The Study On Adsorption,Catalysis And Electrochemistry Of Hyper-Cross-Linked Porous Organic Polymers

Compared with traditional inorganic porous materials,microporous organic polymers(MOPs)as a kind of novel porous materials possess a series of characteristic of low skeleton density,high surface areas,porous structure,and easy modification and so on.Recently,MOPs have attracted more and more attention and had a wide application including energy storage,gas separation,and heterogeneous catalysis.In this thesis,multicomponent bottlebrush copolymers with poly(glycidyl methacrylate)(PGM)as polymeric backbone and diblock copolymers composed of an inner degradable block(polylactide,PLA)and an outer polystyrene(PS)as side chains was designed and synthesized through ring-opening polymerization(ROP)and reversible addition-fragmentation chain-transfer radical polymerization(RAFT)technologies.Then,microporous organic nanotubes(MONTs)can be prepared through Friedel–Crafts alkylation with the prepared bottlebrush copolymers as soft template.The component of precursor and morphology of MONTs were systematically characterized and confirmed by a series of measurements.The effect of precursors on the morphology of MONTs was further discussed.The adsorption performance of MONTs for various dyes with different charges and biomacromolecules with different sizes was investigated.The corresponding results demonstrated that the prepared MONTs possessed ability of ion and size selectivity.Furthermore,MONTs were modified with sulfonic acid and amino successively to give acid-base bifunctional MONTs that can be further used as novel catalyst for deacetalization-Knoevenagel cascade reactions with a high catalytic activity and excellent reusability.The well-defined polylactide-b-polystyrene(PLA-b-PS)diblock copolymers synthesized through ROP and RAFT polymerization successively could undergo Friedel–Crafts alkylation reaction to give hollow microporous organic nanospheres(HMONs)based on hyper-cross-linking mediated self-assembly strategy.The prepared HMONs could be modified with sulfonic acid to form sulphonated HMONs that exhibited higher catalytic activity and rate for biodiesel synthesis due to accelerated diffusion effect resulted from unique hollow structure.Besides,acid-base bifunctional HMONs could be prepared through co-hyper-cross-linking reaction with PLA-b-PS and benzylamine as precursors and showed excellent catalysis performance for deacetalization-Knoevenagel cascade reactions.Using PLA-b-PS and pyrrole as precursors,pyrrole-based HMONs could be prepared through Scholl reaction based on hyper-cross-linking mediated self-assembly strategy.After treated by KOH activated carbonization,pyrrole-base HMONs could be translated into nitrogen-doped activated hollow carbon nanospheres with high surface areas and excellent porous property.The morphology and components were confirmed by a series of measurements.The prepared carbon materials were further used as electrode materials and exhibited excellent supercapacitor performance.