Targeted Design And Praparation Of Porous Aromatic Frameworks And Their Functionlization

Porous organic frameworks (POFs), being famous for their whole organiccomponents, have attracted significant interests in catalysis, gas storage, energyconversion, and optoelectronics. Porous aromatic frameworks (PAFs), as a subclass ofporous organic materials, have made progress in design and synthesis of uniqueporous frameworks. This work chooses the building blocks with different nodes, usingdiverse coupling reaction, prepared a series of porous aromatic frameworks withmultiple functions. In the second and third chapters, we select the tetrahedral buildingblocks with linear (two nodes) and triangle (three nodes) bridges to prepare theamorphous and crystalline porous materials respectively. They could be applied inalcohol-water separation and toxic nitro explosives monitoring fields. In the forth andfifth chapters, we use the triangle building block, cyanogens chloride, to synthesizethe cation skeleton pyridinum-type porous aromatic frameworks. The targeted porousmaterials could serve as the antibacterial coatings and gas adsorbates for separation.First, we choose tetrakis(4-bromophenyl)methane and tetrakis(4-bromophenyl)germanium as the rigid tetrahedral monomers, using benzene-1,4-diboronic acid and4,4’-biphenyldiboronic acid as linear bridges to gain PAF-11, GPAF-1and GPAF-2via Suzuki coupling reaction. The three porous materials reveal a good thermal andsolvent stability. Besides, PAF-11material exhibits a relatively large specific surfacearea. And we process various gas sorption experiments such as hydrogen, toluene,benzene, methanol and water. The results show that PAF-11has stronge interaction toharmful aromatic compounds and the PAF material can be used in the industry forharmful gas capture. Besides, PAF-11with super hydrophobic quality could be usedin industrial alcohol-water separation.Second, we developed a novel tetrahedron building unittetra(4-dihydroxyborylphenyl)germanium using1,2,4,5-tetrahydroxybenzene and2,3,6,7,10,11-hexahydroxytriphenylene as the linkers to prepare the porous aromaticframeworks CPAF-13, PAF-14and PAF-15. Powder X-ray diffraction shows that thethree materials are all crystalline materials. And the experiment results compared withtheoretical simulation results, PAF-14and PAF-15have ctn topology. Fluorescence tests indicate that two materials have high fluorescence quantum efficiency, and theyexhibit a unique fluorescence quenching phenomenon to poisonous and harmfulexplosive nitrobenzene,2,4–dinitrotoluene, and TNT.Third, we use a cheap triangle monomer cyanuric chloride and4-pyridinylboronic, through a classic boronic acid self-coupling reaction and pyridinequaternary ammonium salt coupling reaction, to obtain the porous aromaticframework PAF-50. There are free Cl-ions in the PAF-50channel, together with theAg+ions to form the AgCl. Two PAF materials could be dispersed into variouscommercial polymer materials to gain antibacterial paint. The antibacterial coatinghas excellent antibacterial properties and has the potential application value in thefield of medical devices.Finally, we took the advantage of the free Cl-ions in the PAF-50channel whichcould be exchanged with other ions to form F-PAF-50, Br-PAF,2I-PAF-50, and3I-PAF-50with different pore sizes. Gas sorption and chromatographic columnexperiments show that the materials with different aperture size can separate differentgas molecules by size limited effect. And through a reasonable assembly, the fivecommonly used industrial gases hydrogen, oxygen, nitrogen, methane and carbondioxide can be separated one by one readily.