Preparation Of Functionalized Organic Porous Materials And Their Applications In Selective Adsorption And Catalysis

In recent years,the application of organic porous composites in adsorption and catalysis has attracted much attention.In this paper,the different kind of composites based on the porous materials were prepared through the appropriate synthesis method and interesting post-functionalization methods,which include covalent organic framework composites and conjugate microporous composites,at the same time,the selective catalytic and the adsorption performance of the composites were tested.The main research contents of this paper are as follows:（1）Owing to specific formation of five-membered or six-membered cyclic esters between boric acid groups and cis-diol molecules,boric acid bearing fluorescent materials can not only selectively capture but also specifically identify cis-diol substances.In this work,a novel covalent organic framework containing boric acid groups（COF-BA）was prepared through post-modification via the aza-Diels-Alder cycloaddition reaction.COF-BA with good stability,permanent pore structure,high specific surface area(606 m²g^-1)and uniform pore size（2.59 nm）exhibited unique selectivity toward cis-diol guest molecule 1,2-dihydroxyanthracene-9,10-dione（1,2-Doa）with the high adsorption capacity of 177.95 mg g^-1.However,as for isomers of1,2-Doa（1,4-dihydroxyanthracene-9,10-dione and 2,6-dihydroxyanthracene-9,10-dione）,the corresponding uptake capacities are distinctively decreasing to 40.86 mg g^-1and 3.05 mg g^-1,respectively.It is worthy to note that the COF-BA can be recovered and recycled.Moreover,because the formation of the quinoline enhances the conjugated effect of the COF’s skeleton,it was unexpectedly found that COF-BA possessed intrinsic fluorescence property,which can be used as optical sensor for 1,2-Doa.（2）Porphyrins and fullerenes are suitable for the construction of multi-component reticular polymer due to their coordination interaction.In this work,a novel organic porous structure(PPZ/C₆₀)containing metalloporphyrin and fullerene was designed.Different from the traditional zigzag structure,this material with sandwich structure is fabricated by the combination of covalent and non-covalent interaction between tetrcarbazole zinc porphyrin and fullerene.Then,the PPZ/C₆₀-Pd was obtained by introducing the tetrakis（triphenylphosphine）palladium into the PPZ/C₆₀.Noteworthy,the PPZ/C₆₀ and PPZ/C₆₀-Pd retained the properties of the porous materials,including rich as well as permanent pore structure,high specific surface area(516 m²g^-1,452 m²g^-1),and uniform pore size（0.77 nm,0.66 nm）.Furthermore,the PPZ/C₆₀-Pd could be used to catalyze the deallyl reaction onto the phenyldiallyl ethers with different side-chain groups,which will provide more possibilities for the application of the PPZ/C₆₀-Pd.