表面接枝聚合物磁性硅球的合成及对Pb~（2+）的去除
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摘要
重金属对人体的危害十分明显,当人体内重金属累积到一定程度将会产生各种病变。高效去除环境中的重金属的新材料一直是国内外研究的热点。磁性纳米Fe_3O_4比表面积大、磁感应强、表面易引入多种螯合重金属离子的化学官能团,因此可以改性成为一种理想的吸附材料,使其具有高的吸附重金属离子特性的同时,还便于在外界磁场中进行固液分离,并重复使用。本文研究了强磁性Fe_3O_4微球(MNP)以及核壳式磁性二氧化硅微球(MS)的合成,并采用溶液聚合法将含有螯合官能基IDA的乙烯基单体(GMA-IDA)接枝聚合在MS表面,得到新型磁性硅球吸附剂PMS,同时对PMS和MS吸附重金属离子的特性进行了比较,主要结果如下:
1.采用溶剂热还原法制备了高磁性Fe_3O_4微球,并以其为内核,TEOS为硅源,采用溶胶-凝胶法合成了磁性硅球(MS)。在此基础上将GMA-IDA单体接枝聚合至MS表面得到PMS,并用IR, SEM, VSM及TG等对MS及PMS进行了表征。结果显示MS为单分散球形,饱和磁化率为63.5 emu/g,PMS的聚合物接枝率为46.5%,饱和磁化率为28.4 emu/g ,具有超顺磁性。
2.研究了MS和PMS对重金属铅离子的吸附作用,结果表明:PMS及MS对重金属的吸附去除效率随pH值的增大而增大,PMS在酸性介质中对Pb~(2+)的吸附去除性能大大优于MS,在pH =3或小于3时MS对Pb~(2+)基本没有吸附,而PMS在pH=3时对Pb~(2+)吸附去除率达到80%以上。MS和PMS对铅离子的吸附均符合Langmuir等温吸附,MS和PMS的最大吸附量q*分别为8.94 mg/g与54.35 mg/g。PMS对Pb~(2+)的吸附平衡在5 min内达到,而MS则需要5 h以上。在同样条件下,PMS的重复使用性能也优于MS。
Lots of research have focused on development of new magnetic absorbents for removal of heavy metals from enviroment due to its fast and easy separation from solution using an external magnetic field in recent years In this paper, mono-dispersed magnetic core-shell silic microsphere (MS) was prepared, and then abundant chelator groups (IDA) were grafted on MS by a modified solvent polymerization of GMA-IDA monomer. A novel magnetic absorbent named PMS full of chelators was prepared and characterized, and its application in removal of heavy metal ions was further investigated:
1. MS was prepared in sol-gel method using high magnetic Fe_3O_4 microsphere synthesized by solvent reduction method as core and SiO_2 as shell .and then PMS was prepared in graft polymerization of GMA-IDA monomer with MS. The structures and properties of MS and PMS were characterized by IR,SEM,VSM and TG.. The results showed that MS was mono-dispersed microsphere, and the polymer-grafted ratio of PMS was 46.5%. Both MS and PMS were super-paramagnetism with saturation magnetization of 63.5 and 28.4 emu/g respectively at room temperature.
2. The adsorption properties of PMS and MS to heavy metals especially for Pb~(2+) were investigated. The results indicated that PMS was much better than MS in absorption of Pb~(2+). MS had nearly no adsorption ability when the pH values of the solutions were less than 3, however the removal ratio of PMS was above 80%. The absorption equilibrium for PMS absorption of Pb~(2+)achieved was within 5 min, while for MS was more than 5h. Both absorption pattern of Pb~(2+)onto MS and PMS highly fitted Langmuir adsorption isotherm equation. The maxium adsorption capacity of MS and PMS for Pb~(2+) was 8.94 and 54.35 mg/g, respectively.
1.采用溶剂热还原法制备了高磁性Fe_3O_4微球,并以其为内核,TEOS为硅源,采用溶胶-凝胶法合成了磁性硅球(MS)。在此基础上将GMA-IDA单体接枝聚合至MS表面得到PMS,并用IR, SEM, VSM及TG等对MS及PMS进行了表征。结果显示MS为单分散球形,饱和磁化率为63.5 emu/g,PMS的聚合物接枝率为46.5%,饱和磁化率为28.4 emu/g ,具有超顺磁性。
2.研究了MS和PMS对重金属铅离子的吸附作用,结果表明:PMS及MS对重金属的吸附去除效率随pH值的增大而增大,PMS在酸性介质中对Pb~(2+)的吸附去除性能大大优于MS,在pH =3或小于3时MS对Pb~(2+)基本没有吸附,而PMS在pH=3时对Pb~(2+)吸附去除率达到80%以上。MS和PMS对铅离子的吸附均符合Langmuir等温吸附,MS和PMS的最大吸附量q*分别为8.94 mg/g与54.35 mg/g。PMS对Pb~(2+)的吸附平衡在5 min内达到,而MS则需要5 h以上。在同样条件下,PMS的重复使用性能也优于MS。
Lots of research have focused on development of new magnetic absorbents for removal of heavy metals from enviroment due to its fast and easy separation from solution using an external magnetic field in recent years In this paper, mono-dispersed magnetic core-shell silic microsphere (MS) was prepared, and then abundant chelator groups (IDA) were grafted on MS by a modified solvent polymerization of GMA-IDA monomer. A novel magnetic absorbent named PMS full of chelators was prepared and characterized, and its application in removal of heavy metal ions was further investigated:
1. MS was prepared in sol-gel method using high magnetic Fe_3O_4 microsphere synthesized by solvent reduction method as core and SiO_2 as shell .and then PMS was prepared in graft polymerization of GMA-IDA monomer with MS. The structures and properties of MS and PMS were characterized by IR,SEM,VSM and TG.. The results showed that MS was mono-dispersed microsphere, and the polymer-grafted ratio of PMS was 46.5%. Both MS and PMS were super-paramagnetism with saturation magnetization of 63.5 and 28.4 emu/g respectively at room temperature.
2. The adsorption properties of PMS and MS to heavy metals especially for Pb~(2+) were investigated. The results indicated that PMS was much better than MS in absorption of Pb~(2+). MS had nearly no adsorption ability when the pH values of the solutions were less than 3, however the removal ratio of PMS was above 80%. The absorption equilibrium for PMS absorption of Pb~(2+)achieved was within 5 min, while for MS was more than 5h. Both absorption pattern of Pb~(2+)onto MS and PMS highly fitted Langmuir adsorption isotherm equation. The maxium adsorption capacity of MS and PMS for Pb~(2+) was 8.94 and 54.35 mg/g, respectively.
引文
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[4]林本兰,沈晓冬,崔升.液相共沉淀法制备四氧化三铁纳米粉.无机盐工业[J],2005,37(3):24.
[5]李发伸,王涛,王颖.H2O2氧化法制备Fe3O4纳米颗粒及与共沉淀法制备该样品的比较.物理学报[J],2005,54(7):3100.
[6] Qu SC,Yang HB,Ren DW et al.Magnetite Nanoparticles Prepared by Precipitation from Partially Reduced Ferric Chloride Aqueous Solutions.J.Colloid Interface Sci [J],1999,215:190.
[7]何秋星,杨华,陈权启等.微乳化法制备纳米磁性Fe3O4微粒工艺条件研究.磁性材料及器件[J],2003,34(2):9.
[8]成国祥,张仁柏,万怡灶等.反相胶束微反应器的特征及Fe3O4纳米微粒的制备.兵器材料科学与工程[J],1998,21(6):27.
[9] Li Z, Sun Q, Gao MY.Preparation of Water-Soluble Magnetite Nanocrystals from Hydrated Ferric Salts in 2-Pyrrolidone: Mechanism Leading to Fe3O4. Angew.Chem Int.Ed[J] ,2005,44:l23.
[10]陈捷,薛博,白姝.新型磁性亲和载体的制备及其对溶菌酶的吸附.天津大学学报[J],2001,34(1):l03.
[11] Diamandescu L , Mihaila-Tarabasanu V, Teodorescu D et al.Hydrothermal Synthesis and Structural Characterization of some Substituted Magnetites.Mater Lett [J] ,1998,37:340.
[12] Deng H, Li XL, Peng Q et al.Monodisperse Magnetic Single-Crystal Ferrite Microspheres.Angew.Chem.Int.Ed [J] ,2005, 44:2782.
[13] Lu AH, Salabas EL, Ferdi S. Magnetic Nanoparticles Synthesis, Protection Functionalization, and Application.Angew.Chem.Int.Ed[J] ,2007, 46:1222.
[14] Michaela K, Andre A, Christian G et al.Silica Coating on Colloidal Maghemite Particles.J.Colloid Interface Sci[J] ,1999, 220:357.
[15] ZhangL,GeorgiaCP,RonaldF etal.Novel T-Fe2O3/SiO2 Magnetic Nanocomposites Via Sol-Gel Matrix-Mediated Synthesis. Nanostruct Mater[J] ,1997, 9:185.
[16] Bruce IJ, James T, Michael T et al.Synthesis, Characterisation and Application of Silica-Magnetite Nanocomposites.J.Magn.Magn.Mater [J] ,2004, 284:145.
[17] Deng YH, Wang CC, Hu JH et al.Investigation of Formation of Silica-coated Magnetite Nanoparticles Via Sol–Gel Approach.Colloids Surf A [J] ,2005, 262:87.
[18] Xu H, Tong NH,Cui LL et al.Preparation of Hydrophilic Magnetic Nanospheres with High Saturation Magnetization.J.Magn.Magn.Mater [J] ,2007, 311:125.
[19] Teruoki T,Takatlshii H,Kanta M et al.NoveL Synthesis of Silica-coated Ferrite Nanoparticles Prepared Using Water-in Oil Microemulsion.J.Am.Ceram Soc[J] ,2002, 85(9):2188.
[20] He R, You XG, Shao J et al.Core/Shell Fluorescent Magnetic Silica-Coated Composite Nanoparticles for Bioconjugation.Nano technol [J] ,2007, 18:1.
[21] Huang CZ, Hu B . Silica-Coated Magnetic Nanoparticles Modified withγ-Mercaptopropyltrimethoxysilane for Fast and Selective Solid phase Extraction of Trace Amounts of Cd, Cu, Hg, and Pb in Environmentaland Biological Samples Prior to theirdetermination ByInductively Coupled Plasma Mass Spectrometry.spectrometry.Spectrochimica Acta Part B [J] ,2008,63:437.
[22]贺全国,吴伟,杨云等.表面巯基化修饰的磁性Fe3O4纳米粒子合成与表征.精细化工中间体[J] ,2007,37(2):64.
[23]谭家驹,张阳德,冯彦林等.一种新型生物一磁双重靶向纳米材料的制备.中国医学工程[J] ,2007,15(5):387.
[24]贺全国,吴伟,林琳.表面氨基化磁性Fe3O4纳米粒子合成与表征.南华大学学报[J] ,2007,21(1):20.
[25] Li Y, Yan B, Deng CH et al.Efficient on-chip Proteolysis System based on Functionalized Magnetic Silica Microspheres.Proteomics [J] ,2007, (7):2330.
[26]肖旭贤,何琼琼,覃罡等.新型氨基化磁性纳米粒子的合成.应用化工[J] ,2007,36(7):642.
[27] Xu XQ, Deng CH, Gao MX et al.Synthesis of Magnetic Microspheres with Immobilized Metal Ions for Enrichment and Direct Determination of Phosphopeptides byMatrix-Assisted Laser Desorption Ionization Mass Spectrometry.Adv. Mater[J] ,2006,18:328.
[28] Ma ZY ,Liu XQ, Guan YP et al.Synthesis of Magnetic Silica Nanospheres With Metal Ligandsand Application in Affinity Separation of Proteins.Colloids Surf A [J] ,2006,275:87.
[29] Zeng L, Luo KK, Gong YF.Preparation and Characterization of Dendritic Composite Magneticparticles As a Novel Enzyme Immobilization Carrier.J.Mol.Catal.B Enzym [J] ,2006,38:24.
[30] Chang YC, Chen DH.Preparation and Adsorption Properties of Monodisperse Chitosan-bound Fe3O4 Magnetic Nanoparticles for Removal of Cu(II) Ions.J.Colloid Interface Sci [J] ,2005,283:446.
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