Abstract
The photochemistry of isobutene was examined on the rutile TiO2(110) surface as a function of the surface pretreatment condition and irradiation temperature using temperature programmed desorption (TPD) and photon stimulated desorption (PSD). Isobutene adsorbs molecularly on the clean TiO2(110) surface without detectable thermal decomposition. Preadsorption of oxygen, either as atoms or chemisorbed molecules, did not promote thermal reactions with isobutene, but instead blocked isobutene adsorption sites. Ultraviolet (UV) light irradiation of isobutene adsorbed on the clean surface led to depletion through photodesorption without significant photooxidation. Isobutene PSD yields increased with increasing surface temperature suggesting that photodesorbing molecules sampled the surface during photodesorption. Preadsorption of oxygen promoted partial photooxidation of adsorbed isobutene to acetone, methacrolein, and isobutanal. However, the form of oxygen available for isobutene photooxidation had a significa...
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