ISOLATION AND PROPERTIES OF MOLYBDENUM SERIES OF HETEROPOLY BLUE WITH KEGGIN STRUCTURE

The present paper reports the methods for preparing and isolating 8 kinds of 1:12 molybdenum series of heteropoly blue complexes KyHzXMo12O40 . nH2O (X=Si, P, As, Ge). The products were characterized by elemental analyses, potential titration, polarograms, cyclic voltammetry, IR spectra, visible-UV spectra, X-ray powder diffraction, XPS and P-31 NMR. The single crystal structure of 4-electron molybdenum-silicon heteropoly blue was measured and the positions of reduced molybdenum atoms were determined, i.e. they were located at Mo(3), Mo(7), Mo(8) and Mo(10). The experimental results show that the heteropoly blue remains Keggin structure. ESR spectra of heteropoly blue solids were first studied, from which it was found that the delocalization extent of 2-electron heteropoly blue and 4-electron heteropoly blue is smaller than that of 1-electron heteropoly blue. The study of thermal properties shows that the thermal stability increases with the increase of the reduction extent of heteropoly blue. The study of redox properties shows that the oxidizing power order of heteropoly blue changes in different mediums, and the polarographic half-wave voltage is found to be dependent on the electronegativity of the hetero atom linearly. It is found that the phosphorus heteropoly blue and arsenic heteropoly blue show a strong anti-acid property.

Synthesis and structure of alpha-B-Keggin type heteropoly complex K5H[Co-4(VW9O33)(2)]center dot 5H(2)O

A new complex K5H[Co-4(VW9O33)(2)]. 5H(2)O was prepared and its structure was determined by X - ray diffraction analysis. The anion has alpha - beta - Keggin structure. Two (VW9O33)(7-) moieties (alpha - B isomers) are linked via four Co(11)O-6 groups. The single crystal of the title complex is monoclinic P2(1/n) with a = 1.2307(3) nm, b = 2.1250(4) nm, c = 1.5817(3) nm, beta = 91.86(3)degrees, V = 4.1343 (14) nm(3), R = 0.0895, R-w = 0.2180.

Synthesis, structure and properties of alpha-Keggin-type of K6H3[ZnW11O40Al]center dot 9.5H(2)O

A new heteropolycomplex, K6H3[ZnW11O40Al] . 9.5H(2)O was prepared and characterized by means of elemental analysis, IR, UV spectroscopy, Al-27 NMR, electrochemistry and X-ray crystallography. The crystal of K6H3[ZnW11O40Al] . 9.5H(2)O is cubic, space group Fm-3m, with lattice constants a=b=c=2. 144 8(2) nm, V = 9.866(2) nm(3), Mo radiation, R = 0.057 8 for 497 independent data with [I>2 delta(I)]. The anion is of alpha-type Keggin structure with C-s symmetry.

Hydrothermal synthesis, crystal structure and electrochemical properties of a novel 3D Dawson-type polyoxometalate supramolecular network

A novel Dawson-type polyoxometalate supramolecular architecture of the formula [4,4'-H(2)bipy](2.5)center dot[4,4'-Hbipy]center dot[P2W18O62]center dot 6.25H(2)O (4,4'-bipy = 4,4'-bipyridine) has been hydrothermally synthesised and characterised by means of elemental analysis, IR, CV and X-ray single-crystal diffraction. X-ray crystallography indicates that the title compound consists of Dawson-type polyoxoaions [P2W18O62](6-), water molecules and 4,4'-bipy units. The polyoxoanion clusters together with 4,4'-bipy units and water molecules to construct the three-dimensional supramolecular network through hydrogen bonds. The crystal structure analyses reveal that water molecules and 4,4'-bipy units play the important role on the packing arrangements of crystals. Cyclic voltammetry shows that the title compound exhibits three chemically reversible steps

Structure and catalytic properties of magnesia-supported copper salts of molybdovanadophosphoric acid

The structure and stability of magnesia-supported copper salts of molybdovanadophosphoric acid (Cu2PMo11VO40) were characterized by different techniques. The catalyst was prepared in ethanol by impregnation because this solvent does not hurt texture of the water-sensitive MgO and Cu2PMo11VO40. The Keggin-type structure compound may be degraded partially to form oligomerized polyoxometalate when supported on MgO. However, the oligomers can rebuild as the Keggin structure again after thermal treatment in air or during the reaction. Meanwhile, the V atoms migrate out of the Keggin structure to form a lacunary structure, as observed by Fourier transform IR spectroscopy. Moreover, the presence of Cu2+ as a countercation showed an affirmative influence on the migration of V atoms, and the active sites derived from the lacunary species generated after release of V from the Keggin anion. The electron paramagnetic resonance data imply that V5+ autoreduces to V4+ in the fresh catalyst, and during the catalytic reaction a large number of V4+ ions are produced, which enhance the formation of O2- vacancies around the metal atoms. These oxygen vacancies may also improve the reoxidation function of the catalyst. This behavior is correlated to higher catalytic properties of this catalyst. The oxidative dehydrogenation of hexanol to hexanal was studied over this catalyst.

Synthesis, structure and properties of undecatungstozincate containing 3A elements

New compounds KaHb[ZnW11O39M(H2O)]. xH(2)O (M = Al, Ga or In) were prepared and characterized by elemental analysis, IR and UV and Al-27 NMR spectroscopy, electrochemistry and X-ray crystallography. In the crystals of K6H3[ZnW11AlO40]. 9.5H(2)O, the anion is of the alpha-type Keggin structure with C-s symmetry. The Al and W atoms are statistically distributed in the crystal. (C) 1997 Elsevier Science Ltd.

PHASE-TRANSFER CHEMISTRY OF HETEROPOLYANIONS .1. RESEARCH ON SOLVATION BEHAVIOR OF SUBSTITUTED KEGGIN AND DAWSON ANIONS IN THE NONPOLAR-SOLVENTS

The heteropolyanions of the Keggin structure ZW(11)O(39)M(H2O)(n-)(Z = Si, Ge, P; M = Ni2+, Cu2+, Cr3+, Co2+, n = 4 similar to 6) and Dawson structure P(2)W(17)O(61)M(H2O)(n-)(M = Ni2+, Cu2+, Cr3+, Co2+, n = 7, 8) have been transferred into the non-polar

THE SYNTHESIS AND CRYSTAL-STRUCTURE OF MOLYBDENUM-SILICON BLUE

The single crystal of heteropoly blue, HsSiMo12O40.12H2O, the reduced product of molybdenum-silicon heteropoly acid, was prepared by electrochemical reduction and evaporation in nitrogen atmosphere. The Crystal structure of the product was determined. The heteropoly blue H8SiMo12O40.12H2O, Crystallizes space group P1BAR a = 1.3769 (3) nm, b = 1.4346 (4) nm, c = 1.4134 (4) nm, alpha = 120.47 (2)-degrees, beta = 110.70 (2)-degrees, gamma = 66.11 (2)-degrees, Z = 2, R = 0.0608. The heteropoly blue anion was determined to have Keggin Structure and alpha-isomer and it remained the structure of the unreduced heteropoly acid anion. But the distortion of the structure and the changes of bond length and bond angle take place obviously. The four Mo5+ Positions were determined in the structure.

SYNTHESIS AND CRYSTAL-STRUCTURE OF HETEROPOLY MOLYBDOSILICIC LANTHANIDE K10H3[PR(SIMO11O39)2].18H2O

The intensity data of the title complex were collected at a low temperature of -90-degrees-C. The compound crystallizes in the monoclinic space group P2(1)/n, a = 17.504(2), b = 27.323 (5), c = 21.616(4) angstrom, beta = 104.49 (2)degrees, Z = 4. The structure was solved by Patterson and Fourier techniques and refined by least-squares to an R = 0.088 for 8320 independent reflections. The central Pr ion is bonded to eight oxygen atoms from two molybdosilicic heteropoly ligands to form a square antiprism. The Pr-O average distance is 2.44 (2) angstrom. Both molybdosilicic heteropoly ligands are of a defective alpha-Keggin structure.

Hydrothermal synthesis and crystal structure of cluster compound {[Ni(enMe)(2)][SiW12O40]}[Ni(enMe)(2)(H2O)(2)](2) center dot 3H(2)O

the novel One-dimensional chain structure of the title cluster compound was synthesized and characterized by elemental analysis, IR spectra, TGA and X-ray single-crystal diffraction. The title cluster compound crystallized in a monochnic system with space group C2/c, a = 1.2656 nm, b = 2.20656 (4) nm, c =2.26763 (4) nm, beta = 92.078 degrees, V = 6.32852 (16) nm(3), Z = 4, D-c = 3.801 g/cm(3), A = 2.271 mm(-1), F(000) = 6512, R-1= 0.0549, wR(2) = 0.1087. The structure building block of the structure is the polyanion [SiW12O40](6-) with alpha-Keggin structure. The clusters were linked together with one-dimensional infinite chain through [ Ni ( enMe) (2)] (2+) cations. The [ Ni ( enMe) (2) ( H2O) (2)] (2+) cations and water molecules were filled in the structure. The cluster compound was expanded to three-dimensional framework by hydrogen bond interactions among molecules.

Carbon deposition behavior over copper salts of molybdovanadophosphoric acid catalyst supported by magnesia

MgO supported copper salt of molybdovanadophosphoric acid H4PMo11VO40 catalysts were prepared in alcohol by impregnation and the carbon deposition over these catalysts during the n-hexanol oxidation reaction was studied. The coke predominantly deposited on the catalyst surface in the form of CH., and it was not found that it caused the deactivation of the catalyst. The XRD, IR, XPS characterizations reveal that the Keggin structure of the CPMV was unaffected by carbon deposition. Moreover, it was shown that the supported CPMVs over the MgO surface can be beneficial to eliminate the coke. The temperature programmed oxidation (TPO) study showed that coke was formed over the catalyst on two different sites: (1) deposited on the CPMVs which can be burn off at a low temperature; (2) deposited on the MgO which could only be removed at higher temperature. The coke content reached constant with the reaction time increasing.

New proton exchange membranes based on poly (vinyl alcohol) for DMFCs

A series of new composite proton exchange membranes for direct methanol fuel cells (DMFCs) based on poly (vinyl alcohol) (PVA), phosphotungstic acid (PWA) and silica were prepared. The highest proton conductivity (a) of these membranes is 0.017 S/cm at ambient temperature. The methanol permeability (D) of these composite membranes ranges from 10(-7) to 10(-8) cm(2)/S. From the ratios of sigma/D, it was found that the optimal weight composition of the PVA/PWA/SiO2 membrane is PVA/PWA/SiO2=0.40:0.40:0.20 wt. Infrared (IR) spectrographic measurements indicate that the Keggin structure characteristics of the PW12O403- anion is present in the composite membranes. Cyclic voltammetry shows that the electrochemical stability window of the complex membrane is from -0.5 to 1.5 V vs. Ag/AgCl electrode. The results of differential scanning calorimetry (DSC) show that silica can improve the thermal stability of the complexes and the single Tg of the membrane indicates that the membrane is homogeneous. The complexes behave as X-ray amorphous.

A novel dimer - Heteropolytungstate with a vanadium atom as the centre - Synthesis and structural characterization of (H3O)(4)[VW12O40Na (H2O)(4)](2)

A novel dimer-tungstovanadate, (H3O)(4)[VW12O40Na (H2O)(4)](2), was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectra, TGA-DSC thermal analysis and polarograpy. The yellowish crystal crystallized in the triclinic system, space group P1, a = 1.464 5(3) nm, b = 1.468 6(3) nm, c = 1.411 1(3) nm, alpha = 111.82(2)degrees, beta = 93.17(3)degrees, gamma = 117.47(3)degrees, V = 2.210 6(8) nm(3), Z = 1, D-c = 4.552 g . cm(-3), lambda (Mo K alpha) = 0.071 073 nm, mu = 31.402 mm(-1) F(000) = 2 6481 R = 0.078 0. The title compound consists of two Keggin structure units linked together with two hydrated sodium cations to form a dimer with a porous structure with the pore dimension of 0.766 nm X 0.778 5 nm.

Synthesis and characterization of sandwiched heteropolycompound

New complex K5O4Na4H5 [Sn-3(PW9O34)(2)]. 16N(2)O was prepared and its structure was determined by elemental analysis, IR, P-31, W-183 NMR, polarography, XPS and X-ray crystallography. The anion has A-alpha-Keggin structure. The new complex crystallize is the monoclinic, P2(1)/n with a = 1.3625 (3) nm, b = 2.3625 (5) nm, c = 2.9306 (6) nm, alpha = 90 degrees, beta = 99.67 (3)degrees, gamma = 90 degrees, V = 9.299 nm(3), Z = 4.

(NH4)(3)[PMo12O40]center dot 21H(2)O

The determination of the crystal structure of the title compound, triammonium hexatriacontaoxo(tetraoxophosphato)dodecamolybdate(3-) henicosahydrate, shows that the polyanion has a pseudo-Keggin structure with m (3) over bar m symmetry. The central PO4 group is disordered with P-O distances of 1.55 (3) Angstrom. The Mo-O distances range from 1.617 (14) to 2.414 (14) Angstrom.