氟掺杂多孔聚合物的制备及其吸附性能

Preparation and adsorption properties of fluorine-doped porous polymers

共轭微孔聚合物(CMPs)由于其稳定的孔隙结构、多样的合成方法及在气体吸附、废水染料吸附等领域的应用受到了广泛关注。设计并合成了两种氟掺杂共轭微孔聚合物:首先合成了两种含氟构筑单元1,3,5-三氟-2,4,6-三乙炔基苯(FAB)和5,10,15,20-四(2-氟-4-乙炔基苯基)卟啉(TFPP)。分别以FAB和TFPP为构筑单元,以1,1’-二溴二茂铁(Fc(Br)_(2))为链接单元,基于Sonogashira偶联反应,成功制备了两种氟掺杂多孔聚合物氟掺杂多孔聚合物二茂铁基(Fc)-FAB-CMP和Fc-TFPP-CMP。并进一步对两种多孔聚合物的化学结构、热稳定性、孔隙结构、气体及染料吸附性能等方面进行了详细的分析。结果表明,两种聚合物均表现出良好的热稳定性。Fc-FAB-CMP和Fc-TFPP-CMP的BET比表面积分别为302.89 m^(2)/g和125.2 m^(2)/g,其中Fc-FABCMP表现出更加优异的气体吸附性能。此外,二茂铁单元与氟取代基的引入可成为阳离子染料甲基紫(MV)的吸附位点,Fc-FAB-CMP相较于许多更高比表面积的聚合物表现出对MV更优异的吸附能力,最大吸附量可达318 mg/g。

Conjugated microporous polymers(CMPs)have attracted extensive attention due to their stable pore structure,various synthesis methods and applications in gas adsorption and dye adsorption in wastewater treatment.Based on the Sonogashira coupling reaction,two fluorine-doped porous polymers(synthetic route of ferrocene(Fc)-1,3,5-trifluoro-2,4,6-triethynylbenzene(FAB)-CMP,Fc-5,10,15,20-tetrakis(2-fluoro-4-ethynylphenyl)porphyrin(TFPP)-CMP)were designed and synthesized by using FAB and TFPP as the center construction units,1,1'-dibromoferrocene(Fc(Br)_(2))as a linking unit.The chemical structure,thermal stability,elemental composition and particle morphology of CMPs were investigated in detail.The results show that the fluorine-doped porous polymer is successfully synthesised by the Sonogashira coupling reaction,and the product exhibits good thermal stability and stable porosity.The BET specific surface areas of Fc-FAB-CMP and Fc-TFPP-CMP are 302.89 m^(2)/g and 125.2 m^(2)/g,respectively.Moreover,the introduction of ferrocene and fluorine can be the adsorption site of cationic dye methyl violet(MV),the highest adsorption value of Fc-FAB-CMP for MV reaches 318 mg/g.