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：胡长文[1] 黄如丹[1] 

机构地区：[1]北京理工大学理学院化学系

出　　处：《无机化学学报》2003年第4期337-344,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.20071007;20271007)

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型犤SiNb12O40犦16-和犤Ti2O2犦4+构成的一维链结构及犤H2Si4Nb16O56犦14-簇,Silverton型多阴离子犤GdMo12O42犦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犤Cr3O(OOCH)6(H2O)3犦犤α-SiW12O40犦·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;三明治结构的犤MnⅢ2ZnW(Zn2W9O34)犦活化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?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, K-12[Ti2O2] [SiNb12O40] . 16H(2)O, which contains one-dimensional (1D) chains constructed by [TiO2](4+) and silicododecaniobate Keggin anions [SiNb12O40](16-), and Na-14[H2Si4Nb16O56] . 45. 5H(2)O, a new POM structure type, obtained by hydrothermal synthesis. method, and Silverton type [GdMo12O42](9-) polyanion and a novel 3D framework formed by Silverton type [GdMo12O42](9-) anions and nine coordinated Gd-III cations; hybrid molecular dumbbells consisting of bridging POM clusters with an organic pi-conjugated rod; an unusual mixed-valence Mo-VI-Mo-VI-Fe-III compound containing discrete {Mo-VI (Mo-VI)(5)}(12) {Mo-6(V) Fe-24(III)}-type Keplerate clusters and their ID linking by a novel type of solid-state reaction at room temperature to form chains, (Necklace-type); synthesis Of Mo-368 cluster with a protein size; preparation of organic-inorganic nanoparticles gamma-SiW10-Au bonded with organic -SH group; starlike nanostructures of POMs, K-3[PMo12O40] . nH(2)O synthesized and assembled by an inverse microemulsion method; a breathing ionic crystal displaying selective binding of small alcohols and nitriles, K-3[Cr3O (OOCH)(6) (H2O)(3)] [alpha-SiW12O40] . 16H(2)O; activation of nitrous oxide and selective epoxidation of alkenes catalyzed by the manganese-substituted POM, [(Mn2ZnW)-Zn-III(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 PO

关 键 词：多金属氧酸盐 绿色化学 纳米复合膜 界面配位 合成化学 催化化学 化学研究 

分 类 号：O611.66[理学—无机化学]