金属卟啉、杂多酸仿生框架催化剂的设计合成与性质

发布时间：2018-06-28 21:11

本文选题：金属-有机框架材料 + 共价有机框架材料　；参考：《浙江大学》2017年博士论文

【摘要】：新型多孔材料的设计合成和应用一直以来都是配位化学和材料化学的研究热点,其中包括基于配位键自组装的金属-有机框架材料(MOFs),基于共价键的有机框架材料(COFs)和由多酸阴离子与无机金属簇构筑的有机-无机杂化材料等,这一系列功能型多孔材料因其复杂多变的结构而表现出多样的物理化学性质。通过对生物酶催化机理的研究和学习,设计合成不同种类的仿生配体,从而与无机金属簇构筑仿生框架材料,将其应用于仿生非均相催化具有其重要的科学意义与实际应用价值。本论文主要以仿生金属卟啉配体5,10,15,20-四(3,5-二羧基苯基)卟啉(H10OCPP)、5,10,15,20-四氨基苯基卟啉(H2TAPP)为功能化构筑单元,分别与不同金属离子或有机配体构筑了 6个金属-卟啉框架材料和共价键有机框架材料。同时,利用夹心型杂多酸[WZn{Cu(H20)}2(ZnW9034)2]12-和Gd3+离子合成了二维多孔晶型材料CZJ-11,并实现了单晶到单晶的结构转变,得到了具有三维结构的化合物CZJ-12。此外,利用X-射线单晶衍射、粉末-X射线衍射、固体核磁、红外、紫外、热重、元素分析、扫描电镜、透射电镜、原子吸收光谱等多种实验方法对以上多孔材料进行表征和分析。根据不同化合物在结构、孔道及催化中心等方面的不同,我们还对材料在仿生催化活化分子氧方面进行了针对性的研究,深入探讨了仿生框架材料的结构、金属节点和活性位点对催化效果的影响,将其应用于温和条件下烯烃环氧化、有氧氧化芳香烷烃、选择性氧化脂肪醇等领域,对催化反应的非均相性、催化机理、底物尺寸选择性、转化数等进行调控和研究,取得了良好的催化效果。
[Abstract]:The design, synthesis and application of new porous materials have always been the research focus of coordination chemistry and material chemistry. These materials include metal-organic framework materials (MOFs) based on coordination bond self-assembly, organic frame materials (COFs) based on covalent bonds and organic-inorganic hybrid materials constructed from polyacid anions and inorganic metal clusters. This series of functional porous materials exhibit various physical and chemical properties because of their complex and changeable structure. By studying the mechanism of enzyme catalysis, different bionic ligands were designed and synthesized, and the biomimetic frame materials were constructed with inorganic metal clusters. It has important scientific significance and practical application value to apply it to bionic heterogeneous catalysis. In this paper, the biomimetic metalloporphyrin ligands (5101010) -tetra (3OCPP) (H10OCPP) (H10OCPP) were used as functionalized building units, and the biomimetic metalloporphyrin ligands (510OCPP) (H10OCPP) were used as functional building units. Six metal-porphyrin frame materials and covalent organic frame materials were constructed with different metal ions or organic ligands respectively. At the same time, two dimensional porous crystal material CZJ-11 was synthesized by using [WZn {Cu (H20)} 2 (ZnW9034) 2] 12- and Gd3 ions. The structure of single crystal to single crystal was realized, and the compound CZJ-12 with three-dimensional structure was obtained. In addition, X-ray single crystal diffraction, powder X-ray diffraction, solid nuclear magnetic field, infrared, ultraviolet, thermogravimetric, elemental analysis, scanning electron microscopy, transmission electron microscopy, The porous materials were characterized and analyzed by atomic absorption spectrometry (AAS). According to the different structures, channels and catalytic centers of different compounds, we also studied the biomimetic catalytic activation of molecular oxygen, and discussed the structure of bionic frame materials. The effects of metal nodes and active sites on the catalytic effect were investigated. The catalysts were applied in the fields of epoxidation of olefins, aerobic oxidation of aromatic alkanes and selective oxidation of fatty alcohols under mild conditions. The substrate size selectivity and conversion number were regulated and studied, and good catalytic effect was obtained.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O643.36

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