一维、二维超分子聚合物和异孔共价有机框架的构筑及应用

发布时间：2018-07-05 20:02

本文选题：聚合物刷 + 超分子　；参考：《合肥工业大学》2017年硕士论文

【摘要】：本论文的主要研究内容为基于CB[8]包结增强供体-受体作用构筑的一维、二维(2D)超分子聚合物和异孔共价有机框架(Covalent Organic Frameworks, COFs)的构筑以及碘吸附。主要内容包括以下三个部分。第一部分工作内容为基于CB[8]包结增强供体-受体作用构筑的超分子聚合物刷。在这部分工作中,我们设计合成了一种缺电性紫精片段的刚性分子T1和一种带有两个三缩四乙二醇柔性链的富电性萘酚基元分子T2。通过在水溶液中自组装作用,首次构筑了一种新型的超分子聚合物刷。通过核磁滴定实验,紫外实验,动态光散射(DLS),二维扩散排序核磁共振谱(DOSY)证明了线性的超分子聚合物刷的形成。第二部分的工作内容为通过两亲修饰改善水中的二维自组装:构筑高度内部有序的双面2D超分子有机框架(Supromolecular Organic Framework, SOFs)。这部分工作中,我们设计了一种亲疏水链修饰的以三苯胺为核心骨架的吡啶盐组分,通过与CB[8]的主客体相互作用,形成了高度内部有序的双面2D超分子有机框架。通过透射电子显微镜(TEM),原子力显微镜(AFM),同步辐射X-射线小角散射(SAXS).等实验来直接观察所制备的两种不同超分子聚合物的形貌特征。同时证明了通过两亲性而形成的预组装对制备内部高度有序组装材料的重要影响。第三部分的工作内容为由异孔共价有机框架形成的中空球及其超高挥发性碘单质的吸附。共价有机框架在光电材料、催化、气体吸附、转移客体分子等领域有着广泛的应用。但是其拓扑结构有限,急需拓展新的应用方向。在这部分工作中,我们设计合成了一种六醛,通过与对苯二胺在溶剂热条件下形成了具有六边形结构和平行四边形结构的新型拓扑结构的COF。这种COF可以形成微纳米中空球而且对挥发性碘单质具有超高的吸附量。本部分的工作不仅拓展了共价有机框架的拓扑结构多样性,而且拓展了共价有机框架的多样性应用。
[Abstract]:The main contents of this thesis are the construction of one-dimensional, two-dimensional (2D) supramolecular polymers and covalent organic frameworks (COFs) based on CB [8] inclusion enhanced donor-receptor interaction, as well as iodine adsorption. The main content includes the following three parts. The first part is a supramolecular polymer brush based on CB [8] inclusion to enhance donor-receptor interaction. In this work, we have designed and synthesized a rigid molecule T1 with an electrically deficient violet fragment and a electrically rich naphthol motif T2 with two flexible chains of tetraethylene glycol. By self-assembly in aqueous solution, a novel supramolecular polymer brush was constructed for the first time. The formation of linear supramolecular polymer brushes was proved by nuclear magnetic titration, UV, dynamic light scattering (DLS) and two-dimensional diffusion ordered nuclear magnetic resonance spectroscopy (DOSY). In the second part, the two-dimension self-assembly in water is improved by amphiphilic modification. A highly ordered two-sided 2D supramolecular organic framework (SOFs) is constructed. In this part of the work, we designed a hydrophobic chain modified pyridine salt with trianiline as the core skeleton. By interacting with the host and guest of CB [8], we formed a highly ordered two-sided 2D supramolecular organic framework. Transmission electron microscopy (TEM), atomic force microscope (AFM) and synchrotron radiation small angle scattering (SAXS) were used. The morphologies of the two different supramolecular polymers were observed directly. At the same time, it is proved that the pre-assembly formed by amphiphilicity has an important effect on the preparation of highly ordered internal assembly materials. The third part deals with the adsorption of hollow spheres formed by heteroporous covalent organic frameworks and their ultrahigh volatile iodine elements. Covalent organic frameworks are widely used in photovoltaic materials, catalysis, gas adsorption, transfer of guest molecules and so on. But its topology structure is limited, so it is urgent to develop new application direction. In this part of the work, we designed and synthesized a new topological structure COFwith hexagonal structure and parallelogram structure by using p-phenylenediamine in solvothermal condition. This kind of COF can form micro-nano hollow spheres and has a high adsorption capacity for volatile iodine. The work in this part not only expands the topological diversity of covalent organic frame, but also expands the diversity of application of covalent organic frame.
【学位授予单位】：合肥工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3

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