【作者】 周媛；

【导师】 王永钊； 赵永祥；

【作者基本信息】 山西大学 ， 物理化学， 2011， 硕士

【摘要】 自1999年以来,周期介孔有机硅材料(PMOs)因其具有高的比表面积,高度有序的孔结构,均一可调的孔径,高的水热稳定性、机械稳定性和化学稳定性,同时材料中有机物负载量高、分布均匀可控、化学活性位点多,可进一步被修饰等特点,在色谱、分离、催化、吸附、存储等领域越来越受到人们的关注PMOs材料的物理和化学性质取决于前躯体种类、制备方法和条件等,而其性质决定了这类材料的应用领域。环戊二烯具有共轭双键和亚甲基上的活泼氢原子,性质较为活泼,可进行聚合、氢化、卤化、加成、氧化、缩合及还原等反应；同时它还是稀土金属有机配合物很好的配体。因此,我们选取环戊二烯作为功能基团,采用共聚法创新性的合成了环戊二烯掺杂乙烷桥联有序介孔材(Cp-PMO);在此基础上,我们以Cp-PMO为载体,负载Py-Co(Ⅲ)制备Co-PMO,并采用各种表征手段对样品进行了结构表征,同时以丁醇和乙酸乙酯的酯交换反应以及环己醇氧化反应为探针反应,分别考察了Cp-PMO和Co-PMO的催化性能。在本工作中,主要包括以下内容：首次合成出前躯体(2-(环戊基-1,3-二烯基)乙基)三乙氧基硅烷(TEECp)。整个实验过程均采用无水无氧技术,所有操作均在氮气气氛中进行。合成过程主要分为3个步骤：1)以乙烯基三氯硅烷为原料,与溴化氢气体在过氧化苯甲酰存在下进行反马氏加成反应,生成2-溴乙基三氯硅烷2)2-溴乙基三氯硅烷与无水乙醇进行醇解反应,生成2-溴乙基三乙氧基硅烷,3)与环戊二烯基钠进行金属化反应,即得产物TEECp。我们对合成的中间产物及TEECp进行了NMR、IR表征,结果表明,所合成的产物为目标产物TEECp。以单硅酯(2-(环戊基-1,3-二烯基)乙基)三乙氧基硅烷(TEECp)和含有亚乙基桥键的硅酯1,2-二(三乙氧基硅基)乙烷(BTEE)为硅源,三嵌段共聚物P123为结构导向剂,合成了环戊二烯掺杂乙烷桥联有序介孔材料(Cp-PMO),并采用小角X射线衍射、N2物理吸附、透射电镜、红外光谱和热重等技术对样品进行了表征,结果表明,环戊二烯成功引入到材料中,该材料具有高度有序的二维六方相介孔孔道,随着环戊二烯含量的增加,材料的孔径、比表面积、孔容均有所减少,孔壁变厚；在乙酸乙酯与正丁醇的酯交换反应中,该材料表现出明显的催化活性,其催化性能不仅与活性中心数目有关,也和材料结构有关。在Cp-PMO上,通过Diels-Alder反应将羧基引入PMO材料中,然后通过配位,将Py- Co(Ⅲ)引入到材料中,合成出Co-PMO。采用小角X射线衍射、N2物理吸附、透射电镜、红外光谱和热重等技术对样品进行了表征,结果表明,Py- Co(Ⅲ)引入到材料中,且材料的孔径、比表面积、孔容均有所减少,孔壁变厚；随着环戊二烯含量的增加,Py-Co(Ⅲ)的负载量也逐渐增加,有序性有所降低。在催化环已醇氧化成环己酮的反应中,该材料表现出明显的催化活性。当Co-PMO-x为20%时,材料保持了较好的介孔结构,且活性中心数目较多,呈现出最高的催化性能。更多还原

【Abstract】 Since 1999, periodic mesoporous organic silicon materials (PMOs) play important roles in the fields of chromatography, separation, catalysis, adsorption, storage and other fields. Because of its high specific surface area, highly ordered pore structure, uniform adjustable pore size, high hydrothermal stability, mechanical stability and chemical stability, and the high load of organic material, controlled distribution, and more active sites.The physical and chemical properties of PMOs materials depends on the type of precursor species and preparation methods. The physical and chemical properties of PMOs materials determine these materials applications. Cyclopentadiene which has double bonds and active hydrogen atoms of methylene can be used in polymerization, hydrogenation, halogenation, addition, oxidation, condensation and reduction reactions; and it is also the good ligands of rare earth metal organic complexes. Therefore, we selected cyclopentadienyl group as a functional group, and preparated inovatively the Cp-PMO; On this basis, Co-PMO was preparated by selecting Cp-PMO as carriers and loading Py-Co(Ⅲ). Cp-PMO and Co-PMO were characterized by various technologies. The catalytic performance of Cp-PMO and Co-PMO were investigated for transesterification of butanol and ethyl acetate and oxidation reaction of cyclohexanol to detective a high catalytic performance and environmentally friendly catalyst.This work included the following:precursor(2-(cyclopentyl-1,3-dieneyl)ethyl)triethoxysilane(TEECp) was synthesized firstly. All reactions were carried out under dry N2 using the vacuum-line technique. The whole process was divided into three steps:1) anti-Markovnikov addition reaction was conducted between vinyl trichlorosilane and hydrogen bromide in the presence of benzoyl peroxide, producing 2-bromo-ethyl trichlorosilane;2) Then the product alcoholize with absolute ethyl alcohol to obtain (2-bromoethyl)triethoxysilane; 3)After that, (2-bromoethyl) triethoxysilane reacted with sodium cyclopentadienide to obtain (2-(cyclopenta-1,3-dienyl)- ethyl)triethoxysilane. The TEECp and the intermediate products were confirmed by NMR and FT-IR.Cp-PMO was synthesized by copolymerization, using TEECp and the ethylene bridge silicon ester 1,2-bis(triethoxysilyl silicon)ethane(BTEE) as silica source, triblock copolymer P123 as structure directing agent. The prepared material samples were characterized by X-ray dif-fraction, N2 adsorption-desorption, transmission electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analsis. The results showed that cyclopentadiene was successfully incorporated into the material, which had highly ordered hexagonal mesostructure. With increasing cyclopentadiene loading, the mesostructure order, pore size, BET surface area, and pore volume of Cp-PMO decreased, while the pore wall widths increased. Cp-PMO showed significant catalytic activity in the transesterification reaction of ethyl acetate and n-butyl alcohol. The catalytic performance was not only related to the number of active centers, but also related to structure of material.Carboxyl group was introduced into the Cp-PMO through the Diels-Alder reaction and the Py-Co(Ⅱ) was introduced by coordination, producing Co-PMO. The prepared material samples were characterized by X-ray dif-fraction, N2 adsorption-desorption, transmission electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analsis. The results showed that, Py-Co(Ⅲ) was introduced into the material and the material pore size, surface area, pore volume decreased, while the pore wall widths increased. With the increase of the content of cyclopentadiene, Py-Co(Ⅲ) loading was gradually increased and ordering was gradually decreased. In the catalytic conversion of cyclohexanol into cyclohexanone experiments, the material showed significant catalytic activity. When the x of Co-PMO-x is 20%, the material showed the highest catalytic performance due to the good pore structure, and the more number of active sites.更多还原