Synthesis,Polymerization,Assembly And Catalyticperformance Of Metal Tetra(2-butyl-3-ene-1,4-dithiin) Porphyrazines

Biomimetic catalysis,biomimetic photocatalysis are a kind of technology of green and environmental protection which has the advantages of biology and the chemistry.Recentlymetalloporphyrazines have been successfully appliedas biomimetic catalysts to activate molecular oxygen for theselective photooxidation of organic compounds and photodegradation of organic pollutants as they have similar delocalized ? system with metalloporphyrins.The introduction of electron-rich double bonds on the periphery of porphyrazine ring can not only improve the electronic contribution of the molecule but also as building-block polymerize and self-assemble to a porous nanomaterial with certain morphology using property of olefin polymerization.The nanomaterial can both play a photocatalytic role of metalloporphyrazines embed in the polymerized nanomaterial and use the nanoparticles to suspend in the solvent so as to easily separate from system.In this paper,the 5-hydroxymethylfurfural(HMF),a biomass platform molecule,was catalyzed to oxidate into 2,5-furandicarboxylic acid(FDCA)using the porous nanomaterial so as to assess the catalytic performace of self-assembled metalloporphyrazine.The experimentsdemonstrated that the nanomaterials performed satisfactory catalytic efficiency under differentexperimental conditions nomatter photocatalysis or thermocatalysis.The specific work content of the dissertation is summarized in the following aspects:(1)Firstly,the 5,6-dibromine-1-hexene wasobtained by the addition reaction of 1,5-hexadiene with bromine,then the product reacted with maleonitrile disodium dithiolate to produce cis-2,3-dinitrile-5-(butyl-3-ene)-1,4-dithiin.A novel magnesium tetra-(2-butyl-3-ene-1,4-dithin)porphyrazine with unsaturated double bonds were acquired from the precursor using mgnesium template method.Later,the core metal Mg was removed by trifluoroacetic acid to get metal freetetra-(2-butyl-3-ene-1,4-dithin)porphyrazine.The free-base reacted with corresponding metal acetate to get zinc(II)tetra-(2-butyl-3-ene-1,4-dithin)porphyrazine and cobalt(II)tetra-(2-butyl-3-ene-1,4-dithin)porphyrazine respectively,which were respectively characterized by 1H-NMR,IR,UV-Vis,and Maldi TOF-MS.(2)Based on zinc or cobalt tetra(2-butyl-3-ene-1,4-dithiin)porphyrazines as building-block,whose terminal double bonds were initiated to polymerize by 2,2-azobisisobutyronitrile(AIBN)in dimethyl formamide solvent,finally self-assemble to form nanoball particles.The related factors on polymerization and self-assembly were explored.The nanoballs were characterized by TEM?SEM?DRS UV-Vis?BET.Their morphology were found to be uniform,regular solid ball with diameter distribution in the range of 300-500 nm,BET surface area is 56.8 m2/g,pore diameter is 4.8 nm.(3)Based on the self-assembled nanomaterials as catalysts,the catalytic oxidations of 5-hydroxymethylfurfural(HMF)were used to assess its catalyticactivity through either photocatalysis or thermocatalysis.When TBHP was as oxidant in acetonaitrile solvent,the HMFconversion was 90.6% with the yield 76% of FDCA in the photocatalysis reaction under illumination of light energy density347mW/cm2 for 12h,whereas HMF conversion was 68.3% with yield 52.3% of FDCA at 95 °C for 3hin thermocatalysis process.