Formation mechanisms and crystallographic characteristics of metastable VO2(A) nanofiber hydrothermally synthesised in V2O5–H2C2O4–H2O system

There are many similarities between VO₂(B) and VO₂(A) from crystallographic view. However, missing of VO₂(A) during the preparation of VO₂ polymorph confused many researchers. Here, the preparation of VO₂(A) was studied systemically via a hydrothermal method in V₂O₅–H₂C₂O₄–H₂O system. As a metastable phase, it can be transferred from VO₂(B) by assembling process. Usually, poly-crystal VO₂(A) nano-fibers are formed by this process. On contrast, owing to the small energy gap between meta-stable VO₂(A) and stable VO₂(R), single crystal VO₂(A) with regular shape can also be obtained by exfoliating some parts of VO₂(R) during non-equilibrium cooling process. VO₂(A) has higher phase transition temperature than stable VO₂(R). The hysteresis in this phase transition can be observed by DSC measurement and the phase transition temperature of VO₂(A) can be tuned down by tungsten doping.     

Luminescence of orthovanadates M 3 + M3+(VO4)2 and M 2 + M4+ (VO4)2

The absorption, excitation, and luminescence spectra of vanadates of type M ₃ ⁺ M³⁺(VO₄)₂ and M ₂ ⁺ M⁴⁺(VO₄)₂ are studied, where M⁺ is Na, K, Rb, Cs; M³⁺ is Al, Sc; M⁴⁺ is Zr, Sn, Ti. The luminescence spectra maxima are located at 490–510 nm, while those of the excitation spectra are at 360–375 nm. Temperature characteristics of luminescence and thermostimulated luminescence are studied. The question of activation of complex vanadates by rare-earth ions is considered.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 24–28, March, 1976.     

Belt-like VO2(M) with a rectangular cross section: A new route to prepare, the phase transition and the optical switching properties

Belt-like VO₂(M) with a rectangular cross section was first synthesized by the irreversible transformation of VO₂(A) at the elevated temperatures under the inert atmosphere to the best of our knowledge. The as-obtained samples were characterized by a combination of techniques including XRD, SEM and TEM. The processes of converting VO₂(A) to VO₂(M) were briefly discussed. The as-obtained VO₂(M) has belt-like morphology with a rectangular cross section with typical lengths up to several tens of micrometers, widths ranging from tens of nanometers to several micrometers, and thicknesses about 60-150 nm. The morphology and size of the VO₂(M) were dependent on that of the precursor VO₂(A). The phase transition properties of VO₂(M) were investigated by DSC, indicating that it exhibited a strong phase transition at 67.9 °C in the heating cycle and 61.1 °C in the cooling cycle. Furthermore, the optical switching property of VO₂(M) was studied by the variable-temperature infrared spectra, and it was found that the as-obtained VO₂(M) could be used as the optical switch.     

磁控溅射法制备二氧化钒薄膜最佳参量的研究

用X射线电子能谱仪(XPS)对不同条件下用磁控溅射法制备的VO₂薄膜进行测试,得到VO₂薄膜内部组成成份的信息.研究了获得高含量VO₂薄膜的最佳制备参量.同时还观察到V₂O₃、VO₂、V₂O₅以接近含量共存的现象,这与以前研究所给出的薄膜几乎只由V₂O₃、VO₂、V₂O₅中的两种组成的结论有所不同.     

IR and Raman spectra of Ca8La2(VO4)6O2

The IR and Raman spectra of the oxyapatite Ca₈La₂(VO₄)₆O₂ has been measured and discussed in comparison with those of related species. Data for Ca₈La₂(PO₄)₆O₂ and for a solid solution of composition Ca₈La₂(PO₄)₆O₂ are also reported.     

Yolk–Shell‐Structured Cu/Fe@γ‐Fe2O3 Nanoparticles Loaded Graphitic Porous Carbon for the Oxygen Reduction Reaction

Core–shell Cu/γ‐Fe₂O₃@C and yolk–shell‐structured Cu/Fe@γ‐Fe₂O₃@C particles are prepared by a facile synthesis method using copper oxide as template particles, resorcinol‐formaldehyde as the carbon precursor, and iron nitrate solution as the iron source via pyrolysis. With increasing carbonization temperature and time, solid γ‐Fe₂O₃ cores are formed and then transformed into Fe@γ‐Fe₂O₃ yolk–shell‐structured particles via Ostwald ripening under nitrogen gas flow. The composition variations are studied, and the formation mechanism is proposed for the generation of the hollow and yolk–shell‐structured metal and metal oxides. Moreover, highly graphitic carbons can be obtained by etching the metal and metal oxide nanoparticles through an acid treatment. The electrocatalytic activity for oxygen reduction reaction is investigated on Cu/γ‐Fe₂O₃@C, Cu/Fe@γ‐Fe₂O₃@C, and graphitic carbons, indicating comparable or even superior performance to other Fe‐based nanocatalysts.     

On the modified inverse spinel-LiCo(PO4) x (VO4)1?x as cathode for rechargeable lithium batteries

The structural and electrochemical behavior of a modified and unmodified inverse spinel phases with general formula, LiCo(PO₄) _x (VO₄)_1???x [with x?=?0.0 and 0.1] for the possible application as cathodes in rechargeable lithium batteries have been investigated. The modified and unmodified phases, represented as LiCoP_0.1V_0.9O₄ and LiCoVO₄ have been synthesized by an aqueous route at 700 °C. Both the phases have been shown to crystallize in a cubic inverse spinel structure with Fd-3m (Oh ⁷ ) space group symmetry as corroborated through XRD studies, with the attendant decrease in the cell parameter ??a?? value in LiCoP_0.1V_0.9O₄. Vibrational spectroscopic studies confirm the introduction of PO₄ group existing together with VO₄ framework. SEM of LiCoP_0.1V_0.9O₄ shows highly porous nature of the materials. Cyclic voltammetric studies with the modified spinel evince high lithium ion reversibility in the voltage range of 3.8?C4.3 V. Subsequent galvanostatic charge?Cdischarge studies conducted on Li//LiCoP_0.1V_0.9O₄ test cells has delivered specific discharge capacity of 118 and 96 mAhg^?1, respectively at 1st and the 15th cycle indicating the advantage of doping with phosphate in the vanadate structure.     

Quadrupole interactions at europium sites in Eu3V2O7 and Eu2VO4

The electric-quadrupole interactions at the Eu sites in Eu₃V₂O₇ and Eu₂VO₄ oxides have been studied at room temperature with¹⁵¹Eu Mössbauer spectroscopy. Both divalent and trivalent Eu ions were found in the oxides. The fraction of Eu²⁺ is 17.1(8)% in Eu₃V₂O₇ and 39.0(1.6) % in Eu₂VO₄. The values of the quadrupole coupling constant, eV_zzQ_g, obtained from the fits using a full Hamiltonian method are ?6.594(50) and ?8.043(65) mm/s for Eu³⁺, and ?13.168(402) and ?18.032(134) mm/s for Eu²⁺, respectively in Eu₃V₂O₇ and Eu₂VO₄. The magnitude of eV_zzQ_g in Eu₂VO₄ is the largest ever reported for Eu²⁺ in any Eu oxide system.     

STM characterization of size-selected V1, V2, VO,and VO2 clusters on a TiO2(110)-(1 × 1) surface at room temperature

We use ultra-high vacuum scanning tunneling microscopy (UHV–STM) to probe, at the atomic level, the structure of mass-selected isolated V₁, V₂, VO and VO₂ clusters deposited on rutile TiO₂(110) by ion soft landing. All four species interact differently with the TiO₂ surface and the ultimate binding site and configuration strikes a balance between the gas-phase structure and the ligation of this cluster by the TiO₂ surface. Our results show that vanadium atoms prefer to bind in the upper threefold hollow sites on the surface and have a slight tendency to pair along the [1–10] direction, while vanadium dimers bind to the surface oriented along the [001] direction exclusively. VO clusters bind with the vanadium atom in the upper threefold hollow site and with the oxygen atom bound to an adjacent fivefold coordinated Ti atom (5c-Ti). The VO₂ cluster also binds with the vanadium atom in the upper threefold hollow site and with both oxygen atoms bound to adjacent 5c-Ti atoms or with only one oxygen bound to the surface and the other directed out of the plane of the surface.     

Hydrothermal synthesis of C-doped Zn3(OH)2V2O7 nanorods and their photocatalytic properties under visible light illumination

A visible light-driven photocatalyst, C-doped Zn₃(OH)₂V₂O₇, prepared by a hydrothermal method was studied. The as-prepared catalyst was characterized by SEM, XRD, DRS, and XPS, and exhibited efficient photocatalytic activity in the degradation of methylene blue (MB) under visible-light irradiation. Besides decoloring, the decomposition of MB was also observed, further demonstrating the performance of the photocatalyst. The carbon existing on the surface of Zn₃(OH)₂V₂O₇ nanorods was free and in carbide form. Dye degradation followed first-order kinetics, and was explained on the basis of the Langmuir-Hinshelwood mechanism.     

Synthesis and characterization of TiO2-coated magnetite clusters (nFe3O4@TiO2) as anode materials for Li-ion batteries

TiO₂-coated magnetite clusters (nFe₃O₄@TiO₂) were facilely prepared through the sol–gel reaction between Ti alkoxides (TEOT) and magnetite clusters (nFe₃O₄) with terminated alkoxy groups. The composite particles represented a core–shell nanostructure (nFe₃O₄@TiO₂) consisting of a Fe₃O₄ cluster core and a TiO₂ capsule layer. The capsule layer of nFe₃O₄@TiO₂ was increased with increasing amounts of TEOT (150, 300, 500 μl) in sol–gel reaction. The Fe₃O₄@TiO₂ (150 μl of TEOT) with a thin TiO₂ layer (ca. 10 nm) exhibited two kinds of cathodic (0.79 V and 1.61 V) and anodic (1.78 and 2.1 V) peaks attributed to the reduction and oxidation process by Fe₃O₄ core and TiO₂ layer, respectively. The thin nFe₃O₄@TiO₂ (150 μl of TEOT) exhibited the enhanced capacity retention by ca. 40% probably due to the buffering effect of TiO₂ capsule layer. However, the thick nFe₃O₄@TiO₂ (300–500 μl of TEOT) exhibited a rapid capacity fading due to the disintegrated core–shell nanostructure, i.e., unfavorable hetero-junction between TiO₂ matrix and magnetite clusters.     

Melt synthesis and structural properties of opal-V2O5 and opal-VO2 nanocomposites

A method has been proposed for filling bulk and film opals with V₂O₅ and V₂O₅: W melts under the action of capillary forces. The VO₂ and VO₂: W (1.8 mol %) compounds have been synthesized from the V₂O₅ and V₂O₅: W precursors in opal pores. The phase composition and morphology of the nanocomposites prepared have been investigated. It has been revealed that, in the opal-V₂O₅ composite, the filler compound has a texture formed by the directional crystallization of the melt in pores of the opal film. The tunable photonic crystal heterostructure opal/opal-VO₂ has been synthesized using liquid chemical etching.     

Synthesis of VO2 (B) nanorods for Li battery application

Vanadium dioxide nanorods were synthesized through a hydrothermal reaction from V₂O₅ xerogel, poly(vinyl pyrrolidone) (PVP) and lithium perchlorate (LiClO₄). The prepared samples were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical discharge–charge cycling in lithium battery. SEM images reveal the nanorods to have dimensions on the order of 1–3 μm in length and 10–50 nm in diameter. The measured initial discharge capacity of the lithium battery with a cathode made of VO₂ (B) nanorods was 152 mA h/g.     

Vanadium oxide thin films deposited on indium tin oxide glass by radio—frequency magnetron sputtering

Highly oriented VO₂(B), VO₂(B) + V₆O₁₃ films were grown on indium tin oxide glass by radio-frequency magnetron sputtering. Single phase V₆O₁₃ films were obtained from VO₂(B) +V₆O₁₃ films by annealing at 480℃ in vacuum. The vanadium oxide films were characterized by x-ray diffraction and x-ray photoelectron spectra (XPS). It was found that the formation of vanadium oxide films was affected by substrate temperature and annealing time, because high substrate temperature and annealing were favourable to further oxidation. Therefore, the formation of high valance vanadium oxide films was realized. The V₆O₁₃ crystalline sizes become smaller with the increase of annealing time. XPS analysis revealed that the energy position for all the samples was almost constant, but the broadening of the V_2p3/2 line of the annealed sample was due to the smaller crystal size of V₆O₁₃.     

Synthesis of V O2(A) nanobelts by the transformation of V O2(B) under the hydrothermal treatment and its optical switching properties

V O₂(A) nanobelts had been successfully synthesized by the transformation of V O₂(B) using H₂O as the solvent under the hydrothermal approach at 280 °C for 48 h. Some parameters, such as the reaction temperature and time, had been briefly discussed to reveal the transition from V O₂(B) to V O₂(A). It was found that H₂O played a crucial role in the transition from V O₂(B) to V O₂(A). The phase transition of V O₂(A) nanobelts was at 162 °C. The optical switching properties of V O₂(A) were studied by the variable-temperature infrared spectra for the first time. In addition, V O₂(A) nanobelts were calcined at 700 °C for 2 h under a high purity Ar (99.999%) atmosphere to obtain V O₂(M) which exhibited a strong crystallographic transition at around 65 °C.     

A Raman spectroscopic study of the different vanadate groups in solid‐state compounds—model case: mineral phases vésigniéite [BaCu3(VO4)2(OH)2] and volborthite [Cu3V2O7(OH)2·2H2O]

Raman spectroscopy has been used to study vanadates in the solid state. The molecular structure of the vanadate minerals vésigniéite [BaCu₃(VO₄)₂(OH)₂] and volborthite [Cu₃V₂O₇(OH)₂·2H₂O] have been studied by Raman spectroscopy and infrared spectroscopy. The spectra are related to the structure of the two minerals. The Raman spectrum of vésigniéite is characterized by two intense bands at 821 and 856 cm⁻¹ assigned to ν₁ (VO₄)³⁻ symmetric stretching modes. A series of infrared bands at 755, 787 and 899 cm⁻¹ are assigned to the ν₃ (VO₄)³⁻ antisymmetric stretching vibrational mode. Raman bands at 307 and 332 cm⁻¹ and at 466 and 511 cm⁻¹ are assigned to the ν₂ and ν₄ (VO₄)³⁻ bending modes. The Raman spectrum of volborthite is characterized by the strong band at 888 cm⁻¹, assigned to the ν₁ (VO₃) symmetric stretching vibrations. Raman bands at 858 and 749 cm⁻¹ are assigned to the ν₃ (VO₃) antisymmetric stretching vibrations; those at 814 cm⁻¹ to the ν₃ (VOV) antisymmetric vibrations; that at 508 cm⁻¹ to the ν₁ (VOV) symmetric stretching vibration and those at 442 and 476 cm⁻¹ and 347 and 308 cm⁻¹ to the ν₄ (VO₃) and ν₂ (VO₃) bending vibrations, respectively. The spectra of vésigniéite and volborthite are similar, especially in the region of skeletal vibrations, even though their crystal structures differ. Copyright © 2011 John Wiley & Sons, Ltd.     

Study of the electrochemical performance of VO2+/VO2 + redox couple in sulfamic acid for vanadium redox flow battery

The present work was performed in order to evaluate sulfamic acid as the supporting electrolyte for VO²⁺/VO₂ ⁺ redox couple in vanadium redox flow battery. The oxidation process of VO²⁺ has similar electrochemical kinetics compared with the reduction process of VO₂ ⁺. The exchange current density and standard rate constant of VO²⁺/VO₂ ⁺ redox reaction on a graphite electrode in sulfamic acid are determined as 7.6?×?10^?4 A cm^?2 and 7.9?×?10^?5 cm s^?1, respectively. The energy efficiency of the cell employing sulfamic acid as supporting electrolyte in the positive side can reach 75.87 %, which is adequate for redox flow battery applied in energy storage. The addition of NH₄ ⁺ to the positive electrolyte can enhance the electrochemical performance of the cell, with larger discharge capacity and energy efficiency. The preliminary exploration shows that the vanadium sulfamate electrolyte is promising for vanadium redox flow battery and is worthy of further study.     

Effects of synthetic route on the structural,physical and electrochemical properties of Li3V2(PO4)3 cathode materials

A series of monoclinic Li₃V₂(PO₄)₃ cathode materials were prepared by H₂ reduction (LVP-H₂) and carbothermal reduction (LVP-CTR) methods. LVP-H₂ showed a primary particle size of about 1 μm, which was much larger than the LVP-CTR samples. A uniform surface carbon layer was observed for the LVP-CTR samples by transmission electron microscope. This carbon layer not only limited the particle growth of the materials but also enhanced the material's electronic conductivity by five orders of magnitude. The LVP-CTR samples exhibited much better electrochemical performance than LVP-H₂. The good electrochemical performance of LVP-CTR was attributed to its nano particle size, high electronic conductivity, as well as the surface carbon layer which limited the vanadium dissolution in electrolyte.     

Electrical properties and conductivity mechanism of LiCuFe2(VO4)3

This paper reports conduction mechanism in LiCuFe₂(VO₄)₃ over a wide range of temperatures (300 to 712 K) and frequencies (209 Hz to 5 MHz). The DC conductivity of the material is thermally activated with activation energy about 0.66 eV. In LiCuFe₂(VO₄)₃, the electrical conductivity is probably due to the hopping of alkali lithium ion along the channel [001]. Temperature dependence of AC conductivity is studied at different frequencies. Frequency exponent s is found to decrease with increase in temperature. The results have been explained on the basis of correlated barrier hopping (CBH) model. Numerical calculations agree well with experimental results. The results show that the frequency and temperature-dependent behavior of AC conductivity of the studied materials are predominantly due to single polaron hopping.