Synthesis Of MOFs Materials Based On Transition Metal And Study Of Their Application In Green Catalysis

The morphology, structure and size of the nanomaterial played important influence on the performance and property of the material. As a result, we aim to explore the controllable synthesis of functional material and reveal the structure-activity relationship of the synthesized material. In the way, it is expected to improve the performance and activity of the material effectively. Organic-inorganic hybrid materials, such as metal-organic frameworks (MOFs) are being studied by many research groups taking advantage of its porous nature, uniformed pore structure and high surface area. In additioin, inorganic material, such as TiO2 is drawing lots of attentions because of its low toxicity, high stability and great photo-catalysis performance. This doctoral thesis focused on the controllable synthesis of metal-organic framework and inorganic TiO2. Aming to achieve various functional nanomaterials with various morphology and scale, understand the growing mechanism, explore the utility in the green catalysis. Finally, it would be ideal to reveal the relationship between material morphology and activity of catalytic performance. With this information on hand, the further design and the application of functional material become possible based on our experimental investigation and theoretical study.A novel carboxylate ligand enhanced copper MOFs material at nanoscale was achieved employing coprecipitation method. Copper(II) salt and carboxylate organic ligand were used for the synthesis, as well as the morphology additive. The as-synthesized material was evaluated as green catalytic material for epoxidation reaction. Furthermore, the significant enhanced performance from the carboxylate ligand was studied to reveal the synergic effect of organic ligand and copper(Ⅱ) catalytic site. It shoewed high catalytic activity and recycled stability in the cyclooctene epoxidation model reaction.Au(0) nanoparticles was immobilized on the MIL-53(NH2) MOFs material employing NH2 induced adsorption and in-situ reduction of HAuCl4 precursor. The even distributed Au(0) nanoparticles was achieved taking advantage of nano-porous structure of MOFs material and the strong interaction between HAuCl4 and amino functional group. The as-synthesized Au@MIL-53(NH2) material was evaluated as one-pot multicomponent reaction catalyst and it showed great catalytic efficiency. The activity of Au(0) nanoparticles and amino functional group were studied separated in order to reveal its role in the catalysis. The benzylidenemalononitrile derivative was synthesized efficiently during the one-pot catalytic reaction.A dual functional copper-based MOFs with copper active site and amino function was achieved employing hydrothermal method. The strong covalent-bond was used to assemble copper metal and organic ligand based on Copper(Ⅱ) metal and basic organic ligand. The morphology control reagent and its corresponding material morphology have been studied in detail. Furthermore, the as-synthesized copper MOF material was evaluated as an efficient catalyst for aerobic alcohol oxidation/Knoevenagel condensation reaction sequence. The catalyst showed excellent catalytic activity and selectivity in the model one-pot reaction of benzyl alcohol and malononitrile. It could make the synthetic process much green and inexpensive of benzylidenemalononitrile derivative.Aimed at synthesize 1 D nanoparticle to 3D hierarchical excellent TiO2 structures through a hydrothermal process. The morphology of the products was controllable taking advantage of alkali concentration, which was systematically investigated. As the NaOH concentration rising, morphology transformations from yolk-shell, hollow hierarchical 3D nanospheres to 1 D nanowires are achieved. The crystal phase, the transformation relationship, and the formation mechanisms were studied as well. Furthermore, TiO2 with diversified morphologies was evaluated as styrene oxidation catalyst and showed excellent catalytic activities and chemical stability. This investigation provided further evidence and possibility for more complex TiO2 morphology and novel material properties.