Caroline Smith Lewin, Avinash Kumar, Olivier Herbinet, Philippe Arnoux, Rabbia Asgher, Shawon Barua, Frédérique Battin-Leclerc, Sana Farhoudian, Gustavo A. Garcia, Luc-Sy Tran, Guillaume Vanhove, Laurent Nahon, Matti Rissanen and Jérémy Bourgalais*,
{"title":"通过同步加速器光电子能谱学和化学电离质谱法研究大气和燃烧温度下的 1-己烯臭氧分解。","authors":"Caroline Smith Lewin, Avinash Kumar, Olivier Herbinet, Philippe Arnoux, Rabbia Asgher, Shawon Barua, Frédérique Battin-Leclerc, Sana Farhoudian, Gustavo A. Garcia, Luc-Sy Tran, Guillaume Vanhove, Laurent Nahon, Matti Rissanen and Jérémy Bourgalais*, ","doi":"10.1021/acs.jpca.4c02687","DOIUrl":null,"url":null,"abstract":"<p >This study investigates the complex interaction between ozone and the autoxidation of 1-hexene over a wide temperature range (300–800 K), overlapping atmospheric and combustion regimes. It is found that atmospheric molecular mechanisms initiate the oxidation of 1-hexene from room temperature up to combustion temperatures, leading to the formation of highly oxygenated organic molecules. As temperature rises, the highly oxygenated organic molecules contribute to radical-branching decomposition pathways inducing a high reactivity in the low-temperature combustion region, i.e., from 550 K. Above 650 K, the thermal decomposition of ozone into oxygen atoms becomes the dominant process, and a remarkable enhancement of the conversion is observed due to their diradical nature, counteracting the significant negative temperature coefficient behavior usually observed for 1-hexene. In order to better characterize the formation of heavy oxygenated organic molecules at the lowest temperatures, two analytical performance methods have been combined for the first time: synchrotron-based mass-selected photoelectron spectroscopy and orbitrap chemical ionization mass spectrometry. At the lowest studied temperatures (below 400 K), this analytical work has demonstrated the formation of the ketohydroperoxides usually found during the LTC oxidation of 1-hexene, as well as of molecules containing up to nine O atoms.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"1-Hexene Ozonolysis across Atmospheric and Combustion Temperatures via Synchrotron-Based Photoelectron Spectroscopy and Chemical Ionization Mass Spectrometry\",\"authors\":\"Caroline Smith Lewin, Avinash Kumar, Olivier Herbinet, Philippe Arnoux, Rabbia Asgher, Shawon Barua, Frédérique Battin-Leclerc, Sana Farhoudian, Gustavo A. Garcia, Luc-Sy Tran, Guillaume Vanhove, Laurent Nahon, Matti Rissanen and Jérémy Bourgalais*, \",\"doi\":\"10.1021/acs.jpca.4c02687\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >This study investigates the complex interaction between ozone and the autoxidation of 1-hexene over a wide temperature range (300–800 K), overlapping atmospheric and combustion regimes. It is found that atmospheric molecular mechanisms initiate the oxidation of 1-hexene from room temperature up to combustion temperatures, leading to the formation of highly oxygenated organic molecules. As temperature rises, the highly oxygenated organic molecules contribute to radical-branching decomposition pathways inducing a high reactivity in the low-temperature combustion region, i.e., from 550 K. Above 650 K, the thermal decomposition of ozone into oxygen atoms becomes the dominant process, and a remarkable enhancement of the conversion is observed due to their diradical nature, counteracting the significant negative temperature coefficient behavior usually observed for 1-hexene. In order to better characterize the formation of heavy oxygenated organic molecules at the lowest temperatures, two analytical performance methods have been combined for the first time: synchrotron-based mass-selected photoelectron spectroscopy and orbitrap chemical ionization mass spectrometry. At the lowest studied temperatures (below 400 K), this analytical work has demonstrated the formation of the ketohydroperoxides usually found during the LTC oxidation of 1-hexene, as well as of molecules containing up to nine O atoms.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-06-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpca.4c02687\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpca.4c02687","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
本研究调查了臭氧与 1-hexene 自氧化之间在宽温度范围(300-800 K)内的复杂相互作用,以及大气和燃烧状态的重叠。研究发现,从室温到燃烧温度,大气分子机制启动了 1-己烯的氧化,从而形成高含氧有机分子。随着温度的升高,高含氧有机分子有助于自由基支化分解途径,从而在低温燃烧区域(即从 550 K 开始)产生高反应性。超过 650 K 后,臭氧热分解为氧原子的过程成为主要过程,由于其二元对立性质,转化率显著提高,抵消了通常在 1-己烯中观察到的显著负温度系数行为。为了更好地描述重含氧有机分子在最低温度下的形成过程,我们首次将两种分析性能方法结合在一起:同步辐射质量选择光电子能谱和轨道阱化学电离质谱。在研究的最低温度(低于 400 K)下,这项分析工作证明了在 1-hexene 的 LTC 氧化过程中通常发现的酮氢过氧化物以及含有多达 9 个 O 原子的分子的形成。
1-Hexene Ozonolysis across Atmospheric and Combustion Temperatures via Synchrotron-Based Photoelectron Spectroscopy and Chemical Ionization Mass Spectrometry
This study investigates the complex interaction between ozone and the autoxidation of 1-hexene over a wide temperature range (300–800 K), overlapping atmospheric and combustion regimes. It is found that atmospheric molecular mechanisms initiate the oxidation of 1-hexene from room temperature up to combustion temperatures, leading to the formation of highly oxygenated organic molecules. As temperature rises, the highly oxygenated organic molecules contribute to radical-branching decomposition pathways inducing a high reactivity in the low-temperature combustion region, i.e., from 550 K. Above 650 K, the thermal decomposition of ozone into oxygen atoms becomes the dominant process, and a remarkable enhancement of the conversion is observed due to their diradical nature, counteracting the significant negative temperature coefficient behavior usually observed for 1-hexene. In order to better characterize the formation of heavy oxygenated organic molecules at the lowest temperatures, two analytical performance methods have been combined for the first time: synchrotron-based mass-selected photoelectron spectroscopy and orbitrap chemical ionization mass spectrometry. At the lowest studied temperatures (below 400 K), this analytical work has demonstrated the formation of the ketohydroperoxides usually found during the LTC oxidation of 1-hexene, as well as of molecules containing up to nine O atoms.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.