高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

大气中甲酸硫酸酐增强新粒子形成机制的理论研究

李欣炘1, 安国策2, 宋小鸣1, 倪爽1, 白凤杨1, 潘秀梅3, 赵震1, 4   

  1. 1. 沈阳师范大学化学化工学院，能源与环境催化研究所

    2. 中国刑事警察学院刑事科学技术学院

    3. 东北师范大学化学学院, 动力电池国家地方联合重点实验室 4. 中国石油大学理学院, 重质油国家重点实验室

  • 收稿日期:2025-10-27 修回日期:2025-11-24 网络首发:2025-12-01 发布日期:2025-12-01
  • 通讯作者: 倪爽 E-mail:nis223@nenu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号：22476134, 22306127)、辽宁省自然科学基金(批准号：2024-BS-106)、辽宁省基础科学研究基金(批准号：JYTQN2023419)和国家级大学生创新创业训练计划(批准号：202410166005)资助

Theoretical study on the mechanism of atmospheric nucleation enhanced by formic sulfide anhydride in atmosphere

LI Xinxin1, AN Guoce2, SONG Xiaoming1, NI Shuang1, BAI Fengyang1, PAN Xiumei3, ZHAO Zhen1,4   

  1. 1. Shenyang Normal University, School of Chemistry and Chemical Engineering, Institute of Catalysis for Energy and Environment

    2. Criminal Investigation Police University of China

    3. Northeast Normal University, School of Chemistry, National and Local Joint Key Laboratory of Power Batteries 4. China University of Petroleum, Beijing, College of science, State Key Laboratory of Heavy Oil

  • Received:2025-10-27 Revised:2025-11-24 Online First:2025-12-01 Published:2025-12-01
  • Supported by:
    Supported by the National Natural Science Foundation of China(Nos. 22476134, 22306127), the Natural Science Foundation of Liaoning Province(No. 2024-BS-106), the Basic Scientific Research Foundation Project of Liaoning Province(No.JYTQN2023419) and the National Innovation and Entrepreneurship training program for college students(No. 202410166005)

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摘要： 实验研究表明, 三氧化硫(SO3)和甲酸(HCOOH, FA)可以快速反应形成甲酸硫酸酐(HCOOSO3H, FSA), 相较于公认的成核前驱体硫酸(H2SO4, SA)而言, FSA具有较低的饱和蒸汽压和较多的分子间相互作用位点, 可能对大气新粒子形成(NPF)具有潜在贡献, 然而其成核能力尚不清楚, 本文通过密度泛函理论评估了FSA与大气常见62种物质的成核能力, 并将其与其母体化合物甲酸和典型成核前驱体硫酸的成核潜力进行了对比, 整体评估了FSA对新粒子形成的潜在贡献及大气影响. 结果表明, FSA和大气中的常见单体均可自发形成二聚体, 且在与含胺基的18种物质形成的二聚体团簇内部发生了质子转移, 其中, FSA与单乙醇胺(MEA)二体团簇的ΔG值最负, 表明MEA促进FSA的初始成核能力最强. 其次, 基于形成的最稳定团簇FSA-MEA和FSA的成核前体FA, SA分别与MEA形成的二聚体团簇FA-MEA, SA-MEA探究了团簇的水合作用及吸湿性规律, 发现随着水分子(n=0－6)的增多, 团簇的稳定性增加, 在不同的湿度条件下, 二聚体水合物对湿度的敏感性顺序为SA-MEA＞FSA-MEA＞FA-MEA. 随着尺寸的增大, 团簇的各向同性平均极化率, 瑞利光散射强度均呈线性增加, 其顺序为FSA-MEA＞SA-MEA＞FA-MEA, 表明FSA-MEA增强大气气溶胶的消光特性能力强于FA-MEA, SA-MEA, 对大气可见度产生不利的影响.

关键词: 甲酸硫酸酐, 二聚体, 大气气溶胶, 水合团簇, 成核能力

Abstract: Experimental studies demonstrate that sulfur trioxide (SO3) and formic acid (HCOOH, FA) rapidly react to form formic sulfuric anhydride (HCOOSO3H, FSA). Compared with sulfuric acid (H2SO4, SA), a well-established nucleation precursor, FSA exhibits lower saturation vapor pressure and a greater number of intermolecular interaction sites, suggesting its potential contribution to atmospheric new particle formation (NPF). However, its nucleation capability remains unclear. This study employs density functional theory to evaluate the nucleation potential of FSA with 62 common atmospheric species, and compares it with that of its parent compound formic acid and the typical nucleation precursor sulfuric acid, thereby comprehensively assessing FSA’s potential role in NPF and its atmospheric implications. Results indicate that FSA can spontaneously form dimers with common atmospheric monomers, and proton transfer occurs within dimer clusters formed with 18 amine-containing compounds. Among these, the FSA–monoethanolamine (MEA) dimer exhibits the most negative ΔG value, indicating that MEA possesses the strongest ability to promote initial nucleation of FSA. Furthermore, based on the most stable clusters (FSA–MEA, FA–MEA, and SA–MEA), the hydration behavior and hygroscopicity of these dimers were investigated. It was found that cluster stability increases with the number of water molecules (n=0–6). Under varying humidity conditions, the sensitivity of dimer hydrates to humidity follows the order: SA–MEA > FSA–MEA > FA–MEA. As cluster size increases, both the isotropic mean polarizability and Rayleigh scattering intensity increase linearly, in the order: FSA–MEA > SA–MEA > FA–MEA. This suggests that FSA–MEA has a stronger capacity to enhance the light extinction properties of atmospheric aerosols than FA–MEA and SA–MEA, thereby exerting a more adverse impact on atmospheric visibility.

Key words: Formic acid thionic anhydride, Dimer, Atmospheric aerosol, Hydrated clusters, Nucleation capacity

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