【摘要】 以2-(二苯基膦)乙基三乙氧基硅烷和正硅酸乙酯为混合硅源,采用延时共缩聚法经表面活性剂F127自组装合成了二苯基膦(PPh2)修饰的SBA-16纳米介孔分子筛(PPh2-SBA-16),通过PPh2配体络合Ru(Ⅱ)化合物制备出固载化的Ru(Ⅱ)非均相催化剂(Ru-PPh2-SBA-16),样品仍然保持了SBA-16的规整孔道结构.以水相中高烯丙醇异构化反应为探针,考察了所制备催化剂的催化性能,发现其对目标产物具有高选择性,虽然其催化活性略低于对应的均相Ru(Ⅱ)催化剂,但该催化剂易与产物分离,且重复使用三次后催化效率基本不变,活性相与载体结合牢固,不存在明显的脱落和流失,因此更适合于工业化应用.更多还原

【Abstract】 Based on the self-assembly of F127,a new SBA-16-like mesoporous silica modified with diphe-nylphosphine group（PPh₂-SBA-16） was synthesized by extend co-condensation with tetraethoxysilane（TEOS） and 2-（diphenylphosphino）ethyltriethoxysilane（DPPTS） as the mixed silicon source.The PPh₂-SBA-16 was used as a support to immobilize the Ru（Ⅱ） ions through strong coordination between PPh₂-group and Ru（Ⅱ）, denoted as Ru-PPh₂-SBA-16.The characterizations demonstrate that the Ru-PPh₂-SBA-16 still remained ordered mesoporous structure.During the isomerization of homoallylic alcohols carried in water as a environmentally friendly medium,the as-prepared Ru-PPh₂-SBA-16 catalyst exhibited an excellent selectivity,almost the same as the corresponding homogeneous catalyst[RuCl₂（PPh₃）₃].Although its activity was slightly lower than that of RuCl₂（PPh₃）₃,the Ru-PPh₂-SBA-16 could be considered more suitable for industrial application based on the following benefits:（1） The catalyst could be easily separated from the reaction products.（2） The catalyst could be used repetitively at least for 3 times without significant activity decrease.（3） The Ru（Ⅱ） was strongly immobilized on the support which could effectively inhibit the leaching of active sites and protect the environmental pollution from heavy metals.更多还原