Synthesis, Characterization And Properties Of Coordination Polymers Micro/nanomaterials With Carboxylate- And Nitrogen-containing Ligands

In the past two decades, coordination polymers(CPs) or metalorganic frameworks(MOFs) constructed by metal ions and organic building blocks have drawn tremendous research interest in materials science because of their interesting structures, novel properties and potential applications. Nowadays, with the on-going progress of nanoscience and nanotechnology micro- and nano-sized(CPPs) with clearly identifiable morphology are attracting increasing attention. Due to the small size and specific morphology of coordination polymers micro/ nanomaterials, it will be broad range of applications including gas sorption and separation, heterogeneous catalysts, sensors, biomedical imaging and drug delivery. In addition, they can also be used as precursors to prepare metal oxides, metal sulfides, alloys, metal/carbon composite materials etc under certain conditions.In this thesis, the ligands with nitrogen and carboxylate groups, namely pyridine-2,3-dicarboxylic acid(2,3-H2PDC) and 1,3,5-benzenetricarboxylic acid(H3BTC) were used to react with metal salts to give three coordination polymers micro/nanomaterials. The main contents are displayed as follows:1.Copper acetate(CuAc2) and sodium pyridine-2,3-dicarboxylate(2,3-Na2PDC) were used as the initial reactants. The flowerlike Cu-PDC microstructures were obtained based on a simple direct precipitation between CuAc2 and 2,3-Na2 PDC in a mixed solution of water and methanol with the volume ratio of 20:10 at room temperature. Some factors to affect the morphology and size of the Cu-PDC microstructures were systematically investigated, such as the molar ratio of reactants, the volume ratio of water/methanol, acetic groups and the reaction time. It was found that flowerlike Cu-PDC microstructures could be transformed into flowerlike CuO microstructures by heat-treating in air at 350 ?C for 30 min. Experiments showed that the as-obtained flowerlike CuO microstructure exhibited a high catalytic activity for the reduction of 4-nitrophenol in excess Na BH4 solution.2.One-dimensional Eu(BTC)(H2O)6 nanorods were fabricated by a simple oil bath route. The reactions were carried out in air at 50?C for 30 min, employing Eu(NO3)3?6H2O and H3 BTC as the reactants. The studies of the photoluminescence properties reveal that these nanostructured coordination polymers exhibit red emission, corresponding to the 5D0 / 7F2 transitions of the Eu3+ ions under UV light excitation, which represents highly selective and sensitive sensing for Fe3+ ions in aqueous solution, and the probable sensing mechanisms were discussed in the detail.3. Shape-controlled synthesis of nickel(II)-based coordination polymer particles via a directly mixed approach, using H3 BTC and Ni(Ac)2·4H2O as the reactants in a mixed solution of water and ethanol with the volume ratio of 4:26. The morphology of the microstructures could be tuned by some reactive parameters including the oncentration of reactants, and the volume ratio of water/ethanol. Pure NiO microstructures could be obtained by annealing the coordination polymer particles without significant alterations in morphology. Experiments showed that the as-obtained NiO micro/nanostructure exhibited a high catalytic activity for the thermal decomposition of ammonium perchlorate(AP). Also, the as-prepared flowerlike NiO microstructures exhibited excellent catalytic performance for the oxidation of glucose. This property can be used as sensors for the detection of glucose.