新型磁性核壳纳米印迹聚合物的制备及其对TBBPA的特异性吸附研究
发布时间：2019-03-09 08:40
【摘要】：四溴双酚A(Tetrabromobisphenol A,TBBPA)是具有双酚A结构的酚类化合物,被视为一种环境污染物和内分泌干扰物,广泛应用于溴化阻燃剂领域,对环境、生态系统以及人类健康造成极大的污染和风险。分子印迹材料(Molecular Imprinted Polymers,MIPs)可选择性吸附特定模板分子,因其高选择性、预定性和适用性,已经在分离领域实现了快速发展。同时,其制备简单,性质稳定,成本低,可以有效抵抗具有与模板分子结构类似的分析物的干扰,并实现从复杂的化学体系中选择性绑定模板分子的目的。与传统印迹相比,表面分子印迹技术因为吸附能力高,传质速率快等优点,更利于目标分子的洗脱与绑定。金属有机框架(Metal-Organic Frameworks,MOFs)是一类新型的多孔材料。一般以过渡态金属为配位中心,与有机配体进行配位聚合形成空间三维网络结构。孔径可调、比表面积大、结构多样性、不饱和的金属配位和表面可修饰等显著优点,使得MOFs获得了广泛的关注,并且已经在各研究领域实现了快速发展。鉴于分子印迹聚合物和金属有机框架材料以及磁性纳米粒子具有的优势,本学位论文旨在研究TBBPA分子印迹的制备方法,设计合成了两种形貌良好、吸附容量高、吸附速率快的新型磁性核壳分子印迹材料,并作为吸附剂去除水体中的TBBPA。主要研究内容是:1.磁性核-壳印迹聚合物的制备及其对TBBPA的特异性吸附在通过热溶剂法制备的Fe_3O_4纳米粒子表面上包覆SiO2作为印迹基体,利用自由基聚合制备印迹聚合物层,获得了特异性吸附TBBPA的磁性核壳Fe_3O_4@SiO2@MIPs,并通过改变功能单体、功能单体与交联剂的比例等因素优化MIP层的制备条件。通过分析所得材料对TBBPA及其结构类似物的回收率来探索其特异性吸附性能,同时研究了材料的吸附动力学、吸附等温线和循环使用性。结果表明所制备的分子印迹复合材料,具有高的活性(最大吸附量为58.67 mg g-1),快的吸附动力学(30 min内达到吸附平衡)和磁性分离(20 s)以及高的选择性、可重复使用性(5次使用后回收率可达89.4%以上)。2.新型磁性核-壳金属有机框架载体上印迹聚合物的制备及其对TBBPA的特异性吸附设计合成了一种新型的金属有机骨架——沸石咪唑酯框架(ZIF-8)为基体的磁性印迹聚合物Fe_3O_4@ZIF-8@MIPs,用于快速和特异性识别水溶液中的TBBPA。实验通过在Fe_3O_4核上涂覆ZIF-8层,于室温下在水溶液中进行。Fe_3O_4@ZIF-8@MIPs显示出良好的单分散性,饱和磁化强度为38.4 emu g-1,比表面积为185.9 m2 g-1,孔体积和孔径分别为0.47 m3 g-1和99.15?。由于ZIF-8表面低配位Zn原子的密度较高,Fe_3O_4@ZIF-8本身对TBBPA的吸附能力以及分子印迹对TBBPA的特异性吸附,综合结果显示Fe_3O_4@ZIF-8@MIPs对TBBPA有良好的吸附能力。此外,Fe_3O_4@ZIF-8@MIPs显示了优异的可回收性,5次使用后回收率达85.0%以上,对TBBPA的最大吸附量为117.6 mg g-1和快吸附动力学(15 min内达到吸附平衡)。
[Abstract]:Tetrabromobisphenol A (Tetrabromobisphenol A) is a phenolic compound with bisphenol A structure. It is regarded as an environmental pollutant and endocrine disruptor and is widely used in the field of brominated flame retardants for environmental protection. Ecosystems and human health pose great pollution and risks. Molecularly imprinted material (Molecular Imprinted Polymers,MIPs) can selectively adsorb specific template molecules. Because of its high selectivity, precharacterization and applicability, it has been developed rapidly in the field of separation. At the same time, it has the advantages of simple preparation, stable properties and low cost, which can effectively resist the interference of analytes similar to the molecular structure of templates, and achieve the purpose of selectively binding template molecules from complex chemical systems. Compared with traditional imprinting, surface molecular imprinting is more favorable for elution and binding of target molecules because of its advantages of high adsorption capacity and fast mass transfer rate. Organometallic frame (Metal-Organic Frameworks,MOFs) is a new kind of porous material. Generally, transitional metals are used as coordination centers to form a three-dimensional network structure by coordination polymerization with organic ligands. Due to its obvious advantages such as adjustable pore size, large specific surface area, structural diversity, unsaturated metal coordination and surface modification, MOFs has attracted extensive attention and has been rapidly developed in various research fields. In view of the advantages of molecularly imprinted polymers, organometallic framework materials and magnetic nanoparticles, the purpose of this dissertation is to study the preparation methods of TBBPA molecular imprinting, and to design and synthesize two kinds of imprinted polymers with good morphology and high adsorption capacity. A novel Magnetic Core-shell Molecular imprinting material with High adsorption rate and used as adsorbent to remove TBBPA. from Water The main contents of this study are: 1. The preparation of magnetic core-shell imprinted polymer and the specific adsorption of TBBPA on the surface of Fe_3O_4 nanoparticles prepared by hot solvent method coated with SiO2 as imprinting matrix, and the preparation of imprinted polymer layer by free radical polymerization. Magnetic core-shell Fe_3O_4@SiO2@MIPs, with specific adsorption of TBBPA was obtained and the preparation conditions of MIP layer were optimized by changing the ratio of functional monomer to cross-linking agent and so on. The specific adsorption properties of TBBPA and its structure analogues were investigated by analyzing the recovery rate of the materials. The adsorption kinetics, adsorption isotherms and recycling of the materials were also studied. The results show that the prepared molecularly imprinted composites have high activity (maximum adsorption capacity is 58.67 mg / g / g), fast adsorption kinetics (adsorption equilibrium within 30 min), magnetic separation (20 s) and high selectivity. Repeatability (recovery rate over 89.4% after 5 times of use). 2. Preparation of imprinted polymer on core-shell metal-organic framework carrier and its specific adsorption to TBBPA. A novel metal-organic framework-zeolite imidazolyl ester framework (ZIF-8)-based magnetic properties was synthesized. Imprinted polymer Fe_3O_4@ZIF-8@MIPs, Rapid and specific recognition of TBBPA. in aqueous solution By coating ZIF-8 layer on Fe_3O_4 nucleus at room temperature in aqueous solution, Fe _ 3O_4@ZIF-8@MIPs shows good monodispersity, and the saturation magnetization is 38.4 emu / g ~ (1), and its saturation magnetization is 38.4 emu 路g ~ (- 1). The specific surface area is 185.9 m ~ 2 g / 1, pore volume and pore size are 0.47 m ~ 3 g / 1 and 99.15 渭 m ~ (- 1), respectively. Because of the high density of low coordinated Zn atoms on the surface of ZIF-8, the adsorption ability of Fe_3O_4@ZIF-8 itself to TBBPA and the specific adsorption of TBBPA by molecular imprinting were studied. The comprehensive results show that Fe_3O_4@ZIF-8@MIPs has good adsorption ability to TBBPA. In addition, Fe_3O_4@ZIF-8@MIPs showed excellent recyclability, the recovery rate was more than 85.0% after 5 times of use, the maximum adsorption capacity of TBBPA was 117.6 mg / g / 1 and the fast adsorption kinetics (the adsorption equilibrium was reached within 15 min).
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.3
[Abstract]:Tetrabromobisphenol A (Tetrabromobisphenol A) is a phenolic compound with bisphenol A structure. It is regarded as an environmental pollutant and endocrine disruptor and is widely used in the field of brominated flame retardants for environmental protection. Ecosystems and human health pose great pollution and risks. Molecularly imprinted material (Molecular Imprinted Polymers,MIPs) can selectively adsorb specific template molecules. Because of its high selectivity, precharacterization and applicability, it has been developed rapidly in the field of separation. At the same time, it has the advantages of simple preparation, stable properties and low cost, which can effectively resist the interference of analytes similar to the molecular structure of templates, and achieve the purpose of selectively binding template molecules from complex chemical systems. Compared with traditional imprinting, surface molecular imprinting is more favorable for elution and binding of target molecules because of its advantages of high adsorption capacity and fast mass transfer rate. Organometallic frame (Metal-Organic Frameworks,MOFs) is a new kind of porous material. Generally, transitional metals are used as coordination centers to form a three-dimensional network structure by coordination polymerization with organic ligands. Due to its obvious advantages such as adjustable pore size, large specific surface area, structural diversity, unsaturated metal coordination and surface modification, MOFs has attracted extensive attention and has been rapidly developed in various research fields. In view of the advantages of molecularly imprinted polymers, organometallic framework materials and magnetic nanoparticles, the purpose of this dissertation is to study the preparation methods of TBBPA molecular imprinting, and to design and synthesize two kinds of imprinted polymers with good morphology and high adsorption capacity. A novel Magnetic Core-shell Molecular imprinting material with High adsorption rate and used as adsorbent to remove TBBPA. from Water The main contents of this study are: 1. The preparation of magnetic core-shell imprinted polymer and the specific adsorption of TBBPA on the surface of Fe_3O_4 nanoparticles prepared by hot solvent method coated with SiO2 as imprinting matrix, and the preparation of imprinted polymer layer by free radical polymerization. Magnetic core-shell Fe_3O_4@SiO2@MIPs, with specific adsorption of TBBPA was obtained and the preparation conditions of MIP layer were optimized by changing the ratio of functional monomer to cross-linking agent and so on. The specific adsorption properties of TBBPA and its structure analogues were investigated by analyzing the recovery rate of the materials. The adsorption kinetics, adsorption isotherms and recycling of the materials were also studied. The results show that the prepared molecularly imprinted composites have high activity (maximum adsorption capacity is 58.67 mg / g / g), fast adsorption kinetics (adsorption equilibrium within 30 min), magnetic separation (20 s) and high selectivity. Repeatability (recovery rate over 89.4% after 5 times of use). 2. Preparation of imprinted polymer on core-shell metal-organic framework carrier and its specific adsorption to TBBPA. A novel metal-organic framework-zeolite imidazolyl ester framework (ZIF-8)-based magnetic properties was synthesized. Imprinted polymer Fe_3O_4@ZIF-8@MIPs, Rapid and specific recognition of TBBPA. in aqueous solution By coating ZIF-8 layer on Fe_3O_4 nucleus at room temperature in aqueous solution, Fe _ 3O_4@ZIF-8@MIPs shows good monodispersity, and the saturation magnetization is 38.4 emu / g ~ (1), and its saturation magnetization is 38.4 emu 路g ~ (- 1). The specific surface area is 185.9 m ~ 2 g / 1, pore volume and pore size are 0.47 m ~ 3 g / 1 and 99.15 渭 m ~ (- 1), respectively. Because of the high density of low coordinated Zn atoms on the surface of ZIF-8, the adsorption ability of Fe_3O_4@ZIF-8 itself to TBBPA and the specific adsorption of TBBPA by molecular imprinting were studied. The comprehensive results show that Fe_3O_4@ZIF-8@MIPs has good adsorption ability to TBBPA. In addition, Fe_3O_4@ZIF-8@MIPs showed excellent recyclability, the recovery rate was more than 85.0% after 5 times of use, the maximum adsorption capacity of TBBPA was 117.6 mg / g / 1 and the fast adsorption kinetics (the adsorption equilibrium was reached within 15 min).
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.3
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