Showing papers on "Vanadate published in 2016"

Size controllable synthesis of cobalt vanadate nanostructures with enhanced photocatalytic activity for the degradation of organic dyes

Abstract: Different types of cobalt vanadate nanostructures such as Co3V2O8, Co2V2O7 and CoV2O6 have been successfully prepared via a simple solid-state method. For the first time, cobalt vanadate nanostructures were synthesized via Schiff-base ligand and vanadyl sulfate as a capping agent and vanadium source, respectively. The effect of a Schiff-base ligand (N,N-Bis (salicylaldehyde) ethylenediamine = H2salen) as a capping agent, molar ratio of Co: H2salen and Co:V on type of products, morphology and size of cobalt vanadate nanoparticles was investigated to reach optimum condition. The as-prepared nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmittance electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, energy dispersive X-ray microanalysis (EDX) and ultraviolet–visible (UV–vis) spectroscopy. This work is the first study on photocatalytic activity of cobalt vanadate nanostructures in different conditions. The influence of different parameters such as type of cobalt vanadate nanostructures, type of dye, size of particles and nanostructures dosage as a catalyst on photocatalytic activity of samples were studied.

Facile synthesis, characterization and optical properties of copper vanadate nanostructures for enhanced photocatalytic activity

Abstract: The effect of different chemical approaches on the size, morphology and size distribution of copper vanadate nanostructures in presence of Schiff-base ligand (N,N′-buthylenebis(acetylacetone iminato)dianion = acacbn) was investigated. The as-prepared products were characterized using X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectrum, electron dispersive X-ray spectroscopy and ultraviolet–visible spectroscopy. The optical properties and photocatalytic activity of copper vanadate nano and bulk structures were compared by degradation of cationic dye methylene blue in aqueous solution under UV-light irradiation.

Facile synthesis of amorphous aluminum vanadate hierarchical microspheres for supercapacitors

Abstract: Micro-nanostructured mixed metal vanadates have recently garnered enormous attention owing to their remarkable performances in catalysis, energy storage and conversion. In this work, we report the synthesis of amorphous aluminum vanadate hierarchical microspheres via a simple hydrothermal approach with polyvinylpyrrolidone as a surface directing agent. Amorphous aluminum vanadate hierarchical microspheres are firstly described as a kind of electrode material for supercapacitors. The measured specific capacitance of the amorphous aluminum vanadate electrode is 497 F g−1 at 1 A g−1 with good stability and a retention capacity of 89% after 10 000 cycles. In addition, the fabricated asymmetric supercapacitor device delivered better performance with an extended operating voltage window of 1.5 V, excellent cycle stability (10 000 cycles, 85% capacitance retention), high energy density (37.2 W h kg−1 at 1124.4 W kg−1) and high power density (11 250 W kg−1 at 25 W h kg−1). This study essentially offers a new kind of vanadate as an electrochemical active material for the development of supercapacitors.

Characterization of decavanadate and decaniobate solutions by Raman spectroscopy

Abstract: The decaniobate ion, (Nb10 = [Nb10O28](6-)) being isoelectronic and isostructural with the decavanadate ion (V10 = [V10O28](6-)), but chemically and electrochemically more inert, has been useful in advancing the understanding of V10 toxicology and pharmacological activities. In the present study, the solution chemistry of Nb10 and V10 between pH 4 and 12 is studied by Raman spectroscopy. The Raman spectra of V10 show that this vanadate species dominates up to pH 6.45 whereas it remains detectable until pH 8.59, which is an important range for biochemistry. Similarly, Nb10 is present between pH 5.49 and 9.90 and this species remains detectable in solution up to pH 10.80. V10 dissociates at most pH values into smaller tetrahedral vanadate oligomers such as V1 and V2, whereas Nb10 dissociates into Nb6 under mildly (10 > pH > 7.6) or highly alkaline conditions. Solutions of V10 and Nb10 are both kinetically stable under basic pH conditions for at least two weeks and at moderate temperature. The Raman method provides a means of establishing speciation in the difficult niobate system and these findings have important consequences for toxicology activities and pharmacological applications of vanadate and niobate polyoxometalates.

Structural and spectroscopic studies of a rare non-oxido V( v ) complex crystallized from aqueous solution

Abstract: A non-oxido V(v) complex with glutaroimide-dioxime (H3L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)2]·2H2O, and the structure determined by X-ray diffraction. It is the first non-oxido V(v) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L3-) coordinating to V5+, each in a tridentate mode via the imide N (RV-N = 1.96 A) and oxime O atoms (RV-O = 1.87-1.90 A). Using 17O-labelled vanadate as the starting material, concurrent 17O/51V/1H/13C NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxido V 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O bonds by glutaroimide-dioxime and verified the existence of the "bare" V5+/glutaroimide-dioxime complex, [V(L)2]-, in aqueous solution. In addition, the crystal structure of an intermediate 1 : 1 V(v)/glutaroimide-dioxime complex, [VO2(HL)]-, in which the oxido bonds of vanadate are only partially displaced, corroborates the observations by NMR and ESI-MS. Results from this work provide important insights into the strong sorption of vanadium on poly(amidoxime) sorbents in the recovery of uranium from seawater. Also, because vanadium plays important roles in biological systems, the syntheses of the oxido and non-oxido V5+ complexes and the unprecedented demonstration of the displacement of the oxido VO bonds help with the on-going efforts to develop new vanadium compounds that could be of importance in biological applications.

Antenna Effect on the Organic Spacer-Modified Eu-Doped Layered Gadolinium Hydroxide for the Detection of Vanadate Ions over a Wide pH Range.

Abstract: The excitation of the adsorbed vanadate group led to the red emission arising from the efficient energy transfer to Eu-doped layered gadolinium hydroxide (LGdH:Eu). This light-harvesting antenna effect allowed LGdH:Eu to detect selectively a vanadate in aqueous solution at different pHs. Because vanadate exists in various forms by extensive oligomerization and protonation reactions in aqueous solution depending on pH, it is important to detect a vanadate regardless of its form over a wide pH range. In particular, spacer molecules with long alkyl chains greatly facilitated access of a vanadate antenna into the interlayer surface of LGdH:Eu. The concomitant increase in adsorption capacity of LGdH:Eu achieved a strong antenna effect of vanadate on the red emission from Eu3+. When a suspension containing LGdH:Eu nanosheets (1.0 g/L) was used, the vanadate concentration down to 1 × 10–5 M could even be visually monitored, and the detection limit based on the 5D0 → 7F2 emission intensity could reach 4.5 × 10–8 M.

Crystal chemistry of spinels in the system MgAl2O4-MgV2O4-Mg2VO4

Abstract: Eight spinel single-crystal samples belonging to the spinel sensu stricto-magnesiocoulsonite series (MgAl2O4-MgV2O4) were synthesized and crystal-chemically characterized by X-ray diffraction, electron microprobe and optical absorption spectroscopy. Site populations show that the tetrahedrally coordinated site (T) is populated by Mg and minor Al for the spinel sensu stricto compositions, and only by Mg for the magnesiocoulsonite compositions, while the octahedrally coordinated site (M) is populated by Al, V3+, minor Mg, and very minor amounts of V4+. The latter occurs in appreciable amounts in the Al-free magnesium vanadate spinel, T(Mg)M(Mg0.26V3+1.48V4+0.26)O4, showing the presence of the inverse spinel VMg2O4. The studied samples are characterized by substitution of Al3+ for V3+ and (Mg2++V4+) for 2V3+ described in the system MgAl2O4-MgV2O4-VMg2O4. The present data in conjunction with data from the literature provide a basis for quantitative analyses of two solid-solution series MgAl2O4-MgV23+O4 and MgV23+O4-V4+Mg2O4. Unit-cell parameter increases with increasing V3+ along the series MgAl2O4-MgV2O4 (8.085–8.432 A), but only slightly increases with increasing V3+ along the series VMg2O4-MgV2O4 (8.386–8.432 A). Although a solid solution could be expected between the MgAl2O4 and VMg2O4 end-members, no evidence was found. Amounts of V4+ are nearly insignificant in all synthetic Al-bearing vanadate spinels, but are appreciable in Al-free vanadate spinel. An interesting observation of the present study is that despite the observed complete solid-solution along the MgAl2O4-MgV2O4 and MgV2O4-VMg2O4 series, the spinel structure seems to be unable to stabilize V4+ in any intermediate members on the MgAl2O4-Mg2VO4 join even at high oxygen fugacities. This behavior indicates that the accommodation of specific V-valences can be strongly influenced by crystal-structural constraints, and any evaluation of oxygen fugacities during mineral formation based exclusively on V cation valence distributions in spinel should be treated with caution. The present study underlines that the V valency distribution in spinels is not exclusively reflecting oxygen fugacities, but also depends on activities and solubilities of all chemical components in the crystallization environment.

Antidiabetic, Chemical, and Physical Properties of Organic Vanadates as Presumed Transition‐State Inhibitors for Phosphatases

Abstract: Studies of antidiabetic vanadium compounds, specifically the organic vanadate esters, are reviewed with regard to their chemistry and biological properties. The compounds are described from the perspective of how the fundamental chemistry and properties of organic vanadate esters impact their effects as inhibitors for phosphatases based on the structural information obtained from vanadium-phosphatase complexes. Vanadium compounds have been reported to have antidiabetic properties for more than a century. The structures and properties of organic vanadate complexes are reviewed, and the potency of such vanadium coordination complexes as antidiabetic agents is described. Because such compounds form spontaneously in aqueous environments, the reactions with most components in any assay or cellular environment has potential to be important and should be considered. Generally, the active form of vanadium remains elusive, although studies have been reported of a number of promising vanadium compounds. The description of the antidiabetic properties of vanadium compounds is described here in the context of recent characterization of vanadate-phosphatase protein structures by data mining. Organic vanadate ester compounds are generally four coordinate or five coordinate with the former being substrate analogues and the latter being transition-state analogue inhibitors. These studies demonstrated a framework for characterization of five-coordinate trigonal bipyramidal vanadium inhibitors by comparison with the reported vanadium-protein phosphatase complexes. The binding of the vanadium to the phosphatases is either as a five-coordinate exploded transition-state analogue or as a high energy intermediate, respectively. Even if potency as an inhibitor requires trigonal bipyramidal geometry of the vanadium when bound to the protein, such geometry can be achieved upon binding from compounds with other geometries. Desirable properties of ligands are identified and analyzed. Ligand interactions, as reported in one peptidic substrate, are favorable so that complementarity between phosphatase and coordinating ligand to the vanadium can be established resulting in a dramatic enhancement of the inhibitory potency. These considerations point to a frameshift in ligand design for vanadium complexes as phosphatase inhibitors and are consistent with other small molecule having much lower affinities. Combined, these studies do suggest that if effective delivery of potentially active antidiabetic compound such a the organic vanadate peptidic substrate was possible the toxicity problems currently reported for the salts and some of the complexes may be alleviated and dramatic enhancement of antidiabetic vanadium compounds may result.

Manganese Vanadate Chemistry in Hydrothermal BaF2 Brines: Ba3Mn2(V2O7)2F2 and Ba7Mn8O2(VO4)2F23

Abstract: Manganese vanadate fluorides were synthesized using high-temperature hydrothermal techniques with BaF2 as a mineralizer. Ba3Mn2(V2O7)2F2 crystallizes in space group C2/c and consists of dimers built from edge-sharing MnO4F2 trigonal prisms with linking V2O7 groups. Ba7Mn8O2(VO4)2F23 crystallizes in space group Cmmm, with a manganese oxyfluoride network built from edge- and corner-sharing Mn2+/3+(O,F)6 octahedra. These octahedra form alternating Mn2+ and Mn2+/3+ layers separated by VO4 tetrahedra. This latter compound exhibits a canted antiferromagnetic order below TN = 25 K.

Raman Studies on Species in Single and Mixed Solutions of Molybdate and Vanadate

Abstract: Raman spectroscopy was applied to investigate the speciation in both single and mixed solutions of molybdate and vanadate at pH values from 10.0 to 1.0. Evidence was obtained for the difference of existing forms between these two elements. Vanadium mainly exists as (VO3)nn− while Mo is MoO42− in the pH range of 9.0–7.5. This difference is the theoretical basis for many available separation process. The species in the binary system was identified by comparing the Raman spectra with that in the single systems. Molybvanadates are formed below pH=6.5, which may partly be ascribed to the replacement of V atoms by Mo atoms in some V-O-V groups. Vanadium mainly exists as the decavanadate species in the pH range of 6.0–2.0. The predominant species of Mo are heteropolyanions having structural features of heptamolybdate rather than Mo8O264− and Mo36O1128− which are the predominant Mo species in single solution at pH=2.0–1.0.

Vanadate-induced antiproliferative and apoptotic response in esophageal squamous carcinoma cell line EC109.

Abstract: Vanadate is a transition element that present in nature and was shown to be a nonspecific inhibitor of protein tyrosine phosphatases. It was reported that vanadium (Vd) compounds exhibit antitumor actions in several cancer cell lines. This study aimed to examine the antiproliferative and apoptotic actions of different concentrations of sodium vanadate (NaVd) (+5) in esophageal squamous carcinoma cell line EC109 by determining the protein expression levels of cyclin D1 and caspase-3 following incubation for various times from 15 min up to 4 h. In addition, cell proliferation of EC109 treated with different concentrations (NaVd) was also measured using the MTT assay at 4, 12, 24, and 48 h. The cell cycle of EC109 cells exposed to different concentrations of NaVd was detected using flow cytometry determination at 24 h. Data showed that NaVd greater than 100 µM significantly increased cyclin D1. In contrast, reduced caspase-3 protein expression levels occurred at 50 µM. Cellular proliferation was sign...

Synthesis and characterization of high-quality cobalt vanadate crystals and their applications in lithium-ion batteries

Abstract: High-quality cobalt vanadate crystals have been synthesized by solid-state reaction route. Structure and morphology of the synthesized powders were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) spectroscopy. The XRD patterns revealed that the as prepared materials are of high crystallinity and high quality. The SEM images showed that the crystalline CoV2O6 material is very uniform and well separated, with particle (of) area ~252 μm. The electronic and optical properties were investigated by impedance analyzer and UV–visible spectrophotometer. Temperature-dependent electrical resistivity was measured using four-probe technique. The crystalline CoV2O6 material is a semiconductor and its activation energy is 0.05 eV.

Synthesis of manganese vanadate nanobelts and their visible light photocatalytic activity for methylene blue

Abstract: Manganese vanadate nanobelts have been synthesised by a simple hydrothermal process using polymer polyvinyl pyrrolidone as the surfactant by adjusting the pH value. The X-ray diffraction, selected area electron diffraction and the high-resolution transmission electron microscopy (TEM) show that the manganese vanadate nanobelts are composed of a single crystalline monoclinic Mn2V2O7 phase. Scanning electron microscopy and TEM observations show that the thickness, width and length of the nanobelts are 20 nm, 350 nm–1 μm and several dozens to several hundreds of micrometres, respectively. The photocatalytic activities of the manganese vanadate nanobelts have been evaluated by the photocatalytic degradation of methylene blue (MB) in an aqueous solution as a model pollutant under the solar light irradiation. After 4 h of the irradiation by the solar light, the MB solution with the volume of 10 mL and the concentration of 10 mg·mL−1 can be totally degraded using 10 mg manganese vanadate nanobelts.

Rapid Large‐Scale Synthesis of Vanadate Nanoscrolls with Controllable Lengths

Abstract: A simple one-step solvothermal synthetic approach has been applied to the rapid fabrication of VOx nanoscrolls (NScs) from vanadium pentoxide and either dodecylamine or octadecylamine as the structure-directing agent (SDA). By reaction of the appropriate ratio of SDA to vanadium oxide and solvent at 250 °C, approximately 20 g of NScs per synthesis could be formed within 2 h. Syntheses could be further adjusted so that the average lengths of the NScs could be varied from approximately 383 to 816 nm to 3.3 μm. The effect of synthesis parameters such as temperature, solvothermal reaction duration, and vanadium oxidation state on the formation of NScs was also investigated; detailed studies indicate that the variation between V4+ and V5+ appears to play a critical role in the formation of vanadate NScs.

Crystal structure of (Na0.70)(Na0.70,Mn0.30)(Fe3+,Fe2+)2Fe2+(VO4)3, a sodium-, iron- and manganese-based vanadate with the alluaudite-type structure

Abstract: The title compound, sodium (sodium,manganese) triiron(II,III) tris[vana­date(V)], (Na0.70)(Na0.70,Mn0.30)(Fe3+,Fe2+)2Fe2+(VO4)3, was prepared by solid-state reactions. It crystallizes in an alluaudite-like structure, characterized by a partial cationic disorder. In the structure, four of the 12 sites in the asymmetric unit are located on special positions, three on a twofold rotation axis (Wyckoff position 4e) and one on an inversion centre (4b). Two sites on the twofold rotation axis are entirely filled by Fe2+ and V5+, whereas the third site has a partial occupancy of 70% by Na+. The site on the inversion centre is occupied by Na+ and Mn2+ cations in a 0.7:0.3 ratio. The remaining Fe2+ and Fe3+ atoms are statistically distributed on a general position. The three-dimensional framework of this structure is made up of kinked chains of edge-sharing [FeO6] octa­hedra stacked parallel to [10-1]. These chains are held together by VO4 tetra­hedral groups, forming polyhedral sheets perpendicular to [010]. Within this framework, two types of channels extending along [001] are present. One is occupied by (Na+/Mn2+) while the second is partially occupied by Na+. The mixed site containing (Na+/Mn2+) has an octa­hedral coordination sphere, while the Na+ cations in the second channel are coordinated by eight O atoms.

[Insulin-mimetic property of vanadium compounds].

Abstract: Vanadium is a transition metal which creates a number of inorganic and organic derivatives with various organic substances. Some of these compounds have pharmaceutical significance, e.g. vanadyl cation, vanadate and bis(maltolato) oxovanadium(IV). Vanadium compounds are competence inhibitors of protein tyrosine phosphatases (PTP). They have anti-tumor properties, capable of inhibiting cell proliferation at the concentrations of several micromoles. They also display insulin-mimetic and hypoglycemic properties. As they can increase the activity of the insulin-like growth factor I receptor, they stimulate glycogen synthesis, increase the number of GLUT-4 transporters in the cell membrane and impair gluconeogenesis. In addition to their effects on sugar metabolism, vanadium compounds increase the synthesis of fatty acids, reducing the concentration of glucose in the blood. Thanks to their mitotic properties, low concentrations of vanadium compounds are also able to induce β cell regeneration. Clinical tests have shown that vanadium compounds may be used as antidiabetic drugs with low toxicity. However, the range of therapeutic concentrations is very narrow; at concentrations as low a several micromoles vanadium compounds inhibit cell proliferation and cause apoptosis, necrosis and inflammation.