Abstract：Dibutyl phthalate (DBP), an endocrine disruptor, has been frequently detected in surface water, soil, and groundwater in recent years, posing potential risks to both ecological environments and human health. Catalytic ozonation has been proven effective for DBP removal, albeit its efficacy is significantly influenced by pH level. In this study, carbon nanotube-based catalysts were prepared through an impregnation-calcination method, including zinc-loaded (CNT-Zn), iron-loaded (CNT-Fe), and zinc-iron co-doped (CNT-Fe/Zn) catalysts, whose performances in catalytic ozonation of DBP in water were examined at varying pH levels. The results demonstrate that CNT-Fe/Zn exhibited optimal catalytic performance with a removal rate increase by 22%~52% compared to sole ozone degradation of DBP over a wide pH range. Even after five consecutive uses, CNT-Fe/Zn maintained high catalytic activity and low metal leaching rates. Under conditions of an initial DBP concentration of 4mg/L, initial pH of 4, ozone dosage of 20mg/L, and catalyst addition of 50mg/L, the DBP removal rate was up to 72.4% within 30minutes. The catalyst was characterized to reveal oxygen-containing groups on the surface of CNT-Fe/Zn as the primary active sites. In general, the CNT-Fe/Zn can facilitate the generation of hydroxyl radicals and further enhance DBP removal by forming hydrogen peroxide under acidic conditions, and its robust stability and reusability have been also confirmed by catalysis cycling experiments.
罗艺文,高盼,闫路,等.邻苯二甲酸二(异)丁酯及其替代品的内分泌干扰效应研究进展[J]. 环境化学, 2021,40(1):11-27. LUO Y W, GAO P, YAN L, et al. Research progress on endocrine disruption effect of di-n-butyl phthalate, diisobutyl phthalate and substitutes [J]. Environmental Chemistry, 2021,40(1):11-27.
[2]
Federica A, Federica I, Giuseppe P, et al. Phthalates and their effects on human health:Focus on erythrocytes and the reproductive system [J]. Comparative Biochemistry and Physiology Part C:Toxicology & Pharmacology, 2023,270:109645.
[3]
黄维,冉艳,何艺欣,等.悬移质泥沙影响下水体中DBP的降解[J]. 中国环境科学, 2022,42(3):1230-1239. Huang W, Ran Y, He Y X, et al. The degradation of di-n-butyl phthalate in suspended particulate matter contained waters [J]. China Environmental Science, 2022,42(3):1230-1239.
[4]
Wu J, Lai Y G, Zhu H F, et al. Phthalate esters and their metabolites in paired soil-crop systems from farmland in major provinces of eastern China:Pollution characteristics and implications for human exposure [J]. Science of The Total Environment, 2023,882:163645.
[5]
Wang J, Chen H. Catalytic ozonation for water and wastewater treatment:Recent advances and perspective [J]. Science of The Total Environment, 2020,704,135249.
[6]
Liang L L, Cao P K, Qin X, et al. Oxygen vacancies-driven nonradical oxidation pathway of catalytic ozonation for efficient water decontamination [J]. Applied Catalysis B:Environmental, 2023,325:122321.
[7]
Tian S Q, Qi J Y, Wang Y P, et al. Heterogeneous catalytic ozonation of atrazine with Mn-loaded and Fe-loaded biochar [J]. Water Research, 2021,193:116860.
[8]
Huang Y X, Sun Y R, Xu Z H, et al. Removal of aqueous oxalic acid by heterogeneous catalytic ozonation with MnOx/sewage sludge-derived activated carbon as catalysts [J]. Science of The Total Environment, 2017,575:50-57.
[9]
Nosaka Y, Nosaka A Y. Generation and Detection of Reactive Oxygen Species in Photocatalysis [J]. Chemical Reviews, 2017,117(17):11302-11336.
[10]
Guo Y, Xu B B, Qi F. A novel ceramic membrane coated with MnO2-Co3O4 nanoparticles catalytic ozonation for benzophenone-3degradation in aqueous solution:Fabrication, characterization and performance [J]. Chemical Engineering Journal, 2016,287:381-389.
[11]
Huang R H, Lan B Y, Chen Z Y, et al. Catalytic ozonation of p-chlorobenzoic acid over MCM-41 and Fe loaded MCM-41[J]. Chemical Engineering Journal, 2012,180:19-24.
[12]
Tang Y M, Pan Z Q, Li L S. PH-insusceptible cobalt-manganese immobilizing mesoporous siliceous MCM-41catalyst for ozonation of dimethyl phthalate [J]. Journal of Colloid and Interface Science, 2017, 508:196-202.
[13]
Yang Z C, Yu A Q, Shan C, et al. Enhanced Fe(III)-mediated Fenton oxidation of atrazine in the presence of functionalized multi-walled carbon nanotubes [J]. Water Research, 2018,137:37-46.
[14]
Pan Y W, Zhang Y, Zhou M H, et al. Synergistic degradation of antibiotic sulfamethazine by novel pre-magnetized Fe0/PS process enhanced by ultrasound [J]. Chemical Engineering Journal, 2018,354:777-789.
[15]
Liu Y, Zhou A L, Liu Y L, et al. Enhanced degradation and mineralization of 4-chloro-3-methyl phenol by Zn-CNTs/O3system [J]. Chemosphere, 2018,191:54-63.
[16]
Liu P X, Ren Y M, Ma W J, et al. Degradation of shale gas produced water by magnetic porous MFe2O4 (M=Cu, Ni, Co and Zn) heterogeneous catalyzed ozone [J]. Chemical Engineering Journal, 2018,345:98-106.
[17]
Liu H, Sun P, Feng M B. Nitrogen and sulfur co-doped CNT-COOH as an efficient metal-free catalyst for the degradation of UV filter BP-4based on sulfate radicals [J]. Applied Catalysis B:Environmental, 2016,187:1-10.
[18]
Ren Y M, Lin L Q, Ma J, et al. Sulfate radicals induced from peroxymonosulfate by magnetic ferrospinel MFe2O4 (M=Co, Cu, Mn, and Zn) as heterogeneous catalysts in the water [J]. Applied Catalysis B:Environmental, 2015,165:572-578.
[19]
Sui M H, Xing S C, Sheng L, et al. Heterogeneous catalytic ozonation of ciprofloxacin in water with carbon nanotube supported manganese oxides as catalyst [J]. Journal of Hazardous Materials, 2012,227-228:227-236.
[20]
Zhao Y, An H Z, Dong G J, et al. Elevated removal of di-n-butyl phthalate by catalytic ozonation over magnetic Mn-doped ferrospinel ZnFe2O4 materials:Efficiency and mechanism [J]. Applied Surface Science, 2020,505:144476.
[21]
Liu P X, Ren Y M, Ma W, et al. Degradation of shale gas produced water by magnetic porous MFe2O4 (M=Cu, Ni, Co and Zn) heterogeneous catalyzed ozone [J]. Chemical Engineering Journal, 2018,345:98-106.
[22]
Zhang F Z, Wei H C, Wu K, et al. Mechanistic evaluation of ferrite AFe2O4 (A=Co, Ni, Cu, and Zn) catalytic performance in oxalic acid ozonation [J]. Applied Catalysis A:General, 2017,547:60-68.
[23]
Liu Z Q, Ma J, Cui Y H. Factors affecting the catalytic activity of multi-walled carbon nanotube for ozonation of oxalic acid [J]. Separation and Purification Technology, 2011,78(2):147-153.
[24]
Wang J, Quan X, Chen S, et al. Enhanced catalytic ozonation by highly dispersed CeO2 on carbon nanotubes for mineralization of organic pollutants [J]. Journal of Hazardous Materials, 2019,368:621-629.
[25]
Yang Z C, Yu A Q, Shan C, et al. Enhanced Fe(III)-mediated Fenton oxidation of atrazine in the presence of functionalized multi-walled carbon nanotubes [J]. Water Research, 2018,137:37-46.
[26]
Liu H B, Gao Y, Wang J, et al. Catalytic ozonation performance and mechanism of Mn-CeOx@gamma-Al2O3/O3 in the treatment of sulfate-containing hypersaline antibiotic wastewater [J]. Science of the Total Environment, 2022,807:150876.
[27]
Peng J L, He Y L, Zhou C Y, et al. The carbon nanotubes-based materials and their applications for organic pollutant removal:A critical review [J]. Chinese Chemical Letters, 2021,32(5):1626-1636.
[28]
Clémentine M, Julie M, Stephan B, et al. Coupling catalytic ozonation and membrane separation:A review [J]. Separation and Purification Technology, 2020,236:116221.
[29]
Du Y J, Li Z H, Fan K N. Tuning the catalytic performance of carbon nanotubes by tuning the conjugation between the π orbitals of carbon nanotubes and the active oxygenic functional groups [J]. Chinese Journal of Catalysis, 2013,34(7):1291-1296.
[30]
Staehelin J, Hoigne J. Decomposition of ozone in water in the presence of organic solutes acting as promoters and inhibitors of radical chain reactions [J]. Environmental Science & Technology, 1985,19(12):1206-1213.
[31]
Tian S Q, Wang L, Liu Y L. Degradation of organic pollutants by ferrate/biochar:Enhanced formation of strong intermediate oxidative iron species [J]. Water Research, 2020,183:116054.
[32]
刘永霞,邓宇,邓橙,等. Co/碳纳米管催化剂催化臭氧降解甲基橙研究[J]. 水处理技术, 2022,48(1):70-74. Liu Y X, Deng Y, Deng C, et at. Research on Co/Carbon Nanotube Catalyst Catalytic Ozone Degradation of Methyl Orange [J]. Technology of Water Treatment, 2022,48(1):70-74.
[33]
岳山,杨永哲,杨宏勃,等.CeO2-MgO/AC催化剂开发及催化臭氧氧化深度处理制药废水[J]. 水处理技术, 2017,43(9):109-114. Yue S, Yang Y Z, Yang H B, et at. Development of CeO2-MgO/AC catalyst and catalytic ozone oxidation for deep treatment of pharmaceutical wastewater [J]. Technology of Water Treatment, 2017, 43(9):109-114.
[34]
Alexandra G G, José L F, José J, et al. Influence of the surface chemistry of multi-walled carbon nanotubes on their activity as ozonation catalysts [J]. Carbon, 2010,48(15):4369-4381.
[35]
Fan X L, João R, Alexei A L, et al. The role of multiwalled carbon nanotubes (MWCNTs) in the catalytic ozonation of atrazine [J]. Chemical Engineering Journal, 2014,241:66-76.
[36]
Wang X H, Zhao K Y, Yang B X, et al. Adsorption of dibutyl phthalate in aqueous solution by mesoporous calcium silicate grafted non-woven polypropylene [J]. Chemical Engineering Journal, 2016,306:452-459.
[37]
Cheng Y Y, Alexandre Barras, Lu S X. Fabrication of superhydrophobic/superoleophilic functionalized reduced graphene oxide/polydopa mine/PFDT membrane for efficient oil/water separation [J]. Separation and Purification Technology, 2020,236,116240.
[38]
Rebekah Oulton, Jason P Haase, Sara Kaalberg, et al. Hydroxyl Radical Formation during Ozonation of Multiwalled Carbon Nanotubes:Performance Optimization and Demonstration of a Reactive CNT Filter [J]. Environmental Science & Technology, 2015,49:3687-3697.
[39]
Lu J W, Fu F L, Ding Z C, et al. Removal mechanism of selenite by Fe3O4-precipitated mesoporous magnetic carbon microspheres [J]. Journal of Hazardous Materials, 2017,330:93-104.
[40]
Yu G F, Wang Y X, Cao H B, et al. Reactive Oxygen Species and Catalytic Active Sites in Heterogeneous Catalytic Ozonation for Water Purification [J]. Environmental Science & Technology, 2020,54(10):5931-5946.
[41]
Zhang J, Wu Y, Liu L P, et al. Rapid removal of p-chloronitrobenzene from aqueous solution by a combination of ozone with zero-valent zinc [J]. Separation and Purification Technology, 2015,151:318-323.
[42]
Abbas Alipour Hajiagha, Mojgan Zaeimdar, Seyed Ali Jozi. Combination of Chemical Coagulation and Photo-Fenton Oxidation Process for the Treatment of Beet Sugar Industry Wastewater:Optimization of Process Conditions by Response Surface Methodology [J]. Ozone:Science & Engineering, 2018,41:265-273.
[43]
Liu H, Sun P, Feng M B. Nitrogen and sulfur co-doped CNT-COOH as an efficient metal-free catalyst for the degradation of UV filter BP-4based on sulfate radicals [J]. Applied Catalysis B:Environmental, 2016,187:1-10.
[44]
Bing J S, Hu C, Zhang L. Enhanced mineralization of pharmaceuticals by surface oxidation over mesoporous γ-Ti-Al2O3 suspension with ozone [J]. Applied Catalysis B:Environmental, 2017,202:118-126.
[45]
Minhwan K, Homin K, Youmi J, et al. Performance characterization and kinetic modeling of ozonation using a new method:ROH, O3 concept [J]. Water Research, 2017,122:172-182.
[46]
Tomiyasu H, Fukutomi H, Gordon G, et al. Kinetics and mechanism of ozone decomposition in basic aqueous solution [J]. Inorganic Chemistry, 1985,24:2962-2966.
