OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship

doi:10.5194/acp-22-3693-2022

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	OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship
	Chen, Long 1,2; Huang, Yu 1,2; Xue, Yonggang 1,2; Jia, Zhihui 3; Wang, Wenliang 4
通讯作者	Huang, Yu(huangyu@ieecas.cn)
	2022-03-18
发表期刊	ATMOSPHERIC CHEMISTRY AND PHYSICS
ISSN	1680-7316
卷号	22 期号:5 页码:3693-3711
摘要	Hydroxyalkyl hydroperoxides (HHPs), formed in the reactions of Criegee intermediates (CIs) with water vapor, play essential roles in the formation of secondary organic aerosol (SOA) under atmospheric conditions. However, the transformation mechanisms for the OH-initiated oxidation of HHPs remain incompletely understood. Herein, the quantum chemical and kinetics modeling methods are applied to explore the mechanisms of the OH-initiated oxidation of the distinct HHPs (HOCH2OOH, HOCH(CH3)OOH, and HOC(CH3)(2)OOH) formed from the reactions of CH2OO, anti-CH3CHOO, and (CH3)(2)COO with water vapor. The calculations show that the dominant pathway is H-abstraction from the -OOH group in the initiation reactions of the OH radical with HOCH2OOH and HOC(CH3)(2)OOH. H-abstraction from the -CH group is competitive with that from the -OOH group in the reaction of the OH radical with HOCH(CH3)OOH. The barrier of H-abstraction from the -OOH group slightly increases when the number of methyl groups increase. In pristine environments, the self-reaction of the RO2 radical initially produces a tetroxide intermediate via oxygen-to-oxygen coupling, and then it decomposes into propagation and termination products through asymmetric two-step O-O bond scission, in which the rate-limiting step is the first O-O bond cleavage. The barrier height of the reactions of distinct RO2 radicals with the HO2 radical is not affected by the number of methyl substitutions. In urban environments, the reaction with O-2 to form formic acid and the HO2 radical is the dominant removal pathway for the HOCH2O radical formed from the reaction of the HOCH2OO radical with NO. The beta-site C-C bond scission is the dominant pathway in the dissociation of the HOCH(CH3)O and HOC(CH3)(2)O radicals formed from the reactions of NO with HOCH(CH3)OO and HOC(CH3)(2)OO radicals. These new findings deepen our understanding of the photochemical oxidation of hydroperoxides under realistic atmospheric conditions.
DOI	10.5194/acp-22-3693-2022
关键词[WOS]	SIMPLEST CRIEGEE INTERMEDIATE ; OXIDIZED RO2 RADICALS ; MULTIFUNCTIONAL PRODUCTS ; OLIGOMER FORMATION ; WATER ; REACTIVITY ; OXIDATION ; STATES ; HO2 ; DECOMPOSITION
收录类别	SCI ; SCI
语种	英语
资助项目	National Natural Science Foundation of China[42175134] ; National Natural Science Foundation of China[41805107] ; National Natural Science Foundation of China[22002080] ; Key Projects of Chinese Academy of Sciences, China[ZDRW-ZS-2017-6] ; Strategic Priority Research Program of the Chinese Academy of Sciences, China[XDA23010300] ; Strategic Priority Research Program of the Chinese Academy of Sciences, China[XDA23010000] ; Key Project of International Cooperation of the Chinese Academy of Sciences, China[GJHZ1543] ; Research Grants Council of Hong Kong, China[PolyU 152083/14E] ; CAS Light of West China Program[XAB2019B01] ; General Project of Shaanxi Province[2020JQ-432]
WOS研究方向	Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences
项目资助者	National Natural Science Foundation of China ; Key Projects of Chinese Academy of Sciences, China ; Strategic Priority Research Program of the Chinese Academy of Sciences, China ; Key Project of International Cooperation of the Chinese Academy of Sciences, China ; Research Grants Council of Hong Kong, China ; CAS Light of West China Program ; General Project of Shaanxi Province
WOS类目	Environmental Sciences ; Meteorology & Atmospheric Sciences
WOS记录号	WOS:000773402200001
出版者	COPERNICUS GESELLSCHAFT MBH
引用统计	被引频次：3[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.ieecas.cn/handle/361006/17623
专题	粉尘与环境研究室第四纪科学与全球变化卓越创新中心
通讯作者	Huang, Yu
作者单位	1.Chinese Acad Sci, Inst Earth Environm, State Key Lab Loess & Quaternary Geol SKLLQG, Xian 710061, Peoples R China 2.CAS Ctr Excellence Quaternary Sci & Global Change, Xian 710061, Peoples R China 3.Shaanxi Normal Univ, Sch Mat Sci & Engn, Xian 710119, Shaanxi, Peoples R China 4.Shaanxi Normal Univ, Sch Chem & Chem Engn, Key Lab Macromol Sci Shaanxi Prov, Xian 710119, Shaanxi, Peoples R China
推荐引用方式 GB/T 7714	Chen, Long,Huang, Yu,Xue, Yonggang,et al. OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship[J]. ATMOSPHERIC CHEMISTRY AND PHYSICS,2022,22(5):3693-3711.
APA	Chen, Long,Huang, Yu,Xue, Yonggang,Jia, Zhihui,&Wang, Wenliang.(2022).OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship.ATMOSPHERIC CHEMISTRY AND PHYSICS,22(5),3693-3711.
MLA	Chen, Long,et al."OH-initiated atmospheric degradation of hydroxyalkyl hydroperoxides: mechanism, kinetics, and structure-activity relationship".ATMOSPHERIC CHEMISTRY AND PHYSICS 22.5(2022):3693-3711.