The Study On Design,Synthesis And Application Of Hierarchical Porous Materials Based On Nano-scale Metal-organic Frameworks

Metal organic frameworks(MOFs),as new type of porous materials,have attracted much attention of material scientists due to its potential applications in gas storage,ion exchange,catalysis and nonlinear optics etc.In order to synthesize MOFs generally with mesopores,we develop a new strategy for building the permanent interpartical porosity based on nanoscale metal-organic frameworks(NMOFs).With this strategy,a series of interparticle porosity dominated mesoMOFs(IPD-mesoMOFs)based on three MOF types of MIL-100,MIL-53 and MIL-110,nominated as IPD-mesoMOF-1,-2and-9,have been successfully prepared.Compare with inorganic mesoporous materials,IPD-mesoMOFs have not only the adjustable mesopores,but also the higher surface area and very large mesopore pore volume.The large mesopore apertures and rich carboxyl residues on the mesopore-walls also allow the IPD-mesoMOF series to accommodate large organic and inorganic molecules,especially to immobilize the bulky natural protein,such as hemoglobin.Three research aspects are included in this dissitation:1.Synthesis and characterization of IPD-mesoMOF-1(Fe,Al)(based on the MIL-100(Fe,Al)),IPD-mesoMOF-2(based on MIL-53(Al)),IPD-mesoMOF-9(based on MIL-110(Al)).By adjusting the packing density of NMOF particles,a series of polymorphs of IPD-mesoMOF-1,-3 and-9 were obtained.The series of the materials were characterized by X-ray powder diffraction,SEM,IR,TGA and N2-adsorption.2.The application study on the IPD-mesoMOFs for desulfurization of gasoline:The study on the IPD-mesoMOFs for adsorption of different species of simulated gasoline containing different heterocyclic compounds,such as thiophenes,dibenzothiophene and benzothiophene reveals the adsorption of thiophenes(except thiophene)on the IPD-mesoMOFs,fitting to Langmuir single-sheet adsorption model with high adsorption capacity,especially on the IPD-mesoMOF-2.3.The immobilization study of natural protein on the IPD-mesoMOFs:Being rich with the residues of carboxylic groups on the walls of the IPD-mesoMOFs,the selected polymorphs of some IPD-mesoMOFs can directly immobilize the natural proteins that show excellent adsorption kinetics and high adsorption capacity for natural protein,such as hemoglobin.