【作者】 梁爽；

【导师】 韩金玉；

【作者基本信息】 天津大学 ， 化学工艺， 2007， 硕士

【摘要】 金属-有机配位聚合物是一类由金属中心离子与有机配体自组装而成的具有广阔应用前景的新型固体材料。本文通过水热法和扩散法合成了四种具有新型结构的金属-有机配位聚合物,并通过红外光谱、X射线单晶衍射和热重分析等分析方法,对其的结构和热稳定性进行了表征。利用丁二酸和含氮杂环配体咪唑合成了两种金属-有机配位聚合物:配合物（1）[Cu（succinate）（imidazole）₂]_n、配合物（2）[Nd2（succinate）₃ （H2O）₂]_n。羧酸类与含氮杂环类化合物作为混合配体,形成的复杂结构的配合物,克服了单独使用含氮杂环中性配体时骨架不稳定的缺点。配合物（2）中心为高配位数的金属钕,碳链空间取向多变。利用芳香羧酸均苯三甲酸（H3BTC）合成了两种金属-有机配位聚合物:配合物（3） {[Co₃ （BTC）₂（H₂O）₁₂]·0.25H₂O}n,配合物（4） [Ni₂Zn（BTC）₂（H₂O）₁₂]_n。两种配合物具有相近的空间结构,其中后者是新颖的异核金属中心配位聚合物。以醇氧化反应研究了四种MOFs的催化性能。以苯甲醇氧化反应作为模型反应考察了溶剂、反应温度、反应时间对四种金属-有机配位聚合物催化性能的影响,并比较金属-有机配位聚合物对苯甲醇、α-苯乙醇的催化效果。实验结果表明四种金属-有机配位聚合物都具有一定程度的催化活性,但效果差异较大。对于催化性能较好的配合物（1）,确定了适宜反应条件为:常温下乙腈作为溶剂,底物:氧化剂:催化剂=100:250:3（摩尔比）,反应时间2小时达到较好效果。在上述条件下,配合物（1）催化苯甲醇氧化的转化率为42.67%,催化α-苯乙醇氧化的转化率为58.10%。更多还原

【Abstract】 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%.更多还原