HONO在γ-Al2O3(110)表面非均相氧化SO2机理的第一性原理研究
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P579

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国家自然科学基金(41831285,41872039,51974261);四川省科技计划(2018JY0462);西南科技大学研究生创新基金(19ycx0010)


Heterogeneous oxidation mechanism of SO2 on the surface of γ-Al2O3 (110) by HONO: A first-principle study
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    摘要:

    为研究亚硝酸(HONO)在γ-Al2O3(110)表面非均相氧化SO2的机理,基于密度泛函理论(density functional theory,DFT)的第一性原理计算了SO2和HONO在γ-Al2O3(110)表面的吸附机制和氧化机制。结果表明,SO2以分子的形式吸附在完整或缺陷的γ-Al2O3(110)表面,而HONO仅在完整表面上以分子的形式存在。表面氧缺陷的存在不仅会增强SO2和HONO的吸附强度,而且能诱导HONO在含氧缺陷表面的分解(HONO→NO+·OH)。通过局域态密度(partial density of states,PDOS)和Mulliken电荷布局分析表明,HONO的分解遵循Haber-Weiss机制。当SO2和HONO共同吸附在氧缺陷表面时,HONO分解产生·OH,氧化SO2形成HOSO2团簇分子。该研究不仅有助于理解HONO在矿物氧化物表面氧化SO2的作用,而且为解释大气硫酸盐气溶胶的形成提供了理论依据。

    Abstract:

    In order to study the heterogeneous oxidation mechanism of SO2 on γ-Al2O3 (110) surface by HONO, the authors calculated the adsorption and oxidation mechanism of SO2 and HONO on γ-Al2O3 (110) surface by the first principles based on density functional theory (DFT). The results showed that SO2 was adsorbed on the perfect/defect γ-Al2O3 (110) surface in the form of molecules, while HONO existed only on the perfect surface in the form of molecules. The existence of oxygen vacancies on the surface not only enhanced the adsorption strength of SO2 and HONO, but also induced the decomposition of HONO on the oxygen defect surface (HONO→NO + ·OH). The analysis of partial density of states (PDOS) and Mulliken charge distribution showed that the decomposition of HONO follows the Haber-Weiss mechanism. It is found that SO2 and HONO were adsorbed on the oxygen defect surface, and the OH radicals generated by HONO decomposition oxidized SO2 to form HOSO2 cluster molecules. This study not only helps to understand the role of HONO in the oxidation of SO2 on the surface of mineral oxides, but also provides a theoretical basis for explaining the formation of atmospheric sulfate aerosols.

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林艳辉,边亮,宋绵新,李海龙,李宇,罗伟格,张娇,张金梅,罗伟恢,张琴,2021,HONO在γ-Al2O3(110)表面非均相氧化SO2机理的第一性原理研究[J].岩石矿物学杂志,40(4):804~811.

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  • 收稿日期:2020-10-24
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  • 在线发布日期: 2021-07-16
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