up. Moreover, TiO2 nanotubes were also grown on Ti-based alloys. When fabricating the nanotubes under optimized conditions on Ti-Ta alloys, highly photoactive Ta-doped TiO2 nanotubes were obtained, exhibiting superior water splitting ability. When anodizing Ti-Au alloys, the TiO2 nanotubes resulted decorated with Au nanoclusters. These Au-decorated TiO2 nanotube arrays were used as efficient photocatalyst for H2 production from ethanol-water solutions. Finally, the fabrication of short TiO2 nanotube layers exhibiting an unprecedented level of self-ordering was achieved through an innovative anodization approach. The highly ordered topography allowed the subsequent self-ordering dewetting of Au, leading to Au nanoparticles of controllable size and distribution. These short, Au nanoparticles-filled TiO2 nanotubes exhibited advanced photoactivity ascribed to their reaction vessel-like geometry, fulfilling the requirements in terms of solid state charge carriers diffusion and liquid phase diffusion of oxidizing radicals.