Design of heterogeneous photocatalysts based on metal oxides to control the selectivity of chemical reactions.

Photocatalysis is particularly relevant in order to realize chemical transformations of interest in synthesis and, at the same time, to move towards a "sustainable chemistry" with a minimal environmental impact. Heterogeneous systems with well-defined textural characteristics represent a suitable means to tailor the selectivity of photocatalytic processes. Here, we summarize and classify the significant features of photocatalysts consisting of photoactive metal oxides dispersed on high-surface-area solid supports, or constrained inside their porous network. These systems are based on the use of titanium dioxide, highly dispersed oxides of titanium, chromium, vanadium, and polyoxotungstates. They share similar primary photoprocesses: light absorption induces a charge separation process with formation of positive holes able to oxidize organic substrates. A great number of the papers discussed here concern oxidation reactions carried out in the presence of O₂ for inducing partial oxidation of alcohols and monooxygenation of hydrocarbons. We also devote some attention to photocatalysis in the absence of O₂. In these conditions, the photogenerated charge separation offers the possibility to induce the formation of C-C and C-N bonds. We emphasize that the optimal tailoring of photoactive materials for synthetic purposes can be achieved by combining recent advances in the preparation of nanostructured materials with mechanistic knowledge derived from surface science and molecular level investigations.