Interaction of Molecular Oxygen with the Vacuum-Annealed TiO2(110) Surface: Molecular and Dissociative Channels

We have examined the interaction of molecular oxygen with the TiO2(110) surface using temperature-programmed desorption (TPD), isotopic labeling studies, sticking probability measurements, and electron energy loss spectroscopy (ELS). Molecular oxygen does not adsorb on the TiO2(110) surface in the temperature range between 100 and 300 K unless surface oxygen vacancy sites are present. These vacancy defects are generated by annealing the crystal at 850 K, and can be quantified reliably using water TPD. Adsorption of O2 at 120 K on a TiO2(110) surface with 8% oxygen vacancies (about 4 × 1013 sites/cm2) occurs with an initial sticking probability of 0.5−0.6 that diminishes as the surface is saturated. The saturation coverage at 120 K, as estimated by TPD uptake measurements, is approximately three times the surface vacancy population. Coverage-dependent TPD shows little or no O2 desorption below a coverage of 4 × 1013 molecules/cm2 (the vacancy population), presumably due to dissociative filling of the vacancy sites in a 1:1 ratio. Above a coverage of 4 × 1013 molecules/cm2, a first-order O2 TPD peak appears at 410 K. Oxygen molecules in this peak do not scramble oxygen atoms with either the surface or with other coadsorbed oxygen molecules. Sequential exposures of 16O2 and 18O2 at 120 K indicate that each adsorbed O2 molecule, irrespective of its adsorption sequence, has equivalent probabilities with respect to its neighbors to follow the two channels (molecular and dissociative), suggesting that O2 adsorption is not only precursor-mediated, as the sticking probability measurements indicate, but that all O2 molecules reside in this precursor state at 120 K. This precursor state may be associated with a weak 145 K O2 TPD state observed at high O2 exposures. ELS measurements suggest charge transfer from the surface to the O2 molecule based on disappearance of the vacancy loss feature at 0.8 eV, and the appearance of a 2.8 eV loss that can be assigned to an adsorbed O2- species based on comparisons with Ti−O2 inorganic complexes in the literature. Utilizing results from recent spin-polarized DFT calculations in the literature, we propose a model where three O2 molecules are bound in the vicinity of each vacancy site at 120 K. For adsorption temperatures above 150 K, the dissociation channel completely dominates and the surface adsorbs oxygen in a 1:1 ratio with each vacancy site. ELS measurements indicate that the vacancies are filled, and the remaining oxygen adatom, which is apparent in TPD, is transparent in ELS. On the basis of the variety of oxygen adsorption states observed in this study, further work is needed in order to determine which oxygen-related species play important roles in chemical and photochemical oxidation processes on TiO2 surfaces.