Synthesis And Property Studies Of Functional Microporous Organic Polymers

Microporous Organic Polymers(MOPs)have gained considerable attention by scientists owing to their traits,such as high specific surface areas,low skeletal density,high physical and chemical stability,various synthetic strategies,and easy functionalization according to actual demands.Therefore,they have been widely applied in heterogeneous catalysis,gas storage and separation,organic optoelectronics,etc.Recently,designing the MOPs with higher surface areas to achieve the targeted applications in terms of functionalization and pore–size control is the climatic success in this field.However,some issues associated in MOPs design must be resolved.For instance,usage of expensive noble metal catalysts,organic monomer limitation in the synthesis of CMPs or PIMs;post functionalization and design,poor stability and harsh synthesis condition of COFs,which limits the development of MOPs.Hence,there is the dire need to attain a suitable methodology to synthesize functional MOPs with low–cost as well as large–scale production.This work mainly focuses on two parts: i)Synthesizing functional HCPs via ‘knitting' method by low–cost aromatic compounds.The obtained HCPs were characterized by FTIR,solid–state NMR and nitrogen adsorption–desorption isotherms and so on.Moreover,the obtained HCPs were applied in heterogeneous catalysis and porous carbon preparation;ii)a new method was developed to design COFs and synthesize functional Covalent Triazine Frameworks(CTFs),which were characterized by FTIR,solid–state NMR and nitrogen adsorption–desorption isotherms techniques.The obtained CTFs were applied in gases adsorption(CO2,H2)and optoelectronic applications.Chapter I summarize the development of MOPs,and focuses on the applications and advancements in four classical categories of MOPs in gas adsorption,heterogenous catalysis,and organic optoelectronic.Chapter II: a Hetero(N)–carbene–copper(NHC)complex supported on HCPs was synthesized by 1,3–dibenzyl–1H–benzo[d]imidazol–3–ium chloride and benzene via a simple external cross–linking reaction.The obtained catalyst displayed better catalytic activity than that of the homogeneous catalyst at equal concentrations in multi–component oxidative condensation and Click reactions.In addition,the catalyst also exhibited outstanding stability.These results revealed that the HCPs of NHC are indeed an excellent supporting material for the immobilization of homogeneous copper complex catalysts.Chapter III: a new strategy for synthesizing mono–functionalized acid/base HCPs based on appropriate amount of acid/base monomers was developed.The obtained catalysts were then applied to two acid–base tandem reactions.Compared with difunctionalization acid–base catalyst,this strategy is more cost–effective and easy–to–handle for functionalized heterogeneous catalyst synthesis.Moreover,it achieved the goal of precise control of catalytic sites by directly introducing and controlling the feeding amount of monomers.This study provided a choice of heterogeneous catalysts for the efficient tandem reactions catalyzed by acid/base catalysts with the advantages of avoiding the acid–base neutralization and simplifying the separation process for their recycling.In chapter IV,porous carbons were prepared by core–shell HCPs via direct carbonization,and used them as electrode materials in supercapacitors.In this study,a series of hollow microporous carbon spheres(HCSs)were synthesis from hollow microporous organic capsules(HMOCs)with a good control over the pore morphology(BET surface area,pore volume and pore size),hollow cavity and the shell thickness in the absence of activator and template.The method successfully avoids the interference from activator and template,and the obtained materials have highly stability.Hence,it is suitable for the large–scale production.In their application,15%–HCS–700 with higher BET surface area displayed good excellent electrochemical performance,indicating that such hollow carbon spheres as electrode material has unlimited potential in electrochemical fields.Chapter V: a new method was developed for synthesizing CTFs.The CTF–HUSTs with various structures were synthesized by terephthalimidamide and multi–aldehyde aromatic compounds through addition,condensation,cyclization reactions.Compared with the reported methods,the strategy possesses the advantages of mild reaction condition and diversity of monomer.The obtained CTF–HUSTs were used for carbon dioxide and hydrogen adsorptions because their high BET surface areas.The results indicated that a simple and general strategy was provided for the synthesis of CTFs.