【作者】 陈璐；

【导师】 裘式纶；

【作者基本信息】 吉林大学 ， 无机化学， 2010， 博士

【摘要】 本文致力于介观多级功能化孔材料的合成与性能的研究。针对介孔材料在实际应用中遇到的一些问题,从合成和后处理入手,就如何提高其催化及其他性能的活性和增加其稳定性进行了研究。第一章中介绍了多孔材料特别是介孔材料以及微介孔材料的研究概况和主要研究内容。第二章中我们利用软模板法,以含硅的、较大尺寸的阳离子季铵盐为模板及唯一硅源,一步合成了兼具微介复合孔的材料SAPO-34-H,并通过各种表征手段对其孔道的性质及酸性进行测试。与传统SAPO-34相比,多级孔SAPO-34-H含有一套5.1 nm左右的介孔,并在引入介孔的同时降低了酸性,这样可以降低分子筛的失活速率,延长其寿命。在第三章中合成了一种含苯胺三聚体的桥键型有机硅氧烷。这种前驱体兼具聚苯胺导电聚合物的电活性及其低聚物的可溶、可操作性。以溶剂挥发法、添加葡萄糖和果糖作为有机添加剂,原位合成了含苯胺齐聚物的电活性有机材料;另外,以溶剂热法与无机硅源共聚,合成了含有电活性基团的无机-有机杂化材料。两种材料将扩大介孔材料在电学领域的应用。在第四章中通过一个高速、便捷的微波辅助催化氧化法去除了介孔材料SBA-15、MCM-41中的模板剂。并发现该法能在彻底的去除模板剂的同时,不会引起孔道的收缩和坍塌,并能保留较多的孔壁表面的硅羟基,将对介孔孔壁的进一步修饰有较大帮助。使用不同的芬顿试剂在去除不同合成路线的介孔材料模板剂的效率不同,并针对其提出了较为合理的解释。本文详细的阐述了上述孔材料的合成及处理的方法和条件,并对其进行了结构特点及孔性质的表征。并仔细研究了相应体系下影响产物结构和性质的因素,为介孔材料在实际应用的方面提供了必要的基础。更多还原

【Abstract】 Since the natural zeolite was first found in the eighteenth century, a considerable amount of work has been conducted in the field of porous materials. Zeolite has been widely used in petrochemical industry as a catalyst, but its application of macromolecular catalysis, sorption and separation has been limited by its smaller pore size (less than 2 nm). Mesoporous materials as a branch of porous materials, has been rapidly developed by the actual needs of petrochemical. However, although the mesoporous materials have larger pore size (2~50 nm), which can overcome the pore size limitation of zeolites, their weak catalytic activity and poor stability make them less practical and tend to be deactivated. Accordingly, it’s inevitably to improve its catalytic activity and other performance, such as its stability and hydrothermal stability to realizing its application.Micro-mesoporous materials combine the advantages of microporous materials and mesoporous materials, have lager surface area, well-developed multistage pore structure, superior to microporous materials in the aspects of diffusion and mass transport. With the ordered in the atomic scale, micro-mesoporous materials have better acidity and stability than mesoporous materials at the same time. Currently, there are four methods of the synthesis of micro-mesoporous materials, including one-step synthesis, multiple-step synthesis,“hard-template”approach and“soft-template”approach. Herein, we synthesize hierarchical SAPO-34 by utilization the long-chained organosilane. The hydrophilic quaternary ammonium salt of the organosilane can play an important role as its strong interactions with the inorganic species, and it also can be a structure directing agent as TEAOH. The hydrophobic aliphatic long-chain of the organosilane can be wrapped in the crystals in the crystallization process. In this way, mesopores are introduced into the traditional SAPO-34 crystal simultaneously. Compared with the SAPO-34, SAPO-34-H has a mesoporous distribution at 5.1 nm. And the strong B acid sites are decreased; the weak L acid sites are increased. These features will meet the needs of MTO reaction.In addition, mesoporous materials can get new properties through grafting the functional group to the silanol groups (Si-OH) in the wall of mesoporous materials. Or the organic-inorganic hybrid material can be formed by co-condensation of organosilicon with inorganic silicate.Polyaniline (PANI) is one of the promising conductive polymer materials, which has diversified structure, high conductivity, unique doping mechanism, good physical properties, low cost, easy synthesis and environmental stability. But its rigidity and the strong interaction between molecular chains, make it undissolved, refractory, which would be limited its application. But the aniline oligomers can solve this problem easily. On one hand, the aniline oligomers have the similar electrical activity of the polyaniline, on the other hand, aniline oligomer can be soluble in methanol, ethanol, acetone, tetrahydrofuran and other organic solvents, which can increase its maneuverability, expand the actual application. We synthesize an aniline-oligomers-contained organosilicon, and co-condensate it with inorganic silicon source or carbohydrates. The electroactive inorganic-organic hybrid material will be expanding the field of mesoporous materials in electrical applications.The common way to synthesize mesoporous materials is firstly hydrolyzation and then polymerization inorganic source around the surfactant-type organic templates. According to the previous reports, the weight of mesoporous silica’s templates can be as high as 45-55 %. Clearly, the organic templates must be removed thoroughly to obtain the authentic pore structure. An outstanding template-removal procedure will lead to stable structure, unblocked channel, containing adequate silanol groups, which would be modified by the functional group. To save time and enhance the efficiency, we choose the microwave-assisted catalytic-oxydic approach. Our results show that the templates of the SBA-15 and MCM-41 can be removed completely during a short period by different Fenton agent. It is a high-speed, effectively method of templates removal from mesoporous materials, which can maintain the integrity of meso-structure, and lots of silanol groups at the same time. Finally, we proposed a possible mechanism of how to decompose the templates of SBA-15 and MCM-41 under the different experimental conditions.更多还原