【作者】 刘妍；

【导师】 侯经国； 杨武；

【作者基本信息】 西北师范大学 ， 分析化学， 2006， 硕士

【摘要】 1992年Mobil公司的科学家对M41S（MCM-41、MCM-48、MCM-50）系列硅基（silica-based）介孔分子筛的合成揭开了分子筛科学的新纪元。作为一种新型功能材料，介孔材料由于其具有较大的比表面积和孔容、长程有序的孔道结构、良好的扩散性能以及机械和热稳定性等优点，自问世以来就受到广泛关注，尤其被广泛应用于催化、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，更加拓展了其应用前景随着研究的深入。SBA-15是一种新型的介孔分子筛，与其它介孔材料相比具有孔径大，孔壁厚，具有更高的热和水热稳定性高等优点。固相微萃取（Solid-phase microextraction，SPME）是由Pawliszyn教授在1990年提出的一种新型的集萃取、浓缩、解吸于一体的样品前处理技术。由于该技术具有操作简单、价廉实用等特点而备受分析工作者和仪器制造商的重视。SPME技术在与气相色谱（GC）、高效液相色谱（HPLC）、毛细管电泳（CE）等分析仪器联用后可广泛应用于水、土壤、空气等环境样品和血、尿等生物样品，以及食品、药物等各种复杂样品中痕量有机、无机物的测定。萃取纤维涂层是SPME的核心部位，除了常用的商品化的聚合物涂层材料外，对各种特性涂层材料的开发研究是目前固相微萃取技术研究的热点。本论文将C₂H₅-SBA-15，C₈-SBA-15介孔材料用作SPME纤维涂层，制成萃取头，并以此萃取测定环境样品中的多环芳烃。本论文由两大部分组成，第一部分为综述部分，第二部分为实验部分。第一章：综述了介孔材料的合成及应用，和近几年固相微萃取技术及其涂层研究进展。第二章：以乙基三乙氧基硅烷为偶联剂修饰了介孔分子筛SBA-15，将有机官能团引到介孔分子筛表面，制备了一种无机-有机复合材料C₂H₅-SBA-15，用小角XRD、N₂气吸附-脱咐、元素分析和FT-IR技术对其进行了表征。第三章：以γ-缩水甘油醚基丙基三甲氧基硅烷为偶联剂，将醚基官能团接枝于SBA-15介分子筛孔道中，制备了无机-有机复合介孔材料CH₂OCHCH₂O（CH₂）₃-SBA-15用小角X射线衍射，N₂气吸附-脱咐，元素分析，红外光谱和滴定法对复合材料进行了表征。第四章：将介孔复合材料C₂H₅-SBA-15用作固相微萃取（SPME）中萃取头涂层，与高效液相色谱（HPLC）联用，测定了环境水样中痕量的芘。优化了萃取时间、萃取温度、离子强度、搅拌速度、解吸时间等测定条件。建立了SPME-HPLC测定环境水体中芘的新方法。第五章：将介孔材料C₈-SBA-15用做新型涂层的固相微萃取（SPME）与高效液相色谱（HPLC）联用测定水中萘、蒽、芴三种多环芳烃。在对萃取时间、萃取温度、离子强度、解吸时间等SPME条件优化的同时考察了方法的重现性、线性范围及检出限，对环境水样的分析获得了满意结果。更多还原

【Abstract】 Ordered mesoporous materials have received a great deal of attention, as a novel mesoporous material, M41S, was firstly reported by researchers in the Mobil laboratory in the early 1990s, because of their potential applications in catalysis, separation technology, nanoscience, and biomaterials. Compared with microporous materials, mesoporous materials not only have larger surface area （up to 1500 m²/g） and thicker wall between pores, uniform pore size distribution （1.5-30 nm） and huge pore volume, but also they have excellently mechanical and chemical stability. They were widely used as catalysts, sorbents and separation materials in the past decade. Up to now a great variety of functionalized and morphologic mesoporous materials have been developed in order to obtain higher selectivity and special action sites.Solid-phase microextraction （SPME） as a new solvent-free extraction technique in sample preparation appeared in the early 1990s. Because of its advantages of simplicity, rapid extraction and easy quantification, SPME was successfully applied to extracting and concentrating for various analytes in environmental samples （gas, liquid, solid）, foodstuff, biological samples and materia medica. SPME could be easily coupled with the apparatus, such as gas chromatography （GC） and high performance liquid chromatography （HPLC）. Fiber with coating is the most important part of SPME, the selectivity and the extraction efficiency of the fiber depend considerably on the coating materials. Up to date many experimental coatings have been prepared and investigated for a wide range of applications. The coating materals that were universally used in SPME are various polymer-based coatings, such as polydimethylsiloxane （PDMS） and polyacrylate （PA）, which were coated on fused silica fibers. However, specialized materials have been also developed for special demand in SPME.In this dissertation, our effort is to synthesize new functionalized mesoporous materials and use as coating materials in SPME for analysis of environmental samples by high-performance liquid chromatography coupling with SPME technique. The dissertation consists of five parts:In Chapter 1, the state of art in the mesoporous material research in the past decade is reviewed. The review focus on synthesis and application of the mesoporous materials and especially emphasizes their application in separation science and technology, the technology and theory of SPME are introduced in brief. The current state of the SPME technique and the development of fiber coatings in SPME are reviewed.In Chapter 2, a mesoporous molecular sieve, SBA-15, was modified with ethanetriethoxy silane （ETTS）. Ethane group was successfully grafted on the surface of SBA-15 mesoporous sieve. A new organic-inorganic hybrid material, C₂H₅-SBA-15, was synthesized and characterized by element analysis and FT-IR.In Chapter 3,γ-glycidoxypropyltrimethoxy silane were used as coupling agents for the synthesis of the hybrid mesoporous CH₂OCHCH₂O（CH₂）₃-SBA-15. The inorganic/organic composite mesoporous materials were characterized by XRD,elemental analysis and FT-IR.In Chapter 4, the hybrid mesoporous C₂H₅-SBA-15 was used as solid-phasemicroextraction （SPME） fiber coating. Pyrene in environment water was extracted and determined by SPME-HPLC using C₂H₅-SBA-15 fiber. The experimental conditions of SPME procedure were optimized for extraction and enrichement of the analyte. The method can be used to determine pyrene in environmental water.In Chapter 5, solid-phase microextraction （SPME） using C₈-SBA-15 coated fiber coupled with high-performance liquid chromatography （HPLC） for the determination of polycyclic aromatic hydrocarbons （PAHs） in water in real world （Yellow river water） was reported. Three PAHs （anthrance,naphthalane,fluorene） were studied with the C₈-SBA-15 fiber. The experimental conditions of SPME, such as extraction and desorption time, extraction temperature, salt concenation and agitation were studied and optimized. At the same time, SBA-15 coating has higher extraction capacity and sensitivity, better reproducibility and selectivity than bonded porous silica coating更多还原