화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.118, No.34, 6999-7006, 2014
Heterogeneous Reaction of NO2 on alpha-Al2O3 in the Dark and Simulated Sunlight
Although there have been a number of publications focused on heterogeneous of NO2 on mineral particles, most of these studies were focused on beta-Al2O3 and performed in the dark Less was known about the reaction process of NO2 on alpha-Al2O3, especially the effect of sunlight factor. The heterogeneous reaction between NO2 and alpha-Al2O3 was investigated by using diffuse reflectance infrared Fourier transform spectrometry. The effects of NO2 and O-2 concentrations as well as simulated sunlight were examined, and the reaction mechanism including the consumption of surface OH groups, oxidation process of nitrites, and the formation of water was also discussed in detail. It was observed that the formation rates of nitrates and nitrites were sensitive to NO2 concentrations and O-2 concentrations. Nitrite was identified to be an intermediate production and disappeared very soon as [NO2] was up to 4.035 x 10(15) molecules/cm(3). Light played an important role in the changes of the electronic configuration of mineral dust, such as electronic donating ability, surface OH groups orientation, as well as the conversion efficiency between proton acid and nonproton acid, all of which could significantly enhance the heterogeneous reaction process. The reaction order for NO2 and O-2 was determined to be 0.960 +/- 0.111 and 0.620 +/- 0.028, respectively. The uptake coefficient of NO2, which dominated the first step of the heterogeneous reaction, was calculated by the infrared absorbance with the use of ion chromatography and determined to be 9.9 x 10(-1) in the dark and varied from 2.54 to 3.33 X 10(-9) under simulated sunlight from 0.45 to 1.35 mW/cm(2). It was also found that No, was independent of [NO2] and sunlight increased the uptake coefficient by three times, indicating that the heterogeneous reaction between NO2 and alpha-Al2O3 was enhanced under sunlight.