Study On Synthesis And Properties Of Supramolecular Macrocyclic Porous Materials

Porous materials with high specific surface area and low density have attracted wide attention due to their controllable structure,good thermal and chemical stability.The porous materials with cross-linked pore structure can adsorb many substances.By modifying specific active sites,porous materials have the ability to bind the various targets.Therefore,porous materials are widely used for gas adsorption,separation,sensing,and heterogeneous catalysis.With the development of modern industry,many serious environmental problems have emerged.The irrational discharge of various industrial wastewater and waste gas causes the pollution of groundwater,drinking water,soil and air.For example,the dye wastewater discharged from the printing and dyeing industry has caused a large number of deaths of aquatic animals,and the pollution problems caused by nitrobenzene wastewater from chemical plants,etc.Based on the above considerations,two porous materials based on supramolecular macrocycles（amorphous porous organic polymer Noria-POP-1 and highly ordered supramolecular organic framework material SOF-1） were designed and synthesized.In addition,the applications of their adsorption properties for organic dyes and fluorescence detections were investigated in detail.The specific research contents are as follows:（1）Noria-POP-1 porous organic polymer was prepared based on Noria under mild conditions by diazo-coupling reaction with benzidine.The materials were characterized by scanning electron microscopy,transmission electron microscopy,infrared,thermogravimetric analysis,elemental analyzer,BET test,etc,which proved that the material had good thermal stability and chemical stability.The experimental results show that Noria-POP-1 has an extremely high adsorption capacity for cationic organic dyes,and the maximum adsorption capacity for methylene blue is up to 2434mg·g^-1,which is the highest adsorption capacity for methylene blue reported in the literature.In addition,Noria-POP-1 exhibits excellent adsorption capacity and efficient selectivity for cationic dyes in the pH range of 2-12.The experimental results show that Noria-POP-1 has a good application prospect in the adsorption of cationic organic dyes.（2）A new supramolecular organic framework（SOF-1）was constructed based on the self-assembly of p-sulfonatocalix[4]arenes,2,2’-bipyridine-N,N’-dioxide and ZnCl₂ in aqueous solution.The structure of SOF-1 was characterized by single crystal X-ray diffraction,powder X-ray diffraction,thermogravimetric analyzer,and fluorescence spectrophotometer,which proved its porous properties and highly ordered structure.Due to the SOF-1 framework is negatively charged,the lanthanide Eu³⁺and the laser dye molecule 4-[p-（dimethylamino）styryl]-1-methylpyridine（DSM）are introduced into SOF-1 by ion exchange.SOF-1 modified by the lanthanides Eu³⁺and DSM has a strong fluorescence emission capability,and can effectively detect and respond to nitrobenzene series.