Heterogeneous reaction of NO2 with hematite: The effects of UV irradiation, O2 and relative humidity

Spectrochim Acta A Mol Biomol Spectrosc. 2024 Jun 5:314:124205. doi: 10.1016/j.saa.2024.124205. Epub 2024 Mar 27.

Abstract

Heterogeneous reactions on mineral dust surfaces are increasingly considered important in the removal of gaseous pollutants and the formation of secondary aerosols. Although the heterogeneous reaction of NO2 on the hematite surface has been investigated in many previous studies, little is known about the reaction of NO2 with hematite under ambient conditions. In this work, heterogeneous reactions of NO2 with hematite at 298 K were investigated via a coated-wall flow tube reactor and in situ diffuse reflectance Fourier transformed infrared spectroscopy (DRIFTS). The influence of UV illumination, relative humidity (RH) and O2 on the uptake coefficients and adsorption amount of NO2, as well as the nitrate formation on the hematite surface, has been analyzed comprehensively. UV irradiation shows a significant effect on the true uptake coefficient (γBET), which increases from 2.00 × 10-6 to 4.76 × 10-6 in the N2 stream and 1.32 × 10-6 to 4.07 × 10-6 in the air stream under dry conditions (∼0.3 % RH). RH (in the range of 0-67 %) exhibits an inhibitory effect on the adsorption of NO2 on the hematite surface because of the competition between NO2 and water molecules, that is, γBET and adsorption amount of NO2 decrease with an increase in RH under both the dark and light reaction conditions. Meanwhile, both the γBET and adsorption amount of NO2 on hematite decrease in the air stream compared to those in N2 conditions. In addition, the results from the DRIFTS experiments indicate that the presence of UV irradiation promotes the conversion of NO2 to nitrate and both the RH and O2 suppress the nitrate formation. From this research, the heterogeneous reactions between NO2 with mineral dust under ambient conditions will be better understood.

Keywords: Hematite; Heterogeneous reaction; Mineral dust; NO(2); Uptake coefficient.