The decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by UV-visible light irradiation, by H202 with UV-visible light irradiation, and by a tungstic heteropolyacid photocatalyst was examined to develop a technique to counteract stationary sources of PFOA. Direct photolysis proceeded slowly to produce CO2, F-, and short-chain perfluorocarboxylic acids. Compared to the direct photolysis, H2O2 was less effective in PFOA decomposition. On the other hand, the heteropolyacid photocatalyst led to efficient PFOA decomposition and the production of F- ions and CO2. The photocatalyst also suppressed the accumulation of short-chain perfluorocarboxylic acids in the reaction solution. PFOA in the concentrations of 0.34-3.35 mM, typical of those in wastewaters after an emulsifying process in fluoropolymer manufacture, was completely decomposed by the catalyst within 24 h of irradiation from a 200-W xenon-mercury lamp, with no accompanying catalyst degradation, permitting the catalyst to be reused in consecutive runs. Gas chromatography/mass spectrometry (GC/MS) measurements showed no trace of environmentally undesirable species such as CF4, which has a very high global-warming potential. When the (initial PFOA)/(initial catalyst) molar ratio was 10: 1, the turnover number for PFOA decomposition reached 4.33 over 24 h of irradiation.

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Photocatalytic oxidation of benzene in gas phase was carried out with a flow reactor at room temperature. In a humidified airstream ([H2O] = 2.2%), benzene was quantitatively decomposed to CO2 over UV-irradiated 1.0 wt %-Pt/TiO2 catalyst. When the benzene conversion was decreased, the selectivity to CO2 was decreased, while that to CO was increased. As the amount of Pt loaded on the TiO2 catalyst was increased, the rate of the CO photooxidation was increased, while that of benzene photooxidation was almost unchanged. These findings showed that the photooxidation of benzene to CO2 over Pt/TiO2 catalyst proceeded by the two sequential steps: (i) benzene was decomposed to CO2 and CO with the selectivities of 94% and 6%, respectively, and (ii) CO was subsequently oxidized to CO2. The rate of CO photooxidation over Pt/TiO2 catalyst was greatly decreased by the presence of benzene in the reaction gas stream. The complete oxidation of benzene to CO2 could be also achieved by using the hybrid catalysts comprising pure TiO2 and platinized TiO2.

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