[1]郭钦,庞素艳,姜成春,等.KMnO4氧化降解2,4-二氯酚的产物及机理推测[J].中国给水排水,2018,34(21):53-58.
　GUO Qin,PANG Su yan,JIANG Cheng chun,et al.Degradation of 2,4-Dichlorophenol by Potassium Permanganate: Oxidation Products and Tentative Mechanisms[J].China Water & Wastewater,2018,34(21):53-58.
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KMnO4氧化降解2,4-二氯酚的产物及机理推测

中国给水排水[ISSN:1000-4062/CN:12-1073/TU] 卷: 第34卷 期数: 2018年21期 页码: 53-58 栏目: 技术总结 出版日期: 2018-10-20
Title:
Degradation of 2,4-Dichlorophenol by Potassium Permanganate: Oxidation Products and Tentative Mechanisms
文章编号:
1000-4602(2018)21-0053-06
作者:
郭钦1,庞素艳1，2,姜成春3,江进4，马军4
(1. 哈尔滨理工大学化学与环境工程学院,黑龙江哈尔滨150040；2. 吉林建筑大学市政与环境工程学院,吉林长春130118；3. 深圳职业技术学院建筑与环境工程学院,广东深圳518055；4. 哈尔滨工业大学城市水资源与水环境国家重点实验室,黑龙江哈尔滨150090)
Author(s):
GUO Qin1,PANG Su yan1，2,JIANG Cheng chun3,JIANG Jin4,MA Jun4
(1. College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040, China; 2. School of Municipal and Environmental Engineering, Jilin Jianzhu University, Changchun 130118, China; 3. School of Construction and Environmental Engineering, Shenzhen Polytechnic, Shenzhen 518055, China; 4. State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China)
关键词:
高锰酸钾; 2; 4-二氯酚; LC-MS/MS; 氧化产物; 反应机理
Keywords:
potassium permanganate; 2; 4-dichlorophenol; LCMS/MS; oxidation product;  reaction mechanism
分类号:
YU991
文献标志码:
C
摘要:
为了探讨KMnO4氧化降解2,4-二氯酚（2,4-DClP）的产物与反应机理，利用三重四级杆串联线性离子阱液相-质谱联用仪（LC-MS/MS）对产物进行检测分析。根据氯的天然同位素特性，建立了LC-MS/MS（Cl- m/z35和37）子找母质谱扫描方法，检测得到KMnO4氧化降解2,4-DClP的含氯产物主要有7个。产物Ⅰ和Ⅱ质量数相同，为321/323/325/327（ m/z 35），含有4个氯，推测为同分异构体，是2,4-DClP自由基分别通过C—O、C—C耦合不脱氯产生；产物Ⅲ质量数为287/289/291（m/z 35），含有3个氯，推测是2,4-DClP自由基通过C—O耦合脱掉1个氯产生；产物Ⅳ质量数为303/305/307（m/z 35），含有3个氯，推测是产物Ⅲ羟基化产生；产物Ⅴ质量数为302/303/304/305/306/307（m/z 35），含有3个氯，推测是产物Ⅳ被氧化生成的醌型产物；产物Ⅵ和Ⅶ质量数相同，为143（m/z 35），含有1个氯，推测为同分异构体，由2,4-DClP结构中的1个氯被羟基取代而产生。2,4-DClP自由基发生耦合反应理论上产生的氯代聚合产物并没有全部被检测到，主要是由于酚氧自由基的氧化耦合速率不同，导致聚合产物的生成产率不同。
Abstract:
Experiments were conducted to determine the chlorinated oxidation products of 2,4-DClP by aqueous potassium permanganate using liquid chromatographytriple quadrupole mass spectrometry (LCMS/MS). The results showed that seven chlorinated oxidation products were detected by the precursor scan approach of m/z 35 and 37 developed on the basis of the natural isotope of chlorinate atom. The polymeric products Ⅰ and Ⅱ of m/z 321/323/325/327 (m/z 35), which contained four chlorine atoms, were inferred as two isomers, and they were formed by the C-O and C-C coupling of 2,4-dichlorophenoxy radicals. The polymeric product Ⅲ of m/z 287/289/291 (m/z 35), which contained three chlorine atoms, was formed by the C-O coupling of 2,4-dichlorophenoxy radicals with the release of a chlorine atom. The product Ⅳ of m/z 303/305/307 (m/z 35), which contained three chlorine atoms, was formed by the hydroxylation of product Ⅲ. The quinonetype product Ⅴ of m/z 302/303/304/305/306/307 (m/z 35), which contained three chlorine atoms, was formed by the oxidation of product Ⅳ. The products Ⅵ and Ⅶ of m/z 143 (m/z 35), which contained one chlorine atom, were two isomers, and they were formed by hydroxylation of 2,4-DClP at the chlorine substituted position. According to the phenolic coupling theory, the chlorinated polymeric products were partially detected, probably due to the difference in the coupling rates of the phenoxy radicals.

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备注/Memo

基金项目：国家自然科学基金资助项目(51578203)
通信作者：庞素艳E-mail:psyhit@126.com
作者简介： 郭钦（1992- ），男，山西大同人，硕士研究生，研究方向为化学氧化去除水中有机污染物。
E-mail:gqfy1992@163.com
收稿日期：2018-04-21

更新日期/Last Update: 2018-11-01