Adsorption and desorption can both be promoted by exposure of trans metal oxides to light, the predominant process being controlled by experimental conditions. Adsorption of oxygen by illumination of TiO or ZnO at room temperature with low pressure results in the adsorption of oxygen, while at high pressures illumination leads to photo-assisted desorption. At high temperatures the opposite effect is observed, with low pressure leading to desorption, and high pressure causing adsorption.
Kase et al. conducted a study of the photo-assisted chemisorption of NO on ZnO, finding that under dark conditions a negligible amount of NO was adsorbed to the metal oxide, however under illumination ZnO irreversibly adsorbs NO, their sample showing no desorption after irradiation was stopped.
The process by which adsorption and desorption on metal oxide surfaces takes place is related to the photo generation of holes on the solid surface, which are believed to be trapped by hydroxyl groups on the surface of a transition metal oxides. These trapped holes allow photo-excited electrons to be available for chemisorption. Doping of a cation of either higher or lower valence can change the electronic properties of the metal oxide. Doping with a higher valence cation typically results in an increase in n-type semi-conductivity, or raises its Fermi energy, while doping with a lower valence cation should lower the Fermi energy level and reduce the metal oxides n'-type semi-conductivity. The process of doping indicates that a cation other than the transition metal cation experienced in the majority of the bulk is incorporated into the crystal structure of the semiconductor, either by replacing the cation, or interstitially adding to the matrix. Doping of ZnO with Li leads to greater photo-adsorption of oxygen, while doping with Ga or Al suppresses photo-adsorption of oxygen. Trends in photo-adsorption tend to follow trends in photo-oxidative catalysis, as shown by the high degree of photo-oxidative catalytic activity of TiO and ZnO, while other transition elements like VO shows no photo-oxidative catalytic response as well as no photo-activated adsorption of oxygen.