Synthesis Of Porous Organic Polymers And Their Applications In Electrochemical Energy Storage And Conversion

Porous organic polymers(POPs)are a kind of porous material connected by covalent bonds of C,H,N,O and other light elements.These excellent characteristics such as adjustable porosity,low density,high chemical and thermal stability,controllable composition,simple post-functionalization,and extendedπconjugations,have make become one of the frontier fields of material research.At present,the development of new functional POPs materials and their applications in catalysis,energy storage,gas adsorption and storage,photoconductor,chemical sensing,clean energy and other aspects have been widely studied.At the same time,it is necessary to push through the old and bring forth the new in the optimal design and synthesis of structure and the understanding of structure-activity relationship.For example,(i)develop different synthesis methods and construction units to regulate the configuration of materials;(ii)optimize the preparation of crystalline POPs materials by efficient reversible reaction;(iii)structural fitting and evaluating based on computational simulation and topology;(iv)explore the intrinsic photoelectric properties of materials to achieve performance development and research.Based on the above proposed scheme strategy,this doctoral thesis designed and synthesized a variety of organic monomer building blocks to construct different topology types of POPs materials,and studied their applications in the field of electrochemical storage and conversion.(1)New organic porous polymers with different spatial configurations are constructed.Two kinds of novel covalent triazine porous polymers with adjustable geometry were prepared by using isomerization building blocks.On this basis,the hierarchical porous structure and specific surface area of porous organic polymers were reasonably regulated by heat treatment.At the same time,the preparation of this tailored and expandable organic porous polymer material also provides an effective method for the development of efficient metal-free electrocatalysts.(2)A novel rigid porous organic polymer based on thianthrene linkage was constructed by dynamic S_NAr reaction.Compared with the covalent triazine structure,the material has obvious structural rigidity,coupled with non-planar thianthrene units,which will be very helpful to endow the polymer network with inherent porosity and high surface area.This work enriches the two-dimensional conjugated polymer network connected by thianthrene linkage and studies its application in terms of electrochemical Li~+storage.(3)A kind of thianthrene-linked crystalline POPs was successfully constructed by using perfluorophthalocyanine construction unit and tetramercaptobenzene.The thianthrene based covalent organic framework(COFs)composed of thioether bonds exhibits a non-planar wavy layer,which has unique weak non-planar aromaticity,reversible redox properties,unique electronic properties and high specific surface area,which are very suitable for charge storage applications.The crystallization properties of the novel thianthracene COF convey more views on the structural,chemical and electronic properties,and highlight the potential of thianthracene type crystalline POPs in charge storage applications.(4)A series of novel polyarylether COFs with D-A structure were constructed by screening functional organic monomer building units.These COFs have typical crystalline layered structure,narrow band gap and ultra-low resistance.According to density functional theory,this series of COFs can improve carrier mobility by changing the layered packing mode.Further,the stripped graphene was compounded with COFs to form a self-supporting film with good conductivity.By direct laser etching technique,binders-free interfingered supercapacitors have been prepared.These capacitors exhibit excellent volume capacitance and excellent stability in acidic electrolyte,which provides ideas for the development of high-performance energy storage devices.