SO2 interaction with Zn(0001) and ZnO(0001) and the influence of water

Photoelectron spectroscopy has been used to study room temperature adsorption of sulfur dioxide on clean and water exposed (0001) surfaces of zinc and zinc oxide. Water has no significant effect either on clean or on SO2 exposed Zn(0001) at the low water pressures used (p < 10− 7 mbar). In the case of the zinc-terminated ZnO(0001) surface, however, water adsorbs dissociatively and OH groups are shown to have a considerable effect on SO2 surface reactions. A strong oxidation reaction occurs between Zn(0001) and SO2 giving various sulfur containing species. On ZnO(0001), SO2 interacts mainly with oxygen sites giving SO3 or SO4 species. It is shown that the ZnO(0001) sample preparation procedure can have large effects on surface chemical and physical properties. Samples cleaned by four different preparation procedures are investigated, namely sputtering only and sputtering followed by annealing at 450 °C, 530 °C and 600–650 °C. Annealing at 600 °C leads to a transition from a partly OH-terminated surface to a triangularly structured surface free from OH groups. Adsorption of SO2 on the latter surface leads to a decreased surface conductivity, which hampers photoemission measurements. Water is shown to block SO2 adsorption sites on both 450 °C and 530 °C annealed samples. On the latter sample, SO2 reduction has been observed to a small extent on the clean surface and to a larger extent when the surface is prehydroxylated. Here, we speculate that water, similar to hydrogen, generates surface zinc clusters on ZnO(0001). Zinc clusters could enable charge transfer to the antibonding LUMO of the SO2 molecule and subsequent dissociation.