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投稿时间:2021-06-29 修订日期:2021-09-27
投稿时间:2021-06-29 修订日期:2021-09-27
中文摘要: 运用共沉淀低温水热技术制备软铋矿铁酸铋(sillenite bismuth ferrite,S-BFO),构建S-BFO非均相活化过一硫酸盐(peroxymonosulfate,PMS)降解环丙沙星(ciprofloxacin,CIP)体系。实验结果表明:在初始pH值为(6.5±0.1)和反应温度为(25±1) ℃条件下,向反应溶液中加入0.675 mmol/L PMS、1000 mg/L的催化剂,反应60 min后,溶液中84.8%的CIP被去除(初始浓度为5.0 mg/L);在相同反应条件下,S-BFO活化PMS降解CIP效率高于S-BFO活化过二硫酸盐(persulfate,PS)。采用场发射电子显微镜(scanning electron microscope,SEM)和X射线衍射仪(X-ray diffraction,XRD)分别对S-BFO的微观形貌特征和晶型结构进行了分析。探究了PMS浓度和初始反应pH值对S-BFO活化PMS降解CIP的影响,评估了S-BFO/PMS体系在实际水体条件下处理污染物的应用潜能。通过活性物质淬灭实验,发现体系中对CIP起主要降解作用的活性物质是单线态氧(1O2),而不是硫酸根自由基($\cdot \mathrm{SO}_4^{-} $)和羟基自由基(·OH),并提出了S-BFO活化PMS降解CIP的机理。采用三重四级杆串联液相色谱质谱仪(liquid chromatography tandem mass spectrometry,LC/MS/MS)技术检测到了9种CIP降解过程中的主要中间产物,并确定了CIP被氧化去除的主要降解路径是通过羟基加成反应(路径Ⅰ)及脱羧反应(路径Ⅱ)。本研究为基于过硫酸盐的高级氧化技术在污水处理领域的应用提供了重要的理论支撑。
Abstract:Sillenite bismuth ferrite (S-BFO) was prepared by a co-precipitation-low temperature hydrothermal technique. The catalytic performance of S-BFO was evaluated by activating peroxymonosulfate (PMS) to remove ciprofloxacin (CIP). The results showed that adding 0.675 mmol/L PMS and 1000 mg/L of catalyst at the condition of initial pH value (6.5±0.1) and reaction temperature (25±1)℃, the removal rate of CIP (5.0 mg/L) was reached 84.8%. Under the same reaction conditions, the degradation efficiency of S-BFO activated PMS for CIP was higher than persulfate (PS). The morphology and crystal structure of S-BFO were analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The effects of PMS concentration and initial pH value on the degradation of CIP in S-BFO/PMS system were investigated. The application potential of S-BFO/PMS system in the treatment of pollutants under real water conditions was evaluated. The results of ROS quenching experiments indicated that 1O2 is the main ROS in the S-BFO/PMS system, rather than $\cdot \mathrm{SO}_4^{-} $ or ·OH. The mechanism of degradation of CIP in the S-BFO/PMS system was also proposed. Finally, the 9 main products and intermediates of CIP were analyzed using liquid chromatography tandem mass spectrometry (LC/MS/MS) technology, and two possible degradation pathways was proposed including hydroxyl addition reaction (Pathway Ⅰ) and decarboxylation reaction (Pathway Ⅱ). This study provides important theoretical support for advanced oxidation technology based on persulfate in the field of wastewater treatment.
文章编号:202100622 中图分类号:X131.2 文献标志码:
基金项目:四川大学专职博士后研发基金项目(2020SCU12057)
作者 | 单位 | |
刘杨 | 四川大学 建筑与环境学院,四川 成都 610065 | liuyang_scu@126.com |
张永丽 | 四川大学 建筑与环境学院,四川 成都 610065 | |
周鹏 | 四川大学 建筑与环境学院,四川 成都 610065 |
作者简介:第一作者:刘杨(1991—),男,副研究员,博士. 研究方向:高级氧化、水污染控制技术开发. E-mail:liuyang_scu@126.com
引用文本:
刘杨,张永丽,周鹏.软铋矿铁酸铋活化过一硫酸盐降解环丙沙星机理及产物研究[J].工程科学与技术,2022,54(5):203-209.
LIU Yang,ZHANG Yongli,ZHOU Peng.Study on Mechanism and Products of Degradation of Ciprofloxacin by Sillenite Bismuth Ferrite-activated Persulfate[J].Advanced Engineering Sciences,2022,54(5):203-209.
引用文本:
刘杨,张永丽,周鹏.软铋矿铁酸铋活化过一硫酸盐降解环丙沙星机理及产物研究[J].工程科学与技术,2022,54(5):203-209.
LIU Yang,ZHANG Yongli,ZHOU Peng.Study on Mechanism and Products of Degradation of Ciprofloxacin by Sillenite Bismuth Ferrite-activated Persulfate[J].Advanced Engineering Sciences,2022,54(5):203-209.