In situ ambient pressure studies of the chemistry of NO2 and water on rutile TiO2(110).

The adsorption of NO(2) on the rutile TiO(2)(110) surface has been studied at room temperature in the pressure range from approximately 10(-8) torr to 200 mtorr using ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Atomic nitrogen, chemisorbed NO(2), and NO(3) were formed, each of which saturates at pressures below approximately 10(-6) torr NO(2). Atomic nitrogen originates from decomposition of the NO(x) species. For pressures of up to 10(-3) torr, no significant change in the NO(x) surface species occurred, suggesting that environmentally relevant conditions with typical NO(2) partial pressures in the 1-100 ppb range can be modeled by ultrahigh vacuum (UHV) studies. The chemisorbed surface species can be removed by in situ annealing in UHV: all of the NO(x) species disappear around 400 K, whereas the N 1s signal associated with atomic nitrogen diminishes around 580 K. At higher pressures of NO(2) (p(NO(2)) > or = 10(-6) torr), physisorbed NO(2) and adsorbed water, which was likely due to displacement from the chamber walls, appeared. The water coverage grew significantly above approximately 10(-3) torr. Concurrently with co-condensation of water and NO(2), the population of NO(3) species grew strongly. From this, we conclude that the presence of NO(2) and water leads to the formation of multilayers of nitric acid. In contrast, pure water exposure after saturation of the surface with 200 mtorr NO(2) did not lead to a growth of the NO(3) signals, implying that HNO(3) formation requires weakly adsorbed NO(2) species. These findings have important implications for environmental processes, since they confirm that oxides may facilitate nitric acid formation under ambient humidity conditions encountered in the atmosphere.