Methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) were oxidized in the gas phase by photocatalytic oxidation (PCO). Transient PCO was carried out at room temperature on TiO2 (Degussa P25), 0.2% Pt-TiO2, and 2% Pt-TiO2 catalysts. Surface-adsorbed reaction by-products were characterized by temperature-programmed desorption (TPD) and oxidation (TPO). Continuous flow PCO was also carried out at 373 K on TiO2. Acetone, H2O, and CO2 were the gas-phase products for PCO of TBA and MTBE, and formic acid was adsorbed on the TiO2 surface. Temperature-programmed desorption of TBA and MTBE formed 2-methyl-1-propene, water (TBA), and methanol (MTBE). During continuous-flow PCO, acetone desorbed in molar amounts equal to the amount of decomposed TBA and MTBE. The Pt/TiO2 catalysts had higher rates of complete oxidation during PCO and TPO. Injection of water during transient PCO increased the rates of oxidation of adsorbed TBA, formic acid, and acetone. Photocatalytic oxidation of TBA proceeded faster in humid air than dry air, but MTBE oxidation was less sensitive to humidity. The TiO2 catalyst was stable for MTBE, TBA, and acetone PCO at 373 K. The PCO at low conversions followed the Langmuir-Hinshelwood model.
