Comparison of H3PW12O40 and H4SiW12O40 heteropolyacids supported on silica by H MAS NMR

The H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀ heteropolyacids supported on silica were studied by ¹H MAS NMR as a function of both the coverage and the dehydroxylation temperature. The signal at ca. 8 ppm attributed to the highly acidic protons of the anhydrous form of the heteropolyacid was never observed in the case of the phosphotungstic polyanion supported on silica while it was clearly present in the case of the silicotungstic species. These results explain the different activities of the two supported heteropolyacids in acid reactions involving strong acid sites. To cite this article: A. Thomas et al., C. R. Chimie 8 (2005).     

Heteropolyacids as new catalysts of the Ritter reaction

Some nitriles reacted with camphene in the presence of heteropolyacids (H₃PW₁₂O₄₀, H₄SiW₁₂O₄₀, H₇PMo₁₂O₄₀) as catalyst to give N-(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)-substituted amides in fairly high yields.     

The Catalytic Performance of Preyssler's Anion, [NaP5W30O110]14−, in the Oxidation of Benzyl Alcohols

Under mild conditions, monosubstituted benzyl alcohols were oxidized to benzaldehydes and benzoic acids in the presence of sodium 30-tungstopentaphosphate (Preyssler's anion), [NaP₅W₃₀O₁₂₀]^14? , and hydrogen peroxide as an oxidant. This polyanion with high hydrolytic stability (pH = 0–12), high thermal stability, and high acidic strength shows good activities. The effects of various parameters on the yield of the products, including a catalyst type, a nature of the substitutents, and temperature, were studied. Comparison between Keggin's heteropolyacids, H₃[PW₁₂O₄₀], H₃[PMo₁₂O₄₀], H₄[SiW₁₂O₄₀], and H₄[SiMo₁₂O₄₀], and Preyssler's anion shows that this polyanion reacts similar to Keggin's acids whitout any degradation of the structure.     

Enhanced Electrochemical Response of Isoniazid Electrocatalytic Oxidation on RGO-PPD-SiW Modified Electrode

The electroactive composites based on reduced graphene oxide (RGO), poly-o-phenylenediamine (PPD) and heteropolyacids – H₄SiW₁₂O₄₀nH₂O (SiW) and H₃[PW₁₂O₄₀] ⋅ nH₂O (PW) was applied to a screen-printed carbon electrode (SPCE) as a planar three-electrode cell as the first step to creating various devices, in particular, sensors and catalysts. We studied potential use of the modified and unmodified SPCE planar electrode in determining the concentration of antitubercular antibiotic isoniazid (isonicotinic acid hydrazide C₆H₇N₃O or INH). The best result was observed for SPCE+RGO-PPD-SiW. CV of normal saline with various concentrations of C₆H₇N₃O demonstrated linear dependence of the relevant anodic peak current either in the bulk solution upon immersion of the modified electrode or in a droplet on the electrode surface.     

2‐Methyl‐1,3‐disulfoimidazolium polyoxometalate hybrid catalytic systems as equivalent safer alternatives to concentrated sulfuric acid in nitration of aromatic compounds

Ionic liquid‐derived polyoxometalate salts [mdsim]₃[PM₁₂O₄₀] (where M = W and Mo) of two heteropolyacids H₃PW₁₂O₄₀.nH₂O and H₃PMo₁₂O₄₀.nH₂O were synthesized using 2‐methyl‐1,3‐disulfoimidazolium chloride ([mdsim][Cl]) ionic liquid and the corresponding heteropolyacids. Three equivalents of [mdsim][Cl] were treated with the respective Keggin‐structured heteropolyacids (one equivalent) in aqueous medium at room temperature to afford the water‐stable ionic polyoxometalates as acidic solids. They were completely characterized using spectroscopic and other analytical techniques including thermal analysis and Hammett acidity studies. The inherent Brønsted acidic properties of ─SO₃H group of these polyoxometalate salts were studied for the nitration of aromatic compounds with 69% HNO₃ at normal temperature and 80°C without use of any external concentrated sulfuric acid. These strongly acidic polyoxometalates display good recyclability and efficient reusability.     

Heteropolyacid as an Efficient Catalyst for Synthesis of 3,4-Dihydro-1H-2,3-benzothiazine-2,2-dioxides

A facile and efficient method for the formation of 3,4-dihydro-1H-2,3-benzothiazine 2,2-dioxides 2, compounds from benzylsulfonamides and formaldehyde is described using heteropolyacids H₃PW₁₂O₄₀ and H₃PMo₁₂O₄₀ supported on silica as catalysts.     

Synthesis of 1,2,9-trisubstituted purin-6(9H)-ones catalyzed by heteropolyacids

1,2,9-Trisubstituted purin-6(9H)-ones have been synthesized in high yield by reaction of 5-amino-N,1-dimethyl-1H-imidazole-4-carboxamide with aromatic aldehydes in the presence of heteropolyacids, H₃PMo₁₂O₄₀ and H₅PV₂Mo₁₀O₄₀. The catalytic activity of H₃PMo₁₂O₄₀ is lower than that of H₅PV₂Mo₁₀O₄₀. This is an effective synthesis of l,2,9-trisubstituted guanine derivatives with the advantages of mild reaction conditions, simple operation, and good yields.     

Facile preparation of an α-Keggin-type [H3W12O40] complex: Does it exist in aqueous solution?

The formation processes of α-Keggin-type [H₂W₁₂O₄₀]⁶⁻ and [H₃W₁₂O₄₀]⁵⁻ complexes were investigated in aqueous W^VI (0.05–0.50 M) solutions. The formation of [H₂W₁₂O₄₀]⁶⁻ was ascertained by the appearance of a ¹⁸³W NMR line at −117 ppm, but no evidence was found for the existence of [H₃W₁₂O₄₀]⁵⁻ in the solution at the accessible pH range. The addition of (CH₃)₄N⁺ (Me₄N⁺) to the W^VI solution directly precipitated the (Me₄N)₆[H₂W₁₂O₄₀] salt. On the other hand, the addition of the larger Bu₄N⁺ cation precipitates the (Bu₄N)_4.5H_0.5[H₃W₁₂O₄₀] salt, because a naked proton formed during the crystallization process or in the solid state may enter into the Keggin shell to produce [H₃W₁₂O₄₀]⁵⁻. This explanation is based on the fact that [H₂W₁₂O₄₀]⁶⁻ is not spontaneously converted into [H₃W₁₂O₄₀]⁵⁻ in acidified aqueous solution. On the basis of their voltammetric properties, a simple diagnostic criterion was developed to distinguish between [H₂W₁₂O₄₀]⁶⁻ and [H₃W₁₂O₄₀]⁵⁻.     

Synthesis and physicochemical properties of Zr-MCM-41 mesoporous molecular sieves and Pt/H3PW12O40/Zr-MCM-41 catalysts

For the first time, modifications of the surface and framework of Si-MCM-41 by depositing a heteropolyacid on the surface and by introducing foreign Zr⁴⁺ ions into the framework are investigated. The Zr-modified Si-MCM-41 mesoporous materials (hereafter referred as WSZn, n=Si/Zr=25, 15, 8, 4) were synthesized through a surfactant-templated preparation approach, using low-cost fumed silica as the Si precursor. After impregnation with 25 wt% of H₃PW₁₂O₄₀, the surface Brönsted acidity of the Pt/H₃PW₁₂O₄₀/WSZn catalysts was greatly enhanced by 2-10 times relative to the bare WSZn support. Two kinds of supported heteropolyacids were formed: (i) bulk-like heteropolyacid crystals with unchanged Keggin structures, and (ii) highly dispersed heteropolyacid with distorted Keggin units. The formation of various kinds of heteropolyacid structures is closely related to the interaction between the heteropolyanions and the hydroxyl groups in the host support.     

Highly efficient synthesis of 3-pyrrolyl-indolinones and pyrrolyl-indeno[1,2-b]quinoxalines catalyzed by heteropolyacids

Simple and improved conditions have been found for the synthesis of 3-pyrrolyl-indolinones and pyrrolyl-indeno[1,2-b]quinoxalines by coupling of 4-hydroxyproline with isatins and 11H-indeno[1,2-b]quinoxalin-11-ones using Keggin (H₃PW₁₂O₄₀) and Well-Dawson tungsten heteropolyacids (H₆P₂W₁₈O₆₂).     

Keggin-type H4PVMo11O40-based catalysts for the isobutane selective oxidation

Cesium heteropolysalts Cs₃PMo₁₂O₄₀ and HCs₃PVMo₁₁O₄₀ were synthesized by modifying the preparation conditions in order to get materials with a much higher surface area than the original Keggin-type heteropolyacids (H₃PMo₁₂O₄₀ and H₄PVMo₁₁O₄₀). These solids were used as carriers for the dispersion of H₄PVMo₁₁O₄₀ heteropolyacid by the incipient wetness impregnation technique. The textural and structural properties of supports and catalysts were examined by scanning electron microscopy, N₂ adsorption-desorption isotherms and Raman spectroscopy. The supported catalysts were studied before and after red/ox pretreatments by X-ray photoelectron spectroscopy, which showed that both the surface composition and oxidized to reduced species ratio depend on the used carrier. The catalytic performances of these novel supported catalysts in the selective oxidation of isobutane to methacrylic acid and methacrolein were studied. The best catalytic properties were obtained when H₄PVMo₁₁O₄₀ was supported on HCs₃PVMo₁₁O₄₀. The isobutane conversion and yield of the desired oxygenates increased along the unsupported H₄PVMo₁₁O₄₀ < H₄PVMo₁₁O₄₀/Cs₃PMo₁₂O₄₀ < H₄PVMo₁₁O₄₀/HCs₃PVMo₁₁O₄₀ series.

     

Boehmite nano‐particles functionalized with silylpropylamine‐supported Keggin‐type heteropolyacids: Catalysts for epoxidation of alkenes

Boehmite nano‐particles with a high degree of surface hydroxyl groups were covalently functionalized by 3‐(trimethoxysilyl)‐propylamine to support H₃[PMo₁₂O₄₀], H₃[PW₁₂O₄₀], H₄[SiMo₁₂O₄₀] and H₄[SiW₁₂O₄₀] Keggin‐type heteropolyacids. After characterization of these catalysts by FT‐IR, powder X‐ray diffraction, TG/differential thermal analysis, CHN, inductively coupled plasma and transmission electron microscopy techniques, they were applied to the epoxidation of cis‐cycloocten. The progress of the reactions was investigated by gas–liquid chromatography, and the catalytic procedures were optimized for the parameters involved, such as the solvent and oxidant. The results showed that 25 mg of supported H₃[PMo₁₂O₄₀] catalyst in 1 ml C₂H₄Cl₂ with 0.5 mmol cyclooctene and 1 mmol tert‐butylhydroperoxide at reflux temperature gave 98% yield over 15 min. Recycling experiments revealed that these nanocatalysts could be repeatedly applied up to five times for a nearly complete epoxidation of cis‐cycloocten. The optimized experimental conditions were also used successfully for the epoxidation of some other alkenes, such as cyclohexene, styrene and α‐methyl styrene.     

Catalytic synthesis of diphenolic acid from levulinic acid over cesium partly substituted Wells–Dawson type heteropolyacid

A series of insoluble cesium partly substituted Wells–Dawson type heteropolyacids, Cs_xH_6−xP₂W₁₈O₆₂ (x = 1.5–6.0), were synthesized and characterized using the techniques including UV–vis/DRS, FT-IR, XRD, XPS, and N₂ porosimetry. As the unique and reusable solid acid catalysts, Cs_xH_6−xP₂W₁₈O₆₂ salts were applied to produce diphenolic acid by the condensation reaction of phenol with bio-platform molecule, levulinic acid. For comparison, cesium partly substituted Keggin type heteropolyacids (Cs_xH_3−xPW₁₂O₄₀, x = 1.0–3.0), HCl, HZSM-5, and MCM-49 were also tested. Influences on the catalytic activity and selectivity were considered for factors including solvent, molar ratio of phenol to levulinic acid, amount of catalyst, reaction temperature, stirring speed, and reaction time. The experimental results demonstrated that both Cs_1.5H_4.5P₂W₁₈O₆₂and Cs_2.5H_0.5PW₁₂O₄₀ exhibited excellent catalytic performance under solvent-free conditions. Furthermore, both selectivity and activity of Cs_1.5H_4.5P₂W₁₈O₆₂ were higher than those of Cs_2.5H_0.5PW₁₂O₄₀. Reasons for the different catalytic behaviors between two types of cesium partly substituted heteropolyacids were investigated.     

Effect of heteropolyacids on the hydrocarboxylation of styrene: comparative study on hydrocarboxylation and hydroesterification reactions

The hydrocarboxylation and the hydroesterification of styrene was studied in the presence of PdCl₂(PPh₃)₂ as a catalyst. The effect of the addition of the heteropolyacids of a general formula H_3+nPMo_12-nV_nO₄₀ (HPA-n, n=1-4) on the hydrocarboxylation and the hydroesterification of styrene was considered.     

Hydrothermal syntheses and crystal structures of crystalline catalysts based on 3-D Ln3+–pdc2− frameworks and [BW12O40]5− and their heterogeneous photocatalytic oxidation of thiophene

Five [BW₁₂O₄₀]^{5 ?} -containing metal-organic frameworks (MOFs), {K[Ln(H₂O)₄(pdc)]₄}[BW₁₂O₄₀]·2H₂O (Ln=La 1 and Ce 2, H₂pdc = pyridine-2,6-dicarboxylate) and {K[Ln(H₂O)₃(pdc)]₄}[BW₁₂O₄₀]·6H₂O (Ln=Tb 3, Dy 4 and Er 5), are synthesized hydrothermally. Ln³⁺ and pdc^2? are built into 3-D MOF segments containing large channels and cavities which are occupied by [BW₁₂O₄₀]^{5 ?} . Herein, we report MOF-containing polyoxometalates (POMs) as photocatalysts to oxidize thiophene with O₂ as the oxidant. Photo-excited state species ([BW₁₂O₄₀]^5??) are generated under UV irradiation and then H₂O is oxidized into OH˙ radicals and O₂ is reduced into O₂ ^2?. The active oxygen species (O₂ ^2?, OH˙) oxidize thiophene in the presence of photocatalysts and SO₃, CO₂, and H₂O are obtained as photoproducts. ESR measurements provide evidence that OH˙ species are generated during photocatalysis.     

Selective Hydrolysis of Terminal Glycosidic Bond in α-1-Acid Glycoprotein Promoted by Keggin and Wells–Dawson Type Heteropolyacids

The reactivity of a range of Keggin and Wells–Dawson type heteropolyacids (HPAs): H₃PW₁₂O₄₀ H₄SiW₁₂O₄₀, H₃PMo₁₂O₄₀, K₆P₂W₁₈O₆₂, and NaH₂W₁₂O₄, towards the heavily glycosylated α-1-acid glycoprotein (AGP) is reported. Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) show that after incubation of the protein with HPAs at 80 °C and pH 2.8 complete hydrolysis of terminal glycosidic bond has been achieved, resulting in the removal of sialic acids with no observed destruction of the protein core or the residual glycan chains. The ¹H NMR spectroscopy confirmed that the released sialic acids preserve intact structure upon their excision from the protein, which makes the reported method suitable for the analysis of sialic acid modifications which play an important role in numerous biological processes. The presence of other sugars was not detected by ¹H NMR and HPAEC-PAD, suggesting that HPAs hydrolyze only the terminal glycosidic bond in the glycoprotein, resulting in the selective release of sialic acid from AGP. The kinetic results have shown that under equal temperature and pH conditions, the hydrolysis of the terminal glucosidic bond occurred faster in the presence of HPAs compared to conventional mineral acids. The observed rate constants were in the range 6,7×10⁻² −11,9×10⁻² min⁻¹ and the complete and selective excision of sialic acids could be achieved within 60 min of incubation. The Trp fluorescence and CD spectroscopy show that non-covalent interaction between HPA and protein takes place in solution which could lead to stabilization of the sialosyl cation that is formed during the glycosidic bond hydrolysis by anionic HPA cluster.     

Dehydrogenation activity and structure of polyaniline supported heteropolyacid catalysts

Polyaniline(PAN) supported H₆P₂W₁₈O₆₂(PW) , H₃PMo₁₂O₄₀ (PMo) and H₄PMo₁₁VO₄₀(PMoV) catalysts were prepared and their activities for hexanol conversion were tested. IR, XRD, ICP and SEM measurements proved that the heteropolyacids (HPA) could be supported on this type of polymer. The PAN supported HPA catalysts exhibit higher redox activities and low acid-base activities for the hexanol conversion. The redox activities increase with increasing amount of the heteropolyacid. Substitution of Mo ion by V ion results in an increase of redox activities of the catalysts. This revised version was published online in June 2006 with corrections to the Cover Date.     

Oxydation catalytique de l'octéne-1 en présence de complexes de rhodium(III) ou de palladium(II) associés à des acides phosphomolybdovanadiques et au dioxygéne

Chlororhodium(III) complexes with heteropolyacids HPAH_3+n [PMo_12−nV_nO₄₀]) catalyze the oxidation by molecular oxygen of oct-1-ene to octan-2-one in alcoholic solvents with alcohol cooxidation (T 60° C).The PdSO₄HPA/water-THF/O₂ catalyst system shows the highest activity at room temperature for this ketonization.     

（TEAH）nH3-nPW12O40催化苯甲醇选择氧化及其反应机理

以Keggin结构的磷钨酸和三乙胺（TEA）为原料,通过简单的酸碱反应合成了磷钨酸的TEA盐.并以它们为催化剂,考察了以H₂O₂为氧化剂、以水为溶剂的体系中苯甲醇选择氧化制备苯甲醛的反应性能.结果表明,（TEAH）_nH_3-nPW₁₂O₄₀（n=1,2,3）系列催化剂对苯甲醇的选择氧化反应有很高的活性和选择性,且可被分离和循环使用.在适宜的反应条件下,最佳催化剂（TEAH）H₂PW₁₂O₄₀上,苯甲醇的转化率可达99.6%,苯甲醛的选择性为100%.还采用IR,³¹PNMR谱和元素分析技术,对催化剂和反应过程中催化剂物种的转化和分布进行了考察,进而导出了反应机理.在这个水--油两相反应中,（PW₁₂O₄₀）^3-首先在H₂O₂的作用下,氧化降解为溶于水的小分子过氧物种（PO₄（WO（O₂）₂）₄）^3-和自由W物种.（PO₄（WO（O₂）₂）₄）^3-是真正的活性物种,可将部份溶于水层的苯甲醇氧化为苯甲醛,自身转变为失去活性氧的反应后物种（SAR）.而SAR又可与自由W物种一起聚合为前驱体状态的（PW₁₂O₄₀）^3-,完成催化循环.     

The enthalpies of formation and evolved gas detection

The standard molar enthalpies of formation of H₄SiW₁₂O₄₀·6H₂O (I), H₄SiW₁₂O₄₀·6DMF·H₂O (II), H₄SiW₁₂O₄₀·8DMSO·H₂O (III) have been determined. Thermodynamic cycles were designed, and the heat of reactions in the thermodynamic cycles were measured calorimetrically. The infrared spectra were compared with those of the heteropoly anion α-H₄SiW₁₂O₄₀ [1] and of the ligands DMF and DMSO. The evolved gas from the adducts was monitored by a quadrupole mass spectrometer at a heating rate of 16 deg·min^?1.