基于四醛基配体的三维亚胺类COFs材料的设计合成与结构表征

发布时间：2018-04-27 23:40

本文选题：四醛基配体 + 三维亚胺类COFs　；参考：《吉林大学》2017年硕士论文

【摘要】：共价有机骨架材料(COFs)是一类新兴的多孔结晶聚合物材料,它有着广泛的应用如气体吸附和分离、催化、光电子学、化学传感、药物递送和清洁能源等。与其它结晶多孔材料相比,COFs材料具有很多独特的优势,例如密度低、表面积大、孔径和结构可调、易功能化等。这一领域的快速发展吸引了科研工作者的广泛关注。尽管二维COFs材料设计合成已经很好的建立起来,然而目前三维COFs材料的设计与合成却仍是个挑战。因此探索开发新型三维COFs材料,使它们性能多样化是至关重要的。这些在本论文的第一章绪论中进行了详细的讨论,除此之外,还在第一章绪论中讨论了COFs材料的分类、设计原则、合成方法以及它们在不同领域的应用。在第二章中,一种新型结晶亚胺类共价有机骨架材料TA-COF-1,在溶剂热条件下由四-(4-酰基苯基)甲烷与对苯二胺首次通过缩合反应生成。TA-COF-1晶体结构通过PXRD、SEM、FT-IR以及TGA等表征进行了研究。结果表明TA-COF-1具有良好的热稳定性,高Langmuir表面积(1771.19 m2g-1),小孔径(1.28 nm)和大的孔体积(0.753 cm3g-1)。此外,TA-COF-1对H2的吸附量高达61.78 cm3 g-1的。值得一提的是,这是第一次使用四面体结构的醛基配体来成功合成三维结晶亚胺类COFs。在第三章中,另一种新型结晶亚胺类共价有机骨架材料TA-COF-2,是在溶剂热条件下由四-(4-酰基苯基)甲烷与四-(4-氨基苯基)甲烷首次通过缩合反应生成。TA-COF-2晶体结构通过PXRD、SEM、FT-IR以及TGA等表征进行了研究。结果显示TA-COF-2具有好的热稳定性和化学稳定性,高Langmuir表面积(1313.91 m2 g-1),小孔径(0.73 nm)和大的孔体积(0.474 cm3 g-1)。此外,TA-COF-2对H2的吸附量高达106.02 cm3 g-1,对CO2的吸附量为43.64 cm3 g-1。值得一提的是,这是第一次使用两个同为四面体结构的醛基/氨基配体来成功合成三维COFs.在第四章中,我们借鉴传统多级孔沸石分子筛的合成方法,选取硅藻土作为合成多级孔COFs材料的基底,通过原位合成策略首次成功制备出具有多级孔结构的硅藻土/共价有机骨架复合材料(标记为Dt-EA/TA-COF-2)。该复合材料因硅藻土中大孔的引入,克服了TA-COF-2自身的单级微孔劣势,这也为该复合材料更多的潜在应用优势提供了可能,并且这种基于硅藻土合成多级孔COFs材料的策略也为后续相关合成工作提供了宝贵的参考价值。
[Abstract]:Covalent organic framework material (COFs) is a new class of porous crystalline polymer materials, which has been widely used in gas adsorption and separation, catalysis, optoelectronics, chemical sensing, drug delivery and clean energy. Compared with other crystalline porous materials, COFs have many unique advantages, such as low density, large surface area, adjustable pore size and structure, easy functionalization and so on. The rapid development of this field has attracted wide attention of researchers. Although the design and synthesis of 2D COFs materials have been well established, the design and synthesis of 3D COFs materials is still a challenge. Therefore, it is very important to explore and develop new three-dimensional COFs materials and to diversify their properties. These are discussed in detail in the first chapter of this paper, in addition to the introduction of the first chapter, the classification of COFs materials, design principles, synthesis methods and their applications in different fields are discussed. In the second chapter, a new crystalline imine covalent organic skeleton material, TA-COF-1, was synthesized by condensation reaction of tetrachloro-4-acylphenyl) methane with p-phenylenediamine under solvothermal conditions. The crystal structure of TA-COF-1 was characterized by PXRDNSEMFT-IR and TGA. The results show that TA-COF-1 has good thermal stability, high Langmuir surface area of 1771.19 m2g-1g ~ (-1), small pore size of 1.28 nm) and large pore volume of 0.753 cm ~ (-3) g ~ (-1). In addition, the adsorption capacity of TA-COF-1 for H _ 2 was 61.78 cm3 / g ~ (-1). It is worth mentioning that this is the first time that three dimensional crystalline imines have been successfully synthesized by using tetrahedral aldehydes as ligands. In chapter III, Another new crystalline imine covalent organic skeleton material, TA-COF-2, was first synthesized by condensation reaction of tetramethane-4-acylphenyl) methane with tetra-butadiene-4-aminophenyl) methane in solvothermal condition. The crystal structure of .TA-COF-2 was characterized by PXRDX SEMT-IR and TGA etc. The results show that TA-COF-2 has good thermal and chemical stability, with high Langmuir surface area of 1313.91 m2 / g ~ (-1), small pore size of 0.73 nm) and large pore volume of 0.474 cm3 / g ~ (-1). In addition, the adsorption capacity of TA-COF-2 for H _ 2 and CO2 for H _ 2 and CO2 was 106.02 cm3 g-1 and 43.64 cm3 g-1, respectively. It is worth mentioning that this is the first time that three dimensional COFs have been successfully synthesized using two aldehydes / amino ligands with the same tetrahedron structure. In the fourth chapter, we choose diatomite as the substrate for the synthesis of multi-porous COFs materials by using the traditional synthesis method of multi-porous zeolite molecular sieve. Diatomite / covalent organic skeleton composites with multilevel pore structure (labeled Dt-EA-TA-COF-2) were successfully prepared by in-situ synthesis strategy for the first time. Because of the introduction of macropores in diatomite, the composite overcomes the single-stage micropore disadvantage of TA-COF-2 itself, which provides the possibility for the composite to have more potential application advantages. The strategy of synthesizing multilevel porous COFs materials based on diatomite also provides valuable reference value for the subsequent synthesis work.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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