Modification of palygorskite surface by organofunctionalization for application in immobilization of H3PW12O40

Modified palygorskite with 3-aminopropyltriethoxysilane (KH550) and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (KH792) were used as adsorbent supports for adsorption of 12-phosphotungstic acid (H₃PW₁₂O₄₀, HPW). The effect of some factors, such as adsorbent dosage, contact time, initial HPW concentration and temperature, was investigated. The experimental data were well fitted with the pseudo-second-order kinetic model and the Langmuir adsorption isotherm model at all studied temperatures. The physicochemical properties of the solids were characterized by using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis-simultaneous differential thermal analysis (TGA-SDTA), and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy analysis techniques. The characteristic results indicated that silylated-Pa was a suitable support for adsorption of HPW; and HPW was finely and effectively distributed on silylated-Pa and retained partly strong Bronsted acidity.     

A novel multi-component synthesis of 4-arylaminoquinazolines

A new multi-component synthesis of 4-arylaminoquinazolines from the reaction of 2-aminobenzamide, orthoesters, and substituted anilines in the presence of catalytic amounts of Keggin-type heteropolyacids is reported. The effects of reaction conditions and different heteropolyacids have been studied.     

Kinetics of gas phase synthesis of ethyl-tert-butyl ether (ETBE) on Wells–Dawson catalyst

Mechanism and kinetics of gas phase synthesis of ethyl-tert-butyl ether (ETBE) over Wells–Dawson heteropolyacid H₆P₂W₁₈O₆₂ in an anhydrous system have been discussed. The rates of ETBE synthesis were measured in a differential reactor for ethanol–isobutene system, far from the limitation by chemical equilibrium. In the pressure range studied, kinetic measurements show that isobutene has an enhancing effect on the reaction while ethanol has an inhibitory one.

Catalytic and sorption experiments allowed to formulate the mechanism of ETBE synthesis which assumed isobutene adsorption and oligomerization at the surface of heteropolyacid crystallites and the formation of carbocation using protons supplied from the bulk of catalyst. Kinetic equations were deduced indicating that it is the concentration of protons forming inter-anionic bonds between heteropolyacid anions which determines the catalytic activity of heteropolyacid.     

Studying catalytic activity of ternary mixed-metal Keggin H7SiV3W9O40 as a versatile acid catalyst for the synthesis of β-acetamido ketones

One-pot four-component condensation of an aromatic aldehyde with an enolisable ketone and acetyl chloride is investigated in the presence of H₇SiV₃W₉O₄₀ in acetonitrile. The prepared catalyst was characterized by standard techniques such as XRD, SEM, and FT-IR to verify the Keggin structure of nanocatalyst. Furthermore, findings revealed a very good catalytic activity for the applied vanadium substituted heteropolyacid in this acid catalyzed condensation reaction. A series of Keggin Si and V-substituted heteropolyacids were compared for the synthesis of β-acetamido-β-(4-chlorophenyl)propiophenone, which showed a better catalytic activity for H₇SiV₃W₉O₄₀ and H₄SiW₁₂O₄₀ than the lacunary and mixed metal Keggin H₄SiW₉Mo₃O₄₀ and H₅SiW₉Mo₂VO₄₀. In addition, effect of the nitrilating agent was also demonstrated in this catalytic system and findings show less proficiency for PhCN compared to acetonitrile. Moreover, propiophenone as an α-substituted enolisable ketone was reacted with some aromatic aldehydes and the anti isomer is detected as the major diastereomer. Therefore, H₇SiV₃W₉O₄₀ can be introduced as a new effective, inexpensive, and eco-friendly catalyst for the introduced four-component condensation reaction.     

[Ru(bpy)3] nanocomposites containing heteropolyacids: Simple preparation and stable solid-state electrochemiluminescence detection application

In order to solidify the electrochemiluminescence (ECL) luminophor tris(2,2′-bipyridyl) ruthenium(II) ([Ru(bpy)₃]²⁺) onto the electrode surfaces robustly, the negative charged heteropolyacids (HPAs) moieties were utilized to attract and bond cations [Ru(bpy)₃]²⁺ via an adsorption method. The compositions and microstructures of the hybrid complexes were characterized by elemental analysis (EDS), spectroscopic techniques (UV-vis, FTIR) and field-emission scanning electron microscopy (FE-SEM). The electrochemical and ECL behaviors of the [Ru(bpy)₃]²⁺/[PW₁₂O₄₀]³⁻ hybrid complex contained in the solid film of the nanocomposites formed on the electrode surfaces were also studied. It was found that the corresponding solid membranes exhibited a diffusion-controlled voltammetric feature and excellent electrochemiluminescence behaviors. Hence potential prospects as new electrochemiluminescent materials for application in electroanalytical detection are envisioned.     

磷钨杂多酸类离子液体催化环戊烯选择性氧化制备戊二醛

以H_2O_2为氧化剂,将一系列磷钨杂多酸类离子液体用于催化环戊烯(CPE)选择性氧化制备戊二醛(GA)反应,筛选出催化活性最高的催化剂为[π-C_5H_5NC_(16)H_(33)]_3PW_4O_(16).分别探讨了溶剂种类、用量、催化剂用量、H_2O_2用量、反应温度和反应时间等因素对反应的影响.确定了优化的反应条件:5 mL乙酸乙酯,n(Cat.)∶n(H_2O_2)∶n(CPE)=0.03∶50∶33,35℃,18 h,环戊烯的转化率达100%,戊二醛的选择性达87%.催化剂[π-C_5H_5NC_(16)H_(33)]_3PW_4O_(16)循环使用7次后,戊二醛的选择性仍保持在80%以上.     

Synthesis and Structure of K_8[P_2W_18Mo_2Co_2O_68(H_2O)_2][MoO_6]·15H_2O

Recently, Many tri-component heteropoly compounds have been synthesized, but tetra-component heteropoly compounds have not been reported. It is known that mixtures of Mo and Co oxides are a promoted hydrodesulphurization catalyst. The title compound is a polyoxophosphate containing Mo, Co and W, the divalent anion possesses two-fused Keggin structure, whereas MoO_6 has been confirmed to be an elementary structure unit of isopoly and heteropoly molybdates, but it, as an idependent anion, has not been reported either.     

钨磷酸(钨硅酸)/聚乙烯醇复合物的制备和光、电性质研究

Kessin型的杂多酸及其盐是多酸化学中研究得最多的物种[1],近年来,以Keggin型的钨磷酸、钨硅酸为代表的多种杂多酸在固体和材料化学领域受到人们的关注[2],并在固体修饰电极、光（电）致变色材料、离子选择性电极和传感器等方面得到了广泛应用[3-5]．本文报道了Keggin型的钨磷酸、钨硅酸／聚乙烯醇复合物的合成、表征、光致变色性质及导电性．1实验方法技文献[6]方法制备H4[SiW12O40]·mH2O和H2［PW12O40］·nH对晶体,含水量用热重分析测得．将聚合度为1800士100的聚乙烯酸（PVA）0．5g溶于200mL沸水中,在65C,搅拌条件下分批…     

杂多酯引发四氢呋喃开环聚合反应Ⅶ.以氧杂环丁烷为促进剂

在以低浓度杂多酸(ＨＰＡ)催化四氢呋喃(ＴＨＦ)聚合反应中,我们曾采用环氧乙烷(ＥＯ)、环氧丙烷(ＰＯ)和环氧氯丙烷(ＥＣＨ)等三元环醚为促进剂,发现它们对聚合反应都具有很好的促进效果[1～3].本文进一步研究了具有四元环醚结构的氧杂环丁烷(ＯＸ)对ＴＨＦ聚合的促进效果.ＯＸ用作促进剂有以下优点,由ＯＸ促进ＴＨＦ聚合所得聚醚的端羟基为伯羟基,作为生产嵌段聚醚氨酯或嵌段聚酯弹性体的原料具有与四氢呋喃均聚醚相似的高反应活性;与ＥＯ相比,后者虽然促进ＴＨＦ聚合所得聚醚的端羟基也为伯羟基,但其沸点过低,不利于操作和贮存.1　原料及…     

Wells–Dawson tungsten heteropolyacid-catalyzed reactions of benzylic alcohols, influence of the structure of the substrate

Heterolytic cleavage of the C–OH bond of various benzylic alcohols has been catalyzed with H₆P₂W₁₈O₆₂. Alkenes or symmetric ethers are produced, depending on the structure of the substrate.