Fabrication And Application Of Tetracarboxylate Ligands Based MOFs And Porphyrin Based CMPs

For the characteristics of high specific surface area and devisable pores,metal-organic frameworks and conjugated microporous polymers display a potential application in photoelectricity,electricity,magnetism,gas adsorption/separation and so on.So the design and synthesis of functional metal-organic frameworks and conjugated microporous polymers as well as exploring their application performance,is an active and difficulat research field of polymer chemistry.The main purpose of this dissertation is to construct metal-organic frameworks and conjugated microporous polymers under the guide of function,and studies the application in CO₂ adsorption and catalytic conversion,electrical energy storage device and water treatment field,with an aim to obtain new methods of preparation of functional meatrials and practical devices.The main research contents are as follows:1.The synthesis as well as CO₂ adsorption and catalytic conversion application of tetracarboxylate ligands based metal-organic frameworksThree new metal-organic frameworks?MOFs?{[Zn₂?L??H₂O?₂]·2.5DMF·2-?1,4-dioxane?·6H₂O}_n?UPC-6?,{[Co₂?L??DMA?₂]·2DMA·5EtOH}_n?UPC-8?and{[Ba?H₂H??DMF??H₂O?]·DMF}_n?UPC-17?have been obtained under solvothermal conditions?L=2,3,5,6-tetramethyl-1,4-diisophthalate;H=?2,3,6,7-tetramethoxy-anthracene-9,10-diyl?bis?[1,1?-biphenyl]-diisophthalate??.UPC-6 and UPC-8 were three dimensional frameworks based on Zn/Co-paddlewheel SBUs.Through metal-ion metathesis in a single-crystal-to-single-crystal fashion,two new identical Cu-paddlewheel frameworks?termed Cu-UPC-6 and Cu-UPC-8?were produced,which stability and porosity have been improved significantly.The uptakes of CO₂is 74 cm³·g^-1 at 273K.Based on the 1D open channel,UPC-17 could catalyze the cycloaddition of CO₂ and epoxides,with a yield of 100%was observed in 240 min when epoxy propane was used.In addition,UPC-17 is an excellent fluorescent sensor and the fluorescence quenching percentage will reach 87.2%when the concentration of 4-nitrophenol is 45?mol·L^-1 in EtOH.2.The preparation and supercapacitor performance study of nano-hydroxide/oxide based on metal-organic framework as precursor{[Co₄?OH?₂?L?_1.5?H₂O?₄]·3H₂O·2.5DMA}_n?UPC-9?and reported MCF-35have been synthesized through solvothermal conditions.Using UPC-9 and MCF-35as precursor,hierarchical Co/Ni?OH?₂ has been synthesized via a solid–solid conversion process in alkali solution.Hierarchical Co₃O₄ based on ultrathin hexagonal nano-sheets with a thickness of 3.5 nm could be obtained through a calcination process of UPC-9 derived Co?OH?₂.A remarkable and excellent specific capacitance of 1121 F·g^-1 at a current density of 1 A·g^-1 was achieved for the as-prepared supercapacitor and only 1.81%capacitance faded during 6000 cycles,indicating the good pesudocapacitive behavior for potential applications.The hierarchical MCF-35-Ni?OH?₂-3 structure was stacked by Ni?OH?₂ nano-sheets with a thickness of 1-2 nm,which shows the BET surface of 243 m²·g^-1.A remarkable specific capacitance of 2255 F?g^-1 at a current density of 0.5 A?g^-1 was achieved for the as-prepared electrode.More importantly,this synthesis strategy is environmentally benign and economically viable due to the fact that the organic ligand molecules could be recycled.3.The preparation and water treatment study of porphyrin based conjugated microporous polymersThree new conjugated micro-porous polymers have been successfully synthesized by a Sonogashira–Hagihara coupling reaction between iron?III?5,10,15,20-tetrakis-?4?-bromophenyl?-porphine and different alkynyl-monomers?1,4-diethynylbenzene,1,3-diethynylbenzene or 1,3,5-triethynylbenzene?,which were named as UPC-CMP-1,UPC-CMP-2 and UPC-CMP-3.UPC-CMP-1 could decompose 88.3%of Congo red?CR?molecules under visible light irradiation,within 120 s.Furthermore,based on the cationic skeleton and centralized pore size distribution?1.3-1.7 nm?,UPC-CMP-1 exhibited high selectivity to CR over other dyes.UPC-CMP-2 was successfully coated on stainless steel mesh to fabricate oil/water separation device,and the separation efficiency of gasoline/water could reach 99.8%.UPC-CMP-2 could also be coated on the framework of sponge for oil/water separation and removing trace organic contaminant.The weight of adsorbed ethyl acetate could up to the 86.6 times than the weight of UPC-CMP-2coated sponge,and 93.3%of ethyl acetate could be recycled,after simple squeeze by hands.Besides,the coated sponges could remove 95%of dissolved benzene in90 min.