The Fundamental Study Of Double Walls In A Zn(?)Nanoporous Metal-Organic Framework Chemical Oxidation Pyrrole

Metal-organic frameworks(MOFs)are a new crystalline porous material,which are composed by inorganic metal node and organic heterocyclic ligand containing an aromatic ring or a nitrogen-containing,and can achieve a variety of nano-sized pore structure to be built through topology directional design and expansion of organic ligands.This compounds have adjustable aperture,larger surface area,higher thermal stability,a plurality of active binding sites,excellent regulated adsorption performance,preferable ion exchange properties,amazing conductivity performance,etc.,so that in catalysis,adsorption,separation,proton conductivity,magnetic,optical materials,it has broad application prospects.Currently,the major research of micro-porous coordination polymer is no longer limited to characterize its structure.Among them,the study of MOFs loading functional molecules becomes a hot research,including MOFs adsorbing gas,separation and storage,loading proton carrier materials,fuel,little micromolecule drugs and so on.Monomer reacts polymerization in uniform micro-porous material highly ordered structure,thereby the resultant of reaction has a definite morphology and structure.It has become very attractive research direction.Nanoporous material is used as the polymerization reactor to control reaction,including polymer molecular weight,stereoregularity,structure and sequence,etc.In this paper,we use highly stable,highly ordered double walls in a Zn(?)nanoporous coordination polymer which can load a large number of iodine molecules and also control and release it as nano-reactors to control oxidative polymerization of pyrrole.We mainly research the chemical structure of the coordination polymer,polypyrrole and the polymerization mechanism of coordination polymer release iodine chemical oxidation of pyrrole after gas-solid,liquid-solid reactions.The following is the content of the study:The first chapter is introduction,which introduces the current direction of the metal organic framework compounds of the concept,characteristics,development and research direction.On the other hand,we describe the synthesis of polypyrrole,polymerization mechanism,research progress and the progress of polymerization and other meso-porous.Finally,the significance of the topic of this issue will be considered.The second chapter is a section of synthesizing double walls in a Zn(II)nanoporous coordination polymer.Firstly,adopting a method of Solvothermal to gain coordination polymer containing guest molecules N,N-dimethylformamide(DMF)([Zn3(pybz)2(lac)2]·2.5DMF,compound 1),and then compound 1 is immersed in methanol,in order to replace of DMF and obtain coordination polymerization which load methanol.Finally,the methanol-loading polymer is placed 6 hours in the 120? oven.The aim is to catch the guest molecule.Then the empty structure coordination polymer[Zn3(pybz)2(lac)2],(compound 1')is immersed in a saturated iodine cyclohexane solution for 2-3 days to obtain iodine-loading compound 1'.For each step of the obtained compounds,we use XRD,FTIR,TGA and other analytical tools to analyze the structure.The results demonstrate that the structure is corresponding literature reports.Finally,using thermal gravimetric and the method of sodium thiosulfate titration,we calculate 1g compound 1' containing about 1g iodine.We utilize UV-visible spectrophotometer(UV-vis)to track the release of iodine in the water.The result shows that for lmg compound 1' containing iodine,the rate of controlling and releasing of iodine is 0.0026(mmol·L-1)/min.The third chapter is the section that loading-iodine compound 1' react in-situ oxidation polymerization with pyrrole vapor under certain conditions.We also utilize FTIR,Raman spectroscopy(Raman),XRD,UV-visible-near infrared spectrophoto-meter(UV-vis-NIR),field emission scanning electron microscopy(SEM)and other analytical tools to characterize.FTIR demonstrates that all the surface of compound 1' was generated iodine-doped polypyrrole at different times;The XRD analysis that as the reaction time,the polypyrrole which in-situ growth on the surface of compound 1' gradually masked diffraction peak of compound 1' It indicates that polypyrrole is influenced as the reaction time increased.SEM found that as increasing reaction time,the thickness polypyrrole layer on the surface of compound 1' was increased,and at 30min the thickness of polypyrrole layer is 2.7 ? m.The fourth chapter is the section that explores chemical oxidative polymerization reaction of pyrrole with the loading-iodine compound 1' in the pyrrole aqueous solution.By FTIR and XPS,solid products were proved the existence of polypyrrole.After we utilize ammonia to corrode the structure of compound 1' and obtain eigenstates polypyrrole,the form of the eigenstates polypyrrole is oxidation state and proton states and among them,mainly is oxidation state by XPS.A comparison of the eigenstates polypyrrole at different reaction times,XPS spectra indicates that with increasing reaction time,the intrinsic state of polypyrrole which converted into oxidation state of polypyrrole increase.On the other hand,we use mass spectrometry analysis liquid.The result indicates that there are large amounts of doped-iodine tetramer of pyrrole in solution.This demonstrates that iodine was released from compound 1'to the pyrrole aqueous solution and oxidation polymerization has been occurred.Large amounts of iodine-doped tetramer of pyrrole appear in solution.At the same time,we directly utilize iodine to react with pyrrole in pyrrole aqueous solution.The solution also found the presence of tetramer of pyrrole.The above results show that in the process of the iodine being released from the pores of the crystals of pyrrole solution,the window of the compound 1'surface and the body of the solution had undergone oxidative polymerization pyrrole.Since the amount and rate of releasing of iodine crystals,exchanging of main-guest molecule and other factors were influenced,a large number of iodine-doped polypyrrole has not been obtained in an aqueous solution,but get a lot of intermediates of iodine-doped tetramer of pyrrole.These results provide a reference for further study of the mechanism of iodine oxidative polymerization pyrrole.