CoFe2O4催化陶瓷膜活化过一硫酸盐去除水中典型抗生素

朱荣荣; 徐纪晓; 阮薇薇; 陈儒雅; 夏伊静; 冯华军; 丁养城

PDF(4004 KB)

中国环境科学 ›› 2025, Vol. 45 ›› Issue (10) : 5448-5458.

水污染与控制

CoFe₂O₄催化陶瓷膜活化过一硫酸盐去除水中典型抗生素

朱荣荣¹, 徐纪晓¹, 阮薇薇², 陈儒雅¹, 夏伊静¹, 冯华军³, 丁养城³

作者信息 +

Peroxymonosulfate activation on cobalt ferrite impregnated ceramic membrane for removal of typical antibiotics from water

ZHU Rong-rong¹, XU Ji-xiao¹, RUAN Wei-wei², CHEN Ru-ya¹, XIA Yi-jing¹, FENG Hua-jun³, DING Yang-cheng³

Author information +

文章历史 +

摘要

为实现高效过滤并强化水中抗生素降解,采用浸渍烧结法制备了一种CoFe₂O₄修饰的平板陶瓷膜,并在死端过滤模式下对该陶瓷膜活化过一硫酸盐(PMS)去除氟苯尼考(FLO)等抗生素的性能进行了研究.结果表明,在pH值为6,PMS投加量为0.5mmol/L时,30min内该体系对10mg/L的FLO的去除率高达88%.此外,该体系对Cl⁻、NO₃⁻、HCO₃⁻和腐殖酸等共存物质表现出良好的抗干扰能力.利用CoFe₂O₄陶瓷膜/PMS体系循环降解FLO 7次后,该体系对FLO的去除率仍高达84%.机理研究表明,HO^•、SO₄^•−、O₂^•−和¹O₂是催化降解过程中的主要活性物种.对实际养殖废水的处理结果显示,该体系对COD和浊度的去除率分别为65.4%和99.3%,同时对废水中8种典型抗生素的去除率均达到80%以上,展现出巨大的应用潜力.

Abstract

To achieve efficient filtration and enhance the degradation of antibiotics in water, a CoFe₂O₄-modified flat-sheet ceramic membrane was prepared using the impregnation-sintering method. The performance of this ceramic membrane activated by peroxymonosulfate (PMS) for the removal of florfenicol (FLO) and other antibiotics was investigated under dead-end filtration mode. The results indicated that at a pH value of 6 and a PMS dosage of 0.5mmol/L, the removal efficiency of FLO (10mg/L) was achieved at 88% within 30minutes. Furthermore, the system exhibited excellent resistance to interference from coexisting species such as Cl⁻, NO₃⁻, HCO₃⁻ and humic acid. After 7 cycles of FLO degradation using the CoFe₂O₄ ceramic membrane/PMS system, the removal rate of FLO remained high at 84%. Mechanistic studies revealed that HO^•, SO₄^•−, O₂^•−, ¹O₂ were identified as the primary reactive species responsible for the catalytic degradation. Treatment results of actual aquaculture wastewater showed that the removal efficiencies for COD and turbidity were 65.4% and 99.3%, respectively. Simultaneously, the removal rates for eight typical antibiotics present in the wastewater exceeded 80%, highlighting its significant potential for practical application.

导出引用

朱荣荣, 徐纪晓, 阮薇薇, 陈儒雅, 夏伊静, 冯华军, 丁养城. CoFe₂O₄催化陶瓷膜活化过一硫酸盐去除水中典型抗生素[J]. 中国环境科学. 2025, 45(10): 5448-5458

ZHU Rong-rong, XU Ji-xiao, RUAN Wei-wei, CHEN Ru-ya, XIA Yi-jing, FENG Hua-jun, DING Yang-cheng. Peroxymonosulfate activation on cobalt ferrite impregnated ceramic membrane for removal of typical antibiotics from water[J]. China Environmental Science. 2025, 45(10): 5448-5458

中图分类号： X703

参考文献

[1] Zainab S M, Junaid M, Xu N, et al. Antibiotics and antibiotic resistant genes (ARGs) in groundwater: A global review on dissemination, sources, interactions, environmental and human health risks [J]. Water Research, 2020,187:116455.
[2] Ping Q, Zhang Z, Ma L, et al. The prevalence and removal of antibiotic resistance genes in full-scale wastewater treatment plants: Bacterial host, influencing factors and correlation with nitrogen metabolic pathway [J]. Science of the Total Environment, 2022,827:154154.
[3] Chen L, Maqbool T, Nazir G, et al. Peroxymonosulfate activated by composite ceramic membrane for the removal of pharmaceuticals and personal care products (PPCPs) mixture: Insights of catalytic and noncatalytic oxidation [J]. Water Research, 2023,229:119444.
[4] Yin N, Wang K, Wang L. Amino-functionalized MOFs combining ceramic membrane ultrafiltration for Pb (II) removal [J]. Chemical Engineering Journal, 2016,306:619-628.
[5] Lee N, Amy G, Croué J P, et al. Identification and understanding of fouling in low-pressure membrane (MF/UF) filtration by natural organic matter (NOM) [J]. Water Research, 2004,38(20):4511-4523.
[6] Lotfi S, Fischer K, Schulze A, et al. Photocatalytic degradation of steroid hormone micropollutants by TiO₂-coated polyethersulfone membranes in a continuous flow-through process [J]. Nature Nanotechnology, 2022,17(4):417-423.
[7] Meng C, Ding B, Zhang S, et al. Angstrom-confined catalytic water purification within Co-TiO(x) laminar membrane nanochannels [J]. Nature Communications, 2022,13(1):4010.
[8] Zhao Y, Zhao Y, Yu X, et al. Peracetic acid integrated catalytic ceramic membrane filtration for enhanced membrane fouling control: performance evaluation and mechanism analysis [J]. Water Research, 2022,220:118710.
[9] 朱烨,朱秀荣,金鑫,等.改性陶瓷膜催化PMS氧化的二级出水处理特性 [J]. 中国环境科学, 2023,43(4):1706-1715. Zhu Y, Zhu X R, Jin X, et al. PMS oxidation catalyzed by modified ceramic membrane for the treatment of secondary effluent [J]. China Environmental Science, 2023,43(4):1706-1715.
[10] Xu J, Yao Y, Zhu C, et al. Unveiling enhanced electron-mediated peroxymonosulfate activation for degradation of emerging organic pollutants [J]. Applied Catalysis B: Environmental, 2024,341:123356.
[11] Zhao Y, Lu D, Xu C, et al. Synergistic oxidation - filtration process analysis of catalytic CuFe(2)O(4) - tailored ceramic membrane filtration via peroxymonosulfate activation for humic acid treatment [J]. Water Research, 2020,171:115387.
[12] Zhang W, Zhang S Z, Meng C C, et al. Nanoconfined catalytic membranes assembled by cobalt-functionalized graphitic carbon nitride nanosheets for rapid degradation of pollutants [J]. Applied Catalysis B: Environmental, 2023,322:122098.
[13] Gao D, Junaid M, Lin F, et al. Degradation of sulphachloropyridazine sodium in column reactor packed with CoFe₂O₄−loaded quartz sand via peroxymonosulfate activation: insights into the amorphous phase, efficiency, and mechanism [J]. Chemical Engineering Journal, 2020,390:124549.
[14] Kakavandi B, Alavi S, Ghanbari F, et al. Bisphenol A degradation by peroxymonosulfate photo-activation coupled with carbon-based cobalt ferrite nanocomposite: Performance, upgrading synergy and mechanistic pathway [J]. Chemosphere, 2022,287:132024.
[15] Wu J, Cagnetta G, Wang B, et al. Efficient degradation of carbamazepine by organo-montmorillonite supported nCoFe₂O₄- activated peroxymonosulfate process [J]. Chemical Engineering Journal, 2019,368:824-836.
[16] Sun Y, Li Y, You S, et al. Fe₃C/CoFe₂O₄ nanoparticles wrapped in one-dimensional MIL-53(Fe)-derived carbon nanofibers as efficient dual-function oxygen catalysts [J]. Chemical Engineering Journal, 2021,424:130460.
[17] Sun Y, Ma C, Wu D, et al. Coating CoFe(2)O(4) shell on Fe particles to increase the utilization efficiencies of Fe and peroxymonosulfate for low-cost Fenton-like reactions [J]. Water Research, 2023,244:120542.
[18] Gogoi D, Karmur R S, Das M R, et al. Cu and CoFe₂O₄ nanoparticles decorated hierarchical porous carbon: an excellent catalyst for reduction of nitroaromatics and microwave-assisted antibiotic degradation [J]. Applied Catalysis B: Environmental, 2022,312:121407.
[19] Lu X F, Gu L F, Wang J W, et al. Bimetal-organic framework derived CoFe(2) O(4) /C porous hybrid nanorod arrays as high-performance electrocatalysts for oxygen evolution reaction [J]. Advanced Materials, 2017,29(3):428-436.
[20] Fan Y, Zhou Y, Feng Y, et al. Fabrication of reactive flat-sheet ceramic membranes for oxidative degradation of ofloxacin by peroxymonosulfate [J]. Journal of Membrane Science, 2020,611:118302.
[21] Zou L, Vidalis I, Steele D, et al. Surface hydrophilic modification of RO membranes by plasma polymerization for low organic fouling [J]. Journal of Membrane Science, 2011,369(1):420-428.
[22] 刘彦伶,李天玉,王小,等.高压膜表面性质对膜污染的影响机制 [J]. 环境工程, 2021,39(7):45-53. Liu Y L, Li T Y, Wang X, et al. Influence mechanism of Surface properties on fouling behaviors of high - pressure membranes [J]. Environmental Engineering, 2021,39(7):45-53.
[23] Kochkodan V, Hilal N. A comprehensive review on surface modified polymer membranes for biofouling mitigation [J]. Desalination, 2015, 356:187-207.
[24] Novak S, Maver U, Peternel Š, et al. Electrophoretic deposition as a tool for separation of protein inclusion bodies from host bacteria in suspension [J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2009,340(1):155-160.
[25] Hu J, Dong H, Qu J, et al. Enhanced degradation of iopamidol by peroxymonosulfate catalyzed by two pipe corrosion products (CuO and δ-MnO₂) [J]. Water Research, 2017,112:1-8.
[26] Duan X, Su C, Zhou L, et al. Surface controlled generation of reactive radicals from persulfate by carbocatalysis on nanodiamonds [J]. Applied Catalysis B: Environmental, 2016,194:7-15.
[27] Minh T D, Ncibi M C, Srivastava V, et al. Gingerbread ingredient- derived carbons-assembled CNT foam for the efficient peroxymonosulfate- mediated degradation of emerging pharmaceutical contaminants [J]. Applied Catalysis B: Environmental, 2019,244:367-384.
[28] Anipsitakis G P, Dionysiou D D, Gonzalez M A. Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds. implications of chloride ions [J]. Environmental Science & Technology, 2006,40(3):1000-1007.
[29] Grebel J E, Pignatello J J, Mitch W A. Effect of halide ions and carbonates on organic contaminant degradation by hydroxyl radical-based advanced oxidation processes in saline waters [J]. Environmental Science & Technology, 2010,44(17):6822-6828.
[30] Huang Y, Sheng B, Wang Z, et al. Deciphering the degradation/ chlorination mechanisms of maleic acid in the Fe(II)/ peroxymonosulfate process: An often overlooked effect of chloride [J]. Water Research, 2018,145:453-463.
[31] Peng J, Wang Z, Wang S, et al. Enhanced removal of methylparaben mediated by cobalt/carbon nanotubes (Co/CNTs) activated peroxymonosulfate in chloride-containing water: Reaction kinetics, mechanisms and pathways [J]. Chemical Engineering Journal, 2021, 409:128176.
[32] Lindsey M E, Tarr M A. Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter [J]. Environmental Science & Technology, 2000,34(3):444-449.
[33] Lee N, Amy G, Croué J P. Low-pressure membrane (MF/UF) fouling associated with allochthonous versus autochthonous natural organic matter [J]. Water Research, 2006,40(12):2357-2368.
[34] Tian J, Wu C, Yu H, et al. Applying ultraviolet/persulfate (UV/PS) pre-oxidation for controlling ultrafiltration membrane fouling by natural organic matter (NOM) in surface water [J]. Water Research, 2018,132:190-199.
[35] Qu X, Alvarez P J J, Li Q. Applications of nanotechnology in water and wastewater treatment [J]. Water Research, 2013,47(12):3931-3946.
[36] GB 3838-2002 地表水环境质量标准 [S]. GB 3838-2002 Environmental quality standards for surface water [S].
[37] Li W, Xiao R, Lin H, et al. Electro-activation of peroxymonosulfate by a graphene oxide/iron oxide nanoparticle-doped Ti₄O₇ ceramic membrane: Mechanism of singlet oxygen generation in the removal of 1,4-dioxane [J]. Journal of Hazardous Materials, 2022,424:127342.
[38] Xu Z, Luo G, Fan Y A, et al. Continuous degradation of plasticizer bisphenol A by catalytic Cu(FexAl₂-x)O₄@sediment ceramic membranes combined with peroxymonosulfate activation [J]. Chemical Engineering Journal, 2023,469:143867.
[39] Wang S, Tian J, Wang Q, et al. Development of CuO coated ceramic hollow fiber membrane for peroxymonosulfate activation: A highly efficient singlet oxygen-dominated oxidation process for bisphenol a degradation [J]. Applied Catalysis B: Environmental, 2019,256:117783.
[40] Li J, Xu M, Yao G, et al. Enhancement of the degradation of atrazine through CoFe₂O₄ activated peroxymonosulfate (PMS) process: Kinetic, degradation intermediates, and toxicity evaluation [J]. Chemical Engineering Journal, 2018,348:1012-1024.
[41] Yang J, Bai L, Zhao J, et al. New insights into interfacial interaction and nanoconfinement effect in synergistic oxidation-filtration via CoFe₂O₄-ceramic membrane activated peroxymonosulfate [J]. Chemical Engineering Journal, 2023,461:141846.
[42] Wang Y, Cao D, Zhao X. Heterogeneous degradation of refractory pollutants by peroxymonosulfate activated by CoOx-doped ordered mesoporous carbon [J]. Chemical Engineering Journal, 2017,328: 1112-1121.
[43] Mourid E H, El Mouchtari E M, El Mersly L, et al. Development of a new recyclable nanocomoposite LDH-TiO₂ for the degradation of antibiotic sulfamethoxazole under UVA radiation: An approach towards sunlight [J]. Journal of Photochemistry and Photobiology A: Chemistry, 2020,396:112530.
[44] Dong S, Ding Y, Feng H, et al. Source preventing mechanism of florfenicol resistance risk in water by VUV/UV/sulfite advanced reduction pretreatment [J]. Water Research, 2023,235:119876.
[45] Zhao Z, Xie W, Huang Z, et al. Investigation of the degradation and dehalogenation properties of florfenicol by heterogeneous Fenton reaction activated with MIL-53(Al)-supported nano zero-valent iron [J]. Chemical Engineering Journal, 2023,453:139420.
[46] Zhang Y F, Gao J L, Chen S G, et al. Advanced electrooxidation of florfenicol using 3D printed Nb₂O₅/Ti electrodes: Degradation efficiency, dehalogenation performance, and toxicity reduction [J]. Chemical Engineering Journal, 2023,474:145561.
[47] Periyasamy S, Lin X, Ganiyu S O, et al. Insight into BDD electrochemical oxidation of florfenicol in water: Kinetics, reaction mechanism, and toxicity [J]. Chemosphere, 2022,288:132433.