磁性Fe_3O_4纳米颗粒的制备及其催化降解水中磺胺甲恶唑研究
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摘要
旨在构建一种高效绿色的去除水环境中磺胺甲恶唑(SMZ)的方法。采用溶剂热法制备了Fe_3O_4磁性纳米颗粒,并利用XRD、磁滞回线、SEM及TEM对Fe_3O_4颗粒进行了物相和形貌的表征。研究了SMZ在纳米Fe_3O_4和H_2O_2构成的非均相Fenton体系中的催化氧化特征,并考察了p H值、H_2O_2初始浓度及催化剂用量对SMZ催化氧化的影响。结果表明:制备的Fe_3O_4纳米颗粒呈微球形,具有很强的顺磁性,平均粒径约250 nm,能够有效地活化H_2O_2产生·OH并高效降解SMZ。在25℃,p H=3,Fe_3O_4用量为1. 0 g/L,H_2O_2浓度为5. 0μL/m L时,所建立Fe_3O_4-H_2O_2氧化体系能在5 min内几乎完全降解20 mg/L的SMZ。循环实验表明,所制备的Fe_3O_4磁性纳米颗粒具有较好的稳定性。该实验结论可为水体中SMZ的去除提供一定的理论参考。
This paper aims to establish a efficient and green method to remove sulfamethoxazole( SMZ)in water environment. The Fe_3O_4 magnetic nanoparticles were synthesized via a solvothermal method,and the structure and morphology of the prepared materials were characterized by a series of techniques including XRD,magnetic performance testing,SEM and TEM. The catalytic oxidation characteristics of SMZ in the heterogeneous Fenton system of Fe_3O_4-H_2O_2,as well as the influences of the variables such as p H value,H_2O_2 concentration and catalyst dosage on the degradation processes were investigated. The results showed that the prepared Fe_3O_4 nanoparticles were microspherical with an average particle size of about 250 nm,it has strong paramagnetism and could effectively activate H_2O_2 to produce ·OH,which could degrade SMZ efficiently. In the Fe_3O_4-H_2O_2 oxidation system,20 mg/L of SMZ was almost completely degraded within 5 min under the condition of pH at 3,and a Fe_3O_4 dosage of 1. 0 g/L and a H_2O_2 dosage of 5. 0 μL/m L at 25 ℃. The cycle experiments showed that the synthesized samples possessed the excellent stability. The experimental results in this study could provide some theoretical references for SMX removal in the aqueous environment.
This paper aims to establish a efficient and green method to remove sulfamethoxazole( SMZ)in water environment. The Fe_3O_4 magnetic nanoparticles were synthesized via a solvothermal method,and the structure and morphology of the prepared materials were characterized by a series of techniques including XRD,magnetic performance testing,SEM and TEM. The catalytic oxidation characteristics of SMZ in the heterogeneous Fenton system of Fe_3O_4-H_2O_2,as well as the influences of the variables such as p H value,H_2O_2 concentration and catalyst dosage on the degradation processes were investigated. The results showed that the prepared Fe_3O_4 nanoparticles were microspherical with an average particle size of about 250 nm,it has strong paramagnetism and could effectively activate H_2O_2 to produce ·OH,which could degrade SMZ efficiently. In the Fe_3O_4-H_2O_2 oxidation system,20 mg/L of SMZ was almost completely degraded within 5 min under the condition of pH at 3,and a Fe_3O_4 dosage of 1. 0 g/L and a H_2O_2 dosage of 5. 0 μL/m L at 25 ℃. The cycle experiments showed that the synthesized samples possessed the excellent stability. The experimental results in this study could provide some theoretical references for SMX removal in the aqueous environment.
引文
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[7]苏荣军,韩思宇. Fenton试剂处理磺胺甲恶唑制药废水的研究[J].哈尔滨商业大学学报(自然科学版),2015,31(2):183-186.
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[11]孙青柯,黄亚继,王靓,等.磁性Fe3O4-Ag复合纳米颗粒吸附剂脱汞性能实验研究[J].化工进展,2017,36(3):1101-1106.
[12]展思辉,张宇,朱丹丹,等.磁性Fe3O4纳米颗粒的制备及在水处理中的应用[J].环境工程学报,2016,10(1):1-11.
[13]彭振,姚可夫.磁性纳米Fe3O4颗粒的制备及在染料废水处理中的应用[J].化工新型材料,2014,42(12):223-225.
[14]李丹,李忠海,黎继烈,等. Fe3O4磁性纳米颗粒及其在农兽药残留检测中的应用[J].食品与机械,2014,30(3):252-256.
[15]丁畅越,杨军,胡平,等.氨基化磁性纳米Fe3O4颗粒处理废水中重金属的应用[J].应用化工,2017,46(6):1194-1198.
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[18]WANG Yong,LIN Xihuang,SHAO Zongze,et al. Comparison of Fenton,UV-Fenton and nano-Fe3O4catalyzed UV-Fenton in degradation of phloroglucinol under neutral and alkaline conditions:Role of complexation of Fe3+with hydroxyl group in phloroglucinol[J]. Chemical Engineering Journal,2017,313:938-945.
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[20]孙正男,杨琦,纪冬丽,等.纳米Fe3O4/Ce O2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解[J].环境科学,2015,36(6):2154-2160.
[21]刘焕联,李贤英,魏贝贝,等.超顺磁性纳米Fe3O4的制备及其类Fenton反应性能[J].环境工程学报,2017,11(6):3525-3531.
[22] WANG Xikui,WANG Jingang,GUO Peiquan,et al.Degradation of rhodamine B in aqueous solution by using swirling jet-induced cavitation combined with H2O2[J].Journal of Hazardous Materials,2009,169(1-3):486-491.
[23]龙开先,王鹏伟,张基伟,等. Fe3O4-H2O2类Fenton法降解亚甲基蓝[J].应用化工,2016,45(5):916-919.
[24]ALATON I A,BALCIOGLU I A,BAHNEMANN B W.Advanced oxidation of a reactive dyebath effluent:comparison of O3,H2O2/UV-C and Ti O2/UV-A processes[J]. Water Research,2002,36(5):1143-1154.
[25] YAMAGUCHI R,KUROSU S,SUZUKI M,et al. Hydroxyl radical generation by zero-valent iron/Cu(ZVI/Cu)bimetallic catalyst in wastewater treatment:Heterogeneous Fenton/Fenton-like reactions by Fenton reagents formed in-situ under oxic conditions[J]. Chemical Engineering Journal,2018,334:1537-1549.
[26]HOU Baolin,HAN Hongjun,JIA Shengyong,et al. Heterogeneous electro-Fenton oxidation of catechol catalyzed by nano-Fe3O4:kinetics with the Fermi's equation[J].Journal of the Taiwan Institute of Chemical Engineers,2015,56(4):138-147.
[27]EL-GHENYMY A,OTURAN N,OTURAN M A,et al.Comparative electro-Fenton and UVA photoelectro-Fenton degradation of the antibiotic sulfanilamide using a stirred BDD/air-diffusion tank reactor[J]. Chemical Engineering Journal,2013,234:115-123.
[28]AN Junjian,ZHU Lihua,ZHANG Yingying,et al. Efficient visible light photo-fenton-like degradation of organic pollutants using in situ surface-modified Bi Fe O3as a catalyst[J]. Journal of Environmental Sciences,2013,25(6):1213-1225.
[29]LIU Yong,FAN Qin,WANG Jianlong. Zn-Fe-CNTs catalytic in situ generation of H2O2for Fenton-like degradation of sulfamethoxazole[J]. Journal of Hazardous Materials,2018,342:166-176.
[30]AGUINACO A,BELTRAN F J,SAGASTI J J,et al. In situ generation of hydrogen peroxide from pharmaceuticals single ozonation:A comparative study of its application on Fenton like systems[J]. Chemical Engineering Journal,2014,235:46-51.
[31]WAN Zhong,WANG Jianlong. Degradation of sulfamethazine using Fe3O4-Mn3O4/reduced graphene oxide hybrid as Fenton-like catalyst[J]. Journal of Hazardous Materials,2017,324(Pt B):653-664.
[32]邓景衡,文湘华,李佳喜.碳纳米管负载纳米四氧化三铁多相类芬顿降解亚甲基蓝[J].环境科学学报,2014,34(6):1436-1442.
[33] NGOMSIK A F,BEE A,DRAYE M,et al. Magnetic nano-and microparticles for metal removal and environmental application:a review[J]. Comptes Rendus Chimie,2005,8(6-7):963-970.
[34]ZHANG Shengxiao,ZHAO Xiaoli,NIU Hongyun,et al.Superparamagnetic Fe3O4nanoparticles as catalysts for the catalytic oxidation of phenolic and aniline compounds[J].Journal of Hazardous Materials,2009,167(1-3):560-566.
[35]WEI Hong,HU Da,SU Jie,et al. Intensification of levofloxacin sono-degradation in a US/H2O2system with Fe3O4magnetic nanoparticles[J]. Chinese Journal of Chemical Engineering,2015,23(1):296-302.
[36]张娣,王懿萱,牛红云,等.纳米Fe3O4/H2O2降解诺氟沙星[J].环境科学,2011,32(10):2943-2948.
[37] KWAN W P,VOELKER B. Rates of hydroxyl radical generation and organic compound oxidation in mineral-catalyzed Fenton-like systems[J]. Environmental Science&Technology,2003,37(6):1150-1158.
[38]裴欢,毛飞,司友斌.纳米铁氧化物催化类Fenton反应降解抗生素磺胺[J].农业环境科学学报,2015,34(7):1356-1362.
[39]唐和清,阮玉凤,聂刚,等.溶剂热制备纳米Fe3O4及其高效Fenton降解4-氯苯酚[J].中南民族大学学报(自然科学版),2016,35(2):1-5.
[2]丁杰,沙焕伟,赵双阳,等.磁性氧化石墨烯/壳聚糖制备及其对磺胺嘧啶吸附性能研究[J].环境科学学报,2016,36(10):3691-3700.
[3]XU Jian,XU Yan,WANG Hongmei,et al. Occurrence of antibiotics and antibiotic resistance genes in a sewage treatment plant and its effluent-receiving river[J]. Chemosphere,2015,119:1379-1385.
[4]杨海燕,贾九敏,郭金鹏. UV/H2O2降解磺胺甲恶唑和环丙沙星的对比研究[J].中国给水排水,2016,32(13):82-86.
[5]王佳丽,张玉玲,钱红,等.吸附法去除低温水体中的磺胺类抗生素[J].吉利大学学报(理学版),2016,54(3):663-669.
[6]LI Di,SHI Weidong. Recent developments in visible-light photocatalytic degradation of antibiotics[J]. Chinese Journal of Catalysis,2016,37(6):792-799.
[7]苏荣军,韩思宇. Fenton试剂处理磺胺甲恶唑制药废水的研究[J].哈尔滨商业大学学报(自然科学版),2015,31(2):183-186.
[8] JIHYUN R,KAN E. Heterogeneous photocatalytic degradation of sulfamethoxazole in water using a biochar-supported Ti O2photocatalyst[J]. Journal of Environmental Management,2016,180:94-101.
[9]JUDY AZAR A R,MOHEBBI S. Novel magnetic nanomaterials:Synthesis,characterization and study of their catalytic application[J]. Materials Chemistry and Physics,2015,168:85-94.
[10]胡平,常恬,陈震宇,等.纳米Fe3O4磁性颗粒表面改性及其在医学和环保领域的应用[J].化工学报,2017,68(7):2641-2652.
[11]孙青柯,黄亚继,王靓,等.磁性Fe3O4-Ag复合纳米颗粒吸附剂脱汞性能实验研究[J].化工进展,2017,36(3):1101-1106.
[12]展思辉,张宇,朱丹丹,等.磁性Fe3O4纳米颗粒的制备及在水处理中的应用[J].环境工程学报,2016,10(1):1-11.
[13]彭振,姚可夫.磁性纳米Fe3O4颗粒的制备及在染料废水处理中的应用[J].化工新型材料,2014,42(12):223-225.
[14]李丹,李忠海,黎继烈,等. Fe3O4磁性纳米颗粒及其在农兽药残留检测中的应用[J].食品与机械,2014,30(3):252-256.
[15]丁畅越,杨军,胡平,等.氨基化磁性纳米Fe3O4颗粒处理废水中重金属的应用[J].应用化工,2017,46(6):1194-1198.
[16]GAO Lizeng,ZHUANG Jie,NIE Leng,et al. Intrinsic peroxidase-like activity of ferromagnetic nanoparticles[J].Nature Nanotechnology,2007,2(9):577-583.
[17]吕来,胡春.多相芬顿催化水处理技术与原理[J].化学进展,2017,29(9):981-999.
[18]WANG Yong,LIN Xihuang,SHAO Zongze,et al. Comparison of Fenton,UV-Fenton and nano-Fe3O4catalyzed UV-Fenton in degradation of phloroglucinol under neutral and alkaline conditions:Role of complexation of Fe3+with hydroxyl group in phloroglucinol[J]. Chemical Engineering Journal,2017,313:938-945.
[19]何洁,杨晓芳,张伟军,等.纳米Fe3O4-H2O2非均相Fenton反应催化氧化邻苯二酚[J].环境科学,2013,34(5):1773-1781.
[20]孙正男,杨琦,纪冬丽,等.纳米Fe3O4/Ce O2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解[J].环境科学,2015,36(6):2154-2160.
[21]刘焕联,李贤英,魏贝贝,等.超顺磁性纳米Fe3O4的制备及其类Fenton反应性能[J].环境工程学报,2017,11(6):3525-3531.
[22] WANG Xikui,WANG Jingang,GUO Peiquan,et al.Degradation of rhodamine B in aqueous solution by using swirling jet-induced cavitation combined with H2O2[J].Journal of Hazardous Materials,2009,169(1-3):486-491.
[23]龙开先,王鹏伟,张基伟,等. Fe3O4-H2O2类Fenton法降解亚甲基蓝[J].应用化工,2016,45(5):916-919.
[24]ALATON I A,BALCIOGLU I A,BAHNEMANN B W.Advanced oxidation of a reactive dyebath effluent:comparison of O3,H2O2/UV-C and Ti O2/UV-A processes[J]. Water Research,2002,36(5):1143-1154.
[25] YAMAGUCHI R,KUROSU S,SUZUKI M,et al. Hydroxyl radical generation by zero-valent iron/Cu(ZVI/Cu)bimetallic catalyst in wastewater treatment:Heterogeneous Fenton/Fenton-like reactions by Fenton reagents formed in-situ under oxic conditions[J]. Chemical Engineering Journal,2018,334:1537-1549.
[26]HOU Baolin,HAN Hongjun,JIA Shengyong,et al. Heterogeneous electro-Fenton oxidation of catechol catalyzed by nano-Fe3O4:kinetics with the Fermi's equation[J].Journal of the Taiwan Institute of Chemical Engineers,2015,56(4):138-147.
[27]EL-GHENYMY A,OTURAN N,OTURAN M A,et al.Comparative electro-Fenton and UVA photoelectro-Fenton degradation of the antibiotic sulfanilamide using a stirred BDD/air-diffusion tank reactor[J]. Chemical Engineering Journal,2013,234:115-123.
[28]AN Junjian,ZHU Lihua,ZHANG Yingying,et al. Efficient visible light photo-fenton-like degradation of organic pollutants using in situ surface-modified Bi Fe O3as a catalyst[J]. Journal of Environmental Sciences,2013,25(6):1213-1225.
[29]LIU Yong,FAN Qin,WANG Jianlong. Zn-Fe-CNTs catalytic in situ generation of H2O2for Fenton-like degradation of sulfamethoxazole[J]. Journal of Hazardous Materials,2018,342:166-176.
[30]AGUINACO A,BELTRAN F J,SAGASTI J J,et al. In situ generation of hydrogen peroxide from pharmaceuticals single ozonation:A comparative study of its application on Fenton like systems[J]. Chemical Engineering Journal,2014,235:46-51.
[31]WAN Zhong,WANG Jianlong. Degradation of sulfamethazine using Fe3O4-Mn3O4/reduced graphene oxide hybrid as Fenton-like catalyst[J]. Journal of Hazardous Materials,2017,324(Pt B):653-664.
[32]邓景衡,文湘华,李佳喜.碳纳米管负载纳米四氧化三铁多相类芬顿降解亚甲基蓝[J].环境科学学报,2014,34(6):1436-1442.
[33] NGOMSIK A F,BEE A,DRAYE M,et al. Magnetic nano-and microparticles for metal removal and environmental application:a review[J]. Comptes Rendus Chimie,2005,8(6-7):963-970.
[34]ZHANG Shengxiao,ZHAO Xiaoli,NIU Hongyun,et al.Superparamagnetic Fe3O4nanoparticles as catalysts for the catalytic oxidation of phenolic and aniline compounds[J].Journal of Hazardous Materials,2009,167(1-3):560-566.
[35]WEI Hong,HU Da,SU Jie,et al. Intensification of levofloxacin sono-degradation in a US/H2O2system with Fe3O4magnetic nanoparticles[J]. Chinese Journal of Chemical Engineering,2015,23(1):296-302.
[36]张娣,王懿萱,牛红云,等.纳米Fe3O4/H2O2降解诺氟沙星[J].环境科学,2011,32(10):2943-2948.
[37] KWAN W P,VOELKER B. Rates of hydroxyl radical generation and organic compound oxidation in mineral-catalyzed Fenton-like systems[J]. Environmental Science&Technology,2003,37(6):1150-1158.
[38]裴欢,毛飞,司友斌.纳米铁氧化物催化类Fenton反应降解抗生素磺胺[J].农业环境科学学报,2015,34(7):1356-1362.
[39]唐和清,阮玉凤,聂刚,等.溶剂热制备纳米Fe3O4及其高效Fenton降解4-氯苯酚[J].中南民族大学学报(自然科学版),2016,35(2):1-5.