中国环境科学2024,Vol.44Issue(1) :158-166.

抗坏血酸改性Mn3O4活化过硫酸氢盐降解磺胺甲恶唑

Efficient degradation of sulfamethoxazole by ascorbic acid modified Mn3O4 via peroxymonosulfate activation

陈婧 宋炳皞 朱雷 陈宏 张杰 姜恒 于翰博 储琨 刘紫丹
中国环境科学2024,Vol.44Issue(1) :158-166.

抗坏血酸改性Mn3O4活化过硫酸氢盐降解磺胺甲恶唑

Efficient degradation of sulfamethoxazole by ascorbic acid modified Mn3O4 via peroxymonosulfate activation

陈婧 1宋炳皞 1朱雷 2陈宏 1张杰 2姜恒 2于翰博 1储琨 1刘紫丹1
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作者信息

  • 1. 长沙理工大学水利与环境工程学院,湖南长沙 410114;洞庭湖水环境治理与生态修复湖南省重点实验室,湖南长沙 410114
  • 2. 洞庭湖水环境治理与生态修复湖南省重点实验室,湖南长沙 410114;湖南省水利水电勘测设计规划研究总院有限公司,湖南长沙 410007;湖南省洞庭湖防洪及水资源保障工程技术研究中心,湖南长沙 410007
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摘要

采用水热-超声法制备抗坏血酸(AA)改性的Mn3O4(AA-MO),并通过XRD、FTIR、SEM、TEM和XPS等技术手段表征样品的物理化学性质.将AA-MO用于活化过硫酸氢盐(PMS)降解磺胺甲恶唑(SMX),结果表明,AA-MO/PMS体系在2.0~10.0的pH值范围内催化效能先升后降,在中性和偏中性环境中具有最佳降解效果.PMS浓度和催化剂投加量的增大均能有效促进SMX的降解.稳定性实验显示,在3次循环使用后AA-MO相比MO具有更稳定的催化效能.自由基淬灭结果表明硫酸根自由基(SO4*-)在降解反应中起主导作用.AA-MO与PMS之间的电子转移反应产生自由基降解SMX,AA的抗氧化性维持了复合催化剂的高催化性.通过高效液相色谱-串联质谱联用(HPLC-MS/MS)测定了降解过程中可能的6种中间产物.SMX通过开环、S-N键断裂、羟基化以及氧化作用等3种路径被降解.通过ECOSAR软件计算物质的毒性阈值并进行毒理分析,需要关注产物P2、P5和P7的毒性.

Abstract

A new ascorbic acid modified Mn3O4(AA-MO)was fabricated by a hydrothermal-ultrasonic method.The sample's physical and chemical properties were characteristiced by XRD,FTIR,SEM,TEM and XPS.AA-MO was utilized to activate peroxymonosulfate(PMS)for sulfamethoxazole(SMX)degradation.The results depicted that the SMX degradation efficiency was firstly increased and then decreased in the pH range of 2.0~10.0,and the AA-MO/PMS system exhibited the best catalytic performance in the neutral environment.The increase of PMS concentration and catalyst dosage could both significantly promote the degradation of SMX.Compared with MO,AA-MO displayed a more stable catalytic performance after 3 cycles through reusability experiments.SO4·-was the main active species in the SMX degradation process by scavenging experiments.The electron transfer reactions between AA-MO and PMS could generate free radicals to remove SMX,and the oxidation resistance of AA could maintain the high catalytic performance of MO.Six possible degradation intermediates were identified by HPLC-MS/MS.In the three proposed degradation pathways,SMX was degraded by ring opening,S-N bond breaking,hydroxylation and oxidation.The toxicity threshold of SMX was calculated by ECOSAR model and ecotoxicity analysis was performed,while the toxicity of products P2,P5 and P7 should be concemed.

关键词

抗坏血酸/Mn3O4/过硫酸氢盐/磺胺甲恶唑/催化降解/高级氧化

Key words

ascorbic acid/Mn3O4/peroxymonosulfate/sulfamethoxazole/catalytic degradation/advanced oxidation

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基金项目

湖南省科技厅重点研发项目(2023NK2031)

湖南省科技厅重点研发项目(2022SK2091)

湖南省自然科学基金青年基金(2023JJ40031)

出版年

2024
中国环境科学
中国环境科学学会

中国环境科学

CSTPCDCHSSCD北大核心
影响因子:2.174
ISSN:1000-6923
参考文献量36
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