Coupling-oxidation process promoted ring-opening degradation of 2-mecapto-5-methyl-1,3,4-thiadizaole in wastewater

doi:10.1016/j.watres.2020.116362

	Coupling-oxidation process promoted ring-opening degradation of 2-mecapto-5-methyl-1,3,4-thiadizaole in wastewater
	Zhong, Chen 3,4; Zhao, He 1,5; Han, Qingzhen 5; Cao, Hongbin 5; Duan, Feng 5; Shen, Junyi 2,5; Xie, Yongbing 5; Guo, Wanqian 1; Sun, Shanshan 5
刊名	WATER RESEARCH
	2020-11-01
卷号	186 页码:12
关键词	2-mecapto-5-methyl-1,3,4-thiadizaole (MMTD) Antibiotic wastewater Humic substances Coupling-oxidation Ring-opening degradation
ISSN号	0043-1354
DOI	10.1016/j.watres.2020.116362
英文摘要	As an important raw material and intermediate of widely used antibiotics cefazolin and cefazedone, 2-mecapto-5-methyl-1,3,4-thiadizaole (MMTD) in antibiotic wastewater is hardly decyclized during wastewater treatment, posing great risk to the environment. This work proposed a green "coupling-oxidation" process to enhance ring-opening of MMTD during antibiotic wastewater treatment. In particular, the significant role of humic substances (HS) as pre-coupling reagent was emphasized. Real HS and different model HS, especially quinones, not only efficiently pre-coupled MMTD ( 95%) but also promoted the MMTD removal by MnO2 (from 72.4% to 92.4%). Mass spectrometric analysis indicated that MMTD pre coupled to HS would be oxidized with ring opening to environmental-friendly sulfonated HS, while direct oxidation of MMTD produced MMTD dimers or sulfonated MMTD that would not undergo ring opening. Theoretical calculations indicated that pre-coupling to HS enabled the ring-opening oxidation by increasing the nucleophilicity and decreasing ring-opening barrier of thiadiazole. Based on the density function theory (DFT), the global nucleophilicity index (Nu) followed the trend of HS-MMTD > MMTD dimer > sulfonated MMTD, while the ring-opening barrier followed the trend of HS-MMTD (274 kJ/mol) < first ring of MMTD dimers (286 kJ/mol) < MMTD (338 kJ/mol). Theoretical calculations further confirmed that the cross-coupled HS-MMTD intermediate was more likely to be decyclized than intermediates from direct oxidation. Moreover, nitrogen, acetaldehyde group, sulfate and CO2 were the products of thiadiazole ring degradation. Pre-coupling of MMTD with HS provides a new idea and strategy in developing a green and sustainable scheme for wastewater treatment. (c) 2020 Elsevier Ltd. All rights reserved.
资助项目	National Natural Science Foundation of China[51,978,643] ; Open Project of State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology[HCK201806] ; Strategic Priority Research Program of the Chinese Academy of Sciences[XDA23010400] ; Youth Innovation Promotion Association, CAS[2,014,037]
WOS关键词	HUMIC CONSTITUENTS ; PHOTOCATALYTIC DEGRADATION ; MANGANESE-DIOXIDE ; AQUEOUS-SOLUTIONS ; GALLIC ACID ; TRANSFORMATION ; REMOVAL ; PATHWAYS ; KINETICS ; ACETAMINOPHEN
WOS研究方向	Engineering ; Environmental Sciences & Ecology ; Water Resources
语种	英语
出版者	PERGAMON-ELSEVIER SCIENCE LTD
WOS记录号	WOS:000589968900023
资助机构	National Natural Science Foundation of China ; Open Project of State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology ; Strategic Priority Research Program of the Chinese Academy of Sciences ; Youth Innovation Promotion Association, CAS
内容类型	期刊论文
源URL	[http://ir.ipe.ac.cn/handle/122111/42811]
专题	中国科学院过程工程研究所
通讯作者	Zhao, He
作者单位	1.Harbin Inst Technol, State Key Lab Urban Water Resource & Environm, Harbin 150090, Peoples R China 2.Suzhou Univ Sci & Technol, Suzhou 215009, Jiangsu, Peoples R China 3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 4.Chinese Acad Sci, Inst Proc Engn, Natl Key Lab Biochem Engn, Beijing 100190, Peoples R China 5.Chinese Acad Sci, Innovat Acad Green Mfg, Beijing Engn Res Ctr Proc Pollut Control, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Zhong, Chen,Zhao, He,Han, Qingzhen,et al. Coupling-oxidation process promoted ring-opening degradation of 2-mecapto-5-methyl-1,3,4-thiadizaole in wastewater[J]. WATER RESEARCH,2020,186:12.
APA	Zhong, Chen.,Zhao, He.,Han, Qingzhen.,Cao, Hongbin.,Duan, Feng.,...&Sun, Shanshan.(2020).Coupling-oxidation process promoted ring-opening degradation of 2-mecapto-5-methyl-1,3,4-thiadizaole in wastewater.WATER RESEARCH,186,12.
MLA	Zhong, Chen,et al."Coupling-oxidation process promoted ring-opening degradation of 2-mecapto-5-methyl-1,3,4-thiadizaole in wastewater".WATER RESEARCH 186(2020):12.