Functionalized Porous Organic Frameworks:Synthesis,Characterization And Properties

Covalent organic porous polymers (COPs) are an emerging new type of porous polymers, which are linked by covalent bonds between organic building blocks. COPs mainly including crystalline and amorphous porous organic polymers, such as covalent organic frameworks (COFs) and porous organic polymers (POPs). In the last decade, the research of these porous materials had flourished no matter in synthetic strategies or functional applications. COPs display a number of advantages, such as high surface area, strong stability, designable and tunable structure, etc. Because of these excellent properties, COPs have been widely used in various fields. In current research, especially in the chemical pharmaceutical industry, seeking a green, safe and environment-friendly technology is in great urgency. Therefore, preparing a recyclable catalyst that could minimize the pollution and optimize the efficiency is always the research hotspot.Based on the above background, the present paper designed and synthesized a crystalline COFs material (COF-SDU1) and an amorphous POPs material (TFPA-FePor-POP), and used them for heterogeneous coupling reaction and biomimetic catalytic system, respectively. This paper mainly includes the following aspects in detail:In chapter 1, the characteristics of the organic porous material and its progress in diffluent application was introduced firstly. Then, the status of the silicon-based C-C coupling reactions and examples were briefly discussed. Finally, the overview about the status and significance of bionic artificial enzyme catalyst was expressed.In chapter 2, a triazine-based covalent organic framework (COF-SDU1) was synthesized through facile solvothermal conditions and characterized by IR, solid state 13C NMR, XRD, elemental analysis and BET. By a simple solution infiltration method, Pd(II) species were successfully immobilized into COF-SDU1 due to its two-dimensional eclipsed layer-sheet structure and nitrogen-rich content. High-resolution TEM images showed the uniform loading of the Pd species into the COF-SDU1 matrix. By using this hybrid material, Pd(II)/COF-SDUl, as a sustainable and green catalyst, one-pot cross-coupling of silanes and aryl iodides was realized with high selectivity. The catalyst can be easily recovered by a simple separation process and recycled several times without obvious loss of activity and selectivity.In chapter 3, iron porphyrin-based porous organic polymer (TFPA-FePor-POP) was synthesized and characterized. Although it was an amorphous polymer, it still had a high surface area. To study its intrinsic enzyme-like activity, TFPA-FePor-POP was used as peroxidase mimics in biomimetic catalytic system to quantitatively detect H2O2. TFPA-FePor-POP showed the excellent performance in this biomimetic catalytic system. And it had a higher affinity for substrates than HRP. This will develop a new research direction for porous organic polymers in biochemistry.