Geometries and electronic properties of NbnV(0, ±1) (n = 1−6) clusters studied by density-functional theory

Using density functional theory (DFT) with valence basis set LANL2TZ to study the relative stabilities and electronic properties of the most stable structures of Nb _n V^(0,?±1) (n = 1?6) clusters. The ground state structures of Nb _n V ^(0,?±1) keep the similar geometric structure as the host Nb _n clusters. The doping of vanadium atom enhances the chemical activities of Nb _n clusters. The Nb₃V and Nb₆V are more stable than other clusters. The average binding energy of charged systems (Nb _n V⁺ and Nb _n V^? clusters) are generally larger than neutral Nb _n V clusters natural population analysis shows that there are charge transfers from niobium to vanadium atoms in the small Nb_1?4V, however, for larger clusters (Nb₅V and Nb₆V), the charge transfers are from vanadium to niobium atoms. The vertical and adiabatic ionization potentials (VIP and AIP) are estimated and the vertical one is more close to experimental results.     

Conductivity and spectroscopic studies of Li<Subscript>2</Subscript>O-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

Lithium vanadium-borate glasses with the composition of 0.3Li₂O–(0.7-x)B₂O₃–xV₂O₅ (x?=?0.3, 0.325, 0.35, 0.375, 0.4, 0.425, 0.45, and 0.475) were prepared by melt-quenching method. According to differential scanning calorimetry data, vanadium oxide acts as both glass former and glass modifier, since the thermal stability of glasses decreases with an increase in V₂O₅ concentration. Fourier transform infrared spectroscopy data show that the vibrations of [VO₄] structural units occur at V₂O₅ concentration of 45 mol%. It is established that the concentration of V⁴⁺ ions increases exponentially with the growth of vanadium oxide concentration. Direct and alternative current measurements are carried out to estimate the contribution both electronic and ionic conductivities to the value of total conductivity. It is shown that the electronic conductivity is predominant in the total one. The glass having the composition of 0.3Li₂O-0.275B₂O₃-0.475V₂O₅ shows the highest electrical conductivity that has the value of 7.4?×?10^?5 S cm^?1 at room temperature.     

Decay rate constants of sputtered vanadium oxide clusters

Results from studying the emission and fragmentation of V _n O _m ^± clusters sputtered from a vanadium surface by Xe⁺ ions at O₂ pressures of P = 4–5 × 10^?3 Pa are presented. The average decay rate constants of V _n O _m ^± clusters for major fragmentation channels are determined. It is shown that the decay rate constants for clusters of similar stoichiometry do not depend on their charge states.     

Electronic properties of single-walled V2O5 nanotubes

Atomistic models of quasi-one-dimensional vanadium pentoxide nanostructures—single-walled nanotubes formed by rolling (010) layers of V₂O₅ are constructed and their electronic properties and bond indices are studied using the tight-binding band method. We show that all zigzag (n,0)- and armchair (n,n)-like nanotubes are uniformly semiconducting, and the band gap trends to vanish as the tube diameters decrease. The V-O covalent bonds were found to be the strongest interactions in V₂O₅ tubes, whereas V-V bonds proved to be much weaker.     

Conversion of covalent to ionic character of V2O5–CeO2–PbO–B2O3 glasses for solid state ionic devices

xV₂O₅–xCeO₂–(30−x)PbO–(70−x) B₂O₃ glasses are synthesized by using the melt quench technique. The number of studies such as XRD, density, molar volume, optical band gap, refractive index and FTIR spectroscopy are employed to characterize the glasses. The band gap decreases from 2.20 to 1.78 eV and density increases from 3.49 to 4.25 g/cm³. FTIR spectroscopy reveals that incorporation of V₂O₅ in glass network helps to convert the structural units of [BO₃] into [BO₄]. At higher concentration of vanadium, VO vibration of [VO₅] structural units and V–O–V vibration are present. The bond ionicity of glasses increases with incorporation of V₂O₅ contents.     

Mössbauer and magnetic studies of BaVS3 and V5S8 doped with 57Fe

Iron can be easily introduced in BaVS₃ and V₅S₈. It is located at the vanadium sites and has been used as a probe to analyse by Mössbauer effect the magnetic properties of its surrounding matrix. The electronic state of iron in this matrix has also been studied. It was found that in BaVS₃, the iron is in a low spin Fe³⁺ configuration $\text{(S =}\text{1}\text{2}\text{)}$. In V₅S₈ at 4.2 K, the iron is in low spin Fe²⁺ configuration (S = 0). The rapid decrease of quadrupole splitting observed between 50 and 200 K is attributed to a thermally activated change in electronic structure. The high temperature configuration (above 200 K) seems to be neither pure low spin Fe³⁺ nor high spin Fe²⁺, but a mixture of configurations fluctuating at a rate which is faster than the characteristic time of Mössbauer measurements.     

Magnetic behaviour and site occupation of YFe12-x V x (x=2,3,4)

The effects of vanadium substitution on the iron magnetism in YFe_12-x V _x compounds (x～2–4) have been studied by⁵⁷Fe Mössbauer spectroscopy. The preference of vanadium atoms for the 8i site of these ThMn₁₂-structure type compounds is confirmed. The rapid collapse of the iron sublattice magnetization with increasing vanadium concentration is analysed in terms of the ‘magnetic valence’ model.     

Mössbauer and ESR investigation of the behaviour of iron in vanadium borophosphate glasses

Mössbauer and ESR measurements were performed on vanadium borophosphate glasses containing iron. The glass composition was 78 mole% V₂O₅, 15 mole% P₂O₅, 7 mole% B₂O₃ and different amounts of Fe₂O₃ (0.5–50 mole%) were added. The relative percentage of iron in different states and site positions could be determined for each glass composition. Correlation between the behaviour of iron and its variation in structural units and other physical properties are proposed. A maximum amount of 33 mole% Fe₂O₃ could be incorporated in the glass network, higher concentrations lead to the precipitation of α-Fe₂O₃.     

The influence of PEO on the synthesis and electrochemical properties of VO2 and V3O7·nH2O nanobelts as a cathode for lithium battery

In this paper, we report the hydrothermal synthesis of VO₂, poly(ethylene oxide) (PEO)/VO₂,V₃O₇·nH₂O and PEO/V₃O₇·nH₂O nanobelts by using 1,2-propylene carbonate (1,2-PC (C₄H₆O₃)) and poly(ethylene glycol) (PEG) as templates, respectively. Structure and morphology of the samples were investigated by XRD, FTIR, SEM, and TEM. The vanadium oxide (VO₂) nanobeltcomposite show the initial specific capacity 152?mA?h?g^?1, whereas PEO/VO₂ shows 182?mA?h?g^?1. The pure V₃O₇·nH₂O nanobelts shows the initial specific capacity 192?mA?h?g^?1, while PEO/V₃O₇·nH₂O nanobelts show 297?mA?h?g^?1. It was found that PEO/VO₂ and PEO/V₃O₇·nH₂O nanocomposites show better cyclic performance and high discharge stability compared to pure vanadium oxide nanomaterials. The role of the polymeric PEO component of the hybrid material seems to be the stabilization and improvement of the specific capacity due to probable homogeneous distribution between the nanobelts. The TEM images indicate that PEO works as a surfactant to decrease the dimensions of nanobelts.     

Fragmentation processes of vanadium and niobium oxide clusters sputtered by ion bombardment

The mass distribution of emitted V _n O _m ^? and Nb _n O _m ^? clusters and their unimolecular decay by all stoichiometrically possible fragmentation channels, which takes place under the sputtering of niobium and vanadium surfaces and blowing by oxygen, are studied. It is shown that the formation, excitation, and unimolecular fragmentation of V _n O _m ^? and Nb _n O _m ^? clusters can be described by a statistical recombination mechanism. Clusters are formed over the target surfaces as a result of binary collisions of independently sputtered ions, atoms, and molecules.     

VSe2−xSx materials as battery cathode

The properties of the solid solution VSe_2?xS_x 0 ? x_nom ? 2 have been investigated for secondary battery application. The phase VSe₂ is observed for 0 ? x_nom ? 1.2 and the phase V₅S₈ is found using RX analysis for x_nom >1.2. The amount of lithium chemically incorporated in this structure by reaction with n-butyllithium is 2 Li/vanadium for 0 ? x_nom ? 0.8 and 1.4 Li/vanadium for V₅S₈. An electrochemical technique (galvanostatic) indicates that the amount of lithium incorporated depends on the x_nom values, the grain size and the discharge rate. The best results are obtained for 0.2 ? x_nom ? 0.6 (capacity = 164?172 Ah kg^?1 and energy density = 385?465 Wh kg^?1).     

Structural characterization of the V2O5/TiO2 system obtained by the sol–gel method

The influence of the vanadium load and calcination temperature on the structural characteristics of the V₂O₅/TiO₂ system was studied by X-ray diffraction and X-ray absorption spectroscopy (XAS) techniques. Samples of the V₂O₅/TiO₂ system were prepared by the sol–gel method under acid conditions and calcined at different temperatures. The rutile phase was found to predominate in pure TiO₂ calcined at 450 °C as a result of the reduction of phase transition temperature promoted by the sol–gel method under acid conditions. The anatase phase became predominant at 450 °C as the amount of vanadium increased from 6 to 9 wt%. A structural change in the TiO₂ phase from predominantly anatase to totally rutile with increased calcination temperature was observed in 6 wt% samples. An analysis of the vanadium X-ray Absorption Near Edge Structure (XANES) spectra showed that the oxidation state of vanadium atoms in the samples containing 6 and 9 wt% of vanadium and calcined at 450 °C was predominantly V⁴⁺. However, the presence of V⁵⁺ atoms cannot be ruled out. A qualitative analysis of extended X-ray absorption fine structure (EXAFS) spectra of the samples containing 6 and 9 wt% of vanadium calcined at 450 °C showed that the local structure around vanadium atoms is comparable to that of VO₂ crystalline phase, in which vanadium atoms are fourfold coordinated in a distorted structure. For the sample after calcination at 600 °C, the EXAFS and XANES results showed that a significant portion of vanadium atoms were incorporated in the rutile lattice with a V_xTi_(1−x)O₂ solid solution formation. The conditions of sample preparation used here to prepare V₂O₅/TiO₂ samples associated with different amounts of vanadium and calcination temperatures proved to be useful to modifying the structure of the V₂O₅/TiO₂ system.     

Microstructural, dielectric and spectroscopic properties of Li2O-Nb2O5-ZrO2-SiO2 glass system crystallized with V2O5

Li₂O-Nb₂O₅-ZrO₂-SiO₂ glasses mixed with different concentrations of V₂O₅ were crystallized. The samples were characterized by XRD, SEM and DTA techniques. The SEM pictures indicated that the samples contain well defined and randomly distributed crystal grains. The X-ray diffraction studies have revealed the presence of several crystalline phases in these samples. Optical absorption, ESR and photoluminescence spectral studies on these samples have indicated that a considerable proportion of vanadium ions do exist in V⁴⁺ state in addition to V⁵⁺ state and the redox ratio seems to be increasing with increase in the concentration of crystallizing agent V₂O₅. The infrared spectral studies have pointed out the existence of conventional SiO₄, ZrO₄, NbO₆, VO structural units in the glass ceramic network. The study of dielectric properties suggested a decrease in the insulating character of the glass ceramics with increase in the crystallizing agent. A.C. conductivity in the high temperature region seems to be connected mainly with the polarons involved in the process of transfer from V⁴⁺↔V⁵⁺ ions.     

Microscopic magnetic properties of nonstoichiometric V2O3+x—NMR and inelastic spin-flip neutron scattering measurements

The local magnetic properties of the V sites in the nonstoichiometric V₂O_3+x (0 ? x <0.08) have been examined by nuclear magnetic resonance and inelastic spin-flip neutron scattering techniques. The samples with x = 0.01 and 0.02 show a paramagnetic metal (PM)-antiferromagnetic insulator (AFI) transition. In the AFI phase, two distinct ⁵¹V NMR signals with hyperfine fields H_n = 184.9±0.5 kOe and 71±1 kOe were observed at 1.8 K, which were assigned as due to V³⁺ and V³⁺ sites, respectively. On the other hand, the samples with x = 0.04 and 0.06 were metallic down to 1.4K, and showed a paramagnetic (PM)-antiferromagnetic (AFM) transition at about 10 K. In these samples, a ⁵¹V NMR signal with H_n = 58±2 k0e and one with 〈H_n〉 = 9kOe were observed at 1.8 K, which were assigned as due to V³⁺-like sites and the matrix V sites, respectively. These results are entirely consistent with those obtained from the neutron experiment. We propose that in the metallic phase (0.04 ? x < 0.08) the minority V⁴⁺-like sites are magnetically localized in the delocalized V matrix and may be responsible for the antiferromagnetic long range order below 10 K.     

Local surrounding of vanadium atoms in CuCr1 − x V x S2: X-ray absorption spectroscopy analysis

In the present work local surrounding of vanadium atoms in layered copper-chromium disulfides CuCr_{1 ? x} V _x S₂ is investigated using high-resolution X-ray absorption spectroscopy above vanadium K-edge. Based on experimental and theoretically simulated spectra comparison it is shown that vanadium atoms replace chromium ones even at high concentrations of vanadium and that they are in 3+ oxidation state.     

Nonempirical quantum-chemical calculation of the electric field gradient at the <Superscript>51</Superscript>V nucleus sites in alkali metavanadates

The electric-field gradient tensor at the vanadium nucleus site was calculated ab initio within a cluster model for chained vanadates XVO₃ (X=Li, Na, K). A comparison with experiment showed that it suffices to consider only small (VO₄)^3? and (V₃O₁₀)^5? clusters in crystals of this type. The calculation scheme stability with respect to increasing cluster size was analyzed.     

V4+ brownian motion in splat cooled amorphous V2O5 after water vapor adsorption

Splat cooling of molten V₂O₅ yields an amorphous oxide consisting of strongly entangled polymeric vanadium-oxygen chains. Upon hydration of this powder, a swelling process takes place and a Brownian motion of the fibres occurs. Vanadium pentoxide is usually non-stoichiometric and contains vanadium ions in a reduced oxidation state, namely V₄₊. These paramagnetic ions, which are part of the fibres constituents, can be used as spin probes to study the Brownian motion. X and Q band ESR spectra appear to be drastically modified when water is adsorbed on the powder at a given temperature. They have been analysed according to Kivelson's theory in the fast tumbling region between 293 and 373 K. An apparent activation energy of 3.8 kcal mole^-1 and a correlation time of about 10^?10 sec are observed. These results agree with the polymeric model proposed to explain the solubility of amorphous V₂O₅.     

A simple statistical model for V2O5 catalysis

In this work we propose a model to describe the selective oxidation of hydrocarbons at the surface of the V₂O₅ catalyst. The main ingredients of the model are the concentration of vanadium active sites, the surface and bulk diffusion rates of oxygen vacancies and the probability rate of a hydrocarbon reaction. The reactions take place at the free V₂O₅ (0 1 0) surface, and the diffusion of vacancies occur along the [0 1 0] (bulk) and [0 0 1] (surface) directions. The coupling between V₂O₅ and a given metal oxide support determines the concentration of the active vanadium sites, where the reactions can occur. Only the oxygen atoms, which are coordinated to three vanadium sites, take part of the oxidation process. In our calculations we employed two different approaches, single site and pair approximations, and some Monte Carlo simulations. We have found the dependence of the critical concentration of vacancies on the diffusion rates, probability of reaction, and fraction of active vanadium sites, for the catalyst to operate in an active steady state.     

Characterization and electrical properties of V2O5-CuO-P2O5 glasses

Characterization and electrical properties of vanadium-copper-phosphate glasses of compositions xV₂O₅-(40−x)CuO-60P₂O₅ have been reported. X-ray diffraction (XRD) confirms the amorphous nature of these glasses. It was observed that, the density (d) decreases gradually while the molar volume (V_m) increases with the increase of the vanadium oxide content in such glasses. This may be due to the effect of the polarizing power strength, PPS, which is a measure of ratio of the cation valance to its diameter. The dc conductivity increases while the activation energy decreases with the increase of the V₂O₅ content. The dc conductivity in the present glasses is electronic and depends strongly upon the average distance, R, between the vanadium ions. Analysis of the electrical properties has been made in the light of small polaron hopping model. The parameters obtained from the fits of the experimental data to this model are reasonable and consistent with glass composition. The conduction is attributed to non-adiabatic hopping of small polaron.     

Magnetic susceptibility and nuclear magnetic resonance of vanadium sulfides

Measurements of the magnetic susceptibility in the temperature range 4–1000°K are reported for the vanadium sulfides VS, V₃S₄-V₂S₃ and V₅S₈. At higher temperatures the susceptibility of all compounds approaches a constant, positive value, indicating a Pauli-paramagnetic contribution of itinerant electrons. At lower temperatures an increase of the susceptibility is observed. This effect is particularly pronounced in V₅S₈, and is taken as evidence for the presence of localized magnetic moments.Nuclear magnetic resonance spectra of V₅S₈ show two lines, one with a temperature-independent Knight shift, and one with a positive Knight shift which increases strongly at lower temperatures. The two lines are attributed to vanadium atoms with itinerant d electrons, and to vanadium atoms with localized d electrons, respectively. This interpretation is consistent with the magnetic susceptibility data. The difference in properties between two types of vanadium atoms in V₅S₈ can be understood by considering the crystal structure.