Design And Synthesis Of Multifunctional Porphyrin-based And Viologenbased Porous Organic Polymers

As an emerging kind of porous materials in recent years,porous organic polymers are endowed with many unique properties by covalent crosslinked organic framework,such as the lightweight of the framework and the corresponding high surface area,the high heat/water stability,designable and modifiable in molecular level,showing unique application value and quickly become a research hotspot in materials science in recent years.Under the guidance of organic chemistry and topology,the development of porous organic polymers is extremely rapid,and abundant chemical structures,various topologies and pore structures have been reported.Porous organic polymers show excellent properties in many application fields such as catalysis,separation,optoelectronics,biomedicine and gas storage,and the relationship between chemical structure,topological structure and function has been deeply understood.On this basis,by integrating multiple functions in one material and take the advantage of synergistic effect between different funtions to realize more complex and precise funcions will bring a leap breakthrough for the development of new multifunctional porous organic polymers.The development and application of multifunctional materials will greatly promote the development of porous organic polymers in application fields,realize more complex functions,and provide abundant material basis for meeting the growing and diversified social needs.Based on the above reasons and purposes,a variety of porous organic polymers containing functional monomer porphyrin and viologen have been designed and synthesized.By regulating a variety of factors,such as select functional monomers,design pore structures and control nanoparticles morphology,many porous organic polymer systems have been developed successfully,and their multifunctional applications in biomedicine,wastewater and organic pollutants treatment are studied respectively.The main research results are summarized as follows:1.Porphyrin-based porous organic polymer,Py-POP,as a multifunctional platform for efficient selective adsorption and photocatalytic degradation of cationic dyes.In this part,porphyrin monomers with photocatalytic function are combined into porous organic polymers by an extended aromatic substitution reaction between pyrrole and 4,4-diformyl-1,10-biphenyl in situ,which named as Py-POP.By design and synthesis rigid porphyrin monmers into the structure,Py-POP endowed with photocatalytic ability,high surface area and pore size distribution of1 nm at the same time.Py-POP exhibits excellent adsorption and photocatalytic properties for caionic dyes in water:The adsorption capacity of cationic methylene blue?MB?in aqueous solution is up to 140 mg g^-1,and for the mixture of cationic dyes Rhodamine B?RhB?and MB which with different molecular size,MB can be selectively adsorbed.In photocatalytic test,Py-POP exhibits good photocatalytic ability in the degradation of both rhodamine B?RhB?and MB/RhB mixture under visible light source irradiation.As a stable,recyclable,multifunctional platform integrating selective adsorption and photocatalysis,Py-POP provides multiple modes for industrial dye wastewater treatment:1.The selective recovery of MB from cationic dyes mixture will realized;2.Rapid removal of cationic dyes from dye wastewater will realized;3.Green and recyclable degradation of the dyes in adsorbents in situ will realized.The combination of photocatalysis and adsorbility provides a new technical route for the most widely used adsorption and separation process of porous materials,and this material provides a materials basis for the technical innovation of industrial dye adsorption and separation process.2.pH-activatable porphyrin based porous organic polymers shell for highly efficient and selective photothermal and photodynamic dual therapy for cancer cells.Porphyrins and their derivatives are excellent photosensitizers for photodynamic therapy,while porous organic polymers with rigid and large conjugated porphyrin monomers can usually absorb near-infrared light and convert light energy into heat energy,possessing photothermal properties.Therefore,the combination of porphyrin monomers in porous organic polymers endows the materials with both photothermal and photodynamic properties.However,strong hydrophobicity,uncontrollable morphology,limited solubility of porous organic polymers in water restricts their applications in biomedical field.To solve the above problems,the morphology of porphyrin-based porous organic polymers is effectivelly controlled by hard template method,and the hollow porous organic polymer nanoparticles containing porphyrin groups with very uniform morphology and size are obtained,which named H-POP.H-POP not only has good water dispersibility and biocompatibility,but also has photothermal and photodynamic therapeutic properties.It is worth metioning that the photodynamic therapeutic properties of H-POP are pH-activatable.This property can target H-POP to cancer cells with a lower pH environment,which will greatly reduce the phototoxicity problems occurring in phototherapy.The photothermal therapy,photodynamic therapy and intrinsic pH-activatable capabilities of H-POP made it a promising multifunctional platform in cancer treatment.3.Highly efficient,reversible iodine capture and exceptional uptake of amines in one viologen-based porous organic polymers.It is found that porous organic polymers with multiple adsorption sites have great advantages in harmful vapor adsorption.Based on this,two viologen-based porous organic polymers?POP-V-VI and POP-V-BPY?are synthesized by a facile nucleophilic substitution between the reactive chlorine atoms in cyanuric chloride and the bridging 1,2-bis?4-pyridinium?ethylene?or 4,4'-bipyridine?.These two viologen-based porous organic polymers bear high charge density,phenyl ring and nitrogenous affinity sites,which endow them with excellent iodine and amines uptake capacity.The iodine vapor uptake capacity of POP-V-VI and POP-V-BPY is 4860 mg g^-1and 4200 mg g^-1,respectively,and both POP-V-VI and POP-V-VPY shows remarkably high adsorption capacity for pyridine(4470 mg g^-11 for POP-V-VI and 8880 mg g^-1 for POP-V-BPY).Combined with their good and stable recycling properties,the high adsorption capacities and rapid adsorption kinetics of POP-V-VI and POP-V-BPY made them highly effective adsorbents for iodine and amines,which have promising application prospect in the field of protection hazardous chemicals.