Photocatalysis with Na4W10O32 in water system: Formation and reactivity of OH center dot radicals

Photoexcitation of Na4W10O32 dissolved in water leads to the formation of hydroxyl radicals. These species originate both from H2O oxidation and H2O2 reduction. EPR-spin trapping investigation and laser flash photolysis experiments contribute to clarify their formation mechanism and their involvement in the oxidation of propan-2-ol. Continuous irradiation of water solutions of Na4W10O32 leads to the overoxidation of propan-2-ol to CO2 with high yield. This result may be of interest for the development of photocatalytic systems aimed to pollutants degradation. Entrapment of Na4W10O32 into a microporous silica matrix gives a rather robust photocatalyst where the decatungstate structure is preserved. This material is able to catalyze the photooxidation of propan-2-ol to acetone with appreciable chemoselectivity. In particular, it is seen that the solid photocatalyst yields acetone as main product inhibiting its over-oxidation to carbon dioxide. (C) 2013 Elsevier B.V. All rights reserved.