【作者】 钟立峰；

【导师】 张渊明；

【作者基本信息】 暨南大学 ， 无机化学， 2003， 硕士

【摘要】 杂多化合物兼有酸性和氧化还原性，在催化领域中有着广泛的应用。本文采用酸化—醚化法合成了三种不同钒原子数的P-Mo-V三元杂多酸，并用ICP-AES和TGA确定其化学组成和结构，用FT IR、XRD和UV等手段对其结构和性质进行了表征。FT IR表明它们具有Keggin结构，XRD结果表明这三种化合物是类质同晶体，三种化合物的UV曲线相似，说明它们性质相似。 结合Keggin型P-Mo-V杂多酸的优异电子传递性能，以十八烷基氯化铵为成膜物质，制备了ODA/(PMo₁₀V₂O₄₀)^5-LB膜。用AFM、LAXD、FTIR和UV对其形貌和结构进行了表征，用CV研究了其电化学行为。所有结果证明所得ODA/PMo₁₀V₂O₄₀^5-LB膜结构性质稳定，层间重叠有序，PMo₁₀V₂O₄₀^5-阴离子在层中均匀分布，层中间有足够的空间和通道允许杂多阴离子到达电极表面发生电化学反应，并证明这是一个双电子伴随着双质子的过程。 为了探索所得杂多酸的催化性能，考察了H₄PMo₁₁VO₄₀对苯甲酸和正丁醇酯化反应的催化效果，发现在最佳条件下酯收率达到80％多，证明其为一种较好的酸催化剂。同时探讨了H₅PMo₁₀V₂O₄₀的季铵盐对十八醇氧化成十八酸的催化能力，实验证明有一定的氧化催化能力，但因季铵离子中烷基链不长，相转移效果不是很好。 鉴于Keggin型多聚阳离子[AlO₄（OH）₂₄（H₂O）₁₂]⁷⁺的环境效应和多方应用，本文还对其的合成和表征进行了初步探讨。更多还原

【Abstract】 Heteropoly compounds have great utilities in catalysis because of their acidity and oxidation-reduction quality. In the work, three P-Mo-V heteropoly acids with different Vanadium number have been synthesized by acidification- etherization. Their component and structure have been confirmed by ICP-AES and TGA. They have been characterized by FT IR, XRD and UV. FT IR demonstrates their Keggin structure. The results of XRD show that they are isomorphism. UV spectra display their similarity of properties.Considering outstanding properties of heteropoly acids, ODA/(PMo10V2O40)5- LB film has been prepared using octadecylamine hydrochloride(ODA). Its morphology and structure have been characterized by AFM, LAXD, FT IR and UV. Its electrochemical behavior was studied by Cyclic voltammetry. All of the results prove the ODA/(PMo10V2O40)5- LB film is steady in structure and properties and well-define between layers. The PMo10V2O405- anion distributes homogeneously in layers. There are sufficient space and channel in layers permitting the heteropoly anion to land the area of electrode and carry out the reaction of electrochemistry. And prove this is the process of two electron with two proton.To explore their catalytical capability, the esterification of phenyl formate and 1-butanol was chosen. It is found that the esterification yield exceeds 80%, which demonstrates the heteropoly acid has higher catalytic activity. In the same time, the catalytic activity of the quaternary ammonium of H5PMo10O40 was studied, too. The results of experiment display it has the capacity of catalytic oxidation. But due to the alkyl in quaternary ammonium isn’t long enough, the effect of phase transfer is not very well.Taking account of the environmental protect and many applications, the synthesis and characterization of the polycation, [AlO4(OH)24(H2O)12]7+ has been studied simply.更多还原