二次元ナノ構造をもつゼオライトの合成と触媒応用

首先，本研究着重于控制具有不同晶体对称元素的沸石层堆叠。在受控条件下，1-乙基-3-甲基咪唑鎓的“二聚体”和“单体”有机物分别选择性地引导不同但相关的锗硅酸盐、具有新拓扑结构的ECNU-16和具有UOS拓扑结构的现有IM-16。基于分子力学模拟的综合计算研究表明，沸石相选择性是由“二聚体”和“单体”有机物独特的空间填充行为决定的，这与它们的旋转自由度以及主体沸石通道的包含体积密切相关。一种实现不同层状沸石前驱体间拓扑转化的Ge循环策略（fer-type和pcr-type）通过三维（3D）锗硅酸盐UTL在这项研究中被发现。这种Ge再循环方法的发现使得能够将层状沸石前体从一种结构转换为另一种结构，这两种结构都可以进一步衍生自不同的沸石。该研究不仅在结构不同的层状沸石之间，而且在两个沸石材料家族之间建立了新的关系。

First, the control of the zeolitic layer stacking with different crystal symmetry elements was focused in this research. Under controlled conditions, the “dimer” and “monomer” organics of 1-ethyl-3-methylimidazolium selectively direct different, but related, germanosilicates, the ECNU-16 with a new topology and the existing IM-16 with the UOS topology, respectively. The comprehensive computational study based on the molecular mechanic simulations revealed that the zeolite phase selectivity was determined by the unique space-filling behavior of the “dimer” and “monomer” organics, which was closely correlated with their rotation freedom, as well as the included volume of host zeolite channels.On the other hand, a Ge-recycling strategy that realized the topotatic transformation between different lamellar zeolitic precursors (fer-type and pcr-type) through three-dimensional (3D) germanosilicate UTL was discovered in this research. The discovery of this Ge-recycling process enabled to switch the lamellar zeolitic precursor from one structure to the other, both of which could be further derived of diverse zeolites. This study established new relationships not only between structurally distinct lamellar zeolites but also two families of zeolitic materials.