功能化磁性材料制备及在环境污染物检测中的应用

发布时间：2018-02-04 13:19

本文关键词： 磁性材料双酚A 多环芳烃重金属离子检测　出处：《中国人民解放军军事医学科学院》2015年硕士论文　论文类型：学位论文

【摘要】：环境污染物种类繁多,对人类健康及生态环境造成了严重的威胁。因此建立环境污染物检测技术,对于环境污染风险防控、保护人类健康及生态环境有着重要的意义。由于环境样品复杂多样、环境污染物检测项目千差万别,样品前处理技术一直是环境污染物检测技术建立和发展的关键环节之一。功能化磁性材料作为一种新型的SPE材料,具有快速磁响应性、高度生物相容性、易于表面功能化修饰等一系列优点,在快速高效富集蛋白、细菌、核酸、病毒等特定目标物等方面均显示了良好的应用前景。因此,将功能化磁性材料应用于环境污染物的检测技术研究中,对环境中相关污染物分析技术的完善、保护人类健康有重要的意义。1.功能化磁性材料的制备与表征(1)纳米四氧化三铁(Fe3O4)磁性内核的制备与表征；(2)二氧化硅磁性微球(Fe3O4@TEOS)的制备与表征；(3)聚酰胺66(PA66)功能化磁性材料的制备与表征；(4)氨基功能化磁性材料(Fe3O4@TEOS@APTES)的制备与表征。2.PA66功能化磁性材料在双酚A(BPA)检测中的应用(1)PA66功能化磁性材料对BPA富集条件的优化；(2)基于PA66功能化磁性材料的BPA检测方法的建立；(3)实际样品检测。3. Fe3O4@TEOS@APTES在几种典型环境污染物检测中的初步应用(1) Fe3O4@TEOS@APTES对16种多环芳烃类(PAHs)污染物的吸附效果研究；(2) Fe3O4@TEOS@APTE S对重金属离子Pb、Cd的吸附效果研究。1.功能化磁性材料的制备及表征(1)纳米Fe3O4磁性内核的制备及表征：在传统化学共沉淀法基础上,通过调整反应的碱性体系、三价铁和二价铁比例,结合脱氧、陈化等技术对Fe3O4的制备过程进行优化,并以TEM、XRD对合成的Fe3O4进行表征；(2) Fe3O4@TEOS的制备及表征：利用富含硅氧键的TEOS对磁性Fe3O4内核进行修饰,并以TEM、XRD3寸合成的]Fe3O4@TEOS进行表征；(3)PA66功能化磁性材料的制备及表征：利用反相无水微乳液合成的新方法,完成难溶于水和一般有机相材料在固相亲水性磁性微球表面的修饰,并以TEM、FT-IR对合成的PA66功能化磁性材料进行表征；(4)Fe3O4@TEOS@APTES的制备及表征：利用APTES对制备的Fe3O4@TEOS表面进行修饰,并以TEM、XRD、FT-IR对合成的Fe3O4@TEOS@APTES进行表征。2.PA66功能化磁性材料在BPA检测中的应用(1)探讨PA66功能化磁性材料制备过程中相关影响因素对BPA的预处理效果的影响,并在优化好的条件下验证材料多次重复使用对BPA回收效果的影响；(2)在优化好的实验条件下,建立水中基于PA66功能化磁性材料的BPA检测方法；(3)将制备的材料应用到实际样品的检测中,对海水、河水、地下水、自来水厂出厂水和自来水5种不同的水样中的BPA进行检测,采用高(5μg/L)中(10μg/L)低(15μg/L)三个浓度对实际水样进行加标回收,验证方法的准确性和不同水体基质的适用能力。3.Fe3O4@TEOS@APTES对几种典型环境污染物的吸附效果研究(1)结合HPLC分析技术,初步验证Fe3O4@TEOS@APTES对16种PAHs的吸附效果；(2)结合原子吸收分光光度计,初步验证Fe3O4@TEOS@APTES对水中重金属离子Pb、Cd的吸附效果。1.功能化磁性材料的制备及表征(1)成功制备了粒径约为15-20nm的Fe3O4纳米磁性内核,优化后的方法相对于传统的化学共沉淀法所制得的Fe3O4磁性颗粒形貌更加规则,粒径更加均匀；(2)TEOS在Fe3O4表面修饰成功,成功合成了规则球形、粒径约为3OOnm的Fe3O4@TEOS;(3)利用反相无水微乳液合成新方法,成功制备了PA66功能化磁性材料,其分散性能好,形貌规则；(4)成功合成了形貌规则、粒径均匀的球形Fe3O4@TEOS@APTES。2.PA66功能化磁性材料在BPA检测中的应用(1)完成了PA66功能化磁性材料对BPA富集条件的优化,并在优化好的条件下验证了材料多次重复使用对BPA回收效果的影响,证实了本材料可至少重复使用10次以上；(2)在优化好的实验条件下,建立了水样中基于PA66功能化磁性材料的BPA的检测方法,线性范围0.20-100.00μg/L,检出限为0.05μg/L,富集倍数为250倍；(3)将制备的材料应用到实际样品的检测中,对5种不同的水样中的BPA进行检测,加标回收率88.54%-104.46%。证实该方法对该5种水体基质适用性良好。3. Fe3O4@TEOS@APTES对几种典型环境污染物的吸附效果研究(1)该材料对苯并[a]芘、苊、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽、二苯并[a,h]蒽和茚并芘7种稠环PAHs具有不同程度的吸附效果,吸附效率在61.0-79.0%之间；(2)该材料对水中Pb(5.0mg/I的吸附效率为94.4Cd(5.0mg/I的吸附效率为94.7%。证实了该材料对水中重金属离子Pb、Cd具有较好的吸附效果。本研究制备了Fe3O4纳米磁性内核、二氧化硅磁性微球、PA66功能化磁性材料及氨基功能化磁性材料。确定了PA66功能化磁性材料对BPA吸附的最佳条件,建立了基于PA66功能化磁性材料的BPA检测方法。利用制备的氨基功能化材料,实现了以苯并[a]芘为代表的7种PAHs的同时定量分析,为进一步的风险防控研究提供了依据。制备的氨基功能化磁性材料对重金属离子Pb,Cd的吸附效果较好,为氨基功能化磁性材料在这些重金属离子的去除及检测方面的进一步应用提供了一定的理论依据。本研究所制备的功能化磁性材料在环境污染物的检测中具有进一步研究价值和更广阔的应用前景。
[Abstract]:Many kinds of environmental pollutants, causing a serious threat to human health and ecological environment. Environmental pollutant detection technology is established so for the risk of environmental pollution prevention and control, plays an important role in the protection of human health and ecological environment. Because of complex environmental samples, environmental pollutant detection projects vary, sample pretreatment technology has been one of the key links in establishing environmental pollutant detection technology and the development of functional magnetic materials. As a kind of new SPE materials, with fast magnetic response, high biocompatibility and a series of advantages of easy surface modification, in a fast and efficient enrichment of protein, nucleic acid, bacteria, viruses and other specific target both show a good application prospect. Therefore, will study the detection technology of functional applications of magnetic materials in environmental pollutants, the pollutants in environmental analysis The improvement of the protection of human health, a preparation and characterization of.1. functional magnetic materials important for (1) nano ferroferric oxide (Fe3O4) synthesis and characterization of magnetic core of the system; (2) magnetic silica microspheres (Fe3O4@TEOS) preparation and characterization of polyamide; (3) 66 (PA66) preparation and characterization of functional magnetic materials; (4) the amino functionalized magnetic material (Fe3O4@TEOS@APTES) preparation and characterization of.2.PA66 functional magnetic materials in bisphenol A (BPA) for the detection of PA66 (1) to optimize the functional magnetic materials of BPA enrichment conditions; (2) to establish BPA PA66 method for detection of functional magnetic materials based on the actual application; (3) preliminary sample detection of.3. Fe3O4@TEOS@APTES in the detection of several typical environmental pollutants in Fe3O4@TEOS@APTES (1) of 16 kinds of polycyclic aromatic hydrocarbons (PAHs) on the adsorption effect of pollutants; (2) Fe3O4@TEOS@APTE S of heavy metal Pb, Cd Preparation and characterization of adsorption effects of.1. functional magnetic materials (1) preparation and characterization of nanometer Fe3O4 magnetic core: in the traditional chemical co precipitation method on the basis of system adjustment by alkaline reaction, ferric iron and two valent iron ratio, combined deoxidation, aging technology on the preparation of Fe3O4 process optimization, and in TEM, XRD on the synthesis of Fe3O4 was investigated; (2) preparation and characterization of Fe3O4@TEOS: modification of magnetic Fe3O4 core by using silicon rich oxygen bond TEOS, and TEM, XRD3 inch]Fe3O4@TEOS synthesis characterization; (3) preparation and characterization of PA66 functional magnetic materials. A new method of using reverse microemulsion synthesis of anhydrous, complete insoluble in water and common organic materials in solid phase modification of hydrophilic magnetic microspheres, and to TEM, the PA66 functional magnetic materials synthesis were characterized by FT-IR; (4) preparation and Fe3O4@ TEOS@APTES Sign: modification on the surface of Fe3O4@TEOS prepared by APTES, and in TEM, XRD, FT-IR for the application of functional magnetic materials characterization of.2.PA66 in detection of BPA on the synthesis of Fe3O4@TEOS@APTES (1) the effect of the pretreatment effect related factors of PA66 functional magnetic materials in the preparation process of BPA, and in the optimized conditions to verify materials used repeatedly impact on BPA recovery effect; (2) under the optimized experimental conditions under the established water BPA PA66 detection method based on functional magnetic materials; (3) the preparation of the material applied to the detection of the actual samples of sea water, river water, groundwater the tap water, tap water and 5 kinds of BPA in water samples were detected by high (5 g/L) in (10 g/L) and low (15 g/L) three concentration of water samples spiked, the accuracy of the verification method and different water matrix. Study on adsorption effects of several typical environmental pollutants with the ability of.3.Fe3O4@TEOS@APTES (1) combined with HPLC analysis, preliminary verification of Fe3O4@TEOS@APTES adsorption on 16 PAHs; (2) combined with atomic absorption spectrophotometer, preliminary verification of Fe3O4@TEOS@APTES of water heavy metal ion Pb, adsorption effect of.1. functional magnetic materials preparation and characterization Cd (1) were successfully prepared Fe3O4 nano particle magnetic core size is about 15-20nm, the optimized method of Fe3O4 magnetic particle morphology compared with the traditional chemical precipitation method produced more rules, more uniform particle size; (2) TEOS in Fe3O4 surface modification, synthesis of spherical particles. The size is about 3OOnm Fe3O4@TEOS; (3) by inverse microemulsion anhydrous synthesis method, PA66 functional magnetic materials were prepared successfully, the good dispersion, the rules of morphology; (4) successfully synthesized particle morphology rules The application of spherical Fe3O4@TEOS@APTES.2.PA66 functional magnetic materials with uniform diameter in the detection of BPA (1) completed the optimization of PA66 functional magnetic materials of BPA enrichment conditions, and verify the materials used repeatedly effect on BPA recovery effect in optimized conditions, confirmed that the materials can be reused at least 10 times; (2) under the optimized experimental conditions under the established water detection method of PA66 functional magnetic materials based on BPA, the linear range of g/L 0.20-100.00, the detection limit is 0.05 g/L, the enrichment ratio of 250 times; (3) the preparation of the material applied to the actual samples, detection on 5 kinds of BPA in water samples, the recoveries of 88.54%-104.46%. confirmed the method research on adsorption effect of good.3. Fe3O4@TEOS@APTES on several typical pollutants of the environment for the matrix of 5 kinds of water (1) the material of benzo [a] Acenaphthene, pyrene, benzo [a] anthracene, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a anthracene two, h] and Indeno pyrene 7 fused ring PAHs has adsorption effect in different degree, the adsorption efficiency of 61.0-79.0%; (2) the material of Pb (water adsorption efficiency for 5.0mg/I 94.4Cd (5.0mg/I adsorption efficiency of 94.7%. confirmed that the material of heavy metal ions Pb, Cd has better adsorption effect. The preparation of Fe3O4 nano magnetic core, magnetic silica microspheres, PA66 functionalized amino functionalized magnetic materials and magnetic materials. The PA66 functional magnetic materials on BPA adsorption the optimum conditions were established based on the PA66 functional magnetic materials BPA detection method. The preparation of amino functionalized materials, in order to realize the benzo [a] pyrene as the representative of the 7 kinds of PAHs and quantitative analysis, for further research of risk prevention and control provide the basis. The preparation of amino functionalized magnetic Material for heavy metal ions Pb, good absorption effect of the Cd, provides a theoretical basis for the further application of functionalized magnetic materials in the detection and removal of these heavy metal ions. The preparation of functional magnetic materials has application value and broad prospects for further research in the detection of environmental pollutants.

【学位授予单位】：中国人民解放军军事医学科学院
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X830

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