基于MCM-41分子筛表面的镱离子印迹聚合物的制备及其性能
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摘要
运用离子印迹技术,以3-氯丙基三乙氧基硅烷为锚定剂,将功能单体直链聚乙烯亚胺(PEI)接枝在MCM-41分子筛表面,选择镱离子作为模板离子,以环氧氯丙烷交联制备出基于MCM-41表面的镱离子印迹聚合物Yb(Ⅲ)-ⅡP-PEI/MCM-41,并以同样的方法制备非离子印迹聚合物(NIP-PEI/MCM-41)。利用傅里叶变换红外光谱仪和扫描电子显微镜等技术手段对Yb~(3+)印迹聚合物进行表征,采用静态吸附法确定了Yb(Ⅲ)-ⅡP-PEI/MCM-41对Yb~(3+)的最佳吸附条件及选择性吸附性能。结果表明,Yb(Ⅲ)-ⅡP-PEI/MCM-41和NIP-PEI/MCM-41的最大吸附量分别为229. 93和99. 27 mg/g;印迹材料对Yb~(3+)的吸附符合Langmuir模型;吸附平衡在40 min的时候基本可以达到,可以利用准二级动力学模型来描述其吸附过程; Yb(Ⅲ)-ⅡP-PEI/MCM-41对Yb~(3+)具有较强的选择性,同时也具有很好的重复使用性能。成功地将MCM-41和离子印迹聚合物的优点结合起来,制备出一种对稀土Yb离子既有高吸附量又有高选择性的吸附材料,为进一步将其应用在处理实际废水,分离回收低浓度稀土废水中的稀土元素等方面打下了基础。
By ion-imprinting technology,3-chloropropyltriethoxysilane as anchor,functional monomer linear polyethyleneimine( PEI) was grafted on the surface of MCM-41 molecular sieve. With Yb ions as template ions,and epichlorohydrin as cross-linking agent,a Yb( Ⅲ) ion-imprinted polymer( ⅡP),Yb( Ⅲ)-ⅡP-PEI/MCM-41,was prepared on MCM-41 surface. A non-ion-imprinted polymer( NIP-PEI/MCM-41) was prepared via similar process. Yb~(3+)imprinted polymer was characterized by infrared spectroscopy and scanning electron microscopy. The optimal adsorption conditions and selective adsorption performance of Yb( Ⅲ)-ⅡP-PEI/MCM-41 for Yb~(3+)were determined by static adsorption method. The maximum adsorption capacities of Yb( Ⅲ)-ⅡP-PEI/MCM-41 and NIP-PEI/MCM-41 are 229. 93 mg/g and 99. 27 mg/g,respectively. The adsorption of Yb~(3+)by the imprinted material is conformed to the Langmuir model; The equilibrium can basically be reached in 40 min,and the adsorption process can be described using the pseudo-second-order kinetic model. Yb( Ⅲ)-ⅡP-PEI/MCM-41 has strong selectivity toward Yb~(3+)and also has good recyclability.This adsorbent with high adsorption capacity and high selectivity for rare earth Yb ions combining the advantages of MCM-41 and ion-imprinted polymer thus-prepared lays the foundation for further application in the separation and recovery of low-concentration earth elements from wastewater.
By ion-imprinting technology,3-chloropropyltriethoxysilane as anchor,functional monomer linear polyethyleneimine( PEI) was grafted on the surface of MCM-41 molecular sieve. With Yb ions as template ions,and epichlorohydrin as cross-linking agent,a Yb( Ⅲ) ion-imprinted polymer( ⅡP),Yb( Ⅲ)-ⅡP-PEI/MCM-41,was prepared on MCM-41 surface. A non-ion-imprinted polymer( NIP-PEI/MCM-41) was prepared via similar process. Yb~(3+)imprinted polymer was characterized by infrared spectroscopy and scanning electron microscopy. The optimal adsorption conditions and selective adsorption performance of Yb( Ⅲ)-ⅡP-PEI/MCM-41 for Yb~(3+)were determined by static adsorption method. The maximum adsorption capacities of Yb( Ⅲ)-ⅡP-PEI/MCM-41 and NIP-PEI/MCM-41 are 229. 93 mg/g and 99. 27 mg/g,respectively. The adsorption of Yb~(3+)by the imprinted material is conformed to the Langmuir model; The equilibrium can basically be reached in 40 min,and the adsorption process can be described using the pseudo-second-order kinetic model. Yb( Ⅲ)-ⅡP-PEI/MCM-41 has strong selectivity toward Yb~(3+)and also has good recyclability.This adsorbent with high adsorption capacity and high selectivity for rare earth Yb ions combining the advantages of MCM-41 and ion-imprinted polymer thus-prepared lays the foundation for further application in the separation and recovery of low-concentration earth elements from wastewater.
引文
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[25]Maneechakr P,Karnjanakom S.Adsorption Behaviour of Fe(Ⅱ)and Cr(Ⅵ)on Activated Carbon:Surface Chemistry,Isotherm,Kinetic and Thermodynamic Studies[J].J Chem Thermodyn,2017,106:104-112.
[26]Badawi M A,Negm N A,Abou Kana M T H,et al.Adsorption of Aluminum and Lead from Wastewater by Chitosan-Tannic Acid Modified Biopolymers:Isotherms,Kinetics,Thermodynamics and Process Mechanism[J].Int J Biol Macromol,2017,99:465-476.
[2]LAI Xiaoqi,YANG Yuanqi,XUE Jun.Preparation and Properties of Iridium(Ⅲ)Ion Imprinted Polymers[J].Acta Chim Sin,2009,67(8):863-868(in Chinese).赖晓绮,杨远奇,薛珺.钇(Ⅲ)离子印迹聚合物的制备及性能研究[J].化学学报,2009,67(8):863-868.
[3]Kala R,Biju V M,Rao T P.Synthesis,Characterization,and Analytical Applications of Erbium(Ⅲ)Ion Imprinted Polymer Particles Prepared viaγ-Irradiation with Different Functional and Crosslinking Monomers[J].Anal Chim Acta,2005,549:51-58.
[4]Kala R,Gladis J M,Rao T P.Preconcentrative Separation of Erbium from Y,Dy,Ho,Tb and Tm by Using Ion Imprinted Polymer Particles via Solid Phase Extraction[J].Anal Chim Acta,2004,518:143-150.
[5]WU Xinhua,SHI Hui,YANG Xiaoyu,et al.Progress in Separation and Enrichment of Trace Metal Ions by Surface Imprinting Technique[J].Guangzhou Chem Ind,2015,3:10-12(in Chinese).吴新华,石慧,阳小宇,等.表面印迹技术分离富集痕量金属离子研究进展[J].广州化工,2015,3:10-12.
[6]Guo J J,Cai J B,Su Q D.Ion Imprinted Polymer Particles of Neodymium:Synthesis,Characterization and Selective Recognition[J].J Rare Earth,2009,(27):22-27.
[7]Yang X L,Zhang J W.Recovery of Rare Earth from Ion-adsorption Rare Earth Ores with a Compound Lixiviant[J].Sep Purif Technol,2015,(142):203-208.
[8]LI Xiancai,TIAN Minglei,CHENG Yuwen,et al.Preparation and Properties of Lanthanum Ion MCM-41 Imprinted Polymer[J].J Nanchang Univ(Eng Tech Edit),2018,40(4):307-310(in Chinese).黎先财,田明磊,程玉雯,等.镧离子MCM-41印迹聚合物的制备及其性能[J].南昌大学学报(工科版),2018,40(4):307-310..
[9]LIU Zhigang,WANG Jiangang,YU Shihua,et al.Preparation of MCM-41 and Its Application in the Sustained Release of Piracetam[J].Chem Ind Technol,2013,6:42-44(in Chinese).刘治刚,王建刚,于世华,等.MCM-41的制备及用于吡拉西坦缓释性能研究[J].化工科技,2013,6:42-44.
[10]WANG Huanlong.Synthesis and Properties of MCM-41 Molecular Sieve[D].Inner Mongolia University Science Technology,2012(in Chinese).王欢龙.MCM-41分子筛的合成及性能的研究[D].内蒙古科技大学,2012.
[11]Wang W,Li Y,Gao B,et al.Effective Removal of Fe(Ⅱ)Impurity from Rare Earth Solution Using Surface Imprinted Polymer[J].Chem Eng Res Des,2013,91:2759-2764.
[12]An F,Gao B,Feng X,et al.Adsorption and Recognizing Ability of Molecular Imprinted Polymer MIP-PEI/Si O2Towards Phenol[J].J Hazard Mater,2008,157(2):286-292.
[13]Sarri S,Misaelides P,Zamboulis D,et al.Rhenium(Ⅶ)and Technetium(Ⅶ)Separation from Aqueous Solutions Using a Polyethylenimine-Epichlorohydrin Resin[J].J Radioanal Nucl Chem,2015,307(1):681-689.
[14]Liao S,Zhang W,Wei L,et al.Adsorption Characteristics,Recognition Properties,and Preliminary Application of Nordihydroguaiaretic Acid Molecularly Imprinted Polymers Prepared by Sol-gel Surface Imprinting Technology[J].Appl Surf Sci,2016,364:579-588.
[15]Fasihi J,Shamsipur M,Khanchi A,et al.Imprinted Polymer Grafted from Silica Particles for On-line Trace Enrichment and ICP OES Determination of Uranyl Ion[J].Microchem J,2015,126:316-321.
[16]An F,Gao B,Huang X,et al.Selectively Removal of Al(Ⅲ)from Pr(Ⅲ)and Nd(Ⅲ)Rare Earth Solution Using Surface Imprinted Polymer[J].React Funct Polym,2013,73(1):60-65.
[17]Wu H,Qiu J.Adsorption Performance for Bromine Ion Using Bromide Ion-Lanthanum Nitrate Modified Chitosan Imprinted Polymer[J].Anal Methods-UK,2014,6(6):1890-1896.
[18]Li C X,Pan J M,Gao J,et al.An Ion-imprinted Polymer Supported by Attapulgite with a Chitosan Incorporated Sol-gel Process for Selective Separation of Ce(Ⅲ)[J].Chinese Chem Lett,2009,20(8):985-989.
[19]CHEN Rui.Preparation of SBA-15 Surface Ion-Imprinted Polymer and Its Selective Separation of Medium and Low-level Radioactive Metals[D].Jiangsu University of Science and Technology,2014(in Chinese).陈瑞.SBA-15表面离子印迹聚合物的制备及其对中低放射性金属选择性分离性能研究[D].江苏科技大学,2014.
[20]Gao B,Zhang Y,Xu Y,et al.Study on Recognition and Separation of Rare Earth Ions at Picometre Scale by Using Efficient Ion-Surface Imprinted Polymer Materials[J].Hydrometallurgy,2014,150:83-91.
[21]Kameda T,Umetsu M,Kumagai S,et al.New Principals on the Adsorption of Alkyl Compound by Mg-Al Oxide:Adsorption Kinetics and Equilibrium Studies[J].Colloid Surf A,2017,513:348-354.
[22]Kameda T,Shinmyou T,Yoshioka T.Kinetics and Equilibrium Studies on the Uptake of Nd3+by Zn-Al Layered Double Hydroxide Intercalated with Triethylenetetramine-Hexaacetic Acid[J].Mater Chem Phys,2017,191:96-98.
[23]Adebisi G A,Alaba P A.Equilibrium,Kinetic,and Thermodynamic Studies of Lead Ion and Zinc Ion Adsorption from Aqueous Solution onto Activated Carbon Prepared from Palm Oil Mill Effluent[J].J Clean Prod,2017,148:958-968.
[24]Asuquo E,Martin A,Nzerem P,et al.Adsorption of Cd(Ⅱ)and Pb(Ⅱ)Ions from Aqueous Solutions Using Mesoporous Activated Carbon Adsorbent:Equilibrium,Kinetics and Characterisation Studies[J].J Environ Chem Eng,2017,5(1):679-698.
[25]Maneechakr P,Karnjanakom S.Adsorption Behaviour of Fe(Ⅱ)and Cr(Ⅵ)on Activated Carbon:Surface Chemistry,Isotherm,Kinetic and Thermodynamic Studies[J].J Chem Thermodyn,2017,106:104-112.
[26]Badawi M A,Negm N A,Abou Kana M T H,et al.Adsorption of Aluminum and Lead from Wastewater by Chitosan-Tannic Acid Modified Biopolymers:Isotherms,Kinetics,Thermodynamics and Process Mechanism[J].Int J Biol Macromol,2017,99:465-476.