Enhancing the electrical conductivity of vanadate glass system (Fe2O3, B2O3, V2O5) via doping with sodium or strontium cations

Novel glass-ceramics of the nominal molar compositions 20Fe₂O₃·20B₂O₃·(60-x)V₂O₅· (xNa₂O or xSrO) (where x?=?0 or 10) were prepared by traditional melt technique. Differential thermal analysis (DTA) was implemented to study the thermal behavior of the prepared glasses. Vanadium pentoxide (V₂O₅), iron vanadate (FeVO₄), sodium vanadate (Na₃VO₄) and strontium vanadate (with different formulae) were crystallized and identified by X-ray diffraction (XRD) analysis under certain conditions of heat-treatment. Further characterization of glass and glass ceramics samples were performed using scanning electron microscope (SEM), density, electrical and dielectric measurements. In conclusion, our study elucidated that the substitution of vanadium by Na⁺ and Sr²⁺ ions enhanced the conductivity at 180?°C from 5.11?×?10^?4 for unmodified glass to 2.93?×?10^?3 and 1.03?×?10^?2?S?cm^?1 for Na- and Sr-modified glasses.     

Graphite–graphite oxide composite electrode for vanadium redox flow battery

A graphite/graphite oxide (GO) composite electrode for vanadium redox battery (VRB) was prepared successfully in this paper. The materials were characterized with X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The specific surface area was measured by the Brunauer–Emmett–Teller method. The redox reactions of [VO₂]⁺/[VO]²⁺ and V³⁺/V²⁺ were studied with cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the electrochemical performances of the electrode were improved greatly when 3 wt% GO was added into graphite electrode. The redox peak currents of [VO₂]⁺/[VO]²⁺ and V³⁺/V²⁺ couples on the composite electrode were increased nearly twice as large as that on the graphite electrode, and the charge transfer resistances of the redox pairs on the composite electrode are also reduced. The enhanced electrochemical activity could be ascribed to the presence of plentiful oxygen functional groups on the basal planes and sheet edges of the GO and large specific surface areas introduced by the GO.     

Effects of Sr2+ substitution on the crystal structure,Raman spectra,bond valence and microwave dielectric properties of Ba3-xSrx(VO4)2 solid solutions

The effects of Sr²⁺ substitution for Ba²⁺ on microwave dielectric properties and crystal structure of Ba_3-xSr_x(VO₄)₂ (0 ≤ x ≤ 3, BSVO) solid solution were investigated. Such Sr²⁺ substitution contributes to significant reduction in sintering temperature from 1400 °C to 1150 °C. Both permittivity (∑_r) and quality factor (Q × f) values decreased with increasing x value, which was determined to be related with the descending values of average polarizability and packing fraction, whereas the increase in τ_f value was explained by the decreased average VO bond length, A-site bond valence. BSVO ceramics possessed encouraging dielectric performances with ∑_r = 12.2–15.6 ± 0.1, Q × f = 44,340 - 62,000 ± 800 GHz, and τ_f = 24.5–64.5 ± 0.2 ppm/°C. Low-temperature sintering was manipulated by adding B₂O₃ as sintering additive for the representative Sr₃V₂O₈ (SVO) ceramic and only 1 wt.% B₂O₃ addition successfully contributed to a 21.7% decrease in sintering temperature to 900 °C, showing good chemical compatibility with silver electrodes, which render BSVO series and SVO ceramics potential candidates in multilayer electronic devices fabrication.     

An in-situ Reduction/Oxidation XAS Study on the EL10V8 VO x /TiO2(Anatase) Powder Catalyst

The structural changes of the supported vanadium oxide in the V₂O₅/TiO₂(anatase) EUROCAT EL10V8 powder catalyst during reduction and oxidation at 420 and 490 °C were studied with in-situ X-ray absorption spectroscopy (XAS). The Vanadium K-edge XAS results are compared with pure bulk V₂O₅. For the reduction–oxidation cycle at 420 °C, similar structural changes as for bulk V₂O₅ were observed for the supported vanadium oxide: a reduction to the VO₂ structure and re-oxidation back to V₂O₅. After reduction at 490 °C however, a different structure was obtained: very regular “VO₆” octahedra with a V^2.8+ valence. This may point to a structural support effect.     

Thermodynamic investigation of vanadium oxide in CaO–SiO2–VOx system at 1873 K

Owing to the complexity of the multivalence states of vanadium oxides in slag systems and experimental difficulties, thermodynamic properties of vanadium oxides have not been established yet. In the present study, the mixed-valence states and activities of the vanadium oxides in CaO–SiO₂–VO_x slag were investigated experimentally at 1873 K and oxygen partial pressures of 3.2 × 10^–9 and 3.1 × 10^–7 atm. After the CaO–SiO₂–VO_x slag had equilibrated with a platinum strip, the mixed-valence states of the vanadium oxides in the slag were estimated by performing X-ray photoelectron spectroscopy, and the activities of the vanadium oxides in the slag were calculated using the activity of vanadium in the platinum strip at equilibrium using thermodynamic equations. At an oxygen partial pressure of 3.2 × 10^–9 atm, V³⁺ was the dominant ion and V⁴⁺ was the second most abundant ion. With increasing VO_x content or basicity (CaO/SiO₂ ratio), the fraction of V³⁺ decreased, whereas that of V⁴⁺ increased. The activity of VO_1.5 was greater than those of the other vanadium oxides. On the other hand, when the oxygen partial pressure increased to 3.1 × 10^–7 atm, V⁴⁺ became the dominant ion. As the slag basicity increased, the fraction of V⁴⁺ increased further, whereas that of V³⁺ decreased to less than that of V⁵⁺. The activity of VO_1.5 was greater than those of the other vanadium oxides, limiting the effect of the slag basicity. Consequently, the valence state of vanadium oxide was affected by the slag basicity at a low oxygen partial pressure by acting as a network modifier. In contrast, at a higher oxygen partial pressure, the activity of vanadium oxide increased further but was not affected by the slag basicity because of its contribution to the network structure formation. The present findings can be applied to optimize the slag composition in steel refining or vanadium pentoxide production processes to increase the yield rate of vanadium.     

Hydrogen peroxide sensor based on riboflavin immobilized at the nickel oxide nanoparticle-modified glassy carbon electrode

A simple and sensitive electrochemical sensor based on nickel oxide nanoparticles/riboflavin-modified glassy carbon (NiONPs/RF/GC) electrode was constructed and utilized to determine H₂O₂. By immersing the NiONPs/GC-modified electrode into riboflavin (RF) solution for a short period of time (5–300 s), a thin film of the proposed molecule was immobilized onto the electrode surface. The modified electrode showed stable and a well-defined redox couples at a wide pH range (2–10), with surface-confined characteristics. Experimental results revealed that RF was adsorbed on the surface of NiONPs, and in comparison with usual methods for the immobilization of RF, such as electropolymerization, the electrochemical reversibility and stability of this modified electrode has been improved. The surface coverage and heterogeneous electron transfer rate constants (k _s) of RF immobilized on a NiO _x –GC electrode were approximately 4.83 × 10^?11 mol cm^?2, 54 s^?1, respectively. The sensor exhibits a powerful electrocatalytic activity for the reduction of H₂O₂. The detection limit, sensitivity and catalytic rate constant (k _cat) of the modified electrode toward H₂O₂ were 85 nM, 24 nA μM^?1 and 7.3 (±0.2) × 10³ M^?1 s^?1, respectively, at linear concentration rang up to 3.0 mM. The reproducibility of the sensor was investigated in 10 μM H₂O₂ by amperometry, the value obtained being 2.5 % (n = 10). Furthermore, the fabricated H₂O₂ chemical sensor exhibited an excellent stability, remarkable catalytic activity and reproducibility.     

Active nano-CuPt3 electrocatalyst supported on graphene for enhancing reactions at the cathode in all-vanadium redox flow batteries

Graphene-supported monometallic (Pt) and bimetallic (CuPt₃) cubic nanocatalysts have been investigated as new positive electrode materials for improving the VO₂⁺/VO²⁺ redox process occurring in the vanadium redox flow batteries (VRB). High-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) have been employed to characterize the electrodes. The presence of the CuPt₃ nanocubes on graphene conferred higher electrocatalytic activity due to the much higher electroactive area compared to that obtained with the Pt nanoparticles. The electrochemical surface area of the nano-(CuPt₃)-decorated graphene electrode was 105% higher compared to non-decorated graphene, being then a promising alternative for improving the VRB.     

Adsorption and Diffusion of VO2+ and VO2 + across Cation Membrane for All‐Vanadium Redox Flow Battery

A method based on a selectivity coefficient and the Nernst‐Planck equation is proposed to determine diffusion coefficients of vanadium ions across a cation exchange membrane in VO²⁺/H⁺ and VO₂ ⁺/H⁺ systems. This simplified method can be applied to high concentrations of vanadium ions. Three cation exchange membranes were studied. The logarithmic value of the selectivity coefficient was linearly dependent on the molar fraction of vanadium ions in solution. The diffusion coefficient of vanadium ions decreased with decreasing water content. The membrane with the lowest diffusion coefficient was selected as a battery separator and showed the lowest capacity loss of the studied membranes.     

The key factor determining the anodic deposition of vanadium oxides

This work demonstrates that anodic deposition of vanadium oxide (denoted as VO_x·nH₂O) can be considered as the chemical co-precipitation of V⁵⁺ and V⁴⁺ oxy-/hydroxyl species and the accumulation of V⁵⁺ species at the vicinity of electrode surface is the key factor for the successful anodic deposition of VO_x·nH₂O at a potential much more negative than the equilibrium potential of the oxygen evolution reaction (OER). The results of in situ UV-vis spectra show that the V⁴⁺/V⁵⁺ ratio near the electrode surface can be controlled by varying the applied potential, leading to different, three-dimensional (3D) nanostructures of VO_x·nH₂O. The accumulation of V⁵⁺ species due to V⁴⁺ oxidation at potentials ≥0.4 V (vs. Ag/AgCl) has been found to be very similar to the phenomenon by adding H₂O₂ in the deposition solution. The X-ray photoelectron spectroscopic (XPS) results show that all VO_x·nH₂O deposits can be considered as aggregates consisting of mixed V⁵⁺ and V⁴⁺ oxy-/hydroxyl species with the mean oxidation state significantly increasing with the applied electrode potential.     

Preparation and Characteristics of Ca2NaMg2V3O12:Sm3+ Single-Phased White-Emitting Phosphors

Novel single-phased phosphors Ca₂NaMg₂-V₃O₁₂:xSm³⁺ that exhibit efficient white-light photoluminescence properties have been successfully synthesized by the solid-state reaction method. The formation of a single Ca₂NaMg₂V₃O₁₂ phase has been confirmed by X-ray powder diffraction (XRD). The wavelength-tunable white light is realized by coupling of the broad emission band at 500 nm due to a V⁵⁺?O^2? charge-transfer state transition and the sharp emission peaks at 564, 616, 650 and 708 nm assigned to ⁴G_5/2→⁶H_J (J = 5/2, 7/2, 9/2, 11/2) transitions of the Sm³⁺ ion. The luminescence color can be tuned from green to white by adjusting the doping concentration of Sm³⁺. When the doping concentration of Sm³⁺is increased from x = 0 to x = 0.20, the color rendering index of the Ca₂NaMg₂V₃O₁₂:xSm³⁺ phosphors increased from 55 to 83. The present white phosphors show a great potential for white LEDs.     

Raman spectroscopy studies of concentrated vanadium redox battery positive electrolytes

Spectroscopic changes in highly concentrated vanadium(V)-sulfate solutions to be used in the vanadium redox battery are consistent with the presence of more than one V(V)-sulfate species. The results of Raman spectroscopy indicate that the major species in highly acidic conditions are VO₂SO₄ ^–, VO₂(SO₄)₂ ^3–, VO₂(HSO₄)₂ ^–, VO₃ ^–, V(V) dimers with V₂O₃ ⁴⁺ and V₂O₄ ²⁺ central units. The nature and amount of these species depends upon the V(V) and total sulfate concentrations as well as on S to V and H⁺ to V ratios in the positive half-cell electrolyte. V(V) forms V₂O₃ ⁴⁺, VO₂(SO₄)₂ ^3– and their copolymer species at higher total sulfate concentrations, which tends to stabilize the vanadium (V) positive electrolyte in the vanadium redox battery. The V(V) and V(IV) species show the least interaction with each other. Ageing of concentrated V(V) solutions at elevated temperature (50 °C) produces decomposition of species causing formation of V₂O₅ precipitates with a decrease in the amount of vanadium polymer.     

Characterisation of Zn3(VO4)2 phases in V2O5-doped ZnO varistors

Zinc oxide-rich ZnO–V₂O₅ (ZV), ZnO–V₂O₅–MnO₂ (ZVM) and ZnO–V₂O₅–Sb₂O₃ (ZVS) polycrystalline ceramics have been prepared for detailed microstructural and electrical characterisation. All samples exhibit non-linear current-voltage behaviour, with non-linear coefficients ranging from 5·0 for ZV to 16·7 for ZVM. The use of X-ray powder diffraction together with microstructural examination by transmission electron microscopy and a comparison of measured interplanar spacings with those quoted in the literature for α-, β- and γ-Zn₃(VO₄)₂, has shown evidence for the formation of β-Zn₃(VO₄)₂ in ZV, γ-Zn₃(VO₄)₂ in ZVM and α-Zn₃(VO₄)₂ in ZVS. The Zn₃(VO₄)₂ phases are found to exist as smaller grains embedded in ZnO grains or residing at triple junctions. Electron diffraction suggests that β-Zn₃(VO₄)₂ has an orthorhombic A lattice, while γ-Zn₃(VO₄)₂ has a monoclinic C lattice.     

Effects of Eu3+ doping on the luminescence properties of novel Sr2CaLa(VO4)3 from partial substitution of Sr2+ by Ca2+ in Sr3La(VO4)3

Eu³⁺-activated Sr_3−xCa_xLa(VO₄)₃ phosphors were fabricated via citric-acid-assisted sol combustion. Characterization of the Sr_3−xCa_xLa(VO₄)₃:Eu³⁺ samples with different concentrations of Ca²⁺ revealed a hexagonal crystal structure belonging to the R-3m space group. The amount of Ca²⁺ added (x) was controlled within 0 ≤ x ≤ 2 to yield high-purity phosphors. Scanning electron microscopy results showed that an increase in Ca²⁺ concentration resulted in a decrease in the particle size of Sr_3−xCa_xLa(VO₄)₃:Eu³⁺, with the shape gradually changing from nearly equiaxed to lath-shaped. The Sr₂CaLa(VO₄)₃:Eu³⁺ phosphor (denoted as SCLVO:Eu³⁺) exhibited the strongest photoluminescence (PL) intensity at 618 nm among the samples under excitation of 394-nm near-UV (NUV) light. The study of Eu³⁺ doping concentration confirmed that Eu³⁺ could enter the lattice of the SCLVO matrix without altering its crystal structure. SCLVO:Eu³⁺ was found to strongly absorb 394 nm NUV light and 464 nm blue light. The optimal concentration of the Eu³⁺ dopant in the SCLVO host was 0.11, which resulted in the phosphor achieving an excellent PL intensity and a color purity of 98.68%. Tunable luminescence from the orange area (0.5280, 0.4522) of Commission Internationale de l'éclairage (CIE) to the red area (0.6313, 0.3650) was achieved by adjusting the concentration of Eu³⁺. Under 394 nm excitation, SCLVO:0.11Eu³⁺ phosphor has a quantum yield (QY) of 28.2% and excellent thermal stability with 0.383 eV activation energy. Consequently, White-light-emitting diode (WLED) based on SCLVO:0.11Eu³⁺ phosphor yielded a high color rendering index (CRI), low correlated color temperature (CCT), and CIE coordinates of 91.8, 5196 K, and (0.3407, 0.3612), respectively, under the 20 mA driven current. These results indicated the tremendous potential of SCLVO:0.11Eu³⁺ phosphors for application in WLEDs excited by NUV or blue light.     

Phase structure of V2O5/TiO2 catalyst and catalytic behavior with removal of NO by ammonia

V₂O₅/TiO₂ catalyst with 3% (w/w) V loading has been prepared by sol–gel method. The characterization results of the catalyst structure and catalytic activity show that VO _X state is strongly dependent on the calcination temperature. Little effect is found for phase structure of TiO₂ support on catalytic activity. High catalytic activity in wide temperature range (240–420 °C) is observed for the catalysts calcinated at different temperatures at a space velocity of 50,000 h^?1. Space velocity and alkali metal oxides strongly influence the catalytic activity of the catalyst which was calcinated at 450 °C, furthermore, the one has high tolerance to SO₂ in our test conditions.     

Electrochemical reduction of acetone on mercury electrode in aqueous sulphuric acid solution

Electrochemical reduction of acetone in aqueous H₂SO₄ solution was studied on Hg electrode by galvanostatic, potentiodynamic and polarographic methods. Electrocapillary curves show that acetone molecule adsorbs to a monolayer at concentrations larger than 0·5 M in a potential range of 0 > V > ? 1·0 V (nhe). It orients with the positive end of the dipole toward electrode surface and extends an attractive interaction to its neighbours.Kinetics oberved by galvanostatic pulse method and polarography leads the following conclusions; (1) adsorbed acetone molecule undergoes elecrochemical reduction at potentials more negative than ?1·0 V (nhe), (2) reaction rate is the first and second order with respect to the amount of adsorbed acetone and proton activity, and (3) one electron transfer step determines the reaction rate (Tafel slope is 0·12 V). Reaction intermediate is concluded from the potentiodynamic study to be isopropanol radical, (CH₃)₂??OH, whose amount is proportional to that of adsorbed acetone and to a_H+. From the above results, the rate of the electrochemical reduction of acetone is H₂SO₄ solution is concluded as determined by the step, (CH₃)₂?OH(a) + H⁺ + e^? → (CH₃)₂CHOH.     

A REACTION-EXTRACTION-REGENERATION SYSTEM FOR HIGHLY SELECTIVE OXIDATION OF BENZENE TO PHENOL

The reaction-extraction-regeneration system for the liquid-phase oxidation of benzene to phenol in the benzene-water-oxygen system was investigated. Phenol was extracted in the extractor to reduce the concentration of phenol in the benzene phase. As vanadium catalyst was oxidized to inactive species after the oxidation reaction, the regenerator was installed in the system to reduce the oxidation state of vanadium catalyst from V⁴⁺ or VO²⁺ to the active V³⁺ under H₂ flow. The effects of various operating parameters including concentration of VCl₃ catalyst, O₂ and H₂ flow rates, benzene bubble size, pH, surface area of Pt regeneration catalyst, the metal species, and amount of ascorbic acid were investigated. Ascorbic acid was employed as a reducing agent for helping reduce the V⁴⁺ form to the active form and therefore improving the activity of vanadium catalyst. VCl₃ catalyst concentration of 10 mol/m³ with pH of 3–4 in the reactor and Pt surface area of 0.05 m² in the regenerator showed optimal conditions for the system.     

Effects of additives on the stability of electrolytes for all-vanadium redox flow batteries

The stability of the electrolytes for all-vanadium redox flow battery was investigated with ex-situ heating/cooling treatment and in situ flow-battery testing methods. The effects of inorganic and organic additives have been studied. The additives containing the ions of potassium, phosphate, and polyphosphate are not suitable stabilizing agents because of their reactions with V(V) ions, forming precipitates of KVSO₆ or VOPO₄. Of the chemicals studied, polyacrylic acid and its mixture with CH₃SO₃H are the most promising stabilizing candidates which can stabilize all the four vanadium ions (V²⁺, V³⁺, VO²⁺, and VO₂ ⁺) in electrolyte solutions up to 1.8 M. However, further effort is needed to obtain a stable electrolyte solution with >1.8 M V⁵⁺ at temperatures higher than 40 °C.     

Reduced graphene oxide with tunable C/O ratio and its activity towards vanadium redox pairs for an all vanadium redox flow battery

Electrochemically reduced graphene oxides (ERGO) are obtained under various reducing potentials in the phosphate buffer solution (PBS). Different characterization methods are used to analyse the changes of structure and surface chemical condition for graphene oxide (GO). The results show that GO could be reduced controllably to certain degree and its electrochemical activity towards VO₂⁺/VO²⁺ and V³⁺/V²⁺ redox couples is also tunable using this environmentally friendly method. The catalytic mechanism of the ERGO is discussed in detail, the CO functional groups other than the C–O functional groups on the surface of ERGO more likely provide reactive sites for those redox couples, leading to a more comprehensive understanding about the catalytic process than previous relevant researches. This controllable modification method and the ERGO as electrode reaction catalyst with enhanced battery performance are supposed to have promising applications in the all vanadium redox flow battery.     

The simple one-step solvothermal synthesis of nanostructurated VO2(B)

VO₂(B) has been successfully synthesized by simple, facile and environmental friendly one-step solvothermal method using V₂O₅ and ethanol as a starting agent. Obtained micrometer-sized powder was composed from mutually welded nanosized rod-like, flat and snowflake structures. VO₂(B) powder was tested for possible application as anode material for aqueous lithium ion batteries. Lithium intercalation/deintercalation reaction has been carried out by cyclic voltammetry in a saturated aqueous solution of LiNO₃. At scan rate of 10 mV s^?1 very stable cyclic performance of such obtained VO₂ was established with discharge capacity around 184 mAh g^?1.     

Electrooxidation and inhibition of the antibacterial activity of oxytetracycline hydrochloride using a RuO<Subscript>2</Subscript> electrode

This work reports on the electrochemical oxidation of oxytetracycline hydrochloride (OTCH) [(4S,4aS,5aS,6S,12aS)-4-dimethylamino-1,4,4a,5, 5a,6,11,12a-octahydro-3,6,10,12,12a-hexahydroxy-6-methyl-1,11-dioxonaphthacene-2-carboxamide] on a RuO₂ electrode (DSA^®) by cyclic voltammetry and electrolysis. The electrocatalytic efficiency of the electrode material was investigated as a function of different aqueous buffer solutions with pH values of 2.10 and 5.45 as supporting electrolytes. Spectrophotometric studies have shown that OTCH is stable in such solutions. The electrochemical degradation of OTCH is pseudo-first order at both pH values investigated with rate constants, k, of 9.9 × 10^?5 s^?1 (pH 2.10) and 1.9 × 10^?4 s^?1 (pH 5.45) at 21 ± 1 °C. Microbiological studies with Staphylococcus aureus ATCC 29213 have shown that OTCH lost antibacterial activity after 120 min of electrolysis at 50 mA cm^?2.