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The photofragmentation of butyrophenone yields benzoate and a propyl radical on oxidized TiO2(110). Oxygen dissociates in native oxygen vacancies to produce reactive oxygen adatoms which react with butyrophenone to create photoactive butyrophenone-O complexes that are sensitive to hole oxidation created upon UV illumination. The same O adatoms also trap one of the primary photoproducts, phenyl-CO, to produce benzoate. The reaction proceeds via a Norrish Type I like process involving α-CC cleavage on the surface, in contrast to the gas phase where a Norrish Type II pathway predominates. The mechanism is probed using mass spectrometry and, for the first time, scanning tunneling microscopy (STM). Our STM experiments show that there is a 1-to-1 correspondence between the immobile butyrophenone-O complex and formation of a benzoate on the surface. We also demonstrate that the benzoate species is in close proximity to the original butyrophenone complex, indicating that benzoate is produced on a time scale more rapid than diffusion of the photoproducts. While the photoproducts of butyrophenone decomposition are similar to ketone oxidation reported previously, butyrophenone reacts via a different starting ground state, based on STM and density functional theory studies. Specifically, butyrophenone does not produce a dioxyalkylene species, which has been proposed to be the photoactive state for other ketones. Based on a combination of STM experiments and density functional theory, we propose that a peroxy-like configuration where the oxygen adatom stabilizes the butyrophenone through its carbonyl oxygen is the surface intermediate that photodecomposes. These results demonstrate the importance of the excited state in determining the photochemistry of ketones on surfaces.

We investigate the role of defects—adatoms, vacancies, and steps—in the bonding and reaction of propene on Au(111) containing atomic oxygen, using density functional theory (DFT) calculations. The adsorption of propene is stronger on a surface containing defects compared to the flat, bulk-terminated surface, with the largest gain in binding (∼0.7 eV) on a surface with a 1/9 monolayer (ML) of Au adatoms. Charge-density difference plots reveal that the difference between defective surfaces and the bulk-terminated surface is a more pronounced depletion of electron density from the carbon–carbon π bond and a charge accumulation between the double bond and the gold atom to which the propene is bound. We calculate the energy barriers for two competing reactions that are important in determining the selectivity for propene oxidation. Allylic H abstraction by adsorbed O leads to combustion, whereas O addition to form an oxymetallacycle is the first step in propene epoxide formation. A comparison of the energetics of these two pathways on flat and defect-containing Au surfaces indicates that the reactivity depends on the nature and prevalence of surface defects. Both electronic and geometric factors, such as the path and the distance the oxygen must travel to meet the allylic hydrogen for abstraction, are important in explaining the reaction trends.