纳米CuFe_2O_4活化过一硫酸盐降解诺氟沙星性能
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摘要
为研究使用过一硫酸盐(PMS)的高级氧化技术去除水体中微量有机污染物的高效可行方法,通过柠檬酸辅助溶胶-凝胶法制备纳米CuFe_2O_4材料,以其为非均相催化剂,探究CuFe_2O_4/PMS体系对诺氟沙星(NFX)的降解性能.采用X射线衍射仪、电子透射显微镜、BET手段对材料进行表征,考察煅烧温度对纳米CuFe_2O_4结构及催化性能的影响,并试验纳米CuFe_2O_4的重复使用性和稳定性.探讨纳米CuFe_2O_4投加量、PMS浓度、溶液初始pH对CuFe_2O_4/PMS体系降解NFX性能的影响,并探究该体系的氧化活性物种及降解机理.结果表明:制备纳米CuFe_2O_4的最佳煅烧温度为400℃,该温度下纳米CuFe_2O_4晶型较好,比表面积较大,且表现出较高的催化活性;在纳米CuFe_2O_4/PMS体系中,控制NFX初始质量浓度为5 mg/L,最适宜的反应条件为:纳米CuFe_2O_4投加量为0.1 g/L、PMS浓度为0.5 mmol/L、初始溶液pH为9.5,该条件下反应30 min后NFX的去除率高达99%;纳米CuFe_2O_4能有效活化PMS生成·OH和SO_4~-·,SO_4~-·是实现NFX快速降解的主要活性物种.
To study the efficient method for removal of the trace organic pollutants in water by peroxymonosulfate( PMS) based advanced oxidation processes,CuFe_2O_4 nanoparticles were prepared by sol-gel method and used as heterogeneous catalyst in the CuFe_2O_4/PMS system for the degradation of norfloxacin( NFX). The CuFe_2O_4 nanoparticles were characterized by X-ray diffraction( XRD),Transmission Electron Microscopy( TEM) and Brunner-Emmet-Teller( BET). Several significant factors affecting the catalytic properties in the CuFe_2O_4/PMS system such as calcination temperature,CuFe_2O_4 dosage,PMS concentration and initial pH were investigated,and the reusability and stability of CuFe_2O_4 nanoparticles were tested as well. Besides,the degradation mechanism of NFX in the CuFe_2O_4/PMS heterogeneous system was studied. The results showed that the best calcination temperature was 400 ℃,and in that temperature,better crystalline,larger surface area,higher catalytic activity could be obtained.The optimum of reaction conditions for the removal of NFX in CuFe_2O_4/PMS system was 0. 1 g/L CuFe_2O_4,0.5 mmol/L PMS and initial pH 9.5,under such conditions,NFX removal rate can reach 99% in 30 mins. CuFe_2O_4 could effectively activate PMS to generate ·OH and SO_4~-·,and SO_4~-· was the main active species.
To study the efficient method for removal of the trace organic pollutants in water by peroxymonosulfate( PMS) based advanced oxidation processes,CuFe_2O_4 nanoparticles were prepared by sol-gel method and used as heterogeneous catalyst in the CuFe_2O_4/PMS system for the degradation of norfloxacin( NFX). The CuFe_2O_4 nanoparticles were characterized by X-ray diffraction( XRD),Transmission Electron Microscopy( TEM) and Brunner-Emmet-Teller( BET). Several significant factors affecting the catalytic properties in the CuFe_2O_4/PMS system such as calcination temperature,CuFe_2O_4 dosage,PMS concentration and initial pH were investigated,and the reusability and stability of CuFe_2O_4 nanoparticles were tested as well. Besides,the degradation mechanism of NFX in the CuFe_2O_4/PMS heterogeneous system was studied. The results showed that the best calcination temperature was 400 ℃,and in that temperature,better crystalline,larger surface area,higher catalytic activity could be obtained.The optimum of reaction conditions for the removal of NFX in CuFe_2O_4/PMS system was 0. 1 g/L CuFe_2O_4,0.5 mmol/L PMS and initial pH 9.5,under such conditions,NFX removal rate can reach 99% in 30 mins. CuFe_2O_4 could effectively activate PMS to generate ·OH and SO_4~-·,and SO_4~-· was the main active species.
引文
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[26]SUN Jianhui,SONG Mengke,FENG Jinglan,et al.Highly efficient degradation of ofloxacin by UV/Oxone/Co2+oxidation process[J].Environmental Science Pollution Research,2011,19:1536-1543.
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[28]ZHANG Tao,CHEN Yin,LEIKNESD T,et al.Oxidation of refractory benzothiazoles with PMS/Cu Fe2O4:Kinetics and transformation intermediates[J].Environmental Science&Technology,2016,50:5864-5873.DOI:10.1021/acs.est.6b00701.
[29]ZHANG Tao,LI Weiwei.CROUE J P.A non-acid-assisted and non-hydroxyl-radical-related catalytic ozonation with ceria supported copper oxide in efficient oxalate degradation in water[J].Applied Catalysis B-environmental,2012,121:88-94.
[2]陈涛.HPLC/LC-MS分析广州和珠海污水处理厂废水中多种抗生素污染研究[D].广东:暨南大学,2010.CHEN Tao.Research on a variety of antibiotics of wastewater treatment plant in Guangzhou and Zhuhai by HPLC/LC-MS analysis method[D].Guangdong:Jinan University,2010.
[3]LI Yanwen,WU Xiaolian,MO Cehui,et al.Investigation of sulfonamide,tetracycline,and quinolone antibiotics in vegetable farmland soil in the Pearl River Delta area,Southern China[J].Journal of Agricultural and Food Chemistry,2011,59:7268-7276.
[4]ANIPSITAKIS G P,DIONYSIOU D D.Radical generation by the interaction of transition metals with common oxidants[J].Environmental Science&Technology,2004,38(13):3705-3712.
[5]GAO Yuqiong,GAO Naiyun,DENG Yang,et al.Heat-activated persulfate oxidation of sulfamethoxazole in water[J].Desalination and Water Treatment,2015,56(8):2225-2233.DOI:10.1080/19443994.2014.960471.
[6]GAO Yuqiong,GAO Naiyun,DENG Yang,et al.Ultraviolet(UV)light-activated persulfate oxidation of sulfamethazine in water[J].Chemical Engineering Journal,2012,195:248-253.
[7]SU Shengnan,GUO Weilin,YI Chunliang,et al.Degradation of amoxicillin in aqueous solution using sulphate radicals under ultrasound irradiation[J].Ultrasonics Sonochemistry,2012,19(3):469-474.
[8]FUNMAN O S,TEEL A L,WATTS R J.Mechanism of base activation of persulfate[J].Environmental Science&Technology,2010,44(16):6423-6428.
[9]ZHANG Botao,ZHANG Yang,TENG Yanguo,et al.Sulfate radical and its application in decontamination technologies[J].Critical Reviews in Environmental Science&Technology,2015,45(16):1756-1800.
[10]FANG Guodong,DIONYDIOU D D,AL-ABED S R,et al.Superoxide radical driving the activation of persulfate by magnetite nanoparticles:Implications for the degradation of PCBs[J].Applied Catalysis B-Environmental,2013,129:325-332.
[11]HE Xuexiang,DE L C,ARMAH A,et al.Kinetics and mechanisms of cylindrospermopsin destruction by sulfate radicalbased advanced oxidation processes[J].Water Research,2014,63:168-178.
[12]LIANG C J,BRUELL C J,MARLRY M C,et al.Persulfate oxidation for in situ remediation of TCE.I.Activated by ferrous ion with and without a persulfate-thiosulfate redox couple[J].Chemosphere,2012,55:1213-1223.
[13]YANG Q,CHOI H.Iron-cobalt mixed oxide nanocatalysts:Heterogeneous peroxymonosulfate activation,cobalt leaching,and ferromagnetic properties for environmental applications[J].Applied Catalysis B:Environmental,2009,88(3/4):462-469.
[14]YING Hong.Efficient degradation of atrazine by magnetic porous copper ferrite catalyzed peroxymonosulfate oxidation via the formation of hydroxyl and sulfate radicals[J].Water Research,2013,47:5431-5438.
[15]ZHANG Tao,ZHU H.Production of sulfate radical from peroxymonosulfate induced by a magnetically separable Cu Fe2O4spinel in water:Efficiency,stability,and mechanism[J].Environmental Science&Technology,2013,47:2784-2791.
[16]LAOKUL P,AMOMKITBAMNMG V,SERAPHIN S,et al.Characterization and magnetic properties of nanocrystalline Cu Fe2O4,Ni Fe2O4Zn Fe2O4powders prepared by the Aloe vera extract solution[J].Current Applied Physics,2011,11:101-108.
[17]ZHANG Xiaoling,FENG Mingbao,QU Ruanjuan,et al.Catalytic degradation of diethyl phthalate in aqueous solution by persulfate activated with nano-scaled magnetic Cu Fe2O4/MWCNTs[J].Chemical Engineering Journal,2016,301:1-11.
[18]WANG Zhaohui,BUSH R T,SULLIVAN L A,et al.Selective oxidation of arsenite by peroxymonosulfate with high utilization efficiency of oxidant[J].Environmental Science&Technology,2014,48:3978-3985.
[19]ANIPSITAKIS G P,DIONYSIOU D D.Radical generation by the interaction of transition metals with common oxidants[J].Environmental Science&Technology,2004,38(13):3705-3712.
[20]MA Jun,SUI Minghao,ZHANG Tao,et al.Effect of p H on Mn Ox/GAC catalyzed ozonation for degradation of nitrobenzene[J].Water Research,2005,39(5):779-786.
[21]ROSS D L,RILEY C M.Aqueous solubilities of some variously substituted quinolone antimicrobials[J].International Journal of Pharmaceutics,1900,63:237-250.
[22]BARBOSA T,FONRODONA G,MARQUES I,et al.Factor analysis applied to the correlation between dissociation constants and solvatochromic parameters in water-acetonitrile mixtures.1.Solvent effects on the dissociation of carboxylic acid group in some diuretics,quinolones,buffers and peptides[J].Trac-trends in Analytical Chemistry,1997,16:104-111.
[23]DU Yunchen,MA Wenjie,LIU Pingxin,et al.Magnetic Co Fe2O4nanoparticles supported on titanate nanotubes as a novel heterogeneous catalyst for peroxymonosulfate activation and degradation of organic pollutants[J].Journal of Hazardous Materials,2016,308:58-66.
[24]GUAN Yinghong,MA Jun,LI Xuchun,et al.Influence of p H on the formation of sulfate and hydroxyl radicals in the UV/peroxymonosulfate system[J].Environmental Science&Technology,2011,45:9308-9314.
[25]HUANG Yaohui,HUANG Yifong,HUANG Chuning.Efficient decolorization of azo dye Reactive Black B involving aromatic fragment degradation in buffered Co2+/PMS oxidative processes with a ppb level dosage of Co2+-catalyst[J].Journal of Hazard Materias,2009,170:1110-1118.
[26]SUN Jianhui,SONG Mengke,FENG Jinglan,et al.Highly efficient degradation of ofloxacin by UV/Oxone/Co2+oxidation process[J].Environmental Science Pollution Research,2011,19:1536-1543.
[27]ZHANG Botao,XIANG Weixu,JIANG Xuemei,et al.Oxidation of dyes by alkaline-activated peroxymonosulfate[J].Journal of Environmental Engineering,2016,142(4).DOI:10.1061/(ASCE)EE.1943-7870.0001084.
[28]ZHANG Tao,CHEN Yin,LEIKNESD T,et al.Oxidation of refractory benzothiazoles with PMS/Cu Fe2O4:Kinetics and transformation intermediates[J].Environmental Science&Technology,2016,50:5864-5873.DOI:10.1021/acs.est.6b00701.
[29]ZHANG Tao,LI Weiwei.CROUE J P.A non-acid-assisted and non-hydroxyl-radical-related catalytic ozonation with ceria supported copper oxide in efficient oxalate degradation in water[J].Applied Catalysis B-environmental,2012,121:88-94.