Exafs and electron-microscopy studies on V/SiO2 catalysts

Extended x-ray-absorption fine structure and scanning electron microscopy have been applied to the structure of the vanadium oxide layers on impregnated and grafted vanadium aerosils. When aerosil is impregnated with NH₄VO₃ solution, V₂O₅ crystals are formed; when vanadium is grafted by reacting the oxychloride with carrier OH groups, there are no visible crystals. On the other hand, the EXAFS spectra for the grafted specimens show all the oscillations found for crystalline V₂O₅. It is concluded that the vanadium oxide layers in these grafted materials have a long-range order similar to that in V₂O₅ and contain microcrystals having sizes up to 5 nm.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 5, pp. 652–655, September–October, 1987.     

Temperature-programmed reduction of V2O5 and coprecipitated V2O5−TiO2 by hydrogen

Temperature-programmed reductions (TPR) with H₂ of both pure V₂O₅ and coprecipitated V₂O₅?TiO₂ systems with different titanium concentrations was performed. The original and the reduced samples following each TPR step were characterized by X-ray diffraction, Fourier transform infrared analysis and scanning electron microscopy. Within the temperature range in which TPR analysis was carried out (100–600°C) the V₂O₅ phase was reduced in two or three steps, while no variation in the TiO₂ phase (anatase or rutile) was observed. In the first reduction step only superficial reduction of the oxides was detected. In the following steps, the H₂ reacted with oxygen atoms of the V=O and V?O?V bonds. This led to important changes in the structure and morphology of the system. The experimental evidence allowed the conclusion that titanium stabilizes certain phases of vanadium oxides in which vanadium appears as V(+4) or as a mixture of V(+4) and V(+5). Moreover, when moderate and high titanium concentrations were used, the reduction temperature of the bulk V₂O₅ decreased markedly.     

Phase diagram of V2O5-MoO3-Ag2O

Phase equilibria in the V₂O₅-Ag₂O system were investigated at a constant pressure of oxygen (0.2 atm) and the phase diagram found under these conditions was compared with the results of the authors who investigated the same system in vacuum and at an oxygen pressure of 1 atm. On the basis of all these results, an attempt was made to construct the hypothetical diagram of V₂O₅-Ag₂O-O₂.     

Untersuchungen zum chemischen Transport der Vanadiumoxide V2O5, V3O7 und V6O13

Chemical transport of the vanadium oxides V₂O₅, V₃O₇, and V₆O₁₃ The suitability of water and some halogenating transport agents (NH₄Cl, NH₄Br, I₂) for the chemical transport (temperature gradient 850/750 K) of V₂O₅, V₃O₇, and V₆O₁₃ has been investigated. Transport rates for V₂O₅ and V₆O₁₃ could be measured and reproduced. The best transport agent for V₂O₅ is NH₄Cl or H₂O. For V₃O₇ a combination of the transport agents I₂/H₂O give the best results and for V₆O₁₃ the combination of NH₄Br/H₂O was most appropriate.     

Subsolidus area of the system CdO - V2O5 - Fe2O3

Phase diagrams in the subsolidus area of the systems FeVO₄ - CdO and FeVO₄ - Cd₂V₂O₇ have been deduced using the results of XRD and DTA analyses. On the basis of these diagrams and some additional verifying research, a projection of the subsolidus area of the CdO - V₂O₅ - Fe₂O₃ system onto the plane that comprises the components’ concentration triangle has been presented. The H-type phase is the only phase formed in this system. It co-exists at equilibrium with other phases in six subsidiary subsystems.      

Thermochemische Untersuchungen im System V/Nb/O. II Zum chemischen Transportverhalten im Bereich V2O5/Nb2O5/VO2/NbO2

Thermochemical Investigations in the System V/Nb/O. II. Chemical Transport in the Region V₂O₅/Nb₂O₅/VO₂/NbO₂ Transport experiments were used to support the phase relationships of the V₂O₅/Nb₂O₅/VO₂/NbO₂ system, which were established by annealing experiments of powder mixtures. The phase relations were studied in the NbO₂-rich region of the system by means of X-ray and ESMA methods. The NbO₂-rich section is characterized by the following two phase and three phase regions: Two phase region: V₃Nb₉O₂₉/rutile mixed crystal V_1?xNb_xO₂ Two phase region: BI-mixed crystal/V_xNb_1?xO₂ Three phase region: V₃Nb₉O₂₉/solubility limit LG1 (V_1?xNb_xO₂)/BI-mixed crystal Three phase region: solubility limit LG1 (V_1?xNb_xO₂)/BI-mixed crystal/solubility limit LG2 (V_xNb_1?xO₂). The composition of the solubility limits LG1 and LG2 was ascertained by means of ESMA-investigation: LG1: 57.5 ± 5 mol% NbO₂/43.5 ± 5 mol% VO₂ LG2: 22.5 ± 5 mol% NbO₂/78.5 ± 5 mol% VO_2?     

Determination of heats of aluminothermic redox reaction of V2O5 and MnO2

Differential thermal analysis has been used for quantitative determination of heats of aluminothermic redox reaction of MnO₂ and V₂O₅ over a wide range of temperatures. Heat of reaction V₂O₅?Al and MnO₂?Al systems have been determined using the calibration plot established. The experimentally determined values compare well with those predicted from thermodynamic data available in the literature. It has been found that V₂O₅?Al system involves a higher heat of reaction in comparison to the MnO₂?Al system.     

Crystal growth of SnO2 and other MO2 (M = Ti,Zr, Hf) oxides by flux of B2O3?V2O5 system

Single crystals of SnO₂ and MO₂ (M = Ti, Zr, Hf) oxide were grown from flux of B₂O₃? V₂O₅ system. Mixtures of the flux and the starting powder of Zn₂SnO₄, TiO₂, ZrO₂, or HfO₂ were soaked at a temperature of 1030–1340°C for 10–72 hr and then were cooled down to 900°C at a rate of 5°C/hr. Grown crystals of SnO₂ were pale brown needles. An increase in V₂O₅ content of the flux (up to V₂O₅/B₂O₃ ratio equal to 2) or in the soaking temperature increases the crystal size. A largest crystal with the size of 15.0 × 0.4 × 0.4 mm was obtained in the case of V₂O₅/B₂O₃ = 2. Crystals of TiO₂ were black needles or platelets, and those of ZrO₂ and HfO₂ were yellowish, transparent needles or blocks. The maximum size of TiO₂, ZrO₂ or HfO₂ crystal was 12.0 × 0.1 × 0.1 mm, 4.0 × 0.3 × 0.3 mm or 11.0 × 0.6 × 0.6 mm, respectively. The long axis of the crystals was all C-axis and main faces on the crystals were of {100} and/or {110} families. All these crystals were found to include the impurities of boron and vanadium. The electrical resistivities of SnO₂ and TiO₂ crystals were measured to be 1.4 × 10⁶ and 5.6 × 10⁴ Ω · cm at 25°C, respectively.     

Reactivity of T-Nb2O5 or H-Nb2O5 towards V2O5. Synthesis in the solid state and properties of V4Nb18O55

The IR spectrum of V₄Nb₁₈O₅₅ has been compared with the IR spectra of selected niobates of known structures to show structural relations between these compounds. This comparison shows that V₄Nb₁₈O₅₅ has crystal structure related to T-Nb₂O₅, W16Nb18O94 and Ba₂NaNb₅O₁₅. On the other hand, reaction between V₂O₅ and H-Nb₂O₅ yields a solid solution of V₂O₅ in VNb₉O₂₅. It has been proposed two models of synthesized solid solution with formulas V_1+xNb_9-xO₂₅ or V_1+xNb₉O_25+5x/2.Independently of Nb₂O₅ polymorph, used for synthesis, the metastable compound VNbO5 cannot be synthesized in the solid state below 650°C      

Vapour phase oxidation of 4-methylanisole to anisaldehyde over V2O5 /MgO-Al2O3 catalysts

The vapour phase selective oxidation of 4-methylanisole to anisaldehyde was investigated over different V₂O₅ /MgO-Al₂O₃ catalysts at 673 K and normal atmospheric pressure. Among various catalysts investigated the 16 wt% V₂O₅ /MgO-Al₂O₃ catalyst provided good conversion and product selectivity. The MgO-Al₂O₃ mixed oxide was obtained by a co-precipitation method and V₂O₅ was impregnated from ammonium metavanadate. The MgO-Al₂O₃ support and various V₂O₅ /MgO-Al₂O₃ catalysts were characterized by means of X-ray diffraction, FT-infrared, electron spin resonance, scanning electron microscopy, ammonia and carbon dioxide chemisorption methods. The characterization results suggest that vanadia does not form layer structures on the support surface, instead interacts very strongly with the support, in particular with MgO, and forms amorphous compounds. The NH₃ and CO₂ uptake results provide an interesting information on the acid-base characteristics of these catalysts and correlate with their catalytic properties.     

Phase relations in the system V/Nb/O. V. Investigation of mixed crystals V1-xNbxO2

Mixed crystals V_1-xNb_xO₂ exist over the whole area of the quasibinary line VO₂-NbO₂. The existence of Nb_{5+ beside V3+ and V4+ on the V-rich side and V3+ beside Nb5+ and Nb4+ on the Nb-rich side of the mixed crystals is demonstrated by XANES-measurements. The compound VNbO}4_(V0.5_Nb0.5_O2_{) is described as a double oxide with vanadium only as V3+ and niobium only as Nb5+. At this point the electric resistivity of the solid solution shows a maximum.}     

Crystal growth and structure of V2VSe2IVO9; comparison with V2Te2O9

High quality single crystals of V₂Se₂O₉ have been obtained as a side compound during a study of the CuCl₂-V₂O₅-SeO₂ system. V₂Se₂O₉ crystallises in the monoclinic system, space group P2₁/n with a = 8.0560(2), b=10.3650(2), c = 8.4500(2) Å, β = 102.893(2) °, Z = 4 and ρ_x =3.90 g/cm³. Full matrix least-squares refinement gave an R = 0.0347 and R_w = 0.0802 using 2232 independent reflections. The structure is built up by very distorted octahedra occupied by V⁵⁺ sharing one edge and one apex to form [V₄O₁₈]¹⁶⁻ entities interconnected by SeO₃E tetrahedra (E designs the 4s² lone pair of the Se (IV) cation). V₂Se₂O₉ is not isostructural with V₂Te₂O₉, in which the V⁵⁺O₆ octahedra share edges to form along [011] infinite chains linked together via Te₂O₅E₂ groups.     

Die Vanadin-Koordination in den Phasen 4 PbO · V2O5 und 8 PbO · V2O5

Coordination of Vanadium in the Phases 4 PbO · V₂O₅ and 8 PbO · V₂O₅ It is demonstrated, using infrared spectroscopy, that the coordination of vanadium in the two binary phases 4 PbO · V₂O₅ and 8 PbO · V₂O₅ is tetrahedral. The spectra in the V? O stretching region closely resembles that of the lead(II) orthovanadate, Pb₃(VO₄)₂.     

Non-isothermal crystallization kinetics of V2O5-MoO3-Bi2O3 glasses

Characteristic temperatures, such as T _g (glass transition), T _x (crystallization temperature) and T _l (liquidus temperature) of glasses from the V₂O₅-MoO₃-Bi₂O₃ system were determined by means of differential thermal analysis (DTA). The higher content of MoO₃ improved the thermal stability of the glasses as well as the glass forming ability. The non-isothermal crystallization was investigated and following energies of the crystal growth were obtained: glass #1 (80V₂O₅·20Bi₂O₃) E _G=280 kJ mol^-1, glass #2 (40V₂O₅·30MoO₃·30Bi₂O₃) E _G=422 kJ mol^-1 and glass #3 (80MoO₃·10V₂O₅·10Bi₂O₃) E _G=305 kJ mol^-1. The crystallization mechanism of glass #1 (n=3) is bulk, of glass #3 (n=1) is surface. Bulk and surface crystallization was supposed in glass #2. The presence of high content of a vanadium oxide acts as a nucleation agent and facilitates bulk crystallization. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase relations in the system V/Nb/O. V. Investigation of mixed crystals V1-xNbxO2

Mixed crystals V_1-xNb_xO₂ exist over the whole area of the quasibinary line VO₂-NbO₂. The existence of Nb_{5+ beside V3+ and V4+ on the V-rich side and V3+ beside Nb5+ and Nb4+ on the Nb-rich side of the mixed crystals is demonstrated by XANES-measurements. The compound VNbO}4_(V0.5_Nb0.5_O2_{) is described as a double oxide with vanadium only as V3+ and niobium only as Nb5+. At this point the electric resistivity of the solid solution shows a maximum.} Received: 11 May 1998 / Revised: 4 August 1998 / Accepted: 10 August 1998     

Phase Equilibria in the V2O5-Sb2O4 System

Differential thermal analysis (DTA) and X-ray powder diffraction (XRD) were used to study phase equilibria, established in air in the V₂O₅-Sb₂O₄ system up to 1000°C. It has been found that there is a new phase =SbVO₅. The =SbVO₅ has been prepared by two methods: by heating equimolar mixtures of V₂O₅ and α-Sb₂O₄ in air and by oxidation of the known phase of rutile type obtained in pure argon at temperatures between 550 and 650°C. Thermal decomposition of =SbVO₅ in the solid state starts at 710°C giving off oxygen. The results provide a basis for constructing only a part of the phase diagram of the investigated system (up to 50.00 mol% Sb₂O₄). This revised version was published online in July 2006 with corrections to the Cover Date.     

Röntgen- und photoelektronenspektroskopische Charakterisierung von Elektrodenmaterialien auf der Basis von V2O5

Characterization of Electrode Materials Based on V₂O₅ by X-Ray and Photoelectron Spectroscopy The investigation of various Li_xV₂O₅ compounds and V₂O₅ itself by X-ray and photoelectron spectroscopy resulted in new knowledge about the change of the structure of V₂O₅ during discharge in positive electrodes of secondary lithium batteries. The structures of the compounds produced by electrochemical reduction of V₂O₅ in aprotic lithium salt solutions are similar to these received on a chemical way. In the case of overdischarging of Li_xV₂O₅ (x > 1) the V2p_3/2 binding energy is decreased, the change of the lattice becomes irreversible, and the material is after that only uncompletely rechargeable.     

Zur Bildung und Umwandlung von Oxidphasen im quasibinären System V2O5?Nb2O5

Formation and Transformation of Oxide Phases in the Quasibinary System V₂O₅? Nb₂O₅ In the quasibinary system V₂O₅? Nb₂O₅ three phases exist in addition to the boundary phases: VNbO₅, V₂Nb₉O_27.5, and VNb₉O₂₅. Only the latter phase is a thermodynamically stable one. The metastable phases VNbO₅ and V₂Nb₉O_27.5 are formed by thermal decomposition of freeze-dryed products of alkoxide hydrolysis. VNb₉O₂₅ can be formed by thermal treatment of a metastable solid solution with TT-Nb₂O₅ structure or, beside V₂O₅, by thermal decomposition of the other metastable phases. A reaction scheme of formation and decomposition of phases in the quasi- binary system is given and discussed.     

Solid-state phase equilibria in the V2O5−Fe8V10W16O85 system

Phase equilibria being established in the solid state in the system V₂O₅?Fe₈V₁₀W₁₆O₈₅ were examined by X-ray phase powder diffraction and DTA. It has been found that the system of interest is a real two-component system with an eutectic temperature 620±5°C.     

Zu den Phasenverhältnissen im System V/Nb/O. I. Koexistenzbeziehungen im Bereich V2O5/Nb2O5/VO2/NbO2

The Phase Relations in the System V/Nb/O. I. Coexistence Relations in the Section V₂O₅/Nb₂O₅/VO₂/NbO₂ . Phase relations in the section Nb₂O₅/V₂O₅/VO₂/NbO₂ of the ternary system V/Nb/O have been studied by X-ray diffraction. The investigated samples were prepared by high temperature synthesis at 900°C–1000°C. The section Nb₂O₅/V₂O₅/VO₂/NbO₂ is charakterized by fife three phase regions: The limits of solubility of the pseudobinary system were ascertained by determination of lattic parameters of powder samples: