Metal-Organic Coordination Polymers Synthesis, Characterization And Their Catalytic Performance For Oxidation Of Alcohols

Metal-organic frameworks, also known as coordination polymers, are a type of self-assembly formed by organic ligands and metal ions. They are a new type of solid material, which have an extensive application prospect.In this thesis, four kinds of metal-organic frameworks with novel structures were hydrothermally synthesized. The structures and thermal stabilizations of the coordination polymers were characterized by many kinds of analysis methods, such as infrared spectra, X-ray single crystal diffraction and thermal gravity analysis.Two kinds of coordination polymers were prepared by ligands including succinic acid and imidazole: coordination polymer (1)[Cu(succinate)(imidazole)₂]_n ,coordination polymer (2) [Nd2(succinate)₃ (H₂O)₂]_n. Carboxylic acid and ligands with N atoms were used together to synthesize complicated structures, which conquered the shortcoming of unstability of the coordination polymers casued by the ligands with N atoms. The metal ion in coordination polymer (2) was neodymium, which cause the diverse extending direction of the flexible chain.Two kinds of coordination polymers were prepared by aromatic carboxylic acid ligands-BTC: coordination polymer (3) {[Co₃ (BTC)₂(H₂O)₁₂]·0.25H₂O}n ,coordination polymer (4) [Ni₂Zn(BTC)₂(H₂O)₁₂]_n. These two coordination polymers have nearly the same structure, but polymer (4) is a novel heterometallic complex.In the aspect of catalytic performance of MOFs: four coordination polymers were used as the catalysts respectively in the oxidation of alcohols in order to analyze the impact of the different reaction temperature, time and solvents to the conversion. The results of oxidation of benzyl alcohol andα-phenylethyl alcohol, which were catalyzed by four coordination polymers respectively, were illustrated. The results of the experiments illustrated that these four MOFs all have the catalyst activity in the oxidation of alcohol, but the performance were different.The appropriate reaction condition of oxidation of benzyl alcohol catalyzed by coordination polymer (1) was determined: room temperature; in the acetonitrile; substrate: oxidant: catalyst=100:250:3 (mol scale); two hours reaction. In this condition, the conversion of oxidation of benzyl alcohols catalyzed by coordination polymer (1) was 42.67%, and the conversion of oxidation ofα-phenylethyl alcohol catalyzed by coordination polymer (1) was 58.10%.