具有催化活性的后过渡金属氧合簇的设计与组装

项目名称： 具有催化活性的后过渡金属氧合簇的设计与组装

项目编号： No.21271024

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 黄如丹

作者单位： 北京理工大学

项目金额： 85万元

中文摘要： 多金属氧簇（POMs）在众多的性能中，以催化性质最为突出。其中Keggin型杂多酸是优良的质子酸催化剂和氧化还原催化剂，这与它的笼型结构特征密切相关，受到广泛关注。怎样扩大POMs的催化领域？如何突破POMs限于前过渡金属W、Mo、V、Nb等做多原子的组成模式，得到兼有配位功能和笼型结构特征的新型催化材料，是极具挑战性的创新课题。本世纪初，国际上开始出现由后过渡金属Fe(Ⅲ)做多原子构筑Keggin结构的文献报道。但由于合成难度大，至今鲜有进一步报道。我们在前期工作中已首次得到三个含Co(Ⅱ)、Ni(Ⅱ)Keggin结构衍生物，并用于催化苯乙烯的聚合反应，显示了良好的催化活性。我们拟以Co、Ni、Cu、Mn等后过渡金属构筑多金属氧簇的骨架，将有机配体作为骨架的主要组分，进行结构和功能的调节，并将目标产物用于催化有机合成反应，可望得到在催化功能上显示更奇特性质的新型催化材料。

中文关键词： 后过渡金属；配位聚合物；金属-氧簇；无机-有机杂化；催化活性

英文摘要： Catalysis is the most prominent function in the numerous function of polyoxometalates(POMs), and the Keggin-type polyoxometalates act as perfect protonic acid catalyst and redox catalyst. This is closely related to its cagelike structure. How can we enlarge the areas of POM catalyst? Breaking through the compositional model that only early transition metal W、Mo. V、 Nb can be the polyatoms of POMs, then getting novel catalytic materials with both coordination function and cagelike structure is a very highly challenging innovating program. At the beginning of the century, articles of late transition metal Fe(Ⅲ) acting as polyatom to build Keggin-type structure occur one after the other. Since it is very hard to synthesis, further reports are seldom published. In our early study, we have already obtained three Co(Ⅱ)、Ni(Ⅱ) Keggin-type structure derivatives, and used in polyreaction of catalyzing styrene which showed perfect catalytic activity. We want to use Co、Ni、Cu、Mn to build the frameworks of polyoxometalates. We will use the organic ligands as the main component of the frameworks, adjust the structures and the function, then applied the target products to catalyze organic reactions. We try to obtain novel catalytic materials which have more perfect nature.

英文关键词： late transition metals；coordination polymers；metal-oxygen clusters；inorganic –organic hybridization；catalytic activity