Diffuse reflectance FTIR study of the interaction of alumina surfaces with ozone and water vapor

The interaction of ozone with alumina has been examined at ambient temperature as a function of ozone concentration and relative humidity. The experiments used diffuse reflectance FTIR spectroscopy in a small flow reactor, which provided control of the temperature, pressure, and composition of the gas mixture to which the sample was continuously exposed. Treatment of alumina with ozone produced a new spectroscopic feature at 1380 cm(-1), which we attribute to an aluminum oxide species formed by interaction of O3 with Lewis acid sites on the alumina surface. After exposure of the alumina sample to O3 was stopped, subsequent exposure of the sample to humidified nitrogen resulted in the slow removal of the peak at 1380 cm(-1). Simultaneously, the uptake of water by the alumina increased as indicated by the growth of the adsorbed water features which extend from approximately 3700 to 2500 cm(-1). Treatment of dry alumina with humidified ozone strongly inhibited both the rate of formation of the spectral feature at 1380 cm(-1) and its limiting extent of formation. These observations are analyzed in terms of the adsorption and surface reaction properties of ozone on alumina. The observation that the new oxide feature on alumina, produced by reaction with ozone, can be removed by water is important for assessing the ability of mineral dust aerosols to process atmospheric trace gases over a significant time scale. We believe the work reported here to be the first direct and quantitative kinetic study of the competition between O3 and water for adsorption sites on alumina.