离子印迹共价有机骨架材料对放射性锝的替代物——铼的吸附及应用  

Application of Ion Imprinted Covalent Organic Framework in the Adsorption of Rhenium as a Substitute for Technetium

作　　者：何嘉铧 刘洋洋 朱德荣 刘嘉伟 李尹铮熙 崔安琪 叶俊彬 邬晓忆 孙慧[1,3] HE Jia-hua;LIU Yang-yang;ZHU De-rong;LIU Jia-wei;LI YIN Zheng-xi;CUI An-qi;YE Jun-bin;WU Xiao-yi;SUN Hui(School of Environmental Science&Engineer,Guangzhou University,Guangzhou 510006,China;School of Pharmacy,Guangdong Medical University,Dongguan 523808,China;Guangdong Provincial Key Laboratory of Radionuclides Pollution Control and Resources,Guangzhou 510006,China)

机构地区：[1]广州大学环境科学与工程学院,广东广州510006 [2]广东医科大学药学院,广东东莞523808 [3]广东省放射性核素污染控制以及资源化重点实验室,广东广州510006

出　　处：《分析测试学报》2022年第2期156-163,共8页Journal of Instrumental Analysis

基　　金：国家自然科学基金项目(21876033)。

摘　　要：该文以高铼酸盐作为高锝酸盐的非放射性结构替代物,结合离子印迹技术的特异性、共价有机骨架(COF)材料的多孔性和酸/热稳定性,通过自由基聚合和季胺化反应,制备出表面离子印迹共价有机骨架(IICOF)材料,并将其应用于实际环境样品中高铼酸根离子的高效捕获。首先利用1,4-二醛基-2,5-二乙烯基苯与1,3,5-三(4-氨苯基)苯为构筑基元,通过微波辅助合成出乙烯基功能化的COF-V。然后以N-乙烯基咪唑和4-氯甲基苯乙烯作为功能单体产生带正电的结合位点,通过与模板离子(高铼酸根)的静电作用以及自由基聚合反应在COF-V表面制备出IICOF。考察了吸附剂用量、吸附时间、pH值、温度、初始浓度、共存离子等对IICOF吸附性能的影响。IICOF在<2 min即可达到吸附平衡状态,吸附热力学研究表明其对高铼酸根离子的吸附是一个放热的自发过程,在动力学上遵循准二级模型。在298.15 K时,最大吸附容量为416.67 mg/g。与非印迹复合材料相比,IICOF表现出更高的选择性、更快的动力学和更大的吸附容量。在珠江水以及尾矿渗滤液的加标吸附实验中,吸附效率分别在87%及98%以上,证实了IICOF能够在现实环境中有效去除高铼酸根离子。该技术为环境中高锝酸根的有效吸附、分离提取以及资源回收提供了一条新途径。Technetium-99 has β-radioactivity and a relatively long half-life. With perrhenate as the non-radioactive structural substitute for pertechnetate,an ion imprinted covalent organic frameworks(IICOFs)were prepared in this paper.Owing to the high specific surface area of COF and the selectivity of ion imprinting technology,the prepared IICOFs were applied successfully to the rapid adsorption and extraction of perrhenate anions in real water samples.Firstly,the vinyl functionalized COF-V was obtained, based on the reaction between 1,4-dialdehyde-2,5-divinylbenzene(Dva)and 1,3,5-tris(4-aminophenyl)benzene(Tab)under the microwave assistance. And then,with N-vinylimidazole(VI)and 4-chloromethylstyrene(4-VBC)as the functional monomers,the positively charged binding sites were achieved on the COF-V.Finally,the IICOFs were synthesized through the electrostatic action and radical polymerization.Meanwhile,effects of pH value,adsorption time,temperature,adsorption dose and initial concentration on the adsorption performance of the IICOFs were investigated,and the specific recognition of IICOFs was explored through interference experiments.The adsorption equilibrium could be achieved within 2 min.The study of adsorption thermodynamics showed that the adsorption for perrhenate anions was a spontaneous exothermic process,following a pseudo-second order model in kinetics.At 298. 15 K,the maximum adsorption capacity was calculated to be 416. 67 mg/g according to the Langmuir model.Compared with the non imprinted composites,IICOFs exhibited a higher selectivity,a faster kinetics and a larger adsorption capacity.For the Pearl River water and the tailings leachate water samples that were spiked with perrhenate anion of 2. 0 × 10;mol/L,the adsorption efficiencies reached 87%and 98%,respectively,indicating that the IICOFs could be used for the effective removal of perrhenate anion in real environment.This technique provides a new way for the effective adsorption,separation and extraction of pertechnetate,as well as the recycle of per

关 键 词：铼 共价有机骨架 离子印迹 锝 放射性 

分 类 号：O657.3[理学—分析化学] O615.11[理学—化学]