复合磁性催化剂β-MnO_2/Mn_xZn_(1-x)Fe_2O_4的制备与表征
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摘要
采用化学共沉淀法制备了以MnxZn1-xFe2O4为磁性基体的β-MnO_2/Mn_xZn_(1-x)Fe_2O_4复合磁性催化剂,利用XRD、SEM、FTIR和超导量子干涉仪对复合磁性催化剂的结构和性能进行了表征,以罗丹明B(RhB)为模拟污染物,研究了β-MnO_2/Mn_xZn_(1-x)Fe_2O_4的催化活性,并考察了其稳定性。结果表明,球状的β-MnO2与块状的磁性基体MnxZn1-xFe2O4成功复合,且制备的β-MnO_2/Mn_xZn_(1-x)Fe_2O_4复合磁性催化剂具有良好的催化性能和磁学性能。当MnxZn1-xFe2O4与β-MnO2的质量比为20∶100时,在2mL含量为30%的H2O2作用下,1h内β-MnO_2/Mn_xZn_(1-x)Fe_2O_4复合磁性催化剂对100mL浓度为10mg/L的RhB降解率(93.9%)远高于纯β-MnO2(33.7%);在磁场作用下,β-MnO_2/Mn_xZn_(1-x)Fe_2O_4复合磁性催化剂的回收率为89%,经过5次循环利用之后其对RhB的降解率仍达76%。
The β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 composite magnetic catalyst was synthesized via chemical co-precipitation method,and the structure and performance of the composite were characterized by XRD,SEM,FTIR and superconducting quantum interference device(SQUID).The catalytic activity of β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 was studied by using Rhodamine B(RhB)as a simulated pollutant,and its stability was also studied.The results show that the spherical β-MnO_2 and magnetic substrates Mn_xZn_(1-x)Fe_2O_4 are successfully combined together.The β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 composite magnetic catalyst has good catalytic and magnetic properties.When the mass ratio of Mn_xZn_(1-x)Fe_2O_4 and β-MnO_2 is 20∶100,in the presence of 2 mL of H_2O_2(30%),the degradation rate of RhB at a concentration of 10 mg/L(100 mL)in β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 composite magnetic catalyst(93.9%)is higher than that in pure β-MnO_2(33.7%)within 1 h.Under the magnetic field,the recovery rate of the β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 composite magnetic catalyst is 89%,and the degradation rate of RhB is 76% after five cycles.
The β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 composite magnetic catalyst was synthesized via chemical co-precipitation method,and the structure and performance of the composite were characterized by XRD,SEM,FTIR and superconducting quantum interference device(SQUID).The catalytic activity of β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 was studied by using Rhodamine B(RhB)as a simulated pollutant,and its stability was also studied.The results show that the spherical β-MnO_2 and magnetic substrates Mn_xZn_(1-x)Fe_2O_4 are successfully combined together.The β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 composite magnetic catalyst has good catalytic and magnetic properties.When the mass ratio of Mn_xZn_(1-x)Fe_2O_4 and β-MnO_2 is 20∶100,in the presence of 2 mL of H_2O_2(30%),the degradation rate of RhB at a concentration of 10 mg/L(100 mL)in β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 composite magnetic catalyst(93.9%)is higher than that in pure β-MnO_2(33.7%)within 1 h.Under the magnetic field,the recovery rate of the β-MnO_2/Mn_xZn_(1-x)Fe_2O_4 composite magnetic catalyst is 89%,and the degradation rate of RhB is 76% after five cycles.
引文
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[22]YANG Ruizhi,WANG Zhaoxiang,DAI Lei,et al.Synthesis and characterization of single-crystalline nanorods ofα-MnO2andγ-MnOOH[J].Materials Chemistry&Physics,2005,93(1):149-153.
[23]刘建武,郭成,黄海亮,等.柠檬酸溶胶—凝胶法制备钡铁氧体晶相变化的研究[J].南京工业大学学报(自然科学版),2017,39(1):26-30.LIU Jianwu,GUO Cheng,HUANG Hailiang,et al.Crystal change of barium hexaferrite prepared by citric acid sol-gel method[J].Journal of Nanjing University of Technology(Natural Science Edition),2017,39(1):26-30(in Chinese).
[24]JIE L,ZHAO Z,SHAO P,et al.Activation of peroxymonosulfate with magnetic Fe3O4-MnO2core-shell nanocomposites for 4-chlorophenol degradation[J].Chemical Engineering Journal,2015,262(9):854-861.
[25]YU C,LI G,WEI L,et al.Fabrication,characterization ofβ-MnO2 microrod catalysts and their performance in rapid degradation of dyes of high concentration[J].Catalysis Today,2014,224(224):154-162.
[2]PU Y C,CHEN Y C,HSU Y J.Au-decorated NaxH2-x Ti3O7nanobelts exhibiting remarkable photocatalytic properties under visible-light illumination[J].Applied Catalysis B:Environmental,2010,97(3):389-397.
[3]姜泳波,赵慧宏,马婷婷,等.高级催化氧化法降解甲基橙模拟废水研究[J].环境科学与技术,2014,37(2):57-60.JIANG Yongbo,ZHAO Huihong,MA Tingting,et al.Methyl orange degradation by advanced catalytic oxidation method[J].Environmental Science&Technology,2014,37(2):57-60(in Chinese).
[4]SCHMIT F,BOIS L,CHASSAGNEUX F,et al.Catalytic wet air oxidation of methylamine over supported manganese dioxide catalysts[J].Catalysis Today,2015,258:570-575.
[5]张红艳,陆雪梅,刘志英,等.湿式氧化法处理高盐度难降解农药废水[J].化工进展,2007,26(3):417-421,425.ZHANG Hongyan,LU Xuemei,LIU Zhiying,et al.Treatment of degradation-resistant pesticide wastewater with high salinity by wet air oxidation[J].Chemical Industry and Engineering Progress,2007,26(3):417-421,425(in Chinese).
[6]SUAREZ-OJEDA M E,STBER F,FORTUNY A,et al.Catalytic wet air oxidation of substituted phenols using activated carbon as catalyst[J].Applied Catalysis B:Environmental,2005,58(1):105-114.
[7]王建兵,杨少霞,祝万鹏,等.催化湿式氧化法处理废水的研究进展[J].化工环保,2007,27(4):295-300.WANG Jianbing,YANG Shaoxia,ZHU Wanpeng,et al.Advances in research on wastewater treatment by catalytic wet air oxidation process[J].Environmental Protection of Chemical Industry,2007,27(4):295-300(in Chinese).
[8]GALEANO L A,GIL A,VICENTE M A.Strategies for immobilization of manganese on expanded natural clays:Catalytic activity in the CWPO of methyl orange[J].Applied Catalysis B:Environmental,2011,104(3-4):252-260.
[9]GALEANO L A,GIL A,VICENTE M A.Effect of the atomic active metal ratio in Al/Fe-,Al/Cu-and Al/(Fe-Cu)-intercalating solutions on the physicochemical properties and catalytic activity of pillared clays in the CWPO of methyl orange[J].Applied Catalysis B:Environmental,2010,100(1-2):271-281.
[10]蔡先明,秦侠,张丽,等.催化湿式过氧化氢氧化处理垃圾渗滤液及其DOM光谱分析[J].环境科学学报,2015,35(9):2930-2935.CAI Xianming,QIN Xia,ZHANG Li,et al.Hydrogen peroxide catalytic wet oxidation of leachate and the spectroscopic analysis of dissolved organic matters[J].Acta Scientiae Circumstantiae,2015,35(9):2930-2935(in Chinese).
[11]钮娜,董学伟,董晓丽,等.催化湿式过氧化氢氧化法处理甲基橙[J].大连工业大学学报,2011,30(1):62-64.NIU Na,DONG Xuewei,DONG Xiaoli,et al.The treatment of Acid Orange 52by catalytic wet peroxide oxidation[J].Journal of Dalian Polytechnic University,2011,30(1):62-64(in Chinese).
[12]WANG G S,LEE J W,SANG C K.Analysis of catalytic oxidation of aromatic hydrocarbons over supported palladium catalyst with different pretreatments based on heterogeneous adsorption properties[J].Applied Catalysis B:Environmental,2008,84(1-2):133-141.
[13]DAS D P,PARIDA K M.Mn(III)oxide pillared titanium phosphate(TiP)for catalytic deep oxidation of VOCs[J].Applied Catalysis A:General,2007,324:1-8.
[14]崔丽华,王岩,舒霞,等.MnO2/TiO2复合物电极的制备及超级电容性能[J].复合材料学报,2016,33(8):1794-1802.CUI Lihua,WANG Yan,SHU Xia,et al.Preparation and supercapacitive performance of MnO2/TiO2 composite electrodes[J].Acta Materiae Compositae Sinica,2016,33(8):1794-1802(in Chinese).
[15]李洁,姚超,张珊,等.δ型二氧化锰/埃洛石的制备及其对亚甲基蓝的吸附性能[J].硅酸盐学报,2014,42(2):241-247.LI Jie,YAO Chao,ZHANG Shan,et al.Preparation ofδ-type manganese dioxide/halloysite composites and their adsorption properties for methylene blue[J].Journal of the Chinese Ceramic Society,2014,42(2):241-247(in Chinese).
[16]杨永珍,刘伟峰,郭明聪,等.MnO2/CMSs复合材料的制备及其电化学性能[J].复合材料学报,2011,28(4):149-155.YANG Yongzhen,LIU Weifeng,Guo Mingcong,et al.Preparation and electrochemical property of MnO2/carbon microsphere composite[J].Acta Materiae Compositae Sinica,2011,28(4):149-155(in Chinese).
[17]彭爱国,贺周初,肖伟,等.化学二氧化锰研究进展[J].无机盐工业,2011,43(3):8-10,30.PENG Aiguo,HE Zhouchu,XIAO Wei,et al.Research progress of chemical manganese dioxide[J].Inorganic Chemicals Industry,2011,43(3):8-10,30(in Chinese).
[18]彭轶瑶,陶娟,冯靖雯,等.微波诱导催化氧化六方软锰矿降解四环素[J].人工晶体学报,2014,43(7):1651-1656.PENG Yiyao,TAO Juan,FENG Jingwen,et al.Degradation of tetracycline in water by microwave induced catalytic oxidation of akhtenskite[J].Journal of Synthetic Crystals,2014,43(7):1651-1656(in Chinese).
[19]冯林强,罗汉金,方伟.纳米二氧化锰/还原态氧化石墨烯复合材料催化臭氧降解苯酚的研究[J].环境工程,2016,34(7):56-60.FENG Linqiang,LUO Hanjin,FANG Wei.Study on catalytic ozonation of phenol over nanosized MnO2supported on reduced graphene oxide[J].Environmental Engineering,2016,34(7):56-60(in Chinese).
[20]ZHANG Zhaodi,XU Longjun,LIU Chenglun,et al.Preparation and characterization of composite magnetic photocatalyst MnxZn1-xFe2O4/β-Bi2O3[J].The Royal Society of Chemistry,2015,5(97):79997-80004.
[21]FENG Shan,XU Longjun,LIU Chenglun,et al.Preparation and property of magnetic photocatalyst BiOCl/MnxZn1-x Fe2O4[J].The Journal of Nanoparticle Research,2017,19(2):33.
[22]YANG Ruizhi,WANG Zhaoxiang,DAI Lei,et al.Synthesis and characterization of single-crystalline nanorods ofα-MnO2andγ-MnOOH[J].Materials Chemistry&Physics,2005,93(1):149-153.
[23]刘建武,郭成,黄海亮,等.柠檬酸溶胶—凝胶法制备钡铁氧体晶相变化的研究[J].南京工业大学学报(自然科学版),2017,39(1):26-30.LIU Jianwu,GUO Cheng,HUANG Hailiang,et al.Crystal change of barium hexaferrite prepared by citric acid sol-gel method[J].Journal of Nanjing University of Technology(Natural Science Edition),2017,39(1):26-30(in Chinese).
[24]JIE L,ZHAO Z,SHAO P,et al.Activation of peroxymonosulfate with magnetic Fe3O4-MnO2core-shell nanocomposites for 4-chlorophenol degradation[J].Chemical Engineering Journal,2015,262(9):854-861.
[25]YU C,LI G,WEI L,et al.Fabrication,characterization ofβ-MnO2 microrod catalysts and their performance in rapid degradation of dyes of high concentration[J].Catalysis Today,2014,224(224):154-162.