刘佳荣1， 李浩2
1.赤峰大学 资源环境与建筑工程学院， 内蒙古 赤峰024000；2.中国科学院 生态环境研究中心， 环境模拟与污染控制全国重点联合实验室， 北京 100085
引用格式：
刘佳荣， 李浩. 气液界面硫酸盐气溶胶形成时过渡金属催化和过氧化物氧化路径分子机制研究进展［J］. 中国粉体技术， 2027， 33（2）： 1-14.
Liu Jiarong， Li Hao. Research progress on molecular mechanisms of transition metal‑catalyzed and peroxide‑mediated pathways in sulfate aerosol formation at gas-liquid interface［J］. China Powder Science and Technology， 2027， 33（2）： 1-14.
DOI：10.13732/j.issn.1008-5548.2027.02.017
收稿日期： 2026-08-16， 修回日期： 2026-09-08， 上线日期： 2026-10-11。
基金项目： 国家自然科学基金项目，编号：22476201、22666001、22206017；内蒙古自治区社会科学基金项目，编号：2026AY36；内蒙古自治区自然科学基金项目，编号：2026MS0136；内蒙古自治区教育科学研究“十五五”规划课题，编号：NGJGH2026274。
第一作者： 刘佳荣（1993—），女（蒙古族），副教授，理学博士，研究方向为大气颗粒物的形成机制。E-mail：liujiarong@cfu.edu.cn。
通信作者： 李浩（1990—），女，副研究员，理学博士，硕士生导师，中国科协青年托举人才，研究方向为大气颗粒物的形成机制。E-mail：haol@rcees.ac.cn。
摘要： 【目的】 解析硫酸盐生成反应中的“界面反应为何更快”的微观机制，以及如何依托分子模拟手段从原子、电子层面揭示界面硫氧化的内在规律等。 【研究现状】 系统梳理气-水界面硫酸盐生成化学的最新研究进展，在研究方法层面区分传统实验、界面原位表征与理论计算3类手段的发展进程与各自局限，在反应机制层面重点剖析了过渡金属催化、过氧化物氧化2条典型界面反应路径，并结合作者团队密度泛函理论电子结构计算、玻恩-奥本海默分子动力学模拟及机器学习原子势开发方面的长期积累，对关键微观机制进行深入解读，揭示界面电场、局部溶剂化与配位结构调控硫酸盐生成动力学的内在规律，提出霾期间硫酸盐爆发式增长的额外来源。 【结论与展望】 提出当前对硫酸盐生成机制认知的局限：机器学习原子势泛化能力不足，难以支撑真实大气多组分共存条件下硫酸盐生成路径的系统模拟；多数研究局限于单一组分简化体系，尚不能定量厘清多金属、多元配体条件下硫酸盐生成的机制。认为后续应开发通用型机器学习原子势，构建多因子耦合的显式界面模型，补充大气模式所需的硫酸盐基元反应动力学参数，为成霾过程硫酸盐来源解析和精细化大气污染协同减排提供理论依据。
关键词： 硫酸盐； 非均相反应； 形成机制； 分子模拟； 过渡金属； 过氧化物
Abstract
Significance Sulfate is the most abundant water-soluble inorganic component of atmospheric fine particulate matter， and its formation mechanisms have long been a core issue in atmospheric pollution research. Of particular interest is why interfacial reactions proceed much faster than bulk reactions and what the underlying acceleration mechanisms are. Classical gas- and aqueous-phase frameworks describe dilute cloud water chemistry well， but they systematically underestimate sulfate production during heavy haze episodes. The gas-liquid interface provides a large reactive surface area and a unique microenvironment characterized by asymmetric solvation， strong interfacial electric fields， and ion enrichment， all of which can lower the oxidation barrier of S（IV）. In addition， although experimental techniques can locate reaction sites and measure reaction rates， they cannot capture picosecond-scale intermediates or electron-transfer dynamics. Therefore， it is of great importance to use theoretical simulations to investigate the interfacial reaction mechanisms of sulfate formation.
Progress This review systematically summarizes advances in sulfate chemistry at the gas-liquid interface， with emphasis on three research approaches： traditional experiments， in situ interfacial characterization， and theoretical calculations. It focuses on two representative pathways， namely transition metal-catalyzed oxidation and peroxide-mediated oxidation. Drawing on the authors’ long-term expertise in density functional theory， Born-Oppenheimer molecular dynamics， and machine learning potentials， it interprets key microscopic mechanisms. Multiscale simulations have revealed how interfacial electric fields， local solvation， and coordination structures govern sulfate formation kinetics， identified an additional source of explosive sulfate growth during haze， and provided a critical basis for correcting model simulation biases.
Conclusions and Prospects Sulfate， as a crucial chemical component of fine particulate matter， not only plays a pivotal role in heavy haze formation but also significantly impacts regional and global climate by regulating cloud formation and development as cloud condensation nuclei. In recent years， the rapid advancement of multiscale theoretical simulation methods， including density functional theory， first-principles molecular dynamics， and machine learning atomic potentials， has provided essential technical support for elucidating the microscopic mechanisms of sulfate formation at the molecular and electronic levels at the gas-liquid interface. This has effectively addressed the inherent limitations of traditional experimental methods in capturing transient processes and disentangling multivariable coupling effects. However， existing theoretical research still has significant limitations and cannot fully elucidate the complex coupling effects of multiple components， factors， and processes in real atmospheric aerosol systems. Numerous key scientific issues remain in methodological optimization and the mechanistic analysis of complex systems， highlighting the urgent need for more systematic and in-depth research. This paper reviews two limitations in current research on sulfate formation mechanisms. Firstly， for real multi-component atmospheric systems， machine learning methods lack sufficient generalization ability. Secondly， most studies rely on simplified single-component models and are unable to quantitatively disentangle multi-metal and multi-ligand mechanisms. Future research should focus on developing generalizable machine learning capabilities， constructing explicit interface models for multi-factor coupling， and supplementing basic dynamic parameters for atmospheric models， thereby providing a theoretical foundation for source apportionment of sulfate during haze.
Keywords： sulfate； heterogeneous reaction； formation mechanism； molecular simulation； transition metal； peroxide
参考文献（References）
［1］Chen Fengxia， Qiu Hongquan， Wang Jinzhao， et al. Strong acceleration of SO 2 autoxidation at the subsurface of deliquescedaerosols with surface-active organic acids［J］. Environmental Science & Technology， 2026， 60（8）： 6353-6363.
［2］吴蓬萍， 韩志伟. 中国夏季硫酸盐气溶胶间接辐射强迫的数值模拟［J］. 中国粉体技术， 2010， 16（1）： 65-67.
Wu Pengping， Han Zhiwei. Model study of indirect radiative forcing by sulfate aerosol over China in summer［J］. China Powder Science and Technology， 2010， 16（1）： 65-67.
［3］Hu Ying， Chu Lingzhi， Renzetti S， et al. Spatial and racial/ethnic disparities in cardiovascular mortality attributable to PM 2.5 components in the contiguous United States［J］. Science Advances， 2026， 12（5）： eadx2075.
［4］Sun Hongyue， Chen Xi， Huang Wenzhong， et al. Association between long-term exposure to PM2.5 inorganic chemical compositions and cardiopulmonary mortality： a 22-year cohort study in northern China［J］. Environment & Health， 2024， 2（8）： 530-540.
［5］Ye Can， Lu Keding， Song Huan， et al. A critical review of sulfate aerosol formation mechanisms during winter polluted periods［J］. Journal of Environmental Sciences， 2023， 123： 387-399.
［6］Zhang Chunyan， Wang Yonghong， Liu Jun， et al. Insight into wet scavenging effects on sulfur and nitrogen containing organic compounds in urban Beijing［J］. NPJ Climate and Atmospheric Science， 2024， 7： 205.
［7］Choi M， Park J， Sung M， et al. Long-range transport of secondary inorganic aerosol from China to South Korea［J］. Environmental Science & Technology Letters， 2024， 11（11）： 1233-1238.
［8］Zheng B， Zhang Q， Zhang Y， et al. Heterogeneous chemistry： a mechanism missing in current models to explain secondary inorganic aerosol formation during the January 2013 haze episode in North China［J］. Atmospheric Chemistry and Physics， 2015， 15（4）： 2031-2049.
［9］Liu Pai， Wu Xu， Huang Qishen， et al. Origins of size-dependent kinetics in microdroplets［J］. The Journal of Physical Chemistry Letters， 2026， 17（28）： 7817-7829.
［10］Zhang Zihao， Li Haiwei， Ho W， et al. Critical roles of surface-enhanced heterogeneous oxidation of SO2 in haze chemistry： review of extended pathways for complex air pollution［J］. Current Pollution Reports， 2024， 10（1）： 70-86.
［11］Liu Pai， Huang Qishen， Lei Ting， et al. Sulfur chemistry at the air-water interface［J］. Annual Review of Physical Chemistry， 2026， 77： 17-41.
［12］Kraft J， Van Eldik R. Kinetics and mechanism of the iron（III）-catalyzed autoxidation of sulfur（IV） oxides in aqueous solution. 1. formation of transient iron（III）-sulfur（IV） complexes［J］. Inorganic Chemistry， 1989， 28（12）： 2297-2305.
［13］Alexander B， Park R J， Jacob D J， et al. Transition metal-catalyzed oxidation of atmospheric sulfur： global implications for the sulfur budget［J］. Journal of Geophysical Research： Atmospheres， 2009， 114（D2）： 2008JD010486.
［14］Wang Weigang， Liu Mingyuan， Wang Tiantian， et al. Sulfate formation is dominated by manganese-catalyzed oxidation of SO2 on aerosol surfaces during haze events［J］. Nature Communications， 2021， 12： 1993.
［15］Wang Gehui， Zhang Si， Wu Can， et al. Hartmann Dennis. Atmospheric sulfate aerosol formation enhanced by interfacial anions［J］. PNAS Nexus， 2025， 4（3）：58-65.
［16］Han Xiaokun， Dong Xinyuan， Liu Cong-Qiang， et al. Multiple sulfur isotopic evidence for sulfate formation in haze pollution［J］. Environmental Science & Technology， 2023， 57 （49）， 20647-20656.
［17］Wang Yuxuan， Zhang Qianqian， Jiang Jingkun， et al. Enhanced sulfate formation during China’s severe winter haze episode in January 2013 missing from current models［J］. Journal of Geophysical Research： Atmospheres， 2014， 119（17）：10425-10440.
［18］Zhang Si， Li Dapeng， Ge Shuangshuang， et al. Elucidating the mechanism on the transition-metal ion-synergetic-catalyzed oxidation of SO2 with implications for sulfate formation in Beijing haze［J］. Environmental Science & Technology， 2024， 58（6）： 2912-2921.
［19］Chen Zhe， Liu Pai， Wang Weigang， et al. Rapid sulfate formation via uncatalyzed autoxidation of sulfur dioxide in aerosol microdroplets［J］. Environmental Science & Technology， 2022， 56（12）： 7637-7646.
［20］Li Linfang， Liu Pai， Huang Qishen， et al. Rethinking urban haze formation： atmospheric sulfite conversion rate scales with aerosol surface area， not volume［J］. One Earth， 2024， 7（6）： 1082-1095.
［21］Gong Kedong， Sethuraman S， Tam A， et al. Size dependent uncatalyzed sulfite oxidation in aqueous microdroplets［J］. Environmental Science & Technology， 2025， 59（37）： 19932-19941.
［22］Cao Xue， Liu Yuxin， Huang Qishen， et al. Single droplet tweezer revealing the reaction mechanism of Mn（II）-catalyzed SO2 oxidation［J］. Environmental Science & Technology， 2024， 58（11）： 5068-5078.
［23］Cao Xue， Chen Zhe， Liu Yuxin， et al. Directly measuring Fe（iii）-catalyzed SO2 oxidation rate in single optically levitated droplets［J］. Environmental Science： Atmospheres， 2023， 3（2）： 298-304.
［24］Jing Xinbo， Chen Zhe， Cao Xue， et al. Rapid sulfate formation via Mn2+-catalyzed SO2 oxidation on the surface of NaCl microdroplets［J］. The Journal of Physical Chemistry C， 2023， 127（28）： 13632-13638.
［25］Wang Wei， Liu Yangyang， Wang Tao， et al. Significantly accelerated photosensitized formation of atmospheric sulfate at the air-water interface of microdroplets［J］. Journal of the American Chemical Society， 2024， 146（10）： 6580-6590.
［26］Xia Yu， Gao Xufeng， Li Juan， et al. Droplet-on-demand mass spectrometry reveals curvature-dependent interfacial reactivity in aqueous microdroplets［J］. Proceedings of the National Academy of Sciences of the United States of America， 2025， 122（50）： e2519491122.
［27］Mu Chaonan， Wang Wei， Wang Jie， et al. Probe-free direct identification of Type I and Type II photosensitized oxidation using field-induced droplet ionization mass spectrometry［J］. Angewandte Chemie International Edition， 2020， 59（48）： 21515-21519.
［28］尹佳艺， 张晓武， 黄保坤， 等. 光镊-共聚焦显微技术对微液滴空间分辨拉曼成像［J］. 光散射学报， 2026， 38（1）： 232-239.
Yin Jiayi， Zhang Xiaowu， Huang Baokun， et al. Spatially resolved Raman imaging of microdroplets using an integrated optical tweezer-confocal microscopy platform［J］. The Journal of Light Scattering， 2026， 38（1）： 232-239.
［29］陈哲， 刘湃， 庞树峰， 等. 光镊-受激拉曼光谱技术测量SO2与悬浮NaCl单液滴的氧化反应动力学速率常数［J］. 光散射学报， 2022， 34（1）： 46-52.
Chen Zhe， Liu Pai， Pang Shufeng， et al. Investigating the kinetic rate constant of SO2 oxidation with levitated NaCl single droplet using optical tweezer-stimulated Raman spectroscopy［J］. The Journal of Light Scattering， 2022， 34（1）： 46-52.
［30］Zhang Chunyan， Liu Jiarong， Cao Qing， et al. O2-mediated synergistic oxidation of aqueous bisulfite and nitrite： a key pathway for sulfate and nitrate formation in atmospheric sulfur-nitrogen cycles［J］. Environmental Science & Technology， 2026， 60（14）： 10950-10960.
［31］Liu Jiarong， Ning An， Liu Ling， et al. A pH dependent sulfate formation mechanism caused by hypochlorous acid in the marine atmosphere［J］. Science of the Total Environment， 2021， 787： 147551.
［32］Liu Jiarong， Liang Danli， Liu Ling， et al. Catalytic sulfate formation mechanism influenced by important constituents of cloud water via the reaction of SO2 oxidized by hypobromic acid in marine areas［J］. Physical Chemistry Chemical Physics， 2021， 23（30）： 15935-15949.
［33］Liu Jiarong， Buren J， Ji Lin， et al. The new inspiration from the theoretical re-exploration of traditional autoxidation pathways leading to sulfate formation in the haze episode［J］. Atmospheric Environment， 2022， 287： 119220.
［34］Shostak S， Kim K， Horbatenko Y， et al. Sulfuric acid formation via H2SO3 oxidation by H2O2 in the atmosphere［J］. The Journal of Physical Chemistry A， 2019， 123（39）： 8385-8390.
［35］Li Lei， Kumar M， Zhu Chongqin， et al. Near-barrierless ammonium bisulfate formation via a loop-structure promoted proton-transfer mechanism on the surface of water［J］. Journal of the American Chemical Society， 2016， 138（6）： 1816-1819.
［36］Cao Yiqun， Liu Jiarong， Ma Qingxin， et al. Photoactivation of chlorine and its catalytic role in the formation of sulfate aerosols［J］. Journal of the American Chemical Society， 2024， 146（2）： 1467-1475.
［37］Li Hao， Yin Qi， Cao Qing， et al. Promotion of CO2 reactivity by organic acid on aerosol surfaces［J］. Journal of the American Chemical Society， 2025， 147（37）： 33442-33452.
［38］Ning An， Li Jing， Du Lin， et al. Heterogenous chemistry of I2O3 as a critical step in iodine cycling［J］. Journal of the American Chemical Society， 2024， 146（48）： 33229-33238.
［39］Zu Haotian， Ning An， Liu Ling， et al. Mechanistic insights into the autocatalyzed hydrolysis of I2O4： a paradigm for reactive nucleation［J］. Journal of the American Chemical Society， 2026， 148（5）： 5734-5743.
［40］Zhong Jie， Li Liwen， Kumar M， et al. Solvation and hydrolysis reaction of isocyanic acid at the air-water interface： a computational study［J］. Journal of the American Chemical Society， 2022， 144（12）： 5315-5322.
［41］Zhang Xiaomeng， Li Hao， Chu Biwu， et al. The substitution of bisulfite by water on the hydrated iron（III） center： a mechanistic study［J］. The Journal of Physical Chemistry A， 2026， 130（9）： 1875-1881.
［42］Zhang Xiaomeng， Liu Jiarong， Li Hao， et al. pH-dependent Fe（III） speciation and concerted proton-electron transfer mechanism accelerated S（IV） oxidation at the air-water interface［J］. Journal of the American Chemical Society， 2026， 148（11）： 11812-11821.
［43］Zhang Yuchen， Yang Xiaohua， Gu Jinkai， et al. H2O2-driven sulfate formation at air-water interfaces： stepwise mechanism and accelerated kinetics［J］. Environmental Science & Technology， 2026， 60（30）： 21082-21091.
［44］Liu Jiarong， Yang Xiaohua， Gu Jinkai， et al. Redefining ·CO3-formation chemistry： zundel-like switches drive carbonate-·OH interfacial reactivity［J］. Journal of the American Chemical Society， 2026， 148（25）： 25501-25509.
［45］Zhang Tianle， Liu Junyi， Xiang Yaxin， et al. Quantifying anthropogenic emission of iron in marine aerosol in the Northwest Pacific with shipborne online measurements［J］. Science of the Total Environment， 2024， 912： 169158.
［46］Harris E， Sinha B， van Pinxteren D，et al. Enhanced role of transition metal ion catalysis during in-cloud oxidation of SO2［J］. Science， 2013， 340（6133）： 727-730.
［47］Liang Zhancong， Zhou Liyuan， Chang Yuqing， et al. Biomass-burning organic aerosols as a pool of atmospheric reactive triplets to drive multiphase sulfate formation［J］. Proceedings of the National Academy of Sciences of the United States of America， 2024， 121（51）： e2416803121.
［48］Gao Jie， Wang Haoqi， Liu Wenqi， et al. Hydrogen peroxide serves as pivotal fountainhead for aerosol aqueous sulfate formation from a global perspective［J］. Nature Communications， 2024， 15： 4625.
［49］Liu Tengyu， Clegg S L， Abbatt J P D. Fast oxidation of sulfur dioxide by hydrogen peroxide in deliquesced aerosol particles［J］. Proceedings of the National Academy of Sciences of the United States of America， 2020， 117（3）： 1354-1359.
［50］Liu Pengfei， Jia Shuyuan， Li Shuying， et al. Unexpectedly high levels of H2O2 drive sulfate formation over the residual layer in Beijing［J］. Environmental Science & Technology， 2025， 59（9）： 4551-4559.
［51］Ye Can， Liu Pengfei， Ma Zhuobiao， et al. High H2O2 concentrations observed during haze periods during the winter in Beijing： importance of H2O2 oxidation in sulfate formation［J］. Environmental Science & Technology Letters， 2018， 5（12）： 757-763.
［52］Qin Mengru， Chen Zhongming， Shen Hengqing， et al. Impacts of heterogeneous reactions to atmospheric peroxides： observations and budget analysis study［J］. Atmospheric Environment， 2018， 183： 144-153.
［53］ Li Hao， Wang Xiao， Zhong Jie， et al. Mechanistic study of the aqueous reaction of organic peroxides with HSO3- on the surface of a water droplet［J］. Angewandte Chemie International Edition， 2021， 60（37）： 20200-20203.
［54］Yao Min， Zhao Yue， Hu Minghao， et al. Multiphase reactions between secondary organic aerosol and sulfur dioxide： kinetics and contributions to sulfate formation and aerosol aging［J］. Environmental Science & Technology Letters， 2019， 6（12）： 768-774.
［55］Wang Shunyao， Zhao Yue， Chan A W H， et al. Organic peroxides in aerosol： key reactive intermediates for multiphase processes in the atmosphere［J］. Chemical Reviews， 2023， 123（4）： 1635-1679.
