新型磁性核殼納米印跡聚合物的制備及其對TBBPA的特異性吸附研究
發(fā)布時間：2019-03-09 08:40
【摘要】：四溴雙酚A(Tetrabromobisphenol A,TBBPA)是具有雙酚A結(jié)構(gòu)的酚類化合物,被視為一種環(huán)境污染物和內(nèi)分泌干擾物,廣泛應(yīng)用于溴化阻燃劑領(lǐng)域,對環(huán)境、生態(tài)系統(tǒng)以及人類健康造成極大的污染和風(fēng)險。分子印跡材料(Molecular Imprinted Polymers,MIPs)可選擇性吸附特定模板分子,因其高選擇性、預(yù)定性和適用性,已經(jīng)在分離領(lǐng)域?qū)崿F(xiàn)了快速發(fā)展。同時,其制備簡單,性質(zhì)穩(wěn)定,成本低,可以有效抵抗具有與模板分子結(jié)構(gòu)類似的分析物的干擾,并實現(xiàn)從復(fù)雜的化學(xué)體系中選擇性綁定模板分子的目的。與傳統(tǒng)印跡相比,表面分子印跡技術(shù)因為吸附能力高,傳質(zhì)速率快等優(yōu)點,更利于目標分子的洗脫與綁定。金屬有機框架(Metal-Organic Frameworks,MOFs)是一類新型的多孔材料。一般以過渡態(tài)金屬為配位中心,與有機配體進行配位聚合形成空間三維網(wǎng)絡(luò)結(jié)構(gòu)�？讖娇烧{(diào)、比表面積大、結(jié)構(gòu)多樣性、不飽和的金屬配位和表面可修飾等顯著優(yōu)點,使得MOFs獲得了廣泛的關(guān)注,并且已經(jīng)在各研究領(lǐng)域?qū)崿F(xiàn)了快速發(fā)展。鑒于分子印跡聚合物和金屬有機框架材料以及磁性納米粒子具有的優(yōu)勢,本學(xué)位論文旨在研究TBBPA分子印跡的制備方法,設(shè)計合成了兩種形貌良好、吸附容量高、吸附速率快的新型磁性核殼分子印跡材料,并作為吸附劑去除水體中的TBBPA。主要研究內(nèi)容是:1.磁性核-殼印跡聚合物的制備及其對TBBPA的特異性吸附在通過熱溶劑法制備的Fe_3O_4納米粒子表面上包覆SiO2作為印跡基體,利用自由基聚合制備印跡聚合物層,獲得了特異性吸附TBBPA的磁性核殼Fe_3O_4@SiO2@MIPs,并通過改變功能單體、功能單體與交聯(lián)劑的比例等因素優(yōu)化MIP層的制備條件。通過分析所得材料對TBBPA及其結(jié)構(gòu)類似物的回收率來探索其特異性吸附性能,同時研究了材料的吸附動力學(xué)、吸附等溫線和循環(huán)使用性。結(jié)果表明所制備的分子印跡復(fù)合材料,具有高的活性(最大吸附量為58.67 mg g-1),快的吸附動力學(xué)(30 min內(nèi)達到吸附平衡)和磁性分離(20 s)以及高的選擇性、可重復(fù)使用性(5次使用后回收率可達89.4%以上)。2.新型磁性核-殼金屬有機框架載體上印跡聚合物的制備及其對TBBPA的特異性吸附設(shè)計合成了一種新型的金屬有機骨架——沸石咪唑酯框架(ZIF-8)為基體的磁性印跡聚合物Fe_3O_4@ZIF-8@MIPs,用于快速和特異性識別水溶液中的TBBPA。實驗通過在Fe_3O_4核上涂覆ZIF-8層,于室溫下在水溶液中進行。Fe_3O_4@ZIF-8@MIPs顯示出良好的單分散性,飽和磁化強度為38.4 emu g-1,比表面積為185.9 m2 g-1,孔體積和孔徑分別為0.47 m3 g-1和99.15?。由于ZIF-8表面低配位Zn原子的密度較高,Fe_3O_4@ZIF-8本身對TBBPA的吸附能力以及分子印跡對TBBPA的特異性吸附,綜合結(jié)果顯示Fe_3O_4@ZIF-8@MIPs對TBBPA有良好的吸附能力。此外,Fe_3O_4@ZIF-8@MIPs顯示了優(yōu)異的可回收性,5次使用后回收率達85.0%以上,對TBBPA的最大吸附量為117.6 mg g-1和快吸附動力學(xué)(15 min內(nèi)達到吸附平衡)。
[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).
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：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).
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O631.3
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