Heterogeneous oxidation of carbonyl sulfide on atmospheric particles and alumina
Heterogeneous oxidation of carbonyl sulfide on atmospheric particles and alumina
复制标题
大气颗粒物和氧化铝上硫化羰的非均相氧化
DOI：
10.1021/es048865q
复制
发表时间：
2005-12-15
影响因子：
11.4
通讯作者：
Chen, MX
中科院分区：
文献类型：
--
作者：
He, H;Liu, JF;Chen, MX
利用原位漫反射红外傅里叶变换光谱（DRIFTS）在封闭体系和流动体系中研究了羰基硫（OCS）在大气颗粒物和氧化铝（Al₂O₃）上的非均相氧化。在室温下，OCS可在大气颗粒物和Al₂O₃表面被催化氧化，形成气相的CO₂以及表面的硫酸盐（SO₄²⁻）、亚硫酸盐（HSO₃⁻）和碳酸氢盐（HCO₃⁻）物种。利用X射线荧光（XRF）和布鲁诺尔 - 埃梅特 - 泰勒（BET）方法对实际的大气颗粒物进行了表征。作为一个简化模型，使用Al₂O₃来研究OCS非均相氧化的反应机理。硫代碳酸氢盐表面物种（HSCO₂⁻）是OCS与表面羟基（OH）反应形成的一种中间体，只能在预还原的Al₂O₃样品上观察到。实验结果还表明，大气颗粒物样品和Al₂O₃样品上的表面含氧化合物可能是OCS氧化的关键反应物。讨论了OCS在Al₂O₃表面非均相氧化的反应机理。
Heterogeneous oxidation of carbonyl sulfide (OCS) on atmospheric particles and alumina (Al2O3) was investigated in a closed system and a flowed system using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). At room temperature, OCS could be catalytically oxidized on the surface of atmospheric particles and Al2O3 to form gas-phase CO2 and surface sulfate (SO42-), sulfite (HSO3-), and hydrogen carbonate (HCO3-) species. The real atmospheric particles were characterized using X-ray fluorescence (XRF) and the Brunauer-Emmett-Teller (BET) method. As a simplified model, Al2O3 was used to study the reaction mechanism of heterogeneous oxidation of OCS. The hydrogen thiocarbonate surface (HSCO2-) species, an intermediate formed in the reaction of OCS with surface hydroxyl (OH), could only be observed on the prereduced Al2O3 sample. The experimental results also indicate that surface oxygen containing species on the atmospheric particle sample and the Al2O3 sample might be the key reactant for OCS oxidation. A reaction mechanism of heterogeneous oxidation of OCS on Al2O3 surface is discussed.