Synthesis, structure and magnetic properties of new vanadate PbCo2V2O8

A new vanadate PbCo₂V₂O₈ was obtained through the study of PbO-CoO-V₂O₅ ternary system. The crystal structure was determined by Rietveld method, indicating that PbCo₂V₂O₈ has a tetragonal structure of space group I41cd with a spiral chain along the c-axis. Magnetic properties of the titled compound were investigated by means of susceptibility, magnetization, and heat capacity measurements. The results show that PbCo₂V₂O₈ is a quasi-one-dimensional canted antiferromagnet with Neel temperature of ∼4 K, being consistent with its crystal structure.     

Thin Film Counterelectrodes with High Li Charge Capacity for Electrochromic Windows

Summary.  Ce-V mixed oxide films have been deposited by RF sputtering with the aim of increasing the Li charge capacity of counter electrodes in smart windows. Such mixed oxides have shown high transmittance and optical passivity in the visible region. After electrode pre-conditioning by cyclic voltammetry, a good electrochemical reversibility in LiClO₄– propylene carbonate electrolyte was observed, and large Li-charge capacity under galvanostatic charging (up to 50 mCċcm⁻²) has been measured. The electrode charge capacity decreased after prolonged insertion-deinsertion cycles, whereas the photoptic transmittance remained about constant. After 800 cycles the Li-charge capacity decreased to 40 mCċcm⁻². The Li diffusion coefficient inside the films measured by electrochemical impedance and by galvanostatic titration ranged from 10⁻¹¹ cm²ċs⁻¹ to 10⁻¹³cm²ċs⁻¹. We observed that the Li charge capacity of the film electrodes is a function of the film deposition conditions, because it increased with the vanadium oxide concentration in the target and with the oxygen content in the sputtering atmosphere. Received June 23, 2000. Accepted (revised) August 7, 2000     

Vibrational spectrum of RbVOPO4

The infrared and Raman laser spectra of RbVOPO₄ were recorded and briefly discussed with the aid of factor group analysis. Some comparisons with the spectra of related materials were also made.     

Mechanochemical metathesis synthesis and characterization of nano-structured MnV2O6·xH2O (x=2, 4)

A solid-state metathesis approach for the synthesis of hydrated MnV₂O₆·xH₂O (x=2, 4) materials driven by mechanochemical activation energy has been demonstrated. The metathesis pathway of forming the desired product is confirmed by the presence of high lattice energy by-product such as NaCl. The structural, optical, and chemical properties of the synthesized materials are examined by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis, scanning electron microscopy, transmission electron microscopy, and diffused reflectance measurements in the UV–vis range. The valence state of Mn and V was determined to be +2 and +5, respectively, for the title compounds and the bandgap values determined showed these materials are likely to be semiconductors.     

Edge-defined film-fed growth of Yb:YVO4 single crystal plates

The applicability of the edge-defined film-fed growth (EFG) technique for Yb_xY_(1−x)VO₄ (x=0.05, 0.1 and 1) was approved by successful growth of crystals up to 80 mm in length as the thin plates. Low-angle grain boundaries and the crystal coloration as main defects were found. Optimal seed orientation was suggested on the strength of vanadate crystal plate morphology. Optical properties, chemical composition and the crystalline quality were investigated.     

Hydrothermal syntheses and crystal structures of two transition metal complexes supported by vanadate {V4O12}: {[ M (dpa)2]2V4O12} ( M = Co,Ni. dpa = 2,2′-dipyridylamine)

Hydrothermal reactions have been exploited in the syntheses of two new metavanadates, {[Co(dpa)₂]₂V₄O₁₂}?·?H₂O (1) and {[Ni(dpa)₂]₂V₄O₁₂}?·?H₂O (2), which were characterized by X-ray diffraction, IR and thermogravimetric analysis. Crystal data: C₄₀H₃₈N₁₂O₁₃Co₂V₄ (1) monoclinic. P2(1), a?=?10.126(2), b?=?17.639(4), c?=?12.930(3) Å,?α?= 90°,?β?= 98.356(4)°,?γ?= 90°, Z?=?2; C₄₀H₃₈N₁₂O₁₃Ni₂V₄ (2) monoclinic. P2(1), a?=?10.1037(9), b?=?17.6680(14), c?=?12.8832(10) Å,?α?= 90°,?β?= 98.423(2)°,?γ?= 90°, Z?=?2. The two complexes are isomorphic and their structures consist of a [V₄O₁₂]^4? cluster bound to two [M(dpa)₂]²⁺ moieties through the terminal oxygen atoms in a trans-conformation; the [V₄O₁₂]^4? cluster adopts a chair-like configuration.     

IR spectroelectrochemical studies of Fe2V4O13, FeVO4 and InVO4 thin films obtained via sol-gel synthesis

In this paper we generalize the IR spectroscopic properties of M³⁺VO₄ (M=Fe, In) orthovanadate and Fe₂V₄O₁₃ films. The films were prepared using the sol-gel synthesis route from M³⁺ nitrates and vanadium oxoisopropoxide. The vibrational bands in the IR absorbance spectra of the films are classified in terms of terminal V-O stretching (1050–880 cm^–1), bridging V-O^...Fe and V^...O^...Fe stretching (880–550 cm^–1), mixed V-O-V deformations and Fe-O stretching (<550 cm^–1) modes. Ex situ IR spectra of films were measured after consecutive charging/discharging to various intercalation coefficients x and correlated to the current peaks in the cyclic voltammetry curves measured in 1 M LiClO₄/propylene carbonate electrolyte. We classified the ex situ IR spectra of charged/discharged films according to their vibrational band changes. The results reveal that, for small values of the intercalation coefficient, crystalline FeVO₄, InVO₄ and Fe₂V₄O₁₃ films exhibit a simultaneous decrease in the intensity of all IR bands while the band frequencies remain unaffected. For the higher intercalation levels, IR mode frequencies are shifted, signaling the presence of reduced vanadium. Further charging leads to an amorphization of the film structure, which was established from the similarity of the IR spectra of charged films with those of amorphous films prepared at lower annealing temperatures. The results confirm that ex situ IR spectroelectrochemical measurement is an effective way to assess the structural changes in films with different levels of intercalation. Electronic Publication     

Neutron Diffraction Study of Mg2FeV3O11-δ

The neutron diffraction patterns of Mg₂FeV₃O_11-δ compound at various low temperatures have been investigated. No magnetic ordering was observed in the investigated temperature range down to 10K. These materials have been formed in the triclinic space group but there are specific differences in the positions of atoms as compared to previously determined from XRD method. The iron(III) ions are distributed non-statistically with magnesium(II) ions and this could be responsible for some differences in the structure of the above sample. The method of sample preparation, in particularly thermal annealing processes could be responsible for the differences.