新型Fe_3O_4@α-MnO_2活化过一硫酸盐降解水中偶氮染料
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摘要
采用两步水热法制备了新型磁性纳米Fe_3O_4@α-MnO_2复合材料作为催化剂,用于活化过一硫酸盐(PMS)产生强氧化性的硫酸根自由基(SO4-·)氧化降解偶氮染料活性黑5(RBK5).采用透射电子显微镜(TEM),X射线粉末衍射仪(XRD)和振动样品磁强计(VSM)对制备的催化剂进行表征,证明成功合成了纳米α-MnO_2包覆Fe_3O_4形态的Fe_3O_4@α-MnO_2催化剂,催化剂的饱和磁化强度为39.89emu/g.Fe_3O_4@α-MnO_2催化剂活化PMS与单一的Fe_3O_4和α-MnO_2活化PMS相比,具有更高的催化效率,说明铁锰双金属存在协同作用.同时研究了催化剂的投加量、PMS的浓度和初始pH值等各种因素对RBK5的降解效率以及反应动力学的影响.实验结果表明,Fe_3O_4@α-MnO_2催化剂活化PMS降解RBK5的过程符合准一级反应动力学,在催化剂投加量为1.2g/L,PMS的浓度为4mmol/L,初始pH值为7.0,反应时间为60min的情况下,浓度为30mg/L的RBK5的降解效率可达到91%,此时RBK5的降解速率常数也达到最高值0.023min~(-1).此外,通过加入自由基淬灭剂甲醇、叔丁醇和硝基苯判断了Fe_3O_4@α-MnO_2/PMS体系中起主要氧化降解作用的活性物种为SO4-·.
The degradation of reactive black 5, an azo dye, in aqueous solutions was investigated using novel magnetic nano-Fe_3O_4@α-MnO_2 catalyst, which prepared by two step hydrothermal method. The catalyst was characterized by transmission electron microscope(TEM), X-ray diffraction(XRD) and vibration sample magnetometer(VSM). TEM and XRD results of as-synthesized catalyst showed the nano-α-MnO_2 coated Fe_3O_4 was successfully prepared. VSM indicated the saturation magnetization of nano-Fe_3O_4@α-MnO_2 was reach up to 39.89 emu/g. As all the Fe_3O_4, α-MnO_2 and nano-Fe_3O_4@α-MnO_2 was applied to assess the individual and interaction effects of metals, the higher catalytic efficiency of nano-Fe_3O_4@α-MnO_2 implied the synergistic effect between Fe and Mn. Several operating parameters(catalyst dosage, PMS concentration and initial p H value) on the treatment efficiency and reaction kinetics of RBK5 were also studied. As results, the RBK5 degradation process via Fe_3O_4@α-MnO_2 activated PMS is consistent with the pseudo-first-order reaction. The degradation efficiency of RBK5(30 mg/L) could reach 91% within 60 min under the condition of the catalyst dosage was 1.2 g/L, the PMS concentration was 4 mmol/L, and the initial p H value was 7.0. Under this situation, the degradation rate constant of RBK5 also reached the highest value of 0.023 min~(-1). Moreover, the main active species in RBK5 degradation in Fe_3O_4@α-MnO_2/PMS system was identified as SO4-· by adding radical quencher such as methanol, tert-butanol and nitrobenzene.
The degradation of reactive black 5, an azo dye, in aqueous solutions was investigated using novel magnetic nano-Fe_3O_4@α-MnO_2 catalyst, which prepared by two step hydrothermal method. The catalyst was characterized by transmission electron microscope(TEM), X-ray diffraction(XRD) and vibration sample magnetometer(VSM). TEM and XRD results of as-synthesized catalyst showed the nano-α-MnO_2 coated Fe_3O_4 was successfully prepared. VSM indicated the saturation magnetization of nano-Fe_3O_4@α-MnO_2 was reach up to 39.89 emu/g. As all the Fe_3O_4, α-MnO_2 and nano-Fe_3O_4@α-MnO_2 was applied to assess the individual and interaction effects of metals, the higher catalytic efficiency of nano-Fe_3O_4@α-MnO_2 implied the synergistic effect between Fe and Mn. Several operating parameters(catalyst dosage, PMS concentration and initial p H value) on the treatment efficiency and reaction kinetics of RBK5 were also studied. As results, the RBK5 degradation process via Fe_3O_4@α-MnO_2 activated PMS is consistent with the pseudo-first-order reaction. The degradation efficiency of RBK5(30 mg/L) could reach 91% within 60 min under the condition of the catalyst dosage was 1.2 g/L, the PMS concentration was 4 mmol/L, and the initial p H value was 7.0. Under this situation, the degradation rate constant of RBK5 also reached the highest value of 0.023 min~(-1). Moreover, the main active species in RBK5 degradation in Fe_3O_4@α-MnO_2/PMS system was identified as SO4-· by adding radical quencher such as methanol, tert-butanol and nitrobenzene.
引文
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[23]Xu L,Xu C,Zhao M,et al.Oxidative removal of aqueous steroid estrogens by manganese oxides[J].Water Research,2008,42(20):5038-5044.
[24]Deng J,Feng S,Ma X,et al.Heterogeneous degradation of Orange II with peroxymonosulfate activated by ordered mesoporous Mn Fe2O4[J].Separation and Purification Technology,2016,167:181-189.
[25]田凯勋,杨超,肖泉,等.超声强化零价铁/过硫酸钾体系降解2,4,6-三氯苯酚废水[J].中国环境科学,2017,37(10):3729-3734.
[26]Liu J,Zhao Z,Shao P,et al.Activation of peroxymonosulfate with magnetic Fe3O4-Mn O2 core-shell nanocomposites for 4-chlorophenol degradation[J].Chemical Engineering Journal,2015,262:854-861.
[27]Ghanbari F,Moradi M.Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants:Review[J].Chemical Engineering Journal,2017,310(1):41-62.
[28]Ye P,Wu D,Wang M,et al.Coating magnetic Cu Fe2O4 nanoparticles with OMS-2for enhanced degradation of organic pollutants via peroxymonosulfate activation[J].Applied Surface Science,2018,428:131-139.
[29]Neta P,Huie R,Ross A.Rate Constants for Reactions of Peroxyl Radicals in Fluid Solutions[J].Journal of Physical and Chemical Reference Data,1990,19(2):413-513.
[30]Buxton G,Buxton C,Greenstock W,et al.Critical review of rate constants for reactions of hydrated electrons,hydrogen atoms and hydroxyl radicals?OH/O–in aqueous solution[J].Journal of Physical and Chemical Reference Data,1988,17:513-886.
[31]Neta P,Madhavan V,Zemel H,et al.Rate constants and mechanism of reaction of sulfate radical anion with aromatic compounds[J].Journal of the American Chemical Society,1977,99:163-64.
[32]Hu L,Chen W,Xie X,et al.Symmetrical Mn O2-carbon nanotubetextile nanostructures for wearable pseudo capacitors with high mass loading[J].Acs Nano,2011,5(11):8904-8913.
[33]Saputra E,Muhammad S,Sun H,et al.A comparative study of spinel structured Mn3O4,Co3O4 and Fe3O4 nanoparticles in catalytic oxidation of phenolic contaminants in aqueous solutions[J].Journal of Colloid and Interface Science,2013,407(10):467-473.
[34]Dulman V,Cucu-Man S M,Olariu R I,et al.A new heterogeneous catalytic system for decolorization and mineralization of Orange G acid dye based on hydrogen peroxide and a microporous chelating polymer[J].Dyes and Pigments,2012,95(1):79-88.
[35]El-Ghenymy A,Centellas F,Garrido J A,et al.Decolorization and mineralization of Orange G azo dye solutions by anodic oxidation with a boron-doped diamond anode in divided and undivided tank reactors[J].Electrochimica Acta,2014,130:568-576.
[2]Banerjee P,Dasgupta S,De S.Removal of dye from aqueous solution using a combination of advanced oxidation process and nanofiltration[J].Journal of Hazardous Materials,2007,140(1/2):95-103.
[3]王艳,祖德,冯明明,等.铁氧化物联合低含量亚铁离子催化H2O2降解偶氮染料活性黑5[J].水处理技术,2014,40(2):35-38.
[4]刘琰,孙德智.高级氧化技术处理染料废水的研究进展[J].工业水处理,2006,26(6):1-5.
[5]Ji F,Li C,Wei X,et al.Efficient performance of porous Fe2O3 in heterogeneous activation of peroxymonosulfate for decolorization of Rhodamine B[J].Chemical Engineering Journal,2013,231:434-440.
[6]王兵,李娟,莫正平,等.基于硫酸自由基的高级氧化技术研究及应用进展[J].环境工程,2012,30(4):53-57.
[7]Zhou L,Ferronato C,Chovelon J,et al.Investigations of diatrizoate degradation by photo-activated persulfate[J].Chemical Engineering Journal,2017,311:28-36.
[8]Liang C,Lee I,Hsu I,et al.Persulfate oxidation of trichloroethylene with and without iron activation in porous media[J].Chemosphere,2008,70(3):426-435.
[9]Gong F,Wang L,Li D,et al.An effective heterogeneous iron-based catalyst to activate peroxymonosulfate for organic contaminants removal[J].Chemical Engineering Journal,2015,267:102-110.
[10]冯善方,邓思萍,杜嘉雯,等.三维有序介孔Co3O4非均相活化单过硫酸氢钾降解罗丹明B[J].环境科学,2016,37(11):4247-4254.
[11]吉飞,李朝林,邓磊,等.Cu O/过硫酸氢钾体系催化氧化苯酚[J].环境工程学报,2014,8(1):27-31.
[12]Saputra E,Zhang H,Liu Q,et al.Egg-shaped core/shellα-Mn2O3@α-Mn O2as heterogeneous catalysts for decomposition of phenolics in aqueous solutions[J].Chemosphere,2016,159:351-358.
[13]庞素艳,江进,马军,等.Mn O2催化KMn O4氧化降解酚类化合物[J].环境科学,2010,31(10):2331-2335.
[14]李梦澜,李海青,李刚.纳米α-Mn O2催化臭氧氧化降解水中双酚A[J].化工环保,2014,34(5):484-487.
[15]Saputra E,Muhammad S,Sun H,et al.Different Crystallographic One-dimensional Mn O2 Nanomaterials and Their Superior Performance in Catalytic Phenol Degradation[J].Environmental Science&Technology,2013,47(11):5882-5887.
[16]Deng J,Ge Y,Tan C,et al.Degradation of ciprofloxacin usingα-Mn O2activated peroxymonosulfate process:Effect of water constituents,degradation intermediates and toxicity evaluation[J].Chemical Engineering Journal,2017,330:1390-1400.
[17]Du J,Bao J,Liu Y,et al.Efficient activation of peroxymonosulfate by magnetic Mn-MGO for degradation of bisphenol A[J].Journal of Hazardous Materials,2016,320:150-159.
[18]刘杰,赵志伟,王威,等.以磁性Fe3O4-Mn O2核壳结构复合材料为Fenton催化剂氧化去除水中4-氯酚[J].水处理技术,2014,40(7):20-23.
[19]Wang X,Li Y.Rational synthesis ofα-Mn O2 single-crystal nanorods[J].Chemical Communication,2002,7(7):764-765.
[20]He J,Yang X,Zhang W,et al.Catalyzed oxidation of catechol by the heterogeneous Fenton-like reaction of nano-Fe3O4-H2O2 system[J].Environmental Science,2013,34(5):1773-1781.
[21]刘丽艳,孙至柔,叶文博,等.超声辅助Fe3O4活化过一硫酸盐降解酸性红B[J].化工进展,2016,35(11):3663-3668.
[22]Sui N,Duan Y,Jiao X,et al.Large-Scale Preparation and Catalytic Properties of One-Dimensionalα/β-Mn O2 Nanostructures[J].The Journal of Physical Chemistry C,2009,113(20):8560-8565.
[23]Xu L,Xu C,Zhao M,et al.Oxidative removal of aqueous steroid estrogens by manganese oxides[J].Water Research,2008,42(20):5038-5044.
[24]Deng J,Feng S,Ma X,et al.Heterogeneous degradation of Orange II with peroxymonosulfate activated by ordered mesoporous Mn Fe2O4[J].Separation and Purification Technology,2016,167:181-189.
[25]田凯勋,杨超,肖泉,等.超声强化零价铁/过硫酸钾体系降解2,4,6-三氯苯酚废水[J].中国环境科学,2017,37(10):3729-3734.
[26]Liu J,Zhao Z,Shao P,et al.Activation of peroxymonosulfate with magnetic Fe3O4-Mn O2 core-shell nanocomposites for 4-chlorophenol degradation[J].Chemical Engineering Journal,2015,262:854-861.
[27]Ghanbari F,Moradi M.Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants:Review[J].Chemical Engineering Journal,2017,310(1):41-62.
[28]Ye P,Wu D,Wang M,et al.Coating magnetic Cu Fe2O4 nanoparticles with OMS-2for enhanced degradation of organic pollutants via peroxymonosulfate activation[J].Applied Surface Science,2018,428:131-139.
[29]Neta P,Huie R,Ross A.Rate Constants for Reactions of Peroxyl Radicals in Fluid Solutions[J].Journal of Physical and Chemical Reference Data,1990,19(2):413-513.
[30]Buxton G,Buxton C,Greenstock W,et al.Critical review of rate constants for reactions of hydrated electrons,hydrogen atoms and hydroxyl radicals?OH/O–in aqueous solution[J].Journal of Physical and Chemical Reference Data,1988,17:513-886.
[31]Neta P,Madhavan V,Zemel H,et al.Rate constants and mechanism of reaction of sulfate radical anion with aromatic compounds[J].Journal of the American Chemical Society,1977,99:163-64.
[32]Hu L,Chen W,Xie X,et al.Symmetrical Mn O2-carbon nanotubetextile nanostructures for wearable pseudo capacitors with high mass loading[J].Acs Nano,2011,5(11):8904-8913.
[33]Saputra E,Muhammad S,Sun H,et al.A comparative study of spinel structured Mn3O4,Co3O4 and Fe3O4 nanoparticles in catalytic oxidation of phenolic contaminants in aqueous solutions[J].Journal of Colloid and Interface Science,2013,407(10):467-473.
[34]Dulman V,Cucu-Man S M,Olariu R I,et al.A new heterogeneous catalytic system for decolorization and mineralization of Orange G acid dye based on hydrogen peroxide and a microporous chelating polymer[J].Dyes and Pigments,2012,95(1):79-88.
[35]El-Ghenymy A,Centellas F,Garrido J A,et al.Decolorization and mineralization of Orange G azo dye solutions by anodic oxidation with a boron-doped diamond anode in divided and undivided tank reactors[J].Electrochimica Acta,2014,130:568-576.