화학공학소재연구정보센터
Langmuir, Vol.21, No.8, 3443-3450, 2005
Acetone and water on TiO2(110): Competition for sites
The competitive interaction between acetone and water for surface sites on TiO2(110) was examined using temperature programmed desorption (TPD). Two surface pretreatment methods were employed, one involving vacuum reduction of the surface by annealing at 850 K in ultrahigh vacuum (UHV) and another involving surface oxidation with molecular oxygen. In the former case, the surface possessed about 7% oxygen vacancy sites, and in the latter, reactive oxygen species (adatoms and molecules) were deposited on the surface as a result of oxidative filling of vacancy sites. On the 7% oxygen vacancy surface, excess water displaced all but about 20% of a saturated d(6)-acetone first layer to physisorbed desorption states, whereas about 40% of the first layer d(6)-acetone was stabilized on the oxidized surface against displacement by water through a reaction between oxygen and d(6)-acetone. The displacement of acetone on both surfaces is explained in terms of the relative desorption energies of each molecule on the clean surface and the role of intermolecular repulsions in shifting the respective desorption features to lower temperatures with increasing coverage. Although first layer water desorbs from TiO2(110) at slightly lower temperature (275 K) than submonolayer coverages of d(6)-acetone (340 K), intermolecular repulsions between d(6)-acetone molecules shift its leading edge for desorption to 170 K as the first layer is saturated. In contrast, the desorption leading edge for first layer water (with or without coadsorbed d(6)-acetone) shifted to no lower than 210 K as a function of increasing coverage. This small difference in the onsets for d(6)-acetone and water desorption resulted in the majority of d(6)-acetone being compressed into islands by water and displaced from the first layer at a lower temperature than that observed in the absence of coadsorbed water. On the oxidized surface, the species resulting from reaction of d(6)-acetone and oxygen was not influence by increasing water coverages. This species was stable up to 375 K (well past the first layer water TPD feature) where it decomposed mostly back to d(6)-acetone and atomic oxygen. These results are discussed in terms of the influence of water in inhibiting acetone photo-oxidation on TiO2 surfaces.