The adsorption and photooxidation of CH 3 CN chemisorbed on TiO 2 has been investigated using infrared spectroscopy. It was found that CH 3 CN forms an ice layer on TiO 2 at 126K and above 126K CH 3 CN diffusion into TiO 2 occurs. At 200K, the adsorption of CH 3 CN on both isolated Ti−OH groups and on the Ti 4+ Lewis acid site was observed. Under UV irradiation (350 ± 50 nm; hυ = 3.10−4.13 eV), CH 3 CN was oxidized in the presence of O 2 to form H 2 O, CO 2, surface CO 3 2- and an intermediate partially oxidized isocyanate species, NCO, which was identified by various isotopic experiments. Photooxidation of the CH 3 moiety in adsorbed CH 3 CN occurs more readily does the CN moiety in CH 3 CN. Lattice oxygen of TiO 2 was found to preferentially form adsorbed NCO, compared to oxygen from adsorbed O 2 . A mechanism of the formation of NCO species was postulated.
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Zhuang et al. (1999) studied this question.
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