The Synthesis Of Coordination Polymers Based On Ferrocenvl Acids And Their Application In Hydrogen Storage

With the particular topological structures and excellent optic, electric and magnetic properties, coordination polymers based on ferrocenyl acids have been used in wide areas including magnetic materials, the modified electrode, sensors and hydrogen storage and so on. In this thesis, we have focused on the synthesis, characterization and hydrogen storage investigation of coordination polymers based on ferrocenyl acids.In the second chapter of this thesis, we have prepared mixed-metal coordination polymers by using1,1’-ferrocenedicarboxylic acid as the organic ligand. To be specific, Zn(CH3COO)2·2H2O and MnCl2·4H2O have been used as the metal sources and coordinated with1,1’-ferrocenedicarboxylic acid to construct coordination polymer microspheres Mn-Zn-CPMs via solvothermal method. In order to design the microsphres with good morphology, we investigated the effects of factors including temperature, concentration, molar ratio and time. The conclusion is that the best condition of the preparation of Mn-Zn-CPMs is140℃,12h, the1:1ratio of Mn2+and Zn2+. We also used FT-IR and XPS to confirm that both these two metal ions (Mn2+and Zn2+) have been incorporated in the final products. Moreover, SEM and TEM images show that the final products consist of microspheres with average diameter of3.05μm. The BET surfaces areas and thermostability of Mn-Zn-CPMs have been characterized by N2adsorption and desorption tests and TGA respectively, illustrating that this material has large BET surface areas (259.0m2/g) and high thermostability. The decomposition temperature is more than400℃.In the third chapter, we used1,1-ferrocenedicarboxylic acid and5-aminoisophthalic acid as the raw materials to syntheize5,5’-[bis(1,1’-ferrocenylcarbonylimino)]bis-1,3-benzenedicarboxylic acid, a new ligand characterized by1H-NMR. Then this ligand, CoC12·4H2O or MnCl2·4H2O were dissolved in the mixture of methnol and water to prepare CPM-1and CPM-2with hydrothermal method. SEM images indicate that the products are spheres with inner hollow structures. The average diameters of CPM-1and CPM-2are9.2μm and14.67μm, respectively. The growth mechanism of these coordination polymer spheres was proposed based on time-resolved SEM images, which includes the process of rapid nucleation, particle aggregates and fusion, growth and hollowing. The prepared multidisperse microspheres have high thermostability with the decomposition temperature over400℃. The BET surface areas of CPM-1and CPM-2obtained from N2adsorption and desorption measurements are35.1m2g-1和22.5m2g-1, respectively.In the last part of this research, we measured the hydrogen storage capacities of prepared samples. The equipment is designed according to static volume principles and we have used this equipment for hydrogen storage measurements. We got a series of data that is recorded by the software M400. The hydrogen storage capacity of Mn-Zn-CPMs is1.58wt%under4MPa and163K. For CPM-1and CPM-2, the hydrogen storage capacities under5MPa and170K are1.78wt%and1.24wt%, respectively.