Fundamentals of vanadium dioxide thin films as possible components of intelligent windows

Directory of Open Access Journals (Sweden)

Wu, Z. P.

1999-03-01

Full Text Available In this paper, the research on the vanadium dioxide thin film, which can be used as intelligent windows, is reviewed, including the basic properties of V₂, energy band structure, model of electronic energy and the origin of metal-to-insulator transition (MIT. Finally, the problems existing in the research and the possibility of application for VO₂, as an intelligent thermochromic window are briefly discussed.

En este artículo se revisan las investigaciones realizadas en películas delgadas de dióxido de vanadio que pueden ser usadas en componentes de ventanas inteligentes, incluyendo las propiedades básicas del VO₂, tales como su estructura de bandas, modelo energético de tipo electrónico y el origen del fenómeno de la transición: metal-aislador (MIT en la literatura inglesa que constituye la base de las aplicaciones de estas películas. Finalmente, los problemas que hay en la investigación actual de este tipo de películas, así como sus posibles aplicaciones en ventanas inteligentes de tipo termocrómico, se discuten brevemente.

Anomalous optical switching and thermal hysteresis during semiconductor-metal phase transition of VO2 films on Si substrate

International Nuclear Information System (INIS)

Leahu, G.; Li Voti, R.; Sibilia, C.; Bertolotti, M.

2013-01-01

We present a detailed infrared study of the semiconductor-to-metal transition (SMT) in a vanadium dioxide (VO 2 ) film deposited on silicon wafer. The VO 2 phase transition is studied in the mid-infrared region by analyzing the transmittance and the reflectance measurements, and the calculated emissivity. The reflectance has been measured in two configurations: from the side of the VO 2 film and from that of Si wafer. The results show a strong asymmetry between the emissivity in the two configurations, and the fact that the emissivity dynamic range from the silicon side is twice as large than that from the VO 2 side. The temperature behaviour of the emissivity during the SMT put into evidence the phenomenon of the anomalous absorption in VO 2 , which has been explained by applying the Maxwell Garnett effective medium approximation theory

Characteristics of the Current-Controlled Phase Transition of VO2 Microwires for Hybrid Optoelectronic Devices

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Arash Joushaghani

2015-08-01

Full Text Available The optical and electrical characteristics of the insulator-metal phase transition of vanadium dioxide (VO2 enable the realization of power-efficient, miniaturized hybrid optoelectronic devices. This work studies the current-controlled, two-step insulator-metal phase transition of VO2 in varying microwire geometries. Geometry-dependent scaling trends extracted from current-voltage measurements show that the first step induced by carrier injection is delocalized over the microwire, while the second, thermally-induced step is localized to a filament about 1 to 2 μm wide for 100 nm-thick sputtered VO2 films on SiO2. These effects are confirmed by direct infrared imaging, which also measures the change in optical absorption in the two steps. The difference between the threshold currents of the two steps increases as the microwires are narrowed. Micron- and sub-micron-wide VO2 structures can be used to separate the two phase transition steps in photonic and electronic devices.

The electrochemical catalytic activity of single-walled carbon nanotubes towards VO2+/VO2+ and V3+/V2+ redox pairs for an all vanadium redox flow battery

International Nuclear Information System (INIS)

Li Wenyue; Liu Jianguo; Yan Chuanwei

2012-01-01

Highlights: ► SWCNT shows excellent electrochemical catalytic activity towards VO 2 + /VO 2+ and V 3+ /V 2+ redox couples. ► The anodic reactions are more sensitive to the surface oxygen atom content change compared with the cathodic reactions. ► The enhanced battery performance clearly demonstrated that the SWCNT is suitable to be used as an electrode catalyst for VRFB. - Abstract: Single-walled carbon nanotube (SWCNT) was used as an electrode catalyst for an all vanadium redox flow battery (VRFB). The electrochemical property of SWCNT towards VO 2 + /VO 2+ and V 3+ /V 2+ was carefully characterized by cyclic voltammetric (CV) and electrochemical impedance spectroscopy (EIS) measurements. The peak current values for these redox pairs were significantly higher on the modified glassy carbon electrode compared with those obtained on the bare electrode, suggesting the excellent electrochemical activity of the SWCNT. Moreover, it was proved that the anodic process was more dependent on the surface oxygen of the SWCNT than the cathodic process through changing its surface oxygen content. Detailed EIS analysis of different modified electrodes revealed that the charge and mass transfer processes were accelerated at the modified electrode–electrolyte interface, which could be ascribed to the large specific surface area, the surface defects and the oxygen functional groups of the SWCNT. The enhanced battery performance effectively demonstrated that the SWCNT was suitable to serve as an electrode catalyst for the VRFB.

Gate-tunable gigantic changes in lattice parameters and optical properties in VO2

Science.gov (United States)

Nakano, Masaki; Okuyama, Daisuke; Shibuya, Keisuke; Ogawa, Naoki; Hatano, Takafumi; Kawasaki, Masashi; Arima, Taka-Hisa; Iwasa, Yoshihiro; Tokura, Yoshinori

2014-03-01

The field-effect transistor provides an electrical switching function of current flowing through a channel surface by external gate voltage (VG). We recently reported that an electric-double-layer transistor (EDLT) based on vanadium dioxide (VO2) enables electrical switching of the metal-insulator phase transition, where the low-temperature insulating state can be completely switched to the metallic state by application of VG. Here we demonstrate that VO2-EDLT enables electrical switching of lattice parameters and optical properties as well as electrical current. We performed in-situ x-ray diffraction and optical transmission spectroscopy measurements, and found that the c-axis length and the infrared transmittance of VO2 can be significantly modulated by more than 1% and 40%, respectively, by application of VG. We emphasize that these distinguished features originate from the electric-field induced bulk phase transition available with VO2-EDLT. This work was supported by the Japan Society for the Promotion of Science (JSPS) through its ``Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST Program).''

Optical switching properties of VO2 films driven by using WDM-aligned lasers

International Nuclear Information System (INIS)

Tsai, K.Y.; Wu, F.-H.; Shieh, H.-P.D.; Chin, T.-S.

2006-01-01

Vanadium dioxide (VO 2 ) film had been demonstrated a high speed IR shutter driven by total optical modulation. However, it usually required a higher power heating laser of high power and precise optical systems to cover the probe beam on the sample with a heating beam of larger area. A new optical system, simply composed of wavelength division multiplexing (WDM), fiber lens or convex lens system, and a glass sheet with VO 2 thin film on it, was easily assembled to utilize VO 2 film as an IR shutter, implying the possibility to highly miniaturize the VO 2 -based optical shutter. A permanent low-transmittance (PLT) region forms on the film within the probe beam, resulting in a decrease in average power of the probe beam. Another ring-type switching area (switching ring) forms around the PLT region, resulting in the transmittance switching of the probe beam synchronously with the heating signal. VO 2 films can be switched with the highest rate of a continuous square heating signal of 3 mW at 120 kHz. A heating pulse of 0.7 ns and 13 mW can be used to stimulate an IR pulse with fiber lens

Interaction of titanium and vanadium with carbon dioxide under heating

International Nuclear Information System (INIS)

Vlasyuk, R.Z.; Kurovskij, V.Ya.; Lyapunov, V.P.; Radomysel'skij, I.D.

1986-01-01

The methods of gravitmetric and X-ray phase analysis as well as analysis of composition of gases in the heating chamber have been used to investigate the mechanism of titanium and vanadium interaction with carbon dioxide in the 300-1000 deg C temperature range. The analogy of mechanisms of the interaction of titanium and vanadium with carbon dioxide in oxides production on the metal surface with subsequent carbidizing treatment at temperatures above 800 deg C is shown. Temperature limits of material operation on the base of titanium or vanadium in carbon dioxide must not exceed 400 or 600 deg C, respectively

Tunable subwavelength hot spot of dipole nanostructure based on VO2 phase transition.

Science.gov (United States)

Park, Jun-Bum; Lee, Il-Min; Lee, Seung-Yeol; Kim, Kyuho; Choi, Dawoon; Song, Eui Young; Lee, Byoungho

2013-07-01

We propose a novel approach to generate and tune a hot spot in a dipole nanostructure of vanadium dioxide (VO2) laid on a gold (Au) substrate. By inducing a phase transition of the VO2, the spatial and spectral distributions of the hot spot generated in the feed gap of the dipole can be tuned. Our numerical simulation based on a finite-element method shows a strong intensity enhancement difference and tunability near the wavelength of 678 nm, where the hot spot shows 172-fold intensity enhancement when VO2 is in the semiconductor phase. The physical mechanisms of forming the hot spots at the two-different phases are discussed. Based on our analysis, the effects of geometric parameters in our dipole structure are investigated with an aim of enhancing the intensity and the tunability. We hope that the proposed nanostructure opens up a practical approach for the tunable near-field nano-photonic devices.

Nanoscale Phase Separation and Lattice Complexity in VO2: The Metal–Insulator Transition Investigated by XANES via Auger Electron Yield at the Vanadium L23-Edge and Resonant Photoemission

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Augusto Marcelli

2017-12-01

Full Text Available Among transition metal oxides, VO2 is a particularly interesting and challenging correlated electron material where an insulator to metal transition (MIT occurs near room temperature. Here we investigate a 16 nm thick strained vanadium dioxide film, trying to clarify the dynamic behavior of the insulator/metal transition. We measured (resonant photoemission below and above the MIT transition temperature, focusing on heating and cooling effects at the vanadium L23-edge using X-ray Absorption Near-Edge Structure (XANES. The vanadium L23-edges probe the transitions from the 2p core level to final unoccupied states with 3d orbital symmetry above the Fermi level. The dynamics of the 3d unoccupied states both at the L3- and at the L2-edge are in agreement with the hysteretic behavior of this thin film. In the first stage of the cooling, the 3d unoccupied states do not change while the transition in the insulating phase appears below 60 °C. Finally, Resonant Photoemission Spectra (ResPES point out a shift of the Fermi level of ~0.75 eV, which can be correlated to the dynamics of the 3d// orbitals, the electron–electron correlation, and the stability of the metallic state.

Enhanced Visible Transmittance of Thermochromic VO2 Thin Films by SiO2 Passivation Layer and Their Optical Characterization

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Jung-Hoon Yu

2016-07-01

Full Text Available This paper presents the preparation of high-quality vanadium dioxide (VO2 thermochromic thin films with enhanced visible transmittance (Tvis via radio frequency (RF sputtering and plasma enhanced chemical vapor deposition (PECVD. VO2 thin films with high Tvis and excellent optical switching efficiency (Eos were successfully prepared by employing SiO2 as a passivation layer. After SiO2 deposition, the roughness of the films was decreased 2-fold and a denser structure was formed. These morphological changes corresponded to the results of optical characterization including the haze, reflectance and absorption spectra. In spite of SiO2 coating, the phase transition temperature (Tc of the prepared films was not affected. Compared with pristine VO2, the total layer thickness after SiO2 coating was 160 nm, which is an increase of 80 nm. Despite the thickness change, the VO2 thin films showed a higher Tvis value (λ 650 nm, 58% compared with the pristine samples (λ 650 nm, 43%. This enhancement of Tvis while maintaining high Eos is meaningful for VO2-based smart window applications.

Metal-Insulator Phase Transition in Quasi-One-Dimensional VO2 Structures

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Woong-Ki Hong

2015-01-01

Full Text Available The metal-insulator transition (MIT in strongly correlated oxides has attracted considerable attention from both theoretical and experimental researchers. Among the strongly correlated oxides, vanadium dioxide (VO2 has been extensively studied in the last decade because of a sharp, reversible change in its optical, electrical, and magnetic properties at approximately 341 K, which would be possible and promising to develop functional devices with advanced technology by utilizing MITs. However, taking the step towards successful commercialization requires the comprehensive understanding of MIT mechanisms, enabling us to manipulate the nature of transitions. In this regard, recently, quasi-one-dimensional (quasi-1D VO2 structures have been intensively investigated due to their attractive geometry and unique physical properties to observe new aspects of transitions compared with their bulk counterparts. Thus, in this review, we will address recent research progress in the development of various approaches for the modification of MITs in quasi-1D VO2 structures. Furthermore, we will review recent studies on realizing novel functional devices based on quasi-1D VO2 structures for a wide range of applications, such as a gas sensor, a flexible strain sensor, an electrical switch, a thermal memory, and a nonvolatile electrical memory with multiple resistance.

Dynamically Babinet-invertible metasurface: a capacitive-inductive reconfigurable filter for terahertz waves using vanadium-dioxide metal-insulator transition

Science.gov (United States)

Urade, Yoshiro; Nakata, Yosuke; Okimura, Kunio; Nakanishi, Toshihiro; Miyamaru, Fumiaki; Takeda, Mitsuo W.; Kitano, Masao

2016-03-01

This paper proposes a reconfigurable planar metamaterial that can be switched between capacitive and inductive responses using local changes in the electrical conductivity of its constituent material. The proposed device is based on Babinet's principle and exploits the singular electromagnetic responses of metallic checkerboard structures, which are dependent on the local electrical conductivity. Utilizing the heating-induced metal-insulator transition of vanadium dioxide ($\\mathrm{VO}_2$), the proposed metamaterial is designed to compensate for the effect of the substrate and is experimentally characterized in the terahertz regime. This reconfigurable metamaterial can be utilized as a switchable filter and as a switchable phase shifter for terahertz waves.

Complexation of vanadium with amidoxime and carboxyl groups. Uncovering the competitive role of vanadium in uranium extraction from seawater

Energy Technology Data Exchange (ETDEWEB)

Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Wu, Guo-Zhong [Chinese Academy of Sciences, Shanghai (China). Shanghai Inst. of Applied Physics

2017-09-01

At present, amidoxime-based adsorbents are considered to be the most promising materials for extraction of uranium from seawater. However, the high concentrations of transition metals especially vanadium strongly compete with uranium in the sequestration process, which is extremely limited the commercial use of amidoxime-based adsorbents. In this work, the coordination modes, bonding nature, and stabilities of possible vanadium(IV) (VO{sup 2+}) and (V) (VO{sub 2}{sup +}, VO{sup 3+}, V{sup 5+}) complexes with amidoximate (AO{sup -}), carboxyl (Ac{sup -}), glutarimidedioximate (HA{sup -}) and deprotonated glutarimidedioximate (A{sup 2-}) on single and double alkyl chains (R=C{sub 13}H{sub 26}) are systematically explored by quantum chemical calculations. Different from the uranyl (UO{sub 2}{sup 2+}) complexes, the AO{sup -} groups of the vanadium(IV) and (V) complexes prefer to coordinate as monodentate and chelate ligands, while few species with AO{sup -} groups in η{sup 2}-binding mode have been observed in the vanadium complexes. Besides, the vanadium complexes are predicted to have obvious covalent metal-ligand bonds. According to thermodynamic stability analysis, all the vanadium complexes with AO{sup -}, Ac{sup -}, HA{sup -} and A{sup 2-} ligands on double alkyl chains are found to be more stable than corresponding complexes with ligands on a single chain. The synergistic effect of the amidoxime and carboxyl groups can be observed in most of VO{sub 2}{sup +} and VO{sup 3+} complexes with mixed ligands (AO{sup -}/Ac{sup -}). The vanadium(IV) and (V) complexes are more stable than the corresponding uranyl complexes, and the adsorption capability of the amidoxime-based adsorbents toward vanadium(V) ions decrease in the order of VO{sub 2}{sup +}>VO{sup 3+}> V{sup 5+}. The dioxovanadium cation VO{sub 2}{sup +} is predicted to form multinuclear vanadium complex in the sequestration process, possibly resulting in higher stable VO{sub 2}{sup +} complexes. Therefore

Fast imaging of laser induced plasma emission of vanadium dioxide (VO2) target

CSIR Research Space (South Africa)

Masina, BN

2013-10-01

Full Text Available The main objective of this study is to fully optimise the synthesis of vanadium oxide nanostructures using pulsed laser deposition. We will attempt to realise this by studying the mechanism of the plasma formation and expansion during the pulsed...

Electrochemical catalytic activity of tungsten trioxide- modified graphite felt toward VO2+/VO2+ redox reaction

International Nuclear Information System (INIS)

Shen, Yang; Xu, Hongfeng; Xu, Pengcheng; Wu, Xiaoxin; Dong, Yiming; Lu, Lu

2014-01-01

A novel graphite felt electrode modified with tungsten trioxide (WO 3 ) was developed to improve the electrochemical performance of graphite felt toward the VO 2 + /VO 2+ redox pair. WO 3 was prepared using a hydrothermal method, and the morphology of WO 3 structures was investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical property of WO 3 -modified graphite felt toward VO 2 + /VO 2+ was carefully characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The hydrogen-vanadium redox flow battery (H-VRFB) test indicates that single cells using 1.1 mg cm −2 WO 3 -modified graphite felt exhibited excellent performance at 70 mA cm −2 , and the corresponding coulombic, voltage, and energy efficiencies were 99.1%, 88.66% and 87.86%, respectively

Nano crystalline Bi{sub 2}(VO{sub 5}) phases in lithium bismuth borate glasses containing mixed vanadium-nickel oxides

Energy Technology Data Exchange (ETDEWEB)

Yadav, Arti, E-mail: artidabhur@gmail.com; Khasa, S.; Dahiya, M. S. [Department of Physics, Deenbandhu Chhotu Ram University of Science and Technology, Murthal, India-131039 (India); Agarwal, A. [Department of Applied Physics, G. J. University of Science and Technology, Hisar, India-125001 (India)

2016-05-23

Glass composition 7V{sub 2}O{sub 5}·23Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} and x(2NiO·V{sub 2}O{sub 5})·(30-x)Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3}, x=0, 2, 5, 7 and 10, were produced by conventional melt quenching technique. The quenched amorphous glass samples were annealed at temperatures 400°C and 500°C for 6 hours. The Bi{sub 2}(VO{sub 5}) crystallite were grown in all prepared glass matrix. Tn vanadium lithium bismuth borate glass (annealed), the some phrase of V{sub 2}O{sub 5}-crystal were observed along with the nano crystalline Bi{sub 2}(VO{sub 5}) phase. The sharp peaks in FTTR spectra of all annealed compositions were also compatible with the XRD diffraction peaks of the system under investigation. Average crystalline size (D) of the Bi{sub 2}(VO{sub 5}) nano-crystallite was ~30 nm for samples annealed at 400°C and ~42 nm for samples annealed at 500°C. Lattice parameter and the lattice strain for all the samples was also calculated corresponding to the (113) plane of Bi{sub 2}(VO{sub 5}) crystallite.

Specifics of adsorption and chemical processes on the surface of gamma-irradiated vanadium dioxide

International Nuclear Information System (INIS)

Kaurkovskaya, V.N.; Dzyubenko, L.S.; Doroshenko, V.N.; Chujko, A.A.; Shakhov, A.P.

2006-01-01

Effect of γ-irradiation on electrophysical properties and processes of thermal desorption of water from the surface of vanadium oxides V 2 O 3 -VO 2-δ -VO 2+δ -V 2 O 5 was investigated by derivatography and electric conductivity. Content of adsorbed water at the surface and phase composition of the surface was demonstrated to change under the action of low radiation doses. Surface electric conductivity of the irradiated samples VO 2-δ in the process of chemical reactions of adsorbed following irradiation benzoic acid and ethanol was established to be much above than in irradiated-free ones. It is presumed that metal-semiconductor phase transition at the surface of VO 2-δ during chemical reaction is intensified by irradiation [ru

Nanoscale Engineering in VO2 Nanowires via Direct Electron Writing Process.

Science.gov (United States)

Zhang, Zhenhua; Guo, Hua; Ding, Wenqiang; Zhang, Bin; Lu, Yue; Ke, Xiaoxing; Liu, Weiwei; Chen, Furong; Sui, Manling

2017-02-08

Controlling phase transition in functional materials at nanoscale is not only of broad scientific interest but also important for practical applications in the fields of renewable energy, information storage, transducer, sensor, and so forth. As a model functional material, vanadium dioxide (VO 2 ) has its metal-insulator transition (MIT) usually at a sharp temperature around 68 °C. Here, we report a focused electron beam can directly lower down the transition temperature of a nanoarea to room temperature without prepatterning the VO 2 . This novel process is called radiolysis-assisted MIT (R-MIT). The electron beam irradiation fabricates a unique gradual MIT zone to several times of the beam size in which the temperature-dependent phase transition is achieved in an extended temperature range. The gradual transformation zone offers to precisely control the ratio of metal/insulator phases. This direct electron writing technique can open up an opportunity to precisely engineer nanodomains of diversified electronic properties in functional material-based devices.

Broadband modulation of terahertz waves through electrically driven hybrid bowtie antenna-VO2 devices.

Science.gov (United States)

Han, Chunrui; Parrott, Edward P J; Humbert, Georges; Crunteanu, Aurelian; Pickwell-MacPherson, Emma

2017-10-05

Broadband modulation of terahertz (THz) light is experimentally realized through the electrically driven metal-insulator phase transition of vanadium dioxide (VO 2 ) in hybrid metal antenna-VO 2 devices. The devices consist of VO 2 active layers and bowtie antenna arrays, such that the electrically driven phase transition can be realized by applying an external voltage between adjacent metal wires extended to a large area array. The modulation depth of the terahertz light can be initially enhanced by the metal wires on top of VO 2 and then improved through the addition of specific bowties in between the wires. As a result, a terahertz wave with a large beam size (~10 mm) can be modulated within the measurable spectral range (0.3-2.5 THz) with a frequency independent modulation depth as high as 0.9, and the minimum amplitude transmission down to 0.06. Moreover, the electrical switch on/off phase transition depends very much on the size of the VO 2 area, indicating that smaller VO 2 regions lead to higher modulation speeds and lower phase transition voltages. With the capabilities in actively tuning the beam size, modulation depth, modulation bandwidth as well as the modulation speed of THz waves, our study paves the way in implementing multifunctional components for terahertz applications.

Fluorine doped vanadium dioxide thin films for smart windows

International Nuclear Information System (INIS)

Kiri, Pragna; Warwick, Michael E.A.; Ridley, Ian; Binions, Russell

2011-01-01

Thermochromic fluorine doped thin films of vanadium dioxide were deposited from the aerosol assisted chemical vapour deposition reaction of vanadyl acetylacetonate, ethanol and trifluoroacetic acid on glass substrates. The films were characterised with scanning electron microscopy, variable temperature Raman spectroscopy and variable temperature UV/Vis spectroscopy. The incorporation of fluorine in the films led to an increase in the visible transmittance of the films whilst retaining the thermochromic properties. This approach shows promise for improving the aesthetic properties of vanadium dioxide thin films.

Silver Vanadium Phosphorous Oxide, Ag(2)VO(2)PO(4): Chimie Douce Preparation and Resulting Lithium Cell Electrochemistry.

Science.gov (United States)

Kim, Young Jin; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2011-08-15

Recently, we have shown silver vanadium phosphorous oxide (Ag(2)VO(2)PO(4), SVPO) to be a promising cathode material for lithium based batteries. Whereas the first reported preparation of SVPO employed an elevated pressure, hydrothermal approach, we report herein a novel ambient pressure synthesis method to prepare SVPO, where our chimie douce preparation is readily scalable and provides material with a smaller, more consistent particle size and higher surface area relative to SVPO prepared via the hydrothermal method. Lithium electrochemical cells utilizing SVPO cathodes made by our new process show improved power capability under constant current and pulse conditions over cells containing cathode from SVPO prepared via the hydrothermal method.

Growth of VO2 Nano wires from Supercooled Liquid Nano droplets and E-beam Irradiation for Ultra-sensitive sensor

International Nuclear Information System (INIS)

Byun, Ji Won; Baik, Jeong Min; Lee, Sang Hyun; Lee, Byung Cheol

2011-01-01

Vanadium dioxide is an interesting material on account of its easily accessible and sharp Mott metal-insulator transition at ∼ 68 .deg. C in the bulk, which is of great interest in sensing and catalytic applications. In this Paper, we describe the synthesis and properties of VO 2 nano wires as novel catalytic and gas sensor materials based on electron beam irradiation. High yields of single crystalline VO 2 nano wires are synthesized by atmospheric-pressure, physical vapor deposition using V 2 O 5 layer. Pd-decorated VO 2 nano wire sensors show extraordinary sensitivity towards hydrogen, an almost 3 order-of-magnitude increase in the current through the nano wire. By the Eb irradiation, the conductance of the nano wires significantly increased up to 5 times, reducing the response time by half and the operating temperature. The metal nanoparticles-VO 2 nano wire system will be very promising for high-sensitivity and high-selectivity under low temperature less than 100. deg. C

Control of room-temperature defect-mediated ferromagnetism in VO{sub 2} films

Energy Technology Data Exchange (ETDEWEB)

Yang, Tsung-Han, E-mail: tyang3@ncsu.edu [NSF Center for Advanced Materials and Smart Structures, Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC 27695-7907 (United States); Nori, Sudhakar; Mal, Siddhartha; Narayan, Jagdish [NSF Center for Advanced Materials and Smart Structures, Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC 27695-7907 (United States)

2011-09-15

We report interesting ferromagnetic properties and their control in a vanadium-based oxide system driven by stoichiometric defects. Vanadium oxide (VO{sub 2}) thin films were grown on c-plane sapphire substrates by a pulsed laser deposition technique under different ambient conditions. The ferromagnetism of the epitaxial VO{sub 2} films can be switched on and off by altering the cooling ambient parameters. In addition, the saturated magnetic moments and coercivity of the VO{sub 2} films were found to be a function of the oxygen partial pressure during the growth process. The room-temperature ferromagnetic properties of VO{sub 2} films were correlated with the nature of the microstructure and the growth parameters. The origin of the induced magnetic properties are qualitatively understood to stem from intrinsic structural and stoichiometric defects.

For progress in natural science: Materials international investigations of structural phase transformation and THz properties across metal–insulator transition in VO2/Al2O3 epitaxial films

Directory of Open Access Journals (Sweden)

Mengmeng Yang

2015-10-01

Full Text Available Vanadium dioxide (VO2 epitaxial thin films on (0001-oriented Al2O3 substrates were prepared using radio frequency (RF magnetron sputtering techniques. To study the metal-insulator-transition (MIT mechanism and extend the applications of VO2 epitaxial films at terahertz (THz band, temperature-dependent X-ray diffraction (XRD and THz time domain spectroscopy of the VO2 epitaxial films were performed. Both the lattice constants and THz transmission exhibited a similar and sharp transition that was similar to that observed for the electrical resistance. Consequently, the MIT of the VO2/Al2O3 epitaxial films should be co-triggered by the structural phase transition and electronic transition. Moreover, the very large resistance change (on the order of ~103 and THz response (with a transmission modulation ratio of ~87% in the VO2/Al2O3 epitaxial heterostructures are promising for electrical switch and electro-optical device applications.

Interaction of titanium and vanadium with carbon dioxide in heating

International Nuclear Information System (INIS)

Vlasyuk, R.Z.; Kurovskii, V.Y.; Lyapunov, A.P.; Radomysel'skii, I.D.

1986-01-01

To obtain prediction data on the change in properties of titaniumand vanadium-base powder metallurgy materials operating in a carbon dioxide atmosphere, and also to clarify the mechanism of their interaction with the gas in this work, gravimetric investigations of specimens heated at temperatures of 300-1000 C and an x-ray diffraction analysis of their surface were made and the composition of the gas in the heating chamber was studied. The results of the investigations indicate a similarity between the mechanisms of interaction of titanium and vanadium with carbon dioxide including the formation of oxides on the surface of the metal with subsequent carbidization at temperatures above 800 C. On the basis of the data obtained, it may be concluded that the operating temperature limits of titanium- or vanadium-base materials in carbon dioxide must not exceed 400 and 600 C, respectively

Chromium–niobium co-doped vanadium dioxide films: Large temperature coefficient of resistance and practically no thermal hysteresis of the metal–insulator transition

Directory of Open Access Journals (Sweden)

Kenichi Miyazaki

2016-05-01

Full Text Available We investigated the effects of chromium (Cr and niobium (Nb co-doping on the temperature coefficient of resistance (TCR and the thermal hysteresis of the metal–insulator transition of vanadium dioxide (VO2 films. We determined the TCR and thermal-hysteresis-width diagram of the V1−x−yCrxNbyO2 films by electrical-transport measurements and we found that the doping conditions x ≳ y and x + y ≥ 0.1 are appropriate for simultaneously realizing a large TCR value and an absence of thermal hysteresis in the films. By using these findings, we developed a V0.90Cr0.06Nb0.04O2 film grown on a TiO2-buffered SiO2/Si substrate that showed practically no thermal hysteresis while retaining a large TCR of 11.9%/K. This study has potential applications in the development of VO2-based uncooled bolometers.

Thickness dependence of optical properties of VO2 thin films epitaxially grown on sapphire (0 0 0 1)

International Nuclear Information System (INIS)

Xu Gang; Jin Ping; Tazawa, Masato; Yoshimura, Kazuki

2005-01-01

Vanadium dioxide (VO 2 ) films were epitaxially grown on α-Al 2 O 3 (0 0 0 1) by rf reactive magnetron sputtering. The effects of film thickness ranging from 3 to 150 nm on optical properties were investigated. It revealed that the semiconductor--metal phase transition temperature considerably decreases as film thickness decreases, in particular for the film with thickness less than 10 nm. On the other hand, we found that the difference in visible transmittance between the two phases of VO 2 also varies with film thickness. For the films with thickness less than 50 nm, the semiconductor phase exhibits lower visible transmittance than its metallic phase, while for those with thickness larger than 50 nm the situation is reversed

Raman scattering and x-ray diffractometry studies of epitaxial TiO2 and VO2 thin films and multilayers on α-Al2O3(11 bar 20)

International Nuclear Information System (INIS)

Foster, C.M.; Chiarello, R.P.; Chang, H.L.M.; You, H.; Zhang, T.J.; Frase, H.; Parker, J.C.; Lam, D.J.

1993-01-01

Epitaxial thin films of TiO 2 and VO 2 single layers and TiO 2 /VO 2 multilayers were grown on (11 bar 20) sapphire (α-Al 2 O 3 ) substrates using the metalorganic chemical vapor deposition technique and were characterized using Raman scattering and four x-ray diffractometry. X-ray diffraction results indicate that the films are high quality single crystal material with well defined growth plane and small in-plane and out-of-plane mosaic. Single-layer films are shown to obey the Raman selection rules of TiO 2 and VO 2 single crystals. The close adherence to the Raman selection rules indicates the high degree of orientation of the films, both parallel and perpendicular to the growth plane. Selection rule spectra of two and three layer TiO 2 /VO 2 multilayers are dominated by the VO 2 layers with only minimal signature of the TiO 2 layers. Due to the low band gap of semiconducting vanadium dioxide, we attribute the strong signature of the VO 2 layers to resonant enhancement of the VO 2 Raman component accompanied with absorption of the both the incident and scattered laser light from the TiO 2 layers

Light scattering at the semiconductor-metal phase transition in vanadium dioxide

International Nuclear Information System (INIS)

Valiev, K.A.; Mokerov, V.G.; Sarajkin, V.V.; Petrova, A.G.

1977-01-01

The temperature dependence of optical properties has been investigated of vanadium dioxide thin monocrystals at the phase transition (PT) semiconductor-metal. It is established, that the anomaly arising herein is caused by the light scattering effect. As a result of the study of the scattered light intensity angle distribution and direct investigation of the samples the picture of optical heterogeneities responsible for the given scattering is determined into the polarization optical microscope. It is shown that these heterogeneities are due to the VO 2 two phases co-existence in the PT range and the light scattering effect is caused by the substantial difference of their optical constants, i.e. represents the so-called ''transition'' opalescence. At the PT investigation within the limits of the separate embrios of the new phase it has been found, that the PT temperature in various embrios is different. This is used to explain the PT temperature ''washing out'' in the investigated samples. It is supposed, that formation of the new phase is caused by the presence of elastic stress fields, arising close to the defects

Raman and XPS characterization of vanadium oxide thin films with temperature

Energy Technology Data Exchange (ETDEWEB)

Ureña-Begara, Ferran, E-mail: ferran.urena@uclouvain.be [Université catholique de Louvain, Institute of Information and Communication Technologies, Electronics and Applied Mathematics (ICTEAM), Louvain-la-Neuve (Belgium); Crunteanu, Aurelian [XLIM Research Institute, UMR 7252, CNRS/Université de Limoges, Limoges (France); Raskin, Jean-Pierre [Université catholique de Louvain, Institute of Information and Communication Technologies, Electronics and Applied Mathematics (ICTEAM), Louvain-la-Neuve (Belgium)

2017-05-01

Highlights: • Comprehensive study of the oxidation of VO{sub 2} thin films from R.T. up to 550 °C. • Phase changes and mixed-valence vanadium oxides formed during the oxidation process. • Reported Raman and XPS signatures for each vanadium oxide. • Monitoring of the current and resistance evolution at the surface of the films. • Oxidation model describing the evolution of the vanadium oxides and phase changes. - Abstract: The oxidation mechanisms and the numerous phase transitions undergone by VO{sub 2} thin films deposited on SiO{sub 2}/Si and Al{sub 2}O{sub 3} substrates when heated from room temperature (R.T.) up to 550 °C in air are investigated by Raman and X-ray photoelectron spectroscopy. The results show that the films undergo several intermediate phase transitions between the initial VO{sub 2} monoclinic phase at R.T. and the final V{sub 2}O{sub 5} phase at 550 °C. The information about these intermediate phase transitions is scarce and their identification is important since they are often found during the synthesis of vanadium dioxide films. Significant changes in the film conductivity have also been observed to occur associated to the phase transitions. In this work, current and resistance measurements performed on the surface of the films are implemented in parallel with the Raman measurements to correlate the different phases with the conductivity of the films. A model to explain the oxidation mechanisms and phenomena occurring during the oxidation of the films is proposed. Peak frequencies, full-width half-maxima, binding energies and oxidation states from the Raman and X-ray photoelectron spectroscopy experiments are reported and analyzed for all the phases encountered in VO{sub 2} films prepared on SiO{sub 2}/Si and Al{sub 2}O{sub 3} substrates.

Wet-etching induced abnormal phase transition in highly strained VO{sub 2}/TiO{sub 2} (001) epitaxial film

Energy Technology Data Exchange (ETDEWEB)

Ren, Hui; Chen, Shi; Chen, Yuliang; Luo, Zhenlin; Zhou, Jingtian; Zheng, Xusheng; Wang, Liangxin; Li, Bowen; Zou, Chongwen [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei (China)

2018-01-15

The metal-insulator transition (MIT) behavior in vanadium dioxide (VO{sub 2}) epitaxial film is known to be dramatically affected by interfacial stress due to lattice mismatching. For the VO{sub 2}/TiO{sub 2} (001) system, there exists a considerable strain in ultra-thin VO{sub 2} thin film, which shows a lower T{sub c} value close to room temperature. As the VO{sub 2} epitaxial film grows thicker layer-by-layer along the ''bottom-up'' route, the strain will be gradually relaxed and T{sub c} will increase as well, until the MIT behavior becomes the same as that of bulk material with a T{sub c} of about 68 C. Whereas, in this study, we find that the VO{sub 2}/TiO{sub 2} (001) film thinned by ''top-down'' wet-etching shows an abnormal variation in MIT, which accompanies the potential relaxation of film strain with thinning. It is observed that even when the strained VO{sub 2} film is etched up to several nanometers, the MIT persists, and T{sub c} will increase up to that of bulk material, showing the trend to a stress-free ultra-thin VO{sub 2} film. The current findings demonstrate a facial chemical-etching way to change interfacial strain and modulate the phase transition behavior of ultrathinVO{sub 2} films, which can also be applied to other strained oxide films. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Hydrothermal Synthesis of VO2 Polymorphs: Advantages, Challenges and Prospects for the Application of Energy Efficient Smart Windows.

Science.gov (United States)

Li, Ming; Magdassi, Shlomo; Gao, Yanfeng; Long, Yi

2017-09-01

Vanadium dioxide (VO 2 ) is a widely studied inorganic phase change material, which has a reversible phase transition from semiconducting monoclinic to metallic rutile phase at a critical temperature of τ c ≈ 68 °C. The abrupt decrease of infrared transmittance in the metallic phase makes VO 2 a potential candidate for thermochromic energy efficient windows to cut down building energy consumption. However, there are three long-standing issues that hindered its application in energy efficient windows: high τ c , low luminous transmittance (T lum ), and undesirable solar modulation ability (ΔT sol ). Many approaches, including nano-thermochromism, porous films, biomimetic surface reconstruction, gridded structures, antireflective overcoatings, etc, have been proposed to tackle these issues. The first approach-nano-thermochromism-which is to integrate VO 2 nanoparticles in a transparent matrix, outperforms the rest; while the thermochromic performance is determined by particle size, stoichiometry, and crystallinity. A hydrothermal method is the most common method to fabricate high-quality VO 2 nanoparticles, and has its own advantages of large-scale synthesis and precise phase control of VO 2 . This Review focuses on hydrothermal synthesis, physical properties of VO 2 polymorphs, and their transformation to thermochromic VO 2 (M), and discusses the advantages, challenges, and prospects of VO 2 (M) in energy-efficient smart windows application. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal radiative near field transport between vanadium dioxide and silicon oxide across the metal insulator transition

Energy Technology Data Exchange (ETDEWEB)

Menges, F.; Spieser, M.; Riel, H.; Gotsmann, B., E-mail: bgo@zurich.ibm.com [IBM Research-Zurich, Säumerstrasse 4, CH-8803 Rüschlikon (Switzerland); Dittberner, M. [IBM Research-Zurich, Säumerstrasse 4, CH-8803 Rüschlikon (Switzerland); Photonics Laboratory, ETH Zurich, 8093 Zurich (Switzerland); Novotny, L. [Photonics Laboratory, ETH Zurich, 8093 Zurich (Switzerland); Passarello, D.; Parkin, S. S. P. [IBM Almaden Research Center, 650 Harry Road, San Jose, California 95120 (United States)

2016-04-25

The thermal radiative near field transport between vanadium dioxide and silicon oxide at submicron distances is expected to exhibit a strong dependence on the state of vanadium dioxide which undergoes a metal-insulator transition near room temperature. We report the measurement of near field thermal transport between a heated silicon oxide micro-sphere and a vanadium dioxide thin film on a titanium oxide (rutile) substrate. The temperatures of the 15 nm vanadium dioxide thin film varied to be below and above the metal-insulator-transition, and the sphere temperatures were varied in a range between 100 and 200 °C. The measurements were performed using a vacuum-based scanning thermal microscope with a cantilevered resistive thermal sensor. We observe a thermal conductivity per unit area between the sphere and the film with a distance dependence following a power law trend and a conductance contrast larger than 2 for the two different phase states of the film.

Light-induced ultrafast phase transitions in VO2 thin film

International Nuclear Information System (INIS)

Lysenko, S.; Rua, A.J.; Vikhnin, V.; Jimenez, J.; Fernandez, F.; Liu, H.

2006-01-01

Vanadium dioxide shows a passive and reversible change from a monoclinic insulator phase to a metallic tetragonal rutile structure when the sample temperature is close to and over 68 deg. C. As a kind of functional material, VO 2 thin films deposited on fused quartz substrates were successfully prepared by the pulsed laser deposition (PLD) technique. With laser illumination at 400 nm on the obtained films, the phase transition (PT) occurred. The observed light-induced PT was as fast as the laser pulse duration of 100 fs. Using a femtosecond laser system, the relaxation processes in VO 2 were studied by optical pump-probe spectroscopy. Upon a laser excitation an instantaneous response in the transient reflectivity and transmission was observed followed by a relatively longer relaxation process. The alteration is dependent on pump power. The change in reflectance reached a maximum value at a pump pulse energy between 7 and 14 mJ/cm 2 . The observed PT is associated with the optical interband transition in VO 2 thin film. It suggests that with a pump laser illuminating on the film, excitation from the d θ,ε - state of valence band to the unoccupied excited mixed d θ,ε -π* - state of the conduction band in the insulator phase occurs, followed by a resonant transition to an unoccupied excited mixed d θ,ε -π* - state of the metallic phase band

Invited Article: An active terahertz polarization converter employing vanadium dioxide and a metal wire grating in total internal reflection geometry

Science.gov (United States)

Liu, Xudong; Chen, Xuequan; Parrott, Edward P. J.; Han, Chunrui; Humbert, Georges; Crunteanu, Aurelian; Pickwell-MacPherson, Emma

2018-05-01

Active broadband terahertz (THz) polarization manipulation devices are challenging to realize, but also of great demand in broadband terahertz systems. Vanadium dioxide (VO2) shows a promising phase transition for active control of THz waves and provides broadband polarization characteristics when integrated within grating-type structures. We creatively combine a VO2-based grating structure with a total internal reflection (TIR) geometry providing a novel interaction mechanism between the electromagnetic waves and the device, to realize a powerful active broadband THz polarization-controlling device. The device is based on a Si-substrate coated with a VO2 layer and a metal grating structure on top, attached to a prism for generating the TIR condition on the Si-VO2-grating interface. The grating is connected to electrodes for electrically switching the VO2 between its insulating and conducting phases. By properly selecting the incident angle of the THz waves, the grating direction, and the incident polarization state, we first achieved a broadband intensity modulator under a fused silica prism with an average modulation depth of 99.75% in the 0.2-1.1 THz region. Additionally, we realized an active ultra-broadband quarter-wave converter under a Si prism that can be switched between a 45° linear rotator and a quarter wave converter in the 0.8-1.5 THz region. This is the first demonstration of an active quarter-wave converter with ultra-broad bandwidth performance. Our work shows a highly flexible and multifunctional polarization-controlling device for broadband THz applications.

Bidirectional current triggering in planar devices based on serially connected VO2 thin films using 965 nm laser diode.

Science.gov (United States)

Kim, Jihoon; Park, Kyongsoo; Kim, Bong-Jun; Lee, Yong Wook

2016-08-08

By incorporating a 965 nm laser diode, the bidirectional current triggering of up to 30 mA was demonstrated in a two-terminal planar device based on serially connected vanadium dioxide (VO2) thin films grown by pulsed laser deposition. The bidirectional current triggering was realized by using the focused beams of laser pulses through the photo-thermally induced phase transition of VO2. The transient responses of laser-triggered currents were also investigated when laser pulses excited the device at a variety of pulse widths and repetition rates of up to 4.0 Hz. A switching contrast between off- and on-state currents was obtained as ~8333, and rising and falling times were measured as ~39 and ~29 ms, respectively, for 50 ms laser pulses.

The acidic transformed nano-VO2 causes macrophage cell death by the induction of lysosomal membrane permeabilization and Ca2+ efflux

Directory of Open Access Journals (Sweden)

Shaohai Xu

2015-01-01

Full Text Available Because of its outstanding thermochromic characteristics and metal-insulator transition (MIT property, nano-vanadium dioxide (abbreviated as nano-VO2 or nVO2 has been applied widely in electrical/optical devices and design of intelligent window. However, the biological effect of nVO2 is not well understood, especially when affected by environmental factors or living organisms. For VO2 is an amphoteric oxide, we simulated pH's influence to nVO2’s physicochemical properties by exposure nVO2 in water of different pH values. We found that nVO2 transformed to a new product after exposure in acidic water for two weeks, as revealed by physicochemical characterization such as SEM, TEM, XRD, and DLS. This transformation product formed in acidic water was referred as (acidic transformed nVO2. Both pristine/untransformed and transformed nVO2 displayed no obvious toxicity to common epithelial cells; however, the acidic transformed nVO2 rapidly induced macrophage cell death. Further investigation demonstrated that transformed nVO2 caused macrophage apoptosis by the induction of Ca2+ efflux and the following mitochondrial membrane permeabilization (MMP process. And a more detailed time course study indicated that transformed nVO2 caused lysosomal membrane permeabilization (LMP at the earlier stage, indicating LMP could be chosen as an earlier and sensitive end point for nanotoxicological study. We conclude that although nVO2 displays no acute toxicity, its acidic transformation product induces macrophage apoptosis by the induction of LMP and Ca2+ efflux. This report suggests that the interplay with environmental factors or living organisms can results in physicochemical transformation of nanomaterials and the ensuing distinctive biological effects.

C=C bond cleavage on neutral VO3(V2O5)n clusters.

Science.gov (United States)

Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

2009-01-28

The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

Vaporization study on vanadium monoxide and two-phase mixture of vanadium and vanadium monoxide by mass-spectrometric method

International Nuclear Information System (INIS)

Banchorndhevakul, W.; Matsui, Tsuneo; Naito, Keiji

1986-01-01

The vapor pressures over single phase vanadium monoxide VO 1.022 (s) and the two-phase mixture of vanadium metal (β phase) and vanadium monoxide were measured by mass-spectrometric method in the temperature range of 1,803 ∼ 1,990 and 1,703 ∼ 1,884 K, respectively. The main gas species over both systems were found to be VO(g) and V(g). The vapor pressure of VO(g) over the two-phase mixture of V(s) and VO(s) was a little lower than that over single phase VO(s). The vapor pressure of V(g) over the two-phase mixture was nearly equal to that over single phase. From the vapor pressure data, the enthalpies of vaporization, the enthalpies of formation for VO(g) and V(g) and the dissociation energy of VO(g) were determined. The oxygen partial pressure was calculated as a function of temperature from the vapor pressures of VO(g) and V(g), from which the partial molar enthalpies and entropies of oxygen in both systems were obtained. (author)

Van der Waals MoS2/VO2 heterostructure junction with tunable rectifier behavior and efficient photoresponse.

Science.gov (United States)

Oliva, Nicoló; Casu, Emanuele Andrea; Yan, Chen; Krammer, Anna; Rosca, Teodor; Magrez, Arnaud; Stolichnov, Igor; Schueler, Andreas; Martin, Olivier J F; Ionescu, Adrian Mihai

2017-10-27

Junctions between n-type semiconductors of different electron affinity show rectification if the junction is abrupt enough. With the advent of 2D materials, we are able to realize thin van der Waals (vdW) heterostructures based on a large diversity of materials. In parallel, strongly correlated functional oxides have emerged, having the ability to show reversible insulator-to-metal (IMT) phase transition by collapsing their electronic bandgap under a certain external stimulus. Here, we report for the first time the electronic and optoelectronic characterization of ultra-thin n-n heterojunctions fabricated using deterministic assembly of multilayer molybdenum disulphide (MoS 2 ) on a phase transition material, vanadium dioxide (VO 2 ). The vdW MoS 2 /VO 2 heterojunction combines the excellent blocking capability of an n-n junction with a high conductivity in on-state, and it can be turned into a Schottky rectifier at high applied voltage or at temperatures higher than 68 °C, exploiting the metal state of VO 2 . We report tunable diode-like current rectification with a good diode ideality factor of 1.75 and excellent conductance swing of 120 mV/dec. Finally, we demonstrate unique tunable photosensitivity and excellent junction photoresponse in the 500/650 nm wavelength range.

Preparation, Characterization and Thermo-Chromic Properties of EVA/VO2 Laminate Films for Smart Window Applications and Energy Efficiency in Building

Directory of Open Access Journals (Sweden)

Onruthai Srirodpai

2017-01-01

Full Text Available Thermochromic films based on vanadium dioxide (VO2/ethylene vinyl acetate copolymer (EVA composite were developed. The monoclinic VO2 particles was firstly prepared via hydrothermal and calcination processes. The effects of hydrothermal time and tungsten doping agent on crystal structure and morphology of the calcined metal oxides were reported. After that, 1 wt % of the prepared VO2 powder was mixed with EVA compound, using two different mixing processes. It was found that mechanical properties of the EVA/VO2 films prepared by the melt process were superior to those of which prepared by the solution process. On the other hand, percentage visible light transmittance of the solution casted EVA/VO2 film was greater than that of the melt processed composite film. This was related to the different gel content of EVA rubber and state of dispersion and distribution of VO2 within the polymer matrix phase. Thermochromic behaviors and heat reflectance of the EVA/VO2 film were also verified. In overall, this study demonstrated that it was possible to develop a thermochromic film using the polymer composite approach. In this regard, the mixing condition was found to be one of the most important factors affecting morphology and thermo-mechanical properties of the films.

Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO2 Nanowires.

Science.gov (United States)

Asayesh-Ardakani, Hasti; Nie, Anmin; Marley, Peter M; Zhu, Yihan; Phillips, Patrick J; Singh, Sujay; Mashayek, Farzad; Sambandamurthy, Ganapathy; Low, Ke-Bin; Klie, Robert F; Banerjee, Sarbajit; Odegard, Gregory M; Shahbazian-Yassar, Reza

2015-11-11

There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO2) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO2 are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WxV1-xO2 nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122̅) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO2 structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

Vanadium oxide (VO) based low cost counter electrode in dye sensitized solar cell (DSSC) applications

Energy Technology Data Exchange (ETDEWEB)

Vijayakumar, P.; Pandian, Muthu Senthil; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in [SSN Research Centre, SSN College of Engineering, Kalavakkam-603 110, Chennai, Tamilnadu (India)

2015-06-24

Vanadium oxide nanostars were synthesized by chemical method. The prepared Vanadium oxide nanostars are introduced into dye sensitized solar cell (DSSC) as counter electrode (CE) catalyst to replace the expensive platinum (Pt). The products were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller (BET) method. The photovoltaic performance of the VO as counter electrode based DSSC was evaluated under simulated standard global AM 1.5G sunlight (100 mW/cm{sup 2}). The solar to electrical energy conversion efficiency (η) of the DSSC was found to be 0.38%.This work expands the Counter electrode catalyst, which can help to reduce the cost of DSSC and thereby encourage their fundamental research and commercial application.

Microstructure and thermochromic properties of VO{sub X}-WO{sub X}-VO{sub X} ceramic thin films

Energy Technology Data Exchange (ETDEWEB)

Khamseh, S.; Ghahari, M. [Institute for Color Science and Technology, Department of Nanomaterial and Nanocoatings, Tehran (Iran, Islamic Republic of); Araghi, H. [Islamic Azad University, Department of Materials Engineering, Science and Research Branch, Tehran (Iran, Islamic Republic of); Faghihi Sani, M.A. [Sharif University of Technology, Department of Materials Science and Engineering, Tehran (Iran, Islamic Republic of)

2016-03-15

W-doped VO{sub 2} films have been synthesized via oxygen annealing of V-W-V (vanadium-tungsten-vanadium) multilayered films. The effects of middle layer's thickness of V-W-V multilayered film on structure and properties of VO{sub X}-WO{sub X}-VO{sub X} ceramic thin films were investigated. The as-deposited V-W-V multilayered film showed amorphous-like structure when mixed structure of VO{sub 2} (M) and VO{sub 2} (B) was formed in VO{sub X}-WO{sub X}-VO{sub X} ceramic thin films. Tungsten content of VO{sub X}-WO{sub X}-VO{sub X} ceramic thin films increased with increasing middle layer's thickness. With increasing middle layer's thickness, room temperature square resistance (R{sub sq}) of VO{sub X}-WO{sub X}-VO{sub X} ceramic thin films increased from 65 to 86 kΩ/sq. The VO{sub X}-WO{sub X}-VO{sub X} ceramic thin film with the thinnest middle layer showed significant SMT (semiconductor-metal transition) when SMT became negligible on increasing middle layer's thickness. (orig.)

Crystal structure of ferroelectric Bi{sub 2}VO{sub 5.5}

Energy Technology Data Exchange (ETDEWEB)

Sooryanarayana, K.; Guru Row, T.N.; Varma, K.B.R. [Indian Inst. of Science, Bangalore (India)

1997-12-01

The structure of the {alpha}-phase of bismuth vanadate Bi{sub 2}VO{sub 5.5} has been determined using single crystal X-ray diffraction data in the space group Aba2. The refinement involves a well defined disorder at the vanadium site, which incorporates the features of the superlattice structure with vanadium tetrahedra and oxygen-deficient octahedra that is displaced about the twofold axis.

Synthesis of sub-10 nm VO2 nanoparticles films with plasma-treated glass slides by aqueous sol–gel method

International Nuclear Information System (INIS)

Lan, Shi-Di; Cheng, Chih-Chia; Huang, Chi-Hsien; Chen, Jem-Kun

2015-01-01

Highlights: • Sub-10 nm VO 2 nanoparticles (VNPs) are synthesized on a plasma-treated glass. • Glass slides generate negative charges sites after plasma treatment to attract VO 2 + . • Doping tungsten with 1 wt% in VNPs did not change particle size significantly. • The particle size of VNP can be tuned by the density of negative charge sites. • Sub-10 nm structured VO 2 particle films exhibited high visible transmittance. - Abstract: This paper describes an aqueous sol–gel synthesis of thermochromic thin films consisted of vanadium dioxide nanoparticles (VNPs) on glass slides. The glass slides were treated by argon/oxygen plasma to generate dispersedly negative charge sites on the surface to attract VO 2 + from a sol–gel solution. After heat treatment in a low-pressure carbon monoxide/carbon dioxide (CO/CO 2 ) atmosphere, the VNPs could be generated in sub-10 nm of particle size on the surface. Various levels of doping were achieved by adding small quantities of a water-soluble tungsten compound to the sol; however, the particle size increased slightly with the tungsten doping levels. The change in electrical conductivity with temperature for VNP films were measured and compared to VO 2 crystalline films. VNP films exhibited the lower transition temperature of the semiconductor to metal phase change; at a doping level of 4 wt% the transition temperature was measured at 32.2 ± 1.2 and 24.1 ± 1.2 °C for the VO 2 and VNP films, respectively. The VNP films showed excellent visible transparency and a large change in transmittance at near-infrared (NIR) wavelengths before and after the metal–insulator phase transition (MIT). The current method is a landmark in the development of nanostructured material toward applications in energy-saving smart windows.

Hysteresis Phenomena in Sulfur Dioxide Oxidation over Supported Vanadium Catalysts

DEFF Research Database (Denmark)

Masters, Stephen G.; Eriksen, Kim Michael; Fehrmann, Rasmus

1997-01-01

Catalyst deactivation and hysteresis behavior in industrial SO2-oxidation catalysts have been studied in the temperature region 350-480 C by combined in situ EPR spectroscopy and catalytic activity measurements. The feed gas composition simulated sulfuric acid synthesis gas and wet/dry de......NOx'ed flue gas. The vanadium (IV) compound K4(VO)3(SO4)5 precipitated during all the investigated conditions hence causing catalyst deactivation. Hysteresis behavior of both the catalytic activity and the V(IV) content was observed during reheating....

In-Plane Impedance Spectroscopy measurements in Vanadium Dioxide thin films

Science.gov (United States)

Ramirez, Juan; Patino, Edgar; Schmidt, Rainer; Sharoni, Amos; Gomez, Maria; Schuller, Ivan

2012-02-01

In plane Impedance Spectroscopy measurements have been done in Vanadium Dioxide thin films in the range of 100 Hz to 1 MHz. Our measurements allows distinguishing between the resistive and capacitive response of the Vanadium Dioxide films across the metal-insulator transition. A non ideal RC behavior was found in our thin films from room temperature up to 334 K. Around the MIT, an increase of the total capacitance is observed. A capacitor-network model is able to reproduce the capacitance changes across the MIT. Above the MIT, the system behaves like a metal as expected, and a modified equivalent circuit is necessary to describe the impedance data adequately.

Metal-semiconductor phase transition of order arrays of VO2 nanocrystals

Science.gov (United States)

Lopez, Rene; Suh, Jae; Feldman, Leonard; Haglund, Richard

2004-03-01

The study of solid-state phase transitions at nanometer length scales provides new insights into the effects of material size on the mechanisms of structural transformations. Such research also opens the door to new applications, either because materials properties are modified as a function of particle size, or because the nanoparticles interact with a surrounding matrix material, or with each other. In this paper, we describe the formation of vanadium dioxide nanoparticles in silicon substrates by pulsed laser deposition of ion beam lithographically selected sites and thermal processing. We observe the collective behavior of 50 nm diameter VO2 oblate nanoparticles, 10 nm high, and ordered in square arrays with arbitrary lattice constant. The metal-semiconductor-transition of the VO2 precipitates shows different features in each lattice spacing substrate. The materials are characterized by electron microscopy, x-ray diffraction, Rutherford backscattering. The features of the phase transition are studied via infrared optical spectroscopy. Of particular interest are the enhanced scattering and the surface plasmon resonance when the particles reach the metallic state. This resonance amplifies the optical contrast in the range of near-infrared optical communication wavelengths and it is altered by the particle-particle coupling as in the case of noble metals. In addition the VO2 nanoparticles exhibit sharp transitions with up to 50 K of hysteresis, one of the largest values ever reported for this transition. The optical properties of the VO2 nanoarrays are correlated with the size of the precipitates and their inter-particle distance. Nonlinear and ultra fast optical measurements have shown that the transition is the fastest known solid-solid transformation. The VO2 nanoparticles show the same bulk property, transforming in times shorter than 150 fs. This makes them remarkable candidates for ultrafast optical and electronic switching applications.

Accuracy of ab initio electron correlation and electron densities in vanadium dioxide

Science.gov (United States)

Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan; Heinonen, Olle; Kent, Paul R. C.; Krogel, Jaron T.

2017-11-01

Diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3 d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et al. [Science 355, 371 (2017), 10.1126/science.aag0410] in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VO2, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development. With our reference data, the accuracy of both the energy and the electron density can be monitored simultaneously, which is useful for functional development. So far, this kind of detailed high accuracy reference data for correlated materials has been absent from the literature.

Synthesis of sub-10 nm VO{sub 2} nanoparticles films with plasma-treated glass slides by aqueous sol–gel method

Energy Technology Data Exchange (ETDEWEB)

Lan, Shi-Di [Department of Materials Science and Engineering, National Taiwan University of Science and Technology, 43, Sec. 4, Keelung Rd, Taipei 106, Taiwan, ROC (China); Cheng, Chih-Chia [Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei, Taiwan (China); Huang, Chi-Hsien [Department of Materials Engineering, Ming Chi University of Technology, 84 Gungjuan Road, Taishan Dist., New Taipei City 24301, Taiwan (China); Chen, Jem-Kun, E-mail: jkchen@mail.ntust.edu.tw [Department of Materials Science and Engineering, National Taiwan University of Science and Technology, 43, Sec. 4, Keelung Rd, Taipei 106, Taiwan, ROC (China)

2015-12-01

Highlights: • Sub-10 nm VO{sub 2} nanoparticles (VNPs) are synthesized on a plasma-treated glass. • Glass slides generate negative charges sites after plasma treatment to attract VO{sub 2}{sup +}. • Doping tungsten with 1 wt% in VNPs did not change particle size significantly. • The particle size of VNP can be tuned by the density of negative charge sites. • Sub-10 nm structured VO{sub 2} particle films exhibited high visible transmittance. - Abstract: This paper describes an aqueous sol–gel synthesis of thermochromic thin films consisted of vanadium dioxide nanoparticles (VNPs) on glass slides. The glass slides were treated by argon/oxygen plasma to generate dispersedly negative charge sites on the surface to attract VO{sub 2}{sup +} from a sol–gel solution. After heat treatment in a low-pressure carbon monoxide/carbon dioxide (CO/CO{sub 2}) atmosphere, the VNPs could be generated in sub-10 nm of particle size on the surface. Various levels of doping were achieved by adding small quantities of a water-soluble tungsten compound to the sol; however, the particle size increased slightly with the tungsten doping levels. The change in electrical conductivity with temperature for VNP films were measured and compared to VO{sub 2} crystalline films. VNP films exhibited the lower transition temperature of the semiconductor to metal phase change; at a doping level of 4 wt% the transition temperature was measured at 32.2 ± 1.2 and 24.1 ± 1.2 °C for the VO{sub 2} and VNP films, respectively. The VNP films showed excellent visible transparency and a large change in transmittance at near-infrared (NIR) wavelengths before and after the metal–insulator phase transition (MIT). The current method is a landmark in the development of nanostructured material toward applications in energy-saving smart windows.

VO2 Thermochromic Films on Quartz Glass Substrate Grown by RF-Plasma-Assisted Oxide Molecular Beam Epitaxy

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Dong Zhang

2017-03-01

Full Text Available Vanadium dioxide (VO2 thermochromic thin films with various thicknesses were grown on quartz glass substrates by radio frequency (RF-plasma assisted oxide molecular beam epitaxy (O-MBE. The crystal structure, morphology and chemical stoichiometry were investigated systemically by X-ray diffraction (XRD, atomic force microscopy (AFM, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS analyses. An excellent reversible metal-to-insulator transition (MIT characteristics accompanied by an abrupt change in both electrical resistivity and optical infrared (IR transmittance was observed from the optimized sample. Remarkably, the transition temperature (TMIT deduced from the resistivity-temperature curve was reasonably consistent with that obtained from the temperature-dependent IR transmittance. Based on Raman measurement and XPS analyses, the observations were interpreted in terms of residual stresses and chemical stoichiometry. This achievement will be of great benefit for practical application of VO2-based smart windows.

Voltage- and current-activated metal–insulator transition in VO2-based electrical switches: a lifetime operation analysis

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Aurelian Crunteanu, Julien Givernaud, Jonathan Leroy, David Mardivirin, Corinne Champeaux, Jean-Christophe Orlianges, Alain Catherinot and Pierre Blondy

2010-01-01

Full Text Available Vanadium dioxide is an intensively studied material that undergoes a temperature-induced metal–insulator phase transition accompanied by a large change in electrical resistivity. Electrical switches based on this material show promising properties in terms of speed and broadband operation. The exploration of the failure behavior and reliability of such devices is very important in view of their integration in practical electronic circuits. We performed systematic lifetime investigations of two-terminal switches based on the electrical activation of the metal–insulator transition in VO2 thin films. The devices were integrated in coplanar microwave waveguides (CPWs in series configuration. We detected the evolution of a 10 GHz microwave signal transmitted through the CPW, modulated by the activation of the VO2 switches in both voltage- and current-controlled modes. We demonstrated enhanced lifetime operation of current-controlled VO2-based switching (more than 260 million cycles without failure compared with the voltage-activated mode (breakdown at around 16 million activation cycles. The evolution of the electrical self-oscillations of a VO2-based switch induced in the current-operated mode is a subtle indicator of the material properties modification and can be used to monitor its behavior under various external stresses in sensor applications.

Eu-emission quenching by electron screening in VO2 thin films

International Nuclear Information System (INIS)

Liu, H.; Lysenko, S.; Rua, A.; Vikhnin, V.; Vasquez, O.; Fernandez, F.E.

2006-01-01

As a kind of phase transition functional material, Vanadium dioxide (VO 2 ) thin films deposited on fused quartz substrate were fabricated using pulsed laser deposition (PLD) technique. Europium was introduced for structure study. By laser excitation at 526 nm, VO 2 thin film undergoes a reversible and ultrafast phase transition from semiconductor to metallic state, which results in a change of optical properties. In fluorescence measurement, Eu emission was found severely quenched in all as-grown thin films. After annealing the sample in air, a red Eu-emission appeared. The emission spectrum is characterized by a pronounced twin peak, centered at 617 nm ( 5 D - 7 F 2 ), surrounded by a set of broad, but relatively weaker bands (emission from 5 D to 7 F j manifold). The emission lifetime increased when the sample annealed at higher temperature for longer time. Each spectral component is actually a doublet which is the spectral overlap of emissions from Eu 3+ situated in two sites with different configurations. One is a linear h-Eu 3+ -h, where h stands for holes. Another is a right-angle configuration of h-Eu 3+ -h with Eu 3+ in the corner. In as-grown VO 2 film, Eu 3+ ions can either substitute V 4+ , leaving a negative charge around (Eu 3+ -O) - , or substitute V 5+ , leaving two negative charges around (Eu 3+ -O) -- . Due to trapped electrons in a large radius state, it covers Eu 3+ V 4+ -V 5+ complexes. It suggests that the screening by degenerate electronic gas may result in switching off the Eu-related optical response for a wide spectral region, causing emission quenching in VO 2 films

Advancements, Challenges and Prospects of Chemical Vapour Pressure at Atmospheric Pressure on Vanadium Dioxide Structures

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Charalampos Drosos

2018-03-01

Full Text Available Vanadium (IV oxide (VO2 layers have received extensive interest for applications in smart windows to batteries and gas sensors due to the multi-phases of the oxide. Among the methods utilized for their growth, chemical vapour deposition is a technology that is proven to be industrially competitive because of its simplicity when performed at atmospheric pressure (APCVD. APCVD’s success has shown that it is possible to create tough and stable materials in which their stoichiometry may be precisely controlled. Initially, we give a brief overview of the basic processes taking place during this procedure. Then, we present recent progress on experimental procedures for isolating different polymorphs of VO2. We outline emerging techniques and processes that yield in optimum characteristics for potentially useful layers. Finally, we discuss the possibility to grow 2D VO2 by APCVD.

Effects of V2O3 buffer layers on sputtered VO2 smart windows: Improved thermochromic properties, tunable width of hysteresis loops and enhanced durability

Science.gov (United States)

Long, Shiwei; Cao, Xun; Sun, Guangyao; Li, Ning; Chang, Tianci; Shao, Zewei; Jin, Ping

2018-05-01

Vanadium dioxide (VO2) is one of the most well-known thermochromic materials, which exhibits a notable optical change from transparent to reflecting in the infrared region upon a metal-insulator phase transition. For practical applications, VO2 thin films should be in high crystalline quality to obtain a strong solar modulation ability (ΔTsol). Meanwhile, narrow hysteresis loops and robust ambient durability are also indispensable for sensitivity and long-lived utilization, respectively. In this work, a series of high-quality V2O3/VO2 bilayer structures were grown on quartz glass substrates by reactive magnetron sputtering. Basically, the bottom V2O3 acts as the buffer layer to improve the crystallinity of the top VO2, while the VO2 serves as the thermochromic layer to guarantee the solar modulation ability for energy-saving. We observed an obvious increase in ΔTsol of 76% (from 7.5% to 13.2%) for VO2 films after introducing V2O3 buffer layers. Simultaneously, a remarkable reduction by 79% (from 21.9 °C to 4.7 °C) in width of hysteresis loop was obtained when embedding 60 nm V2O3 buffer for 60 nm VO2. In addition, VO2 with non-stoichiometry of V2O3±x buffer demonstrates a broadening hysteresis loops width, which is derived from the lattice distortion caused by lattice imperfection. Finally, durability of VO2 has been significantly improved due to positive effects of V2O3 buffer layer. Our results lead to a comprehensive enhancement in crystallinity of VO2 and shed new light on the promotion of thermochromic property by homologous oxides for VO2.

One-Dimensional Vanadium Dioxide Nanostructures for Room Temperature Hydrogen Sensors

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Aline Simo

2015-06-01

Full Text Available In relation to hydrogen (H2 economy in general and gas sensing in particular, an extensive set of one dimensional (1-D nano-scaled oxide materials are being investigated as ideal candidates for potential gas sensing applications. This is correlated to their set of singular surface characteristics, shape anisotropy and readiness for integrated devices. Nanostructures of well- established gas sensing materials such as Tin Oxide (SnO2, Zinc Oxide (ZnO, Indium (III Oxide (In2O3, and Tungsten Trioxide (WO3 have shown higher sensitivity and gas selectivity, quicker response, faster time recovery, as well as an enhanced capability to detect gases at low concentrations. While the overall sensing characteristics of these so called 1-D nanomaterials are superior, they are efficient at high temperature; generally above 200 0C. This operational impediment results in device complexities in integration that limit their technological applications, specifically in their miniaturized arrangements. Unfortunately, for room temperature applications, there is a necessity to dope the above mentioned nano-scaled oxides with noble metals such as Platinum (Pt, Palladium (Pd, Gold (Au, Ruthenium (Ru. This comes at a cost. This communication reports, for the first time, on the room temperature enhanced H2 sensing properties of a specific phase of pure Vanadium Dioxide (VO2 phase A in their nanobelt form. The relatively observed large H2 room temperature sensing in this Mott type specific oxide seems to reach values as low as 14 ppm H2 which makes it an ideal gas sensing in H2 fuelled systems.

Room-temperature subnanosecond waveguide lasers in Nd:YVO4 Q-switched by phase-change VO2: A comparison with 2D materials.

Science.gov (United States)

Nie, Weijie; Li, Rang; Cheng, Chen; Chen, Yanxue; Lu, Qingming; Romero, Carolina; Vázquez de Aldana, Javier R; Hao, Xiaotao; Chen, Feng

2017-04-06

We report on room-temperature subnanosecond waveguide laser operation at 1064 nm in a Nd:YVO 4 crystal waveguide through Q-switching of phase-change nanomaterial vanadium dioxide (VO 2 ). The unique feature of VO 2 nanomaterial from the insulating to metallic phases offers low-saturation-intensity nonlinear absorptions of light for subnanosecond pulse generation. The low-loss waveguide is fabricated by using the femtosecond laser writing with depressed cladding geometry. Under optical pump at 808 nm, efficient pulsed laser has been achieved in the Nd:YVO 4 waveguide, reaching minimum pulse duration of 690 ps and maximum output average power of 66.7 mW. To compare the Q-switched laser performances by VO 2 saturable absorber with those based on two-dimensional materials, the 1064-nm laser pulses have been realized in the same waveguide platform with either graphene or transition metal dichalcogenide (in this work, WS 2 ) coated mirror. The results on 2D material Q-switched waveguide lasers have shown that the shortest pulses are with 22-ns duration, whilst the maximum output average powers reach ~161.9 mW. This work shows the obvious difference on the lasing properties based on phase-change material and 2D materials, and suggests potential applications of VO 2 as low-cost saturable absorber for subnanosecond laser generation.

Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction

Science.gov (United States)

Ge, Zhijun; Wang, Ling; He, Zhangxing; Li, Yuehua; Jiang, Yingqiao; Meng, Wei; Dai, Lei

2018-04-01

A novel strategy for improving the electro-catalytic properties of graphite felt (GF) electrode in vanadium redox flow battery (VRFB) is designed by depositing cobalt phosphide (CoP) onto GF surface. The CoP powder is synthesized by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Cyclic voltammetry results confirm that the CoP-modified graphite felt (GF-CoP) electrode has excellent reversibility and electro-catalytic activity to the VO2+/VO2+ cathodic reaction compared with the pristine GF electrode. The cell using GF-CoP electrode shows apparently higher discharge capacity over that based on GF electrode. The cell using GF-CoP electrode has the capacity of 67.2 mA h at 100 mA cm-2, 32.7 mA h larger than that using GF electrode. Compared with cell using GF electrode, the voltage efficiency of the cell based on GF-CoP electrode increases by 5.9% and energy efficiency by 5.4% at a current density of 100 mA cm-2. The cell using GF-CoP electrode can reach 94.31% capacity retention after 50 cycles at a current density of 30 mA cm-2. The results show that the CoP can effectively promote the VO2+/VO2+ redox reaction, implying that metal phosphides are a new kind of potential catalytic materials for VRFB.

X-ray absorption spectroscopy of single-crystalline (VO)2P2O7: Electronic structure and possible exchange paths

International Nuclear Information System (INIS)

Gerhold, S.; Nu''cker, N.; Kuntscher, C. A.; Schuppler, S.; Stadler, S.; Idzerda, Y. U.; Prokofiev, A. V.; Bu''llesfeld, F.; Assmus, W.

2001-01-01

Using polarization-dependent V2p and O1s near-edge x-ray absorption spectroscopy, we studied the unoccupied electronic structure of single-crystalline (VO) 2 P 2 O 7 . It is highly anisotropic, and shows similarities to vanadium oxides like VO 2 and V 2 O 5 at the V2p edge and at the O1s threshold. The contributions from V-O and P-O orbitals could be identified. The results rule out the spin ladder model for the magnetic behavior of (VO) 2 P 2 O 7 , but are consistent with the alternating chain scenario

Size and composition-controlled fabrication of VO2 nanocrystals by terminated cluster growth

Energy Technology Data Exchange (ETDEWEB)

Anders, Andre; Slack, Jonathan

2013-05-14

A physical vapor deposition-based route for the fabrication of VO2 nanoparticles is demonstrated, consisting of reactive sputtering and vapor condensation at elevated pressures. The oxidation of vanadium atoms is an efficient heterogeneous nucleation method, leading to high nanoparticle throughtput. Fine control of the nanoparticle size and composition is obtained. Post growth annealing leads to crystalline VO2 nanoparticles with optimum thermocromic and plasmonic properties.

Sharpness and intensity modulation of the metal-insulator transition in ultrathin VO2 films by interfacial structure manipulation

Science.gov (United States)

McGee, Ryan; Goswami, Ankur; Pal, Soupitak; Schofield, Kalvin; Bukhari, Syed Asad Manzoor; Thundat, Thomas

2018-03-01

Vanadium dioxide (VO2) undergoes a structural transformation from monoclinic (insulator) to tetragonal (metallic) upon heating above 340 K, accompanied by abrupt changes to its electronic, optical, and mechanical properties. Not only is this transition scientifically intriguing, but there are also numerous applications in sensing, memory, and optoelectronics. Here we investigate the effect different substrates and the processing conditions have on the characteristics metal-insulator transition (MIT), and how the properties can be tuned for specific applications. VO2 thin films were grown on c -plane sapphire (0001) and p-type silicon by pulsed laser deposition. High-resolution x-ray diffraction along with transmission electron microscopy reveals textured epitaxial growth on sapphire by domain-matching epitaxy, while the presence of a native oxide layer on silicon prevented any preferential growth resulting in a polycrystalline film. An orientation relationship of (010)VO2|| (0001)Al 2O3 was established for VO2 grown on sapphire, while no such relationship was found for VO2 grown on silicon. Surface-energy minimization is the driving force behind grain growth, as the lowest energy VO2 plane grew on silicon, while on sapphire the desire for epitaxial growth was dominant. Polycrystallinity of films grown on silicon caused a weaker and less prominent MIT than observed on sapphire, whose MIT was higher in magnitude and steeper in slope. The position of the MIT was shown to depend on the competing effects of misfit strain and grain growth. Higher deposition temperatures caused an increase in the MIT, while compressive strain resulted in a decreased MIT.

Physicochemical properties of vanadium impregnated Al-PILCs: Effect of vanadium source

Energy Technology Data Exchange (ETDEWEB)

Balci, Suna, E-mail: sunabalci@gazi.edu.tr; Tecimer, Aylin

2015-03-01

Graphical abstract: - Highlights: • Vanadium was incorporated into Al-PILC using NaVO{sub 3} or VOSO{sub 4}·3H{sub 2}O precursors by wet impregnation, washing after wet impregnation and impregnation from solution methods. • The layered structure of the supports was retained after the vanadium incorporation. • Incorporation took place both by settling and ion exchange mechanism with the treatment VOSO{sub 4}·3H{sub 2}O precursor while settling was dominant in the use of NaVO{sub 3} precursor. • Treatment with VOSO{sub 4}·3H{sub 2}O which was acidic in solution resulted in more structural deformation. • V{sub 2}O{sub 5} and VO{sub 2} were found as the major oxide forms on the impregnated samples. Loading of vanadyl sulfate hydrate (VOSO{sub 4}·H{sub 2}O) resulted in higher V/Si ratio. Most of the vanadium was bonded in +5 oxide form. • Changes in the FTIR signals after vanadium incorporation caused by Brønsted and Lewis sites, silanol, water and vanadium vibrations were occured. • Dehydroxylation of the structure took place around 300 °C. Samples obtained by impregnation and washing after wet impregnation methods resulted in similar mass losses and the wet impregnated sample showed the highest mass loss among the impregnated samples. - Summary: Clay from the Middle Anatolian previously pillared by Al{sub 13}-Keggin ions and then calcined at 300 °C (Al-PILC) was impregnated with aqueous solutions of vanadium precursors by impregnation from solution (I), wet impregnation (WI) and washing after wet impregnation (WWI) methods. The crystal and textural properties were evaluated by X-ray powder diffraction (XRD), nitrogen sorption and transmission electron microscopy (TEM) images. Vanadium incorporation into the Al-PILC resulted decreases in the basal spacing from 1.75 nm to 1.35 nm with the preserved typical layered structure. The use of sodium metavanadate (NaVO{sub 3}) as the source and the impregnation from solution as the incorporation method

Vanadium oxide V2O5 reaction with calcium metavanadate

International Nuclear Information System (INIS)

Krasnenko, T.I.; Slobodin, B.V.; Zhilyaev, V.A.

1983-01-01

Complex physicochemical studies on the V 2 O 5 Ca(VO 3 ) 2 mixtures, annealed under different conditions, were conducted. It was established that the V 2 O 5 -Ca(VO 3 ) 2 system is characterized by the following features: defective structure of initial components, which are in equilibrium state; irreversible structural transformation without changes in the macrosymmetry (530 deg C) of calcium metavanadate, deficient in calcium and oxygen; melting of eutectic mixture of components which are in equilibrium at 616+-3 deg C; Ca(VO 3 ) 2 melting with decomposition at 775+-3 deg C. Besides this, the formation of oxide vanadium bronze of β-type calcium is possible under some conditions (narrow temperature range, certain partial oxygen pressure, etc)

Vacancy distribution in nonstoichiometric vanadium monoxide

International Nuclear Information System (INIS)

Gusev, A.I.; Davydov, D.A.; Valeeva, A.A.

2011-01-01

Graphical abstract: Display Omitted Research highlights: → A certain fraction of vanadium atoms in disordered cubic vanadium monoxide VO y and ordered tetragonal phase V 52 O 64 is located in tetrahedral positions of a basic cubic lattice. → These positions are never occupied by any atoms in other strongly nonstoichiometric carbides, nitrides and oxides. → Both disordered and ordered structures of vanadium monoxide are characterized by the presence of short-range order of displacements in the oxygen sublattice and short-range order of substitution in the metal sublattice. → The short-range order of displacement is caused by the local displacements of O atoms from V (t) atoms occupying tetrahedral positions. The short-range order of substitution appears because V (t) atoms in the tetrahedral positions are always in the environment of four vacancies □ of the vanadium sublattice. - Abstract: Structural vacancy distribution in the crystal lattice of the tetragonal V 52 O 64 superstructure which is formed on the basis of disordered superstoichiometric cubic vanadium monoxide VO y ≡V x O z is experimentally determined and the presence of significant local atomic displacements and large local microstrains in a crystal lattice of real ordered phase is established. It is shown that the relaxation of local microstrains takes place owing to the basic disordered cubic phase grain refinement and a formation of ordered phase domains. The ordered phase domains grow in the direction from the boundaries to the centre of grains of the disordered basic cubic phase. Isothermal evolution at 970 K of the average domain size in ordered VO 1.29 vanadium monoxide is established. It is shown that the short-range order presents in a metal sublattice of disordered cubic VO y vanadium monoxide. The character of the short-range order is such that vanadium atoms occupying tetrahedral positions are in the environment of four vacant sites of the vanadium sublattice. This means that the

The influence of deposition temperature on vanadium dioxide thin films microstructure and physical properties

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Velaphi Msomi

2010-10-01

Full Text Available Vanadium dioxide thin films were successfully prepared on soda lime glass substrates using the optimised conditions for r.f-inverted cylindrical magnetron sputtering. The optimised deposition parameters were fixed and then a systematic study of the effect of deposition temperature, ranging from 450 °C to 550 °C, on the microstructure of thermochromic thin films was carried out. The deposited films were found to be well crystallised, showing strong texture corresponding to the (011 plane, indicating the presence of vanadium dioxide.

Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO 2 Nanowires

KAUST Repository

Asayesh-Ardakani, Hasti

2015-10-12

There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WVO nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122¯) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO 2 Nanowires

KAUST Repository

Asayesh-Ardakani, Hasti; Nie, Anmin; Marley, Peter M.; Zhu, Yihan; Phillips, Patrick J.; Singh, Sujay; Mashayek, Farzad; Sambandamurthy, Ganapathy; Low, Ke Bin; Klie, Robert F.; Banerjee, Sarbajit; Odegard, Gregory M.; Shahbazian-Yassar, Reza

2015-01-01

There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WVO nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122¯) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

Uncommon potential hysteresis in the Li/Li2xVO(H2-xPO4)2 (0 ≤ x ≤ 2) system

International Nuclear Information System (INIS)

Dubarry, M.; Gaubicher, J.; Guyomard, D.; Wallez, G.; Quarton, M.; Baehtz, C.

2008-01-01

Physical and electrochemical investigations of vanadium phosphates, Li 2x VO(H 2-x PO 4 ) 2 (0 + /Li + ionic exchange from VO(H 2 PO 4 ) 2 to Li 2 VO(HPO 4 ) 2 leads to grain decrepitation. Further ionic exchange toward formation of Li 4 VO(PO 4 ) 2 lowers the symmetry. As inferred from potentiodynamic cycling correlated to ex situ and in situ X-ray diffraction (XRD), the system Li/Li 4 VO(PO 4 ) 2 shows several phase transformations that are associated with thermodynamical potential hysteresis that span from roughly 15 mV to more than 1.8 V. Small hysteresis are associated with topotactic reactions and with V V /V IV and V III /V II redox couples. Large potential hysteresis values (>1 V) were observed when oxidation of V III to V IV is involved

Confirmation of vanadium complex formation using electrospray mass spectrometry and determination of vanadium speciation by sample stacking capillary electrophoresis

International Nuclear Information System (INIS)

Chen Zuliang; Owens, Gary; Naidu, Ravendra

2007-01-01

Capillary zone electrophoresis (CZE) with UV detection was used to determine vanadium species. Nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA) and 2,6-pyridinedicarboxylic acid (PDCA) were investigated to determine whether these ligands formed stable anionic complexes with vanadium. Of all the ligands studied HEDTA was the most suitable ligand because it gave the largest UV response with reasonable migration time. Electrospray mass spectrometry (ES-MS) was used to confirm the formation of [VO 2 (HEDTA)] 2- and [VO(HEDTA)] 1- in solution. An electrolyte containing 25 mM phosphate, 0.25 mM tetradecyltrimethylammonium bromide (TTAB) at pH 5.5 was optimum for the separation of these anionic vanadium complexes. Sample stacking techniques, including large-volume sample stacking (LVSS) and field-amplified sample injection (FASI), were tested to improve the sensitivity. Best sensitivity was obtained using FASI, with detection limits of 0.001 μM, equivalent to 0.4 μg L -1 , for [VO 2 (HEDTA)] 2- and 0.01 μM, equivalent to 3.4 μg L -1 for [VO(HEDTA)] 1- . The utility of the method for the speciation of V(IV) and V(V) was demonstrated using ground water samples

Facile and Low-Temperature Fabrication of Thermochromic Cr2O3/VO2 Smart Coatings: Enhanced Solar Modulation Ability, High Luminous Transmittance and UV-Shielding Function.

Science.gov (United States)

Chang, Tianci; Cao, Xun; Li, Ning; Long, Shiwei; Gao, Xiang; Dedon, Liv R; Sun, Guangyao; Luo, Hongjie; Jin, Ping

2017-08-09

In the pursuit of energy efficient materials, vanadium dioxide (VO 2 ) based smart coatings have gained much attention in recent years. For smart window applications, VO 2 thin films should be fabricated at low temperature to reduce the cost in commercial fabrication and solve compatibility problems. Meanwhile, thermochromic performance with high luminous transmittance and solar modulation ability, as well as effective UV shielding function has become the most important developing strategy for ideal smart windows. In this work, facile Cr 2 O 3 /VO 2 bilayer coatings on quartz glasses were designed and fabricated by magnetron sputtering at low temperatures ranging from 250 to 350 °C as compared with typical high growth temperatures (>450 °C). The bottom Cr 2 O 3 layer not only provides a structural template for the growth of VO 2 (R), but also serves as an antireflection layer for improving the luminous transmittance. It was found that the deposition of Cr 2 O 3 layer resulted in a dramatic enhancement of the solar modulation ability (56.4%) and improvement of luminous transmittance (26.4%) when compared to single-layer VO 2 coating. According to optical measurements, the Cr 2 O 3 /VO 2 bilayer structure exhibits excellent optical performances with an enhanced solar modulation ability (ΔT sol = 12.2%) and a high luminous transmittance (T lum,lt = 46.0%), which makes a good balance between ΔT sol and T lum for smart windows applications. As for UV-shielding properties, more than 95.8% UV radiation (250-400 nm) can be blocked out by the Cr 2 O 3 /VO 2 structure. In addition, the visualized energy-efficient effect was modeled by heating a beaker of water using infrared imaging method with/without a Cr 2 O 3 /VO 2 coating glass.

Structural and Redox Properties of Vanadium Complexes in Molten Salts of Interest for the Catalytic Oxidation of Sulfur Dioxide

DEFF Research Database (Denmark)

Boghosian, S.; Chrissanthopoulos, A.; Fehrmann, Rasmus

2000-01-01

Electronic absorption (UV/VIS) spectra have been obtained at 450 degrees C from V2O5-K2S2O7 molten mixtures in SO2 ( P-SO2 = 0 - 1.2 atm) gas atmospheres. The data are in agreement with the V-V reversible arrow V-IV equilibrium: (VO)(2)O(SO4)(4)(4-)(l) + SO2(g) - 2VO(SO4)(2)(2-)(l) + SO3(g). Sulfur...... and vibrational properties of the vanadium complexes formed in the molten salt-gas system V2O5-M2S2O7-M2SO4/SO2-O-2 (M = K or Cs). The spectral features and the exploitation of the relative Raman intensities indicate that the (VO)(2)O(SO4)(4)(+) dimeric complex unit which possesses a V-O-V bridge is formed...

Controlled synthesis and electrochemical properties of vanadium oxides with different nanostructures

International Nuclear Information System (INIS)

Zhang, Yifu; Zhou, Min; Huang, Chi; Chen, Chongxue; Cao, Yuliang; Fan, Meijuan; Li, Houbin; Liu, Xinghai; Xie, Guangyong

2012-01-01

Vanadium oxides (V 3 O 7 .H 2 O and VO 2 ) with different morphologies have been selectively synthesized by a facile hydrothermal approach using glucose as the reducing and structure-directing reagent. The as-obtained V 3 O 7 .H 2 O nanobelts have a length up to several tens of micrometers, width of about 60-150 nm and thickness of about 5-10 nm, while the as-prepared VO 2 (B) nanobelts have a length of about 1.0- 7 μm, width, 80-140 nm and thickness, 2-8 nm. It was found that the quantity of glucose, the reaction temperature and the reaction time had significant influence on the compositions and morphologies of final products. Vanadium oxides with different morphologies were easily synthesized by controlling the concentration of glucose. The formation mechanism was also briefly discussed, indicating that glucose played different roles in synthesizing various vanadium oxides. The phase transition from VO 2 (B) to VO 2 (M) were investigated and the phase transition temperature of the VO 2 (M) appeared at around 68 deg C. Furthermore, the electrochemical properties of V 3 O 7 .H 2 O nanobelts, VO 2 (B) nanobelts and VO 2 (B) nanosheets were investigated and they exhibited a high initial discharge capacity of 296, 247 and 227 mAh/g, respectively. (author)

n-VO{sub 2}/p-GaN based nitride–oxide heterostructure with various thickness of VO{sub 2} layer grown by MBE

Energy Technology Data Exchange (ETDEWEB)

Wang, Minhuan [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Ministry of Education), School of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116024 (China); Bian, Jiming, E-mail: jmbian@dlut.edu.cn [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Ministry of Education), School of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116024 (China); Key Laboratory of Inorganic Coating Materials, Chinese Academy of Sciences, Shanghai 200050, China (China); Sun, Hongjun; Liu, Weifeng [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Ministry of Education), School of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116024 (China); Zhang, Yuzhi [Key Laboratory of Inorganic Coating Materials, Chinese Academy of Sciences, Shanghai 200050, China (China); Luo, Yingmin [Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Ministry of Education), School of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116024 (China)

2016-12-15

Graphical abstract: The significant influences of VO{sub 2} layer thickness on the structural, electrical and contact properties of the n-VO{sub 2}/p-GaN based nitride-oxide heterostructure were investigated systemically. - Highlights: • High quality VO{sub 2} films with precisely controlled thickness were grown on p-GaN/sapphire substrates by oxide molecular beam epitaxy (O-MBE). • A distinct reversible SMT phase transition was observed for the n-VO{sub 2}/p-GaN based nitride-oxide heterostructure. • The clear rectifying transport characteristics originated from the n-VO{sub 2}/p-GaN interface were demonstrated before and after SMT of the VO{sub 2} over layer. • The XPS analyses confirmed the valence state of V in VO{sub 2} films was principally composed of V{sup 4+} with trace amount of V{sup 5+}. • The design and modulation of the n-VO{sub 2}/p-GaN based heterostructure devices will benefit significantly from these achievements. - Abstract: High quality VO{sub 2} films with precisely controlled thickness were grown on p-GaN/sapphire substrates by oxide molecular beam epitaxy (O-MBE). Results indicated that a distinct reversible semiconductor-to-metal (SMT) phase transition was observed for all the samples in the temperature dependent electrical resistance measurement, and the influence of VO{sub 2} layer thickness on the SMT properties of the as-grown n-VO{sub 2}/p-GaN based nitride-oxide heterostructure was investigated. Meanwhile, the clear rectifying transport characteristics originated from the n-VO{sub 2}/p-GaN interface were demonstrated before and after SMT of the VO{sub 2} over layer, which were attributed to the p-n junction behavior and Schottky contact character, respectively. Moreover, the X-ray photoelectron spectroscopy (XPS) analyses confirmed the valence state of vanadium (V) in VO{sub 2} films was principally composed of V{sup 4+} with trace amount of V{sup 5+}. The design and modulation of the n-VO{sub 2}/p-GaN based heterostructure

Oxygen source-oriented control of atmospheric pressure chemical vapor deposition of VO2 for capacitive applications

Directory of Open Access Journals (Sweden)

Dimitra Vernardou

2016-06-01

Full Text Available Vanadium dioxides of different crystalline orientation planes have successfully been fabricated by chemical vapor deposition at atmospheric pressure using propanol, ethanol and O2 gas as oxygen sources. The thick a-axis textured monoclinic vanadium dioxide obtained through propanol presented the best electrochemical response in terms of the highest specific discharge capacity of 459 mAh g-1 with a capacitance retention of 97 % after 1000 scans under constant specific current of 2 A g-1. Finally, the electrochemical impedance spectroscopy indicated that the charge transfer of Li+ through the vanadium dioxide / electrolyte interface was easier for this sample enhancing significantly its capacitance performance.

A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries

Science.gov (United States)

Intan, Nadia N.; Klyukin, Konstantin; Zimudzi, Tawanda J.; Hickner, Michael A.; Alexandrov, Vitaly

2018-01-01

Vanadium redox flow batteries (VRFBs) are a promising solution for large-scale energy storage, but a number of problems still impede the deployment of long-lifetime VRFBs. One important aspect of efficient operation of VRFBs is understanding interactions between vanadium species and the membrane. Herein, we investigate the interactions between all four vanadium cations and Nafion membrane by a combination of infrared (IR) spectroscopy and density-functional-theory (DFT)-based static and molecular dynamics simulations. It is observed that vanadium species primarily lead to changes in the IR spectrum of Nafion in the SO3- spectral region which is attributed to the interaction between vanadium species and the SO3- exchange sites. DFT calculations of vanadium -Nafion complexes in the gas phase show that it is thermodynamically favorable for all vanadium cations to bind to SO3- via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that V2+ and V3+ species coordinate spontaneously to SO3-, which is not the case for VO2+ and VO2+ . The interaction behavior of the uncycled membrane determined in this study is used to explain the experimentally observed changes in the vibrational spectra, and is discussed in light of previous results on device-cycled membranes.

Speciation in the aqueous H+/H2VO4-/H2O2/citrate system of biomedical interest.

Science.gov (United States)

Gorzsás, András; Getty, Kendra; Andersson, Ingegärd; Pettersson, Lage

2004-09-21

The speciation in the quaternary aqueous H+/H2VO4-/H2O2/citrate (Cit3-) and H+/H2VO4-/Cit3-/L-(+)-lactate (Lac-) systems has been determined at 25 degrees C in the physiological medium of 0.150 M Na(Cl). A combination of 51V NMR integral intensities and chemical shift (Bruker AMX500) as well as potentiometric data (glass electrode) have been collected and evaluated with the computer program LAKE, which is able to treat multimethod data simultaneously. The pKa-values for citric acid have been determined as 2.94, 4.34 and 5.61. Altogether six vanadate-citrate species have been found in the ternary H+/H2VO4-/Cit3- system in the pH region 2-10, only two of which are mononuclear. Reduction of vanadium(V) becomes more pronounced at pH acidic solutions limited the final model to pH > 4. In the quaternary H+/H2VO4-/Cit3-/Lac- system, two mixed-ligand species have been determined, with the compositions V2CitLac2- and V2CitLac3- (pKa = 5.0). To our knowledge, this is the first time such complexes have been reported for vanadium(V). 51V NMR chemical shifts, compositions and formation constants are given, and equilibrium conditions are illustrated in distribution diagrams as well as the fit of the model to the experimental data. When suitable, structural proposals are given, based on 13C NMR measurements and available literature data of related compounds.

Fabrication and electrical resistivity of Mo-doped VO2 thin films coated on graphite conductive plates by a sol-gel method

Energy Technology Data Exchange (ETDEWEB)

Choi, W.; Jung, H.M.; Um, S. [Hanyang Univ., Seoul (Korea, Republic of). School of Mechanical Engineering

2008-07-01

Vanadium oxides (VO2) can be used in optical devices, thermochromic smart windows and sensors. This paper reported on a study in which vanadium pentoxide (V2O5) powder was prepared and mixed with Molybdenum Oxides (MoO3) to form Mo-doped and -undoped VO2 thin films by a sol-gel method on graphite conductive substrates. The micro-structure and chemical compositions of the Mo-doped and -undoped VO2 thin films was investigated using X-Ray diffraction and scanning electron microscopy. Changes in electrical resistivity were measured as a function of the stoichiometric compositions between vanadium and molybdenum. In this study. Mo-doped and -undoped VO2 thin films showed the typical metal to insulator transition (MIT), where temperature range could be adjusted by modifying the dopant atomic ratio. The through-plane substrate structure of the Mo-doped layer influences the electrical resistivity of the graphite substrate. As the amount of the molybdenum increases, the electrical resistivity of the graphite conductive substrate decreases in the lower temperature range below the freezing point of water. The experimental results showed that if carefully controlled, thermal dissipation of VO2 thin films can be used as a self-heating source to melt frozen water with the electrical current flowing through the graphite substrate. 3 refs., 3 figs.

Femtosecond Near Edge X-ray Absorption Measurement of the VO2 Phase Transition

International Nuclear Information System (INIS)

Cavalleri, A.; Chong, H.H.W.; Fourmaux, S.; Glover, T.E.; Heimann, P.A; Kieffer, J.C.; Padmore, H.A.; Schoenlein, R.W.

2004-01-01

The authors measure the insulator-to-metal transition in VO 2 using femtosecond Near-Edge X-ray Absorption. Sliced pulses of synchrotron radiation are used to detect the photo-induced dynamics at the 516-eV Vanadium L 3 edge

Confirmation of vanadium complex formation using electrospray mass spectrometry and determination of vanadium speciation by sample stacking capillary electrophoresis

Energy Technology Data Exchange (ETDEWEB)

Chen Zuliang [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia)]. E-mail: zuliang.chen@unisa.edu.au; Owens, Gary [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia); Naidu, Ravendra [Centre for Environmental Risk Assessment and Remediation, University of South Australia, Mawson Lakes, SA 5095 (Australia); CRC for Contamination Assessment and Remediation of Environments, Mawson Lakes Boulevard, Mawson Lakes, SA 5095 (Australia)

2007-02-28

Capillary zone electrophoresis (CZE) with UV detection was used to determine vanadium species. Nitrilotriacetic acid (NTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA) and 2,6-pyridinedicarboxylic acid (PDCA) were investigated to determine whether these ligands formed stable anionic complexes with vanadium. Of all the ligands studied HEDTA was the most suitable ligand because it gave the largest UV response with reasonable migration time. Electrospray mass spectrometry (ES-MS) was used to confirm the formation of [VO{sub 2}(HEDTA)]{sup 2-} and [VO(HEDTA)]{sup 1-} in solution. An electrolyte containing 25 mM phosphate, 0.25 mM tetradecyltrimethylammonium bromide (TTAB) at pH 5.5 was optimum for the separation of these anionic vanadium complexes. Sample stacking techniques, including large-volume sample stacking (LVSS) and field-amplified sample injection (FASI), were tested to improve the sensitivity. Best sensitivity was obtained using FASI, with detection limits of 0.001 {mu}M, equivalent to 0.4 {mu}g L{sup -1}, for [VO{sub 2}(HEDTA)]{sup 2-} and 0.01 {mu}M, equivalent to 3.4 {mu}g L{sup -1} for [VO(HEDTA)]{sup 1-}. The utility of the method for the speciation of V(IV) and V(V) was demonstrated using ground water samples.

Spectrophotometric investigation of vanadium(4) complexing with monoamine complexones

International Nuclear Information System (INIS)

Merkulov, D.A.; Kornev, V.I.

1998-01-01

Interaction of vanadium(4) with iminodiacetic (H 2 Ida) and methyliminodiacetic (H 2 Mida) acids by μ = 0.1 (NaClO 4 ) and t = 20±2 deg C is studied through the spectrophotometric method. It is established that the process of complex formation in quasi-binary systems due to competitive effect of hydroxide ions depends to a large degree on the ligands concentration and properties. The VOIda, VO(OH)Ida - , VOMida, VO(OH)Mida - complexes are identified. The stability constants logarithms of these complexes are equal correspondingly to 9.81±0.02, 18.19±0.03, 10.15±0.03, 18.34±0.02. The results of the study on the VO 2+ -HIda and VO 2+ -H 2 Mida systems agree well with the regularities, identified by the study on the vanadium(4) complex formation with other complexones of the iminodiacetate series

The influence of charge transfers effects in monazite-type LaVO{sub 4} and perovskite-type LaVO{sub 3} prepared by sol-gel acrylamide polymerization

Energy Technology Data Exchange (ETDEWEB)

Herrera-Pérez, G., E-mail: guillermo.herrera@cimav.edu.mx [CONACYT Research Fellow. Centro de Investigación en Materiales Avanzados (CIMAV), Miguel de Cervantes 120, Chihuahua 31136, Chihuahua (Mexico); Jiménez-Mier, J. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, 04510 Mexico D. F (Mexico); Yang, W.-L. [The Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Reyes-Rojas, A.; Fuentes-Cobas, L.E. [Department of Physics of Materials Department. Centro de Investigación en Materiales Avanzados (CIMAV), Miguel de Cervantes 120, Chihuahua 31136, Chihuahua (Mexico)

2016-08-15

Highlights: • We elucidate the electronic structure through the vanadium L{sub 2,3} edge in LaVO{sub 4} by XAS. • The interpretation of XAS spectrum was performed by the multiplet calculation. • Our results suggest that LaVO{sub 4} can be considered in the charge transfer regime. - Abstract: Core-hole spectroscopy such as X-ray absorption spectroscopy (XAS) is useful to determine the electronic structure of strongly correlated and strongly hybridized compounds such as vanadates. Monazite-type LaVO{sub 4} and perovskite-type LaVO{sub 3} are good candidates to elucidate the electronic structure through the vanadium L{sub 2,3} edge. LaVO{sub 4} was prepared by sol-gel acrylamide polymerization and solid-state reaction. LaVO{sub 3} was obtained by reduction of LaVO{sub 4} using Zr as gatherer. Monoclinic crystal phase for LaVO{sub 4} and orthorhombic crystal phase for LaVO{sub 3} were confirmed by the Rietveld refinement of X-ray diffraction patterns. XAS comparison between Vanadium L{sub 2,3} edge confirms the presence of V{sup 5+} for the monazite and V{sup 3+} for the orthorhombic perovskite. Multiplet calculations including crystal field and charge transfer effects (CTM) were performed in order to elucidate the tetragonal (D{sub 4h} symmetry) parameters Dq, Ds and Dt, the charge transfer energy Δ, and d-d Coulomb repulsion energy U parameters. CTM confirms for LaVO{sub 3} the strong V 3d–O 2p hybridization with a significant contribution of covalent character due to the delocalization of 3d electrons. For LaVO{sub 4} this work suggest the reclassification of this band insulator as charge transfer insulator that shows a significant contribution of ionic character.

Reduction of V{sub 2}O{sub 5} thin films deposited by aqueous sol–gel method to VO{sub 2}(B) and investigation of its photocatalytic activity

Energy Technology Data Exchange (ETDEWEB)

Monfort, Olivier [Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University, 842 15 Bratislava (Slovakia); Roch, Tomas; Satrapinskyy, Leonid; Gregor, Maros; Plecenik, Tomas; Plecenik, Andrej [Department of Experimental Physics, Faculty of Mathematics, Physics and Informatics, Comenius University, 842 48 Bratislava (Slovakia); Plesch, Gustav, E-mail: plesch@fns.uniba.sk [Department of Inorganic Chemistry, Faculty of Natural Sciences, Comenius University, 842 15 Bratislava (Slovakia)

2014-12-15

Graphical abstract: - Highlights: • Preparation of VO{sub 2}(B) films by aqueous sol–gel method and their characterization. • Influence of annealing conditions on the mechanism of V{sub 2}O{sub 5} film reduction. • The VO{sub 2}(B) films with energy gap of 2.8 eV show photocatalytic activity. • The films with higher roughness exhibit increased photoactivity. - Abstract: A way of preparation of VO{sub 2}(B) thin films by reduction of V{sub 2}O{sub 5} films synthesized from an aqueous sol–gel system has been developed and photocatalytic properties of the obtained films were studied. The reduction was performed by annealing of the V{sub 2}O{sub 5} film in vacuum as well as in H{sub 2}/Ar atmosphere, which was followed by temperature dependent XRD. It has been shown that the reduction is influenced by the layered-structure of the vanadium oxides. It is a two-step process, where the mixed-valence vanadium oxide V{sub 4}O{sub 9} is first formed before reaching the VO{sub 2}(B) phase. The film microstructure was characterized by SEM and AFM and the valence states of vanadium in VO{sub 2}(B) films were evaluated by XPS. The VO{sub 2}(B) polymorph shows an energy band-gap around 2.8 eV and it exhibits photocatalytic properties. It was measured by following the degradation of rhodamine B under UVA as well as metalhalogenide lamp irradiation, which has similar spectral distribution as natural sunlight. The VO{sub 2}(B) films show distinct photoactivities under both lamps, although they were found to be more active under the UVA irradiation. The film annealed under reducing hydrogen atmosphere, which exhibits higher granularity and surface roughness, shows higher photoactivity than the vacuum-annealed film.

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

Science.gov (United States)

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.

Science.gov (United States)

Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui

2008-02-13

Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.

One-step preparation and photocatalytic performance of vanadium doped TiO2 coatings

International Nuclear Information System (INIS)

Vasilić, R.; Stojadinović, S.; Radić, N.; Stefanov, P.; Dohčević-Mitrović, Z.; Grbić, B.

2015-01-01

In this paper, we have investigated one-step preparation of vanadium doped TiO 2 coatings formed by plasma electrolytic oxidation (PEO) of titanium in electrolyte containing 10 g/L Na 3 PO 4 ·12H 2 O + 0.5 g/L NH 4 VO 3 . The morphology, phase structure, and elemental composition of the formed coatings were characterized by atomic force microscopy (AFM), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) techniques. Ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS) was employed to evaluate the band gap energy of obtained coatings. Vanadium doped TiO 2 coatings are partly crystallized and mainly composed of anatase phase TiO 2 , with up to about 2 wt% of vanadium present in the surface layer of the oxide. The valence band photoelectron spectra and UV–Vis DRS showed that vanadium doped TiO 2 coatings exhibit notable red shift with respect to the pure TiO 2 coatings. The photocatalytic activity was evaluated by monitoring the degradation of methyl orange under simulated sunlight conditions. Photocatalytic activity of vanadium doped TiO 2 coatings increases with PEO time. Prolonged PEO times result in higher roughness of obtained coatings, thus increasing surface area available for methyl orange degradation. Vanadium doped TiO 2 coatings obtained after 180 s of PEO time exhibit the best photocatalytic activity and about 67% of methyl orange is degraded after 12 h of irradiation under simulated sunlight. - Highlights: • One-step preparation of V-doped TiO 2 coatings in 10 g/L Na 3 PO 4 ·12H 2 O + 0.5 g/L NH 4 VO 3 . • Properties of obtained coatings strongly depend on microdischarge characteristics. • Band gap of V-doped TiO 2 coatings is shifted towards red side of the spectrum. • V-doped TiO 2 coatings have better photocatalytic activity than pure TiO 2 . • After 12 h of simulated sunlight irradiation, 67% of methyl orange was decomposed

Broad temperature adaptability of vanadium redox flow battery—Part 1: Electrolyte research

International Nuclear Information System (INIS)

Xiao, Shuibo; Yu, Lihong; Wu, Lantao; Liu, Le; Qiu, Xinping; Xi, Jingyu

2016-01-01

Highlights: • Impact of temperature (-35 °C-50 °C) on properties of VRFB electrolyte is studied. • V 2+ , V 3+ , V 3.5+ , V 4+ (VO 2+ ) and V 5+ (VO 2 + ) electrolytes are tested respectively. • V 2+ , V 3+ and V 3.5+ precipitates at low temperature can redissolve when temperature increases. • V 5+ precipitates at high temperature cannot redissolve when temperature decreases. • Conductivity and viscosity of the electrolytes are greatly affected by temperature. - Abstract: The broad temperature adaptability of vanadium redox flow battery (VRFB) is one of the key issues which affects the large-scale and safety application of VRFB. Typically, five types of vanadium electrolytes, namely V 2+ , V 3+ , V 3.5+ (V 3+ :VO 2+ = 1:1), V 4+ (VO 2+ ) and V 5+ (VO 2 + ), are the most common electrolytes' status existing in VRFB system. In this work, the physicochemical and electrochemical properties of these vanadium electrolytes are studied in detail at a broad temperature range (-35 °C–50 °C). The results show that all types of vanadium electrolytes are stable between -25 °C–30 °C. The temperature fluctuation will largely influence the conductivity and viscosity of the electrolytes. Besides, the electrochemical properties of the positive (VO 2+ ) and negative (V 3+ ) electrolytes are greatly affected by the temperature; and the charge transfer process fluctuates more greatly with the temperature variation than the charge diffusion process does. These results enable us to better and more comprehensively evaluate the performance of the electrolyte changing with the temperature, which will be beneficial for the rational choice of electrolyte for VRFB operation under various conditions.

Vanadium Flow Battery Electrolyte Synthesis via Chemical Reduction of V2O5 in Aqueous HCl and H2SO4.

Energy Technology Data Exchange (ETDEWEB)

Small, Leo J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Pratt, Harry [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Staiger, Chad [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Martin, Rachel Irene [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Anderson, Travis Mark [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Chalamala, Babu [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Soundappan, Thiagarajan [Univ. of Washington, Seattle, WA (United States); Tiwari, Monika [Univ. of Washington, Seattle, WA (United States); Subarmanian, Venkat R. [Univ. of Washington, Seattle, WA (United States)

2017-01-01

We report a simple method to synthesize V 4+ (VO 2+ ) electrolytes as feedstock for all- vanadium redox flow batteries (RFB). By dissolving V 2 O 5 in aqueous HCl and H 2 SO 4 , subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V 4+ (VO 2+ ). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65 degC) for V 4+ (VO 2+ ) electrolytes in HCl compared to in H 2 SO 4 electrolytes.

Silver vanadium diphosphate Ag2VP2O8: Electrochemistry and characterization of reduced material providing mechanistic insights

International Nuclear Information System (INIS)

Takeuchi, Esther S.; Lee, Chia-Ying; Cheng, Po-Jen; Menard, Melissa C.; Marschilok, Amy C.; Takeuchi, Kenneth J.

2013-01-01

Silver vanadium phosphorous oxides (Ag w V x P y O z ) are notable battery cathode materials due to their high energy density and demonstrated ability to form in-situ Ag metal nanostructured electrically conductive networks within the cathode. While analogous silver vanadium diphosphate materials have been prepared, electrochemical evaluations of these diphosphate based materials have been limited. We report here the first electrochemical study of a silver vanadium diphosphate, Ag 2 VP 2 O 8 , where the structural differences associated with phosphorous oxides versus diphosphates profoundly affect the associated electrochemistry. Reminiscent of Ag 2 VO 2 PO 4 reduction, in-situ formation of silver metal nanoparticles was observed with reduction of Ag 2 VP 2 O 8 . However, counter to Ag 2 VO 2 PO 4 reduction, Ag 2 VP 2 O 8 demonstrates a significant decrease in conductivity upon continued electrochemical reduction. Structural analysis contrasting the crystallography of the parent Ag 2 VP 2 O 8 with that of the proposed Li 2 VP 2 O 8 reduction product is employed to gain insight into the observed electrochemical reduction behavior, where the structural rigidity associated with the diphosphate anion may be associated with the observed particle fracturing upon deep electrochemical reduction. Further, the diphosphate anion structure may be associated with the high thermal stability of the partially reduced Ag 2 VP 2 O 8 materials, which bodes well for enhanced safety of batteries incorporating this material. - Graphical abstract: Structure and galvanostatic intermittent titration-type test data for silver vanadium diphosphate, Ag 2 VP 2 O 8 . Highlights: ► First electrochemical study of a silver vanadium diphosphate, Ag 2 VP 2 O 8 . ► In-situ formation of Ag 0 nanoparticles was observed upon electrochemical reduction. ► Structural analysis used to provide insight of the electrochemical behavior

Controlled synthesis and electrochemical properties of vanadium ...

Indian Academy of Sciences (India)

Vanadium oxides (V3O7·H2O and VO2) with different morphologies have been selectively synthesized ... appeared at around 68 ◦C. Furthermore, the electrochemical properties of V3O7·H2O nanobelts, VO2(B) .... morphologies of shape-controlled orthorhombic V3O7·H2O ..... condition, as shown in figures S14i and j.

Study of vanadium(IV) species and corresponding electrochemical performance in concentrated sulfuric acid media

International Nuclear Information System (INIS)

Wu Xuewen; Wang Jinjin; Liu Suqin; Wu Xiongwei; Li Sha

2011-01-01

Highlights: → Two new UV/Vis absorbance peaks are found in V(IV) sulfuric acid solutions. → We give the structural information on the new corresponding V(IV) species. → Reaction route is given with increasing sulfuric acid and V(IV) concentrations. → We find V(IV) species corresponding to the reversible electrochemical reaction. → A mixed-valence intermediate is invoked in the reversible reaction. - Abstract: The vanadium(IV) ion is found to form the [VO(SO 4 )(H 2 O) 4 ].H 2 O complex, as well as the dimer, [VO(H 2 O) 3 ] 2 (μ-SO 4 ) 2 , in concentrated H 2 SO 4 media. Their formation mechanisms were investigated by UV-Visible spectroscopy (UV-Vis), Raman spectroscopy, X-ray diffraction (XRD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). UV-Vis spectroscopy study showed that [VO(SO 4 )(H 2 O) 4 ].H 2 O concentration in H 2 SO 4 solution was proportional to concentrations of VO 2+ and SO 4 2- . The increased deviation from the near centrosymmetry of the octahedral complexes is due to the replacement of an equatorial water oxygen in [VO(H 2 O) 5 ]SO 4 by a sulfate oxygen in [VO(SO 4 )(H 2 O) 4 ].H 2 O. The dimer shows symmetrical structure, which correlates very well with non-activity in UV-Vis spectroscopic analysis. Structural information on both vanadium(IV) species can be confirmed by Raman and XRD measurements of crystals from the supersaturated solution of VOSO 4 in 1 M, 6 M and 12 M sulfuric acid. A solution of vanadium(IV) (0.05 M) in 12 M H 2 SO 4 , in which the vanadium(IV) species is [VO(H 2 O) 3 ] 2 (μ-SO 4 ) 2 , exhibits a reversible redox behavior near 1.14 V (vs. SCE) on the carbon paper electrode.

Influence of intoxication with vanadium compounds on the intestinal absorption of calcium in the rat

International Nuclear Information System (INIS)

Witkowska, D.; Oledzka, R.; Pietrzyk, B.

1986-01-01

Calcium is transferred to the plasma after absorption from the gastrointestinal tract and by resorption from the bone. It is recognized that many environmental poisons, e.g. heavy metal, pesticides etc. cause alterations in calcium homeosthasis in human beings and experimental animals. Although vanadium is not considered to be as important a health hazard to man as lead or cadmium it must be nevertheless regarded as a dangerous pollutant. There exists an obvious risk of pollution by and poisoning due to the high vanadium content of crude oil and the industrial use of vanadium as a steel additive. The toxic effects of this element and its compounds in many biological systems have been reviewed in detail but little is known about vanadium influence on calcium metabolism. The present study was undertaken to determine the effect of various treatments with vanadium compounds, containing vanadium as VO 2+ (VOSO 4 ) and VO 3 (NaVO 3 ) ions, exert on calcium transport through the rat duodenum

Structural and silver/vanadium ratio effects on silver vanadium phosphorous oxide solution formation kinetics: impact on battery electrochemistry.

Science.gov (United States)

Bock, David C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

2015-01-21

The detailed understanding of non-faradaic parasitic reactions which diminish battery calendar life is essential to the development of effective batteries for use in long life applications. The dissolution of cathode materials including manganese, cobalt and vanadium oxides in battery systems has been identified as a battery failure mechanism, yet detailed dissolution studies including kinetic analysis are absent from the literature. The results presented here provide a framework for the quantitative and kinetic analyses of the dissolution of cathode materials which will aid the broader community in more fully understanding this battery failure mechanism. In this study, the dissolution of silver vanadium oxide, representing the primary battery powering implantable cardioverter defibrillators (ICD), is compared with the dissolution of silver vanadium phosphorous oxide (Ag(w)VxPyOz) materials which were targeted as alternatives to minimize solubility. This study contains the first kinetic analyses of silver and vanadium solution formation from Ag0.48VOPO4·1.9H2O and Ag2VP2O8, in a non-aqueous battery electrolyte. The kinetic results are compared with those of Ag2VO2PO4 and Ag2V4O11 to probe the relationships among crystal structure, stoichiometry, and solubility. For vanadium, significant dissolution was observed for Ag2V4O11 as well as for the phosphate oxide Ag0.49VOPO4·1.9H2O, which may involve structural water or the existence of multiple vanadium oxidation states. Notably, the materials from the SVPO family with the lowest vanadium solubility are Ag2VO2PO4 and Ag2VP2O8. The low concentrations and solution rates coupled with their electrochemical performance make these materials interesting alternatives to Ag2V4O11 for the ICD application.

Synthesis of vanadium oxides 5 wt.%VO2–MxOy by sol–gel process ...

Indian Academy of Sciences (India)

Experimental results indicated that the VO2–SiO2 catalysts .... crucible, which was supported by the beam of a balance in the oven. ... Epoxidation of cyclohexene on VO2–Mx Oy (M = Si, Al, Ti). 1189 ... tially amorphous nature of silica.

Insulator-metal transition in substrate-independent VO2 thin film for phase-change devices.

Science.gov (United States)

Taha, Mohammad; Walia, Sumeet; Ahmed, Taimur; Headland, Daniel; Withayachumnankul, Withawat; Sriram, Sharath; Bhaskaran, Madhu

2017-12-20

Vanadium has 11 oxide phases, with the binary VO 2 presenting stimuli-dependent phase transitions that manifest as switchable electronic and optical features. An elevated temperature induces an insulator-to-metal transition (IMT) as the crystal reorients from a monoclinic state (insulator) to a tetragonal arrangement (metallic). This transition is accompanied by a simultaneous change in optical properties making VO 2 a versatile optoelectronic material. However, its deployment in scalable devices suffers because of the requirement of specialised substrates to retain the functionality of the material. Sensitivity to oxygen concentration and larger-scale VO 2 synthesis have also been standing issues in VO 2 fabrication. Here, we address these major challenges in harnessing the functionality in VO 2 by demonstrating an approach that enables crystalline, switchable VO 2 on any substrate. Glass, silicon, and quartz are used as model platforms to show the effectiveness of the process. Temperature-dependent electrical and optical characterisation is used demonstrating three to four orders of magnitude in resistive switching, >60% chromic discrimination at infrared wavelengths, and terahertz property extraction. This capability will significantly broaden the horizon of applications that have been envisioned but remained unrealised due to the lack of ability to realise VO 2 on any substrate, thereby exploiting its untapped potential.

Uncommon potential hysteresis in the Li/Li{sub 2x}VO(H{sub 2-x}PO{sub 4}){sub 2} (0 {<=} x {<=} 2) system

Energy Technology Data Exchange (ETDEWEB)

Dubarry, M. [Institut des Materiaux Jean Rouxel, 2 rue de la Houssiniere, BP32229, 44322 Nantes Cedex 3 (France); Gaubicher, J. [Institut des Materiaux Jean Rouxel, 2 rue de la Houssiniere, BP32229, 44322 Nantes Cedex 3 (France)], E-mail: joel.gaubicher@cnrs-imn.fr; Guyomard, D. [Institut des Materiaux Jean Rouxel, 2 rue de la Houssiniere, BP32229, 44322 Nantes Cedex 3 (France); Wallez, G.; Quarton, M. [Laboratoire de Cristallochimie du Solide, Universite Pierre et Marie Curie-Paris VI, 4 place Jussieu, 75252 Paris Cedex 05 (France); Baehtz, C. [Deutsches Elektronen Synchrotron HASYLAB, Notkestr. 85, 22607 Hamburg (Germany)

2008-05-20

Physical and electrochemical investigations of vanadium phosphates, Li{sub 2x}VO(H{sub 2-x}PO{sub 4}){sub 2} (0 < x < 2), have been undertaken. H{sup +}/Li{sup +} ionic exchange from VO(H{sub 2}PO{sub 4}){sub 2} to Li{sub 2}VO(HPO{sub 4}){sub 2} leads to grain decrepitation. Further ionic exchange toward formation of Li{sub 4}VO(PO{sub 4}){sub 2} lowers the symmetry. As inferred from potentiodynamic cycling correlated to ex situ and in situ X-ray diffraction (XRD), the system Li/Li{sub 4}VO(PO{sub 4}){sub 2} shows several phase transformations that are associated with thermodynamical potential hysteresis that span from roughly 15 mV to more than 1.8 V. Small hysteresis are associated with topotactic reactions and with V{sup V}/V{sup IV} and V{sup III}/V{sup II} redox couples. Large potential hysteresis values (>1 V) were observed when oxidation of V{sup III} to V{sup IV} is involved.

Imaging Nanometer Phase Coexistence at Defects During the Insulator-Metal Phase Transformation in VO2 Thin Films by Resonant Soft X-ray Holography.

Science.gov (United States)

Vidas, Luciana; Günther, Christian M; Miller, Timothy A; Pfau, Bastian; Perez-Salinas, Daniel; Martínez, Elías; Schneider, Michael; Gührs, Erik; Gargiani, Pierluigi; Valvidares, Manuel; Marvel, Robert E; Hallman, Kent A; Haglund, Richard F; Eisebitt, Stefan; Wall, Simon

2018-05-18

We use resonant soft X-ray holography to image the insulator-metal phase transition in vanadium dioxide with element and polarization specificity and nanometer spatial resolution. We observe that nanoscale inhomogeneity in the film results in spatial-dependent transition pathways between the insulating and metallic states. Additional nanoscale phases form in the vicinity of defects which are not apparent in the initial or final states of the system, which would be missed in area-integrated X-ray absorption measurements. These intermediate phases are vital to understand the phase transition in VO 2 , and our results demonstrate how resonant imaging can be used to understand the electronic properties of phase-separated correlated materials obtained by X-ray absorption.

Effect of vanadium on the obtaining of the titanium dioxide by Sol-Gel Method

International Nuclear Information System (INIS)

Granado, S.R.; Silva, D.W.; Lopes, S.A.; Cavalheiro, A.A.

2011-01-01

The obtaining of transition metal modified titanium dioxide (TiO 2 ) can be a promising path to promote changes in crystal structure of anatase phase in order to displace the band gap toward frequencies near to visible region. The insertion of the heterovalent ions such as vanadium can be shift the titanium coordination number in the anatase matrix, leading to important changes in the photonic characteristics of the material. In Sol-Gel method, the presence of the non alkoxide precursors can affects the stability of the solution and the gelifying process, with consequences on the characteristics of the material. In this work, it was investigated the effect of 5mol% of vanadium by thermal analysis of the dried gel and XRD and adsorption isotherm in the samples obtained at different temperatures. The decomposition steps of the precursor were associated to phase formation in the material, leading to conclusion that the presence of vanadium affects the stability of anatase phase. (author)

Graphene/VO2 hybrid material for high performance electrochemical capacitor

International Nuclear Information System (INIS)

Deng, Lingjuan; Zhang, Gaini; Kang, Liping; Lei, Zhibin; Liu, Chunling; Liu, Zong-Huai

2013-01-01

Graphical abstract: Graphene/VO 2 hybrid materials are prepared by one-step simultaneous hydrothermal reduction technology. The prepared graphene (1.0)/VO 2 hybrid material shows a specific capacitances of 225 F g −1 in 0.5 mol L −1 K 2 SO 4 solution. Furthermore, an asymmetric electrochemical capacitor with graphene (1.0)/VO 2 as a positive electrode and graphene as a negative electrode is assembled, and it can work in a cell voltage of 1.7 V and show excellent capacitive property. - Highlights: • Graphene/VO 2 hybrid material has been prepared by one-step hydrothermal reduction. • Graphene/VO 2 hybrid material exhibits high specific capacitance. • An asymmetric capacitor working at 1.7 V in aqueous solution is assembled based on graphene/VO 2 electrode. • The asymmetric capacitor exhibits high energy density. - Abstract: Vanadium oxides have attracted significant attention for electrochemical capacitor because of their extensive multifunctional properties. In the present work, graphene/VO 2 (RG/VO 2 ) hybrid materials with different RG amounts are prepared in a mixture of ammonium vanadate, formic acid and graphite oxide (GO) nanosheets by one-step simultaneous hydrothermal reduction technology. The hydrothermal treatment makes the reduction of GO into RG and the formation of VO 2 particles with starfruit morphology. The starfruit-like VO 2 particles are uniformly embedded in the hole constructed by RG nanosheets, which makes the electrode–electrolyte contact better. A high specific capacitance of 225 F g −1 has been achieved for RG(1.0)/VO 2 electrode with RG content of 26 wt% in 0.5 mol L −1 K 2 SO 4 electrolyte. An asymmetrical electrochemical capacitor is assembled by using RG(1.0)/VO 2 as positive electrode and RG as negative electrode, and it can be reversibly charged–discharged at a cell voltage of 1.7 V in 0.5 mol L −1 K 2 SO 4 electrolyte. The asymmetrical capacitor can deliver an energy density of 22.8 Wh kg −1 at a power density

Experimental investigation of new low-dimensional spin systems in vanadium oxides

International Nuclear Information System (INIS)

Kaul, E.E.

2005-01-01

In this dissertation we reported our experimental investigation of the magnetic properties of nine low-dimensional vanadium compounds. Two of these materials are completely new (Pb 2 V 5 O 12 and Pb 2 VO(PO 4 ) 2 ) and were found during our search for new low-dimensional vanadium oxides. Among the other seven vanadium compounds studied, three were physically investigated for the first time (Sr 2 VO(PO 4 ) 2 , BaZnVO(PO 4 ) 2 and SrZnVO(PO 4 ) 2 ). Two had hitherto only preliminary, and wrongly interpreted, susceptibility measurements reported in the literature (Sr 2 V 3 O 9 and Ba 2 V 3 O 9 ) while the remaining two (Li 2 VOSiO 4 and Li 2 VOGeO 4 ) were previously investigated in some detail but the interpretation of the data was controversial. We investigated the magnetic properties of these materials by means of magnetic susceptibility and specific heat (C p (T)) measurements (as well as single crystal ESR measurements in the case of Sr 2 V 3 O 9 ). We synthesized the samples necessary for our physical studies. That required a search of the optimal synthesis conditions for obtaining pure, high quality, polycrystalline samples. Single crystals of Sr 2 V 3 O 9 and Pb 2 VO(PO 4 ) 2 were also successfully grown. Pb 2 VO(PO 4 ) 2 , BaZnVO(PO 4 ) 2 , SrZnVO(PO 4 ) 2 , Li 2 VOSiO 4 and Li 2 VOGeO 4 were found to be experimental examples of frustrated square-lattice systems which are described by theJ 1 -J 2 model. We found that Li 2 VOSiO 4 and Li 2 VOGeO 4 posses a weakly frustrated antiferromagnetic square lattice while Pb 2 VO(PO 4 ) 2 , BaZnVO(PO 4 ) 2 and SrZnVO(PO 4 ) 2 form a more strongly frustrated ferromagnetic square lattice. Pb 2 V 5 O 12 is structurally and compositionally related to the two dimensional A 2+ V 4+ n O 2n+1 vanadates. Its structure consists of layers formed by edge- and corner-shared square VO 5 pyramids. The basic structural units are plaquettes consisting of six corner-shared pyramids pointing in the same direction, which form a spin

Performance demonstration and evaluation of the synergetic application of vanadium dioxide glazing and phase change material in passive buildings

International Nuclear Information System (INIS)

Long, Linshuang; Ye, Hong; Gao, Yanfeng; Zou, Ruqiang

2014-01-01

Highlights: • VO 2 and PCM were combined in passive building application for the first time. • Synergetic performance of them is demonstrated in a full size room. • Synergetic application has a better performance than the solo ones. • The materials interact with each other in synergetic application. • ESI can be used to evaluate the performance of the synergetic application. - Abstract: One of the key methods to improve the energy saving performance of a building is to apply advanced materials or components to the building envelope. However, the two parts of a building’s envelope, the transparent one and the non-transparent one, are usually investigated individually by existing literature. In this study, vanadium dioxide (VO 2 ) glazing, an advanced energy-efficient element applied to the transparent parts of the building envelope, and phase change material (PCM), a typical thermal storage material used to improve the non-transparent parts of the building envelope, were adopted simultaneously for the first time. The synergetic performance of VO 2 glazing and PCM, demonstrated in a full-scale, lightweight, passive room, resulted in a significant improvement in the thermal comfort degree. The Energy Saving Index (ESI) is a simple and effective indicator that can be used to evaluate the passive application performance of a single energy-efficient material or component on a common standpoint. In this work, the index was broadened to evaluate the performance of more than one material, showing that ESI is feasible and favorable to analyze the coefficient application of several building materials and/or components. Using the ESI, the performance of the synergetic application was also compared with those of the sole materials, indicating that the synergetic application has a better performance during the cooling period. Furthermore the synergetic application involves an interplay rather than a simple combination of the energy-efficient materials. The

Crystal Structure and Spectroscopic Characterization of K8(VO)2O(SO4)6:

DEFF Research Database (Denmark)

Rasmussen, Søren Birk; Rasmussen, Rikke Christina; Fehrmann, Rasmus

2003-01-01

Red and yellow dichroistic crystals of a vanadium(V) compound, potassium (mu-oxo, di-mu-suifato)bis(oxodisulfato-vanadate), K-8(VO)(2)O(SO4)(6), have been obtained from the ternary catalytic model melt system K2S2O7-K2SO4-V2O5. By slow cooling of the melt from 420 to 355 degreesC, crystal growth...

One-step preparation and photocatalytic performance of vanadium doped TiO{sub 2} coatings

Energy Technology Data Exchange (ETDEWEB)

Vasilić, R., E-mail: rastko.vasilic@ff.bg.ac.rs [University of Belgrade, Faculty of Physics, Studentski trg 12-16, 11000 Belgrade (Serbia); Stojadinović, S. [University of Belgrade, Faculty of Physics, Studentski trg 12-16, 11000 Belgrade (Serbia); Radić, N. [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Department of Catalysis and Chemical Engineering, Njegoševa 12, 11000 Belgrade (Serbia); Stefanov, P. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Block 11, Sofia 1113 (Bulgaria); Dohčević-Mitrović, Z. [University of Belgrade, Institute of Physics, Pregrevica 118, 11080 Belgrade (Serbia); Grbić, B. [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Department of Catalysis and Chemical Engineering, Njegoševa 12, 11000 Belgrade (Serbia)

2015-02-01

In this paper, we have investigated one-step preparation of vanadium doped TiO{sub 2} coatings formed by plasma electrolytic oxidation (PEO) of titanium in electrolyte containing 10 g/L Na{sub 3}PO{sub 4}·12H{sub 2}O + 0.5 g/L NH{sub 4}VO{sub 3}. The morphology, phase structure, and elemental composition of the formed coatings were characterized by atomic force microscopy (AFM), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) techniques. Ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS) was employed to evaluate the band gap energy of obtained coatings. Vanadium doped TiO{sub 2} coatings are partly crystallized and mainly composed of anatase phase TiO{sub 2}, with up to about 2 wt% of vanadium present in the surface layer of the oxide. The valence band photoelectron spectra and UV–Vis DRS showed that vanadium doped TiO{sub 2} coatings exhibit notable red shift with respect to the pure TiO{sub 2} coatings. The photocatalytic activity was evaluated by monitoring the degradation of methyl orange under simulated sunlight conditions. Photocatalytic activity of vanadium doped TiO{sub 2} coatings increases with PEO time. Prolonged PEO times result in higher roughness of obtained coatings, thus increasing surface area available for methyl orange degradation. Vanadium doped TiO{sub 2} coatings obtained after 180 s of PEO time exhibit the best photocatalytic activity and about 67% of methyl orange is degraded after 12 h of irradiation under simulated sunlight. - Highlights: • One-step preparation of V-doped TiO{sub 2} coatings in 10 g/L Na{sub 3}PO{sub 4}·12H{sub 2}O + 0.5 g/L NH{sub 4}VO{sub 3}. • Properties of obtained coatings strongly depend on microdischarge characteristics. • Band gap of V-doped TiO{sub 2} coatings is shifted towards red side of the spectrum. • V-doped TiO{sub 2} coatings have better photocatalytic activity than pure TiO{sub 2}. • After 12 h of simulated sunlight irradiation, 67% of

Synthesis of boron and nitrogen co-doped carbon nanofiber as efficient metal-free electrocatalyst for the VO"2"+/VO_2"+ Redox Reaction

International Nuclear Information System (INIS)

Shi, Lang; Liu, Suqin; He, Zhen; Yuan, Hao; Shen, Junxi

2015-01-01

Boron or nitrogen mono-doped carbon nanofiber (CNF), and boron, nitrogen co-doped CNF are intentionally prepared as positive electrodes in a vanadium redox flow battery (VRFB). The structures and electrochemical properties of the materials are investigated by Scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry and electrochemical impendence spectroscopy. The experimental results indicate that either B or N mono-doped CNF shown better electrochemical performance than untreated one. Interestingly, for the B and N co-doped CNF, the separated case exhibited an outstanding electrochemical activity better than either B or N mono-doped case, while the bonded case leading to a sharp drop in conductivity and shown poor electrochemical performances. These results demonstrated that not the total amount of incorporated B and N but how the B and N are incorporated into carbon nanostructures determines the catalytic activity toward VO"2"+/VO_2"+ reaction. Moreover, the individual mechanism of the nitrogen and boron containing functional groups act as active sites have been analyzed.

Preparation and Characterization of Epitaxial VO2 Films on Sapphire Using Postepitaxial Topotaxy Route via Epitaxial V2O3 Films

Science.gov (United States)

Yamaguchi, Iwao; Manabe, Takaaki; Tsuchiya, Tetsuo; Nakajima, Tomohiko; Sohma, Mitsugu; Kumagai, Toshiya

2008-02-01

Epitaxial VO2 films were prepared on the C-planes of α-Al2O3 substrates by a metal organic deposition (MOD) process. It was difficult to obtain the single phase of (010)M-oriented VO2 films, in which the subscript M refers to the monoclinic indices, by the heat treatment of amorphous precursor films in the VO2-stable region after the pyrolysis of the coating solution. The product films consisted of discontinuous circular grains of 1-2 µm size on the substrate surface. Therefore, we prepared the (010)M-oriented epitaxial VO2 films using postepitaxial topotaxy (PET), that is, topotactic oxidation of (0001)-oriented epitaxial V2O3 films. First, epitaxial V2O3(0001) films were obtained by MOD starting with a vanadium naphthenate solution. Second, the epitaxial V2O3(0001) films were topotactically oxidized at 500 °C in an Ar-O2 gas mixture with pO2 = 10-4 atm to obtain (010)M-oriented epitaxial VO2 films. The epitaxial relationships were VO2(010)M ∥ α-Al2O3(0001) and VO2[100]M ∥ α-Al2O3[0110], [1010], [1100]. The VO2(010)M films exhibited metal-semiconductor transitions with hysteresis loops at 60-80 °C. The resistivity change before and after the transition of the VO2(010)M film oxidized for 6 h was three orders of magnitude.

Preparation and characterization of vanadium oxide thin films

Energy Technology Data Exchange (ETDEWEB)

Monfort, O.; Plesch, G. [Comenius University of Bratislava, Faculty of Natural Sciences, Department of Inorganic Chemistry, 84215 Bratislava (Slovakia); Roch, T. [Comenius University of Bratislava, Faculty of Mathematics Physics and Informatics, Department of Experimental Physics, 84248 Bratislava (Slovakia)

2013-04-16

The thermotropic VO{sub 2} films have many applications, since they exhibit semiconductor-conductor switching properties at temperature around 70 grad C. Vanadium oxide thin films were prepared via sol-gel method. Spin coater was used to depose these films on Si/SiO{sub 2} and lime glass substrates. Thin films of V{sub 2}O{sub 5} can be reduced to metastable VO{sub 2} thin films at the temperature of 450 grad C under the pressure of 10{sup -2} Pa. These films are then converted to thermotropic VO{sub 2} at 700 grad C in argon under normal pressure. (authors)

Highly repeatable nanoscale phase coexistence in vanadium dioxide films

Science.gov (United States)

Huffman, T. J.; Lahneman, D. J.; Wang, S. L.; Slusar, T.; Kim, Bong-Jun; Kim, Hyun-Tak; Qazilbash, M. M.

2018-02-01

It is generally believed that in first-order phase transitions in materials with imperfections, the formation of phase domains must be affected to some extent by stochastic (probabilistic) processes. The stochasticity would lead to unreliable performance in nanoscale devices that have the potential to exploit the transformation of physical properties in a phase transition. Here we show that stochasticity at nanometer length scales is completely suppressed in the thermally driven metal-insulator transition (MIT) in sputtered vanadium dioxide (V O2 ) films. The nucleation and growth of domain patterns of metallic and insulating phases occur in a strikingly reproducible way. The completely deterministic nature of domain formation and growth in films with imperfections is a fundamental and unexpected finding about the kinetics of this material. Moreover, it opens the door for realizing reliable nanoscale devices based on the MIT in V O2 and similar phase-change materials.

Dehydrogenation of Ethylbenzene with Carbon Dioxide as Soft Oxidant over Supported Vanadium-Antimony Oxide Catalyst

Energy Technology Data Exchange (ETDEWEB)

Hong, Do Young; Vislovskiy, Vladislav P.; Yoo, Jin S.; Chang, Jong San [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Sang Eon [Inha University, Incheon (Korea, Republic of); Park, Min Seok [Mongolia International University, Ulaanbaatar (Mongolia)

2005-11-15

This work presents that carbon dioxide, which is a main contributor to the global warming effect, could be utilized as a selective oxidant in the oxidative dehydrogenation of ethylbenzene. The dehydrogenation of ethylbenzene over alumina-supported vanadium-antimony oxide catalyst has been studied under different atmospheres such as inert nitrogen, steam, oxygen or carbon dioxide as diluent or oxidant. Among them, the addition of carbon dioxide gave the highest styrene yield (up to 82%) and styrene selectivity (up to 97%) along with stable activity. Carbon dioxide could play a beneficial role of a selective oxidant in the improvement of the catalytic behavior through the oxidative pathway.

The bioinorganic electrochemistry of vanadium-penicillamine complexes

International Nuclear Information System (INIS)

Bagal, U.A.; Riechel, T.L.

1989-01-01

Vanadium (V) has been found to inhibit (Na + , K + )-ATPase in the sodium pump reaction in erythrocytes. Glutathione has been suggested as the reducing agent that reverses the effect by reducing vanadium to the (IV) oxidation state. Penicillamine is being studied as a model for glutathione since both have sulfhydryl groups which are involved in redox and coordination chemistry. The electrochemistry in DMSO of penicillamine, its carboxylic ester, and their VO 2 + complexes are discussed in this paper

Surface charge sensing by altering the phase transition in VO2

Science.gov (United States)

Kumar, S.; Esfandyarpour, R.; Davis, R.; Nishi, Y.

2014-08-01

Detection of surface charges has various applications in medicine, electronics, biotechnology, etc. The source of surface charge induction may range from simple charge-polarized molecules like water to complicated proteins. It was recently discovered that surface charge accumulation can alter the temperature at which VO2 undergoes a Mott transition. Here, we deposited polar molecules onto the surface of two-terminal thin-film VO2 lateral devices and monitored the joule-heating-driven Mott transition, or conductance switching. We observed that the power required to induce the conductance switching reduced upon treatment with polar molecules and, using in-situ blackbody-emission direct measurement of local temperature, we show that this reduction in power was accompanied by reduction in the Mott transition temperature. Further evidence suggested that this effect has specificity to the nature of the species used to induce surface charges. Using x-ray absorption spectroscopy, we also show that there is no detectable change in oxidation state of vanadium or structural phase in the bulk of the 40 nm VO2 thin-film even as the phase transition temperature is reduced by up to 20 K by the polar molecules. The ability to alter the phase transition parameters by depositing polar molecules suggests a potential application in sensing surface charges of different origins and this set of results also highlights interesting aspects of the phase transition in VO2.

Electron-beam deposition of vanadium dioxide thin films

Energy Technology Data Exchange (ETDEWEB)

Marvel, R.E.; Appavoo, K. [Vanderbilt University, Interdisciplinary Materials Science Program, Nashville, TN (United States); Choi, B.K. [Vanderbilt University, Department of Electrical Engineering and Computer Science, Nashville, TN (United States); Nag, J. [Vanderbilt University, Department of Physics and Astronomy, Nashville, TN (United States); Haglund, R.F. [Vanderbilt University, Interdisciplinary Materials Science Program, Nashville, TN (United States); Vanderbilt University, Institute for Nanoscale Science and Engineering, Nashville, TN (United States); Vanderbilt University, Department of Physics and Astronomy, Nashville, TN (United States)

2013-06-15

Developing a reliable and efficient fabrication method for phase-transition thin-film technology is critical for electronic and photonic applications. We demonstrate a novel method for fabricating polycrystalline, switchable vanadium dioxide thin films on glass and silicon substrates and show that the optical switching contrast is not strongly affected by post-processing annealing times. The method relies on electron-beam evaporation of a nominally stoichiometric powder, followed by fast annealing. As a result of the short annealing procedure we demonstrate that films deposited on silicon substrates appear to be smoother, in comparison to pulsed laser deposition and sputtering. However, optical performance of e-beam evaporated film on silicon is affected by annealing time, in contrast to glass. (orig.)

Three-dimensional Nitrogen-Doped Reduced Graphene Oxide/Carbon Nanotube Composite Catalysts for Vanadium Flow Batteries

Energy Technology Data Exchange (ETDEWEB)

Fu, Shaofang [School of Mechanical and Materials Engineering, Washington State University, WA, 99164 USA.; Zhu, Chengzhou [School of Mechanical and Materials Engineering, Washington State University, WA, 99164 USA.; Song, Junhua [School of Mechanical and Materials Engineering, Washington State University, WA, 99164 USA.; Engelhard, Mark H. [Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, WA 99354 USA.; Du, Dan [School of Mechanical and Materials Engineering, Washington State University, WA, 99164 USA.; Lin, Yuehe [School of Mechanical and Materials Engineering, Washington State University, WA, 99164 USA.; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, WA 99354 USA.

2017-02-22

The development of vanadium redox flow battery is limited by the sluggish kinetics of the reaction, especially the cathodic VO2+/VO2+ redox couples. Therefore, it is vital to develop new electrocatalyst with enhanced activity to improve the battery performance. Herein, we first synthesized the hydrogel precursor by a facile hydrothermal method. After the following carbonization, nitrogen-doped reduced graphene oxide/carbon nanotube composite was obtained. By virtue of the large surface area and good conductivey, which are ensured by the unique hybrid structure, as well as the proper nitrogen doping, the as-prepared composite presents enhanced catalytic performance toward the VO2+/VO2+ redox reaction. We also demonstrated the composite with carbon nanotube loading of 2 mg/mL exhibits the highest activity and remarkable stability in aqueous solution due to the strong synergy between reduced graphene oxide and carbon nanotubes, indicating that this composite might show promising applications in vanadium redox flow battery.

Effect of vanadium on plant growth and its accumulation in plant tissues

Directory of Open Access Journals (Sweden)

Narumol Vachirapatama

2011-06-01

Full Text Available Hydroponic experiments were conducted to investigate vanadium uptake by Chinese green mustard and tomato plantsand its effect on their growth. Twenty-eight (Chinese green mustard and 79 days (tomato after germination, the plants wereexposed for a further seven days to a solution containing six different concentrations of ammonium metavanadate (0-80 mg/lNH4VO3. The vanadium accumulated in the plant tissues were determined by ion-interaction high performance liquid chromatography,with confirmation by magnetic sector ICP-MS.The results indicated that nutrient solution containing more than 40 mg/l NH4VO3 affected plant growth for bothChinese green mustard and tomato plant. Chinese green mustard grown in the solution containing NH4VO3 at the concentrationsof 40 and 80 mg/l had stem length, number of leaves, dry weight of leaf, stem and root significantly lower than those ofplants grown in the solution containing 0-20 mg/l NH4VO3. Tomato plants were observed to wilt after four days in contactwith the nutrient solutions containing 40 and 80 mg/l NH4VO3. As the vanadium concentrations increased, a resultantdecrease in the stem length, root fresh weight, and fruit fresh weight were noted. The accumulation of vanadium was higher inthe root compared with leaf, stem, or fruit. Measured levels of vanadium, from a nutrient solution containing 40 mg/l NH4VO3,were 328, 340, and 9.66x103 g/g in the leaf, stem and root for Chinese green mustard, and 4.04 and 4.01x103 g/g in the fruitand roots for tomato plants, respectively.

Preparation and modification of VO2 thin film on R-sapphire substrate by rapid thermal process

Science.gov (United States)

Zhu, Nai-Wei; Hu, Ming; Xia, Xiao-Xu; Wei, Xiao-Ying; Liang, Ji-Ran

2014-04-01

The VO2 thin film with high performance of metal-insulator transition (MIT) is prepared on R-sapphire substrate for the first time by magnetron sputtering with rapid thermal process (RTP). The electrical characteristic and THz transmittance of MIT in VO2 film are studied by four-point probe method and THz time domain spectrum (THz-TDS). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and search engine marketing (SEM) are employed to analyze the crystalline structure, valence state, surface morphology of the film. Results indicate that the properties of VO2 film which is oxidized from the metal vanadium film in oxygen atmosphere are improved with a follow-up RTP modification in nitrogen atmosphere. The crystallization and components of VO2 film are improved and the film becomes compact and uniform. A better phase transition performance is shown that the resistance changes nearly 3 orders of magnitude with a 2-°C hysteresis width and the THz transmittances are reduced by 64% and 60% in thermal and optical excitation respectively.

Mass spectrometric investigation of evaporation of lithium-vanadium bronze

International Nuclear Information System (INIS)

Kudin, L.S.; Pogrebnoj, A.M.

1996-01-01

The composition of ionic and neutral components of vapour above lithium-vanadium bronze Li 0.2 VO 2.6 has been studied. It is ascertained that molecules of LiVO 3 and O 2 and Li + ions (2.2±0.2); Li + ·LiVO 3 (2.4±0.3); Li + ·(LiVO 3 ) 2 (2.4±0.9); Li + ·V 2 O 5 (2.3±0.9); Cs + (2.1±0.3); Cs + ·LiVO 3 (2.6±1.0) are basic components of saturated vapour, the values of ionic work functions in eV are given in parentheses. Sublimation enthalpy of lithium metavanadate Δ S H 0 (LiVO 3 , 298 K)=457±30 kJ/mol and its formation enthalpy Δ f H 0 (LiVO 3 , gas, 298 k)=-704±30 kJ/mol. have been defined. Using law 2 of thermodynamics the enthalpies of ion-molecular reactions have been defined. ion formation enthalpies being calculated on their basis. 18 refs., 3 figs., 3 tabs

Dynamical heat transport amplification in a far-field thermal transistor of VO{sub 2} excited with a laser of modulated intensity

Energy Technology Data Exchange (ETDEWEB)

Ordonez-Miranda, Jose, E-mail: jose.ordonez@cnrs.pprime.fr; Ezzahri, Younès; Drevillon, Jérémie; Joulain, Karl [Institut Pprime, CNRS, Université de Poitiers, ISAE-ENSMA, F-86962 Futuroscope Chasseneuil (France)

2016-05-28

Far-field radiative heat transport in a thermal transistor made up of a vanadium dioxide base excited with a laser of modulated intensity is analytically studied and optimized. This is done by solving the equation of energy conservation for the steady-state and modulated components of the temperature and heat fluxes that the base exchanges with the collector and emitter. The thermal bistability of VO{sub 2} is used to find an explicit condition on the laser intensity required to maximize these heat fluxes to values higher than the incident flux. For a 1 μm-thick base heated with a modulation frequency of 0.5 Hz, it is shown that both the DC and AC components of the heat fluxes are about 4 times the laser intensity, while the AC temperature remains an order of magnitude smaller than the DC one at around 343 K. Higher AC heat fluxes are obtained for thinner bases and/or lower frequencies. Furthermore, we find that out of the bistability temperatures associated with the dielectric-to-metal and metal-to-dielectric transitions of VO{sub 2}, the amplification of the collector-to-base and base-to-emitter heat fluxes is still possible, but at modulation frequencies lower than 0.1 Hz.

High Temperature Corrosion of Nickel in NaVO3-V2O5 Melts

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J. Porcayo-Calderon

2017-01-01

Full Text Available Many alloys used at high temperature in industrial processes are Ni-based and many others contain it in appreciable quantities, so it is of interest to evaluate the performance of pure nickel in order to determine the behavior of its alloys once the elements responsible for their protection have been depleted due to accelerated corrosion processes in the presence of vanadium-rich molten salts. Due to this, this work presents the study of Ni behavior in NaVO3-V2O5 mixtures at different temperatures. The behavior of pure nickel was determined by both electrochemical and mass loss measurements. The results show that the aggressiveness of the vanadium salts is increased by increasing both the V2O5 content and temperature. V2O5 addition considerably increases the current densities of the anodic and cathodic reactions. The corrosion process of Ni is modified due to the presence of its corrosion products, and its presence increases the activation energy by at least one order of magnitude. Although nickel shows a high reactivity in vanadium-rich salts, its reaction products are highly stable and protect it from the corrosive medium because the corrosion reactions trap the vanadium and block the migration of nickel ions.

Current-induced metal-insulator transition in VO x thin film prepared by rapid-thermal-annealing

International Nuclear Information System (INIS)

Cho, Choong-Rae; Cho, SungIl; Vadim, Sidorkin; Jung, Ranju; Yoo, Inkyeong

2006-01-01

The phenomenon of metal-insulator transition (MIT) in polycrystalline VO x thin films and their preparations have been studied. The films were prepared by sputtering of vanadium thin films succeeded by Rapid Thermal Annealing (RTA) in oxygen ambient at 500 deg. C. Crystalline, compositional, and morphological characterizations reveal a continuous change of phase from vanadium metal to the highest oxide phase, V 2 O 5 , with the time of annealing. Electrical MIT switching has been observed in these films. Sweeping mode, electrode area, and temperature dependent MIT has been studied in Pt/VO x /Pt vertical structure. The important parameters for MIT in VO x have been found to be the current density and the electric field, which depend on carrier density in the films

Synthesis, Magnetism, and X-ray Molecular Structure of the Mixed-Valence Vanadium(IV/V)-Oxygen Cluster [VO(4) subset(V(18)O(45))](9-).

Science.gov (United States)

Suber, Lorenza; Bonamico, Mario; Fares, Vincenzo

1997-05-07

Within the transition metal oxide systems, vanadium presents a unique chemistry due to its capacity to form a great number of mixed-valence oxo clusters which often have the peculiarity to incorporate species that function, for size, shape, and charge, as templates. Prismatic, lustrous dark brown crystals of [(n-C(4)H(9))NH(3)](9)[V(19)O(49)].7H(2)O are obtained by reacting (n-C(4)H(9)NH(3))VO(3), VOSO(4), and (n-C(4)H(9))NH(2) in H(2)O. The X-ray crystal structure shows an ellipsoidal metal-oxo cluster formed by 15 VO(5) and 3 VO(4) polyhedra surrounding an almost regular VO(4) tetrahedron located on the 3-fold axis of a trigonal cell of dimensions a = 19.113(5) Å and c = 13.743(5) Å with space group P&thremacr; and Z = 2. Exponentially weighted bond valence sum calculations, manganometric titration of the V(IV) centers, and magnetic measurements are consistent with the presence of three localized and three delocalized electrons. Variable-temperature solid-state susceptibility studies indicate antiferromagnetic coupling between V(IV) centers. Cyclic voltammetry in acetonitrile shows a irreversible reduction at -1.24 V and a reversible oxidation at +0.17 V (vs Ag/AgCl). The title compound converts quantitatively to the metal oxide K(2)V(3)O(8) with an extended layered structure as soon as a potassium salt is added to a neutral aqueous solution of the polyoxoanion.

Graphite-graphite oxide composite electrode for vanadium redox flow battery

International Nuclear Information System (INIS)

Li Wenyue; Liu Jianguo; Yan Chuanwei

2011-01-01

Highlights: → A new composite electrode is designed for vanadium redox flow battery (VRB). → The graphite oxide (GO) is used as electrode reactions catalyst. → The excellent electrode activity is attributed to the oxygen-containing groups attached on the GO surface. → A catalytic mechanism of the GO towards the redox reactions is presumed. - Abstract: 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 [VO 2 ] + /[VO] 2+ and V 3+ /V 2+ 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 [VO 2 ] + /[VO] 2+ and V 3+ /V 2+ 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.

Selective formation of VO2(A) or VO2(R) polymorph by controlling the hydrothermal pressure

International Nuclear Information System (INIS)

Ji Shidong; Zhang Feng; Jin Ping

2011-01-01

Missing VO 2 (A) usually occurs during the preparation of VO 2 polymorphs. This leads to an ambiguous understanding of the transformation between VO 2 polymorphs. The calculation of the ground state energies for different VO 2 polymorphs indicated that there is only a small energy gap between VO 2 (A) and VO 2 (R), which destined that the transformation from VO 2 (A) to VO 2 (R) should be pressure sensitive. This hypothesis was verified during the synthesizing of VO 2 polymorphs by reducing V 2 O 5 with oxalic acid through hydrothermal treatment process. Selective formation of pure phase VO 2 (A) or VO 2 (R) was achieved by controlling the hydrothermal pressure through varying the filling ratio at 270 deg. C. It was found that a filling ratio over 0.5 favors the formation of pure VO 2 (R) while a reduced filling ratio to 0.4 or lower results in the formation of VO 2 (A). Based on our experiments, VO 2 (B) nanobelts were always first formed and then it transformed to VO 2 (A) by assembling process at increased temperature or extended reaction time. Under further higher pressure, the VO 2 (A) transformed spontaneously to VO 2 (R) initialized from the volume shrinkage due to the formation of denser VO 2 (R). - Graphical abstract: Selective formation of VO 2 (A) or VO 2 (R) could be achieved by controlling the system pressure through varying the filling ratio during hydrothermal treatment. Highlights: → Selective formation of VO 2 polymorphs by controlling hydrothermal pressure. → Ground state energy characteristics were revealed for the first time. → Phase transformation mechanism was clearly elucidated.

Preparation and modification of VO2 thin film on R-sapphire substrate by rapid thermal process

International Nuclear Information System (INIS)

Zhu Nai-Wei; Hu Ming; Xia Xiao-Xu; Wei Xiao-Ying; Liang Ji-Ran

2014-01-01

The VO 2 thin film with high performance of metal–insulator transition (MIT) is prepared on R-sapphire substrate for the first time by magnetron sputtering with rapid thermal process (RTP). The electrical characteristic and THz transmittance of MIT in VO 2 film are studied by four-point probe method and THz time domain spectrum (THz-TDS). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and search engine marketing (SEM) are employed to analyze the crystalline structure, valence state, surface morphology of the film. Results indicate that the properties of VO 2 film which is oxidized from the metal vanadium film in oxygen atmosphere are improved with a follow-up RTP modification in nitrogen atmosphere. The crystallization and components of VO 2 film are improved and the film becomes compact and uniform. A better phase transition performance is shown that the resistance changes nearly 3 orders of magnitude with a 2-°C hysteresis width and the THz transmittances are reduced by 64% and 60% in thermal and optical excitation respectively. (interdisciplinary physics and related areas of science and technology)

K2V2O2(AsO42

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Thierry Roisnel

2012-07-01

Full Text Available The vanadium oxide arsenate with formula K2V2O2(AsO42, dipotassium divanadium(IV dioxide diarsenate, has been synthesized by solid-state reaction in an evacuated silica ampoule. Its structure is isotypic with K2V2O2(PO42. The framework is built up from corner-sharing VO6 octahedra and AsO4 tetrahedra, creating an infinite [VAsO8]∞ chain running along the a- and c-axis directions. The K+ cations are located in hexagonal tunnels, which are delimited by the connection of the [VAsO8]∞ chains.

HF/H2O2 treated graphite felt as the positive electrode for vanadium redox flow battery

Science.gov (United States)

He, Zhangxing; Jiang, Yingqiao; Meng, Wei; Jiang, Fengyun; Zhou, Huizhu; Li, Yuehua; Zhu, Jing; Wang, Ling; Dai, Lei

2017-11-01

In order to improve the electrochemical performance of the positive graphite felt electrode in vanadium flow redox battery, a novel method is developed to effectively modify the graphite felt by combination of etching of HF and oxidation of H2O2. After the etching of HF for the graphite felt at ambient temperature, abundant oxygen-containing functional groups were further introduced on the surface of graphite felt by hydrothermal treatment using H2O2 as oxidant. Benefiting from the surface etching and introduction of functional groups, mass transfer and electrode process can be improved significantly on the surface of graphite felt. VO2+/VO2+ redox reaction on the graphite felt modified by HF and H2O2 jointly (denote: GF-HF/H2O2) exhibits superior electrochemical kinetics in comparison with the graphite felt modified by single HF or H2O2 treatment. The cell using GF-HF/H2O2 as the positive electrode was assembled and its electrochemical properties were evaluated. The increase of energy efficiency of 4.1% for GF-HF/H2O2 at a current density of 50 mA cm-2 was obtained compared with the pristine graphite felt. The cell using GF-HF/H2O2 also demonstrated higher discharge capacity. Our study revealed that HF/H2O2 treatment is an efficient method to enhance the electrochemical performance of graphite felt, further improving the comprehensive energy storage performance of the vanadium flow redox battery.

Vanadium oxide thin films and fibers obtained by acetylacetonate sol–gel method

Energy Technology Data Exchange (ETDEWEB)

Berezina, O.; Kirienko, D. [Department of Physical Engineering, Petrozavodsk State University, 185910 Petrozavodsk (Russian Federation); Pergament, A., E-mail: aperg@psu.karelia.ru [Department of Physical Engineering, Petrozavodsk State University, 185910 Petrozavodsk (Russian Federation); Stefanovich, G.; Velichko, A. [Department of Physical Engineering, Petrozavodsk State University, 185910 Petrozavodsk (Russian Federation); Zlomanov, V. [Department of Chemistry, Moscow State University, 119991 Moscow (Russian Federation)

2015-01-01

Vanadium oxide films and fibers have been fabricated by the acetylacetonate sol–gel method followed by annealing in wet nitrogen. The samples are characterized by X-ray diffraction and electrical conductivity measurements. The effects of a sol aging, the precursor decomposition and the gas atmosphere composition on the annealing process, structure and properties of the films are discussed. The two-stage temperature regime of annealing of amorphous films in wet nitrogen for formation of the well crystallized VO{sub 2} phase is chosen: 1) 25–550 °C and 2) 550–600 °C. The obtained films demonstrate the metal–insulator transition and electrical switching. Also, the effect of the polyvinylpyrrolidone additive concentration and electrospinning parameters on qualitative (absence of defects and gel drops) and quantitative (length and diameter) characteristics of vanadium oxide fibers is studied. - Highlights: • Vanadium oxide thin films and fibers are synthesized by sol–gel method. • The effect of annealing, atmosphere, time and electrospinning parameters is studied. • Produced VO{sub 2} structures exhibit metal–insulator transition and electrical switching.

Ultrafast electron crystallography of the cooperative reaction path in vanadium dioxide

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Ding-Shyue Yang

2016-05-01

Full Text Available Time-resolved electron diffraction with atomic-scale spatial and temporal resolution was used to unravel the transformation pathway in the photoinduced structural phase transition of vanadium dioxide. Results from bulk crystals and single-crystalline thin-films reveal a common, stepwise mechanism: First, there is a femtosecond V−V bond dilation within 300 fs, second, an intracell adjustment in picoseconds and, third, a nanoscale shear motion within tens of picoseconds. Experiments at different ambient temperatures and pump laser fluences reveal a temperature-dependent excitation threshold required to trigger the transitional reaction path of the atomic motions.

Modification of the Properties of Vanadium Oxide Thin Films by Plasma-Immersion Ion Implantation

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Sergey Burdyukh

2018-01-01

Full Text Available The paper describes the effect of doping with hydrogen and tungsten by means of plasma-immersion ion implantation (PIII on the properties of vanadium dioxide and hydrated vanadium pentoxide films. It is shown that the parameters of the metal-insulator phase transition in VO2 thin films depend on the hydrogen implantation dose. Next, we explore the effect of PIII on composition, optical properties, and the internal electrochromic effect (IECE in V2O5·nH2O films. The variations in the composition and structure caused by the hydrogen insertion, as well as those caused by the electrochromic effect, are studied by nuclear magnetic resonance, thermogravimetry, Raman spectroscopy, and X-ray structural analysis. It is shown that the ion implantation-induced hydrogenation can substantially enhance the manifestation and performance of the IECE in V2O5 xerogel films. Finally, the effect of PIII-assisted doping with W on the parameters of electrical switching in Au/V2O5·nH2O/Au sandwich structures is examined. It is shown that implanting small tungsten doses improves the switching parameters after forming. When implanting large doses, switching is observed without electroforming, and if electroforming is applied, the switching effect, on the contrary, disappears.

Kinetic investigation of vanadium (V)/(IV) redox couple on electrochemically oxidized graphite electrodes

International Nuclear Information System (INIS)

Wang, Wenjun; Wei, Zengfu; Su, Wei; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei; Zeng, Chaoliu

2016-01-01

Highlights: • The VO_2"+/VO"2"+ redox reaction of the electrode could be facilitated to some extent with the increasing anodic corrosion. • A real reaction kinetic equation for the oxidation of VO"2"+ on the electrochemically oxidized electrode has been firstly obtained. • The establishment of the kinetic equation is conducive to predict polarization behaviors of the electrodes in engineering application. - Abstract: The morphology, surface composition, wettability and the kinetic parameters of the electrochemically oxidized graphite electrodes obtained under different anodic polarization conditions have been examined by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), contact angle measurements, steady-state polarization and cyclic voltammetry (CV) tests, with an attempt to investigate the inherent correlation between the physicochemical properties and the kinetic characteristics for carbon electrodes used in an all-vanadium redox flow battery (VRFB). When the anodic polarization potential raises up to 1.8 V vs. SCE, the anodic corrosion of the graphite might happen and a large number of oxygen-containing functional groups generate. The VO_2"+/VO"2"+ redox reaction can be facilitated and the reaction reversibility tends to become better with the increasing anodic potential, possibly owing to the increased surface oxides and the resulting improved wettability of the electrode. Based on this, a real reaction kinetic equation for the oxidation of VO"2"+ has been obtained on the electrode polarized at 1.8 V vs. SCE and it can be also well used to predict the polarization behavior of the oxidized electrode in vanadium (IV) acidic solutions.

Investigation of structural, morphological and electrical properties of APCVD vanadium oxide thin films

International Nuclear Information System (INIS)

Papadimitropoulos, Georgios; Trantalidis, Stelios; Tsiatouras, Athanasios; Vasilopoulou, Maria; Davazoglou, Dimitrios; Kostis, Ioannis

2015-01-01

Vanadium oxide films were chemically vapor deposited (CVD) on oxidized Si substrates covered with CVD tungsten (W) thin films and on glass substrates covered with indium tin oxide (ITO) films, using vanadium(V) oxy-tri-isopropoxide (C 9 H 21 O 4 V) vapors. X-ray diffraction (XRD) measurements showed that the deposited films were composed of a mixture of vanadium oxides; the composition was determined mainly by the deposition temperature and less by the precursor temperature. At temperatures up to 450 C the films were mostly composed by monoclinic VO 2 . Other peaks corresponding to various vanadium oxides were also observed. X-ray microanalysis confirmed the composition of the films. The surface morphology was studied with atomic force microscopy (AFM) and scanning electron microscopy (SEM). These measurements revealed that the morphology strongly depends on the used substrate and the deposition conditions. The well-known metal-insulator transition was observed near 75 C for films mostly composed by monoclinic VO 2 . Films deposited at 450 C exhibited two transitions one near 50 C and the other near 60 C possibly related to the presence of other vanadium phases or of important stresses in them. Finally, the vanadium oxide thin films exhibited significant sensory capabilities decreasing their resistance in the presence of hydrogen gas with response times in the order of a few seconds and working temperature at 40 C. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Ultrafast Hot Electron Induced Phase Transitions in Vanadium Dioxide

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Haglund R. F.

2013-03-01

Full Text Available The Au/Cr/VO2/Si system was investigated in pump–probe experiments. Hot-electrons generated in the Au were found to penetrate into the underlying VO2 and couple with its lattice inducing a semiconductor-to-metal phase transition in ~2 picoseconds.

Fine hierarchy of the V-O bonds by advanced solid state NMR: novel Pb4(VO2)(PO4)3 structure as a textbook case.

Science.gov (United States)

Tricot, Grégory; Mentré, Olivier; Cristol, Sylvain; Delevoye, Laurent

2012-12-17

We report here a complete structural characterization of a new lead Pb(4)(VO(2))(PO(4))(3) vanadophosphate compound by single crystal X-ray diffraction and (51)V and (31)P solid-state NMR spectroscopy. Although structural data are commonly used for the estimation of bond lengths and further delimitation of the true coordination number (e.g., octahedral: 6 versus 5 + 1 versus 4 + 2), we show here for the first time by solid-state NMR a more accurate appreciation of the V-O bonding scheme in this complex oxide which appears well adapted to the full series of vanado-phosphate materials. The direct characterization of V-O-P bridges through the J-mediated correlation (51)V{(31)P} heteronuclear multiple quantum coherence (J-HMQC) technique allows a contrasted hierarchy of the V-O electronic delocalization and indirectly supports the presence or not of the V-O bond. In the reported lead vanado-phosphate structure, the two vanadium polyhedra that have been assigned to octahedra from a bond length point of view have been finally reclassified as tetra- and penta-coordinated units on the basis of the solid-state NMR results. More generally, we believe that the improved characterization of interatomic bonds in various vanado-phosphate structures by solid-state NMR will contribute to a better understanding of the structure/property relationships in this important class of materials.

Structure-property relationships in NO_x sensor materials composed of arrays of vanadium oxide nanoclusters

Energy Technology Data Exchange (ETDEWEB)

Putrevu, Naga Ravikanth; Darling, Seth B.; Segre, Carlo U.; Ganegoda, Hasitha; Khan, M. Ishaque

2017-10-04

The mixed-valent vanadium oxide based three-dimensional framework structure species [Cd₃(H₂O)₁₂V₁₆^IVV₂^VO₃₆(OH)₆(AO₄)]∙24H₂O, (A=V,S) (Cd₃(VO)_o) represents a rare example of an interesting sensor material which exhibits NO_x {NO+NO₂} semiconducting gas sensor properties under ambient conditions. The electrical resistance of the sensor material Cd₃(VO)_o decreases in air. Combined characterization studies revealed that the building block, {V₁₈O₄₂(AO₄)} cluster, of 3-D framework undergoes oxidation and remains intact for at least 2 months. The decrease in resistance is attributable to the reactivity of molecular oxygen towards vanadium which results in an increase in the oxidation state as well as the coordination number of vanadium center and decrease in band gap of Cd₃(VO)_o. Based on these results we propose that the changes in semiconducting properties of Cd₃(VO)_o under ambient conditions are due to the greater overlap between the O 2p and V 3d orbitals occurring during the oxidation.

Reaction between vanadium trichloride oxide and hydrogen sulfide

International Nuclear Information System (INIS)

Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo

1978-01-01

The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)

Phase evolution and infrared transmittance in monophasic VO{sub 2} synthesized by a rapid non-equilibrium process

Energy Technology Data Exchange (ETDEWEB)

Rajeswaran, Bharathi, E-mail: rajeswaran.bharathi@gmail.com; Umarji, A.M.

2017-04-01

VO{sub 2} displays a semiconducting to metallic (SMT) transition accessible near room temperature. This makes it one of the most sought after materials for electrical and optical switching. But this can be utilized only when the synthesis process yields phase pure VO{sub 2} without other oxides of vanadium. Across the SMT, VO{sub 2} exhibits difference crystal structures with a rich phase behavior of insulating monoclinic M1, M2 and T phases. The objective of this study is to synthesize phase pure VO{sub 2} and to investigate its structural evolution and infrared switching during the transition. In this work, a rapid non-equilibrium process namely Solution Combustion Synthesis (SCS) was employed. The structural phase transition (SPT) of VO{sub 2} nanostructures synthesized by SCS was investigated by in-situ temperature controlled XRD across the SMT. Gaussian curve fittings for measured XRD patterns revealed that competing phases of M1 and R significantly contribute to the observed pattern at every increase in temperature. The powders were further characterized by FTIR, DSC and DC electrical conductivity. These studies show that a sharp SMT was observed at 68–70 °C. Infrared transmittance experiments pinpointed the transition. Carrier density and mobility of VO{sub 2} were calculated. This suggests that this VO{sub 2} thus synthesized displays excellent phase transition behavior and can be utilized in optical and electrical switching. - Highlights: • VO{sub 2} has been synthesized by an easy, rapid, cost-effective, two-step, novel reaction. • High temperature XRD and DSC showed first order phase transition. • IR transmittance showed a decrease in transmittance at high temperatures enabling it to be used for IR sensing.

Luminescence Properties of Self-Activated Mm(VO4)2 (M = Mg, Ca, Sr, and Ba) Phosphors Synthesized by Solid-State Reaction Method.

Science.gov (United States)

Min, Xin; Huang, Zhaohui; Fang, Minghao; Liu, Yan'gai; Tang, Chao; Wu, Xiaowen

2016-04-01

In this paper, M3(VO4)2 (M = Mg, Ca, Sr, and Ba) self-activated phosphors were prepared by a solid-state reaction method at 1,000 °C for 5 h. The phase formation and micrographs were analyzed by X-ray diffraction and scanning electron microscopy. The Ca3(VO4)2 phosphor does not show any emission peaks under excitation with ultraviolet (UV) light. However, the M3(VO4)2 (M = Mg, Sr, and Ba) samples are effectively excited by UV light chips ranging from 200 nm to 400 nm and exhibit broad emission bands due to the charge transfer from the oxygen 2p orbital to the vacant 3d orbital of the vanadium in the VO4. The color of these phosphors changes from yellow to light blue via blue-green with increasing ionic radius from Mg to Sr to Ba. The luminescence lifetimes and quantum yield decrease with the increasing unit cell volume and V-V distance, in the order of Mg3(VO4)2 to Sr3(VO4)2 to Ba3(VO4)2. The emission intensity decreases with the increase of temperatures, but presents no color shift. This confirms that these self-activated M3(VO4)2 phosphors can be suggested as candidates of the single-phase phosphors for light using UV light emitting diodes (LEDs).

Hydrothermal encapsulation of VO2(A) nanorods in amorphous carbon by carbonization of glucose for energy storage devices.

Science.gov (United States)

Zheng, Jiqi; Zhang, Yifu; Wang, Qiushi; Jiang, Hanmei; Liu, Yanyan; Lv, Tianming; Meng, Changgong

2018-01-02

In recent decades, tremendous attention has been paid to the development of new electrode materials with high capacitance to meet the requirements of electrode materials in supercapacitors. Among vanadium oxides, VO 2 (A) has recently received increasing attention due to its unique layered structure, phase transformation and applications in Li-ion batteries. However, few studies have focused on the electrochemical properties of VO 2 (A) as electrochemical capacitors. Herein, we develop a facile hydrothermal method to prepare VO 2 (A)@C core-shell structured composites by carbonization of glucose in the presence of V 2 O 5 nanowires. The electrochemical properties of the VO 2 (A)@C core-shell composites are investigated as a supercapacitor electrode material for the first time; the composites show excellent pseudocapacitive behavior and display a specific capacitance as high as 179 F g -1 at 1 A g -1 . A flexible asymmetric supercapacitor device is fabricated using VO 2 (A)@C composites and activated carbon and delivers an excellent capacitance of 0.5 F cm -2 at a scan rate of 5 mV s -1 . Replacing the aqueous electrolyte with a LiCl/PVA gel electrolyte can efficiently improve the cycling performance to 85% retention after 1600 cycles. The good electrochemical performance of the composites indicates their high potential as electrode materials for supercapacitors.

Preparation and characterization of graphene-based vanadium oxide composite semiconducting films with horizontally aligned nanowire arrays

International Nuclear Information System (INIS)

Jung, Hye-Mi; Um, Sukkee

2016-01-01

Highly oriented crystalline hybrid thin films primarily consisting of Magnéli-phase VO 2 and conductive graphene nanoplatelets are fabricated by a sol–gel process via dipping pyrolysis. A combination of chemical, microstructural, and electrical analyses reveals that graphene oxide (GO)-templated vanadium oxide (VO x ) nanocomposite films exhibit a vertically stacked multi-lamellar nanostructure consisting of horizontally aligned vanadium oxide nanowire (VNW) arrays along the (hk0) set of planes on a GO template, with an average crystallite size of 41.4 Å and a crystallographic tensile strain of 0.83%. In addition, GO-derived VO x composite semiconducting films, which have an sp 3 /sp 2 bonding ratio of 0.862, display thermally induced electrical switching properties in the temperature range of − 20 °C to 140 °C, with a transition temperature of approximately 65 °C. We ascribe these results to the use of GO sheets, which serve as a morphological growth template as well as an electrochemically tunable platform for enhancing the charge-carrier mobility. Moreover, the experimental studies demonstrate that graphene-based Magnéli-phase VO x composite semiconducting films can be used in advanced thermo-sensitive smart sensing/switching applications because of their outstanding thermo-electrodynamic properties and high surface charge density induced by the planar-type VNWs. - Highlights: • VO x -graphene oxide composite (G/VO x ) films were fabricated by sol–gel process. • The G/VO x films mainly consisted of Magnéli-phase VO 2 and reduced graphene sheets. • The G/VO x films exhibited multi-lamellar textures with planar VO x nanowire arrays. • The G/VO x films showed the thermo-sensitive electrical switching properties. • Effects of GOs on the electrical characteristics of the G/VO x films were discussed.

Electron spin resonance of vanadium(4)-thallium(1) dithiocarbamate complexes

International Nuclear Information System (INIS)

Ivanov, A.V.; Solozhenkin, P.M.; Baratova, Z.R.; Klyashtornyj, V.B.; Uskov, V.Yu.

1990-01-01

Heteronuclear vanadium(4), thallium(1) dithiocarbanate complexes of the composition TlVO(Dtc) 3 and Tl 2 VO(Dtc) 4 under conditions of magnetic dilution were studied by ESR spectroscopy. Magnetically diluted complexes were prepared by coprecipitation from aqueous solutions of thallium(1) and oxovanadium(2) by solutions of sodium diethyldithiocarbamate, dibutyldithiocarbamate, hexamethylenedithiocarbamate, taken in superstoichiometric excess. Analysis of parameters of ESR spectra of the complexes synthesized shows that thallium atoms are not included in the first coordination sphere of oxovanadium(2), and chelate node VS 4 in thallium(1) complex lattice practically preserves its plane quadratic structure

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

International Nuclear Information System (INIS)

Zhang, Jianlu; Li, Liyu; Nie, Zimin; Chen, Baowei; Vijayakumar, M.; Kim, Soowhan; Wang, Wei; Schwenzer, Birgit; Liu, Jun; Yang, Zhenguo

2011-01-01

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.

Numerical studies of carbon paper-based vanadium redox flow batteries

International Nuclear Information System (INIS)

Won, Seongyeon; Oh, Kyeongmin; Ju, Hyunchul

2016-01-01

ABSTRACT: This study analyzed theoretically the effects of a carbon paper (CP)-based electrode on the performance of a vanadium redox flow battery (VRFB). Compared to conventional carbon felt-based electrode materials, the CP-based electrode showed superior characteristics in facilitating the redox reactions of VO"2"+/VO_2"+ and V"2"+/V"3"+ couples, such as better electrochemical activity and higher electronic conductivity. A three-dimensional, non-isothermal VRFB model developed in a previous study was applied to a range of single cell structures equipped with CP-based electrodes and flow channels in the current collectors. The model was then validated using the experimental data measured under the CP- and channel-based VRFB geometries. The model successfully captured the experimental trend that showed a higher discharging performance with increasing number of CP layers used for each electrode. The simulation results clearly showed that the activation overpotentials in the electrodes were reduced significantly using more CP layers, which dominated over the effects of increased mass transport limitation of vanadium ions due to the thicker electrode.

Excited State Dynamics and Semiconductor-to-Metallic Phase Transition of VO2 Thin Film

National Research Council Canada - National Science Library

Liu, Huimin

2004-01-01

.... Vanadium dioxide shows an ultrafast, passive phase transition (PT) from a monoclinic semiconductor phase to a metallic tetragonal rutile structure when the sample temperature is above 68 degrees C...

Time limit and VO2 slow component at intensities corresponding to VO2max in swimmers.

Science.gov (United States)

Fernandes, R J; Cardoso, C S; Soares, S M; Ascensão, A; Colaço, P J; Vilas-Boas, J P

2003-11-01

The purpose of this study was to measure, in swimming pool conditions and with high level swimmers, the time to exhaustion at the minimum velocity that elicits maximal oxygen consumption (TLim at vVO(2)max), and the corresponding VO(2) slow component (O(2)SC). The vVO(2)max was determined through an intermittent incremental test (n = 15). Forty-eight hours later, TLim was assessed using an all-out swim at vVO(2)max until exhaustion. VO(2) was measured through direct oximetry and the swimming velocity was controlled using a visual light-pacer. Blood lactate concentrations and heart rate values were also measured. Mean VO(2)max for the incremental test was 5.09 +/- 0.53 l/min and the corresponding vVO(2)max was 1.46 +/- 0.06 m/s. Mean TLim value was 260.20 +/- 60.73 s and it was inversely correlated with the velocity of anaerobic threshold (r = -0.54, p energy cost of the respiratory muscles (r = 0.51), for p swimming pool, in high level swimmers performing at vVO(2)max, and that higher TLim seems to correspond to higher expected O(2)SC amplitude. These findings seem to bring new data with application in middle distance swimming.

Structural, thermal and optical properties of TeO2-ZnO-CdO-BaO glasses doped with VO(2+).

Science.gov (United States)

Sreenivasulu, V; Upender, G; Chandra Mouli, V; Prasad, M

2015-09-05

The glasses with composition 64TeO2-15ZnO-(20-x)CdO-xBaO-1V2O5 (0⩽x⩽20 mol%) were prepared by conventional melt quenching technique. X-ray diffraction analysis was used to confirm the amorphous nature of the glasses. The optical absorption studies revealed that the cut-off wavelength (λα) decreases while optical band gap energy (Eopt) and Urbach energy (ΔE) values increase with an increase of BaO content. Refractive index (n) evaluated from Eopt was found to decrease with an increase of BaO content. The physical parameters such as density (ρ), molar volume (Vm), oxygen packing density (OPD), optical basicity (Λ), molar refraction (Rm), and metallization criterion (M) evaluated and discussed. FTIR and Raman spectroscopic studies showed that the glass network consists of TeO4, TeO3+1/TeO3 and ZnO4 units as basic structural units. The glass transition temperature (Tg) of glass sample, onset crystallization temperature (To) and thermal stability ΔT were determined from Differential Scanning Calorimetry (DSC). Using electron paramagnetic resonance (EPR) spectra of vanadium glasses the spin Hamiltonian parameters and dipolar hyperfine coupling parameters of VO(2+) ions were calculated. It was found that V(4+) ions in these glasses exist as VO(2+) in octahedral coordination with a tetragonal distortion and have C4V symmetry with ground state dxy. Tetragonality (Δg∥/Δg⊥) of vanadium ion sites exhibited non-linear variation with BaO content. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of V2O5 Content on the Gas-Based Direct Reduction of Hongge Vanadium Titanomagnetite Pellets with Simulated Shaft Furnace Gases

Science.gov (United States)

Li, Wei; Fu, Guiqin; Chu, Mansheng; Zhu, Miaoyong

2018-01-01

The influence of V2O5 content on the gas-based direct reduction of Hongge vanadium titanomagnetite pellets (HVTMP) was investigated with simulated shaft furnace gases, and the content levels were selected as 0 wt.%, 2 wt.%, 4 wt.%, and 6 wt.%, respectively. The results indicated that, with the increase of V2O5 content, the reduction was accelerated at an early stage due to the increase of the original porosity of the HVTMP. However, as the reduction proceeded, a slowing down in the reduction rate was observed, which was attributed to the formation of hardly reducible Fe2VO4. Major phases of reduced HVTMP were Fe2VO4, FeTiO3, and metallic iron. The morphology showed that the size of metallic iron particles of reduced HVTMP decreased with the increase of V2O5 content, V-bearing oxides embedded into the Ti-rich phases, and further reduction was restricted. This study not only established a relationship between the V2O5 content of HVTMP and its reduction behavior but could also contribute greatly to the effective utilization of Hongge vanadium titanomagnetite in shaft furnace.

Vaporization study on vanadium-oxygen solid solution by mass spectrometric method

International Nuclear Information System (INIS)

Banchorndhevakul, W.; Matsui, Tsuneo; Naito, Keiji

1986-01-01

The vapor pressures over vanadium-oxygen solid solution (0.001 ≤ O/V ≤ 0.145) were measured by mass-spectrometric method in the temperature range of 1,855 ∼ 2,117 K. The main vapor species were observed to be V(g) and VO(g). The vapor pressure of V(g) is higher than that of VO(g) over the solid solutions with all O/V ratios except for O/V = 0.145. The vapor pressure of V(g) is nearly independent of O/V ratio. The vapor pressure of VO(g) decreases with decreasing O/V ratio. The oxygen partial pressure was calculated as a function of temperature and O/V ratio from the vapor pressures of V(g) and VO(g), from which the partial molar enthalpy and entropy of oxygen in the solid solution were determined. The partial molar enthalpy of oxygen was observed to be independent of composition, suggesting the presence of very weak interaction between interstitial oxygens. The compositional dependence of the partial molar entropy of oxygen can be explained by assuming the occupation of the octahedral site in bcc vanadium lattice by the interstitial oxygens. The excess partial molar entropy of oxygen was compared with the value derived from the sum of the contributions from the volume expansion, electronic heat capacity and vibrational terms. (author)

Strategies for enhancing electrochemical activity of carbon-based electrodes for all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Flox, Cristina; Skoumal, Marcel; Rubio-Garcia, Javier; Andreu, Teresa; Morante, Juan Ramón

2013-01-01

Highlights: ► Improved reactions at the positive electrode in all-vanadium redox flow batteries. ► Graphene-derived and PAN-modified electrodes have been successfully prepared. ► Modification with bimetallic CuPt 3 nanocubes yielded the best catalytic behavior. ► N and O-containing groups enhances the vanadium flow battery performance. - Abstract: Two strategies for improving the electroactivity towards VO 2+ /VO 2 + redox pair, the limiting process in all-vanadium redox flow batteries (VFBs), were presented. CuPt 3 nanoparticles supported onto graphene substrate and nitrogen and oxygen polyacrylonitrile (PAN)-functionalized electrodes materials have been evaluated. The morphology, composition, electrochemical properties of all electrodes prepared was characterized with field emission-scanning electrode microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy and cell charge–discharge test. The presence of the CuPt 3 nanocubes and nitrogen and oxygen functionalities enhance the electrocatalytic activity of the electrodes materials accelerating the oxygen and electron transfer processes. The battery performance was also evaluated using PAN-functionalized electrodes exhibiting a high of energy efficiency of 84% (at current density 20 mA cm −2 ) up to 30th cycle, indicating a promising alternative for improving the VFB

A novel inorganic precipitation-peptization method for VO2 sol and VO2 nanoparticles preparation: Synthesis, characterization and mechanism.

Science.gov (United States)

Li, Yao; Jiang, Peng; Xiang, Wei; Ran, Fanyong; Cao, Wenbin

2016-01-15

In this paper, a simple, safe and cost-saving precipitation-peptization method was proposed to prepare VO2 sol by using inorganic VOSO4-NH3⋅H2O-H2O2 reactants system in air under room temperature. In this process, VOSO4 was firstly precipitated to form VO(OH)2, then monometallic species of VO(O2)(OH)(-) were formed through the coordination between VO(OH)2 and H2O2. The rearrangement of VO(O2)(OH)(-) in a nonplanar pattern and intermolecular condensation reactions result in multinuclear species. Finally, VO2 sol is prepared through the condensation reactions between the multinuclear species. After drying the obtained sol at 40°C, VO2 xerogel exhibiting monoclinic crystal structure with the space group of C2/m was prepared. The crystal structure of VO2 nanoparticles was transferred to monoclinic crystal structure with the space group of P21/c (VO2(M)) by annealing the xerogel at 550°C. Both XRD and TEM analysis indicated that the nanoparticles possess good crystallinity with crystallite size of 34.5nm as estimated by Scherrer's method. These results suggest that the VO2 sol has been prepared successfully through the proposed simple method. Copyright © 2015 Elsevier Inc. All rights reserved.

Effect of vanadium treatment on tissue distribution of biotrace elements in normal and streptozotocin-induced diabetic rats. Simultaneous analysis of V and Zn using radioactive multitracer

International Nuclear Information System (INIS)

Yasui, Hiroyuki; Takino, Toshikazu; Fugono, Jun; Sakurai, Hiromu; Hirunuma, Rieko; Enomoto, Shuichi

2001-01-01

Because vanadium ions such as vanadyl (VO 2+ ) and vanadate (VO 3- ) ions were demonstrated to normalize blood glucose levels of diabetic animals and patients, the action mechanism of vanadium treatment has been of interest. In this study, we focused on understanding interactions among trace elements in diabetic rats, in which a multitracer technique was used. The effects of vanadyl sulfate (VS)-treatment on the tissue distribution of trace vanadium ( 48 V) and zinc ( 65 Zn) in normal and streptozotocin (STZ)-induced diabetic rats were examined, and were evaluated in terms of the uptake ratio. The uptake ratio of both elements in tissues significantly changed between STZ-rats and those treated with VS. These results indicated that vanadium treatment in STZ-rats alters the tissue distribution of endogenous elements, suggesting the importance of the relationship between biotrace elements and pathophysiology. (author)

Efficient photocarrier injection in a transition metal oxide heterostructure

CERN Document Server

Muraoka, Y; Ueda, Y; Hiroi, Z

2002-01-01

An efficient method for doping a transition metal oxide (TMO) with hole carriers is presented: photocarrier injection (PCI) in an oxide heterostructure. It is shown that an insulating vanadium dioxide (VO sub 2) film is rendered metallic under light irradiation by PCI from an n-type titanium dioxide (TiO sub 2) substrate doped with Nb. Consequently, a large photoconductivity, which is exceptional for TMOs, is found in the VO sub 2 /TiO sub 2 :Nb heterostructure. We propose an electronic band structure where photoinduced holes created in TiO sub 2 :Nb can be transferred into the filled V 3d band via the low-lying O 2p band of VO sub 2. (letter to the editor)

Structural Modification of Sol-Gel Synthesized V2O5 and TiO2 Thin Films with/without Erbium Doping

Directory of Open Access Journals (Sweden)

Fatma Pınar Gökdemir

2014-01-01

Full Text Available Comparative work of with/without erbium- (Er- doped vanadium pentoxide (V2O5 and titanium dioxide (TiO2 thin films were carried out via sol-gel technique by dissolving erbium (III nitrate pentahydrate (Er(NO33·5H2O in vanadium (V oxoisopropoxide (OV[OCH(CH32]3 and titanium (IV isopropoxide (Ti[OCH(CH32]4. Effect of Er doping was traced by Fourier transform IR (FTIR, thermogravimetric/differential thermal (TG/DTA, and photoluminescence measurements. UV-Vis transmission/absorption measurement indicated a blue shift upon Er doping in V2O5 film due to the softening of V=O bond while appearance of typical absorption peaks in Er-doped TiO2 film. Granule size of the films increased (reduced upon Er substitution on host material compared to undoped V2O5 and TiO2 films, respectively.

Rapid characterization of thermoelectric properties of composition spread (La1-xCax)VO3 films

International Nuclear Information System (INIS)

Itaka, K.; Wang, Q.J.; Minami, H.; Kawaji, H.; Koinuma, H.

2004-01-01

Vanadium oxides possess various interesting properties due to multivalence of a vanadium atom and attract our interest as a target material for the exploration of new applications. We investigated vanadates (La 1-x Ca x )VO 3 with a perovskite structure as thermoelectric (TE) materials because heavy electrons in vanadates are expected to generate large thermopower. To proceed the investigation of thermoelectric properties of the composition spread library more efficiently, we devised a new instrument of multi-channel measurement of their thermoelectric properties. The polarity of Seebeck coefficients changed from positive (0≤x≤0.2) to negative (0.2 3 (x∼0)

Preparation and characterization of phosphate glasses containing titanium and vanadium

Energy Technology Data Exchange (ETDEWEB)

Kaoua, S. [Laboratoire de Chimie du Solide, Faculte des Sciences Ain Chock, Casablanca (Morocco); Krimi, S. [Laboratoire de Chimie du Solide, Faculte des Sciences Ain Chock, Casablanca (Morocco)]. E-mail: krimisaida@yahoo.fr; El Jazouli, A. [Laboratoire de Chimie des Materiaux Solides, Faculte des Sciences Ben M' Sik, Casablanca (Morocco); Hlil, E.K. [Laboratoire de Cristallographie du CNRS, Grenoble (France)]. E-mail: hlil@grenoble.cnrs.fr; Waal, D. de [Department of Chemistry, University of Pretoria, 0002 Pretoria (South Africa)

2007-02-21

Na{sub 5-x}Ti{sub 1-x}V {sub x}(PO{sub 4}){sub 3} (0 {<=} x {<=} 1) phosphates glasses have been obtained in air by direct fusion of Na{sub 2}CO{sub 3}, TiO{sub 2}, V{sub 2}O{sub 5} and (NH{sub 4}){sub 2}HPO{sub 4}. Vitreous Na{sub 5}Ti(PO{sub 4}){sub 3} is colourless while the glasses containing vanadium are green, due to the reduction of V{sup 5+} to V{sup 4+}. Glass transition and crystallization temperatures (T {sub g}, T {sub c}) decrease when the amount of vanadium increases. EPR, Raman and UV-vis spectra have been investigated. The results are consistent with the presence of V{sup 4+} ions in distorted octahedra with very strong V-O bond.

New Methods for Processing and Quantifying VO2 Kinetics to Steady State: VO2 Onset Kinetics

Directory of Open Access Journals (Sweden)

Craig R. McNulty

2017-09-01

Full Text Available Current methods of oxygen uptake (VO2 kinetics data handling may be too simplistic for the complex physiology involved in the underlying physiological processes. Therefore, the aim of this study was to quantify the VO2 kinetics to steady state across the full range of sub-ventilatory threshold work rates, with a particular focus on the VO2 onset kinetics. Ten healthy, moderately trained males participated in five bouts of cycling. Each bout involved 10 min at a percentage of the subject's ventilation threshold (30, 45, 60, 75, 90% from unloaded cycling. The VO2 kinetics was quantified using the conventional mono-exponential time constant (tau, τ, as well as the new methods for VO2 onset kinetics. Compared to linear modeling, non-linear modeling caused a deterioration of goodness of fit (main effect, p < 0.001 across all exercise intensities. Remainder kinetics were also improved using a modified application of the mono-exponential model (main effect, p < 0.001. Interestingly, the slope from the linear regression of the onset kinetics data is similar across all subjects and absolute exercise intensities, and thereby independent of subject fitness and τ. This could indicate that there are no functional limitations between subjects during this onset phase, with limitations occurring for the latter transition to steady state. Finally, the continuing use of mono-exponential modeling could mask important underlying physiology of more instantaneous VO2 responses to steady state. Consequently, further research should be conducted on this new approach to VO2 onset kinetics.

Effect of vanadium treatment on tissue distribution of biotrace elements in normal and streptozotocin-induced diabetic rats. Simultaneous analysis of V and Zn using radioactive multitracer

Energy Technology Data Exchange (ETDEWEB)

Yasui, Hiroyuki; Takino, Toshikazu; Fugono, Jun; Sakurai, Hiromu [Department of Analytical and Bioinorganic Chemistry, Kyoto Pharmaceutical University, Kyoto (Japan); Hirunuma, Rieko; Enomoto, Shuichi [Radioisotope Technology Division, Cyclotron Center, Institute of Physical and Chemical Research (RIKEN), Wako, Saitama (Japan)

2001-05-01

Because vanadium ions such as vanadyl (VO{sup 2+}) and vanadate (VO{sup 3-}) ions were demonstrated to normalize blood glucose levels of diabetic animals and patients, the action mechanism of vanadium treatment has been of interest. In this study, we focused on understanding interactions among trace elements in diabetic rats, in which a multitracer technique was used. The effects of vanadyl sulfate (VS)-treatment on the tissue distribution of trace vanadium ({sup 48}V) and zinc ({sup 65}Zn) in normal and streptozotocin (STZ)-induced diabetic rats were examined, and were evaluated in terms of the uptake ratio. The uptake ratio of both elements in tissues significantly changed between STZ-rats and those treated with VS. These results indicated that vanadium treatment in STZ-rats alters the tissue distribution of endogenous elements, suggesting the importance of the relationship between biotrace elements and pathophysiology. (author)

Partial Oxidation of n-Butane over a Sol-Gel Prepared Vanadium Phosphorous Oxide

Directory of Open Access Journals (Sweden)

Juan M. Salazar

2013-01-01

Full Text Available Vanadium phosphorous oxide (VPO is traditionally manufactured from solid vanadium oxides by synthesizing VOHPO4∙0.5H2O (the precursor followed by in situ activation to produce (VO2P2O7 (the active phase. This paper discusses an alternative synthesis method based on sol-gel techniques. Vanadium (V triisopropoxide oxide was reacted with ortho-phosphoric acid in an aprotic solvent. The products were dried at high pressure in an autoclave with a controlled excess of solvent. This procedure produced a gel of VOPO4 with interlayer entrapped molecules. The surface area of the obtained materials was between 50 and 120 m2/g. Alcohol produced by the alkoxide hydrolysis reduced the vanadium during the drying step, thus VOPO4 was converted to the precursor. This procedure yielded non-agglomerated platelets, which were dehydrated and evaluated in a butane-air mixture. Catalysts were significantly more selective than the traditionally prepared materials with similar intrinsic activity. It is suggested that the small crystallite size obtained increased their selectivity towards maleic anhydride.

Fabrication of polypyrrole/vanadium oxide nanotube composite with enhanced electrochemical performance as cathode in rechargeable batteries

International Nuclear Information System (INIS)

Zhou, Xiaowei; Chen, Xu; He, Taoling; Bi, Qinsong; Sun, Li; Liu, Zhu

2017-01-01

Highlights: • VO_xNTs were hydrothermally prepared using C_1_2H_2_7N as soft template with scalability. • Polypyrrole/VO_xNTs with less C_1_2H_2_7N template and higher conductivity were obtained. • Polypyrrole/VO_xNTs exhibit better performance as cathode for LIBs compared to VO_xNTs. • Further modification to VO_xNTs with desired electrochemical property can be expected. - Abstract: Vanadium oxide nanotubes (VO_xNTs) with hollow as well as multi-walled features were fabricated under hydrothermal condition by soft-template method. This novel VO_xNTs can be used as cathode material for lithium ion batteries (LIBs), but displaying low specific capacity and poor cycling performance owing to the residual of a mass of soft-template (C_1_2H_2_7N) and intrinsic low conductivity of VO_x. Cation exchange technique and oxidative polymerization process of pyrrole monomers were conducted to wipe off partial soft-template without electrochemical activity within VO_xNTs and simultaneously form polypyrrole coating on VO_xNTs, respectively. The resulting polypyrrole/VO_xNTs nanocomposite delivers much improved capacity and cyclic stability. Further optimizations, such as complete elimination of organic template and enhancing the crystallinity, can make this unique nanostructure a promising cathode for LIBs.

Vanadium oxide nanotubes as cathode material for Mg-ion batteries

DEFF Research Database (Denmark)

Christensen, Christian Kolle; Sørensen, Daniel Risskov; Bøjesen, Espen Drath

Vanadium oxide compounds as cathode material for secondary Li-ion batteries gained interest in the 1970’s due to high specific capacity (>250mAh/g), but showed substantial capacity fading.1 Developments in the control of nanostructured morphologies have led to more advanced materials, and recently...... vanadium oxide nanotubes (VOx-NT) were shown to perform well as a cathode material for Mg-ion batteries.2 The VOx-NTs are easily prepared via a hydrothermal process to form multiwalled scrolls of VO layer with primary amines interlayer spacer molecules.3 The tunable and relative large layer spacing 1-3 nm...... synchrotron powder X-ray diffraction measured during battery operation. These results indicate Mg-intercalation in the multiwalled VOx-NTs occurs within the space between the individual vanadium oxide layers while the underlying VOx frameworks constructing the walls are affected only to a minor degree...

Color and vanadium valency in V-doped ZrO2

International Nuclear Information System (INIS)

Ren, Feng; Ishida, Shingo; Takeuchi, Nobuyuki

1993-01-01

The distribution and chemical states of vanadium in V-doped ZrO 2 were studied to clarify the origin of the color of vanadium-zirconium yellow pigment in comparison with vanadium-tin yellow pigment. ESCA data and measurements of lattice constants of V-doped ZrO 2 revealed that vanadium was dissolved mainly as V 4+ substituting for Zr in ZrO 2 lattice, and its solubility limit was 0.5 wt% as V 2 O 5 . It was found that the yellow color of vanadium-zirconium yellow was produced predominantly by the dissolved vanadium and that the contribution of vanadium oxide on ZrO 2 grains to the yellow color was about 1.30 of that of the dissolved vanadium when compared on the basis of equimolar quantity of vanadium. Most of the undissolved vanadium oxide was in an amorphous or a poorly crystallized state

A novel vanadium oxide deposit for the cathode of asymmetric lithium-ion supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Li, Jing-Mei; Hu, Chi-Chang [Department of Chemical Engineering, National Tsing Hua University, Hsin-Chu (China); Chang, Kuo-Hsin [Department of Chemical Engineering, National Chung Cheng University, Chia-Yi (China)

2010-12-15

Hydrous vanadium oxide (denoted as VO{sub x}.yH{sub 2}O) deposited at 0.4 V shows promising capacitive behavior in aqueous media containing concentrated Li ions. VO{sub x}.yH{sub 2}O annealed in air at 300 C for 1 h shows highly reversible Li-ion intercalation/de-intercalation behavior with specific capacitance reaching ca. 737 and 606 F g{sup -} {sup 1} at 25 and 500 mV s{sup -1} in 12 M LiCl between -0.2 and 0.8 V. In 14 M LiCl, retention of specific capacitance is about 95% when the scan rate is increased from 25 to 500 mV s{sup -} {sup 1}. This work is the first report showing the ultrahigh rate of Li-ion intercalation/de-intercalation in VO{sub x}.yH{sub 2}O. A so-called Li-ion supercapacitor of the asymmetric type consisting of a VO{sub x}.yH{sub 2}O cathode and a WO{sub 3}{sup .}zH{sub 2}O anode is proposed here. (author)

Effect of organic additives on positive electrolyte for vanadium redox battery

International Nuclear Information System (INIS)

Li Sha; Huang Kelong; Liu Suqin; Fang Dong; Wu Xiongwei; Lu Dan; Wu Tao

2011-01-01

Highlights: → Four organics as electrolyte additives of vanadium redox battery. → Changes are examined in the electrochemical properties of vanadium redox battery. → D-sorbitol is a suitable additive to the electrolyte for the vanadium redox battery. → The mechanism of improvement is discussed in detail. - Abstract: Fructose, mannitol, glucose, D-sorbitol are explored as additives in electrolyte for vanadium redox battery (VRB), respectively. The effects of additives on electrolyte are studied by cyclic voltammetry (CV), charge-discharge technique, electrochemical impedance spectroscopy (EIS) and Raman spectroscopy. The results indicate that the vanadium redox cell using the electrolyte with the additive of D-sorbitol exhibits the best electrochemical performance (the energy efficiency 81.8%). The EIS results indicate that the electrochemical activity of the electrolyte is improved by adding D-sorbitol, which can be interpreted as the increase of available (-OH) groups providing active sites for electron transfer. The Raman spectra show that VO 2+ ions take part in forming a complex with the D-sorbitol, which not only improve solubility of V(V) electrolyte, but also provide more activity sites for the V(IV)/V(V) redox reaction.

Effect of organic additives on positive electrolyte for vanadium redox battery

Energy Technology Data Exchange (ETDEWEB)

Li Sha [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Huang Kelong, E-mail: lisha_csu@163.com [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Liu Suqin; Fang Dong; Wu Xiongwei; Lu Dan; Wu Tao [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

2011-06-30

Highlights: > Four organics as electrolyte additives of vanadium redox battery. > Changes are examined in the electrochemical properties of vanadium redox battery. > D-sorbitol is a suitable additive to the electrolyte for the vanadium redox battery. > The mechanism of improvement is discussed in detail. - Abstract: Fructose, mannitol, glucose, D-sorbitol are explored as additives in electrolyte for vanadium redox battery (VRB), respectively. The effects of additives on electrolyte are studied by cyclic voltammetry (CV), charge-discharge technique, electrochemical impedance spectroscopy (EIS) and Raman spectroscopy. The results indicate that the vanadium redox cell using the electrolyte with the additive of D-sorbitol exhibits the best electrochemical performance (the energy efficiency 81.8%). The EIS results indicate that the electrochemical activity of the electrolyte is improved by adding D-sorbitol, which can be interpreted as the increase of available (-OH) groups providing active sites for electron transfer. The Raman spectra show that VO{sup 2+} ions take part in forming a complex with the D-sorbitol, which not only improve solubility of V(V) electrolyte, but also provide more activity sites for the V(IV)/V(V) redox reaction.

Comparison of distribution and toxicity following repeated oral dosing of different vanadium oxide nanoparticles in mice

Energy Technology Data Exchange (ETDEWEB)

Park, Eun-Jung, E-mail: pejtoxic@hanmail.net [Myunggok Eye Research Institute, Konyang University, Daejeon 302-718 (Korea, Republic of); Lee, Gwang-Hee [School of Civil, Environmental, and Architectural Engineering, Korea University, Seoul 136-713 (Korea, Republic of); Yoon, Cheolho [Seoul Center, Korea Basic Science Institute, Seoul 126-16 (Korea, Republic of); Kim, Dong-Wan, E-mail: dwkim1@korea.ac.kr [School of Civil, Environmental, and Architectural Engineering, Korea University, Seoul 136-713 (Korea, Republic of)

2016-10-15

Vanadium is an important ultra-trace element derived from fuel product combustion. With the development of nanotechnology, vanadium oxide nanoparticles (VO NPs) have been considered for application in various fields, thus the possibility of release into the environment and human exposure is also increasing. Considering that verification of bioaccumulation and relevant biological responses are essential for safe application of products, in this study, we aimed to identify the physicochemical properties that determine their health effects by comparing the biological effects and tissue distribution of different types of VO NPs in mice. For this, we prepared five types of VO NPs, commercial (C)-VO{sub 2} and -V{sub 2}O{sub 5} NPs and synthetic (S)-VO{sub 2}, -V{sub 2}O{sub 3,} and -V{sub 2}O{sub 5} NPs. While the hydrodynamic diameter of the two types of C-VO NPs was irregular and impossible to measure, those of the three types of S-VO NPs was in the range of 125–170 nm. The S- and C-V{sub 2}O{sub 5} NPs showed higher dissolution rates compared to other VO NPs. We orally dosed the five types of VO NPs (70 and 210 μg/mouse, approximately 2 and 6 mg/kg) to mice for 28 days and compared their biodistribution and toxic effects. We found that S-V{sub 2}O{sub 5} and S-V{sub 2}O{sub 3} NPs more accumulated in tissues compared to other three types of VO NPs, and the accumulated level was in order of heart>liver>kidney>spleen. Additionally, tissue levels of redox reaction-related elements and electrolytes (Na{sup +}, K{sup +}, and Ca{sup 2+}) were most clearly altered in the heart of treated mice. Notably, all S- and C-VO NPs decreased the number of WBCs at the higher dose, while total protein and albumin levels were reduced at the higher dose of S-V{sub 2}O{sub 5} and S-V{sub 2}O{sub 3} NPs. Taken together, we conclude that the biodistribution and toxic effects of VO NPs depend on their dissolution rates and size (surface area). Additionally, we suggest that further studies

Nitrogen-Doped Graphene:Effects of nitrogen species on the properties of the vanadium redox flow battery

International Nuclear Information System (INIS)

Shi, Lang; Liu, Suqin; He, Zhen; Shen, Junxi

2014-01-01

Nitrogen-doped graphene nanosheets (NGS), prepared by a simple hydrothermal reaction of graphene oxide (GO) with urea as nitrogen source were studied as positive electrodes in vanadium redox flow battery (VRFB). The synthesized NGS with the nitrogen level as high as 10.12 atom% is proven to be a promising material for VRFB. The structures and electrochemical properties of the materials are investigated by scanning electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry and electrochemical impendence spectroscopy. The results demonstrate that not only the nitrogen doping level but the nitrogen type in the NGS are significant for its catalytic activity towards the [VO] 2+ /[VO 2 ] + redox couple reaction. In more detail, among four types of nitrogen species (pyridinic-N, pyrrolic-N, quaternary-N, oxidic-N) doped into the graphene lattice, quaternary-N play mainly roles for improving the catalytic activity toward the [VO] 2+ /[VO 2 ] + couple reaction

A comparison of VO2max and metabolic variables between treadmill running and treadmill skating.

Science.gov (United States)

Koepp, Kriston K; Janot, Jeffrey M

2008-03-01

The purpose of this study was to determine differences in VO2max and metabolic variables between treadmill running and treadmill skating. This study also examined VO2max responses during a continuous skating treadmill protocol and a discontinuous skating treadmill protocol. Sixteen male high school hockey players, who had a mean age of 16 +/- 1 years and were of an above-average fitness level, participated in this study. All subjects completed 4 exercise trials: a 1-hour skating treadmill familiarization trial, a treadmill running trial, and 2 randomized skating treadmill trials. Minute ventilation (VE), oxygen consumption VO2), carbon dioxide production VCO2), respiratory exchange ratio (RER), and heart rate were averaged every 15 seconds up to VO2max for each exercise test. The results showed that there was a significant difference (P skating treadmill protocol. There was also a significant difference for maximal RER between the discontinuous and continuous skating treadmill protocol and between the discontinuous skating treadmill protocol and running treadmill protocol. In conclusion, the running treadmill elicited a greater VO2max (mL.kg.min) than the skating treadmill did, but when it comes to specificity of ice skating, the skating treadmill may be ideal. Also, there was no significant difference between the discontinuous and continuous skating treadmill protocols. Therefore, a continuous protocol is possible on the skating treadmill without compromising correct skating position and physiologic responses. However, the continuous skating treadmill protocol should undergo validation before other scientists, coaches, and strength and conditioning professionals can apply it correctly.

Outstanding electrochemical performance of a graphene-modified graphite felt for vanadium redox flow battery application

Science.gov (United States)

González, Zoraida; Flox, Cristina; Blanco, Clara; Granda, Marcos; Morante, Juan R.; Menéndez, Rosa; Santamaría, Ricardo

2017-01-01

The development of more efficient electrode materials is essential to obtain vanadium redox flow batteries (VRFBs) with enhanced energy densities and to make these electrochemical energy storage devices more competitive. A graphene-modified graphite felt synthesized from a raw graphite felt and a graphene oxide water suspension by means of electrophoretic deposition (EPD) is investigated as a suitable electrode material in the positive side of a VRFB cell by means of cyclic voltammetry, impedance spectroscopy and charge/discharge experiments. The remarkably enhanced performance of the resultant hybrid material, in terms of electrochemical activity and kinetic reversibility towards the VO2+/VO2+, and mainly the markedly high energy efficiency of the VRFB cell (c.a. 95.8% at 25 mA cm-2) can be ascribed to the exceptional morphological and chemical characteristics of this tailored material. The 3D-architecture consisting of fibers interconnected by graphene-like sheets positively contributes to the proper development of the vanadium redox reactions and so represents a significant advance in the design of effective electrode materials.

Effect of vanadium on the obtaining of the titanium dioxide by Sol-Gel Method; Efeito do vanadio na obtencao de dioxido de titanio pelo Metodo Sol-Gel

Energy Technology Data Exchange (ETDEWEB)

Granado, S.R.; Silva, D.W.; Lopes, S.A.; Cavalheiro, A.A., E-mail: sandrogranado02@gmail.com [Universidade Estadual de Mato Grosso do Sul (CPTREN/UEMS), Navirai, MS (Brazil). Centro de Pesquisas Tecnologicas em Recursos Naturais

2011-07-01

The obtaining of transition metal modified titanium dioxide (TiO{sub 2}) can be a promising path to promote changes in crystal structure of anatase phase in order to displace the band gap toward frequencies near to visible region. The insertion of the heterovalent ions such as vanadium can be shift the titanium coordination number in the anatase matrix, leading to important changes in the photonic characteristics of the material. In Sol-Gel method, the presence of the non alkoxide precursors can affects the stability of the solution and the gelifying process, with consequences on the characteristics of the material. In this work, it was investigated the effect of 5mol% of vanadium by thermal analysis of the dried gel and XRD and adsorption isotherm in the samples obtained at different temperatures. The decomposition steps of the precursor were associated to phase formation in the material, leading to conclusion that the presence of vanadium affects the stability of anatase phase. (author)

Extrinsic and intrinsic properties in metal–insulator transition of hydrothermally prepared vanadium dioxide crystals

International Nuclear Information System (INIS)

Lee, Myeongsoon; Kim, Don

2014-01-01

The clear insulator (monoclinic-VO 2 ) to metal (rutile-VO 2 ) transition (IMT) was observed in electrical conductivity and differential scanning calorimeter (DSC) measurements at around 340 K, which is IMT temperature (T H ), in the hydrothermally prepared VO 2 crystals. The occurrence of metal to insulator transition (MIT) temperature (T C ) was observed below 333 K during the first resistance measurement cycle in the most of cases. The sudden jump of the electrical resistance at IMT and MIT points was amplified several times than that of the first cycle during the repeated successive thermal cycles (heating and cooling across the IMT and MIT temperatures). T C and T H shifted to higher temperature by the repeated successive thermal cycles. This shift and the amplified jump might be related to the mechanical stress between the VO 2 crystals, i.e. extrinsic properties. However, the starting point of MIT, T CS = ∼ 336 K, and the starting point of IMT, T HS = ∼ 338 K, kept almost constant during the repeated thermal cycles (< 10 times). These two temperatures may be related to the intrinsic properties of the VO 2 : the phase transitions initiated at these temperatures regardless of the number of the repeated thermal cycles. The neat surface of the VO 2 crystals was severely damaged and the average size of particles reduced from 110 nm to 70–90 nm after extensively repeated thermal cycles (> 70 times). The damaged surface and the smaller particles, which would be originated from the mechanical stress caused by crystal volume change during the first order transition of the VO 2 , would weaken the electrical conduction path (loosen grain boundaries) between the VO 2 single crystals and would result in the amplified jump at the following MIT. This report may boost the study for the improved stability and lifetime of the VO 2 based electronic devices. - Highlights: • The sharp phase transition in cluster of VO 2 crystals depends on repeated thermal cycles. �

Spectroscopic and optical properties of the VO2+ ion doped TeO2-TiO2-ZnO-Nb2O5 glass system

Science.gov (United States)

Swapna; Upender, G.; Sreenivasulu, V.; Prasad, M.

2016-04-01

Studies such as optical absorption, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Electron paramagnetic resonance (EPR) spectroscopy and Differential scanning calorimetry (DSC) were carried out on VO2+ ion doped TeO2-TiO2-ZnO-Nb2O5 glass system. Raman and FTIR spectra of the glasses revealed the presence of [TeO3], [TeO4] and [NbO6] structural units in the glass network. The Urbach energy (Δ E), cut-off wavelength (λ c ), optical band gap ( E opt ), optical basicity (Λ) and electron polarizability ( α) of the glasses were determined from optical absorption studies. The density ( ρ), molar volume ( V m ), oxygen molar volume ( V o ) and refractive index ( n) were also measured. Spin-Hamiltonian parameters were calculated from the EPR studies. When Nb2O5 was increased at the expense of ZnO, the density, optical band gap and Urbach energy of the glasses increased, and the electronic polarizability and optical basicity decreased. The EPR spectra clearly showed that vanadium was in the glass as VO2+ and occupied octahedral sites with tetrahedral compression. Spin-Hamiltonian parameters g‖ and g⊥ decreased as Nb2O5 content increased in the glass. The glass transition temperature ( T g ) also increased with increasing Nb2O5 content in the glass.

Water-activated graphite felt as a high-performance electrode for vanadium redox flow batteries

Science.gov (United States)

Kabtamu, Daniel Manaye; Chen, Jian-Yu; Chang, Yu-Chung; Wang, Chen-Hao

2017-02-01

A simple, green, novel, time-efficient, and potentially cost-effective water activation method was employed to enhance the electrochemical activity of graphite felt (GF) electrodes for vanadium redox flow batteries (VRFBs). The GF electrode prepared with a water vapor injection time of 5 min at 700 °C exhibits the highest electrochemical activity for the VO2+/VO2+ couple among all the tested electrodes. This is attributed to the small, controlled amount of water vapor that was introduced producing high contents of oxygen-containing functional groups, such as sbnd OH groups, on the surface of the GF fibers, which are known to be electrochemically active sites for vanadium redox reactions. Charge-discharge tests further confirm that only 5 min of GF water activation is required to improve the efficiency of the VRFB cell. The average coulombic efficiency, voltage efficiency, and energy efficiency are 95.06%, 87.42%, and 83.10%, respectively, at a current density of 50 mA cm-2. These voltage and energy efficiencies are determined to be considerably higher than those of VRFB cells assembled using heat-treated GF electrodes without water activation and pristine GF electrodes.

Vanadium

Science.gov (United States)

Kelley, Karen D.; Scott, Clinton T.; Polyak, Désirée E.; Kimball, Bryn E.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

Vanadium is used primarily in the production of steel alloys; as a catalyst for the chemical industry; in the making of ceramics, glasses, and pigments; and in vanadium redox-flow batteries (VRBs) for large-scale storage of electricity. World vanadium resources in 2012 were estimated to be 63 million metric tons, which include about 14 million metric tons of reserves. The majority of the vanadium produced in 2012 was from China, Russia, and South Africa.Vanadium is extracted from several different types of mineral deposits and from fossil fuels. These deposits include vanadiferous titanomagnetite (VTM) deposits, sandstone-hosted vanadium (with or without uranium) deposits (SSV deposits), and vanadium-rich black shales. VTM deposits are the principal source of vanadium and consist of magmatic accumulations of ilmenite and magnetite containing 0.2 to 1 weight percent vanadium pentoxide (V2O5). SSV deposits are another important source; these deposits have average ore grades that range from 0.1 to greater than 1 weight percent V2O5. The United States has been and is currently the main producer of vanadium from SSV deposits, particularly those on the Colorado Plateau. Vanadium-rich black shales occur in marine successions that were deposited in epeiric (inland) seas and on continental margins. Concentrations in these shales regularly exceed 0.18 weight percent V2O5 and can be as high as 1.7 weight percent V2O5. Small amounts of vanadium have been produced from the Alum Shale in Sweden and from ferrophosphorus slag generated during the reduction of phosphate to elemental phosphorus in ore from shales of the Phosphoria Formation in Idaho and Wyoming. Because vanadium enrichment occurs in beds that are typically only a few meters thick, most of the vanadiferous black shales are not currently economic, although they may become an important resource in the future. Significant amounts of vanadium are recovered as byproducts of petroleum refining, and processing of coal, tar

Studies on electronic spectrum and electron spin resonance of vanadium (IV) complexes with organophosphorus compounds and high molecular weight amines

International Nuclear Information System (INIS)

Sato, Taichi; Nakamura, Takato

1981-01-01

In the extraction of vanadium (IV) from aqueous solutions containing hydrochloric acid and/or a mixture of hydrochloric acid and lithium chloride by bis(2-ethylhexyl) hydrogenphosphate (DEHPA; HX), trioctylmethylammonium chloride (Aliquat-336), trioctylamine (TOA), trioctylphosphine oxide (TOPO) and tributyl phosphate (TBP), the complexes formed in the organic phases have been examined by spectrophotometry and electron spin resonance spectroscopy. It is found that in the extraction by DEHPA, the vanadium in the organic phase exists as the monomeric species, VO(X 2 H) 2 , or the polymeric one, (VOX 2 )sub(n), and that in the extractions by Aliquat-336, TOA, TOPO, and TBP, tetravalent vanadium complexes are stable in the organic phases extracted from a mixed solution of hydrochloric acid and lithium chloride, while complexes containing pentavalent vanadium and VOV 4+ ions are formed in the organic phases extracted from hydrochloric acid solutions. (author)

Vanadium oxide thin films deposited on silicon dioxide buffer layers by magnetron sputtering

International Nuclear Information System (INIS)

Chen Sihai; Ma Hong; Wang Shuangbao; Shen Nan; Xiao Jing; Zhou Hao; Zhao Xiaomei; Li Yi; Yi Xinjian

2006-01-01

Thin films made by vanadium oxide have been obtained by direct current magnetron sputtering method on SiO 2 buffer layers. A detailed electrical and structural characterization has been performed on the deposited films by four-point probe method and scanning electron microscopy (SEM). At room temperature, the four-point probe measurement result presents the resistance of the film to be 25 kU/sheet. The temperature coefficient of resistance is - 2.0%/K. SEM image indicates that the vanadium oxide exhibits a submicrostructure with lamella size ranging from 60 nm to 300 nm. A 32 x 32-element test microbolometer was fabricated based on the deposited thin film. The infrared response testing showed that the response was 200 mV. The obtained results allow us to conclude that the vanadium oxide thin films on SiO 2 buffer layers is suitable for uncooled focal plane arrays applications

An electrochemical study of the systems Li1+-xV2O4 and Li1-xVO2 (0≤x≤1)

International Nuclear Information System (INIS)

De Picciotto, L.A.; Thackeray, M.M.; Pistoia, G.

1988-01-01

Electrochemical properties of the systems Li 1±x V 2 O 4 (0≤x≤1), Li 1-x VO 2 (0≤x 2 O 4 is reversible, which confirms that lithium may be cycled, topotactically, in and out of the Li 1+x V 2 O 4 spinel structure. Delithiation of the LiV 2 O 4 spinel is irreversible; during this process the vanadium ions migrate through the oxide layers. This results in a defect rocksalt phase, which can, in turn, be relithiated by a different mechanism. Lithium extraction for the layered compound LiVO 2 yields a structure similar to the delithiated LiV 2 O 4 product. The spinel-derived compounds Li 1 +-x/V 2 O 4 (0 -3 Ω -1 cm -1 at x=0 and 10 -6 Ω -1 cm -1 at x=1. Lithium diffusion rates in Li 1±x V 2 O 4 samples increase with lithiation from D=4x10 -10 cm 2 /s in LiV 2 O 4 to D=6x10 -8 cm 2 /s in Li 2 V 2 O 4 . Intermediate values of D are obtained in the delithiated compound Li 0.28 V 2 O 4 and in the layered oxide LiVO 2 ; significantly lower values of D, viz. 1x10 -11 cm 2 /s and 4x10 -11 cm 2 /s , are found in the spinels LiMn 2 O 4 and Fe 3 O 4 respectively. 28 refs.; 5 figs.; 1 table

Doping-controlled Coherent Electron-Phonon Coupling in Vanadium Dioxide

Energy Technology Data Exchange (ETDEWEB)

Appavoo, Kannatassen [Vanderbilt Univ., Nashville, TN (United States) Interdisciplinary Materials Science; Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Wang, Bin [Vanderbilt Univ., Nashville, TN (United States) Dept. of Physics and Astronomy; Nag, Joyeeta [Vanderbilt Univ., Nashville, TN (United States) Dept. of Physics and Astronomy; Sfeir, Matthew Y. [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Pantelides, Sokrates T. [Vanderbilt Univ., Nashville, TN (United States) Dept. of Physics and Astronomy; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States). Dept. of Electrical Engineering and Computer Science; Haglund, Richard F. [Vanderbilt Univ., Nashville, TN (United States) Interdisciplinary Materials Science and Dept. of Physics and Astronomy

2015-05-10

Broadband femtosecond transient spectroscopy and density functional calculations reveal that substitutional tungsten doping of a VO₂ film changes the coherent phonon response compared to the undoped film due to altered electronic and structural dynamics.

The electronic structure and metal-insulator transitions in vanadium oxides

International Nuclear Information System (INIS)

Mossanek, Rodrigo Jose Ochekoski

2010-01-01

The electronic structure and metal-insulator transitions in vanadium oxides (SrVO_3, CaVO_3, LaVO_3 and YVO_3) are studied here. The purpose is to show a new interpretation to the spectra which is coherent with the changes across the metal-insulator transition. The main experimental techniques are the X-ray photoemission (PES) and X-ray absorption (XAS) spectroscopies. The spectra are interpreted with cluster model, band structure and atomic multiplet calculations. The presence of charge-transfer satellites in the core-level PES spectra showed that these vanadium oxides cannot be classified in the Mott-Hubbard regime. Further, the valence band and core-level spectra presented a similar behavior across the metal insulator transition. In fact, the structures in the spectra and their changes are determined by the different screening channels present in the metallic or insulating phases. The calculated spectral weight showed that the coherent fluctuations dominate the spectra at the Fermi level and give the metallic character to the SrVO_3 and CaVO_3 compounds. The vanishing of this charge fluctuation and the replacement by the Mott-Hubbard screening in the LaVO_3 and YVO_3 systems is ultimately responsible for the opening of a band gap and the insulating character. Further, the correlation effects are, indeed, important to the occupied electronic structure (coherent and incoherent peaks). On the other hand, the unoccupied electronic structure is dominated by exchange and crystal field effects (t2g and eg sub-bands of majority and minority spins). The optical conductivity spectrum was obtained by convoluting the removal and addition states. It showed that the oxygen states, as well as the crystal field and exchange effects are necessary to correctly compare and interpret the experimental results. Further, a correlation at the charge-transfer region of the core-level and valence band optical spectra was observed, which could be extended to other transition metal oxides

Topotactic insertion of lithium in the layered structure Li4VO(PO4)2: The tunnel structure Li5VO(PO4)2

International Nuclear Information System (INIS)

Satya Kishore, M.; Pralong, V.; Caignaert, V.; Malo, S.; Hebert, S.; Varadaraju, U.V.; Raveau, B.

2008-01-01

A new V(III) lithium phosphate Li 5 VO(PO 4 ) 2 has been synthesized by electrochemical insertion of lithium into Li 4 VO(PO 4 ) 2 . This phase, which crystallizes in the space group I4/mcm, exhibits a tunnel structure closely related to the layered structure of Li 4 VO(PO 4 ) 2 and to the tunnel structure of VO(H 2 PO 4 ) 2 . The topotactic reactions that take place during lithium exchange and intercalation, starting from VO(H 2 PO 4 ) 2 and going to the final phase Li 5 VO(PO 4 ) 2 are explained on the basis of the flexible coordinations of V 4+ and V 3+ species. The electrochemical and magnetic properties of this new phase are also presented and explained on the basis of the structure dimensionality. - Graphical abstract: Electrochemical synthesis of a new 3D V(III) lithium phosphate, Li 5 VO(PO 4 ) 2 . Starting from the 2D Li 4 VO(PO 4 ) 2 , the topotactic reaction that take place during lithium intercalation is explained on the basis of the flexible coordinations of V 4+ and V 3+ species

New vanadium oxides with perovskite type structure: AThV/sub 2/O/sub 6/ (A=Ca,Sr)

Energy Technology Data Exchange (ETDEWEB)

Vidyasagar, K; Gopalakrishnan, J

1982-07-01

New perovskite oxides of the formula AThV/sub 2/O/sub 6/ (A=Ca,Sr) have been prepared by reduction of the corresponding AThV/sub 2/O/sub 8/ under hydrogen atmosphere. CaThV/sub 2/O/sub 6/ crystallizes in an orthorhombic LaVO/sub 3/ type structure, while the strontium compound exhibiting cation-deficient nonstoichiometry. SrThsub(1-x)V/sub 2/O/sub 6/ (x approx. 0.4), is cubic. The magnetic susceptibility behaviour of the calcium compound is similar to that of V/sup 3 +/ perovskites, while the strontium compound exhibits a large increase in susceptibility below 130K, the behaviour being likely to be associated with the mixed-valence character of vanadium.

Reactions of vanadium(5) with aluminium(3) in weakly acid aqueous solutions

International Nuclear Information System (INIS)

Ditrikh, I.V.; Makhno, A.Ya.

1996-01-01

Conditions of vanadium(5) heteropolycompounds formation in aqueous solutions containing aluminium(3) have been studied. By the methods of potentiometry and conductometry in solutions of Al(NO 3 ) 3 -NaVO 3 salt mixture the formation of complexes with the ratios [Al 3+ ]:[V 5+ ]=1:3, 1:6 and 1:12 has been ascertained. A salt of gross formula 3NaO · Al 2 ) 3 · 12V 2 O 5 · 67H 2 O has been isolated. 3 refs.; 2 figs

Synthesis， Characterization and Inhibition Effects of Vanadium Substituted Dawson-type Heteropoly Acids(Mo， P)

Institute of Scientific and Technical Information of China (English)

YIN Yan-bing; YANG Yu-lin; FAN Rui-qing; ZHU Yang-qing; SUN Ji-ru

2011-01-01

Four new vanadium substituted Dawson-type heteropoly acids H7[P2Mo17VO62]·39H2O(1),H8[P2Mo16V2O62]·41H2O(2), H9[P2Mo15V3O62]·51H2O(3) and H8[P2Mo14V4O62H2]·45H2O(4) were prepared respectively. Their structures were determined by IR and ICP. The inhibition effects of vanadium substituted Dawson-type heteropoly acids(Mo, P) on free radical polymerization of methyl methacrylate(MMA) were investigated by dilatometry. The results show that the rate of the polymerization of MMA decreases and the inhibition effects of the four heteropoly acids reach the inhibitor performance of hydroquinone at a certain ratio.

In situ self-sacrificed template synthesis of vanadium nitride/nitrogen-doped graphene nanocomposites for electrochemical capacitors.

Science.gov (United States)

Liu, Hong-Hui; Zhang, Hong-Ling; Xu, Hong-Bin; Lou, Tai-Ping; Sui, Zhi-Tong; Zhang, Yi

2018-03-15

Vanadium nitride and graphene have been widely used as pseudo-capacitive and electric double-layer capacitor electrode materials for electrochemical capacitors, respectively. However, the poor cycling stability of vanadium nitride and the low capacitance of graphene impeded their practical applications. Herein, we demonstrated an in situ self-sacrificed template method for the synthesis of vanadium nitride/nitrogen-doped graphene (VN/NGr) nanocomposites by the pyrolysis of a mixture of dicyandiamide, glucose, and NH 4 VO 3 . Vanadium nitride nanoparticles of the size in the range of 2 to 7 nm were uniformly embedded into the nitrogen-doped graphene skeleton. Furthermore, the VN/NGr nanocomposites with a high specific surface area and pore volume showed a high specific capacitance of 255 F g -1 at 10 mV s -1 , and an excellent cycling stability (94% capacitance retention after 2000 cycles). The excellent capacitive properties were ascribed to the excellent conductivity of nitrogen-doped graphene, high surface area, high pore volume, and the synergistic effect between vanadium nitride and nitrogen-doped graphene.

Influence of Na diffusion on thermochromism of vanadium oxide films and suppression through mixed-alkali effect

Energy Technology Data Exchange (ETDEWEB)

Miller, Mark J.; Wang, Junlan, E-mail: junlan@u.washington.edu

2015-10-15

Highlights: • Vanadium oxide films were reactively sputtered on three types of glass substrates. • Na diffusion from soda-lime glass undesirably inhibited thermochromism. • Na diffusion was suppressed by replacing half of sodium in glass with potassium. • Mixed-alkali effect promotes thermochromic VO{sub 2} films on glass substrates. - Abstract: Vanadium(IV) oxide possesses a reversible first-order phase transformation near 68 °C. Potential applications of the material include advanced optical devices and thermochromic smart windows. In this study, vanadium oxide films were grown on three types of glass substrates using reactive DC magnetron sputtering and were then annealed in air. The substrates were characterized with energy-dispersive X-ray spectroscopy, and the films were characterized with X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and UV-Vis-NIR spectrophotometry. The results show that the composition of the substrate has a major impact on the microstructure and optical properties of the deposited films. Sodium (Na) in the glass can undesirably inhibit thermochromism; however, replacing half of the Na with potassium (K) suppresses the Na diffusion and promotes the nucleation of pure VO{sub 2} with superior thermochromic functionality. The improved performance is attributed to the mixed-alkali effect between Na and K. These findings are both scientifically and technologically important since soda (Na{sub 2}O) is an essential flux material in glass products such as windows.

Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

Science.gov (United States)

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2013-12-30

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

Vanadium extraction by combined process of lixiviation and toasting

International Nuclear Information System (INIS)

Coral, Aldo

1992-01-01

Combinated toasting and leaching processes were applied at laboratory level to vanadiferous ore from Puyango deposit in order to evaluate different rates. Before leaching, a pretreatment consisting in toasting at open atmosphere was given to the ore. Both raw and toasted ore were later washed in organic solvents. In reason of mineralogical and petrographic characteristics of the ore, only alcaline leaching was tested under different pressure temperature and pH conditions of leaching solution (pH=9.8) in order to optimize time and efficiency of each individual process. Four different unitary alcaline leaching processes were studied: MECHANICAL STIRRING, PNEUMATIC STIRRING, LEACHING IN AUTOCLAVE AND LEACHING IN COLUMNS. For these four processes were obtained recovery rates (in percentage) of 18.63 and 87.82; 17.03 and 82.57; 60.42 and 99.55; 2.5 and 30.10; respectively from raw and pre-toasted ore. After filtration, vanadium was extracted from enriched solutions by using liquid resin ALAMINE 336, selective for vanadium at pH=2.8. Vanadium was later discharged with a Sodium Carbonate solution (10 per cent) and finally precipitated as the commercial compound Ammonium Vanadate, NH4VO3. Nuclear techniques as X-ray fluorescence and Atomic Absorption spectroscopy were used for analysis all over the investigation

Synthesis, characterization and formation mechanism of metastable phase VO2(A) nanorods

International Nuclear Information System (INIS)

Cheng, X.H.; Xu, H.F.; Wang, Z.Z.; Zhu, K.R.; Li, G.; Jin, Shaowei

2013-01-01

Graphical abstract: - Highlights: • Pure phases of VO 2 (B) and VO 2 (A) were prepared by a facile hydrothermal method. • Belt-like particles prepared at 180 °C was indexed as monoclinic VO 2 (B) phase. • Rod-like particles prepared at 230 °C was indexed as tetragonal VO 2 (A) phase. • VO 2 (A) nanorods resulted from VO 2 (B) nanobelts by assembly and crystal adjustment. - Abstract: Pure phase VO 2 (A) nanorods were synthesized via the reduction of V 2 O 5 by oxalic acid during the hydrothermal treatment. Two sets of samples were prepared by varying both system temperature and reaction time under a filling ratio of 0.40 for observing the formation and evolution of VO 2 (A) nanorods. Structures were characterized by X-ray diffraction, scanning and transmission electron microscopies, respectively. It was found that VO 2 (B) was firstly formed and then transformed into VO 2 (A) as the increasing system temperature or extending reaction time. An assembling and following crystal adjustment was proposed for explanation the formation process of VO 2 (A) from VO 2 (B). For VO 2 (A) nanorods, the phase transition temperature of 169.7 °C was higher than that of the VO 2 (A) bulk, it might be ascribed to the lower crystallinity or nonstoichiometry in VO 2 (A) nanorods. VO 2 nanostructures with controllable phases and properties should find their promising applications in a single VO 2 nanodevice

Theoretical Study of Terminal Vanadium(V Chalcogenido Complexes Bearing Chlorido and Methoxido Ligands

Directory of Open Access Journals (Sweden)

Samuel Tetteh

2017-01-01

Full Text Available Solvent (methanol coordinated vanadium(V chalcogenido complexes bearing chlorido and methoxido ligands have been studied computationally by means of density functional (DFT methods. The gas phase complexes were fully optimized using B3LYP/GEN functionals with 6-31+G⁎⁎ and LANL2DZ basis sets. The optimized complexes show distorted octahedral geometries around the central vanadium atom. The ligand pπ-vanadium dπ interactions were analyzed by natural bond order (NBO and natural population analyses (NPA. These results show strong stabilization of the V=O bond as was further confirmed by the analyses of the frontier molecular orbitals (FMOs. Second-order perturbation analyses also revealed substantial delocalization of lone pair electrons from the oxido ligand into vacant non-Lewis (Rydberg orbitals as compared to the sulfido and seleno analogues. These results show significant ligand-to-metal charge transfer (LMCT interactions. Full interaction map (FIM of the reference complex confirms hydrogen bond interactions involving the methanol (O-H and the chlorido ligand.

In situ X-ray powder diffraction, synthesis, and magnetic properties of InVO 3

Science.gov (United States)

Lundgren, Rylan J.; Cranswick, Lachlan M. D.; Bieringer, Mario

2006-12-01

We report the first synthesis and high-temperature in situ X-ray diffraction study of InVO 3. Polycrystalline InVO 3 has been prepared via reduction of InVO 4 using a carbon monoxide/carbon dioxide buffer gas. InVO 3 crystallizes in the bixbyite structure in space group Ia-3 (206) with a=9.80636(31) Å with In 3+/V 3+ disorder on the (8 b) and (24 d) cation sites. In situ powder X-ray diffraction experiments and thermal gravimetric analysis in a CO/CO 2 buffer gas revealed the existence of the metastable phase InVO 3. Bulk samples with 98.5(2)% purity were prepared using low-temperature reduction methods. The preparative methods limited the crystallinity of this new phase to approximately 225(50) Å. Magnetic susceptibility and neutron diffraction experiments suggest a spin-glass ground state for InVO 3.

Structural study of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} single crystals

Energy Technology Data Exchange (ETDEWEB)

Ishii, Yuto [Department of Physics, Hokkaido University, Sapporo 060-0810 (Japan); Matsushita, Yoshitaka [National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Oda, Migaku; Yoshida, Hiroyuki [Department of Physics, Hokkaido University, Sapporo 060-0810 (Japan)

2017-02-15

Single crystals of quasi-one-dimensional vanadium pyroxene LiVSi{sub 2}O{sub 6} were synthesized and the crystal structures at 293 K and 113 K were studied using X-ray diffraction experiments. We found a structural phase transition from the room-temperature crystal structure with space group C2/c to a low-temperature structure with space group P2{sub 1}/c, resulting from a rotational displacement of SiO{sub 4} tetrahedra. The temperature dependence of magnetic susceptibility shows a broad maximum around 116 K, suggesting an opening of the Haldane gap expected for one-dimensional antiferromagnets with S=1. However, an antiferromagnetic long-range order was developed below 24 K, probably caused by a weak inter-chain magnetic coupling in the compound. - Graphical abstract: Low temperature crystal structure of LiVSi{sub 2}O{sub 6} and an orbital arrangement within the V-O zig-zag chain along the c-axis. - Highlights: • A low temperature structure of LiVSi{sub 2}O{sub 6} was determined by single crystal X-ray diffraction measurements. • The origin of the structural transition is a rotational displacement of SiO{sub 4} tetrahedra. • The uniform orbital overlap in the V-O zigzag chain makes the system a quasi one-dimensional antiferromagnet.

Microstructural and microchemical studies of phase stability in V-O solid solution

Energy Technology Data Exchange (ETDEWEB)

Ghosh, Chanchal, E-mail: chanchal@igcar.gov.in [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, HBNI, Kalpakkam 603102, Tamil Nadu (India); Singh, Akash [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, HBNI, Kalpakkam 603102, Tamil Nadu (India); Basu, Joysurya [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, HBNI, Kalpakkam 603102, Tamil Nadu (India); Department of Metallurgical Engineering, Indian Institute of Technology (BHU), Varanasi 221005, Uttar Pradesh (India); Ramachandran, Divakar; Mohandas, E [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, HBNI, Kalpakkam 603102, Tamil Nadu (India)

2017-02-15

Over the last couple of decades vanadium and V-based alloys have received significant attention as a potential structural material for fusion power applications because of their favourable mechanical properties under irradiation and at elevated temperatures. They are also considered as the advanced options of storage materials for hydrogen and its isotopes. However, the higher affinity of V for O, C and N poses critical challenges in its engineering applications since they lead to degradation of mechanical properties. They can further interact with the matrix to produce metallic oxy-carbo-nitride precipitates. To a certain limit, these precipitates are beneficial and can be exploited to enhance the mechanical behaviour of the alloy through suitable microstructural design. However, this requires a prior knowledge of the interaction between the alloy and the impurity solutes. In the present work vanadium specific experiments have been designed and carried out to bring out the V-interstitial solute interaction by charging oxygen in the near surface region of vanadium. Microstructural and microchemical behaviour of the V-O solid solution has been studied through HRTEM (high resolution transmission electron microscopy) and HAADF (high angle annular dark field) coupled with EELS. Quantitative electron microscopy has been carried out to study structural modification of the alloy in atomic level caused by O charging. - Highlights: •Controlled experiments were carried out in pulsed laser ablation set-up to promote V-O interaction. • As a consequence of O dissolution, V transformed into a bct structure which is otherwise a bcc structure. •In V-O solid solution, dissolved O in the V matrix introduces significant amount of lattice strain. • Present work can be extended for introducing interstitial O in other pure transition metals and their alloys.

Thermally tunable VO2-SiO2 nanocomposite thin-film capacitors

Science.gov (United States)

Sun, Yifei; Narayanachari, K. V. L. V.; Wan, Chenghao; Sun, Xing; Wang, Haiyan; Cooley, Kayla A.; Mohney, Suzanne E.; White, Doug; Duwel, Amy; Kats, Mikhail A.; Ramanathan, Shriram

2018-03-01

We present a study of co-sputtered VO2-SiO2 nanocomposite dielectric thin-film media possessing continuous temperature tunability of the dielectric constant. The smooth thermal tunability is a result of the insulator-metal transition in the VO2 inclusions dispersed within an insulating matrix. We present a detailed comparison of the dielectric characteristics of this nanocomposite with those of a VO2 control layer and of VO2/SiO2 laminate multilayers of comparable overall thickness. We demonstrated a nanocomposite capacitor that has a thermal capacitance tunability of ˜60% between 25 °C and 100 °C at 1 MHz, with low leakage current. Such thermally tunable capacitors could find potential use in applications such as sensing, thermal cloaks, and phase-change energy storage devices.

EPR Study of Vanadium Ion in Zinc-Boro-Vanadate Glasses

International Nuclear Information System (INIS)

Renuka, C.; Gowda, V. C. Veeranna; Chakradhar, R. P. S.; Reddy, C. Narayana

2011-01-01

This paper describes EPR studies on x V 2 O 5 -(40-x)ZnO-60B 2 O 3 (where x 5, 10, 15 and 20 mol %) glass system. These studies indicate a strong compositional dependent trend and existence of characteristic boro-vanadate groups in these glasses. The EPR spectra show a distinct hyperfine structure of 51 V. Spectral analysis shows that the vanadium is present in the glass as vanadyl ion [VO] 2+ at tetragonally distorted octahedral site. The decrease of A || and A perpendicular with increase of V 2 O 5 concentration suggests an increase in the covalence between the central atom and the surrounding oxygen ligands.

Thermal desorption of toluene from Vanadium-containing catalysts coated onto various carriers

Directory of Open Access Journals (Sweden)

Z. Zheksenbaeva

2012-12-01

Full Text Available The method temperature-programmed desorption has been studied the state of toluene on the surface-modified vanadium catalysts on different carriers. Among the investigated carriers the most active in the reaction of partial oxidation of toluene is anatase structural titanium dioxide. For the partial oxidation of toluene on modified vanadium-containing catalysts deposited on TiO2 was tested. It was found that on the catalyst 20%V2O5-5%MoO3-2%Sb2O3/TiO2 at a temperature of 673K, volume rate of 15 thousand hours-1 oxidation of toluene is 80% c yield of benzoic acid with a selectivity of  70% of 87.5%.

Pore-Size-Tuned Graphene Oxide Frameworks as Ion-Selective and Protective Layers on Hydrocarbon Membranes for Vanadium Redox-Flow Batteries.

Science.gov (United States)

Kim, Soohyun; Choi, Junghoon; Choi, Chanyong; Heo, Jiyun; Kim, Dae Woo; Lee, Jang Yong; Hong, Young Taik; Jung, Hee-Tae; Kim, Hee-Tak

2018-05-07

The laminated structure of graphene oxide (GO) membranes provides exceptional ion-separation properties due to the regular interlayer spacing ( d) between laminate layers. However, a larger effective pore size of the laminate immersed in water (∼11.1 Å) than the hydrated diameter of vanadium ions (>6.0 Å) prevents its use in vanadium redox-flow batteries (VRFB). In this work, we report an ion-selective graphene oxide framework (GOF) with a d tuned by cross-linking the GO nanosheets. Its effective pore size (∼5.9 Å) excludes vanadium ions by size but allows proton conduction. The GOF membrane is employed as a protective layer to address the poor chemical stability of sulfonated poly(arylene ether sulfone) (SPAES) membranes against VO 2 + in VRFB. By effectively blocking vanadium ions, the GOF/SPAES membrane exhibits vanadium-ion permeability 4.2 times lower and a durability 5 times longer than that of the pristine SPAES membrane. Moreover, the VRFB with the GOF/SPAES membrane achieves an energy efficiency of 89% at 80 mA cm -2 and a capacity retention of 88% even after 400 cycles, far exceeding results for Nafion 115 and demonstrating its practical applicability for VRFB.

Preliminary studies of vanadium-base alloys intended for use in fabrication of cans for fast reactors; Etudes preliminaires sur les alliages a base de vanadium envisages pour la fabrication de gaines de reacteurs rapides

Energy Technology Data Exchange (ETDEWEB)

Conte, M [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1967-03-15

Preliminary research has been carried out on a series of vanadium-based alloys: V, 0.5 per cent Si; V, 5 per cent Ca; V, 5 per cent Mo; V, 5 per cent Nb; V, 2 per cent Zr; V, 20 per cent Ti; V, 10 per cent Al; V, 10 per cent Sn and v, 10 per cent Ti liable to be used as canning material in fast reactors. The transformation by forging at about 1000 deg. C and rolling between 200 deg. C and room temperature is satisfactory for all types of alloys except V with 10 per cent Sn and V with 10 per cent Al. The mechanical properties deduced from tensile strength tests carried out on alloy samples annealed 1 hour at 1050 deg. C in a vacuum show that, generally speaking, the addition elements lead to an improvement in these properties as compared to those of pure vanadium. After undergoing corrosion tests in a liquid sodium loop purified by a cold trap, the alloys become brittle at room temperature. Only the vanadium containing 20 per cent Ti keeps its plastic properties. These alloys are covered by a layer of vanadium carbide VC. After undergoing treatment in a liquid sodium loop purified by a hot trap, all the alloys keep their good mechanical characteristics. The surface layer with which they are covered is composed of two vanadium carbides VC and {sub {gamma}}VC, and a vanadium sub-oxide VO{sub 0.9}. (author) [French] Des etudes preliminaires ont ete faites sur une serie d'alliages a base de vanadium: V-0,5 pour cent Si, V-5 pour cent Ca, V-5 pour cent Mo, V-5 pour cent Nb, V-2 pour cent Zr, V-20 pour cent Ti, V-10 pour cent Al, V-10 pour cent Sn et V-10 pour cent Ti susceptibles d'etre utilises comme materiau de gainage pour les reacteurs rapides. La transformation par forgeage a 1000 deg. C environ et laminage entre 200 deg. C et la temperature ambiante est satisfaisante pour toutes les nuances d'alliage sauf le V-10 pour cent Sn et le V-10 pour cent Al. Les proprietes mecaniques deduites des essais de traction realises sur des eprouvettes d'alliages recuits 1 heure a

Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK Membranes for a Vanadium/Air Redox Flow Battery

Directory of Open Access Journals (Sweden)

Géraldine Merle

2013-12-01

Full Text Available Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone (cSPEEK membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a crosslinking on the sulfonic acid groups; and (b crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery

Science.gov (United States)

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2014-01-01

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion. PMID:24957118

Preparation, properties, and ESCA characterization of vanadium surface compounds on silicagel. 1

International Nuclear Information System (INIS)

Horvath, B.; Strutz, J.; Geyer-Lippmann, J.; Horvath, E.G.

1981-01-01

Binding energies (BE) or 18 pure vanadium compounds (V 2psup(3/2) niveau) were measured in selected oxygen and chlorine environments, linearity of BE vs. oxidation states scrutinized and appropriate model compounds chosen as comparative standards. The general trend is an increase of BE with formal oxidation state; in particular, it could be counterbalanced by electron donating/withdrawing ligands on the V atom. A graphical (computerized) background substraction method was utilized to remove an interfering O 1s satellite peak and to enhance accuracy of BE values in surface compounds. BEs of (triple bond Si-O) 3 V=O, (triple bond Si-O) 3 V, and (triple bond Si-O) 3 V-(O 2 ) were determined. By comparison to standards positive BE shifts of about 2.1 eV were derived indicating the strong electron withdrawing ('electron sink') effect of the support on V in surface compounds. This is the first reported ESCA data on a surface peroxo complex. (author)

Synthesis, characterization and catalytic activity of two novel cis - dioxovanadium(V) complexes: [VO{sub 2}(L)] and [VO{sub 2}(HLox)

Energy Technology Data Exchange (ETDEWEB)

Silva, Natalia M.L.; Chacon, Eluzir P.; Resende, Jackson A.L.C.; Carneiro, Jose Walkimar de M.; Lanznaster, Mauricio, E-mail: mlanz@vm.uff.b [Universidade Federal Fluminense (IQ/UFF), Niteroi, RJ (Brazil). Inst. de Quimica; Pinheiro, Carlos B. [Universidade Federal de Minas Gerais (DF/UFMG), Belo Horizonte (Brazil). Dept. de Fisica; Fernandez, Tatiana L.; Scarpellini, Marciela [Universidade Federal do Rio de Janeiro (IQ/UFRJ), RJ (Brazil). Inst. de Quimica

2011-07-01

Two novel complexes, [VO{sub 2}(L)] (1) and [VO{sub 2}(HLox)] (2), were synthesized and characterized by IV, UV-Vis and NMR spectroscopy, cyclic voltammetry, elemental analysis and X-ray diffraction. The synthesis of a new ligand, H{sub 2}Lox, is also described. Complexes 1 and 2 were obtained by the reaction of [VO(acac){sub 2}] with the ligands HL and H{sub 2}Lox, respectively. Alternatively, 2 was also obtained by the reaction of HL with [VO(acac)2] in the presence of hydroxylamine, and by the reaction of 1 with hydroxylamine. Crystallographic data show that complexes 1 and 2 have similar molecular structures, in which the cis-dioxovanadium(V) center is coordinated to L- or HLox{sup -}, respectively, in a distorted octahedral environment. The catalytic activity of these compounds towards cyclohexane oxidation was evaluated using H{sub 2}O{sub 2} and t-BuOOH as oxidants. Both complexes presented > 70% selectivity for cyclohexylhydroperoxide formation. B3LYP/6.31G(d) calculations were used to confirm the geometry and to help assign the electronic spectra. (author)

Hydrothermal synthesis and electrochemical characterization of VO2 (B) with controlled crystal structures

International Nuclear Information System (INIS)

Jiang Wentao; Ni Juan; Yu Ke; Zhu Ziqiang

2011-01-01

Three different VO 2 (B) nanostructures, including urchin-like VO 2 (B), VO 2 (B) honeycombs and VO 2 (B) nanorods have been successfully fabricated through hydrothermal process by adjusting the concentrations of the oxalic acid. The microstructure and morphology of the VO 2 nanostructures were evaluated by using X-ray diffraction and scanning and transmission electron microscopies. Electrochemical properties measurements of urchin-like VO 2 (B) and VO 2 (B) honeycombs showed excellent cycling performance, especially the urchin-like VO 2 (B) exhibited higher discharge capacity and better capacity retention.

Tunable optical switching in the near-infrared spectral regime by employing plasmonic nanoantennas containing phase change materials.

Science.gov (United States)

Savaliya, Priten B; Thomas, Arun; Dua, Rishi; Dhawan, Anuj

2017-10-02

We propose the design of switchable plasmonic nanoantennas (SPNs) that can be employed for optical switching in the near-infrared regime. The proposed SPNs consist of nanoantenna structures made up of a plasmonic metal (gold) such that these nanoantennas are filled with a switchable material (vanadium dioxide). We compare the results of these SPNs with inverted SPN structures that consist of gold nanoantenna structures surrounded by a layer of vanadium dioxide (VO 2 ) on their outer surface. These nanoantennas demonstrate switching of electric-field intensity enhancement (EFIE) between two states (On and Off states), which can be induced thermally, optically or electrically. The On and Off states of the nanoantennas correspond to the metallic and semiconductor states, respectively of the VO 2 film inside or around the nanoantennas, as the VO 2 film exhibits phase transition from its semiconductor state to the metallic state upon application of thermal, optical, or electrical energy. We employ finite-difference time-domain (FDTD) simulations to demonstrate switching in the EFIE for four different SPN geometries - nanorod-dipole, bowtie, planar trapezoidal toothed log-periodic, and rod-disk - and compare their near-field distributions for the On and Off states of the SPNs. We also demonstrate that the resonance wavelength of the EFIE spectra gets substantially modified when these SPNs switch between the two states.

Structures, physicochemical and cytoprotective properties of new oxidovanadium(IV) complexes -[VO(mIDA)(dmbipy)]·1.5H2O and [VO(IDA)(dmbipy)]·2H2O

Science.gov (United States)

Drzeżdżon, Joanna; Jacewicz, Dagmara; Wyrzykowski, Dariusz; Inkielewicz-Stępniak, Iwona; Sikorski, Artur; Tesmar, Aleksandra; Chmurzyński, Lech

2017-09-01

New oxidovanadium(IV) complexes with a modification of the ligand in the VO2+ coordination sphere were synthesized. [VO(mIDA)(dmbipy)]•1.5H2O and [VO(IDA)(dmbipy)]•2H2O were obtained as dark green crystals and grey-green powder, respectively (mIDA = N-methyliminodiacetic anion, IDA = iminodiacetic anion, dmbipy = 4,4‧-dimethoxy-2,2‧-dipyridyl). The crystal structure of [VO(mIDA)(dmbipy)]·1.5H2O has been determined by the X-ray diffraction method. The studies of structure of [VO(mIDA)(dmbipy)]•1.5H2O have shown that this compound occurs in the crystal as two rotational conformers. Furthermore, the stability constants of [VO(mIDA)(dmbipy)]•1.5H2O and [VO(IDA)(dmbipy)]•2H2O complexes in aqueous solutions were studied by using the potentiometric titration method and, consequently, determined using the Hyperquad2008 program. Moreover, the title complexes were investigated as antioxidant substances. The impact of the structure modification in the VO2+ complexes on the radical scavenging activity has been studied. The ability to scavenge the superoxide radical by two complexes - [VO(mIDA)(dmbipy)]·1.5H2O and [VO(IDA)(dmbipy)]·2H2O was studied by cyclic voltammetry (CV) and nitrobluetetrazolium (NBT) methods. The title complexes were also examined by the spectrophotometric method as scavengers of neutral organic radical - 1,1-diphenyl-2-picrylhydrazyl (DPPH•) and radical cation - 2,2'-azinobis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS•+). Furthermore, the biological properties of two oxidovanadium(IV) complexes were investigated in relation to its cytoprotective properties by the MTT and LDH tests based on the hippocampal HT22 neuronal cell line during the oxidative damage induced by hydrogen peroxide. Finally, the results presented in this paper have shown that the both new oxidovanadium(IV) complexes with the 4,4‧-dimethoxy-2,2‧-dipyridyl ligand can be treated as the cytoprotective substances.

Thermal coupling and effect of subharmonic synchronization in a system of two VO2 based oscillators

Science.gov (United States)

Velichko, Andrey; Belyaev, Maksim; Putrolaynen, Vadim; Perminov, Valentin; Pergament, Alexander

2018-03-01

We explore a prototype of an oscillatory neural network (ONN) based on vanadium dioxide switching devices. The model system under study represents two oscillators based on thermally coupled VO2 switches. Numerical simulation shows that the effective action radius RTC of coupling depends both on the total energy released during switching and on the average power. It is experimentally and numerically proved that the temperature change ΔT commences almost synchronously with the released power peak and T-coupling reveals itself up to a frequency of about 10 kHz. For the studied switching structure configuration, the RTC value varies over a wide range from 4 to 45 μm, depending on the external circuit capacitance C and resistance Ri, but the variation of Ri is more promising from the practical viewpoint. In the case of a "weak" coupling, synchronization is accompanied by attraction effect and decrease of the main spectra harmonics width. In the case of a "strong" coupling, the number of effects increases, synchronization can occur on subharmonics resulting in multilevel stable synchronization of two oscillators. An advanced algorithm for synchronization efficiency and subharmonic ratio calculation is proposed. It is shown that of the two oscillators the leading one is that with a higher main frequency, and, in addition, the frequency stabilization effect is observed. Also, in the case of a strong thermal coupling, the limit of the supply current parameters, for which the oscillations exist, expands by ∼10%. The obtained results have a universal character and open up a new kind of coupling in ONNs, namely, T-coupling, which allows for easy transition from 2D to 3D integration. The effect of subharmonic synchronization hold promise for application in classification and pattern recognition.

Chemical vapour deposition of vanadium oxide thermochromic thin films

Science.gov (United States)

Piccirillo, Clara

Thermochromic materials change optical properties, such as transmittance or reflectance, with a variation in temperature. An ideal intelligent (smart) material will allow solar radiation in through a window in cold conditions, but reflect that radiation in warmer conditions. The variation in the properties is often associated with a phase change, which takes place at a definite temperature, and is normally reversible. Such materials are usually applied to window glass as thin films. This thesis presents the work on the development of thermochromic vanadium (IV) oxide (VO2) thin films - both undoped and doped with tungsten, niobium and gold nanoparticles - which could be employed as solar control coatings. The films were deposited using Chemical Vapour Deposition (CVD), using improved Atmospheric Pressure (APCVD), novel Aerosol Assisted (AACVD) and novel hybrid AP/AACVD techniques. The effects of dopants on the metalto- semiconductor transition temperature and transmittance/reflectance characteristics were also investigated. This work significantly increased the understanding of the mechanisms behind thermochromic behaviour, and resulted in thermochromic materials based on VO2 with greatly improved properties.

Vanadium dioxide nanobelts: Hydrothermal synthesis and magnetic properties

Energy Technology Data Exchange (ETDEWEB)

Zakharova, G.S., E-mail: volkov@ihim.uran.ru [Institute of Solid State Chemistry, Ural Division, Russian Academy of Sciences, Pervomaiskaya ul. 91, Yekaterinburg 620041 (Russian Federation); Hellmann, I. [Leibniz-Institut fuer Festkoerper- und Werkstoffforschung (IFW) Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany); Volkov, V.L. [Institute of Solid State Chemistry, Ural Division, Russian Academy of Sciences, Pervomaiskaya ul. 91, Yekaterinburg 620041 (Russian Federation); Taeschner, Ch.; Bachmatiuk, A.; Leonhardt, A.; Klingeler, R.; Buechner, B. [Leibniz-Institut fuer Festkoerper- und Werkstoffforschung (IFW) Dresden, Helmholtzstr. 20, D-01069 Dresden (Germany)

2010-09-15

VO{sub 2} (B) nanobelts were prepared by a hydrothermal method at 180 {sup o}C using V{sub 2}O{sub 5}.nH{sub 2}O sol and H{sub 2}C{sub 2}O{sub 4}.2H{sub 2}O as starting agents. The obtained nanobelts have diameters ranging from 50 to 100 nm in width, 20-30 nm in thickness with lengths up to 1.5 {mu}m. Measurements of the static magnetic susceptibility provide evidence for two phase transitions at T{sub 1} = 225 K and T{sub 2} = 290 K, respectively. Below T{sub 1}, the data suggest the presence quasi-free as well as of strongly antiferromagnetic correlated spins associated to V{sup 4+}-ions.

Improving the Accuracy of Predicting Maximal Oxygen Consumption (VO2pk)

Science.gov (United States)

Downs, Meghan E.; Lee, Stuart M. C.; Ploutz-Snyder, Lori; Feiveson, Alan

2016-01-01

Maximal oxygen (VO2pk) is the maximum amount of oxygen that the body can use during intense exercise and is used for benchmarking endurance exercise capacity. The most accurate method to determineVO2pk requires continuous measurements of ventilation and gas exchange during an exercise test to maximal effort, which necessitates expensive equipment, a trained staff, and time to set-up the equipment. For astronauts, accurate VO2pk measures are important to assess mission critical task performance capabilities and to prescribe exercise intensities to optimize performance. Currently, astronauts perform submaximal exercise tests during flight to predict VO2pk; however, while submaximal VO2pk prediction equations provide reliable estimates of mean VO2pk for populations, they can be unacceptably inaccurate for a given individual. The error in current predictions and logistical limitations of measuring VO2pk, particularly during spaceflight, highlights the need for improved estimation methods.

Influence of preparation conditions on structural elements ordering in vanadium pentaoxide xerogels

International Nuclear Information System (INIS)

Peryshkov, D.V.; Grigor'eva, A.V.; Gudilin, E.A.; Semenenko, D.A.; Volkov, V.V.; Dembo, K.A.; Tret'yakov, Yu.D.

2006-01-01

Complex analysis of vanadium pentaoxide xerogel films prepared by three different methods, i.e. by V 2 O 5 dissolution in H 2 O 2 , by hydrolysis of VO(t-Bu) 3 and by ion exchange, has been carried out for the first time using the methods of small-angle X-ray scattering, IR spectroscopy, scanning electron microscopy and thermal analysis. A correlation between chemical prehistory of the samples prepared and their structural features has been established. It is shown that the prehistory influence stems from the differences in gelation process when different precursors are used [ru

Influence of VO2+ ions on structural and optical properties of potassium succinate-succinic acid single crystal for non-linear optical applications

Science.gov (United States)

Juliet sheela, K.; Subramanian, P.

2018-04-01

A transparent and good optical quality semi organic single crystal of vanadium doped potassium succinate-succinic acid (KSSA) was synthesized by slow evaporation technique at room temperature. The structural perfection was supported by the powder XRD of the KSSA-VO2+ single crystal. Optical behavior of the material was discovered from the absorption and transmission spectra of UV-vis-NIR characterization. Functional group and presence of metal ion in the specimen are depicted from FTIR traces. From the photoluminescence studies, emission of wavelength in the violet region (418 nm) at the excitation of 243 nm could be ascertained. EDAX, SEM measurements identify presence of elements and pictures the step-line growth and the imperfection presents in the grown crystal. EPR analysis extracts the information about the local site symmetry around the impurity ion, molecular orbital coefficients, admixture coefficients and ground state wave function of VO2+ doped KSSA single crystal. Second harmonic generation (SHG) efficiency of the grown crystal was investigated to explore the NLO characteristic of the material.

Performance enhancement in vanadium redox flow battery using platinum-based electrocatalyst synthesized by polyol process

International Nuclear Information System (INIS)

Jeong, Sanghyun; Kim, Sunhoe; Kwon, Yongchai

2013-01-01

Sluggish reaction rate of [VO] 2+ /[VO 2 ] + redox couple is an obstacle to be addressed in vanadium redox flow battery (VRFB). To improve the slow reaction rate, Pt/C catalyst synthesized by polyol method is suggested. Its catalytic activity, reaction reversibility and charge–discharge performance are evaluated by half cell and single cell tests, while its crystal structure, particle size and particle distribution are measured by XRD and TEM. The XRD and TEM measurements show the polyol Pt/C catalyst has larger electrochemically active surface (EAS) area and smaller particle size than commercial Pt/C catalyst. When catalytic activities of all the catalysts are estimated, the Pt-included catalysts demonstrate high peak current ratio, small peak potential difference and high electron transfer rate constant, confirming that their catalytic activity and reaction reversibility are excellent. In charge–discharge performance tests, the catalysts indicate high efficiencies as well as low overpotential and internal resistance. Excellent performances of the Pt-included catalysts are attributed to positively charged Pts that serve as active sites for activating [VO] 2+ /[VO 2 ] + reaction. Indeed, adoption of the Pt-included catalysts, especially, use of the polyol Pt/C consisting of uniform and small particles helps improve performance of VRFB

Research progress of VO2 thin film as laser protecting material

Science.gov (United States)

Liu, Zhiwei; Lu, Yuan; Hou, Dianxin

2018-03-01

With the development of laser technology, the battlefield threat of directional laser weapons is becoming more and more serious. The blinding and destruction caused by laser weapons on the photoelectric equipment is an important part of the current photo-electronic warfare. The research on the defense technology of directional laser weapons based on the phase transition characteristics of VO2 thin films is an important subject. The researches of VO2 thin films are summarized based on review these points: the preparation methods of VO2 thin films, phase transition mechanism, phase transition temperature regulating, interaction between VO2 thin films and laser, and the application prospect of vo2 thin film as laser protecting material. This paper has some guiding significance for further research on the VO2 thin films in the field of defense directional laser weapons.

Improvement of diabetes, obesity and hypertension in type 2 diabetic KKAy mice by bis(allixinato)oxovanadium(IV) complex

International Nuclear Information System (INIS)

Adachi, Yusuke; Yoshikawa, Yutaka; Yoshida, Jiro; Kodera, Yukihiro; Katoh, Akira; Takada, Jitsuya; Sakurai, Hiromu

2006-01-01

Previously, we found that bis(allixinato)oxovanadium(IV) (VO(alx) 2 ) exhibits a potent hypoglycemic activity in type 1-like diabetic mice. Since the enhancement of insulin sensitivity is involved in one of the mechanisms by which vanadium exerts its anti-diabetic effects, VO(alx) 2 was further tested in type 2 diabetes with low insulin sensitivity. The effect of oral administration of VO(alx) 2 was examined in obesity-linked type 2 diabetic KKA y mice. Treatment of VO(alx) 2 for 4 weeks normalized hyperglycemia, glucose intolerance, hyperinsulinemia, hypercholesterolemia and hypertension in KKA y mice; however, it had no effect on hypoadiponectinemia. VO(alx) 2 also improved hyperleptinemia, following attenuation of obesity in KKA y mice. This is the first example in which a vanadium compound improved leptin resistance in type 2 diabetes by oral administration. On the basis of these results, VO(alx) 2 is proposed to enhance not only insulin sensitivity but also leptin sensitivity, which in turn improves diabetes, obesity and hypertension in an obesity-linked type 2 diabetic animal

Ab Initio Calculations of Transport Properties of Vanadium Oxides

Science.gov (United States)

Lamsal, Chiranjivi; Ravindra, N. M.

2018-04-01

The temperature-dependent transport properties of vanadium oxides have been studied near the Fermi energy using the Kohn-Sham band structure approach combined with Boltzmann transport equations. V2O5 exhibits significant thermoelectric properties, which can be attributed to its layered structure and stability. Highly anisotropic electrical conduction in V2O5 is clearly manifested in the calculations. Due to specific details of the band structure and anisotropic electron-phonon interactions, maxima and crossovers are also seen in the temperature-dependent Seebeck coefficient of V2O5. During the phase transition of VO2, the Seebeck coefficient changes by 18.9 µV/K, which is close to (within 10% of) the observed discontinuity of 17.3 µV/K.

Crosslinked anion exchange membranes with primary diamine-based crosslinkers for vanadium redox flow battery application

Science.gov (United States)

Cha, Min Suc; Jeong, Hwan Yeop; Shin, Hee Young; Hong, Soo Hyun; Kim, Tae-Ho; Oh, Seong-Geun; Lee, Jang Yong; Hong, Young Taik

2017-09-01

A series of polysulfone-based crosslinked anion exchange membranes (AEMs) with primary diamine-based crosslinkers has been prepared via simple a crosslinking process as low-cost and durable membranes for vanadium redox flow batteries (VRFBs). Chloromethylated polysulfone is used as a precursor polymer for crosslinked AEMs (CAPSU-x) with different degrees of crosslinking. Among the developed AEMs, CAPSU-2.5 shows outstanding dimensional stability and anion (Cl-, SO42-, and OH-) conductivity. Moreover, CAPSU-2.5 exhibits much lower vanadium ion permeability (2.72 × 10-8 cm2 min-1) than Nafion 115 (2.88 × 10-6 cm2 min-1), which results in an excellent coulombic efficiency of 100%. The chemical and operational stabilities of the membranes have been investigated via ex situ soaking tests in 0.1 M VO2+ solution and in situ operation tests for 100 cycles, respectively. The excellent chemical, physical, and electrochemical properties of the CAPSU-2.5 membrane make it suitable for use in VRFBs.

First-principles study of adsorption-desorption kinetics of aqueous V2+/V3+ redox species on graphite in a vanadium redox flow battery.

Science.gov (United States)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2017-06-14

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (112[combining macron]0) graphite facets with water and aqueous V 2+ /V 3+ redox species at 300 K employing Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V 2+ /V 3+ species. The formation of V-O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

Operando studies of all-vanadium flow batteries: Easy-to-make reference electrode based on silver-silver sulfate

Science.gov (United States)

Ventosa, Edgar; Skoumal, Marcel; Vázquez, Francisco Javier; Flox, Cristina; Morante, Joan Ramon

2014-12-01

In-depth evaluation of the electrochemical performance of all-vanadium redox flow batteries (VRFBs) under operando conditions requires the insertion of a reliable reference electrode in the battery cell. In this work, an easy-to-make reference electrode based on silver-silver sulfate is proposed and described for VRFBs. The relevance and feasibility of the information obtained by inserting the reference electrode is illustrated with the study of ammoxidized graphite felts. In this case, we show that the kinetic of the electrochemical reaction VO2+/VO2+ is slower than that of V2+/V3+ at the electrode. While the slow kinetics at the positive electrode limits the voltage efficiency, the operating potential of the negative electrode, which is outside the stability widow of water, reduces the coulombic efficiency due to the hydrogen evolution.

Vanadium Bioleaching Behavior by Acidithiobacillus ferrooxidans from a Vanadium-Bearing Shale

Directory of Open Access Journals (Sweden)

Dunpei Wei

2018-01-01

Full Text Available This study investigated bioleaching behavior of vanadium from a vanadium-bearing shale using Acidithiobacillus ferrooxidans (A. ferrooxidans. Results showed a maximum recovery of 62% vanadium in 1.2-day bioleaching, which was 22.45% higher than the controls. Then, the vanadium leaching efficiency decreased significantly, only 24% of that was obtained on the tenth day. The vanadium extraction in 1.2 days was mainly attributed to the dissolution of vanadium in free oxides of shale. Fe3+ produced by A. ferrooxidans promoted the dissolution process. X-ray diffraction (XRD patterns of the leached residues confirmed the generation of jarosite. SEM-EDS analysis of the residues indicated that jarosite adsorbed on the shale and inhibited the further dissolution of vanadium. The relevance of V, Fe, S, O was quite good in the energy disperse X-ray spectrometry (EDS element mapping of jarosite, and acid-washing of the jarosite resulted in 31.6% of the vanadium in the precipitates desorption, indicating that the decrease of vanadium leaching efficiency in bioleaching process was caused by both adsorption and co-precipitation with jarosite.

Study of vanadium-based chemical conversion coating on the corrosion resistance of magnesium alloy

International Nuclear Information System (INIS)

Yang, K.H.; Ger, M.D.; Hwu, W.H.; Sung, Y.; Liu, Y.C.

2007-01-01

In this study, magnesium alloy (AZ61) was immersed in vanadium containing bath with various conditions, such as the vanadium concentration, immersion time and bath temperature. The results indicate that increase of both vanadium concentration and immersion time produces a thicker conversion layer. However, when immersion time is too long, it will worsen the corrosion resistance due to the increasing of the crack density. The experimental parameter of bath temperature has no significant effect on corrosion resistance. Our results demonstrated that the better corrosion resistance coating can be obtained when the samples are submitted to an immersion in the conversion bath containing NaVO 3 with concentration of 30 g l -1 for 10 min at 80 deg. C. The presented conversion treatment has its potential to replace the chrome-based conversion coating treatment

VO2/TiO2 Nanosponges as Binder-Free Electrodes for High-Performance Supercapacitors

Science.gov (United States)

Hu, Chenchen; Xu, Henghui; Liu, Xiaoxiao; Zou, Feng; Qie, Long; Huang, Yunhui; Hu, Xianluo

2015-11-01

VO2/TiO2 nanosponges with easily tailored nanoarchitectures and composition were synthesized by electrostatic spray deposition as binder-free electrodes for supercapacitors. Benefiting from the unique interconnected pore network of the VO2/TiO2 electrodes and the synergistic effect of high-capacity VO2 and stable TiO2, the as-formed binder-free VO2/TiO2 electrode exhibits a high capacity of 86.2 mF cm-2 (~548 F g-1) and satisfactory cyclability with 84.3% retention after 1000 cycles. This work offers an effective and facile strategy for fabricating additive-free composites as high-performance electrodes for supercapacitors.

VO2/TiO2 Nanosponges as Binder-Free Electrodes for High-Performance Supercapacitors.

Science.gov (United States)

Hu, Chenchen; Xu, Henghui; Liu, Xiaoxiao; Zou, Feng; Qie, Long; Huang, Yunhui; Hu, Xianluo

2015-11-04

VO2/TiO2 nanosponges with easily tailored nanoarchitectures and composition were synthesized by electrostatic spray deposition as binder-free electrodes for supercapacitors. Benefiting from the unique interconnected pore network of the VO2/TiO2 electrodes and the synergistic effect of high-capacity VO2 and stable TiO2, the as-formed binder-free VO2/TiO2 electrode exhibits a high capacity of 86.2 mF cm(-2) (~548 F g(-1)) and satisfactory cyclability with 84.3% retention after 1000 cycles. This work offers an effective and facile strategy for fabricating additive-free composites as high-performance electrodes for supercapacitors.

Vanadium(IV)-stimulated hydrolysis of 2,3-diphosphoglycerate.

Science.gov (United States)

Stankiewicz, P J

1989-05-01

Vanadium(IV) stimulates the hydrolysis of 2,3-diphosphoglycerate at 23 degrees C. The pH optimum is 5.0. Reactions were analyzed by enzymatic and phosphate release assays. The products of 2,3-diphosphoglycerate hydrolysis are inorganic phosphate and 3-phosphoglycerate. The reaction is inhibited by high concentrations of 2,3-diphosphoglycerate and an equation has been formulated that describes the kinetic constants for this reaction at pH 7. The possible relevance of the reaction to the therapeutic lowering by vanadium(IV) of red cell 2,3-diphosphoglycerate in sickle-cell disease is discussed.

Mesoscopic quantum effects in a bad metal, hydrogen-doped vanadium dioxide

Science.gov (United States)

Hardy, Will J.; Ji, Heng; Paik, Hanjong; Schlom, Darrell G.; Natelson, Douglas

2017-05-01

The standard treatment of quantum corrections to semiclassical electronic conduction assumes that charge carriers propagate many wavelengths between scattering events, and succeeds in explaining multiple phenomena (weak localization magnetoresistance (WLMR), universal conductance fluctuations, Aharonov-Bohm oscillations) observed in polycrystalline metals and doped semiconductors in various dimensionalities. We report apparent WLMR and conductance fluctuations in H x VO2, a poor metal (in violation of the Mott-Ioffe-Regel limit) stabilized by the suppression of the VO2 metal-insulator transition through atomic hydrogen doping. Epitaxial thin films, single-crystal nanobeams, and nanosheets show similar phenomenology, though the details of the apparent WLMR seem to depend on the combined effects of the strain environment and presumed doping level. Self-consistent quantitative analysis of the WLMR is challenging given this and the high resistivity of the material, since the quantitative expressions for WLMR are derived assuming good metallicity. These observations raise the issue of how to assess and analyze mesoscopic quantum effects in poor metals.

Luminous transmittance and phase transition temperature of VO 2 ...

African Journals Online (AJOL)

The phase transition temperature (τc) of the films was obtained from both the transmittance and sheet resistance against temperature curves. A change in sheet resistance of 2 to 3 orders of magnitude was observed for both undoped and Ce-doped VO2 films. Comparison between undoped and doped VO2 films revealed ...

Thin-film VO2 submillimeter-wave modulators and polarizers

International Nuclear Information System (INIS)

Fan, J.C.C.; Fetterman, H.R.; Bachner, F.J.; Zavracky, P.M.; Parker, C.D.

1977-01-01

Submillimeter-wave modulators and switchable polarizers have been fabricated from VO 2 thin films deposited on sapphire substrates. By passing electric current pulses through elements made from these films, the films can be thermally cycled through the insulator-to-metal transition that occurs in VO 2 at about 65 degreeC. In the insulating state, the films are found to have negligible effect on the transmission at submillimeter wavelengths, while above the phase transition the transmission is strongly reduced by the free-electron effects characteristic of a metal. Other possible applications of such switchable VO 2 elements include variable bandpass filters and diffraction grating beam-steering devices

Direct and remarkably efficient conversion of methane into acetic acid catalyzed by amavadine and related vanadium complexes. A synthetic and a theoretical DFT mechanistic study.

Science.gov (United States)

Kirillova, Marina V; Kuznetsov, Maxim L; Reis, Patrícia M; da Silva, José A L; da Silva, João J R Fraústo; Pombeiro, Armando J L

2007-08-29

Vanadium(IV or V) complexes with N,O- or O,O-ligands, i.e., [VO{N(CH2CH2O)3}], Ca[V(HIDPA)2] (synthetic amavadine), Ca[V(HIDA)2], or [Bu4N]2[V(HIDA)2] [HIDPA, HIDA = basic form of 2,2'-(hydroxyimino)dipropionic or -diacetic acid, respectively], [VO(CF3SO3)2], Ba[VO(nta)(H2O)]2 (nta = nitrilotriacetate), [VO(ada)(H2O)] (ada = N-2-acetamidoiminodiacetate), [VO(Hheida)(H2O)] (Hheida = 2-hydroxyethyliminodiacetate), [VO(bicine)] [bicine = basic form of N,N-bis(2-hydroxyethyl)glycine], and [VO(dipic)(OCH2CH3)] (dipic = pyridine-2,6-dicarboxylate), are catalyst precursors for the efficient single-pot conversion of methane into acetic acid, in trifluoroacetic acid (TFA) under moderate conditions, using peroxodisulfate as oxidant. Effects on the yields and TONs of various factors are reported. TFA acts as a carbonylating agent and CO is an inhibitor for some systems, although for others there is an optimum CO pressure. The most effective catalysts (as amavadine) bear triethanolaminate or (hydroxyimino)dicarboxylates and lead, in a single batch, to CH3COOH yields > 50% (based on CH4) or remarkably high TONs up to 5.6 x 103. The catalyst can remain active upon multiple recycling of its solution. Carboxylation proceeds via free radical mechanisms (CH3* can be trapped by CBrCl3), and theoretical calculations disclose a particularly favorable process involving the sequential formation of CH3*, CH3CO*, and CH3COO* which, upon H-abstraction (from TFA or CH4), yields acetic acid. The CH3COO* radical is formed by oxygenation of CH3CO* by a peroxo-V complex via a V{eta1-OOC(O)CH3} intermediate. Less favorable processes involve the oxidation of CH3CO* by the protonated (hydroperoxo) form of that peroxo-V complex or by peroxodisulfate. The calculations also indicate that (i) peroxodisulfate behaves as a source of sulfate radicals which are methane H-abstractors, as a peroxidative and oxidizing agent for vanadium, and as an oxidizing and coupling agent for CH3CO* and that (ii) TFA is

A comparative study of species migration and diffusion mechanisms in all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Oh, Kyeongmin; Won, Seongyeon; Ju, Hyunchul

2015-01-01

Highlights: • Migration effects on crossover phenomena is examined. • Crossover and migration model is newly implemented. • Totally opposite crossover trend is observed with migration during charging. • During discharging, the crossover is enhanced due to migration. - ABSTRACT: According to the Nernst–Planck equation, the transport of charged species in porous electrodes is mainly driven by diffusion and migration. Although a number of all-vanadium redox flow battery (VRFB) models have been developed by several VRFB modeling groups, a comparative study of these two ion transport mechanisms has not been clearly reported in the literature. In this study, we develop a three-dimensional (3-D), transient VRFB model that rigorously accounts for both diffusion and migration mechanisms of charged species, including V 2+ , V 3+ , VO 2+ ,VO 2 + and H + . The VRFB model relies upon five principles of conservation: mass, momentum, species, electric charge, and thermal energy. Due to the general form of the conservation equations, both species migration effects on species transport and species diffusion effects on charge transport are considered in the source terms of the model equations. The model calculates species migration and diffusion fluxes through the membrane and compares their relative magnitudes under various charging and discharging stages. This paper clearly elucidates the role of species migration on vanadium crossover and the subsequent capacity losses, demonstrating that the present VRFB model is a valuable tool for optimizing the component design and operation of VRFBs.

Structure and dielectric properties in the radio frequency range of polymer composites based on vanadium dioxide

Directory of Open Access Journals (Sweden)

Kolbunov V.R.

2015-06-01

Full Text Available Polymer composites with active fillers are recently considered to be promising materials for the design of new functional devices with controllable properties and are intensively investigated. Dielectric studies are one of the most effective methods for studying structural features and mechanisms of conductivity formation for this type of two-component systems. The paper presents research results of the dielectric characteristics in the range of radio frequency of 50 kHz — 10 MHz and temperature range of 30—60°C of polyethylene composites of vanadium dioxide with different volume fractions of filler. Two dispersion areas were found: a high-frequency area caused by the Maxwell charge separation on the boundaries of the polyethylene matrix — conductive filler of VI2 crystallites, and a low frequency area associated with the presence of the transition layer at this boundary. The relative permittivity of the composite has a tendency to a decrease in absolute value with increasing temperature. The analysis of the low-frequency dependence of the dielectric constant of the value of the filler’s volume fraction revealed that the investigated composite belongs to two-component statistical mixtures with a transition layer between the components.

Fabrication of polypyrrole/vanadium oxide nanotube composite with enhanced electrochemical performance as cathode in rechargeable batteries

Energy Technology Data Exchange (ETDEWEB)

Zhou, Xiaowei, E-mail: zhouxiaowei@ynu.edu.cn [Department of Physics, School of Physics and Astronomy, Yunnan University, Kunming 650504, Yunnan (China); Chen, Xu; He, Taoling; Bi, Qinsong [Department of Physics, School of Physics and Astronomy, Yunnan University, Kunming 650504, Yunnan (China); Sun, Li [Department of Physics, School of Physics and Astronomy, Yunnan University, Kunming 650504, Yunnan (China); Department of Mechanical Engineering, University of Houston, Houston 77204, TX (United States); Liu, Zhu, E-mail: zhuliu@ynu.edu.cn [Department of Physics, School of Physics and Astronomy, Yunnan University, Kunming 650504, Yunnan (China); Yunnan Key Laboratory of Micro/Nano-Materials and Technology, Yunnan University, Kunming 650091, Yunnan (China)

2017-05-31

Highlights: • VO{sub x}NTs were hydrothermally prepared using C{sub 12}H{sub 27}N as soft template with scalability. • Polypyrrole/VO{sub x}NTs with less C{sub 12}H{sub 27}N template and higher conductivity were obtained. • Polypyrrole/VO{sub x}NTs exhibit better performance as cathode for LIBs compared to VO{sub x}NTs. • Further modification to VO{sub x}NTs with desired electrochemical property can be expected. - Abstract: Vanadium oxide nanotubes (VO{sub x}NTs) with hollow as well as multi-walled features were fabricated under hydrothermal condition by soft-template method. This novel VO{sub x}NTs can be used as cathode material for lithium ion batteries (LIBs), but displaying low specific capacity and poor cycling performance owing to the residual of a mass of soft-template (C{sub 12}H{sub 27}N) and intrinsic low conductivity of VO{sub x}. Cation exchange technique and oxidative polymerization process of pyrrole monomers were conducted to wipe off partial soft-template without electrochemical activity within VO{sub x}NTs and simultaneously form polypyrrole coating on VO{sub x}NTs, respectively. The resulting polypyrrole/VO{sub x}NTs nanocomposite delivers much improved capacity and cyclic stability. Further optimizations, such as complete elimination of organic template and enhancing the crystallinity, can make this unique nanostructure a promising cathode for LIBs.

Effects of erythrocyte infusion on VO2max at high altitude

DEFF Research Database (Denmark)

Young, Jette Feveile; Sawka, M N; Muza, S R

1996-01-01

This study investigated whether autologous erythrocyte infusion would ameliorate the decrement in maximal O2 uptake (VO2max) experienced by lowlanders when they ascend to high altitude. VO2max was measured in 16 men (treadmill running) at sea level (SL) and on the 1st (HA1) and 9th (HA9) days...... of high-altitude (4,300 m) residence. After VO2max was measured at SL, subjects were divided into two matched groups (n = 8). Twenty-four hours before ascent to high altitude, the experimental group received a 700-ml infusion of autologous erythrocytes and saline (42% hematocrit), whereas the control...... group received only saline. The VO2max of erythrocyte-infused [54 +/- 1 (SE) ml.kg-1.min-1] and control subjects (52 +/- 2 ml.kg-1.min-1) did not differ at SL before infusion. The decrement in VO2max on HA1 did not differ between groups, averaging 26% overall, despite higher (P

Electronic structure and insulating gap in epitaxial VO2 polymorphs

Directory of Open Access Journals (Sweden)

Shinbuhm Lee

2015-12-01

Full Text Available Determining the origin of the insulating gap in the monoclinic V O2(M1 is a long-standing issue. The difficulty of this study arises from the simultaneous occurrence of structural and electronic transitions upon thermal cycling. Here, we compare the electronic structure of the M1 phase with that of single crystalline insulating V O2(A and V O2(B thin films to better understand the insulating phase of VO2. As these A and B phases do not undergo a structural transition upon thermal cycling, we comparatively study the origin of the gap opening in the insulating VO2 phases. By x-ray absorption and optical spectroscopy, we find that the shift of unoccupied t2g orbitals away from the Fermi level is a common feature, which plays an important role for the insulating behavior in VO2 polymorphs. The distinct splitting of the half-filled t2g orbital is observed only in the M1 phase, widening the bandgap up to ∼0.6 eV. Our approach of comparing all three insulating VO2 phases provides insight into a better understanding of the electronic structure and the origin of the insulating gap in VO2.

Electrically tunable sign of capacitance in planar W-doped vanadium dioxide micro-switches

Directory of Open Access Journals (Sweden)

Mohammed Soltani, Mohamed Chaker and Joelle Margot

2011-01-01

Full Text Available Negative capacitance (NC in a planar W-doped VO2 micro-switch was observed at room temperature in the low-frequency range 1 kHz–10 MHz. The capacitance changed from positive to negative values as the W-doped VO2 active layer switched from semiconducting to metallic state under applied voltage. In addition, a capacitance–voltage hysteresis was observed as the applied voltage was cycled from −35 to 35 V. These observations suggest that NC results from the increase of the electrically induced conductivity in the active layer. This NC phenomenon could be exploited in advanced multifunctional devices including ultrafast switches, field-effect transistors and memcapacitive systems.

KOH etched graphite felt with improved wettability and activity for vanadium flow batteries

International Nuclear Information System (INIS)

Zhang, Zhengyang; Xi, Jingyu; Zhou, Haipeng; Qiu, Xinping

2016-01-01

Highlights: • GF electrode is activated by KOH etching method for VFB application. • The wettability and activity of eGF electrode towards VO 2+ /VO 2 + and V 2+ /V 3+ couples are improved. • VFB with eGF electrode can run stable at current densities range from 50 to 250 mA cm −2 . • Cycling test at current density of 150 mA cm −2 confirms the superior durability of eGF electrode. - Abstract: In this work, a simple and effective method to activate graphite felt (GF) electrode by using KOH as etching agent is studied for vanadium flow battery (VFB) application. The surface of GF is etched by KOH at 800 °C to generate micropores and attain oxygen-containing functional groups, resulting in greatly improved electrolyte accessibility. Surface morphology, oxygen distribution and microstructure of the KOH etched graphite felts (eGFs) are characterized by SEM, EDX, XPS, XRD and Raman techniques. Due to the abundant exposed edge carbon sites and oxygen-containing functional groups introduced by KOH activation, electrochemical activity of eGFs towards both VO 2+ /VO 2 + and V 2+ /V 3+ redox couples are remarkably improved comparing with GF. In particular, eGF-2 (mass ratio of KOH/GF = 1.25) exhibits the best electrochemical activity and VFB performance among all eGFs. Moreover, the VFB with eGF-2 electrode can run at current density up to 250 mA cm −2 with the energy efficiency of 64%. Long-term cycle life test at higher current density of 150 mA cm −2 confirms the outstanding stability of eGF-2 electrode.

Vanadium recovery process

International Nuclear Information System (INIS)

Pyrih, R.Z.; Rickard, R.S.

1978-01-01

A process for recovering vanadium values from carbonaceous type vanadium ores, and vanadium scrap, such as vanadium contaminated spent catalyst, is disclosed which comprises roasting the vanadium containing material in air at a temperature less than about 600 0 C to produce a material substantially devoid of organic matter, subjecting said roasted material to a further oxidizing roast in an oxygen atmosphere at a temperature of at least about 800 0 C for a period sufficient to convert substantially all of the vanadium to the soluble form, leaching the calcine with a suitable dilute mineral acid or water at a pH of neutral to about 2 to recover vanadium values, precipitating vanadium values as iron vanadate from the leach solution with a soluble iron compound at a pH from neutral to about 1, and recovering ferrovanadium from the iron vanadate by a reduction vacuum smelting operation. The conversion of vanadium in the ore to the soluble form by the oxidizing roast is accomplished without the addition of an alkaline salt during calcining

An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite

Energy Technology Data Exchange (ETDEWEB)

Chen, Desheng; Zhao, Hongxin; Hu, Guoping [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Qi, Tao, E-mail: tqgreen@ipe.ac.cn [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Yu, Hongdong; Zhang, Guozhi [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Wang, Lina, E-mail: linawang@ipe.ac.cn [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Wang, Weijing [National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Beijing 100190 (China); Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China)

2015-08-30

Highlights: • The leaching solution contains high concentration of acid, iron, impurities and lower vanadium. • 99.4% of vanadium and 4.2% of iron were extracted by three-stage extraction process. • 99.6% of vanadium and 5.4% of iron were stripped by three-stage stripping process. • The stripping solution contains 40.16 g/L V{sub 2}O{sub 5}, 0.691 g/L Fe, 0.007 g/L TiO{sub 2} and 0.247 g/L CaO. • The vanadium product of V{sub 2}O{sub 5} with purity of 99.12%, 0.026% Fe and well crystallized. - Abstract: An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite was developed. In this study, a mixed solvent system of di(2-ethylhexyl) phosphate (D2EHPA) and tri-n-butyl phosphate (TBP) diluted with kerosene was used for the selective extraction of vanadium from a hydrochloric acid leaching solution that contained low vanadium concentration with high concentrations of iron and impurities of Ca, Mg, and Al. In the extraction process, the initial solution pH and the phase ratio had considerable functions in the extraction of vanadium from the hydrochloric acid leaching solution. Under optimal extraction conditions (i.e., 30–40 °C for 10 min, 1:3 phase ratio (O/A), 20% D2EHPA concentration (v/v), and 0–0.8 initial solution pH), 99.4% vanadium and only 4.2% iron were extracted by the three-stage counter-current extraction process. In the stripping process with H{sub 2}SO{sub 4} as the stripping agent and under optimal stripping conditions (i.e., 20% H{sub 2}SO{sub 4} concentration, 5:1 phase ratio (O/A), 20 min stripping time, and 40 °C stripping temperature), 99.6% vanadium and only 5.4% iron were stripped by the three-stage counter-current stripping process. The stripping solution contained 40.16 g/L V{sub 2}O{sub 5}, 0.691g/L Fe, 0.007 g/L TiO{sub 2}, 0.006 g/L SiO{sub 2} and 0.247 g/L CaO. A V{sub 2}O{sub 5} product with a purity of 99.12% V{sub 2}O{sub 5} and only 0.026% Fe was obtained after the oxidation, precipitation

Infrared-transmittance tunable metal-insulator conversion device with thin-film-transistor-type structure on a glass substrate

Directory of Open Access Journals (Sweden)

Takayoshi Katase

2017-05-01

Full Text Available Infrared (IR transmittance tunable metal-insulator conversion was demonstrated on a glass substrate by using thermochromic vanadium dioxide (VO2 as the active layer in a three-terminal thin-film-transistor-type device with water-infiltrated glass as the gate insulator. Alternative positive/negative gate-voltage applications induce the reversible protonation/deprotonation of a VO2 channel, and two-orders of magnitude modulation of sheet-resistance and 49% modulation of IR-transmittance were simultaneously demonstrated at room temperature by the metal-insulator phase conversion of VO2 in a non-volatile manner. The present device is operable by the room-temperature protonation in an all-solid-state structure, and thus it will provide a new gateway to future energy-saving technology as an advanced smart window.

Electron paramagnetic resonance studies on conformation states and metal ion exchange properties of vanadium bromoperoxidase

International Nuclear Information System (INIS)

de Boer, E.; Boon, K.; Wever, R.

1988-01-01

An electron paramagnetic resonance (EPR) study was carried out to examine structural aspects of vanadium-containing bromoperoxidase from the brown seaweed Ascophyllum nodosum. At high pH, the reduced form of bromoperoxidase showed an apparently axially symmetric EPR signal with 16 hyperfine lines. When the pH was lowered, a new EPR spectrum was formed. When EPR spectra of the reduced enzyme were recorded in the pH range from 4.2 to 8.4, it appeared that these changes were linked to a functional group with an apparent pK/sub a/ of about 5.4. In D 2 O this value for the pK/sub a/ was 5.3. It is suggested that these effects arise from protonation of histidine or aspartate/glutamate residues near the metal ion. The values for the isotropic hyperfine coupling constant of the reduced enzyme at both high and low pH are also consistent with a ligand field containing nitrogen and/or oxygen donor atoms. When reduced bromoperoxidase was dissolved in D 2 O or H 2 17 O instead of H 2 16 O, vanadium (IV) hyperfine line widths were markedly affected, demonstrating that water is a ligand of the metal ion. Together with previous work these findings suggest that vanadium (IV) is not involved in catalytic turnover and confirm the model in which the vanadium (V) ion of the native enzyme only serves to bind both hydrogen peroxide and bromide. After excess vanadate was added to a homogeneous preparation of purified bromoperoxidase, the extent of vanadium bound to the protein increased from 0.5 to 1.1, with a concomitant enhancement of enzymic activity. Finally, it is demonstrated that both vanadate (VO 4 3- ) and molybdate (MoO 4 2- ) compete for the same site on apobromoperoxidase

Influence of oxygen flow rate on metal-insulator transition of vanadium oxide thin films grown by RF magnetron sputtering

Energy Technology Data Exchange (ETDEWEB)

Ma, Xu; Liu, Xinkun; Li, Haizhu; Huang, Mingju [Henan University, Key Lab of Informational Opto-Electronical Materials and Apparatus, School of Physics and Electronics, Kaifeng (China); Zhang, Angran [South China Normal University, Institute of Electronic Paper Displays, South China Academy of Advanced Optoelectronics, Guangzhou (China)

2017-03-15

High-quality vanadium oxide (VO{sub 2}) films have been fabricated on Si (111) substrates by radio frequency (RF) magnetron sputtering deposition method. The sheet resistance of VO{sub 2} has a significant change (close to 5 orders of magnitude) in the process of the metal-insulator phase transition (MIT). The field emission-scanning electron microscope (FE-SEM) results show the grain size of VO{sub 2} thin films is larger with the increase of oxygen flow. The X-ray diffraction (XRD) results indicate the thin films fabricated at different oxygen flow rates grow along the (011) crystalline orientation. As the oxygen flow rate increases from 3 sccm to 6 sccm, the phase transition temperature of the films reduces from 341 to 320 K, the width of the thermal hysteresis loop decreases from 32 to 9 K. The thin films fabricated in the condition of 5 sccm have a high temperature coefficient of resistance (TCR) -3.455%/K with a small resistivity of 2.795 ρ/Ω cm. (orig.)

Electron beam modification of vanadium dioxide oscillators

Energy Technology Data Exchange (ETDEWEB)

Belyaev, Maksim; Velichko, Andrey; Putrolaynen, Vadim; Perminov, Valentin; Pergament, Alexander [Petrozavodsk State University, Petrozavodsk (Russian Federation)

2017-03-15

The paper presents the results of a study of electron-beam modification (EBM) of VO{sub 2}-switch I-V curve threshold parameters and the self-oscillation frequency of a circuit containing such a switching device. EBM in vacuum is reversible and the parameters are restored when exposed to air at pressure of 150 Pa. At EBM with a dose of 3 C cm{sup -2}, the voltages of switching-on (V{sub th}) and off (V{sub h}), as well as the OFF-state resistance R{sub off}, decrease down to 50% of the initial values, and the oscillation frequency increases by 30% at a dose of 0.7 C cm{sup -2}. Features of physics of EBM of an oscillator are outlined considering the contribution of the metal and semiconductor phases of the switching channel. Controlled modification allows EBM forming of switches with preset parameters. Also, it might be used in artificial oscillatory neural networks for pattern recognition based on frequency shift keying. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Strain engineering and one-dimensional organization of metal-insulator domains in single-crystal vanadium dioxide beams.

Science.gov (United States)

Cao, J; Ertekin, E; Srinivasan, V; Fan, W; Huang, S; Zheng, H; Yim, J W L; Khanal, D R; Ogletree, D F; Grossman, J C; Wu, J

2009-11-01

Correlated electron materials can undergo a variety of phase transitions, including superconductivity, the metal-insulator transition and colossal magnetoresistance. Moreover, multiple physical phases or domains with dimensions of nanometres to micrometres can coexist in these materials at temperatures where a pure phase is expected. Making use of the properties of correlated electron materials in device applications will require the ability to control domain structures and phase transitions in these materials. Lattice strain has been shown to cause the coexistence of metallic and insulating phases in the Mott insulator VO(2). Here, we show that we can nucleate and manipulate ordered arrays of metallic and insulating domains along single-crystal beams of VO(2) by continuously tuning the strain over a wide range of values. The Mott transition between a low-temperature insulating phase and a high-temperature metallic phase usually occurs at 341 K in VO(2), but the active control of strain allows us to reduce this transition temperature to room temperature. In addition to device applications, the ability to control the phase structure of VO(2) with strain could lead to a deeper understanding of the correlated electron materials in general.

Chemically induced porosity on BiVO4 films produced by double magnetron sputtering to enhance the photo-electrochemical response.

Science.gov (United States)

Thalluri, Sitaramanjaneya Mouli; Rojas, Roberto Mirabal; Rivera, Osmary Depablos; Hernández, Simelys; Russo, Nunzio; Rodil, Sandra Elizabeth

2015-07-21

Double magnetron sputtering (DMS) is an efficient system that is well known because of its precise control of the thin film synthesizing process over any kind of substrate. Here, DMS has been adopted to synthesize BiVO4 films over a conducting substrate (FTO), using metallic vanadium and ceramic Bi2O3 targets simultaneously. The films were characterized using different techniques, such as X-ray diffraction (XRD), UV-Vis spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and profilometry. The photo-electrochemical analysis was performed using linear scan voltammetry, chronoamperometry and electrochemical impedance spectroscopy (EIS) under the illumination of simulated solar light at 1 Sun. The photocurrent density of the sputtered BiVO4 thin films could be improved from 0.01 mA cm(-2) to 1.19 mA cm(-2) at 1.23 V vs. RHE by chemical treatment using potassium hydroxide (KOH). The effect of KOH was the removal of impurities from the grain boundaries, leading to a more porous structure and more pure crystalline monoclinic BiVO4 particles. Such variations in the microstructure as well as the improvement of the charge transfer properties of the BiVO4 film after the KOH treatment were confirmed and studied in depth by EIS analysis.

Highly active, bi-functional and metal-free B4C-nanoparticle-modified graphite felt electrodes for vanadium redox flow batteries

Science.gov (United States)

Jiang, H. R.; Shyy, W.; Wu, M. C.; Wei, L.; Zhao, T. S.

2017-10-01

The potential of B4C as a metal-free catalyst for vanadium redox reactions is investigated by first-principles calculations. Results show that the central carbon atom of B4C can act as a highly active reaction site for redox reactions, due primarily to the abundant unpaired electrons around it. The catalytic effect is then verified experimentally by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests, both of which demonstrate that B4C nanoparticles can enhance the kinetics for both V2+/V3+ and VO2+/VO2+ redox reactions, indicating a bi-functional effect. The B4C-nanoparticle-modified graphite felt electrodes are finally prepared and tested in vanadium redox flow batteries (VRFBs). It is shown that the batteries with the prepared electrodes exhibit energy efficiencies of 88.9% and 80.0% at the current densities of 80 and 160 mA cm-2, which are 16.6% and 18.8% higher than those with the original graphite felt electrodes. With a further increase in current densities to 240 and 320 mA cm-2, the batteries can still maintain energy efficiencies of 72.0% and 63.8%, respectively. All these results show that the B4C-nanoparticle-modified graphite felt electrode outperforms existing metal-free catalyst modified electrodes, and thus can be promising electrodes for VRFBs.

Vanadium

International Nuclear Information System (INIS)

Duke, V.W.A.

1983-07-01

Although a relatively abundant element, vanadium occurs only rarely in sufficient concentration to be worked commercially. In most cases, vanadium is produced as a co-product of some other element, most commonly iron. The principal ore deposits of vanadium occur in titaniferous magnetites that have been formed by magnetic segregation. Important commercial deposits of vanadium also occur associated with uranium, and with phosphate deposits. The principal uses of vanadium are in the production of special purpose, particularly high-strength low-alloy steels, in the manufacture of titanium alloys, and as a catalyst, notably in the manufacture of sulphuric acid. Small quantities of vanadium, often in combination with niobium, are added to steel to bring about toughening through grain refinement, and increased tensile strength through precipitation hardening. Known world reserves of vanadium are very large and fully adequate to meet any foreseeable demand. By far the largest known deposits of vanadium occur in South Africa. Many other similar deposits are known, but are only exploited in the USSR and China. The present total world demand for vanadium amounts to about 40 000 tons of metal annually and this is produced primarily in four countries, South Africa, the USSR, the People's Republic of China and the United States of America, in that order. South Africa is the principal vanadium producing country in the world, supplying vanadium in various forms. Vanadium has a very low and non-accumulative toxicity; recovery plants can be operated in such a manner to ensure no air or steam pollution results

Structure and properties of vanadium(V)-doped hexagonal turbostratic birnessite and its enhanced scavenging of Pb{sup 2+} from solutions

Energy Technology Data Exchange (ETDEWEB)

Yin, Hui; Feng, Xionghan; Tan, Wenfeng [Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtze River), Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070 (China); Koopal, Luuk K. [Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtze River), Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070 (China); Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703HB Wageningen (Netherlands); Hu, Tiandou [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100039 (China); Zhu, Mengqiang, E-mail: mzhu6@uwyo.edu [Department of Ecosystem Science and Management, University of Wyoming, 1000 E. University Ave., Laramie, WY 82071 (United States); Liu, Fan, E-mail: liufan@mail.hzau.edu.cn [Key Laboratory of Arable Land Conservation (Middle and Lower Reaches of Yangtze River), Ministry of Agriculture, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070 (China)

2015-05-15

Highlights: • V was coprecipitated with birnessite at a series of V/Mn molar ratios. • V-doped birnessites have greatly reduced particle sizes and increased SSAs. • V exists as V(V) oxyanions, including [V{sub 6}O{sub 16}] and [VO{sub 4}], on birnessite surfaces. • Scavenging of Pb{sup 2+} by these V-doped birnessites is greatly enhanced. - Abstract: Vanadium(V)-doped hexagonal turbostratic birnessites were synthesized and characterized by multiple techniques and were used to remove Pb{sup 2+} from aqueous solutions. With increasing V content, the V(V)-doped birnessites have significantly decreased crystallinity, i.e., the thickness of crystals in the c axis decreases from 9.8 nm to ∼0.7 nm, and the amount of vacancies slightly increases from 0.063 to 0.089. The specific surface areas of these samples increase after doping while the Mn average oxidation sates are almost constant. V has a valence of +5 and tetrahedral symmetry, and exists as oxyanions, including V{sub 6}O{sub 16}{sup 2−}, and VO{sub 4}{sup 3−} on birnessite edge sites by forming monodentate corning-sharing complexes. Pb L{sub III}-edge extended X-ray absorption fine structure (EXAFS) spectra analysis shows that, at low V contents (V/Mn ≤ 0.07) Pb{sup 2+} mainly binds with birnessite on octahedral vacancy and especially edge sites whereas at higher V contents (V/Mn > 0.07) more Pb{sup 2+} associates with V oxyanions and form vanadinite [Pb{sub 5}(VO{sub 4}){sub 3}Cl]-like precipitates. With increasing V(V) content, the Pb{sup 2+} binding affinity on the V-doped birnessites significantly increases, ascribing to both the formation of the vanadinite precipitates and decreased particle sizes of birnessite. These results are useful to design environmentally benign materials for treatment of metal-polluted water.

Exploring the coordination change of vanadium and structure transformation of metavanadate MgV2O6 under high pressure

Science.gov (United States)

Tang, Ruilian; Li, Yan; Xie, Shengyi; Li, Nana; Chen, Jiuhua; Gao, Chunxiao; Zhu, Pinwen; Wang, Xin

2016-01-01

Raman spectroscopy, synchrotron angle-dispersive X-ray diffraction (ADXRD), first-principles calculations, and electrical resistivity measurements were carried out under high pressure to investigate the structural stability and electrical transport properties of metavanadate MgV2O6. The results have revealed the coordination change of vanadium ions (from 5+1 to 6) at around 4 GPa. In addition, a pressure-induced structure transformation from the C2/m phase to the C2 phase in MgV2O6 was detected above 20 GPa, and both phases coexisted up to the highest pressure. This structural phase transition was induced by the enhanced distortions of MgO6 octahedra and VO6 octahedra under high pressure. Furthermore, the electrical resistivity decreased with pressure but exhibited different slope for these two phases, indicating that the pressure-induced structural phase transitions of MgV2O6 was also accompanied by the obvious changes in its electrical transport behavior. PMID:27924843

Critical V2O5/TeO2 Ratio Inducing Abrupt Property Changes in Vanadium Tellurite Glasses.

Science.gov (United States)

Kjeldsen, Jonas; Rodrigues, Ana C M; Mossin, Susanne; Yue, Yuanzheng

2014-12-26

Transition metal containing glasses have unique electrical properties and are therefore often used for electrochemical applications, such as in batteries. Among oxide glasses, vanadium tellurite glasses exhibit the highest electronic conductivity and thus the high potential for applications. In this work, we investigate how the dynamic and physical properties vary with composition in the vanadium tellurite system. The results show that there exists a critical V(2)O(5) concentration of 45 mol %, above which the local structure is subjected to a drastic change with increasing V(2)O(5), leading to abrupt changes in both hardness and liquid fragility. Electronic conductivity does not follow the expected correlation to the valence state of the vanadium as predicted by the Mott-Austin equation but shows a linear correlation to the mean distance between vanadium ions. These findings could contribute to designing optimum vanadium tellurite compositions for electrochemical devices. The work gives insight into the mechanism of electron conduction in the vanadium tellurite systems.

Epitaxial growth and electronic structure of oxyhydride SrVO2H thin films

Science.gov (United States)

Katayama, Tsukasa; Chikamatsu, Akira; Yamada, Keisuke; Shigematsu, Kei; Onozuka, Tomoya; Minohara, Makoto; Kumigashira, Hiroshi; Ikenaga, Eiji; Hasegawa, Tetsuya

2016-08-01

Oxyhydride SrVO2H epitaxial thin films were fabricated on SrTiO3 substrates via topotactic hydridation of oxide SrVO3 films using CaH2. Structural and composition analyses suggested that the SrVO2H film possessed one-dimensionally ordered V-H--V bonds along the out-of-plane direction. The synthesis temperature could be lowered by reducing the film thickness, and the SrVO2H film was reversible to SrVO3 by oxidation through annealing in air. Photoemission and X-ray absorption spectroscopy measurements revealed the V3+ valence state in the SrVO2H film, indicating that the hydrogen existed as hydride. Furthermore, the electronic density of states was highly suppressed at the Fermi energy, consistent with the prediction that tetragonal distortion induces metal to insulation transition.

Characteristics of Vanadium Doped And Bamboo Activated Carbon Coated LiFePO4 And Its Performance For Lithium Ion Battery Cathode

Directory of Open Access Journals (Sweden)

Nofrijon Sofyan

2018-04-01

Full Text Available Vanadium doped and bamboo activated carbon coated lithium iron phosphate (LiFePO4 used for lithium ion battery cathode has been successfully prepared. Lithium iron phosphate was prepared through a wet chemical method followed by a hydrothermal process from the starting materials of LiOH, NH4H2PO4, and FeSO4.7H2O. The dopant variations of 0 wt.%, 3 wt.%, 5 wt.%, and 7 wt.% of vanadium and a fixed 3 wt.% of bamboo activated carbon were carried out via a solid-state reaction process each by using NH4VO3 as a source of vanadium and carbon pyrolyzed from bamboo tree, respectively. The characterization was carried out using X-ray Diffraction (XRD for the phase formed and its crystal structure, Scanning Electron Microscope (SEM for the surface morphology, Electrochemical Impedance Spectroscopy (EIS for the conductivity, and battery analyzer for the performance of lithium ion battery cathode. The XRD results show that the phase formed has an olivine based structure with an orthorhombic space group. Morphology examination revealed that the particle agglomeration decreased with the increasing level of vanadium concentrations. Conductivity test showed that the impedance of solid electrolyte interface decreased with the increase of vanadium concentration indicated by increasing conductivity of 1.25 x 10-5 S/cm, 2.02 x 10-5 S/cm, 4.37 x 10-5 S/cm, and 5.69 x 10-5 S/cm, each for 0 wt.%, 3 wt.%, 5 wt.%, and 7 wt.% vanadium, respectively. Vanadium doping and bamboo activated carbon coating are promising candidate for improving lithium ion battery cathode as the initial charge and discharge capacity at 0.5C for LiFePO4/C at 7 wt.% vanadium is in the range of 8.0 mAh/g.

The VO-Dance web application at the IA2 data center

Science.gov (United States)

Molinaro, Marco; Knapic, Cristina; Smareglia, Riccardo

2012-09-01

Italian center for Astronomical Archives (IA2, http://ia2.oats.inaf.it) is a national infrastructure project of the Italian National Institute for Astrophysics (Istituto Nazionale di AstroFisica, INAF) that provides services for the astronomical community. Besides data hosting for the Large Binocular Telescope (LBT) Corporation, the Galileo National Telescope (Telescopio Nazionale Galileo, TNG) Consortium and other telescopes and instruments, IA2 offers proprietary and public data access through user portals (both developed and mirrored) and deploys resources complying the Virtual Observatory (VO) standards. Archiving systems and web interfaces are developed to be extremely flexible about adding new instruments from other telescopes. VO resources publishing, along with data access portals, implements the International Virtual Observatory Alliance (IVOA) protocols providing astronomers with new ways of analyzing data. Given the large variety of data flavours and IVOA standards, the need for tools to easily accomplish data ingestion and data publishing arises. This paper describes the VO-Dance tool, that IA2 started developing to address VO resources publishing in a dynamical way from already existent database tables or views. The tool consists in a Java web application, potentially DBMS and platform independent, that stores internally the services' metadata and information, exposes restful endpoints to accept VO queries for these services and dynamically translates calls to these endpoints to SQL queries coherent with the published table or view. In response to the call VO-Dance translates back the database answer in a VO compliant way.

Ultrafast Silicon-based Modulators using Optical Switching of Vanadium Dioxide

Science.gov (United States)

2014-12-04

away from the central device, and mounted on an XY positioning stage. Piezo -controled XYZ stages were used to position and couple light to/from...circuit consisting of our device in series with a current limiting resistor of 50Ω (see Fig. 10c inset) [23]. The voltage across this resistor was...across the current limiting resistor when two different 10ns voltage pulses are applied: one below the threshold voltage needed to induce the VO2

VO{sub x} effectively doping CVD-graphene for transparent conductive films

Energy Technology Data Exchange (ETDEWEB)

Ji, Qinghua; Shi, Liangjing [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China); Zhang, Qinghong [State Key Laboratory of Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, 2999 North Renmin Road, Shanghai 201620 (China); Wang, Weiqi; Zheng, Huifeng [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China); Zhang, Yuzhi [The Key Laboratory of Inorganic Coating Materials, Shanghai Institute of Ceramics, Chinese Academy of Sciences,1295 Dingxi Road, Shanghai 200050 (China); Liu, Yangqiao, E-mail: yqliu@mail.sic.ac.cn [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China); Sun, Jing, E-mail: jingsun@mail.sic.ac.cn [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China)

2016-11-30

Highlights: • Doping process operated easily. • Sheet resistance decreased efficiently after doping. • Sheet resistance of doped graphene is stable after exposed in the air. • Mechanism of doping process is studied. - Abstract: Chemical vapor deposition(CVD)-synthesized graphene is potentially an alternative for tin-doped indium oxide (ITO) transparent conductive films (TCFs), however its sheet resistance is still too high to meet many demands. Vanadium oxide has been widely applied as smart window materials, however, no study has been reported to use it as dopant to improve the conductivity of graphene TCFs. In this study, we firstly reported that VO{sub x} doping can effectively lower the sheet resistance of CVD-graphene films while keeping its good optical properties, whose transmittance is as high as 86–90%. The optimized VO{sub x}-doped graphene exhibits a sheet resistance as low as 176 Ω/□, which decreases by 56% compared to the undoped graphene films. The doping process is convenient, stable, economical and easy to operate. What is more, VO{sub x} can effectively increase the work function(WF) of the film, making it more appropriate for use in solar cells. The evolution of the VO{sub x} species annealed at different temperatures below 400 °C has been detailed studied for the first time, based on which the doping mechanism is proposed. The prepared VO{sub x} doped graphene is expected to be a promising candidate for transparent conductive film purposes.

o-Iminobenzosemiquinonate and o-imino-p-methylbenzosemiquinonate anion radicals coupled VO2+ stabilization.

Science.gov (United States)

Roy, Amit Saha; Saha, Pinaki; Adhikary, Nirmal Das; Ghosh, Prasanta

2011-03-21

The diamagnetic VO(2+)-iminobenzosemiquinonate anion radical (L(R)(IS)(•-), R = H, Me) complexes, (L(-))(VO(2+))(L(R)(IS)(•-)): (L(1)(-))(VO(2+))(L(H)(IS)(•-))•3/2MeOH (1•3/2MeOH), (L(2)(-))(VO(2+))(L(H)(IS)(•-)) (2), and (L(2)(-))(VO(2+))(L(Me)(IS)(•-))•1/2 L(Me)(AP) (3•1/2 L(Me)(AP)), incorporating tridentate monoanionic NNO-donor ligands {L = L(1)(-) or L(2)(-), L(1)H = (2-[(phenylpyridin-2-yl-methylene)amino]phenol; L(2)H = 1-(2-pyridylazo)-2-naphthol; L(H)(IS)(•-) = o-iminobenzosemiquinonate anion radical; L(Me)(IS)(•-) = o-imino-p-methylbenzosemiquinonate anion radical; and L(Me)(AP) = o-amino-p-methylphenol} have been isolated and characterized by elemental analyses, IR, mass, NMR, and UV-vis spectra, including the single-crystal X-ray structure determinations of 1•3/2MeOH and 3•1/2 L(Me)(AP). Complexes 1•3/2MeOH, 2, and 3•1/2 L(Me)(AP) absorb strongly in the visible region because of intraligand (IL) and ligand-to-metal charge transfers (LMCT). 1•3/2MeOH is luminescent (λ(ext), 333 nm; λ(em), 522, 553 nm) in frozen dichloromethane-toluene glass at 77 K due to π(diimine→)π(diimine)* transition. The V-O(phenolato) (cis to the V═O) lengths, 1.940(2) and 1.984(2) Å, respectively, in 1•3/2MeOH and 3•1/2 L(Me)(AP) are consistent with the VO(2+) description. The V-O(iminosemiquinonate) (trans to the V═O) lengths, 2.1324(19) in 1•3/2MeOH and 2.083(2) Å in 3•1/2 L(Me)(AP), are expectedly ∼0.20 Å longer due to the trans influence of the V═O bond. Because of the stronger affinity of the paramagnetic VO(2+) ion to the L(H)(IS)(•-) or L(Me)(IS)(•-), the V-N(iminosemiquinonate) lengths, 1.908(2) and 1.921(2) Å, respectively, in 1•3/2MeOH and 3•1/2 L(Me)(AP), are unexpectedly shorter. Density functional theory (DFT) calculations using B3LYP, B3PW91, and PBE1PBE functionals on 1 and 2 have established that the closed shell singlet (CSS) solutions (VO(3+)-amidophenolato (L(R)(AP)(2-)) coordination) of these

Fast response of sprayed vanadium pentoxide (V2O5) nanorods towards nitrogen dioxide (NO2) gas detection

Science.gov (United States)

Mane, A. A.; Suryawanshi, M. P.; Kim, J. H.; Moholkar, A. V.

2017-05-01

The V2O5 nanorods have been successfully spray deposited at optimized substrate temperature of 400 °C onto the glass substrates using vanadium trichloride (VCl3) solution of different concentrations. The effect of solution concentration on the physicochemical and NO2 gas sensing properties of sprayed V2O5 nanorods is studied at different operating temperatures and gas concentrations. The XRD study reveals the formation of V2O5 having an orthorhombic symmetry. The FE-SEM micrographs show the nanorods-like morphology of V2O5. The AFM micrographs exhibit a well covered granular surface topography. For direct allowed transition, the band gap energy values are found to be decreased from 2.45 eV to 2.42 eV. The nanorods deposited with 30 mM solution concentration shows the maximum response of 24.2% for 100 ppm NO2 gas concentration at an operating temperature of 200 °C with response and recovery times of 13 s and 140 s, respectively. Finally, the chemisorption mechanism of NO2 gas on the V2O5 nanorods is discussed.

Investigation into isomolar series of Al(NO3)3, Na3VO4 solution mixture and composition of solid phases

International Nuclear Information System (INIS)

Chernysh, L.F.; Nakhodnova, A.P.; Makarova, R.A.

1979-01-01

Conducted is investigation of properties of isomolar series of aluminium nitrate and sodiUm vanadate solutions at pH of the latter 12.5; 10.0; 7.0 and the temperature of 25 deg C using the methods of pH-metry, conductometry, ''seeming'' volume of precipitations, residual concentration of aluminium and vanadium. It is shown, that the composition property diagram of the system investigated does not reflect the true composition of solid-phase products of the reaction, which depends on the component ratio in solution. Bottom phases of isomolar series are mainly heterogeneous. At the excess of sodium vanadate solution and its high pH values conditions for the basic salt formation are created. At pH of the Na 3 VO 4 solution of 12.5 and 10.0 and Al(NO 3 ) 3 : Na 3 VO 4 ratios 4:6 and 3:7 respectively obtained are the basic aluminium vanadates of the (AlOH) 3 (VO 4 ) 2 x 7.5H 2 O and (AlOH) 2 V 2 O 7 x5H 2 O composition, some of their physicochemical properties being investigated

Thermodynamics of oxygen in solid solution in vanadium and niobium--vanadium alloys

International Nuclear Information System (INIS)

Steckel, G.L.

1977-01-01

A thermodynamic study was made of the vanadium-oxygen and niobium-vanadium-oxygen systems utilizing the solid state galvanic cell technique. Investigations were made with a ThO 2 /Y 2 O 3 electrolyte over the temperature ranges 700 to 1200 0 C (973 to 1473 K) for the binary system and 650 to 1150 0 C (923 to 1423 K) for the ternary system. The activity of oxygen in vanadium obeys Henry's law for the temperatures of this investigation for concentrations up to 3.2 at. percent oxygen. For higher concentrations the activity coefficient shows positive deviations from Henry's law. The terminal solubility of oxygen in vanadium was determined. The activity of oxygen in Nb--V alloys obeys Henry's law for the temperatures of this study for oxygen concentrations less than approximately 2 at. percent. For certain Nb/V ratios Henry's law is obeyed for concentrations as high as 6.5 at. percent oxygen. First order entropy and enthalpy interaction coefficients have been determined to describe the effect on the oxygen activity of niobium additions to vanadium-rich alloys with dilute oxygen concentrations. Niobium causes relatively small decreases in the oxygen activity of V-rich alloys and increases the oxygen solubility limit. Vanadium additions to Nb-rich alloys also increases the oxygen solubility and causes substantial decreases in the dilute solution oxygen activities. The change in the thermodynamic properties when molecular oxygen dissolves in vanadium and niobium--vanadium alloys and the equilibrium oxygen pressure over the binary and ternary systems were also determined

Studies of vanadium-phosphorus-oxygen selective oxidation catalysts by sup 31 P and sup 51 V NMR spin-echo and volume susceptibility measurements

Energy Technology Data Exchange (ETDEWEB)

Li, Juan.

1991-10-01

The purpose of this work is to characterize the vanadium-phosphorous oxide (V-P-O) catalysts for the selective oxidation of n-butane and 1-butene to maleic anhydride. The utility of solid state nuclear magnetic resonance as an analytical tool in this investigation lies in its sensitivity to the electronic environment surrounding the phosphorous and vanadium nuclei, and proximity of paramagnetic species. Spin-echo mapping NMR of {sup 31}p and {sup 51}v and volume magnetic susceptibility measurements were used as local microscopic probes of the presence of V{sup 5+}, V{sup 4+}, V{sup 3+} species in the model compounds: {beta}-VOPO{sub 4}, {beta}-VOPO{sub 4} treated with n-butane/1-butene, (VO){sub 2}P{sub 2}O{sub 7} treated with n-butane/1-butene; and industrial catalysts with P/V (phosphorus to vanadium) ratio of 0.9, 1.0 and 1.1, before and after treatment with n-butane and 1-butene. The NMR spectra provide a picture of how the oxidation states of vanadium are distributed in these catalysts. 73 refs., 32 figs., 8 tabs.

Compare the phase transition properties of VO2 films from infrared to terahertz range

Science.gov (United States)

Liang, Shan; Shi, Qiwu; Huang, Wanxia; Peng, Bo; Mao, Zhenya; Zhu, Hongfu

2018-06-01

VO2 with reversible semiconductor-metal phase transition properties is particularly available for the application in smart opto-electrical devices. However, there are rare reports on comparing its phase transition properties at different ranges. In this study, the VO2 films are designed with the similar crystalline structure and stoichiometry, but different morphologies by inorganic and organic sol-gel methods, and their phase transition characteristics are compared both at infrared and terahertz range. The results indicate that the VO2 film prepared by inorganic sol-gel method shows more compact nanostructure. It results in larger resistivity change, infrared and terahertz switching ratio in the VO2 film. Moreover, it presents that the phase transition intensity of VO2 film in terahertz range is more sensitive to its microstructure. This work is helpful for understanding the susceptibility of terahertz switching properties of VO2 to its microstructure. And it can provide insights for the applications of VO2 in terahertz smart devices.

Vanadium Oxyfluoride/Few-Layer Graphene Composite as a High-Performance Cathode Material for Lithium Batteries.

Science.gov (United States)

Cambaz, Musa Ali; Vinayan, B P; Clemens, Oliver; Munnangi, Anji Reddy; Chakravadhanula, Venkata Sai Kiran; Kübel, Christian; Fichtner, Maximilian

2016-04-18

Metal oxyfluoride compounds are gathering significant interest as cathode materials for lithium ion batteries at the moment because of their high theoretical capacity and resulting high energy density. In this regard, a new and direct approach is presented to synthesize phase-pure vanadium oxyfluoride (VO2F). The structure of VO2F was identified by Rietveld refinement of the powder X-ray diffraction (XRD) pattern. It crystallizes in a perovskite-type structure with disorder of the oxide and fluoride ions. The as-synthesized VO2F was tested as a cathode material for lithium ion batteries after being surface-coated with few-layer graphene. The VO2F delivered a first discharge capacity of 254 mA h g(-1) and a reversible capacity of 208 mA h g(-1) at a rate of C/20 for the first 20 cycles with an average discharge voltage of 2.84 V, yielding an energy density of 591 W h kg(-1). Improved rate capability that outperforms the previous report has been achieved, showing a discharge capacity of 150 mA h g(-1) for 1 C. The structural changes during lithium insertion and extraction were monitored by ex-situ XRD analysis of the electrodes discharged and charged to various stages. Lithium insertion results in an irreversible structural change of the anion lattice from (3)/4 cubic close packing to hexagonal close packing to accommodate the inserted lithium ions while keeping the overall space-group symmetry. For the first time we have revealed a structural change for the ReO3-type structure of as-prepared VO2F to the RhF3 structure after lithiation/delithiation, with structural changes that have not been observed in previous reports. Furthermore, the new synthetic approach described here would be a platform for the synthesis of new oxyfluoride compounds.

Temperature-agile and structure-tunable optical properties of VO2/Ag thin films

International Nuclear Information System (INIS)

Zhang, X.R.; Hu, X.; Wang, W.; Zhao, Y.; Reinhardt, K.; Knize, R.J.; Lu, Yalin

2012-01-01

By integrating together VO 2 's unique near-room-temperature (RT) semiconductor-metal (S-M) phase transition with a thin silver (Ag) layer's plasmonic properties, VO 2 /Ag multilayers could present a much enhanced optical transmission change when increasing the temperature from RT to over VO 2 's S-M phase-transition temperature. Changing VO 2 and Ag layer thicknesses can also significantly tune their transmission and absorption properties, which could lead to a few useful designs in optoelectronic and energy-saving industries. (orig.)

Synthesis of flexible electrodes based on electrospun carbon nanofibers with Mn_3O_4 nanoparticles for vanadium redox flow battery application

International Nuclear Information System (INIS)

Di Blasi, A.; Busaccaa, C.; Di Blasia, O.; Briguglioa, N.; Squadritoa, G.; Antonuccia, V.

2017-01-01

Highlights: • Mn_3O_4/CNF electrode is investigated for vanadium redox flow battery application. • The high reversibility is ascribed to the several type of redox couples on the spinel structure. • Cell electrochemical parameters confirm the high reversibility for Mn_3O_4/CNF electrodes. - Abstract: Flexible carbon nanofiber (CNF)-based electrodes and CNF with a 20% of manganese oxide incorporated (Mn_3O_4/CNF) are prepared by using the electrospinning method for vanadium redox flow battery (VRFB) application. A blend consisting of manganese acetate (Mn(OAc)_2) and polyacrilonitrile (PAN) is electrospun and successively subjected to different thermal treatments in which the growth of Mn_3O_4 particles and CNFs occurred together guaranteeing an appropriate electron conductivity for electrodes thus synthesized. Cyclic voltammetry (CV) measurements show an interesting electrocatalytic activity toward the [VO]"2"+/[VO_2]"+ as well as the V"2"+/V"3"+ redox reactions for the Mn_3O_4/CNF electrospun sample. Charge-discharge tests, carried out at 80 mA cm"−"2, show a state of charge (SOC) and a depth of discharge (DoD) of 81% and 73%, respectively, for the cells assembled with Mn_3O_4/CNF electrodes. These data are indicative of a high vanadium active species utilization thanks to the better electrocatalytic activity at high current densities. Furthermore, the cell with Mn_3O_4/CNF shows EE values of about 81% (88% of VE and 92% of CE) vs. 70% (75% of VE and 93% of CE) with respect to a commercial carbon felt (CF) electrode used for comparison. These results are attributable to the higher oxygen species content as well as the improved electron conductivity due to the synergetic effect of the more graphitic carbon and to the structural defects within the Mn_3O_4 spinel structure.

The electronic structure of VO in its ground and electronically excited states: A combined matrix isolation and quantum chemical (MRCI) study

International Nuclear Information System (INIS)

Hübner, Olaf; Hornung, Julius; Himmel, Hans-Jörg

2015-01-01

The electronic ground and excited states of the vanadium monoxide (VO) molecule were studied in detail. Electronic absorption spectra for the molecule isolated in Ne matrices complement the previous gas-phase spectra. A thorough quantum chemical (multi-reference configuration interaction) study essentially confirms the assignment and characterization of the electronic excitations observed for VO in the gas-phase and in Ne matrices and allows the clarification of open issues. It provides a complete overview over the electronically excited states up to about 3 eV of this archetypical compound