中文摘要
本项目研究了具有MWW结构的钛硅分子筛的合成、结构修饰和液相选择氧化催化性能。在此基础上开展了具有烯烃选择氧化和环氧化物碳酸酯化双功能催化剂，以及兼备醛类氨氧化和醛肟贝克曼重排制备酰胺的双功能催化材料的设计、制备和催化性能的研究。采用结构可逆转变后处理补钛法，成功将钛不受空间位阻的影响引入脱硼MWW分子筛的晶体骨架,制备得到了高活性Ti-MWW分子筛。利用该层状分子筛结构具有可塑性的特点，通过采用表面活性剂层间溶胀和超生波处理相结合的手段，成功制备得到了层间结构剥离的具有大比表面积、满足大分子催化氧化的层剥离钛硅分子筛。将有机客体季铵盐以化学键方式嫁接到所合成的钛硅分子筛表面，制备得到了由丙烯、双氧水和二氧化碳一步合成碳酸丙烯酯的催化材料。在Ti-MWW上用浸渍法负载氢氧化铑负载制备得到了Rh(OH)x/Ti-MWW双功能催化剂，将其用于一步法催化醛类合成酰胺具有高的活性和选择性，从而开拓Ti-MWW除了在催化氧化直链烃、环烷烃、氨肟化反应以外的应用，为实现合成酰胺的反应步骤简单化，反应过程绿色化，提供了一种合成酰胺的新途径。
英文摘要
This research has carried out the study on the synthesis, structural modification and liquid-phase selective oxidation properties of MWW-type titanosilicate catalysts. Furthermore, two kinds of bifunctional catalysts, one combining together the alkene epoxidation and cycloaddition catalytic activity and the other having both the ammoximation of aldehydes and Beckmann rearrangement ability, have been designed and prepared. Highly actively and selective Ti-MWW has been prepared by incorporating Ti species into the framework of deboronated MWW zeolite through a reversible structure conversion postsynthesis, in which the steric hindrance of the pore windows has been avoided. Taking the advantage of structural diversity of layered materials, Ti-MWW was converted by interlayer swelling with surfactant and untrasound treatment into delaminated materials which had high external surface, open porosity and showed high activity for bulky molecules. A bifunctional catalyst for one-pot synthesis of propylene carbonate was prepared successfully through grafting quaternary ammonium halides onto delaminated Ti-MWW. A novel bifunctional catalyst Rh(OH)x/Ti-MWW was prepared by impregnation method. Rh(OH)x/Ti-MWW possessed two kinds of metals which could simultaneously catalyze ammoximation and rearrangement of aldehyde oximes. It proved to be useful in catalyzing one-pot synthesis amide from aldehyde. This novel method is a green and convenient approach for amide synthesis
结题摘要
本项目研究了具有MWW结构的钛硅分子筛的合成、结构修饰和液相选择氧化催化性能。在此基础上开展了具有烯烃选择氧化和环氧化物碳酸酯化双功能催化剂，以及兼备醛类氨氧化和醛肟贝克曼重排制备酰胺的双功能催化材料的设计、制备和催化性能的研究。采用结构可逆转变后处理补钛法，成功将钛不受空间位阻的影响引入脱硼MWW分子筛的晶体骨架,制备得到了高活性Ti-MWW分子筛。利用该层状分子筛结构具有可塑性的特点，通过采用表面活性剂层间溶胀和超生波处理相结合的手段，成功制备得到了层间结构剥离的具有大比表面积、满足大分子催化氧化的层剥离钛硅分子筛。将有机客体季铵盐以化学键方式嫁接到所合成的钛硅分子筛表面，制备得到了由丙烯、双氧水和二氧化碳一步合成碳酸丙烯酯的催化材料。在Ti-MWW上用浸渍法负载氢氧化铑负载制备得到了Rh(OH)x/Ti-MWW双功能催化剂，将其用于一步法催化醛类合成酰胺具有高的活性和选择性，从而开拓Ti-MWW除了在催化氧化直链烃、环烷烃、氨肟化反应以外的应用，为实现合成酰胺的反应步骤简单化，反应过程绿色化，提供了一种合成酰胺的新途径。