钍（Ⅳ）离子印迹聚合物的制备及吸附性能研究
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摘要
钍是一种赋存在自然界中的天然放射性元素,在核能方面具有广阔的应用前景,未来可有效地补充铀资源的不足。但钍像其它重金属一样具有化学毒性,钍及其化合物会造成许多环境问题,因此建立可靠的方法对其在环境和地质样品中进行准确的测定和回收是非常重要的。然而由于钍在实际环境样品含量很低、基体干扰严重,常常导致其检测结果的不准确。对样品进行分离富集,是解决这一问题的关键。固相萃取(SPE)是当今最流行的样品预处理方法,但传统的固相萃取材料对于目标离子的选择性差,最新的离子印迹技术可以实现对目标离子的高选择性萃取。离子印迹材料的显著特点是在高温高压等苛刻环境下性能稳定的同时,表现出对模板的高度选择性和特异识别能力。使用此类材料对痕量目标物进行固相萃取预富集以及从复杂基体和其他共存元素中选择性分离目标物,可以有效净化目标物的存在环境,这是普通固相萃取材料所无法实现的。因此,本论文主要研究是基于离子印迹技术的钍(IV)离子印迹聚合物的制备及其固相萃取性能研究。主要包括以下三个方面的工作:
1.对钍的概况及其分离富集方法、分子(离子)印迹技术的基本原理、分子(离子)印迹聚合物的制备方法进行了较为全面的综述,概述了IIPs-SPE领域的相关研究进展。
2.合成了一种新的功能单体,1-苯基-3甲硫基-4腈基-5-丙烯酸酰胺基-吡唑(PMTCAACP),通过氨基和马来酸酐反应将双键引入硅胶表面,制备了表面接枝钍(IV)离子印迹硅胶吸附剂。详细地研究了该吸附剂吸附钍(IV)的各种实验条件、动力学性质、热力学性质和吸附机理。该印迹吸附剂对钍(IV)具有高吸附选择性和亲和力。其最大的静态吸附容量和动态吸附容量分别为64.8 mg/g和37.4 mg/g。Th(IV)/U(VI),Th(IV)/Ce(III),Th(IV)/La(III)和Th(IV)/Zr(IV)的相对选择性系数分别为72.9,89.6,93.8和137.2。建立了用该印迹材料作为固相萃取吸附剂与分光光度法相结合在测定钍(IV)的新方法,该方法的相对标准偏差为2.47%(n=7),富集因子为20.2,检出限为0.43μg/L,并将该方法用于实际样品钍的富集和测定取得了满意的结果。
3.采用硅胶表面接枝技术,以甲基丙烯酸(MAA)为功能单体,制备了一种新型的钍(IV)离子印迹聚合物。研究了该吸附剂对钍(IV)的分离富集特性。该印迹微粒对钍(IV)有很好的识别性和相对快速的动力学过程。其最大的静态吸附容量和动态吸附容量分别为33.2 mg/g和17.3 mg/g。Th(IV)/U(VI),Th(IV)/Ce(III),Th(IV)/La(III)和Th(IV)/Zr(IV)的相对选择性系数分别为58.8, 107, 106.4和151.7。用该印迹材料作为固相萃取吸附剂与分光光度法相结合在最佳实验条件下测定钍(IV)时,其相对标准偏差为2.1%(n=7),富集因子为14.6,检出限为0.59μg/L,并将该方法用于实际水样品钍的富集和测定取得了满意的结果。
Thorium, which is an important radioactive element widely distributed over the earth's crust, can provide supplement to the insuffieient uranium resources effectively in the future, so it has broad prospects for nuclear power. However, thorium not only has chemical toxicity like other heavy metals do, but aslo is hazardous causing many environmental problems. Therefore, the development of the reliable methods for the determination and recovery of thorium in environmental and geological samples is of a particular significance. Direct determination of thorium is still difficult, owing to thorium's trace concentration in nature and presence of interferential matrix. At present, one of the methods, to solve the problem, is using a sample pretreatment teehnique including separation and preconcentration. Solid-phase extraction(SPE) is today the most popular method of the sample preparation. Unfortunately, the common materials of SPE are usually having poor selectivity for separation of coexistent metal ions, which can be solved by ion-imprinting technique. An especially appealing feature of the imprinted polymers is their potential to have the affinity and selectivity analogous to antibodies, while retaining several benefits including stability in harsh environments such as high temperatures and pressures. A particularly promising application of ion-imprinted polymers is the SPE preconcentration of analytes present in trace amouts and the separation from other coexisting species or complex matrix, which may lead to selective environmental clean up of analytes, not achievable by the conventional methods. Thereby, this work is focused on the preparation of Th(IV) ion imprinted polymers and the research of the properties of SPE. This dissertation consists of three parts, as follows:
1. A brief overview is given for the profile and the methods of separation and preconcentration of Th(IV), the principle of Molecular(Ion) Imprinting Iechnology, the preparation of Molecular(Ion) Imprinted Polymers, and the studies in the rapidly developing and exciting area of IIPs-SPE.
2. A new pyrazole derivative 1-phenyl-3-methylthio-4-cyano-5-acrylicacid- carbamoyl-pyrazole(PMTCAACP) was synthesized and chosen as a complexing monomer for the preparation of surface-grafted ion-imprinted polymers for selective solid phase extraction of thorium(IV). Polymerizable double bond was introduced to silica gel surface by amidation reaction between NH2 and maleic anhydride. The experimental conditions, kinetics, thermodynamics, and mechanism for the adsorption of Th(IV) on the imprinted polymers were investigated in detail. The obtained ion-imprinted particles for Th(IV) showed excellent selectivity and high affinity. The maximum static and dynamic adsorption capacity of the ion-imprinted polymers (IIPs) for Th(IV) was 64.8 and 37.4 mg/g, respectively. The relative selectivity coefficient values of the imprinted adsorbent for Th(IV)/U(VI), Th(IV)/Ce(III), Th(IV)/La(III), and Th(IV)/Zr(IV) were 72.9, 89.6, 93.8, and 137.2 times greater than non-imprinted matrix, respectively. The enhancement factor of 20.2, the detection limit of 0.43μg/L, and the precision of 2.47% (n=7) of the method under the optimized conditions were obtained. The prepared IIPs were shown to be promising for solid phase extraction coupled with UV-Vis spectrophotometry for determination of trace Th(IV) in real samples.
3. A novel ion-imprinted adsorbent for selective preconcentration of thorium(IV) based on a surface of silica gel was prepared by a surface-grafted technique with methacrylic acid(MAA) as a functional monomer. The property of separation and preconcentration for Th(IV) onto the imprinted polymers was investigated. The obtained imprinted particles for Th(IV) exhibited specific recognition and relatively rapid kinetic process. The maximum static and dynamic adsorption capacity of the ion-imprinted polymers (IIPs) for Th(IV) was 33.2 and 17.3 mg/g, respectively. The relative selectivity coefficients of the imprinted polymers for Th(IV)/U(VI), Th(IV)/Ce(III), Th(IV)/La(III), and Th(IV)/Zr(IV) were 58.8, 107, 106.4, and 151.7, respectively. With a series of samples loading flow rate of 3 mL/min for preconcentration, an enrichment factor of 14.6 and the detection limit of 0.59μg/L were obtained. The relative standard deviation of the method under optimum conditions was 2.1% (n=7). The prepared IIPs were shown to be promising for solid phase extraction coupled with UV-Vis spectrophotometry for determination of trace Th(IV) in real water samples.
1.对钍的概况及其分离富集方法、分子(离子)印迹技术的基本原理、分子(离子)印迹聚合物的制备方法进行了较为全面的综述,概述了IIPs-SPE领域的相关研究进展。
2.合成了一种新的功能单体,1-苯基-3甲硫基-4腈基-5-丙烯酸酰胺基-吡唑(PMTCAACP),通过氨基和马来酸酐反应将双键引入硅胶表面,制备了表面接枝钍(IV)离子印迹硅胶吸附剂。详细地研究了该吸附剂吸附钍(IV)的各种实验条件、动力学性质、热力学性质和吸附机理。该印迹吸附剂对钍(IV)具有高吸附选择性和亲和力。其最大的静态吸附容量和动态吸附容量分别为64.8 mg/g和37.4 mg/g。Th(IV)/U(VI),Th(IV)/Ce(III),Th(IV)/La(III)和Th(IV)/Zr(IV)的相对选择性系数分别为72.9,89.6,93.8和137.2。建立了用该印迹材料作为固相萃取吸附剂与分光光度法相结合在测定钍(IV)的新方法,该方法的相对标准偏差为2.47%(n=7),富集因子为20.2,检出限为0.43μg/L,并将该方法用于实际样品钍的富集和测定取得了满意的结果。
3.采用硅胶表面接枝技术,以甲基丙烯酸(MAA)为功能单体,制备了一种新型的钍(IV)离子印迹聚合物。研究了该吸附剂对钍(IV)的分离富集特性。该印迹微粒对钍(IV)有很好的识别性和相对快速的动力学过程。其最大的静态吸附容量和动态吸附容量分别为33.2 mg/g和17.3 mg/g。Th(IV)/U(VI),Th(IV)/Ce(III),Th(IV)/La(III)和Th(IV)/Zr(IV)的相对选择性系数分别为58.8, 107, 106.4和151.7。用该印迹材料作为固相萃取吸附剂与分光光度法相结合在最佳实验条件下测定钍(IV)时,其相对标准偏差为2.1%(n=7),富集因子为14.6,检出限为0.59μg/L,并将该方法用于实际水样品钍的富集和测定取得了满意的结果。
Thorium, which is an important radioactive element widely distributed over the earth's crust, can provide supplement to the insuffieient uranium resources effectively in the future, so it has broad prospects for nuclear power. However, thorium not only has chemical toxicity like other heavy metals do, but aslo is hazardous causing many environmental problems. Therefore, the development of the reliable methods for the determination and recovery of thorium in environmental and geological samples is of a particular significance. Direct determination of thorium is still difficult, owing to thorium's trace concentration in nature and presence of interferential matrix. At present, one of the methods, to solve the problem, is using a sample pretreatment teehnique including separation and preconcentration. Solid-phase extraction(SPE) is today the most popular method of the sample preparation. Unfortunately, the common materials of SPE are usually having poor selectivity for separation of coexistent metal ions, which can be solved by ion-imprinting technique. An especially appealing feature of the imprinted polymers is their potential to have the affinity and selectivity analogous to antibodies, while retaining several benefits including stability in harsh environments such as high temperatures and pressures. A particularly promising application of ion-imprinted polymers is the SPE preconcentration of analytes present in trace amouts and the separation from other coexisting species or complex matrix, which may lead to selective environmental clean up of analytes, not achievable by the conventional methods. Thereby, this work is focused on the preparation of Th(IV) ion imprinted polymers and the research of the properties of SPE. This dissertation consists of three parts, as follows:
1. A brief overview is given for the profile and the methods of separation and preconcentration of Th(IV), the principle of Molecular(Ion) Imprinting Iechnology, the preparation of Molecular(Ion) Imprinted Polymers, and the studies in the rapidly developing and exciting area of IIPs-SPE.
2. A new pyrazole derivative 1-phenyl-3-methylthio-4-cyano-5-acrylicacid- carbamoyl-pyrazole(PMTCAACP) was synthesized and chosen as a complexing monomer for the preparation of surface-grafted ion-imprinted polymers for selective solid phase extraction of thorium(IV). Polymerizable double bond was introduced to silica gel surface by amidation reaction between NH2 and maleic anhydride. The experimental conditions, kinetics, thermodynamics, and mechanism for the adsorption of Th(IV) on the imprinted polymers were investigated in detail. The obtained ion-imprinted particles for Th(IV) showed excellent selectivity and high affinity. The maximum static and dynamic adsorption capacity of the ion-imprinted polymers (IIPs) for Th(IV) was 64.8 and 37.4 mg/g, respectively. The relative selectivity coefficient values of the imprinted adsorbent for Th(IV)/U(VI), Th(IV)/Ce(III), Th(IV)/La(III), and Th(IV)/Zr(IV) were 72.9, 89.6, 93.8, and 137.2 times greater than non-imprinted matrix, respectively. The enhancement factor of 20.2, the detection limit of 0.43μg/L, and the precision of 2.47% (n=7) of the method under the optimized conditions were obtained. The prepared IIPs were shown to be promising for solid phase extraction coupled with UV-Vis spectrophotometry for determination of trace Th(IV) in real samples.
3. A novel ion-imprinted adsorbent for selective preconcentration of thorium(IV) based on a surface of silica gel was prepared by a surface-grafted technique with methacrylic acid(MAA) as a functional monomer. The property of separation and preconcentration for Th(IV) onto the imprinted polymers was investigated. The obtained imprinted particles for Th(IV) exhibited specific recognition and relatively rapid kinetic process. The maximum static and dynamic adsorption capacity of the ion-imprinted polymers (IIPs) for Th(IV) was 33.2 and 17.3 mg/g, respectively. The relative selectivity coefficients of the imprinted polymers for Th(IV)/U(VI), Th(IV)/Ce(III), Th(IV)/La(III), and Th(IV)/Zr(IV) were 58.8, 107, 106.4, and 151.7, respectively. With a series of samples loading flow rate of 3 mL/min for preconcentration, an enrichment factor of 14.6 and the detection limit of 0.59μg/L were obtained. The relative standard deviation of the method under optimum conditions was 2.1% (n=7). The prepared IIPs were shown to be promising for solid phase extraction coupled with UV-Vis spectrophotometry for determination of trace Th(IV) in real water samples.
引文
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