STUDIES ON REDOX PROPERTIES OF HETEROPOLY ACIDS (SALTS) AND THEIR DERIVATIVES WITH KEGGIN AND DAWSON STRUCTURES

We have systematically studied redox properties of two series of several dozen heteropoly acids (salts) and their derivatives with vanadium and rare-earth elements with Keggin and Dawson structures, e. g. LnHSiMo_(12), SiMo_(12-n)V_n, M_(1.5)PMo_(12), PMo_(12-n)V_n, PW_(12-n_V_n, Ln(PMo_(11))_2, Sm(XMo_(11))_2 and P_2Mo_(18-n)V_n, etc., and obtained their sequence of oxidation. It was found that there is a linear relationship between the reduction potentials of heteropoly anions and the derivatives of heteropoly anions with rare-earth elements with Keggin structure and nq~2 (n and q are the principal quantum number and charge of the central ion respectively). On the basis of the electrostatic model the regularity of oxidation and reduction was rationalized.     

四金属簇钨砷夹心型化合物[M4(H2O)2·(AsW9O34)2]10-(M=CuⅡ, CoⅡ, MnⅡ, NiⅡ, ZnⅡ)的合成、结构和磁特性研究

取代型杂多化合物可改变多酸化合物的酸碱性、氧化还原性和热稳定性,因而受到关注[1]. 夹心型化合物是一类新型化合物,具有大的摩尔质量,高的负电荷,且含有多个磁性中心,近年来已引起国内外的兴趣[2].     

多金属氧酸盐α-Na6H[GeW9Fe3(H2O)3O37]·16H2O的合成和光谱

合成了多金属氧酸盐α-Na6H[GeW9Fe3(H2O)3O37]16H2O，通过元素分析、红外、紫外、光电子能谱、极谱和穆斯堡尔谱等手段进行了表征，并讨论和研究了该配合物的谱学性质。     

杂多蓝研究的进展

杂多酸及其盐类以其特有的结构和物理化学性质,已经成为一类有广阔应用前景的酸型和氧化还原型催化剂,在催化领域越来越引人关注。杂多蓝是杂多酸及其盐的还原产物,由于杂多酸及其盐被还原后,大多数呈现深蓝色,所以习惯上称为“杂多蓝”(Heteropoly     

新型层柱材料ZnAl─CuW11In的合成、表征及催化活性

本文用水热离子交换法首次将中心原子为铜的钨系取代型杂多阴离子［ＣｕＷ１１Ｏ３９Ｉｎ（Ｈ２Ｏ）］７－嵌入ＺｎＡｌ型阴离子粘土层间，通过ＸＲＤ、ＩＲ及ＥＳＲ等对柱撑产物进行了表征。ＸＲＤ研究表明柱撑产物的底面间距为１．７５ｎｍ，通道高度达１．２８ｎｍ。ＥＳＲ结果显示杂多阴离子进入粘土层间后ＣｕＯ４四面体中Ｃｕ－Ｏ键的共价性减弱。催化实验则表明柱撑产物对邻苯二甲酸二辛酯（ＤＯＰ）的合成反应有较高的催化活性     

Syntheses, characterization and catalytic reactivities of heteropolyanion-pillared clay of anions of Zn-Al type

Mono-substituted Keggin ions PW11O39Cr(H2O)4 , PW11TiO403 and PW11VO404 were intercalated between the layers of the clay of anions of Zn-Al type using the ion exchange method to obtain a new type of pillared layered microporous materials ZnAl-PW11Cr, ZnAl-PW11Ti and ZnAl-PW11V with basal spacing (1.48±0.02) run. On the basis of the MAS NMR results of 27A1 and 31P, a steric pillared layered structure model of orientation localization of PW11VO40,4- in the orientation in which the C2 axis of PW11VO404-is perpendicular to the host layer. It has been found that this kind of pillared layered microporous materials possess a higher catalytic activity for the esterification of acetic acid with n-butanol than H-type molecular sieves.     

镧系元素杂多钨铬酸盐的合成与性质研究

自镧系元素双-11-钨硅(磷)酸钾于1971年问世以来,对此类配合物的研究引人注目。由于其具有优异的催化活性,可为催化剂研究提供依据。因此该领域的研究日趋活跃。本文首次合成了十种镧系元素双-11-钨铬酸钾固体配合物,研究了它们的组成和性质。 (一)实验 1.仪器与试剂 DDS-11A型电导率仪;Alpha Centauri FT/IR红外光谱仪;Q-Derivatograph综合热分析仪;Escalab-MKⅡ型电子能谱仪。试剂均为AR级。     

稀土双(11-钨硅酸)钾的质子导电性研究(英)

研究了K13［Ln（SiW11O39）2］nH2O（Ln=La，Ce，Pr，Nd，Sm，Gd）的质子导电性研究表明其导电性不仅与物质本性有关，也与外界条件如温度、频率等有关，不同结构的杂多化合物给出不同结构的质子导电性．总结了质子导电性随温度、结晶水数目、频率的变化总趋势．基于实验数据得出一些重要结论，所得数据未见文献报道．     

稀土元素1∶12系列钨硅杂多配合物的合成及性质

用复分解法合成了七种稀土元素Keggin结构钨硅杂多配合物:LnHSiW_(12)O_(40)·xH_2O。用ICP、~(29)SiNMR、XPS、XRD、IR.UV、极谱、CV和TG—DTA对它们进行了系统研究,并讨论了其结构和性质的关系。     

双-11钨钛希土三元杂多化合物的合成与性质研究

本文报道了双-11钨钛希土三元杂多化合物K_(13)[Ln(TiW_(11)O_(39))_2]·xH_2O(Ln=La,Ce,Pr,NdSm,Eu,Gd,Tb,Dy,Ho,Er,Yb,Y,Ce(Ⅳ))的合成方法,溶液性质,红外光谱,紫外光谱,X光电子能谱,热分析等的研究结果.