Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties

NASA Astrophysics Data System (ADS)

Dey, Arjun; Nayak, Manish Kumar; Esther, A. Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A. K.; Bera, Parthasarathi; Barshilia, Harish C.; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D. Raghavendra; Sridhara, N.; Sharma, Anand Kumar

2016-11-01

Vanadium oxide-molybdenum oxide (VO-MO) thin (21-475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V2O5, V2O3 and VO2 along with MoO3. Reversible or smart transition was found to occur just above the room temperature i.e., at ~45-50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10-5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films.

Characterization of pulsed laser deposition grown V2O3 converted VO2

NASA Astrophysics Data System (ADS)

Majid, Suhail; Shukla, D. K.; Rahman, F.; Gautam, Kamini; Sathe, V. G.; Choudhary, R. J.; Phase, D. M.

2016-10-01

Controllable tuning of Metal-insulator transition in VxOy thin film has been a field of extensive research. However controlled synthesis of desired Vanadium oxide phase is a challenging task. We have successfully achieved VO2 phase on Silicon substrate after post deposition annealing treatment to the PLD grown as deposited V2O3 thin films. The annealed thin film was characterized by x-ray diffraction (XRD), resistivity, Raman spectroscopy, X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) measurements. XRD confirms the crystalline nature and growth of VO2 phase in thin film. The characteristic MIT was observed from resistivity measurements and transition temperature appeared at lower value around 336 K, compared to bulk VO2. The structural transition accompanied with MIT from lower temperature monoclinic phase to higher temperature Rutile phase became evident from temperature dependent Raman measurements. Chemical state of vanadium was examined using XAS and XPS measurements which confirm the presence of +4 oxidation state of vanadium in thin film.

Thermally Stable Solution Processed Vanadium Oxide as a Hole Extraction Layer in Organic Solar Cells

PubMed Central

Alsulami, Abdullah; Griffin, Jonathan; Alqurashi, Rania; Yi, Hunan; Iraqi, Ahmed; Lidzey, David; Buckley, Alastair

2016-01-01

Low-temperature solution-processable vanadium oxide (V2Ox) thin films have been employed as hole extraction layers (HELs) in polymer bulk heterojunction solar cells. V2Ox films were fabricated in air by spin-coating vanadium(V) oxytriisopropoxide (s-V2Ox) at room temperature without the need for further thermal annealing. The deposited vanadium(V) oxytriisopropoxide film undergoes hydrolysis in air, converting to V2Ox with optical and electronic properties comparable to vacuum-deposited V2O5. When s-V2Ox thin films were annealed in air at temperatures of 100 °C and 200 °C, OPV devices showed similar results with good thermal stability and better light transparency. Annealing at 300 °C and 400 °C resulted in a power conversion efficiency (PCE) of 5% with a decrement approximately 15% lower than that of unannealed films; this is due to the relative decrease in the shunt resistance (Rsh) and an increase in the series resistance (Rs) related to changes in the oxidation state of vanadium. PMID:28773356

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties

PubMed Central

Dey, Arjun; Nayak, Manish Kumar; Esther, A. Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A. K.; Bera, Parthasarathi; Barshilia, Harish C.; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D. Raghavendra; Sridhara, N.; Sharma, Anand Kumar

2016-01-01

Vanadium oxide-molybdenum oxide (VO-MO) thin (21–475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V2O5, V2O3 and VO2 along with MoO3. Reversible or smart transition was found to occur just above the room temperature i.e., at ~45–50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10−5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films. PMID:27853234

Comparative study of structural, optical and impedance measurements on V{sub 2}O{sub 5} and V-Ce mixed oxide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malini, D. Rachel; Sanjeeviraja, C., E-mail: sanjeeviraja@rediffmail.com

Vanadium pentoxide (V{sub 2}O{sub 5}) and Vanadium-Cerium mixed oxide thin films at different molar ratios of V{sub 2}O{sub 5} and CeO{sub 2} have been deposited at 200 W rf power by rf planar magnetron sputtering in pure argon atmosphere. The structural and optical properties were studied by taking X-ray diffraction and transmittance and absorption spectra respectively. The amorphous thin films show an increase in transmittance and optical bandgap with increase in CeO{sub 2} content in as-prepared thin films. The impedance measurements for as-deposited thin films show an increase in electrical conductivity with increase in CeO{sub 2} material.

Investigation of physicochemical and tribological properties of transparent oxide semiconducting thin films based on Ti-V oxides

NASA Astrophysics Data System (ADS)

Mazur, M.; Sieradzka, K.; Kaczmarek, D.; Domaradzki, J.; Wojcieszak, D.; Domanowski, P.

2013-08-01

In this paper investigations of structural and optical properties of nanocrystalline Ti-V oxide thin films are described. The films were deposited onto Corning 7059 glass using a modified reactive magnetron sputtering method. Structural investigations of prepared Ti-V oxides with vanadium addition of 19 at. % revealed amorphous structure, while incorporation of 21 and 23 at. % of vanadium resulted in V2O5 formation with crystallites sizes of 12.7 and 32.4 nm, respectively. All prepared thin films belong to transparent oxide semiconductors due to their high transmission level of ca. 60-75 % in the visible light range, and resistivity in the range of 3.3·102-1.4·105 Ωcm. Additionally, wettability and hardness tests were performed in order to evaluate the usefulness of the films for functional coatings.

Linking Precursor Alterations to Nanoscale Structure and Optical Transparency in Polymer Assisted Fast-Rate Dip-Coating of Vanadium Oxide Thin Films

PubMed Central

Glynn, Colm; Creedon, Donal; Geaney, Hugh; Armstrong, Eileen; Collins, Timothy; Morris, Michael A.; Dwyer, Colm O’

2015-01-01

Solution processed metal oxide thin films are important for modern optoelectronic devices ranging from thin film transistors to photovoltaics and for functional optical coatings. Solution processed techniques such as dip-coating, allow thin films to be rapidly deposited over a large range of surfaces including curved, flexible or plastic substrates without extensive processing of comparative vapour or physical deposition methods. To increase the effectiveness and versatility of dip-coated thin films, alterations to commonly used precursors can be made that facilitate controlled thin film deposition. The effects of polymer assisted deposition and changes in solvent-alkoxide dilution on the morphology, structure, optoelectronic properties and crystallinity of vanadium pentoxide thin films was studied using a dip-coating method using a substrate withdrawal speed within the fast-rate draining regime. The formation of sub-100 nm thin films could be achieved rapidly from dilute alkoxide based precursor solutions with high optical transmission in the visible, linked to the phase and film structure. The effects of the polymer addition was shown to change the crystallized vanadium pentoxide thin films from a granular surface structure to a polycrystalline structure composed of a high density of smaller in-plane grains, resulting in a uniform surface morphology with lower thickness and roughness. PMID:26123117

Structural, optical and electrochemical properties of F-doped vanadium oxide transparent semiconducting thin films

NASA Astrophysics Data System (ADS)

Mousavi, M.; Khorrami, Gh. H.; Kompany, A.; Yazdi, Sh. Tabatabai

2017-12-01

In this study, F-doped vanadium oxide thin films with doping levels up to 60 at % were prepared by spray pyrolysis method on glass substrates. To measure the electrochemical properties, some films were deposited on fluorine-tin oxide coated glass substrates. The effect of F-doping on the structural, electrical, optical and electrochemical properties of vanadium oxide samples was investigated. The X-ray diffractographs analysis has shown that all the samples grow in tetragonal β-V2O5 phase structure with the preferred orientation of [200]. The intensity of (200) peak belonging to β-V2O5 phase was strongest in the undoped vanadium oxide film. The scanning electron microscopy images show that the samples have nanorod- and nanobelt-shaped structure. The size of the nanobelts in the F-doped vanadium oxide films is smaller than that in the pure sample and the width of the nanobelts increases from 30 to 70 nm with F concentration. With increasing F-doping level from 10 to 60 at %, the resistivity, the transparency and the optical band gap decrease from 111 to 20 Ω cm, 70 to 50% and 2.4 to 2.36 eV, respectively. The cyclic voltammogram (CV) results show that the undoped sample has the most extensive CV and by increasing F-doping level from 20 to 60 at %, the area of the CV is expanded. The anodic and cathodic peaks in F-doped samples are stronger.

Electro-thermal control of aluminum-doped zinc oxide/vanadium dioxide multilayered thin films for smart-device applications

PubMed Central

Skuza, J. R.; Scott, D. W.; Mundle, R. M.; Pradhan, A. K.

2016-01-01

We demonstrate the electro-thermal control of aluminum-doped zinc oxide (Al:ZnO) /vanadium dioxide (VO2) multilayered thin films, where the application of a small electric field enables precise control of the applied heat to the VO2 thin film to induce its semiconductor-metal transition (SMT). The transparent conducting oxide nature of the top Al:ZnO film can be tuned to facilitate the fine control of the SMT of the VO2 thin film and its associated properties. In addition, the Al:ZnO film provides a capping layer to the VO2 thin film, which inhibits oxidation to a more energetically favorable and stable V2O5 phase. It also decreases the SMT of the VO2 thin film by approximately 5–10 °C because of an additional stress induced on the VO2 thin film and/or an alteration of the oxygen vacancy concentration in the VO2 thin film. These results have significant impacts on technological applications for both passive and active devices by exploiting this near-room-temperature SMT. PMID:26884225

Bipolar resistive switching in room temperature grown disordered vanadium oxide thin-film devices

NASA Astrophysics Data System (ADS)

Wong, Franklin J.; Sriram, Tirunelveli S.; Smith, Brian R.; Ramanathan, Shriram

2013-09-01

We demonstrate bipolar switching with high OFF/ON resistance ratios (>104) in Pt/vanadium oxide/Cu structures deposited entirely at room temperature. The SET (RESET) process occurs when negative (positive) bias is applied to the top Cu electrode. The vanadium oxide (VOx) films are amorphous and close to the vanadium pentoxide stoichiometry. We also investigated Cu/VOx/W structures, reversing the position of the Cu electrode, and found the same polarity dependence with respect to the top and bottom electrodes, which suggests that the bipolar nature is linked to the VOx layer itself. Bipolar switching can be observed at 100 °C, indicating that it not due to a temperature-induced metal-insulator transition of a vanadium dioxide second phase. We discuss how ionic drift can lead to the bipolar electrical behavior of our junctions, similar to those observed in devices based on several other defective oxides. Such low-temperature processed oxide switches could be of relevance to back-end or package integration processing schemes.

Effect of S-doping on structural, optical and electrochemical properties of vanadium oxide thin films prepared by spray pyrolysis

NASA Astrophysics Data System (ADS)

Mousavi, M.; Kompany, A.; Shahtahmasebi, N.; Bagheri-Mohagheghi, M.-M.

2013-12-01

In this research, S-doped vanadium oxide thin films, with doping levels from 0 to 40 at.%, are prepared by spray pyrolysis technique on glass substrates. For electrochemical measurements, the films were deposited on florin-tin oxide coated glass substrates. The effect of S-doping on structural, electrical, optical and electrochemical properties of vanadium oxide thin films was studied. The x-ray diffractometer analysis indicated that most of the samples have cubic β-V2O5 phase structure with preferred orientation along [200]. With increase in the doping levels, the structure of the samples tends to be amorphous. The scanning electron microscopy images show that the structure of the samples is nanobelt-shaped and the width of the nanobelts decreases from nearly 100 to 40 nm with increase in the S concentration. With increase in the S-doping level, the sheet resistance and the optical band gap increase from 940 to 4015 kΩ/square and 2.41 to 2.7 eV, respectively. The cyclic voltammogram results obtained for different samples show that the undoped sample is expanded and the sample prepared at 20 at.% S-doping level has sharper anodic and cathodic peaks.

The optical and electrochemical properties of electrochromic films: WO3+xV2O5

NASA Astrophysics Data System (ADS)

Li, Zhuying; Liu, Hui; Liu, Ye; Yang, Shaohong; Liu, Yan; Wang, Chong

2010-05-01

Since Deb's experiment in 1973 on the electrochromic effect, transmissive electrochromic films exhibit outstanding potential as energy efficient window controls which allow dynamic control of the solar energy transmission. These films with non-volatile memory, once in the coloured state, remain in the same state even after removal of the field. The optical and electrochemical properties of electrochromic films using magnetron sputter deposition tungsten oxide thin films and vanadium oxide doped tungsten-vanadium oxide thin films on ITO coated glass were investigated. From the UV region of the transmittance spectra, the optical band gap energy from the fundamental absorption edge can be determined. And the Cyclic voltammograms of these thin films in 1 mol LiClO4 propylene carbonate electrolyte (LIPC) were measured and analysed. The anode electrochromic V2O5 doped cathode electrochromic WO3 could make films colour changing while the transmittance of films keeped invariance. These performance characteristics make tungstenvanadium oxide colour changeably thin films are suitable for electrochromic windows applications.

Phase formation polycrystalline vanadium oxide via thermal annealing process under controlled nitrogen pressure

NASA Astrophysics Data System (ADS)

Jessadaluk, S.; Khemasiri, N.; Rahong, S.; Rangkasikorn, A.; Kayunkid, N.; Wirunchit, S.; Horprathum, M.; Chananonnawathron, C.; Klamchuen, A.; Nukeaw, J.

2017-09-01

This article provides an approach to improve and control crystal phases of the sputtering vanadium oxide (VxOy) thin films by post-thermal annealing process. Usually, as-deposited VxOy thin films at room temperature are amorphous phase: post-thermal annealing processes (400 °C, 2 hrs) under the various nitrogen (N2) pressures are applied to improve and control the crystal phase of VxOy thin films. The crystallinity of VxOy thin films changes from amorphous to α-V2O5 phase or V9O17 polycrystalline, which depend on the pressure of N2 carrier during annealing process. Moreover, the electrical resistivity of the VxOy thin films decrease from 105 Ω cm (amorphous) to 6×10-1 Ω cm (V9O17). Base on the results, our study show a simply method to improve and control phase formation of VxOy thin films.

V6O13 films by control of the oxidation state from aqueous precursor to crystalline phase.

PubMed

Peys, Nick; Ling, Yun; Dewulf, Daan; Gielis, Sven; De Dobbelaere, Christopher; Cuypers, Daniel; Adriaensens, Peter; Van Doorslaer, Sabine; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

2013-01-28

An aqueous deposition process for V(6)O(13) films is developed whereby the vanadium oxidation state is continuously controlled throughout the entire process. In the precursor stage, a controlled wet chemical reduction of the vanadium(V) source with oxalic acid is achieved and monitored by (51)Vanadium Nuclear Magnetic Resonance ((51)V-NMR) and Ultraviolet-Visible (UV-Vis) spectroscopy. The resulting vanadium(IV) species in the aqueous solution are identified as mononuclear citrato-oxovanadate(IV) complexes by Electron Paramagnetic Resonance (EPR) and Fourier Transform Infra-Red (FTIR) spectroscopy. This precursor is successfully employed for the deposition of uniform, thin films. The optimal deposition and annealing conditions for the formation of crystalline V(6)O(13), including the control of the vanadium oxidation state, are determined through an elaborate study of processing temperature and O(2) partial pressure. To ensure a sub 100 nm adjustable film thickness, a non-oxidative intermediate thermal treatment is carried out at the end of each deposition cycle, allowing maximal precursor decomposition while still avoiding V(IV) oxidation. The resulting surface hydrophilicity, indispensable for the homogeneous deposition of the next layer, is explained by an increased surface roughness and the increased availability of surface vanadyl groups. Crystalline V(6)O(13) with a preferential (002) orientation is obtained after a post deposition annealing in a 0.1% O(2) ambient for thin films with a thickness of 20 nm.

Effect of substrate temperature on thermochromic vanadium dioxide thin films sputtered from vanadium target

NASA Astrophysics Data System (ADS)

Madiba, I. G.; Kotsedi, L.; Ngom, B. D.; Khanyile, B. S.; Maaza, M.

2018-05-01

Vanadium dioxide films have been known as the most promising thermochromic thin films for smart windows which self-control the solar radiation and heat transfer for energy saving, comfort in houses and automotives. Such an attractive technological application is due to the fact that vanadium dioxide crystals exhibit a fast semiconductor-to-metal phase transition at a transition temperature Tc of about 68 °C, together with sharp optical changes from high transmitive to high reflective coatings in the IR spectral region. The phase transition has been associated with the nature of the microstructure, stoichiometry and stresses related to the oxide. This study reports on the effect of the crystallographic quality controlled by the substrate temperature on the thermochromic properties of vanadium dioxide thin films synthesized by reactive radio frequency inverted cylindrical magnetron sputtering from vanadium target. The reports results are based on X-ray diffraction, Atomic force microscopy, and UV-Visible spectrophotometer. The average crystalline grain size of VO2 increases with the substrate temperature, inducing stress related phenomena within the films.

Influence of Heat Treatment Conditions on the Properties of Vanadium Oxide Thin Films for Thermochromic Applications.

PubMed

Kim, Donguk; Kwon, Samyoung; Park, Young; Boo, Jin-Hyo; Nam, Sang-Hun; Joo, Yang Tae; Kim, Minha; Lee, Jaehyeong

2016-05-01

In present work, the effects of the heat treatment on the structural, optical, and thermochromic properties of vanadium oxide films were investigated. Vanadium dioxide (VO2) thin films were deposited on glass substrate by reactive pulsed DC magnetron sputtering from a vanadium metal target in mixture atmosphere of argon and oxygen gas. Various heat treatment conditions were applied in order to evaluate their influence on the crystal phases formed, surface morphology, and optical properties. The films were characterized by an X-ray diffraction (XRD) in order to investigate the crystal structure and identify the phase change as post-annealing temperature of 500-600 degrees C for 5 minutes. Surface conditions of the obtained VO2(M) films were analyzed by field emission scanning electron microscopy (FE-SEM) and the semiconductor-metal transition (SMT) characteristics of the VO2 films were evaluate by optical spectrophotometry in the UV-VIS-NIR, controlling temperature of the films.

Deposition and characterization of vanadium oxide based thin films for MOS device applications

NASA Astrophysics Data System (ADS)

Rakshit, Abhishek; Biswas, Debaleen; Chakraborty, Supratic

2018-04-01

Vanadium Oxide films are deposited on Si (100) substrate by reactive RF-sputtering of a pure Vanadium metallic target in an Argon-Oxygen plasma environment. The ratio of partial pressures of Argon to Oxygen in the sputtering-chamber is varied by controlling their respective flow rates and the resultant oxide films are obtained. MOS Capacitor based devices are then fabricated using the deposited oxide films. High frequency Capacitance-Voltage (C-V) and gate current-gate voltage (I-V) measurements reveal a significant dependence of electrical characteristics of the deposited films on their sputtering deposition parameters mainly, the relative content of Argon/Oxygen in the plasma chamber. A noteworthy change in the electrical properties is observed for the films deposited under higher relative oxygen content in the plasma atmosphere. Our results show that reactive sputtering serves as an indispensable deposition-setup for fabricating vanadium oxide based MOS devices tailor-made for Non-Volatile Memory (NVM) applications.

Vanadium Oxide Thin Film Formation on Graphene Oxide by Microexplosive Decomposition of Ammonium Peroxovanadate and Its Application as a Sodium Ion Battery Anode.

PubMed

Mikhaylov, Alexey A; Medvedev, Alexander G; Grishanov, Dmitry A; Sladkevich, Sergey; Gun, Jenny; Prikhodchenko, Petr V; Xu, Zhichuan J; Nagasubramanian, Arun; Srinivasan, Madhavi; Lev, Ovadia

2018-02-27

Formation of vanadium oxide nanofilm-coated graphene oxide (GO) is achieved by thermally induced explosive disintegration of a microcrystalline ammonium peroxovanadate-GO composite. GO sheets isolate the microcrystalline grains and capture and contain the microexplosion products, resulting in the deposition of the nanoscale products on the GO. Thermal treatment of the supported nanofilm yields a sequence of nanocrystalline phases of vanadium oxide (V 3 O 7 , VO 2 ) as a function of temperature. This is the first demonstration of microexplosive disintegration of a crystalline peroxo compound to yield a nanocoating. The large number of recently reported peroxide-rich crystalline materials suggests that the process can be a useful general route for nanofilm formation. The V 3 O 7 @GO composite product was tested as a sodium ion battery anode and showed high charge capacity at high rate charge-discharge cycling (150 mAh g -1 at 3000 mA g -1 vs 300 mAh g -1 at 100 mA g -1 ) due to the nanomorphology of the vanadium oxide.

Facile Phase Control of Multivalent Vanadium Oxide Thin Films (V2O5 and VO2) by Atomic Layer Deposition and Postdeposition Annealing.

PubMed

Song, Gwang Yeom; Oh, Chadol; Sinha, Soumyadeep; Son, Junwoo; Heo, Jaeyeong

2017-07-19

Atomic layer deposition was adopted to deposit VO x thin films using vanadyl tri-isopropoxide {VO[O(C 3 H 7 )] 3 , VTIP} and water (H 2 O) at 135 °C. The self-limiting and purge-time-dependent growth behaviors were studied by ex situ ellipsometry to determine the saturated growth conditions for atomic-layer-deposited VO x . The as-deposited films were found to be amorphous. The structural, chemical, and optical properties of the crystalline thin films with controlled phase formation were investigated after postdeposition annealing at various atmospheres and temperatures. Reducing and oxidizing atmospheres enabled the formation of pure VO 2 and V 2 O 5 phases, respectively. The possible band structures of the crystalline VO 2 and V 2 O 5 thin films were established. Furthermore, an electrochemical response and a voltage-induced insulator-to-metal transition in the vertical metal-vanadium oxide-metal device structure were observed for V 2 O 5 and VO 2 films, respectively.

Characterization and Electrochromic Properties of Vanadium Oxide Thin Films Prepared via Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Mousavi, M.; Kompany, A.; Shahtahmasebi, N.; Bagheri-Mohagheghi, M.-M.

2013-08-01

Vanadium oxide thin films were grown on glass substrates using spray pyrolysis technique. The effects of substrate temperature, vanadium concentration in the initial solution and the solution spray rate on the nanostructural and the electrochromic properties of deposited films are investigated. Characterization and the electrochromic measurements were carried out using X-ray diffraction, scanning electron microscopy and cyclic voltammogram. XRD patterns showed that the prepared films have polycrystalline structure and are mostly mixed phases of orthorhombic α-V2O5 along with minor β-V2O5 and V4O9 tetragonal structures. The preferred orientation of the deposited films was found to be along [101] plane. The cyclic voltammogram results obtained for different samples showed that only the films with 0.2 M solution concentration, 5 ml/min solution spray rate and 450°C substrate temperature exhibit two-step electrochromic properties. The results show a correlation between cycle voltammogram, morphology and resistance of the films.

Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides

DOE PAGES

Weimer, Matthew S.; Kim, In Soo; Guo, Peijun; ...

2017-06-02

We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V 2O 3, VO 2, and V 2O 5 are realized via four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O 3, H 2O 2, H 2O/O 2, and H 2O 2/H 2. A clear distinction between non-oxidative protic ligand exchange and metal oxidation ismore » demonstrated through sequential surface reactions with different non-metal precursors. This synergistic effect, provides greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H 2 gas. When H 2 is dosed after H 2O 2 during growth, amorphous films of VO 2 are deposited that are readily crystallized with a low temperature anneal. These VO 2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VO 2.« less

Deposition of vanadium oxide films by direct-current magnetron reactive sputtering

NASA Astrophysics Data System (ADS)

Kusano, E.; Theil, J. A.; Thornton, John A.

1988-06-01

It is demonstrated here that thin films of vanadium oxide can be deposited at modest substrate temperatures by dc reactive sputtering from a vanadium target in an O2-Ar working gas using a planar magnetron source. Resistivity ratios of about 5000 are found between a semiconductor phase with a resistivity of about 5 Ohm cm and a metallic phase with a resistivity of about 0.001 Ohm cm for films deposited onto borosilicate glass substrates at about 400 C. X-ray diffraction shows the films to be single-phase VO2 with a monoclinic structure. The VO2 films are obtained for a narrow range of O2 injection rates which correspond to conditions where cathode poisoning is just starting to occur.

Deposition of vanadium oxide films by direct-current magnetron reactive sputtering

NASA Technical Reports Server (NTRS)

Kusano, E.; Theil, J. A.; Thornton, John A.

1988-01-01

It is demonstrated here that thin films of vanadium oxide can be deposited at modest substrate temperatures by dc reactive sputtering from a vanadium target in an O2-Ar working gas using a planar magnetron source. Resistivity ratios of about 5000 are found between a semiconductor phase with a resistivity of about 5 Ohm cm and a metallic phase with a resistivity of about 0.001 Ohm cm for films deposited onto borosilicate glass substrates at about 400 C. X-ray diffraction shows the films to be single-phase VO2 with a monoclinic structure. The VO2 films are obtained for a narrow range of O2 injection rates which correspond to conditions where cathode poisoning is just starting to occur.

Dependence of annealing temperature on microstructure and photoelectrical properties of vanadium oxide thin films prepared by DC reactive sputtering

NASA Astrophysics Data System (ADS)

Li, Yan; Zhang, Dongping; Wang, Bo; Liang, Guangxing; Zheng, Zhuanghao; Luo, Jingting; Cai, Xingmin; Fan, Ping

2013-12-01

Vanadium oxide thin films were prepared by DC reactive sputtering method, and the samples were annealed in Ar atmosphere under different temperature for 2 hours. The microstructure, optical and electrical properties of the as-grown and treated samples were characterized by XRD, spectrophotometer, and four-probe technique, respectively. XRD results investigated that the main content of the annealed sample are VO2 and V2O5. With annealing temperature increasing, the intensity of the VO2 phase diffraction peak strengthened. The electrical properties reveal that the annealed samples exhibit semiconductor-to-metal transition characteristic at about 40°C. Comparison of transmission spectra of the samples at room temperature and 100°C, a drastic drop in IR region is found.

Ultrafast electron-lattice coupling dynamics in VO2 and V2O3 thin films

NASA Astrophysics Data System (ADS)

Abreu, Elsa; Gilbert Corder, Stephanie N.; Yun, Sun Jin; Wang, Siming; Ramírez, Juan Gabriel; West, Kevin; Zhang, Jingdi; Kittiwatanakul, Salinporn; Schuller, Ivan K.; Lu, Jiwei; Wolf, Stuart A.; Kim, Hyun-Tak; Liu, Mengkun; Averitt, Richard D.

2017-09-01

Ultrafast optical pump-optical probe and optical pump-terahertz probe spectroscopy were performed on vanadium dioxide (VO2) and vanadium sesquioxide (V2O3 ) thin films over a wide temperature range. A comparison of the experimental data from these two different techniques and two different vanadium oxides, in particular a comparison of the spectral weight oscillations generated by the photoinduced longitudinal acoustic modulation, reveals the strong electron-phonon coupling that exists in both materials. The low-energy Drude response of V2O3 appears more amenable than VO2 to ultrafast strain control. Additionally, our results provide a measurement of the temperature dependence of the sound velocity in both systems, revealing a four- to fivefold increase in VO2 and a three- to fivefold increase in V2O3 across the insulator-to-metal phase transition. Our data also confirm observations of strong damping and phonon anharmonicity in the metallic phase of VO2, and suggest that a similar phenomenon might be at play in the metallic phase of V2O3 . More generally, our simple table-top approach provides relevant and detailed information about dynamical lattice properties of vanadium oxides, paving the way to similar studies in other complex materials.

Dynamic structural colour using vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Wilson, K.; Marocico, C. A.; Bradley, A. L.

2018-06-01

A thin film stack consisting of layers of indium tin oxide (ITO) with an intermediate vanadium oxide (VO2) layer on an optically thick silver film has been investigated for dynamic structural colour. The structure benefits from the phase change properties of VO2. Compared with other phase change materials, such as germanium antimony telluride (GST), VO2 can be offered as a lower power consumption alternative. It has been overlooked in the visible spectral range due to its smaller refractive index change below 700 nm. We demonstrate that the sensitivity of the visible reflectance spectrum to the change in phase of a 30 nm VO2 layer is increased after it is incorporated in a thin film stack, with performance comparable to other phase change materials. The extent to which dynamic tuning of the reflectance spectra of ITO–VO2–ITO–Ag thin film stacks can be exploited for colour switching is reported, with approximately 25% change in reflectance demonstrated at 550 nm. Inclusion of a top ITO layer is also shown to improve the chromaticity change on phase transition.

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

NASA Astrophysics Data System (ADS)

Ma, Xu; Liu, Xinkun; Li, Haizhu; Zhang, Angran; Huang, Mingju

2017-03-01

High-quality vanadium oxide ( VO2) films have been fabricated on Si (111) substrates by radio frequency (RF) magnetron sputtering deposition method. The sheet resistance of VO2 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 VO2 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.

Fabrication and design of vanadium oxide microbolometer

NASA Astrophysics Data System (ADS)

Abdel-Rahman, M.; Al-Khalli, N.; Zia, M. F.; Alduraibi, M.; Ilahi, B.; Awad, E.; Debbar, N.

2017-02-01

Vanadium oxide (VxOy) multilayer sandwich structures previously studied by our group were found to yield a sensitive thermometer thin film material suitable for microbolometer applications. In this work, we aim to estimate the performance of a proposed air-bridge microbolometer configuration based on VxOy multilayer sandwich structure thermometer thin films. For this purpose, a microbolometer was fabricated on silicon (Si) substrate covered with a silicon nitride (Si3N4) insulating layer using VxOy thermometer thin film material. The fabricated microbolometer was patterned using electron-beam lithography and liftoff techniques and it was characterized in terms of its voltage repsonsivity (Rv), signal to noise ratio (SNR), noise equivalent power (NEP) and detectivity D*. A model was then developed by the aid of numerical optical/thermal simulations and experimentally measured parameters to estimate the performance of the microbolometer when fabricated in an air-bridge configuration. The estimated D* was found to be 1.55×107 cm.√Hz/ W.

Monolithic Silicon Microbolometer Materials forUncooled Infrared Detectors

DTIC Science & Technology

2015-05-21

L. Allara, Mark W. Horn. Vanadium Oxide Thin Films Alloyed with Ti, Zr , Nb , and Mo for Uncooled Infrared Imaging Applications, Journal of...entitled "Thin Film Materials and Devices for Resistive Temperature Sensing Applications" by Hitesh Basantani and the other entitled "Reactive...extension. One was entitled "Thin Film Materials and Devices for Resistive Temperature Sensing Applications" by Hitesh Basantani and the other

Fabrication of VO2 thin film by rapid thermal annealing in oxygen atmosphere and its metal—insulator phase transition properties

NASA Astrophysics Data System (ADS)

Liang, Ji-Ran; Wu, Mai-Jun; Hu, Ming; Liu, Jian; Zhu, Nai-Wei; Xia, Xiao-Xu; Chen, Hong-Da

2014-07-01

Vanadium dioxide thin films have been fabricated through sputtering vanadium thin films and rapid thermal annealing in oxygen. The microstructure and the metal—insulator transition properties of the vanadium dioxide thin films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and a spectrometer. It is found that the preferred orientation of the vanadium dioxide changes from (1¯11) to (011) with increasing thickness of the vanadium thin film after rapid thermal annealing. The vanadium dioxide thin films exhibit an obvious metal—insulator transition with increasing temperature, and the phase transition temperature decreases as the film thickness increases. The transition shows hysteretic behaviors, and the hysteresis width decreases as the film thickness increases due to the higher concentration carriers resulted from the uncompleted lattice. The fabrication of vanadium dioxide thin films with higher concentration carriers will facilitate the nature study of the metal—insulator transition.

An Exploration and Optimization of the Metal Insulator Transition in Vanadium Dioxide Thin Films

DTIC Science & Technology

2009-12-02

Executive summary Vanadium dioxide ( VO2 ) is an archetypal strongly correlated oxide and could offer many opportunities for new paradigms of information...experimental understanding of the metal-insulator transition in VO2 and explored the various ways to control the transition temperature and hysteresis...Beyond attempts to understand the strong correlation phenomena in VO2 , we hope to demonstrate a phase transition switch based on the electrically

Elevated transition temperature in Ge doped VO2 thin films

NASA Astrophysics Data System (ADS)

Krammer, Anna; Magrez, Arnaud; Vitale, Wolfgang A.; Mocny, Piotr; Jeanneret, Patrick; Guibert, Edouard; Whitlow, Harry J.; Ionescu, Adrian M.; Schüler, Andreas

2017-07-01

Thermochromic GexV1-xO2+y thin films have been deposited on Si (100) substrates by means of reactive magnetron sputtering. The films were then characterized by Rutherford backscattering spectrometry (RBS), four-point probe electrical resistivity measurements, X-ray diffraction, and atomic force microscopy. From the temperature dependent resistivity measurements, the effect of Ge doping on the semiconductor-to-metal phase transition in vanadium oxide thin films was investigated. The transition temperature was shown to increase significantly upon Ge doping (˜95 °C), while the hysteresis width and resistivity contrast gradually decreased. The precise Ge concentration and the film thickness have been determined by RBS. The crystallinity of phase-pure VO2 monoclinic films was confirmed by XRD. These findings make the use of vanadium dioxide thin films in solar and electronic device applications—where higher critical temperatures than 68 °C of pristine VO2 are needed—a viable and promising solution.

Solution-processed phase-change VO(2) metamaterials from colloidal vanadium oxide (VO(x)) nanocrystals.

PubMed

Paik, Taejong; Hong, Sung-Hoon; Gaulding, E Ashley; Caglayan, Humeyra; Gordon, Thomas R; Engheta, Nader; Kagan, Cherie R; Murray, Christopher B

2014-01-28

We demonstrate thermally switchable VO2 metamaterials fabricated using solution-processable colloidal nanocrystals (NCs). Vanadium oxide (VOx) NCs are synthesized through a nonhydrolytic reaction and deposited from stable colloidal dispersions to form NC thin films. Rapid thermal annealing transforms the VOx NC thin films into monoclinic, nanocrystalline VO2 thin films that show a sharp, reversible metal-insulator phase transition. Introduction of precise concentrations of tungsten dopings into the colloidal VOx NCs enables the still sharp phase transition of the VO2 thin films to be tuned to lower temperatures as the doping level increases. We fabricate "smart", differentially doped, multilayered VO2 films to program the phase and therefore the metal-insulator behavior of constituent vertically structured layers with temperature. With increasing temperature, we tailored the optical response of multilayered films in the near-IR and IR regions from that of a strong light absorber, in a metal-insulator structure, to that of a Drude-like reflector, characteristic of a pure metallic structure. We demonstrate that nanocrystal-based nanoimprinting can be employed to pattern multilayered subwavelength nanostructures, such as three-dimensional VO2 nanopillar arrays, that exhibit plasmonic dipolar responses tunable with a temperature change.

Different threshold and bipolar resistive switching mechanisms in reactively sputtered amorphous undoped and Cr-doped vanadium oxide thin films

NASA Astrophysics Data System (ADS)

Rupp, Jonathan A. J.; Querré, Madec; Kindsmüller, Andreas; Besland, Marie-Paule; Janod, Etienne; Dittmann, Regina; Waser, Rainer; Wouters, Dirk J.

2018-01-01

This study investigates resistive switching in amorphous undoped and Cr-doped vanadium oxide thin films synthesized by sputtering deposition at low oxygen partial pressure. Two different volatile threshold switching characteristics can occur as well as a non-volatile bipolar switching mechanism, depending on device stack symmetry and Cr-doping. The two threshold switching types are associated with different crystalline phases in the conduction filament created during an initial forming step. The first kind of threshold switching, observed for undoped vanadium oxide films, was, by its temperature dependence, proven to be associated with a thermally triggered insulator-to-metal transition in a crystalline VO2 phase, whereas the threshold switch observed in chromium doped films is stable up to 90 °C and shows characteristics of an electronically induced Mott transition. This different behaviour for undoped versus doped films has been attributed to an increased stability of V3+ due to the Cr3+ doping (as evidenced by X-ray photoelectron spectroscopy analysis), probably favouring the creation of a crystalline Cr-doped V2O3 phase (rather than a Cr-doped VO2 phase) during the energetic forming step. The symmetric Pt/a-(VCr)Ox/Pt device showing high temperature stable threshold switching may find interesting applications as a possible new selector device for resistive switching memory (ReRAM) crossbar arrays.

X-Ray Spectroscopy of Ultra-Thin Oxide/Oxide Heteroepitaxial Films: A Case Study of Single-Nanometer VO2/TiO2.

PubMed

Quackenbush, Nicholas F; Paik, Hanjong; Woicik, Joseph C; Arena, Dario A; Schlom, Darrell G; Piper, Louis F J

2015-08-21

Epitaxial ultra-thin oxide films can support large percent level strains well beyond their bulk counterparts, thereby enabling strain-engineering in oxides that can tailor various phenomena. At these reduced dimensions (typically < 10 nm), contributions from the substrate can dwarf the signal from the epilayer, making it difficult to distinguish the properties of the epilayer from the bulk. This is especially true for oxide on oxide systems. Here, we have employed a combination of hard X-ray photoelectron spectroscopy (HAXPES) and angular soft X-ray absorption spectroscopy (XAS) to study epitaxial VO2/TiO2 (100) films ranging from 7.5 to 1 nm. We observe a low-temperature (300 K) insulating phase with evidence of vanadium-vanadium (V-V) dimers and a high-temperature (400 K) metallic phase absent of V-V dimers irrespective of film thickness. Our results confirm that the metal insulator transition can exist at atomic dimensions and that biaxial strain can still be used to control the temperature of its transition when the interfaces are atomically sharp. More generally, our case study highlights the benefits of using non-destructive XAS and HAXPES to extract out information regarding the interfacial quality of the epilayers and spectroscopic signatures associated with exotic phenomena at these dimensions.

Enhanced electrical and noise properties of nanocomposite vanadium oxide thin films by reactive pulsed-dc magnetron sputtering

NASA Astrophysics Data System (ADS)

Basantani, H. A.; Kozlowski, S.; Lee, Myung-Yoon; Li, J.; Dickey, E. C.; Jackson, T. N.; Bharadwaja, S. S. N.; Horn, M.

2012-06-01

Thin films of VOx (1.3 ≤ x ≤ 2) were deposited by reactive pulsed-dc magnetron sputtering of a vanadium metal target while RF-biasing the substrate. Rutherford back scattering, glancing angle x-ray, and cross-sectional transmission electron microscopy measurements revealed the formation of nanocolumns with nanotwins within VOx samples. The resistivity of nanotwinned VOx films ranged from 4 mΩ.cm to 0.6 Ω.cm and corresponding temperature coefficient of resistance between -0.1% and -2.6% per K, respectively. The 1/f electrical noise was analyzed in these VOx samples using the Hooge-Vandamme relation. These VOx films are comparable or surpass commercial VOx films deposited by ion beam sputtering.

Analyzing optical properties of thin vanadium oxide films through semiconductor-to-metal phase transition using spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Sun, Jianing; Pribil, Greg K.

2017-11-01

We investigated the optical behaviors of vanadium dioxide (VO2) films through the semiconductor-to-metal (STM) phase transition using spectroscopic ellipsometry. Correlations between film thickness and refractive index were observed resulting from the absorbing nature of these films. Simultaneously analyzing data at multiple temperatures using Kramers-Kronig consistent oscillator models help identify film thickness. Nontrivial variations in resulting optical constants were observed through STM transition. As temperature increases, a clear increase is observed in near infrared absorption due to Drude losses that accompany the transition from semiconducting to metallic phases. Thin films grown on silicon and sapphire substrate present different optical properties and thermal hysteresis due to lattice stress and compositional differences.

Plasma assisted synthesis of vanadium pentoxide nanoplates

NASA Astrophysics Data System (ADS)

Singh, Megha; Sharma, Rabindar Kumar; Kumar, Prabhat; Reddy, G. B.

2015-08-01

In this work, we report the growth of α-V2O5 (orthorhombic) nanoplates on glass substrate using plasma assisted sublimation process (PASP) and Nickel as catalyst. 100 nm thick film of Ni is deposited over glass substrate by thermal evaporation process. Vanadium oxide nanoplates have been deposited treating vanadium metal foil under high vacuum conditions with oxygen plasma. Vanadium foil is kept at fixed temperature growth of nanoplates of V2O5 to take place. Samples grown have been studied using XPS, XRD and HRTEM to confirm the growth of α-phase of V2O5, which revealed pure single crystal of α- V2O5 in orthorhombic crystallographic plane. Surface morphological studies using SEM and TEM show nanostructured thin film in form of plates. Uniform, vertically aligned randomly oriented nanoplates of V2O5 have been deposited.

High quality transparent conducting oxide thin films

DOEpatents

Gessert, Timothy A.; Duenow, Joel N.; Barnes, Teresa; Coutts, Timothy J.

2012-08-28

A transparent conducting oxide (TCO) film comprising: a TCO layer, and dopants selected from the elements consisting of Vanadium, Molybdenum, Tantalum, Niobium, Antimony, Titanium, Zirconium, and Hafnium, wherein the elements are n-type dopants; and wherein the transparent conducting oxide is characterized by an improved electron mobility of about 42 cm.sup.2/V-sec while simultaneously maintaining a high carrier density of .about.4.4e.times.10.sup.20 cm.sup.-3.

Structural and electrical properties of different vanadium oxide phases in thin film form synthesized using pulsed laser deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Majid, S. S., E-mail: suhailphy276@gmail.com; Rahman, F.; Shukla, D. K.

2015-06-24

We present here the structural and electrical properties of the thin films of V{sub 2}O{sub 3} (Vanadium sesquioxide) and V{sub 5}O{sub 9}. Both these oxide phases, V{sub 2}O{sub 3} and V{sub 5}O{sub 9}, have beenachieved on (001) orientedSi substrate using the V{sub 2}O{sub 5} target by optimizing the deposition parameters using pulsed laser deposition technique (PLD).Deposited films were characterized by X-ray diffraction(XRD)and four probe temperature dependent resistivity measurements. XRD studies reveal the V{sub 2}O{sub 3} and V{sub 5}O{sub 9} phases and the amount of strain present in both these films. The temperature dependency of electrical resistivity confirmed the characteristic metal-insulatormore » transitions (MIT) for both the films, V{sub 2}O{sub 3} and V{sub 5}O{sub 9}.« less

Control of the metal-insulator transition in vanadium dioxide by modifying orbital occupancy

NASA Astrophysics Data System (ADS)

Aetukuri, Nagaphani B.; Gray, Alexander X.; Drouard, Marc; Cossale, Matteo; Gao, Li; Reid, Alexander H.; Kukreja, Roopali; Ohldag, Hendrik; Jenkins, Catherine A.; Arenholz, Elke; Roche, Kevin P.; Dürr, Hermann A.; Samant, Mahesh G.; Parkin, Stuart S. P.

2013-10-01

External control of the conductivity of correlated oxides is one of the most promising schemes for realizing energy-efficient electronic devices. Vanadium dioxide (VO2), an archetypal correlated oxide compound, undergoes a temperature-driven metal-insulator transition near room temperature with a concomitant change in crystal symmetry. Here, we show that the metal-insulator transition temperature of thin VO2(001) films can be changed continuously from ~285 to ~345K by varying the thickness of the RuO2 buffer layer (resulting in different epitaxial strains). Using strain-, polarization- and temperature-dependent X-ray absorption spectroscopy, in combination with X-ray diffraction and electronic transport measurements, we demonstrate that the transition temperature and the structural distortion across the transition depend on the orbital occupancy in the metallic state. Our findings open up the possibility of controlling the conductivity in atomically thin VO2 layers by manipulating the orbital occupancy by, for example, heterostructural engineering.

X-Ray Spectroscopy of Ultra-Thin Oxide/Oxide Heteroepitaxial Films: A Case Study of Single-Nanometer VO2/TiO2

PubMed Central

Quackenbush, Nicholas F.; Paik, Hanjong; Woicik, Joseph C.; Arena, Dario A.; Schlom, Darrell G.; Piper, Louis F. J.

2015-01-01

Epitaxial ultra-thin oxide films can support large percent level strains well beyond their bulk counterparts, thereby enabling strain-engineering in oxides that can tailor various phenomena. At these reduced dimensions (typically < 10 nm), contributions from the substrate can dwarf the signal from the epilayer, making it difficult to distinguish the properties of the epilayer from the bulk. This is especially true for oxide on oxide systems. Here, we have employed a combination of hard X-ray photoelectron spectroscopy (HAXPES) and angular soft X-ray absorption spectroscopy (XAS) to study epitaxial VO2/TiO2 (100) films ranging from 7.5 to 1 nm. We observe a low-temperature (300 K) insulating phase with evidence of vanadium-vanadium (V-V) dimers and a high-temperature (400 K) metallic phase absent of V-V dimers irrespective of film thickness. Our results confirm that the metal insulator transition can exist at atomic dimensions and that biaxial strain can still be used to control the temperature of its transition when the interfaces are atomically sharp. More generally, our case study highlights the benefits of using non-destructive XAS and HAXPES to extract out information regarding the interfacial quality of the epilayers and spectroscopic signatures associated with exotic phenomena at these dimensions. PMID:28793516

X-ray Spectroscopy of Ultra-thin Oxide/oxide Heteroepitaxial Films: A Case Study of Single-nanometer VO2/TiO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Quackenbush, Nicholas F.; Paik, Hanjong; Woicik, Joseph C.

2015-08-21

Epitaxial ultra-thin oxide films can support large percent level strains well beyond their bulk counterparts, thereby enabling strain-engineering in oxides that can tailor various phenomena. At these reduced dimensions (typically < 10 nm), contributions from the substrate can dwarf the signal from the epilayer, making it difficult to distinguish the properties of the epilayer from the bulk. This is especially true for oxide on oxide systems. Here, we have employed a combination of hard X-ray photoelectron spectroscopy (HAXPES) and angular soft X-ray absorption spectroscopy (XAS) to study epitaxial VO2/TiO2 (100) films ranging from 7.5 to 1 nm. We observe amore » low-temperature (300 K) insulating phase with evidence of vanadium-vanadium (V-V) dimers and a high-temperature (400 K) metallic phase absent of V-V dimers irrespective of film thickness. Results confirm that the metal insulator transition can exist at atomic dimensions and that biaxial strain can still be used to control the temperature of its transition when the interfaces are atomically sharp. Generally, our case study highlights the benefits of using non-destructive XAS and HAXPES to extract out information regarding the interfacial quality of the epilayers and spectroscopic signatures associated with exotic phenomena at these dimensions.« less

Near-zero IR transmission of VO2 thin films deposited on Si substrate

NASA Astrophysics Data System (ADS)

Zhang, Chunzi; Koughia, Cyril; Li, Yuanshi; Cui, Xiaoyu; Ye, Fan; Shiri, Sheida; Sanayei, Mohsen; Wen, Shi-Jie; Yang, Qiaoqin; Kasap, Safa

2018-05-01

Vanadium dioxide (VO2) thin films of different thickness have been deposited on Si substrates by using DC magnetron sputtering. The effects of substrate pre-treatment by means of seeding (spin coating and ultrasonic bathing) and biasing on the structure and optical properties were investigated. Seeding results in a smaller grain size in the oxide film, whereas biasing results in square-textured crystals. VO2 thin films of 150 nm thick show a near-zero IR transmission in switched state. Especially, the 150 nm thick VO2 thin film with seeding treatment shows an enhanced switching efficiency.

Fundamental Studies on Confinement Effects in Ionic Conduction and Inversion Layers in 2-D Single Crystal Free Standing Oxide Membranes

DTIC Science & Technology

2014-02-14

properties of VO2 films and membranes and compare the results with annealing VO2 films and membranes in hydrogen to provide insight into the doping...2-dimensional free standing membrane with correlated oxides may also lead to new insights into mesoscopic electronic phenomena. Vanadium oxide ( VO2 ...well as for potential applications in switching devices. While studies have been conducted on thin films, hybrid layers of VO2 supported on other

The effect of solution concentration on the physical and electrochemical properties of vanadium oxide films deposited by spray pyrolysis

NASA Astrophysics Data System (ADS)

Mousavi, M.; Kompany, A.; Shahtahmasebi, N.; Bagheri-Mohagheghi, M. M.

2013-10-01

Vanadium oxide thin films were prepared on glass substrates by using the spray pyrolysis technique. The effect of solution concentration (0.1 M, 0.2 M and 0.3 M) on the nanostructural, electrical, optical, and electrochromic properties of deposited films were investigated using X-ray diffraction, scanning electron microscopy, UV—vis spectroscopy, and cyclic volta-metrics. The X-ray diffraction shows that only the sample at 0.1 M has a single β-V2O5 phase and the others have mixed phases of vanadium oxide. The lowest sheet resistance was obtained for the samples prepared at 0.3 M solution. It was also found that the optical transparency of the samples changes from 70% to 35% and the optical band gap of the samples was in the range of 2.20 to 2.41 eV, depending on the morality of solution. The cycle voltammogram shows that the sample prepared at 0.3 M has one-step electerochoromic but the other samples have two-step electerochoromic. The results show a correlation between the cycle voltammogram and the physical properties of the films.

Vanadium Oxide Thin Films Alloyed with Ti, Zr, Nb, and Mo for Uncooled Infrared Imaging Applications

NASA Astrophysics Data System (ADS)

Ozcelik, Adem; Cabarcos, Orlando; Allara, David L.; Horn, Mark W.

2013-05-01

Microbolometer-grade vanadium oxide (VO x ) thin films with 1.3 < x < 2.0 were prepared by pulsed direct-current (DC) sputtering using substrate bias in a controlled oxygen and argon environment. These films were systematically alloyed with Ti, Nb, Mo, and Zr using a second gun and radiofrequency (RF) reactive co-sputtering to probe the effects of the transition metals on the film charge transport characteristics. The results reveal that the temperature coefficient of resistance (TCR) and resistivity are unexpectedly similar for alloyed and unalloyed films up to alloy compositions in the ˜20 at.% range. Analysis of the film structures for the case of the 17% Nb-alloyed film by glancing-angle x-ray diffraction and transmission electron microscopy shows that the microstructure remains even with the addition of high concentrations of alloy metal, demonstrating the robust character of the VO x films to maintain favorable electrical transport properties for bolometer applications. Postdeposition thermal annealing of the alloyed VO x films further reveals improvement of electrical properties compared with unalloyed films, indicating a direction for further improvements in the materials.

Methods for making lithium vanadium oxide electrode materials

DOEpatents

Schutts, Scott M.; Kinney, Robert J.

2000-01-01

A method of making vanadium oxide formulations is presented. In one method of preparing lithium vanadium oxide for use as an electrode material, the method involves: admixing a particulate form of a lithium compound and a particulate form of a vanadium compound; jet milling the particulate admixture of the lithium and vanadium compounds; and heating the jet milled particulate admixture at a temperature below the melting temperature of the admixture to form lithium vanadium oxide.

Reduction of V2O5 thin films deposited by aqueous sol-gel method to VO2(B) and investigation of its photocatalytic activity

NASA Astrophysics Data System (ADS)

Monfort, Olivier; Roch, Tomas; Satrapinskyy, Leonid; Gregor, Maros; Plecenik, Tomas; Plecenik, Andrej; Plesch, Gustav

2014-12-01

A way of preparation of VO2(B) thin films by reduction of V2O5 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 V2O5 film in vacuum as well as in H2/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 V4O9 is first formed before reaching the VO2(B) phase. The film microstructure was characterized by SEM and AFM and the valence states of vanadium in VO2(B) films were evaluated by XPS. The VO2(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 VO2(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.

Release kinetics of vanadium from vanadium (III, IV and V) oxides: Effect of pH, temperature and oxide dose.

PubMed

Hu, Xingyun; Yue, Yuyan; Peng, Xianjia

2018-05-01

Batch experiments were performed to derive the rate laws for the proton-promoted dissolution of the main vanadium (III, IV and V) oxides at pH 3.1-10.0. The release rates of vanadium are closely related to the aqueous pH, and several obvious differences were observed in the release behavior of vanadium from the dissolution of V 2 O 5 and vanadium(III, IV) oxides. In the first 2hr, the release rates of vanadium from V 2 O 3 were r=1.14·([H + ]) 0.269 at pH 3.0-6.0 and r=0.016·([H + ]) -0.048 at pH 6.0-10.0; the release rates from VO 2 were r=0.362·([H + ]) 0.129 at pH 3.0-6.0 and r=0.017·([H + ]) -0.097 at pH 6.0-10.0; and the release rates from V 2 O 5 were r=0.131·([H + ]) -0.104 at pH 3.1-10.0. The release rates of vanadium from the three oxides increased with increasing temperature, and the effect of temperature was different at pH 3.8, pH 6.0 and pH 7.7. The activation energies of vanadium (III, IV and V) oxides (33.4-87.5kJ/mol) were determined at pH 3.8, pH6.0 and pH 7.7, showing that the release of vanadium from dissolution of vanadium oxides follows a surface-controlled reaction mechanism. The release rates of vanadium increased with increasing vanadium oxides dose, albeit not proportionally. This study, as part of a broader study of the release behavior of vanadium, can help to elucidate the pollution problem of vanadium and to clarify the fate of vanadium in the environment. Copyright © 2017. Published by Elsevier B.V.

Multifunctional overcoats on vanadium dioxide thermochromic thin films with enhanced luminous transmission and solar modulation, hydrophobicity and anti-oxidation

NASA Astrophysics Data System (ADS)

Liu, Chang; Wang, Ning; Long, Yi

2013-10-01

Vanadium dioxide (VO2) has a great potential to be utilized as solar energy switching glazing, even though there exist some intrinsic problems of low luminous transmittance (Tlum) and poor oxidation resistance. Si-Al based anti-reflection (AR) sol-gel coatings processed at low temperature have been developed to tackle these issues assisted by adjusting ramping rate and annealing temperature. Si-Al based AR coating gives large relative enhancement on the transmittance (22% for Tlum, 14% for the whole solar spectrum Tsol,) and successfully maintains IR contrast at 2500 nm wavelength with 18% relative increase in solar modulation (ΔTsol). The optimized Si-Al based AR coating annealing conditions are recorded at 3 °C/min ramping rate and 100 °C annealing temperature. Fluorinated-Si based gel offers a new direction of multifunctional overcoat on thermochromic smart windows with hydrophobicity (contact angle 111°), averaged 14% relatively increased luminous transmittance and enhanced oxidation resistance.

Naturally formed ultrathin V2O5 heteroepitaxial layer on VO2/sapphire(001) film

NASA Astrophysics Data System (ADS)

Littlejohn, Aaron J.; Yang, Yunbo; Lu, Zonghuan; Shin, Eunsung; Pan, KuanChang; Subramanyam, Guru; Vasilyev, Vladimir; Leedy, Kevin; Quach, Tony; Lu, Toh-Ming; Wang, Gwo-Ching

2017-10-01

Vanadium dioxide (VO2) and vanadium pentoxide (V2O5) thin films change their properties in response to external stimuli such as photons, temperature, electric field and magnetic field and have applications in electronics, optical devices, and sensors. Due to the multiple valence states of V and non-stoichiometry in thin films, it is challenging to grow epitaxial, single-phase V-oxide on a substrate, or a heterostructure of two epitaxial V-oxides. We report the formation of a heterostructure consisting of a few nm thick ultrathin V2O5 epitaxial layer on pulsed laser deposited tens of nm thick epitaxial VO2 thin films grown on single crystal Al2O3(001) substrates without post annealing of the VO2 film. The simultaneous observation of the ultrathin epitaxial V2O5 layer and VO2 epitaxial film is only possible by our unique reflection high energy electron diffraction pole figure analysis. The out-of-plane and in-plane epitaxial relationships are V2O5[100]||VO2[010]||Al2O3[001] and V2O5[03 2 bar ]||VO2[100]||Al2O3[1 1 bar 0], respectively. The existence of the V2O5 layer on the surface of the VO2 film is also supported by X-ray photoelectron spectroscopy and Raman spectroscopy.

The controlled deposition of metal oxides onto carbon nanotubes by atomic layer deposition: examples and a case study on the application of V2O4 coated nanotubes in gas sensing.

PubMed

Willinger, Marc-Georg; Neri, Giovanni; Bonavita, Anna; Micali, Giuseppe; Rauwel, Erwan; Herntrich, Tobias; Pinna, Nicola

2009-05-21

A new atomic layer deposition (ALD) process was applied for the uniform coating of carbon nanotubes with a number of transition-metal oxide thin films (vanadium, titanium, and hafnium oxide). The presented approach is adapted from non-aqueous sol-gel chemistry and utilizes metal alkoxides and carboxylic acids as precursors. It allows the coating of the inner and outer surface of the tubes with a highly conformal film of controllable thickness and hence, the production of high surface area hybrid materials. The morphology and the chemical composition as well as the high purity of the films are evidenced through a combination of electron microscopic and electron-energy-loss spectrometric techniques. Furthermore, in order to highlight a possible application of the obtained hybrids, the electrical and sensing properties of resistive gas sensors based on hybrid vanadium oxide-coated carbon nanotubes (V2O4-CNTs) are reported and the effect of thermal treatment on the gas sensing properties is studied.

Amorphous Mixed-Valence Vanadium Oxide/Exfoliated Carbon Cloth Structure Shows a Record High Cycling Stability.

PubMed

Song, Yu; Liu, Tian-Yu; Yao, Bin; Kou, Tian-Yi; Feng, Dong-Yang; Liu, Xiao-Xia; Li, Yat

2017-04-01

Previous studies show that vanadium oxides suffer from severe capacity loss during cycling in the liquid electrolyte, which has hindered their applications in electrochemical energy storage. The electrochemical instability is mainly due to chemical dissolution and structural pulverization of vanadium oxides during charge/discharge cyclings. In this study the authors demonstrate that amorphous mixed-valence vanadium oxide deposited on exfoliated carbon cloth (CC) can address these two limitations simultaneously. The results suggest that tuning the V 4+ /V 5+ ratio of vanadium oxide can efficiently suppress the dissolution of the active materials. The oxygen-functionalized carbon shell on exfoliated CC can bind strongly with VO x via the formation of COV bonding, which retains the electrode integrity and suppresses the structural degradation of the oxide during charging/discharging. The uptake of structural water during charging and discharging processes also plays an important role in activating the electrode material. The amorphous mixed-valence vanadium oxide without any protective coating exhibits record-high cycling stability in the aqueous electrolyte with no capacitive decay in 100 000 cycles. This work provides new insights on stabilizing vanadium oxide, which is critical for the development of vanadium oxide based energy storage devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Influence of Vanadium Microalloying on the Production of Thin Slab Casting and Direct Rolled Steel Strip

NASA Astrophysics Data System (ADS)

Li, Yu; Milbourn, David

Vanadium microalloying is highly effective in high strength strip steels produced by thin slab casting and direct rolled process. Because of the high solubility of V(C,N) in austenite, vanadium is likely to remain in solution during casting, equalisation and rolling. Vanadium microalloyed steels have better hot ductility and are less prone to transverse cracking than niobium containing steels. Despite a coarse as-cast austenite grain size before rolling, significant grain refinement can be achieved in vanadium microalloyed steels by repeated recrystallization during rolling, resulting in a fine uniform ferrite microstructure in final strip. Almost all vanadium present in microalloyed steels is available to precipitate in ferrite as very fine particles, contributing to precipitation strengthening. Vanadium microalloyed steels show less sensitivity to rolling process variables and exhibit excellent combination of strength and toughness.

Epitaxial growth of VO2 by periodic annealing

NASA Astrophysics Data System (ADS)

Tashman, J. W.; Lee, J. H.; Paik, H.; Moyer, J. A.; Misra, R.; Mundy, J. A.; Spila, T.; Merz, T. A.; Schubert, J.; Muller, D. A.; Schiffer, P.; Schlom, D. G.

2014-02-01

We report the growth of ultrathin VO2 films on rutile TiO2 (001) substrates via reactive molecular-beam epitaxy. The films were formed by the cyclical deposition of amorphous vanadium and its subsequent oxidation and transformation to VO2 via solid-phase epitaxy. Significant metal-insulator transitions were observed in films as thin as 2.3 nm, where a resistance change ΔR/R of 25 was measured. Low angle annular dark field scanning transmission electron microscopy was used in conjunction with electron energy loss spectroscopy to study the film/substrate interface and revealed the vanadium to be tetravalent and the titanium interdiffusion to be limited to 1.6 nm.

[Oxidative Stress Level of Vanadium-exposed Workers].

PubMed

Wei, Teng-da; Li, Shun-pin; Liu, Yun-xing; Tan, Chun-ping; Li, Juan; Zhang, Zu-hui; Lan, Ya-jia; Zhang, Qin

2015-11-01

To determine the oxidative stress level in peripheral blood of vanadium-exposed workers, as an indication of population health effect of vanadium on human neurobehavioral system. 86 vanadium-exposed workers and 65 non-exposed workers were recruited by cluster sampling. A questionnaire was administered to collect demographic and occupational exposure information. Serum activity of superoxide dismutase (SOD), inducible nitric oxide synthase (iNOS) and malonaldehyde (MDA) contents were detected by kit assay. The differences in oxidative stress level between vanadium-exposed and non-exposed workers were compared. Vanadium-exposed workers had higher levels of MDA contents than the controls. The total superoxide dismutase(T-SOD) activity in vanadium-exposed workers was significantly lower than that in the controls, which was associated with lowered levels of manganese superoxide dismutase (Mn-SOD) activity. No changes in serum levels of cupro-zinc superoxide dismutase (CuZn-SOD) was found in vanadium-exposed workers. No difference in iNOS activity was found between vanadium-exposed workers and controls. Vanadium exposure increases free radical production in serum and reduces antioxidant capacity. But the relationship between vanadium exposure and iNOS damage remains uncertain.

Modified lithium vanadium oxide electrode materials products and methods

DOEpatents

Thackeray, Michael M.; Kahaian, Arthur J.; Visser, Donald R.; Dees, Dennis W.; Benedek, Roy

1999-12-21

A method of improving certain vanadium oxide formulations is presented. The method concerns fluorine doping formulations having a nominal formula of LiV.sub.3 O.sub.8. Preferred average formulations are provided wherein the average oxidation state of the vanadium is at least 4.6. Herein preferred fluorine doped vanadium oxide materials, electrodes using such materials, and batteries including at least one electrode therein comprising such materials are provided.

Growth of different V2O5 nanostructures as a function of deposition duration

NASA Astrophysics Data System (ADS)

Saini, Sujit K.; Sharma, Rabindar K.; Singh, Megha; Kumar, Prabhat; Reddy, G. B.

2018-05-01

Vanadium pentoxide nanostructured thin films are synthesized using plasma assisted sublimation process (PASP). The effect of deposition duration on the growth of V2O5 nanostructured thin films (NSTs) is studied in present paper. Raman and XRD results depict that all films exhibited only orthorhombic crystalline phase of vanadium oxide (i.e. V2O5). As duration increases the growth of V2O5 nanostructures preferentially aligned along (101) crystallographic plane. Scanning electron micrographs show that different morphologies are obtained with different duration of deposition. For low durations (i.e. 30 and 40 min.) the 1D nanostructures with random alignments are obtained, whereas for prolonged durations of deposition (50 and 60 min) the embedded nanopillers having vertical alignments with uniform distribution on entire substrate are found. The occurrence of remarkable increase in visible radiation from 8% to 13% on increasing duration again implies that the crystallinity and alignments of V2O5 nanostructures is getting improved with duration.

Suspended sub-50 nm vanadium dioxide membrane transistors: fabrication and ionic liquid gating studies

NASA Astrophysics Data System (ADS)

Sim, Jai S.; Zhou, You; Ramanathan, Shriram

2012-10-01

We demonstrate a robust lithographic patterning method to fabricate self-supported sub-50 nm VO2 membranes that undergo a phase transition. Utilizing such self-supported membranes, we directly observed a shift in the metal-insulator transition temperature arising from stress relaxation and consistent opening of the hysteresis. Electric double layer transistors were then fabricated with the membranes and compared to thin film devices. The ionic liquid allowed reversible modulation of channel resistance and distinguishing bulk processes from the surface effects. From the shift in the metal-insulator transition temperature, the carrier density doped through electrolyte gating is estimated to be 1 × 1020 cm-3. Hydrogen annealing studies showed little difference in resistivity between the film and the membrane indicating rapid diffusion of hydrogen in the vanadium oxide rutile lattice consistent with previous observations. The ability to fabricate electrically-wired, suspended VO2 ultra-thin membranes creates new opportunities to study mesoscopic size effects on phase transitions and may also be of interest in sensor devices.

Mineralogy and geochemistry of vanadium in the Colorado Plateau

USGS Publications Warehouse

Weeks, A.D.

1961-01-01

The chief domestic source of vanadium is uraniferous sandstone in the Colorado Plateau. Vanadium is 3-, 4-, or 5-valent in nature and, as oxides or combined with other elements, it forms more than 40 minerals in the Plateau ores. These ores have been studied with regard to the relative amounts of vanadium silicates and oxide-vanadates, uranium-vanadium ratios, the progressive oxidation of black low-valent ores to high-valent carnotite-type ores, and theories of origin. ?? 1961.

Consolidation and fabrication techniques for vanadium-20 w/o titanium /TV-20/

NASA Technical Reports Server (NTRS)

Burt, W. R.; Karasek, F. J.; Kramer, W. C.; Mayfield, R. M.; Mc Gowan, R. D.

1968-01-01

Tests of the mechanical properties, fuel compatibility, sodium corrosion and irradiation behavior were made for vanadium and vanadium alloy. Improved methods for consolidation and fabrication of bar, rod, sheet, and high-quality, small diameter, thin-wall tubing of vanadium-20 without titanium are reported.

Aqueous vanadium ion dynamics relevant to bioinorganic chemistry: A review.

PubMed

Kustin, Kenneth

2015-06-01

Aqueous solutions of the four highest vanadium oxidation states exhibit four diverse colors, which only hint at the diverse reactions that these ions can undergo. Cationic vanadium ions form complexes with ligands; anionic vanadium ions form complexes with ligands and self-react to form isopolyanions. All vanadium species undergo oxidation-reduction reactions. With a few exceptions, elucidation of the dynamics of these reactions awaited the development of fast reaction techniques before the kinetics of elementary ligation, condensation, reduction, and oxidation of the aqueous vanadium ions could be investigated. As the biological roles played by endogenous and therapeutic vanadium expand, it is appropriate to bring the results of the diverse kinetics studies under one umbrella. To achieve this goal this review presents a systematic examination of elementary aqueous vanadium ion dynamics. Copyright © 2014 Elsevier Inc. All rights reserved.

Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

NASA Astrophysics Data System (ADS)

Mueller, Michael; Baik, Seungyun; Jeon, Hojeong; Kim, Yuchan; Kim, Jungtae; Kim, Young Jun

2015-05-01

The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V2O5 precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V2O5 precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V2O5 precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/VxOx composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V2O5 composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure, kinetics and the presence of a mineralizing aid, such as the two cysteine-constrained peptides on the phage surface, and has potential for use in nanotechnology applications.

In-Plane Impedance Spectroscopy measurements in Vanadium Dioxide thin films

NASA Astrophysics Data System (ADS)

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.

A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

NASA Astrophysics Data System (ADS)

Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

2018-02-01

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

Homology of vanadium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasyutinskii, N.A.

1987-05-01

The authors examine the homology of vanadium oxide and note that data on the existence of phases and homogeneity limits in the V-O system are very contradictory. A graphical illustration shows the homologous series of vanadium oxides. The predominant part of the discrete formations in the system V-O is characterized by integral stoichiometry and forms six homologous series. It is found that homologous series of vanadium oxides are not only a basis for systematization of such oxides, but also may serve as a means for predicting the composition of new phases, limits of homogeneity, their structure, and properties.

Facile synthesis of hierarchical porous VOx@carbon composites for supercapacitors.

PubMed

Zhao, Chunxia; Cao, Jinqiao; Yang, Yunxia; Chen, Wen; Li, Junshen

2014-08-01

Hierarchical or micro-nano structured porous VOx@carbon composites were synthesized by a one-step method using phenolic resin as the carbon precursor and ammonium metavanadate as the source of vanadium oxides. The effects of the vanadium source loading on the microstructure and electrochemical properties of the composites were investigated. X-ray diffraction results showed that as the vanadium oxides source loading increased, vanadium oxides in the composites changed oxidation states from V2O3 to mixed states of V2O3 and VO2. Electrochemical test results indicated that the micro-nano porous structure of the composites could facilitate the ion diffusion in the rich porous structure and then promote the electrochemical reaction. More importantly, we found that vanadium oxides greatly enhanced the electrochemical performance of the materials, due to the faradic capacitance generated from vanadium oxide nanoparticles. A maximum specific capacitance of 171 F/g was obtained from VOx@carbon composite with vanadium loading of ∼44 wt%. Further increasing the VOx loading over this fraction was not beneficial. Our results suggested that hierarchical porous VOx@carbon composites were promising candidates for supercapacitor applications. Copyright © 2013 Elsevier Inc. All rights reserved.

The Electronic Structure and Field Effects of an Organic-Based Room Temperature Magnetic Semiconductor

DTIC Science & Technology

2007-01-01

used. Other materials used in this study include: microscope slide glass for transistor substrates (Gold Seal), silicon nitride, Si3N4, sputtering...with the top in place. At LBNL the glass tubes were placed in a nitrogen filled glove bag attached to the XAS sample chamber where they were...valences such as vanadium(II) oxide (VO), vanadium(III) oxide (V2O3), vanadium(IV) oxide (VO2), and vanadium(IV) oxide ( V2O5 ). V2O3 in particular is an

One-step hydrothermal synthesis of hexangular starfruit-like vanadium oxide for high power aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Shao, Jie; Li, Xinyong; Qu, Qunting; Zheng, Honghe

2012-12-01

Homogenous hexangular starfruit-like vanadium oxide was prepared for the first time by a one-step hydrothermal method. The assembly process of hexangular starfruit-like structure was observed from TEM images. The electrochemical performance of starfruit-like vanadium oxide was examined by cyclic voltammetry and galvanostatic charge/discharge. The obtained starfruit-like vanadium oxide exhibits a high power capability (19 Wh kg-1 at the specific power of 3.4 kW kg-1) and good cycling stability for supercapacitors application.

Protective effects of Sesamum indicum extract against oxidative stress induced by vanadium on isolated rat hepatocytes.

PubMed

Hosseini, Mir-Jamal; Shahraki, Jafar; Tafreshian, Saman; Salimi, Ahmad; Kamalinejad, Mohammad; Pourahmad, Jalal

2016-08-01

Vanadium toxicity is a challenging problem to human and animal health with no entirely understanding cytotoxic mechanisms. Previous studies in vanadium toxicity showed involvement of oxidative stress in isolated liver hepatocytes and mitochondria via increasing of ROS formation, release of cytochrome c and ATP depletion after incubation with different concentrations (25-200 µM). Therefore, we aimed to investigate the protective effects of Sesamum indicum seed extract (100-300 μg/mL) against oxidative stress induced by vanadium on isolated rat hepatocytes. Our results showed that quite similar to Alpha-tocopherol (100 µM), different concentrations of extract (100-300 μg/mL) protected the isolated hepatocyte against all oxidative stress/cytotoxicity markers induced by vanadium in including cell lysis, ROS generation, mitochondrial membrane potential decrease and lysosomal membrane damage. Besides, vanadium induced mitochondrial/lysosomal toxic interaction and vanadium reductive activation mediated by glutathione in vanadium toxicity was significantly (P < 0.05) ameliorated by Sesamum indicum extracts. These findings suggested a hepato-protective role for extracts against liver injury resulted from vanadium toxicity. © 2015 Wiley Periodicals, Inc. Environ Toxicol 31: 979-985, 2016. © 2015 Wiley Periodicals, Inc.

Vanadium distribution in rats and DNA cleavage by vanadyl complex: implication for vanadium toxicity and biological effects.

PubMed Central

Sakurai, H

1994-01-01

Vanadium ion is toxic to animals. However, vanadium is also an agent used for chemoprotection against cancers in animals. To understand both the toxic and beneficial effects we studied vanadium distribution in rats. Accumulation of vanadium in the liver nuclei of rats given low doses of compounds in the +4 or +5 oxidation state was greater than in the liver nuclei of rats given high doses of vanadium compounds or the vanadate (+5 oxidation state) compound. Vanadium was incorporated exclusively in the vanadyl (+4 oxidation state) form. We also investigated the reactions of vanadyl ion and found that incubation of DNA with vanadyl ion and hydrogen peroxide (H2O2) led to intense DNA cleavage. ESR spin trapping demonstrated that hydroxyl radicals are generated during the reactions of vanadyl ion and H2O2. Thus, we propose that the mechanism for vanadium-dependent toxicity and antineoplastic action is due to DNA cleavage by hydroxyl radicals generated in living systems. PMID:7843133

The structural studies of vanadium substituted lithium-bismuth-boro-tellurite glass

NASA Astrophysics Data System (ADS)

Madhu, A.; Eraiah, B.

2018-05-01

The structural studies of vanadium substituted lithium-bismuth-boro-tellurite glass is successfully prepared and certain analysis like XRD,FTIR,DTA/TGA with density, molar volume are done. The amorphous phase has been identified based on X-ray diffraction analysis. The vanadium oxide plays the role as a glass-modifier and influences on BO3 ↔ BO4 conversion. The observed nonlinear variation in Tg with vanadium oxide increase, it reflects structural changes. The nonlinear variation of density and molar volume can be attributed to vanadium oxide incorporation have increased the number of Non-bridging oxygen (NBO'S).

Effect of vanadium content on remanent polarization in bismuth titanate thin films prepared by liquid source misted chemical deposition

NASA Astrophysics Data System (ADS)

Kim, Tai Suk; Kim, Ki Woong; Jeon, Min Ku; Jung, Chang Hwa; Woo, Seong Ihl

2007-01-01

Bi4-x/3Ti3-xVxO12 (BTV) ferroelectric thin films were fabricated by liquid source misted chemical deposition. The substitution of vanadium for titanium site changed the crystalline orientation and surface morphology of the thin film, which in turn influenced the remanent polarization (Pr). 2Pr of BTV thin film increased with increase of vanadium content and reached a maximum value (21.5μC/cm2) at x =0.03, as this corresponded with the largest degree of a-axis orientation. However, at 0.05⩽x⩽0.09, 2Pr reduced with decrease in the degree of a-axis orientation. These results indicate that the Pr of the films is dependent on the degree of a-axis orientation.

Solution processable broadband transparent mixed metal oxide nanofilm optical coatings via substrate diffusion doping.

PubMed

Glynn, Colm; Aureau, Damien; Collins, Gillian; O'Hanlon, Sally; Etcheberry, Arnaud; O'Dwyer, Colm

2015-12-21

Devices composed of transparent materials, particularly those utilizing metal oxides, are of significant interest due to increased demand from industry for higher fidelity transparent thin film transistors, photovoltaics and a myriad of other optoelectronic devices and optics that require more cost-effective and simplified processing techniques for functional oxides and coatings. Here, we report a facile solution processed technique for the formation of a transparent thin film through an inter-diffusion process involving substrate dopant species at a range of low annealing temperatures compatible with processing conditions required by many state-of-the-art devices. The inter-diffusion process facilitates the movement of Si, Na and O species from the substrate into the as-deposited vanadium oxide thin film forming a composite fully transparent V0.0352O0.547Si0.4078Na0.01. Thin film X-ray diffraction and Raman scattering spectroscopy show the crystalline component of the structure to be α-NaVO3 within a glassy matrix. This optical coating exhibits high broadband transparency, exceeding 90-97% absolute transmission across the UV-to-NIR spectral range, while having low roughness and free of surface defects and pinholes. The production of transparent films for advanced optoelectronic devices, optical coatings, and low- or high-k oxides is important for planar or complex shaped optics or surfaces. It provides opportunities for doping metal oxides to ternary, quaternary or other mixed metal oxides on glass, encapsulants or other substrates that facilitate diffusional movement of dopant species.

Switchable vanadium oxide films by a sol-gel process

NASA Astrophysics Data System (ADS)

Partlow, D. P.; Gurkovich, S. R.; Radford, K. C.; Denes, L. J.

1991-07-01

Thin polycrystalline films of VO2 and V2O3 were deposited on a variety of substrates using a sol-gel process. The orientation, microstructure, optical constants, and optical and electrical switching behavior are presented. These films exhibited sharp optical switching behavior even on an amorphous substrate such as fused silica. The method yields reproducible results and is amenable to the coating of large substrates and curved surfaces such as mirrors and lenses.

Thin film battery and method for making same

DOEpatents

Bates, J.B.; Dudney, N.J.; Gruzalski, G.R.; Luck, C.F.

1994-08-16

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode. Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between [minus]15 C and 150 C. 9 figs.

Thin film battery and method for making same

DOEpatents

Bates, John B.; Dudney, Nancy J.; Gruzalski, Greg R.; Luck, Christopher F.

1994-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Lithium vanadium oxides (Li1+xV3O8) as cathode materials in lithium-ion batteries for soldier portable power systems

NASA Astrophysics Data System (ADS)

Wang, Gaojun; Chen, Linfeng; Mathur, Gyanesh N.; Varadan, Vijay K.

2011-04-01

Improving soldier portable power systems is very important for saving soldiers' lives and having a strategic advantage in a war. This paper reports our work on synthesizing lithium vanadium oxides (Li1+xV3O8) and developing their applications as the cathode (positive) materials in lithium-ion batteries for soldier portable power systems. Two synthesizing methods, solid-state reaction method and sol-gel method, are used in synthesizing lithium vanadium oxides, and the chemical reaction conditions are determined mainly based on thermogravimetric and differential thermogravimetric (TG-DTG) analysis. The synthesized lithium vanadium oxides are used as the active positive materials in the cathodes of prototype lithium-ion batteries. By using the new solid-state reaction technique proposed in this paper, lithium vanadium oxides can be synthesized at a lower temperature and in a shorter time, and the synthesized lithium vanadium oxide powders exhibit good crystal structures and good electrochemical properties. In the sol-gel method, different lithium source materials are used, and it is found that lithium nitrate (LiNO3) is better than lithium carbonate (Li2CO3) and lithium hydroxide (LiOH). The lithium vanadium oxides synthesized in this work have high specific charge and discharge capacities, which are helpful for reducing the sizes and weights, or increasing the power capacities, of soldier portable power systems.

Structural study of VO {sub x} doped aluminium fluoride and aluminium oxide catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheurell, Kerstin; Scholz, Gudrun; Kemnitz, Erhard

The structural properties of vanadium doped aluminium oxyfluorides and aluminium oxides, prepared by a modified sol-gel synthesis route, were thoroughly investigated. The influence of the preparation technique and the calcination temperature on the coordination of vanadium, aluminium and fluorine was analysed by different spectroscopic methods such as Raman, MAS NMR and ESR spectroscopy. In all samples calcined at low temperatures (350 deg. C), vanadium coexists in two oxidation states V{sup IV} and V{sup V}, with V{sup IV} as dominating species in the vanadium doped aluminium oxyfluorides. In the fluoride containing solids aluminium as well as vanadium are coordinated by fluorinemore » and oxygen. Thermal annealing of 800 deg. C leads to an extensive reorganisation of the original matrices and to the oxidation of V{sup IV} to V{sup V} in both systems. - Graphical abstract: Structure model for VO {sub x} doped aluminium oxide.« less

Atomic layer deposition of VO2 films with Tetrakis-dimethyl-amino vanadium (IV) as vanadium precursor

NASA Astrophysics Data System (ADS)

Lv, Xinrui; Cao, Yunzhen; Yan, Lu; Li, Ying; Song, Lixin

2017-02-01

VO2 thin films have been grown on Si(100) (VO2/Si) and fused silica substrates (VO2/SiO2) by atomic layer deposition (ALD) using tetrakis-dimethyl-amino vanadium (IV) (TDMAV) as a novel vanadium precursor and water as reactant gas. The quartz crystal microbalance (QCM) measurement was performed to study the ALD process of VO2 thin film deposition, and a constant growth rate of about 0.95 Å/cycle was obtained at the temperature range of 150-200 °C. XRD measurement was performed to study the influence of deposition temperature and post-annealing condition on the crystallization of VO2 films, which indicated that the films deposited between 150 and 200 °C showed well crystallinity after annealing at 475 °C for 100 min in Ar atmosphere. XPS measurement verified that the vanadium oxidation state was 4+ for both as-deposited film and post-annealed VO2/Si film. AFM was applied to study the surface morphology of VO2/Si films, which showed a dense polycrystalline film with roughness of about 1 nm. The resistance of VO2/Si films deposited between 150 °C and 200 °C as a function of temperature showed similar semiconductor-to-metal transition (SMT) characters with the transition temperature for heating branch (Tc,h) of about 72 °C, a hysteresis width of about 10 °C and the resistance change of two orders of magnitude. The increase of Tc,h compared with the bulk VO2 (68 °C) may be attributed to the tensile stress along the c-axis in the film. Transmittance measurement of VO2/SiO2 films showed typical thermochromic property with a NIR switching efficiency of above 50% at 2 μm across the transition.

Vanadium dioxide thin films prepared on silicon by low temperature MBE growth and ex-situ annealing

NASA Astrophysics Data System (ADS)

Homm, Pia; van Bilzen, Bart; Menghini, Mariela; Locquet, Jean-Pierre; Ivanova, Todora; Sanchez, Luis; Sanchis, Pablo

Vanadium dioxide (VO2) is a material that shows an insulator to metal transition (IMT) near room temperature. This property can be exploited for applications in field effect devices, electro-optical switches and nonlinear circuit components. We have prepared VO2 thin films on silicon wafers by combining a low temperature MBE growth with an ex-situ annealing at high temperature. We investigated the structural, electrical and optical characteristics of films with thicknesses ranging from 10 to 100 nm. We have also studied the influence of the substrate cleaning. The films grown with our method are polycrystalline with a preferred orientation in the (011) direction of the monoclinic phase. For the films produced on silicon with a native oxide, an IMT at around 75 °C is observed. The magnitude of the resistance change across the IMT decreases with thickness while the refractive index at room temperature corresponds with values reported in the literature for thin films. The successful growth of VO2 films on silicon with good electrical and optical properties is an important step towards the integration of VO2 in novel devices. The authors acknowledge financial support from the FWO project G052010N10 and EU-FP7 SITOGA project. PH acknowledges support from Becas Chile - CONICYT.

DNA damage induction in human cells exposed to vanadium oxides in vitro.

PubMed

Rodríguez-Mercado, Juan J; Mateos-Nava, Rodrigo A; Altamirano-Lozano, Mario A

2011-12-01

Vanadium and vanadium salts cause genotoxicity and elicit variable biological effects depending on several factors. In the present study, we analyzed and compared the DNA damage and repair processes induced by vanadium in three oxidation states. We used human blood leukocytes in vitro and in a single cell gel electrophoresis assay at two pH values. We observed that vanadium(III) trioxide and vanadium(V) pentoxide produced DNA single-strand breaks at all of the concentrations (1, 2, 4, or 8 μg/ml) and treatment times (2, 4, or 6 h) tested. Vanadium(IV) tetraoxide treatment significantly increased DNA damage at all concentrations for 4 or 6 h of treatment but not for 2 h of treatment. The DNA repair kinetics indicated that most of the cells exposed to vanadium III and V for 4 h recovered within the repair incubation time of 90 min; however, those exposed to vanadium(IV) repaired their DNA within 120 min. The data at pH 9 indicated that vanadium(IV) tetraoxide induced DNA double-strand breaks. Our results show that the genotoxic effect of vanadium can be produced by any of its three oxidation states. However, vanadium(IV) induces double-strand breaks, and it is known that these lesions are linked with forming structural chromosomal aberrations. Copyright © 2011 Elsevier Ltd. All rights reserved.

Enhancing of catalytic properties of vanadia via surface doping with phosphorus using atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strempel, Verena E.; Naumann d'Alnoncourt, Raoul, E-mail: r.naumann@bascat.tu-berlin.de; Löffler, Daniel

2016-01-15

Atomic layer deposition is mainly used to deposit thin films on flat substrates. Here, the authors deposit a submonolayer of phosphorus on V{sub 2}O{sub 5} in the form of catalyst powder. The goal is to prepare a model catalyst related to the vanadyl pyrophosphate catalyst (VO){sub 2}P{sub 2}O{sub 7} industrially used for the oxidation of n-butane to maleic anhydride. The oxidation state of vanadium in vanadyl pyrophosphate is 4+. In literature, it was shown that the surface of vanadyl pyrophosphate contains V{sup 5+} and is enriched in phosphorus under reaction conditions. On account of this, V{sub 2}O{sub 5} with themore » oxidation state of 5+ for vanadium partially covered with phosphorus can be regarded as a suitable model catalyst. The catalytic performance of the model catalyst prepared via atomic layer deposition was measured and compared to the performance of catalysts prepared via incipient wetness impregnation and the original V{sub 2}O{sub 5} substrate. It could be clearly shown that the dedicated deposition of phosphorus by atomic layer deposition enhances the catalytic performance of V{sub 2}O{sub 5} by suppression of total oxidation reactions, thereby increasing the selectivity to maleic anhydride.« less

Seedless Growth of Bismuth Nanowire Array via Vacuum Thermal Evaporation

PubMed Central

Liu, Mingzhao; Nam, Chang-Yong; Zhang, Lihua

2015-01-01

Here a seedless and template-free technique is demonstrated to scalably grow bismuth nanowires, through thermal evaporation in high vacuum at RT. Conventionally reserved for the fabrication of metal thin films, thermal evaporation deposits bismuth into an array of vertical single crystalline nanowires over a flat thin film of vanadium held at RT, which is freshly deposited by magnetron sputtering or thermal evaporation. By controlling the temperature of the growth substrate the length and width of the nanowires can be tuned over a wide range. Responsible for this novel technique is a previously unknown nanowire growth mechanism that roots in the mild porosity of the vanadium thin film. Infiltrated into the vanadium pores, the bismuth domains (~ 1 nm) carry excessive surface energy that suppresses their melting point and continuously expels them out of the vanadium matrix to form nanowires. This discovery demonstrates the feasibility of scalable vapor phase synthesis of high purity nanomaterials without using any catalysts. PMID:26709727

Effects of V2O5/Au bi-layer electrodes on the top contact Pentacene-based organic thin film transistors

NASA Astrophysics Data System (ADS)

Borthakur, Tribeni; Sarma, Ranjit

2017-05-01

Top-contact Pentacene-based organic thin film transistors (OTFTs) with a thin layer of Vanadium Pent-oxide between Pentacene and Au layer are fabricated. Here we have found that the devices with V2O5/Au bi-layer source-drain electrode exhibit better field-effect mobility, high on-off ratio, low threshold voltage and low sub-threshold slope than the devices with Au only. The field-effect mobility, current on-off ratio, threshold voltage and sub-threshold slope of V2O5/Au bi-layer OTFT estimated from the device with 15 nm thick V2O5 layer is .77 cm2 v-1 s-1, 7.5×105, -2.9 V and .36 V/decade respectively.

SELECTIVE OXIDATION OF ALCOHOLS OVER VANADIUM PHOSPHORUS OXIDE CATALYST USING HYDROGEN PEROXIDE

EPA Science Inventory

Oxidation of various alcohols is studied in liquid phase under nitrogen atmosphere over vanadium phosphorus oxide catalyst in an environmentally friendly protocol using hydrogen peroxide. The catalyst and the method are found to be suitable for the selective oxidation of a variet...

Investigating the air oxidation of V(II) ions in a vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Ngamsai, Kittima; Arpornwichanop, Amornchai

2015-11-01

The air oxidation of vanadium (V(II)) ions in a negative electrolyte reservoir is a major side reaction in a vanadium redox flow battery (VRB), which leads to electrolyte imbalance and self-discharge of the system during long-term operation. In this study, an 80% charged negative electrolyte solution is employed to investigate the mechanism and influential factors of the reaction in a negative-electrolyte reservoir. The results show that the air oxidation of V(II) ions occurs at the air-electrolyte solution interface area and leads to a concentration gradient of vanadium ions in the electrolyte solution and to the diffusion of V(II) and V(III) ions. The effect of the ratio of the electrolyte volume to the air-electrolyte solution interface area and the concentrations of vanadium and sulfuric acid in an electrolyte solution is investigated. A higher ratio of electrolyte volume to the air-electrolyte solution interface area results in a slower oxidation reaction rate. The high concentrations of vanadium and sulfuric acid solution also retard the air oxidation of V(II) ions. This information can be utilized to design an appropriate electrolyte reservoir for the VRB system and to prepare suitable ingredients for the electrolyte solution.

Effects of gamma irradiations on reactive pulsed laser deposited vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Madiba, I. G.; Émond, N.; Chaker, M.; Thema, F. T.; Tadadjeu, S. I.; Muller, U.; Zolliker, P.; Braun, A.; Kotsedi, L.; Maaza, M.

2017-07-01

Vanadium oxide films are considered suitable coatings for various applications such as thermal protective coating of small spacecrafts because of their thermochromic properties. While in outer space, such coating will be exposed to cosmic radiations which include γ-rays. To study the effect of these γ-rays on the coating properties, we have deposited vanadium dioxide (VO2) films on silicon substrates and subjected them to extensive γ-irradiations with typical doses encountered in space missions. The prevalent crystallographic phase after irradiation remains the monoclinic VO2 phase but the films preferential orientation shifts to lower angles due to the presence of disordered regions caused by radiations. Raman spectroscopy measurements also evidences that the VO2 structure is slightly affected by gamma irradiation. Indeed, increasing the gamma rays dose locally alters the crystalline and electronic structures of the films by modifying the V-V inter-dimer distance, which in turns favours the presence of the VO2 metallic phase. From the XPS measurements of V2p and O1s core level spectra, an oxidation of vanadium from V4+ towards V5+ is revealed. The data also reveal a hydroxylation upon irradiation which is corroborated by the vanishing of a low oxidation state peak near the Fermi energy in the valence band. Our observations suggest that gamma radiations induce the formation of Frenkel pairs. Moreover, THz transmission measurements show that the long range structure of VO2 remains intact after irradiation whilst the electrical measurements evidence that the coating resistivity decreases with gamma irradiation and that their transition temperature is slightly reduced for high gamma ray doses. Even though gamma rays are only one of the sources of radiations that are encountered in space environment, these results are very promising with regards to the potential of integration of such VO2 films as a protective coating for spacecrafts.

Electra-optical device including a nitrogen containing electrolyte

DOEpatents

Bates, J.B.; Dudney, N.J.; Gruzalski, G.R.; Luck, C.F.

1995-10-03

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode. Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between {minus}15 C and 150 C.

Cathode for an electrochemical cell

DOEpatents

Bates, John B.; Dudney, Nancy J.; Gruzalski, Greg R.; Luck, Christopher F.

2001-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode. Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Method for making an electrochemical cell

DOEpatents

Bates, John B.; Dudney, Nancy J.

1996-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage.

PubMed

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; Neuefeind, Joerg; Xu, Wenqian; Teng, Xiaowei

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate of 5 mV s -1 , corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full cells after 5,000 cycles at 10 C). The promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE PAGES

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine; ...

2017-05-23

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charles, Daniel Scott; Feygenson, Mikhail; Page, Katharine

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets. The vanadium oxide nanosheets engaged by structural water achieves high capacity (183 mAh g -1 in half-cells at a scan rate ofmore » 5 mV s -1, corresponding to 0.89 charge per vanadium) and excellent cyclability (62.5 mAh g -1 in full-cells after 5,000 cycles at 10 C). Finally, the promotional effects of structural water on the disordered vanadium oxide nanosheets will contribute to the exploration of disordered structures from earth-abundant elements for electrochemical energy storage.« less

Amorphous vanadium oxide coating on graphene by atomic layer deposition for stable high energy lithium ion anodes.

PubMed

Sun, Xiang; Zhou, Changgong; Xie, Ming; Hu, Tao; Sun, Hongtao; Xin, Guoqing; Wang, Gongkai; George, Steven M; Lian, Jie

2014-09-21

Uniform amorphous vanadium oxide films were coated on graphene via atomic layer deposition and the nano-composite displays an exceptional capacity of ~900 mA h g(-1) at 200 mAg(-1) with an excellent capacity retention at 1 A g(-1) after 200 cycles. The capacity contribution (1161 mA h g(-1)) from vanadium oxide only almost reaches its theoretical value.

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

PubMed

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.

Role of microstructures on the M1-M2 phase transition in epitaxial VO2 thin films

PubMed Central

Ji, Yanda; Zhang, Yin; Gao, Min; Yuan, Zhen; Xia, Yudong; Jin, Changqing; Tao, Bowan; Chen, Chonglin; Jia, Quanxi; Lin, Yuan

2014-01-01

Vanadium dioxide (VO2) with its unique sharp resistivity change at the metal-insulator transition (MIT) has been extensively considered for the near-future terahertz/infrared devices and energy harvesting systems. Controlling the epitaxial quality and microstructures of vanadium dioxide thin films and understanding the metal-insulator transition behaviors are therefore critical to novel device development. The metal-insulator transition behaviors of the epitaxial vanadium dioxide thin films deposited on Al2O3 (0001) substrates were systematically studied by characterizing the temperature dependency of both Raman spectrum and Fourier transform infrared spectroscopy. Our findings on the correlation between the nucleation dynamics of intermediate monoclinic (M2) phase with microstructures will open a new avenue for the design and integration of advanced heterostructures with controllable multifunctionalities for sensing and imaging system applications. PMID:24798056

Vanadium As a Potential Membrane Material for Carbon Capture: Effects of Minor Flue Gas Species.

PubMed

Yuan, Mengyao; Liguori, Simona; Lee, Kyoungjin; Van Campen, Douglas G; Toney, Michael F; Wilcox, Jennifer

2017-10-03

Vanadium and its surface oxides were studied as a potential nitrogen-selective membrane material for indirect carbon capture from coal or natural gas power plants. The effects of minor flue gas components (SO 2 , NO, NO 2 , H 2 O, and O 2 ) on vanadium at 500-600 °C were investigated by thermochemical exposure in combination with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and in situ X-ray diffraction (XRD). The results showed that SO 2 , NO, and NO 2 are unlikely to have adsorbed on the surface vanadium oxides at 600 °C after exposure for up to 10 h, although NO and NO 2 may have exhibited oxidizing effects (e.g., exposure to 250 ppmv NO/N 2 resulted in an 2.4 times increase in surface V 2 O 5 compared to exposure to just N 2 ). We hypothesize that decomposition of surface vanadium oxides and diffusion of surface oxygen into the metal bulk are both important mechanisms affecting the composition and morphology of the vanadium membrane. The results and hypothesis suggest that the carbon capture performance of the vanadium membrane can potentially be strengthened by material and process improvements such as alloying, operating temperature reduction, and flue gas treatment.

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.

Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm andmore » two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.« less

Method for preparing high purity vanadium

DOEpatents

Schmidt, Frederick; Carlson, O. Norman

1986-09-09

A method for preparing high purity vanadium having a low silicon content has been developed. Vanadium pentoxide is reduced with a stoichiometric, or slightly deficient amount of aluminum to produce a vanadium-aluminum alloy containing an excess of oxygen. Silicon is removed by electron-beam melting the alloy under oxidizing conditions to promote the formation of SiO which is volatile at elevated temperatures. Excess oxygen is removed by heating the alloy in the presence of calcium metal to form calcium oxide.

Method for preparing high purity vanadium

DOEpatents

Schmidt, F.; Carlson, O.N.

1984-05-16

A method for preparing high purity vanadium having a low silicon content has been developed. Vanadium pentoxide is reduced with a stoichiometric, or slightly deficient amount of aluminum to produce a vanadium-aluminum alloy containing an excess of oxygen. Silicon is removed by electron-beam melting the alloy under oxidizing conditions to promote the formation of SiO which is volatile at elevated temperatures. Excess oxygen is removed by heating the alloy in the presence of calcium metal to form calcium oxide.

Positron lifetime in vanadium oxide bronzes

NASA Astrophysics Data System (ADS)

Dryzek, J.; Dryzek, E.

2003-09-01

The positron lifetime (PL) and Doppler broadening (DB) of annihilation line measurements have been performed in vanadium oxide bronzes MxV2O5. The dependence of these annihilation characteristics on the kind and concentration of the metal M donor has been observed. In the PL spectrum only one lifetime component has been detected in all studied bronzes. The results indicate the positron localization in the structural tunnels present in the crystalline lattice of the vanadium oxide bronzes. (

Butanol Dehydration over V₂O₅-TiO₂/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition.

PubMed

Choi, Hyeonhee; Bae, Jung-Hyun; Kim, Do Heui; Park, Young-Kwon; Jeon, Jong-Ki

2013-04-29

MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO₂-V₂O₅/MCM-41 catalysts were analyzed using XRF, BET, NH₃-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO₂/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH₃-TPD and Py-IR results indicated that weak acid sites were produced over the TiO₂/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V₂O₅(12.1)-TiO₂/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.

Summary of the mineralogy of the Colorado Plateau uranium ores

USGS Publications Warehouse

Weeks, Alice D.; Coleman, Robert Griffin; Thompson, Mary E.

1956-01-01

In the Colorado Plateau uranium has been produced chiefly from very shallow mines in carnotite ores (oxidized vanadiferous uranium ores) until recent deeper mining penetrated black unoxidized ores in water-saturated rocks and extensive exploration has discovered many deposits of low to nonvanadiferous ores. The uranium ores include a wide range from highly vanadiferous and from as much as one percent to a trace of copper, and contain a small amount of iron and traces of lead, zinc, molybdenum, cobalt, nickel, silver, manganese, and other metals. Recent investigation indicates that the carnotite ores have been derived by progressive oxidation of primary (unoxidized) black ores that contain low-valent uranium and vanadium oxides and silicates. The uranium minerals, uraninite and coffinite, are associated with coalified wood or other carbonaceous material. The vanadium minerals, chiefly montroseite, roscoelite, and other vanadium silicates, occur in the interstices of the sandstone and in siltstone and clay pellets as well as associated with fossil wood. Calcite, dolomite, barite and minor amounts of sulfides, arsenides, and selenides occur in the unoxidized ore. Partially oxidized vanadiferous ore is blue black, purplish brown, or greenish black in contrast to the black or dark gray unoxidized ore. Vanadium combines with uranium to form rauvite. The excess vanadium is present in corvusite, fernandinite, melanovanadite and many other quadrivalent and quinquevalent vanadium minerals as well as in vanadium silicates. Pyrite and part or all of the calcite are replaced by iron oxides and gypsum. In oxidized vanadiferous uranium ores the uranium is fixed in the relatively insoluble minerals carnotite and tyuyamunite, and the excess vanadium commonly combines with one or more of the following: calcium, sodium, potassium, magnesium, aluminum, iron, copper, manganese, or barium, or rarely it forms the hydrated pentoxide. The relatively stable vanadium silicates are little affected by oxidation. The unoxidized nonvanadiferous ores contain uraninite and coffinite in close association with coalified wood and iron and copper sulfides, and traces of many other sulfides, arsenides and selenides. The oxidized nonvanadiferous ores differ from the vanadiferous ores because, in the absence of vanadium to complex the uranium, a great variety of secondary yellow and greenish-yellow uranyl minerals are formed. The uranyl sulfates and carbonates are more common than the oxides, phosphates, arsenates, and silicates. Because the sulfates and carbonates are much less stable that carnotite, the oxidized nonvanadiferous ores occure only as halos around cores of unoxidized ore and do not form large oxidized deposits close to the surface of the ground as carnotite ores. Oxidation has taken place since the lowering of the water table in the present erosion cycle. Because of local structures and the highly lenticular character of the fluviatile host rocks perched water tables and water-saturated lenses of sandstone are common high above the regional water table. Unoxidized ore has been preserved in these water-saturated rocks and the boundary between oxidized and unoxidized ore is very irregular.

Roll-to-Roll Processing of Inverted Polymer Solar Cells using Hydrated Vanadium(V)Oxide as a PEDOT:PSS Replacement

PubMed Central

Espinosa, Nieves; Dam, Henrik Friis; Tanenbaum, David M.; Andreasen, Jens W.; Jørgensen, Mikkel; Krebs, Frederik C.

2011-01-01

The use of hydrated vanadium(V)oxide as a replacement of the commonly employed hole transporting material PEDOT:PSS was explored in this work. Polymer solar cells were prepared by spin coating on glass. Polymer solar cells and modules comprising 16 serially connected cells were prepared using full roll-to-roll (R2R) processing of all layers. The devices were prepared on flexible polyethyleneterphthalate (PET) and had the structure PET/ITO/ZnO/P3HT:PCBM/V2O5·(H2O)n/Ag. The ITO and silver electrodes were processed and patterned by use of screen printing. The zinc oxide, P3HT:PCBM and vanadium(V)oxide layers were processed by slot-die coating. The hydrated vanadium(V)oxide layer was slot-die coated using an isopropanol solution of vanadyl-triisopropoxide (VTIP). Coating experiments were carried out to establish the critical thickness of the hydrated vanadium(V)oxide layer by varying the concentration of the VTIP precursor over two orders of magnitude. Hydrated vanadium(V)oxide layers were characterized by profilometry, scanning electron microscopy, energy dispersive X-ray spectroscopy, and grazing incidence wide angle X-ray scattering. The power conversion efficiency (PCE) for completed modules was up to 0.18%, in contrast to single cells where efficiencies of 0.4% were achieved. Stability tests under indoor and outdoor conditions were accomplished over three weeks on a solar tracker. PMID:28879984

Roll-to-Roll Processing of Inverted Polymer Solar Cells using Hydrated Vanadium(V)Oxide as a PEDOT:PSS Replacement.

PubMed

Espinosa, Nieves; Dam, Henrik Friis; Tanenbaum, David M; Andreasen, Jens W; Jørgensen, Mikkel; Krebs, Frederik C

2011-01-11

The use of hydrated vanadium(V)oxide as a replacement of the commonly employed hole transporting material PEDOT:PSS was explored in this work. Polymer solar cells were prepared by spin coating on glass. Polymer solar cells and modules comprising 16 serially connected cells were prepared using full roll-to-roll (R2R) processing of all layers. The devices were prepared on flexible polyethyleneterphthalate (PET) and had the structure PET/ITO/ZnO/P3HT:PCBM/V₂O₅·(H₂O) n /Ag. The ITO and silver electrodes were processed and patterned by use of screen printing. The zinc oxide, P3HT:PCBM and vanadium(V)oxide layers were processed by slot-die coating. The hydrated vanadium(V)oxide layer was slot-die coated using an isopropanol solution of vanadyl-triisopropoxide (VTIP). Coating experiments were carried out to establish the critical thickness of the hydrated vanadium(V)oxide layer by varying the concentration of the VTIP precursor over two orders of magnitude. Hydrated vanadium(V)oxide layers were characterized by profilometry, scanning electron microscopy, energy dispersive X-ray spectroscopy, and grazing incidence wide angle X-ray scattering. The power conversion efficiency (PCE) for completed modules was up to 0.18%, in contrast to single cells where efficiencies of 0.4% were achieved. Stability tests under indoor and outdoor conditions were accomplished over three weeks on a solar tracker.

Nanostructured vanadium oxide thin film with high TCR at room temperature for microbolometer

NASA Astrophysics Data System (ADS)

Wang, Bin; Lai, Jianjun; Li, Hui; Hu, Haoming; Chen, Sihai

2013-03-01

In order to obtain high quality of thermal sensitive material, VOx thin film of high temperature coefficient of resistance (TCR) of 6.5%/K at room temperature has been deposited by reactive ion beam sputtering and post annealing method. AFM and XRD measurements indicate that the VOx thin film with nanostructured crystalline is composed of VO2 and V2O3. The nanostructured VOx microbolometer has been designed and fabricated. The measurement of the film system with TiN absorbing layer indicates that it has about 92% infrared absorption in the range of 8-14 μm. The performance of this bolometer, comparing with that of bolometer with common VOx, has a better result. At 20 Hz frequency and 10 μA bias current, the bolometer with high TCR has reached detectivity of 1.0 × 109 cm Hz1/2/W. It also indicates that this nanostructured VOx thin film has not only a higher TCR but also a lower noise than common VOx thin film without annealing.

Role of copper/vanadium on the optoelectronic properties of reactive RF magnetron sputtered NiO thin films

NASA Astrophysics Data System (ADS)

Panneerselvam, Vengatesh; Chinnakutti, Karthik Kumar; Thankaraj Salammal, Shyju; Soman, Ajith Kumar; Parasuraman, Kuppusami; Vishwakarma, Vinita; Kanagasabai, Viswanathan

2018-04-01

In this study, pristine nickel oxide (NiO), copper-doped NiO (Cu-NiO) and vanadium-doped NiO (V-NiO) thin films were deposited using reactive RF magnetron co-sputtering as a function of dopant sputtering power. Cu (0-8 at%) and V (0-1 at%) were doped into the NiO lattice by varying the sputtering power of Cu and V in the range of 5-15 W. The effect of dopant concentration on optoelectronic behavior is investigated by UV-Vis-NIR spectrophotometer and Hall measurements. XRD analysis showed that the preferred orientation of the cubic phase for undoped NiO changes from (200) to (111) plane when the sputtering parameters are varied. The observed changes in the lattice parameters and bonding states of the doped NiO indicate the substitution of Ni ions by monovalent Cu and trivalent V ions. The optical bandgap of pristine NiO, Cu-NiO, and V-NiO was found to be 3.6, 3.45, and 3.05 eV, respectively, with decreased transmittance and resistivity. Further analysis using SEM and AFM described the morphological behavior of doped NiO thin films and Raman spectroscopy indicated the structural changes on doping. These findings would be helpful in fabricating solid-state solar cells using doped NiO as efficient hole transporting material.

Ceramic oxide reactions with V2O5 and SO3

NASA Technical Reports Server (NTRS)

Jones, R. L.; Williams, C. E.

1985-01-01

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Using a Semiconductor-to-Metal Transition to Control Optical Transmission through Subwavelength Hole Arrays

DOE PAGES

Donev, E. U.; Suh, J. Y.; Lopez, R.; ...

2008-01-01

We describe a simple configuration in which the extraordinary optical transmission effect through subwavelength hole arrays in noble-metal films can be switched by the semiconductor-to-metal transition in an underlying thin film of vanadium dioxide. In these experiments, the transition is brought about by thermal heating of the bilayer film. The surprising reverse hysteretic behavior of the transmission through the subwavelength holes in the vanadium oxide suggest that this modulation is accomplished by a dielectric-matching condition rather than plasmon coupling through the bilayer film. The results of this switching, including the wavelength dependence, are qualitatively reproduced by a transfer matrix model.more » The prospects for effecting a similar modulation on a much faster time scale by using ultrafast laser pulses to trigger the semiconductor-to-metal transition are also discussed.« less

Novel hybrid materials based on the vanadium oxide nanobelts

NASA Astrophysics Data System (ADS)

Zabrodina, G. S.; Makarov, S. G.; Kremlev, K. V.; Yunin, P. A.; Gusev, S. A.; Kaverin, B. S.; Kaverina, L. B.; Ketkov, S. Yu.

2016-04-01

Novel hybrid materials based on zinc phthalocyanine and nanostructured vanadium oxides have attracted extensive attention for the development of academic research and innovative industrial applications such as flexible electronics, optical sensors and heterogeneous catalysts. Vanadium oxides nanobelts were synthesized via a hydrothermal treatment V2O5·nH2O gel with surfactants (TBAB, CTAB) used as structure-directing agents, where CTAB - cetyltrimethylammonium bromide, TBAB - tetrabutylammonium bromide. Hybrid materials were prepared decoration of (CTA)0.33V2O5 flexible nanobelts with cationic zinc phthalocyanine by the ion-exchange route. Investigations of the thermal stability, morphologies and structures of the (CTA)0.33V2O5, (TBA)0.16V2O5 nanobelts and zinc phthalocyanine exchange product were carried out. The hybrid materials based on the nanostructured vanadium oxide and zinc phthalocyanine were tested as photocatalysts for oxidation of citronellol and 2-mercaptoethanol by dioxygen.

Evolution of Metallicity in Vanadium Dioxide by Creation of Oxygen Vacancies

NASA Astrophysics Data System (ADS)

Zhang, Zhen; Zuo, Fan; Wan, Chenghao; Dutta, Aveek; Kim, Jongbum; Rensberg, Jura; Nawrodt, Ronny; Park, Helen Hejin; Larrabee, Thomas J.; Guan, Xiaofei; Zhou, You; Prokes, S. M.; Ronning, Carsten; Shalaev, Vladimir M.; Boltasseva, Alexandra; Kats, Mikhail A.; Ramanathan, Shriram

2017-03-01

Tuning of the electronic state of correlated materials is key to their eventual use in advanced electronics and photonics. The prototypical correlated oxide (VO2 ) is insulating at room temperature and transforms to a metallic state when heated to 67 °C (340 K). We report the emergence of a metallic state that is preserved down to 1.8 K by annealing thin films of VO2 at an ultralow oxygen partial pressure (PO2˜10-24 atm ). The films can be reverted back to their original state by annealing in oxygen, and this process can be iterated multiple times. The metallic phase created by oxygen deficiency has a tetragonal rutile structure and contains a large number of oxygen vacancies far beyond the solubility at equilibrium (greater than approximately 50 times). The oxygen starvation reduces the oxidation state of vanadium from V4 + to V3 + and leads to the metallization. The extent of resistance reduction (concurrent with tuning of optical properties) can be controlled by the time-temperature envelope of the annealing conditions since the process is diffusionally driven. This experimental platform, which can extensively tune oxygen vacancies in correlated oxides, provides an approach to study emergent phases and defect-mediated adaptive electronic and structural phase boundary crossovers.

Effect of ZnO buffer layer on phase transition properties of vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Zhu, Huiqun; Li, Lekang; Li, Chunbo

2016-03-01

VO2 thin films were prepared on ZnO buffer layers by DC magnetron sputtering at room temperature using vanadium target and post annealing at 400 °C. The ZnO buffer layers with different thickness deposited on glass substrates by magnetron sputtering have a high visible and near infrared optical transmittance. The electrical resistivity and the phase transition properties of the VO2/ZnO composite thin films in terms of temperature were investigated. The results showed that the resistivity variation of VO2 thin film with ZnO buffer layer deposited for 35 min was 16 KΩ-cm. The VO2/ZnO composite thin films exhibit a reversible semiconductor-metal phase transition at 48 °C.

Adhesive Bonding Experiments for Titanium 6 Aluminum 4 Vanadium (Ti6Al4V). Part I. Anodization Treatments.

DTIC Science & Technology

1979-12-01

Identification of Surface Treat- 4 ments of Ti 6-4 II Effect of Increasing Oxide Porosity on H20 Contact Angle on Titanium 6 Aluminum 4 Vanadium 26 viii SECTIONI...and a high SIMS yield. The lithium does not appear in the oxide formed on titanium by this mixture. Similarly porosity may be induced by anodization at...Porous Oxide (B). 25 TABLE II EFFECT OF INCREASING OXIDE POROSITY ON H2 0 CONTACT ANGLE ON TITANIUM 6 ALUMINUM 4 VANADIUM - I H 2 0Sample Electrolyte

Uranium resources in the Silver Reef (Harrisburg) district, Washington County, Utah

USGS Publications Warehouse

Stugard, Frederick

1951-01-01

The Silver Reef district is near Leeds, about 16 miles north of St. George, Utah. The major structural feature of the district is the Virgin anticline, a fold extending southwestward toward St. George. The anticline has been breached by erosion, and sandstone hogbacks or 'reefs' are carved from the Shinarump conglomerate mud sandstone members of the Chinle formation, both of Triassic age. Thirteen occurrences of uranium-vanadium minerals, all within the Tecumseh sandstone, which is the upper part of the Silver Reef sandstone member of the Chinle formation, have been examined over an area about 1.75 miles wide and 3 miles long. Two shipments of uranium-vanadium ore have been produced from the Chloride Chief and Silver Point claims. Samples from the deposits contain as much as 0.94 percent U3O8. The ore contains several times as much vanadium oxide as uranium, some copper, and traces of silver. It occurs in thinly bedded cross-bedded shales and sandstones within the fluviatile Tecumseh sandstone member of the Chinle formation. The ore beds are lenticular and are localized 2 near the base, center, and top of this sandstone member. The uranium-vanadium ore contains several yellow and green minerals not yet identified; the occurrences are similar to, but not associated with, the cerargyrite ore that made the district famous from 1879 to 1909.

Ab initio Investigation of Helium in Vanadium Oxide Nanoclusters

NASA Astrophysics Data System (ADS)

Danielson, Thomas; Tea, Eric; Hin, Celine

Nanostructured ferritic alloys (NFAs) are strong candidate materials for the next generation of fission reactors and future fusion reactors. They are characterized by a large number density of oxide nanoclusters dispersed throughout a BCC iron matrix, where current oxide nanoclusters are primarily comprised of Y-Ti-O compounds. The oxide nanoclusters provide the alloy with high resistance to neutron irradiation, high yield strength and high creep strength at the elevated temperatures of a reactor environment. In addition, the oxide nanoclusters serve as trapping sites for transmutation product helium providing substantially increased resistance to catastrophic cracking and embrittlement. Although the mechanical properties and radiation resistance of the existing NFAs is promising, the problem of forming large scale reactor components continues to present a formidable challenge due to the high hardness and unpredictable fracture behavior of the alloys. An alternative alloy has been previously proposed and fabricated where vanadium is added in order to form vanadium oxide nanoclusters that serve as deflection sites for crack propagation. Although experiments have shown evidence that the fracture behavior of the alloys is improved, it is unknown whether or not the vanadium oxide nanoclusters are effective trapping sites for helium. We present results obtained using density functional theory investigating the thermodynamic stability of helium with the vanadium oxide matrix to make a comparison of trapping effectiveness to traditional Y-Ti-O compounds.

Pro-Oxidant Biological Effects of Inorganic Component of Petroleum: Vanadium and Oxidative Stress

DTIC Science & Technology

1996-08-01

independent existence. Pro-Oxidant Chemicals and Free Radicals Involved in Oxidative Stress Pro-Oxidant Chemicals Chemical and Metabolic Generation... metabolic reactions may generate primary free radicals (Fig. 1). Then, in an avalanche-type process, secondary free radicals and reactive oxygen species...vanadium absorption, distribution, metabolism , and disposition, and no pharmacokinetic model is available describing comparative kinetics and toxicity

Electra-optical device including a nitrogen containing electrolyte

DOEpatents

Bates, John B.; Dudney, Nancy J.; Gruzalski, Greg R.; Luck, Christopher F.

1995-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Electrolyte for an electrochemical cell

DOEpatents

Bates, John B.; Dudney, Nancy J.

1997-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte amorphous lithium phosphorus oxynitride which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Electrolyte for an electrochemical cell

DOEpatents

Bates, J.B.; Dudney, N.J.

1997-01-28

Described is a thin-film battery, especially a thin-film microbattery, and a method for making the same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte amorphous lithium phosphorus oxynitride which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between {minus}15 C and 150 C. 9 figs.

Method of making an electrolyte for an electrochemical cell

DOEpatents

Bates, J.B.; Dudney, N.J.

1996-04-30

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode. Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between {minus}15 C and 150 C. 9 figs.

Method of making an electrolyte for an electrochemical cell

DOEpatents

Bates, John B.; Dudney, Nancy J.

1996-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Method for making an electrochemical cell

DOEpatents

Bates, J.B.; Dudney, N.J.

1996-10-22

Described is a thin-film battery, especially a thin-film microbattery, and a method for making the same, having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode. Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between {minus}15 C and 150 C. 9 figs.

The role of vanadium in biology.

PubMed

Rehder, Dieter

2015-05-01

Vanadium is special in at least two respects: on the one hand, the tetrahedral anion vanadate(v) is similar to the phosphate anion; vanadate can thus interact with various physiological substrates that are otherwise functionalized by phosphate. On the other hand, the transition metal vanadium can easily expand its sphere beyond tetrahedral coordination, and switch between the oxidation states +v, +iv and +iii in a physiological environment. The similarity between vanadate and phosphate may account for the antidiabetic potential of vanadium compounds with carrier ligands such as maltolate and picolinate, and also for vanadium's mediation in cardiovascular and neuronal defects. Other potential medicinal applications of more complex vanadium coordination compounds, for example in the treatment of parasitic tropical diseases, may also be rooted in the specific properties of the ligand sphere. The ease of the change in the oxidation state of vanadium is employed by prokarya (bacteria and cyanobacteria) as well as by eukarya (algae and fungi) in respiratory and enzymatic functions. Macroalgae (seaweeds), fungi, lichens and Streptomyces bacteria have available haloperoxidases, and hence enzymes that enable the 2-electron oxidation of halide X(-) with peroxide, catalyzed by a Lewis-acidic V(V) center. The X(+) species thus formed can be employed to oxidatively halogenate organic substrates, a fact with implications also for the chemical processes in the atmosphere. Vanadium-dependent nitrogenases in bacteria (Azotobacter) and cyanobacteria (Anabaena) convert N2 + H(+) to NH4(+) + H2, but are also receptive for alternative substrates such as CO and C2H2. Among the enigmas to be solved with respect to the utilization of vanadium in nature is the accumulation of V(III) by some sea squirts and fan worms, as well as the purport of the nonoxido V(IV) compound amavadin in the fly agaric.

ALTERNATIVE ROUTES FOR CATALYST PREPARATION: USE OF ULTRASOUND AND MICROWAVE IRRADIATION FOR THE PREPARATION OF VANADIUM PHOSPHORUS OXIDE CATALYST AND THEIR ACTIVITY FOR HYDROCARBON OXIDATION

EPA Science Inventory

Vanadium phosphorus oxide (VPO) has been prepared using ultrasound and microwave irradiation methods and compared with the catalyst prepared by conventional method for both the phase composition and activity for hydrocarbon oxidation. It is found that ultrasound irradiation metho...

Effect of Variable Oxidation States of Vanadium on the Structural, Optical, and Dielectric Properties of B2O3-Li2O-ZnO-V2O5 Glasses.

PubMed

Arya, S K; Danewalia, S S; Arora, Manju; Singh, K

2016-12-01

In the present study, the effect of variable vanadium oxidation states on the structural, optical, and dielectric properties of vanadium oxide containing lithium borate glasses has been investigated. Electron paramagnetic resonance studies indicate that vanadium in these glasses is mostly in the V 4+ state, having a tetragonal symmetry. As the glass composition of V 2 O 5 increases, tetragonality also increases at the cost of octahedral symmetry. The photoluminescence (PL) spectra of these glasses are dominated by zinc oxide transition, whereas the peaks pertaining to the vanadyl group are not visible in the PL spectra. The optical absorption spectra show a single wide absorption band, which is attributed to V 4+ ions in these glasses. The ac conductivity of the glasses increases with an increase in vanadium content. The highest electrical conductivity observed is ∼10 -5 S cm -1 at 250 °C for the glass with 2.5 mol % V 2 O 5 . Electrical conductivity is dominated by electron conduction, as indicated by the activation energy calculation.

Photoconductivity in nanostructured sulfur-doped V2O5 thin films

NASA Astrophysics Data System (ADS)

Mousavi, M.; Yazdi, Sh. Tabatabai

2016-03-01

In this paper, S-doped vanadium oxide thin films with doping levels up to 40 at.% are prepared via spray pyrolysis method on glass substrates, and the effect of S-doping on the structural and photoconductivity related properties of β-V2O5 thin films is studied. The results show that most of the films have been grown in the tetragonal β-V2O5 phase structure with the preferred orientation along [200]. With increasing the doping level, the samples tend to be amorphous. The structure of the samples reveals to be nanobelt-shaped whose width decreases from nearly 100 nm to 40 nm with S concentration. The photoconductivity measurements show that by increasing the S-doping level, the photosensitivity increases, which is due to the prolonged electron’s lifetime as a result of enhanced defect states acting as trap levels.

Reactions of sulfur dioxide with neutral vanadium oxide clusters in the gas phase. I. Density functional theory study.

PubMed

Jakubikova, Elena; Bernstein, Elliot R

2007-12-27

Thermodynamics of reactions of vanadium oxide clusters with SO2 are studied at the BPW91/LANL2DZ level of theory. BPW91/LANL2DZ is insufficient to properly describe relative V-O and S-O bond strengths of vanadium and sulfur oxides. Calibration of theoretical results with experimental data is necessary to compute reliable enthalpy changes for reactions between VxOy and SO2. Theoretical results indicate SO2 to SO conversion occurs for oxygen-deficient clusters and SO2 to SO3 conversion occurs for oxygen-rich clusters. Stable intermediate structures of VOy (y = 1 - 4) clusters with SO2 are also obtained at the BPW91/TZVP level of theory. Some possible mechanisms for SO3 formation and catalyst regeneration for condensed-phase systems are suggested. These results are in agreement with, and complement, gas-phase experimental studies of neutral vanadium oxide clusters.

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

PubMed

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

2013-06-01

Silver vanadium oxide (Ag 2 V 4 O 11 , SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag 2 VO 2 PO 4 , SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO 4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.

Studies on annealed ZnO:V thin films deposited by nebulised spray pyrolysis method

NASA Astrophysics Data System (ADS)

Malini, D. Rachel

2018-04-01

Structural, optical and photoluminescence properties of annealed ZnO:V thin films deposited by nebulized spray pyrolysis technique by varying vanadium concentration are studied. Thickness of thin films varies from 1.52µm to 7.78µm. V2O5, VO2 and ZnO peaks are observed in XRD patterns deposited with high vanadium concentration and the intensity of peaks corresponding to ZnO decreases in those samples. Morphological properties were studied by analysing SEM images and annealed thin films deposited at ZnO:V = 50:50 possess dumb bell shape grains. Emission peaks corresponding to both Augur transition and deep level transition are observed in the PL spectra of the samples.

Microstructure et proprietes electriques de l'oxyde de vanadium pour les microbolometres

NASA Astrophysics Data System (ADS)

Cadieux, Catherine

Recent technological breakthroughs in the fabrication of microsystems will soon allow the mass production of infrared cameras. Subsequent price cut will open many new sectors of application. Because of its electrical properties, sputtered vanadium oxide has already been identified as the leading candidate for the active material of microbolometers. However, the large number of different crystallographic phases, as well as the instable nature of reactive sputtering, haveled to numerous contradictions in the existing literature. With the objective of understanding the impact of the deposition parameters on the microstructure, and of the microstructure on the electrical properties, vanadium oxide thin films have been deposited and characterised. In order to study their impact on the microstructure, oxidation state and pulse at the target, substrate bias and temperature, power, and film thickness were varied independently. The resulting thin films have been characterised by X-ray diffraction, Rutherford backscattering spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, atomic force microscopy, spectral reflectometry, optical interferometry as well as four-point probe and Van Der Pauw electrical measurements. Because of the instability of the poisoning regime, the actual system configuration forbids the deposition of phases with composition between V 3O7 and V7O3. Films deposited under a strong bias in the poisoned regime having the best properties, their growth mechanism has been thoroughly investigated. Under those conditions, the bombarding ions are energetic enough to modify the structure of the underlying thin film without resputtering it. A complex relation linking temperature, thickness and microstructure is observed. As the thickness is increased, the structure changes from amorphous, to almost monocristalline V2O5 (001) oriented, to polycristalline. For higher deposition power, the polycristalline section contains V3O7 in addition to the multiple orientations of V2O5. Those germinations which have already been observed but not explained in literature can be attributed to the accumulation of germination centers, a stress buildup for the crystalline sections, and a substrate heating caused by the ions bombardment. This last effect is also suggested to be the cause of the amorphous phase crystallisation for the films with longer deposition times. Films deposited at different temperatures show the same microstructure transitions. Two different behavior regimes can be proposed as function of the adatoms' energy. For low temperature, increasing the adatom energy increases the diffusion which promotes the formation of the lowest surface energy stoichiometry and orientation, V2O 5(001). At higher temperature, energy is sufficient to form more energetically expensive orientation and phases. Resistivity is strongly dependant on grain boundaries density as seen by its relationship with lateral grain size. The thin film resistivity is also increased with the number of different crystallographic orientation present in it. To circumvent the high sheet resistance of the deposited single layer films, a multilayer stacking of alternating oxides and metal layers has been deposited. This approach has permitted this project's industrial collaborator to obtain a sheet resistance of 250 kO/□and a TCR of -1.59 %/K. The microstructure of the multilayer is however very heterogeneous. Not only can the metal layers be identified, it is also possible to observe the amorphous to polycrystalline transition described higher for every oxide layer. This multilayer, as well as the best single layer film produced have been annealed for 2 hours at 400°C in high vacuum. The annealed multilayer doesn't show any diffraction peaks, has very low resistance, and an almost null TCR generally attributed to metallic compounds We suggest that the diffusion of the vanadium layers into the stack created a polycrystalline structure with grains that are too small to be seen by XRD. The single layer underwent thermal reduction to form the VO2(B)phase and also became very conductive. Its TCR was afterward measured at the interesting value of -1.74 %/K. Is it suggested that the low resistivity is caused by the presence of small grains of the metallic phase of VO2, which happens to be the next step in the reduction process. Single layer annealing seems to be a promising avenue for the development of films adequate for microbolometer integration with the present deposition system. It is nonetheless recommended to pursue this avenue using films that are homogenous on their thickness in order to decouple the thickness dependence of deposition and thermal reduction. Multilayers using already homogenous amorphous oxides can also be a solution. Finally, non-reactive deposition of tungsten doped thin films followed by an oxidizing anneal may be an option that would bypass the uniformity and stability problems of the present project.

Study on the poisoning effect-of non-vanadium catalysts by potassium

NASA Astrophysics Data System (ADS)

Zeng, Huanmu; Liu, Ying; Yu, Xiaowei; Lin, Yasi

2018-02-01

The poisoning effect of catalyst by alkali metals is one of the problems in the selective catalytic reduction (SCR) of NO by NH3. Serious deactivation by alkali poisoning have been proved to take place in the commercial vanadium catalyst. Recently, non-vanadium catalysts such as copper oxides, manganese oxides, chromium oxides and cerium oxides have attracted special attentions in SCR application. However, their tolerance in the presence of alkali metals is still doubtful. In this paper, copper oxides, manganese oxides, chromium oxides and cerium oxides supported on TiO2 nanoparticle was prepared by impregnating method. Potassium nitrate was chosen as the precursor of poisoner. Catalytic activities of these catalysts were evaluated before and after the addition of potassium. Some characterization methods including X-ray diffraction and temperature programmed desorption was utilized to reveal the main reason of alkali deactivation.

Graphite furnace atomic absorption spectrometric determination of vanadium after cloud point extraction in the presence of graphene oxide

NASA Astrophysics Data System (ADS)

López-García, Ignacio; Marín-Hernández, Juan José; Hernández-Córdoba, Manuel

2018-05-01

Vanadium (V) and vanadium (IV) in the presence of a small concentration of graphene oxide (0.05 mg mL-1) are quantitatively transferred to the coacervate obtained with Triton X-114 in a cloud point microextraction process. The surfactant-rich phase is directly injected into the graphite atomizer of an atomic absorption spectrometer. Using a 10-mL aliquot sample and 150 μL of a 15% Triton X-114 solution, the enrichment factor for the analyte is 103, which results in a detection limit of 0.02 μg L-1 vanadium. The separation of V(V) and V(IV) using an ion-exchanger allows speciation of the element at low concentrations. Data for seven reference water samples with certified vanadium contents confirm the reliability of the procedure. Several beer samples are also analyzed, those supplied as canned drinks showing low levels of tetravalent vanadium.

Correlation between molten vanadium salts and the structural degradation of HK-type steel superheater tubes

NASA Astrophysics Data System (ADS)

de Carvalho Nunes, Frederico; de Almeida, Luiz Henrique; Ribeiro, André Freitas

2006-12-01

HK steels are among the most used heat-resistant cast stainless steels, being corrosion-resistant and showing good mechanical properties at high service temperatures. These steels are widely used in reformer furnaces and as superheater tubes. During service, combustion gases leaving the burners come in contact with these tubes, resulting in corrosive attack and a large weight loss occurs due to the presence of vanadium, which forms low melting point salts, removing the protective oxide layer. In this work the external surface of a tube with dramatic wall thickness reduction was analyzed using light microscopy, scanning electron microscopy, and transmission electron microscopy. The identification of the phases was achieved by energy dispersive spectroscopy (EDS) analyses. The results showed oxides arising from the external surface. In this oxidized region vanadium compounds inside chromium carbide particles were also observed, due to inward vanadium diffusion during corrosion attack. A chemical reaction was proposed to explain the presence of vanadium in the metal microstructure.

Microstructure and thermochromic properties of VOX-WOX-VOX ceramic thin films

NASA Astrophysics Data System (ADS)

Khamseh, S.; Araghi, H.; Ghahari, M.; Faghihi Sani, M. A.

2016-03-01

W-doped VO2 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 VOX-WOX-VOX ceramic thin films were investigated. The as-deposited V-W-V multilayered film showed amorphous-like structure when mixed structure of VO2 (M) and VO2 (B) was formed in VOX-WOX-VOX ceramic thin films. Tungsten content of VOX-WOX-VOX ceramic thin films increased with increasing middle layer's thickness. With increasing middle layer's thickness, room temperature square resistance ( R sq) of VOX-WOX-VOX ceramic thin films increased from 65 to 86 kΩ/sq. The VOX-WOX-VOX ceramic thin film with the thinnest middle layer showed significant SMT (semiconductor-metal transition) when SMT became negligible on increasing middle layer's thickness.

ALTERNATIVE ROUTES FOR CATALYST PREPARATION: USE OF ULTRASOUND AND MICROWAVE IRRADIATION FOR THE PREPARATION OF VANADIUM PHOSPHORUS OXIDE CATALYST AND ITS ACTIVITY FOR HYDROCARBON OXIDATION

EPA Science Inventory

Vanadium phosphorus oxide (VPO) is a well-known catalyst used for the vapor phase n-butane oxidation to maleic anhydride. It is prepared by a variety of methods, all of which, however, eventually result in the same active phase. The two main methods for the preparation of its pr...

Role of annealing duration on the microstructure and electrochemical performance of β-V2O5 thin films

NASA Astrophysics Data System (ADS)

Jeyalakshmi, K.; Muralidharan, G.

2014-03-01

Vanadium pentoxide thin films have been prepared by sol-gel spin coating method. The eight-layered films coated on fluorine-doped tin oxide substrate and glass substrate were subjected to different durations of annealing under a constant annealing temperature of 300 °C from 30 to 120 min. The X-ray diffraction spectrum reveals crystallinity along (2 0 0) direction. The SEM images of these films show the variation in the surface morphology with increase in annealing duration. The supercapacitor behaviour has been studied using cyclic voltammetry technique and electrochemical impedance spectroscopy. The film annealed for 60 min exhibits a maximum specific capacitance of 346 F/g at a scan rate of 5 mV/s with a charge transfer resistance of 172 Ω.

Catalytic destruction of PCDD/Fs over vanadium oxide-based catalysts.

PubMed

Yu, Ming-Feng; Lin, Xiao-Qing; Li, Xiao-Dong; Yan, Mi; Prabowo, Bayu; Li, Wen-Wei; Chen, Tong; Yan, Jian-Hua

2016-08-01

Vanadium oxide-based catalysts were developed for the destruction of vapour phase PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans). A vapour phase PCDD/Fs generating system was designed to supply stable PCDD/Fs steam with initial concentration of 3.2 ng I-TEQ Nm(-3). Two kinds of titania (nano-TiO2 and conventional TiO2) and alumina were used as catalyst supports. For vanadium-based catalysts supported on nano-TiO2, catalyst activity is enhanced with operating temperature increasing from 160 to 300 °C and then reduces with temperature rising further to 350 °C. It is mainly due to the fact that high volatility of organic compounds at 350 °C suppresses adsorption of PCDD/Fs on catalysts surface and then further inhibits the reaction between catalyst and PCDD/Fs. The optimum loading of vanadium on nano-TiO2 support is 5 wt.% where vanadium oxide presents highly dispersed amorphous state according to the Raman spectra and XRD patterns. Excessive vanadium will block the pore space and form microcrystalline V2O5 on the support surface. At the vanadium loading of 5 wt.%, nano-TiO2-supported catalyst performs best on PCDD/Fs destruction compared to Al2O3 and conventional TiO2. Chemical states of vanadium in the fresh, used and reoxidized VOx(5 %)/TiO2 catalysts at different operating temperature are also analysed by XPS.

Oxidative Stress as a Mechanism Involved in Kidney Damage After Subchronic Exposure to Vanadium Inhalation and Oral Sweetened Beverages in a Mouse Model.

PubMed

Espinosa-Zurutuza, Maribel; González-Villalva, Adriana; Albarrán-Alonso, Juan Carlos; Colín-Barenque, Laura; Bizarro-Nevares, Patricia; Rojas-Lemus, Marcela; López-Valdéz, Nelly; Fortoul, Teresa I

Kidney diseases have notably increased in the last few years. This is partially explained by the increase in metabolic syndrome, diabetes, and systemic blood hypertension. However, there is a segment of the population that has neither of the previous risk factors, yet suffers kidney damage. Exposure to atmospheric pollutants has been suggested as a possible risk factor. Air-suspended particles carry on their surface a variety of fuel combustion-related residues such as metals, and vanadium is one of these. Vanadium might produce oxidative stress resulting in the damage of some organs such as the kidney. Additionally, in countries like Mexico, the ingestion of sweetened beverages is a major issue; whether these beverages alone are responsible for direct kidney damage or whether their ingestion promotes the progression of an existing renal damage generates controversy. In this study, we report the combined effect of vanadium inhalation and sweetened beverages ingestion in a mouse model. Forty CD-1 male mice were distributed in 4 groups: control, vanadium inhalation, 30% sucrose in drinking water, and vanadium inhalation plus sucrose 30% in drinking water. Our results support that vanadium inhalation and the ingestion of 30% sucrose induce functional and histological kidney damage and an increase in oxidative stress biomarkers, which were higher in the combined effect of vanadium plus 30% sucrose. The results also support that the ingestion of 30% sucrose alone without hyperglycemia also produces kidney damage.

Optimization of conditions for growth of vanadium dioxide thin films on silicon by pulsed-laser deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shibuya, Keisuke, E-mail: k.shibuya@aist.go.jp; Sawa, Akihito

2015-10-15

We systematically examined the effects of the substrate temperature (T{sub S}) and the oxygen pressure (P{sub O2}) on the structural and optical properties polycrystalline V O{sub 2} films grown directly on Si(100) substrates by pulsed-laser deposition. A rutile-type V O{sub 2} phase was formed at a T{sub S} ≥ 450 °C at P{sub O2} values ranging from 5 to 20 mTorr, whereas other structures of vanadium oxides were stabilized at lower temperatures or higher oxygen pressures. The surface roughness of the V O{sub 2} films significantly increased at growth temperatures of 550 °C or more due to agglomeration of Vmore » O{sub 2} on the surface of the silicon substrate. An apparent change in the refractive index across the metal–insulator transition (MIT) temperature was observed in V O{sub 2} films grown at a T{sub S} of 450 °C or more. The difference in the refractive index at a wavelength of 1550 nm above and below the MIT temperature was influenced by both the T{sub S} and P{sub O2}, and was maximal for a V O{sub 2} film grown at 450 °C under 20 mTorr. Based on the results, we derived the P{sub O2} versus 1/T{sub S} phase diagram for the films of vanadium oxides, which will provide a guide to optimizing the conditions for growth of V O{sub 2} films on silicon platforms.« less

Phase-selective vanadium dioxide (VO2) nanostructured thin films by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Masina, B. N.; Lafane, S.; Wu, L.; Akande, A. A.; Mwakikunga, B.; Abdelli-Messaci, S.; Kerdja, T.; Forbes, A.

2015-10-01

Thin films of monoclinic nanostructured vanadium dioxide are notoriously difficult to produce in a selective manner. To date, post-annealing, after pulsed laser deposition (PLD), has been used to revert the crystal phase or to remove impurities, and non-glass substrates have been employed, thus reducing the efficacy of the transparency switching. Here, we overcome these limitations in PLD by optimizing a laser-ablation and deposition process through optical imaging of the laser-induced plasma. We report high quality monoclinic rutile-type vanadium dioxide (VO2) (M1) nanoparticles without post-annealing, and on a glass substrate. Our samples demonstrate a reversible metal-to-insulator transition at ˜43 °C, without any doping, paving the way to switchable transparency in optical materials at room temperature.

Can Supported Reduced Vanadium Oxides form H2 from CH3OH? A Computational Gas-Phase Mechanistic Study.

PubMed

González-Navarrete, Patricio; Andrés, Juan; Calatayud, Monica

2018-02-01

A detailed density functional theory study is presented to clarify the mechanistic aspects of the methanol (CH 3 OH) dehydrogenation process to yield hydrogen (H 2 ) and formaldehyde (CH 2 O). A gas-phase vanadium oxide cluster is used as a model system to represent reduced V(III) oxides supported on TiO 2 catalyst. The theoretical results provide a complete scenario, involving several reaction pathways in which different methanol adsorption sites are considered, with presence of hydride and methoxide intermediates. Methanol dissociative adsorption process is both kinetically and thermodynamically feasible on V-O-Ti and V═O sites, and it might lead to form hydride species with interesting catalytic reactivity. The formation of H 2 and CH 2 O on reduced vanadium sites, V(III), is found to be more favorable than for oxidized vanadium species, V(V), taking place along energy barriers of 29.9 and 41.0 kcal/mol, respectively.

Fabrication of photocatalytically active vanadium oxide nanostructures via plasma route

NASA Astrophysics Data System (ADS)

Kajita, Shin; Yoshida, Tomoko; Ohno, Noriyasu; Ichino, Yusuke; Yoshida, Naoaki

2018-05-01

Plasma irradiation was used to create nanostructured vanadium oxide with potential commercial and industrial applications. Morphology changes were induced at the nano- and micro-meter scale, accompanied by the growth of helium nanobubbles. Micrometer-sized pillars, cube-shaped nanostructures, and fuzzy fiberform nanostructures were grown on the surface; the necessary conditions in terms of the incident ion energy and the surface temperature for those morphology changes were revealed. Hydrogen production experiments using a photocatalytic reaction with aqueous methanol solution were conducted on the fabricated samples. Enhanced H2 production was confirmed with the plasma irradiated nanostructured sample that had been oxidized in air atmosphere. Photocatalytically inactive vanadium oxide exhibited a high photocatalytic activity after nanostructurization of the surface by helium plasma irradiation.

Dynamics of ultrathin V-oxide layers on Rh(111) in catalytic oxidation of ammonia and CO.

PubMed

von Boehn, B; Preiss, A; Imbihl, R

2016-07-20

Catalytic oxidation of ammonia and CO has been studied in the 10(-4) mbar range using a catalyst prepared by depositing ultra-thin vanadium oxide layers on Rh(111) (θV ≈ 0.2 MLE). Using photoemission electron microscopy (PEEM) as a spatially resolving method, we observe that upon heating in an atmosphere of NH3 and O2 the spatial homogeneity of the VOx layer is removed at 800 K and a pattern consisting of macroscopic stripes develops; at elevated temperatures this pattern transforms into a pattern of circular VOx islands. Under reaction conditions the neighboring VOx islands become attracted by each other and coalesce. Similar processes of pattern formation and island coalescence are observed in catalytic CO oxidation. Reoxidation of the reduced VOx catalyst proceeds via surface diffusion of oxygen adsorbed onto Rh(111). A pattern consisting of macroscopic circular VOx islands can also be obtained by heating a Rh(111)/VOx catalyst in pure O2.

Vanadium Induces Dopaminergic Neurotoxicity Via Protein Kinase C-Delta Dependent Oxidative Signaling Mechanisms: Relevance to Etiopathogenesis of Parkinson's Disease

PubMed Central

Afeseh Ngwa, Hilary; Kanthasamy, Arthi; Anantharam, Vellareddy; Song, Chunjuan; Witte, Travis; Houk, R. S.; Kanthasamy, Anumantha G.

2009-01-01

Environmental exposure to neurotoxic metals through various sources including exposure to welding fumes has been linked to an increased incidence of Parkinson's disease (PD). Welding fumes contain many different metals including vanadium typically present as particulates containing vanadium pentoxide (V2O5). However, possible neurotoxic effects of this metal oxide on dopaminergic neuronal cells are not well studied. In the present study, we characterized vanadium-induced oxidative stress-dependent cellular events in cell culture models of PD. V2O5 was neurotoxic to dopaminergic neuronal cells including primary nigral dopaminergic neurons and the EC50 was determined to be 37 μM in N27 dopaminergic neuronal cell model. The neurotoxic effect was accompanied by a time-dependent uptake of vanadium and upregulation of metal transporter proteins Tf and DMT1 in N27 cells. Additionally, vanadium resulted in a threefold increase in reactive oxygen species generation, followed by release of mitochondrial cytochrome c into cytoplasm and subsequent activation of caspase-9 (>fourfold) and caspase-3 (>ninefold). Interestingly, vanadium exposure induced proteolytic cleavage of native protein kinase Cdelta (PKCδ, 72-74 kDa) to yield a 41 kDa catalytically active fragment resulting in a persistent increase in PKCδ kinase activity. Co-treatment with pan-caspase inhibitor ZVAD-FMK significantly blocked vanadium-induced PKCδ proteolytic activation, indicating that caspases mediate PKCδ cleavage. Also, co-treatment with Z-VAD-FMK almost completely inhibited V2O5-induced DNA fragmentation. Furthermore, PKCδ knockdown using siRNA protected N27 cells from V2O5-induced apoptotic cell death. Collectively, these results demonstrate vanadium can exert neurotoxic effects in dopaminergic neuronal cells via caspase-3-dependent PKCδ cleavage, suggesting that metal exposure may promote nigral dopaminergic degeneration. PMID:19646462

Switching adhesion forces by crossing the metal–insulator transition in Magnéli-type vanadium oxide crystals

PubMed Central

Klemm, Matthias; Horn, Siegfried; Woydt, Mathias

2011-01-01

Summary Magnéli-type vanadium oxides form the homologous series VnO2 n -1 and exhibit a temperature-induced, reversible metal–insulator first order phase transition (MIT). We studied the change of the adhesion force across the transition temperature between the cleavage planes of various vanadium oxide Magnéli phases (n = 3 … 7) and spherical titanium atomic force microscope (AFM) tips by systematic force–distance measurements with a variable-temperature AFM under ultrahigh vacuum conditions (UHV). The results show, for all investigated samples, that crossing the transition temperatures leads to a distinct change of the adhesion force. Low adhesion corresponds consistently to the metallic state. Accordingly, the ability to modify the electronic structure of the vanadium Magnéli phases while maintaining composition, stoichiometry and crystallographic integrity, allows for relating frictional and electronic material properties at the nano scale. This behavior makes the vanadium Magnéli phases interesting candidates for technology, e.g., as intelligent devices or coatings where switching of adhesion or friction is desired. PMID:21977416

Synthesis and characterization of polymeric V2O5/AlO(OH) with nanopores on alumina support.

PubMed

Ahmad, A L; Abd Shukor, S R; Leo, C P

2006-12-01

Polymeric vanadium pentoxide gel was formed via the reaction of V2O5 powder with hydrogen peroxide. The polymeric vanadium pentoxide gel was then dispersed in alumina gel. Different vanadium loading composites were coated on alumina support and calcined at 500 degrees C for 1 hr. These composite layers were characterized using TGA, FT-IR, XRD, SEM, and Autosorb. It was found that the lamellar structure of polymerized vanadium pentoxide was retained in the inorganic matrix. Crystalline alumina in gamma phase was formed after calcinations. However, the vanadium-alumina mixed oxides are lack of the well defined PXRD peaks for polycrystalline V2O5. This is possibly because the vanadia species are highly dispersed in the alumina matrix or the vanadia species are dispersed as crystalline which is smaller than 4 nm. In addition, the imbedded polymeric vanadium oxide improved the specific area and average pore diameter of the composite layer.

Hierarchical Branched Vanadium Oxide Nanorod@Si Nanowire Architecture for High Performance Supercapacitors.

PubMed

Li, Zhaodong; Wang, Fei; Wang, Xudong

2017-01-01

Vanadium oxide (VO x ) nanorods are uniformly synthesized on dense Si nanowire arrays. This 3D hierarchical nanoarchitecture offers a novel high-performance supercapacitor electrode design with significantly improved specific capacitance and high-rate capability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organometalic carbosilane polymers containing vanadium and their preparation

NASA Technical Reports Server (NTRS)

Yajima, S.; Okamura, K.; Shishido, T.; Fukuda, K.

1983-01-01

The present invention concerns a new organometallic polymer material containing in part a vanadium-siloxane linkage (V-0-Si), which has excellent resistance to heat and oxidation and a high residue ratio after high temperature treatment in a non-oxidizing atmosphere, for example, nitrogen, argon, helium, ammonia, or hydrogen.

CATALYTIC PROMOTION OF THE ADSORPTION OF VANADIUM ON AN ANIONIC EXCHANGE RESIN

DOEpatents

Bailes, R.H.; Ellis, D.A.

1958-08-26

An improvement in the process for the recovery of vanadium from acidic phosphatic solutions is presented. In this process the vanadium is first oxidized to the pentavaleat state, and is then separated by contacting such solutions with an anion exchange resin whereby adsorption of the complexed pentavalent vanadium is effected. The improvement lies in the fact that adsorp tion of the vanadium complex by the anion exchange resin is promoted and improved by providing fiuoride ions in solution to be contacted.

High Power Electrochemical Capacitors

DTIC Science & Technology

2012-03-23

electrochemical properties of vanadium oxide aerogels prepared by a freeze-drying process. Journal of the Electrochemical Society, 2004. 151(5): p...Electrochemical Society, 2002. 149(1): p. A26-A30. 12. Rolison, D.R. and B. Dunn, Electrically conductive oxide aerogels : new materials in...surface area vanadium oxide aerogels . Electrochemical and Solid-State Letters, 2000. 3(10): p. 457-459. 14. Shembel, E., et al., Synthesis, investigation

Phase-selective vanadium dioxide (VO{sub 2}) nanostructured thin films by pulsed laser deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masina, B. N., E-mail: BMasina@csir.co.za, E-mail: slafane@cdta.dz; School of Physics, University of KwaZulu-Natal, Private Bag X54001, Durban 4000; Lafane, S., E-mail: BMasina@csir.co.za, E-mail: slafane@cdta.dz

2015-10-28

Thin films of monoclinic nanostructured vanadium dioxide are notoriously difficult to produce in a selective manner. To date, post-annealing, after pulsed laser deposition (PLD), has been used to revert the crystal phase or to remove impurities, and non-glass substrates have been employed, thus reducing the efficacy of the transparency switching. Here, we overcome these limitations in PLD by optimizing a laser-ablation and deposition process through optical imaging of the laser-induced plasma. We report high quality monoclinic rutile-type vanadium dioxide (VO{sub 2}) (M1) nanoparticles without post-annealing, and on a glass substrate. Our samples demonstrate a reversible metal-to-insulator transition at ∼43 °C, withoutmore » any doping, paving the way to switchable transparency in optical materials at room temperature.« less

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

PubMed

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.

Encapsulated Vanadium-Based Hybrids in Amorphous N-Doped Carbon Matrix as Anode Materials for Lithium-Ion Batteries.

PubMed

Long, Bei; Balogun, Muhammad-Sadeeq; Luo, Lei; Luo, Yang; Qiu, Weitao; Song, Shuqin; Zhang, Lei; Tong, Yexiang

2017-11-01

Recently, researchers have made significant advancement in employing transition metal compound hybrids as anode material for lithium-ion batteries and developing simple preparation of these hybrids. To this end, this study reports a facile and scalable method for fabricating a vanadium oxide-nitride composite encapsulated in amorphous carbon matrix by simply mixing ammonium metavanadate and melamine as anode materials for lithium-ion batteries. By tuning the annealing temperature of the mixture, different hybrids of vanadium oxide-nitride compounds are synthesized. The electrode material prepared at 700 °C, i.e., VM-700, exhibits excellent cyclic stability retaining 92% of its reversible capacity after 200 cycles at a current density of 0.5 A g -1 and attractive rate performance (220 mAh g -1 ) under the current density of up to 2 A g -1 . The outstanding electrochemical properties can be attributed to the synergistic effect from heterojunction form by the vanadium compound hybrids, the improved ability of the excellent conductive carbon for electron transfer, and restraining the expansion and aggregation of vanadium oxide-nitride in cycling. These interesting findings will provide a reference for the preparation of transition metal oxide and nitride composites as well. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Roasting and leaching behaviors of vanadium and chromium in calcification roasting-acid leaching of high-chromium vanadium slag

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Zhou, Mi; Gao, Hui-yang; Liu, Jia-yi; Xue, Xiang-xin

2018-05-01

Calcification roasting-acid leaching of high-chromium vanadium slag (HCVS) was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium. The effects of the purity of CaO, molar ratio between CaO and V2O5 ( n(CaO)/ n(V2O5)), roasting temperature, holding time, and the heating rate used in the oxidation-calcification processes were investigated. The roasting process and mechanism were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetry-differential scanning calorimetry (TG-DSC). The results show that most of vanadium reacted with CaO to generate calcium vanadates and transferred into the leaching liquid, whereas almost all of the chromium remained in the leaching residue in the form of (Fe0.6Cr0.4)2O3. Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with CaO. Moreover, CaO was more likely to combine with vanadium, as further confirmed by thermodynamic analysis. When the HCVS with CaO added in an n(CaO)/ n(V2O5) ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10°C/min from room temperature to 950°C and maintained at this temperature for 60 min, the leaching ratios of vanadium and chromium reached 91.14% and 0.49%, respectively; thus, efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium. Furthermore, the oxidation and calcification reactions of the spinel phases occurred at 592 and 630°C for n(CaO)/ n(V2O5) ratios of 0.5 and 5, respectively.

Formation, structure and bond dissociation thresholds of gas-phase vanadium oxide cluster ions

NASA Astrophysics Data System (ADS)

Bell, R. C.; Zemski, K. A.; Justes, D. R.; Castleman, A. W.

2001-01-01

The formation and structure of gas-phase vanadium oxide cluster anions are examined using a guided ion beam mass spectrometer coupled with a laser vaporization source. The dominant peaks in the anion total mass distribution correspond to clusters having stoichiometries of the form (VO2)n(VO3)m(O2)q-. Collision-induced dissociation studies of the vanadium oxide species V2O4-6-, V3O6-9-, V4O8-10-, V5O11-13-, V6O13-15-, and V7O16-18- indicate that VO2, VO3, and V2O5 units are the main building blocks of these clusters. There are many similarities between the anion mass distribution and that of the cation distribution studied previously. The principal difference is a shift to higher oxygen content by one additional oxygen atom for the stoichiometric anions (VxOy-) as compared to the cations with the same number of vanadium atoms, which is attributed to the extra pair of electrons of the anionic species. The oxygen-rich clusters, VxOy(O2)-, are shown to more tightly adsorb molecular oxygen than those of the corresponding cationic clusters. In addition, the bond dissociation thresholds for the vanadium oxide clusters ΔE(V+-O)=6.09±0.28 eV, ΔE(OV+-O)=3.51±0.36 eV, and ΔE(O2V--O)=5.43±0.31 eV are determined from the energy-dependent collision-induced dissociation cross sections with Xe as the collision partner. To the best of our knowledge, this is the first bond dissociation energy reported for the breaking of the V-O bond of a vanadium oxide anion.

V2O5 thin film deposition for application in organic solar cells

NASA Astrophysics Data System (ADS)

Arbab, Elhadi A. A.; Mola, Genene Tessema

2016-04-01

Vanadium pentoxide V2O5 films were fabricated by way of electrochemical deposition technique for application as hole transport buffer layer in organic solar cell. A thin and uniform V2O5 films were successfully deposited on indium tin oxide-coated glass substrate. The characterization of surface morphology and optical properties of the deposition suggest that the films are suitable for photovoltaic application. Organic solar cell fabricated using V2O5 as hole transport buffer layer showed better devices performance and environmental stability than those devices fabricated with PEDOT:PSS. In an ambient device preparation condition, the power conversion efficiency increases by nearly 80 % compared with PEDOT:PSS-based devices. The devices lifetime using V2O5 buffer layer has improved by a factor of 10 over those devices with PEDOT:PSS.

Low Temperature Chemical Vapor Deposition Of Thin Film Magnets

DOEpatents

Miller, Joel S.; Pokhodnya, Kostyantyn I.

2003-12-09

A thin-film magnet formed from a gas-phase reaction of tetracyanoetheylene (TCNE) OR (TCNQ), 7,7,8,8-tetracyano-P-quinodimethane, and a vanadium-containing compound such as vanadium hexcarbonyl (V(CO).sub.6) and bis(benzene)vanalium (V(C.sub.6 H.sub.6).sub.2) and a process of forming a magnetic thin film upon at least one substrate by chemical vapor deposition (CVD) at a process temperature not exceeding approximately 90.degree. C. and in the absence of a solvent. The magnetic thin film is particularly suitable for being disposed upon rigid or flexible substrates at temperatures in the range of 40.degree. C. and 70.degree. C. The present invention exhibits air-stable characteristics and qualities and is particularly suitable for providing being disposed upon a wide variety of substrates.

Hydrophilic Channel Alignment of Perfluoronated Sulfonic-Acid Ionomers for Vanadium Redox Flow Batteries.

PubMed

So, Soonyong; Cha, Min Suc; Jo, Sang-Woo; Kim, Tae-Ho; Lee, Jang Yong; Hong, Young Taik

2018-06-13

It is known that uniaxially drawn perfluoronated sulfonic-acid ionomers (PFSAs) show diffusion anisotropy because of the aligned water channels along the deformation direction. We apply the uniaxially stretched membranes to vanadium redox flow batteries (VRFBs) to suppress the permeation of active species, vanadium ions through the transverse directions. The aligned water channels render much lower vanadium permeability, resulting in higher Coulombic efficiency (>98%) and longer self-discharge time (>250 h). Similar to vanadium ions, proton conduction through the membranes also decreases as the stretching ratio increases, but the thinned membranes show the enhanced voltage and energy efficiencies over the range of current density, 50-100 mA/cm 2 . Hydrophilic channel alignment of PFSAs is also beneficial for long-term cycling of VRFBs in terms of capacity retention and cell performances. This simple pretreatment of membranes offers an effective and facile way to overcome high vanadium permeability of PFSAs for VRFBs.

Reversible phase transition in vanadium oxide films sputtered on metal substrates

NASA Astrophysics Data System (ADS)

Palai, Debajyoti; Carmel Mary Esther, A.; Porwal, Deeksha; Pradeepkumar, Maurya Sandeep; Raghavendra Kumar, D.; Bera, Parthasarathi; Sridhara, N.; Dey, Arjun

2016-11-01

Vanadium oxide films, deposited on aluminium (Al), titanium (Ti) and tantalum (Ta) metal substrates by pulsed RF magnetron sputtering at a working pressure of 1.5 x10-2 mbar at room temperature are found to display mixed crystalline vanadium oxide phases viz., VO2, V2O3, V2O5. The films have been characterized by field-emission scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy, and their thermo-optical and electrical properties have been investigated. Studies of the deposited films by DSC have revealed a reversible-phase transition found in the temperature range of 45-49 °C.

Vanadium

USGS Publications Warehouse

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 sands, and oil shales may be important future sources.Vanadium occurs in one of four oxidation states in nature: +2, +3, +4, and +5. The V3+ ion has an octahedral radius that is almost identical to that of (Fe3+) and (Al3+) and, therefore, it substitutes in ferromagnesian minerals. During weathering, much of the vanadium may partition into newly formed clay minerals, and it either remains in the +3 valence state or oxidizes to the +4 valence state, both of which are relatively insoluble. If erosion is insignificant but chemical leaching is intense, the residual material may be enriched in vanadium, as are some bauxites and laterites. During the weathering of igneous, residual, or sedimentary rocks, some vanadium oxidizes to the +5 valence state, especially in the intensive oxidizing conditions that are characteristic of arid climates.The average contents of vanadium in the environment are as follows: soils [10 to 500 parts per million (ppm)]; streams and rivers [0.2 to 2.9 parts per billion (ppb)]; and coastal seawater (0.3 to 2.8 ppb). Concentrations of vanadium in soils (548 to 7,160 ppm) collected near vanadium mines in China, the Czech Republic, and South Africa are many times greater than natural concentrations in soils. Additionally, if deposits contain sulfide minerals such as chalcocite, pyrite, and sphalerite, high levels of acidity may be present if sulfide dissolution is not balanced by the presence of acid-neutralizing carbonate minerals. Some of the vanadium-bearing deposit types, particularly some SSV and black-shale deposits, contain appreciable amounts of carbonate minerals, which lowers the acid-generation potential.Vanadium is a micronutrient with a postulated requirement for humans of less than 10 micrograms per day, which can be met through dietary intake. Primary and secondary drinking water regulations for vanadium are not currently in place in the United States. Vanadium toxicity is thought to result from an intake of more than 10 to 20 milligrams per day. Vanadium is essential for some biological processes and organisms. For example, some nitrogen-fixing bacteria require vanadium for producing enzymes necessary to convert nitrogen from the atmosphere into ammonia, which is a more biologically accessible form of nitrogen.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

The mixed-valent vanadium oxide based three-dimensional framework structure species [Cd3(H2O)12V16IVV2VO36(OH)6 (AO4)]·24H2O, (A = V,S) (Cd3(VO)o) represents a rare example of an interesting sensor material which exhibits NOx {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.

Characterization and Electrical Response to Humidity of Sintered Polymeric Electrospun Fibers of Vanadium Oxide-({TiO}_{{2}} /{WO}_{{3}} )

NASA Astrophysics Data System (ADS)

Araújo, E. S.; Libardi, J.; Faia, P. M.; de Oliveira, H. P.

2018-02-01

Metal oxide composites have attracted much consideration due to their promising applications in humidity sensors in response to the physical and chemical property modifications of the resulting materials. This work focused on the preparation, microstructural characterization and analysis of humidity-dependent electrical properties of undoped and vanadium oxide (V2O5)-doped titanium oxide/tungsten oxide (TiO2/WO3) sintered ceramic films obtained by electrospinning. The electrical properties were investigated by impedance spectroscopy (400 Hz-40 MHz) as a function of relative humidity (RH). The results revealed a typical transition in the transport mechanisms controlled by the appropriated doping level of V2O5, which introduces important advantages to RH detection due to the atomic substitution of titanium by vanadium atoms in highly doped structures. These aspects are directly related to the microstructure modification and structure fabrication procedure.

Vanadium based materials as electrode materials for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Yan, Yan; Li, Bing; Guo, Wei; Pang, Huan; Xue, Huaiguo

2016-10-01

As a kind of supercapacitors, pseudocapacitors have attracted wide attention in recent years. The capacitance of the electrochemical capacitors based on pseudocapacitance arises mainly from redox reactions between electrolytes and active materials. These materials usually have several oxidation states for oxidation and reduction. Many research teams have focused on the development of an alternative material for electrochemical capacitors. Many transition metal oxides have been shown to be suitable as electrode materials of electrochemical capacitors. Among them, vanadium based materials are being developed for this purpose. Vanadium based materials are known as one of the best active materials for high power/energy density electrochemical capacitors due to its outstanding specific capacitance and long cycle life, high conductivity and good electrochemical reversibility. There are different kinds of synthetic methods such as sol-gel hydrothermal/solvothermal method, template method, electrospinning method, atomic layer deposition, and electrodeposition method that have been successfully applied to prepare vanadium based electrode materials. In our review, we give an overall summary and evaluation of the recent progress in the research of vanadium based materials for electrochemical capacitors that include synthesis methods, the electrochemical performances of the electrode materials and the devices.

Sulfonated graphene oxide/nafion composite membrane for vanadium redox flow battery.

PubMed

Kim, Byung Guk; Han, Tae Hee; Cho, Chang Gi

2014-12-01

Nafion is the most frequently used as the membrane material due to its good proton conductivity, and excellent chemical and mechanical stabilities. But it is known to have poor barrier property due to its well-developed water channels. In order to overcome this drawback, graphene oxide (GO) derivatives were introduced for Nafion composite membranes. Sulfonated graphene oxide (sGO) was prepared from GO. Both sGO and GO were treated each with phenyl isocyanate and transformed into corresponding isGO and iGO in order to promote miscibility with Nafion. Then composite membranes were obtained, and the adaptability as a membrane for vanadium redox flow battery (VRFB) was investigated in terms of proton conductivity and vanadium permeability. Compared to a pristine Nafion, proton conductivities of both isGO/Nafion and iGO/Nafion membranes showed less temperature sensitivity. Both membranes also showed quite lower vanadium permeability at room temperature. Selectivity of the membrane was the highest for isGO/Nafion and the lowest for the pristine Nafion.

A comparative assessment of the acute inhalation toxicity of vanadium compounds.

PubMed

Rajendran, N; Seagrave, J C; Plunkett, L M; MacGregor, J A

2016-11-01

Vanadium compounds have become important in industrial processes, resulting in workplace exposure potential and are present in ambient air as a result of fossil fuel combustion. A series of acute nose-only inhalation toxicity studies was conducted in both rats and mice in order to obtain comparative data on the acute toxicity potential of compounds used commercially. V 2 O 3 , V 2 O 4 , and V 2 O 5 , which have different oxidation states (+3, +4, +5, respectively), were delivered as micronized powders; the highly water-soluble and hygroscopic VOSO 4 (+4) could not be micronized and was instead delivered as a liquid aerosol from an aqueous solution. V 2 O 5 was the most acutely toxic micronized powder in both species. Despite its lower overall percentage vanadium content, a liquid aerosol of VOSO 4 was more toxic than the V 2 O 5 particles in mice, but not in rats. These data suggest that an interaction of characteristics, i.e., bioavailability, solubility and oxidation state, as well as species sensitivity, likely affect the toxicity potential of vanadium compounds. Based on clinical observations and gross necropsy findings, the lung appeared to be the target organ for all compounds. The level of hazard posed will depend on the specific chemical form of the vanadium. Future work to define the inhalation toxicity potential of vanadium compounds of various oxidation states after repeated exposures will be important in understanding how the physico-chemical and biological characteristics of specific vanadium compounds interact to affect toxicity potential and the potential risks posed to human health.

Mechanochemical processing of molybdenum and vanadium sulfides for metal recovery from spent catalysts wastes.

PubMed

Li, Zhao; Chen, Min; Zhang, Qiwu; Liu, Xinzhong; Saito, Fumio

2017-02-01

This work describes the mechanochemical transformations of molybdenum and vanadium sulfides into corresponding molybdate and vanadate, to serve as a new environment-friendly approach for processing hazardous spent hydrodesulphurization (HDS) catalysts solid waste to achieve an easy recovery of not only molybdenum and vanadium but also nickel and cobalt. Co-grinding the molybdenum and vanadium sulfides with oxidants and sodium carbonate stimulates solid-state reactions without any heating aid to form metal molybdates and vanadates. The reactions proceed with an increase in grinding time and were enhanced by using more sodium carbonate and stronger oxidant. The necessary conditions for the successful transformation can be explained on the basis of thermodynamic analyses, namely a negative change in Gibbs free energy. Copyright © 2016 Elsevier Ltd. All rights reserved.

URANIUM LEACHING AND RECOVERY PROCESS

DOEpatents

McClaine, L.A.

1959-08-18

A process is described for recovering uranium from carbonate leach solutions by precipitating uranium as a mixed oxidation state compound. Uranium is recovered by adding a quadrivalent uranium carbon;te solution to the carbonate solution, adjusting the pH to 13 or greater, and precipitating the uranium as a filterable mixed oxidation state compound. In the event vanadium occurs with the uranium, the vanadium is unaffected by the uranium precipitation step and remains in the carbonate solution. The uranium-free solution is electrolyzed in the cathode compartment of a mercury cathode diaphragm cell to reduce and precipitate the vanadium.

Novel catalytic effects of Mn3O4 for all vanadium redox flow batteries.

PubMed

Kim, Ki Jae; Park, Min-Sik; Kim, Jae-Hun; Hwang, Uk; Lee, Nam Jin; Jeong, Goojin; Kim, Young-Jun

2012-06-04

A new approach for enhancing the electrochemical performance of carbon felt electrodes by employing non-precious metal oxides is designed. The outstanding electro-catalytic activity and mechanical stability of Mn(3)O(4) are advantageous in facilitating the redox reaction of vanadium ions, leading to efficient operation of a vanadium redox flow battery.

Effective role of deposition duration on the growth of V2O5 nanostructured thin films

NASA Astrophysics Data System (ADS)

Sharma, Rabindar Kumar; Saini, Sujit Kumar; Singh, Megha; Reddy, G. B.

2016-05-01

In this report, vanadium pentoxide nanostructured thin films (NSTs) with nanoplates (NPs) have synthesized on Ni coated glass substrate employing plasma assisted sublimation process (PASP), as a function of deposition/growth durations. The effect of deposition durations on the morphological, structural, vibrational, and compositional properties have been investigated one by one. The structural and vibrational studies endorsed that the grown NPs have only orthorhombic phase, no other sub oxide phases are recorded in the limit of resolution. The morphological results of all samples using SEM, revealed that the features, coverage density, and alignments of NPs are greatly controlled by deposition duration and the best sample is obtained for 25 min (S2). Further, the more insight information is accomplished by HRTEM/SAED on the best featured sample, which confirmed the single crystalline nature of NPs. The XPS result again confirmed the compositional purity and the nearly stoichiometric nature of NPs.

Comparison of the optical responses of O-poor and O-rich thermochromic VOX films during semiconductor-to-metal transition

NASA Astrophysics Data System (ADS)

Luo, Zhenfei; Wu, Zhiming; Wang, Tao; Xu, Xiangdong; Li, Weizhi; Li, Wei; Jiang, Yadong

2012-09-01

O-poor and O-rich thermochromic vanadium oxide (VOX) nanostructured thin films were prepared by applying reactive direct current magnetron sputtering and post-annealing in oxygen ambient. UV-visible spectrophotometer and spectroscopic ellipsometry were used to investigate the optical properties of films. It was found that, when the O-poor VOX thin film underwent semiconductor-to-metal transition, the values of optical conductivity and extinction coefficient in the visible region increased due to the existence of occupied band-gap states. This noticeable feature, however, was not observed for the O-rich film, which showed a similar optical behavior with the stoichiometric crystalline VO2 films reported in the literatures. Moreover, the O-poor VOX film exhibits consistent variations of transmission values in the visible/near-infrared region when it undergoes semiconductor-to-metal transition.

High Performance Pillared Vanadium Oxide Cathode for Lithium Ion Batteries

DTIC Science & Technology

2015-04-24

As a result, two major approaches have been taken to increase electrode- electrolyte interfacial area while minimizing lithium diffusion lengths...Performance Pillared Vanadium Oxide Cathode for Lithium Ion Batteries Siu on Tung, Krista L. Hawthorne, Yi Ding, James Mainero, and Levi T. Thompson...Automotive Research Development and Engineering Center, Warren, MI 48387, USA Keywords: nanostructured materials, lithium ion batteries, cathode

Pd/V.sub.2O.sub.5 device for colorimetric H.sub.2 detection

DOEpatents

Liu, Ping [San Diego, CA; Tracy, C Edwin [Golden, CO; Pitts, J Roland [Lakewood, CO; Smith, II, R. Davis; Lee, Se-Hee [Lakewood, CO

2008-09-02

A sensor structure for chemochromic optical detection of hydrogen gas over a wide response range, that exhibits stability during repeated coloring/bleaching cycles upon exposure and removal of hydrogen gas, comprising: a glass substrate (20); a vanadium oxide layer (21) coated on the glass substrate; and a palladium layer (22) coated on the vanadium oxide layer.

Rate Dependency of Silver Vanadium Phosphorous Oxide Reduction

NASA Astrophysics Data System (ADS)

Cheng, Po-Jen

2011-12-01

The silver vanadium phosphorus oxide (Ag2VO2PO 4) is a high-capacity and good-compatibility material for the cathode in the battery. Due to their innovative properties, they are used as cathode in lithium batteries. Therefore, when the lithium batteries begin to discharge, the anodes of the cell perform an electrochemical oxidation and release electrons. In the mean time, the cathodes in the cells perform the electrochemical reduction and catch the electrons. For reduction of Ag2VO2PO 4, two silver ions (Ag+) catch two electrons to form silver particles, and the vanadium ions (V5+) catch two electrons to form V3+. It means that four electrons will be released by lithium anode. We call this four electrons discharge as 100% discharge. In my most of the projects, the Ag2VO2PO4 material is tested by differential scanning calorimetry (DSC) to check purity. My study is based on the discharge of batteries, and I focus on the morphology and the intensity of silver particles on the cathode after discharge. Depending on different adjustment of factors, such as discharge time, discharge rate, storage time, storage temperature, I try to investigate the silver intensity, conductivity as a function of DOD (Depth of Discharge). The silver particles could be examined by optical microscope, and scanning electron microscope (SEM). Moreover, I do some x-ray diffraction analysis to quantify the silver particles after discharge. Also, I perform magnetic susceptibility measurement to check the mechanism of the reduction of vanadium ions. Under the research on silver ions and vanadium ions, I will know a big frame of reduction process on silver vanadium phosphorous oxide and the time effect on this cathode material.

Atomic Layer Deposition of Bismuth Vanadates for Solar Energy Materials.

PubMed

Stefik, Morgan

2016-07-07

The fabrication of porous nanocomposites is key to the advancement of energy conversion and storage devices that interface with electrolytes. Bismuth vanadate, BiVO4 , is a promising oxide for solar water splitting where the controlled fabrication of BiVO4 layers within porous, conducting scaffolds has remained a challenge. Here, the atomic layer deposition of bismuth vanadates is reported from BiPh3 , vanadium(V) oxytriisopropoxide, and water. The resulting films have tunable stoichiometry and may be crystallized to form the photoactive scheelite structure of BiVO4 . A selective etching process was used with vanadium-rich depositions to enable the synthesis of phase-pure BiVO4 after spinodal decomposition. BiVO4 thin films were measured for photoelectrochemical performance under AM 1.5 illumination. The average photocurrents were 1.17 mA cm(-2) at 1.23 V versus the reversible hydrogen electrode using a hole-scavenging sulfite electrolyte. The capability to deposit conformal bismuth vanadates will enable a new generation of nanocomposite architectures for solar water splitting. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Au doping effects on electrical and optical properties of vanadium dioxides

NASA Astrophysics Data System (ADS)

Zhu, YaBin; He, Fan; Na, Jie

2012-03-01

Vanadium dioxides were fabricated on normal glass substrates using reactive radio frequency (RF) magnetron sputtering. The oxygen flow volume and annealed temperatures as growth parameters are systematically investigated. The electrical and optical properties of VO2 and Au:VO2 thin films with different growth conditions are discussed. The semiconductor-metal phase transition temperature decreased by ˜10°C for the sample with Au doping compared to the sample without Au doping. However, the optical transmittance of Au:VO2 thin films is much lower than that of bare VO2. These results show that Au doping has a marked effect on the electrical and optical properties.

Flake like V{sub 2}O{sub 5} nanoparticles for ethanol sensing at room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chitra, M.; Uthayarani, K.; Rajasekaran, N.

2016-05-23

The versatile redox property of vanadium oxide explores it in various applications like catalysis, electrochromism, electrochemistry, energy storage, sensors, microelectronics, batteries etc., In this present work, vanadium oxide was prepared via hydrothermal route followed by calcination. The structural and lattice parameters were analysed from the powder X-ray diffraction (XRD) pattern. The morphology and the composition of the sample were obtained from Field emission Scanning electron microscopic (FeSEM) and Energy Dispersive X-ray (EDAX) Spectrometric analysis respectively. The sensitivity, response – recovery time of the sample towards ethanol (0 ppm – 300 ppm) sensing at room temperature was measured and the present investigation onmore » vanadium oxide nanoparticles over the flakes shows better sensitivity (30%) at room temperature.« less

The oxidation of organic additives in the positive vanadium electrolyte and its effect on the performance of vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Nguyen, Tam D.; Whitehead, Adam; Scherer, Günther G.; Wai, Nyunt; Oo, Moe O.; Bhattarai, Arjun; Chandra, Ghimire P.; Xu, Zhichuan J.

2016-12-01

Despite many desirable properties, the vanadium redox flow battery is limited, in the maximum operation temperature that can be continuously endured, before precipitation begins in the positive electrolyte. Many additives have been proposed to improve the thermal stability of the charged positive electrolyte. However, we have found that the apparent stability, revealed in laboratory testing, is often simply an artifact of the test method and arises from the oxidation of the additive, with corresponding partial reduction of V(V) to V(IV). This does not improve the stability of the electrolyte in an operating system. Here, we examined the oxidation of some typical organic additives with carboxyl, alcohol, and multi-functional groups, in sulfuric acid solutions containing V(V). The UV-vis measurements and titration results showed that many compounds reduced the state-of-charge (SOC) of vanadium electrolyte, for example, by 27.8, 88.5, and 81.9% with the addition of 1%wt of EDTA disodium salt, pyrogallol, and ascorbic acid, respectively. The cell cycling also indicated the effect of organic additives on the cell performance, with significant reduction in the usable charge capacity. In addition, a standard screening method for thermally stable additives was introduced, to quickly screen suitable additives for the positive vanadium electrolyte.

Low-temperature solution-processed hydrogen molybdenum and vanadium bronzes for an efficient hole-transport layer in organic electronics.

PubMed

Xie, Fengxian; Choy, Wallace C H; Wang, Chuandao; Li, Xinchen; Zhang, Shaoqing; Hou, Jianhui

2013-04-11

A simple one-step method is reported to synthesize low-temperature solution-processed transition metal oxides (TMOs) of molybdenum oxide and vanadium oxide with oxygen vacancies for a good hole-transport layer (HTL). The oxygen vacancy plays an essential role for TMOs when they are employed as HTLs: TMO films with excess oxygen are highly undesirable for their application in organic electronics. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metalized, three-dimensional structured oxygen cathode materials for lithium/air batteries and method for making and using the same

DOEpatents

Xing, Weibing; Buettner-Garrett, Josh

2017-04-18

This disclosure relates generally to cathode materials for electrochemical energy cells, more particularly to metal/air electrochemical energy cell cathode materials containing silver vanadium oxide and methods of making and using the same. The metal/air electrochemical energy cell can be a lithium/air electrochemical energy cell. Moreover the silver vanadium oxide can be a catalyst for one or more of oxidation and reduction processes of the electrochemical energy cell.

Vanadium Recovery from Oil Fly Ash by Carbon Removal and Roast-Leach Process

NASA Astrophysics Data System (ADS)

Jung, Myungwon; Mishra, Brajendra

2018-02-01

This research mainly focuses on the recovery of vanadium from oil fly ash by carbon removal and the roast-leach process. The oil fly ash contained about 85% unburned carbon and 2.2% vanadium by weight. A vanadium-enriched product was obtained after carbon removal, and the vanadium content of this product was 19% by weight. Next, the vanadium-enriched product was roasted with sodium carbonate to convert vanadium oxides to water-soluble sodium metavanadate. The roasted sample was leached with water at 60°C, and the extraction percentage of vanadium was about 92% by weight. Several analytical techniques, such as inductively coupled plasma atomic emission spectroscopy (ICP-AES), x-ray fluorescence (XRF), and thermogravimetric and differential thermal analysis (TG-DTA), were utilized for sample analyses. Thermodynamic modeling was also conducted with HSC chemistry software to explain the experimental results.

Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Xinbo; Wang, Danjun; College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an 716000

2014-09-15

Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalystmore » is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.« less

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

PubMed

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.

Protective effect of alpha glucosyl hesperidin (G-hesperidin) on chronic vanadium induced testicular toxicity and sperm nuclear DNA damage in male Sprague Dawley rats.

PubMed

Vijaya Bharathi, B; Jaya Prakash, G; Krishna, K M; Ravi Krishna, C H; Sivanarayana, T; Madan, K; Rama Raju, G A; Annapurna, A

2015-06-01

The study was conducted to evaluate the vanadium-induced testicular toxicity and its effect on sperm parameters, sperm nuclear DNA damage and histological alterations in Sprague Dawley rats and to assess the protective effect of G-hesperidin against this damage. Treatment of rats with vanadium at a dose of 1 mg kg bw(-1) for 90 days resulted in significant reduction in serum testosterone levels, sperm count and motility. Further, a parallel increase in abnormal sperm morphology and adverse histopathological changes in testis was also associated with vanadium administration when compared to normal control. Moreover, sperm chromatin dispersion assay revealed that vanadium induces sperm nuclear DNA fragmentation. A marked increase in testicular malondialdehyde levels and decreased activity of antioxidant enzymes such as superoxide dismutase and catalase indicates vanadium-induced oxidative stress. Co-administration of G-hesperidin at a dose of 25 and 50 mg kg bw(-1) significantly attenuated the sperm parameters and histological changes by restoring the antioxidant levels in rat testis. These results suggested that vanadium exposure caused reduced bioavailability of androgens to the tissue and increased free radical formation, thereby causing structural and functional changes in spermatozoa. G-hesperidin exhibited antioxidant effect by protecting the rat testis against vanadium-induced oxidative damage, further ensures antioxidant potential of bioflavonoids. © 2014 Blackwell Verlag GmbH.

Effect of annealing on optical properties and structure of the vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Zhu, Huiqun; Li, Yi; Li, Yuming; Huang, Yize; Tong, Guoxiang; Fang, Baoying; Zheng, Qiuxin; Li, Liu; Shen, Yujian

2012-10-01

VO2 thin films were prepared on soda-lime glass substrates by DC magnetron sputtering at room temperature using vanadium target and post annealing in air. X-ray diffraction and FTIR spectroscopy analyses showed that the films obtained at the optimized parameters have high VO2 (011) orientation. Both low temperature deposition and post annealing method were beneficial to grow the nano-films with pure VO2 phase-structure and composition. Metalinsulator transition properties of the VO2 films in terms of infrared transmittance, transmittance variation and film thickness were investigated under varying annealing temperature. Results showed that infrared transmittance variation and transition temperature of the nano-films were significantly improved and reduced respectively. Therefore, this study was able to develop practical low-cost preparation methods for high-performance intelligent energy-saving thin films.

ION EXCHANGE PROCESS FOR THE RECOVERY AND PURIFICATION OF MATERIALS

DOEpatents

Long, R.S.; Bailes, R.H.

1958-04-15

A process for the recovery of certain metallic ions from aqueous solutions by ion exchange techniques is described. It is applicable to elements such as vanadium, chromium, nnanganese, and the like, which are capable of forming lower valent cations soluble in aqueous solutions and which also form ldgher valent anions soluble in aqueous acidic solutions. For example, small amounts of vanadium occurring in phosphoric acid prepared from phosphate rock may be recovered by reducing the vanadium to a trivalent cation adsorbing; the vanadium in a cationic exchange resin, then treating the resin with a suitable oxidizing agent to convert the adsorbed vanadium to a higher valent state, and finally eluting; the vanadium as an anion from the resin by means of an aqueous acidic solution.

Effect of vanadium compounds on acid phosphatase activity.

PubMed

Vescina, C M; Sálice, V C; Cortizo, A M; Etcheverry, S B

1996-01-01

The direct effect of different vanadium compounds on acid phosphatase (ACP) activity was investigated. Vanadate and vanadyl but not pervanadate inhibited the wheat germ ACP activity. These vanadium derivatives did not alter the fibroblast Swiss 3T3 soluble fraction ACP activity. Using inhibitors of tyrosine phosphatases (PTPases), the wheat germ ACP was partially characterized as a PTPase. This study suggests that the inhibitory ability of different vanadium derivatives to modulate ACP activity seems to depend on the geometry around the vanadium atom more than on the oxidation state. Our results indicate a correlation between the PTPase activity and the sensitivity to vanadate and vanadyl cation.

Insulin and vanadium protect against osteoarthritis development secondary to diabetes mellitus in rats.

PubMed

El Karib, Abbas O; Al-Ani, Bahjat; Al-Hashem, Fahaid; Dallak, Mohammad; Bin-Jaliah, Ismaeel; El-Gamal, Basiouny; Bashir, Salah O; Eid, Refaat A; Haidara, Mohamed A

2016-07-01

Diabetic complications such as cardiovascular disease and osteoarthritis (OA) are among the common public health problems. The effect of insulin on OA secondary to diabetes has not been investigated before in animal models. Therefore, we sought to determine whether insulin and the insulin-mimicking agent, vanadium can protect from developing OA in diabetic rats. Type 1 diabetes mellitus (T1DM) was induced in Sprague-Dawley rats and treated with insulin and/or vanadium. Tissues harvested from the articular cartilage of the knee joint were examined by scanning electron microscopy, and blood samples were assayed for oxidative stress and inflammatory biomarkers. Eight weeks following the induction of diabetes, a profound damage to the knee joint compared to the control non-diabetic group was observed. Treatment of diabetic rats with insulin and/or vanadium differentially protected from diabetes-induced cartilage damage and deteriorated fibrils of collagen fibers. The relative biological potencies were insulin + vanadium > insulin > vanadium. Furthermore, there was about 2- to 5-fold increase in TNF-α (from 31.02 ± 1.92 to 60.5 ± 1.18 pg/ml, p < 0.0001) and IL-6 (from 64.67 ± 8.16 to 338.0 ± 38.9 pg/ml, p < 0.0001) cytokines and free radicals measured as TBARS (from 3.21 ± 0.37 to 11.48 ± 1.5 µM, p < 0.0001) in the diabetic group, which was significantly reduced with insulin and or vanadium. Meanwhile, SOD decreased (from 17.79 ± 8.9 to 8.250.29, p < 0.0001) and was increased with insulin and vanadium. The relative potencies of the treating agents on inflammatory and oxidative stress biomarkers were insulin + vanadium > insulin > vanadium. The present study demonstrates that co-administration of insulin and vanadium to T1DM rats protect against diabetes-induced OA possibly by lowering biomarkers of inflammation and oxidative stress.

[An in vitro study on toxic effect of vanadium-titanium-magnetite dust on alveolar macrophage in rabbits].

PubMed

Song, Y; Chen, Q; Guan, Y

1998-11-01

To study the toxic effect of vanadium-titanium-magnetite (VTM) dust on alveolar macrophage (AM) and its hazardous extent. Survival rates, morphology and function of AM were compared in rabbits exposed to dust of VTM, vanadium oxide, titanium dioxide and silica in various doses and length of time with in vitro cell culture and putamen membrane cover glass transmission electron microscopy, and changes in activities of lactic dehydrogenase (LDH) and acid phosphatase (ACP) in cell culture were measured. Exposure to all the four kinds of dust could lead to decrease in survival rate of AM, increase in activities of LDH and ACP in the cell culture, and changes in their morphology and function to the extent dependent on the nature of dust. Toxic effect of exposure to VTM dust was lower than that to vanadium oxide and silica, but higher than that to titanium dioxide, which had slight toxic effect.

Induced Superconductivity and Engineered Josephson Tunneling Devices in Epitaxial (111)-Oriented Gold/Vanadium Heterostructures.

PubMed

Wei, Peng; Katmis, Ferhat; Chang, Cui-Zu; Moodera, Jagadeesh S

2016-04-13

We report a unique experimental approach to create topological superconductors by inducing superconductivity into epitaxial metallic thin film with strong spin-orbit coupling. Utilizing molecular beam epitaxy technique under ultrahigh vacuum conditions, we are able to achieve (111) oriented single phase of gold (Au) thin film grown on a well-oriented vanadium (V) s-wave superconductor film with clean interface. We obtained atomically smooth Au thin films with thicknesses even down to below a nanometer showing near-ideal surface quality. The as-grown V/Au bilayer heterostructure exhibits superconducting transition at around 3.9 K. Clear Josephson tunneling and Andreev reflection are observed in S-I-S tunnel junctions fabricated from the epitaxial bilayers. The barrier thickness dependent tunneling and the associated subharmonic gap structures (SGS) confirmed the induced superconductivity in Au (111), paving the way for engineering thin film heterostructures based on p-wave superconductivity and nano devices exploiting Majorana Fermions for quantum computing.

Catalytic determination of vanadium in water

USGS Publications Warehouse

Fishman, M. J.; Skougstad, M.W.

1964-01-01

A rapid, accurate, and sensitive spectrophotometric method for the quantitative determination of trace amounts of vanadium in water is based on the catalytic effect of vanadium on the rate of oxidation of gallic acid by persulfate in acid solution. Under given conditions of concentrations of reactants, temperature, and reaction time, the extent of oxidation of gallic acid is proportional to the concentration of vanadium present. Vanadium is determined by measuring the absorbance of the sample at 415 m?? and comparison with standard solutions treated in an identical manner. Concentrations in the range of from 0.1 to 8.0 ??g. per liter may be determined with a standard deviation of 0.2 or less. By reducing the reaction time, the method may be extended to cover the range from 1 to 100 ??g. with a standard deviation of 0.8 or less. Several substances interfere, including chloride above 100 p.p.m., and bromide and iodide in much lower concentrations. Interference from the halides is eliminated or minimized by the addition of mercuric nitrate solution. Most other substances do not interfere at the concentration levels at which they commonly occur in natural waters.

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium- uranium deposit, Henry Basin, Utah

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.; Northrop, H.R.

1990-01-01

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Measurements of the relative amounts of V+3 and V +4 in ore minerals show that V+3 is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V+4. The ore formed as V+4 was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V+3 in oxide minerals or chlorite. Uranium was transported as uranyl ion (U+6), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. Vanadium most likely was derived from the dissolution of iron-titanium oxides. Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation. Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. -from Authors

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

PubMed Central

Zhang, Dong; Sun, Hong-Jun; Wang, Min-Huan; Miao, Li-Hua; Liu, Hong-Zhu; Zhang, Yu-Zhi; Bian, Ji-Ming

2017-01-01

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. PMID:28772673

Design and synthesis of inorganic/organic hybrid electrochemical materials

NASA Astrophysics Data System (ADS)

Harreld, John H.

An ambient pressure method for drying sol-gel materials is developed to synthesize high porosity (80--90%), high surface area vanadium oxide and silica aerogel materials (150--300 and 1000 m2/g for vanadium pentoxide and silica, respectively). The synthesis approach uses liquid exchange to replace the pore fluid with a low surface tension, nonpolar solvent which reduces the capillary pressures developed during drying. The Good-Girifalco interaction parameter is used to calculate pore stresses resulting from drying silica gels from various liquids. Vanadium oxide/polypyrrole hybrid aerogels are prepared using three strategies. These approaches focus on either sequential or consecutive polymerization of the inorganic and organic networks. Microcomposite aerogels are synthesized by encapsulating a dispersion of preformed polypyrrole in a vanadium pentoxide gel. In the second approach, pyrrole is polymerized and doped within the pore volume of preformed vanadium pentoxide gel. When the inorganic and organic precursors are polymerized simultaneously, the resulting gels exhibited a nanometer scaled microstructure with homogeneous distributions of either phases. Through this route, a suitable microstructure and composition for a lithium secondary battery cathode is obtained. Lithiated aerogels of hydrated nickel, cobalt, and mixed nickel-cobalt oxides are synthesized from lithium hydroxide and transition metal acetate precursors. The XRD analyses indicate that the nickel containing gels exhibit a lithium deficiency (less than 1 Li/transition metal. By increasing the concentration of the lithium precursor the lithium content in nickel oxides is increased, and additional base solution is no longer required to catalyze gelation. A non-hydrolytic sol-gel approach is utilized to create tin oxide and tin-aluminum binary oxide aerogels with high porosity (90%) and high surface area (300 m2/g). XRD data from single phase tin oxide aerogel indicates the growth of SnO2 crystallites between 150--400°C in air, accompanied by a reduction in surface area (30 m2/g). Heated tin oxide aerogel exhibits comparable reversible specific capacity (390 mAh/g) as that of commercial SnO2 (420 mAh/g). Amorphous tin oxide aerogel is stabilized to higher temperatures when aluminum oxide is incorporated into the structure. The tin oxide phase remains electrochemically active towards lithium insertion and exhibits excellent reversibility during cycling.

Low-temperature direct synthesis of mesoporous vanadium nitrides for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Lee, Hae-Min; Jeong, Gyoung Hwa; Kim, Sang-Wook; Kim, Chang-Koo

2017-04-01

Mesoporous vanadium nitrides are directly synthesized by a one-step chemical precipitation method at a low temperature (70 °C). Structural and morphological analyses reveal that vanadium nitride consist of long and slender nanowhiskers, and mesopores with diameters of 2-5 nm. Compositional analysis confirms the presence of vanadium in the VN structure, along with oxidized vanadium. The cyclic voltammetry and charge-discharge tests indicate that the obtained material stores charges via a combination of electric double-layer capacitance and pseudocapacitance mechanisms. The vanadium nitride electrode exhibits a specific capacitance of 598 F/g at a current density of 4 A/g. After 5000 charge-discharge cycles, the electrode has an equivalent series resistance of 1.42 Ω and retains 83% of its initial specific capacitance. This direct low-temperature synthesis of mesoporous vanadium nitrides is a simple and promising method to achieve high specific capacitance and low equivalent series resistance for electrochemical capacitor applications.

ROLE OF THE NETWORK FORMER IN SEMICONDUCTING OXIDE GLASSES.

DTIC Science & Technology

SEMICONDUCTOR DEVICES, * GLASS ), (*ELECTRICAL NETWORKS, GLASS ), ELECTRICAL PROPERTIES, SEEBECK EFFECT, BORATES, PHOSPHATES, ELECTRICAL RESISTANCE, X RAY DIFFRACTION, ANNEALING, OXIDATION, OXIDES, ELECTRODES, VANADIUM

Vanadium dioxide as a material to control light polarization in the visible and near infrared

NASA Astrophysics Data System (ADS)

Cormier, Patrick; Son, Tran Vinh; Thibodeau, Jacques; Doucet, Alexandre; Truong, Vo-Van; Haché, Alain

2017-01-01

We report on the possible use of vanadium dioxide to produce ultrathin (<100 nm) adjustable phase retarders working over a wide spectral range. The refractive index of vanadium dioxide undergoes large changes when the material undergoes a phase transition from semiconductor to metal at a temperature of 68 °C. In a thin film, the resulting optical phase shift is different for s- and p-polarizations in both reflection and transmission, and under certain conditions the polarization state changes between linear or circular or between linear polarizations oriented differently when the material phase transitions. Specific ultrathin modulators are proposed based on the results.

Vanadium Electrolyte Studies for the Vanadium Redox Battery-A Review.

PubMed

Skyllas-Kazacos, Maria; Cao, Liuyue; Kazacos, Michael; Kausar, Nadeem; Mousa, Asem

2016-07-07

The electrolyte is one of the most important components of the vanadium redox flow battery and its properties will affect cell performance and behavior in addition to the overall battery cost. Vanadium exists in several oxidation states with significantly different half-cell potentials that can produce practical cell voltages. It is thus possible to use the same element in both half-cells and thereby eliminate problems of cross-contamination inherent in all other flow battery chemistries. Electrolyte properties vary with supporting electrolyte composition, state-of-charge, and temperature and this will impact on the characteristics, behavior, and performance of the vanadium battery in practical applications. This Review provides a broad overview of the physical properties and characteristics of the vanadium battery electrolyte under different conditions, together with a description of some of the processing methods that have been developed to produce vanadium electrolytes for vanadium redox flow battery applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vanadium recycling in the United States in 2004

USGS Publications Warehouse

Goonan, Thomas G.

2011-01-01

As one of a series of reports that describe the recycling of metal commodities in the United States, this report discusses the flow of vanadium in the U.S. economy in 2004. This report includes a description of vanadium supply and demand in the United States and illustrates the extent of vanadium recycling and recycling trends. In 2004, apparent vanadium consumption, by end use, in the United States was 3,820 metric tons (t) in steelmaking and 232 t in manufacturing, of which 17 t was for the production of superalloys and 215 t was for the production of other alloys, cast iron, catalysts, and chemicals. Vanadium use in steel is almost entirely dissipative because recovery of vanadium from steel scrap is chemically impeded under the oxidizing conditions in steelmaking furnaces. The greatest amount of vanadium recycling is in the superalloy, other-alloy, and catalyst sectors of the vanadium market. Vanadium-bearing catalysts are associated with hydrocarbon recovery and refining in the oil industry. In 2004, 2,850 t of vanadium contained in alloy scrap and spent catalysts was recycled, which amounted to about 44 percent of U.S. domestic production. About 94 percent of vanadium use in the United States was dissipative (3,820 t in steel/4,050 t in steel+fabricated products).

Exploratory Phase Transition-Based Switches Using Functional Oxides

DTIC Science & Technology

2011-02-02

TECHNICAL REPORT Abstract Vanadium dioxide ( VO2 ) undergoes a sharp metal-insulator transition (MIT) in the vicinity of room temperature and there is...18 The mechanisms governing metal-insulator transition (MIT) in vanadium dioxide ( VO2 ) is an intensively explored subject in condensed matter...textured vanadium dioxide films were grown on single crystal Al2O3 (0001) substrates by RF-sputtering from a VO2 target (99.5%, AJA International Inc

Effect of W addition on the electrical switching of VO{sub 2} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajeswaran, Bharathi, E-mail: rajeswaran.bharathi@gmail.com, E-mail: rbharathi@mrc.iisc.ernet.in; Umarji, Arun M.

2016-03-15

Vanadium Oxide has been a frontrunner in the field of oxide electronics because of its metal-insulator transition (MIT). The interplay of different structures of VO{sub 2} has played a crucial role in deciding the magnitude of the first order MIT. Substitution doping has been found to introduce different polymorphs of VO{sub 2}. Hence the role of substitution doping in stabilizing the competing phases of VO{sub 2} in the thin film form remains underexplored. Consequently there have been reports both discounting and approving such a stabilization of competing phases in VO{sub 2}. It is reported in the literature that the bandwidthmore » of the hysteresis and transition temperature of VO{sub 2} can be tuned by substitutional doping of VO{sub 2} with W. In this work, we have adopted a novel technique called, Ultrasonic Nebulized Spray Pyrolysis of Aqueous Combustion Mixture (UNSPACM) to deposit VO{sub 2} and W- doped VO{sub 2} as thin films. XRD and Raman spectroscopy were used to investigate the role of tungsten on the structure of VO{sub 2} thin films. Morphology of the thin films was found to be consisting of globular and porous nanoparticles of size ∼ 20 nm. Transition temperature decreased with the addition of W. We found that for 2.0 at % W doping in VO{sub 2}, the transition temperature has reduced from 68 {sup o} C to 25 {sup o} C. It is noted that W-doping in the process of reducing the transition temperature, alters the local structure and also increases room temperature carrier concentration.« less

Exploring the Chemistry and Biology of Vanadium-dependent Haloperoxidases*

PubMed Central

Winter, Jaclyn M.; Moore, Bradley S.

2009-01-01

Nature has developed an exquisite array of methods to introduce halogen atoms into organic compounds. Most of these enzymes are oxidative and require either hydrogen peroxide or molecular oxygen as a cosubstrate to generate a reactive halogen atom for catalysis. Vanadium-dependent haloperoxidases contain a vanadate prosthetic group and utilize hydrogen peroxide to oxidize a halide ion into a reactive electrophilic intermediate. These metalloenzymes have a large distribution in nature, where they are present in macroalgae, fungi, and bacteria, but have been exclusively characterized in eukaryotes. In this minireview, we highlight the chemistry and biology of vanadium-dependent haloperoxidases from fungi and marine algae and the emergence of new bacterial members that extend the biological function of these poorly understood halogenating enzymes. PMID:19363038

Adsorption of Vanadium (V) from SCR Catalyst Leaching Solution and Application in Methyl Orange.

PubMed

Sha, Xuelong; Ma, Wei; Meng, Fanqing; Wang, Ren; Fuping, Tian; Wei, Linsen

2016-12-01

  In this study, we explored an effective and low-cost catalyst and its adsorption capacity and catalytic capacity for Methyl Orange Fenton oxidation degradation were investigated. The catalyst was directly prepared by reuse of magnetic iron oxide (Fe3O4) after saturated adsorption of vanadium (V) from waste SCR (Selective Catalytic Reduction) catalyst. The obtained catalyst was characterized by FTIR, XPS and the results showed that vanadium (V) adsorption process of Fe3O4 nanoparticles was non-redox reaction. The effects of pH, adsorption kinetics and equilibrium isotherms of adsorption were assessed. Adsorption of vanadium (V) ions by Fe3O4 nanoparticles could be well described by the Sips isotherm model which controlled by the mixed surface reaction and diffusion (MSRDC) adsorption kinetic model. The results show that vanadium (V) was mainly adsorbed on external surface of the Fe3O4 nanoparticles. The separation-recovering tungsten (VI) and vanadium (V) from waste SCR catalyst alkaline solution through pH adjustment was also investigated in this study. The results obtained from the experiments indicated that tungsten (VI) was selectively adsorbed from vanadium (V)/tungsten (VI) mixed solution in certain acidic condition by Fe3O4 nanoparticle to realize their recovery. Tungsten (V) with some impurity can be obtained by releasing from adsorbent, which can be confirmed by ICP-AES. The Methyl Orange degradation catalytic performance illustrated that the catalyst could improve Fenton reaction effectively at pH = 3.0 compare to Fe3O4 nanoparticles alone. Therefore, Fe3O4 nanoparticle adsorbed vanadium (V) has a potential to be employed as a heterogeneous Fenton-like catalyst in the present contribution, and its catalytic activity was mainly evaluated in terms of the decoloration efficiency of Methyl Orange.

Microbial Reduction and Precipitation of Vanadium by Shewanella oneidensis

PubMed Central

Carpentier, W.; Sandra, K.; De Smet, I.; Brigé, A.; De Smet, L.; Van Beeumen, J.

2003-01-01

Shewanella oneidensis couples anaerobic oxidation of lactate, formate, and pyruvate to the reduction of vanadium pentoxide (VV). The bacterium reduces VV (vanadate ion) to VIV (vanadyl ion) in an anaerobic atmosphere. The resulting vanadyl ion precipitates as a VIV-containing solid. PMID:12788772

The fabrication and visible-near-infrared optical modulation of vanadium dioxide/silicon dioxide composite photonic crystal structure

NASA Astrophysics Data System (ADS)

Liang, Jiran; Li, Peng; Song, Xiaolong; Zhou, Liwei

2017-12-01

We demonstrated a visible and near-infrared light tunable photonic nanostructure, which is composed of vanadium dioxide (VO2) thin film and silicon dioxide (SiO2) ordered nanosphere arrays. The vanadium films were sputtered on two-dimensional (2D) SiO2 sphere arrays. VO2 thin films were prepared by rapid thermal annealing (RTA) method with different oxygen flow rates. The close-packed VO2 shell formed a continuous surface, the composition of VO2 films in the structure changed when the oxygen flow rates increased. The 2D VO2/SiO2 composite photonic crystal structure exhibited transmittance trough tunability and near-infrared (NIR) transmittance modulation. When the oxygen flow rate increased from 3 slpm to 4 slpm, the largest transmittance trough can be regulated from 904 to 929 nm at low temperature, the transmittance troughs also appear blue shift when the VO2 phase changes from insulator to metal. The composite nanostructure based on VO2 films showed visible transmittance tunability, which would provide insights into the glass color changing in smart windows.

An Ultrastable Heterobimetallic Uranium(IV)/Vanadium(III) Solid Compound Protected by a Redox-Active Phosphite Ligand: Crystal Structure, Oxidative Dissolution, and First-Principles Simulation.

PubMed

Gui, Daxiang; Dai, Xing; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Chen, Lanhua; Zhang, Chao; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2018-02-05

The first heterobimetallic uranium(IV)/vanadium(III) phosphite compound, Na 2 UV 2 (HPO 3 ) 6 (denoted as UVP), was synthesized via an in situ redox-active hydrothermal reaction. It exhibits superior hydrolytic and antioxidant stability compared to the majority of structures containing low-valent uranium or vanadium, further elucidated by first-principles simulations, and therefore shows potential applications in nuclear waste management.

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

PubMed

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.

Structure-property relationships in NO x sensor materials composed of arrays of vanadium oxide nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Putrevu, Naga Ravikanth; Darling, Seth B.; Segre, Carlo U.

The mixed-valent vanadium oxide based three-dimensional framework structure species [Cd 3(H 2O) 12V 16 IVV 2 VO 36(OH) 6(AO 4)]∙24H 2O, (A=V,S) (Cd 3(VO) o) represents a rare example of an interesting sensor material which exhibits NO x {NO+NO 2} semiconducting gas sensor properties under ambient conditions. The electrical resistance of the sensor material Cd 3(VO) o decreases in air. Combined characterization studies revealed that the building block, {V 18O 42(AO 4)} 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 vanadiummore » which results in an increase in the oxidation state as well as the coordination number of vanadium center and decrease in band gap of Cd 3(VO) o. Based on these results we propose that the changes in semiconducting properties of Cd 3(VO) o under ambient conditions are due to the greater overlap between the O 2p and V 3d orbitals occurring during the oxidation.« less

Vanadium Redox Flow Batteries Using meta-Polybenzimidazole-Based Membranes of Different Thicknesses.

PubMed

Noh, Chanho; Jung, Mina; Henkensmeier, Dirk; Nam, Suk Woo; Kwon, Yongchai

2017-10-25

15, 25, and 35 μm thick meta-polybenzimidazole (PBI) membranes are doped with H 2 SO 4 and tested in a vanadium redox flow battery (VRFB). Their performances are compared with those of Nafion membranes. Immersed in 2 M H 2 SO 4 , PBI absorbs about 2 mol of H 2 SO 4 per mole of repeat unit. This results in low conductivity and low voltage efficiency (VE). In ex-situ tests, meta-PBI shows a negligible crossover of V 3+ and V 4+ ions, much lower than that of Nafion. This is due to electrostatic repulsive forces between vanadium cations and positively charged protonated PBI backbones, and the molecular sieving effect of PBI's nanosized pores. It turns out that charge efficiency (CE) of VRFBs using meta-PBI-based membranes is unaffected by or slightly increases with decreasing membrane thickness. Thick meta-PBI membranes require about 100 mV larger potentials to achieve the same charging current as thin meta-PBI membranes. This additional potential may increase side reactions or enable more vanadium ions to overcome the electrostatic energy barrier and to enter the membrane. On this basis, H 2 SO 4 -doped meta-PBI membranes should be thin to achieve high VE and CE. The energy efficiency of 15 μm thick PBI reaches 92%, exceeding that of Nafion 212 and 117 (N212 and N117) at 40 mA cm -2 .

BRIEF COMMUNICATIONS: Q switching of a resonator by the metal-semiconductor phase transition

NASA Astrophysics Data System (ADS)

Bugaev, A. A.; Zakharchenya, Boris P.; Chudnovskiĭ, F. A.

1981-12-01

An experimental study was made of Q switching in a resonator by a mirror with a nonlinear reflection coefficient. This mirror was an interference reflecting structure containing a vanadium oxide film capable of undergoing a metal-semiconductor transition. The nonlinearity of the reflection coefficient was due to initiation of this phase transition by laser radiation. A determination was made of the parameters of a giant radiation pulse obtained using such a passive switch with a vanadium oxide film.

Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

DOEpatents

Rohrmann, Charles A.

1978-01-01

A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

Vanadium doped tin dioxide as a novel sulfur dioxide sensor.

PubMed

Das, S; Chakraborty, S; Parkash, O; Kumar, D; Bandyopadhyay, S; Samudrala, S K; Sen, A; Maiti, H S

2008-04-15

Considering the short-term exposure limit of SO2 to be 5 ppm, we first time report that semiconductor sensors based on vanadium doped SnO2 can be used for SO2 leak detection because of their good sensitivity towards SO2 at concentrations down to 5 ppm. Such sensors are quite selective in presence of other gases like carbon monoxide, methane and butane. The high sensitivity of vanadium doped tin dioxide towards SO2 may be understood by considering the oxidation of sulfur dioxide to sulfur trioxide on SnO2 surface through redox cycles of vanadium-sulfur-oxygen adsorbed species.

Influence of low concentration V and Co oxide doping on the dissolution behaviors of simplified nuclear waste glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Xiaonan; Neeway, James J.; Ryan, Joseph V.

Transition metal oxides are commonly present in nuclear waste and they can alter the structure, property and especially dissolution behaviors of the glasses used for waste immobilization. In this paper, we investigated vanadium and cobalt oxide induced structural and properties changes, especially dissolution behaviors, of International Simple Glass (ISG), a model nuclear waste glass system. Static chemical durability tests were performed at 90 °C with a pH value of 7 and a surface-area-to-solution-volume of 200 m-1 for 112 days on three glasses: ISG, ISG doped with 0.5 mol% Co2O3, and ISG doped with 2.0 mol% V2O5. ICP-MS was used tomore » analyze the dissolved ion concentrations. It was found that doping with vanadium and cobalt oxide, even at the low doping concentration, significantly reduced the extent of the ISG glass dissolution. Differential Scanning Calorimetry (DSC) analysis showed that vanadium oxide doping reduced the glass transition temperature (Tg) while cobalt oxide did not significantly change the Tg of ISG. X-ray diffraction (XRD), Raman spectrometry and scanning electron microscopy (SEM) were used to analyze the glass samples before and after corrosion to understand the phase and microstructure changes.« less

A general synthesis strategy for the multifunctional 3D polypyrrole foam of thin 2D nanosheets

NASA Astrophysics Data System (ADS)

Xue, Jiangli; Mo, Maosong; Liu, Zhuming; Ye, Dapeng; Cheng, Zhihua; Xu, Tong; Qu, Liangti

2018-05-01

A 3D macroporous conductive polymer foam of thin 2D polypyrrole (PPy) nanosheets is developed by adopting a novel intercalation of guest (monomer Py) between the layers of the lamellar host (3D vanadium oxide foam) template-replication strategy. The 3D PPy foam of thin 2D nanosheets exhibits diverse functions including reversible compressibility, shape memory, absorption/adsorption and mechanically deformable supercapacitor characteristics. The as-prepared 3D PPy foam of thin nanosheets is highly light weight with a density of 12 mg·cm-3 which can bear the large compressive strain up to 80% whether in wet or dry states; and can absorb organic solutions or extract dye molecules fast and efficiently. In particular, the PPy nanosheet-based foamas a mechanically deformable electrode material for supercapacitors exhibits high specific capacitance of 70 F·g-1 at a fast charge-discharge rate of 50 mA·g-1, superior to that of any other typical pure PPy-based capacitor. We envision that the strategy presented here should be applicable to fabrication of a wide variety of organic polymer foams and hydrogels of low-dimensional nanostructures and even inorganic foams and hydrogels of low-dimensional nanostructures, and thus allow for exploration of their advanced physical and chemical properties.

A general synthesis strategy for the multifunctional 3D polypyrrole foam of thin 2D nanosheets

NASA Astrophysics Data System (ADS)

Xue, Jiangli; Mo, Maosong; Liu, Zhuming; Ye, Dapeng; Cheng, Zhihua; Xu, Tong; Qu, Liangti

2018-06-01

A 3D macroporous conductive polymer foam of thin 2D polypyrrole (PPy) nanosheets is developed by adopting a novel intercalation of guest (monomer Py) between the layers of the lamellar host (3D vanadium oxide foam) template-replication strategy. The 3D PPy foam of thin 2D nanosheets exhibits diverse functions including reversible compressibility, shape memory, absorption/adsorption and mechanically deformable supercapacitor characteristics. The as-prepared 3D PPy foam of thin nanosheets is highly light weight with a density of 12 mg·cm-3 which can bear the large compressive strain up to 80% whether in wet or dry states; and can absorb organic solutions or extract dye molecules fast and efficiently. In particular, the PPy nanosheet-based foam as a mechanically deformable electrode material for supercapacitors exhibits high specific capacitance of 70 F·g-1 at a fast charge-discharge rate of 50 mA·g-1, superior to that of any other typical pure PPy-based capacitor. We envision that the strategy presented here should be applicable to fabrication of a wide variety of organic polymer foams and hydrogels of low-dimensional nanostructures and even inorganic foams and hydrogels of low-dimensional nanostructures, and thus allow for exploration of their advanced physical and chemical properties.

Iron Drinking Water Pipe Corrosion Products: Concentrators of Toxic Metals

DTIC Science & Technology

2013-01-01

health risk. In addition Pb corrosion products may be sinks for other metals such as chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn). These...Vanadium K-Edge X-ray Absorption Near-Edge Structure Interpretation: Application to the Speciation of Vanadium in Oxide Phases from Steel Slag ’, Journal

New High Capacity Cathode Materials for Rechargeable Li-ion Batteries: Vanadate-Borate Glasses

NASA Astrophysics Data System (ADS)

Afyon, Semih; Krumeich, Frank; Mensing, Christian; Borgschulte, Andreas; Nesper, Reinhard

2014-11-01

V2O5 based materials are attractive cathode alternatives due to the many oxidation state switches of vanadium bringing about a high theoretical specific capacity. However, significant capacity losses are eminent for crystalline V2O5 phases related to the irreversible phase transformations and/or vanadium dissolution starting from the first discharge cycle. These problems can be circumvented if amorphous or glassy vanadium oxide phases are employed. Here, we demonstrate vanadate-borate glasses as high capacity cathode materials for rechargeable Li-ion batteries for the first time. The composite electrodes of V2O5 - LiBO2 glass with reduced graphite oxide (RGO) deliver specific energies around 1000 Wh/kg and retain high specific capacities in the range of ~ 300 mAh/g for the first 100 cycles. V2O5 - LiBO2 glasses are considered as promising cathode materials for rechargeable Li-ion batteries fabricated through rather simple and cost-efficient methods.

New high capacity cathode materials for rechargeable Li-ion batteries: vanadate-borate glasses.

PubMed

Afyon, Semih; Krumeich, Frank; Mensing, Christian; Borgschulte, Andreas; Nesper, Reinhard

2014-11-19

V2O5 based materials are attractive cathode alternatives due to the many oxidation state switches of vanadium bringing about a high theoretical specific capacity. However, significant capacity losses are eminent for crystalline V2O5 phases related to the irreversible phase transformations and/or vanadium dissolution starting from the first discharge cycle. These problems can be circumvented if amorphous or glassy vanadium oxide phases are employed. Here, we demonstrate vanadate-borate glasses as high capacity cathode materials for rechargeable Li-ion batteries for the first time. The composite electrodes of V2O5 - LiBO(2) glass with reduced graphite oxide (RGO) deliver specific energies around 1000 Wh/kg and retain high specific capacities in the range of ~ 300 mAh/g for the first 100 cycles. V2O5 - LiBO(2) glasses are considered as promising cathode materials for rechargeable Li-ion batteries fabricated through rather simple and cost-efficient methods.

Structural investigation of phosphate - bismuth glasses with vanadium

NASA Astrophysics Data System (ADS)

Stǎnescu, R.; Vedeanu, N.; Cozar, I. B.; Mǎgdaş, A.

2013-11-01

The xV2O5(1-dx)[0.5P2O5ṡ0.5Bi2O3] glass system with 0 ≤ x ≤ 50 mol% is investigated by IR and Raman spectroscopy. Both P2O5 and Bi2O3 oxides are known as network formers, but Bi2O3 is an unconventional one. At low content of vanadium oxide (x ≤ 5 mol%), both IR and Raman spectra are dominated by vibration bands characteristics to structural groups of phosphate and bismuthate lattices. Due to the network modifier role, vanadium oxide acts mainly on the Bi2O3 network allowing the phosphate groups to impose their characteristics absorption bands in spectra. These bands are strongly reduced for x ≥ 20 mol% due to the phosphate network depolymerization and the appearance of new vibrations characteristic to P-O-V, Bi-O-V and V-O-V groups showing the network former role of V2O5.

New High Capacity Cathode Materials for Rechargeable Li-ion Batteries: Vanadate-Borate Glasses

PubMed Central

Afyon, Semih; Krumeich, Frank; Mensing, Christian; Borgschulte, Andreas; Nesper, Reinhard

2014-01-01

V2O5 based materials are attractive cathode alternatives due to the many oxidation state switches of vanadium bringing about a high theoretical specific capacity. However, significant capacity losses are eminent for crystalline V2O5 phases related to the irreversible phase transformations and/or vanadium dissolution starting from the first discharge cycle. These problems can be circumvented if amorphous or glassy vanadium oxide phases are employed. Here, we demonstrate vanadate-borate glasses as high capacity cathode materials for rechargeable Li-ion batteries for the first time. The composite electrodes of V2O5 – LiBO2 glass with reduced graphite oxide (RGO) deliver specific energies around 1000 Wh/kg and retain high specific capacities in the range of ~ 300 mAh/g for the first 100 cycles. V2O5 – LiBO2 glasses are considered as promising cathode materials for rechargeable Li-ion batteries fabricated through rather simple and cost-efficient methods. PMID:25408200

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

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. Wemore » 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.« less

Ultrahigh-Power Pseudocapacitors Based on Ordered Porous Heterostructures of Electron-Correlated Oxides.

PubMed

Lang, Xing-You; Liu, Bo-Tian; Shi, Xiang-Mei; Li, Ying-Qi; Wen, Zi; Jiang, Qing

2016-05-01

Nanostructured transition-metal oxides can store high-density energy in fast surface redox reactions, but their poor conductivity causes remarkable reductions in the energy storage of most pseudocapacitors at high power delivery (fast charge/discharge rates). Here it is shown that electron-correlated oxide hybrid electrodes made of nanocrystalline vanadium sesquioxide and manganese dioxide with 3D and bicontinuous nanoporous architecture (NP V 2 O 3 /MnO 2 ) have enhanced conductivity because of metallization of electron-correlated V 2 O 3 skeleton via insulator-to-metal transition. The conductive V 2 O 3 skeleton at ambient temperature enables fast electron and ion transports in the entire electrode and facilitates charge transfer at abundant V 2 O 3 /MnO 2 interface. These merits significantly improve the pseudocapacitive behavior and rate capability of the constituent MnO 2 . Symmetric pseudocapacitors assembled with binder-free NP V 2 O 3 /MnO 2 electrodes deliver ultrahigh electrical powers (up to ≈422 W cm 23 ) while maintaining the high volumetric energy of thin-film lithium battery with excellent stability.

Electron affinity of cubic boron nitride terminated with vanadium oxide

NASA Astrophysics Data System (ADS)

Yang, Yu; Sun, Tianyin; Shammas, Joseph; Kaur, Manpuneet; Hao, Mei; Nemanich, Robert J.

2015-10-01

A thermally stable negative electron affinity (NEA) for a cubic boron nitride (c-BN) surface with vanadium-oxide-termination is achieved, and its electronic structure was analyzed with in-situ photoelectron spectroscopy. The c-BN films were prepared by electron cyclotron resonance plasma-enhanced chemical vapor deposition employing BF3 and N2 as precursors. Vanadium layers of ˜0.1 and 0.5 nm thickness were deposited on the c-BN surface in an electron beam deposition system. Oxidation of the metal layer was achieved by an oxygen plasma treatment. After 650 °C thermal annealing, the vanadium oxide on the c-BN surface was determined to be VO2, and the surfaces were found to be thermally stable, exhibiting an NEA. In comparison, the oxygen-terminated c-BN surface, where B2O3 was detected, showed a positive electron affinity of ˜1.2 eV. The B2O3 evidently acts as a negatively charged layer introducing a surface dipole directed into the c-BN. Through the interaction of VO2 with the B2O3 layer, a B-O-V layer structure would contribute a dipole between the O and V layers with the positive side facing vacuum. The lower enthalpy of formation for B2O3 is favorable for the formation of the B-O-V layer structure, which provides a thermally stable surface dipole and an NEA surface.

Thin film materials and devices for resistive temperature sensing applications

NASA Astrophysics Data System (ADS)

Basantani, Hitesh A.

Thin films of vanadium oxide (VOx) and hydrogenated amorphous silicon (a-Si:H) are the two dominant material systems used in resistive infrared radiation detectors (microbolometers) for sensing long wave infrared (LWIR) wavelengths in the 8--14 microm range. Typical thin films of VO x (x < 2) currently used in the bolometer industry have a magnitude of temperature coefficient of resistance (TCR) between 2%/K -- 3%/K. In contrast, thin films of hydrogenated germanium (SiGe:H) have |TCR| between 3%/K to 4%/K. Devices made from either of these materials have resulted in similar device performance with NETD ≈ 25 mK. The performance of the microbolometers is limited by the electronic noise, especially 1/f noise. Therefore, regardless of the choice of bolometer sensing material and read out circuitry, manufacturers are constantly striving to reduce 1/f noise while simultaneously increasing TCR to give better signal to noise ratios in their bolometers and ultimately, better image quality with more thermal information to the end user. In this work, thin films of VOx and hydrogenated germanium (Ge:H), having TCR values > 4 %/K are investigated as potential candidates for higher sensitivity next generation of microbolometers. Thin films of VO x were deposited by Biased Target Ion Beam Deposition (BTIBD) (˜85 nm thick). Electrical characterization of lateral resistor structures showed resistivity ranging from 104 O--cm to 2.1 x 104 O--cm, TCR varying from --4%/K to --5%/K, normalized Hooge parameter (alphaH/n) of 5 x 10 -21 to 5 x 10-18 cm3. Thin films of Ge:H were deposited by plasma enhanced chemical vapor deposition (PECVD) by incorporating an increasing amount of crystal fraction in the growing thin films. Thin films of Ge:H having a mixed phase, amorphous + nanocrystalline, having a |TCR| > 6 %/K were deposited with resistivity < 2,300 O--cm and a normalized Hooge's parameter 'alphaH/n' < 2 x 10-20 cm3. Higher TCR materials are desired, however, such materials have higher resistivity and therefore unacceptable large electrical resistance in a lateral resistor configuration. This work looks at an alternate bolometer device design which incorporates higher TCR materials in a vertically integrated configuration. Thin films of high TCR hydrogenated germanium (Ge:H, |TCR| > 6%/K) and vanadium oxide (VOx, TCR > 5%/K) were integrated in lateral and through film configuration. The electrical performance of the vertically integrated devices is compared with lateral resistance structures. It was confirmed experimentally that the device impedance was significantly lowered while maintaining the signal to noise ratio of the lateral resistor configuration. The vertically integrated devices allow higher device currents without any increase in self heating. These structures may help reduce integration time and may result in higher frame rate. Finally, one dimensional arrays were fabricated using both lateral and vertically integrated configurations and their performance was evaluated. It was found that the performance of the lateral devices was limited by noise floor of the measurement setup used. However, due to the lower impedance of the vertically integrated resistors, a higher signal and therefore higher signal to noise ratio could be obtained. These vertically integrated devices exhibited low RMS noise values of 12 mK.

System Assessment of Carbon Dioxide Used as Gas Oxidant and Coolant in Vanadium-Extraction Converter

NASA Astrophysics Data System (ADS)

Du, Wei Tong; Wang, Yu; Liang, Xiao Ping

2017-10-01

With the aim of reducing carbon dioxide (CO2) emissions and of using waste resources in steel plants, the use of CO2 as a gas oxidant and coolant in the converter to increase productivity and energy efficiency was investigated in this study. Experiments were performed in combination with thermodynamic theory on vanadium-extraction with CO2 and oxygen (O2) mixed injections. The results indicate that the temperature of the hot metal bath decreased as the amount of CO2 introduced into O2 increased. At an injection of 85 vol.% O2 and 15 vol.% CO2, approximately 12% of additional carbon was retained in the hot metal. Moreover, the content of vanadium trioxide in the slag was higher. In addition, the O2 consumption per ton of hot metal was reduced by 8.5% and additional chemical energy was recovered by the controlled injection of CO2 into the converter. Therefore, using CO2 as a gas coolant was conducive to vanadium extraction, and O2 consumption was reduced.

Evaluating electrically insulating films deposited on V-4% Cr-4% Ti by reactive CVD

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, J.H.; Cho, W.D.

1997-04-01

Previous CaO coatings on V-4%Cr-4%Ti exhibited high-ohmic insulator behavior even though a small amount of vanadium from the alloy was incorporated in the coating. However, when the vanadium concentration in the coatings is > 15 wt%, the coating becomes conductive. When the vanadium concentration is high in localized areas, a calcium vanadate phase that exhibits semiconductor behavior can form. To explore this situation, CaO and Ca-V-O coatings were produced on vanadium alloys by chemical vapor deposition (CVD) and by a metallic-vapor process to investigate the electrical resistance of the coatings. Initially, the vanadium alloy specimens were either charged with oxygenmore » in argon that contained trace levels of oxygen, or oxidized for 1.5-3 h in a 1% CO-CO{sub 2} gas mixture or in air to form vanadium oxide at 625-650{degrees}C. Most of the specimens were exposed to calcium vapor at 800-850{degrees}C. Initial and final weights were obtained to monitor each step, and surveillance samples were removed for examination by optical and scanning electron microscopy and electron-energy-dispersive and X-ray diffraction analysis; the electrical resistivity was also measured. The authors found that Ca-V-O films exhibited insulator behavior when the ratio of calcium concentration to vanadium concentration R in the film was > 0.9, and semiconductor or conductor behavior for R < 0.8. However, in some cases, semiconductor behavior was observed when CaO-coated samples with R > 0.98 were exposed in liquid lithium. Based on these studies, the authors conclude that semiconductor behavior occurs if a conductive calcium vanadate phase is present in localized regions in the CaO coating.« less

Stopped-in-loop flow analysis system for successive determination of trace vanadium and iron in drinking water using their catalytic reactions.

PubMed

Ayala Quezada, Alejandro; Ohara, Keisuke; Ratanawimarnwong, Nuanlaor; Nacapricha, Duangjai; Murakami, Hiroya; Teshima, Norio; Sakai, Tadao

2015-11-01

An automated stopped-in-loop flow analysis (SILFA) system is proposed for the successive catalytic determination of vanadium and iron. The determination of vanadium was based on the p-anisidine oxidation by potassium bromate in the presence of Tiron as an activator to form a reddish dye, which has an absorption maximum at 510 nm. The selectivity of the vanadium determination was greatly improved by adding diphosphate as a masking agent of iron. For the iron determination, an iron-catalyzed oxidative reaction of p-anisidine by hydrogen peroxide with 1,10-phenanthroline as an activator to produce a reddish dye (510 nm) was employed. The SILFA system consisted of two peristaltic pumps, two six-port injection valves, a four-port selection valve, a heater device, a spectrophotometric detector and a data acquisition device. One six-port injection valve was used for the isolation of a mixed solution of standard/sample and reagent to promote each catalytic reaction, and another six-port injection valve was used for switching the reagent for vanadium or iron to achieve selective determination of each analyte. The above mentioned four-port selection valve was used to select standard solutions or sample. These three valves and the two peristaltic pumps were controlled by a built-in programmable logic controller in a touchscreen controller. The obtained results showed that the proposed SILFA monitoring system constituted an effective approach for the selective determination of vanadium and iron. The limits of detection, 0.052 and 0.55 µg L(-1), were obtained for vanadium and iron, respectively. The proposed system was successfully applied to drinking water samples without any preconcentration procedures. Copyright © 2015 Elsevier B.V. All rights reserved.

High-Fat Diet Increased Renal and Hepatic Oxidative Stress Induced by Vanadium of Wistar Rat.

PubMed

Wang, J P; Cui, R Y; Zhang, K Y; Ding, X M; Luo, Y H; Bai, S P; Zeng, Q F; Xuan, Y; Su, Z W

2016-04-01

The study was conducted to assess the effect of vanadium (V) in high-fat diet on the liver and kidney of rats in a 5-week trial. Seventy-two female Wistar rats (BW = 95 ± 5 g) were randomly allotted into eight groups. Groups I, II, III, and IV obtained low-fat diet containing 0, 3, 15, and 30 mg/kg V, and V, VI, VII, and VIII groups received the respective vanadium doses with high-fat diet, respectively. There were lesions in the liver and kidney of V, VI, VII, and VIII groups, granular degeneration and vacuolar degeneration were observed in the renal tubular and glomerulus epithelial cells, and hepatocytes showed granular degeneration and vacuolar degeneration. Supplemented high-fat diet with vanadium was shown to decrease (P < 0.05) activities of superoxide dismutase, total antioxidant capacity, glutathione-S transferase, and NAD(P)H/quinone oxidoreductase 1 (NQO1) and increase malondialdehyde content in the liver and kidney. The relative expression of hepatic nuclear factor erythroid 2-related factor 2 (Nrf-2) and NQO1 mRNA was downregulated by V addition and high-fat diet, and the effect of V was more pronounced in high-fat diet (interaction, P < 0.05), with VIII group having the lowest mRNA expression of Nrf-2 and NQO1 in the liver and kidney. In conclusion, it suggested that dietary vanadium ranging from 15 to 30 mg/kg could lead to oxidative damage and vanadium accumulation in the liver and kidney, which caused renal and hepatic toxicity. The high-fat diet enhanced vanadium-induced hepatic and renal damage, and the mechanism was related to the modulation of the hepatic and renal mRNA expression of Nrf-2 and NQO1.

Reduction and Smelting of Vanadium Titanomagnetite Metallized Pellets

NASA Astrophysics Data System (ADS)

Wang, Shuai; Chen, Mao; Guo, Yufeng; Jiang, Tao; Zhao, Baojun

2018-04-01

Reduction and smelting of the vanadium titanomagnetite metallized pellets have been experimentally investigated in this study. By using the high-temperature smelting, rapid quenching, and electron probe x-ray microanalysis (EPMA) technique, the effects of basicity, reaction time, and graphite reductant amount were investigated. The vanadium contents in iron alloys increase with increasing basicity, reaction time, and graphite amount, whereas the FeO and V2O3 concentrations in the liquid phase decrease with the increase of graphite amount and reaction time. Increasing the reaction time and reductant content promotes the reduction of titanium oxide, whereas the reduction of titanium oxides can be suppressed with increasing the slag basicity. Titanium carbide (TiC) was not observed in all the quenched samples under the present conditions. The experimental results and the FactSage calculations are also compared in the present study.

A method for the determination of vanadium and iron oxidation states in naturally occurring oxides and silicates

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.

1985-01-01

A valence-specific analytical method for determining V3+ in ore minerals has been developed that involves two steps: dissolution of a mineral sample without disturbing the V3+/Vtot ratio, followed by determination of V3+ in the presence of V4+. The samples are dissolved in a mixture of hydrofluoric and sulphuric acids at 100?? in Teflon-lined reaction vessels. Tervalent vanadium is then determined colorimetrically by formation of a V3+-thiocyanate complex in aqueous-acetone medium. Fe3+ is measured semi-quantitatively in the same solution. The method has been tested with two naturally occurring samples containing vanadium and iron. The results obtained were supported by those obtained by other methods, including electron spin resonance spectroscopy, thermogravimetric analysis, and Mo??ssbauer spectroscopy. ?? 1985.

Scandia-Stabilized Zirconia Coating for Composites.

DTIC Science & Technology

1990-04-03

are present as oxides, acids and as in U.S. Pat. No. 4,328,285, describes some of the prior free sulfur . art attempts to coat engine parts with ceramic...base Because vanadium pentoxide (V205 ) is an acidic ox- materials, and Siemers teaches using cerium oxide or ide, it reacts with Na2O (a highly...surfaces exposed to vanadium and compounds decreases with the V2Os/Na2O ratio from sulfur compound corrosion. Na2V 120 31 (most acidic ) to Na3VO4(least

Hydrothermal Synthesis of Nanostructured Vanadium Oxides

PubMed Central

Livage, Jacques

2010-01-01

A wide range of vanadium oxides have been obtained via the hydrothermal treatment of aqueous V(V) solutions. They exhibit a large variety of nanostructures ranging from molecular clusters to 1D and 2D layered compounds. Nanotubes are obtained via a self-rolling process while amazing morphologies such as nano-spheres, nano-flowers and even nano-urchins are formed via the self-assembling of nano-particles. This paper provides some correlation between the molecular structure of precursors in the solution and the nanostructure of the solid phases obtained by hydrothermal treatment. PMID:28883325

Effectively suppressing vanadium permeation in vanadium redox flow battery application with modified Nafion membrane with nacre-like nanoarchitectures

NASA Astrophysics Data System (ADS)

Zhang, Lesi; Ling, Ling; Xiao, Min; Han, Dongmei; Wang, Shuanjin; Meng, Yuezhong

2017-06-01

A novel self-assembled composite membrane, Nafion-[PDDA/ZrP]n with nacre-like nanostructures was successfully fabricated by a layer-by-layer (LbL) method and used as proton exchange membrane for vanadium redox flow battery applications. Poly(diallyldimethylammonium chloride) (PDDA) with positive charges and zirconium phosphate (ZrP) nanosheets with negative charges can form ultra-thin nacre-like nanostructure on the surface of Nafion membrane via the ionic crosslinking of tightly folded macromolecules. The lamellar structure of ZrP nanosheets and Donnan exclusion effect of PDDA can greatly decrease the vanadium ion permeability and improve the selectivity of proton conductivity. The fabricated Nafion-[PDDA/ZrP]4 membrane shows two orders of magnitude lower vanadium ion permeability (1.05 × 10-6 cm2 min-1) and 12 times higher ion selectivity than those of pristine Nafion membrane at room temperature. Consequently, the performance of vanadium redox flow batteries (VRFBs) assembled with Nafion-[PDDA/ZrP]3 membrane achieved a highly coulombic efficiency (CE) and energy efficiency (EE) together with a very slow self-discharge rate. When comparing with pristine Nafion VRFB, the CE and EE values of Nafion-[PDDA/ZrP]3 VRFB are 10% and 7% higher at 30 mA cm-2, respectively.

A HIGHLY EFFICIENT OXIDATION OF CYCLOHEXANE OVER VPO CATALYSTS USING HYDROGEN PEROXIDE

EPA Science Inventory

An unprecedented and highly efficient oxidation of cyclohexane to cyclohexanol and cyclohexanone is accomplished over calcined vanadium phosphorus oxide (VPO) catalysts in a relatively mild condition using hydrogen peroxide under a nitrogen atmosphere.

Geochemical controls on vanadium accumulation in fossil fuels

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1989-01-01

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Geochemical controls of vanadium accumulation in fossil fuels

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1989-01-01

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

High capacity electrode materials for batteries and process for their manufacture

DOEpatents

Johnson, Christopher S.; Xiong, Hui; Rajh, Tijana; Shevchenko, Elena; Tepavcevic, Sanja

2018-04-03

The present invention provides a nanostructured metal oxide material for use as a component of an electrode in a lithium-ion or sodium-ion battery. The material comprises a nanostructured titanium oxide or vanadium oxide film on a metal foil substrate, produced by depositing or forming a nanostructured titanium dioxide or vanadium oxide material on the substrate, and then charging and discharging the material in an electrochemical cell from a high voltage in the range of about 2.8 to 3.8 V, to a low voltage in the range of about 0.8 to 1.4 V over a period of about 1/30 of an hour or less. Lithium-ion and sodium-ion electrochemical cells comprising electrodes formed from the nanostructured metal oxide materials, as well as batteries formed from the cells, also are provided.

Catalytic properties of the VO x /Ce0.46Zr0.54O2 oxide system in the oxidative dehydrogenation of propane

NASA Astrophysics Data System (ADS)

Turakulova, A. O.; Kharlanov, A. N.; Levanov, A. V.; Isaikina, O. Ya.; Lunin, V. V.

2017-01-01

Ce0.46Zr0.54O2 solid solution prepared using a cellulose template was employed as a carrier for vanadium catalysts of the oxidative dehydrogenation of propane. The properties of VO x /Ce0.46Zr0.54O2 catalyst (5 wt % vanadium) are compared with the properties of the neat support. The carrier and catalyst are studied by means of BET, SEM, DTA, XRD, and Raman spectroscopy. It is shown that the CeVO4 phase responsible for the ODH process is formed upon interaction between vanadate ions and cerium ions on the surface of the solid solution. The catalytic properties of the catalyst and the support are studied in the propane oxidation reaction at temperatures of 450 and 500°C with pulse feeding of the reagent. It is found that the complete oxidation of propane occurs on the support with formation of CO2 and H2O. Three products (propene, CO2, and H2O) form in the presence of the vanadium catalyst. It is suggested that there are two types of catalytic centers on the catalyst's surface. It is concluded that the centers responsible for the complete oxidation of propane are concentrated mainly on the carrier, while the centers responsible for propane ODH are on the CeVO4.

Low Permeable Hydrocarbon Polymer Electrolyte Membrane for Vanadium Redox Flow Battery.

PubMed

Jung, Ho-Young; Moon, Geon-O; Jung, Seunghun; Kim, Hee Tak; Kim, Sang-Chai; Roh, Sung-Hee

2017-04-01

Polymer electrolyte membrane (PEM) confirms the life span of vanadium redox flow battery (VRFB). Products from Dupont, Nafion membrane, is mainly used for PEM in VRFB. However, permeation of vanadium ion occurs because of Nafion’s high permeability. Therefore, the efficiency of VRFB decreases and the prices becomes higher, which hinders VRFB’s commercialization. In order to solve this problem, poly(phenylene oxide) (PPO) is sulfonated for the preparation of low-priced hydrocarbon polymer electrolyte membrane. sPPO membrane is characterized by fundamental properties and VRFB cell test.

The Reactivity and Structure of Size Selected VxO y Clusters on a TiO2 (110)-(1 X 1) Surface of Variable Oxidation State

NASA Astrophysics Data System (ADS)

Neilson, Hunter L.

The Reactivity and Structure of Size Selected VxOy Clusters on a TiO2 (110) Surface of Variable Oxidation State by Hunter L Neilson The selective oxidative dehydrogenation of methanol by vanadium oxide/TiO2 model systems has received a great deal of interest in the surface science community. Previous studies using temperature programmed desorption and reaction (TPD/R) to probe the oxidation of methanol to formaldehyde by vanadia/TiO2 model catalysts have shown that the activity of these systems vary considerably based on the way in which the model system is prepared with formaldehyde desorption temperatures observed anywhere from room temperature to 660 K. The principle reason for this variation is that the preparation of sub-monolayer films of vanadia on TiO2 produces clusters with a multitude of VxOy structures and a mixture of vanadium oxidation states. As a result the stoichiometry of the active vanadium oxide catalyst as well as the oxidation state of vanadium in the active catalyst remain unknown. To better understand this system, our group has probed the reactivity and structure of size-selected Vx, VOy and VxOy clusters on a reduced TiO2 (110) support in ultra-high vacuum (UHV) via TPD/R and scanning tunneling microscopy (STM). Ex situ preparation of these clusters in the gas phase prior to deposition has allowed us to systematically vary the stoichiometry of the vanadia clusters; a layer of control not available via the usual routes to vanadium oxide. The most active catalysts are shown to have (VO3)n stoichiometry in agreement with the theoretical models of the Metiu group. We have shown that both the activity and selectivity of V2O6 and V3O9 cluster catalysts depend sensitively on the oxidation state of the TiO2 (110) support. For example, V2O6 on a reduced surface is selective for the oxidation of methanol to formaldehyde while the selectivity shifts to favor methyl formate as the surface becomes increasingly oxidized. STM studies show that the structure of size-selected V2O6 clusters, upon adsorption to the surface, varies considerably with the oxidation state of the support, in good agreement with our reactivity studies. V 3O9 was shown to catalyze the oxidation of methanol to both formaldehyde and methyl formate on a reduced surface while STM suggests that, unlike V2O6, these clusters are prone to decomposition upon adsorption to the surface. Furthermore, TPD/R of size selected V 2O5 and V2O7 on TiO2 suggests that altering the stoichiometry of the (VO3)n clusters by a single oxygen atom significantly inhibits the activity of these catalysts.

Influence of amorphous structure on polymorphism in vanadia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stone, Kevin H.; Schelhas, Laura T.; Garten, Lauren M.

Normally we think of the glassy state as a single phase and therefore crystallization from chemically identical amorphous precursors should be identical. Here we show that the local structure of an amorphous precursor is distinct depending on the initial deposition conditions, resulting in significant differences in the final state material. Using grazing incidence total x-ray scattering, we have determined the local structure in amorphous thin films of vanadium oxide grown under different conditions using pulsed laser deposition (PLD). Here we show that the subsequent crystallization of films deposited using different initial PLD conditions result in the formation of different polymorphsmore » of VO 2. Ultimately this suggests the possibility of controlling the formation of metastable polymorphs by tuning the initial amorphous structure to different formation pathways.« less

Influence of amorphous structure on polymorphism in vanadia

DOE PAGES

Stone, Kevin H.; Schelhas, Laura T.; Garten, Lauren M.; ...

2016-07-13

Normally we think of the glassy state as a single phase and therefore crystallization from chemically identical amorphous precursors should be identical. Here we show that the local structure of an amorphous precursor is distinct depending on the initial deposition conditions, resulting in significant differences in the final state material. Using grazing incidence total x-ray scattering, we have determined the local structure in amorphous thin films of vanadium oxide grown under different conditions using pulsed laser deposition (PLD). Here we show that the subsequent crystallization of films deposited using different initial PLD conditions result in the formation of different polymorphsmore » of VO 2. Ultimately this suggests the possibility of controlling the formation of metastable polymorphs by tuning the initial amorphous structure to different formation pathways.« less

HYDROCARBON OXIDATION OVER VANADIUM PHOSPHORUS OXIDE CATALYST USING HYDROGEN PEROXIDE

EPA Science Inventory

Selective oxidation of hydrocarbons is one of the very important and challenging areas in industrial chemistry due to the wide ranging utility of the resulting oxygenates in fine chemical synthesis. Most of the existing processes for their oxidations employ toxic and often stoich...

Electrochemically-Induced Redox Reactions in Basalt at High Pressure and Temperature: An Iron and Vanadium K-edge XANES Study

NASA Astrophysics Data System (ADS)

Kavner, A.; Walker, D.; Newville, M.; Sutton, S. R.

2005-12-01

An applied electric field across a silicate sample at high pressures and temperatures in a piston cylinder apparatus can generate a wide range of oxidation states of polyvalent cations within a single experiment. If two or more polyvalent cations are included, this technique can be used to cross-calibrate oxybarometers within a single experiment. The redox state of Fe and V within a partially melted basaltic silicate was manipulated in situ in a piston-cylinder experiment with a DC power supply providing a source and sink of electrons to the sample. A 1V electrical potential differential was applied across vanadium-doped and Fe-bearing synthetic basalt samples for 24 hrs. at 20 kbar and 1400°C in a specially-designed piston cylinder sample assembly. Three experiments were performed: a control sample with no applied voltage, one with bottom cathode and top anode, and a third with top cathode and bottom anode. Synchrotron-based x-ray absorption near edge structure (XANES) spectroscopy was used to provide spot analysis of iron and vanadium oxidation states with 5μm x 5μm spatial resolution throughout the recovered samples. Systematic spatial changes of increasing oxidation states of V and Fe were observed approaching the anode. The differences in oxidation states were mapped to a corresponding local effective oxygen fugacity by comparison and extension of a calibration of vanadium oxidation states as a function of controlled oxygen fugacity from a previous study (Sutton et al., 2005, GCA, vol. 69, pp. 2333-2348). The vanadium mapping indicates that a 1V potential drop across the sample induces effective oxygen fugacity perturbations in excess of ten orders of magnitude. The presence of both Fe and V within the same sample provides a wide range of oxygen fugacity cross-calibration in these recovered samples. A relationship between oxygen fugacity and electrochemical driving force is derived. The experimental results are in good agreement with the derived relationship between applied electrochemical potential difference (the 1V in this experiment), and corresponding calculated oxygen fugacity.

Hydrothermal vanadium manganese oxides: Anode and cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Simões, Mário; Surace, Yuri; Yoon, Songhak; Battaglia, Corsin; Pokrant, Simone; Weidenkaff, Anke

2015-09-01

Vanadium manganese oxides with Mn content up to 33 at% were synthesized by a low temperature hydrothermal route allowing for the preparation of both anodic and cathodic materials for Li-ion batteries. Low amounts of manganese (below 13 at%) lead to the formation of elongated particles of layered hydrated vanadium oxides with manganese and water intercalated between the V2O5 slabs, while for higher Mn content of 33 at%, monoclinic MnV2O6 is formed. Former materials are suitable for high energy cathodes while the latter one is an anodic compound. The material containing 10 at% Mn has the composition Mn0.2V2O5·0.9H2O and shows the best cathodic activity with 20% capacity improvement over V2O5·0.5H2O. Lithiated MnV2O6 with Li5MnV2O6 composition prepared electrochemically was evaluated for the first time as anode in a full-cell against Mn0.2V2O5·0.9H2O cathode. An initial capacity ca. 300 A h kg-1 was measured with this battery corresponding to more than 500 Wh kg-1. These results confirm the prospect of using Li5MnV2O6 anodes in lithium-ion batteries as well as high-capacity layered hydrated vanadium oxides cathodes such as V2O5·0.5H2O and Mn0.2V2O5·0.9H2O.

Template-free vapor-phase growth of patrónite by atomic layer deposition

DOE PAGES

Weimer, Matthew S.; McCarthy, Robert F.; Emery, Jonathan D.; ...

2017-03-09

Despite challenges to control stoichiometry in the vanadium-sulfur system, template-free growth of patrónite, VS 4, thin films is demonstrated for the first time. A novel atomic layer deposition (ALD) process enables the growth of phase pure films and the study of electrical and vibrational properties of the quasi-one-dimensional (1D) transition metal sulfide. Self-limiting surface chemistry during ALD of VS4 is established via in situ quartz crystal microbalance and quadrupole mass spectrometry between 150 to 200 °C. The V precursor, unconventionally, sheds all organic components in the first half-cycle, while the H 2S half-cycle generates the disulfide dimer moiety, S 2more » -2, and oxidizes V 3+ to V 4+. X-ray analysis establishes VS 4 crystallinity and phase purity, as well as a self-limiting growth rate of 0.33 Å/cy, modest roughness (2.4 nm) and expected density (2.7g/cm 3 ). Phase pure films enable a new assignment of vibrational modes and corresponding Raman activity of VS4 that is corroborated by density functional theory (DFT) calculations. Lastly, at elevated growth temperatures, a change in the surface mechanism provides a synthetic route to a second vanadium-sulfur phase, V 2S 3.« less

Effect of Vanadium and Sodium Compounds on Accelerated Oxidation of Nickel-Base Alloys.

DTIC Science & Technology

The product of the reaction between V2O5 and the substrates is dependent upon the alloying elements present in the alloy. In the absence of alloying...reaction appears to be a glass . The study is related to corrosion inhibitions in vanadium containing fuels in gas turbines. (Modified author abstract)

Vanadium-Catalyzed C(sp3)–H Fluorination Reactions†

PubMed Central

Xia, Ji-Bao; Ma, Yuyong; Chen, Chuo

2014-01-01

Vanadium(III) oxide catalyzes the direct fluorination of C(sp3)–H groups with Selectfluor. This reaction is operationally simple. The catalyst and the reaction byproduct can be removed easily by filtration. Using this method, a fluorine atom can be introduced to the tertiary position of 1,4-cineole and L-menthone selectively. PMID:24976971

Determination of the oxidation states of metals and metalloids: An analytical review

NASA Astrophysics Data System (ADS)

Vodyanitskii, Yu. N.

2013-12-01

The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

Computational studies of small neutral vanadium oxide clusters and their reactions with sulfur dioxide

NASA Astrophysics Data System (ADS)

Jakubikova, Elena; He, Sheng-Gui; Xie, Yan; Matsuda, Yoshiyuki; Bernstein, Elliot

2007-03-01

Vanadium oxide is a catalytic system that plays an important role in the conversion of SO2 to SO3. Density functional theory at the BPW91/LANL2DZ level is employed to obtain structures of VOy (y=1,,5), V2Oy (y=2,,7), V3Oy (y=4,,9), V4Oy (y=7,,12) and their complexes with SO2. BPW91/LANL2DZ is insufficient to describe properly relative V-O and S-O bond strengths of vanadium and sulfur oxides. Calibration of theoretical results with experimental data is necessary to compute enthalpies of reactions between VxOy and SO2. Theoretical results indicate SO2 to SO conversion occurs for oxygen-deficient clusters and SO2 to SO3 conversion occurs for oxygen-rich clusters. Subsequent experimental studies confirm the presence of SO in the molecular beam as well as the presence of VxOy complexes with SO2. Some possible mechanisms for SO3 formation and catalyst regeneration for solids are also suggested.

Substrate Temperature effect on the transition characteristics of Vanadium (IV) oxide

NASA Astrophysics Data System (ADS)

Yang, Tsung-Han; Wei, Wei; Jin, Chunming; Narayan, Jay

2008-10-01

One of the semiconductor to metal transition material (SMT) is Vanadium Oxide (VO2) which has a very sharp transition temperature close to 340 K as the crystal structure changes from monoclinic phase (semiconductor) into tetragonal phase (metal phase). We have grown high-quality epitaxial vanadium oxide (VO2) films on sapphire (0001) substrates by pulsed laser deposition for oxygen pressure 10-2torr and obtained interesting results without further annealing treatments. The epitaxial growth via domain matching epitaxy, where integral multiples of planes matched across the film-substrate interface. We were able to control the transition characteristics such as the sharpness (T), amplitude (A) of SMT transition and the width of thermal hysteresis (H) by altering the substrate temperature from 300 ^oC, 400 ^oC, 500 ^oC, and 600 ^oC. We use the XRD to identify the microstructure of film and measure the optical properties of film. Finally the transition characteristics is observed by the resistance with the increase of temperature by Van Der Pauw method from 25 to 100 ^oC to measure the electrical resistivity hystersis loop during the transition temperature.

A well-defined terminal vanadium(III) oxo complex.

PubMed

King, Amanda E; Nippe, Michael; Atanasov, Mihail; Chantarojsiri, Teera; Wray, Curtis A; Bill, Eckhard; Neese, Frank; Long, Jeffrey R; Chang, Christopher J

2014-11-03

The ubiquity of vanadium oxo complexes in the V+ and IV+ oxidation states has contributed to a comprehensive understanding of their electronic structure and reactivity. However, despite being predicted to be stable by ligand-field theory, the isolation and characterization of a well-defined terminal mononuclear vanadium(III) oxo complex has remained elusive. We present the synthesis and characterization of a unique terminal mononuclear vanadium(III) oxo species supported by the pentadentate polypyridyl ligand 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine (PY5Me2). Exposure of [V(II)(NCCH3)(PY5Me2)](2+) (1) to either dioxygen or selected O-atom-transfer reagents yields [V(IV)(O)(PY5Me2)](2+) (2). The metal-centered one-electron reduction of this vanadium(IV) oxo complex furnishes a stable, diamagnetic [V(III)(O)(PY5Me2)](+) (3) species. The vanadium(III) oxo species is unreactive toward H- and O-atom transfer but readily reacts with protons to form a putative vanadium hydroxo complex. Computational results predict that further one-electron reduction of the vanadium(III) oxo species will result in ligand-based reduction, even though pyridine is generally considered to be a poor π-accepting ligand. These results have implications for future efforts toward low-valent vanadyl chemistry, particularly with regard to the isolation and study of formal vanadium(II) oxo species.

Trimetallic oxide nanocomposites of transition metals titanium and vanadium by sol-gel technique: synthesis, characterization and electronic properties

NASA Astrophysics Data System (ADS)

Kumar, Amit; Mishra, Neeraj Kumar; Sachan, Komal; Ali, Md Asif; Soaham Gupta, Sachchidanand; Singh, Rajeev

2018-04-01

Novel titanium and vanadium based trimetallic oxide nanocomposites (TMONCs) have been synthesized using metal salts of titanium-vanadium along with three others metals viz. tin, aluminium and zinc as precursors by the sol-gel method. Aqueous ammonia and hydrazine hydrate were used as the reducing agents. The preparations of nanocomposites were monitored by observing the visual changes during each step of synthesis. The synthesized TMONCs were characterized using UV–vis, SEM, EDX, TEM and DLS. Band gap of the synthesized TMONCs ranges from 3–4.5 eV determined using tauc plot. FTIR study revealed the molecular stretching and bending peaks of corresponding M–O/M–O–M bonds thus confirming their formation. Molecular composition and particle size were determined using EDX and DLS respectively. Molecular shape, size and surface morphology have been examined by SEM and TEM.

Reductive transformation of V(iii) precursors into vanadium(ii) oxide nanowires.

PubMed

Ojelere, Olusola; Graf, David; Ludwig, Tim; Vogt, Nicholas; Klein, Axel; Mathur, Sanjay

2018-05-15

Vanadium(ii) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium(iii) complexes with bi-dentate O,N-chelating heteroarylalkenol ligands (DmoxCH[double bond, length as m-dash]COCF3, PyCH[double bond, length as m-dash]COCF3 and PyN[double bond, length as m-dash]COCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. The chemical identity of V(iii) complexes and their redox behaviour were unambiguously established by single crystal X-ray diffraction studies, cyclic voltammetry, spectrometric studies and DFT calculations. Transformation into the metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures, respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Zhicheng; Rao, Linfeng; Abney, Carter W.

Adsorbents developed for the recovery of uranium from seawater display poor selectivity over other transition metals present in the ocean, with vanadium particularly problematic. To improve selectivity, an indispensable step is the positive identification of metal binding environments following actual seawater deployment. In this work we apply x-ray absorption fine structure (XAFS) spectroscopy to directly investigate the vanadium binding environment on seawater-deployed polyamidoxime adsorbents. Comparison of the x-ray absorption near edge spectra (XANES) reveal marked similarities to recently a reported non-oxido vanadium (V) structure formed upon binding with cyclic imidedioxime, a byproduct of generating amidoxime functionalities. Density functional theory (DFT)more » calculations provided a series of putative vanadium binding environments for both vanadium (IV) and vanadium (V) oxidation states, and with both amidoxime and cyclic imidedioxime. Fits of the extended XAFS (EXAFS) data confirmed vanadium (V) is bound exclusively by the cyclic imidedioxime moiety in a 1:2 metal:ligand fashion, though a modest structural distortion is also observed compared to crystal structure data and computationally optimized geometries which is attributed to morphology effects from the polymer graft chain and the absence of crystal packing interactions. These results demonstrate that improved selectivity for uranium over vanadium can be achieved by suppressing the formation of cyclic imidedioxime during preparation of polyamidoxime adsorbents for seawater uranium recovery.« less

Effect of film thickness on NO2 gas sensing properties of sprayed orthorhombic nanocrystalline V2O5 thin films

NASA Astrophysics Data System (ADS)

Mane, A. A.; Moholkar, A. V.

2017-09-01

The nanocrystalline V2O5 thin films with different thicknesses have been grown onto the glass substrates using chemical spray pyrolysis (CSP) deposition method. The XRD study shows that the films exhibit an orthorhombic crystal structure. The narrow scan X-ray photoelectron spectrum of V-2p core level doublet gives the binding energy difference of 7.3 eV, indicating that the V5+ oxidation state of vanadium. The FE-SEM micrographs show the formation of nanorods-like morphology. The AFM micrographs show the high surface area to volume ratio of nanocrystalline V2O5 thin films. The optical study gives the band gap energy values of 2.41 eV, 2.44 eV, 2.47 eV and 2.38 eV for V2O5 thin films deposited with the thicknesses of 423 nm, 559 nm, 694 nm and 730 nm, respectively. The V2O5 film of thickness 559 nm shows the NO2 gas response of 41% for 100 ppm concentration at operating temperature of 200 °C with response and recovery times of 20 s and 150 s, respectively. Further, it shows the rapid response and reproducibility towards 10 ppm NO2 gas concentration at 200 °C. Finally, NO2 gas sensing mechanism based on chemisorption process is discussed.

CATALYTIC OXIDATION OF ALCOHOLS AND EPOXIDATION OF OLEFINS WITH HYDROGEN PEROXIDE AS OXIDANT

EPA Science Inventory

Hydrogen peroxide (H2O2) is an ideal oxidant of choice for these oxidations due to economic and environmental reasons by giving water as a by-product. Two catalysts used are vanadium phosphorus oxide (VPO) and Fe3+/montmorillonite-K10 catalyst prepared by ion-exchange method at a...

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

NASA Astrophysics Data System (ADS)

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.

Impression of plasma voltage on growth of α-V2O5 nanostructured thin films

NASA Astrophysics Data System (ADS)

Sharma, Rabindar Kumar; Kumar, Prabhat; Reddy, G. B.

2015-06-01

In this communication, we synthesized vanadium pentoxide (α-V2O5) nanostructured thin films (NSTs) accompanied with nanoflakes/ nanoplates on the Ni-coated glass substrates employing plasma assisted sublimation process (PASP) as a function of plasma voltage (Vp). The effect of plasma voltage on structural, morphological, compositional, and vibrational properties have been studied systematically. The structural analysis divulged that all films deposited at different Vp have pure orthorhombic phase, no impurity phase is detected under resolution limit of XRD and XPS. The morphological studies of samples is carried out by SEM, revealed that features as well as alignment of V2O5 NSTs is greatly monitored by Vp and the film possessing the best features is obtained at 2500volt. In addition, XPS results reveal that V5+ oxidation state is the most prominent state in sample V2, which represents better stoichiometric nature of film. The vibrational study of all samples is performed by FTIR and strongly support the XRD observations. All the results are in consonance with each other.

Influence of solution deposition rate on properties of V2O5 thin films deposited by spray pyrolysis technique

NASA Astrophysics Data System (ADS)

Abd-Alghafour, N. M.; Ahmed, Naser M.; Hassan, Zai; Mohammad, Sabah M.

2016-07-01

Vanadium oxide (V2O5) thin films were deposited on glass substrates by using a cost-efficient spray pyrolysis technique. The films were grown at 350° through thermal decomposition of VCl3 in deionized water with different solution spray rates. The high resolution X-ray diffraction results revealed the formation of nanocrystalline films having orthorhombic structures with preferential orientation along (101) direction. The spray rate influenced the surface morphology and crystallite size of the films. The crystallite size was found to increase whereas the micro-strain was decreased by increasing the spray deposition rates. The increase in crystallite size and decrease in the macrostrain resulted in an improvement in the films' crystallinity. The UV-Visible spectroscopy analysis indicated that the average transmittance of all films lies in the range 75-80 %. The band gap of V2O5 film was decreased from 2.65 to 2.46 eV with increase of the spray deposition rate from 5 ml/min to 10 ml/min. first, second, and third level headings (first level heading).

Low temperature fabrication of VO x thin films for uncooled IR detectors by direct current reactive magnetron sputtering method

NASA Astrophysics Data System (ADS)

Dai, Jun; Wang, Xingzhi; He, Shaowei; Huang, Ying; Yi, Xinjian

2008-03-01

Vanadium oxide films have been fabricated on Si3N4-film-coated silicon substrates by direct current reactive magnetron sputtering method. Conditions of deposition are optimized making use of parameters such as sputtering time, dc power, oxygen partial pressure and substrate temperature. X-ray diffraction indicates that the film is a mixture of VO2, V2O3, and V3O5. Four-probe measurement shows that the VOx thin film owns high temperature coefficient of resistance (TCR ∼-2.05%/°C) and suitable square resistance 18.40 kΩ/□ (measured at 25 °C), indicating it is a well candidate material for uncooled IR detectors. In addition, IR absorption in the wavelength of 2-16 μm has been characterized. It is worth noting that the films are sputtered at a relatively low temperature of 210 °C in a controlled Ar/O2 atmosphere. Compared to traditional craft, this method needs no post-anneal at high temperature (400-500 °C).

Template-free synthesis of vanadium oxides nanobelt arrays as high-rate cathode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Qin, Mulan; Liang, Qiang; Pan, Anqiang; Liang, Shuquan; Zhang, Qing; Tang, Yan; Tan, Xiaoping

2014-12-01

A facile hydrothermal route has been developed to fabricate the metastable VO2 (B) ultra-thin nanobelt arrays, which can be converted into V2O5 porous nanobelt arrays after calcinating VO2 (B) in air at 400 °C for 1 h. The influence of hydrothermal time to the crystallinity and morphology of the VO2 phase has been studied. A possible mechanism for the formation of VO2 nanobelt arrays has been proposed in this paper. As a cathode material for lithium ion batteries, the V2O5 nanobelt arrays show excellent rate capability and cycling stability. An initial discharge capacity of 142 mA h g-1 can be delivered at a current density of 50 mA g-1 with almost no capacity fading after 100 cycles. Even at a current density of 1000 mA g-1, they still exhibit the capacity of 130 mA h g-1 and superior capacity retention capability. The excellent electrochemical properties are attributed to the ultra-thin thickness and the porous structures of the nanobelts.

Low temperature electrolytes for lithium/silver vanadium oxide cells

NASA Technical Reports Server (NTRS)

Tuhovak, Denise R.; Takeuchi, Esther S.

1991-01-01

Combinations of methyl formate (MF) and propylene carbonate (PC) using salt concentrations of 0.6 to 2.4 M, with lithium hexafluoroarsenate and lithium tetrafluoroborate in a five to one molar ratio, were investigated as electrolytes in lithium/silver vanadium oxide batteries. The composition of the electrolyte affected cell performance at low temperature, self-discharge and abuse resistance as characterized by short circuit and crush testing. The electrolyte that provided the best combination of good low temperature performance, low cell self-discharge and abuse resistance was 0.6 M salt in 10:90 PC/MF.

Solid-to-solid oxidation of a vanadium(IV) to a vanadium(V) compound: chemisty of a sulfur-containing siderophore.

PubMed

Chatterjee, Pabitra B; Crans, Debbie C

2012-09-03

Visible light facilitates a solid-to-solid photochemical aerobic oxidation of a hunter-green microcrystalline oxidovanadium(IV) compound (1) to form a black powder of cis-dioxidovanadium(V) (2) at ambient temperature. The siderophore ligand pyridine-2,6-bis(thiocarboxylic acid), H(2)L, is secreted by a microorganism from the Pseudomonas genus. This irreversible transformation of a metal monooxo to a metal dioxo complex in the solid state in the absence of solvent is unprecedented. It serves as a proof-of-concept reaction for green chemistry occurring in solid matrixes.

Superconducting and Magnetic Properties of Vanadium/iron Superlattices.

NASA Astrophysics Data System (ADS)

Wong, Hong-Kuen

A novel ultrahigh vacuum evaporator was constructed for the preparation of superlattice samples. The thickness control was much better than an atomic plane. With this evaporator we prepared V/Fe superlattice samples on (0001) sapphire substrates with different thicknesses. All samples showed a good bcc(110) structure. Mossbauer experiments showed that the interface mixing extended a distance of about one atomic plane indicating an almost rectangular composition profile. Because of this we were able to prepare samples with layer thickness approaching one atomic plane. Even with ultrathin Fe layers, the samples are ferromagnetic, at least at lower temperatures. Superparamagnetism and spin glass states were not seen. In the absence of an external field, the magnetic moments lie close to the film plane. In addition to this shape anisotropy, there is some uniaxial anisotropy. No magnetic dead layers have been observed. The magnetic moments within the Fe layers vary little with the distance from the interfaces. At the interfaces the Fe moment is reduced and an antiparallel moment is induced on the vanadium atoms. It is observed that ultrathin Fe layers behave in a 2D fashion when isolated by sufficiently thick vanadium layers; however, on thinning the vanadium layers, a magnetic coupling between the Fe layers has been observed. We also studied the superconducting properties of V/Fe sandwiches and superlattices. In both cases, the Fe layer, a strong pair-breaker, suppresses the superconducting transition temperature consistent with the current knowledge of the magnetic proximity effect. For the sandwiches with thin (thick) vanadium layers, the temperature dependence of the upper critical fields is consistent with the simple theory for a 2D (3D) superconductor. For the superlattices, when the vanadium layer is on the order of the BCS coherence length and the Fe layer is only a few atomic planes thick, a 2D-3D crossover has been observed in the temperature dependence of the parallel upper critical field. This implies the coexistence of superconductivity and ferromagnetism. We observe three dimensional behavior for thinner Fe layers ((TURN)1 atomic plane) and two dimensional behavior for thicker Fe layers (greater than 10 atomic planes).

Enhanced luminous transmittance of thermochromic VO2 thin film patterned by SiO2 nanospheres

NASA Astrophysics Data System (ADS)

Zhou, Liwei; Liang, Jiran; Hu, Ming; Li, Peng; Song, Xiaolong; Zhao, Yirui; Qiang, Xiaoyong

2017-05-01

In this study, an ordered SiO2 nanosphere array coated with vanadium dioxide (VO2) has been fabricated to enhance transmittance with the potential application as an energy-efficient coating in the field of smart windows. SiO2 arrays were formed using the methods of self-assembly, and VO2 thin films were prepared by rapid thermal annealing (RTA) of sputtered vanadium films. VO2@SiO2 arrays were characterized by scanning electron microscopy, X-ray diffraction, a four-point probe, and UV-vis-NIR spectrophotometry. Compared with the planar films, the films deposited on 300 nm diameter SiO2 nanospheres can offer approximately 18% enhancement of luminous transmission (Tlum) because the diameter is smaller than the given wavelength and the protuberance of the surface array behaves as a gradation of refractive index producing antireflection. The solar regulation efficiency was not much deteriorated.

Thermally controlled femtosecond pulse shaping using metasurface based optical filters

NASA Astrophysics Data System (ADS)

Rahimi, Eesa; Şendur, Kürşat

2018-02-01

Shaping of the temporal distribution of the ultrashort pulses, compensation of pulse deformations due to phase shift in transmission and amplification are of interest in various optical applications. To address these problems, in this study, we have demonstrated an ultra-thin reconfigurable localized surface plasmon (LSP) band-stop optical filter driven by insulator-metal phase transition of vanadium dioxide. A Joule heating mechanism is proposed to control the thermal phase transition of the material. The resulting permittivity variation of vanadium dioxide tailors spectral response of the transmitted pulse from the stack. Depending on how the pulse's spectrum is located with respect to the resonance of the band-stop filter, the thin film stack can dynamically compress/expand the output pulse span up to 20% or shift its phase up to 360°. Multi-stacked filters have shown the ability to dynamically compensate input carrier frequency shifts and pulse span variations besides their higher span expansion rates.

Enhancing Modulation of Thermal Conduction in Vanadium Dioxide Thin Film by Nanostructured Nanogaps

DOE PAGES

Choe, Hwan Sung; Suh, Joonki; Ko, Changhyun; ...

2017-08-02

Efficient thermal management at the nanoscale is important for reducing energy consumption and dissipation in electronic devices, lab-on-a-chip platforms and energy harvest/conversion systems. For many of these applications, it is much desired to have a solid-state structure that reversibly switches thermal conduction with high ON/OFF ratios and at high speed. We describe design and implementation of a novel, all-solid-state thermal switching device by nanostructured phase transformation, i.e., modulation of contact pressure an d area between two poly-silicon surfaces activated by microstructural change of a vanadium dioxide (VO 2 ) thin film. Our solid-state devices demonstrate large and reversible alteration ofmore » cross-plane thermal conductance as a function of temperature, achieving a conductance ratio of at least 2.5. This new approach using nanostructured phase transformation provides new opportunities for applications that require advanced temperature and heat regulations.« less

Enhancing Modulation of Thermal Conduction in Vanadium Dioxide Thin Film by Nanostructured Nanogaps

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choe, Hwan Sung; Suh, Joonki; Ko, Changhyun

Efficient thermal management at the nanoscale is important for reducing energy consumption and dissipation in electronic devices, lab-on-a-chip platforms and energy harvest/conversion systems. For many of these applications, it is much desired to have a solid-state structure that reversibly switches thermal conduction with high ON/OFF ratios and at high speed. We describe design and implementation of a novel, all-solid-state thermal switching device by nanostructured phase transformation, i.e., modulation of contact pressure an d area between two poly-silicon surfaces activated by microstructural change of a vanadium dioxide (VO 2 ) thin film. Our solid-state devices demonstrate large and reversible alteration ofmore » cross-plane thermal conductance as a function of temperature, achieving a conductance ratio of at least 2.5. This new approach using nanostructured phase transformation provides new opportunities for applications that require advanced temperature and heat regulations.« less

Effective Recovery of Vanadium from Oil Refinery Waste into Vanadium-Based Metal-Organic Frameworks.

PubMed

Zhan, Guowu; Ng, Wei Cheng; Lin, Wenlin Yvonne; Koh, Shin Nuo; Wang, Chi-Hwa

2018-03-06

Carbon black waste, an oil refinery waste, contains a high concentration of vanadium(V) leftover from the processing of crude oil. For the sake of environmental sustainability, it is therefore of interest to recover the vanadium as useful products instead of disposing of it. In this work, V was recovered in the form of vanadium-based metal-organic frameworks (V-MOFs) via a novel pathway by using the leaching solution of carbon black waste instead of commercially available vanadium chemicals. Two different types of V-MOFs with high levels of crystallinity and phase purity were fabricated in very high yields (>98%) based on a coordination modulation method. The V-MOFs exhibited well-defined and controlled shapes such as nanofibers (length: > 10 μm) and nanorods (length: ∼270 nm). Furthermore, the V-MOFs showed high catalytic activities for the oxidation of benzyl alcohol to benzaldehyde, indicating the strong potential of the waste-derived V-MOFs in catalysis applications. Overall, our work offers a green synthesis pathway for the preparation of V-MOFs by using heavy metals of industrial waste as the metal source.

The determination of vanadium in brines by atomic absorption spectroscopy

USGS Publications Warehouse

Crump-Wiesner, Hans J.; Feltz, H.R.; Purdy, W.C.

1971-01-01

A standard addition method is described for the determination of vanadium in brines by atomic absorption spectroscopy with a nitrous oxide-acetylene flame. Sample pH is adjusted to 1.0 with concentrated hydrochloric acid and the vanadium is directly extracted with 5% cupferron in methyl isobutyl ketone (MIBK). The ketone layer is then aspirated into the flame and the recorded absorption values are plotted as a function of the concentration of the added metal. As little as 2.5 ??g l-1 of vanadium can be detected under the conditions of the procedure. Tungsten and tin interfere when present in excess of 5 and 10 ??g ml-1, respectively. The concentrations of the two interfering ions normally found in brines are well below interference levels. ?? 1971.

Investigation of Phenols Activity in Early Stage Oxidation of Edible Oils by Electron Paramagnetic Resonance and 19F NMR Spectroscopies Using Novel Lipid Vanadium Complexes As Radical Initiators.

PubMed

Drouza, Chryssoula; Dieronitou, Anthi; Hadjiadamou, Ioanna; Stylianou, Marios

2017-06-21

A novel dynamic method for the investigation of the phenols activity in early stage oxidation of edible oils based on the formation of α-tocopheryl radicals initiated by oil-soluble vanadium complexes is developed. Two new vanadium complexes in oxidation states V and IV were synthesized by reacting 2,2'-((2-hydroxyoctadecyl)azanediyl)bis(ethan-1-ol) (C18DEA) with [VO(acac) 2 ] and 1-(bis(pyridin-2-ylmethyl)amino)octadecan-2-ol (C18DPA) with VOCl 2 . Addition of a solution of either complex in edible oils resulted in the formation of α-tocopheryl radical, which was monitored by electron paramagnetic resonance (EPR) spectroscopy. The intensity of the α-tocopheryl signal in the EPR spectra was measured versus time. It was found that the profile of the intensity of the α-tocopheryl signal versus time depends on the type of oil, the phenolic content, and the storage time of the oil. The time interval until the occurrence of maximum peak intensity be reached (t m ), the height of the maximum intensity, and the rate of the quenching of the α-tocopheryl radical were used for the investigation of the mechanism of the edible oils oxidation. 19 F NMR of the 19 F labeled phenolic compounds (through trifluoroacetate esters) and radical trap experiments showed that the vanadium complexes in edible oil activate the one electron reduction of dioxygen to superperoxide radical. Superperoxide reacts with the lipids to form alkoperoxyl and alkoxyl lipid radicals, and all these radicals react with the phenols contained in oils.

Structural direction of hybrid organic-inorganic materials: Synthesis of vanadium oxyfluoride, copper vanadate, and copper molybdate solid state materials through solvuthermal and solution methods

NASA Astrophysics Data System (ADS)

Deburgomaster, Paul

The vast structural complexity of inorganic oxides with structure directing organocations, nitrogen containing ligands and organophosphonate ligands was explored. The hydrothermal reaction conditions utilized herein include the variables of temperature, pH, fill volume and stoichiometry. The systems studied included: (1) the complex materials rendered from reactions of organoamine cations on the structure of vanadium oxides, oxyfluorides and fluorides. As with other systems, the influence of the mineralizer HF was not limited to pH as fluorine incorporation was not uncommon. In specific cases this coincided with reduction of vanadium sites. (2) The copper-organonitrogen ligand/vanadium oxide/aromatic phosphonate system has been studied. The rigid aromatic di- and tri-phosphonate tethers have provided a series of materials which are structurally distinct from the previously investigated aliphatic series. The inclusion of copper-coordinated nitrogen bi- and tri-dentate ligands also provided structural diversity. Product composition was highly influenced by the HF/V ratio. A similar study was conducted with the ligand 1,4-carboxy-phenylphosphonic acid. (3) The preparation of a series of bimetallic organic-inorganic hybrid materials of the M(II)/VxOy/organonitrogen ligand class was further evidence of the utility of thermodynamically driven hydrothermal synthesis. (4) While decomposition of the spherical Keplerate molybdenum clusters is encountered under hydrothermal conditions, this highly soluble form of molybdate was investigated for the development of hybrid organic-inorganic room temperature solution synthesis.

Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

PubMed

Sepehr, Fatemeh; Paddison, Stephen J

2015-06-04

Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane.

UV-vis-DR study of VO x/SiO 2 catalysts prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Moussa, N.; Ghorbel, A.

2008-12-01

Vanadia-silica catalysts with different vanadium loadings were prepared by sol-gel process. UV-vis diffuse-reflectance spectroscopy was used to elucidate the effect of drying mode (i.e., xerogel vs. aerogel), vanadium loading and calcination on the molecular structure of supported vanadium species. The results indicate that for vanadium loading ranging from 2.8 to 11.2 wt.%, the band-gap energies of all catalysts varying from 2.28 to 2.68 eV which demonstrate that vanadium oxides are predominantly in octahedral structure with the presence of tetrahedral species. The discrimination of different surface VO x species has been based on their characteristic Ligand to Metal Charge Transfer (LMCT) O → V(V) and d-d transition. It was found that the LMCT band position of V dbnd O bond is not affected by calcination either in xerogels or in aerogels but the position and the shape of bands relative to bridging V sbnd O sbnd V bonds are affected by vanadium loading, calcination and drying mode. For the same V/Si ratio, band-gap energy of xerogel is lower than that of aerogel which indicate that vanadium species are more dispersed in aerogels than in xerogels. Drying and calcination led to rearrangement, dehydration, cleavage and crystallization of vanadium species which explain the presence of some amount of crystalline V 2O 5 in calcined samples.

A novel process for recovery of iron, titanium, and vanadium from titanomagnetite concentrates: NaOH molten salt roasting and water leaching processes.

PubMed

Chen, Desheng; Zhao, Longsheng; Liu, Yahui; Qi, Tao; Wang, Jianchong; Wang, Lina

2013-01-15

A novel process for recovering iron, titanium, and vanadium from titanomagnetite concentrates has been developed. In the present paper, the treatment of rich titanium-vanadium slag by NaOH molten salt roasting and water leaching processes is investigated. In the NaOH molten salt roasting process, the metallic iron is oxidized into ferriferous oxide, MgTi(2)O(5) is converted to NaCl-type structure of Na(2)TiO(3), and M(3)O(5) (M=Ti, Mg, Fe) is converted to α-NaFeO(2)-type structure of NaMO(2), respectively. Roasting temperature and NaOH-slag mass ratio played a considerable role in the conversion of titanium in the rich titanium-vanadium slag during the NaOH molten salt roasting process. Roasting at 500 °C for 60 min and a 1:1 NaOH-slag mass ratio produces 96.3% titanium conversion. In the water leaching process, the Na(+) was exchanged with H(+), Na(2)TiO(3) is converted to undefined structure of H(2)TiO(3), and NaMO(2) is converted to α-NaFeO(2)-type structure of HMO(2). Under the optimal conditions, 87.3% of the sodium, 42.3% of the silicon, 43.2% of the aluminum, 22.8% of the manganese, and 96.6% of the vanadium are leached out. Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.

Graphene-modified nanostructured vanadium pentoxide hybrids with extraordinary electrochemical performance for Li-ion batteries

DOE PAGES

Liu, Qi; Li, Zhe-Fei; Liu, Yadong; ...

2015-01-20

The long-standing issues of low intrinsic electronic conductivity, slow lithium-ion diffusion and irreversible phase transitions on deep discharge prevent the high specific capacity/energy (443 mAh g -1 and 1,550 Wh kg -1) vanadium pentoxide from being used as the cathode material in practical battery applications. Here we develop a method to incorporate graphene sheets into vanadium pentoxide nanoribbons via the sol–gel process. The resulting graphene-modified nanostructured vanadium pentoxide hybrids contain only 2 wt. % graphene, yet exhibits extraordinary electrochemical performance: a specific capacity of 438 mAh g -1, approaching the theoretical value (443 mAh g -1), a long cyclability andmore » significantly enhanced rate capability. Such performance is the result of the combined effects of the graphene on structural stability, electronic conduction, vanadium redox reaction and lithium-ion diffusion supported by various experimental studies. Finally, this method provides a new avenue to create nanostructured metal oxide/graphene materials for advanced battery applications.« less

Fabrication of vanadium dioxide polycrystalline films with higher temperature coefficient of resistance

NASA Astrophysics Data System (ADS)

Li, Jinhua; Yuan, Ningyi; Jiang, Meiping; Kun, Li

2011-08-01

Vanadium Dioxide Polycrystalline Films with High Temperature Coefficient of Resistance(TCR) were fabricated by modified Ion Beam Enhanced Deposition(IBED) method. The TCR of the Un-doping VO2 was about -4%/K at room temperature after appropriate thermal annealing. The XRD results clearly showed that IBED polycrystalline VO2 films had a single [002] orientation of VO2(M). The TCR of 5at.%W and 7at.% Ta doped Vanadium Dioxide Polycrystalline Films were high up to -18%/K and -12%/K at room temperature, respectively. Using 7at.% Ta and 2at.% Ti co-doping, the TCR of the co-doped vanadium oxide film was -7%/K and without hysteresis during temperature increasing and decresing from 0-80°C. It should indicate that the W-doped vanadium dioxide films colud be used for high sensing IR detect and the Ta/Ti co-doped film without hysteresis is suitable for infrarid imaging application.

Vanadium pentoxide nanoparticles mimic vanadium haloperoxidases and thwart biofilm formation

NASA Astrophysics Data System (ADS)

Natalio, Filipe; André, Rute; Hartog, Aloysius F.; Stoll, Brigitte; Jochum, Klaus Peter; Wever, Ron; Tremel, Wolfgang

2012-08-01

Marine biofouling--the colonization of small marine microorganisms on surfaces that are directly exposed to seawater, such as ships' hulls--is an expensive problem that is currently without an environmentally compatible solution. Biofouling leads to increased hydrodynamic drag, which, in turn, causes increased fuel consumption and greenhouse gas emissions. Tributyltin-free antifouling coatings and paints based on metal complexes or biocides have been shown to efficiently prevent marine biofouling. However, these materials can damage the environment through metal leaching (for example, of copper and zinc) and bacteria resistance. Here, we show that vanadium pentoxide nanowires act like naturally occurring vanadium haloperoxidases to prevent marine biofouling. In the presence of bromide ions and hydrogen peroxide, the nanowires catalyse the oxidation of bromide ions to hypobromous acid (HOBr). Singlet molecular oxygen (1O2) is formed and this exerts strong antibacterial activity, which prevents marine biofouling without being toxic to marine biota. Vanadium pentoxide nanowires have the potential to be an alternative approach to conventional anti-biofouling agents.

Preparation of VO2 thin film and its direct optical bit recording characteristics.

PubMed

Fukuma, M; Zembutsu, S; Miyazawa, S

1983-01-15

Vanadium dioxide (VO2) film which has nearly the same transition point as single crystal has been obtained by reactive evaporation of vanadium on glass and subsequent annealing in N2 gas. Relations between optical properties of V02 film and its preparation conditions are presented. We made optical direct bit recording on V02 film using a laser diode as the light source. The threshold recording energy and bit density are 2 mJ/cm 2 and 350 bits/mm, respectively. We also made tungsten doping to lower the V02 film transition temperature.

Ultrafast electron crystallography of the cooperative reaction path in vanadium dioxide

PubMed Central

Yang, Ding-Shyue; Baum, Peter; Zewail, Ahmed H.

2016-01-01

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. PMID:27376103

Investigation of crossover processes in a unitized bidirectional vanadium/air redox flow battery

NASA Astrophysics Data System (ADS)

grosse Austing, Jan; Nunes Kirchner, Carolina; Komsiyska, Lidiya; Wittstock, Gunther

2016-02-01

In this paper the losses in coulombic efficiency are investigated for a vanadium/air redox flow battery (VARFB) comprising a two-layered positive electrode. Ultraviolet/visible (UV/Vis) spectroscopy is used to monitor the concentrations cV2+ and cV3+ during operation. The most likely cause for the largest part of the coulombic losses is the permeation of oxygen from the positive to the negative electrode followed by an oxidation of V2+ to V3+. The total vanadium crossover is followed by inductively coupled plasma mass spectroscopy (ICP-MS) analysis of the positive electrolyte after one VARFB cycle. During one cycle 6% of the vanadium species initially present in the negative electrolyte are transferred to the positive electrolyte, which can account at most for 20% of the coulombic losses. The diffusion coefficients of V2+ and V3+ through Nafion® 117 are determined as DV2+ ,N 117 = 9.05 ·10-6 cm2 min-1 and DV3+ ,N 117 = 4.35 ·10-6 cm2 min-1 and are used to calculate vanadium crossover due to diffusion which allows differentiation between vanadium crossover due to diffusion and migration/electroosmotic convection. In order to optimize coulombic efficiency of VARFB, membranes need to be designed with reduced oxygen permeation and vanadium crossover.

Determination of the Mass Absorption Coefficient in Two-Layer Ti/V and V/Ti Thin Film Systems by the X-Ray Fluorescence Method

NASA Astrophysics Data System (ADS)

Mashin, N. I.; Chernyaeva, E. A.; Tumanova, A. N.; Gafarova, L. M.

2016-03-01

A new XRF procedure for the determination of the mass absorption coefficient in thin film Ti/V and V/Ti two-layer systems has been proposed. The procedure uses easy-to-make thin-film layers of sputtered titanium and vanadium on a polymer film substrate. Correction coefficients have been calculated that take into account attenuation of primary radiation of the X-ray tube, as well as attenuation of the spectral line of the bottom layer element in the top layer.

Novel sulfonated polyimide/zwitterionic polymer-functionalized graphene oxide hybrid membranes for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Cao, Li; Kong, Lei; Kong, Lingqian; Zhang, Xingxiang; Shi, Haifeng

2015-12-01

Hybrid membranes (SPI/ZGO) composed of sulfonated polyimide (SPI) and zwitterionic polymer-functionalized graphene oxide (ZGO) are fabricated via a solution-casting method for vanadium redox flow battery (VRB). Successful preparation of ZGO fillers and SPI/ZGO hybrid membranes are demonstrated by FT-IR, XPS and SEM, indicating that ZGO fillers is homogeneously dispersed into SPI matrix. Through controlling the interfacial interaction between SPI matrix and ZGO fillers, the physicochemical properties, e.g., vanadium ion barrier and proton transport pathway, of hybrid membranes are tuned via the zwitterionic acid-base interaction in the hybrid membrane, showing a high ion selectivity and good stability with the incorporated ZGO fillers. SPI/ZGO-4 hybrid membrane proves a higher cell efficiencies (CE: 92-98%, EE: 65-79%) than commercial Nafion 117 membrane (CE: 89-94%, EE: 59-70%) for VRB application at 30-80 mA cm-2. The assembled VRB with SPI/ZGO-4 membrane presents a stable cycling charge-discharge performance over 280 times, which demonstrates its excellent chemical stability under the strong acidic and oxidizing conditions. SPI/ZGO hybrid membranes show a brilliant perspective for VRB application.

Modeling of CMOS compatible ring resonator switch with intermediate vanadium oxide as the switching element

NASA Astrophysics Data System (ADS)

Singh, Mandeep; Datta, Arnab

2018-05-01

In this paper, silicon based dual ring resonator with hybrid plasmonic bus waveguides (Cu-SiO2-Si-SiO2-Cu) is investigated for achieving switching in the telecommunication C-band (λ = 1.54-1.553µm). The switch element uses vanadium oxide (VO2) as the switching medium when inserted between the rings in order to tailor transmission from one ring to the other through heating induced phase transition. In this manner, the proposed switch element uses one vanadium oxide medium instead of refractive index tailoring of the whole ring as in the prior reported works and achieves switching response. From two-dimensional finite element analysis we have found that, the proposed switch can achieve maximum extinction ratio of 2.72 dB at λ = 1.5434µm, exclusively by tailoring VO2 phase. Furthermore, impact of aperture width, and gap (separation between the bus waveguide and rings) are investigated to gain insight on the improvement of extinction ratio. From our numerical simulations, we find that free spectral range (FSR) and figure of merit (Q) for OFF and ON states are (173.36 nm, 92.63), and (173.58 nm, 65.39), respectively.

Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

NASA Technical Reports Server (NTRS)

Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

2000-01-01

Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

Synthesis of Nanostructured Carbides of Titanium and Vanadium from Metal Oxides and Ferroalloys Through High-energy Mechanical Milling and Heat Treatment

NASA Astrophysics Data System (ADS)

Basu, P.; Jian, P. F.; Seong, K. Y.; Seng, G. S.; Masrom, A. K.; Hussain, Z.; Aziz, A.

2010-03-01

Carbides of Ti and V have been synthesized directly from their oxides and ferroalloys through mechanical milling and heat treatment. The powder mixtures are milled in a planetary ball mill from 15-80 hours and subsequently heat treated at 1000-1300° C for TiO2-C mixtures, at 500-550° C for V2O5-C mixtures and at 600-1000° C for (Fe-V)-C mixtures. The milled and heat treated powders are characterized by SEM, EDAX, XRD, and BET techniques. Nanostructured TiC has been successfully synthesized under suitable processing conditions. However, carbides of vanadium is unidentified even though possibilities of V2O5-C reaction are indicated with an extent of induced amorphism in the powder mixture. Density, specific surface area and particle size of the milled and heat treated mixtures are correlated with heat treatment temperatures. Similar attempts are also made to synthesize vanadium carbides from industrial grade Fe-V.

Communication—Sol-Gel Synthesized Magnesium Vanadium Oxide, Mg x V 2 O 5 · nH 2 O: The Role of Structural Mg 2+ on Battery Performance

DOE PAGES

Yin, Jiefu; Pelliccione, Christopher J.; Lee, Shu Han; ...

2016-07-12

Magnesium intercalated vanadium oxide xerogels, Mg 0.1V 2O 5 · 2.35H 2O and Mg 0.2V 2O 5 · 2.46H 2O were synthesized using an ion removal sol gel strategy. X-ray diffraction indicated lamellar ordering with turbostratic character. X-ray absorption spectroscopy indicated greater distortion of the vanadium-oxygen coordination environment in Mg 0.2V 2O 5 · 2.46H 2O. Elemental analysis after cycling in Li + or Mg 2+ based electrolytes revealed that the magnesium content was unchanged, indicating structural Mg 2+ are retained. Furthermore, the Mg 0.1V 2O 5 · 2.35H 2O material displayed high voltage, energy density, and discharge/charge efficiency, indicatingmore » promise as a cathode material for future magnesium based batteries.« less

Solid state electrochemical current source

DOEpatents

Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

2002-04-30

A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

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

PubMed

Chen, Desheng; Zhao, Hongxin; Hu, Guoping; Qi, Tao; Yu, Hongdong; Zhang, Guozhi; Wang, Lina; Wang, Weijing

2015-08-30

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 10min, 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 H2SO4 as the stripping agent and under optimal stripping conditions (i.e., 20% H2SO4 concentration, 5:1 phase ratio (O/A), 20min 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 40.16g/LV2O5,0.691g/L Fe, 0.007g/L TiO2, 0.006g/L SiO2 and 0.247g/L CaO. A V2O5 product with a purity of 99.12% V2O5 and only 0.026% Fe was obtained after the oxidation, precipitation, and calcination processes. The total vanadium recovered from the hydrochloric acid leaching solution was 85.5%. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparative erythropoietic effects of three vanadium compounds.

PubMed

Hogan, G R

2000-07-10

The biotoxic effects of vanadium are variable depending upon a number of factors including the oxidation state of the test compound. This study reports the effects of three vanadium compounds on peripheral erythrocytes. On day 0 female ICR mice received a single injection of vanadium chloride (V-III), vanadyl sulfate (V-IV), or sodium orthovandate (V-V). At scheduled intervals post-injection, the number of circulating erythrocytes [red blood cells per millimeter cubed (RBC/mm3)], reticulocyte percentages, and radioiron uptake percentages were determined and compared to mice receiving saline only. Data show that all three test substances promoted a significant lowering of RBC/mm3 beginning on day 1 for V-IV and V-V and on day 2 for V-III through day 4. The reticulocyte percentages increase followed the same time course as that of the peripheral RBC decrease. Peak reticulocytosis was noted on days 2 and 4 for all three vanadium-treated groups; for V-IV and V-V the increase continued to day 6. Radioiron data showed an erythropoietic stimulation by a significant increase in uptake percentages on days 4-6 after vanadium injections compared to saline-treated controls.

Microstructural and opto-electrical properties of chromium nitride films implanted with vanadium ions

NASA Astrophysics Data System (ADS)

Novaković, M.; Traverse, A.; Popović, M.; Lieb, K. P.; Zhang, K.; Bibić, N.

2012-07-01

We report on modifications of 280-nm thin polycrystalline CrN layers caused by vanadium ion implantation. The CrN layers were deposited at 150°C by d.c. reactive sputtering on Si(100) wafers and then implanted at room temperature with 80-keV V+ ions to fluences of 1×1017 and 2×1017 ions/cm2. Rutherford backscattering spectroscopy, cross-sectional transmission electron microscopy, and X-ray diffraction were used to characterize changes in the structural properties of the films. Their optical and electrical properties were analyzed by infrared spectroscopy in reflection mode and electrical resistivity measurements. CrN was found to keep its cubic structure under the conditions of vanadium ion implantation used here. The initially partially non-metallic CrN layer displays metallic character under implantation, which may be related to the possible formation of Cr1-x V x N.

Broadband planar multilayered absorbers tuned by VO2 phase transition

NASA Astrophysics Data System (ADS)

Peng, Hao; Ji, Chunhui; Lu, Lulu; Li, Zhe; Li, Haoyang; Wang, Jun; Wu, Zhiming; Jiang, Yadong; Xu, Jimmy; Liu, Zhijun

2017-08-01

The metal-insulator transition makes vanadium dioxide an attractive material for developing reconfigurable optoelectronic components. Here we report on dynamically tunable broadband absorbers consisting of planar multilayered thin films. By thermally triggering the phase transition of vanadium dioxide, the effective impedance of multilayered structures is tuned in or out of the condition of impedance matching to free-space, leading to switchable broadband absorptions. Two types of absorbers are designed and demonstrated by using either the insulating or metallic state of vanadium dioxide at the impedance matched condition. The planar multilayered absorbers exhibit tunable absorption bands over the wavelength ranges of 5-9.3 μm and 3.9-8.2 μm, respectively. A large modulation depth up to 88% is measured. The demonstrated broadband absorbance tunability is of potential interest for reconfigurable bolometric sensing, camouflaging, and modulation of mid-infrared lights.

Lead-free piezoelectrics: V3+ to V5+ ion conversion promoting the performances of V-doped Zinc Oxide.

PubMed

Laurenti, M; Castellino, M; Perrone, D; Asvarov, A; Canavese, G; Chiolerio, A

2017-02-06

Vanadium doped ZnO (VZO) thin films were grown by RF magnetron sputtering, starting from a ZnO:V ceramic target. The crystal structure, chemical composition, electric and piezoelectric properties of the films were investigated either on the as-grown thin films or after a post-deposition rapid thermal annealing (RTA) treatment performed at 600 °C for different lengths of time (1 and 5 min) in an oxygen atmosphere. Substitutional doping of Zn 2+ with V 3+ and V 5+ ions strongly deteriorated the hexagonal wurtzite ZnO structure of the as-grown thin films due to lattice distortion. The resulting slight amorphization led to a poor piezoelectric response and higher resistivity. After the RTA treatment, strong c-axis oriented VZO thin films were obtained, together with a partial conversion of the starting V 3+ ions into V 5+ . The improvement of the crystal structure and the stronger polarity of both V 3+ - O and V 5+ - O chemical bonds, together with the corresponding easier rotation under the application of an external electric field, positively affected the piezoelectric response and increased conductivity. This was confirmed by closed-loop butterfly piezoelectric curves, by a maximum d 33 piezoelectric coefficient of 85 pm·V -1 , and also by ferroelectric switching domains with a well-defined polarization hysteresis curve, featuring a residual polarization of 12.5 μC∙cm -2 .

Lead-free piezoelectrics: V3+ to V5+ ion conversion promoting the performances of V-doped Zinc Oxide

PubMed Central

Laurenti, M.; Castellino, M.; Perrone, D.; Asvarov, A.; Canavese, G.; Chiolerio, A.

2017-01-01

Vanadium doped ZnO (VZO) thin films were grown by RF magnetron sputtering, starting from a ZnO:V ceramic target. The crystal structure, chemical composition, electric and piezoelectric properties of the films were investigated either on the as-grown thin films or after a post-deposition rapid thermal annealing (RTA) treatment performed at 600 °C for different lengths of time (1 and 5 min) in an oxygen atmosphere. Substitutional doping of Zn2+ with V3+ and V5+ ions strongly deteriorated the hexagonal wurtzite ZnO structure of the as-grown thin films due to lattice distortion. The resulting slight amorphization led to a poor piezoelectric response and higher resistivity. After the RTA treatment, strong c-axis oriented VZO thin films were obtained, together with a partial conversion of the starting V3+ ions into V5+. The improvement of the crystal structure and the stronger polarity of both V3+ – O and V5+ – O chemical bonds, together with the corresponding easier rotation under the application of an external electric field, positively affected the piezoelectric response and increased conductivity. This was confirmed by closed-loop butterfly piezoelectric curves, by a maximum d33 piezoelectric coefficient of 85 pm·V−1, and also by ferroelectric switching domains with a well-defined polarization hysteresis curve, featuring a residual polarization of 12.5 μC∙cm−2. PMID:28165040

Investigation of electron beam lithography effects on metal-insulator transition behavior of vanadium dioxide

NASA Astrophysics Data System (ADS)

Yuce, H.; Alaboz, H.; Demirhan, Y.; Ozdemir, M.; Ozyuzer, L.; Aygun, G.

2017-11-01

Vanadium dioxide (VO2) shows metal-insulator phase transition at nearly 68 °C. This metal-insulator transition (MIT) in VO2 leads to a significant change in near-infrared transmittance and an abrupt change in the resistivity of VO2. Due to these characteristics, VO2 plays an important role on optic and electronic devices, such as thermochromic windows, meta-materials with tunable frequency, uncooled bolometers and switching devices. In this work, VO2 thin films were fabricated by reactive direct current magnetron sputtering in O2/Ar atmosphere on sapphire substrates without any further post annealing processes. The effect of sputtering parameters on optical characteristics and structural properties of grown thin films was investigated by SEM, XRD, Raman and UV/VIS spectrophotometer measurements. Patterning process of VO2 thin films was realized by e-beam lithography technique to monitor the temperature dependent electrical characterization. Electrical properties of VO2 samples were characterized using microprobe station in a vacuum system. MIT with hysteresis behavior was observed for the unpatterned square samples at around 68 °C. By four orders of magnitude of resistivity change was measured for the deposited VO2 thin films at transition temperature. After e-beam lithography process, substantial results in patterned VO2 thin films were observed. In this stage, for patterned VO2 thin films as stripes, the change in resistivity of VO2 was reduced by a factor of 10. As a consequence of electrical resistivity measurements, MIT temperature was shifted from 68 °C to 50 °C. The influence of e-beam process on the properties of VO2 thin films and the mechanism of the effects are discussed. The presented results contribute to the achievement of VO2 based thermochromic windows and bolometer applications.

Vanadium Pentoxide Nanobelt-Reduced Graphene Oxide Nanosheet Composites as High-Performance Pseudocapacitive Electrodes: ac Impedance Spectroscopy Data Modeling and Theoretical Calculations

PubMed Central

Gupta, Sanju; Aberg, Bryce; Carrizosa, Sara B.; Dimakis, Nicholas

2016-01-01

Graphene nanosheets and graphene nanoribbons, G combined with vanadium pentoxide (VO) nanobelts (VNBs) and VNBs forming GVNB composites with varying compositions were synthesized via a one-step low temperature facile hydrothermal decomposition method as high-performance electrochemical pseudocapacitive electrodes. VNBs from vanadium pentoxides (VO) are formed in the presence of graphene oxide (GO), a mild oxidant, which transforms into reduced GO (rGOHT), assisting in enhancing the electronic conductivity coupled with the mechanical robustness of VNBs. From electron microscopy, surface sensitive spectroscopy and other complementary structural characterization, hydrothermally-produced rGO nanosheets/nanoribbons are decorated with and inserted within the VNBs’ layered crystal structure, which further confirmed the enhanced electronic conductivity of VNBs. Following the electrochemical properties of GVNBs being investigated, the specific capacitance Csp is determined from cyclic voltammetry (CV) with a varying scan rate and galvanostatic charging-discharging (V–t) profiles with varying current density. The rGO-rich composite V1G3 (i.e., VO/GO = 1:3) showed superior specific capacitance followed by VO-rich composite V3G1 (VO/GO = 3:1), as compared to V1G1 (VO/GO = 1:1) composite, besides the constituents, i.e., rGO, rGOHT and VNBs. Composites V1G3 and V3G1 also showed excellent cyclic stability and a capacitance retention of >80% after 500 cycles at the highest specific current density. Furthermore, by performing extensive simulations and modeling of electrochemical impedance spectroscopy data, we determined various circuit parameters, including charge transfer and solution resistance, double layer and low frequency capacitance, Warburg impedance and the constant phase element. The detailed analyses provided greater insights into physical-chemical processes occurring at the electrode-electrolyte interface and highlighted the comparative performance of thin heterogeneous composite electrodes. We attribute the superior performance to the open graphene topological network being beneficial to available ion diffusion sites and the faster transport kinetics having a larger accessible geometric surface area and synergistic integration with optimal nanostructured VO loading. Computational simulations via periodic density functional theory (DFT) with and without V2O5 adatoms on graphene sheets are also performed. These calculations determine the total and partial electronic density of state (DOS) in the vicinity of the Fermi level (i.e., higher electroactive sites), in turn complementing the experimental results toward surface/interfacial charge transfer on heterogeneous electrodes. PMID:28773738

Solution XAS Analysis for Exploring the Active Species in Homogeneous Vanadium Complex Catalysis

NASA Astrophysics Data System (ADS)

Nomura, Kotohiro; Mitsudome, Takato; Tsutsumi, Ken; Yamazoe, Seiji

2018-06-01

Selected examples in V K-edge X-ray Absorption Near Edge Structure (XANES) analysis of a series of vanadium complexes containing imido ligands (possessing metal-nitrogen double bond) in toluene solution have been introduced, and their pre-edge and the edge were affected by their structures and nature of ligands. Selected results in exploring the oxidation states of the active species in ethylene dimerization/polymerization using homogeneous vanadium catalysts [consisting of (imido)vanadium(V) complexes and Al cocatalysts] by X-ray absorption spectroscopy (XAS) analyses have been introduced. It has been demonstrated that the method should provide more clear information concerning the active species in situ, especially by combination with the other methods (NMR and ESR spectra, X-ray crystallographic analysis, and reaction chemistry), and should be powerful tool for study of catalysis mechanism as well as for the structural analysis in solution.

Bismuth-based oxide semiconductors: Mild synthesis and practical applications

NASA Astrophysics Data System (ADS)

Timmaji, Hari Krishna

In this dissertation study, bismuth based oxide semiconductors were prepared using 'mild' synthesis techniques---electrodeposition and solution combustion synthesis. Potential environmental remediation and solar energy applications of the prepared oxides were evaluated. Bismuth vanadate (BiVO4) was prepared by electrodeposition and solution combustion synthesis. A two step electrosynthesis strategy was developed and demonstrated for the first time. In the first step, a Bi film was first electrodeposited on a Pt substrate from an acidic BiCl3 medium. Then, this film was anodically stripped in a medium containing hydrolyzed vanadium precursor, to generate Bi3+, and subsequent BiVO4 formation by in situ precipitation. The photoelectrochemical data were consistent with the in situ formation of n-type semiconductor films. In the solution combustion synthesis procedure, BiVO4 powders were prepared using bismuth nitrate pentahydrate as the bismuth precursor and either vanadium chloride or vanadium oxysulfate as the vanadium precursor. Urea, glycine, or citric acid was used as the fuel. The effect of the vanadium precursor on the photocatalytic activity of combustion synthesized BiVO 4 was evaluated in this study. Methyl orange was used as a probe to test the photocatalytic attributes of the combustion synthesized (CS) samples, and benchmarked against a commercial bismuth vanadate sample. The CS samples showed superior activity to the commercial benchmark sample, and samples derived from vanadium chloride were superior to vanadium oxysulfate counterparts. The photoelectrochemical properties of the various CS samples were also studied and these samples were shown to be useful both for environmental photocatalytic remediation and water photooxidation applications. Silver bismuth tungstate (AgBiW2O8) nanoparticles were prepared for the first time by solution combustion synthesis by using silver nitrate, bismuth nitrate, sodium tungstate as precursors for Ag, Bi, and W respectively and urea as the fuel. The photocatalytic activity of these nanoparticles was superior to a sample prepared by solid-state synthesis. The combustion-synthesized particles were subsequently modified with Pt catalyst islands using a photodeposition technique and then used for the photo-generation of syngas (CO + H2). Formic acid was used in these experiments for in situ generation of CO2 and its subsequent reduction to CO. In the absence of Pt modification, H2 was not obtained. These results were compared with those obtained with acetic acid in place of formic acid, and finally the mechanistic pathways for syngas and methane photogeneration are presented.

High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Xun-Lei, E-mail: dingxl@ncepu.edu.cn, E-mail: chemzyx@iccas.ac.cn; Wang, Dan; Wu, Xiao-Nan

2015-09-28

The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters decreases as the N increases, and it is higher than that of (V {sub 2}O{sub 5}){sub N}{sup +} for N ≥ 4. Theoretical studies were conducted on (Nb{sub 2}O{sub 5}){sub N}{sup +} (N = 2–6) by density functional calculations. HAA reactions on these clusters are all favorablemore » thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion.« less

Self-assembly of a tetrahedral 58-nuclear barium vanadium oxide cluster.

PubMed

Kastner, Katharina; Puscher, Bianka; Streb, Carsten

2013-01-07

We report the synthesis and characterization of a molecular barium vanadium oxide cluster featuring high nuclearity and high symmetry. The tetrameric, 2.3 nm cluster H(5)[Ba(10)(NMP)(14)(H(2)O)(8)[V(12)O(33)](4)Br] is based on a bromide-centred, octahedral barium scaffold which is capped by four previously unknown [V(12)O(33)](6-) clusters in a tetrahedral fashion. The compound represents the largest polyoxovanadate-based heterometallic cluster known to date. The cluster is formed in organic solution and it is suggested that the bulky N-methyl-2-pyrrolidone (NMP) solvent ligands allow the isolation of this giant molecule and prevent further condensation to a solid-state metal oxide. The cluster is fully characterized using single-crystal XRD, elemental analysis, ESI mass spectrometry and other spectroscopic techniques.

Investigation of activation cross-sections of deuteron induced reactions on vanadium up to 40 MeV

NASA Astrophysics Data System (ADS)

Tárkányi, F.; Ditrói, F.; Takács, S.; Hermanne, A.; Baba, M.; Ignatyuk, A. V.

2011-08-01

Experimental excitation functions for deuteron induced reactions up to 40 MeV on natural vanadium were measured with the activation method using a stacked foil irradiation technique. From high resolution gamma spectrometry cross-section data for the production of 51Cr, 48V, 48,47,46Sc and 47Ca were determined. Comparisons with the earlier published data are presented and results for values predicted by different theoretical codes are included. Thick target yields were calculated from a fit to our experimental excitation curves and compared with the earlier experimental data. Depth distribution curves used for thin layer activation (TLA) are also presented.

Semiconductor to Metal Transition Characteristics of VO2/NiO Epitaxial Heterostructures Integrated with Si(100)

NASA Astrophysics Data System (ADS)

Molaei, Roya

The novel functionalities of Vanadium dioxide (VO2), such as, several orders of magnitude transition in resistivity and IR transmittance, provide the exciting opportunity for the development of next generation memory, sensor, and field-effect based devices. A critical issue in the development of practical devices based on metal oxides is the integration of high quality epitaxial oxide thin films with the existing silicon technology which is based on silicon (100) substrates. However, silicon is not suitable for epitaxial growth of oxides owing to its tendency to readily form an amorphous oxide layer or silicide at the film-substrate interface. The oxide films deposited directly on silicon exhibit poor crystallinity and are not suitable for device applications. To overcome this challenge, appropriate substrate templates must be developed for the growth of oxide thin films on silicon substrates. The primary objective of this dissertation was to develop an integration methodology of VO2 with Si (100) substrates so they could be used in "smart" sensor type of devices along with other multifunctional devices on the same silicon chip. This was achieved by using a NiO/c- YSZ template layer deposited in situ. It will be shown that if the deposition conditions are controlled properly. This approach was used to integrate VO 2 thin films with Si (100) substrates using pulsed laser deposition (PLD) technique. The deposition methodology of integrating VO2 thin films on silicon using various other template layers will also be discussed. Detailed epitaxial relationship of NiO/c-YSZ/Si(100) heterostructures as a template to growth of VO2 as well as were studied. We also were able to create a p-n junction within a single NiO epilayer through subsequent nanosecond laser annealing, as well as established a structure-property correlation in NiO/c-YSZ/Si(100) thin film epitaxial heterostructures with especial emphasis on the stoichiometry and crystallographic characteristics. NiO/c-YSZ/Si(100) heterostructures were used as template to grow fully relaxed VO2 thin films. The detailed x-ray diffraction, transmission electron microscopy (TEM), electrical characterization results for the deposited films will be presented. In the framework on domain matching epitaxy, epitaxial growth of VO2 (tetragonal crystal structure at growth temperature) on NiO has been explained. Our detailed phi-scan X-ray diffraction measurements corroborate our understanding of the epitaxial growth and in-plane atomic arrangements at the interface. It was observed that the transition characteristics (sharpness, over which electrical property changes are completed, amplitude, transition temperature, and hysteresis) are a strong function of microstructure, strain, and stoichiometry. We have shown that by the choosing the right template layer, strain in the VO2 thin films can be fully relaxed and near-bulk VO2 transition temperatures can be achieved. Finally, I will present my research work on modification of semiconductor-to-metal transition characteristics and effect on room temperature magnetic properties of VO2 thin films upon laser annealing. While the microstructure (epitaxy, crystalline quality etc.) and phase were preserved, we envisage these changes to occur as a result of introduction of oxygen vacancies upon laser treatment.

Optical switching and photoluminescence in erbium-implanted vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Lim, Herianto; Stavrias, Nikolas; Johnson, Brett C.; Marvel, Robert E.; Haglund, Richard F.; McCallum, Jeffrey C.

2014-03-01

Vanadium dioxide (VO2) is under intensive consideration for optical switching due to its reversible phase transition, which features a drastic and rapid shift in infrared reflectivity. Classified as an insulator-to-metal transition, the phase transition in VO2 can be induced thermally, electrically, and optically. When induced optically, the transition can occur on sub-picosecond time scales. It is interesting to dope VO2 with erbium ions (Er3+) and observe their combined properties. The first excited-state luminescence of Er3+ lies within the wavelength window of minimal transmission-loss in silicon and has been widely utilized for signal amplification and generation in silicon photonics. The incorporation of Er3+ into VO2 could therefore result in a novel photonic material capable of simultaneous optical switching and amplification. In this work, we investigate the optical switching and photoluminescence in Er-implanted VO2 thin films. Thermally driven optical switching is demonstrated in the Er-implanted VO2 by infrared reflectometry. Photoluminescence is observed in the thin films annealed at ˜800 °C or above. In addition, Raman spectroscopy and a statistical analysis of switching hysteresis are carried out to assess the effects of the ion implantation on the VO2 thin films. We conclude that Er-implanted VO2 can function as an optical switch and amplifier, but with reduced switching quality compared to pure VO2.

Electrolysis-induced protonation of VO2 thin film transistor for the metal-insulator phase modulation

NASA Astrophysics Data System (ADS)

Katase, Takayoshi; Endo, Kenji; Ohta, Hiromichi

2016-02-01

Compared to state-of-the-art modulation techniques, protonation is the most ideal to control the electrical and optical properties of transition metal oxides (TMOs) due to its intrinsic non-volatile operation. However, the protonation of TMOs is not typically utilized for solid-state devices because of imperative high-temperature annealing treatment in hydrogen source. Although one solution for room temperature (RT) protonation of TMOs is liquid-phase electrochemistry, it is unsuited for practical purposes due to liquid-leakage problem. Herein we demonstrate solid-state RT-protonation of vanadium dioxide (VO2), which is a well-known thermochromic TMO. We fabricated the three terminal thin-film-transistor structure on an insulating VO2 film using a water-infiltrated nanoporous glass, which serves as a solid electrolyte. For gate voltage application, water electrolysis and protonation/deprotonation of VO2 film surface occurred, leading to reversible metal-insulator phase conversion of ~11-nm-thick VO2 layer. The protonation was clearly accompanied by the structural change from an insulating monoclinic to a metallic tetragonal phase. Present results offer a new route for the development of electro-optically active solid-state devices with TMO materials by engineering RT protonation.

Influence of solution deposition rate on properties of V{sub 2}O{sub 5} thin films deposited by spray pyrolysis technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abd–Alghafour, N. M., E-mail: na2013bil@gmail.com; Ahmed, Naser M.; Hassan, Zai

Vanadium oxide (V{sub 2}O{sub 5}) thin films were deposited on glass substrates by using a cost-efficient spray pyrolysis technique. The films were grown at 350° through thermal decomposition of VCl{sub 3} in deionized water with different solution spray rates. The high resolution X-ray diffraction results revealed the formation of nanocrystalline films having orthorhombic structures with preferential orientation along (101) direction. The spray rate influenced the surface morphology and crystallite size of the films. The crystallite size was found to increase whereas the micro-strain was decreased by increasing the spray deposition rates. The increase in crystallite size and decrease in themore » macrostrain resulted in an improvement in the films’ crystallinity. The UV-Visible spectroscopy analysis indicated that the average transmittance of all films lies in the range 75-80 %. The band gap of V{sub 2}O{sub 5} film was decreased from 2.65 to 2.46 eV with increase of the spray deposition rate from 5 ml/min to 10 ml/min. first, second, and third level headings (first level heading).« less

Impression of plasma voltage on growth of α-V{sub 2}O{sub 5} nanostructured thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Rabindar Kumar, E-mail: rkrksharma6@gmail.com; Kumar, Prabhat; Reddy, G. B.

2015-06-24

In this communication, we synthesized vanadium pentoxide (α-V{sub 2}O{sub 5}) nanostructured thin films (NST{sub s}) accompanied with nanoflakes/ nanoplates on the Ni-coated glass substrates employing plasma assisted sublimation process (PASP) as a function of plasma voltage (V{sub p}). The effect of plasma voltage on structural, morphological, compositional, and vibrational properties have been studied systematically. The structural analysis divulged that all films deposited at different V{sub p} have pure orthorhombic phase, no impurity phase is detected under resolution limit of XRD and XPS. The morphological studies of samples is carried out by SEM, revealed that features as well as alignment ofmore » V{sub 2}O{sub 5} NST{sub s} is greatly monitored by V{sub p} and the film possessing the best features is obtained at 2500volt. In addition, XPS results reveal that V{sup 5+} oxidation state is the most prominent state in sample V{sub 2}, which represents better stoichiometric nature of film. The vibrational study of all samples is performed by FTIR and strongly support the XRD observations. All the results are in consonance with each other.« less

Low-Cost and Facile Synthesis of the Vanadium Oxides V2O3, VO2, and V2O5 and Their Magnetic, Thermochromic and Electrochromic Properties.

PubMed

Mjejri, Issam; Rougier, Aline; Gaudon, Manuel

2017-02-06

In this study, vanadium sesquioxide (V 2 O 3 ), dioxide (VO 2 ), and pentoxide (V 2 O 5 ) were all synthesized from a single polyol route through the precipitation of an intermediate precursor: vanadium ethylene glycolate (VEG). Various annealing treatments of the VEG precursor, under controlled atmosphere and temperature, led to the successful synthesis of the three pure oxides, with sub-micrometer crystallite size. To the best of our knowledge, the synthesis of the three oxides V 2 O 5 , VO 2 , and V 2 O 3 from a single polyol batch has never been reported in the literature. In a second part of the study, the potentialities brought about by the successful preparation of sub-micrometer V 2 O 5 , VO 2 , and V 2 O 3 are illustrated by the characterization of the electrochromic properties of V 2 O 5 films, a discussion about the metal to insulator transition of VO 2 on the basis of in situ measurements versus temperature of its electrical and optical properties, and the characterization of the magnetic transition of V 2 O 3 powder from SQUID measurements. For the latter compound, the influence of the crystallite size on the magnetic properties is discussed.

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

NASA Astrophysics Data System (ADS)

González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

2016-08-01

A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

DTIC Science & Technology

2012-05-09

cation it replaces in the host oxide. For example, a La dopant in CeO2 is a low-valence dopant because La is trivalent when it combines with oxygen...Kim, H. M. Lee, R. G. S. Pala, and H. Metiu, Oxidative dehydrogenation of methanol to formaldehyde by isolated vanadium, molybdenum, and chromium

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

Vanadium oxide nanotubes (VOxNTs) with hollow as well as multi-walled features were fabricated under hydrothermal condition by soft-template method. This novel VOxNTs 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 (C12H27N) and intrinsic low conductivity of VOx. Cation exchange technique and oxidative polymerization process of pyrrole monomers were conducted to wipe off partial soft-template without electrochemical activity within VOxNTs and simultaneously form polypyrrole coating on VOxNTs, respectively. The resulting polypyrrole/VOxNTs 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.

Selected fretting-wear-resistant coatings for titanium - 6-percent-aluminum - 4-percent-vanadium alloy

NASA Technical Reports Server (NTRS)

Bill, R. C.

1976-01-01

A titanium - 6-percent-aluminum - 4-percent-vanadium alloy (Ti-6Al-4V) was subjected to fretting-wear exposures against uncoated Ti-6Al-4V as a baseline and against various coatings and surface treatments applied to Ti-6Al-4V. The coatings evaluated included plasma-sprayed tungsten carbide with 12 percent cobalt, aluminum oxide with 13 percent titanium oxide, chromium oxide, and aluminum bronze with 10 percent aromatic polyester; polymer-bonded polyimide, polyimide with graphite fluoride, polyimide with molybdenum disulfide (MoS2), and methyl phenyl silicone bonded MoS2, preoxidation surface treatment, a nitride surface treatment, and a sputtered MoS2 coating. Results of wear measurements on both the coated and uncoated surfaces after 300,000 fretting cycles indicated that the polyimide coating was the most wear resistant and caused the least wear to the uncoated mating surface.

Preparation and characterization of vanadia-titania mixed oxide for immobilization of Serratia rubidaea CCT 5732 and Klebsiella marcescens bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saragiotto Colpini, Leda Maria; Correia Goncalves, Regina A.; Goncalves, Jose Eduardo

2008-08-04

Vanadia-titania mixed oxide was synthesized by sol-gel method and characterized by several techniques. Texturally, it is formed by mesopores and presents high-specific surface area and controlled porosity. Scanning electron microscopy revealed that vanadium is homogeneously distributed in the material. Structurally, it was possible to identify characteristic V=O stretching bands by IR. The analysis of X-ray diffraction showed that the material, particularly vanadium, is highly dispersed. Application experiments were carried out through the immobilization of Serratia rubidae CCT 5732 and Klebsiella marcescens bacteria by adsorption on the surface of mixed oxide. The micrographies revealed that the bacteria were adsorbed on themore » entire support, with average surface densities of 8.55 x 10{sup 11} cells/m{sup 2} (Serratia rubidae CCT 5732) and 3.40 x 10{sup 11} cells/m{sup 2} (K. marcescens)« less

Ultra-thin, single-layer polarization rotator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Son, T. V.; Truong, V. V., E-mail: Truong.Vo-Van@Concordia.Ca; Do, P. A.

We demonstrate light polarization control over a broad spectral range by a uniform layer of vanadium dioxide as it undergoes a phase transition from insulator to metal. Changes in refractive indices create unequal phase shifts on s- and p-polarization components of incident light, and rotation of linear polarization shows intensity modulation by a factor of 10{sup 3} when transmitted through polarizers. This makes possible polarization rotation devices as thin as 50 nm that would be activated thermally, optically or electrically.

Detailed mineral and chemical relations in two uranium-vanadium ores

USGS Publications Warehouse

Garrels, Robert M.; Larsen, E. S.; Pommer, A.M.; Coleman, R.G.

1956-01-01

Channel samples from two mines on the Colorado Plateau have been studied in detail both mineralogically and chemically. A channel sample from the Mineral Joe No. 1 mine, Montrose County, Colo., extends from unmineralized rock on one side, through a zone of variable mineralization, into only weakly mineralized rock. The unmineralized rock is a fairly clean quartz sand cemented with gypsum and contains only minor amounts of clay minerals. One boundary between unmineralized and mineralized rock is quite sharo and is nearly at right angles to the bedding. Vanadium clay minerals, chiefly mixed layered mica-montmorillonite and chlorite-monmorillonite, are abundant throughout the mineralized zone. Except in the dark "eye" of the channel sample, the vanadium clay minerals are accompanied by hewettite, carnotite, tyuyamunite, and probably unidentified vanadates. In the dark "eye," paramontroseite, pyrite, and marcasite are abundant, and bordered on each side by a zone containing abundant corvusite. No recognizable uranium minerals were seen in the paramontroseite zone although uranium is abundant there. Coaly material is recognizable throughout all of the channel but is most abundant in and near the dark "eye." Detailed chemical studies show a general increase in Fe, Al, U, and V, and a decrease in SO4 toward the "eye" of the channel. Reducing capacity studies indicate that V(IV) and Fe(II) are present in the clay mineral throughout the channel, but only in and near the "eye" are other V(IV) minerals present (paramontroseite and corvusite). The uranium is sexivalent, although its state of combination is conjectural where it is associated with paramontroseite. Where the ore boundary is sharp, the boundary of introduced trace elements is equally sharp. Textural and chemical relations leave no doubt that the "eye: is a partially oxidized remnant of a former lower-valence ore, and the remainder of the channel is a much more fully oxidized remnant. A channel sample from the Virgin No. 3 mine, Montrose County, Colo., extends from weakly mineralized sandstone on both sides through a strongly mineralized central zone. The weakly mineralized zone is a poorly sorted sandstone with common detrital clay partings; chlorite and mixed layer mica-montmorrillonite are abundant interstitial to the quartz grains. No distinct vanadium or uranium minerals are recognizable, although the clay minerals are vanadium bearing. Euherdral pyrite grains and selenian galena are present but rare. The strongly mineralized rock is separated from the weakly mineralized rock by a narrow transition zone which only apporiximates the bedding planes. It contains abundant vanadium-bearing clay minerals (predominantly chlorite) interstitial to the quartz grains, and apparently replacing them. Paramontroseite is common and is intergrown with the clay minerals. Pyrite and marcasite are present, chiefly in or near the abundant blebs and fragments of carbonaceous material. Selenian galena is rarely present, and generally in or near carbonaceous material. Coffinite is the only uranium mineral idenitified; it is extremely fine grained and was identified only in X-ray diffraction patterns of heavy separates. Distribution of trace elements is not clear; some are consistently high in the strongly mineralized rocks, and some are consistently low. The trace element composition of the unmineralized rock is not known. Chemical studies show a very abrupt rise in the total U, V, and Fe from the weakly mineralized to strongly mineralized rock. Reducing-capacity studies indicate that most of the vanadium is present as V(IV), but some is present as V(V); that iron is present as both Fe(II) and Fe(III), the latter believed to have been present in the primary clays of the unmineralized rock; and that come of the uranium is present as U(VI) in addition to the U(IV) in the coffinite. All evidence points to weak oxidation of an ore once having a somewhat lower valence state. The channel samples from both the Mineral Joe No. 1 mine and the Virgin No. 3 mine are believe to have been essentially identical in mineralogy prior to oxidation by weathering: vanadium was present as V(III) in montroseite and V(IV) in the vanadium clays; uranium was present largely as U(IV) in coffinite and/or uraninite. The Mineral Joe No. 1 mine channel sample is now more fully oxidized. Vanadium clays are unquestionably formed abundantly during the primary mineralization, and they persist with a minimum of alteration during much of the weathering. They suggest that the vanadium is carried as V(IV) in the ore-forming fluids; it seems likely too that the uranium is carried as a U(VI) ion.

Study of the resonant frequencies of silicon microcantilevers coated with vanadium dioxide films during the insulator-to-metal transition

NASA Astrophysics Data System (ADS)

Rúa, Armando; Fernández, Félix E.; Hines, Melissa A.; Sepúlveda, Nelson

2010-03-01

Vanadium dioxide (VO2) thin films were grown on silicon microcantilevers and companion test substrates by pulsed laser deposition followed by in situ annealing in an oxidizing atmosphere, with annealing times used to control crystallite sizes. Annealing times of 18 min produced VO2 films with average crystallite sizes of ˜10 nm or less, while those annealed for 35 min had crystallites of average size ˜90 nm, comparable to sample thickness. X-ray diffraction and x-ray photoelectron spectroscopy studies of the samples showed that films with crystallite sizes ˜40 nm or greater consisted of substoichiometric VO2 in its monoclinic phase, with preferential orientation with (011) planes parallel to the sample surface, while finer structured samples had a substantially similar composition, but showed no clear evidence of preferential orientation and were probably partially amorphous. Forced vibration experiments were performed with the cantilevers as they were thermally cycled through the VO2 insulator-to-metal transition (IMT). Very large reversible changes in the resonant frequencies of up to 5% (3.6 kHz) as well as hysteretic behavior were observed, which depend strongly on film crystallite size. The average value of Young's modulus for VO2 films with crystallite sizes of ˜90 nm was estimated from the mechanical resonance data at room temperature to be ˜120 GPa, but the large tensile stresses which develop between film and substrate through the IMT impede a similar determination for the VO2 tetragonal phase, since the commonly used relationships for cantilever frequencies derived from elasticity theory are not applicable for strongly curved composite beams. The results presented show that VO2 thin films can be useful in novel microscale and nanoscale electromechanical resonators in which effective stiffness can be tuned thermally or optically. This response can provide additional functionality to VO2—based devices which take advantage of other property changes through the IMT.

Electrochemical behaviour of vanadium(V)/vanadium(IV) redox couple at graphite electrodes

NASA Astrophysics Data System (ADS)

Zhong, S.; Skyllas-Kazacos, M.

The electrochemical behaviour of the V(V)/V(IV) couple has been studied at a graphite disc electrode in sulfuric acid using both cyclic and rotating-disc voltammetry. The results from the latter technique have revealed that the cathodic and anodic characteristics of this redox couple are quite different. The diffusion coefficient for V(IV), 2.14×10-6 cm2 s-1, is independent of the vanadium concentration. For V(IV) oxidation, the electrode kinetic parameters i0 and α have values of 2.47×10-4 A cm-2 and 0.71, respectively. The exchange current density, i0, for the V(V)/V(IV) reaction has been obtained at both graphite felt and reticulated vitreous carbon electrodes.

Ab Initio Calculations of Transport Properties of Vanadium Oxides

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

Studies on Molecular and Ion Transport in Silicalite Membranes and Applications as Ion Separator for Redox Flow Battery

NASA Astrophysics Data System (ADS)

Yang, Ruidong

Microporous zeolite membranes have been widely studied for molecular separations based on size exclusion or preferential adsorption-diffusion mechanisms. The MFI-type zeolite membranes were also demonstrated for brine water desalination by molecular sieving effect. In this research, the pure silica MFI-type zeolite (i.e. silicalite) membrane has been for the first time demonstrated for selective permeation of hydrated proton (i.e. H3O+) in acidic electrolyte solutions. The silicalite membrane allows for permeation of H 3O+ ions, but is inaccessible to the large hydrated multivalent vanadium ions due to steric effect. The silicalite membrane has been further demonstrated as an effective ion separator in the all-vanadium redox flow battery (RFB).The silicalite is nonionic and its proton conductivity relies on the electric field-driven H3O+ transport through the sub nanometer-sized pores under the RFB operation conditions. The silicalite membrane displayed a significantly reduced self-discharge rate because of its high proton-to-vanadium ion transport selectivity. However, the nonionic nature of the silicalite membrane and very small diffusion channel size render low proton conductivity and is therefore inefficient as ion exchange membranes (IEMs) for practical applications. The proton transport efficiency may be improved by reducing the membrane thickness. However, the zeolite thin films are extremely fragile and must be supported on mechanically strong and rigid porous substrates. In this work, silicalite-Nafion composite membranes were synthesized to achieve a colloidal silicalite skin on the Nafion thin film base. The "colloidal zeolite-ionic polymer" layered composite membrane combines the advantages of high proton-selectivity of the zeolite layer and the mechanical flexibility and low proton transport resistance of the ionic polymer membrane. The composite membrane exhibited higher proton/vanadium ion separation selectivity and lower electrical resistance than the commercial Nafion 117 membrane. The high proton transport selectivity is a result of the molecular sieving effect between the H3O+ and multivalent vanadium ions by the zeolitic pores; thus the zeolite particles significantly reduced the effective membrane surface area for vanadium ion permeation. The low resistance of the composite membrane can be attributed to the reduced thickness of the Nafion base film and the thinness of the colloidal silicalite top layer. The composite membrane outperformed the Nafion 117 membrane in the vanadium RFB operation in terms of the overall charge-discharge energy efficiency. Efforts have been made in further investigation of ion and molecular transport diffusivity in the polycrystalline silicalite film using zeolite-coated optical fiber interferometers. A physical model has been established for analyzing the molecular diffusivity in the zeolite layer based on the temporal responses of the optical interferometric signals during the transient process of molecular sorption. Experiments were first carried out to study the diffusivity of isobutane to evaluate the effectiveness of the proposed optical method. The isobutane diffusivities in silicalite measured by this method were in good agreement with the values reported in literature. The zeolite coated fiber optic interferometer was however ineffective in monitoring ion sorption or ion exchange in the silicalite films. It is suggested that more sensitive fiber optic devices are needed for studying the ion diffusion.

A Highly Ion-Selective Zeolite Flake Layer on Porous Membranes for Flow Battery Applications.

PubMed

Yuan, Zhizhang; Zhu, Xiangxue; Li, Mingrun; Lu, Wenjing; Li, Xianfeng; Zhang, Huamin

2016-02-24

Zeolites are crystalline microporous aluminosilicates with periodic arrangements of cages and well-defined channels, which make them very suitable for separating ions of different sizes, and thus also for use in battery applications. Herein, an ultra-thin ZSM-35 zeolite flake was introduced onto a poly(ether sulfone) based porous membrane. The pore size of the zeolite (ca. 0.5 nm) is intermediary between that of hydrated vanadium ions (>0.6 nm) and protons (<0.24 nm). The resultant membrane can thus be used to perfectly separate vanadium ions and protons, making this technology useful in vanadium flow batteries (VFB). A VFB with a zeolite-coated membrane exhibits a columbic efficiency of >99 % and an energy efficiency of >81 % at 200 mA cm(-2), which is by far the highest value ever reported. These convincing results indicate that zeolite-coated membranes are promising in battery applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation Catalysts in the Dark and the Light

DTIC Science & Technology

2010-01-01

TiO2 with added silver, chromium, vanadium, manganese, carbon, and/or sulfur (selected transition metal ions and selected non- metals ) are very...Ranjit, Koodali T.; Klabunde, Kenneth J.; “ Catalysis by Metal Oxides,” Surface and Nanomolecular Catalysis , ed. Ryan Richards, CRC Press, NY, Ch. 2, pgs...REPORT Oxidation Catalysts in the Dark and the Light--Final Report 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: Extensive research on mixed metal oxide

Microbial reduction and precipitation of vanadium (V) in groundwater by immobilized mixed anaerobic culture.

PubMed

Zhang, Baogang; Hao, Liting; Tian, Caixing; Yuan, Songhu; Feng, Chuanping; Ni, Jinren; Borthwick, Alistair G L

2015-09-01

Vanadium is an important contaminant impacted by natural and industrial activities. Vanadium (V) reduction efficiency as high as 87.0% was achieved by employing immobilized mixed anaerobic sludge as inoculated seed within 12h operation, while V(IV) was the main reduction product which precipitated instantly. Increasing initial V(V) concentration resulted in the decrease of V(V) removal efficiency, while this index increased first and then decreased with the increase of initial COD concentration, pH and conductivity. High-throughput 16S rRNA gene pyrosequencing analysis indicated the decreased microbial diversity. V(V) reduction was realized through dissimilatory reduction process by significantly enhanced Lactococcus and Enterobacter with oxidation of lactic and acetic acids from fermentative microorganisms such as the enriched Paludibacter and the newly appeared Acetobacterium, Oscillibacter. This study is helpful to detect new functional species for V(V) reduction and constitutes a step ahead in developing in situ bioremediations of vanadium contamination. Copyright © 2015 Elsevier Ltd. All rights reserved.

Methanol Oxidation Using Ozone on Titania-Supported Vanadium Catalyst

EPA Science Inventory

Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100 to 250NC using V2O5/TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. ...

Two-Stage Separation of V(IV) and Al(III) by Crystallization and Solvent Extraction from Aluminum-Rich Sulfuric Acid Leaching Solution of Stone Coal

NASA Astrophysics Data System (ADS)

Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing; Liu, Hong

2017-10-01

To improve separation of V(IV) and Al(III) from aluminum-rich sulfuric acid leaching solution of stone coal, the two-stage separation by crystallization and solvent extraction methods have been developed. A co-extraction coefficient ( k) was put forward to evaluate comprehensively co-extraction extent in different solutions. In the crystallization stage, 68.2% of aluminum can be removed from the solution. In the solvent extraction stage, vanadium was selectively extracted using di-2-ethylhexyl phosphoric acid/tri-n-butyl phosphate from the crystalline mother solution, followed by H2SO4 stripped efficiently. A V2O5 product with purity of 98.39% and only 0.10% Al was obtained after oxidation, precipitation, and calcination. Compared with vanadium extraction from solution without crystallization, the counter-current extraction stage of vanadium can be decreased from 6 to 3 and co-extraction coefficient ( k) decreased from 2.51 to 0.58 with two-stage separation. It is suggested that the aluminum removal by crystallization can evidently weaken the influence of aluminum co-extraction on vanadium extraction and improve the selectivity of solvent extraction for vanadium.

Process optimization for diffusion bonding of tungsten with EUROFER97 using a vanadium interlayer

NASA Astrophysics Data System (ADS)

Basuki, Widodo Widjaja; Aktaa, Jarir

2015-04-01

Solid-state diffusion bonding is a selected joining technology to bond divertor components consisting of tungsten and EUROFER97 for application in fusion power plants. Due to the large mismatch in their coefficient of thermal expansions, which leads to serious thermally induced residual stresses after bonding, a thin vanadium plate is introduced as an interlayer. However, the diffusion of carbon originated from EUROFER97 in the vanadium interlayer during the bonding process can form a vanadium carbide layer, which has detrimental influences on the mechanical properties of the joint. For optimal bonding results, the thickness of this layer and the residual stresses has to be decreased sufficiently without a significant reduction of material transport especially at the vanadium/tungsten interface, which can be achieved by varying the diffusion bonding temperature and duration. The investigation results show that at a sufficiently low bonding temperature of 700 °C and a bonding duration of 4 h, the joint reaches a reasonable high ductility and toughness especially at elevated test temperature of 550 °C with elongation to fracture of 20% and mean absorbed Charpy impact energy of 2 J (using miniaturized Charpy impact specimens). The strength of the bonded materials is about 332 MPa at RT and 291 MPa at 550 °C. Furthermore, a low bonding temperature of 700 °C can also help to avoid the grain coarsening and the alteration of the grain structure especially of the EUROFER97 close to the bond interface.

Zirconium oxide nanotube-Nafion composite as high performance membrane for all vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Aziz, Md. Abdul; Shanmugam, Sangaraju

2017-01-01

A high-performance composite membrane for vanadium redox flow battery (VRB) consisting of ZrO2 nanotubes (ZrNT) and perfluorosulfonic acid (Nafion) was fabricated. The VRB operated with a composite (Nafion-ZrNT) membrane showed the improved ion-selectivity (ratio of proton conductivity to permeability), low self-discharge rate, high discharge capacity and high energy efficiency in comparison with a pristine commercial Nafion-117 membrane. The incorporation of zirconium oxide nanotubes in the Nafion matrix exhibits high proton conductivity (95.2 mS cm-1) and high oxidative stability (99.9%). The Nafion-ZrNT composite membrane exhibited low vanadium ion permeability (3.2 × 10-9 cm2 min-1) and superior ion selectivity (2.95 × 107 S min cm-3). The VRB constructed with a Nafion-ZrNT composite membrane has lower self-discharge rate maintaining an open-circuit voltage of 1.3 V for 330 h relative to a pristine Nafion membrane (29 h). The discharge capacity of Nafion-ZrNT membrane (987 mAh) was 3.5-times higher than Nafion-117 membrane (280 mAh) after 100 charge-discharge cycles. These superior properties resulted in higher coulombic and voltage efficiencies with Nafion-ZrNT membranes compared to VRB with Nafion-117 membrane at a 40 mA cm-2 current density.

Enhanced photocatalytic activity of hydrogenated and vanadium doped TiO2 nanotube arrays grown by anodization of sputtered Ti layers

NASA Astrophysics Data System (ADS)

Motola, Martin; Satrapinskyy, Leonid; Čaplovicová, Mária; Roch, Tomáš; Gregor, Maroš; Grančič, Branislav; Greguš, Ján; Čaplovič, Ľubomír; Plesch, Gustav

2018-03-01

TiO2 nanotube (TiNT) arrays were grown on silicon substrate via electrochemical anodization of titanium films sputtered by magnetron. To improve the photocatalytic activity of arrays annealed in air (o-TiNT), doping of o-TiNT with vanadium was performed (o-V/TiNT). These non-doped and doped TiNT arrays were also hydrogenated in H2/Ar atmosphere to r-TiNT and r-V/TiNT samples, respectively. Investigation of composition and morphology by X-ray diffraction (XRD), electron microscopy (SEM and TEM) and X-ray photoelectron spectroscopy (XPS) showed the presence of well-ordered arrays of anatase nanotubes with average diameter and length of 100 nm and 1.3 μm, respectively. In both oxidized and reduced V-doped samples, vanadium is partly dissolved in the structure of anatase and partly deposited in form of oxide on the nanotube surface. Vanadium-doped and reduced samples exhibited higher rates in the photodegradation of organic dyes (compared to non-modified o-TiNT sample) and this is caused by limitation of electron-hole recombination rates and by shift of the energy gap into visible region. The photocatalytic activity was measured under UV, sunlight and visible irradiation, and the corresponding efficiency increased in the order (o-TiNT) < (r-TiNT) < (o-V/TiNT) < (r-V/TiNT). Under visible light, only r-TiNT and r-V/TiNT showed significant photocatalytic activity.

Comparison of Elemental Mercury Oxidation Across Vanadium and Cerium Based Catalysts in Coal Combustion Flue Gas: Catalytic Performances and Particulate Matter Effects.

PubMed

Wan, Qi; Yao, Qiang; Duan, Lei; Li, Xinghua; Zhang, Lei; Hao, Jiming

2018-03-06

This paper discussed the field test results of mercury oxidation activities over vanadium and cerium based catalysts in both coal-fired circulating fluidized bed boiler (CFBB) and chain grate boiler (CGB) flue gases. The characterizations of the catalysts and effects of flue gas components, specifically the particulate matter (PM) species, were also discussed. The catalytic performance results indicated that both catalysts exhibited mercury oxidation preference in CGB flue gas rather than in CFBB flue gas. Flue gas component studies before and after dust removal equipment implied that the mercury oxidation was well related to PM, together with gaseous components such as NO, SO 2 , and NH 3 . Further investigations demonstrated a negative PM concentration-induced effect on the mercury oxidation activity in the flue gases before the dust removal, which was attributed to the surface coverage by the large amount of PM. In addition, the PM concentrations in the flue gases after the dust removal failed in determining the mercury oxidation efficiency, wherein the presence of different chemical species in PM, such as elemental carbon (EC), organic carbon (OC) and alkali (earth) metals (Na, Mg, K, and Ca) in the flue gases dominated the catalytic oxidation of mercury.

Phase Stability and Transformations in Vanadium Oxide Nanocrystals

NASA Astrophysics Data System (ADS)

Bergerud, Amy Jo

Vanadium oxides are both fascinating and complex, due in part to the many compounds and phases that can be stabilized as well as the phase transformations which occur between them. The metal to insulator transitions (MITs) that take place in vanadium oxides are particularly interesting for both fundamental and applied study as they can be induced by a variety of stimuli ( i.e., temperature, pressure, doping) and utilized in many applications (i.e., smart windows, sensors, phase change memory). Nanocrystals also tend to demonstrate interesting phase behavior, due in part to the enhanced influence of surface energy on material thermodynamics. Vanadium oxide nanocrystals are thus expected to demonstrate very interesting properties in regard to phase stability and phase transformations, although synthesizing vanadium oxides in nanocrystal form remains a challenge. Vanadium sesquioxide (V2O3) is an example of a material that undergoes a MIT. For decades, the low temperature monoclinic phase and high temperature corundum phase were the only known crystal structures of V2O3. However, in 2011, a new metastable polymorph of V2O3 was reported with a cubic, bixbyite crystal structure. In Chapter 2, a colloidal route to bixbyite V2O 3 nanocrystals is presented. In addition to being one of the first reported observations of the bixbyite phase in V2O3, it is also one of the first successful colloidal syntheses of any of the vanadium oxides. The nanocrystals possess a flower-like morphology, the size and shape of which are dependent on synthesis time and temperature, respectively. An aminolysis reaction mechanism is determined from Fourier transform infrared spectroscopy data and the bixbyite crystal structure is confirmed by Rietveld refinement of X-ray diffraction (XRD) data. Phase stability is assessed in both air and inert environments, confirming the metastable nature of the material. Upon heating in an inert atmosphere above 700°C, the nanocrystals irreversibly transform to the bulk stable corundum phase of V2O3 with concurrent particle coarsening. This, in combination with the enhanced stability of the nanocrystals over bulk, suggests that the bixbyite phase may be stabilized due to surface energy effects, a well-known phenomenon in nanocrystal research. In Chapter 3, the reversible incorporation of oxygen in bixbyite V 2O3 is reported, which can be controlled by varying temperature and oxygen partial pressure. Based on XRD and thermogravimetric analysis, it is found that oxygen occupies interstitial sites in the bixbyite lattice. Two oxygen atoms per unit cell can be incorporated rapidly and with minimal changes to the structure while the addition of three or more oxygen atoms destabilizes the structure, resulting in a phase change that can be reversed upon oxygen removal. Density functional theory (DFT) supports the reversible occupation of interstitial sites in bixbyite by oxygen and the 1.1 eV barrier to oxygen diffusion predicted by DFT matches the activation energy of the oxidation process derived from observations by in situ XRD. The observed rapid oxidation kinetics are thus facilitated by short diffusion paths through the bixbyite nanocrystals. Due to the exceptionally low temperatures of oxidation and reduction, this material, made from earth-abundant atoms, is proposed for use in oxygen storage applications, where oxygen is reversibly stored and released. Further oxidation of bixbyite V2O3 under controlled oxygen partial pressure can lead to the formation of nanocrystalline vanadium dioxide (VO2), a material that is studied for its MIT that occurs at 68 C in the bulk. This transformation is accompanied by a change in crystal structure, from monoclinic to rutile phase, and a change in optical properties, from infrared transparent to infrared blocking. Because of this, VO2 is promising for thermochromic smart window applications, where optical properties vary with temperature. Recently, alternative stimuli have been utilized to trigger MITs in VO2, including electrochemical gating. Rather than inducing the expected monoclinic to rutile phase transition as originally proposed, electrochemical gating of the insulating phase was recently shown to induce oxygen vacancy formation in VO2, thereby inducing metallization, while the characteristic V-V dimerization of the monoclinic phase was retained. In Chapter 4, the preparation and electrochemical reduction of VO2 nanocrystal films is presented. The nanocrystalline morphology allows for the study of transformations under conditions that enhance the gating effect by creating a large VO2-electrolyte interfacial area and by reducing the path length for diffusion. The resulting transitions are observed optically, from insulator to metal to insulator and back, with in situ visible-near infrared spectroelectrochemistry and correlated with structural changes monitored by Raman and X-ray absorption spectroscopies. The never-before-seen transition to an insulating phase under progressive electrochemical reduction is attributed to an oxygen defect induced phase transition to a new phase. This is likely enabled by the nanocrystalline nature of the sample, which may enhance the kinetics of oxygen diffusion, support a higher degree of lattice expansion-induced strain, or simply alter the thermodynamics of the system.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eaton, Craig; Brahlek, Matthew; Engel-Herbert, Roman, E-mail: rue2@psu.edu

The authors report the growth of stoichiometric SrVO{sub 3} thin films on (LaAlO{sub 3}){sub 0.3}(Sr{sub 2}AlTaO{sub 6}){sub 0.7} (001) substrates using hybrid molecular beam epitaxy. This growth approach employs a conventional effusion cell to supply elemental A-site Sr and the metalorganic precursor vanadium oxytriisopropoxide (VTIP) to supply vanadium. Oxygen is supplied in its molecular form through a gas inlet. An optimal VTIP:Sr flux ratio has been identified using reflection high-energy electron-diffraction, x-ray diffraction, atomic force microscopy, and scanning transmission electron microscopy, demonstrating stoichiometric SrVO{sub 3} films with atomically flat surface morphology. Away from the optimal VTIP:Sr flux, characteristic changes inmore » the crystalline structure and surface morphology of the films were found, enabling identification of the type of nonstoichiometry. For optimal VTIP:Sr flux ratios, high quality SrVO{sub 3} thin films were obtained with smallest deviation of the lattice parameter from the ideal value and with atomically smooth surfaces, indicative of the good cation stoichiometry achieved by this growth technique.« less

Fabrication and Characteristics of Pentacene/Vanadium Pentoxide Field-Effect Transistors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minagawa, M.; Nakai, K.; Baba, A.

2011-12-23

Organic field-effect transistors (OFETs) were fabricated using pentacene thin layer, and the effects of inserted Lewis-acid thin layers on electrical properties were investigated. The OFETs have active layers of pentacene and vanadium pentoxide (V{sub 2}O{sub 5}) as a Lewis-acid layer. Typical source-drain current (I{sub DS}) vs. source-drain voltage (V{sub DS}) curves were observed under negative gate voltages (V{sub G}S) application, and the shift of the threshold voltage for FET driving (V{sub t}) to positive side was also observed by V{sub 2}O{sub 5} layer insertion, that is, -2.5 V for device with V{sub 2}O{sub 5} layer and -5.7 V for devicemore » without V{sub 2}O{sub 5} layer. It was thought that charge transfer (CT) complexes which were formed at the interface between pentacene and V{sub 2}O{sub 5} layer were dissociated by the applied gate voltage, and the generated holes seem to contribute to drain current and the apparent V{sub t} improvement.« less

Hydrothermal synthesis and characterization of novel vanadium oxides and their application as cathodes in lithium secondary batteries

NASA Astrophysics Data System (ADS)

Chirayil, Thomas George

Novel layered or tunneled vanadium oxides are sought as a substitute for the expensive Lisb{x}CoOsb2 cathode material in lithium rechargeable batteries. The hydrothermal synthesis approach was taken in search of new vanadium oxides in the presence of a structure directing cation, TMA. A systematic study was done on the hydrothermal synthesis of the Vsb{2}Osb{5}-TMAOH-LiOH system. It was determined from this study that the pH of the reaction mixture was very critical in the formation of many compounds. Acetic acid utilized to adjust the pH of the reaction mixture in the presence of TMA behaved as a buffer and maintained a constant pH during the reaction. Hydrothermal synthesis conducted between pH 10 and 2 resulted in the formation of 7 compounds. At the highest pH, a well known compound Lisb3VOsb4, was formed. Between pH 5.2-9, a layered compound, TMAVsb3Osb7 resulted. The thermal treatment of TMAVsb3Osb7 under oxygen lead to an oxidized phase, TMAVsb3Osb8, which increased its lithium capacity significantly. Between pH 5-6, a cluster compound, TMAsb8lbrack Vsb{22}Osb{54}(CHsb3COO)rbrack{*}4Hsb2O with the acetate ion trapped inside the caged Vsb{22}Osb{54} cluster, and a layered vanadium oxide, Lisb{x}Vsb{2-delta}Osb{4-delta}{*}Hsb2O was obtained. The Lisb{x}Vsb{2-delta}Osb{4-delta}{*}Hsb2O compound was dehydrated to form Lisb{x}Vsb{2-delta}Osb{4-delta} and the lithium was removed electrochemically to form a new type of "VOsb2". Several alkylamines, DMSO and an additional water molecule were intercalated to swell the layers of Lisb{x}Vsb{2-delta}Osb{4-delta}{*}Hsb2O. Lowering the pH between 3.0-3.5, resulted in layered compound, TMAVsb4Osb{10}, with TMA residing between the layers. Layered compounds, TMAVsb8Osb{20} and TMAsb{0.17}Hsp+sb{0.1}Vsb2Osb5, were obtained at very acidic conditions. The hydrothermally grown TMAsb{0.17}Hsp+sb{0.1}Vsb2Osb5 is similar to the xerogel Vsb2Osb5 intercalated with TMA synthesized by the sol-gel process. Several trends were observed as the pH was varied, in this study. The vanadium coordination changed from only tetrahedra at the highest pH in Lisb3VOsb4, to tetrahedra and square pyramids in TMAVsb3Osb7, to only square pyramids in TMAsb8lbrack Vsb{22}Osb{54}(CHsb3COO)rbrack{*}4Hsb2O,\\ Lisb{x}Vsb{2-delta}Osb{4-delta}{*}Hsb2O and TMAVsb4Osb{10}, to octahedra in TMAVsb8Osb{20} and TMAsb{0.17}Hsp+sb{0.1}Vsb2Osb5. The TMA content in the compounds decreased as the pH was decreased. Electrochemical studies indicated that the lithium capacity of the TMA containing layered compounds increased as the content of TMA decreased. Preliminary shadies indicated that the acids used to adjust the pH of the reaction mixture can also influence the type of products obtained by the hydrothermal method. The synthesis and the detailed characterization of these vanadium oxides are thoroughly discussed in this dissertation.

Studies of electronic and magnetic properties of LaVO3 thin film

NASA Astrophysics Data System (ADS)

Jana, Anupam; Karwal, Sharad; Choudhary, R. J.; Phase, D. M.

2018-04-01

We have investigated the electronic and magnetic properties of pulsed laser deposited Mott insulator LaVO3 (LVO) thin film. Structural characterization revels the single phase [00l] oriented LVO thin film. Enhancement of out of plane lattice parameter indicates the compressively strained LVO film. Electron spectroscopic studies demonstrate that vanadium is present in V3+ state. An energy dispersive X-ray spectroscopic study ensures the stoichiometric growth of the film. Very smooth surface is observed in scanning electron micrograph. Colour mapping for elemental distribution reflect the homogeneity of LVO film. The bifurcation between zero-field-cooled and Field-cooled curves clearly points towards the weak ferromagnetic phase presence in compressively strained LVO thin film. A finite value of coercivity at 300 K reflects the possibility of room temperature ferromagnetism of LVO thin film.

Structural characterization of vanadium oxide catalysts supported on nanostructured silica SBA-15 using X-ray absorption spectroscopy

PubMed Central

2010-01-01

The local structure of vanadium oxide supported on nanostructured SiO2 (VxOy/SBA-15) was investigated by in situ X-ray absorption spectroscopy (XAS). Because the number of potential parameters in XAS data analysis often exceeds the number of "independent" parameters, evaluating the reliability and significance of a particular fitting procedure is mandatory. The number of independent parameters (Nyquist) may not be sufficient. Hence, in addition to the number of independent parameters, a novel approach to evaluate the significance of structural fitting parameters in XAS data analysis is introduced. Three samples with different V loadings (i.e. 2.7 wt %, 5.4 wt %, and 10.8 wt %) were employed. Thermal treatment in air at 623 K resulted in characteristic structural changes of the V oxide species. Independent of the V loading, the local structure around V centers in dehydrated VxOy/SBA-15 corresponded to an ordered arrangement of adjacent V2O7 units. Moreover, the V2O7 units were found to persist under selective oxidation reaction conditions. PMID:20181222

Structural characterization of vanadium oxide catalysts supported on nanostructured silica SBA-15 using X-ray absorption spectroscopy.

PubMed

Walter, Anke; Herbert, Rita; Hess, Christian; Ressler, Thorsten

2010-02-11

The local structure of vanadium oxide supported on nanostructured SiO2 (VxOy/SBA-15) was investigated by in situ X-ray absorption spectroscopy (XAS). Because the number of potential parameters in XAS data analysis often exceeds the number of "independent" parameters, evaluating the reliability and significance of a particular fitting procedure is mandatory. The number of independent parameters (Nyquist) may not be sufficient. Hence, in addition to the number of independent parameters, a novel approach to evaluate the significance of structural fitting parameters in XAS data analysis is introduced. Three samples with different V loadings (i.e. 2.7 wt %, 5.4 wt %, and 10.8 wt %) were employed. Thermal treatment in air at 623 K resulted in characteristic structural changes of the V oxide species. Independent of the V loading, the local structure around V centers in dehydrated VxOy/SBA-15 corresponded to an ordered arrangement of adjacent V2O7 units. Moreover, the V2O7 units were found to persist under selective oxidation reaction conditions.

Noise Spectroscopy in Strongly Correlated Oxides

NASA Astrophysics Data System (ADS)

Alsaqqa, Ali M.

Strongly correlated materials are an interesting class of materials, thanks to the novel electronic and magnetic phenomena they exhibit as a result of the interplay of various degrees of freedom. This gives rise to an array of potential applications, from Mott-FET to magnetic storage. Many experimental probes have been used to study phase transitions in strongly correlated oxides. Among these, resistance noise spectroscopy, together with conventional transport measurements, provides a unique viewpoint to understand the microscopic dynamics near the phase transitions in these oxides. In this thesis, utilizing noise spectroscopy and transport measurements, four different strongly correlated materials were studied: (1) neodymium nickel oxide (NdNiO 3) ultrathin films, (2) vanadium dioxide (VO2) microribbons, (3) copper vanadium bronze (CuxV2O 5) microribbons and (4) niobium triselenide (NbSe3) microribbons. Ultra thin films of rare-earth nickelates exhibit several temperature-driven phase transitions. In this thesis, we studied the metal-insulator and Neel transitions in a series of NdNiO3 films with different lattice mismatches. Upon colling down, the metal-insulator phase transition is accompanied by a structural (orthorohombic to monoclinic) and magnetic (paramagnetic to antiferromagnetic) transitions as well, making the problem more interesting and complex at the same time. The noise is of the 1/f type and is Gaussian in the high temperature phase, however deviations are seen in the low temperature phases. Below the metal-insulator transition, noise magnitude increases by orders of magnitude: a sign of inhomogeneous electrical conduction as result of phase separation. This is further assured by the non-Gaussian noise signature. At very low temperatures (T < 50 K), the noise behavior switches between Gaussian and non-Gaussian over several hours, possibly arising from dynamically competing ground states. VO2 is one of the most widely studied strongly correlated oxides and is important from the fundamental physics point of view and for applications. Its transition from a metal to an insulator (MIT) with simple application of voltage is quite interesting. For use in applications, e.g. transistors, it is very important to have a clear understanding of the MIT. Equally important is the question of whether the thermally- and electrically-driven transitions have the same origin. In this thesis, we tried to answer this question by utilizing three different tuning parameters: temperature, voltage bias and strain. Our results point to an unusual noise behavior in the high-temperature metallic phase, and provide valuable insight into the transport dynamics of this material. CuxV2O5 exhibit a metal-insulator transition and, more interestingly, a superconductivity transition. Unlike VO2, copper vanadium bronzes are much less studied and many questions are still open, including the possibility of charge ordering transition, just like in other members of the vanadium family. In this thesis, we studied this material and found evidences for charge ordering transitions and possibly other transitions as well. The last material, NbSe3, is a prototypical example of charge density wave systems, where Peierls transitions exist. Here, we study the effects of contacts on resistance noise in the 1D limit. The study aimed to confirm that the electric field threshold is sample length independent, to find out if there is a relation between contact separation and the noise generated and to explore the characteristics of the contact noise. The results confirm that the electric field threshold is independent of the sample length. It was also found that the separation between the contacts does not affect the noise. Finally, the contact noise is of the 1/f-type and has a Gaussian distribution. These results are timely for future device applications utilizing NbSe3.

Tuning of thermally induced first-order semiconductor-to-metal transition in pulsed laser deposited VO2 epitaxial thin films

NASA Astrophysics Data System (ADS)

Behera, Makhes K.; Pradhan, Dhiren K.; Pradhan, Sangram K.; Pradhan, Aswini K.

2017-12-01

Vanadium oxide (VO2) thin films have drawn significant research and development interest in recent years because of their intriguing physical origin and wide range of functionalities useful for many potential applications, including infrared imaging, smart windows, and energy and information technologies. However, the growth of highly epitaxial films of VO2, with a sharp and distinct controllable transition, has remained a challenge. Here, we report the structural and electronic properties of high quality and reproducible epitaxial thin films of VO2, grown on c-axis oriented sapphire substrates using pulsed laser deposition at different deposition pressures and temperatures, followed by various annealing schedules. Our results demonstrate that the annealing of epitaxial VO2 films significantly enhances the Semiconductor to Metal Transition (SMT) to that of bulk VO2 transition. The effect of oxygen partial pressure during the growth of VO2 films creates a significant modulation of the SMT from around room temperature to as high as the theoretical value of 68 °C. We obtained a bulk order transition ≥104 while reducing the transition temperature close to 60 °C, which is comparatively less than the theoretical value of 68 °C, demonstrating a clear and drastic improvement in the SMT switching characteristics. The results reported here will open the door to fundamental studies of VO2, along with tuning of the transition temperatures for potential applications for multifunctional devices.

Brain Metal Distribution and Neuro-Inflammatory Profiles after Chronic Vanadium Administration and Withdrawal in Mice

PubMed Central

Folarin, Oluwabusayo R.; Snyder, Amanda M.; Peters, Douglas G.; Olopade, Funmilayo; Connor, James R.; Olopade, James O.

2017-01-01

Vanadium is a potentially toxic environmental pollutant and induces oxidative damage in biological systems including the central nervous system (CNS). Its deposition in brain tissue may be involved in the pathogenesis of certain neurological disorders which after prolonged exposure can culminate into more severe pathology. Most studies on vanadium neurotoxicity have been done after acute exposure but in reality some populations are exposed for a lifetime. This work was designed to ascertain neurodegenerative consequences of chronic vanadium administration and to investigate the progressive changes in the brain after withdrawal from vanadium treatment. A total of 85 male BALB/c mice were used for the experiment and divided into three major groups of vanadium treated (intraperitoneally (i.p.) injected with 3 mg/kg body weight of sodium metavanadate and sacrificed every 3 months till 18 months); matched controls; and animals that were exposed to vanadium for 3 months and thereafter the metal was withdrawn. Brain tissues were obtained after animal sacrifice. Sagittal cut sections of paraffin embedded tissue (5 μm) were analyzed by the Laser ablation-inductively coupled plasma-mass spectrometry (LA–ICP–MS) to show the absorption and distribution of vanadium metal. Also, Haematoxylin and Eosin (H&E) staining of brain sections, and immunohistochemistry for Microglia (Iba-1), Astrocytes (GFAP), Neurons (Neu-N) and Neu-N + 4′,6-diamidine-2′-pheynylindole dihydrochloride (Dapi) Immunofluorescent labeling were observed for morphological and morphometric parameters. The LA–ICP–MS results showed progressive increase in vanadium uptake with time in different brain regions with prediction for regions like the olfactory bulb, brain stem and cerebellum. The withdrawal brains still show presence of vanadium metal in the brain slightly more than the controls. There were morphological alterations (of the layering profile, nuclear shrinkage) in the prefrontal cortex, cellular degeneration (loss of dendritic arborization) and cell death in the Hippocampal CA1 pyramidal cells and Purkinje cells of the cerebellum, including astrocytic and microglial activation in vanadium exposed brains which were all attenuated in the withdrawal group. With exposure into old age, the evident neuropathology was microgliosis, while progressive astrogliosis became more attenuated. We have shown that chronic administration of vanadium over a lifetime in mice resulted in metal accumulation which showed regional variabilities with time. The metal profile and pathological effects were not completely eliminated from the brain even after a long time withdrawal from vanadium metal. PMID:28790895

Activation cross-sections of proton induced reactions on vanadium in the 37-65 MeV energy range

NASA Astrophysics Data System (ADS)

Ditrói, F.; Tárkányi, F.; Takács, S.; Hermanne, A.

2016-08-01

Experimental excitation functions for proton induced reactions on natural vanadium in the 37-65 MeV energy range were measured with the activation method using a stacked foil irradiation technique. By using high resolution gamma spectrometry cross-section data for the production of 51,48Cr, 48V, 48,47,46,44m,44g,43Sc and 43,42K were determined. Comparisons with the earlier published data are presented and results predicted by different theoretical codes (EMPIRE and TALYS) are included. Thick target yields were calculated from a fit to our experimental excitation curves and compared with the earlier experimental yield data. Depth distribution curves to be used for thin layer activation (TLA) are also presented.

Knocking on wood: base metal complexes as catalysts for selective oxidation of lignin models and extracts.

PubMed

Hanson, Susan K; Baker, R Tom

2015-07-21

This work began as part of a biomass conversion catalysis project with UC Santa Barbara funded by the first NSF Chemical Bonding Center, CATSB. Recognizing that catalytic aerobic oxidation of diol C-C bonds could potentially be used to break down lignocellulose, we began to synthesize oxovanadium complexes and explore their fundamental reactivity. Of course there were theories regarding the oxidation mechanism, but our mechanistic studies soon revealed a number of surprises of the type that keep all chemists coming back to the bench! We realized that these reactions were also exciting in that they actually used the oxygen-on-every-carbon property of biomass-derived molecules to control the selectivity of the oxidation. When we found that these oxovanadium complexes tended to convert sugars predominantly to formic acid and carbon dioxide, we replaced one of the OH groups with an ether and entered the dark world of lignin chemistry. In this Account, we summarize results from our collaboration and from our individual labs. In particular, we show that oxidation selectivity (C-C vs C-O bond cleavage) of lignin models using air and vanadium complexes depends on the ancillary ligands, the reaction solvent, and the substrate structure (i.e., phenolic vs non-phenolic). Selected vanadium complexes in the presence of added base serve as effective alcohol oxidation catalysts via a novel base-assisted dehydrogenation pathway. In contrast, copper catalysts effect direct C-C bond cleavage of these lignin models, presumably through a radical pathway. The most active vanadium catalyst exhibits unique activity for the depolymerization of organosolv lignin. After Weckhuysen's excellent 2010 review on lignin valorization, the number of catalysis studies and approaches on both lignin models and extracts has expanded rapidly. Today we are seeing new start-ups and lignin production facilities sprouting up across the globe as we all work to prove wrong the old pulp and paper chemist's adage: you can make anything from lignin except money!

Residual oil fly ash induces cytotoxicity and mucin secretion by guinea pig tracheal epithelial cells via an oxidant-mediated mechanism.

PubMed

Jiang, N; Dreher, K L; Dye, J A; Li, Y; Richards, J H; Martin, L D; Adler, K B

2000-03-15

Inhalation of ambient air particulate matter (PM) is associated with pulmonary injury and inflammation. Using primary cultures of guinea pig tracheal epithelial (GPTE) cells as an in vitro model of airway epithelium, we examined effects of exposure to suspensions of six different emission and ambient air PM samples: residual oil fly ash (ROFA) from an electrical power plant; fly ash from a domestic oil burning furnace (DOFA); ambient air dust from St. Louis (STL), Ottawa (OT), and Washington, DC (WDC); and volcanic ash from the eruption of Mount Saint Helens (MSH) in 1980. Effects of these particulates on cell viability (assessed via LDH assay), secretion of mucin (measured by a monoclonal antibody-based ELISA), and steady-state mRNA levels of the mucin gene MUC2 were determined. ROFA was the most toxic of the dusts tested, as it significantly increased LDH release following a 24-h incubation with 50 microg/cm(2) ROFA. ROFA also enhanced MUC2 mRNA after 4-h exposure, and mucin secretion after 8 h. ROFA-induced mucin secretion and cytotoxicity were attenuated by the oxidant scavenger, dimethylthiourea (DMTU). ROFA exposure also depleted cells of glutathione (GSH). Relatedly, depletion of intracellular GSH by treatment of the cells with buthionine sulfoxamine (BSO) also provoked mucin secretion, as well as enhancing the secretory effect of ROFA when the two agents were added together. L-NMA, the nitric oxide synthase (NOS) inhibitor, did not affect ROFA-induced mucin secretion. Of the soluble transition metals in ROFA (nickel, iron, vanadium), only vanadium individually, or combinations of the metals containing vanadium, provoked secretion. The results suggest ROFA enhances mucin secretion and generates toxicity in vitro to airway epithelium via a mechanism(s) involving generation of oxidant stress, perhaps related to depletion of cellular antioxidant capacity. Deleterious effects of inhalation of ROFA in the respiratory tract in vivo may relate to these cellular responses. Vanadium, a component of ROFA, may be important in generating these reactions. Copyright 2000 Academic Press.

Diel cycles in dissolved barium, lead, iron, vanadium, and nitrite in a stream draining a former zinc smelter site near Hegeler, Illinois

USGS Publications Warehouse

Kay, R.T.; Groschen, G.E.; Cygan, G.; Dupre, David H.

2011-01-01

Diel variations in the concentrations of a number of constituents have the potential to substantially affect the appropriate sampling regimen in acidic streams. Samples taken once during the course of the day cannot adequately reflect diel variations in water quality and may result in an inaccurate understanding of biogeochemical processes, ecological conditions, and of the threat posed by the water to human health and the associated wildlife. Surface water and groundwater affected by acid drainage were sampled every 60 to 90. min over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, near Hegeler, Illinois. Diel variations related to water quality in the aquifer were not observed in groundwater. Diel variations were observed in the temperature, pH, and concentration of dissolved oxygen, nitrite, barium, iron, lead, vanadium, and possibly uranium in surface water. Temperature, dissolved oxygen, nitrite, barium, lead, and uranium generally attained maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally attained minimum values during the afternoon and maximum values during the night. Concentrations of dissolved oxygen were affected by the intensity of photosynthetic activity and respiration, which are dependent upon insolation. Nitrite, an intermediary in many nitrogen reactions, may have been formed by the oxidation of ammonium by dissolved oxygen and converted to other nitrogen species as part of the decomposition of organic matter. The timing of the pH cycles was distinctly different from the cycles found in Midwestern alkaline streams and likely was the result of the photoreduction of Fe3+ to Fe 2+ and variations in the intensity of precipitation of hydrous ferric oxide minerals. Diel cycles of iron and vanadium also were primarily the result of variations in the intensity of precipitation of hydrous ferric oxide minerals. The diel variation in the concentrations of lead, uranium, and barium may have been affected by competition with Fe+2 for sorption sites on hydrous ferric oxide minerals. ?? 2010.

Electrochemical cell structure including an ionomeric barrier

DOEpatents

Lambert, Timothy N.; Hibbs, Michael

2017-06-20

An apparatus includes an electrochemical half-cell comprising: an electrolyte, an anode; and an ionomeric barrier positioned between the electrolyte and the anode. The anode may comprise a multi-electron vanadium phosphorous alloy, such as VP.sub.x, wherein x is 1-5. The electrochemical half-cell is configured to oxidize the vanadium and phosphorous alloy to release electrons. A method of mitigating corrosion in an electrochemical cell includes disposing an ionomeric barrier in a path of electrolyte or ion flow to an anode and mitigating anion accumulation on the surface of the anode.

Geometric confinement effects on the metal-insulator transition temperature and stress relaxation in VO2 thin films grown on silicon

NASA Astrophysics Data System (ADS)

Viswanath, Changhyun Ko, B.; Yang, Zheng; Ramanathan, Shriram

2011-03-01

VO2 undergoes a sharp metal-insulator transition at ˜67 °C with several orders of change in conductivity and optical transmittance. Understanding and control of the properties of vanadium oxide layers grown on technologically relevant substrates such as Si (100) single crystals is therefore of great interest. In this work, we show tunability of metal-insulator transition temperature as well as recoverable stress in VO2 thin films grown on Si substrate by introducing nanoscale atomic layer deposited HfO2 interfacial layers with no degradation in the resistance ratio. For a confined VO2 film, the metal-insulator transition temperature is suppressed by ˜16 °C and the recoverable stress is 150 MPa, compared to 400 MPa for a bare film. These observations are further correlated with in situ variable temperature measurement of stress changes occurring during the phase transition. Structural and microstructural studies on the various samples have been carried out by x ray diffraction and cross-sectional transmission electron microscopy. The strategy of tuning the metal-insulator transition characteristics by nanoscale interfacial dielectrics is of broader relevance in design of programmable materials and integration into solid state devices for electronics.

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

PubMed

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.

Highly stable pyridinium-functionalized cross-linked anion exchange membranes for all vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

2016-11-01

It has recently been demonstrated that the use of anion exchange membranes (AEMs) in vanadium redox flow batteries (VRFBs) can reduce the migration of vanadium ions through the membrane due to the Donnan exclusion effect among the positively charged functional groups and vanadium ions. However, AEMs are plagued by low chemical stability in harsh chemical environments. Here we propose and fabricate a pyridinium-functionalized cross-linked AEM for VRFBs. The pyridinium-functionalized bromomethylated poly (2,6-dimethyl-1,4-phenylene oxide) exhibits a superior chemical stability as a result of the strengthened internal cross-linking networks and the chemical inertness of the polymer backbone. Therefore, the membrane exhibits littler decay in a harsh environment for 20 days during the course of an ex situ immersion test. A cycling test also demonstrates that the VRFB assembled with the membrane enable to retain 80% of the initial discharge capacity over 537 cycles with a capacity decay rate of 0.037% cycle-1. Meanwhile, the membrane also shows a low vanadium permeability and a reasonably high conductivity in supporting electrolytes. Hence, all the measurements and performance tests reported in this work suggest that the membrane is a promising AEM for redox flow batteries to achieve excellent cycling stability and superior cell performance.

Hydrothermal synthesis, crystal structure, and magnetic properties of a new inorganic vanadium(III) phosphate with a chain structure.

PubMed

Ferdov, Stanislav; Reis, Mario S; Lin, Zhi; Ferreira, Rute A Sá

2008-11-03

A new vanadium(III) phosphate, Na3V(OH)(HPO4)(PO4), has been synthesized by using mild hydrothermal conditions under autogeneous pressure. This material represents a very rare example of sodium vanadium(III) phosphate with a chain structure. The crystal structure has been determined by refinement of powder X-ray diffraction data, starting from the atomic coordinates of an isotypic compound, Na3Al(OH)(HPO4)(PO4), which was obtained under high temperature and high pressure. The phase crystallizes in monoclinic space group C2/m (No. 12) with lattice parameters a = 15.423(9) A, b = 7.280(0) A, c = 7.070(9) A, beta = 96.79(7) degrees, V = 788.3(9) A(3), and Z = 4. The structure consists of one-dimensional chains composed of corner-sharing VO5(OH) octahedra running along the b direction. They are decorated by isolated PO4 and HPO4 tetrahedra sharing two of their corners with the ones of the vanadium octahedra. The interconnection between the chains is assured by three crystallographically distinct Na(+) cations. Magnetic investigation confirms the 3+ oxidation state of the vanadium ions and reveals an antiferromagnetic arrangement between those ions through the chain.

Insulin mimesis of vanadium derivatives. Oxidation of cysteine by V(V) oxo diperoxo complexes.

PubMed

Ballistreri, F P; Barbuzzi, E G; Tomaselli, G A; Toscano, R M

2000-05-30

Kinetics of the oxidation of cysteine to cystine by four V(V) oxo diperoxo complexes [VO(O2)2L] possessing insulin mimetic activity, where L = oxalate(oxa), picolinate (pic), bipyridil (bipy), phenanthroline(phen), were performed in water at 10 degrees C by the UV or stopped-flow technique. 51V NMR spectra indicate that oxa undergoes a total ligand dissociation differently from pic, bipy and phen which hold their ligands also in solution. The observed reactivity is deeply affected by the identity of the ligand. The process seems to require coordination of the cysteine to the metal, followed by oxidation within the coordination sphere. In this respect phen and bipy make the coordination of cysteine much easier than oxa and pic. It is suggested, also on the basis of some preliminary observations concerning the oxidation of C6H5CH2SH, that the oxidation process is triggered by an electron transfer step. The rate of this step would be higher for oxa and pic than for phen and bipy. The observation that the oxidative ability of these vanadium peroxo complexes is dependent upon the nature of the ligands might match the analogous finding that their insulin mimetic activity is also modulated by the ligand identities.

Synthesis and luminescence properties of vanadium-doped nanosized zinc oxide aerogel

NASA Astrophysics Data System (ADS)

El Mir, L.; El Ghoul, J.; Alaya, S.; Ben Salem, M.; Barthou, C.; von Bardeleben, H. J.

2008-05-01

We report the elaboration of vanadium-doped ZnO nanoparticles prepared by a sol-gel processing technique. In our approach, the water for hydrolysis was slowly released by esterification reaction followed by a supercritical drying in ethyl alcohol. Vanadium doping concentration of 10 at% has been investigated. The obtained nanopowder was characterised by various techniques such as particle size analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence (PL). In the as-prepared state, the powder with an average particle size of 25 nm presents a strong luminescence band in the visible range after thermal treatment at 500 °C in air. The energy position of the obtained PL band depends on the wavelength excitation and presents a blue shift with measurement temperature increase. Different possible attributions of this emission band will be discussed.

Glassy carbon/multi walled carbon nanotube/cadmium sulphide photoanode for light energy storage in vanadium photoelectrochemical cell

NASA Astrophysics Data System (ADS)

Peimanifard, Zahra; Rashid-Nadimi, Sahar

2015-12-01

The aim of this study is utilizing the artificial photosynthesis, which is an attractive and challenging theme in the photoelectrocatalytic water splitting, to charge the vanadium redox flow battery (VRFB). In this work multi walled carbon nanotube/cadmium sulphide hybrid is employed as a photoanode material to oxidize VO2+ toVO2+ for charging the positive vanadium redox flow battery's half-cell. Characterization studies are also described using the scanning electron microscopic-energy-dispersive X-ray spectroscopy (SEM-EDS), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and UV-Visible methods. The phtoelectrochemical performance is characterized by cyclic voltammetry and chronoamperometry. Applied bias photon-to-current efficiency (ABPE) is achieved for both two and three-electrode configurations. The glassy carbon/multi walled carbon nanotube/cadmium sulphide yields high maximum ABPE of 2.6% and 2.12% in three and two-electrode setups, respectively. These results provide a useful guideline in designing photoelectrochemical cells for charging the vanadium redox flow batteries by sunlight as a low cost, free and abundant energy source, which does not rely on an external power input.

Effect of catalyst on deposition of vanadium oxide in plasma ambient

NASA Astrophysics Data System (ADS)

Singh, Megha; Kumar, Prabhat; Saini, Sujit K.; Reddy, G. B.

2018-05-01

In this paper, we have studied effect of catalyst (buffer layer) on structure, morphology, crystallinity, uniformity of nanostructured thin films deposited in nitrogen plasma ambient keeping all other process parameters constant. The process used for deposition is novel known as Plasma Assisted Sublimation Process (PASP). Samples were then studied using SEM, TEM, HRTEM, Raman spectroscopy. By structural analysis it was found out that samples deposited on Ni layer composed chiefly of α-V2O5 but minor amount of other phases were present in the sample. Samples deposited on Al catalyst layer revealed different phase of V2O5, where sample deposited on Ag was composed chiefly of VO2±x phase. Further analysis revealed that morphology of samples is also affected by catalyst. While samples deposited in Al and Ag layer tend to have reasonably defined geometry, sample deposited on Ni layer were irregular in shape and size. All the results well corroborate with each other.

Temperature and electric field induced metal-insulator transition in atomic layer deposited VO2 thin films

NASA Astrophysics Data System (ADS)

Tadjer, Marko J.; Wheeler, Virginia D.; Downey, Brian P.; Robinson, Zachary R.; Meyer, David J.; Eddy, Charles R.; Kub, Fritz J.

2017-10-01

Amorphous vanadium oxide (VO2) films deposited by atomic layer deposition (ALD) were crystallized with an ex situ anneal at 660-670 °C for 1-2 h under a low oxygen pressure (10-4 to 10-5 Torr). Under these conditions the crystalline VO2 phase was maintained, while formation of the V2O5 phase was suppressed. Electrical transition from the insulator to the metallic phase was observed in the 37-60 °C range, with an ROFF/RON ratio of up to about 750 and ΔTC ≅ 7-10 °C. Lateral electric field applied across two-terminal device structures induced a reversible phase change, with a room temperature transition field of about 25 kV/cm in the VO2 sample processed with the 2 h long O2 anneal. Both the width and slope of the field induced MIT I-V hysteresis were dependent upon the VO2 crystalline quality.

Electronic Structure of C60/Zinc Phthalocyanine/V₂O₅ Interfaces Studied Using Photoemission Spectroscopy for Organic Photovoltaic Applications.

PubMed

Lim, Chang Jin; Park, Min Gyu; Kim, Min Su; Han, Jeong Hwa; Cho, Soohaeng; Cho, Mann-Ho; Yi, Yeonjin; Lee, Hyunbok; Cho, Sang Wan

2018-02-18

The interfacial electronic structures of a bilayer of fullerene (C 60 ) and zinc phthalocyanine (ZnPc) grown on vanadium pentoxide (V₂O₅) thin films deposited using radio frequency sputtering under various conditions were studied using X-ray and ultraviolet photoelectron spectroscopy. The energy difference between the highest occupied molecular orbital (HOMO) level of the ZnPc layer and the lowest unoccupied molecular orbital (LUMO) level of the C 60 layer was determined and compared with that grown on an indium tin oxide (ITO) substrate. The energy difference of a heterojunction on all V₂O₅ was found to be 1.3~1.4 eV, while that on ITO was 1.1 eV. This difference could be due to the higher binding energy of the HOMO of ZnPc on V₂O₅ than that on ITO regardless of work functions of the substrates. We also determined the complete energy level diagrams of C 60 /ZnPc on V₂O₅ and ITO.

NH3-SCR denitration catalyst performance over vanadium-titanium with the addition of Ce and Sb.

PubMed

Xu, Chi; Liu, Jian; Zhao, Zhen; Yu, Fei; Cheng, Kai; Wei, Yuechang; Duan, Aijun; Jiang, Guiyuan

2015-05-01

Selective catalytic reduction technology using NH3 as a reducing agent (NH3-SCR) is an effective control method to remove nitrogen oxides. TiO2-supported vanadium oxide catalysts with different levels of Ce and Sb modification were prepared by an impregnation method and were characterized by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), Raman and Hydrogen temperature-programmed reduction (H2-TPR). The catalytic activities of V5CexSby/TiO2 catalysts for denitration were investigated in a fixed bed flow microreactor. The results showed that cerium, vanadium and antimony oxide as the active components were well dispersed on TiO2, and the catalysts exhibited a large number of d-d electronic transitions, which were helpful to strengthen SCR reactivity. The V5CexSby/TiO2 catalysts exhibited a good low temperature NH3-SCR catalytic activity. In the temperature range of 210 to 400°C, the V5CexSby/TiO2 catalysts gave NO conversion rates above 90%. For the best V5Ce35Sb2/TiO2 catalyst, at a reaction temperature of 210°C, the NO conversion rate had already reached 90%. The catalysts had different catalytic activity with different Ce loadings. With the increase of Ce loading, the NO conversion rate also increased. Copyright © 2015. Published by Elsevier B.V.

The Vanadium Iodoperoxidase from the Marine Flavobacteriaceae Species Zobellia galactanivorans Reveals Novel Molecular and Evolutionary Features of Halide Specificity in the Vanadium Haloperoxidase Enzyme Family

PubMed Central

Fournier, Jean-Baptiste; Rebuffet, Etienne; Delage, Ludovic; Grijol, Romain; Meslet-Cladière, Laurence; Rzonca, Justyna; Potin, Philippe; Michel, Gurvan; Czjzek, Mirjam

2014-01-01

Vanadium haloperoxidases (VHPO) are key enzymes that oxidize halides and are involved in the biosynthesis of organo-halogens. Until now, only chloroperoxidases (VCPO) and bromoperoxidases (VBPO) have been characterized structurally, mainly from eukaryotic species. Three putative VHPO genes were predicted in the genome of the flavobacterium Zobellia galactanivorans, a marine bacterium associated with macroalgae. In a phylogenetic analysis, these putative bacterial VHPO were closely related to other VHPO from diverse bacterial phyla but clustered independently from eukaryotic algal VBPO and fungal VCPO. Two of these bacterial VHPO, heterogeneously produced in Escherichia coli, were found to be strictly specific for iodide oxidation. The crystal structure of one of these vanadium-dependent iodoperoxidases, Zg-VIPO1, was solved by multiwavelength anomalous diffraction at 1.8 Å, revealing a monomeric structure mainly folded into α-helices. This three-dimensional structure is relatively similar to those of VCPO of the fungus Curvularia inaequalis and of Streptomyces sp. and is superimposable onto the dimeric structure of algal VBPO. Surprisingly, the vanadate binding site of Zg-VIPO1 is strictly conserved with the fungal VCPO active site. Using site-directed mutagenesis, we showed that specific amino acids and the associated hydrogen bonding network around the vanadate center are essential for the catalytic properties and also the iodide specificity of Zg-VIPO1. Altogether, phylogeny and structure-function data support the finding that iodoperoxidase activities evolved independently in bacterial and algal lineages, and this sheds light on the evolution of the VHPO enzyme family. PMID:25261522

Lithium Vanadium Oxide (Li 1.1V 3O 8) Coated with Amorphous Lithium Phosphorous Oxynitride (LiPON): Role of Material Morphology and Interfacial Structure on Resulting Electrochemistry

DOE PAGES

Zhang, Qing; Kercher, Andrew K.; Veith, Gabriel M.; ...

2017-05-16

In the present work, lithium vanadium oxide (Li 1.1V 3O 8) particles synthesized at two different temperatures were coated with an amorphous lithium phosphorous oxynitride (LiPON) film for the first time, and the effects of the LiPON coating on the electrochemistry of the Li 1.1V 3O 8 materials with different morphologies were systematically investigated by comparing uncoated Li 1.1V 3O 8 and Li 1.1V 3O 8 coated with LiPON of various thicknesses. Galvanostatic discharge-charge cycling revealed increased functional capacity for the LiPON-coated materials. Post-cycling electrochemical impedance spectroscopy showed that LiPON-coated Li 1.1V 3O 8 materials developed less interfacial resistance withmore » extended cycling, rationalized by vanadium migration into the LiPON coating seen by electron energy loss spectra. Post-mortem quantitative analysis of the anodes revealed more severe vanadium dissolution for the more irregularly shaped Li 1.1V 3O 8 materials with less LiPON coverage. Thus, this study highlights the specific benefits and limitations of LiPON coatings for stabilizing a moderate voltage Li 1.1V 3O 8 cathode material under extended cycling in liquid electrolyte, and describes a generally applicable approach for comprehensive characterization of a composite electroactive material which can be used to understand interfacial transport properties in other functional systems.« less

Lithium Vanadium Oxide (Li 1.1V 3O 8) Coated with Amorphous Lithium Phosphorous Oxynitride (LiPON): Role of Material Morphology and Interfacial Structure on Resulting Electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qing; Kercher, Andrew K.; Veith, Gabriel M.

In the present work, lithium vanadium oxide (Li 1.1V 3O 8) particles synthesized at two different temperatures were coated with an amorphous lithium phosphorous oxynitride (LiPON) film for the first time, and the effects of the LiPON coating on the electrochemistry of the Li 1.1V 3O 8 materials with different morphologies were systematically investigated by comparing uncoated Li 1.1V 3O 8 and Li 1.1V 3O 8 coated with LiPON of various thicknesses. Galvanostatic discharge-charge cycling revealed increased functional capacity for the LiPON-coated materials. Post-cycling electrochemical impedance spectroscopy showed that LiPON-coated Li 1.1V 3O 8 materials developed less interfacial resistance withmore » extended cycling, rationalized by vanadium migration into the LiPON coating seen by electron energy loss spectra. Post-mortem quantitative analysis of the anodes revealed more severe vanadium dissolution for the more irregularly shaped Li 1.1V 3O 8 materials with less LiPON coverage. Thus, this study highlights the specific benefits and limitations of LiPON coatings for stabilizing a moderate voltage Li 1.1V 3O 8 cathode material under extended cycling in liquid electrolyte, and describes a generally applicable approach for comprehensive characterization of a composite electroactive material which can be used to understand interfacial transport properties in other functional systems.« less

(S)TEM analysis of functional transition metal oxides

NASA Astrophysics Data System (ADS)

Chi, Miaofang

Perovskite vanadates (AVO3) form an ideal family to study the structure-property relationships in transition metal oxides because their physical properties can easily be tailored by varying the A-site cations. (S)TEM is an ideal tool for this type of study due to its capacity for simultaneous imaging and chemical analysis. Determination of the oxidation state of vanadium in complex oxides have been carried out by electron energy loss spectroscopy. SrVO3/LaAlO3 is then studied both experimentally and theoretically as a prototype system. Extra electrons have been detected on the interface layer, and further proven to originate mainly from a change in the local bonding configuration of V at the La-O terminated substrate surface. Cr-containing stainless steel deposited with a LaCrO3 thin-film layer is a promising interconnect material of Solid Oxide Fuel Cells (SOFC). Our investigation on its microstructural evolution reveals that the LaCrO 3 thin film plays a role in inhibiting the growth of an oxide layer on the metal surface and thus protects the surface of the stainless steel. Ca-doped LaCoO3 is a promising SOFC cathode material. The domain structures and the oxidation state of Co in Ca-doped LaCoO3, which are directly related to its mechanical properties and electronic conductivity, are investigated by in-situ TEM and EELS. The formation of microcracks is observed during thermal cycles. Ca-doping in LaCoO3 is shown to not only improve the electronic conductivity of the material, but is also likely to strengthen the grain boundaries. The realization of its application in SOFCs depends on depressing the ferroelastisity to reduce strain formation during thermal cycles. The application of the (S)TEM techniques used for studying the perovskite systems are further extended to other compounds containing transition metal elements. The refractory minerals from Comet 81 P/Wild-2 are studied to investigate the formation of the early solar system. A relatively high Ti3+/Ti 4+ ratio in fassaite and the presence of osbornite indicate that the Comet refractory minerals formed in the inner solar nebula and were later transported to the outer solar system where the comet formed. This implies a much more dynamic and perhaps more violent solar nebula than was previously suspected.

Redox properties of vanadium ions in SBA-15-supported vanadium oxide: an FTIR spectroscopic study.

PubMed

Venkov, Tzvetomir V; Hess, Christian; Jentoft, Friederike C

2007-02-13

The state of vanadium ions in VxOy/SBA-15 (2.7 wt % V) was studied with FTIR spectroscopy using CO and NO as probe molecules. Neither CO (at 85 K) nor NO (at RT) adsorb on the oxidized sample because of the coordinative saturation of V5+ ions and the covalent character of the V5+=O bond. After treatment of the sample in 50 kPa H2 at 673 K, the V5+ ions are reduced to two different types of V3+ sites, as manifested by carbonyl bands at 2189 and 2177 cm-1. In the presence of O2 at 85 K, thus formed V3+ ions are partly oxidized to V4+ sites showing carbonylic bands at 2202 and 2190 cm-1. When the reduced sample is exposed to O2 at room temperature, the V3+ ions are fully oxidized to V5+. The adsorption of NO on the reduced VxOy/SBA-15 shows that the V3+ and V4+ ions possess two effective coordinative vacancies and as a result can adsorb two NO molecules forming the respective V3+(NO)2 and V4+(NO)2 dinitrosyls. The introduction of O2 to the VxOy/SBA-15-NO system leads to reoxidation of the V3+ and V4+ ions to V5+ and formation of bridged (1639 cm-1) and bidentate (1573 cm-1) surface nitrates. After coadsorption of CO and NO on the reduced sample the formation of surface mixed carbonyl-nitrosyls (2108 and 1723 cm-1) was observed for the first time.

Sodium metavanadate induced cognitive decline, behavioral impairments, oxidative stress and down regulation of myelin basic protein in mice hippocampus: Ameliorative roles of β-spinasterol, and stigmasterol.

PubMed

Adebiyi, Olamide Elizabeth; Olopade, James Olukayode; Olayemi, Funsho Olakitike

2018-06-01

Exposures to toxic levels of vanadium and soluble vanadium compounds cause behavioral impairments and neurodegeneration via free radical production. Consequently, natural antioxidant sources have been explored for effective and cheap remedy following toxicity. Grewia carpinifolia has been shown to improve behavioral impairments in vanadium-induced neurotoxicity, however, the active compounds implicated remains unknown. Therefore, this study was conducted to investigate ameliorative effects of bioactive compounds from G. carpinifolia on memory and behavioral impairments in vanadium-induced neurotoxicity. Sixty BALB/c mice were equally divided into five groups (A-E). A (control); administered distilled water, B (standard); administered α-tocopherol (500 mg/kg) every 72 hr orally with daily dose of sodium metavanadate (3 mg/kg) intraperitoneally, test groups C, and D; received single oral dose of 100 μg β-spinasterol or stigmasterol (bioactive compounds from G. carpinifolia), respectively, along with sodium metavanadate and the model group E, received sodium metavanadate only for seven consecutive days. Memory, locomotion and muscular strength were accessed using Morris water maze, Open field and hanging wire tests. In vivo antioxidant and neuroprotective activities were evaluated by measuring catalase, superoxide dismutase, MDA, H 2 O 2 , and myelin basic protein (MBP) expression in the hippocampus. In Morris water maze, stigmasterol significantly (p ≤ 0.05) decreased escape latency and increased swimming time in target quadrant (28.01 ± 0.02; 98.24 ± 17.38 s), respectively, better than α-tocopherol (52.43 ± 13.25; 80.32 ± 15.21) and β-spinasterol (42.09 ± 14.27; 70.91 ± 19.24) in sodium metavanadate-induced memory loss (112.31 ± 9.35; 42.35 ± 11.05). β-Spinasterol and stigmasterol significantly increased exploration and latency in open field and hanging wire tests respectively. Stigmasterol also increased activities of antioxidant enzymes, decreased oxidative stress markers and lipid peroxidation in mice hippocampal homogenates, and increased MBP expression. The findings of this study indicate a potential for stigmasterol, a bioactive compound from G. carpinifolia in improving cognitive decline, motor coordination, and ameliorating oxidative stress in vanadium-induced neurotoxicity. © 2018 The Authors. Brain and Behavior published by Wiley Periodicals, Inc.

Studies on potassium chlorate as a primary oxidimetric reagent.

PubMed

Murty, C R; Rao, G G

1972-01-01

Conditions have been established for the use of potassium chlorate as a primary oxidizing agent in the direct titration of vanadium(III), tin(II) and titanium(III) with visual or potentiometric end-points.

System and method for regeneration and recirculation of a reducing agent using highly exothermic reactions induced by mixed industrial slags

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakano, Jinichiro; Bennett, James P.; Nakano, Anna

Embodiments relate to systems and methods for regenerating and recirculating a CO, H.sub.2 or combinations thereof utilized for metal oxide reduction in a reduction furnace. The reduction furnace receives the reducing agent, reduces the metal oxide, and generates an exhaust of the oxidized product. The oxidized product is transferred to a mixing vessel, where the oxidized product, a calcium oxide, and a vanadium oxide interact to regenerate the reducing agent from the oxidized product. The regenerated reducing agent is transferred back to the reduction furnace for continued metal oxide reductions.

Thermal annealing induced multiple phase in V/V2O5 alternating multilayer structure

NASA Astrophysics Data System (ADS)

Ilahi, B.; Abdel-Rahman, M.; Zaaboub, Z.; Zia, M. F.; Alduraibi, M.; Maaref, H.

2016-09-01

In this paper, we report on microstructural, optical and electrical properties of alternating multilayer of vanadium pentoxide (V2O5), 25 nm, and vanadium (V), 5 nm, thin films deposited at room temperature by radio frequency (RF) and DC magnetron sputtering, respectively. Raman and photoluminescence (PL) spectroscopy have been employed to investigate the effects of thermal annealing for 20, 30 and 40 min at 400∘C in Nitrogen (N2) atmosphere on the multiple phase formation and its impact on the film resistance and temperature coefficient of resistance (TCR). We demonstrate that the oxygen free annealing environment allows the formation of multiple phases including V2O5, V6O13 and VO2 through oxygen diffusion and consequent deficiency in V2O5 layer.

Electrical quadruple hysteresis in Pd-doped vanadium pentoxide nanowires due to water adsorption

PubMed Central

Kim, Byung Hoon; Oh, Soon-Young; Yu, Han Young; Hong, Won G; Yun, Yong Ju; Kim, Yark Yeon; Kim, Hae Jin

2010-01-01

Humidity-dependent current–voltage (I–V) characteristics of Pd-doped vanadium pentoxide nanowires (Pd-VONs) were investigated. Electrical quadruple hysteresis (QH) was observed and attributed to the large amount of water molecules adsorbed on the nanowires. Using QH in Pd-VONs, the reaction of water with PdO was interpreted as the water molecules are desorbed and then dissociated with increasing bias voltage. Owing to the dissociated H+ and OH− ions, PdO is reduced and oxidized. As a result, water molecules recombine as the bias voltage is decreased. PMID:27877370

Substrate bias effect on the fabrication of thermochromic VO2 films by reactive RF sputtering

NASA Astrophysics Data System (ADS)

Miyazaki, H.; Yasui, I.

2006-05-01

Vanadium oxide VOx films were deposited by reactive RF magnetron sputtering by applying a substrate bias, in which the Ar ions in plasma impacted the growing film surface. The vanadium valence of the VOx film decreased when the substrate negative bias voltage was increased. The VO2 film was successfully deposited at a substrate temperature of 400 °C and with a bias voltage of -50 to -80 V. The transition temperatures of the VO2 films with a substrate bias of -50 and -80 V were about 56 °C and 44 °C, respectively.

Organic matter diagenesis as the key to a unifying theory for the genesis of tabular uranium-vanadium deposits in the Morrison Formation, Colorado Plateau

USGS Publications Warehouse

Hansley, P.L.; Spirakis, C.S.

1992-01-01

Interstitial, epigenetic amorphous organic matter is intimately associated with uranium in the Grants uranium region and is considered essential to genetic models for these deposits. In contrast, uranium minerals are intimately associated with authigenic vanadium chlorite and vanadium oxides in amorphous organic matter-poor ores of the Slick Rock and Henry Mountains mining districts and therefore, in some genetic models amorphous organic matter is not considered crucial to the formation of these deposits. Differences in organic matter content can be explained by recognizing that amorphous organic matter-poor deposits have been subjected to more advanced stages of diagenesis than amorphous organic matter-rich deposits. Evidence that amorphous organic matter was involved in the genesis of organic matter-poor, as well as organic matter-rich, deposits is described. -from Authors

Synthesis, structural and optical properties of nanocrystalline vanadium doped zinc oxide aerogel

NASA Astrophysics Data System (ADS)

El Ghoul, J.; Barthou, C.; El Mir, L.

2012-06-01

We report the synthesis of vanadium-doped ZnO nanoparticles prepared by a sol-gel processing technique. In our approach, the water for hydrolysis was slowly released by esterification reaction followed by a supercritical drying in ethyl alcohol. Vanadium doping concentration of 10 at% has been investigated. After treatment in air at different temperatures, the obtained nanopowder was characterized by various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence (PL). Analysis by scanning electron microscopy at high resolution shows that the grain size increases with increasing temperature. Thus, in the case of thermal treatment at 500 °C in air, the powder with an average particle size of 25 nm shows a strong luminescence band in the visible range. The intensity and energy position of the obtained PL band depends on the temperature measurement increase. The mechanism of this emission band is discussed.

Assessing the solubility controls on vanadium in groundwater, northeastern San Joaquin Valley, CA

USGS Publications Warehouse

Wright, Michael T.; Stollenwerk, Kenneth G.; Belitz, Kenneth

2014-01-01

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from 25 μg/L) and lowest in samples collected from anoxic groundwater (70% 2VO4−. Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V5+ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH)3+]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH)3 molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V3+- or mixed V3+/Fe3+-oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions. Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO3) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO3 extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.

Vapor-Phase Catalytic Oxidation of Mixed Volatile Organic Compounds

DTIC Science & Technology

1989-09-01

18 3. Hopcalite . . . . . . . . . 18 4. Potassium Chloride/Copper Oxide . . . 19 5. Vanadium Pentoxide . . . . . . . 19 6. Potassium...decomposition of 19 halogenated hydrocarbons, associated with submarine burners, using a hopcalite catalyst. Bond, et al. (Reference 9) have studied the...The catalyst can be easily regenerated, but deactivation occurs within a matter of minutes. 3. Hopcalite This mineral, containing primarily CuD and

Detection of H2O and Evidence for TiO VO in an Ultra Hot Exoplanet Atmosphere.

NASA Technical Reports Server (NTRS)

Evans, Thomas M.; Sing, David K.; Wakeford, Hannah R.; Nikolov, Nikolay; Ballester, Gilda E.; Drummond, Benjamin; Kataria, Tiffany; Gibson, Neale P.; Amundsen, David S.; Spake, Jessica

2016-01-01

We present a primary transit observation for the ultra-hot (Teq approx. 2400 K) gas giant expolanet WASP-121b, made using the Hubble Space Telescope Wide Field Camera 3 in spectroscopic mode across the 1.12-1.64 micron wavelength range. The 1.4 microns water absorption band is detected at high confidence (5.4(sigma)) in the planetary atmosphere. We also reanalyze ground-based photometric light curves taken in the B, r', and z' filters. Significantly deeper transits are measured in these optical bandpasses relative to the near-infrared wavelengths. We conclude that scattering by high-altitude haze alone is unlikely to account for this difference and instead interpret it as evidence for titanium oxide and vanadium oxide absorption. Enhanced opacity is also inferred across the 1.12-1.3 micron wavelength range, possibly due to iron hydride absorption. If confirmed, WASP-121b will be the first exoplanet with titanium oxide, vanadium oxide, and iron hydride detected in transmission. The latter are important species in M/L dwarfs and their presence is likely to have a significant effect on the overall physics and chemistry of the atmosphere, including the production of a strong thermal inversion.

Highly Efficient Gas-Phase Oxidation of Renewable Furfural to Maleic Anhydride over Plate Vanadium Phosphorus Oxide Catalyst.

PubMed

Li, Xiukai; Ko, Jogie; Zhang, Yugen

2018-02-09

Maleic anhydride (MAnh) and its acids are critical intermediates in chemical industry. The synthesis of maleic anhydride from renewable furfural is one of the most sought after processes in the field of sustainable chemistry. In this study, a plate vanadium phosphorus oxide (VPO) catalyst synthesized by a hydrothermal method with glucose as a green reducing agent catalyzes furfural oxidation to MAnh in the gas phase. The plate catalyst-denoted as VPO HT -has a preferentially exposed (200) crystal plane and exhibited dramatically enhanced activity, selectivity and stability as compared to conventional VPO catalysts and other state-of-the-art catalytic systems. At 360 °C reaction temperature with air as an oxidant, about 90 % yield of MAnh was obtained at 10 vol % of furfural in the feed, a furfural concentration value that is much higher than those (<2 vol %) reported for other catalytic systems. The catalyst showed good long-term stability and there was no decrease in activity or selectivity for MAnh during the time-on-stream of 25 h. The high efficiency and catalyst stability indicate the great potential of this system for the synthesis of maleic anhydride from renewable furfural. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bifunctional Crosslinking Agents Enhance Anion Exchange Membrane Efficacy for Vanadium Redox Flow Batteries.

PubMed

Wang, Wenpin; Xu, Min; Wang, Shubo; Xie, Xiaofeng; Lv, Yafei; Ramani, Vijay K

2014-06-02

A series of cross-linked fluorinated poly (aryl ether oxadiazole) membranes (FPAEOM) derivatized with imidazolium groups were prepared. Poly (N-vinylimidazole) (PVI) was used as the bifunctional cross-linking agent to: a) lower vanadium permeability, b) enhance dimensional stability, and c) concomitantly provide added ion exchange capacity in the resultant anion exchange membranes. At a molar ratio of PVI to FPAEOM of 1.5, the resultant membrane (FPAEOM-1.5 PVI) had an ion exchange capacity of 2.2 meq g-1, a vanadium permeability of 6.8×10-7 cm2 min-1, a water uptake of 68 wt.%, and an ionic conductivity of 22.0 mS cm-1, all at 25°C. Single cells prepared with the FPAEOM-1.5 PVI membrane exhibited a higher coulombic efficiency (> 92%) and energy efficiency (> 86%) after 40 test cycles in vanadium redox flow battery. The imidazolium cation showed high chemical stability in highly acidic and oxidizing vanadium solution as opposed to poor stability in alkaline solutions. Based on our DFT studies, this was attributed to the lower HOMO energy (-7.265 eV) of the HSO4- ion (compared to the OH- ion; -5.496 eV) and the larger HOMO-LUMO energy gap (6.394 eV) of dimethylimidazolium bisulfate ([DMIM] [HSO4]) as compared to [DMIM] [OH] (5.387 eV).

Regional Myelin and Axon Damage and Neuroinflammation in the Adult Mouse Brain After Long-Term Postnatal Vanadium Exposure.

PubMed

Azeez, Idris A; Olopade, Funmilayo; Laperchia, Claudia; Andrioli, Anna; Scambi, Ilaria; Onwuka, Silas K; Bentivoglio, Marina; Olopade, James O

2016-09-01

Environmental exposure to vanadium occurs in areas of persistent burning of fossil fuels; this metal is known to induce oxidative stress and oligodendrocyte damage. Here, we determined whether vanadium exposure (3 mg/kg) in mice during the first 3 postnatal months leads to a sustained neuroinflammatory response. Body weight monitoring, and muscle strength and open field tests showed reduction of body weight gain and locomotor impairment in vanadium-exposed mice. Myelin histochemistry and immunohistochemistry for astrocytes, microglia, and nonphosphorylated neurofilaments revealed striking regional heterogeneity. Myelin damage involved the midline corpus callosum and fibers in cortical gray matter, hippocampus, and diencephalon that were associated with axonal damage. Astrocyte and microglial activation was identified in the same regions and in the internal capsule; however, no overt myelin and axon damage was observed in the latter. Double immunofluorescence revealed induction of high tumor necrosis factor (TNF) immunoreactivity in reactive astrocytes. Western blotting analysis showed significant induction of TNF and interleukin-1β expression. Together these findings show that chronic postnatal vanadium exposure leads to functional deficit and region-dependent myelin damage that does not spare axons. This injury is associated with glial cell activation and proinflammatory cytokine induction, which may reflect both neurotoxic and neuroprotective responses. © 2016 American Association of Neuropathologists, Inc. All rights reserved.

Leaching of vanadium from waste V2O5-WO3/TiO2 catalyst catalyzed by functional microorganisms.

PubMed

Wang, Shuhua; Xie, Yaling; Yan, Weifu; Wu, Xuee; Wang, Chin-Tsan; Zhao, Feng

2018-05-22

Solid wastes are currently produced in large amounts. Although bioleaching of metals from solid wastes is an economical and sustainable technology, it has seldom been used to recycle metals from abandoned catalyst. In this study, the bioleaching of vanadium from V 2 O 5 -WO 3 /TiO 2 catalyst were comprehensively investigated through five methods: Oligotrophic way, Eutrophic way, S-mediated way, Fe-mediated way and Mixed way of S-mediated and Fe-mediated. The observed vanadium bioleaching effectiveness of the assayed methods was follows: S-mediated > Mixed > Oligotrophic > Eutrophic > Fe-mediated, which yielded the maximum bioleaching efficiencies of approximately 90%, 35%, 33%, 20% and 7%, respectively. The microbial community analysis suggested that the predominant genera Acidithiobacillus and Sulfobacillus from the S-mediated bioleaching way effectively catalyzed the vanadium leaching, which could have occurred through the indirect mechanism from the microbial oxidation of S 0 . In addition, the direct mechanism, involving direct electron transfer between the catalyst and the microorganisms that attached to the catalyst surface, should also help the vanadium to be leached more effectively. Therefore, this work provides guidance for future research and practical application on the treatment of waste V 2 O 5 -WO 3 /TiO 2 catalyst. Copyright © 2018 Elsevier B.V. All rights reserved.

Carbon-dot-based dual-emission silica nanoparticles as a ratiometric fluorescent probe for vanadium(V) detection in mineral water samples

NASA Astrophysics Data System (ADS)

He, Lijun; Zhang, Heng; Fan, Huanhuan; Jiang, Xiuming; Zhao, Wenjie; Xiang, Guo Qiang

2018-01-01

Herein, we propose a simple and effective strategy for designing a ratiometric fluorescent nanosensor. We designed and developed a carbon dots (CDs) based dual-emission nanosensor for vanadium(V) by coating the surface of dye-doped silica nanoparticles with CDs. The fluorescence of dual-emission silica nanoparticles was quenched in acetic acid through potassium bromate (KBrO3) oxidation. V(V) could catalyze KBrO3 oxidation reaction process, resulting in the ratiometric fluorescence quenching of dual-emission silica nanoparticles. We investigated several important parameters affecting the performance of the nanosensor. Under the optimized conditions, the detection limit of this nanosensor reached 1.1 ng mL- 1 and the linear range from 10 to 800 ng mL- 1. Furthermore, we found that the sensor was suitable for determination of V(V) in different mineral water samples with satisfactory results.

Graphene/vanadium oxide nanotubes composite as electrode material for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Fu, Meimei; Ge, Chongyong; Hou, Zhaohui; Cao, Jianguo; He, Binhong; Zeng, Fanyan; Kuang, Yafei

2013-07-01

Graphene/vanadium oxide nanotubes (VOx-NTs) composite was successfully synthesized through the hydrothermal process in which acetone as solvent and 1-hexadecylamine (HDA) as structure-directing template were used. Morphology, structure and composition of the as-obtained composite were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, nitrogen isothermal adsorption/desorption and thermo gravimetric analysis (TGA). The composite with the VOx-NTs amount of 69.0 wt% can deliver a specific capacitance of 210 F/g at a current density of 1 A/g in 1 M Na2SO4 aqueous solution, which is nearly twice as that of pristine graphene (128 F/g) or VOx-NTs (127 F/g), and exhibit a good performance rate. Compared with pure VOx-NTs, the cycle stability of the composite was also greatly improved due to the enhanced conductivity of the electrode and the structure buffer role of graphene.

Microwave assisted growth of nanorods vanadium dioxide VO2 (R): structural and electrical properties

NASA Astrophysics Data System (ADS)

Derkaoui, I.; Khenfouch, M.; Mothudi, B. M.; Moloi, S. J.; Zorkani, I.; Jorio, A.; Maaza, M.

2018-03-01

Nanostructured metal oxides have attracted a lot of attention recently owning to their unique structural advantages and demonstrated promising chemical and physical properties for various applications. In this study, we report the structural and electrical properties of vanadium dioxide VO2 (R) prepared via a single reaction microwave (SRC) synthesis. Our results are revealing that the components of VO2 (R) films have a rod-like shape with a uniform size distribution. The nanorods with very smooth and flat surfaces have a typical length of up to 2μm and a width of about several nanometers. The structural investigations reveal the high crystallinity of VO2 (R) ensuring good electrical contact and showing a high conductivity as a function of temperature. This synthesis method provides a new simple route to fabricate one-dimensional nanostructured metal oxides which is suitable for a large field of applications especially for smart windows.

Iron-based alloy and nitridation treatment for PEM fuel cell bipolar plates

DOEpatents

Brady, Michael P [Oak Ridge, TN; Yang, Bing [Oak Ridge, TN; Maziasz, Philip J [Oak Ridge, TN

2010-11-09

A corrosion resistant electrically conductive component that can be used as a bipolar plate in a PEM fuel cell application is composed of an alloy substrate which has 10-30 wt. % Cr, 0.5 to 7 wt. % V, and base metal being Fe, and a continuous surface layer of chromium nitride and vanadium nitride essentially free of base metal. A oxide layer of chromium vanadium oxide can be disposed between the alloy substrate and the continuous surface nitride layer. A method to prepare the corrosion resistant electrically conductive component involves a two-step nitridization sequence by exposing the alloy to a oxygen containing gas at an elevated temperature, and subsequently exposing the alloy to an oxygen free nitrogen containing gas at an elevated temperature to yield a component where a continuous chromium nitride layer free of iron has formed at the surface.

Metals in Devonian kerogenous marine strata at Gibellini and Bisoni properties in southern Fish Creek Range, Eureka County, Nevada

USGS Publications Warehouse

Desborough, George A.; Poole, F.G.; Hose, R.K.; Radtke, A.S.

1979-01-01

A kerogen-rich sequence of siliceous mudstone, siltstone, and chert as much as 60 m thick on ridge 7129 in the southern Fish Creek Range, referred to as Gibellini facies of the Woodruff Formation, has been evaluated on the surface and in drill holes principally for its potential resources of vanadium, zinc, selenium, molybdenum, and syncrude oil content. The strata are part of a strongly deformed allochthonous mass of eugeosynclinal Devonian marine rocks that overlie deformed allochthonous Mississippian siliceous rocks and relatively undeformed autochthonous Mississippian Antler flysch at this locality. The vanadium in fresh black rocks obtained from drill holes and fresh exposures in trenches and roadcuts occurs chiefly in organic matter. Concentrations of vanadium oxide (V2O5) in unoxidized samples range from 3,000 to 7,000 ppm. In oxidized and bleached rock that is prevalent at the surface, concentrations of vanadium oxide range from 6,000 to 8,000 ppm, suggesting a tendency toward enrichment due to surficial weathering and ground-water movement. Zinc occurs in sphalerite, and selenium occurs in organic matter; molybdenum appears to occur both in molybdenite and in organic matter. Concentrations of zinc in unoxidized rock range from 4,000 to 18,000 ppm, whereas in oxidized rock they range from 30 to 100 ppm, showing strong depletion due to weathering. Concentrations of selenium in unoxidized rock range from 30 to 200 ppm, whereas in oxidized rock they range from 200 to 400 ppm, indicating some enrichment upon weathering. Concentrations of molybdenum in unoxidized rock range from 70 to 960 ppm, whereas in oxidized rock they range from 30 to 80 ppm, indicating strong depletion upon weathering. Most fresh black rock is low-grade oil shale, and yields as much as 12 gallons/short ton of syncrude oil. Metahewettite is the principal vanadium mineral in the oxidized zone, but it also occurs sparsely as small nodules and fillings of microfractures in unweathered strata. In fresh rock, bluish-white opaline-like silica (chalcedonic quartz) fills microfractures, and is believed to have originated by diagenetic mobilization of opaline silica from radiolarian tests and sponge spicules. As revealed by microscopic study, the Gibellini facies originally consisted of siliceous muds, slimes, and oozes high in organic constituents. The organic matter is amorphous flaky and stringy sapropel, and probably includes remains of bacteria, phytoplankton, zooplankton, and minor higher plants. Recognizable organic remnants include radiolarian tests, sponge spicules, conodonts, brachiopod shells, algae, and humic debris. Diagnostic radiolarians indicate a Late Devonian age for the Gibellini facies of the Woodruff Formation. Some pyrite is disseminated through the rock and may be primary (syngenetic) but significant pyrite and marcasite occur in chalcedonic quartz veinlets and appear to be diagenetic. In fresh rock, black solid bitumen and liquid oil fill voids and microfractures. These early phase hydrocarbons probably were released during diagenesis from complex nonhydrocarbon molecular structures originating from living organisms, and formed without any major thermal degradation of the kerogen. Gas chromatographic analysis of the saturated hydrocarbon fraction indicates a very complex mixture dominated by branched and cyclic compounds. Conodont and palynomorph color alteration, vitrinite reflectance, and other organic geochemical data suggest that the organic matter in the rock is thermally immature and has not been subjected to temperatures greater than 60?C since deposition in Devonian time. All of these characteristics are consistent with the interpretation of a relatively low temperature and a shallow-burial history for the Gibellini facies on ridge 7129.

Mass Spectroscopy of Neutral Metal Oxide Clusters Using a Desk-Top Soft X-Ray Laser

NASA Astrophysics Data System (ADS)

Dong, F.; Heinbuch, S.; Bernstein, E. R.; Rocca, J. J.

We report the use of a compact 46.9 nm capillary discharge soft x-ray laser in the study of metal-oxide nanoclusters using mass spectroscopy. Transition metal oxides are widely used as heterogeneous catalysts and catalytic supports in industrial processes. There are numerous applications for transition metal oxide catalysts, and although they are widely used, there is a lack of fundamental understanding of the complicated processes that occur on the metal oxide surface during catalysis. Conventional nanocluster spectroscopy techniques have used 193 nm radiation from an ArF excimer laser corresponding to a photon energy of 6.4 eV in order to photoionize a sample. Typical metal oxide nanocluster ionization energies fall into the range of 7-12 eV while some have even higher energies. Therefore a single 6.4 eV photon can not ionize the cluster making multiphoton processes the dominant ionization method. A major problem associated with mass spectroscopy can become evident during the multiphoton ionization of clusters. Specifically, the clusters may fragment during the ionization process and the identification of the neutral parent cluster can become difficult. In the present experiment neutral vanadium, niobium and tantalum oxide clusters are studied by single photon ionization with the 26.5 eV photons produced by a capillary discharge soft x-ray laser.1 During ionization, the metal oxide clusters are observed to be almost free of serious fragmentation. The most stable neutral cluster of vanadium, niobium, and tantalum oxide growth in a saturated oxygen condition are identified as MO2, M2O4/M2O5, M3O7, M4O10, M5O12, M6O15, M7O17, M8O20, and M9O22, which can be represented as a form (MO2)0,1(M2O5)y. M2O5 is identified as a basic unit to build-up the three kinds of metal oxide clusters. In the case of niobium and tantalum oxide clusters, the oxygen-deficient clusters with a structure of (MO2)2(M2O5)y are detected for groups that contain an even number of metal atoms. For vanadium oxide clusters, the oxygen-deficient clusters are detected for every family, indicating a stable structure of (VO2)x(V2O5)y. The stoichiometry of oxygen-rich clusters can be expressed as (MO2)0,1(M2O5)yO1-3 and their structures are consistent with chemically bonded species.

Manufacturing Methods for the Production of Field Effect Electron Emitters from Oxide-Metal Composites.

DTIC Science & Technology

1977-12-01

Internal Zone Melting, Oxide-Metal Eutectic Structures ABSTRACT (Continue X reverae elde II neceaetrry end Identity by block nwbor* -^>This report...To- Uranium (0/U) Ratio B. Storage of "As-Received" Powders C. Moisture Content D. Oxidation Properties E. Sintering Properties F. Particle Size... Nickel - Vanadium 3.3 Nickel -Al203 3.4 Nickel -Tungsten 3.5 Copper-410 Stainless Steel C. Etching 1. Chemical Etching 2. Thermal Annealing 3. Ion

Development studies for a novel wet oxidation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhooge, P.M.; Hakim, L.B.

1994-01-01

A catalytic wet oxidation process (DETOX), which uses an acidic iron solution to oxidize organic compounds to carbon dioxide, water, and other simple products, was investigated as a potential method for the treatment of multicomponent hazardous and mixed wastes. The organic compounds picric acid, poly(vinyl chloride), tetrachlorothiophene, pentachloropyridine, Aroclor 1260 (a polychlorinated biphenyl), and hexachlorobenzene were oxidized in 125 ml reaction vessels. The metals arsenic, barium, beryllium, cadmium, cerium (as a surrogate for plutonium), chromium, lead, mercury, neodymium (as a surrogate for uranium), nickel, and vanadium were tested in the DETOX solution. Barium, beryllium, cerium, chromium, mercury, neodymium, nickel, andmore » vanadium were all found to be very soluble (>100 g/l) in the DETOX chloride-based solution. Arsenic, barium, cadmium, and lead solubilities were lower. Lead could be selectively precipitated from the DETOX solution. Chromium(VI) was reduced to relatively non-toxic chromium(III) by the solution. Six soils were contaminated with arsenic, barium, beryllium, chromium, lead, and neodymium oxides at approximately 0.1% by weight, and benzene, trichloroethene, mineral oil, and Aroclor 1260 at approximately 5% by weight total, and 5.g amounts treated with the DETOX solution in unstirred 125. ml reaction bombs. It is felt that soil treatment in a properly designed system is entirely possible despite incomplete oxidation of the less volatile organic materials in these unstirred tests.« less

RF Magnetron Sputtering Deposited W/Ti Thin Film For Smart Window Applications

NASA Astrophysics Data System (ADS)

Oksuz, Lutfi; Kiristi, Melek; Bozduman, Ferhat; Uygun Oksuz, Aysegul

2014-10-01

Electrochromic (EC) devices can change reversible and persistent their optical properties in the visible region (400-800 nm) upon charge insertion/extraction according to the applied voltage. A complementary type EC is a device containing two electrochromic layers, one of which is anodically colored such as vanadium oxide (V2 O5) while the other cathodically colored such as tungsten oxide (WO3) which is separated by an ionic conduction layer (electrolyte). The use of a solid electrolyte such as Nafion eliminates the need for containment of the liquid electrolyte, which simplifies the cell design, as well as improves safety and durability. In this work, the EC device was fabricated on a ITO/glass slide. The WO3-TiO2 thin film was deposited by reactive RF magnetron sputtering using a 2-in W/Ti (9:1%wt) target with purity of 99.9% in a mixture gas of argon and oxygen. As a counter electrode layer, V2O5 film was deposited on an ITO/glass substrate using V2O3 target with the same conditions of reactive RF magnetron sputtering. Modified Nafion was used as an electrolyte to complete EC device. The transmittance spectra of the complementary EC device was measured by optical spectrophotometry when a voltage of +/-3 V was applied to the EC device by computer controlled system. The surface morphology of the films was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM) (Fig. 2). The cyclic voltammetry (CV) for EC device was performed by sweeping the potential between +/-3 V at a scan rate of 50 mV/s.

Synthesis and characterization of sodium vanadium oxide gels: the effects of water (n) and sodium (x) content on the electrochemistry of Na(x)V2O5·nH2O.

PubMed

Lee, Chia-Ying; Marschilok, Amy C; Subramanian, Aditya; Takeuchi, Kenneth J; Takeuchi, Esther S

2011-10-28

Sodium vanadium oxide gels, Na(x)V(2)O(5)·nH(2)O, of varying sodium content (0.12 < x < 0.32) were prepared by careful control of an ion exchange process. The water content (0.23 > n > 0.01) and interlayer spacing were found to be inversely proportional to the sodium level (x), thus control of sodium (x) content provided a direct, chimie douce approach for control of hydration level (n) and interlayer spacing, without the need for high temperature treatment to affect dehydration. Notably, the use of high temperatures to modify hydration levels can result in crystallization and collapse of the interlayer structure, highlighting the distinct advantage of our novel chimie douce synthesis strategy. Subsequent to synthesis and characterization, results from an electrochemical study of a series of Na(x)V(2)O(5)·nH(2)O samples highlight the significant impact of interlayer water on delivered capacity of the layered materials. Specifically, the sodium vanadium oxide gels with higher sodium content and lower water content provided higher capacities in lithium based cells, where capacity delivered to 2.0 V under C/20 discharge ranged from 170 mAh/g for Na(0.12)V(2)O(5)·0.23H(2)O to 300 mAh/g for Na(0.32)V(2)O(5)·0.01H(2)O. The capacity differences were maintained as the cells were cycled. This journal is © the Owner Societies 2011

⁵¹V NMR Crystallography of Vanadium Chloroperoxidase and Its Directed Evolution P395D/L241V/T343A Mutant: Protonation Environments of the Active Site.

PubMed

Gupta, Rupal; Hou, Guangjin; Renirie, Rokus; Wever, Ron; Polenova, Tatyana

2015-04-29

Vanadium-dependent haloperoxidases (VHPOs) perform two-electron oxidation of halides using hydrogen peroxide. Their mechanism, including the factors determining the substrate specificity and the pH-dependence of the catalytic rates, is poorly understood. The vanadate cofactor in the active site of VHPOs contains "spectroscopically silent" V(V), which does not change oxidation state during the reaction. We employed an NMR crystallography approach based on (51)V magic angle spinning NMR spectroscopy and Density Functional Theory, to gain insights into the structure and coordination environment of the cofactor in the resting state of vanadium-dependent chloroperoxidases (VCPO). The cofactor environments in the wild-type VCPO and its P395D/L241V/T343A mutant exhibiting 5-100-fold improved catalytic activity are examined at various pH values. Optimal sensitivity attained due to the fast MAS probe technologies enabled the assignment of the location and number of protons on the vanadate as a function of pH. The vanadate cofactor changes its protonation from quadruply protonated at pH 6.3 to triply protonated at pH 7.3 to doubly protonated at pH 8.3. In contrast, in the mutant, the vanadate protonation is the same at pH 5.0 and 8.3, and the cofactor is doubly protonated. This methodology to identify the distinct protonation environments of the cofactor, which are also pH-dependent, could help explain the different reactivities of the wild-type and mutant VCPO and their pH-dependence. This study demonstrates that (51)V-based NMR crystallography can be used to derive the detailed coordination environments of vanadium centers in large biological molecules.

X-ray absorption near-edge structure micro-spectroscopy study of vanadium speciation in Phycomyces blakesleeanus mycelium.

PubMed

Žižić, Milan; Dučić, Tanja; Grolimund, Daniel; Bajuk-Bogdanović, Danica; Nikolic, Miroslav; Stanić, Marina; Križak, Strahinja; Zakrzewska, Joanna

2015-09-01

Vanadium speciation in the fungus Phycomyces blakesleeanus was examined by X-ray absorption near-edge structure (XANES) spectroscopy, enabling assessment of oxidation states and related molecular symmetries of this transition element in the fungus. The exposure of P. blakesleeanus to two physiologically important vanadium species (V(5+) and V(4+)) resulted in the accumulation of this metal in central compartments of 24 h old mycelia, most probably in vacuoles. Tetrahedral V(5+), octahedral V(4+), and proposed intracellular complexes of V(5+) were detected simultaneously after addition of a physiologically relevant concentration of V(5+) to the mycelium. A substantial fraction of the externally added V(4+) remained mostly in its original form. However, observable variations in the pre-edge-peak intensities in the XANES spectra indicated intracellular complexation and corresponding changes in the molecular coordination symmetry. Vanadate complexation was confirmed by (51)V NMR and Raman spectroscopy, and potential binding compounds including cell-wall constituents (chitosan and/or chitin), (poly)phosphates, DNA, and proteins are proposed. The evidenced vanadate complexation and reduction could also explain the resistance of P. blakesleeanus to high extracellular concentrations of vanadium.

The role of interfacial metal silicates on the magnetism in FeCo/SiO 2 and Fe 49% Co 49% V 2% /SiO 2 core/shell nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desautels, R. D.; Freeland, J. W.; Rowe, M. P.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO2 and Fe49%Co49%V2%/SiO2 core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments havemore » shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO2-based interfacial shell.« less

Hydrometallurgical methods of recovery of scandium from the wastes of various technologies

NASA Astrophysics Data System (ADS)

Molchanova, T. V.; Akimova, I. D.; Smirnov, K. M.; Krylova, O. K.; Zharova, E. V.

2017-03-01

The recovery of scandium from the wastes of the production of uranium, titanium, iron-vanadium, and alumina is studied. The applied acid schemes of scandium transfer to a solution followed by ion-exchange recovery and extraction concentration of scandium ensure the precipitation of crude scandium oxides containing up to 5% Sc2O3. Scandium oxides of 99.96-99.99% purity are formed after additional refining of these crude oxides according to an extraction technology using a mixture 15% multiradical phosphine oxide or Cyanex-925 + 15% tributyl phosphate in kerosene.

Study on the decomposition of trace benzene over V2O5–WO3/TiO2-based catalysts in simulated flue gas

EPA Science Inventory

Trace levels (1 and 10 ppm) of gaseous benzene were catalytically decomposed in a fixed-bed catalytic reactor with monolithic oxides of vanadium and tungsten supported on titanium oxide (V2O5–WO3/TiO2) catalysts under conditions simulating the cooling of waste incineration flue g...

Metal-insulator and charge ordering transitions in oxide nanostructures

NASA Astrophysics Data System (ADS)

Singh, Sujay Kumar

Strongly correlated oxides are a class of materials wherein interplay of various degrees of freedom results in novel electronic and magnetic phenomena. Vanadium oxides are widely studied correlated materials that exhibit metal-insulator transitions (MIT) in a wide temperature range from 70 K to 380 K. In this Thesis, results from electrical transport measurements on vanadium dioxide (VO2) and vanadium oxide bronze (MxV 2O5) (where M: alkali, alkaline earth, and transition metal cations) are presented and discussed. Although the MIT in VO2 has been studied for more than 50 years, the microscopic origin of the transition is still debated since a slew of external parameters such as light, voltage, and strain are found to significantly alter the transition. Furthermore, recent works on electrically driven switching in VO2 have shown that the role of Joule heating to be a major cause as opposed to electric field. We explore the mechanisms behind the electrically driven switching in single crystalline nanobeams of VO2 through DC and AC transport measurements. The harmonic analysis of the AC measurement data shows that non-uniform Joule heating causes electronic inhomogeneities to develop within the nanobeam and is responsible for driving the transition in VO2. Surprisingly, field assisted emission mechanisms such as Poole-Frenkel effect is found to be absent and the role of percolation is also identified in the electrically driven transition. This Thesis also provides a new insight into the mechanisms behind the electrolyte gating induced resistance modulation and the suppression of MIT in VO2. We show that the metallic phase of VO2 induced by electrolyte gating is due to an electrochemical process and can be both reversible and irreversible under different conditions. The kinetics of the redox processes increase with temperature; a complete suppression of the transition and the stabilization of the metallic phase are achievable by gating in the rutile metallic phase. First principles calculations show that the destabilization of the insulating phase during the gating arises due to the formation of oxygen vacancies in VO2; the rutile phase is far more amenable to electrochemical reduction as compared to the monoclinic phase, likely due to its higher electrical conductivity. The generation of oxygen vacancies appears thermodynamically favorable if the removed oxygen atoms from VO2 oxidize the anions in the ionic liquid. Finally, electronic properties of single crystalline, individual nanowires of vanadium oxide bronzes (MxVO 2O5) are presented. The intercalation effects of metal cation and the stoichiometry (x) are explored and discussed. These nanowires exhibit thermally and electrically driven charge ordering and metal to insulator transitions. The electrolyte gating measurements show resistance modulations across the phase transition but the effect is not as dramatic as in VO2.

Application of an Al-doped zinc oxide subcontact layer on vanadium-compensated 6H-SiC photoconductive switches

NASA Astrophysics Data System (ADS)

Zhou, Tian-Yu; Liu, Xue-Chao; Huang, Wei; Dai, Chong-Chong; Zheng, Yan-Qing; Shi, Er-Wei

2015-04-01

Al-doped ZnO thin film (AZO) is used as a subcontact layer in 6H-SiC photoconductive semiconductor switches (PCSSs) to reduce the on-state resistance and optimize the device structure. Our photoconductive test shows that the on-state resistance of lateral PCSS with an n+-AZO subcontact layer is 14.7% lower than that of PCSS without an n+-AZO subcontact layer. This occurs because a heavy-doped AZO thin film can improve Ohmic contact properties, reduce contact resistance, and alleviate Joule heating. Combined with the high transparance characteristic at 532 nm of AZO film, vertical structural PCSS devices are designed and their structural superiority is discussed. This paper provides a feasible route for fabricating high performance SiC PCSS by using conductive and transparent ZnO-based materials. Project supported by the Innovation Program of the Shanghai Institute of Ceramics (Grant No. Y39ZC1110G), the Innovation Program of the Chinese Academy of Sciences (Grant No. KJCX2-EW-W10), the Industry-Academic Joint Technological Innovations Fund Project of Jiangsu Province, China (Grant No. BY2011119), the Natural Science Foundation of Shanghai (Grant No. 14ZR1419000), the Young Scientists Fund of the National Natural Science Foundation of China (Grant No. 61404146), and the National High-tech R & D Program of China (Grant Nos. 2013AA031603 and 2014AA032602).

Photoelectrochemical performance of W-doped BiVO4 thin films deposited by spray pyrolysis

NASA Astrophysics Data System (ADS)

Holland, S. Keith; Dutter, Melissa R.; Lawrence, David J.; Reisner, Barbara A.; DeVore, Thomas C.

2014-01-01

The effects of tungsten doping and hydrogen annealing on the photoelectrochemical (PEC) performance of bismuth vanadate (BiVO4) photoanodes for solar water splitting were studied. Thin films of BiVO were deposited on indium tin oxide-coated glass slides by ultrasonic spray pyrolysis of an aqueous solution containing bismuth nitrate and vanadium oxysulfate. Tungsten doping was achieved by adding either silicotungstic acid (STA) or ammonium metatungstate (AMT) to the precursor. The 1.7- to 2.2-μm-thick films exhibited a highly porous microstructure. Undoped films that were reduced at 375°C in 3% H exhibited the largest photocurrent densities under 0.1 W cm-2 AM1.5 illumination, where photocurrent densities of up to 1.3 mA cm-2 at 0.5 V with respect to Ag/AgCl were achieved. Films doped with 1% or 5% (atomic percent) tungsten from either STA or AMT exhibited reduced PEC performance and greater sample-to-sample performance variations. Powder x-ray diffraction data indicated that the films continue to crystallize in the monoclinic polymorph at low doping levels but crystallize in the tetragonal scheelite structure at higher doping. It is surmised that the phase and morphology differences promoted by the addition of W during the deposition process reduced the PEC performance as measured by photovoltammetry.

Surface charge sensing by altering the phase transition in VO2

NASA Astrophysics Data System (ADS)

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.

CATALYTIC COMBUSTION OF ATMOSPHERIC CONTAMINANTS IN SPACE VEHICLE ATMOSPHERES.

DTIC Science & Technology

preheater were devised which allowed precise temperature control. Hopcalite , palladium supported on alumina, vanadium pentoxide, and silver permanganate...were the catalysts considered. Palladium was found to be more effective catalyst than Hopcalite for oxidizing methane. Palladium was also effective in

Vanadium Exposure Induces Olfactory Dysfunction in an Animal Model of Metal Neurotoxicity

PubMed Central

Ngwa, Hilary Afeseh; Kanthasamy, Arthi; Jin, Huajun; Anantharam, Vellareddy; Kanthasamy, Anumantha G.

2014-01-01

Epidemiological evidence indicates chronic environmental exposure to transition metals may play a role in chronic neurodegenerative conditions such as Parkinson’s disease (PD). Chronic inhalation exposure to welding fumes containing metal mixtures may be associated with development of PD. A significant amount of vanadium is present in welding fumes, as vanadium pentoxide (V2O5), and incorporation of vanadium in the production of high strength steel has become more common. Despite the increased vanadium use in recent years, the neurotoxicological effects of this metal are not well characterized. Recently, we demonstrated that V2O5 induces dopaminergic neurotoxicity via protein kinase C delta (PKCδ)-dependent oxidative signaling mechanisms in dopaminergic neuronal cells. Since anosmia (inability to perceive odors) and non-motor deficits are considered to be early symptoms of neurological diseases, in the present study, we examined the effect of V2O5 on the olfactory bulb in animal models. To mimic the inhalation exposure, we intranasally administered C57 black mice a low-dose of 182 µg of V2O5 three times a week for one month, and behavioral, neurochemical and biochemical studies were performed. Our results revealed a significant decrease in olfactory bulb weights, tyrosine hydroxylase (TH) levels, levels of dopamine (DA) and its metabolite, 3, 4-dihydroxyphenylacetic acid (DOPAC) and increases in astroglia of the glomerular layer of the olfactory bulb in the treatment groups relative to vehicle controls. Neurochemical changes were accompanied by impaired olfaction and locomotion. These findings suggest that nasal exposure to V2O5 adversely affects olfactory bulbs, resulting in neurobehavioral and neurochemical impairments. These results expand our understanding of vanadium neurotoxicity in environmentally-linked neurological conditions. PMID:24362016

Infrared characteristics of VO2 thin films for smart window and laser protection applications

NASA Astrophysics Data System (ADS)

Huang, Zhangli; Chen, Sihai; Lv, Chaohong; Huang, Ying; Lai, Jianjun

2012-11-01

Vanadium dioxide (VO2) films with a low semiconductor-to-metal transition temperature of 45 °C were fabricated through direct current magnetron sputtering followed by a post-annealing. Atomic force microscopy measurements show that the VO2 grain size is about one hundred of nanometers. Infrared (IR) characteristic is well investigated by applying a He-Ne laser power intensity measurement, and the result reveals that the VO2 film exhibits excellent IR switching property. Furthermore, solar smart window and laser protection experiments demonstrate that the obtained VO2 thin film is a promising material for the application in related fields.

Application of Novel Anion-Exchange Blend Membranes (AEBMs) to Vanadium Redox Flow Batteries.

PubMed

Cho, Hyeongrae; Krieg, Henning M; Kerres, Jochen A

2018-06-19

Both cation-exchange membranes and anion-exchange membranes are used as ion conducting membranes in vanadium redox flow batteries (VRFBs). Anion-exchange membranes (AEMs) are applied in vanadium redox flow batteries due to the high blocking property of vanadium ions via the Donnan exclusion effect. In this study, novel anion-exchange blend membranes (AEBMs) were prepared, characterized, and applied in VRFBs. Bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide), poly[(1-(4,4′-diphenylether)-5-oxybenzimidazole)-benzimidazole] (PBI-OO) and sulfonated polyether sulfone polymer were combined to prepare 3-component AEBMs with 1,2,4,5-tetramethylimidazole (TMIm) for quaternization. 3-component AEBMs showed significantly enhanced chemical and mechanical properties compared with those of 2-component AEBMs, resulting in an improved performance in VRFBs. The compositions of the anion-exchange polymers in 3-component AEBMs were systematically varied to optimize the AEBMs for the redox-flow battery application. While the 3-component AEBMs showed comparable efficiencies with Nafion ® 212 membranes, they displayed improved vanadium ions cross-over as was confirmed by open circuit voltage tests and capacity fade tests conducted in VRFBs. In addition, one of the synthesized 3-component AEBM had a superior coulombic efficiency and capacity retention in a charging⁻discharging test over 300 cycles at a current density of 40 mA/cm². It can thus be concluded that 3-component AEBMs are promising candidates for long-term operation in VRFBs.

Automated stopped-in-dual-loop flow analysis system for catalytic determination of vanadium in drinking water.

PubMed

Teshima, Norio; Kuno, Masami; Ueda, Minoru; Ueda, Hisashi; Ohno, Shinsuke; Sakai, Tadao

2009-07-15

An automated stopped-in-dual-loop flow analysis (SIDL-FA) system is proposed for the determination of vanadium in drinking water. The chemistry is based on the vanadium-catalyzed oxidation reaction of p-anisidine by bromate in the presence of Tiron as an activator to produce a dye (lambda(max)=510 nm). A SIDL-FA system basically consists of a selection valve, three pumps (one is for delivering of standard/sample, and others are for reagents), two six-way injection valves, a spectrophotometric detector and a data acquisition device. A 100-microL coiled loop around a heated device is fitted onto each six-way injection valve. A well-mixed solution containing reagents and standard/sample is loaded into the first loop on a six-way valve, and then the same solution is loaded into the second loop on another six-way valve. The solutions are isolated by switching these two six-way valves, so that the catalytic reaction can be promoted. The net waste can be zero in this stage, because all pumps are turned off. Then each resulting solution is dispensed to the detector with suitable time lag. A touchscreen controller is developed to automatically carry out the original SIDL-FA protocol. The proposed SIDL-FA method allows vanadium to be quantified in the range of 0.1-2 microg L(-1) and is applied to the determination of vanadium in drinking water samples.

Transformers: the changing phases of low-dimensional vanadium oxide bronzes.

PubMed

Marley, Peter M; Horrocks, Gregory A; Pelcher, Kate E; Banerjee, Sarbajit

2015-03-28

In this feature article, we explore the electronic and structural phase transformations of ternary vanadium oxides with the composition MxV2O5 where M is an intercalated cation. The periodic arrays of intercalated cations ordered along quasi-1D tunnels or layered between 2D sheets of the V2O5 framework induce partial reduction of the framework vanadium atoms giving rise to charge ordering patterns that are specific to the metal M and stoichiometry x. This periodic charge ordering makes these materials remarkably versatile platforms for studying electron correlation and underpins the manifestation of phenomena such as colossal metal-insulator transitions, quantized charge corrals, and superconductivity. We describe current mechanistic understanding of these emergent phenomena with a particular emphasis on the benefits derived from scaling these materials to nanostructured dimensions wherein precise ordering of cations can be obtained and phase relationships can be derived that are entirely inaccessible in the bulk. In particular, structural transformations induced by intercalation are dramatically accelerated due to the shorter diffusion path lengths at nanometer-sized dimensions, which cause a dramatic reduction of kinetic barriers to phase transformations and facilitate interconversion between the different frameworks. We conclude by summarizing numerous technological applications that have become feasible due to recent advances in controlling the structural chemistry and both electronic and structural phase transitions in these versatile frameworks.

Liquid Metal Anode for JP-8 Fuel Cell

DTIC Science & Technology

2009-01-15

bases. They react preferentially with acidic sulfur and its compounds, S, SO2 and H2S. These reactions of cerium oxides with sulfur and its...by sulfur . The dominating thermodynamic reaction is the formation of metal sulfides or sulfates , not the desired electrochemical reduction...oxidation of sulfur to make sulfuric acid . Vanadium carbide used as a fuel cell anode has been evaluated by Japanese researchers and CellTech Power. Its

DETECTION OF H{sub 2}O AND EVIDENCE FOR TiO/VO IN AN ULTRA-HOT EXOPLANET ATMOSPHERE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, Thomas M.; Sing, David K.; Nikolov, Nikolay

2016-05-01

We present a primary transit observation for the ultra-hot ( T {sub eq} ∼ 2400 K) gas giant expolanet WASP-121b, made using the Hubble Space Telescope Wide Field Camera 3 in spectroscopic mode across the 1.12–1.64 μ m wavelength range. The 1.4 μ m water absorption band is detected at high confidence (5.4 σ ) in the planetary atmosphere. We also reanalyze ground-based photometric light curves taken in the B , r ′, and z ′ filters. Significantly deeper transits are measured in these optical bandpasses relative to the near-infrared wavelengths. We conclude that scattering by high-altitude haze alone ismore » unlikely to account for this difference and instead interpret it as evidence for titanium oxide and vanadium oxide absorption. Enhanced opacity is also inferred across the 1.12–1.3 μ m wavelength range, possibly due to iron hydride absorption. If confirmed, WASP-121b will be the first exoplanet with titanium oxide, vanadium oxide, and iron hydride detected in transmission. The latter are important species in M/L dwarfs and their presence is likely to have a significant effect on the overall physics and chemistry of the atmosphere, including the production of a strong thermal inversion.« less

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

2010-01-01

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Synthesis by sol-gel process, structural and optical properties of nanoparticles of zinc oxide doped vanadium

NASA Astrophysics Data System (ADS)

El Ghoul, J.; Barthou, C.; El Mir, L.

2012-06-01

We report the elaboration of vanadium-doped ZnO nanoparticles prepared by a sol-gel processing technique. In our approach, the water for hydrolysis was slowly released by esterification reaction followed by a supercritical drying in ethyl alcohol. Vanadium doping concentration of 10 at.% has been investigated. After treatment in air at different temperatures, the obtained nanopowder was characterised by various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence (PL). Analysis by scanning electron microscopy at high resolution shows that the grain size increases with increasing temperature. Thus, in the case of thermal treatment at 500 °C in air, the powder with an average particle size of 25 nm shows a strong luminescence band in the visible range. The intensity and energy position of the obtained PL band depends on the temperature measurement increase. The mechanism of this emission band is discussed.

Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams.

PubMed

Hong, Woong-Ki; Park, Jong Bae; Yoon, Jongwon; Kim, Bong-Joong; Sohn, Jung Inn; Lee, Young Boo; Bae, Tae-Sung; Chang, Sung-Jin; Huh, Yun Suk; Son, Byoungchul; Stach, Eric A; Lee, Takhee; Welland, Mark E

2013-04-10

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Biodesulfurization of vanadium-bearing titanomagnetite concentrates and pH control of bioleaching solution

NASA Astrophysics Data System (ADS)

Liu, Xiao-rong; Jiang, Sheng-cai; Liu, Yan-jun; Li, Hui; Wang, Hua-jun

2013-10-01

Vanadium-bearing titanomagnetite concentrates were desulfurized with Acidithiobacillus ferrooxidans ( A. ferrooxidans). The sulfur content of the concentrates was reduced from 0.69wt% to 0.14wt% after bioleaching for 15 d with a 10% pulp density at 30°C. Maintaining a stable pH value during biodesulfurization was critical because of high acid consumption, resulting from a combination of nonoxidative and oxidative dissolution of pyrrhotite in acid solution. It is discovered that the citric acid-disodium hydrogen phosphate buffer of pH 2.0 can control the solution pH value smoothly in the optimal range of 2.0-3.0 for A. ferrooxidans growth. Using the buffer in the volume fraction range of 5.0%-15.0% stimulates A. ferrooxidans growth and improves the biodesulfurization efficiency. Compared with the buffer-free control case, the maximum increase of biodesulfurization rate is 29.7% using a 10.0vol% buffer. Bioleaching provides an alternative process for desulfurization of vanadium-bearing titanomagnetite ores.

Switchable vanadium dioxide (VO2) metamaterials fabricated from tungsten doped vanadia-based colloidal nanocrystals

NASA Astrophysics Data System (ADS)

Paik, Taejong; Hong, Sung-Hoon; Gordon, Thomas; Gaulding, Ashley; Kagan, Cherie; Murray, Christopher

2013-03-01

We report the fabrication of thermochromic VO2-based metamaterials using solution-processable colloidal nanocrystals. Vanadium-based nanoparticles are prepared through a non-hydrolytic reaction, resulting in stable colloidal dispersions in solution. Thermochromic nanocrystalline VO2 thin-films are prepared via rapid thermal annealing of colloidal nanoparticles coated on a variety of substrates. Nanostructured VO2 can be patterned over large areas by nanoimprint lithography. Precise control of tungsten (W) doping concentration in colloidal nanoparticles enables tuning of the phase transition temperature of the nanocrystalline VO2 thin-films. W-doped VO2 films display a sharp temperature dependent phase transition, similar to the undoped VO2 film, but at lower temperatures tunable with the doping level. By sequential coating of doped VO2 with different doping concentrations, we fabricate ?smart? multi-layered VO2 films displaying multiple phase transition temperatures within a single structure, allowing for dynamic modulation of the metal-dielectric layered structure. The optical properties programmed into the layered structure are switchable with temperature, which provides additional degrees of freedom to design tunable optical metamaterials. This work is supported by the US Office of Naval Research Multidisciplinary University Research Initiative (MURI) program grant number ONR-N00014-10-1-0942.

Integration and High-Temperature Characterization of Ferroelectric Vanadium-Doped Bismuth Titanate Thin Films on Silicon Carbide

NASA Astrophysics Data System (ADS)

Ekström, Mattias; Khartsev, Sergiy; Östling, Mikael; Zetterling, Carl-Mikael

2017-07-01

4H-SiC electronics can operate at high temperature (HT), e.g., 300°C to 500°C, for extended times. Systems using sensors and amplifiers that operate at HT would benefit from microcontrollers which can also operate at HT. Microcontrollers require nonvolatile memory (NVM) for computer programs. In this work, we demonstrate the possibility of integrating ferroelectric vanadium-doped bismuth titanate (BiTV) thin films on 4H-SiC for HT memory applications, with BiTV ferroelectric capacitors providing memory functionality. Film deposition was achieved by laser ablation on Pt (111)/TiO2/4H-SiC substrates, with magnetron-sputtered Pt used as bottom electrode and thermally evaporated Au as upper contacts. Film characterization by x-ray diffraction analysis revealed predominately (117) orientation. P- E hysteresis loops measured at room temperature showed maximum 2 P r of 48 μC/cm2, large enough for wide read margins. P- E loops were measurable up to 450°C, with losses limiting measurements above 450°C. The phase-transition temperature was determined to be about 660°C from the discontinuity in dielectric permittivity, close to what is achieved for ceramics. These BiTV ferroelectric capacitors demonstrate potential for use in HT NVM applications for SiC digital electronics.

New thin films of NiO doped with V2O5 for electrochromic applications

NASA Astrophysics Data System (ADS)

Azevedo, Cristiane F.; Balboni, Raphael D. C.; Cholant, Camila M.; Moura, Elton A.; Lemos, Rafaela M. J.; Pawlicka, Agnieszka; Gündel, Andre; Flores, Wladimir H.; Pereira, Marcelo; Avellaneda, César O.

2017-11-01

This paper reports on synthesis and characterization of new electrochromic thin films of NiO doped with V2O5 that were prepared by the sol-gel method and deposited by the spin coating technique. The confirmation of the presence of the dopant in the structure of the films was given by energy-dispersive X-ray spectroscopy (EDX). The effect of the addition of vanadium to the films of NiO was evaluated by electrochemical techniques such as cyclic voltammetry, chronocoulometry, and chronoamperometry in 0.5 mol/L KOH electrolyte. The morphology and the structure of the films, determined by microscopies (SEM and AFM), reveal smooth and slightly rough surfaces. The addition of vanadium as a dopant does not produce changes in the host NiO matrix as evidenced by X-ray diffractometry (XRD). However, the addition of the dopant causes a significant improvement in a charge density values of the films that increase more than twice from 25.5 mC/cm2 for NiO to 52.8 mC/cm2 for NiO with 10 mol% of V2O5. V2O5 doping of NiO films also improved their optical properties as well as kinetics of insertion and extraction processes.

Thermal aging effect of vanadyl acetylacetonate precursor for deposition of VO{sub 2} thin films with thermochromic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Jung-Hoon; Nam, Sang-Hun; Kim, Donguk

Highlights: • 7 day aged VO(acac){sub 2} sol shows enhanced adhesivity on the SiO{sub 2} compared with non-aged sol. • The aging process has significantly affected the morphologies of VO{sub 2} films. • From the FT-IR spectra, thermal aging process provides the deformation of precursor. • The metal insulator transition (MIT) efficiency (ΔT{sub at2000} {sub nm}) reached a maximum value of 51% at 7 day aging. • Thermal aging process could shorten the aging time of sol solution. - Abstract: Thermochromic properties of vanadium dioxide (VO{sub 2}) have been studied extensively due to their IR reflection applications in energy smartmore » windows. In this paper, we studied the optical switching property of VO{sub 2} thin film, depending on the thermal aging time of the vanadyl acetylacetonate (VO(acac){sub 2}) precursor. We found the alteration of the IR spectra of the precursor by tuning the aging time as well as heat treatments of the precursor. An aging effect of vanadium precursor directly affects the morphologies, optical switching property and crystallinity of VO{sub 2} films. The optimum condition was achieved at the 7 day aging time with metal insulator transition (MIT) efficiency of 50%.« less

Attosecond transient absorption instrumentation for thin film materials: Phase transitions, heat dissipation, signal stabilization, timing correction, and rapid sample rotation.

PubMed

Jager, Marieke F; Ott, Christian; Kaplan, Christopher J; Kraus, Peter M; Neumark, Daniel M; Leone, Stephen R

2018-01-01

We present an extreme ultraviolet (XUV) transient absorption apparatus tailored to attosecond and femtosecond measurements on bulk solid-state thin-film samples, specifically when the sample dynamics are sensitive to heating effects. The setup combines methodology for stabilizing sub-femtosecond time-resolution measurements over 48 h and techniques for mitigating heat buildup in temperature-dependent samples. Single-point beam stabilization in pump and probe arms and periodic time-zero reference measurements are described for accurate timing and stabilization. A hollow-shaft motor configuration for rapid sample rotation, raster scanning capability, and additional diagnostics are described for heat mitigation. Heat transfer simulations performed using a finite element analysis allow comparison of sample rotation and traditional raster scanning techniques for 100 Hz pulsed laser measurements on vanadium dioxide, a material that undergoes an insulator-to-metal transition at a modest temperature of 340 K. Experimental results are presented confirming that the vanadium dioxide (VO 2 ) sample cannot cool below its phase transition temperature between laser pulses without rapid rotation, in agreement with the simulations. The findings indicate the stringent conditions required to perform rigorous broadband XUV time-resolved absorption measurements on bulk solid-state samples, particularly those with temperature sensitivity, and elucidate a clear methodology to perform them.

Attosecond transient absorption instrumentation for thin film materials: Phase transitions, heat dissipation, signal stabilization, timing correction, and rapid sample rotation

NASA Astrophysics Data System (ADS)

Jager, Marieke F.; Ott, Christian; Kaplan, Christopher J.; Kraus, Peter M.; Neumark, Daniel M.; Leone, Stephen R.

2018-01-01

We present an extreme ultraviolet (XUV) transient absorption apparatus tailored to attosecond and femtosecond measurements on bulk solid-state thin-film samples, specifically when the sample dynamics are sensitive to heating effects. The setup combines methodology for stabilizing sub-femtosecond time-resolution measurements over 48 h and techniques for mitigating heat buildup in temperature-dependent samples. Single-point beam stabilization in pump and probe arms and periodic time-zero reference measurements are described for accurate timing and stabilization. A hollow-shaft motor configuration for rapid sample rotation, raster scanning capability, and additional diagnostics are described for heat mitigation. Heat transfer simulations performed using a finite element analysis allow comparison of sample rotation and traditional raster scanning techniques for 100 Hz pulsed laser measurements on vanadium dioxide, a material that undergoes an insulator-to-metal transition at a modest temperature of 340 K. Experimental results are presented confirming that the vanadium dioxide (VO2) sample cannot cool below its phase transition temperature between laser pulses without rapid rotation, in agreement with the simulations. The findings indicate the stringent conditions required to perform rigorous broadband XUV time-resolved absorption measurements on bulk solid-state samples, particularly those with temperature sensitivity, and elucidate a clear methodology to perform them.

Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}): Peroxovanadate sol gel synthesis and structural study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langie da Silva, Douglas, E-mail: douglas.langie@ufpel.edu.br; Moreira, Eduardo Ceretta; Dias, Fábio Teixeira

2015-01-15

Nanostructured cobalt vanadium oxide (V{sub 2}O{sub 5}) xerogels spread onto crystalline Si substrates were synthesized via peroxovanadate sol gel route. The resulting products were characterized by distinct experimental techniques. The surface morphology and the nanostructure of xerogels correlate with Co concentration. The decrease of the structural coherence length is followed by the formation of a loose network of nanopores when the concentration of intercalated species was greater than 4 at% of Co. The efficiency of the synthesis route also drops with the increase of Co concentration. The interaction between the Co(OH{sub 2}){sub 6}{sup 2+} cations and the (H{sub 2}V{sub 10}O{submore » 28}){sup 4−} anions during the synthesis was suggested as a possible explanation for the incomplete condensation of the V{sub 2}O{sub 5} gel. Finally the experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5}. In this scenario two possible preferential occupation sites for the metallic atoms in the framework of the xerogel were proposed. - Graphical abstract: Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}) nanoribbons synthesized by peroxovanadate sol gel route. - Highlights: • Nanostructured cobalt V{sub 2}O{sub 5} gel spread onto c{sub S}i were synthesized via peroxovanadate sol gel route. • The micro and nanostructure correlates with the cobalt content. • The efficiency of the synthesis route shows to be also dependent of Co content. • The experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5} xerogel.« less

Ozone assisted oxidation of gaseous PCDD/Fs over CNTs-containing composite catalysts at low temperature.

PubMed

Wang, Qiulin; Tang, Minghui; Peng, Yaqi; Du, Cuicui; Lu, Shengyong

2018-05-01

Ozone assisted carbon nanotubes (CNTs) supported vanadium oxide/titanium dioxide (V/Ti-CNTs) or vanadium oxide-manganese oxide/titanium dioxide (V-Mn/Ti-CNTs) catalysts towards gaseous PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) catalytic oxidations at low temperature (150 °C) were investigated. The removal efficiency (RE) and decomposition efficiency (DE) of PCDD/Fs achieved with V-Mn/Ti-CNTs alone were 95% and 45% at 150 °C under a space velocity (SV) of 14000 h -1 ; yet, these values reached 99% and 91% when catalyst and low concentration (50 ppm) ozone were used in combined. The ozone promotion effect on catalytic activity was further enhanced with the addition of manganese oxide (MnO x ) and CNTs. Adding MnO x and CNTs in V/Ti catalysts facilitated the ozone decomposition (creating more active species on catalyst surface), thus, improved ozone utilization (demanding relatively lower ozone addition concentration). On the other hand, this study threw light upon ozone promotion mechanism based on the comparison of catalyst properties (i.e. components, surface area, surface acidity, redox ability and oxidation state) before and after ozone treatment. The experimental results indicate that a synergistic effect exists between catalyst and ozone: ozone is captured and decomposed on catalyst surface; meanwhile, the catalyst properties are changed by ozone in return. Reactive oxygen species from ozone decomposition and the accompanied catalyst properties optimization are crucial reasons for catalyst activation at low temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.

The role of interfacial metal silicates on the magnetism in FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Desautels, R. D., E-mail: rddesautels@physics.umanitoba.ca; Toyota Research Institute of North America, Ann Arbor, Michigan 48169; Freeland, J. W.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, andmore » vanadium silicates. Magnetometry experiments have shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO{sub 2}-based interfacial shell.« less

NOX REMOVAL WITH COMBINED SELECTIVE CATALYTIC REDUCTION AND SELECTIVE NONCATALYTIC REDUCTION: PILOT- SCALE TEST RESULTS

EPA Science Inventory

Pilot-scale tests were conducted to develop a combined nitrogen oxide (NOx) reduction technology using both selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR). A commercially available vanadium-and titatnium-based composite honeycomb catalyst and enh...

New Insights into the Diverse Electronic Phases of a Novel Vanadium Dioxide Polymorph: A Terahertz Spectroscopy Study

PubMed Central

Lourembam, James; Srivastava, Amar; La-o-vorakiat, Chan; Rotella, H.; Venkatesan, T.; Chia, Elbert E. M.

2015-01-01

A remarkable feature of vanadium dioxide is that it can be synthesized in a number of polymorphs. The conductivity mechanism in the metastable layered polymorph VO2(B) thin films has been investigated by terahertz time-domain spectroscopy (THz-TDS). In VO2(B), a critical temperature of 240 K marks the appearance of a non-zero Drude term in the observed complex conductivity, indicating the evolution from a pure insulating state towards a metallic state. In contrast, the THz conductivity of the well-known VO2(M1) is well fitted only by a modification of the Drude model to include backscattering. We also identified two different THz conductivity regimes separated by temperature in these two polymorphs. The electronic phase diagram is constructed, revealing that the width and onset of the metal-insulator transition in the B phase develop differently from the M1 phase. PMID:25777320

Emptying and filling a tunnel bronze

DOE PAGES

Marley, Peter M.; Abtew, Tesfaye A.; Farley, Katie E.; ...

2015-01-13

The classical orthorhombic layered phase of V 2O 5 has long been regarded as the thermodynamic sink for binary vanadium oxides and has found great practical utility as a result of its open framework and easily accessible redox states. Herein, we exploit a cation-exchange mechanism to synthesize a new stable tunnel-structured polymorph of V 2O 5 (ζ-V 2O 5) and demonstrate the subsequent ability of this framework to accommodate Li and Mg ions. The facile extraction and insertion of cations and stabilization of the novel tunnel framework is facilitated by the nanometer-sized dimensions of the materials, which leads to accommodationmore » of strain without amorphization. The topotactic approach demonstrated here indicates not just novel intercalation chemistry accessible at nanoscale dimensions but also suggests a facile synthetic route to ternary vanadium oxide bronzes (MxV 2O 5) exhibiting intriguing physical properties that range from electronic phase transitions to charge ordering and superconductivity.« less

Tunable Oxygen Functional Groups as Electrocatalysts on Graphite Felt Surfaces for All-Vanadium Flow Batteries.

PubMed

Estevez, Luis; Reed, David; Nie, Zimin; Schwarz, Ashleigh M; Nandasiri, Manjula I; Kizewski, James P; Wang, Wei; Thomsen, Edwin; Liu, Jun; Zhang, Ji-Guang; Sprenkle, Vincent; Li, Bin

2016-06-22

A dual oxidative approach using O2 plasma followed by treatment with H2 O2 to impart oxygen functional groups onto the surface of a graphite felt electrode. When used as electrodes for an all-vanadium redox flow battery (VRB) system, the energy efficiency of the cell is enhanced by 8.2 % at a current density of 150 mA cm(-2) compared with one oxidized by thermal treatment in air. More importantly, by varying the oxidative techniques, the amount and type of oxygen groups was tailored and their effects were elucidated. It was found that O-C=O groups improve the cells performance whereas the C-O and C=O groups degrade it. The reason for the increased performance was found to be a reduction in the cell overpotential after functionalization of the graphite felt electrode. This work reveals a route for functionalizing carbon electrodes to improve the performance of VRB cells. This approach can lower the cost of VRB cells and pave the way for more commercially viable stationary energy storage systems that can be used for intermittent renewable energy storage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrophobic Catalysts For Removal Of NOx From Flue Gases

NASA Technical Reports Server (NTRS)

Sharma, Pramod K.; Hickey, Gregory S.; Voecks, Gerald E.

1995-01-01

Improved catalysts for removal of nitrogen oxides (NO and NO2) from combustion flue gases formulated as composites of vanadium pentoxide in carbon molecular sieves. Promotes highly efficient selective catalytic reduction of NOx at relatively low temperatures while not being adversely affected by presence of water vapor and sulfur oxide gases in flue gas. Apparatus utilizing catalyst of this type easily integrated into exhaust stream of power plant to remove nitrogen oxides, generated in combustion of fossil fuels and contribute to formation of acid rain and photochemical smog.

Long range superhyperfine interactions in polycrystalline vanadium doped SnO 2 investigated by CW and pulsed ENDOR spectroscopy

NASA Astrophysics Data System (ADS)

Murphy, Damien M.; Farley, Robert D.; Marshall, Joanne; Willock, David J.

2004-06-01

CW and pulsed ENDOR was used to probe the electron nuclear superhyperfine interactions between V 4+ ions and distant Sn nuclei in vanadium doped tin oxide (V/SnO 2). Whilst interactions with two sets of nearest neighbour Sn nuclei (with a V-Sn distance of 3.185 and 3.708 Å respectively) are observed by EPR, superhyperfine couplings to two remote sets of tins (with a V-Sn distance of 6.370 and ˜7.42 Å) are detected by ENDOR. The interaction was found to be largely isotropic and largest along the crystal c axis. Small differences in the remote tin environments were also detected by ENDOR.

Photoinduced surface plasmon switching at VO2/Au interface.

PubMed

Kumar, Nardeep; Rúa, Armando; Aldama, Jennifer; Echeverría, Karla; Fernández, Félix E; Lysenko, Sergiy

2018-05-28

Angle-resolved reflection, light scattering and ultrafast pump-probe spectroscopy combined with a surface plasmon-polariton (SPP) resonance technique in attenuated total reflection geometry was used to investigate the light-induced plasmonic switching in a photorefractive VO 2 /Au hybrid structure. Measurements of SPP scattering and reflection shows that the optically-induced formation of metallic state in a vanadium dioxide layer deposited on a gold film significantly alters the electromagnetic field enhancement and SPP propagation length at the VO 2 /Au interface. The ultrafast optical manipulation of SPP resonance is shown on a picosecond timescale. Obtained results demonstrate high potential of photorefractive vanadium oxides as efficient plasmonic modulating materials for ultrafast optoelectronic devices.

[New iron-porphyrin/vanadium-substituted polyoxometalate catalyst: synthesis, characterization and catalytic activity].

PubMed

Dong, Xiao-li; Zhang, Zhen-cheng; An, Qing-da; Zhang, Shao-yin; Wang, Shao-jun

2007-12-01

A new kind of iron-porphyrin/vanadium-substituted polyoxometalate coordination compound was synthesized by the ion exchange reaction of FeTTMAPPI and H5PMo10V2o40 in solution. The new catalyst was characterized by IR spectrometry and UV-Vis spectrometry. As an excellent catalyst, its effects on benzene hydroxylation and catalytic capabilities were studied with H2O2 solution as the oxidant. The results indicated that the products contained the conjugated structure of porphyrin and the cage structure of polyoxometalate, the V atom in polyoxometalate is the main centre of catalytic activity, meanwhile the presence of iron-porphyrin could increase its catalytic activity greatly.

Phase transition in bulk single crystals and thin films of V O 2 by nanoscale infrared spectroscopy and imaging

DOE PAGES

Liu, Mengkun; Sternbach, Aaron J.; Wagner, Martin; ...

2015-06-29

We have systematically studied a variety of vanadium dioxide (VO 2) crystalline forms, including bulk single crystals and oriented thin films, using infrared (IR) near-field spectroscopic imaging techniques. By measuring the IR spectroscopic responses of electrons and phonons in VO 2 with sub-grain-size spatial resolution (~20nm), we show that epitaxial strain in VO 2 thin films not only triggers spontaneous local phase separations, but leads to intermediate electronic and lattice states that are intrinsically different from those found in bulk. Generalized rules of strain- and symmetry-dependent mesoscopic phase inhomogeneity are also discussed. Furthermore, these results set the stage for amore » comprehensive understanding of complex energy landscapes that may not be readily determined by macroscopic approaches.« less

High-performance ferroelectric and magnetoresistive materials for next-generation thermal detector arrays

NASA Astrophysics Data System (ADS)

Todd, Michael A.; Donohue, Paul P.; Watton, Rex; Williams, Dennis J.; Anthony, Carl J.; Blamire, Mark G.

2002-12-01

This paper discusses the potential thermal imaging performance achievable from thermal detector arrays and concludes that the current generation of thin-film ferroelectric and resistance bolometer based detector arrays are limited by the detector materials used. It is proposed that the next generation of large uncooled focal plane arrays will need to look towards higher performance detector materials - particularly if they aim to approach the fundamental performance limits and compete with cooled photon detector arrays. Two examples of bolometer thin-film materials are described that achieve high performance from operating around phase transitions. The material Lead Scandium Tantalate (PST) has a paraelectric-to-ferroelectric phase transition around room temperature and is used with an applied field in the dielectric bolometer mode for thermal imaging. PST films grown by sputtering and liquid-source CVD have shown merit figures for thermal imaging a factor of 2 to 3 times higher than PZT-based pyroelectric thin films. The material Lanthanum Calcium Manganite (LCMO) has a paramagnetic to ferromagnetic phase transition around -20oC. This paper describes recent measurements of TCR and 1/f noise in pulsed laser-deposited LCMO films on Neodymium Gallate substrates. These results show that LCMO not only has high TCR's - up to 30%/K - but also low 1/f excess noise, with bolometer merit figures at least an order of magnitude higher than Vanadium Oxide, making it ideal for the next generation of microbolometer arrays. These high performance properties come at the expense of processing complexities and novel device designs will need to be introduced to realize the potential of these materials in the next generation of thermal detectors.

Carbon-carbon bond cleavage of 1,2-hydroxy ethers b7 vanadium(V) dipicolinate complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanson, Susan K; Gordon, John C; Thorn, David L

2009-01-01

The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress hasmore » been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A), 2-phenoxyethanol (B), and 1,2-diphenyl-2-methoxyethanol (C) (Figure 1). Reaction of (dipic)V{sup V}(O)O{sup i}Pr (1a) or (dipic)V{sup v}(O)OEt (lb) with A, B, or C in acetonitrile yielded new vanadium(V) complexes where the alcohol-ether ligand was bound in a chelating fashion. From the reaction of 1b with pinacol monomethyl ether (A) in acetonitrile solution, (dipic)V{sup v}(O)(pinOMe) (2) (PinOMe = 2,3-dimethyl-3-methoxy-2-butanoxide) was isolated in 61 % yield. Reaction of 1b with 2-phenoxyethanol (B) in acetonitrile gave the new complex (dipic)V{sup v}(O)(OPE) (3) (OPE = 2-phenoxyethoxide), which was isolated in 76% yield. In a similar fashion, 1a reacted with 1,2-diphenyl-2-methoxyethanol (C) to give (dipic)V(O)(DPME) (4) (DPME = 1,2-diphenyl-2-methoxyethoxide), which was isolated in 39% yield. Complexes 2, 3, and 4 were characterized by {sup 1}H NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Compared to the previously reported vanadium(V) pinacolate complex (dipic)V(O)(pinOH) the X-ray structure of complex 2 reveals a slightly shorter V = O bond, 1.573(2) {angstrom} vs 1.588(2) {angstrom} for the pinOH structure. Complexes 3 and 4 display similar vanadium oxo bond distances of 1.568(2) {angstrom} and 1.576(2) {angstrom}, respectively. All three complexes show longer bonds to the ether-oxygen trans to the oxo (2.388(2) {angstrom} for 2, 2.547(2) {angstrom} for 3, and 2.438(2) {angstrom} for 4) than to the hydroxy-oxygen in the pinOH structure (2.252(2) {angstrom}).« less

Equivalent circuit for VO{sub 2} phase change material film in reconfigurable frequency selective surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanphuang, Varittha; Ghalichechian, Nima; Nahar, Niru K.

We developed equivalent circuits of phase change materials based on vanadium dioxide (VO{sub 2}) thin films. These circuits are used to model VO{sub 2} thin films for reconfigurable frequency selective surfaces (FSSs). This is important as it provides a way for designing complex structures. A reconfigurable FSS filter using VO{sub 2} ON/OFF switches is designed demonstrating −60 dB isolation between the states. This filter is used to provide the transmission and reflection responses of the FSS in the frequency range of 0.1–0.6 THz. The comparison between equivalent circuit and full-wave simulation shows excellent agreement.

Vanadium sorption by mineral soils: Development of a predictive model.

PubMed

Larsson, Maja A; Hadialhejazi, Golshid; Gustafsson, Jon Petter

2017-02-01

The toxicity of vanadium in soils depends on its sorption to soil components. Here we studied the vanadate(V) sorption properties of 26 mineral soils. The data were used to optimise parameters for a Freundlich equation with a pH term. Vanadium K-edge XANES spectroscopy for three selected soils confirmed that the added vanadate(V) had accumulated mostly as adsorbed vanadate(V) on Fe and Al hydrous oxides, with only minor contributions from organically complexed vanadium(IV). Data on pH-dependent V solubility for seven soils showed that on average 0.36 H + accompanied each V during adsorption and desorption. The resulting model provided reasonable fits to the V sorption data, with r 2  > 0.99 for 20 of 26 soils. The observed K dS value, i.e. the ratio of total to dissolved V, was strongly dependent on V addition and soil; it varied between 3 and 4 orders of magnitude. The model was used to calculate the Freundlich sorption strength (FSS), i.e. the amount of V sorbed at [V] = 2.5 mg L -1 , in the concentration range of observed plant toxicities. A close relationship between FSS and oxalate-extractable Fe and Al was found (r 2  = 0.85) when one acidic soil was removed from the regression. The FSS varied between 27 and 8718 mg V kg -1 , showing that the current environmental guidelines can be both under- and overprotective for vanadium. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermodynamic effects of calcium and iron oxides on crystal phase formation in synthetic gasifier slags containing from 0 to 27wt.% V 2O 3

DOE PAGES

Nakano, Jinichiro; Duchesne, Marc; Bennett, James; ...

2014-11-15

Thermodynamic phase equilibria in synthetic slags (Al 2O 3–CaO–FeO–SiO 2–V 2O 3) were investigated with 0–27 wt.% vanadium oxide corresponding to industrial coal–petroleum coke (petcoke) feedstock blends in a simulated gasifier environment. Samples encompassing coal–petcoke mixed slag compositions were equilibrated at 1500 °C in a 64 vol.% CO/36 vol.% CO 2 atmosphere (Po 2 ≈ 10 –8 atm at 1500 °C) for 72 h, followed by rapid water quench, then analyzed by inductively coupled plasma optical emission spectrometry, X-ray diffractometry, and scanning electron microscopy with wavelength dispersive spectroscopy. With increasing CaO content, FeO content, or both; the slag homogeneity regionmore » expanded and a composition range exhibiting crystals was reduced. The mullite (Al 6Si 2O 13) crystalline phase was not present in the slags above 9 wt.% FeO while the karelianite (V 2O 3) crystalline phase was always present in compositions studied if a sufficient amount of vanadium existed in the slag. Furthermore, based on the present experimental equilibrium evaluation, a set of isothermal phase diagrams showing effects of CaO and FeO on thermodynamic phase stabilities in the vanadium-bearing slags is proposed. Some uses of the diagrams for potential industrial practice are discussed.« less

Association of expired nitric oxide with urinary metal concentrations in boilermakers exposed to residual oil fly ash.

PubMed

Kim, Jee Young; Hauser, Russ; Wand, Matthew P; Herrick, Robert F; Houk, R S; Aeschliman, David B; Woodin, Mark A; Christiani, David C

2003-11-01

Exposure to metal-containing particulate matter has been associated with adverse pulmonary responses. Metals in particulate matter are soluble, hence are readily recovered in urine of exposed individuals. This study investigated the association between urinary metal concentrations and the fractional concentration of expired nitric oxide (F(E)NO) in boilermakers (N = 32) exposed to residual oil fly ash (ROFA). Subjects were monitored at a boiler overhaul site located in the New England area, USA. F(E)NO and urine samples were collected pre- and post-workshift for 5 consecutive workdays. Metals investigated included vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu), and lead (Pb). The median F(E)NO was 7.5 ppb (95% CI: 7.4-8.0), and the median creatinine-adjusted urinary metal concentrations (mug/g creatinine) were: vanadium, 1.37; chromium, 0.48; manganese, 0.30; nickel, 1.52; copper, 3.70; and lead, 2.32. Linear mixed-effects models indicated significant inverse exposure-response relationships between log F(E)NO and the log-transformed urinary concentrations of vanadium, manganese, nickel, copper, and lead at several lag times, after adjusting for smoking status. Urine samples may be utilized as a biomarker of occupational metal exposure. The inverse association between F(E)NO and urinary metal concentrations suggests that exposure to metals in particulate matter may have an adverse effect on respiratory health. Copyright 2003 Wiley-Liss, Inc.

A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state

PubMed Central

Krakowiak, Joanna; Lundberg, Daniel

2012-01-01

The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen donor solvents water, dimethylsulfoxide (dmso) and N,N′-dimethylpropyleneurea (dmpu) has been studied in solution by EXAFS and large angle X-ray scattering (LAXS) and in solid state by single crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and dimethylsulfoxide solvated oxovanadium(IV) ions vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O=V-Operp bond angle is ca. 98°. In the dmpu solvated oxovanadium(IV) ion, the space demanding properties of the dmpu molecule leaving no solvent molecule in the trans position to the oxo group which reduces the coordination number to 5. The O=V-O bond angle is consequently much larger, 106°, and the mean V=O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and dimethylsulfoxide solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in cis position with mean V=O bond distances of 1.6 Å and a O=V=O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen donor ligands. PMID:22950803

Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

NASA Astrophysics Data System (ADS)

Sossi, Paolo A.; Prytulak, Julie; O'Neill, Hugh St. C.

2018-04-01

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities ({f_{{{O}2}}}), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V3+ and V4+ in magnetite, and a mixture of IV- and VI-fold V5+ and V4+ in the melt. The magnitude of the fractionation factor systematically increases with increasing log{f_{{{O}2}}} relative to the Fayalite-Magnetite-Quartz buffer (FMQ), from Δ51Vmag-gl = - 0.63 ± 0.09‰ at FMQ - 1 to - 0.92 ± 0.11‰ (SD) at ≈ FMQ + 5, reflecting constant V3+/V4+ in magnetite but increasing V5+/V4+ in the melt with increasing log{f_{{{O}2}}}. These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.

Novel composite material polyoxovanadate@MIL-101(Cr): a highly efficient electrocatalyst for ascorbic acid oxidation.

PubMed

Fernandes, Diana M; Barbosa, André D S; Pires, João; Balula, Salete S; Cunha-Silva, Luís; Freire, Cristina

2013-12-26

A novel hybrid composite material, PMo10V2@MIL-101 was prepared by the encapsulation of the tetra-butylammonium (TBA) salt of the vanadium-substituted phosphomolybdate [PMo10V2O40](5-) (PMo10V2) into the porous metal-organic framework (MOF) MIL-101(Cr). The materials characterization by powder X-ray diffraction, Fourier transform infrared spectra and scanning electron microscopy confirmed the preparation of the composite material without disruption of the MOF porous structure. Pyrolytic graphite electrodes modified with the original components (MIL-101(Cr), PMo10V2), and the composite material PMo10V2@MIL-101 were prepared and their electrochemical responses were studied by cyclic voltammetry. Surface confined redox processes were observed for all the immobilized materials. MIL-101(Cr) showed one-electron reduction process due to chromium centers (Cr(III) → Cr(II)), while PMo10V2 presented five reduction processes: the peak at more positive potentials is attributed to two superimposed 1-electron vanadium reduction processes (V(V) → V(IV)) and the other four peaks to Mo-centred two-electron reduction processes (Mo(VI) → Mo(V)). The electrochemical behavior of the composite material PMo10V2@MIL-101 showed both MIL-101(Cr) and PMo10V2 redox features, although with the splitting of the two vanadium processes and the shift of the Mo- and Cr- centered processes to more negative potentials. Finally, PMo10V2@MIL-101 modified electrode showed outstanding enhanced vanadium-based electrocatalytic properties towards ascorbic acid oxidation, in comparison with the free PMo10V2, as a result of its immobilization into the porous structure of the MOF. Furthermore, PMo10V2@MIL-101 modified electrode showed successful simultaneous detection of ascorbic acid and dopamine.

Developing V-Xanes Oxybarometry for Probing Materials Formed in Reducing Environments in the Early Solar Disk

NASA Technical Reports Server (NTRS)

Butterworth, A. L.; Gainsforth, Z.; Jilly-Rehak, C. E.; Righter, K.; Westphal, A. J.

2017-01-01

Vanadium exhibits four oxidation states (V(sup 2+), V(sup 3+), V(sup 4+) and V(sup 5+)) that have been shown to preferentially partition between melt phases dependent on redox conditions, spanning oxygen fugacity across more than 10 log units. We are developing synchrotron-based x-ray absorption spectroscopy of low-fugacity standards for the determination of V oxidation state in highly reducing conditions relevant to the early solar nebula.

Li/Ag 2VO 2PO 4 batteries: the roles of composite electrode constituents on electrochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bock, David C.; Bruck, Andrea M.; Pelliccione, Christopher J.

2016-11-01

Silver vanadium phosphorous oxide, Ag 2V 2OPO 4, was used as a model system to systematically study the impact on the constituents of a composite electrode, including polymeric and conductive additives, on electrochemistry. Three different electrode compositions were investigated.

Effect of Cr2O3 addition on the oxidation induration mechanism of Hongge vanadium titanomagnetite pellets

NASA Astrophysics Data System (ADS)

Li, Wei; Wang, Nan; Fu, Gui-qin; Chu, Man-sheng; Zhu, Miao-yong

2018-04-01

As part of a research project to develop a novel clean smelting process for the comprehensive utilization of Hongge vanadium titanomagnetite (HVTM), in this study, the effect of Cr2O3 addition on the oxidation induration mechanism of HVTM pellets (HVTMPs) was investigated in detail. The results showed that the compressive strength of the HVTMPs was greatly weakened by the Cr2O3 addition, mainly because of a substantial increase in the porosity of the HVTMPs. The Cr2O3 addition marginally affected the phase composition but greatly affected the microstructural changes of the HVTMPs. Increased amounts of Cr2O3 resulted in a decrease in the uniform distribution of the hematite grains and in an increase in the Fe-Cr solid solutions (Fe1.2Cr0.8O3 and Fe0.7Cr1.3O3) embedded in the hematite grains. Moreover, the compact hematite was destroyed by forming a dispersed structure and the hematite recrystallization was hindered during the oxidation induration, which adversely affected the compressive strength. On the basis of these results, a schematic was formulated to describe the oxidation induration mechanism with different amounts of added Cr2O3. This study provides theoretical and technical foundations for the effective production of HVTMPs and a reference for chromium-bearing minerals.

Melt quenched vanadium oxide embedded in graphene oxide sheets as composite electrodes for amperometric dopamine sensing and lithium ion battery applications

NASA Astrophysics Data System (ADS)

Sreejesh, M.; Shenoy, Sulakshana; Sridharan, Kishore; Kufian, D.; Arof, A. K.; Nagaraja, H. S.

2017-07-01

Electrochemical sensors and lithium-ion batteries are two important topics in electrochemistry that have attracted much attention owing to their extensive applications in enzyme-free biosensors and portable electronic devices. Herein, we report a simple hydrothermal approach for synthesizing composites of melt quenched vanadium oxide embedded on graphene oxide of equal proportion (MVGO50) for the fabrication of electrodes for nonenzymatic amperometic dopamine sensor and lithium-ion battery applications. The sensing performance of MVGO50 electrodes through chronoamperometry studies in 0.1 M PBS solution (at pH 7) over a wide range of dopamine concentration exhibited a highest sensitivity of 25.02 μA mM-1 cm-2 with the lowest detection limit of 0.07 μM. In addition, the selective sensing capability of MVGO50 was also tested through chronoamperometry studies by the addition of a very small concentration of dopamine (10 μM) in the presence of a fairly higher concentration of uric acid (10 mM) as the interfering species. Furthermore, the reversible lithium cycling properties of MVGO50 are evaluated by galvanostatic charge-discharge cycling studies. MVGO50 electrodes exhibited enhanced rate capacity of up to 200 mAhg-1 at a current of 0.1C rate and remained stable during cycling. These results indicate that MVGO composites are potential candidates for electrochemical device applications.

Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.

1992-01-01

A critical review of thermodynamic data for aqueous and solid V species is presented to evaluate dissolution, transport, and precipitation of V under natural conditions. Emphasis is given to results of experimental studies of V chemistry, especially those for which the experimental conditions are near those found in nature. Where possible, data are obtained for or corrected to the reference conditions of 298.15K, 1 atm (1.01325 bar) and zero ionic strength. Vanadium [IV] (VIV) and vanadium[V] (VV) are the most soluble forms of V in nature, and their complexes with fluoride, sulfate, and oxalate may act to increase V solubility under oxidizing conditions. Because redox behavior is of fundamental importance to understanding natural V chemistry, the kinetics of reduction of VIV to VIII H2S were studied. Although H2S is predicted from thermodynamic data to be capable of reducing VIV to VIII, this reaction has not been demonstrated experimentally. Experiments were carried out under conditions of temperature (45??C), pH (3.6-6.8), ionic strength (0.05-0.1 m), and V concentrations (9.8-240 ??molar) likely to be found in nature. Because the reaction is very slow, H2S concentrations in excess of natural conditions were used (8.1 ?? 10-4 to 0.41 atm). The results show that VIV is reduced to VIII under a variety of conditions. The rate increases with increasing pH, but is not appreciably affected by ionic strength (as represented by the concentration of KCl, which was used as the supporting electrolyte in all cases). Prior to initiation of the reaction, there is an induction period, the length of which increases with increasing KCl concentration or decreasing pH. Attempts to model the reaction mechanism by numerical methods have failed to produce a satisfying fit of the results, indicating partial reaction orders, a complex mechanism, or involvement of a variety of intermediate species. The results of the thermodynamic and kinetic studies were applied to understanding the genesis of V deposits such as those commonly found on the Colorado Plateau. Vanadium in these sandstone-hosted deposits is present mostly in the reduced oxidation state, VIII. Because of the insolubility of VIII oxyhydroxides, it is likely that a more oxidized form of V (either [IV] or [V]) was transported to the site of mineralization, and that the V was reduced in situ and subsequently precipitated. A probable reductant is hydrogen sulfide; the presence of pyrite cogenetic with the V minerals documents the presence of H2S during mineralization. The experiments described here show that H2S could have reduced VIV to V III, and thus led to the formation of these deposits. ?? 1992.

Kinetic-spectrophotometric determination of trace amounts of vanadium(V) based on its catalytic effect on the reaction of DBM-arsenazo and potassium bromate

NASA Astrophysics Data System (ADS)

Zhai, Qing-zhou; Zhang, Xiao-xia; Huang, Chong

2008-03-01

A simple and sensitive kinetic-spectrophotometric method is developed for the determination of trace vanadium(V), based on the catalytic effect of vanadium(V) on the oxidation of DBM-arsenazo by potassium bromate in 0.0138 mol l -1 phosphoric acid medium and at 100 °C in the presence of citric acid as activator. The absorbance is measured at 528 nm with the fixed-time method. The optimization of the operating conditions regarding concentrations of the reagents, temperature and interferences are also investigated. The working curve is linear over the concentration range 0-20 ng ml -1 of vanadium(V) with good precision and accuracy and the detection limit was down to 3.44 ng l -1. The relative standard deviation for a standard solution of 14 ng ml -1 is 0.28% ( n = 11). The apparent activity energies of the catalytic reaction and the non-catalytic reaction are 73.48, 113.5 kJ/mol, respectively. The proposed method proved highly sensitive, selective and relatively rapid for the assay of vanadium at low-level range of 0-20 ng ml -1 without any pre-concentration step. Thw method was applied to the determination of vanadium(V) in steels, rice, flour, cabbage, potato, fish, shrimp and tea samples with satisfactory results. The obtained results for the steel samples were excellent agreement with the standard reference values. The analytical results of the rice, flour, cabbage, potato, fish, shrimp and tea samples were excellent agreement with those of atomic absorption spectrometry. The recovery experiments have been made for the rice, flour, cabbage, potato, fish, shrimp and tea samples except the steels; excellent results were obtained. The relative standard deviations were over the range of 0.18-2.60% and the recoveries were over the range of 98.00-102.4%, respectively. The analytical results obtained were satisfactory.

Atomic-scale visualization of oxide thin-film surfaces.

PubMed

Iwaya, Katsuya; Ohsawa, Takeo; Shimizu, Ryota; Okada, Yoshinori; Hitosugi, Taro

2018-01-01

The interfaces of complex oxide heterostructures exhibit intriguing phenomena not observed in their constituent materials. The oxide thin-film growth of such heterostructures has been successfully controlled with unit-cell precision; however, atomic-scale understandings of oxide thin-film surfaces and interfaces have remained insufficient. We examined, with atomic precision, the surface and electronic structures of oxide thin films and their growth processes using low-temperature scanning tunneling microscopy. Our results reveal that oxide thin-film surface structures are complicated in contrast to the general perception and that atomically ordered surfaces can be achieved with careful attention to the surface preparation. Such atomically ordered oxide thin-film surfaces offer great opportunities not only for investigating the microscopic origins of interfacial phenomena but also for exploring new surface phenomena and for studying the electronic states of complex oxides that are inaccessible using bulk samples.

Spectroscopic ellipsometry investigation of the optical properties of graphene oxide dip-coated on magnetron sputtered gold thin films

NASA Astrophysics Data System (ADS)

Politano, Grazia Giuseppina; Vena, Carlo; Desiderio, Giovanni; Versace, Carlo

2018-02-01

Despite intensive investigations on graphene oxide-gold nanocomposites, the interaction of graphene oxide sheets with magnetron sputtered gold thin films has not been studied yet. The optical constants of graphene oxide thin films dip-coated on magnetron sputtered gold thin films were determined by spectroscopic ellipsometry in the [300-1000] wavelength range. Moreover, the morphologic properties of the samples were investigated by SEM analysis. Graphene oxide absorbs mainly in the ultraviolet region, but when it is dip-coated on magnetron sputtered gold thin films, its optical constants show dramatic changes, becoming absorbing in the visible region, with a peak of the extinction coefficient at 3.1 eV. Using magnetron sputtered gold thin films as a substrate for graphene oxide thin films could therefore be the key to enhance graphene oxide optical sheets' properties for several technological applications, preserving their oxygen content and avoiding the reduction process.

Demonstration of high-performance p-type tin oxide thin-film transistors using argon-plasma surface treatments

NASA Astrophysics Data System (ADS)

Bae, Sang-Dae; Kwon, Soo-Hun; Jeong, Hwan-Seok; Kwon, Hyuck-In

2017-07-01

In this work, we investigated the effects of low-temperature argon (Ar)-plasma surface treatments on the physical and chemical structures of p-type tin oxide thin-films and the electrical performance of p-type tin oxide thin-film transistors (TFTs). From the x-ray photoelectron spectroscopy measurement, we found that SnO was the dominant phase in the deposited tin oxide thin-film, and the Ar-plasma treatment partially transformed the tin oxide phase from SnO to SnO2 by oxidation. The resistivity of the tin oxide thin-film increased with the plasma-treatment time because of the reduced hole concentration. In addition, the root-mean-square roughness of the tin oxide thin-film decreased as the plasma-treatment time increased. The p-type oxide TFT with an Ar-plasma-treated tin oxide thin-film exhibited excellent electrical performance with a high current on-off ratio (5.2 × 106) and a low off-current (1.2 × 10-12 A), which demonstrates that the low-temperature Ar-plasma treatment is a simple and effective method for improving the electrical performance of p-type tin oxide TFTs.

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

NASA Astrophysics Data System (ADS)

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.

Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Zhang, Bengui; Zhang, Shouhai; Weng, Zhihuan; Wang, Guosheng; Zhang, Enlei; Yu, Ping; Chen, Xiaomeng; Wang, Xinwei

2016-09-01

Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes (QADMPEK) are prepared and investigated for vanadium redox flow batteries (VRFB) application. The bulky, rigid and highly hydrophobic adamantane segment incorporated into the backbone of membrane material makes QADMPEK membranes have low water uptake and swelling ratio, and the as-prepared membranes display significantly lower permeability of vanadium ions than that of Nafion117 membrane. As a consequence, the VRFB cell with QADMPEK-3 membrane shows higher coulombic efficiency (99.4%) and energy efficiency (84.0%) than those for Nafion117 membrane (95.2% and 80.5%, respectively) at the current density of 80 mA cm-2. Furthermore, at a much higher current density of 140 mA cm-2, QADMPEK membrane still exhibits better coulombic efficiency and energy efficiency than Nafion117 membrane (coulombic efficiency 99.2% vs 96.5% and energy efficiency 76.0% vs 74.0%). Moreover, QADMPEK membranes show high stability in in-situ VRFB cycle test and ex-situ oxidation stability test. These results indicate that QADMPEK membranes are good candidates for VRFB applications.

Characterization and electrical properties of V 2O 5-CuO-P 2O 5 glasses

NASA Astrophysics Data System (ADS)

Al-Assiri, M. S.

2008-08-01

Characterization and electrical properties of vanadium-copper-phosphate glasses of compositions xV 2O 5-(40- x)CuO-60P 2O 5 have been reported. X-ray diffraction (XRD) confirms the amorphous nature of these glasses. It was observed that, the density ( d) decreases gradually while the molar volume ( Vm) increases with the increase of the vanadium oxide content in such glasses. This may be due to the effect of the polarizing power strength, PPS, which is a measure of ratio of the cation valance to its diameter. The dc conductivity increases while the activation energy decreases with the increase of the V 2O 5 content. The dc conductivity in the present glasses is electronic and depends strongly upon the average distance, R, between the vanadium ions. Analysis of the electrical properties has been made in the light of small polaron hopping model. The parameters obtained from the fits of the experimental data to this model are reasonable and consistent with glass composition. The conduction is attributed to non-adiabatic hopping of small polaron.

Chromium, nickel and vanadium mobility in soils derived from fluvioglacial sands.

PubMed

Agnieszka, Jeske; Barbara, Gworek

2012-10-30

The presented study was focused on soils developed from fluvioglacial sands from the Puszcza Borecka forest complex. The mobility of chromium, nickel and vanadium was evaluated with regard to litho- and pedogenic factors. The aim of the study was to determine with which soil constituents fractions of heavy metals are bound with particular attention drawn on the mobile fractions (F1+F2). Heavy metal fractions in the soils were determined using the sequential extraction method of Tessier et al. The purpose of sequential extraction methods to soil samples provides relevant information about possible toxicity when they are discharged into the soil environment. Chromium, nickel, and vanadium occurred predominantly in the fraction bound with iron and manganese oxides and in the residual fraction, thus showed low mobility. With regard to mobility, the elements studied can be arranged as follows: V

Direct electrochemical reduction of solid vanadium oxide to metal vanadium at low temperature in molten CaCl2-NaCl

NASA Astrophysics Data System (ADS)

Cai, Zhuo-fei; Zhang, Zhi-mei; Guo, Zhan-cheng; Tang, Hui-qing

2012-06-01

V2O5 sintered pellets and graphite rods were employed as the cathode and the anode, respectively; a molten CaCl2-NaCl salt was used as the electrolyte. Then, V2O5 was directly reduced to metal vanadium by the Fray-Farthing-Chen (FFC) method at 873 K to realize low-temperature electrolysis. Two typical experimental conditions, electrolysis time and voltage, were taken into account to investigate the current efficiency and remaining oxygen content in electrolyzed products. The composition and microstructure of the products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). SEM observations show that a higher voltage (1.8-3.4 V) and a longer electrolysis time (2-5 h) can improve the product quality separately, that is, a lower remaining oxygen content and a more uniform microstructure. The products with an oxygen content of 0.205wt% are successfully obtained below 3.4 V for 10 h. However, the current efficiency is low, and further work is required.

A Safe High-Performance All-Solid-State Lithium-Vanadium Battery with a Freestanding V2O5 Nanowire Composite Paper Cathode.

PubMed

Zhang, Yue; Lai, Jingyuan; Gong, Yudong; Hu, Yongming; Liu, Jin; Sun, Chunwen; Wang, Zhong Lin

2016-12-21

The electronic conductivity and structural stability are still challenges for vanadium pentoxide (V 2 O 5 ) as cathode materials in batteries. Here, we report a V 2 O 5 nanowire-reduced graphene oxide (rGO) composite paper for direct use as a cathode without any additives for high-temperature and high-safety solid polymer electrolyte [PEO-MIL-53(Al)-LiTFSI] lithium-vanadium batteries. The batteries can show a fast and stable lithium-ion-storage performance in a wide voltage window of 1.0-4.0 V versus Li + /Li at 80 °C, in which with an average capacity of 329.2 mAh g -1 at 17 mA g -1 and a stable cycling performance over 40 cycles are achieved. The excellent electrochemical performance is mainly ascribed to integration of the electronic conductivity of rGO and interconnected networks of the V 2 O 5 nanowires and solid electrolyte. This is a promising lithium battery for flexible and highly safe energy-storage devices.

Enhanced electronic and electrochemical properties of core-shelled V2O5-Pt nanowires

NASA Astrophysics Data System (ADS)

Pan, Ko-Ying; Wei, Da-Hua

2018-01-01

Platinum nanoparticles (Pt NPs) were decorated on vanadium pentoxide nanowires (V2O5 NWs) to form the core-shelled vanadium-platinum nanowires (Pt@V2O5 NWs) and their electrochemical activities for methanol oxidation were investigated. The synthetic procedure involved the synthesis of abundant vanadium pentoxide nanowires (V2O5 NWs) by a direct vapor-solid growth process (VS method), followed by atomic layer depositions (ALD) of platinum nanoparticles (Pt NPs) onto the V2O5 NWs. After the physical examinations, three designed deposition parameters (50, 100 and 150 cycles) of Pt NPs onto the V2O5 NWs by ALD process were successful. From the measurements of current-voltage (I-V) and cyclic voltammetry (CV) curves respectively, both the conductivity and the ratio of the forward anodic peak current (IF) to the reverse anodic peak current (IR) are enhancing proportionately to the deposition cycles of ALD process, which denotes that coating Pt atomic layers onto V2O5 nanowires indeed improves the catalytic performances than that of pure V2O5 nanowires.

Effect of annealing temperature on thermochromic properties of vanadium dioxide thin films deposited by organic sol-gel method

NASA Astrophysics Data System (ADS)

Wu, Jing; Huang, Wanxia; Shi, Qiwu; Cai, Jinghan; Zhao, Dong; Zhang, Yubo; Yan, Jiazhen

2013-03-01

This paper described the synthesis of vanadium dioxide (VO2) thin films on mica substrates with different annealing temperatures by an organic sol-gel method. We performed X-ray diffraction, scanning electron microscope and optical transmission measurements to investigate the effect of the annealing temperature on the crystalline structure, morphology, and phase transition properties of these films. The results showed that a polycrystalline structure with high crystallinity and compact surface at the annealing temperature of 500 °C. The film exhibited a V6O13 phase and a flat surface with small grain size at 440 °C. By contrast, the VnO2n-1 appeared when the annealing temperature at 540 °C, and the film surface split into segregation of spherical grain and aggregates of continuously dendritic particles. Accordingly, the optimal annealing temperature was 500 °C using the organic sol-gel method. And it turned out that the films mainly contained VO2 (M) phase at room temperature with high content of V4+ valence. Particularly, the films showed different changes in the infrared transmittance and hysteresis width during the phase transition. The largest transformation of the infrared transmittance before and after MIT was 73%, while the narrowest temperature hysteresis width was 8 °C at 500 °C.

V x In (2–x) S 3 Intermediate Band Absorbers Deposited by Atomic Layer Deposition

DOE PAGES

McCarthy, Robert F.; Weimer, Matthew S.; Haasch, Richard T.; ...

2016-03-21

Substitutional alloys of several thin film semiconductors have been proposed as intermediate band (IB) materials for use in next-generation photovoltaics, which aim to utilize a larger fraction of the solar spectrum without sacrificing significant photovoltage. Here, we demonstrate a novel approach to IB material growth, namely atomic layer deposition (ALD), to enable unique control over substitutional-dopant location and density. Two new ALD processes for vanadium sulfide incorporation are introduced, one of which incorporates a vanadium (III) amidinate previously untested for ALD. We synthesize the first thin film V xIn (2-x)S 3 intermediate band semiconductors, using this process, and further demonstratemore » that the V:In ratio, and therefore intraband gap density of states, can be finely tuned according to the ALD dosing schedule. Deposition on a crystalline In 2S 3 underlayer promotes the growth of a tetragonal β-In 2S 3-like phase V xIn (2-x)S 3, which exhibits a distinct sub-band gap absorption peak with onset near 1.1 eV in agreement with computational predictions. But, the V xIn (2-x)S 3 films lack the lower energy transition predicted for a partially filled IB, and photoelectrochemical devices reveal a photocurrent response only from illumination with energy sufficient to span the parent band-gap.« less

Porous Silica Sol-Gel Glasses Containing Reactive V2O5 Groups

NASA Technical Reports Server (NTRS)

Stiegman, Albert E.

1995-01-01

Porous silica sol-gel glasses into which reactive vanadium oxide functional groups incorporated exhibit number of unique characteristics. Because they bind molecules of some species both reversibly and selectively, useful as chemical sensors or indicators or as scrubbers to remove toxic or hazardous contaminants. Materials also oxidize methane gas photochemically: suggests they're useful as catalysts for conversion of methane to alcohol and for oxidation of hydrocarbons in general. By incorporating various amounts of other metals into silica sol-gel glasses, possible to synthesize new materials with broad range of new characteristics.

Microelectronic components and metallic oxide studies and applications

NASA Technical Reports Server (NTRS)

Williams, L., Jr.

1976-01-01

The project involved work in two basic areas: (1) Evaluation of commercial screen printable thick film conductors, resistors, thermistors and dielectrics as well as alumina substrates used in hybird microelectronics industries. Results of tests made on materials produced by seven companies are presented. (2) Experimental studies on metallic oxides of copper and vanadium, in an effort to determine their electrochemical properties in crystalline, powder mixtures and as screen printable thick films constituted the second phase of the research effort. Oxide investigations were aimed at finding possible applications of these materials as switching devices memory elements and sensors.

Vanadium and tungsten release from V-based selective catalytic reduction diesel aftertreatment

NASA Astrophysics Data System (ADS)

Liu, Z. Gerald; Ottinger, Nathan A.; Cremeens, Christopher M.

2015-03-01

Vanadium-based selective catalytic reduction (V-SCR) catalysts are currently used for the reduction of nitrogen oxides (NOx) in worldwide diesel applications including Euro IV, V, and VI as well as U.S. nonroad Tier 4 Final. Although V-SCR catalysts are attractive because of their high NOx conversion, low cost, resistance to sulfur poisoning, and ability to reduce hydrocarbon emissions, there is concern that V-SCR washcoat material (e.g., vanadium and tungsten) and its derivatives may be released into the atmosphere, potentially harming human health and the environment. In this study, vanadium and tungsten release measurements are made with both a reactor- and engine-based approach in order to determine the potential release of these metals from diesel exhaust aftertreatment systems that contain a V-SCR catalyst. Results for a commercially available V-SCR reveal that both V and W release begin at 500 °C, and both reactor- and engine-based methods are capable of measuring qualitatively similar release. Emissions with the engine-based method are higher at all temperatures evaluated, likely due to this method's ability to capture particle-phase and vapor-phase emissions which become particle-bound after their evolution from the catalyst surface. Certification relevant data (NRTC and NRSC) from a nonroad engine is used to understand probable emissions from V-SCR aftertreatment architectures. Finally, results from a V-SCR catalyst formulated for improved thermal durability illustrate that it is possible to increase the maximum temperature for V-SCR catalysts. This comprehensive understanding of the temperature dependence of vanadium and tungsten volatility can be used to further analyze the full impact of diesel aftertreatment on exhaust emissions and their impact on human health and environmental toxicity.

Extraordinary TCR in Carbon Nanotube-Polymer Composites and Device Implications in Bolometric Infrared Detection

DTIC Science & Technology

2015-03-24

were made via filtration of 1 mL of 1 mg/L SWCNT solution (Nanointegris Inc.) through a 20 nm pore anodized aluminum oxide ( AAO ) membrane filter to...prepared by attaching a rectangular piece cut from the AAO membrane filter onto a glass substrate. Contacts were made with silver paste to the extremities...NUMBER(S) 14. ABSTRACT _ The development of high TCR materials, such as vanadium oxide (VOx), has enabled the introduction of bolometric infrared

Inorganic Photocatalytic Enhancement: Activated RhB Photodegradation by Surface Modification of SnO2 Nanocrystals with V2O5-like species

PubMed Central

Epifani, Mauro; Kaciulis, Saulius; Mezzi, Alessio; Altamura, Davide; Giannini, Cinzia; Díaz, Raül; Force, Carmen; Genç, Aziz; Arbiol, Jordi; Siciliano, Pietro; Comini, Elisabetta; Concina, Isabella

2017-01-01

SnO2 nanocrystals were prepared by precipitation in dodecylamine at 100 °C, then they were reacted with vanadium chloromethoxide in oleic acid at 250 °C. The resulting materials were heat-treated at various temperatures up to 650 °C for thermal stabilization, chemical purification and for studying the overall structural transformations. From the crossed use of various characterization techniques, it emerged that the as-prepared materials were constituted by cassiterite SnO2 nanocrystals with a surface modified by isolated V(IV) oxide species. After heat-treatment at 400 °C, the SnO2 nanocrystals were wrapped by layers composed of vanadium oxide (IV-V mixed oxidation state) and carbon residuals. After heating at 500 °C, only SnO2 cassiterite nanocrystals were obtained, with a mean size of 2.8 nm and wrapped by only V2O5-like species. The samples heat-treated at 500 °C were tested as RhB photodegradation catalysts. At 10−7 M concentration, all RhB was degraded within 1 h of reaction, at a much faster rate than all pure SnO2 materials reported until now. PMID:28300185

Thermoelectric properties of V2O5 thin films deposited by thermal evaporation

NASA Astrophysics Data System (ADS)

Santos, R.; Loureiro, J.; Nogueira, A.; Elangovan, E.; Pinto, J. V.; Veiga, J. P.; Busani, T.; Fortunato, E.; Martins, R.; Ferreira, I.

2013-10-01

This work reports the structural, optical, electrical and thermoelectric properties of vanadium pentoxide (V2O5) thin films deposited at room temperature by thermal evaporation on Corning glass substrates. A post-deposition thermal treatment up to 973 K under atmospheric conditions induces the crystallization of the as-deposited amorphous films with an orthorhombic V2O5 phase with grain sizes around 26 nm. As the annealing temperature rises up to 773 K the electrical conductivity increases. The films exhibit thermoelectric properties with a maximum Seebeck coefficient of -218 μV/K and electrical conductivity of 5.5 (Ω m)-1. All the films show NIR-Vis optical transmittance above 60% and optical band gap of 2.8 eV.

Photochemical metal organic deposition of metal oxides

NASA Astrophysics Data System (ADS)

Law, Wai Lung (Simon)

This thesis pertains to the study of the deposition of metal oxide thin films via the process of Photochemical Metal Organic Deposition (PMOD). In this process, an amorphous metal organic precursor thin film is subjected to irradiation under ambient conditions. Fragmentation of the metal precursor results from the photoreaction, leading to the formation of metal oxide thin films in the presence of oxygen. The advantage of PMOD lies in its ability to perform lithography of metal oxide thin film without the application of photoresist. The metal organic precursor can be imaged directly by photolysis through a lithography mask under ambient conditions. Thus the PMOD process provides an attractive alternative to the conventional VLSI fabrication process. Metal carboxylates and metal acetylacetonates complexes were used as the precursors for PMOD process in this thesis. Transition metal carboxylate and metal acetylacetonate complexes have shown previously that when deposited as amorphous thin films, they will undergo fragmentation upon photolysis, leading to the formation of metal oxide thin films under ambient conditions. In this thesis, the formation of main group metal oxides of aluminum, indium and tin, as well as the formation of rare-earth metal oxides of cerium and europium by PMOD from its corresponding metal organic precursor will be presented. The nature of the photoreactions as well as the properties of the thin films deposited by PMOD will be investigated. Doped metal oxide thin films can also be prepared using the PMOD process. By mixing the metal precursors prior to deposition in the desired ratio, precursor films containing more than one metal precursor can be obtained. Mixed metal oxide thin films corresponding to the original metal ratio, in the precursor mixture, can be obtained upon photolysis under ambient conditions. In this thesis, the properties of doped metal oxide thin films of europium doped aluminum oxide as well as tin doped indium oxide thin films will also be presented.

PREPARATION, CHARACTERIZATION AND ACTIVITY OF AL2O3-SUPPORTED V2O5 CATALYSTS

EPA Science Inventory

A series of activated alumina supported vanadium oxide catalysts with various V2O5 loadings ranging from 5 to 25 wt% has been prepared by wet impregnation technique. A combination of various physico-chemical techniques such as BET surface areas, oxygen chemisorption, X-ray diffra...

OXIDATION OF METHANOL USING OZONE ON TITANIA-SUPPORTED VANADIUM CATALYST

EPA Science Inventory

Catalytic ozone decomposition of methanol has been conducted at mild temperatures of 100 to 250°C using V2O5/TiO2 catalyst prepared by either sol-gel or wet impregnation methods. The catalysts were characterized using XRD, surface area measurements, and desorption of CH3OH. Gas p...

Preparation of .alpha., .beta.-unsaturated carboxylic acids and anhydrides

DOEpatents

Spivey, James Jerry; Gogate, Makarand Ratnakav; Zoeller, Joseph Robert; Tustin, Gerald Charles

1998-01-01

Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Preparation of {alpha}, {beta}-unsaturated carboxylic acids and anhydrides

DOEpatents

Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Tustin, G.C.

1998-01-20

Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Standard methods for chemical analysis of steel, cast iron, open-hearth iron, and wrought iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1973-01-01

Methods are described for determining manganese, phosphorus, sulfur, selenium, copper, nickel, chromium, vanadium, tungsten, titanium, lead, boron, molybdenum ( alpha -benzoin oxime method), zirconium (cupferron --phosphate method), niobium and tantalum (hydrolysis with perchloric and sulfurous acids (gravimetric, titrimetric, and photometric methods)), and beryllium (oxide method). (DHM)

The electric field gradient at111Cd in vanadium oxides

NASA Astrophysics Data System (ADS)

Naicker, V.; Bartos, A.; Lieb, K. P.; Uhrmacher, M.; Wenzel, T.; Wiarda, D.

1993-03-01

The electric field gradient (efg) of111Cd in polycrystalline V2O5 was studied using perturbed angular correlation (PAC) spectroscopy, with the111In activity ion-implanted at 400 keV. Between the individual steps of an isochronal annealing program, a distinct efg ( v Q 1=88.1(3) MHz, ν1=0.62(2)) was recorded the contribution of which increased with annealing temperature up to 74% at 870 K. Corresponding X-ray analysis of inactive V2O5 samples, which underwent the same annealing treatment, proved that the sample always stayed as V2O5. Since V2O5 has only one equivalent cation site, it is concluded that this efg belongs to111Cd at this site. Oxidation of a vanadium foil at T=675 and 800 K at p_{{{O}}_{{2}} } =200 mbar also yielded this efg. From PAC measurements in VO2, two well-defined efg's were found above and below the metal-semiconductor transition at 340 K, which are tentatively attributed to the monoclinic and the tetragonal phase.

Photocatalytic Water Splitting for O2 Production under Visible Light Irradiation Using NdVO4-V2O5 Hybrid Powders

PubMed Central

Chiang, Tzu Hsuan; Chen, Tso-Ming

2017-01-01

The study investigated photocatalytic water splitting for O2 production under visible light irradiation using neodymium vanadium oxide (NdVO4) and vanadium oxide (V2O5) hybrid powders. The results in a sacrificial agent of 0.01 M AgNO3 solution were obtained, and the highest photocatalytic O2 evolution was 2.63 μmol/h, when the hybrid powders were prepared by mixing Nd and V at a volume ratio of 1:3 at a calcination temperature of 350 °C for 1 h. The hybrid powders were synthesized by neodymium nitrate and ammonium metavanadate using the glycothermal method in ethylene glycol at 120 °C for 1 h. The hybrid powders consisted of two shapes, NdVO4 nanoparticles and the cylindrical V2O5 particles, and they possessed the ability for photocatalytic oxygen (O2) evolution during irradiation with visible light. The band gaps and structures of the hybrid powders were analyzed using UV-visible spectroscopy and transmission electron microscopy. PMID:28772692

Synthesis, characterization and oxidation of metallic cobalt (Co) thin film into semiconducting cobalt oxide (Co3O4)thin film using microwave plasma CVD

NASA Astrophysics Data System (ADS)

Rahman Ansari, Akhalakur; Hussain, Shahir; Imran, Mohd; Abdel-wahab, M. Sh; Alshahrie, Ahmed

2018-06-01

The pure cobalt thin film was deposited on the glass substrate by using DC magnetron sputtering and then exposed to microwave assist oxygen plasma generated in microwave plasma CVD. The oxidation process of Co thin film into Co3O4 thin films with different microwave power and temperature were studied. The influences of microwave power, temperature and irradiation time were investigated on the morphology and particle size of oxide thin films. The crystal structure, chemical conformation, morphologies and optical properties of oxidized Co thin films (Co3O4) were studied by using x-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Raman Spectroscopy and UV–vis Spectroscopy. The data of these films showed complete oxidation pure metallic cobalt (Co) into cobalt oxide (Co3O4). The optical properties were studied for calculating the direct band gaps which ranges from 1.35 to 1.8 eV.

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

PubMed

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.

Electrospinning of ceramic nanofibers

NASA Astrophysics Data System (ADS)

Eick, Benjamin M.

Silicon Carbide (SiC) nanofibers of diameters as low as 20 nm are fabricated. The fibers were produced through the electrostatic spinning of the preceramic poly(carbomethylsilane) with pyrolysis to ceramic. A new technique was used where the preceramic was blended with polystyrene (PS) and, subsequent to electrospinning, was exposed to UV to crosslink the PS and prevent fibers flowing during pyrolysis. Electrospun SiC fibers were characterized by FTIR, TGA-DTA, SEM, TEM, XRD, and SAED. Fibers were shown to be polycrystalline and nanograined with alpha-SiC 15R polytype being dominant, where commercial fiber production methods form beta-SiC 3C. Pyrolysis of the bulk polymer blend to SiC produced alpha-SiC 15R as the dominant polytype with larger grains showing that electrospinning nanofibers affects resultant crystallinity. Fibers produced were shown to have a core-shell structure of an oxide scale that was variable by pyrolysis conditions. Metal oxide powders (chromium oxide, cobalt oxide, iron oxide, silicon oxide, tantalum oxide, titanium oxide, tungsten oxide, vanadium oxide, and zirconium oxide), were converted to metal carbide powders and metal nitride powders by the process of carbothermal reduction (CTR). Synthetic pitch was explored as an alternative to graphite which is a common carbon source for CTR. It was shown via characterization with XRD that pitch performs as well and in some cases better than graphite and is therefore a viable alternative in CTR. Conversion of metal oxide powders with pitch led to conversion of sol-gel based metal oxide nanofibers produced by electrospinning. Pitch was soluble in the solutions xv that were electrospun allowing for intimate contact between the sol-gel and the carbon source for CTR. This method became a two step processing method to produce metal carbide and nitride nanofibers: first electrospin sol-gel based metal oxide nanofibers and subsequently pyrolize them in the manner of CTR to transform them. Results indicate that this method was capable of transforming hafnium, niobium, tantalum, titanium, vanadium, and zirconium sol-gel nanofibers to metal carbides and nitrides.

The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ebbinghaus, B.B.

1991-05-01

The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cellmore » technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF[sub 2], ThO[sub 2], YDT(0.85ThO[sub 2]-0.15YO[sub 1.5]), and LDT(0.85ThO[sub 2]- 0.15LaO[sub 1.5]) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.« less

The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ebbinghaus, Bartley B.

1991-05-01

The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cellmore » technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF 2, ThO 2, YDT(0.85ThO 2-0.15YO 1.5), and LDT(0.85ThO 2- 0.15LaO 1.5) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.« less

Vanadium Oxide Deposited on Strontium Titanate and Related Supports: Structural, Redox, and Catalytic Properties in Oxidative Dehydrogenation Reactions

NASA Astrophysics Data System (ADS)

McCarthy, James A.

The field of heterogeneous catalysis has advanced largely through the understanding of structure-function relationships, and novel support materials constitute one possible strategy to further this knowledge through the determination of support effects. To this end, the synthesis, characterization, and reactivity of a new catalytic system are reported herein. Vanadium oxide supported on SrTiO3 (VOx/STO) was prepared by atomic layer deposition, and its activity was investigated in various oxidative dehydrogenation (ODH) reactions. In cyclohexane and propane ODH experiments at 500 °C, selectivity toward COx was found to decrease with greater VOx density and minimal STO surface exposure. This indicates that the support itself is an effective total oxidation catalyst, which complicates VOx performance measurements. In the propane studies, VOx/STO achieved lower turnover frequency (TOF) and propylene yield compared to conventional supported VO x materials. The lower activity of VOx/STO catalysts was correlated with their VOx species being less easily reducible, as determined by temperature-programmed reduction (TPR). The suppressed reducibility is attributed to the stronger surface basicity of STO, which is induced by the presence of relatively electropositive Sr2+ within the perovskite lattice. Studies of cyclohexene ODH at 300 °C were conducted to minimize intrinsic conversion from the supports. The VOx/STO catalysts were mostly found to be less active than VOx/TiO2 and VOx/Al 2O3, in accordance with reducibility measurements. However, one sample containing 0.75% vanadium on STO was particularly active, achieving a TOF greater than 0.01 s-1, while maintaining almost 90% dehydrogenation selectivity. In general, VOx/STO materials were found to be more selective for 1,3-cyclohexadiene compared to traditional catalysts. Other titanates of the form A2+TiO3 were also investigated as supports, and the reducibility of VOx was found to trend with the electronegativity of the A-site cation and the basicity of the titanate. When applied to cyclohexene ODH however, no discernable relationship between reducibility and TOF could be observed, implying that other factors play a major role in this reaction. Through this work, a deeper understanding has been developed concerning the impact of titanate supports on VOx redox and catalytic properties. These findings demonstrate the ability of novel support materials to reveal new insights into structure-function relationships.

Hole patterns in ultrathin vanadium oxide layers on a Rh(111) surface during catalytic oxidation reactions with NO

NASA Astrophysics Data System (ADS)

von Boehn, Bernhard; Mehrwald, Sarah; Imbihl, Ronald

2018-04-01

Various oxidation reactions with NO as oxidant have been investigated on a partially VOx covered Rh(111) surface (θV = 0.3 MLE) in the 10-4 mbar range, using photoelectron emission microscopy (PEEM) as spatially resolving method. The PEEM studies are complemented by rate measurements and by low-energy electron diffraction. In catalytic methanol oxidation with NO and in the NH3 + NO reaction, we observe that starting from a homogeneous surface with increasing temperature first a stripe pattern develops, followed by a pattern in which macroscopic holes of nearly bare metal surface are surrounded by a VOx film. These hole patterns represent just the inverse of the VOx distribution patterns seen if O2 instead of NO is used as oxidant.

Chemical composition of an aqueous oxalato-/citrato-VO(2+) solution as determinant for vanadium oxide phase formation.

PubMed

Peys, Nick; Maurelli, Sara; Reekmans, Gunter; Adriaensens, Peter; De Gendt, Stefan; Hardy, An; Van Doorslaer, Sabine; Van Bael, Marlies K

2015-01-05

Aqueous solutions of oxalato- and citrato-VO(2+) complexes are prepared, and their ligand exchange reaction is investigated as a function of the amount of citrate present in the aqueous solution via continuous-wave electron paramagnetic resonance (CW EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopy. With a low amount of citrate, monomeric cis-oxalato-VO(2+) complexes occur with a distorted square-pyramidal geometry. As the amount of citrate increases, oxalate is gradually exchanged for citrate. This leads to (i) an intermediate situation of monomeric VO(2+) complexes with a mix of oxalate/citrate ligands and (ii) a final situation of both monomeric and dimeric complexes with exclusively citrato ligands. The monomeric citrato-VO(2+) complexes dominate (abundance > 80%) and are characterized by a 6-fold chelation of the vanadium(IV) ion by 4 RCO2(-) ligands at the equatorial positions and a H2O/R-OH ligand at the axial position. The different redox stabilities of these complexes, relative to that of dissolved O2 in the aqueous solution, is analyzed via (51)V NMR. It is shown that the oxidation rate is the highest for the oxalato-VO(2+) complexes. In addition, the stability of the VO(2+) complexes can be drastically improved by evacuation of the dissolved O2 from the solution and subsequent storage in a N2 ambient atmosphere. The vanadium oxide phase formation process, starting with the chemical solution deposition of the aqueous solutions and continuing with subsequent processing in an ambient 0.1% O2 atmosphere, differs for the two complexes. The oxalato-VO(2+) complexes turn into the oxygen-deficient crystalline VO2 B at 400 °C, which then turns into crystalline V6O13 at 500 °C. In contrast, the citrato-VO(2+) complexes form an amorphous film at 400 °C that crystallizes into VO2 M1 and V6O13 at 500 °C.

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

NASA Astrophysics Data System (ADS)

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.

Inhalative Exposure to Vanadium Pentoxide Causes DNA Damage in Workers: Results of a Multiple End Point Study

PubMed Central

Ehrlich, Veronika A.; Nersesyan, Armen K.; Hoelzl, Christine; Ferk, Franziska; Bichler, Julia; Valic, Eva; Schaffer, Andreas; Schulte-Hermann, Rolf; Fenech, Michael; Wagner, Karl-Heinz; Knasmüller, Siegfried

2008-01-01

Background Inhalative exposure to vanadium pentoxide (V2O5) causes lung cancer in rodents. Objective The aim of the study was to investigate the impact of V2O5 on DNA stability in workers from a V2O5 factory. Methods We determined DNA strand breaks in leukocytes of 52 workers and controls using the alkaline comet assay. We also investigated different parameters of chromosomal instability in lymphocytes of 23 workers and 24 controls using the cytokinesis-block micronucleus (MN) cytome method. Results Seven of eight biomarkers were increased in blood cells of the workers, and vanadium plasma concentrations in plasma were 7-fold higher than in the controls (0.31 μg/L). We observed no difference in DNA migration under standard conditions, but we found increased tail lengths due to formation of oxidized purines (7%) and pyrimidines (30%) with lesion-specific enzymes (formamidopyrimidine glycosylase and endonuclease III) in the workers. Bleomycin-induced DNA migration was higher in the exposed group (25%), whereas the repair of bleomycin-induced lesions was reduced. Workers had a 2.5-fold higher MN frequency, and nucleoplasmic bridges (NPBs) and nuclear buds (Nbuds) were increased 7-fold and 3-fold, respectively. Also, apoptosis and necrosis rates were higher, but only the latter parameter reached statistical significance. Conclusions V2O5 causes oxidation of DNA bases, affects DNA repair, and induces formation of MNs, NPBs, and Nbuds in blood cells, suggesting that the workers are at increased risk for cancer and other diseases that are related to DNA instability. PMID:19079721

Growth, Structure, and Photocatalytic Properties of Hierarchical V₂O₅-TiO₂ Nanotube Arrays Obtained from the One-step Anodic Oxidation of Ti-V Alloys.

PubMed

Nevárez-Martínez, María C; Mazierski, Paweł; Kobylański, Marek P; Szczepańska, Grażyna; Trykowski, Grzegorz; Malankowska, Anna; Kozak, Magda; Espinoza-Montero, Patricio J; Zaleska-Medynska, Adriana

2017-04-05

V₂O₅-TiO₂ mixed oxide nanotube (NT) layers were successfully prepared via the one-step anodization of Ti-V alloys. The obtained samples were characterized by scanning electron microscopy (SEM), UV-Vis absorption, photoluminescence spectroscopy, energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (DRX), and micro-Raman spectroscopy. The effect of the applied voltage (30-50 V), vanadium content (5-15 wt %) in the alloy, and water content (2-10 vol %) in an ethylene glycol-based electrolyte was studied systematically to determine their influence on the morphology, and for the first-time, on the photocatalytic properties of these nanomaterials. The morphology of the samples varied from sponge-like to highly-organized nanotubular structures. The vanadium content in the alloy was found to have the highest influence on the morphology and the sample with the lowest vanadium content (5 wt %) exhibited the best auto-alignment and self-organization (length = 1 μm, diameter = 86 nm and wall thickness = 11 nm). Additionally, a probable growth mechanism of V₂O₅-TiO₂ nanotubes (NTs) over the Ti-V alloys was presented. Toluene, in the gas phase, was effectively removed through photodegradation under visible light (LEDs, λ max = 465 nm) in the presence of the modified TiO₂ nanostructures. The highest degradation value was 35% after 60 min of irradiation. V₂O₅ species were ascribed as the main structures responsible for the generation of photoactive e - and h⁺ under Vis light and a possible excitation mechanism was proposed.

Influence of architecture and material properties on vanadium redox flow battery performance

NASA Astrophysics Data System (ADS)

Houser, Jacob; Clement, Jason; Pezeshki, Alan; Mench, Matthew M.

2016-01-01

This publication reports a design optimization study of all-vanadium redox flow batteries (VRBs), including performance testing, distributed current measurements, and flow visualization. Additionally, a computational flow simulation is used to support the conclusions made from the experimental results. This study demonstrates that optimal flow field design is not simply related to the best architecture, but is instead a more complex interplay between architecture, electrode properties, electrolyte properties, and operating conditions which combine to affect electrode convective transport. For example, an interdigitated design outperforms a serpentine design at low flow rates and with a thin electrode, accessing up to an additional 30% of discharge capacity; but a serpentine design can match the available discharge capacity of the interdigitated design by increasing the flow rate or the electrode thickness due to differing responses between the two flow fields. The results of this study should be useful to design engineers seeking to optimize VRB systems through enhanced performance and reduced pressure drop.

Auger electron diffraction study of V/Fe(100) interface formation

NASA Astrophysics Data System (ADS)

Huttel, Y.; Avila, J.; Asensio, M. C.; Bencok, P.; Richter, C.; Ilakovac, V.; Heckmann, O.; Hricovini, K.

1998-05-01

Vanadium atoms present a magnetic moment different to zero when they are part of a thin film deposited on Fe or as a bimetallic Fe-V alloy. The understanding of this phenomenon can only be achieved with a correct structural description of these types of systems. We report an Auger electron diffraction investigation of V films grown on body cubic centred (b.c.c.) Fe(100) substrates. Angular-scanned Auger electron diffraction (AED) patterns of V L 23M 23M 4 (473 eV) and Fe L 3VV (703 eV) show the formation of a well-ordered V/Fe interface even at room temperature. The AED patterns of V films in the range of vanadium submonolayer provide evidence of an isotropic Auger emission, indicating the absence of interdiffusion of V atoms into the Fe substrate and absence of cluster growth of the V film. The annealing of these films up to 400°C does not activate the substitution of the topmost Fe surface layers by V atoms.

Structural Changes in the Vanadium Sample Surface Induced by Pulsed High-Temperature Deuterium Plasma and Deuterium Ion Fluxes

NASA Astrophysics Data System (ADS)

Borovitskaya, I. V.; Pimenov, V. N.; Gribkov, V. A.; Padukh, M.; Bondarenko, G. G.; Gaidar, A. I.; Paramonova, V. V.; Morozov, E. V.

2017-11-01

The structural changes in the vanadium sample surface are studied as functions of the conditions of irradiation by pulsed high-temperature deuterium plasma and deuterium ion fluxes in the Plasma Focus installation. It is found that processes of partial evaporation, melting, and crystallization of the surface layer of vanadium samples take place in the plasma flux power density range q = 108-1010 W/cm2 and the ion flux density range q = 1010-1012 W/cm2. The surface relief is wavelike. There are microcracks, gas-filled bubbles (blisters), and traces of fracture on the surface. The blisters are failed in the solid state. The character of blister fracture is similar to that observed during usual ion irradiation in accelerators. The samples irradiated at relatively low power density ( q = 107-108 W/cm2) demonstrate the ejection of microparticles (surface fragments) on the side facing plasma. This process is assumed to be due to the fact that the unloading wave formed in the sample-target volume reaches its irradiated surface. Under certain irradiation conditions (sample-anode distance, the number of plasma pulses), a block microstructure with block sizes of several tens of microns forms on the sample surfaces. This structure is likely to form via directional crack propagation upon cooling of a thin melted surface layer.