气相条件下Criegee中间体与痕量酸碱物种的双分子反应研究进展  

Advances of the bimolecular reaction of Criegee intermediates with trace acid and base species in the atmosphere

作　　者：王兴[1,2] 蒋友凌 周莉 马嫣 郑军[1,2] WANG Xing;JIANG Youling;ZHOU Li;MA Yan;ZHENG Jun(School of Environmental Science and Engineering,Nanjing University of Information Science and Technology,Nanjing,210044,China;Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control,Nanjing,210044,China)

机构地区：[1]南京信息工程大学环境科学与工程学院,南京210044 [2]江苏省大气环境与监测污染控制高技术研究重点实验室,南京210044

出　　处：《环境化学》2024年第8期2741-2757,共17页Environmental Chemistry

基　　金：国家自然科学基金(41975172,42275116,41730106)资助.

摘　　要：气相臭氧化反应是不饱和烯烃在大气中重要的降解途径之一.反应会生成一个关键的Criegee中间体,该中间体有非常活跃的反应活性,可以发生单分子分解反应生成羟基自由基和烷氧自由基,也可以与大气中其他化合物发生双分子反应,生成复杂的反应产物.受测量手段的限制和大气丰度的影响,关于Criegee中间体双分子反应的研究主要集中在与H_(2)O、(H_(2)O)2及SO_(2)的反应.大气中的无机酸、有机酸、氨和有机胺是大气中痕量、具有高反应活性的化合物,在维持大气酸碱平衡、新粒子生成及二次有机气溶胶形成过程中发挥重要作用.近年的研究指出,Criegee中间体与这些痕量酸碱气体反应速率接近碰撞极限,并生成低挥发性有机物,颠覆了以往研究中认为的反应可以忽略的结论.结合前人的研究成果,对Criegee中间体双分子反应机理做了简要总结,着重阐述了Criegee中间体与无机酸和有机酸以及与氨和有机胺在大气中的双分子反应过程.从文献的梳理中我们发现Criegee中间体与有机酸和有机胺的双分子反应均可以无势垒发生,并且有低聚产物生成,这些机理的提出对于现有的全球化学传输模型和新粒子形成模型可能有重要影响.Gas-phase ozonation reaction is one of the important degradation pathways of unsaturated olefins in the atmosphere.The reaction produces a key Criegee intermediate,which is very reactive and can undergo single molecule decomposition reactions to form hydroxyl radicals and alkoxy radicals,or bimolecular reactions with other compounds in the atmosphere to produce complex reaction products.Due to the limitation of measurement means and atmospheric abundance,studies on the bimolecular reactions of Criegee intermediates have mainly focused on the reactions with H_(2)O,(H_(2)O)_(2)and SO_(2).Atmospheric inorganic acids,organic acids,ammonia and organic amines are trace,highly reactive compounds in the atmosphere and play an important role in maintaining atmospheric acid-base equilibrium,new particle generation and secondary organic aerosol formation.Recent studies have pointed out that Criegee intermediates react with these trace acid and base gases at rates close to the collision limit and produce low volatile organics,reversing the conclusion of previous studies that the reaction was negligible.Combined with the previous research results,this paper briefly summarizes the bimolecular reaction mechanism of Criegee intermediates,focusing on the bimolecular reaction process of Criegee intermediates with inorganic acids and organic acids and with ammonia and amines in the atmosphere.From the literature,we found that the bimolecular reactions of Criegee intermediates with both organic acids and organic amines can occur without potential barriers and form oligomeric products are formed.The proposed mechanisms may have important implications for existing global chemical transport models and new particle formation models.

关 键 词：Criegee 中间体 双分子反应 无机酸 有机酸 氨 有机胺. 

分 类 号：X-1[环境科学与工程] O6[理学—化学]