Controllable Preparation Of Ferrocene-based Porous Organic Polymers Materials And Its Property

Recently,novel porous polymers materials via “bottom-up” methods have drew tremendous attentions due to potential applications in the field such as gas storage and separation and helped to development of novel energy and reducing the effect of greenhouse gas.This paper provides one step method to prepare ferrocene-based porous polymers in order to explore the diversity of organic porous polymers materials in structure,reaction type,the stability of the materials,porosity and applications in the field of clear energy and environment.Finally,basic characterization and property study of the materials was performed.1.Novel ferrocene-based porous polymers networks?MPOPs?were successfully prepared based on “sandwich-liked” 1,1'-ferrocenedicarboxaldehyde and mesodiamines with different degree of nitrogen content via Schiff chemistry.The pore structures and gas adsorption properties of MPOPs were studied by adsorption analysis using nitrogen and small gas?H2,CO₂,CH4?uptake were investigated,suggesting the incorporation of ferrocene units improve the porosity of the materials.MPOPs displayed excellent CO₂ capacity,MPOP-3 have a CO₂ capacity of 14.8wt%,and 11.6wt% and 10.4wt% for MPOP-1 and MPOP-2,respectively,surpassing most of porous organic polymers under the same condition.Furthermore,MPOP-3 showed excellent gas separation,namely S?CO₂/CH4?and S?CO₂/N2?being 5.95 and40.2?273K/1bar?,respectively.In addition,higher content of nitrogen leads to high CO₂ uptake and the large amount of C=N and iron improve CO₂ uptake.2.Novel ferrocene-based magnetic conjugated microporous polymers?MF-CMP-1 and MF-CMP-2?were prepared based on 1,1'-dibromoferrocene and muti-ethynyl compounds with different conjugated degree via Sonogashira-Hagihara cross coupling reaction.Basic characterization and property were performed.MF-CMPs displayed excellent porosity,the BET surface areas of MF-CMP-1 and MF-CMP-2were 519 and 356 m2/g,and the pore volume were 0.57 and 0.4 cm3/g,respectively.The CO₂ capacity of MF-CMP-1 was 1.45mmol/g?6wt%,273K/ 1bar?,and the isosteric heats was up to 27.2k J/mol and CO₂ selectivity over CH4 reached 4.35.Magnetic response study showed high degree of conjugated system improve the magnetism.The saturation magnetization took place at 0.805 emu/g for MF-CMP-1and at 2.41 emu/g for MF-CMP-2,respectively.Magnetic porous polymers materials have potential applications in industrial waste water treatment and fast magnetic separation.3.Stacked magnetic ferrocene-based imine covalent organic networks?FMI-CON?was prepared based nitrogen-electron rich plan macrocircle porphine and1,1'-ferrocenedicarboxaldehyde via Schiff-based chemistry.TGA,FIIR,13 C CP/MAS NMR,XPS,TGA,SEM,HR-TEM and gas adsorption/desorption were used to characterize the material.HR-TEM image showed FMI-CON had nanoscale layered structure.The BET surface area of FMI-CON was up to 602m2/g,and pore volume 0.4cm3/g.The microsurface area and micropore volume were 263m2/g and0.12cm3/g,respectively.Gas uptake for CO₂ and CH4 were 11.2 wt% and1.11wt%?273K/1bar?,respectively.In addition,the CO₂ selective adsorption over CH4 and N2 were 4.97 and 27.98,respectively.Magnetism study showed that the saturation magnetization of FMI-CON reached 1.82emu/g and waste water treatment of the material will be further investigated.