, Volume 3, Issue 1, pp 73-84

Room temperature photocatalytic oxidation of liquid cyclohexane into cyclohexanone over neat and modified TiO2

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The oxidation of liquid cyclohexane by O2 over UV-illuminated TiO2 at room temperature has been studied in a static slurry reactor. From the effects of the mass of catalyst, the temperature, the radiant flux, the concentration of C6H12 (using acetonitrile as a solvent), it is concluded that the reaction is photocatalytic. Using mainly the 365 nm-ray of a mercury-lamp, an initial quantum yield of 0.1 is found for pure cyclohexane and radiant fluxes < ca.5mWcm−2 (6×1015 photons s−1 cm−2). A high selectivity to cyclohexanone is observed (83%), the other products being cyclohexanol (5%) and CO2 (12%). The low amount of cyclohexanol is explained by the higher rate of oxidation of this alcohol compared to that of cyclohexane. Smaller oxidation rates are observed when TiO2 is loaded with 0.5 to 10 wt%Pt and the cyclohexanone/cyclohexanol ratio decreases to ca. 4. Finally, the C6H12 oxidation has been employed as a test reaction to confirm the detrimental effect of the doping with several tri or pentavalent cations upon the photocatalytic activity of TiO2.