PNNL

Abstract

Photon-stimulated reactions between chemisorbed and physisorbed oxygen on TiO2(110) are investigated. Experiments using O2 isotopologues show that UV irradiation results in the exchange of atoms between chemisorbed and physisorbed oxygen. Annealing chemisorbed oxygen to ~350 K maximizes these exchange reactions, while dissociatively adsorbing oxygen on TiO2(110) at 300 - 350 K does not lead to reactions with physisorbed O2. After annealing to 350 K, the exchange products photodesorb in the plane perpendicular to the bridge-bonded oxygen rows at an angle of 45°. In contrast, the chemisorbed O2 photodesorbs normal to the surface. Remarkably, the chemisorbed species is stable under multiple cycles of UV irradiation with physisorbed O2. The active atoms in the chemisorbed species can be changed from 18O to 16O and then back to 18O via the exchange reactions. The results show that annealing oxygen adsorbed on TiO2(110) to ~350 K produces a stable chemical species with interesting photochemical properties. Possible forms for the photoactive species include O2 adsorbed in a bridging oxygen vacancy or tetraoxygen.