Design,Synthesis And Adsorption Properties Of Porphyrin-based Conjugated Microporous Polymers

In recent years,many porous materials with outstanding physical/chemical properties have been designed and synthesized by researchers.For example,conjugated microporous polymers,polymers of intrinsic microporosity,covalent organic frameworks and other organic porous polymers are synthesized by simple and effective programming.These materials have unique properties such as large specific surface area,narrow pore size distribution and low skeletal density,which make them widely used in gas storage and separation,catalysis,chemical sensing,energy storage and other fields.In addition,porphyrin-based polymers generally possess large specifc surface area,permanent pore structure,and high thermal and chemical stability,which show potential applications in gases storage and separation,catalytic and luminescent materials.In this paper,we designed and synthesized a series of porphyrin-based conjugated microporous polymers,and carried out a series of studies on their adsorption properties.1.In this paper,a series of conjugated microporous polymers(ZnP-XN₃-CMPs?X=5,25,50,75 and 100%?were synthesized based on the zinc-porphyrin building blocks.The azide group incorporated into the pores of the CMPs is subjected to a“clicking post-synthetic modification procedure”to obtain a fluoride-functionalized conjugated microporous polymer under relatively mild conditions.The fluoride content in the CMPs skeletons can be tuned by controlling the percentage of azide groups.The successful implementation of this strategy developed the new fluoride functionalized polymer ZnP-XF-CMP?X=5,25 and 50%?.Under the same conditions,ZnP-XF-CMP?X=5,25and 50%?has more effective CO₂ adsorption properties than the original CMPs?ZnP-XN3-CMP?X=5,25 and 50%??.Moreover,all fluoride functionalized CMPs exhibited good CO₂ adsorption heat(32-37 kJ mol^-1).This work not only shows that highly complex three-dimensional polymer structures can be easily constructed from simple building blocks,but also proposes effective methods to improve the adsorption heat and carbon dioxide adsorption properties of porous materials.2.Two novel porphyrin-based conjugated microporous polymers?Porp-TPE-CMP,Porp-Py-CMP?were formed by the polymerization of pyrrole and aromatic aldehyde monomers by FeCl3 catalysis.The BET specific surface areas of Porp-TPE-CMP and Porp-Py-CMP were 547 and 31 m² g^-1,and their CO₂/N₂ and CO₂/CH₄ selectivity are 55.28and 4.11 for Porp-TPE-CMP,40.75 and 5.11 for Porp-Py-CMP,respectively.More interestingly,at 298 K and 1.0 bar,the two polymers have excellent vapor absorption of benzene,toluene,cyclohexane and water.The high vapor adsorption capacities of polymers is important for the recovery and selective removal of toxic organic vapors from polluted air.In addition,this method provides an effective way for large-scale and low-cost synthesis of organic adsorbent.