Abstract
Thermal- and photon-stimulated reactions of acetone coadsorbed with oxygen on rutile TiO2(110) surface are studied with infrared reflection–absorption spectroscopy (IRAS) combined with temperature-programmed desorption and angle-resolved photon stimulated desorption. IRAS results show that η2-acetone diolate ((CH3)2COO) is produced via thermally activated reactions between the chemisorbed oxygen and coadsorbed acetone. Formation of acetone diolate is also consistent with 18O/16O isotopic exchange experiments. During UV irradiation at 30 K, CH3 radicals are ejected from the acetone diolate with a distribution that is peaked at ∼±66° from the surface normal along the [110] azimuth (i.e., perpendicular to the rows of bridging oxygen and Ti5c ions). This distribution is also consistent with the orientation of the C–CH3 bonds in the η2-acetone diolate on TiO2(110). The acetone diolate peaks disappear from the IRAS spectra after UV irradiation, and new peaks are observed and associated with η2-acetate. The dat...
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