基于真空紫外光电离质谱的氯原子引发诺蒎酮氧化反应研究  

Investigation of Chlorine-initiated Oxidation Reactions of Nopinone by Vacuum Ultraviolet Photoionization Mass Spectrometry

作　　者：胡荣荣 马子吉 岳浩 林晓晓 温作赢 张为俊[1] 顾学军[1] 唐小锋 HU Rong-Rong;MA Zi-Ji;YUE Hao;LIN Xiao-Xiao;WEN Zuo-Ying;ZHANG Wei-Jun;GU Xue-Jun;TANG Xiao-Feng(Anhui Institute of Optics&Fine Mechanics,Hefei Institutes of Physical Science,Chinese Academy of Sciences,Hefei 230031,China;Science Island Branch,Graduate School,University of Science and Technology of China,Hefei 230026,China)

机构地区：[1]中国科学院合肥物质科学研究院安徽光学精密机械研究所,合肥230031 [2]中国科学技术大学研究生院科学岛分院,合肥230026

出　　处：《分析化学》2022年第6期948-956,共9页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(Nos.42075113,42120104007,91961123)资助。

摘　　要：采用微波放电流动管反应器模拟大气中氯原子(Cl)引发的诺蒎酮(C_(9)H_(14)O)氧化反应,结合自行研制的真空紫外光电离飞行时间质谱仪,在线检测获得反应中的关键物种,包含反应物、自由基和产物,并开展其反应动力学研究,通过比较关键物种的动力学实验与模拟计算结果,探讨了反应中关键物种的反应路径。结果表明,Cl原子和诺蒎酮分子之间的反应经夺氢通道生成自由基C_(9)H_(13)O,产生的自由基C_(9)H_(13)O与O_(2)分子反应主要生成过氧自由基C_(9)H_(13)OO_(2),并且新生成的C_(9)H_(13)OO_(2)在无NO或NO_(2)条件下进一步与HO_(2)自由基反应生成氢过氧化物C_(9)H_(13)OO_(2)H,以及与自身发生双分子反应生成自由基C_(9)H_(13)OO、羰基化合物C_(9)H_(12)O_(2)和C_(9)H_(13)OOH。本研究通过实验研究和模拟计算揭示了Cl原子引发的诺蒎酮大气氧化反应机理。A microwave discharge fast flow tube reactor was used to simulate chlorine-initiated oxidation of nopinone(C_(9)H_(14)O).The chemical compositions of radicals and stable products from the oxidation reactions were measured via a home-made vacuum ultraviolet photoionization time of flight mass spectrometer(VUVPI-TOFMS).The kinetic experiments of main radicals and products were also performed.By comparing the results of kinetic experiments and simulation calculations of key species,the reaction pathways of key species in the reaction were further explored.This study showed that the reaction of nopinone with Cl produced radical C_(9)H_(13)O via the hydrogen abstraction pathway.The radical C_(9)H_(13)O reacted with O_(2) to mainly generate peroxy radical C_(9)H_(13)OO_(2).Under NOx(NO and NO_(2))free condition,peroxy radical C_(9)H_(13)OO_(2) reacted with itself to produce radical C_(9)H_(13)OO,carbonyl compounds C9H12O_(2) and C_(9)H_(13)OOH.In addition,the peroxy radical C_(9)H_(13)OO_(2) could also react with HO_(2) to produce hydroperoxide C_(9)H_(13)OO_(2)H.The mechanism of chlorine-initiated oxidation reactions of nopinone was also revealed through experimental studies and simulation calcu lations.

关 键 词：诺蒎酮 氯原子 光电离质谱 氧化机理 过氧自由基 

分 类 号：X131.1[环境科学与工程—环境科学] O657.63[理学—分析化学]