【作者】 安文佳；

【导师】 许林；

【作者基本信息】 东北师范大学 ， 无机化学， 2006， 硕士

【摘要】 近年来人们越来越重视多酸在催化领域中的应用。本世纪七十年代以来,日本在应用催化方面做了许多前驱性工作。仅日本至今采用多酸催化剂实现工业化的项目已达8个,一些装置是万吨级以上“世界瞩目的先进工艺”。杂多酸作催化剂的优点是在均相和非均相体系中,可作为性能优异的酸碱、氧化还原或双功能催化剂。活性高,选择性好,腐蚀轻微,反应条件温和,是节约型环保型催化剂。它具有传统催化剂所不具有的优秀特性:1,具有确定的结构;2,通常溶于极性溶剂;3,独特的假液相反应场;4,杂多酸阴离子具有软性;这些特点使他们很好的应用于有机物有选择性的转化成产物,以及烃类的水合,不饱和化合物的氧化。本文采用环境友好的、绿色的过氧化氢（H₂O₂ 30 %）为氧化剂,做催化氧化脂环烃的研究,主要开展了如下四个方面的工作:1,主要探索了1 , 2-二氯乙烷做溶剂,催化氧化环己烯的体系中三缺位的Keggin型磷钨杂多酸季铵盐[（C₄H₉）₄N]₉[A-α-PW₉O₃₄]和[（C₄H₉）₄N]₉[（Fe^Ш（OH₂）₂）₃(A-α-PW₉O₃₄)₂]以及[（C₄H₉）₄N]₄H₃[PW₁₁O₃₉]的催化性能来研究缺位结构磷钨杂多酸季铵盐的催化活性。本文探讨了可能的反应机理。2,研究了1 , 2-二氯乙烷做溶剂,催化氧化环己烯的体系中杂多酸所含配位水的数量对催化剂活性的影响。我们选取了含六个配位水的夹心结构铋钨杂多酸[（M^Ⅱ（H₂O）₃）₂（WO₂）₂(BiW₉O₃₃)₂]₁₀-（M=Co, Mn, Ni ）和三个配位水的[（M^Ⅲ（H₂O））₃(BiW₉O₃₃)₂] 12-（M=Co, Mn, Ni ）做催化剂。3,探索了H₂O₂（30 %）做氧化剂,乙腈做溶剂催化氧化环己烷的反应体系中,杂多酸催化剂夹心铁原子数量的不同对催化剂活性的影响。我们考察了两铁夹心的Dawson结构（TBA）₁₆[Fe₂（NaOH₂）₂(P₂W₁₅O₅₆)₂]和三、四个夹心铁的Keggin结构（TBA）₁₂[(SiW₁₀O₃₇)₂Fe₄（OH）₄]和（TBA）₉[（Fe^Ⅲ（OH₂）₂）₃(A-a-PW₉O₃₄)₂]催化剂,在此反应体系中的活性。4,用微乳液法制备纳米粒子[Ag₆ (PMo₁₀V₂O₄₀)]（CH₃COO） .8H₂O并且与非纳米级别的[Ag₆ (PMo₁₀V₂O₄₀)]（CH₃COO） .8H₂O做活性比较,乙腈做溶剂来催化氧化环己烷。更多还原

【Abstract】 Catalysis by polyoxometalates is a field of increasing importance. In applied catalysis,most of the pioneering work has been done since the 1970s mainly by Japanese, eightworld-famous industrial processes of ten thousand products per year based onpolyoxometalates. In the heterogeneous as well as homogenous catalytic system, using polyoxometalates asacid-base, oxide-redox or bifunctional catalysts, there are several advantages such as highcatalytic activity, products selectivity, mild reaction conditions, light atmospherecontaminated. On the other hand several advantages that traditional catalysts has none, whichmake them economically and environmentally attractive especially in selectivetransformations of organic substances, oxidation of unsaturated compounds, hydration ofolefins: 1, the stable structure;2, very high solubility in polar solvents;3, unique“pseudoliquid phase”;4, heteropoly acid anions exhibit an extremely high proton mobility.This catalytic oxidation of alicyclic alkene used H₂O₂ （30 %） as “green” and “friendly”oxidant. This work had four aspects as follows:1,We explored the catalytic activity of vacant polyoxometalate. Oxidation reaction ofcyclohexene in 1,2-dichloroethane solvent was catalyzed by trivacant Keggin-typepolyoxometalate tetra-butylammonium salts [（C₄H₉）₄N]₉[A-α-PW₉O₃₄] 、[（C₄H₉）₄N]₉[（Fe^Ш（OH₂）₂）₃(A-α-PW₉O₃₄)₂] and [（C₄H₉）₄N]₄H₃[PW₁₁O₃₉]. The probablemechanisms were discussed in this paper .2, We studied the number of ordinated water of polyoxometalate catalysts how to affect thecatalytic activity. Oxidation of cyclohexene with hydrogenperoxide （30%） solution asoxidant in 1,2-dichloroethane solvent was catalyzed by tri-ordination water Keggin-typesandwich polyoxometalate tetra-butylammonium salts [（M^Ⅲ （H₂O））₃(BiW₉O₃₃)₂]₁₂-（M=Co,Mn, Ni ） and double tri-ordination water [（M^Ⅱ（H₂O）₃）₂（WO₂）₂(BiW₉O_<sub>33)₂]_<sub>10（-M=Co, Mn, Ni ）.3, We investigated the catalytic activity of the number of transition-metal-iron insandwich-type polyoxometalate catalysts. Oxidation of cyclohexane in acetonitrile solventcatalyzed by two transition-metal-iron sandwich Dawson-type（TBA）₁₆[Fe₂（NaOH₂）₂(P₂W_<sub>15O₅₆)₂ and three or four Keggin-type （TBA）₉[（Fe^Ⅲ（OH₂）₂）₃(A-a-PW₉O₃₄)₂] or （TBA）₁₂[(SiW₁₀O₃₇)₂Fe₄（OH）₄].4, We prepared polyoxometate [Ag6（PMo10V2O40）]（CH3COO）.8H2O nanoparticles inmiremulsions comparing the catalytic activity with [Ag6 （PMo10V2O40）]（CH3COO）.8H2Oin the catalytic oxidant cyclohexane system in acetonitrile.更多还原