氧化镁负载钼钒磷酸铜催化剂上正己醇氧化脱氢制正己醛

 采用乙醇溶液浸渍法制备了MgO负载的Cu2PMo11VO40催化剂,考察了催化剂对正己醇氧化脱氢生成正己醛的催化性能,确定了最佳反应条件. 催化剂经50 h反应后活性没有下降,生成正己醛的选择性保持在96.0%以上. IR光谱和TPR结果表明,在反应条件下催化剂上不断有V5+从Keggin结构中移出,与Cu2+一起作为抗衡离子存在于Keggin结构单元之外,形成缺位的Keggin型结构,使催化剂处于活化状态; Cu2+的存在使催化剂的还原温度降低,Keggin结构之外的V5+与Cu2+之间存在相互作用,可使催化剂活性提高.     

H4PMo11Vo40杂多酸及其镧盐的合成与性质

本文提出主要用~(51)V NMR、CV并辅以IR、XRD、DTG、元素分析等作为有效地核查纯度和表征催化剂的手段。     

杂多酸盐K_4H[SiMO_(11)VO_(40)]·18H_2O 1和K_4H_2[PMo_9V_3O_(40)]·18H_2O 2的晶体结构

在-90℃下用X线单晶衍射法测定了标题化合物的晶体结构。晶体属P_(421)~c〔P4/mnc〕,α=12.540(2)〔12.515(3)〕,c=17.565(5)〔17.636(7)〕A,z=2.用1672〔788〕个独立可观测反射精修结构参数得R=0.059〔0.057〕。1中的Si是4配位。Si-O=1.58A。M(M=Mo,V)是6配位,M-O=1.64-2.37A。K是7配位,K-O=2.80～3.11A。在化合物2中,PO_4是无序的,P-O=1.51A,M-O=1.63～2.47A,K是7配位,K-O=2.85～3.10A。两个晶体都是多层二维的网状结构。     

模板合成H4PMo11VO40/聚苯胺纳米线列阵及其聚合机理探讨

在氧化铝模板中制备了HPA/PANI纳米线列阵,SEM、TEM表明列阵中纳米线直径约为80 nm;XRD与FT-IR证明形成了有效掺杂;单根纳米线的导电率为16.2 S.cm-1;材料的TG-DTA表明PANI纳米线材料有三步失重过程,失去吸附水过程,多酸失去结晶水和PANI结构持续分解过程,多酸结构分解过程;在氧化聚合过程中H4PMo11VO40即为质子酸又为氧化剂和掺杂剂;聚合反应采用自由基机理进行,掺杂反应发生在形成醌二亚胺式自由基正离子和双苯胺式自由基正离子和醌二亚胺式自由基正离子偶联聚合成链结构时.     

同多酸和杂多酸修饰微电极的电化学研究——Ⅶ.磷钒钼杂多酸薄膜修饰…

本文详细描述了磷钒钼杂多酸（ＰＶ２Ｍｏ１０）极薄膜修饰碳纤维（ＣＦ）微电极和ＰＶ２Ｍｏ１０／聚苯胺（ＰＡｎ）薄膜修饰微电极的制备及其电化学性质。     

氧化镁负载磷钼钒杂多酸催化剂的结构和催化性能

采用乙醇溶液中浸渍的方法制备了氧化镁负载的磷钼钒酸铜(Cu₂PMo₁₁VO₄0)催化剂,考察了正己醇选择氧化生成正己醛的催化反应性能.催化剂的IR,XRD,UV-DRS,NMR,DTA-TG和比表面积等测试结果表明,Cu₂PMo₁₁VO₄0在氧化镁表面单层分散,形成缺位型Keggin结构.反应后催化剂表面分散状态及结构未发生明显改变,Keggin型对称结构有所恢复,形成活化状态的缺位型Keggin结构.     

钼钒磷杂多酸的合成及催化性能研究

Three heteropoly acids containing different amounts of V and Mo have been prepared by multi-step method. The methed was simple, economic in raw materials’ cost, and with relatively higher yield. ICP, TGA, Potentiometric Titrations, Infrared, XRD and ⁵¹V NMR characterizations revealed that the compounds synthesized in present work had Keggin structure. The catalytic performance of the heteropoly acids obtained for the direct hydroxylation of benzene to phenol was also investigated, 26% phenol yield with more than 90% selectivity was obtained.     

杂多酸盐K_4H(SiMo_(11)VO_(40))·14H_2O的合成及晶体结构

杂多酸是种类多,应用广的重要的无机化合物。其中有一类是12-系列化合物Z,(XM_(12-n)M_n′O_(40))·mH_2O,中心离子X可以是过渡元素或非过渡元素;M常是Mo、W;M′为V_(5 )、Mn_(2 )、CO_(2 )等;n=0,1,2…;Z为H~ 或一价阳离子;y=1,2,…。它们同其相应氧化型化合物比较具有引人注目的特性,但迄今尚未见到还原型化合物晶体结构文章,只是     

Na_3H_2[PMo_(10)V_2O_(40)]·16H_2O的合成与晶体结构

标题化合物的晶体属P2_1/m空间群,α=13.821(2),b=15.355(3),c=11.597(2),β=107.50(2)°,V=2347.2~3,M_r=2091.46,Z=2,D_c=2.959 g·cm~(-3),μ(MoK_o)=30.77cm~(-1),F(000)=1992。用4049个独立可观测衍射精修结构,R=0.033。杂多酸阴离子[PMo_(10)V_2O_(40)]~(5-)具有准Keggin结构,12个金属原子呈无序分布,中心原子P与两个齿顶原子M(Mo/V)在对称面上。P—O平均键长1.541(2),M—O键长1.671(2)-2.432(2)。除一个Na—O配位多面体为畸变三方锥外,其余四个Na—O配位体均为六配位。讨论了Na~+离子呈无序分布的晶体结构特征并初步总结[PMo_(10)V_2O_(40)]~(5-)在不同晶相中的构型。     

Catalytic Performance of Divanadium-Substituted Molybdophosphate Acid,H5PMo10V2O40, in Liquid-Phase Esterification of Hexanoic Acid

Divanadium-substituted molybdophosphate acid, H₅PMo₁₀V₂O₄₀, efficiently catalyzes the synthesis of ethylhexanoate from hexanoic acid and ethanol at reflux temperature and under solventless conditions. Comparison of H₅PMo₁₀V₂O₄₀ with the other heteropolyacids showed that this catalyst gives the highest total yield of ethylhexanoate. The effects of the molar ratio of acid:alcohol, reaction times, and temperatures were studied.     

制备方法对氧化镁负载的钼钒磷酸铜催化剂结构和催化性能的影响

在乙醇溶液中采用不同的浸渍方法制备了氧化镁负载的钼钒磷酸铜催化剂，利用XRD、IR和BET比表面测定等测试手段对催化剂进行了表征．XRD和IR表征结果表明，负载的钼钒磷酸铜在载体表面均匀分散，而且能够保持Keggin型结构．XRD和BET比表面测定结果说明，经12h浸渍制备的催化剂（H4PMo11VO40-CuO／MgO12H）化学和结构性能发生变化；其它两种方法制备的催化剂（H4PMo11VO40-CuO／MgO和Cu2PMo11VO40／MgO）没有化学和结构性能的变化，而且这两种催化剂具有相近的表征结果，说明两种催化剂具有相似的结构特征，以正己醇氧化脱氢生成正己醛反应评价了催化剂的催化反应性能，结果表明，H4PMo11VO40-CuO／MgO和Cu2PMO11VO40／MgO催化剂显示出比H4PM011VO40-CuO／MgO12H更高的催化反应活性。     

Partial Gas-Phase Oxidation of Toluene by the Heteropoly Acid H4PMo11VO40 Supported on ShAS-2 Aluminosilicate

The effects of reaction conditions and concentration of the heteropoly acid H₄PMo₁₁VO₄₀ supported onto ShAS-2 bead aluminosilicate on the conversion of toluene into benzoic acid in the partial oxidation of toluene by atmospheric oxygen were studied. The results demonstrated that the conversion of toluene was an extremal function of temperature, space velocity (v), and toluene concentration (C ₀) in the initial air mixture. An increase in the heteropoly acid concentration from 2 to 30% increased the conversion of toluene into benzoic acid in the partial oxidation of toluene from 1.5 to 12.6% at optimum process parameters: T = 300°C, v = 2000 h^-1, and C ₀ = 13.72 g/m³.     

甲基丙烯醛与H4PMo11V1/SiO2催化剂相互作用的红外光谱研究

本文报告了甲基丙烯醛(MAL)在杂多酸催化剂H₄PMo₁₁V₁/SiO₃上吸附的红外光谱研究结果。在表面上生成了三种表面络合物,CH₂=C(CH₃)-CHO(Ⅰ)、CH₂=C(CH₃)-(这里有图片198707-635-2.gif)。认为它们是生成甲基丙烯酸(MAA)的中间物。发现在较高温度(300℃)抽空处理的催化剂上不发生MAL的化学吸附,同时表征杂多酸阴离子结构的υ(P-O)和一个υ(Me-O-Me,Me代表Mo或V)谱带也消失了。     

Thermal behavior of the polyoxometalates derived from H3PMo12O40 and H4PVMo11O40

The aim of this study is to investigate the influence of some monovalent counter-ions (NH₄ ⁺, K⁺ and Cs⁺) on thermal behavior of polyoxometalates derived from H₃PMo₁₂O₄₀ (HPM) and H₄PVMo₁₁O₄₀ (HPVM) by replacing the protons. The IR and UV-VIS-DRS spectra of some acid and neutral NH₄ ⁺, K⁺, Cs⁺ salts, which derived from HPM and HPVM, confirmed the preservation of Keggin units (KU) structure. The X-ray diffraction spectra clearly showed the presence of a cubic structure. The non-isothermal decomposition of studied polyoxometalates proceeds by a series of processes: the loss of crystallization water; the loss of O₂ accompanying with a reduction of V⁵⁺→V⁴⁺ and Mo⁶⁺→Mo⁵⁺; the loss of constitution water started at 360°C for HPVM salts and 420°C for HPM salts; the decomposition of ammonium ion over 420°C with NH₃, N² and H₂O elimination and simultaneous processes of reduction (V⁵⁺→ V⁴⁺ and Mo⁶⁺→ Mo⁵⁺ or Mo⁴⁺) associating with endothermic effects; reoxidation of Mo⁵⁺, Mo⁴⁺ and V⁴⁺with a strong exothermic effect; destruction of KU to the oxides: P₂O₅, MoO₃ and V₂O₅ and the crystallization of MoO₃. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and Crystal Structure of [VO2（C17H11N3O2） ] [VO （C4H13N3）（C6H5N3O） ]（C2H5OH）

The reaction of VO（acac）2 with 2-hydroxyl-1-naphthaldehyde isonicotinyl hydrazone and amines （ethylenediamine or diethylenetriamine） in CH3OH yields crystals of novel vanadium compounds characterized by IR, NMR spectroscopic methods and X-ray single-crystal structure determination. Two different vanadium units exist in the crystal cell of [VO2（C17H11N3O2）][VO- （C4H13N3）（C6H5N3O）]（C2H5OH） which crystallizes in the triclinic system, space group P1 with a = 8.0104（17）, b = 13.898（3）, c = 14.955（3）A, α = 89.103（4）, β = 79.551（4）, γ = 78.352（4）°, V = 1603.3（6）A^3, Mr = 723.54, Dc = 1.499 g/cm^3, Z = 2, λ（MoKα） = 0.71073 ]A,μ= 0.644 mm^-1, F（000） = 748, the final R = 0.0547 and wR = 0.0997 for 8920 observed reflections with I 〉 2σ（I）. According to structure analysis, two different molecules are arranged in the lattice and the two vanadium atoms adopt octahedral and square pyramidal coordination geometries, respectively. The interactions between DNA and vanadium complexes have been investigated by UV-Vis absorption spectro- photometry.