磁性锰铁尖晶石@CeO<sub>2</sub>活化过氧乙酸降解水中四环素

孙娜; 杨昱清; 刘占孟; 尧骞慧; 崔培涛; 王励卿

doi:10.13205/j.hjgc.202601010

磁性锰铁尖晶石@CeO₂活化过氧乙酸降解水中四环素

doi: 10.13205/j.hjgc.202601010

1. 华东交通大学规划设计研究院, 南昌 330013;
2. 华东交通大学土木建筑学院, 南昌 330013;
3. 南昌工程学院土木与建筑工程学院, 南昌 330099

详细信息

作者简介:
孙娜，女，高级工程师，主要研究方向为水处理理论与技术。2794152736@qq.com

通讯作者:
刘占孟，男，教授，主要研究方向为水处理理论与技术。654095077@qq.com

计量
- 文章访问数: 1
- HTML全文浏览量: 0
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2024-11-07
- 网络出版日期: 2026-02-26
- 刊出日期: 2026-01-22

Magnetic manganese ferrite spinel decorated with CeO₂ （MnFe₂O₄@CeO₂） for activation of peracetic acid to degrade tetracycline in water

1. School of Planning and Design, East China Jiaotong University, Nanchang 330013, China;
2. School of Civil Engineering and Architecture, East China Jiaotong University, Nanchang 330013, China;
3. School of Civil Engineering and Architecture, Nanchang Institute of Technology, Nanchang 330099, China

摘要

摘要: 为解决水中四环素污染问题，通过共沉淀法制备了磁性MnFe₂O₄@CeO₂复合材料，并构建了MnFe₂O₄@CeO₂/PAA催化降解体系。采用SEM、XRD等对MnFe₂O₄@CeO₂进行表征，并考察了PAA浓度、催化剂投加量、初始pH值等因素对MnFe₂O₄@CeO₂/PAA体系去除四环素效能的影响。结果表明：当n（Ce）∶n（Mn）为1∶3、pH为7、PAA浓度为200 μmol/L、催化剂投加量为0.1g/L时，30 min内即可降解97.3%TC，在pH值为3~9内均对TC具有良好的降解效果。阴离子和腐殖酸对体系具有不同程度的抑制作用。EPR、淬灭实验和XPS分析共同揭示了体系对TC的降解机理：Mn与Ce是活化PAA的主体，CH₃C（O）OO•是降解TC的主要活性物质。此外，考察了体系在不同实际水体以及对其他难降解有机污染的适用性。最后，对MnFe₂O₄@CeO₂材料的稳定性和重复利用性进行测试，经过CeO₂负载的磁性MnFe₂O₄降低了金属离子浸出且稳定性较好，经过5次循环利用实验后，体系对TC去除率仍可达到86.9%。
- 磁性锰铁尖晶石（MnFe₂O₄） /
- 二氧化铈（CeO₂） /
- 过氧乙酸 /
- 抗生素 /
- 四环素 /
- 高级氧化
Abstract: Heterogeneous catalysts have shown great potential in the activation of peracetic acid （PAA） for the degradation of antibiotics in water. Taking tetracycline in water as the object， this study prepared magnetic MnFe₂O₄@CeO₂ composite materials via a one-step low-temperature co-precipitation method， and characterized them using SEM， BET， VSM， FT-IR， and XPS. The effects of Mn/Ce molar ratio， PAA concentration， catalyst dosage， initial pH， co-existing anions， and humic acid concentration on catalytic degradation efficiency of tetracycline （TC） by the MnFe₂O₄@CeO₂/PAA system were investigated. The results indicated that at an initial TC concentration of 10 mg/L， a Ce/Mn molar ratio of 1∶3， pH of 7， and PAA concentration of 200 μmol/L， with a MnFe₂O₄@CeO₂ dosage of 0.1 g/L， the system could degrade 97.3% of TC within 30 minutes. MnFe₂O₄@CeO₂ exhibited a good degradation effect on TC within a pH range of 3 to 9. Anions and humic acid had varying degrees of inhibitory effects on the degradation efficiency of the MnFe₂O₄@CeO₂/PAA system. Electron paramagnetic resonance （EPR）， quenching experiments， and XPS analysis collectively revealed the degradation mechanism of TC by the MnFe₂O₄@CeO₂/PAA system， where Mn and Ce are the key elements to activating PAA. CH₃C（O）OO•， •OH， and ¹O₂ were the main reactive species involved in TC degradation， with CH₃C（O）OO• playing a primary role. Additionally， the MnFe₂O₄@CeO₂/PAA system was tested for its broad applicability in different real water bodies and against other refractory organic pollutants. Finally， the stability and reusability of the MnFe₂O₄@CeO₂ composite materials were assessed. The magnetic MnFe₂O₄ loaded with CeO₂ reduced the leaching of metal ions and exhibited good stability. After five cycles of reuse， the TC removal rate of the MnFe₂O₄@CeO₂/PAA system remained at 86.9%.
- magnetic manganese ferrite （MnFe₂O₄） /
- cerium dioxide （CeO₂） /
- peracetic acid /
- antibiotic /
- tetracycline /
- advanced oxidation

HTML全文

参考文献(37)

[1]	SUN F，YANG X，SHAO F，et al. In-situ construction of Co（OH）₂nanoparticles decorated biochar for highly efficient degradation of tetracycline hydrochloride via peracetic acid activation[J]. Chinese Chemical Letters，2023，34（9）：101860.
[2]	LEICHTWEIS J，VIEIRA Y，WELTER N，et al. A review of the occurrence，disposal，determination，toxicity and remediation technologies of the tetracycline antibiotic[J]. Process Safety and Environmental Protection，2022，160：25-40.
[3]	AHMAD F，ZHU D，SUN J. Environmental fate of tetracycline antibiotics：degradation pathway mechanisms，challenges，and perspectives[J]. Environmental Sciences Europe，2021，33（1）：1-17.
[4]	AMANGELSIN Y，SEMENOVA Y，DADAR M，et al. The impact of tetracycline pollution on the aquatic environment and removal strategies[J]. Antibiotics，2023，12（3）：440-440.
[5]	GASPARRINI A J，MARKLEY J L，KUMAR H，et al. Tetracycline-inactivating enzymes from environmental，human commensal，and pathogenic bacteria cause broad-spectrum tetracycline resistance[J]. Communications Biology，2020，3（1）：68.
[6]	WANG J，WANG S. Reactive species in advanced oxidation processes：Formation，identification and reaction mechanism[J]. Chemical Engineering Journal，2020，401：126158.
[7]	KUMAR V，SHAH M P. Advanced oxidation processes for complex wastewater treatment[M]. Advanced Oxidation Processes for Effluent Treatment Plants，2021：1-31.
[8]	CHENG Z，LI S，NGUYEN T T，et al. Biochar loaded on MnFe₂O₄ as Fenton catalyst for Rhodamine B removal：Characterizations，catalytic performance，process optimization and mechanism[J]. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2021，631：127708.
[9]	XIAO T，DAI X，WANG X，et al. Enhanced sludge dewaterability via ozonation catalyzed by sludge derived biochar loaded with MnFe₂O₄：Performance and mechanism investigation[J]. Journal of Cleaner Production，2021，323：129217.
[10]	MEENA S，ANANTHARAJU K S，VIDYA Y S，et al. Enhanced sunlight driven photocatalytic activity and electrochemical sensing properties of Ce-doped MnFe₂O₄ nano magnetic ferrites[J]. Ceramics International，2021，47（10）：14760-14774.
[11]	YAO K，FANG L，LIAO P，et al. Ultrasound-activated peracetic acid to degrade tetracycline hydrochloride：Efficiency and mechanism[J]. Separation and Purification Technology，2023，306：112492.
[12]	TANG X，HUANG J，LIU K，et al. Synthesis of magnetically separable MnO₂/Fe₃O₄/silica nanofiber composite with enhanced Fenton-like catalytic activity for degradation of Acid Red 73[J]. Surface and Coatings Technology，2018，354：18-27.
[13]	MENG L，DONG J，CHEN J，et al. Degradation of tetracyclines by peracetic acid and UV/peracetic acid：Reactive species and theoretical computations[J]. Chemosphere，2023，320：138582.
[14]	CORREA-SANCHEZ S，PEñUELA G A. Peracetic acid-based advanced oxidation processes for the degradation of emerging pollutants：A critical review[J]. Journal of Water Process Engineering，2022，49：103192.
[15]	HU J，LI T，ZHANG X，et al. Degradation of steroid estrogens by UV/peracetic acid：Influencing factors，free radical contribution and toxicity analysis[J]. Chemosphere，2022，287：132993.
[16]	HU Q，YANG T Y，ZHU F C，et al. Peracetic acid activation for efficient degradation of p-nitrophenolby mixed-valence iron-based metal-organic framework[J]. Journal of Textile Research，2022，43（11）：133-140. 胡倩，杨涛语，朱斐超，等. 混合价态铁基金属有机框架催化过氧乙酸高效降解对硝基苯酚[J]. 纺织学报，2022，43（11）：133-140.
[17]	GASIM M F，BAO Y，ELGARAHY A M，et al. Peracetic acid activation using heterogeneous catalysts for environmental decontamination：A review[J]. Catalysis Communications，2023，180：106431.
[18]	CHEN J，XU J，LIU T，et al. Oxidation of tetracycline antibiotics by peracetic acid：Reaction kinetics，mechanism，and antibacterial activity change[J]. Chemical Engineering Journal，2022，431：129433.
[19]	AKHLAGHI N，NAJAFPOUR-DARZI G. Manganese ferrite（MnFe₂O₄）Nanoparticles：From synthesis to application-A review[J]. Journal of Industrial and Engineering Chemistry，2021，103：292-304.
[20]	XU L S，SUN X B，HONG J-M，et al. Peroxymonosulfate activation by α-MnO₂/MnFe₂O₄ for norfloxacin degradation：Efficiency and mechanism[J]. Journal of Physics and Chemistry of Solids，2021，153：109836.
[21]	NIU L，ZHANG G，XIAN G，et al. Tetracycline degradation by persulfate activated with magnetic γ-Fe₂O₃/CeO₂ catalyst：Performance，activation mechanism and degradation pathway[J]. Separation and Purification Technology，2021，259：118637.
[22]	LI J，GOU G，ZHAO H，et al. Efficient peroxymonosulfate activation by CoFe₂O₄-CeO₂ composite：Performance and catalytic mechanism[J]. Chemical Engineering Journal，2022，435：134961.
[23]	LIU Z，GAO Z，WU Q. Activation of persulfate by magnetic zirconium-doped manganese ferrite for efficient degradation of tetracycline[J]. Chemical Engineering Journal，2021，423：130217.
[24]	OKLA M K，HARINI G，DAWOUD T M，et al. Fabrication of MnFe₂O₄ spheres modified CeO₂ nano-flakes for sustainable photodegradation of MB dye and antimicrobial activity：A brief computational investigation on reactive sites and degradation pathway[J]. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2022，641：128642.
[25]	LIU Z，CHEN G，LI X，et al. Removal of rare earth elements by MnFe₂O₄ based mesoporous adsorbents：Synthesis，isotherms，kinetics，thermodynamics[J]. Journal of Alloys and Compounds，2021，856：158246.
[26]	CHEN M，HAN Y，SUN C，et al. Rapid degradation of organic pollutants by enhanced persulfate activation using CeO₂-MnFe₂O₄ nanostructures：A polymetallic synergistic effect[J]. Process Safety and Environmental Protection，2023，177：818-830.
[27]	DONG C-D，HUANG C P，NGUYEN T-B，et al. The degradation of phthalate esters in marine sediments by persulfate over iron-cerium oxide catalyst[J]. Science of the Total Environment，2019，696：133973.
[28]	ZHAO X，ZHANG T，ZHOU Y，et al. Preparation of peracetic acid from hydrogen peroxide[J]. Journal of Molecular Catalysis A：Chemical，2007，271（1/2）：246-252.
[29]	DONG J，XU W，LIU S，et al. Lignin-derived biochar to support CoFe₂O₄：Effective activation of peracetic acid for sulfamethoxazole degradation[J]. Chemical Engineering Journal，2022，430：129331.
[30]	YU C，ZHENG L，HONG Y，et al. Activation of peracetic acid with CuFe₂O₄ for rhodamine B degradation：activation by Cu and the contribution of acetylperoxyl radicals[J]. Molecules，2022，27（19）：6313.
[31]	LIU Z Z，WANG S W，WU Y，et al. Highly Efficient Degradation of Sulfamethoxazole Using Activating Peracetic Acid with CoFe₂O₄/CuO[J]. Acta Physico-Chimica Sinica，2023，39（5）：136-144. 刘振中，万思文，吴阳，et al. CoFe₂O₄/CuO活化过氧乙酸高效降解磺胺甲恶唑（英文）[J]. 物理化学学报，2023，39（5）：136-144.
[32]	LI X，LIU X，LIN C，et al. Cobalt ferrite nanoparticles supported on drinking water treatment residuals：An efficient magnetic heterogeneous catalyst to activate peroxymonosulfate for the degradation of atrazine[J]. Chemical Engineering Journal，2019，367：208-218.
[33]	WANG J，XIONG B，MIAO L，et al. Applying a novel advanced oxidation process of activated peracetic acid by CoFe₂O₄ to efficiently degrade sulfamethoxazole[J]. Applied Catalysis B：Environmental，2021，280：119406.
[34]	FAN G，YAO L，WANG Y，et al. The dual pathway mechanisms of peroxyacetic acid activation by CoMn₂O₄ spinel for efficient levofloxacin degradation[J]. Journal of Environmental Chemical Engineering，2023，11（3）：109117.
[35]	HOU J，XU J，TANG R，et al. Activation of peracetic acid by biochar for sulfamethoxazole degradation：Revealing roles of the active sites[J]. Journal of the Taiwan Institute of Chemical Engineers，2023，152：106977.
[36]	ZHANG Z，DUAN Y，DAI C，et al. Oxidation of sulfamethazine by peracetic acid activated with biochar：Reactive oxygen species contribution and toxicity change[J]. Environmental Pollution，2022，313：119981.
[37]	SHAO S，ZHANG P，CHEN Y，et al. Enhanced tetracycline abatement by peracetic acid activation with sulfidation of nanoscale zerovalent iron[J]. Environmental Science and Pollution Research，2023，30（30）：76157-76170.