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富勒烯(C60)作为一种大气中存在的新型污染物，在雾霾天气中对硫酸盐的形成具有潜在的影响。过氧化氢(H_2O2)作为硫酸盐气溶胶最主要的氧化剂，对硫酸盐形成的贡献至关重要。本文深入研究了C60在H_2O2氧化反应路径中对硫酸盐形成的作用及其影响机理。通过进行实验室模拟实验，研究了C60颗粒和稳定聚集体nC60在H_2O2液相氧化途径下对硫酸盐生成的贡献，结果表明，在C60颗粒存在时，硫酸盐产量有明显增加，稳定聚集体n C60对硫酸盐的贡献微乎其微。通过FT-IR和XPS表征进一步分析其影响机制，整个反应过程是一个先吸附后氧化的过程，期间C60表面通过电子转移降低了反应能垒，使表面的S(Ⅳ)更容易演变成S(Ⅵ)。经由自由基定量检测实验发现，C60能够有效促进H_2O2分解生成羟基自由基(·OH)和超氧自由基(·O2~-)，两种活性基团的存在会改变反应体系的氧化能力并进一步促进SO2的氧化。本研究证实了C60对大气硫酸盐生成具有重要贡献，这可能是加剧雾霾污染的潜在因素。
Abstract：Fullerene (C60),as a new type of pollutant in the atmosphere,has a potential impact on the formation of sulfate in haze weather.Exploring the contribution of C60 and mechanism to sulfate formation through the H_2O2 oxidation pathway,this paper focuses on the significant role of hydrogen peroxide (H_2O2) as the primary oxidant of sulfate aerosol in its contribution to sulfate.In this paper,the contribution of C60 particles and stable aggregates n C60 to sulfate formation under the H_2O2 liquid phase oxidation pathway was investigated by performing laboratory simulation experiments.The results showed that there was a significant increase in sulfate production in the presence of C60 particles,and the contribution of stable aggregates n C60to sulfate was negligible.FT-IR and XPS characterization of the influence mechanism revealed that S(VI) had been present on the surface of C60 after the reaction,suggesting that the effect of fullerene C60 on the liquid phase oxidation of SO2 is a typical oxidation process post-adsorption,which can be accomplished through the interface's strong electronic interactions that foster the formation of sulfate.Quantitative experiments of free radicals revealed that C60 can induce the decomposition of H_2O2 to create hydroxyl radicals (OH) and superoxide radicals (O2~-).This research further enhances the source of sulfate in haze conditions,which has a significant practical importance in controlling air pollution and improving global climate.
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基本信息:
DOI：10.16026/j.cnki.iea.2023060512
中图分类号:X51
引用信息:
[1]杜亚宁,郭仕祥,郭照冰.富勒烯对过氧化氢氧化路径中硫酸盐形成的影响[J].离子交换与吸附,2023,39(06):512-521.DOI:10.16026/j.cnki.iea.2023060512.
基金信息:
国家自然科学基金资助项目(41873016、41625006); 江苏省333人才项目(BRA2018033)
2023-12-18
2023-12-18