【作者】 王春雷；

【导师】 裘式纶； 朱广山；

【作者基本信息】 吉林大学 ， 无机化学， 2005， 博士

【摘要】 本论文致力于:1 以非离子型表面活性剂为结构导向剂,以沸石原粉或沸石结构导向剂为原料,合成各种具有不同有序度、铝含量、结构和酸性的介孔硅铝材料,并采用原位硅铝核磁对其形成过程进行表征;2 以各种形貌的SBA-15和SBA-16 为模板剂,仿生合成各种氧化锰纳米结构;3 采用分子工程学方法,在介孔SBA-15 表面接枝具有纳米级空腔的PAMAM 树枝形聚合物,并通过金属离子配位,再还原,制备出金属或双金属纳米粒子-介孔硅复合物,通过邻苯二甲酰亚胺修饰的不同代数的PAMAM 接枝的介孔硅与稀土Eu3+配位,敏化铕离子的荧光,共缩合方法合成出了手性离子液体接枝的介孔硅。在第二章中,以沸石FAU-X 原粉合成出了具有不同有序度的MAS-X1-MAS-X7,由于盐效应的影响,MAS-X3 比MAS-X1 的孔壁厚度增加;以FAU-Y沸石结构导向剂为原料,合成出了具有不同酸度的介孔硅铝材料MAS-Y、MAS-Y1 和MAS-TY,原位的硅铝核磁研究表明,介孔硅铝材料在形成过程中沸石结构单元被破坏,硅物种不断聚合形成介孔骨架并伴随铝物种流失。在第三章中,透射电镜结果表明,通过模拟仿生合成的各种氧化锰纳米结构均沿着MnO2(001)方向生长;第四章中,利用PAMAM 纳米级空腔和SBA-15 的介孔孔道的限域作用以及PAMAM 对不同金属离子的配位能力的差异,控制生成纳米粒子的尺寸和在介孔孔道中的位置,生成的铜和钯纳米粒子小于2 nm,位于介孔孔道的边缘;铂-钯双金属纳米粒子大约4 nm,位于孔道的中部。外围邻苯二甲酰亚胺修饰的PAMAM-SBA-15 依靠邻苯二甲酰亚胺基团的天线作用和树枝形聚合物的壳体效应,使Eu3+的荧光得到敏化。振动圆二色谱表征说明手性离子液体修饰的SBA-15 具有明显的手性特征。更多还原

【Abstract】 In 1992, the Mobil Scientists reported the synthesis of a new family of inorganic/organic hybrid materials by the use of self-assembled surfactant molecular aggregates as the structure-directing agents. After removing the organic species, mesoporous aluminosilicates M41S were obtained with uniform pore size and high surface areas. For the past ten years, such materials have attracted considerable attention in the areas such as separation of large molecular, biosensors, catalysis, adsorption, microelectronics, optics, and fabrication of novel nano-objects because of their uniform and adjustable pore properties (pore sizes and pore structures), rich surface functional groups, and designable morphologies (film, fiber, sphere, etc.). However, the application of mesoporous materials was limited due to: 1 difficulty in controlled preparation of mesoporous materials (especial non-silica mesoporous materials), the detail formation of the mesostruture is not very clear, and short of proper in-situ characterization tools for the mechanism of the mesoporous materials; 2 can not achieve function direct synthesis of mesoporous materials; 3 properties of mesoporous materials such as hydrothermal stability and acidity etc. are expect to be improved; 4 new application fields are urgent needed to be explored; 5 more convenient and time-saving as well as low-cost synthesis methods are also obligatory. The current contribution concerning on the following topics: 1 preparation of mesoporous aluminosilicates in strong acidic media, in-situ NMR technique are used to investigate the conversion of inorganic species during the formation of mesostructure; 2 biomimetic preparation of MnO2 nanostructure using mesostructured silica (SBA-15 and SBA-16) with different morphologies; 3 modify the mesoporous silica SBA-15 tunnels and surface using molecular engineering method. Mesoporous aluminosilicates (MAS-X1-7) with different mesophase are prepared by using Pluronic P123, F127, Brij 56, 76, and Triton X100 as structure-directing agents (SDA) and high aluminum content zeolite such as FAU-X, LTA, and SOD etc. as silica source in a strong acidic media. Both the mesophase and cell parameter of the MAS-X1 and MAS-X3 are the same, but the pore size of MAS-X3 is 6 nm while the pore size of MAS-X1 is 8.5 nm. And the wall thickness of MAS-X3 (6 nm) is much thicker than that of MAS-X1 (3.5 nm). The Si/Al ratio of MAS-X1 is 16, and that of MAS-X3 is lower than 8. High ordered cubic Im3m mesoporous aluminosilicates MAS-X2 and MAS-X4 are prepared using F127 or F108 as SDA. Low ordered MAS-X5-7 are also prepared using Brij 56, 76 and Triton X100 as SDA. The salt NaCl, which is introduced by dissolving the zeolite FAU-X, can dramatic enhance the self-assembly ability of organic species, thus high ordered mesoporous aluminosilicates (MAS-X1, MAS-X2 and MAS-X4) are resulted. The dynamics radius of P123 micell decreased due to the salt effect, led to formation p6mm mesoporous aluminosilicates MAS-X1 and MAS-X3 with different wall-thickness. Mesoporous aluminosilicates MAS-Y, MAS-Y1, and MAS-TY with different acidity are prepared using zeolite FAU-Y structure directing agent (performed zeolite seeds) as precursor in a strong acidic media. The formation procedure is characterized by in-situ 27 Al NMR and 29 Si NMR techniques. The formation of the inorganic framework is due to the condensation of the silica species,accompanied by loss of the aluminum species form the inorganic framework. Zeolite primary and secondary structured units decomposed in acidic media, and re-assembled each other. So, any operation that can avoid the decomposition of the zeolite primary and secondary structured units will lead more zeolite units in the inorganic wall of mesoporous aluminosilicates. As the properties of the mesoporous solid such as acidity are directly relative to the composition of the wall of the mesoporous materials, MAS-Y synthesized by adjusting pH value slowly can preserve more zeolite units in the wall so the acidity of MAS-Y are higher than that of MAS-Y1 and MAS-TY. Mesostructured silica templated by block copolymer such as P123 or F127 possess periodical array of inorganic-organic structure with organic chain penetrated into inorganic wall. Mesoporous tunnels and micropore are leave after removal of organic template. When mesostructured silica SBA-15 or SBA-16 with different morphology is impregnated in high oxidated solution of acidic potassium permanganate, the organic template can be oxidated to small molecule, such as formaldehyde, glycoldehyde, formalacid, and acetic acid etc.. These small molecules released from the mesopore and micropore of mesoporous silica, then react with potassium permanganate, MnO2 nanostructures with different morphology are then formed on the surface of the mesoporous solid. Such a procedure is terribly similar to the biomimetic progress, which characterized by the nucleation and growth of inorganic mineral are controlled by organic species secreted by organism. Disordered nanostructured MnO2 composed of 1-D nanorods with diameter 20 ~ 50 nm, length several handed nm are grew on the surface of the wheat like SBA-15; when rod like SBA-15 with mesopore parallel to long-axel of the rod is used as template, the growth direction of MnO2 nanorods are nearly upright to the mesoporous silica rod; flower like MnO2 nanostructure are formed on the surface of single crystalline like mesoporous silica SBA-16; crew like MnO2 nanostructure composed of nanowire with diameter about 20 nm are formed on the surface of monolith of SBA-15 under更多还原