Fe_3O_4@离子印迹聚(St-HPMA-DVB)复合材料的合成及其对水中高氯酸盐选择性吸附  

Preparation of Fe_3O_4@ion imprinted poly(St-HPMA-DVB) magnetic composite and its selective adsorption to perchlorate

作　　者：郑雯静 闻自强 孙美娜 沈昊宇[1] 胡美琴[1] ZHENG Wenjing;WEN Ziqiang;SUN Meina;SHEN Haoyu;HU Meiqin(Ningbo Institute of Technology,Zhejiang University,Ningbo 315100,China;Greentown Agricultural Testing Technology Co.Ltd,Hangzhou 310052,China)

机构地区：[1]浙江大学宁波理工学院,宁波315100 [2]绿城农科检测技术有限公司,杭州310052

出　　处：《复合材料学报》2019年第1期234-244,共11页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(51608479;81502421);浙江省自然科学基金(LY14B04003);宁波市自然科学基金(2018A610206);国家级大学生创新创业训练计划项目(201713022009);宁波市新苗计划项目(甬教基2016-415)

摘　　要：采用超声协助悬浮聚合法以高氯酸根(ClO-4)为模板制备了Fe_3O_4@离子印迹聚(苯乙烯-3-(2-氨基三乙基四胺)-2-甲基丙烯酸羟丙酯-二乙烯苯)(Fe_3O_4@IIP(St-HPMA-DVB))磁性复合材料,通过TEM、振动样品磁强计(VSM)、TGA、XRD、元素分析(EA)、FTIR等对其进行表征,考察了交联剂DVB用量对材料结构与性能的影响。结果表明:合成的Fe_3O_4@IIP(St-HPMA-DVB)磁性复合材料平均粒径为500～2 000nm,随DVB用量的增加而增大;磁化强度为9.77～12.78emu/g,随DVB用量的增加而减小;DVB的加入有利于Fe_3O_4@IIP(StHPMA-DVB)磁性复合材料的离子印迹空腔的形成和稳定。考察了不同溶液pH值、ClO-4的初始浓度、吸附时间等条件下Fe_3O_4@IIP(St-HPMA-DVB)吸附水中ClO-4的性能,发现溶液pH值能显著影响Fe_3O_4@IIP(St-HPMA-DVB)磁性复合材料对ClO-4的吸附效果,pH为3.0时效果最佳;不同DVB用量Fe_3O_4@IIP(St-HPMADVB)磁性复合材料对ClO-4的吸附量和选择性有影响,当DVB用量为0.5g时,Fe_3O_4@IIP(St-HPMA-DVB)磁性复合材料的吸附量和选择性最佳;吸附机制以离子交换和静电引力为主。等温吸附线符合Langmuir模型,Fe_3O_4@IIP(St-HPMA-DVB)磁性复合材料的饱和吸附量(qm,c=76.9～111.1mg/g)高于非离子印迹材料Fe_3O_4@非离子印迹聚(NIP)(St-HPMA-DVB)磁性复合材料(qm,c=62.5mg/g)。吸附过程可在10min内达到平衡,符合准二级动力学模型;Fe_3O_4@IIP(St-HPMA-DVB)磁性复合材料能高选择性地有效吸附水中ClO-4,对ClO-4的印迹因子α为1.8,对几种常见共存离子的选择性因子β>5.8,是潜在的高选择性吸附和回收ClO-4的功能材料。A Fe3O4@ion imprinted poly(Styrene-3-(2-amino triethylenetetramine)-2-hydroxypropyl methacrylatedivinylbenzene)(Fe3O4@IIP(St-HPMA-DVB))magnetic composite was synthesized via ultrasonic assisted suspension polymerization with perchlorate(ClO-4)as the ion imprinting template.The Fe3O4@IIP(St-HPMA-DVB)magnetic composite was characterized by TEM,vibrating sample magnetometer(VSM),TGA,XRD,elemental analysis(EA).The effect of the usage amount of crosslinking agent DVB while preparation on the structure and performance of Fe3O4 @IIP(St-HPMA-DVB)magnetic composite was investigated.The results show that the Fe3O4@IIP(St-HPMA-DVB)magnetic composite has an average size of 500-2 000 nm,which increases with the increase of the amount of DVB.The saturation magnetization intensity is 9.77-12.78 emu/g,which decreases withthe increase of the amount of DVB.The addition of DVB is beneficial to the formation and stability of the ion imprinted cavity of Fe3O4@IIP(St-HPMA-DVB)magnetic composite.The effects of solution pH value,initial concentration of ClO-4,and adsorption time on the adsorption properties of ClO-4 in aqueous solutions were investigated.The results show that the adsorption capability is affected significantly by solution pH value and reaches the maximum at pH=3.0.The best adsorption capacity and selectivity of Fe3O4@IIP(St-HPMA-DVB)magnetic composite to ClO-4 can be obtained when the usage amount of DVB is 0.5 g for synthesis.The adsorption mechanisms may be including both ion exchange and electrostatic interaction.The isothermal adsorption curves mainly obey the Langmuir mode with the maximum adsorption capacity(qm,c=76.9-111.1 mg/g)much higher than that of none-ion imprinted polymer magnetic material Fe3O4@non-ion imprinted poly(NIP)(St-HPMA-DVB)magnetic composite(qm,c=62.5 mg/g).The adsorption kinetic studies show that the adsorption processes reach the equilibrium within10 min and the kinetic data are well fitted to the pseudo-second-order model.There is almost no interference by the coexisting components in water

关 键 词：离子印迹聚合物 纳米FE3O4 磁性复合材料 高氯酸根(ClO4^-) 选择性吸附 

分 类 号：TB332[一般工业技术—材料科学与工程]