H3PW12O40/MCM-41 nanoparticles as efficient and reusable solid acid catalyst for the synthesis of quinoxalines

The condensation reaction of 1,2-diketones and o-phenylenediamines was investigated in the presence of nano-sized mesoporous silica (MCM-41) supported 12-tungstophosphoric acid (TPA) as solid acid catalyst. Nano-sized MCM-41 was synthesized and the catalysts with different loading amounts of TPA (5–15 wt.%) were prepared and characterized by XRD, FT-IR and SEM techniques. The results confirm good dispersion of TPA on the solid support. The catalyst is reusable many times without loss in its activity.     

Heteropoly-12-tungstophosphoric acid H3[PW12O40] over natural bentonite as a heterogeneous catalyst for the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones

Heteropolyacid 12-tungstophosphoric acid H₃[PW₁₂O₄₀] (TPA) immobilized over natural bentonite (bent) using the impregnation method. Prepared catalyst were well characterized by XRD, FT-IR and FeSEM. The catalytic activity of three catalysts 10%, 20% and 30% TPA/bent examined for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones known as Biginelli reaction. The catalyst 30% TPA/bent exhibited a high yield of the product towards the synthesis of a variety of dihydropyrimidones (DHPMs). The high yield of dihydropyrimidone (DHPM) was obtained in model reaction in ethanol, acetonitrile and solvent - free condition. The reusability test indicated that 5% of yield of product decreased after 5th cycle.     

Phenylimido Functionalization of alpha-[PW12O40]3-

A synthetic route of potentially wide scope is reported herein for the organoimido functionalization of polyoxotungstates. This report focuses on the reaction between the monovacant lacunary polyoxotungstate, alpha-((n-C4H9)4N)4H3[PW11O39], and W(NC6H5)Cl4 in anhydrous acetonitrile. Evidence from 1H, 31P, 183W, and 1H-183W HMQC NMR spectroscopy, as well as cyclic voltammetry, electronic absorption, and elemental analysis, is presented for the formation of alpha-[PW12O39(NC6H5)]3- (2) of Cs symmetry, which is structurally related to Td alpha-[PW12O40]3- (3) by formal oxide substitution. The electronic structure of 2 is significantly perturbed from 3 with significant arylimido-->tungsten charge transfer, primarily localized to the W(NC6H5) fragment with secondary charge delocalization onto the remaining W and corner-shared bridging O atoms. This is consistent with the approximately 800 ppm downfield 183W NMR shift for the phenylimido-tungsten, modest cathodic shifts in reversible redox potentials, electronic and IR spectra, and density functional theory calculations.     

Silica-coated magnetic NiFe2O4 nanoparticles-supported H3PW12O40; synthesis,preparation, and application as an efficient,magnetic, green catalyst for one-pot synthesis of tetrahydrobenzo[b]pyran and pyrano[2,3-c]pyrazole derivatives

Research on Chemical Intermediates - A powerful, magnetic, supported, acid catalyst, NiFe2O4@SiO2–H3PW12O40, was prepared by chemical support of Keggin (H3PW12O40) heteropolyacid (HPA) on...     

MCM-41负载钨磷杂多酸催化剂的性能研究

制备并表征MCM-41负载H~3PW~1~2O~4~0(PW)催化剂.PW杂多酸在MCM-41上负载量高达70%(质量分数)时,XRD中仍未检测到其晶相峰.PW杂多酸与MCM-41载体的相互作用要比与SiO~2载体的强.PW杂多酸中的质子位是非常强的酸中心,它们对NH~3的微分吸附热在160-180kJ/mol的范围.与PW杂多酸相比,PW/MCM-41催化剂的酸中心强度变弱并且分布不均匀,其酸量和酸中心分布可以通过改变PW杂多酸的负载量来调节.PW/MCM-41是一类适合于中强酸和弱酸催化反应的新型固体酸催化剂。     

Structural studies of high dispersion H3PW12O40/SiO2 solid acid catalysts

Highly dispersed H(3)PW(12)O(40)/SiO(2) catalysts with loadings between 3.6 and 62.5 wt% have been synthesised and characterised. The formation of a chemically distinct interfacial HPW species is identified by XPS, attributed to pertubation of W atoms within the Keggin cage in direct contact with the SiO(2) surface. EXAFS confirms the Keggin unit remains intact for all loadings, while NH(3) adsorption calorimetery reveals the acid strength >0.14 monolayers of HPW is loading invariant with initial DeltaH(ads) = approximately -164 kJ mol(-1). Lower loading catalysts exhibit weaker acidity which is attributed to an inability of highly dispersed clusters to form crystalline water. For reactions involving non-polar hydrocarbons the interfacial species where the accessible tungstate is highest confer the greatest reactivity, while polar chemistry is favoured by higher loadings which can take advantage of the H(3)PW(12)O(40) pseudo-liquid phase available within supported multilayers.     

Synthesis and structure of triphenylbutyl phosphonium dodecatungstophosphate [(C6H5)3PC4H9]3[PW12O40]

The salt [(C₆H₅)₃PC₄H₉]₃[PW₁₂O₄₀] has been synthesized by a reaction between triphenylbutyl phosphonium bromide and dodecatungstophosphoric heteropoly acid in water and structurally characterized. The phosphorus atoms in the two types of crystallographically independent [(C₆H₅)₃PC₄H₉]⁺ cations each have a distorted tetragonal coordination (P-C distances, 1.745(16)–1.823(15) Å; CPC angles, 107.2(8)°–112.1(9)°). In centrosymmetric [PW₁₂O₄₀]^3? anions (with a phosphorus atom at the inversion center) the W-O_end, W-O(μ₂), and W-O(μ₄) bonds are 1.61(1)–1.71(2), 1.87(2)–1.94(2), and 2.44(2)–2.50(2) Å, respectively.     

Hydroisomerization of n-heptane over bimetal-bearing H3PW12O40 catalysts supported on dealuminated USY zeolite

The bimetal-bearing (CePt or LaPt) 12-tungstophosphoric acid (H₃PW₁₂O₄₀ (PW)) catalysts supported on dealuminated USY zeolite (DUSY) were prepared by impregnation and characterized by XRD, BET, IR, and H₂-chemisorption. Their catalytic activities were tested in the hydroisomerization of n-heptane with a continuous atmospheric fixed-bed reactor. After the steam treatment combined with the acid leaching, as well as the supporting with PW and the bimetals, the DUSY support retains the Y zeolite porosity and the PW well keeps its Keggin structure in catalysts. The doping of Ce into the catalysts enhances the dispersion of Pt on the catalyst surface. The Pt-bearing PW catalysts doped with Ce or La, especially Ce, exhibit much higher catalytic activity and selectivity than the catalysts without dopants at lowered reaction temperatures. At the optimal reaction conditions, i.e., the reaction temperature of 250°C and WHSV of 1.4 h^?1, the catalyst with a Pt loading of 0.4%, PW loading of 10% and a molar ratio of Ce to Pt of 15:1 shows a conversion of n-heptane of 70.3% with a high selectivity for isomerization products of 94.1%.     

H3PW12O40@[bmim][FeCl4]: A green catalytic system for alkoxymethylation of alcohols and their one-pot interconversion to acetates and TMS-ethers

12-Tungstophosphoric acid immobilized on [bmim][FeCl₄] was found to be an efficient catalyst for chemoselective methoxymethylation and ethxoymethylation of alcohols and also one-pot conversion of MOM- or EOM-ethers to their corresponding acetates and TMS-ethers under thermal conditions and microwave irradiation. These procedures were simple, rapid and the corresponding products were obtained in high yields. The catalyst exhibited remarkable reactivity and was reusable.     

Smoke suppression of [Glu]H2PW12O40 in thermoplastic polyurethane elastomer

Journal of Thermal Analysis and Calorimetry - As is known there is a large amount of smoke released from the combustion process of thermoplastic polyurethane elastomer (TPU). To reduce the fire...     

Methods of preparing the heteropolyacid H3PW12O40

Ionexchange and electrochemical methods of preparing the heteropolyacid H₃PW₁₂O₄₀ are studied. Conditions are found for preparing H₃PW₁₂O₄₀ in quantitative yield using electrodialysis without ether extraction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1944–1947, September, 1990.The authors thank K. I. Matveev for initiating the work with electrodialysis at the Institute of Catalysis, Siberian Branch, Academy of Sciences of the USSR.     

Synthesis and Characterization of H3PW12O40 and H3PMo12O40 Nanoparticles by a Simple Method

In this study H₃PW₁₂O₄₀·9H₂O and H₃PMo₁₂O₄₀·6H₂O (HPA) particles were changed into nano forms by heat-treatment in an autoclave as a simple, repaid, inexpensive and one step method. The particle size of these nanoparticles was around 25 nm. The as-synthesized nanostructures were characterized by dynamic light scattering, X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and inductively coupled plasma analyzer. Thermal stability of nanoparticles was surveyed by thermal gravimeter analyse. Acidity of prepared nanoparticles was investigated by pyridine adsorption method. Results showed rising acidity by declining particle size of HPA.     

Study of reactions in the phosphate-tungstate system: Electromembrane synthesis of the heteropoly acid H3PW12O40

We have studied the electromembrane method for obtaining H₃PW₁₂O₄₀. using³¹P,¹⁸³W and¹⁷O NMR, we have studied the conversions of isopoly-and heteropolytungstates over a broad pH range. Depending on the acidity of the medium and the form of the isopolytungstate, we propose two schemes for reaction of isopolytungstates with phosphate ions during formation of H₃PW₁₂O₄₀.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1726–1732, August, 1991.     

Preparation of PVA／H3PW12O40 Fiber Mats

Poly(vinyl alcohol) (PVA) fiber mats containing 20 and 80wt% H3PW12O40 were prepared by using electrospinning technique. The fiber mats were characterized by IR, XRD spectra and scanning electron microscope (SEM). The diameter of the fiber mats is ca. 400nm.     

Adsorption of H3PW12O40 by porous carbon materials

Adsorption of H₃PW₁₂O₄₀ from water and organic oxygen-containing solvents (AcOH, Me₂CO, MeOH) by carbon mesoporous materials, viz., Sibunit and catalytic filamentous carbons (CFC), was studied. The amount of irreversibly sorbed heteropolyacid is 50—100 mg g^–1 of support and decreases in the series of solvents: H₂O > Me₂CO > AcOH > MeOH. The adsorption capacity of CFC depends on the specific surface, total pore volume, and microstructure of the CFC fiber.     

Keggin结构杂多酸盐[(C2H5)4N]3[PMo12O40]单晶的水热合成及其结构表征

将苯基磷酸和CoCl2.6H2O,Na2MoO4.2H2O,MoO3混合,采用水热合成的方法制备出了标题化合物[(C2H5)4N]3[PMo12O40],并对其结构进行了X射线单晶衍射的测定.此晶体属于立方晶系,空间群为Cmca,晶体数据为a=1.9777(2)nm,b=1.6882(2)nm,c=1.7161(3)nm,α=90.00°,β=90.00°,γ=90.00°,V=5.7299(13)nm3,Z=4,R1=0.0533,wR2=0.1219.标题化合物含有四乙基胺阳离子和十二钼磷酸的阴离子,其中十二钼磷酸的阴离子具有典型的Keggin结构.     

水分子在均三嗪基g-C3N4上的吸附

气体分子与光催化剂之间的相互作用对于光催化反应的触发非常重要.对于TiO2,ZnO和WO3等传统金属氧化物光催化剂上的水分解反应而言,已有许多报道研究了水分子在它们表面的吸附行为.结果表明,水分子与催化剂表面的原子形成了O-H…O氢键.石墨相氮化碳(g-C3N4)是一种具有可见光响应且化学性质稳定的光催化剂,对其进行修饰以增强其分解水产氢性能的研究非常多.本文通过密度泛函理论计算,全面研究了水分子在均三嗪(s-triazine)基g-C3N4上的吸附情况.首先构建了一系列初始吸附模型,考察了各种吸附位和水分子的朝向.通过比较分析计算得到的吸附能,确定了一种最优的吸附构型,即水分子以竖直的朝向吸附于褶皱的单层g-C3N4表面.水分子中的一个极性O-H键与g-C3N4中一个二配位富电子的氮原子结合形成了分子间的O-H…N氢键.其中,H原子与N原子的间距为1.92?,O-H键的键长由0.976?增至0.994?.进一步通过计算Mulliken电荷,态密度和静电势曲线分析了该吸附体系的电子性质.结果发现在分子间氢键的桥接作用下,g-C3N4上的电子转移至水分子,由此导致g-C3N4的费米能级降低,功函数由4.21 eV增至5.30 eV.在该吸附模型的基础上,考查了不同的吸附距离.当水分子与g-C3N4的间距设为1至4?时,几何优化后总是能得到相同的吸附构型,吸附能和氢键长度也十分相近.随后,通过改变吸附基底g-C3N4的大小和形状,验证了这种吸附构型具有很强的重复性.将2′2单层g-C3N4吸附基底替换为2′2多层g-C3N4(2至5层),3′3和4′4单层g-C3N4,以及具有不同管径的单壁g-C3N4纳米管后,水分子的吸附能随着体系原子数的增多而增大,但吸附模型的几何结构和电子性质基本不变,包括O-H…N氢键的形成和键长,以及电子转移和增大的功函数.另外还研究了非金属元素(P,O,S,Se,F,Cl和Br)掺杂对吸附能的影响.构建模型时,杂质原子以取代二配位氮原子的方式进行掺杂,水分子放置于杂质原子上方.结果显示,引入杂质原子后水分子的吸附能增大,在理论上从吸附的角度解释了元素掺杂增强g-C3N4分解水活性.总之,本文揭示了一种在分子间氢键的作用下,具有高取向性的水分子吸附的g-C3N4构型,这有助于g-C3N4基光催化剂上水分解过程的理解和优化设计.     

Microcalorimetric study of ammonia chemisorption on H3PW12O40 supported onto mesoporous synthetic carbons and SBA-15

Keggin tungstophosphoric acid supported onto mesoporous and meso-microporous materials was studied by ammonia microcalorimetry. Experiments were performed at high and low temperatures to separate the contributions of chemisorption and physisorption, low-temperature data being potentially important for the ambient temperature purification processes. Analysis of thermokinetic data obtained from heat output curves at an elevated temperature allows one to distinguish the transition between reaction of ammonia with the acid sites and the onset of physical sorption. Thermokinetic data are also sensitive to the pore structure of the support materials, with faster sorption registered in the case of materials with the open mesoporous structure. The SBA-15 supported acid shows the maximum ammonia uptake and the strongest acid sites among the three materials studied. The dynamics of sorption, characterized by the thermokinetic parameter, appears to be better in the two materials possessing open pore structure, mesoporous carbon Novacarb and especially the mesoporous silica SBA-15.