【作者】 马骞；

【导师】 侯经国；

【作者基本信息】 西北师范大学 ， 分析化学， 2004， 硕士

【摘要】 介孔材料作为一种新型功能材料，由于其具有较大的比表面积、长程有序的孔道结构、较大的孔容、良好的扩散性能和能够减小分子扩散中的瓶颈效应等特点，以及作为无机材料所具有的机械和热稳定性，所以自1992年Mobil公司开发研制了以MCM-41为代表的M41S系列介孔材料以来，被广泛应用于催化、吸附和分离等领域。尤其是官能团衍生化或不同形貌特征的介孔材料具有较高的吸附选择性和活性作用位点，更加拓宽了其应用前景。 固相微萃取（SPME）是由Pawlisayn在1990年提出的一种新型的无溶剂样品处理技术，在与气相色谱（GC）、高效液相色谱（HPLC）、毛细管电泳（CE）以及紫外光谱（UVAS）等联用后，广泛应用于水、土壤、空气等环境样品和血、尿等生物样品，以及食品、药物等样品的分析测定。纤维涂层是SPME的核心部位，常用的涂层材料多为液相聚合物，如聚二甲基硅氧烷（PDMS）、聚丙烯酸酯（PA）等。后来又发展了一些有特点的涂层材料，如离子交换涂层、极性的Nation全氟化树脂涂层、导电聚合物聚吡咯（PPY）和聚-N-苯基吡咯（PPPY）等。为提高萃取效率和萃取灵敏度，一些多孔固体如石墨化碳黑（GBC）、活性炭多孔层（PLAC）、HPLC反相键合固定相C₂、C₈、C₁₈等也被用做涂层材料，效果显著。另外，溶胶-凝胶技术（sol-gel）拓宽了涂层制备的新前景。 本文首次将C₁₆-MCM-41介孔材料用作SPME纤维涂层，制成萃取头，并以此萃取测定了环境样品中的多环芳烃。 本论文分为两大部分，共计七章。 第一章：综述了介孔材料的合成及其在分离科学上的应用情况。 第二章：分别以γ-氨基丙基三乙氧基硅烷（APTES）γ-环氧丙氧基丙基三甲氧基硅烷（GPTES）为偶联剂，成功地将氨基和醚基官能团接枝于MCM-41介孔分子筛孔道中，制备了无机-有机复合介孔材料NH₂（CH₂）₃-MCM-41和CH₂OCHCH₂O（CH₂）₃-MCM-41。用XRD、N₂吸附-脱附、元素分析和FT-IR对复合材料进行了表征。 第三章：尝试以γ-环氧丙氧基丙基三甲氧基硅烷（GPTS）为偶联剂，将β-环糊精键合到MCM-41介孔分子筛孔道表面，成功制备了β-CD-MCM-41有机-无机复合材料。用XRD、N₂吸附-脱附、元素分析、FT-IR和荧光光度法对复合材料进行了表征，荧光光度法是本文首次用于介孔复合材料的表征。硕士学位论文介孔材料的合成及用作固相微萃取涂层的研究 第四章:在室温，酸性介质中，首次将合成球形硅胶的“PICA法”与介孔材料合成方法相结合，尝试合成球形MCM一41，用XRD、NZ吸附一脱附、SEM和FT-IR对合成材料进行了表征。结果表明，所合成的材料介孔特征明显，并具有相对规则、均匀的球形几何形态。 第五章:综述了固相微萃取涂层研究进展。 第六章:将介孔材料作为一种快速、高效、高灵敏度的固相微萃取（SPME）涂层材料。将3协m的C16一MCM一41介孔固体微粒固定于不锈钢丝上，制成100林m的涂层。与高效液相色谱联用，考察了新涂层的萃取效率和选择性。同时还以葱为例，考察了新涂层的定量性能、线性范围、检测限为和精密度等。 第七章:建立了一种用C16一MCM一41介孔复合材料作纤维涂层的固相微萃取 （SPME）与高效液相色谱（HPLC）联用，测定环境水样中多环芳烃的方法;对SPME的实验条件，如萃取和解吸时间、萃取温度、搅拌速度以及离子强度等进行了优化;考察了方法的线性范围、检出限、精密度和回收率等。该方法体现了SPME在样品前处理过程中的快速、灵敏、简单和无溶剂的特点。硕士研究生:马鸯;专业:分析化学;研究方向:分离科学及纳米生物分析技术导师:侯经国教授父更多还原

【Abstract】 Since the novel M41S mesoporous materials (particularly MCM-41) was firstly reported by Mobil’s researchers, much attention has been paid to this kind of materials. They have not only larger surface area, uniform pore structure and huge pore volume, which can reduce bottleneck phenomenon in molecular diffusion, but also higher mechanically and chemically stability as new inorganic materials. These materials have been widely used as catalysts, sorbents and separation materials as they were synthesized firstly. Especially, the mesoporous materials with functionalization and various morphologies have been developed in order to obtain higher selectivity and special action sites in past decades.At the same time, solid-phase microextraction (SPME) as a new solvent-free extraction technique in sample preparation appeared in early 1990s. Because of its advantages of simplicity, rapid extraction and easy quantification, SPME was successfully applied to extraction and concentrating of many compounds in environment, food, biological fluids and pesticide matrices, the samples included gas, liquid and solid. SPME could be easily utilized with gas chromatography (GC) and high performance liquid chromatography (HPLC). Latterly, it coupled with Ultraviolet Absorption Spectroscopy (UVAS), Capillary Electrophoresis (CE) and other apparatuses.Up to date, many experimental coatings were prepared and investigated for a wide range of applications. The general applications for SPME are that fused silicate fibers were coated with various liquid polymeric coatings, such as polydimethylsiloxane (PDMS) and polyacrylate (PA). Lately, other more specialized materials have been developed, including ion-exchange coatings, liquid crystalline films, carbowax and Nafion coatings. Conducting polymers, such as polypyrrole, polythiephene and polyaniline were also used as coating materials. In order to increase selectivity, polymer imprinting was also introduced to fiber coatings. Contrast to liquid polymeric coatings, solid coatings were also utilized as SPME coating, for example GBC, porous layer activated carbon (PLAC) and PVC-activated charcoal. Porous silica, especially silica bonded phases (SBP) of HPLC, was also introduced to SPME as fiber coating, which had higher extraction capacity, shorter analysis time and higher sensitivity.In this paper, we introduced novel mesoporous material C16-MCM-41 to prepare SPME fibers. Coating was prepared by fixing C16-MCM-41 particles onto the stainless steel wire. Because of C16-MCM-41 with larger surface area and uniform pore structure, the extraction capacity of coating could be greatly increased. As a result, the sensitivity of method was enhanced. The extraction efficiency, stability, selectivity and quantity capability of C16-MCM-41 coated fibers to the samples were investigated.The dissertation consists of seven parts:Chapter 1, reviews the current state of the art in mesoporous materials research, simply introduces its synthesis according to different channel structure, shape as well as derivative production. But the emphasis is focused on its application in separation science and technology, such as membrane separation, selective adsorption of gases, liquids and metal ions. The chromatographic applications for mesoporous materials are also reviewed firstly in this chapter. All of these applications are presented by elaborating. We also make an outlook to the future of mesoporous research and separation application.In Chapter 2, amino and ether organic group were successfully grafted into the pore of MCM-41 mesoporous sieve using y-aminopropyltriethoxy silane and y-glycidoxypropyltrimethoxy silane as a coupling agent. The inorganic/organic composite mesoporous materials, NH2(CH2)3-MCM-41 and CH2OCHCH2O(CH2)3-MCM-41, were synthesized, and characterized by XRD, nitrogen adsorption-desorption, elemental analysis and FT-IR..In Chapter 3, the B-CD was first successfully introduced into the pore of MCM-41 mesoporous sieve using r-glycidoxypropyltrimethoxy silane (GPTS) as a coupling更多还原