苯光氧化形成硝基酚化合物的真空紫外光电离质谱研究

Vacuum Ultraviolet Photoionization Mass Spectrometry Study on the Formation of Nitrophenols Generated by Photooxidation of Benzene

摘要

硝基酚化合物(NPs)是大气气溶胶中一类常见的含氮有机物组分, 主要来源是汽车尾气等人为源中的苯、 甲苯等芳香化合物发生大气化学反应二次形成NPs. 本文利用烟雾箱模拟硝酸钠(NaNO₃)细颗粒存在下苯光氧化产生二次有机气溶胶(SOA)的大气化学过程, 利用同步辐射真空紫外光电离气溶胶质谱仪(VUV-PIAMS)对苯SOA进行化学组分在线测量. 基于VUV-PIAMS测得的光电离质谱和各离子峰的光电离效率曲线, 获得了电离势定性分析组分结构. 实验结果表明, 当NaNO₃细颗粒存在时, 苯光氧化产生SOA的质量显著增加, SOA的光电离质谱新增m/z 139, 155, 171, 184 和200 质谱峰, 这些质谱峰的电离势分别为(8.81±0.03), (9.36±0.03), (8.68±0.03), (8.75±0.03), (9.55±0.03)和(9.17±0.03) eV. 结合量子化学计算分析, 确定硝基苯酚、 硝基邻苯二酚、 硝基邻苯三酚、 二硝基苯酚和二硝基邻苯二酚等NPs是NaNO₃细颗粒存在时苯SOA的主要组分. 研究结果为NaNO₃细颗粒存在背景下, 大气SOA颗粒NPs组分的来源指认和形成机理研究提供了实验依据.

Abstract

Nitrophenols(NPs) are a common type of nitrogen-containing organic components in atmospheric aerosols. Aromatic compounds such as benzene and toluene from vehicle exhaust and other anthropogenic sources can undergo atmospheric chemical reactions and secondary formation of NPs. The atmospheric chemical process for photooxidation of benzene in the presence of sodium nitrate(NaNO₃) fine particles to form secondary organic aerosol(SOA) was simulated with a smog chamber in this study. The on-line measurement of chemical components of benzene SOA was studied by using a synchrotron radiation vacuum ultraviolet photoionization aerosol mass spectrometer(VUV-PIAMS). Based on the photoionization mass spectra and the photoionization efficiency curves of ion peaks detected by VUV-PIAMS, the ionization potentials were obtained for qualitative analysis of the chemical components. The experimental results demonstrated that in the presence of NaNO₃ fine particles, the mass of SOA produced by benzene photooxidation significantly increased. The photoionization mass spectra of SOA showed new peaks with m/z 139, 155, 171, 184 and 200, and the ionization potentials of these peaks were (8.81±0.03), (9.36±0.03), (8.68±0.03), (8.75±0.03), (9.55±0.03) and (9.17±0.03) eV, respectively. Combining quantum chemical calculations, it was analyzed and identified that NPs such as nitrophenol, nitrocatechol, nitropyrogallol, dinitrophenol and dinitrocatechol were the main components of benzene SOA in the presence of NaNO₃ fine particles. These provide the experimental basis for source identification and formation mechanism study of NPs components in atmospheric SOA particles under the background of the presence of NaNO₃ fine particles.

关键词

硝基酚 / 苯 / 二次有机气溶胶 / 同步辐射 / 光电离质谱

Key words

Nitrophenols / Benzene / Secondary organic aerosol / Synchrotron radiation / Photoionization mass spectra

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基金资助

国家自然科学基金(42275136)

福建省自然科学基金(2025J01972)