【作者】 张昉；

【导师】 李和兴；

【作者基本信息】 上海师范大学 ， 物理化学， 2006， 硕士

【摘要】 开发出能够在无毒无害的水介质中使用高效催化剂是实现绿色化学目标的重要组成部分。介孔硅材料具有大比表面积、规整的孔道结构，能够保证负载催化剂活性位的高分散，维持均相催化剂原有的活性和选择性。同时，介孔硅材料表面具有丰富的羟基，易于表面功能化，为固载化均相催化剂提供了良好的基础。最重要的是非均相催化剂能够克服均相催化剂与产物分离难、无法重复使用的不足，因此更适合于工业化应用。 本论文采用表面活性剂自组装法合成了一系列具有不同结构的介孔硅材料和NH₂-MCM-41、NH₂-SBA-15、PPh₂-SBA-15、PPh₂-SBA-16、PPh₂-KIT-6以及PPh₂-FDU-12系列有机-无机杂化硅材料，以此为载体，采用共价键接枝方法固载过渡金属化合物RuCl₂（PPh₃）₃，得到具有纳米介孔结构的有机金属催化剂。选择高烯丙醇异构化反应为探针，尝试以水代替有机溶剂，开辟在环境友好介质中进行有机合成的新途经。结合催化剂表征和反应机理，阐述构效关系和催化反应机理。主要内容如下： 1．通过无机硅烷预水解的方法，制备了较高修饰量的NH₂-SBA-15。该材料具有有序的六方排列孔道结构，有机基团均匀锚定在载体的孔壁上。同时还以共缩聚法合成了NH₂-MCM-41，样品比表面积大，孔径均一。以上述材料为载体，通过胺基配位的方式合成了具有纳米介孔结构的负载型Ru（Ⅱ）催化剂。该类催化剂在高烯丙醇异构化反应显示出高选择性和良好的活性。其中胺基修饰量为10％的Ru-NH₂-SBA-15催化水中高烯丙醇异构化反应10h后，4-苯基-3-丁烯-2-醇得率为54％，选择性可达91％，且催化剂可重复套用4次，反应的转化率和选择性没有太大的变化。但胺基修饰量为10％的Ru-NH₂-MCM-41，4-苯基-3-丁烯-2-醇得率却只有31％，这主要是由于MCM-41型催化剂孔径较小，当有机大分子催化剂锚定到孔道后，材料的有序性较SBA-15型催化剂差的缘故。 2．采用预水解共聚法制备了二苯基膦基修饰的PPh₂-SBA-15，修饰量可达10％，样品结构类似于SBA-15介孔材料。以该材料为载体，通过二苯基膦基络合的方式制备了具有纳米介孔结构的负载型Ru（Ⅱ）催化剂。当二苯基膦基修饰量为10％时，该催化剂在水溶剂中高烯丙醇异构化反应中显示出优良的催化活性，更多还原

【Abstract】 Development of harmless and highly effective catalysts used in water phase is one of important goal of "Green Chemistry". Mesoporous silicate materials are of uniform and tailored pore size, stable framework, suitable wall thickness, high surface area and the plenty silanol groups on its inner surface, which are favourable for modification. Organic-metal catalysts supported on these mesoporous materials can exhibit comparable activity and selectivity with their corresponding homogeneous catalysts and are more preferable for industrial application because of easy separation and repeated use.In this paper, modified mesoporous silicate materials, such as NH₂-MCM-41、 NH₂-SBA-15、 PPh₂-SBA-15、 PPh₂-SBA-16、 PPh₂-KIT-6 and PPh₂-FDU-12, were synthesized by self-assembly of surfactant. Ru（II） catalysts supported these materils were prepared by covalent bonding method and characterized by XRD, TEM, N2 adsorption-desorption and Solid NMR etc. Their catalytic performance was evaluated with homoallylic isomerization reactions as the probe in water media instead of traditionally used organic solvents, which could be considered as an example in green chemistry. The relationship between their catalytic behaviors and structural characters of the as-prepared catalysts was discussed briefly, and the reaction mechanism was studied. The detail is as follows:1. By prehydrolysis of inorganic silica sources, NH2-SBA-15 with high contents of amine groups was synthesized. It was of well-ordered arrays of mesochannels and a typical two-dimensional p6mm hexagonal symmetry. While the method of co-condensation of organic and inorganic silicon sources at room temperature was employed to synthize NH₂-modified mesoporous NH2-MCM-41 materials, which has large surface area and narrow pore size distribution. Ru（II） catalysts supported these materials were prepared by coordination, which exhibited high selectivity and good activity for homoallylic isomerization reactions in water. For example, yields of 4-phenyl-3-buten-2-ol can reach 54% and selectivity to 4-phenyl-3-buten-2-ol exceed更多还原