Abstract
Optimum conditions have been established for the selective semiconductor-photocatalyzed oxidation by long-wavelength ultraviolet light of the primary alcohol functionality in 1,4-pentanediol. On platinized (2%) TiO{sub 2} powder suspended in oxygenated aqueous (4 vol %) acetonitrile, the initial rate ratio for oxidation of the primary/secondary alcohol site was >7. Analysis of further oxidation products allowed for mechanistic delineation of the course of the semiconductor-mediated reaction. The selectivity is attributed to the essential role of adsorption, with the critical photoinduced electron transfer occurring at the surface of the irradiated particle. ZrO{sub 2} and SnO{sub 2} samples were much less active than TiO{sub 2} as photocatalysts. The effects of oxygen pressure, metal cocatalyst loading, and water content of acetonitrile are discussed.
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