Journal of Physical Chemistry A, Vol.110, No.51, 13827-13835, 2006
Chain photoreduction of CCl3F in TiO2 suspensions: Enhancement induced by O-2
Trichlorofluoromethane (CFC 11) was photoreduced in aqueous suspensions of TiO2 particles containing HCO2- ions and air. Dissolved O-2 inhibited the reaction during an induction period that preceded the rapid formation of chloride ions. Reaction rates were higher in systems containing O-2 as compared to analogous reactions that occurred in anaerobic suspensions. High photonic efficiencies of Cl- formation (>= 15) were achieved using suspensions with pH >= 5. As was the case for studies with air-free suspensions, reactions are best described using a photoinitiated chain mechanism that produced CHCl2F and Cl- during the propagation steps. The enhanced yields obtained in the presence of air are attributed to the removal by O-2 of electrons trapped in the oxide, which are converted first into H2O2 and then into reducing radicals that participate in the chain process. Enhanced yields of Freon photoreduction were also observed during illumination of air-free suspensions containing hydrogen peroxide, which were interpreted using a similar mechanism.