Beijing National Laboratory for Molecular Science (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China.
J Phys Chem A. 2013 May 16;117(19):3972-9. doi: 10.1021/jp400195f. Epub 2013 May 3.
Heterogeneous reactions on mineral aerosols remain an important subject in atmospheric chemistry because of their role in altering the properties of particles and the budget of trace gases. Yet, the role of coadsorption of trace gases onto mineral aerosols and potential synergistic effects are largely uncertain, especially synergistic effects between inorganic and organic gas-phase pollutants. In this study, synergistic effects between HCOOH and SO2 were investigated for the first time using in situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS). It was found that the heterogeneous reaction of HCOOH is hindered significantly by coexisting SO2. The total amount of formate decreased, whereas the total amount of sulfate was not affected during coadsorption on the surface of α-Fe2O3. Futhermore, part of the formate on the surface was catalytically decomposed to CO2 by α-Fe2O3 with the help of SO2. These results suggest a possible mechanism for the observed correlations between sulfate and carboxylate in the atmosphere.
矿物气溶胶上的非均相反应仍然是大气化学中的一个重要课题,因为它们在改变粒子性质和痕量气体预算方面发挥着作用。然而,痕量气体在矿物气溶胶上的共吸附作用及其潜在的协同效应在很大程度上是不确定的,特别是无机和气态有机污染物之间的协同效应。在这项研究中,首次使用原位漫反射红外傅里叶变换光谱(DRIFTS)研究了 HCOOH 和 SO2 之间的协同效应。结果发现,共存的 SO2 显著阻碍了 HCOOH 的非均相反应。甲酸根的总量减少,而在 α-Fe2O3 表面共吸附时硫酸盐的总量不受影响。此外,在 SO2 的帮助下,部分表面上的甲酸根被α-Fe2O3 催化分解为 CO2。这些结果为大气中观察到的硫酸盐和羧酸盐之间的相关性提供了一种可能的机制。