烷基咪唑溴盐离子液体修饰磁性纳米材料的制备及吸附多环芳烃的研究

发布时间：2018-03-28 10:35

本文选题：离子液体　切入点：结构表征　出处：《河南师范大学》2017年硕士论文

【摘要】：离子液体作为新兴的“绿色溶剂”具有可塑性,可通过改变其物化性能获得一些具有特殊性质的功能化离子液体,以满足特定用途的需求。由于离子液体不易分离提纯、粘度大等缺点,限制了其发展。为解决这些问题,人们通常将其负载在固体材料表面。由于磁性纳米粒子独特的磁学性质和优异的物理化学性质,将新型功能化的离子液体修饰到其表面合成磁固相萃取材料,已成为人们研究的热点。磁固相萃取材料能够快速精准地富集、分离出样品中的污染物,经清洗后,可实现重复使用。本文通过“一步合成法”合成烷基咪唑溴离子液体,将该离子液体修饰到磁性纳米颗粒表面制备出功能化磁性纳米材料,并应用于水中PAHs的萃取。论文的主要内容有:(1)介绍了离子液体作为“绿色溶剂”的特点,综述了环境有机污染物样品前处理方法及存在的问题,特别是功能化磁固相萃取材料在样品前处理中的应用;针对环境优先污染物多环芳烃(PAHs)的分析研究进行了阐述。(2)采用“无水无氧一步合成法”技术制备出两种新型的咪唑类离子液体,即1-十六烷基-3-三乙氧基丙基硅烷咪唑溴盐离子液体([HDTIm]Br)和1-十八烷基-3-三乙氧基丙基硅烷咪唑溴盐离子液体([ODTIm]Br)。利用核磁共振(NMR)、傅立叶变换红外光谱(FTIR)、元素分析等手段对其进行了结构表征。(3)在氮气保护下,碱性环境中分别将制备的离子液体[HDTIm]Br和[ODTIm]Br修饰到磁性纳米颗粒(MNPs)表面,制备功能化的磁固相萃取材料[HDTIm]Br-MNPs和[ODTIm]Br-MNPs。对制备材料进行了傅里叶变换红外光谱(FTIR)、热重分析(TG)、X射线衍射(XRD)、透射电镜(TEM)和磁性能分析(VSM)等表征分析。(4)以15种多环芳烃(PAHs)为研究对象,建立了[HDTIm]Br-MNPs的MSPE-HPLC-FLD的分析方法,方法线性范围0.02~100.0 ng/m L,检出限(LOD)为0.901~129ng/L。在最佳条件下,考察了[HDTIm]Br-MNPs对新乡市牧野湖水中PAHs的萃取,加标回收率8.51~105.39%,相对标准偏差(Relation standard deviation,RSD)为1.70~10.10%。同时考察了材料对科技学院内西湖水中PAHs的萃取,加标回收率为9.82~109.07%,RSD为3.12~10.86%。(5)以15种多环芳烃(PAHs)为研究对象,建立了[ODTIm]Br-MNPs的MSPE-HPLC-FLD分析方法,方法线性范围0.02~100.0 ng/mL,检出限(LOD)为0.342~336 ng/L。在最佳条件下,考察了[ODTIm]Br-MNPs对新乡市牧野湖水中PAHs的萃取,加标回收率4.21~109.90%,RSD为0.91~10.58%。考察了材料对科技学院内西湖水中PAHs萃取,加标回收率5.37~109.55%,RSD为0.13%~12.79%。(6)讨论了制备的两种磁固相材料[TDTIm]Br-MNPs和[ODTIm]Br-MNPs结构表征上的差异性,分析探讨了不同碳链长度的两种磁固相萃取材料[TDTIm]Br-MNPs和[ODTIm]Br-MNPs在相同的萃取条件下,对水中PAHs的富集萃取性能的比较。
[Abstract]:As a new "green solvent", ionic liquids have plasticity. Some functional ionic liquids with special properties can be obtained by changing their physical and chemical properties to meet the needs of specific applications. In order to solve these problems, people usually load them on the surface of solid materials because of their unique magnetic properties and excellent physical and chemical properties. It has become a hot topic to synthesize magnetically solid phase extraction materials by modifying the new functionalized ionic liquids onto its surface. The magnetic solid phase extraction materials can be rapidly and accurately enriched, the contaminants in the samples can be separated, and then cleaned up. In this paper, the alkyl imidazolium ionic liquid was synthesized by one-step synthesis method, and the functionalized magnetic nanomaterials were prepared by modifying the ionic liquid onto the surface of magnetic nanoparticles. The main contents of this paper are as follows: (1) the characteristics of ionic liquids as "green solvent" are introduced, and the pretreatment methods and existing problems of environmental organic pollutants are summarized. Especially the application of functionalized magnetic solid phase extraction materials in sample pretreatment; Based on the analysis of PAHs, a new type of imidazole ionic liquids was prepared by anhydrous and anoxic one-step synthesis method. That is, 1-hexadecyl -3-triethoxy propylsilane imidazolium bromide ionic liquid ([HDTIm] Br) and 1-octadecyl -3-triethoxy propylsilane imidazolium bromide ionic liquid ([ODTIm] BrN]. Using NMR, Fourier transform infrared spectroscopy (FTIR), elemental analysis, etc. The method was used to characterize its structure. The prepared ionic liquids [HDTIm] Br and [ODTIm] Br were modified to the surface of magnetic nanoparticles in alkaline environment, respectively. The functional materials [HDTIm] Br-MNPs and [ODTIm] Br-MNPs were prepared. Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and magnetic properties analysis (VSM) were used to characterize and analyze 15 polycyclic aromatic hydrocarbons (PAHs). A method for the analysis of [HDTIm] Br-MNPs by MSPE-HPLC-FLD was established. The linear range of the method was 0.02o 100.0 ng/m / L, and the detection limit was 0.901ng / L. Under the optimum conditions, the extraction of PAHs from the water of Xinxiang City by [HDTIm] Br-MNPs was investigated, and the detection limit was 0.901ng / L. under the optimum conditions, the extraction of PAHs by [HDTIm] Br-MNPs was investigated. The recovery rate was 8.51 ~ 105.39 and the relative standard deviation standard deviation was 1.70 ~ 10.10. Meanwhile, the extraction of PAHs from the West Lake water of the Institute of Science and Technology was investigated. The recovery rate was 9.82 ~ 109.07 (RSD = 3.12 ~ 10.86. 05). The MSPE-HPLC-FLD analysis method of [ODTIm] Br-MNPs was established with 15 kinds of polycyclic aromatic hydrocarbons (PAHs) as the research object. Methods the linear range was 0.02 ~ 100.0 ng 路mL ~ (-1) and the detection limit was 0.342 ~ 336ng / L. under the optimum conditions, the extraction of [ODTIm] Br-MNPs for PAHs in Xinxiang City's Muye Lake water was investigated. The recovery rate of PAHs was 4.21 ~ 109.90% (RSD = 0.911) 10.58. The extraction of PAHs from the water of West Lake in the Institute of Science and Technology was investigated. The difference in structure characterization between [TDTIm] Br-MNPs and [ODTIm] Br-MNPs was discussed. Two kinds of MSPE materials [TDTIm] Br-MNPs and [ODTIm] Br-MNPs with different carbon chain lengths were analyzed under the same extraction conditions. Comparison of enrichment and extraction properties of PAHs in water.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O658.2

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