Oxidation of isobutane catalyzed by vanadyl, copper and cesium substituted H3PMo12O40

Effects of Cs⁺, H⁺ and Cu²⁺ counterions in the vanadium containing heteropoly compounds Cs_xH_1-xVO[PMo₁₂O₄₀] and Cs_yH_0.5-yCu_0.25VO[PMo₁₂O₄₀] on the catalytic oxidation of isobutane and characterization by TGA, IR and ESR spectroscopies are reported. A high selectivity of 76% for methacrylic acid and methacrolein together has been obtained with Cs_0.75H_0.25VO[PMo₁₂O₄₀] catalysts at a reactivity of 5.3x10^-1 mmol/h cm³.     

Raman spectra of hybrid materials based on carbon nanotubes and Cs3PMo12O40

A route for the synthesis of hybrid materials using multiwalled carbon nanotubes (MWCNTS) and Cs₃PMo₁₂O₄₀ was confirmed. The Cs₃PMo₁₂O₄₀ salt was synthesized from H₃PMo₁₂O₄₀·14H₂O and CsCl. All compounds were characterized by Raman spectroscopy. The synthesis method can produce a chemically stable Cs₃PMo₁₂O₄₀ molecule and pure and oxidized MWCNTS. Raman spectroscopy showed that the chemical interaction between MWCNTS and Cs₃PMo₁₂O₄₀ was essentially of electrostatic nature. Raman spectra obtained with different wavelengths showed thermal decomposition of H₃PMo₁₂O₄₀·14H₂O (raw materials) from laser heating process. On the contrary, the synthesized compound (i.e. Cs₃PMo₁₂O₄₀) was stable under the experimental conditions.     

Catalytic Decomposition of Lignin Model Compounds to Aromatics over Acidic Catalysts

Recent progress on the catalytic decomposition of lignin model compounds to aromatics was reported in this review. Cesium-exchanged heteropolyacid catalysts (Cs_xH_3.0?xPW₁₂O₄₀), palladium catalysts supported on cesium-exchanged heteropolyacid (Pd/Cs_xH_3.0?xPW₁₂O₄₀), and palladium catalysts supported on various activated carbon aerogels (ACAs) (Pd/ACA-SO₃H (X), Pd/XCs_2.5H_0.5PW₁₂O₄₀/ACA, Pd/Cs_xH_3.0?xPW₁₂O₄₀/ACA, and Pd/Cs_2.5H_0.5PW₁₂O₄₀/ACA-SO₃H) were prepared, and they were employed for the decomposition of C–O bond in lignin to aromatics. Phenethyl phenyl ether, benzyl phenyl ether, and 4-phenoxyphenol were used as dimeric lignin model compounds representing for β-O-4, α-O-4, and 4-O-5 bonds in lignin, respectively. It was observed that Cs_xH_3.0?xPW₁₂O₄₀ and Pd/Cs_xH_3.0?xPW₁₂O₄₀ were highly active for the decomposition of phenethyl phenyl ether and benzyl phenyl ether to aromatics. However, these catalysts showed very low catalytic performance in the decomposition of 4-phenoxyphenol. Palladium catalysts supported on various ACAs (Pd/ACA-SO₃H (X), Pd/XCs_2.5H_0.5PW₁₂O₄₀/ACA, Pd/Cs_xH_3.0?xPW₁₂O₄₀/ACA, and Pd/XCs_2.5H_0.5PW₁₂O₄₀/ACA-SO₃H) were efficient for the decomposition of 4-phenoxyphenol to aromatics. Acidity of the catalysts played a key role in determining the catalytic performance in the decomposition of 4-phenoxyphenol to aromatics.     

UV-visible spectroscopic study of solid state 12-molybdophosphoricacid catalyst

Summary UV-visible spectroscopic studies of solid H₃PMo₁₂O₄₀were carried out to elucidate the effect of crystalline water molecules, and in turn, to provide a guideline for utilizing UV-visible spectra of solids to probe reduction potentials of HPA catalysts. UV-visible spectra of reduced/reoxidized H₃PMo₁₂O₄₀were also measured to check the possibility of utilizing UV-visible spectroscopy as a probe of reduction/oxidation states of H₃PMo₁₂O₄₀catalyst. Absorption edges of solid H₃PMo₁₂O₄₀ shifted to longer wavelength with heating to decrease the number of crystalline water molecules. It was also revealed that UV-visible spectra of the H₃PMo₁₂O₄₀catalyst varied in a systematic way depending on the reduction/oxidation states of the H₃PMo₁₂O₄₀catalyst.</o:p>     

Vapor-phase synthesis of ethyltert-butyl ether on heteropoly acid-polymer composite film catalysts

H₃PMo₁₂O₄₀-polysulfone and H₃PMo₁₂O₄₀-polyphenylene oxide composite film catalysts were prepared by a membrane preparation technique. They showed the higher catalytic activities than H₃PMo₁₂O₄₀ in the vapor-phase synthesis of ethyl tert-butyl ether.     

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.     

Hydrocarbon oxidation with an oxygen-hydrogen mixture: Catalytic systems based on the interaction of platinum or palladium with a heteropoly compound

A series of studies of hydrocarbon oxidation by the O₂ + H₂ mixture in the presence of catalytic systems based on Pt or Pd and a heteropoly compound (HPC) is reviewed. The catalytic systems were prepared from Pd(II) complexes with the heteropoly tungstate anions PW₁₁O ₂₉ ^7? and PW₉O ₃₄ ^9? , the complex salt [Pt(NH₃)₄][H₂Mo₁₂O₄₀]₂ · 7H₂O, mixtures of H₂PtCl₄ or H₂PtCl₆ with H_{3 + n} PMo_{12 ? n} V _n O₄₀ (n = 0–3) heteropoly acids, or supported platinum dispersed in HPC solutions. The interaction of metal ions and particles with HPCs in the initial state and after thermal and redox treatments was investigated by NMR, IR spectroscopy, XPS, EXAFS, HREM, and TPR. The catalytic systems were tested in the liquid-phase oxidation of alkanes, cyclohexane, cycloalkenes, benzene, toluene, and phenol with the O₂ + H₂ mixture at low temperatures. Effective supported catalysts based on platinum nanoparticles associated with the redox-active HPCs H₃PMo₁₂O₄₀ and H₄PMo₁₁VO₄₀ were prepared for gas-phase benzene oxidation into phenol. The oxidation mechanism includes the interaction between dioxygen and platinum (or palladium) and the participation of the HPC in the formation of active oxygen species of radical nature.     

Titania-supported mixed HPMoV polyoxometallates as precursors of hydrodesulfurization catalysts

HDS catalysts were prepared by loading H₃PMo₁₂O₄₀ or H₄PMo₁₁V₁O₄₀ polyoxometallates on TiO₂ (0.5 and 1.0 mmol (Mo+V)). Activity of the catalysts was tested in the HDS of thiophene. The activity of catalysts of low concentration was 2–3 times higher than the activity of those of high concentration. Temperature programmed reduction (TPR) and IR spectroscopy were used to determine the properties of the catalyst. TPR measurements proved that vanadium promotes and stabilizes HDS activity due to an increase in the Mo⁵⁺/Mo⁴⁺ ratio.     

Catalytic activity of V-substituted Cs2Te0.2H0.6 + xPMo12 ? xVxOn heteropoly compounds in selective oxidation of isobutane

A series of Cs₂Te_0.2H_{0.6 + x} PMo_{12 − x} V _x O _n (x = 0–3) heteropoly compounds has been prepared and tested in the partial oxidation of isobutane. Catalytic tests show that at 350°C very high selectivity to methacrylic acid (60.1%) can be achieved at isobutane conversion of 12.2% over a Cs_2.0Te_0.2H_1.6PMo₁₁VO _n catalyst with only one molybdenum atom per unit cell substituted by vanadium. The presence of Te⁴⁺ in the heteropoly compounds appears to interfere with the dehydrqgenation step and favor the formation of methacrolein and methacrylic acid.     

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.     

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.     

常温常压下硅氨基化介孔SBA-15负载Keggin型钼钒杂多酸催化氧化乙醛的反应研究

Keggin-type molybdovanadophosphoric acids(HPA),H_4PMo_(11)VO_(40)(1),H_5PMo_(10)V_2O_(40)(2)and H_6PMo_9V_3O_(40)(3)were anchored onto γ-aminopropyltriethoxysilane(APTS)aminosilylated silica mesoporous SBA-15 throughacid-base neutralization and the resulting HPA/APTS/SBA-15 were characterized by BET,TEM,XRD,ICP,FTIRand ~(31)P MAS NMR.The characterization results indicate that the Keggin-structure of these HPAs is preservedwithin the mesoporous silica host.The samples were tested for catalytic aerobic oxidation of acetaldehyde hetero-geneously in liquid phase under ambient condition.The electrostatic force between heteropoly acid and aminogroups grafted on the silica channel surface leads to strong immobilization of HPA inside SBA-15 which is againstthe leaching during the reaction.The good catalytic performance and easy recycle of these catalysts make them aspotential environmental friendly catalysts for elimination of indoor air pollutants.     

Catalytic properties of platinum-promoted acid cesium salts of molybdophosphoric and molybdovanadophosphoric heteropoly acids in the gas-phase oxidation of benzene to phenol with an O<Subscript>2</Subscript> + H<Subscript>2</Subscript> mixture

Acid salts Cs _x H_{3 + n ? x} PMo_{12 ? n} V _n O₄₀ (n = 0, 1, 2, or 3; x = 2.5 or 3.5) with coprecipitated or supported platinum were studied using thermogravimetry, IR spectroscopy, and temperature-programmed reduction. The thermal region of the full stability of these salts is limited by the decomposition temperature of the corresponding acid H₃PMo₁₂O₄₀ (～400°C) or H_{3 + n} PMo_{12 ? n} V _n O₄₀ (～300–350°C). The degree of reduction of heteropoly anions with hydrogen is regulated by temperature. Deeply reduced heteropoly anions (at 300°C) are slowly oxidized with oxygen with structure and composition regeneration. The states of molybdenum and vanadium on the surface of samples with coprecipitated platinum Pt_0.1-Cs_2.5H_0.5PMo₁₂O₄₀ (1) and Pt_0.1-Cs_2.5H_2.5PMo₁₀V₂O₄₀ (2), which were studied using XPS, correspond to reduced or reoxidized heteropoly anions in the bulk. Platinum metal particles of ～5 nm in size were observed in high-resolution TEM images obtained after the reduction and storage of sample 1 in air. A heteropoly compound forms two texture levels: spherical nanoparticles of 10–20 nm in size are collected in closely packed globules of 100–300 nm in size. Detailed texture studies, which were performed using nitrogen adsorption isotherms, demonstrated texture mobility under the ambient conditions. The cesium salts of the heteropoly acids were tested in the gas-phase oxidation of benzene to phenol with an O₂ + H₂ mixture at 180°. The effect of platinum concentration on the specific catalytic activity in the presence of deeply reduced heteropoly anions was monitored. The samples containing the salt Cs_2.5H_0.5PMo₁₂O₄₀ exhibited the highest activity in the formation of phenol. The introduction of vanadium into the heteropoly anion impaired the catalytic performance of both deeply and slightly reduced samples.     

Acetylation of Alcohols Catalyzed by Dodeca-tungsto(molybdo)phosphoric acid

Summary. Acetylation of primary, secondary, and tertiary alcohols was carried out in some refluxing alkyl acetates and in two carboxylic acids with the participation of catalytic amounts of H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₁₄P₅W₃₀O₁₁₀ with good yields and high stereo(regio)specificity under mild reaction condition. H₃PW₁₂O₄₀ and H₃PMo₁₂O₄₀ have also shown excellent reactivity in the formylation of 1-butanol with ethyl formate at room temperature and in short reaction times. Heteropolyacid catalysts could be separated after a simple work up and reused for several times.     

Triethylamine-modified Keggin heteropolyacid: a novel phase-transfer catalyst for hydroxylation of benzene with H2O2

The Keggin-structured heteropolyacid H₄PMo₁₁VO₄₀ and its triethylamine-modified derivative [(C₂H₅)₃NH]₄PMo₁₁VO₄₀ were prepared and characterized by FT-IR and UV–visible spectrometry, and elemental analysis. Direct hydroxylation of benzene to phenol by H₂O₂ over these two catalysts was then compared. The effect of the triethylamine in [(C₂H₅)₃NH]₄PMo₁₁VO₄₀ on the catalytic hydroxylation of benzene was investigated in detail. The results showed that although the triethylamine-modified catalyst is not significantly more active than the parent heteropolyacid catalyst, its reaction-controlled phase-transfer characteristics enable easy separation of the catalyst from the reaction medium, and its reuse, suggesting its potential for application to the hydroxylation of benzene to phenol with H₂O₂.     

Keggin-type heteropoly-11-molybdo-1-vanadophosphoric acid supported montmorillonite K-10 clay-catalysed one-pot multi-component synthesis of chromeno[2,3-b]indoles

One-pot three-component synthesis of twelve different chromeno[2,3-b]indole derivatives were achieved by the condensation of β-naphthol, oxindole and various substituted aldehydes. Two more chromeno[2,3-b]indole derivatives were also synthesized through one-pot two-component condensation of salicylaldehyde with oxindole/chlorooxindole. Both the condensations were achieved by using Keggin-type heteropoly-11-molybdo-1-vanadophosphoric acid, H₄[PVMo₁₁O₄₀] supported on montmorillonite K-10 clay for about 10% as catalyst under environmentally benign solvent-free reaction condition. Shorter reaction time, excellent yield of product, sustainability of catalytic material and simple workup procedure under green experimental conditions are the advantages of this protocol.

     

Molybdovanadophosphoric Acid Catalyzed Oxidation of Hydrocarbons by H2O2 to Oxygenates

Heteropoly acids of the general formula H_3+x[PMo_12-xV_xO₄₀] (where x = 1,2,3) catalyzed the oxidation of aromatic hydrocarbons at 65°C with H₂O₂ to give oxygenated products. Among the catalysts, H₄[PMo₁₁VO₄₀] was found to be a more active catalyst and its activities have been reported in the oxidation of cyclohexane, methyl cyclohexane, naphthalene, 1-methyl naphthalene and biphenyl.     

Study of iron state in titania-supported FeMo catalysts of hydrodesulfurization

Summary Thiophene conversion on, and Mössbauer spectra of sulfided FePMo/TiO₂ catalysts prepared using H₃PMo₁₂O₄₀ and its Fe salt have been studied. Iron and phosphorus promoting effect on catalytic activity of the HDS catalysts is discussed.     

Synthesis, physical–chemical, and catalytic properties of mixed compositions Ag/H3PMo12O40/SiO2

Deposited catalysts composition H₃PMo₁₂O₄₀/SiO₂ and Ag/H₃PMo₁₂O₄₀/SiO₂ have been synthesized on the basis of fumed silica, including milling technique. Physical–chemical characteristics of prepared catalysts have been studied by means of XRD, DTA-TG, FTIR, UV–Vis spectroscopy, and adsorption of nitrogen. Catalysts possess meso- or meso-macroporous structure and contain deposited Keggin heteropolycompounds. Deposition of heteropolycompounds on support with high specific surface area results in increase of selectivity to epoxide in epoxidation reactions. The use of milling during catalyst synthesis leads to further growth of selectivity of epoxides formation.     

Ultrasonic Auxiliary Ozone Oxidation-Extraction Desulfurization: A Highly Efficient and Stable Process for Ultra-Deep Desulfurization

For ultra-deep desulfurization of diesel fuel, this study applied the ultrasound-assisted catalytic ozonation process to the dibenzothiophene (DBT) removal process with four Keggin-type heteropolyacids (HPA) as catalysts and acetonitrile as extractant. Through experimental evaluations, H₃PMo₁₂O₄₀ was found to be the most effective catalyst for the oxidative removal of DBT. Under favorable operating conditions with a temperature of 0 °C, H₃PMo₁₂O₄₀ dosage of 2.5 wt.% of n-octane, and ultrasonic irradiation, DBT can be effectively removed from simulated diesel. Moreover, the reused catalyst exhibited good catalytic activity in recovery experiments. This desulfurization process has high potential for ultra-deep desulfurization of diesel.