Synthesis And Applications Of Novel Hyper-Crosslinked Microporous Polymers Based On Carbon Materials

Porous Organic Polymers（POPs）are a kind of porous materials with relatively low skeleton density and high specific surface area which are made up of organic elements（such as C,H,O,N,S,B,etc.）.Compared with the traditional zeolite（SiO₂,Al₂O₃,etc.）inorganic porous materials,activated carbon porous materials and metal organic frameworks（MOFs）,POPs have many outstanding advantages such as diverse synthesis methods and monomers,high physical and chemical stability,purposeful functional design,and POPs have been widely applied in many fields like gas adsorption,separation of materials,heterogeneous catalysis,energy storage and conversion,photoelectric and sensing fields.In recent years,POPs materials have attracted much attention from researchers.Among POPs materials,the Hyper-crosslinked Polymers（HCPs）are a kind of POPs materials with a low cost of synthesis procedure,simple synthesis operation,good physical and chemical stability and it’s suitable for large-scale mass industrial production.The crosslinking reaction is mainly based on the Friedel-Crafts alkylation reactions.The reaction conditions are mild,and the source of building monomer is extensive.Until now,a lot of research works have reported the synthesis of HCPs materials,morphology adjustment and functional application.The synthesis and application of the HCPs which based on carbon materials（fullerenes,carbon nanotubes and graphene）building units are a new direction in the research fields of HCPs.The carbon materials have a certain surface area and affinity with H₂ and CO₂,as well as the special morphology of carbon materials and its good mechanical strength and electrical conductivity,it is conceivable that the synthesis of HCPs composites with carbon materials as the building unit can fully combine the advantages of both and it is of great research significance.Based on the novel solvent knitting method,a series of new HCPs materials with special micromorphology and function are designed and synthesized by using different functional monomers and carbon materials as the building units or templates.We studied the microstructure,morphologies and functions of these novel HCPs materials through FTIR,PXRD,Raman,TGA,XPS,liquid/solid NMR,field emission scanning electron microscope,field emission transmission electron microscope,pore size analyzer and other instruments.Also,we explore the applications of these HCPs materials preliminary in many fields such as gas adsorption and CO₂ electroreduction.The main contents are as follows:Chapter one introduced the research background,classification,structural characteristics,development history and synthetic strategies of porous organic polymers（POPs）,and the progress in the research of porous organic polymers in gas adsorption,heterogeneous catalysis,energy storage and transformation,sensing and photoelectricity are also introduced.In Chapter Two,the low cost and efficient Solvent Knitting Method was used to synthesize novel C₆₀ based HCPs in which a simple fullerene C₆₀ derivative molecule NC₆₀BA as the reaction monomer,and dichloromethane（or 1,2-dichloroethane）was used as the solvent and crosslinking agent in the reaction system,and a class of fullerene-based HCPs materials with high specific surface area was reported.The HCP material named N-H-1 has a higher specific surface area(753 m² g^-1),CO₂ gas adsorption(2.41 mmol g^-1,273 K/1.12 bar)and H₂ adsorption(4.60 mmol g^-1,77 K/1.12 bar).In Chapter Three,based on the novel solvent knitting strategy,a series of novel HCPs materials based on carbon nanotubes have been synthesized.The functionalized multi-walled carbon nanotube（MWCNT-f）was dispersed uniformly in the dichloromethane by ultrasonication,and a homogeneous porous organic layer was constructed on the surface of the MWCNT-f by adding small molecule monomer,such as triphenylbenzene,to the reaction system.The organic porous layer uniformly covered on the surface of MWCNT-f,and its thickness can be regulated by adjusting the amount of monomer,and the surface area of materials and the amount of gas adsorption can also be regulated.In Chapter Four,based on the solvent knitting method,a series of novel graphene-based HCPs materials by using FRGO as a 2D-planar template and tetraphenyl porphyrin（TPP）as monomer were synthesized.The materials were complexed with a certain amount of Co²⁺and then carbonized to obtain a 2D graphene-based carbon materials with good conductivity and CoO/Co nanoparticles uniformly dispersed on materials.The carbonized materials were applied to the CO₂ electrochemical reduction field.It was found that these materials have good stability and CO₂ can be reduced to CO without any other gas or liquid phase products.the materials and high reaction specificity of CO production.Among them,the volume ratio of H₂/CO in electroreduction products of TG-HCP-3-Co-C is most close to 1,and it could be directly used as an industrial syngas after a simple proportional regulation,for the reaction of syngas fermentation（preparation of ethanol）.This study will have a good prospect of application.It can be conceived that the HCPs materials with carbon materials as the building unit have a wider development space and profound potential for development,and the researches in the related fields will have a brilliant future.