Synthesis Of Functionalized Hyper-crosslinking Organic Porous Materials And Their Property Study In Adsorption And Catalysis

The development of science and technology and society has not only brought many amenities,but also improved people's living environment.Many researchers are committed to exploring new materials that are more practical and efficient.In recent years,organic porous materials with the advantages of high specific surface area,excellent pore structure and good modifiability have aroused striking attention of many scientific researchers,gradually become a new material with strong application prospects and been widely applied in multiple domains of adsorption,catalysis,electrochemical devices,gas storage and separation.The dissertation contains three chapters.The first chapter mainly includes the classification,functionalization methods and applications of porous organic polymers,focusing on the synthesis of functional organic porous materials,the harm of heavy metal ions to people and the development background and applications of nitrogen-doped porous carbon materials.In the second chapter,the organic porous adsorbent material for heavy metal ions was successfully prepared using one-pot hyper-crosslinking and post-modification strategy.In this chapter,benzylamine functionalized hollow organic porous nanospheres(HMONs-BA)were synthesized by hyper-crosslinking with polylactide-b-polystyrene diblock copolymer(PLA-b-PS)and benzylamine as precursors.Then,HMONs-BA was modified with ethylenediaminetetraacetic acid anhydride and the ethylenediaminetetraacetic acid modified hollow porous organic nanospheres(EDTA-HMONs-BA)was obtained.The hollow morphology of EDTA-HMONs-BA and high specific surface area(226.86 m~2 g^-1)can be seen from the characterization of transmission electron microscope,nitrogen adsorption desorption test,infrared and elemental analysis.The adsorbent possesses a good removal effect on Cu²⁺in aqueous solution and the adsorption process satisfied the characteristics of quasi-second-order kinetic model.Meanwhile,the maximum adsorption capacity calculated by Langmuir isotherm model is 236 mg g^-1.After 5 cycles,EDTA-HMONs-BA still manifested high adsorption capacity and good stability.In addition,the adsorbent also possesses good adsorption capacity(>60 mg g^-1)for three different types of metal ions(Cr³⁺,Ag⁺,Cd²⁺,Ni²⁺and Zn²⁺).This indicates that EDTA-HMONS-BA has an excellent application prospect in treatment of wastewater containing heavy metal ions.In the third chapter,a palladium-supported porous carbon heterogeneous catalyst(Pd TPP@PCNs)was designed and synthesized based on porphyrin hyper-crosslinking porous organic polymer.In this chapter,a porphyrin hyper-crosslinking organic porous material was prepared by the method of Friedel-crafts alkylation reaction with tetraphenylporphyrin and carbazole as monomers as well as dimethoxymethane as external crosslinking agent.Then,palladium-supported porous carbon materials(Pd TPP@PCNs)were prepared by impregnation in-situ reduction and hydrogen peroxide post-treatment.The prepared catalysts were investigated by X-ray diffraction,transmission electron microscopy,nitrogen adsorption desorption.The results indicate that the palladium nanoparticles are uniformly dispersed in the carrier material with the size of 1.95±0.7 nm and the palladium content is 1.10 wt%.Pd TPP@PCNs catalyst possesses good catalytic effect on Suzuki coupling reaction,the TOF value of bromobenzene and iodobenzene are 1950 h^-1 and 3988 h^-1,respectively.At the same time,it can catalyze reactions of substrates well with various substituents and the catalyst can be recycled 8 times.In addition,Pd TPP@PCNs can catalyze the cycloaddition of carbon dioxide under mild conditions and also shows good catalytic activity after 8 cycles.The TOF value is 223 h^-1.This synthetic route provides opportunities for immobilizing metal nanoparticles and preparing carbon catalytic materials with uniformly dispersed metal nanoparticles.