Design,Preparation And Application Of Ferrocene-Based Conjugated Microporous Polymers

Due to high BET specific surface area,good thermal stability,chemical stability and light weight,conjugated microporous polymers have found potential applications for solving some enviromental problems,such as developing new energy,alleviating environmental pollution and so on.In the present dissertation,3 series of Ferrocen-based conjugated microporous polymers were designed and synthesized,and gas adsorption and dye adsorption properties of the products were systematically investigated.Firstly,ferrocene-based conjugated microporous polymers（FcNOP-1 and FcNOP-2）were successfully produced by Yamamoto coupling reaction from1,1’-dibromo-ferrocene（FcBr）and 5,10,15,20-tetrakis（4-bromophenyl）porphyrin（TBPP）or tetrakis（4-bromophenyl）methane（TBPM）.The results indicated that both FcNOP-1 and FcNOP-2 have good porosity with BET specific surface area of638.1 and 422.3 m²/g,respectively.The selective adsorption coefficient of FcNOP-1 was 51.3 for a CO₂/CH₄ mixture at 273 K/1 bar.Uptake of methyl violet for FcNOP-1 reached 32.5mg/g,and the recycling adsorption efficiency of FcNOP-1 and FcNOP-2 exceeded 94%.Secondly,two kinds of carbazole-ferroceneyl conjugated microporous polymers（P-DCPFc and P-DCFc）were designed and synthesized in the presence of FeCl₃ as a catalyst.1,1’-Di（9-Carbazolyl）)phenylferrocene（DCPFc）and1,1’-Di（9-carbazolyl）ferrocene（DCFc）were synthesized from 1,1’-dibromoferro-cene（FcBr）,respectively.Characterization results indicated that the BET specific surface area and the pore volumeof P-DCPFc and P-DCFc were 429.7,594.0 m²/g and 0.2,0.4 cm³/g,respectively.P-DCPFc and P-DCFc exhibited similar gas storage and dye adsorption properties.After three cycles,adsorption efficiency of organic dye of P-DCPFc still exceeded 90%.Finally,a series of Azo-based conjugated microporous polymers（AzNOP-1,AzNOP-2,AzNOP-3）were prepared by using 5,10,15,20-tetrakis（4-nitrophenyl）porphyrin（TNPP-H₂）as the central building unit,tetra-or bi-amino aromatic compounds as linking units.The chemical structure,porous properties,and the application in gas adsorption and dye adsorption of AzNOPs were systematically studied.The BET surface areas of AzNOP-1 and AzNOP-2 exceeded 400 m²/g,and had good selective adsorption property for the CO₂/CH₄ mixture at 273 K/1bar/The methyl violet adsorption efficiency of AzNOP-1 and AzNOP-2 after three cycles is 98.8%and 97.5%,respectively.