多金属氧酸盐化学研究进展与展望
The Research Progress and Prospects in Polyoxometalate Chemistry
作者单位
胡长文 北京理工大学理学院化学系北京 100081;东北师范大学多酸化学研究所长春 130024 
黄如丹 北京理工大学理学院化学系北京 100081 
摘要: 本文在简介多金属氧酸盐(Polyoxometalate,缩为POM)的主要性质与应用领域基础上,主要评述近一两年来的POM化学研究领域中取得的合成化学和催化化学新进展,具体内容包括:用水热方法合成的Keggin型[SiNb12O40]16-和[Ti2O2]4+构成的一维链结构及[H2Si4Nb16O56]14-簇,Silverton型多阴离子[GdMo12O42]9-及其三维网结构;POM和有机共轭体系构成的杂化分子亚铃;室温固相条件下得到的项链型多钼铁氧酸盐簇;具有蛋白质尺寸的Mo368簇;通过有机基团(-SH基)联接成的无机/有机杂化纳米粒子γ-SiW10-Au;反胶束体系中制备的星型结构K3PMo12O40纳米棒;具有选择性吸附和分离混合低碳脂肪醇和低碳氰分子的K3[Cr3O(OOCH)6(H2O)3][α-SiW12O40]·16H2O三维孔道结构;总结了POM催化的八个典型工业化项目,固体POM的三种催化作用类型及在催化过程中的几种反应场;三明治结构的[Mn2ZnW(Zn2W9O34)]活化N2O分子及其对烯烃环氧化催化作用;H5PV2Mo10O40在PEG体系中的选择性氧化催化作用;超临界CO2体系中POM催化高收率合成环氧碳酸酯;高活性PW11O397-/TiO2纳米复合膜及其三维有序大孔材料光催化降解含氮有机染料等;有机硅对SiO2离子的表面修饰及其与取代型POM的界面配位键合状态;浅析我国POM化学研究现状并提出几点展望。
关键词: 多金属氧酸盐 催化 绿色化学 纳米复合膜 界面配位
基金项目: 
Abstract: On the basis of introduction of the properties and application fields of polyoxometalates (POMs), a review has been mainly given to the new development of POM chemistry at the aspects of synthesis and catalysis. The concrete contents mainly include: heteropolyniobates, K12[Ti2O2][SiNb12O40]·16H2O, which contains one-dimensional (1D) chains constructed by [Ti2O2]4+ and silicododecaniobate Keggin anions [SiNb12O40]16-, and Na14[H2Si4Nb16O56]·45.5H2O, a new POM structure type, obtained by hydrothermal synthesis method, and Sil-verton type [GdMo12O42]9- polyanion and a novel 3D framework formed by Silverton type [GdMo12O42]9- anions and nine coordinated Gd cations; hybrid molecular dumbbells consisting of bridging POM clusters with an organic π-conjugated rod; an unusual mixed-valence Mo-Mo-Fe compound containing discrete {Mo(Mo)5}12{Mo6 Fe24}-type Keplerate clusters and their 1D linking by a novel type of solid-state reaction at room temperature to form chains (Necklace-type); synthesis of Mo368 cluster with a protein size; preparation of organic-inorganic nano- particles γ-SiW10-Au bonded with organic -SH group; starlike nanostructures of POMs, K3[PMo12O40nH2O synthesized and assembled by an inverse microemulsion method; a breathing ionic crystal displaying selective binding of small alcohols and nitriles, K3[Cr3O(OOCH)6(H2O)3][α-SiW12O40]·16H2O; activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted POM, [Mn2ZnW(Zn2W9O34)2]10-; selective oxidative-catalysis of H5PV2Mo10O40 in the PEG system; POM-catalyzed synthesis of propylene oxide in supercritical carbon dioxide system; preparation of highly active nano-composite film and three-dimension order macropore materials, and their function on the photodegradation of nitrogen-containing dyes and other organic pollutants; modification of surface for silicon dioxide and its interfacial coordination state with substituted type POMs. In addition, eight typical industrialized projects involving POM catalysts, three catalyst types of solid POM and several reaction fields during catalysis processes are summarized. This paper also includes the analyses of re-searching actuality for POM chemistry in china and prospects for them.
Keywords: polyoxometalate catalysis green chemistry nano composite films interfacial coordination
 
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全文下载次数:  1960
胡长文,黄如丹.多金属氧酸盐化学研究进展与展望[J].无机化学学报,2003,19(4):337-344.
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