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.

Phosphorus oxide gate dielectric for black phosphorus field effect transistors

NASA Astrophysics Data System (ADS)

Dickerson, W.; Tayari, V.; Fakih, I.; Korinek, A.; Caporali, M.; Serrano-Ruiz, M.; Peruzzini, M.; Heun, S.; Botton, G. A.; Szkopek, T.

2018-04-01

The environmental stability of the layered semiconductor black phosphorus (bP) remains a challenge. Passivation of the bP surface with phosphorus oxide, POx, grown by a reactive ion etch with oxygen plasma is known to improve photoluminescence efficiency of exfoliated bP flakes. We apply phosphorus oxide passivation in the fabrication of bP field effect transistors using a gate stack consisting of a POx layer grown by reactive ion etching followed by atomic layer deposition of Al2O3. We observe room temperature top-gate mobilities of 115 cm2 V-1 s-1 in ambient conditions, which we attribute to the low defect density of the bP/POx interface.

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.

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.

[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.

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.

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.

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

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.

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.

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

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.

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

Electrical and Infrared Optical Properties of Vanadium Oxide Semiconducting Thin-Film Thermometers

NASA Astrophysics Data System (ADS)

Zia, Muhammad Fakhar; Abdel-Rahman, Mohamed; Alduraibi, Mohammad; Ilahi, Bouraoui; Awad, Ehab; Majzoub, Sohaib

2017-10-01

A synthesis method has been developed for preparation of vanadium oxide thermometer thin film for microbolometer application. The structure presented is a 95-nm thin film prepared by sputter-depositing nine alternating multilayer thin films of vanadium pentoxide (V2O5) with thickness of 15 nm and vanadium with thickness of 5 nm followed by postdeposition annealing at 300°C in nitrogen (N2) and oxygen (O2) atmospheres. The resulting vanadium oxide (V x O y ) thermometer thin films exhibited temperature coefficient of resistance (TCR) of -3.55%/°C with room-temperature resistivity of 2.68 Ω cm for structures annealed in N2 atmosphere, and TCR of -3.06%/°C with room-temperature resistivity of 0.84 Ω cm for structures annealed in O2 atmosphere. Furthermore, optical measurements of N2- and O2-annealed samples were performed by Fourier-transform infrared ellipsometry to determine their dispersion curves, refractive index ( n), and extinction coefficient ( k) at wavelength from 7000 nm to 14,000 nm. The results indicate the possibility of applying the developed materials in thermometers for microbolometers.

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.

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.

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. (

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.

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.

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

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.

Assessment of Dephosphorization During Vanadium Extraction Process in Converter

NASA Astrophysics Data System (ADS)

Chen, Lian; Diao, Jiang; Wang, Guang; Xie, Bing

2018-06-01

Dephosphorization during the vanadium extraction process in the converter was studied. The effects of the slag basicity and FeO content on the dephosphorization and the mineral phases in the phosphorus-containing vanadium slag are discussed. The results show that removal of phosphorus from the hot metal during the vanadium extraction process can be achieved by adding lime into the vanadium extraction converter. The highest dephosphorization rate was obtained at slag basicity of 1.93. The phosphorus distribution ratio increased with increasing FeO content up to 16-18% but decreased thereafter. Vanadium was present in the slag only as spinels rather than calcium vanadate. Phosphorus was still present in the form of calcium phosphate eutectic in calcium silicate. The present work proves that the vanadium extraction and dephosphorization processes are nonconflicting reactions.

Oxidizer Selection for the ISTAR Program (Liquid Oxygen versus Hydrogen Peroxide)

NASA Technical Reports Server (NTRS)

Quinn, Jason Eugene; Koelbl, Mary E. (Technical Monitor)

2002-01-01

This paper discusses a study of two alternate oxidizers, liquid oxygen and hydrogen peroxide, for use in a rocket based combined cycle (RBCC) demonstrator vehicle. The flight vehicle is baselined as an airlaunched self-powered Mach 0.7 to 7 demonstration of an RBCC engine through all or its air breathing propulsion modes. Selection of an alternate oxidizer has the potential to lower overall vehicle size, system complexity/ cost and ultimately the total program risk. This trade study examined the oxidizer selection effects upon the overall vehicle performance, safety and operations. After consideration of all the technical and programmatic details available at this time, 90% hydrogen peroxide was selected over liquid oxygen for use in this program.

Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts

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

Schroeder, William David

2001-01-01

The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m 2/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO 3/(MoO 3 + V 2O 5). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V +4 and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of watermore » to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V 2O 5-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V 2O 5, solid solutions of Mo in V 2O 5, V 9Mo 6O 40, and other reduced VMoO compounds, characterized by laser Raman spectroscopy. The natural composition gradient imposed by the sputter deposition apparatus was used to create VMoO arrays containing 225 samples ranging from 7.0-42 mol% MoO 3/(V 2O 5 + MoO 3), determined by EDS analysis.« less

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.

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.

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).

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.

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.

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.

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.

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.

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.

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

Two-Dimensional Phosphorus Oxides as Energy and Information Materials.

PubMed

Luo, Wei; Xiang, Hongjun

2016-07-18

Phosphorene is a rising star in electronics. Recently, 2D phosphorus oxides with higher stability have been synthesized. In this study, we theoretically explored the structures and properties of 2D phosphorus oxides. We found that the structural features of Px Oy vary with the oxygen content. When the oxygen content is low, the most stable Px Oy material can be obtained by the adsorption of O atoms on phosphorene. Otherwise, stable structures are no longer based on phosphorene and will contain P-O-P motifs. We found that P4 O4 has a direct band gap (about 2.24 eV), good optical absorption, and high stability in water, so it may be suitable for photochemical water splitting. P2 O3 adopts two possible stable ferroelectric structures (P2 O3 -I and P2 O3 -II) with electric polarization perpendicular and parallel to the lateral plane, respectively, as the lowest-energy configurations, depending on the layer thickness. We propose that P2 O3 could be used in novel nanoscale multiple-state memory devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction of Black Phosphorus with Oxygen and Water

DOE PAGES

Huang, Yuan; Qiao, Jingsi; He, Kai; ...

2016-10-24

Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. Chemical reactions with different ambient species, notably oxygen and water, are important as they govern key properties such as stability in air, electronic structure and charge transport, wetting by aqueous solutions, etc. Here, we report experiments combined with ab-initio calculations that address the effects of oxygen and water in contact with BP. Our results show that the reaction with oxygen is primarily responsible for changing properties of BP. Oxidation involving the dissociative chemisorption of O 2 causes the decomposition of BPmore » and continuously lowers the conductance of BP field-effect transistors (FETs). In contrast, BP is stable in contact with deaerated (i.e., O 2 depleted) water and the carrier mobility in BP FETs gated by H 2O increases significantly due to efficient dielectric screening of scattering centers by the high-k dielectric. Isotope labeling experiments, contact angle measurements and calculations show that the pristine BP surface is hydrophobic, but is turned progressively hydrophilic by oxidation. Lastly, our results open new avenues for exploring applications that require contact of BP with aqueous solutions including solution gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP.« less

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.

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.

Microwave-Assisted Synthesis of Silver Vanadium Phosphorus Oxide, Ag 2VO 2PO 4 : Crystallite Size Control and Impact on Electrochemistry

DOE PAGES

Huang, Jianping; Marschilok, Amy C.; Takeuchi, Esther S.; ...

2016-03-07

We study silver vanadium phosphorus oxide, Ag 2VO 2PO 4, that is a promising cathode material for Li batteries due in part to its large capacity and high current capability. Herein, a new synthesis of Ag 2VO 2PO 4 based on microwave heating is presented, where the reaction time is reduced by approximately 100× relative to other reported methods, and the crystallite size is controlled via synthesis temperature, showing a linear correlation of crystallite size with temperature. Notably, under galvanostatic reduction, the Ag 2VO 2PO 4 sample with the smallest crystallite size delivers the highest capacity and shows the highestmore » loaded voltage. Further, pulse discharge tests show a significant resistance decrease during the initial discharge coincident with the formation of Ag metal. Thus, the magnitude of the resistance decrease observed during pulse tests depends on the Ag 2VO 2PO 4 crystallite size, with the largest resistance decrease observed for the smallest crystallite size. Additional electrochemical measurements indicate a quasi-reversible redox reaction involving Li + insertion/deinsertion, with capacity fade due to structural changes associated with the discharge/charge process. In summary, this work demonstrates a faster synthetic approach for bimetallic polyanionic materials which also provides the opportunity for tuning of electrochemical properties through control of material physical properties such as crystallite size.« less

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.

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.

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

Selective oxidation of alkanes and/or alkenes to valuable oxygenates

DOEpatents

Lin, Manhua; Pillai, Krishnan S.

2011-02-15

A catalyst, its method of preparation and its use for producing at least one of methacrolein and methacrylic acid, for example, by subjecting isobutane or isobutylene or a mixture thereof to a vapor phase catalytic oxidation in the presence of air or oxygen. In the case where isobutane alone is subjected to a vapor phase catalytic oxidation in the presence of air or oxygen, the product is at least one of isobutylene, methacrolein and methacrylic acid. The catalyst comprises a compound having the formula A.sub.aB.sub.bX.sub.xY.sub.yZ.sub.zO.sub.o wherein A is one or more elements selected from the group of Mo, W and Zr, B is one or more elements selected from the group of Bi, Sb, Se, and Te, X is one or more elements selected from the group of Al, Bi, Ca, Ce, Co, Fe, Ga, Mg, Ni, Nb, Sn, W and Zn, Y is one or more elements selected from the group of Ag, Au, B, Cr, Cs, Cu, K, La, Li, Mg, Mn, Na, Nb, Ni, P, Pb, Rb, Re, Ru, Sn, Te, Ti, V and Zr, and Z is one or more element from the X or Y groups or from the following: As, Ba, Pd, Pt, Sr, or mixtures thereof, and wherein a=1, 0.05oxidation state of the other elements.

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.

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...

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.

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.

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.

Efficient Separation and Extraction of Vanadium and Chromium in High Chromium Vanadium Slag by Selective Two-Stage Roasting-Leaching

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Xu, Yingzhe; Liu, Jiayi; Xue, Xiangxin

2018-06-01

Vanadium and chromium are important rare metals, leading to a focus on high chromium vanadium slag (HCVS) as a potential raw material to extract vanadium and chromium in China. In this work, a novel method based on selective two-stage roasting-leaching was proposed to separate and extract vanadium and chromium efficiently in HCVS. XRD, FT-IR, and SEM were utilized to analyze the phase evolutions and microstructure during the whole process. Calcification roasting, which can calcify vanadium selectively using thermodynamics, was carried out in the first roasting stage to transfer vanadium into acid-soluble vanadate and leave chromium in the leaching residue as (Fe0.6Cr0.4)2O3 after H2SO4 leaching. When HCVS and CaO were mixed in the molar ratio CaO/V2O3 (n(CaO)/n(V2O3)) of 0.5 to 1.25, around 90 pct vanadium and less than 1 pct chromium were extracted in the first leaching liquid, thus achieving the separation of vanadium and chromium. In the second roasting stage, sodium salt, which combines with chromium easily, was added to the first leaching residue to extract chromium and 95.16 pct chromium was extracted under the optimal conditions. The total vanadium and chromium leaching rates were above 95 pct, achieving the efficient separation and extraction of vanadium and chromium. The established method provides a new technique to separate vanadium and chromium during roasting rather than in the liquid form, which is useful for the comprehensive application of HCVS.

Efficient Separation and Extraction of Vanadium and Chromium in High Chromium Vanadium Slag by Selective Two-Stage Roasting-Leaching

NASA Astrophysics Data System (ADS)

Wen, Jing; Jiang, Tao; Xu, Yingzhe; Liu, Jiayi; Xue, Xiangxin

2018-04-01

Vanadium and chromium are important rare metals, leading to a focus on high chromium vanadium slag (HCVS) as a potential raw material to extract vanadium and chromium in China. In this work, a novel method based on selective two-stage roasting-leaching was proposed to separate and extract vanadium and chromium efficiently in HCVS. XRD, FT-IR, and SEM were utilized to analyze the phase evolutions and microstructure during the whole process. Calcification roasting, which can calcify vanadium selectively using thermodynamics, was carried out in the first roasting stage to transfer vanadium into acid-soluble vanadate and leave chromium in the leaching residue as (Fe0.6Cr0.4)2O3 after H2SO4 leaching. When HCVS and CaO were mixed in the molar ratio CaO/V2O3 (n(CaO)/n(V2O3)) of 0.5 to 1.25, around 90 pct vanadium and less than 1 pct chromium were extracted in the first leaching liquid, thus achieving the separation of vanadium and chromium. In the second roasting stage, sodium salt, which combines with chromium easily, was added to the first leaching residue to extract chromium and 95.16 pct chromium was extracted under the optimal conditions. The total vanadium and chromium leaching rates were above 95 pct, achieving the efficient separation and extraction of vanadium and chromium. The established method provides a new technique to separate vanadium and chromium during roasting rather than in the liquid form, which is useful for the comprehensive application of HCVS.

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.

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.

Application of indigenous sulfur-oxidizing bacteria from municipal wastewater to selectively bioleach phosphorus from high-phosphorus iron ore: effect of particle size.

PubMed

Shen, Shaobo; Rao, Ruirui; Wang, Jincao

2013-01-01

The effects of ore particle size on selectively bioleaching phosphorus (P) from high-phosphorus iron ore were studied. The average contents of P and Fe in the iron ore were 1.06 and 47.90% (w/w), respectively. The particle sizes of the ores used ranged from 58 to 3350 microm. It was found that the indigenous sulfur-oxidizing bacteria from municipal wastewater could grow well in the slurries of solid high-phosphorus iron ore and municipal wastewater. The minimum bioleaching pH reached for the current work was 0.33. The P content in bioleached iron ore reduced slightly with decreasing particle size, while the removal percentage of Fe decreased appreciably with decreasing particle size. The optimal particle size fraction was 58-75 microm, because the P content in bioleached iron ore reached a minimum of 0.16% (w/w), the removal percentage of P attained a maximum of 86.7%, while the removal percentage of Fe dropped to a minimum of 1.3% and the Fe content in bioleached iron ore was a maximum of 56.4% (w/w) in this case. The iron ores thus obtained were suitable to be used in the iron-making process. The removal percentage of ore solid decreased with decreasing particle size at particle size range of 106-3350 microm. The possible reasons resulting in above phenomena were explored in the current work. It was inferred that the particle sizes of the iron ore used in this work have no significant effect on the viability of the sulfur-oxidizing bacteria.

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.

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

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

-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.

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

Area-Selective Atomic Layer Deposition of Metal Oxides on Noble Metals through Catalytic Oxygen Activation

PubMed Central

2017-01-01

Area-selective atomic layer deposition (ALD) is envisioned to play a key role in next-generation semiconductor processing and can also provide new opportunities in the field of catalysis. In this work, we developed an approach for the area-selective deposition of metal oxides on noble metals. Using O2 gas as co-reactant, area-selective ALD has been achieved by relying on the catalytic dissociation of the oxygen molecules on the noble metal surface, while no deposition takes place on inert surfaces that do not dissociate oxygen (i.e., SiO2, Al2O3, Au). The process is demonstrated for selective deposition of iron oxide and nickel oxide on platinum and iridium substrates. Characterization by in situ spectroscopic ellipsometry, transmission electron microscopy, scanning Auger electron spectroscopy, and X-ray photoelectron spectroscopy confirms a very high degree of selectivity, with a constant ALD growth rate on the catalytic metal substrates and no deposition on inert substrates, even after 300 ALD cycles. We demonstrate the area-selective ALD approach on planar and patterned substrates and use it to prepare Pt/Fe2O3 core/shell nanoparticles. Finally, the approach is proposed to be extendable beyond the materials presented here, specifically to other metal oxide ALD processes for which the precursor requires a strong oxidizing agent for growth. PMID:29503508

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.

Equilibrating metal-oxide cluster ensembles for oxidation reactions using oxygen in water

Treesearch

Ira A. Weinstock; Elena M. G. Barbuzzi; Michael W. Wemple; Jennifer J. Cowan; Richard S. Reiner; Dan M. Sonnen; Robert A. Heintz; James S. Bond; Craig L. Hill

2001-01-01

Although many enzymes can readily and selectively use oxygen in water--the most familiar and attractive of all oxidants and solvents, respectively–-the design of synthetic catalysts for selective water-based oxidation processes utilizing molecular oxygen remains a daunting task. Particularly problematic is the fact that oxidation of substrates by O2 involves radical...

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

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.

Oxygen sensitive, refractory oxide composition

DOEpatents

Holcombe, Jr., Cressie E.; Smith, Douglas D.

1976-01-01

Oxide compositions containing niobium pentoxide and an oxide selected from the group consisting of hafnia, titania, and zirconia have electrical conductivity characteristics which vary greatly depending on the oxygen content.

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.

Molecular origin of the selectivity differences between palladium and gold-palladium in benzyl alcohol oxidation: Different oxygen adsorption properties

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

Savara, Aditya Ashi; Chan-Thaw, Carine E.; Sutton, Jonathan E.

The same mechanism and microkinetic model used for benzyl alcohol oxidation over Pd/C was shown to apply to benzyl alcohol oxidation over AuPd/C. Almost all of the selectivity differences could be explained by a decrease in oxygen adsorption on AuPd. After isolating oxygen adsorption as being the origin of the selectivity differences, density functional theory was used to investigate the oxygen adsorption properties of a pure Pd surface, a pure Au surface, and an alloyed AuPd surface. Finally, the calculations showed that Au–Pd alloying decreased the oxygen adsorption properties relative to pure Pd, which explained the selectivity differences, consistent withmore » the microkinetic modeling.« less

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

The Role of Phosphorus and Soot on the Deactivation of Diesel Oxidation Catalysts

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

Eaton, Scott J; Nguyen, Ke; Bunting, Bruce G

The deactivation of diesel oxidation catalysts (DOCs) by soot contamination and lube-oil derived phosphorus poisoning is investigated. Pt/CeO2/-Al2O3 DOCs aged using three different protocols developed by the authors and six high mileage field-returned DOCs of similar formulation are evaluated for THC and CO oxidation performance using a bench-flow reactor. Collectively, these catalysts exhibit a variety of phosphorus and soot morphologies contributing to performance deactivation. To isolate and examine the contribution of each deactivation mechanism, performance evaluations are carried out for each DOC ''as received'' and after removal of surface carbon in a high-temperature oxidizing environment. In such a manner themore » deactivation contribution of soot contamination is de-convoluted from that of phosphorus poisoning. It will be shown that this is accomplished while preserving phosphorus (and to a lesser degree sulfur, calcium and zinc) chemistries and concentrations within the washcoat. Washcoat contaminant information and materials changes are characterized using electron-probe microanalysis (EPMA), X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS), BET surface area, oxygen storage capacity (OSC), X-ray fluorescence (XRF) and inductively coupled plasma (ICP) analysis, from which the relative severity of each mechanism can be quantified. Results show that soot contamination from diesel exhaust severely degrades THC and CO oxidation performance by acting as a catalyst surface diffusion barrier. This results in a considerable increase of light-off temperatures. In contrast, phosphorus poisoning, which is considered a significant deactivation mechanism in three-way catalysts, is shown to have minimal effect on DOC oxidation performance for the conditions studied here. Material changes include the formation of both Ce(III-IV) and aluminum phosphates which do not significantly hinder the THC and CO oxidation in

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.

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.

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.

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

Release kinetics of vanadium from vanadium titano-magnetite: The effects of pH, dissolved oxygen, temperature and foreign ions.

PubMed

Hu, Xingyun; Yue, Yuyan; Peng, Xianjia

2018-02-01

As part of a broader study of the environmental geochemistry behavior of vanadium (V), the release kinetics of V from the dissolution of natural vanadium titano-magnetite under environmentally relevant conditions was investigated. In both the acidic and basic domains, the V release rate was found to be proportional to fractional powers of hydrogen ion and dissolved oxygen activities. The dependence of the rate on dissolved oxygen can also be described in terms of the Langmuir adsorption model. The empirical rate equation is given by: r [Formula: see text] where, α=0.099-0.265, k'=3.2×10 -6 -1.7×10 -5 , K=2.7×10 4 -3.9×10 4 mol/L in acid solution (pH4.1), and α=-0.494-(-0.527), k'=2.0×10 4 -2.5×10 -11 , and K=4.1×10 3 -6.5×10 3 mol/L in basic solution (pH8.8) at 20°C. Based on the effect of temperature on the release rate of V, the activation energies of minerals at pH8.8 were determined to be 148-235kJ/mol, suggesting that the dissolution of vanadium titano-magnetite is a surface-controlled process. The presence of Na + , Ca 2+ , Mg 2+ , K + , NO 3 - , Cl - , SO 4 2- and CO 3 2- was found to accelerate the V release rates. This study improves the understanding of both the V pollution risk in some mine areas and the fate of V in the environment. Copyright © 2017. Published by Elsevier B.V.

Vanadium K-edge XAS studies on the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis.

PubMed

Renirie, Rokus; Charnock, John M; Garner, C David; Wever, Ron

2010-06-01

Vanadium K-edge X-ray Absorption Spectra have been recorded for the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis at pH 6.0. The Extended X-ray Absorption Fine Structure (EXAFS) regions provide a refinement of previously reported crystallographic data; one short V=O bond (1.54A) is present in both forms. For the native enzyme, the vanadium is coordinated to two other oxygen atoms at 1.69A, another oxygen atom at 1.93A and the nitrogen of an imidazole group at 2.02A. In the peroxo-form, the vanadium is coordinated to two other oxygen atoms at 1.67A, another oxygen atom at 1.88A and the nitrogen of an imidazole group at 1.93A. When combined with the available crystallographic and kinetic data, a likely interpretation of the EXAFS distances is a side-on bound peroxide involving V-O bonds of 1.67 and 1.88A; thus, the latter oxygen would be 'activated' for transfer. The shorter V-N bond observed in the peroxo-form is in line with the previously reported stronger binding of the cofactor in this form of the enzyme. Reduction of the enzyme with dithionite has a clear influence on the spectrum, showing a change from vanadium(V) to vanadium(IV).

Selective Sensitization of Zinc Finger Protein Oxidation by Reactive Oxygen Species through Arsenic Binding*

PubMed Central

Zhou, Xixi; Cooper, Karen L.; Sun, Xi; Liu, Ke J.; Hudson, Laurie G.

2015-01-01

Cysteine oxidation induced by reactive oxygen species (ROS) on redox-sensitive targets such as zinc finger proteins plays a critical role in redox signaling and subsequent biological outcomes. We found that arsenic exposure led to oxidation of certain zinc finger proteins based on arsenic interaction with zinc finger motifs. Analysis of zinc finger proteins isolated from arsenic-exposed cells and zinc finger peptides by mass spectrometry demonstrated preferential oxidation of C3H1 and C4 zinc finger configurations. C2H2 zinc finger proteins that do not bind arsenic were not oxidized by arsenic-generated ROS in the cellular environment. The findings suggest that selectivity in arsenic binding to zinc fingers with three or more cysteines defines the target proteins for oxidation by ROS. This represents a novel mechanism of selective protein oxidation and demonstrates how an environmental factor may sensitize certain target proteins for oxidation, thus altering the oxidation profile and redox regulation. PMID:26063799

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

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

A model study of warming-induced phosphorus-oxygen feedbacks in open-ocean oxygen minimum zones on millennial timescales

NASA Astrophysics Data System (ADS)

Niemeyer, Daniela; Kemena, Tronje P.; Meissner, Katrin J.; Oschlies, Andreas

2017-05-01

Observations indicate an expansion of oxygen minimum zones (OMZs) over the past 50 years, likely related to ongoing deoxygenation caused by reduced oxygen solubility, changes in stratification and circulation, and a potential acceleration of organic matter turnover in a warming climate. The overall area of ocean sediments that are in direct contact with low-oxygen bottom waters also increases with expanding OMZs. This leads to a release of phosphorus from ocean sediments. If anthropogenic carbon dioxide emissions continue unabated, higher temperatures will cause enhanced weathering on land, which, in turn, will increase the phosphorus and alkalinity fluxes into the ocean and therefore raise the ocean's phosphorus inventory even further. A higher availability of phosphorus enhances biological production, remineralisation and oxygen consumption, and might therefore lead to further expansions of OMZs, representing a positive feedback. A negative feedback arises from the enhanced productivity-induced drawdown of carbon and also increased uptake of CO2 due to weathering-induced alkalinity input. This feedback leads to a decrease in atmospheric CO2 and weathering rates. Here, we quantify these two competing feedbacks on millennial timescales for a high CO2 emission scenario. Using the University of Victoria (UVic) Earth System Climate Model of intermediate complexity, our model results suggest that the positive benthic phosphorus release feedback has only a minor impact on the size of OMZs in the next 1000 years. The increase in the marine phosphorus inventory under assumed business-as-usual global warming conditions originates, on millennial timescales, almost exclusively (> 80 %) from the input via terrestrial weathering and causes a 4- to 5-fold expansion of the suboxic water volume in the model.

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.

Defect-mediated room temperature ferromagnetism in vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Yang, Tsung-Han; Nori, Sudhakar; Zhou, Honghui; Narayan, Jagdish

2009-09-01

High quality epitaxial undoped vanadium oxide (VO2) thin films on c-plane sapphire (0001) substrate have been grown using pulsed laser deposition technique. The as-grown films exhibited excellent structural and transport properties without requiring further annealing treatments for these oxygen-deficient oxide films. The epitaxial growth has been achieved via domain matching epitaxy, where matching of integral multiples of planes occurs across the film-substrate interface. The magnetic properties of vanadium oxide (VO2) films investigated at different temperatures in the range of 10-360 K showed significant magnetic hysteresis as well as saturation of the magnetic moment. The origin of ferromagnetic properties with an estimated Curie temperature above 500 K is discussed in the absence of magnetic impurities in VO2 thin films as determined by x-ray photoelectron spectroscopy, x-ray diffraction, and transmission electron microscopy.

Oxidation of white phosphorus by peroxides in water

NASA Astrophysics Data System (ADS)

Abdreimova, R. R.; Akbaeva, D. N.; Polimbetova, G. S.

2017-10-01

A mixture of hypophosphorous, phosphorous, and phosphoric acids is formed during the anaerobic oxidation of white phosphorus by peroxides [ROOH; R = H, 3-ClC6H4CO, (CH3)3C] in water. The rate of reactions grows considerably upon adding nonpolar organic solvents. The activity series of peroxides and solvents are determined experimentally. NMR spectroscopy shows that the main product of the reaction is phosphorous acid, regardless of the nature of the peroxide and solvent. A radical mechanism of oxidation of white phosphorus by peroxides in water is proposed. It is initiated by the homolysis of peroxide with the formation of HO• radicals that are responsible for the homolytic opening of phosphoric tetrahedrons. Further oxidation and stages of the hydrolysis of intermediate phosphorus-containing compounds yield products of the reaction.

Superior Electrocatalytic Activity of a Robust Carbon-Felt Electrode with Oxygen-Rich Phosphate Groups for All-Vanadium Redox Flow Batteries.

PubMed

Kim, Ki Jae; Lee, Heon Seong; Kim, Jeonghun; Park, Min-Sik; Kim, Jung Ho; Kim, Young-Jun; Skyllas-Kazacos, Maria

2016-06-08

A newly prepared type of carbon felt with oxygen-rich phosphate groups is proposed as a promising electrode with good stability for all-vanadium redox flow batteries (VRFBs). Through direct surface modification with ammonium hexafluorophosphate (NH4 PF6 ), phosphorus can be successfully incorporated onto the surface of the carbon felt by forming phosphate functional groups with -OH chemical moieties that exhibit good hydrophilicity. The electrochemical reactivity of the carbon felt toward the redox reactions of VO(2+) /VO2 (+) (in the catholyte) and V(3+) /V(2+) (in the anolyte) can be effectively improved owing to the superior catalytic effects of the oxygen-rich phosphate groups. Furthermore, undesirable hydrogen evolution can be suppressed by minimizing the overpotential for the V(3+) /V(2+) redox reaction in the anolyte of the VRFB. Cell-cycling tests with the catalyzed electrodes show improved energy efficiencies of 88.2 and 87.2 % in the 1(st) and 20(th)  cycles compared with 83.0 and 81.1 %, respectively, for the pristine electrodes at a constant current density of 32 mA cm(-2) . These improvements are mainly attributed to the faster charge transfer allowed by the integration of the oxygen-rich phosphate groups on the carbon-felt electrode. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micro-XANES Measurements on Experimental Spinels and the Oxidation State of Vanadium in Spinel-Melt Pairs

NASA Technical Reports Server (NTRS)

Righter, K.; Sutton, S.R.; Newville, M.

2004-01-01

Spinel can be a significant host phase for V as well as other transition metals such as Ni and Co. However, vanadium has multiple oxidation states V(2+), V(3+), V(4+) or V(5+) at oxygen fugacities relevant to natural systems. We do know that D(V) spinel/melt is correlated with V and TiO2 content and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(4+) will be stable across the range of natural oxygen fugacities in nature. In order to gain a better understanding of D(V) spinel/melt we have equilibrated spinel-melt pairs at controlled oxygen fugacities, between HM to NNO, where V is present in the spinel at natural levels (approx. 300 ppm V). These spinel-melt pairs were analyzed using micro-XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with spinel compositional data (Ti, V content) and oxygen fugacity, to unravel the effects of these variables on D(V) spinel/melt.

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

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.

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.

Amorphous and Crystalline Vanadium Oxides as High-Energy and High-Power Cathodes for Three-Dimensional Thin-Film Lithium Ion Batteries.

PubMed

Mattelaer, Felix; Geryl, Kobe; Rampelberg, Geert; Dendooven, Jolien; Detavernier, Christophe

2017-04-19

Flexible wearable electronics and on-chip energy storage for wireless sensors drive rechargeable batteries toward thin-film lithium ion batteries. To enable more charge storage on a given surface, higher energy density materials are required, while faster energy storage and release can be obtained by going to thinner films. Vanadium oxides have been examined as cathodes in classical and thin-film lithium ion batteries for decades, but amorphous vanadium oxide thin films have been mostly discarded. Here, we investigate the use of atomic layer deposition, which enables electrode deposition on complex three-dimensional (3D) battery architectures, to obtain both amorphous and crystalline VO 2 and V 2 O 5 , and we evaluate their thin-film cathode performance. Very high volumetric capacities are found, alongside excellent kinetics and good cycling stability. Better kinetics and higher volumetric capacities were observed for the amorphous vanadium oxides compared to their crystalline counterparts. The conformal deposition of these vanadium oxides on silicon micropillar structures is demonstrated. This study shows the promising potential of these atomic layer deposited vanadium oxides as cathodes for 3D all-solid-state thin-film lithium ion batteries.

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.

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.

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.

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

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.

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

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.

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.

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.

Selective thermal oxidation of hydrocarbons in zeolites by oxygen

DOEpatents

Frei, Heinz; Blatter, Fritz; Sun, Hai

2000-01-01

A process for selective thermal oxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls is carried out in solvent free zeolites under dark thermal conditions. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

Nuclear reactor fuel element with vanadium getter on cladding

DOEpatents

Johnson, Carl E.; Carroll, Kenneth G.

1977-01-01

A nuclear reactor fuel element is described which has an outer cladding, a central core of fissionable or mixed fissionable and fertile fuel material and a layer of vanadium as an oxygen getter on the inner surface of the cladding. The vanadium reacts with oxygen released by the fissionable material during irradiation of the core to prevent the oxygen from reacting with and corroding the cladding. Also described is a method for coating the inner surface of small diameter tubes of cladding with a layer of vanadium.

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.

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.

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

PubMed

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

2016-11-17

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., V 2 O 5 , V 2 O 3 and VO 2 along with MoO 3 . 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.

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.

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

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.

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.

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.

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

Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotopes in phosphate

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

Jaisi, Deb P.; Kukkadapu, Ravi K.; Stout, Lisa M.

2011-07-06

A key question to address in the development of oxygen isotope ratios in phosphate (18Op) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here we present experimental results aimed at understanding the biotic and abiotic pathway of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of specific sedimentary phosphate phases by Escherichia coli, Vibrio fischeri and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction ofmore » phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 hrs) due to efficient O-isotope exchange between phosphate and water (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate promoted the exchange of intact phosphate radicals (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli and V. fischeri ‘extracted’ loosely sorbed phosphate first while M. aquaeolei preferred iron-oxide bound phosphate. Each bacterium imprinted a biotic isotopic signature on each P phase that it took up and cycled. For example, the 18Op value of the sorbed phosphate phase shifted gradually towards equilibrium isotopic composition and the value of Fe oxide-bound phosphate showed slight changes at first, but when new iron oxides were formed, co-precipitated/occluded phosphate retained 18O values of aqueous phosphate at that time. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of 18Op as a tracer of phosphorus cycling in sediments, soils and

[Optimization and comparison of nitrogen and phosphorus removal by different aeration modes in oxidation ditch].

PubMed

Guo, Chang-Zi; Peng, Dang-Cong; Cheng, Xue-Mei; Wang, Dan

2012-03-01

The oxidation ditch operation mode was simulated by sequencing batch reactor (SBR) system with alternate stirring and aeration. The nitrogen and phosphorus removal efficiencies were investigated in two different aeration modes: point aeration and step aeration. Experimental results show that oxygen is dissolved more efficiently in point aeration mode with a longer aerobic region in the same air supply capacity, but dissolved oxygen (DO) utilization efficiency for nitrogen and phosphorus removal is high in step aeration mode. Nitrification abilities of the two modes are equal with ammonia-nitrogen (NH4(+) -N) removal efficiency of 96.68% and 97.03%, respectively. Nitrifier activities are 4.65 and 4.66 mg x (g x h)(-1) respectively. When the ratio of anoxic zones and the aerobic zones were 1, the total nitrogen (TN) removal efficiency of point aeration mode in 2, 4 or 7 partitions was respectively 60.14%, 47.93% and 33.7%. The total phosphorus (TP) removal efficiency was respectively 28.96%, 23.75% and 24.31%. The less the partitions, the higher the nitrogen and phosphorus removal efficiencies, but it is in more favor of TN removal. As for step aeration mode with only one partitioning zone, the TN and TP removal efficiencies are respectively 64.21% and 49.09%, which is better than in point aeration mode, but more conducive to the improvement of TP removal efficiency. Under the condition of sufficient nitrification in step aeration mode, the nitrogen and phosphorus removal is better with the increase of anoxic zone. The removal efficiencies of TN and TP respectively rose to 73.94% and 54.18% when the ratio of anoxic zones and the aerobic zones was increased from 1 : 1 to 1. 8 : 1. As the proportion of anoxic zones was enlarged further, nitrification and operation stability were weakened so as to affect the nitrogen and phosphorus removal efficiencies.

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.

Experimental evidence of six-fold oxygen coordination for phosphorus and XANES calculations

NASA Astrophysics Data System (ADS)

Flank, A.-M.; Trcera, N.; Brunet, F.; Itié, J.-P.; Irifune, T.; Lagarde, P.

2009-11-01

Phosphorus, a group V element, has always been found so far in minerals, biological systems and synthetic compounds with an oxygen coordination number of four (i.e, PO4 groups). We demonstrate here using phosphorus K-edge XANES spectroscopy that this element can also adopt a six-fold oxygen coordination (i.e, PO6 groups). This new coordination was achieved in AlPO4 doped SiO2 stishovite synthesized at 18 GPa and 1873 K and quenched down to ambient conditions. The well-crystallized P-bearing stishovite grains (up to 100μm diameter) were embedded in the back-transformation products of high pressure form of AlPO4 matrix. They were identified by elemental mapping (μ-XRF). μ-XANES spectra collected at the Si and P K edges in the Si rich region with a very low concentration of P present striking resemblance, Si itself being characteristic of pure stishovite. We can therefore infer that phosphorus in the corresponding stishovite crystal is involved in an octahedral coordination made of six oxygen atoms. First principle XANES calculations using a plane-wave density functional formalism with core-hole effects treated in a supercell approach at the P K edge for a P atom substituting an Si one in the stishovite structure confirm this assertion. This result shows that in the lower-mantle where all silicon is six-fold coordinated, phosphorus has the crystal-chemical ability to remain incorporated into silicate structures.

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

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.

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.

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.

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.

Evaluation of a novel oxidation ditch system for biological nitrogen and phosphorus removal from domestic sewage.

PubMed

Chen, X; Fujiwara, T; Ohtoshi, K; Inamori, S; Nakamachi, K; Tsuno, H

2010-01-01

A novel oxidation ditch system using anaerobic tanks and innovative dual dissolved oxygen (DO) control technology is proposed for biological nitrogen and phosphorus removal from domestic sewage. A continuous bench-scale experiment running for more than 300 days was performed to evaluate the system. Monitoring and controlling the airflow and recirculation flow rate independently using DO values at two points along the ditch permitted maintenance of aerobic and anoxic zone ratios of around 0.30 and 0.50, respectively. The ability to optimize aerobic and anoxic zone ratios using the dual DO control technology meant that a total nitrogen removal efficiency of 83.2-92.9% could be maintained. This remarkable nitrogen removal performance minimized the nitrate recycle to anaerobic tanks inhibiting the phosphorus release. Hence, the total phosphorus removal efficiency was also improved and ranged within 72.6-88.0%. These results demonstrated that stabilization of the aerobic and anoxic zone ratio by dual DO control technology not only resulted in a marked improvement of nitrogen removal, but it also enhanced phosphorus removal.

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

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.

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.

Plasma assisted facile synthesis of vanadium oxide (V3O7) nanostructured thin films

NASA Astrophysics Data System (ADS)

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

2018-05-01

Vanadium oxides nanostructured thin films are synthesized using plasma assisted sublimation process. The effect of temperatures on growth of V2O5 and V3O7 thin films is studied. Scanning electron micrographs shows different morphologies are obtained at different temperatures i.e. at 450 °C nano cubes-like structures are obtained, whereas at 550 °C and 650 °C nanorods are obtained. Sample deposited at 450 °C is entirely composed of V2O5 and sample at higher temperatures are composed of mixed phase of vanadium oxides i.e. V2O5 and V3O7. As temperature increased, so the content of V3O7 in the sample is increased as confirmed by XRD and Raman analyses.

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.

Synthesis of γ-hydroxypropyl P-chirogenic (±)-phosphorus oxide derivatives by regioselective ring-opening of oxaphospholane 2-oxide precursors

PubMed Central

Binyamin, Iris; Meidan-Shani, Shoval

2015-01-01

Summary The synthesis of P-chirogenic (±)-phosphine oxides and phosphinates via selective nucleophilic ring opening of the corresponding oxaphospholanes is described. Two representative substrates: the phosphonate 2-ethoxy-1,2-oxaphospholane 2-oxide and the phosphinate 2-phenyl-1,2-oxaphospholane 2-oxide were reacted with various Grignard reagents to produce a single alkyl/aryl product. These products may possess further functionalities in addition to the phosphorus center such as the γ-hydroxypropyl group which results from the ring opening and π-donor moieties such as aryl, allyl, propargyl and allene which originates from the Grignard reagent. PMID:26425187

Biomass recycling and Earth’s early phosphorus cycle

PubMed Central

Kipp, Michael A.; Stüeken, Eva E.

2017-01-01

Phosphorus sets the pace of marine biological productivity on geological time scales. Recent estimates of Precambrian phosphorus levels suggest a severe deficit of this macronutrient, with the depletion attributed to scavenging by iron minerals. We propose that the size of the marine phosphorus reservoir was instead constrained by muted liberation of phosphorus during the remineralization of biomass. In the modern ocean, most biomass-bound phosphorus gets aerobically recycled; but a dearth of oxidizing power in Earth’s early oceans would have limited the stoichiometric capacity for remineralization, particularly during the Archean. The resulting low phosphorus concentrations would have substantially hampered primary productivity, contributing to the delayed rise of atmospheric oxygen. PMID:29202032

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

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

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, II

NASA Technical Reports Server (NTRS)

2004-01-01

The Special Session: Oxygen in the Solar System, II, included the following reports:Evolution of Oxygen Isotopes in the Solar Nebula; Disequilibrium Melting of Refractory Inclusions: A Mechanism for High-Temperature Oxygen; Isotope Exchange in the Solar Nebula; Oxygen Isotopic Compositions of the Al-rich Chondrules in the CR Carbonaceous Chondrites: Evidence for a Genetic Link to Ca-Al-rich Inclusions and for Oxygen Isotope Exchange During Chondrule Melting; Nebular Formation of Fayalitic Olivine: Ineffectiveness of Dust Enrichment; Water in Terrestrial Planets: Always an Oxidant?; Oxygen Barometry of Basaltic Glasses Based on Vanadium Valence Determination Using Synchrotron MicroXANES; A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence; The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity ; and Olivine-Silicate Melt Partitioning of Iridium.

SELECTIVE OXIDATION OF ALCOHOLS BY MOLECULAR OXYGEN OVER A PD/MGO CATALYST IN THE ABSENCE OF ANY ADDITIVES

EPA Science Inventory

Selective oxidation of alcohols to the corresponding carbonyl products using molecular oxygen is achieved over a simple and easily recyclable 1% Pd/MgO impregnated heterogeneous catalyst in the presence of trifluorotoluene. A variety of activated and non-activated alcohols are ef...

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.

Partial pressures of oxygen, phosphorus and fluorine in some lunar lavas

NASA Technical Reports Server (NTRS)

Nash, W. P.; Hausel, W. D.

1973-01-01

Lunar sample 14310 is a feldspar-rich basalt which shows no evidence of shock deformation or recrystallization. Pyroxenes include Mg-rich orthopyroxene, pigeonite and augite; pyroxferroite occurs in the interstitial residuum. Plagioclase feldspars are zoned from An(96) to An(67), and variations in feldspar compositions do not necessarily indicate loss of Na during eruption of the lava. Opaque phases include ilmenite, ulvospinel, metallic iron, troilite, and schreibersite. Both whitlockite and apatite are present, and the interstitial residua contain baddeleyite, tranquillityite and barium-rich sanidine. Theoretical calculations provide estimates of partial pressures of oxygen, phosphorus, and fluorine in lunar magmas. In general, partial pressures of oxygen are restricted by the limiting assemblages of iron-wuestite and ilmenite-iron-rutile; phosphorus partial pressures are higher in lunar magmas than in terrestrial lavas. The occurrence of whitlockite indicates significantly lower fugacities of fluorine in lunar magmas than in terrestrial magmas.

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.

High performance electrodes in vanadium redox flow batteries through oxygen-enriched thermal activation

NASA Astrophysics Data System (ADS)

Pezeshki, Alan M.; Clement, Jason T.; Veith, Gabriel M.; Zawodzinski, Thomas A.; Mench, Matthew M.

2015-10-01

The roundtrip electrochemical energy efficiency is improved from 63% to 76% at a current density of 200 mA cm-2 in an all-vanadium redox flow battery (VRFB) by utilizing modified carbon paper electrodes in the high-performance no-gap design. Heat treatment of the carbon paper electrodes in a 42% oxygen/58% nitrogen atmosphere increases the electrochemically wetted surface area from 0.24 to 51.22 m2 g-1, resulting in a 100-140 mV decrease in activation overpotential at operationally relevant current densities. An enriched oxygen environment decreases the amount of treatment time required to achieve high surface area. The increased efficiency and greater depth of discharge doubles the total usable energy stored in a fixed amount of electrolyte during operation at 200 mA cm-2.

Extraction of Vanadium from Vanadium Slag Via Non-salt Roasting and Ammonium Oxalate Leaching

NASA Astrophysics Data System (ADS)

Li, Meng; Du, Hao; Zheng, Shili; Wang, Shaona; Zhang, Yang; Liu, Biao; Dreisinger, David Bruce; Zhang, Yi

2017-10-01

A clean method featuring non-salt roasting followed by (NH4)2C2O4 leaching to recover vanadium from vanadium slag was proposed. The carcinogenic Cr6+ compounds and exhaust gases were avoided, and the water generated from vanadate precipitation may be recycled and reused in this new leaching process. The leaching residues may be easily used by a blast furnace. Moreover, (NH4)2C2O4 solution was used as a leaching medium to avoid expensive and complicated ammonium controlling operations as a result of the stability of (NH4)2C2O4 at a high temperature. The transformation mechanisms of vanadium- and chromium-bearing phases were systematically investigated by x-ray diffraction analysis and scanning electron microscopy with energy-disperse x-ray spectrometry, respectively. In addition, the effects of oxygen concentration, roasting temperature, and holding time on vanadium recovery were investigated. Finally, the effects of leaching variables on the vanadium leaching rate were also examined.

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.

Vanadium proton exchange membrane water electrolyser

NASA Astrophysics Data System (ADS)

Noack, Jens; Roznyatovskaya, Nataliya; Pinkwart, Karsten; Tübke, Jens

2017-05-01

In order to reverse the reactions of vanadium oxygen fuel cells and to regenerate vanadium redox flow battery electrolytes that have been oxidised by atmospheric oxygen, a vanadium proton exchange membrane water electrolyser was set up and investigated. Using an existing cell with a commercial and iridium-based catalyst coated membrane, it was possible to fully reduce V3.5+ and V3+ solutions to V2+ with the formation of oxygen and with coulomb efficiencies of over 96%. The cell achieved a maximum current density of 75 mA/cm2 during this process and was limited by the proximity of the V(III) reduction to the hydrogen evolution reaction. Due to the specific reaction mechanisms of V(IV) and V(III) ions, V(III) solutions were reduced with an energy efficiency of 61%, making this process nearly twice as energy efficient as the reduction of V(IV) to V(III). Polarisation curves and electrochemical impedance spectroscopy were used to further investigate the losses of half-cell reactions and to find ways of further increasing efficiency and performance levels.

Atomic Layer-Deposited Titanium-Doped Vanadium Oxide Thin Films and Their Thermistor Applications

DOE PAGES

Wang, Shuyu; Yu, Shifeng; Lu, Ming; ...

2016-11-30

In this paper, we report the enhancement in the temperature coefficient of resistance (TCR) of atomic layer-deposited vanadium oxide thin films through the doping of titanium oxide. The Hall effect measurement provides a potential explanation for the phenomenon. The composition and morphology of the thin films are investigated by x-ray diffraction and scanning electron microscopy techniques. The high TCR, good uniformity, and low processing temperature of the material make it a good candidate for thermistor application.

Novel synthesis of manganese and vanadium mixed oxide (V{sub 2}O{sub 5}/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

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

Mahdavi, Vahid, E-mail: v-mahdavi@araku.ac.ir; Soleimani, Shima

2014-03-01

Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V{sub 2}O{sub 5}/OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V{sub 2}O{sub 5}/OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V{sub 2}O{sub 5}/K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V{sub 2}O{sub 5}/K-OMS-2 catalyst. • V{sub 2}O{sub 5}/K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidationmore » using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V{sub 2}O{sub 5}/K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V{sub 2}O{sub 5} species. Oxidation of various alcohols was studied in the liquid phase over the V{sub 2}O{sub 5}/K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H{sub 2}O{sub 2} as the oxidant. Activity of the V{sub 2}O{sub 5}/K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V{sub 2}O{sub 5}. The kinetic of benzyl alcohol oxidation using excess TBHP over V{sub 2}O{sub 5}/K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential

Simultaneous nitrification, denitrification, and phosphorus removal in single-tank low-dissolved-oxygen systems under cyclic aeration.

PubMed

Ju, Lu-Kwang; Huang, Lin; Trivedi, Hiren

2007-08-01

Simultaneous nitrification and denitrification (SND or SNdN) may occur at low dissolved oxygen concentrations. In this study, bench-scale (approximately 6 L) bioreactors treating a continuous feed of synthetic wastewater were used to evaluate the effects of solids retention time and low dissolved oxygen concentration, under cyclic aeration, on the removal of organics, nitrogen, and phosphorus. The cyclic aeration was carried out with repeated cycles of 1 hour at a higher dissolved oxygen concentration (HDO) and 30 minutes at a lower (or zero) dissolved oxygen concentration (LDO). Compared with aeration at constant dissolved oxygen concentrations, the cyclic aeration, when operated with proper combinations of HDO and LDO, produced better-settling sludge and more complete nitrogen and phosphorus removal. For nitrogen removal, the advantage resulted from the more readily available nitrate and nitrite (generated by nitrification during the HDO period) for denitrification (during the LDO period). For phosphorus removal, the advantage of cyclic aeration came from the development of a higher population of polyphosphate-accumulating organisms, as indicated by the higher phosphorus contents in the sludge solids of the cyclically aerated systems. Nitrite shunt was also observed to occur in the LDO systems. Higher ratios of nitrite to nitrate were found in the systems of lower HDO (and, to less dependency, higher LDO), suggesting that the nitrite shunt took place mainly because of the disrupted nitrification at lower HDO. The study results indicated that the HDO used should be kept reasonably high (approximately 0.8 mg/L) or the HDO period prolonged, to promote adequate nitrification, and the LDO kept low (< or =0.2 mg/L), to achieve more complete denitrification and higher phosphorus removal. The above findings in the laboratory systems find strong support from the results obtained in full-scale plant implementation. Two plant case studies using the cyclic low-dissolved-oxygen

Land-use impact on selected forms of arsenic and phosphorus in soils of different functions

NASA Astrophysics Data System (ADS)

Plak, Andrzej; Bartmiński, Piotr; Dębicki, Ryszard

2017-10-01

The aim of the study was to assess the impact of technosols and geomechanically unchanged soils of the Lublin agglomeration on the concentrations of arsenic and phosphorus, and on selected forms of these elements. Arsenic and phosphorus concentrations were determined in the urban soils of Lublin (Poland), and the relationship between their degree of contamination and different types of land use was estimated. The samples collected were subjected to sequential analysis, using ammonium sulphate, acid ammonium phosphate, oxalate buffer (also with ascorbic acid) and aqua regia for arsenic, and ammonium chloride, sodium hydroxide, hydrochloric acid and aqua regia for phosphorus. The influence of the land use forms was observed in the study. The greatest amount of arsenic (19.62 mg kg-1) was found in the industrial soils of Lublin, while the greatest amount of phosphorus (580.4 mg kg-1) was observed in non-anthropogenic soils (mainly due to the natural accumulation processes of this element). Fractions of arsenic and phosphorus obtained during analysis showed strong differentiation. Amorphic and crystalline fractions of arsenic, bound with iron oxides, proved to have the highest share in the total arsenic pool. The same situation was noted for phosphorus.

Biomimetic catalytic system driven by electron transfer for selective oxygenation of hydrocarbon.

PubMed

Yang, Guanyu; Ma, Yinfa; Xu, Jie

2004-09-01

Hydrocarbon oxyfunctionalization is a crucial industrial process. Most metallic catalysts require higher temperatures and often show lower selectivities. One of the intellectual approaches is the mimicry for bio-oxidation. We have established a biomimetic system with a nonmetallic redox center, composed of anthraquinones, N-hydroxyphthalimide, and zeolite HY, for selective hydrocarbon oxygenation by molecular oxygen. Selectivity of 95.8% for acetophenone and 66.2% conversion were accomplished for oxygenation of ethylbenzene at temperatures as low as 80 degrees C. The redox cycle, driven by one-electron transfer and product orientation by Zeolite HY, opens up the possibility of mimicking bio-oxidation under mild conditions.

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

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

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.

Phosphorus speciation by coupled HPLC-ICPMS: low level determination of reduced phosphorus in natural materials

NASA Astrophysics Data System (ADS)

Atlas, Zachary; Pasek, Matthew; Sampson, Jacqueline

2015-04-01

Phosphorus is a geologically important minor element in the Earth's crust commonly found as relatively insoluble apatite. This constraint causes phosphorus to be a key limiting nutrient in biologic processes. Despite this, phosphorus plays a direct role in the formation of DNA, RNA and other cellular materials. Recent works suggest that since reduced phosphorus is considerably more soluble than oxidized phosphorus that it was integrally involved in the development of life on the early Earth and may continue to play a role in biologic productivity to this day. This work examines a new method for quantification and identification of reduced phosphorus as well as applications to the speciation of organo-phosphates separated by coupled HPLC - ICP-MS. We show that reduced phosphorus species (P1+, P3+ and P5+) are cleanly separated in the HPLC and coupled with the ICPMS reaction cell, using oxygen as a reaction gas to effectively convert elemental P to P-O. Analysis at M/Z= 47 producing lower background and flatter baseline chromatography than analyses performed at M/Z = 31. Results suggest very low detection limits (0.05 μM) for P species analyzed as P-O. Additionally we show that this technique has potential to speciate at least 5 other forms of phosphorus compounds. We verified the efficacy of method on numerous materials including leached Archean rocks, suburban retention pond waters, blood and urine samples and most samples show small but detectible levels of reduced phosphorus and or organo-phaospates. This finding in nearly all substances analyzed supports the assumption that the redox processing of phosphorus has played a significant role throughout the history of the Earth and it's presence in the present environment is nearly ubiquitous with the reduced oxidation state phosphorus compounds, phosphite and hypophosphite, potentially acting as significant constituents in the anaerobic environment.

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.

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

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.

Phosphorus Doping Effect in a Zinc Oxide Channel Layer to Improve the Performance of Oxide Thin-Film Transistors

NASA Astrophysics Data System (ADS)

Han, Dong-Suk; Moon, Yeon-Keon; Lee, Sih; Kim, Kyung-Taek; Moon, Dae-Yong; Lee, Sang-Ho; Kim, Woong-Sun; Park, Jong-Wan

2012-09-01

In this study, we fabricated phosphorus-doped zinc oxide-based thin-film transistors (TFTs) using direct current (DC) magnetron sputtering at a relatively low temperature of 100°C. To improve the TFT device performance, including field-effect mobility and bias stress stability, phosphorus dopants were employed to suppress the generation of intrinsic defects in the ZnO-based semiconductor. The positive and negative bias stress stabilities were dramatically improved by introducing the phosphorus dopants, which could prevent turn-on voltage ( V ON) shift in the TFTs caused by charge trapping within the active channel layer. The study showed that phosphorus doping in ZnO was an effective method to control the electrical properties of the active channel layers and improve the bias stress stability of oxide-based TFTs.

[Effects of carbon sources, temperature and electron acceptors on biological phosphorus removal].

PubMed

Han, Yun; Xu, Song; Dong, Tao; Wang, Bin-Fan; Wang, Xian-Yao; Peng, Dang-Cong

2015-02-01

Effects of carbon sources, temperature and electron acceptors on phosphorus uptake and release were investigated in a pilot-scale oxidation ditch. Phosphorus uptake and release rates were measured with different carbon sources (domestic sewage, sodium acetate, glucose) at 25 degrees C. The results showed that the minimum phosphorus uptake and release rates of glucose were 5.12 mg x (g x h)(-1) and 6.43 mg x (g x h)(-1), respectively, and those of domestic sewage are similar to those of sodium acetate. Phosphorus uptake and release rates increased with the increase of temperature (12, 16, 20 and 25 degrees C) using sodium acetate as carbon sources. Anoxic phosphorus uptake rate decreased with added COD. Electron acceptors (oxygen, nitrate, nitrite) had significant effects on phosphorus uptake rate and their order was in accordance with oxygen > nitrate > nitrite. The mass ratio of anoxic P uptake and N consumption (P(uptake)/N (consumption)) of nitrate and nitrite were 0.96 and 0.65, respectively.

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.

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.

Mathematical Modeling of Nitrous Oxide Production during Denitrifying Phosphorus Removal Process.

PubMed

Liu, Yiwen; Peng, Lai; Chen, Xueming; Ni, Bing-Jie

2015-07-21

A denitrifying phosphorus removal process undergoes frequent alternating anaerobic/anoxic conditions to achieve phosphate release and uptake, during which microbial internal storage polymers (e.g., Polyhydroxyalkanoate (PHA)) could be produced and consumed dynamically. The PHA turnovers play important roles in nitrous oxide (N2O) accumulation during the denitrifying phosphorus removal process. In this work, a mathematical model is developed to describe N2O dynamics and the key role of PHA consumption on N2O accumulation during the denitrifying phosphorus removal process for the first time. In this model, the four-step anoxic storage of polyphosphate and four-step anoxic growth on PHA using nitrate, nitrite, nitric oxide (NO), and N2O consecutively by denitrifying polyphosphate accumulating organisms (DPAOs) are taken into account for describing all potential N2O accumulation steps in the denitrifying phosphorus removal process. The developed model is successfully applied to reproduce experimental data on N2O production obtained from four independent denitrifying phosphorus removal study reports with different experimental conditions. The model satisfactorily describes the N2O accumulation, nitrogen reduction, phosphate release and uptake, and PHA dynamics for all systems, suggesting the validity and applicability of the model. The results indicated a substantial role of PHA consumption in N2O accumulation due to the relatively low N2O reduction rate by using PHA during denitrifying phosphorus removal.

Vanadium Partitioning and Mantle Oxidation State: New Experimental Data

NASA Astrophysics Data System (ADS)

Mallmann, G.; O'Neill, H. S.

2007-12-01

Vanadium exists in multiple valences in natural basaltic melts, namely V2+, V3+, V4+ and V5+. Because most crystalline phases prefer to incorporate V3+ rather than V4+ and V5+, the crystal/silicate-melt partitioning of vanadium (DVcry/melt) tends to decrease with increasing oxygen fugacity (fO2). Such dependence has been experimentally demonstrated and used to estimate the fO2 of mantle and mantle-derived rocks. Recent modelling of V and V/Sc systematics in basalts has lead to the view that the relative fO2 of the upper mantle is constant, both through time and among the sources of different types of basaltic magmas (i.e. MORB, OIB and IAB). This is contrary to the notion given by other oxygen barometric methods on peridotites and basalts, which indicate an upper mantle heterogeneous in relative fO2. To explore further the potential of V abundances and V/Sc ratios to estimate the relative fO2 of mantle peridotites and basalts, and in particular to understand variations in mantle oxidation state better, we carried out an experimental campaign aimed at measuring DVcry/melt for all the relevant phases of the upper mantle (i.e. olivine, orthopyroxene, clinopyroxene, garnet and spinel) over a range of fO2 conditions large enough to pin down not only the behaviour of V3+ and V4+ but also V2+ and V5+. Experiments were done in 1-atm vertical tube furnaces (1300°C) and piston-cylinder apparatus (1275-1450°C and 1.5-3.2 GPa). For the high-pressure experiments, fO2 was controlled by the Re-ReOx/2 equilibrium (10-9 to 10-0.7 bar), whereas for the 1-atm experiments, fO2 was controlled by Ar-CO-CO2- O2 gas mixes (10-18 to 10-0.7 bar). Five starting compositions were used to ensure the presence of all the desired phases. Experimental products were analysed for major elements by electron microprobe and for trace elements by laser-ablation ICP-MS, which enables V to be measured precisely even at very low concentrations. Partition coefficients for all phases plot as approximately

Electronic and Structural Parameters of Phosphorus-Oxygen Bonds in Inorganic Phosphate Crystals

NASA Astrophysics Data System (ADS)

Atuchin, V. V.; Kesler, V. G.; Pervukhina, N. V.

Wide set of experimental results on binding energy of photoelectrons emitted from P 2p, P 2s, and O 1s core levels has been observed for inorganic phosphate crystals and the parameters were compared using energy differences Δ(O 1s - P 2p) and Δ (O 1s - P 2s) as most robust characteristics. Linear dependence of the binding energy difference on mean chemical bond length L(P-O) between phosphorus and oxygen atoms has been found. The functions are of the forms: Δ (O 1s - P 2p) (eV) = 375.54 + 0.146 · L(P-O) (pm) and Δ (O 1s - P 2s) (eV) = 320.77 + 0.129 · L(P-O) (pm). The dependencies are general for inorganic phosphates and may be used in quantitative component analysis of X-ray photoemission spectra of complex oxide compounds including functional groups with different coordination of P and O atoms.

Linking the rise of atmospheric oxygen to growth in the continental phosphorus inventory

NASA Astrophysics Data System (ADS)

Cox, Grant M.; Lyons, Timothy W.; Mitchell, Ross N.; Hasterok, Derrick; Gard, Matthew

2018-05-01

The concentration of atmospheric oxygen (pO2) is thought to have increased throughout Earth history, punctuated by rapid increases ca. 2.4 and 0.8 billion years ago near the beginning and end of the Proterozoic Eon. As photosynthesis is the largest source of free O2, the reigning paradigm of rising O2 levels centres around biologic metabolism. Here we show that the phosphorus content of igneous rocks correlates, in a first-order sense, with secular increases in O2 through time, suggesting that rising O2 levels are affected by long-term mantle cooling and its effect on the continental phosphorus inventory. Because phosphorus is the limiting nutrient for primary productivity, its availability has fundamental control over the efficiency of oxygenic photosynthesis, pointing to a previously unrecognized role of the solid Earth in biologic and atmospheric evolution. Furthermore, as many bio-essential elements are effectively incompatible in the mantle, this relationship has implications for any terrestrial planet. All planets will cool, and those with efficient plate tectonic convection will cool more rapidly. We are left concluding that the speed of such cooling may affect pattern of biological evolution on any habitable planet.

Fast oxygen diffusion in bismuth oxide probed by quasielastic neutron scattering

DOE PAGES

Mamontov, Eugene

2016-09-24

In this paper, we present the first, to our knowledge, study of solid state oxygen translational diffusion by quasielastic neutron scattering. Such studies in the past might have been precluded by relatively low diffusivities of oxygen anions in the temperature range amenable to neutron scattering experiments. To explore the potential of the quasielastic scattering technique, which can deduce atomic diffusion jump length of oxygen anions through the momentum transfer dependence of the scattering signal, we have selected the fastest known oxygen conductor, bismuth oxide. Finally, we have found the oxygen anion jump length in excellent agreement with the nearest oxygen-vacancymore » distance in the anion sublattice of the fluorite-related structure of bismuth oxide.« less

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

Controlled coordination in vanadium(V) dimethylhydrazido compounds.

PubMed

Sakuramoto, Takashi; Moriuchi, Toshiyuki; Hirao, Toshikazu

2016-11-01

The vanadium(V) dimethylhydrazido compounds were structurally characterized to elucidate the effect of the alkoxide ligands in the coordination environment of vanadium(V) hydrazido center. The single-crystal X-ray structure determination of the vanadium(V) dimethylhydrazido compound with isopropoxide ligands revealed a dimeric structure with the V(1)-N(1) distance of 1.680(5)Å, in which each vanadium atom is coordinated in a distorted trigonal-bipyramidal geometry (τ 5 =0.81) with the hydrazido and bridging isopropoxide ligands in the apical positions. On the contrary, nearly tetrahedral arrangement around the vanadium metal center (τ 4 =0.06) with the V(1)-N(1) distance of 1.660(2)Å was observed in the vanadium(V) dimethylhydrazido compound with tert-butoxide ligands. The introduction of the 2,2',2″-nitrilotriethoxide ligand led to a pseudo-trigonal-bipyramidal geometry (τ 5 =0.92) at the vanadium center with the V(1)-N(1) distance of 1.691(5)Å, wherein vanadium atom is pulled out of the plane formed by the nitrilotriethoxide oxygen atoms in the direction of the hydrazido nitrogen. The coordination from the apical ligand in the vanadium(V) dimethylhydrazido compound was found to result in the longer V(1)-N(1) distance. Copyright © 2016 Elsevier Inc. All rights reserved.

Memory Deficit Recovery after Chronic Vanadium Exposure in Mice.

PubMed

Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

2016-01-01

Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal.

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

Predicting Selectivity of Uranium vs. Vanadium from First Principles: Complete Molecular Design and Adsorption Modeling

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

Ivanov, Aleksandr; Das, Sadananda; Bryantsev, Vyacheslav

SUMMARYBackground: Uranium is used as the basic fuel for nuclear power plants, which generate significant amounts of electricity and have life cycle carbon emissions that are as low as renewable energy sources. The extraction of this valuable energy commodity from the ground remains controversial, however, mainly because of environmental and health impacts. Alternatively, seawater offers an enormous uranium resource that may be tapped at minimal environmental cost. Currently, amidoxime polymers are the most widely considered adsorbent materials for large-scale extraction of uranium from seawater, but they are not perfectly selective for uranyl, UO22+. In particular, the competition between UO22+ andmore » vanadium (VO2+/VO2+) cations poses a significant challenge to the efficient mining of UO22+. Thus, accelerating progress in the discovery and deployment of advanced materials for the recovery of uranium relies on the design of new ligands with high binding affinity and selectivity for uranium over competing metal ions. A cost-effective route to aid the discovery of new ligands is to apply computational methods to rapidly test attractive candidates and elucidate data-driven guidelines for rational design.Objectives: One of the key components in achieving rational design of highly selective ligands is the establishment of computational tools capable of assessing ligand selectivity trends. Therefore, the objectives of this study include:1.Establish first-principles methods, based on computational chemistry techniques, to calculate stability constants for UO22+ and VO2+/VO2+ complexes.2.Develop computational protocols to assess the binding strengths and selectivity of ligands that can be present in the actual poly(acrylamidoxime) adsorbents.3.Develop adsorption models that can use information from first-principles computational methods to predict the adsorption behavior of uranium and vanadium by adsorbents synthesized at ORNL and compare results with experimental

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.

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.

A bench-scale assessment for phosphorus release control of sediment by an oxygen-releasing compound (ORC).

PubMed

Yang, Jie; Lin, Feng K; Yang, Lei; Hua, Dan Y

2015-01-01

The effects of oxygen-releasing compound (ORC) on the control of phosphorus (P) release as well as the spatial and temporal distribution of P fractions in sediment were studied through a bench-scale test. An ORC with an extended oxygen-releasing capacity was prepared. The results of the oxygen-releasing test showed that the ORC provided a prolonged period of oxygen release with a highly effective oxygen content of 60.6% when compared with powdery CaO2. In the bench-scale test, an ORC dose of 180 g·m(-2) provided a higher inhibition efficiency for P release within 50 days. With the application of the ORC, the dissolved oxygen (DO) concentration and redox potential (ORP) of the overlying water were notably improved, and the dissolved total phosphorus (DTP) was maintained below 0.689 mg·L(-1) compared to 2.906 mg·L(-1) without the ORC treatment. According to the P fractions distribution, the summation of all detectable P fractions in each sediment layer exhibited an enhanced accumulation tendency with the application of ORC. Higher phosphorus retention efficiencies were observed in the second and third layers of sediment from days 10 to 20 with the ORC. Phosphorus was trapped mainly in the form of iron bound P (Fe-P) and organically bound P (O-P) in sediment with the ORC, whereas the effects of the ORC on exchangeable P (EX-P), apatite-associated P (A-P) and detrital P (De-P) in the sediment sample were not significant. The microbial activities of the sediment samples demonstrated that both the dehydrogenase activity (DHA) and alkaline phosphatase activity (APA) in the upper sediment layer increased with the ORC treatment, which indicated that the mineralization of P was accelerated and the microbial biomass was increased. As the accumulation of P suppressed the release of P, the sediment exhibited an increased P retention efficiency with the application of the ORC.

Method and reaction pathway for selectively oxidizing organic compounds

DOEpatents

Camaioni, Donald M.; Lilga, Michael A.

1998-01-01

A method of selectively oxidizing an organic compound in a single vessel comprises: a) combining an organic compound, an acid solution in which the organic compound is soluble, a compound containing two oxygen atoms bonded to one another, and a metal ion reducing agent capable of reducing one of such oxygen atoms, and thereby forming a mixture; b) reducing the compound containing the two oxygen atoms by reducing one of such oxygen atoms with the metal ion reducing agent to, 1) oxidize the metal ion reducing agent to a higher valence state, and 2) produce an oxygen containing intermediate capable of oxidizing the organic compound; c) reacting the oxygen containing intermediate with the organic compound to oxidize the organic compound into an oxidized organic intermediate, the oxidized organic intermediate having an oxidized carbon atom; d) reacting the oxidized organic intermediate with the acid counter ion and higher valence state metal ion to bond the acid counter ion to the oxidized carbon atom and thereby produce a quantity of an ester incorporating the organic intermediate and acid counter ion; and e) reacting the oxidized organic intermediate with the higher valence state metal ion and water to produce a quantity of alcohol which is less than the quantity of ester, the acid counter ion incorporated in the ester rendering the carbon atom bonded to the counter ion less reactive with the oxygen containing intermediate in the mixture than is the alcohol with the oxygen containing intermediate.

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.

Controlling Oxygen Mobility in Ruddlesden–Popper Oxides

PubMed Central

Lee, Dongkyu; Lee, Ho Nyung

2017-01-01

Discovering new energy materials is a key step toward satisfying the needs for next-generation energy conversion and storage devices. Among the various types of oxides, Ruddlesden–Popper (RP) oxides (A2BO4) are promising candidates for electrochemical energy devices, such as solid oxide fuel cells, owing to their attractive physicochemical properties, including the anisotropic nature of oxygen migration and controllable stoichiometry from oxygen excess to oxygen deficiency. Thus, understanding and controlling the kinetics of oxygen transport are essential for designing optimized materials to use in electrochemical energy devices. In this review, we first discuss the basic mechanisms of oxygen migration in RP oxides depending on oxygen nonstoichiometry. We then focus on the effect of changes in the defect concentration, crystallographic orientation, and strain on the oxygen migration in RP oxides. We also briefly review their thermal and chemical stability. Finally, we conclude with a perspective on potential research directions for future investigation to facilitate controlling oxygen ion migration in RP oxides. PMID:28772732

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.

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

Dependence of nitrite oxidation on nitrite and oxygen in low-oxygen seawater

NASA Astrophysics Data System (ADS)

Sun, Xin; Ji, Qixing; Jayakumar, Amal; Ward, Bess B.

2017-08-01

Nitrite oxidation is an essential step in transformations of fixed nitrogen. The physiology of nitrite oxidizing bacteria (NOB) implies that the rates of nitrite oxidation should be controlled by concentration of their substrate, nitrite, and the terminal electron acceptor, oxygen. The sensitivities of nitrite oxidation to oxygen and nitrite concentrations were investigated using 15N tracer incubations in the Eastern Tropical North Pacific. Nitrite stimulated nitrite oxidation under low in situ nitrite conditions, following Michaelis-Menten kinetics, indicating that nitrite was the limiting substrate. The nitrite half-saturation constant (Ks = 0.254 ± 0.161 μM) was 1-3 orders of magnitude lower than in cultivated NOB, indicating higher affinity of marine NOB for nitrite. The highest rates of nitrite oxidation were measured in the oxygen depleted zone (ODZ), and were partially inhibited by additions of oxygen. This oxygen sensitivity suggests that ODZ specialist NOB, adapted to low-oxygen conditions, are responsible for apparently anaerobic nitrite oxidation.

Reduction behavior and kinetics of vanadium-titanium sinters under high potential oxygen enriched pulverized coal injection

NASA Astrophysics Data System (ADS)

Ma, Jin-fang; Wang, Guang-wei; Zhang, Jian-liang; Li, Xin-yu; Liu, Zheng-jian; Jiao, Ke-xin; Guo, Jian

2017-05-01

In this work, the reduction behavior of vanadium-titanium sinters was studied under five different sets of conditions of pulverized coal injection with oxygen enrichment. The modified random pore model was established to analyze the reduction kinetics. The results show that the reduction rate of sinters was accelerated by an increase of CO and H2 contents. Meanwhile, with the increase in CO and H2 contents, the increasing range of the medium reduction index (MRE) of sinters decreased. The increasing oxygen enrichment ratio played a diminishing role in improving the reduction behavior of the sinters. The reducing process kinetic parameters were solved using the modified random role model. The results indicated that, with increasing oxygen enrichment, the contents of CO and H2 in the reducing gas increased. The reduction activation energy of the sinters decreased to between 20.4 and 23.2 kJ/mol.

Memory Deficit Recovery after Chronic Vanadium Exposure in Mice

PubMed Central

Folarin, Oluwabusayo; Olopade, Funmilayo; Onwuka, Silas; Olopade, James

2016-01-01

Vanadium is a transitional metal with an ability to generate reactive oxygen species in the biological system. This work was designed to assess memory deficits in mice chronically exposed to vanadium. A total of 132 male BALB/c mice (4 weeks old) were used for the experiment and were divided into three major groups of vanadium treated, matched controls, and animals exposed to vanadium for three months and thereafter vanadium was withdrawn. Animals were tested using Morris water maze and forelimb grip test at 3, 6, 9, and 12 months of age. The results showed that animals across the groups showed no difference in learning but had significant loss in memory abilities after 3 months of vanadium exposure and this trend continued in all vanadium-exposed groups relative to the controls. Animals exposed to vanadium for three months recovered significantly only 9 months after vanadium withdrawal. There was no significant difference in latency to fall in the forelimb grip test between vanadium-exposed groups and the controls in all age groups. In conclusion, we have shown that chronic administration of vanadium in mice leads to memory deficit which is reversible but only after a long period of vanadium withdrawal. PMID:26962395

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.

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.

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

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.

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.

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.

GAS PHASE SELECTIVE PHOTOXIDATION OF ALCOHOLS USING LIGHT-ACTIVATED TITANIUM DIOXIDE AND MOLECULAR OXYGEN

EPA Science Inventory

Gas Phase Selective Oxidation of Alcohols Using Light-Activated Titanium Dioxide and Molecular Oxygen

Gas phase selective oxidations of various primary and secondary alcohols are studied in an indigenously built stainless steel up-flow photochemical reactor using ultravi...

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

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).

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.

Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Wankel, S. D.; Hansel, C. M.

2016-12-01

Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be

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.

A vanadium(IV) pyrazolate metal-organic polyhedron with permanent porosity and adsorption selectivity.

PubMed

Augustyniak, A W; Fandzloch, M; Domingo, M; Łakomska, I; Navarro, J A R

2015-10-11

A vanadium(IV) pyrazolate-based open metal-organic polyhedron of [V3(μ3-O)O(OH)2(μ4-BPD)1.5(μ-HCOO)3] (BDP = benzene-1,4-bipyrazolate) formulation gives rise to a porous crystal structure exhibiting micro and mesoporosity which is useful for selective adsorption of gases.

Selective speciation improves efficacy and lowers toxicity of platinum anticancer and vanadium antidiabetic drugs.

PubMed

Doucette, Kaitlin A; Hassell, Kelly N; Crans, Debbie C

2016-12-01

Improving efficacy and lowering resistance to metal-based drugs can be addressed by consideration of the coordination complex speciation and key reactions important to vanadium antidiabetic drugs or platinum anticancer drugs under biological conditions. The methods of analyses vary depending on the specific metal ion chemistry. The vanadium compounds interconvert readily, whereas the reactions of the platinum compounds are much slower and thus much easier to study. However, the vanadium species are readily differentiated due to vanadium complexes differing in color. For both vanadium and platinum systems, understanding the processes as the compounds, Lipoplatin and Satraplatin, enter cells is needed to better combat the disease; there are many cellular metabolites, which may affect processing and thus the efficacy of the drugs. Examples of two formulations of platinum compounds illustrate how changing the chemistry of the platinum will result in less toxic and better tolerated drugs. The consequence of the much lower toxicity of the drug, can be readily realized because cisplatin administration requires hospital stay whereas Lipoplatin can be done in an outpatient manner. Similarly, the properties of Satraplatin allow for development of an oral drug. These forms of platinum demonstrate that the direct consequence of more selective speciation is lower side effects and cheaper administration of the anticancer agent. Therefore we urge that as the community goes forward in development of new drugs, control of speciation chemistry will be considered as one of the key strategies in the future development of anticancer drugs. Copyright © 2016 Elsevier Inc. All rights reserved.

Rethinking early Earth phosphorus geochemistry

PubMed Central

Pasek, Matthew A.

2008-01-01

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO32−), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks. PMID:18195373

Rethinking early Earth phosphorus geochemistry.

PubMed

Pasek, Matthew A

2008-01-22

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO(3)(2-)), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks.

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.

Nitrogen and phosphorus removal in pilot-scale anaerobic-anoxic oxidation ditch system.

PubMed

Peng, Yongzhen; Hou, Hongxun; Wang, Shuying; Cui, Youwei; Zhiguo, Yuan

2008-01-01

To achieve high efficiency of nitrogen and phosphorus removal and to investigate the rule of simultaneous nitrification and denitrification phosphorus removal (SNDPR), a whole course of SNDPR damage and recovery was studied in a pilot-scale, anaerobic-anoxic oxidation ditch (OD), where the volumes of anaerobic zone, anoxic zone, and ditches zone of the OD system were 7, 21, and 280 L, respectively. The reactor was fed with municipal wastewater with a flow rate of 336 L/d. The concept of simultaneous nitrification and denitrification (SND) rate (r(SND)) was put forward to quantify SND. The results indicate that: (1) high nitrogen and phosphorus removal efficiencies were achieved during the stable SND phase, total nitrogen (TN) and total phosphate (TP) removal rates were 80% and 85%, respectively; (2) when the system was aerated excessively, the stability of SND was damaged, and r(SND) dropped from 80% to 20% or less; (3) the natural logarithm of the ratio of NO(x) to NH4+ in the effluent had a linear correlation to oxidation-reduction potential (ORP); (4) when NO3- was less than 6 mg/L, high phosphorus removal efficiency could be achieved; (5) denitrifying phosphorus removal (DNPR) could take place in the anaerobic-anoxic OD system. The major innovation was that the SND rate was devised and quantified.

Addition of anaerobic tanks to an oxidation ditch system to enhance removal of phosphorus from wastewater.

PubMed

Liu, Jun-xin; van Groenestijn, J W; Doddema, H J; Wang, Bao-zhen

2002-04-01

The oxidation ditch has been used for many years all over the world as an economic and efficient wastewater treatment technology. It can remove COD, nitrogen and a part of phosphorus efficiently. In the experiment described, a pilot scale Pasveer oxidation ditch system has been tested to investigate the removal of phosphorus from wastewater. The experimental results showed that influent total phosphorus(TP) was removed for 35%-50%. After this, two anaerobic tanks with total volume of 11 m3 were added to the system to release phosphorus. As a result, the TP removal efficiency increased by about 20%. At an anaerobic HRT of about 6 hours, a TP removal efficiency of 71% was achieved.

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.

Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.

PubMed

Komaszylo Née Siedlecka, Joanna; Kania, Magdalena; Masnyk, Marek; Cmoch, Piotr; Lozinska, Iwona; Czarnocki, Zbigniew; Skorupinska-Tudek, Karolina; Danikiewicz, Witold; Swiezewska, Ewa

2016-02-01

Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents--reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol-2 and -10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy-, peroxy- and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI-MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI-MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time.

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.

Vanadium K-edge X-ray absorption spectroscopy of bromoperoxidase from Ascophyllum nodosum

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

Arber, J.M.; de Boer, E.; Garner, C.D.

Bromoperoxidase from Ascophyllum nodusum was the first vanadium-containing enzyme to be isolated. X-ray absorption spectra have now been collected in order to investigate the coordination of vanadium in the native, native plus bromide, native plus hydrogen peroxide, and dithionite-reduced forms of the enzyme. The edge and X-ray absorption near-edge structures show that, in the four samples studied, it is only on reduction of the native enzyme that the metal site is substantially altered. In addition, these data are consistent with the presence of vanadium(IV) in the reduced enzyme and vanadium(V) in the other samples. Extended X-ray absorption fine structure datamore » confirm that there are structural changes at the metal site on reduction of the native enzyme, notably a lengthening of the average inner-shell distance, and the presence of terminal oxygen together with histidine and oxygen-donating residues.« less

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.

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.

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.

Stable Vanadium Isotopes as a Redox Proxy at High Temperatures?

NASA Astrophysics Data System (ADS)

Prytulak, J.; Sossi, P.; Halliday, A.; Plank, T. A.; Savage, P.; Woodhead, J. D.

2016-12-01

There is currently no consensus on the relative oxygen fugacity (fO2) of the mantle source of mid-ocean ridge basalts compared to the sub-arc mantle, the region that is central to the mediation of crust-mantle mass balances. Vanadium is a multivalent transition metal whose stable isotope fractionation may reflect oxygen fugacity (fO2). However, a direct link between V isotope composition and fO2 is currently far from convincingly demonstrated. Furthermore, differences in co-ordination environment also play a large role in causing stable isotope fractionation. Here we present V isotope measurements of two suites of co-genetic magmas from contrasting tectonic settings: the Mariana arc and Hekla volcano, Iceland. We use this data alongside the tightly constrained V isotope composition of MORB [1] to assess the effects of fO2 and crystal fractionation on stable vanadium isotopes. We show that, for a given MgO content, V isotopes are identical within analytical error between arc basalts from the Marianas, lavas from Hekla, and MORB. The most striking aspect of our igneous, high temperature V isotope data is the large isotope fractionation (on the order of 2 ‰) towards heavier values in magmatic suites from both Hekla and the Marianas with progressive differentiation. We use a self consistent model of fractionating cotectic phases in both igneous suites to match major, trace and V isotope data. Vanadium partition coefficients required for (titano)magnetite are significantly higher in Hekla (DVmag = 42) than Mariana lavas (DVmag = 32), consistent with a more oxidised source in the latter. Calculated Rayleigh fractionation factors are similar in both suites (Δ51Vmin-melt of -0.4 to -0.5‰) and strongly implicate co-ordination differences between oxides and melt are the dominant driving force for V isotope fractionation. Thus, although fO2likely has a second order effect on V isotopes, they are not a direct proxy for oxygen fugacity in magmatic systems. [1] Prytulak, et

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.

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.

Neurotoxicity of Vanadium.

PubMed

Ngwa, Hilary Afeseh; Ay, Muhammet; Jin, Huajun; Anantharam, Vellareddy; Kanthasamy, Arthi; Kanthasamy, Anumantha G

2017-01-01

Vanadium (V) is a transition metal that presents in multiple oxidation states and numerous inorganic compounds and is also an ultra-trace element considered to be essential for most living organisms. Despite being one of the lightest metals, V offers high structural strength and good corrosion resistance and thus has been widely adopted for high-strength steel manufacturing. High doses of V exposure are toxic, and inhalation exposure to V adversely affects the respiratory system. The neurotoxicological properties of V are just beginning to be identified. Recent studies by our group and others demonstrate the neurotoxic potential of this metal in the nigrostriatal system and other parts of the central nervous system (CNS). The neurotoxic effects of V have been mainly attributed to its ability to induce the generation of reactive oxygen species (ROS). It is noteworthy that the neurotoxicity induced by occupational V exposure commonly occurs with co-exposure to other metals, especially manganese (Mn). This review focuses on the chemistry, pharmacology, toxicology, and neurotoxicity of V.

Selective electrochemical generation of hydrogen peroxide from water oxidation

DOE PAGES

Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

2015-10-08

Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, wemore » show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e– water oxidation to H 2O 2 and the 4e– oxidation to O 2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO 2, can activate hydrogen peroxide evolution. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H 2O 2 evolution selectively.« 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...

Evolution of the global phosphorus cycle.

PubMed

Reinhard, Christopher T; Planavsky, Noah J; Gill, Benjamin C; Ozaki, Kazumi; Robbins, Leslie J; Lyons, Timothy W; Fischer, Woodward W; Wang, Chunjiang; Cole, Devon B; Konhauser, Kurt O

2017-01-19

The macronutrient phosphorus is thought to limit primary productivity in the oceans on geological timescales. Although there has been a sustained effort to reconstruct the dynamics of the phosphorus cycle over the past 3.5 billion years, it remains uncertain whether phosphorus limitation persisted throughout Earth's history and therefore whether the phosphorus cycle has consistently modulated biospheric productivity and ocean-atmosphere oxygen levels over time. Here we present a compilation of phosphorus abundances in marine sedimentary rocks spanning the past 3.5 billion years. We find evidence for relatively low authigenic phosphorus burial in shallow marine environments until about 800 to 700 million years ago. Our interpretation of the database leads us to propose that limited marginal phosphorus burial before that time was linked to phosphorus biolimitation, resulting in elemental stoichiometries in primary producers that diverged strongly from the Redfield ratio (the atomic ratio of carbon, nitrogen and phosphorus found in phytoplankton). We place our phosphorus record in a quantitative biogeochemical model framework and find that a combination of enhanced phosphorus scavenging in anoxic, iron-rich oceans and a nutrient-based bistability in atmospheric oxygen levels could have resulted in a stable low-oxygen world. The combination of these factors may explain the protracted oxygenation of Earth's surface over the last 3.5 billion years of Earth history. However, our analysis also suggests that a fundamental shift in the phosphorus cycle may have occurred during the late Proterozoic eon (between 800 and 635 million years ago), coincident with a previously inferred shift in marine redox states, severe perturbations to Earth's climate system, and the emergence of animals.

Origin of the selectivity in the gold-mediated oxidation of benzyl alcohol

NASA Astrophysics Data System (ADS)

Rodríguez-Reyes, Juan Carlos F.; Friend, Cynthia M.; Madix, Robert J.

2012-08-01

Benzyl alcohol has received substantial attention as a probe molecule to test the selectivity and efficiency of novel metallic gold catalysts. Herein, the mechanisms of benzyl alcohol oxidation on a gold surface covered with atomic oxygen are elucidated; the results show direct correspondence to the reaction on gold-based catalysts. The selective, partial oxidation of benzyl alcohol to benzaldehyde is achieved with low oxygen surface concentrations and takes place through dehydrogenation of the alcohol to form benzaldehyde via a benzyloxy (C6H5-CH2O) intermediate. While in this case atomic oxygen plays solely a dehydrogenating role, at higher concentrations it leads to the formation of intermediates from benzaldehyde, producing benzoic acid and CO2. Facile ester (benzyl benzoate) formation also occurs at low oxygen concentrations, which indicates that benzoic acid is not a precursor of further oxidation of the ester; instead, the ester is produced by the coupling of adsorbed benzyloxy and benzaldehyde. Key to the high selectivity seen at low oxygen concentrations is the fact that the production of the aldehyde (and esters) is kinetically favored over the production of benzoic acid.

How plasma induced oxidation, oxygenation, and de-oxygenation influences viability of skin cells

NASA Astrophysics Data System (ADS)

Oh, Jun-Seok; Strudwick, Xanthe; Short, Robert D.; Ogawa, Kotaro; Hatta, Akimitsu; Furuta, Hiroshi; Gaur, Nishtha; Hong, Sung-Ha; Cowin, Allison J.; Fukuhara, Hideo; Inoue, Keiji; Ito, Masafumi; Charles, Christine; Boswell, Roderick W.; Bradley, James W.; Graves, David B.; Szili, Endre J.

2016-11-01

The effect of oxidation, oxygenation, and de-oxygenation arising from He gas jet and He plasma jet treatments on the viability of skin cells cultured in vitro has been investigated. He gas jet treatment de-oxygenated cell culture medium in a process referred to as "sparging." He plasma jet treatments oxidized, as well as oxygenated or de-oxygenated cell culture medium depending on the dissolved oxygen concentration at the time of treatment. He gas and plasma jets were shown to have beneficial or deleterious effects on skin cells depending on the concentration of dissolved oxygen and other oxidative molecules at the time of treatment. Different combinations of treatments with He gas and plasma jets can be used to modulate the concentrations of dissolved oxygen and other oxidative molecules to influence cell viability. This study highlights the importance of a priori knowledge of the concentration of dissolved oxygen at the time of plasma jet treatment, given the potential for significant impact on the biological or medical outcome. Monitoring and controlling the dynamic changes in dissolved oxygen is essential in order to develop effective strategies for the use of cold atmospheric plasma jets in biology and medicine.

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

Phosphorus improves arsenic phytoremediation by Anadenanthera peregrina by alleviating induced oxidative stress.

PubMed

Gomes, M P; Carvalho, M; Carvalho, G S; Marques, T C L L S M; Garcia, Q S; Guilherme, L R G; Soares, A M

2013-01-01

Due to similarities in their chemical behaviors, studies examining interactions between arsenic (As)--in special arsenate--and phosphorus (P) are important for better understanding arsenate uptake, toxicity, and accumulation in plants. We evaluated the effects of phosphate addition on plant biomass and on arsenate and phosphate uptake by Anadenanthera peregrina, an important Brazilian savanna legume. Plants were grown for 35 days in substrates that received combinations of 0, 10, 50, and 100 mg kg(-1) arsenate and 0, 200, and 400 mg kg(-1) phosphate. The addition of P increased the arsenic-phytoremediation capacity of A. peregrina by increasing As accumulation, while also alleviating As-induced oxidative stress. Arsenate phytotoxicity in A. peregrina is due to lipid peroxidation, but not hydrogen peroxide accumulation. Added P also increased the activity of important reactive oxygen species-scavenging enzymes (catalase and ascorbate peroxidase) that help prevent lipid peroxidation in leaves. Our findings suggest that applying P represents a feasible strategy for more efficient As phytoremediation using A. peregrina.

Effects of ZnO nanoparticles on wastewater biological nitrogen and phosphorus removal.

PubMed

Zheng, Xiong; Wu, Rui; Chen, Yinguang

2011-04-01

With the increasing utilization of nanomaterials, zinc oxide nanoparticles (ZnO NPs) have been reported to induce adverse effects on human health and aquatic organisms. However, the potential impacts of ZnO NPs on wastewater nitrogen and phosphorus removal with an activated sludge process are unknown. In this paper, short-term exposure experiments were conducted to determine whether ZnO NPs caused adverse impacts on biological nitrogen and phosphorus removal in the unacclimated anaerobic-low dissolved oxygen sequencing batch reactor. Compared with the absence of ZnO NPs, the presence of 10 and 50 mg/L of ZnO NPs decreased total nitrogen removal efficiencies from 81.5% to 75.6% and 70.8%, respectively. The corresponding effluent phosphorus concentrations increased from nondetectable to 10.3 and 16.5 mg/L, respectively, which were higher than the influent phosphorus (9.8 mg/L), suggesting that higher concentration of ZnO NPs induced the loss of normal phosphorus removal. It was found that the inhibition of nitrogen and phosphorus removal induced by higher concentrations of ZnO NPs was due to the release of zinc ions from ZnO NPs dissolution and increase of reactive oxygen species (ROS) production, which caused inhibitory effect on polyphosphate-accumulating organisms and decreased nitrate reductase, exopolyphosphatase, and polyphosphate kinase activities.

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

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.

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.

Application of a fast Newton-Krylov solver for equilibrium simulations of phosphorus and oxygen

NASA Astrophysics Data System (ADS)

Fu, Weiwei; Primeau, François

2017-11-01

Model drift due to inadequate spinup is a serious problem that complicates the interpretation of climate change simulations. Even after a 300 year spinup we show that solutions are not only still drifting but often drifting away from their eventual equilibrium over large parts of the ocean. Here we present a Newton-Krylov solver for computing cyclostationary equilibrium solutions of a biogeochemical model for the cycling of phosphorus and oxygen. In addition to using previously developed preconditioning strategies - time-averaging and coarse-graining the Jacobian matrix - we also introduce a new strategy: the adiabatic elimination of a fast variable (particulate organic phosphorus) by slaving it to a slow variable (dissolved inorganic phosphorus). We use transport matrices derived from the Community Earth System Model (CESM) with a nominal horizontal resolution of 1° × 1° and 60 vertical levels to implement and test the solver. We find that the new solver obtains seasonally-varying equilibrium solutions with no visible drift using no more than 80 simulation years.

Mild and selective vanadium-catalyzed oxidation of benzylic, allylic, and propargylic alcohols using air

DOEpatents

Hanson, Susan Kloek; Silks, Louis A; Wu, Ruilian

2013-08-27

The invention concerns processes for oxidizing an alcohol to produce a carbonyl compound. The processes comprise contacting the alcohol with (i) a gaseous mixture comprising oxygen; and (ii) an amine compound in the presence of a catalyst, having the formula: ##STR00001## where each of R.sup.1-R.sup.12 are independently H, alkyl, aryl, CF.sub.3, halogen, OR.sup.13, SO.sub.3R.sup.14, C(O)R.sup.15, CONR.sup.16R.sup.17 or CO.sub.2R.sup.18; each of R.sup.13-R.sup.18 is independently alkyl or aryl; and Z is alkl or aryl.

Investigations into the chemical structure based selectivity of the microfabricated nitrogen-phosphorus detector

DOE PAGES

Brocato, Terisse A.; Hess, Ryan F.; Moorman, Matthew; ...

2015-10-28

The nitrogen and phosphorus atoms are constituents of some of the most toxic chemical vapors. Nitrogen-phosphorus gas chromatograph detectors (NPDs) rely on selective ionization of such compounds using ionization temperatures typically greater than 600 °C. NPDs have previously been reported to be 7*10 4× and 10 5× more sensitive for nitrogen and phosphorus, respectively, than for carbon. Presented here is an investigation of the structure-based selectivity of a microfabricated nitrogen-phosphorus detector (μNPD). The μNPD presented here is smaller than a dime and can be placed in a system that is 1/100th the size of a commercial NPD. Comparison of responsesmore » of such devices to homologous anilines (p-methoxyaniline, p-fluoroaniline, and aniline) revealed that detection selectivity, determined by the ratio of μNPD to nonselective flame ionization detector (FID) peak areas, is correlated with acid disassociation pK a values for the respective analine. Selectivity was determined to be greatest for p-methoxyaniline, followed by p-fluoroaniline, with aniline having the smallest response. The limit of detection for a nitrogen containing chemical, p-methoxyaniline, using the μNPD was determined to be 0.29 ng compared to 59 ng for a carbon chemical containing no nitrogen or phosphorus, 1,3,5-trimethybenzene. The μNPD presented here has increased detection for nitrogen and phosphorus compared to the FID and with a slight increase in detection of carbon compounds compared to commercial NPD's sensitivity to nitrogen and carbon.« less

Oxygen isotope analysis of bacterial and fungal manganese oxidation.

PubMed

Sutherland, K M; Wankel, S D; Hansel, C M

2018-07-01

The ability of micro-organisms to oxidize manganese (Mn) from Mn(II) to Mn(III/IV) oxides transcends boundaries of biological clade or domain. Many bacteria and fungi oxidize Mn(II) to Mn(III/IV) oxides directly through enzymatic activity or indirectly through the production of reactive oxygen species. Here, we determine the oxygen isotope fractionation factors associated with Mn(II) oxidation via various biotic (bacteria and fungi) and abiotic Mn(II) reaction pathways. As oxygen in Mn(III/IV) oxides may be derived from precursor water and molecular oxygen, we use a twofold approach to determine the isotope fractionation with respect to each oxygen source. Using both 18 O-labeled water and closed-system Rayleigh distillation approaches, we constrain the kinetic isotope fractionation factors associated with O atom incorporation during Mn(II) oxidation to -17.3‰ to -25.9‰ for O 2 and -1.9‰ to +1.8‰ for water. Results demonstrate that stable oxygen isotopes of Mn(III/IV) oxides have potential to distinguish between two main classes of biotic Mn(II) oxidation: direct enzymatic oxidation in which O 2 is the oxidant and indirect enzymatic oxidation in which superoxide is the oxidant. The fraction of Mn(III/IV) oxide-associated oxygen derived from water varies significantly (38%-62%) among these bio-oxides with only weak relationship to Mn oxidation state, suggesting Mn(III) disproportionation may account for differences in the fraction of mineral-bound oxygen from water and O 2 . Additionally, direct incorporation of molecular O 2 suggests that Mn(III/IV) oxides contain a yet untapped proxy of δ18OO2 of environmental O 2 , a parameter reflecting the integrated influence of global respiration, photorespiration, and several other biogeochemical reactions of global significance. © 2018 John Wiley & Sons Ltd.

Enhanced phosphorus removal from wastewater by growing deep-sea bacterium combined with basic oxygen furnace slag.

PubMed

Zhou, Weizhi; Huang, Zhaosong; Sun, Cuiping; Zhao, Haixia; Zhang, Yuzhong

2016-08-01

As one solid waste with potential for phosphorus removal, application of slags in water treatment merits attention. But it was inhibited greatly by alkaline solution (pH>9.5) and cemented clogging generated. To give one solution, phosphorus removal was investigated by combining deep-sea bacterium Alteromonas 522-1 and basic oxygen furnace slag (BOFS). Results showed that by the combination, not only higher phosphorous removal efficiency (>90%) but also neutral solution pH of 7.8-8.0 were achieved at wide ranges of initial solution pH value of 5.0-9.0, phosphorus concentration of 5-30mg/L, salinity of 0.5-3.5%, and temperature of 15-35°C. Moreover, sedimentary property was also improved with lower amount of sludge production and alleviated BOFS cementation with increased porosity and enlarged particle size. These results provided a promising strategy for the phosphorus recovery with slags in large-scale wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reactive oxygen species, oxidative stress, glaucoma and hyperbaric oxygen therapy.

PubMed

McMonnies, Charles

This review examines the role of oxidative stress in damage to cells of the trabecular meshwork and associated impaired aqueous drainage as well as damage to retinal ganglion cells and associated visual field losses. Consideration is given to the interaction between vascular and mechanical explanations for pathological changes in glaucoma. For example, elevated intraocular pressure (IOP) forces may contribute to ischaemia but there is increasing evidence that altered blood flow in a wider sense is also involved. Both vascular and mechanical theories are involved through fluctuations in intraocular pressure and dysregulation of blood flow. Retinal function is very sensitive to changes in haemoglobin oxygen concentration and the associated variations in the production of reactive oxygen species. Reperfusion injury and production of reactive oxygen species occurs when IOP is elevated or blood pressure is low and beyond the capacity for blood flow autoregulation to maintain appropriate oxygen concentration. Activities such as those associated with postural changes, muscular effort, eye wiping and rubbing which cause IOP fluctuation, may have significant vascular, mechanical, reperfusion and oxidative stress consequences. Hyperbaric oxygen therapy exposes the eye to increased oxygen concentration and the risk of oxidative damage in susceptible individuals. However, oxygen concentration in aqueous humour, and the risk of damage to trabecular meshwork cells may be greater if hyperbaric oxygen is delivered by a hood which exposes the anterior ocular surface to higher than normal oxygen levels. Oronasal mask delivery of hyperbaric oxygen therapy appears to be indicated in these cases. Copyright © 2017 Spanish General Council of Optometry. Published by Elsevier España, S.L.U. All rights reserved.

Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems

DOEpatents

Park, Paul W.

2004-03-16

A lean NOx catalyst and method of preparing the same is disclosed. The lean NOx catalyst includes a ceramic substrate, an oxide support material, preferably .gamma.-alumina, deposited on the substrate and a metal promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium, cerium, vanadium, oxides thereof, and combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between about 80 to 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

Sources and Contributions of Oxygen During Microbial Pyrite Oxidation: the Triple Oxygen Isotopes of Sulfate

NASA Astrophysics Data System (ADS)

Ziegler, K.; Coleman, M. L.; Mielke, R. E.; Young, E. D.

2008-12-01

The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (< 3 days) is characterized by subtle and multiple changes in oxygen source and contribution that is likely due to the adjustment of the microbial metabolism from S to Fe2+-oxidation. A more detailed understanding of the microbial mechanisms and behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of

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

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.

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.

Influence of Thermal Annealing Treatment on Bipolar Switching Properties of Vanadium Oxide Thin-Film Resistance Random-Access Memory Devices

NASA Astrophysics Data System (ADS)

Chen, Kai-Huang; Cheng, Chien-Min; Kao, Ming-Cheng; Chang, Kuan-Chang; Chang, Ting-Chang; Tsai, Tsung-Ming; Wu, Sean; Su, Feng-Yi

2017-04-01

The bipolar switching properties and electrical conduction mechanism of vanadium oxide thin-film resistive random-access memory (RRAM) devices obtained using a rapid thermal annealing (RTA) process have been investigated in high-resistive status/low-resistive status (HRS/LRS) and are discussed herein. In addition, the resistance switching properties and quality improvement of the vanadium oxide thin-film RRAM devices were measured by x-ray diffraction (XRD) analysis, x-ray photoelectron spectrometry (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), and current-voltage ( I- V) measurements. The activation energy of the hopping conduction mechanism in the devices was investigated based on Arrhenius plots in HRS and LRS. The hopping conduction distance and activation energy barrier were obtained as 12 nm and 45 meV, respectively. The thermal annealing process is recognized as a candidate method for fabrication of thin-film RRAM devices, being compatible with integrated circuit technology for nonvolatile memory devices.

Ultrasonic-assisted synthesis of phosphorus graphene oxide/poly (vinyl alcohol) polymer and surface resistivity research of phosphorus graphene oxide/poly (vinyl alcohol) film.

PubMed

Li, Jihui; Li, Yongshen; Niu, Shuai; Li, Ning

2017-05-01

In this paper, phosphorus graphene oxide/poly (vinyl alcohol) polymer (PGO/PVA polymer) was synthesized by PGO and PVA via the esterification in the case of faint acidity and the ultrasound irradiation and characterized; moreover, phosphorus graphene oxide/poly (vinyl alcohol) film (PGO/PVA film) was prepared by PGO/PVA polymer and characterized; also, the surface resistivity of PGO/PVA film was investigated in the case of the different amount of PGO. Based on those, it had been found that PGO reacted with PVA to produce PGO/PVA polymer via the esterification under the ultrasonic-assisted condition, and PGO/PVA polymer was structured by 2D lattice of PGO and the chain of PVA connected in the form of six-member lactone ring and phosphonic ester, and PGO/PVA film was constituted by PGO/PVA polymer, and surface resistivity of 0.00, 0.75, 1.50, 2.25 and 3.00wt% of PGO/PVA film were 6.85×10 8 , 2.98×10 8 , 1.42×10 6 , 7.66×10 4 and 1.29×10 5 Ω/sq, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Commercialization of the Chevron FCC vanadium trap

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

Kennedy, J.V.; Kuehler, C.W.; Krishna, A.S.

1995-09-01

Vanadium, present to varying degrees in FCC feed, deposits on the catalyst virtually quantitatively in the cracking process. In resid operations, vanadium levels on catalyst can reach 10,000 ppm at typical catalyst make-up rates. Once on the catalyst, vanadium destroys the zeolite and restricts access to active sites. This reduces catalyst activity. A vanadium trap is a material that when introduced into the catalyst inventory selectively reacts with migrating vanadium, thus protecting the zeolite and other active components of the catalyst. The trap may be incorporated into the catalyst, or introduced as a separate particle. Only a limited amount ofmore » trap can be incorporated into the catalyst without limiting the amount of zeolite that can be included. Gulf began development of a vanadium trap during the early 1980`s. The work produced a variety of promising materials whose use as vanadium traps was subsequently patented. The work ultimately led to a formulation with a phase very active for trapping vanadium while still quite sulfur tolerant. Based on these results, an extensive pilot plant evaluation was undertaken by Chevron after the Chevron-Gulf merger to better simulate commercial operation. The paper describes pilot plant tests as well as 3 commercial tests of this vanadium trap.« less

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.

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.

Investigation on the oxidation behavior of AlCrVxN thin films by means of synchrotron radiation and influence on the high temperature friction

NASA Astrophysics Data System (ADS)

Tillmann, Wolfgang; Kokalj, David; Stangier, Dominic; Paulus, Michael; Sternemann, Christian; Tolan, Metin

2018-01-01

Friction minimization is an important topic which is pursued in research and industry. In addition to the use of lubricants, friction-reducing oxide phases can be utilized which occur during. These oxides are called Magnéli phases and especially vanadium oxides exhibit good friction reducing properties. Thereby, the lubrication effect can be traced back to oxygen deficiencies. AlCrN thin films are being used as coatings for tools which have to withstand high temperatures. A further improvement of AlCrN thin films concerning their friction properties is possible by incorporation of vanadium. This study analyzes the temperature dependent oxidation behavior of magnetron sputtered AlCrVN thin films with different vanadium contents up to 13.5 at.-% by means of X-ray diffraction and X-ray absorption near-edge spectroscopy. Up to 400 °C the coatings show no oxidation. A higher temperature of 700 °C leads to an oxidation and formation of Magnéli phases of the coatings with vanadium contents above 10.7 at.-%. Friction coefficients, measured by ball-on-disk test are correlated with the oxide formation in order to figure out the effect of vanadium oxides. At 700 °C a decrease of the friction coefficient with increasing vanadium content can be observed, due to the formation of VO2, V2O3 and the Magnéli phase V4O7.

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.

Evolution of Near-Surface Internal and External Oxide Morphology During High-Temperature Selective Oxidation of Steels

NASA Astrophysics Data System (ADS)

Story, Mary E.; Webler, Bryan A.

2018-05-01

In this work we examine some observations made using high-temperature confocal scanning laser microscopy (HT-CSLM) during selective oxidation experiments. A plain carbon steel and advanced high-strength steel (AHSS) were selectively oxidized at high temperature (850-900°C) in either low oxygen or water vapor atmospheres. Surface evolution, including thermal grooving along grain boundaries and oxide growth, was viewed in situ during heating. Experiments investigated the influence of the microstructure and oxidizing atmosphere on selective oxidation behavior. Sequences of CSLM still frames collected during the experiment were processed with ImageJ to obtain histograms that showed a general darkening trend indicative of oxidation over time with all samples. Additional ex situ scanning electron microscopy and energy dispersive spectroscopy analysis supported in situ observations. Distinct oxidation behavior was observed for each case. Segregation, grain orientation, and extent of internal oxidation were all found to strongly influence surface evolution.

Selective oxidation of dual phase steel after annealing at different dew points

NASA Astrophysics Data System (ADS)

Lins, Vanessa de Freitas Cunha; Madeira, Laureanny; Vilela, Jose Mario Carneiro; Andrade, Margareth Spangler; Buono, Vicente Tadeu Lopes; Guimarães, Juliana Porto; Alvarenga, Evandro de Azevedo

2011-04-01

Hot galvanized steels have been extensively used in the automotive industry. Selective oxidation on the steel surface affects the wettability of zinc on steel and the grain orientation of inhibition layer (Fe-Al-Zn alloy) and reduces the iron diffusion to the zinc layer. The aim of this work is to identify and quantify selective oxidation on the surface of a dual phase steel, and an experimental steel with a lower content of manganese, annealed at different dew points. The techniques employed were atomic force microscopy, X-ray photoelectron spectroscopy, and glow discharge optical emission spectroscopy. External selective oxidation was observed for phosphorus on steel surface annealed at 0 °C dp, and for manganese, silicon, and aluminum at a lower dew point. The concentration of manganese was higher on the dual phase steel surface than on the surface of the experimental steel. The concentration of molybdenum on the surface of both steels increased as the depth increased.

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.

Phosphorus cycling. Major role of planktonic phosphate reduction in the marine phosphorus redox cycle.

PubMed

Van Mooy, B A S; Krupke, A; Dyhrman, S T; Fredricks, H F; Frischkorn, K R; Ossolinski, J E; Repeta, D J; Rouco, M; Seewald, J D; Sylva, S P

2015-05-15

Phosphorus in the +5 oxidation state (i.e., phosphate) is the most abundant form of phosphorus in the global ocean. An enigmatic pool of dissolved phosphonate molecules, with phosphorus in the +3 oxidation state, is also ubiquitous; however, cycling of phosphorus between oxidation states has remained poorly constrained. Using simple incubation and chromatography approaches, we measured the rate of the chemical reduction of phosphate to P(III) compounds in the western tropical North Atlantic Ocean. Colonial nitrogen-fixing cyanobacteria in surface waters played a critical role in phosphate reduction, but other classes of plankton, including potentially deep-water archaea, were also involved. These data are consistent with marine geochemical evidence and microbial genomic information, which together suggest the existence of a vast oceanic phosphorus redox cycle. Copyright © 2015, American Association for the Advancement of Science.

CMOS compatible electrode materials selection in oxide-based memory devices

NASA Astrophysics Data System (ADS)

Zhuo, V. Y.-Q.; Li, M.; Guo, Y.; Wang, W.; Yang, Y.; Jiang, Y.; Robertson, J.

2016-07-01

Electrode materials selection guidelines for oxide-based memory devices are constructed from the combined knowledge of observed device operation characteristics, ab-initio calculations, and nano-material characterization. It is demonstrated that changing the top electrode material from Ge to Cr to Ta in the Ta2O5-based memory devices resulted in a reduction of the operation voltages and current. Energy Dispersed X-ray (EDX) Spectrometer analysis clearly shows that the different top electrode materials scavenge oxygen ions from the Ta2O5 memory layer at various degrees, leading to different oxygen vacancy concentrations within the Ta2O5, thus the observed trends in the device performance. Replacing the Pt bottom electrode material with CMOS compatible materials (Ru and Ir) further reduces the power consumption and can be attributed to the modification of the Schottky barrier height and oxygen vacancy concentration at the electrode/oxide interface. Both trends in the device performance and EDX results are corroborated by the ab-initio calculations which reveal that the electrode material tunes the oxygen vacancy concentration via the oxygen chemical potential and defect formation energy. This experimental-theoretical approach strongly suggests that the proper selection of CMOS compatible electrode materials will create the critical oxygen vacancy concentration to attain low power memory performance.

Response of the nitrogen-fixing lichen Lobaria pulmonaria to phosphorus, molybdenum, and vanadium

USGS Publications Warehouse

Marks, Jade A; Pett-Ridge, Julie; Perakis, Steven S.; Allen, Jessica L; McCune, Bruce

2015-01-01

Nitrogen-fixing lichens (cyanolichens) are an important source of nitrogen (N) in Pacific Northwest forests, but limitation of lichen growth by elements essential for N fixation is poorly understood. To investigate how nutrient limitation may affect cyanolichen growth rates, we fertilized a tripartite cyanobacterial lichen (Lobaria pulmonaria) and a green algal non-nitrogen fixing lichen (Usnea longissima) with the micronutrients molybdenum (Mo) and vanadium (V), both known cofactors for enzymes involved in N fixation, and the macronutrient phosphorus (P). We then grew treated lichens in the field for one year in western Oregon, USA. Lichen growth was very rapid for both species and did not differ across treatments, despite a previous demonstration of P-limitation in L. pulmonaria at a nearby location. To reconcile these disparate findings, we analyzed P, Mo, and V concentrations, natural abundance δ15N isotopes, %N and change in thallus N in Lobaria pulmonaria from both growth experiments. Nitrogen levels in deposition and in lichens could not explain the large difference in growth or P limitation observed between the two studies. Instead, we provide evidence that local differences in P availability may have caused site-specific responses of Lobaria to P fertilization. In the previous experiment, Lobaria had low background levels of P, and treatment with P more than doubled growth. In contrast, Lobaria from the current experiment had much higher background P concentrations, similar to P-treated lichens in the previous experiment, consistent with the idea that ambient variation in P availability influences the degree of P limitation in cyanolichens. We conclude that insufficient P, Mo, and V did not limit the growth of either cyanolichens or chlorolichens at the site of the current experiment. Our findings point to the need to understand landscape-scale variation in P availability to cyanolichens, and its effect on spatial patterns of cyanolichen nutrient

Levels of selected minerals, nitric oxide, and vitamins in aborted Sakis sheep raised under semitropical conditions

PubMed Central

Aypak, Serap Unubol

2010-01-01

The serum levels of calcium, phosphorus, magnesium, copper, zinc and iron and of nitric oxide, retinol, and β-carotene were determined in Sakiz ewes that had experienced an abortion and in healthy controls. Ten healthy and 25 aborted Sakiz sheep were selected from Afyon zone in western Turkey. Their ages ranged between 2 and 4 years weighing between 40 and 60 kg at the time of experiment. All of the abortions occurred in October. The concentrations of retinol, β-carotene, phosphorus, and zinc were significantly lower and those of calcium and nitric oxide were increased in aborted ewes relative to healthy controls. The serum levels of iron, copper, and magnesium were not significantly different among the two groups. In conclusion, abortion is an important problem in commercially important species of ruminants in many regions in the tropics including of western Turkey. Deficiencies of retinol, β-carotene, phosphorus and zinc, and the increase of calcium and nitric oxide concentration may play an important role in the etiology of abortion in ewes. Prophylactic measures such as vitamin and mineral supplementation may be of help to prevent or reduce the incidence of abortion in sheep. PMID:21076941

Passivation of hematite nanorod photoanodes with a phosphorus overlayer for enhanced photoelectrochemical water oxidation

NASA Astrophysics Data System (ADS)

Xiong, Dehua; Li, Wei; Wang, Xiaoguang; Liu, Lifeng

2016-09-01

Hematite (i.e., α-Fe2O3) nanorod photoanodes passivated with a phosphorus overlayer have been fabricated by decomposing sodium hypophosphite (NaH2PO2) at a low temperature over the hematite nanorod surface. Extensive scanning electron microscopy, transmission electron microscopy, x-ray diffractometry and UV-vis spectroscopy characterizations confirm that conformal deposition of an amorphous phosphorus overlayer does not change the crystal structure, morphology, and optical absorption properties of hematite photoanodes. X-ray photoelectron spectroscopy reveals that phosphorus in the deposited overlayer exists in an oxidized state. Comprehensive steady-state polarization, transient photocurrent response, and impedance spectroscopy measurements as well as Mott-Schottky analysis manifest that the phosphorus overlayer is able to effectively passivate surface states and suppress electron-hole recombination, substantially enhancing the photocurrent for water oxidation. Combining the phosphorization treatment with two-step thermal activation, a photocurrent density of 1.1 mA cm-2 is achieved at 1.23 V versus reversible hydrogen electrode under illumination of 100 mW cm-2, ca 55 times higher than that of the non-activated pristine hematite photoanode measured under the same conditions. The simple and fast phosphorization strategy we present here can be readily applied to passivate surfaces of other semiconductor photoelectrodes to improve their photoelectrochemical performance.

Oxygen content and oxidation in frying oil.

PubMed

Totani, Nagao; Yawata, Miho; Mori, Terutoshi; Hammond, Earl G

2013-01-01

The relation between oxygen content and oxidation was investigated in frying oils. When canola oil, a canola-soybean oil blend or a trioctanoylglycerol (glycerol tricaprate) sample were heated with stirring, their dissolved oxygen content decreased abruptly at about 120°C and the carbonyl values (CV) increased gradually with heating and reached values of 6-7 at 180°C in the blended and canola oils, while the CV of trioctanoylglycerol was zero up to 150°C. Probably this abrupt decrease in oxygen content above 120°C can be attributed to the solubility of oxygen in oil rather than because of oxidative reactions. The oxygen content of oil that has been stripped of part of its oxygen, increased at temperatures between 25 and 120°C. In oils that have lost their oxygen by being heated to 180°C, standing at room temperature will slowly restore their oxygen content as the oil cools. Intermittent simple heating of oil promoted oxygen absorbance during cooling periods and standing times, and it resulted in an elevated content of polar compounds (PC). Domestic deep-frying conditions also favor the presence of oxygen in oil below 120°C and during the oil's long standing at room temperature. The oxygen content in oil was low during deep-frying, but oxidation was active at the oil/air interface of bubbles generated by foods being fried. Repeated use of oil at temperatures between 25-180°C resulted in oil with low oxygen values.

Phosphorus Control in DRI-EAF Steelmaking: Thermodynamics, Effect of Alumina, and Process Modeling

NASA Astrophysics Data System (ADS)

Tayeb, Mohammed A.

Flexibility in raw materials, the lower natural gas prices, and the increased use of nonconventional Electric Arc Furnace (EAF) steelmaking using up to 100% Direct Reduced Iron (DRI) have prompted a renewed interest in better control of phosphorus. Iron ore and DRI have higher phosphorus and silica compared to scrap. Although significant work has been done on understanding the partitioning of phosphorus between slag and metal for slags with chemistries relevant to those used in the Basic Oxygen Furnace (BOF), there is little reported work on slag chemistries corresponding to that in the EAF when DRI is used (EAF-DRI). In the current research, phosphorus equilibria between molten Fe-P alloys and CaO-SiO2-Al2O3-P 2O5-FeO-MgOsaturated slag system were investigated. An equilibrium correlation for phosphorus partition as a function of slag composition and temperature has been developed and resulted in better predictions compared with those proposed by earlier workers. As well, it is suitable for both BOF and EAF slags and includes coefficients for silica and alumina, unlike previous correlations. Low amounts of Al2O3 are present in EAF and BOF slags, but no appreciable work has been carried out to study the effect of alumina on the phosphorus partition. When DRI is used, the Al2O 3 contents can also be much higher. The data from this work indicates that there is significant reduction in Lp as the alumina fraction in the slag increases. The observed effect of alumina is attributed to its acidity, which contributes to the reduction of the phosphorus capacity of the slag by lowering the activities of iron oxide and calcium oxide. This in turn lowers the activity of oxygen and oxygen ions needed for phosphorus partition to the slag phase. Alumina in such situation is believed to elongate the silicate slag structure by forming [AlO45-]-tetrahedra. However, it is apparent that for higher alumina, lower silica slags the behavior of alumina changes and dephosphorization would

Simultaneous phosphorus uptake and denitrification by EBPR-r biofilm under aerobic conditions: effect of dissolved oxygen.

PubMed

Wong, Pan Yu; Ginige, Maneesha P; Kaksonen, Anna H; Cord-Ruwisch, Ralf; Sutton, David C; Cheng, Ka Yu

2015-01-01

A biofilm process, termed enhanced biological phosphorus removal and recovery (EBPR-r), was recently developed as a post-denitrification approach to facilitate phosphorus (P) recovery from wastewater. Although simultaneous P uptake and denitrification was achieved despite substantial intrusion of dissolved oxygen (DO >6 mg/L), to what extent DO affects the process was unclear. Hence, in this study a series of batch experiments was conducted to assess the activity of the biofilm under various DO concentrations. The biofilm was first allowed to store acetate (as internal storage) under anaerobic conditions, and was then subjected to various conditions for P uptake (DO: 0-8 mg/L; nitrate: 10 mg-N/L; phosphate: 8 mg-P/L). The results suggest that even at a saturating DO concentration (8 mg/L), the biofilm could take up P and denitrify efficiently (0.70 mmol e(-)/g total solids*h). However, such aerobic denitrification activity was reduced when the biofilm structure was physically disturbed, suggesting that this phenomenon was a consequence of the presence of oxygen gradient across the biofilm. We conclude that when a biofilm system is used, EBPR-r can be effectively operated as a post-denitrification process, even when oxygen intrusion occurs.

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

2011-01-01

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

PubMed

Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

2018-04-06

Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 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

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.

Innovative oxide materials for electrochemical energy conversion and oxygen separation

NASA Astrophysics Data System (ADS)

Belousov, V. V.

2017-10-01

Ion-conducting solid metal oxides are widely used in high-temperature electrochemical devices for energy conversion and oxygen separation. However, liquid metal oxides possessing unique electrochemical properties still remain of limited use. The review demonstrates the potential for practical applications of molten oxides. The transport properties of molten oxide materials are discussed. The emphasis is placed on the chemical diffusion of oxygen in the molten oxide membrane materials for electrochemical energy conversion and oxygen separation. The thermodynamics of these materials is considered. The dynamic polymer chain model developed to describe the oxygen ion transport in molten oxides is discussed. Prospects for further research into molten oxide materials are outlined. The bibliography includes 145 references.

THE COLORIMETRIC DETERMINATION OF VANADIUM IN NIOBIUM-VANADIUM ALLOYS

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

Articolo, O.J.

1959-06-26

A procedure is described for the analysis of vanadium in niobium-- vanadium alloys in the range >0.1% vanadium with an accuracy of better than 3%. The method was applied to the analysis of niobium alloys in which the nominal per cent vanadium varied between 0.3 to 4.6%. The sample is dissolved in a mixture of nitric and hydrofluoric acid and then evaporated to fumes with sulfuric acid. The niobium is hydrolyzed with sulfurous acid and separated from the vanadium by filtration. Hydrogen peroxide is added to the filtrate to form a reddish brown complex with the vanadium. The optical densitymore » of the resulting solution is obtained at 450 m mu on a model B Beckman spectrophotometer. (auth)« less

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.

Effect of Oxygen Defects on the Catalytic Performance of VOx/CeO2 Catalysts for Oxidative Dehydrogenation of Methanol

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

Li, Yan; Wei, Zhehao; Gao, Feng

2015-05-01

In this work, CeO2 nanocubes with controlled particle size and dominating (100) facets are synthesized as supports for VOx catalysts. Combined TEM, SEM, XRD, and Raman study reveals that the oxygen vacancy density of CeO2 supports can be tuned by tailoring the particle sizes without altering the dominating facets, where smaller particle sizes result in larger oxygen vacancy densities. At the same vanadium coverage, the VOx catalysts supported on small-sized CeO2 supports with higher oxygen defect densities exhibit promoted redox property and lower activation energy for methoxyl group decomposition, as evidenced by H2-TPR and methanol TPD study. These results furthermore » confirm that the presence of oxygen vacancies plays an important role in promoting the activity of VOx species in methanol oxidation. We gratefully acknowledge financial support from the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Part of this work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle.« less

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.

Migration of interfacial oxygen ions modulated resistive switching in oxide-based memory devices

NASA Astrophysics Data System (ADS)

Chen, C.; Gao, S.; Zeng, F.; Tang, G. S.; Li, S. Z.; Song, C.; Fu, H. D.; Pan, F.

2013-07-01

Oxides-based resistive switching memory induced by oxygen ions migration is attractive for future nonvolatile memories. Numerous works had focused their attentions on the sandwiched oxide materials for depressing the characteristic variations, but the comprehensive studies of the dependence of electrodes on the migration behavior of oxygen ions are overshadowed. Here, we investigated the interaction of various metals (Ni, Co, Al, Ti, Zr, and Hf) with oxygen atoms at the metal/Ta2O5 interface under electric stress and explored the effect of top electrode on the characteristic variations of Ta2O5-based memory device. It is demonstrated that chemically inert electrodes (Ni and Co) lead to the scattering switching characteristics and destructive gas bubbles, while the highly chemically active metals (Hf and Zr) formed a thick and dense interfacial intermediate oxide layer at the metal/Ta2O5 interface, which also degraded the resistive switching behavior. The relatively chemically active metals (Al and Ti) can absorb oxygen ions from the Ta2O5 film and avoid forming the problematic interfacial layer, which is benefit to the formation of oxygen vacancies composed conduction filaments in Ta2O5 film thus exhibit the minimum variations of switching characteristics. The clarification of oxygen ions migration behavior at the interface can lead further optimization of resistive switching performance in Ta2O5-based memory device and guide the rule of electrode selection for other oxide-based resistive switching memories.

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.

Duttonite, a new quadrivalent vanadium oxide from the Peanut mine, Montrose County, Colorado

USGS Publications Warehouse

Thompson, Mary Eleanor; Roach, Carl Houston; Meyrowitz, Robert

1956-01-01

Duttonite, a new quadrivalent vanadium oxide from the Peanut mine, Montrose County, Colo., has the formula VO(OH)2. The mineral occurs as crusts and coatings of pale-brown transparent platy crystals, as one of the first oxidation products of montroseite ore. It is associated with melanovanadite and abundant crystals of hexagonal native selenium. Duttonite is biaxial positive, 2V is about 60°, dispersion is r v, moderate; X = a, pale pinkish brown; Y = c, pale yellow-brown; Z = b, pale brown; α = 1.810 ± 0.003, β = 1.900 ± 0.003, γ > 2.01. The hardness is about 2.5; the calculated specific gravity is 3.24. The chemical analysis shows, in percent: V2o3 2.6, V2O4 75.3, FeO 0.4, H2O 18.1, insoluble 4.2, total 100.6. Duttonite is monoclinic, ao = 8.80 ± 0.02A, bo - 3.95 ± 0.01A, co - 5.96 ± 0.02A, β = 90°401 ± 51. The space group is I2/c, (C62h); the cell contents are 4[VO(OH)2]. The crystals are strongly pseudo-orthorhombic, and the structure departs only slightly from the space group Imcm. Duttonite is named for Captain Clarence Edward Dutton (1841-1912). A detailed study of the geology, geochemistry, and mineralogy of the vanadium-uranium ore at the Peanut mine, Montrose County, Colo., was begun early in 1954 by Carl H. Roach of the U. S. Geological Survey. A number of rare and new minerals were found in the ore and the study of these samples was undertaken by Mary E. Thompson. Duttonite is the first new vanadium mineral to be described from the Peanut mine. It is named for Captain Clarence Edward Dutton (1841-1912), who was one of the first geologists to work in the Colorado Plateau region and who was a member of the U. s. Geological Survey from 1879-91. We are indebted to the following members of the Geological Surbey: K. E. Valentine for spectrographic analyses of duttonite, and M. E. Mrose and H. T. Evans, Jr., for measurement of the unit cell constants. This work is part of a program being conducted by the U. S. Geological Survey on behalf of the

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.

The Oxidation of AlN in Dry and Wet Oxygen

NASA Technical Reports Server (NTRS)

Opila, Elizabeth; Humphrey, Donald; Jacobson, Nathan; Yoshio, Tetsuo; Oda, Kohei

1998-01-01

The oxidation kinetics of AlN containing 3.5 wt% Y2O3 were studied by thermogravimetric analysis in dry oxygen and 10% H2O/balance oxygen at temperatures between 1000 and 1200 C for times between 48 and 100 h. The oxidation kinetics for AlN in dry oxygen were parabolic and of approximately the same magnitude and temperature dependence as other alumina forming materials. In this case, diffusion of oxygen and/or aluminum through the alumina scale is the rate limiting mechanism. The oxidation kinetics for AlN in wet oxygen were nearly linear and much more rapid than rates observed in dry oxygen. Numerous micropores were observed in the alumina formed on AIN in wet oxygen. These pores provide a fast path for oxygen transport. The linear kinetics observed in this case suggest that the interface reaction rate of AlN with wet oxygen is the oxidation rate limiting step.

Benthic phosphorus regeneration in the Potomac River Estuary

USGS Publications Warehouse

Callender, E.

1982-01-01

The flux of dissolved reactive phosphate from Potomac riverine and estuarine sediments is controlled by processes occurring at the water-sediment interface and within surficial sediment. In situ benthic fluxes (0.1 to 2.0 mmoles m-2 day-1) are generally five to ten times higher than calculated diffusive fluxes (0.020 to 0.30 mmoles m-2 day-1). The discrepancy between the two flux estimates is greatest in the transition zone (river mile 50 to 70) and is attributd to macrofaunal irrigation. Both in situ and diffusive fluxes of dissolved reactive phosphate from Potomac tidal river sediments are low while those from anoxic lower estuarine sediments are high. The net accumulation rate of phosphorus in benthic sediment exhibits an inverse pattern. Thus a large fraction of phosphorus is retained by Potomac tidal river sediments, which contain a surficial oxidized layer and oligochaete worms tolerant of low oxygen conditions, and a large fraction of phosphorus is released from anoxic lower estuary sediments. Tidal river sediment pore waters are in equilibrium with amorphous Fe (OH)3 while lower estuary pore waters are significantly undersaturated with respect to this phase. Benthic regeneration of dissolved reactive phosphorus is sufficient to supply all the phosphorus requirements for net primary production in the lower tidal river and transition-zone waters of the Potomac River Estuary. Benthic regeneration supplies approximately 25% as much phosphorus as inputs from sewage treatment plants and 10% of all phosphorus inputs to the tidal Potomac River. When all available point source phosphorus data are put into a steady-state conservation of mass model and reasonable coefficients for uptake of dissolved phosphorus, remineralization of particulate phosphorus, and sedimentation of particulate phosphorus are used in the model, a reasonably accurate simulation of dissolved and particulate phosphorus in the water column is obtained for the summer of 1980. ?? 1982 Dr W. Junk

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.

Oxygen Vacancy Linear Clustering in a Perovskite Oxide

DOE PAGES

Eom, Kitae; Choi, Euiyoung; Choi, Minsu; ...

2017-07-14

Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

Oxygen Vacancy Linear Clustering in a Perovskite Oxide

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

Eom, Kitae; Choi, Euiyoung; Choi, Minsu

Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

Oxygen Isotope Signatures of Biogenic Manganese(III/IV) Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Hansel, C. M.; Wankel, S. D.

2015-12-01

Manganese (Mn) oxide minerals are pervasive throughout a number of surface earth environments as rock varnishes, ferromanganese nodules, crusts around deep-sea vents, and cave deposits among many other marine, freshwater, and terrestrial deposits. Mn(III,IV) oxides are also among the strongest sorbents and oxidants in surface earth environments and are crucial to understanding the fate of organic matter in sedimentary environments. The precipitation of Mn oxide minerals proceeds via both abiotic and biotic oxidation pathways, the latter due to the indirect or direct activity of Mn(II)- oxidizing microorganisms, including bacteria and fungi. Although the precipitation of Mn oxides is believed to be primarily controlled by Mn(II)-oxidizing organisms in most surface earth environments, confirmation of this generally held notion has remained illusive and limits our understanding of their formation on Earth and beyond (e.g., Mars). Previous work provided evidence that O atom incorporation by specific Mn oxidation pathways may exhibit unique and predictable isotopic fractionation. In this study, we expand upon this evidence by measuring the oxygen isotope signature of several biogenic and abiogenic Mn oxide minerals synthesized under a range of oxygen-18 labeled water. These results allow us to determine the relative amount oxygen atoms derived from water and molecular oxygen that are incorporated in the oxide and shed light on corresponding isotope fractionation factors. Additionally, we show that, once precipitated, Mn oxide isotope signatures are robust with respect to aqueous oxygen isotope exchange. The study provides a foundation on which to study and interpret Mn oxides in natural environments and determine which environmental controls may govern Mn(II) oxidation.

A new strategy for integrating abundant oxygen functional groups into carbon felt electrode for vanadium redox flow batteries

PubMed Central

Kim, Ki Jae; Lee, Seung-Wook; Yim, Taeeun; Kim, Jae-Geun; Choi, Jang Wook; Kim, Jung Ho; Park, Min-Sik; Kim, Young-Jun

2014-01-01

The effects of surface treatment combining corona discharge and hydrogen peroxide (H2O2) on the electrochemical performance of carbon felt electrodes for vanadium redox flow batteries (VRFBs) have been thoroughly investigated. A high concentration of oxygen functional groups has been successfully introduced onto the surface of the carbon felt electrodes by a specially designed surface treatment, which is mainly responsible for improving the energy efficiency of VRFBs. In addition, the wettability of the carbon felt electrodes also can be significantly improved. The energy efficiency of the VRFB cell employing the surface modified carbon felt electrodes is improved by 7% at high current density (148 mA cm−2). Such improvement is attributed to the faster charge transfer and better wettability allowed by surface-active oxygen functional groups. Moreover, this method is much more competitive than other surface treatments in terms of processing time, production costs, and electrochemical performance. PMID:25366060

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

Dopants Diffusion in Silicon during Molecular Oxygen/nitrogen Trifluoride Oxidation and Related Phenomena

NASA Astrophysics Data System (ADS)

Kim, U. S.

1990-01-01

To date, chlorine has been used as useful additives in silicon oxidation. However, rapid scaling of device dimensions motivates the development of a new dielectric layer or modification of the silicon dioxide itself. More recently, chemically enhanced thermal oxidation by the use of fluorine containing species has been introduced to verify the potential of fluorine in the silicon oxidation process. In this study, gaseous nitrogen trifluoride (NF _3) was selected as the fluorine oxidizing source based on ease of use and was compared with the dichlorofluoroethane (C_2H _3Cl_2F) source. Two different kinds of boron marker samples were prepared and oxidized in O_2/NF_3 ambient for the comparison of surface vs bulk oxidation enhanced/retarded diffusion (OED/ORD). The phosphorus, arsenic and antimony diffusion in silicon during fluorine oxidation has been studied using the various covering layers such as SiO_2, Si_3 N_4, and SiO_2 + Si_3N_4 layers. The oxidation related phenomena, i.e. enhanced silicon and silicon nitride oxidation in fluorine ambient were studied and correlated with the point defect balance at the oxidizing interface. The results of this investigation were discussed with special emphasis on the effect of fluorine on enhanced oxidation and dopant diffusion.

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.

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.

Oxygen, pH, and mitochondrial oxidative phosphorylation.

PubMed

Wilson, David F; Harrison, David K; Vinogradov, Sergei A

2012-12-15

The oxygen dependence of mitochondrial oxidative phosphorylation was measured in suspensions of isolated rat liver mitochondria using recently developed methods for measuring oxygen and cytochrome c reduction. Cytochrome-c oxidase (energy conservation site 3) activity of the mitochondrial respiratory chain was measured using an artificial electron donor (N,N,N',N'-tetramethyl-p-phenylenediamine) and ascorbate to directly reduce the cytochrome c, bypassing sites 1 and 2. For mitochondrial suspensions with added ATP, metabolic conditions approximating those in intact cells and decreasing oxygen pressure both increased reduction of cytochrome c and decreased respiratory rate. The kinetic parameters [K(M) and maximal rate (V(M))] for oxygen were determined from the respiratory rates calculated for 100% reduction of cytochrome c. At 22°C, the K(M) for oxygen is near 3 Torr (5 μM), 12 Torr (22 μM), and 18 Torr (32 μM) at pH 6.9, 7.4, and 7.9, respectively, and V(M) corresponds to a turnover number for cytochrome c at 100% reduction of near 80/s and is independent of pH. Uncoupling oxidative phosphorylation increased the respiratory rate at saturating oxygen pressures by twofold and decreased the K(M) for oxygen to <2 Torr at all tested pH values. Mitochondrial oxidative phosphorylation is an important oxygen sensor for regulation of metabolism, nutrient delivery to tissues, and cardiopulmonary function. The decrease in K(M) for oxygen with acidification of the cellular environment impacts many tissue functions and may give transformed cells a significant survival advantage over normal cells at low-pH, oxygen-limited environment in growing tumors.

Oxygen and oxidative stress in the perinatal period.

PubMed

Torres-Cuevas, Isabel; Parra-Llorca, Anna; Sánchez-Illana, Angel; Nuñez-Ramiro, Antonio; Kuligowski, Julia; Cháfer-Pericás, Consuelo; Cernada, María; Escobar, Justo; Vento, Máximo

2017-08-01

Fetal life evolves in a hypoxic environment. Changes in the oxygen content in utero caused by conditions such as pre-eclampsia or type I diabetes or by oxygen supplementation to the mother lead to increased free radical production and correlate with perinatal outcomes. In the fetal-to-neonatal transition asphyxia is characterized by intermittent periods of hypoxia ischemia that may evolve to hypoxic ischemic encephalopathy associated with neurocognitive, motor, and neurosensorial impairment. Free radicals generated upon reoxygenation may notably increase brain damage. Hence, clinical trials have shown that the use of 100% oxygen given with positive pressure in the airways of the newborn infant during resuscitation causes more oxidative stress than using air, and increases mortality. Preterm infants are endowed with an immature lung and antioxidant system. Clinical stabilization of preterm infants after birth frequently requires positive pressure ventilation with a gas admixture that contains oxygen to achieve a normal heart rate and arterial oxygen saturation. In randomized controlled trials the use high oxygen concentrations (90% to 100%) has caused more oxidative stress and clinical complications that the use of lower oxygen concentrations (30-60%). A correlation between the amount of oxygen received during resuscitation and the level of biomarkers of oxidative stress and clinical outcomes was established. Thus, based on clinical outcomes and analytical results of oxidative stress biomarkers relevant changes were introduced in the resuscitation policies. However, it should be underscored that analysis of oxidative stress biomarkers in biofluids has only been used in experimental and clinical research but not in clinical routine. The complexity of the technical procedures, lack of automation, and cost of these determinations have hindered the routine use of biomarkers in the clinical setting. Overcoming these technical and economical difficulties constitutes a

Effects of biological activity, light, temperature and oxygen on phosphorus release processes at the sediment and water interface of Taihu Lake, China.

PubMed

Jiang, Xia; Jin, Xiangcan; Yao, Yang; Li, Lihe; Wu, Fengchang

2008-04-01

Effects of biological activity, light, temperature and oxygen on the phosphorus (P) release processes at the sediment and water interface of a shallow lake, Taihu Lake, China, were investigated. The results show that organisms at the sediment and water interface can stimulate P release from sediments, and their metabolism can alter the surrounding micro-environmental conditions. The extent of P release and its effects on P concentration in the overlying water were affected by factors such as light, temperature and dissolved oxygen. The organism biomass increased as temperature increased, which was beneficial for P release. Dissolved total phosphorus (DTP) and dissolved inorganic phosphorus (DIP) concentrations in the corresponding overlying water were mainly controlled by light. P release occurred in both aerobic and anoxic conditions with the presence of organisms. However in the presence of light , P release in an anoxic environment was much greater than in an aerobic environment, which may stimulate alga bloom and result in an increase in total phosphorus (TP) in the overlying water. This information aids the understanding of P biogeochemical cycling at the interface and its relationship with eutrophication in shallow lakes.

Thymic cytoarchitecture changes in mice exposed to vanadium.

PubMed

Ustarroz-Cano, Martha; Garcia-Pelaez, Isabel; Cervantes-Yepez, Silvana; Lopez-Valdez, Nelly; Fortoul, Teresa I

2017-12-01

The thymus is a vital immune system organ wherein selection of T-lymphocytes occurs in a process regulated by dendritic and epithelial thymic cells. Previously, we have reported that in a mouse model of vanadium inhalation, a decrease in CD11c dendritic cells was observed. In the present study, we report on a thymic cortex-medulla distribution distortion in these hosts due to apparent effects of the inhaled vanadium on cytokeratin-5 (K5 + ) epithelial cells in the same mouse model - after 1, 2, and 4 weeks of exposure - by immunohistochemistry. These cells - together with dendritic cells - eliminate autoreactive T-cell clones and regulate the production of regulatory T-cells in situ. Because both cell types are involved in the negative selection of autoreactive clones, a potential for an increase in development of autoimmune conditions could be a possible consequence among individuals who might be exposed often to vanadium in air pollution, including dwellers of highly polluted cities with elevated levels of particulate matter onto which vanadium is often adsorbed.

Selective oxidation of methanol and ethanol on supported ruthenium oxide clusters at low temperatures

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

Liu, Haichao; Iglesia, Enrique

RuO2 domains supported on SnO2, ZrO2, TiO2, Al2O3, and SiO2 catalyze the oxidative conversion of methanol to formaldehyde, methylformate, and dimethoxymethane with unprecedented rates and high combined selectivity (>99 percent) and yield at low temperatures (300-400 K). Supports influence turnover rates and the ability of RuO2 domains to undergo redox cycles required for oxidation turnovers. Oxidative dehydrogenation turnover rates and rates of stoichiometric reduction of RuO2 in H2 increased in parallel when RuO2 domains were dispersed on more reducible supports. These support effects, the kinetic effects of CH3OH and O2 on reaction rates, and the observed kinetic isotope effects withmore » CH3OD and CD3OD reactants are consistent with a sequence of elementary steps involving kinetically relevant H-abstraction from adsorbed methoxide species using lattice oxygen atoms and with methoxide formation in quasi-equilibrated CH3OH dissociation on nearly stoichiometric RuO2 surfaces. Anaerobic transient experiments confirmed that CH3OH oxidation to HCHO requires lattice oxygen atoms and that selectivities are not influenced by the presence of O2. Residence time effects on selectivity indicate that secondary HCHO-CH3OH acetalization reactions lead to hemiacetal or methoxymethanol intermediates that convert to dimethoxymethane in reactions with CH3OH on support acid sites or dehydrogenate to form methylformate on RuO2 and support redox sites. These conclusions are consistent with the tendency of Al2O3 and SiO2 supports to favor dimethoxymethane formation, while SnO2, ZrO2, and TiO2 preferentially form methylformate. These support effects on secondary reactions were confirmed by measured CH3OH oxidation rates and selectivities on physical mixtures of supported RuO2 catalysts and pure supports. Ethanol also reacts on supported RuO2 domains to form predominately acetaldehyde and diethoxyethane at 300-400 K. The bifunctional nature of these reaction pathways and the

Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural to 5-Formyl-2-furancarboxylic Acid in Water.

PubMed

Ventura, Maria; Aresta, Michele; Dibenedetto, Angela

2016-05-23

A simple, cheap, and selective catalyst based on copper/cerium oxides is described for the oxidation of 5-(hydroxymethyl)furfural (5-HMF) in water. An almost quantitative conversion (99 %) with excellent (90 %) selectivity towards the formation of 5-formyl-2-furancarboxylic acid, a platform molecule for other high value chemicals, is observed. The catalyst does not require any pretreatment or additives, such as bases, to obtain high yield and selectivity in water as solvent and using oxygen as oxidant. When a physical mixture of the oxides is used, low conversion and selectivity are observed. Air can be used instead of oxygen, but a lower conversion rate is observed if the same overall pressure is used, and the selectivity remains high. The catalyst can be recovered almost quantitatively and reused. Deactivation of the catalyst, observed in repeated runs, is due to the deposition of humins on its surface. Upon calcination the catalyst almost completely recovers its activity and selectivity, proving that the catalyst is robust. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Properties of the correlated metal phase induced by electrolyte gating of insulating vanadium dioxide nanobeams

NASA Astrophysics Data System (ADS)

Singh, Sujay; Horrocks, Gregory; Marley, Peter; Banerjee, Sarbajit; Sambandamurthy, G.

2014-03-01

Vanadium oxide (VO2) undergoes a first order metal to insulator transition (MIT) and a structural phase transition (monoclinic insulator to rutile metal) near 340 K. Over the past few years, several attempts are made to trigger the MIT in VO2 using ionic liquids (IL). Parkin's group has recently showed that IL gating leads to the creation of oxygen vacancies in VO2 and stabilizes the metallic phase. Our goal is to study the electronic properties, changes in the stoichiometry and structure of this metallic phase created by oxygen vacancies. Electrical transport measurements on single crystal nanobeams show that the metallic phase has a higher resistance while IL gating is applied and results from Raman spectroscopy studies on any structural change during IL gating will be presented. The role of substitutional dopants (such as W, Mo) on the creation of oxygen vacancies and subsequent stabilization of metallic phase in IL gated experiments will also be discussed. The work is supported by NSF DMR 0847324 and 0847169.

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.

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.

Phosphorus recovery from fosfomycin pharmaceutical wastewater by wet air oxidation and phosphate crystallization.

PubMed

Qiu, Guanglei; Song, Yonghui; Zeng, Ping; Xiao, Shuhu; Duan, Liang

2011-06-01

Fosfomycin pharmaceutical wastewater contains highly concentrated and refractory antibiotic organic phosphorus (OP) compounds. Wet air oxidation (WAO)-phosphate crystallization process was developed and applied to fosfomycin pharmaceutical wastewater pretreatment and phosphorus recovery. Firstly, WAO was used to transform concentrated and refractory OP substances into inorganic phosphate (IP). At 200°C, 1.0MPa and pH 11.2, 99% total OP (TOP) was transformed into IP and 58% COD was reduced. Subsequently, the WAO effluent was subjected to phosphate crystallization process for phosphorus recovery. At Ca/P molar ratio 2.0:1.0 or Mg/N/P molar ratio 1.1:1.0:1.0, 99.9% phosphate removal and recovery were obtained and the recovered products were proven to be hydroxyapatite and struvite, respectively. After WAO-phosphate crystallization, the BOD/COD ratio of the wastewater increased from 0 to more than 0.5, which was suitable for biological treatment. The WAO-phosphate crystallization process was proven to be an effective method for phosphorus recovery and for fosfomycin pharmaceutical wastewater pretreatment. Copyright © 2011 Elsevier Ltd. All rights reserved.

Bistability of atmospheric oxygen and the Great Oxidation.

PubMed

Goldblatt, Colin; Lenton, Timothy M; Watson, Andrew J

2006-10-12

The history of the Earth has been characterized by a series of major transitions separated by long periods of relative stability. The largest chemical transition was the 'Great Oxidation', approximately 2.4 billion years ago, when atmospheric oxygen concentrations rose from less than 10(-5) of the present atmospheric level (PAL) to more than 0.01 PAL, and possibly to more than 0.1 PAL. This transition took place long after oxygenic photosynthesis is thought to have evolved, but the causes of this delay and of the Great Oxidation itself remain uncertain. Here we show that the origin of oxygenic photosynthesis gave rise to two simultaneously stable steady states for atmospheric oxygen. The existence of a low-oxygen (less than 10(-5) PAL) steady state explains how a reducing atmosphere persisted for at least 300 million years after the onset of oxygenic photosynthesis. The Great Oxidation can be understood as a switch to the high-oxygen (more than 5 x 10(-3) PAL) steady state. The bistability arises because ultraviolet shielding of the troposphere by ozone becomes effective once oxygen levels exceed 10(-5) PAL, causing a nonlinear increase in the lifetime of atmospheric oxygen. Our results indicate that the existence of oxygenic photosynthesis is not a sufficient condition for either an oxygen-rich atmosphere or the presence of an ozone layer, which has implications for detecting life on other planets using atmospheric analysis and for the evolution of multicellular life.

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.

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.

49 CFR 175.501 - Special requirements for oxidizers and compressed oxygen.

Code of Federal Regulations, 2012 CFR

2012-10-01

... oxygen. 175.501 Section 175.501 Transportation Other Regulations Relating to Transportation PIPELINE AND... Special requirements for oxidizers and compressed oxygen. (a) Compressed oxygen, when properly labeled Oxidizer or Oxygen, may be loaded and transported as provided in this section. Except for Oxygen...

49 CFR 175.501 - Special requirements for oxidizers and compressed oxygen.

Code of Federal Regulations, 2014 CFR

2014-10-01

... oxygen. 175.501 Section 175.501 Transportation Other Regulations Relating to Transportation PIPELINE AND... Special requirements for oxidizers and compressed oxygen. (a) Compressed oxygen, when properly labeled Oxidizer or Oxygen, may be loaded and transported as provided in this section. Except for Oxygen...

49 CFR 175.501 - Special requirements for oxidizers and compressed oxygen.

Code of Federal Regulations, 2010 CFR

2010-10-01

... oxygen. 175.501 Section 175.501 Transportation Other Regulations Relating to Transportation PIPELINE AND... Special requirements for oxidizers and compressed oxygen. (a) Compressed oxygen, when properly labeled Oxidizer or Oxygen, may be loaded and transported as provided in this section. Except for Oxygen...

49 CFR 175.501 - Special requirements for oxidizers and compressed oxygen.

Code of Federal Regulations, 2013 CFR

2013-10-01

... oxygen. 175.501 Section 175.501 Transportation Other Regulations Relating to Transportation PIPELINE AND... Special requirements for oxidizers and compressed oxygen. (a) Compressed oxygen, when properly labeled Oxidizer or Oxygen, may be loaded and transported as provided in this section. Except for Oxygen...

49 CFR 175.501 - Special requirements for oxidizers and compressed oxygen.

Code of Federal Regulations, 2011 CFR

2011-10-01

... oxygen. 175.501 Section 175.501 Transportation Other Regulations Relating to Transportation PIPELINE AND... Special requirements for oxidizers and compressed oxygen. (a) Compressed oxygen, when properly labeled Oxidizer or Oxygen, may be loaded and transported as provided in this section. Except for Oxygen...

A heterojunction photocatalyst composed of zinc rhodium oxide, single crystal-derived bismuth vanadium oxide, and silver for overall pure-water splitting under visible light up to 740 nm.

PubMed

Kobayashi, Ryoya; Takashima, Toshihiro; Tanigawa, Satoshi; Takeuchi, Shugo; Ohtani, Bunsho; Irie, Hiroshi

2016-10-12

We recently reported the synthesis of a solid-state heterojunction photocatalyst consisting of zinc rhodium oxide (ZnRh 2 O 4 ) and bismuth vanadium oxide (Bi 4 V 2 O 11 ), which functioned as hydrogen (H 2 ) and oxygen (O 2 ) evolution photocatalysts, respectively, connected with silver (Ag). Polycrystalline Bi 4 V 2 O 11 (p-Bi 4 V 2 O 11 ) powders were utilized to form ZnRh 2 O 4 /Ag/p-Bi 4 V 2 O 11 , which was able to photocatalyze overall pure-water splitting under red-light irradiation with a wavelength of 700 nm (R. Kobayashi et al., J. Mater. Chem. A, 2016, 4, 3061). In the present study, we replaced p-Bi 4 V 2 O 11 with a powder obtained by pulverizing single crystals of Bi 4 V 2 O 11 (s-Bi 4 V 2 O 11 ) to form ZnRh 2 O 4 /Ag/s-Bi 4 V 2 O 11 , and demonstrated that this heterojunction photocatalyst had enhanced water-splitting activity. In addition, ZnRh 2 O 4 /Ag/s-Bi 4 V 2 O 11 was able to utilize nearly the entire range of visible light up to a wavelength of 740 nm. These properties were attributable to the higher O 2 evolution activity of s-Bi 4 V 2 O 11 .

Manganese oxide particles as cytoprotective, oxygen generating agents.

PubMed

Tootoonchi, Mohammad Hossein; Hashempour, Mazdak; Blackwelder, Patricia L; Fraker, Christopher A

2017-09-01

Cell culture and cellular transplant therapies are adversely affected by oxidative species and radicals. Herein, we present the production of bioactive manganese oxide nanoparticles for the purpose of radical scavenging and cytoprotection. Manganese comprises the core active structure of somatic enzymes that perform the same function, in vivo. Formulated nanoparticles were characterized structurally and surveyed for maximal activity (superoxide scavenging, hydrogen peroxide scavenging with resultant oxygen generation) and minimal cytotoxicity (48-h direct exposure to titrated manganese oxide concentrations). Cytoprotective capacity was tested using cell exposure to hydrogen peroxide in the presence or absence of the nanoparticles. Several ideal compounds were manufactured and utilized that showed complete disproportionation of superoxide produced by the xanthine/xanthine oxidase reaction. Further, the nanoparticles showed catalase-like activity by completely converting hydrogen peroxide into the corresponding concentration of oxygen. Finally, the particles protected cells (murine β-cell insulinoma) against insult from hydrogen peroxide exposure. Based on these observed properties, these particles could be utilized to combat oxidative stress and inflammatory response in a variety of cell therapy applications. Maintaining viability once cells have been removed from their physiological niche, e.g. culture and transplant, demands proper control of critical variables such as oxygenation and removal of harmful substances e.g. reactive oxygen species. Limited catalysts can transform reactive oxygen species into molecular oxygen and, thereby, have the potential to maintain cell viability and function. Among these are manganese oxide particles which are the subject of this study. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Thermochemical analyses of the oxidative vaporization of metals and oxides by oxygen molecules and atoms

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Leisz, D. M.; Fryburg, G. C.; Stearns, C. A.

1977-01-01

Equilibrium thermochemical analyses are employed to describe the vaporization processes of metals and metal oxides upon exposure to molecular and atomic oxygen. Specific analytic results for the chromium-, platinum-, aluminum-, and silicon-oxygen systems are presented. Maximum rates of oxidative vaporization predicted from the thermochemical considerations are compared with experimental results for chromium and platinum. The oxidative vaporization rates of chromium and platinum are considerably enhanced by oxygen atoms.

Hydrothermal synthesis of red phosphorus @reduced graphene oxide nanohybrid with enhanced electrochemical performance as anode material of lithium-ion battery

NASA Astrophysics Data System (ADS)

Zhu, Xing; Yuan, Zewei; Wang, Xiaobo; Jiang, Guodong; Xiong, Jian; Yuan, Songdong

2018-03-01

Red phosphorus @reduced graphene oxide (P @rGO) nanohybrid was synthesized via a two-step hydrothermal process. The obtained P @rGO nanohybrid was characterized by TEM, SEM, Raman, XRD and XPS. It was found that the nano-scale red phosphorus encapsulated in the reduced graphene oxide and the existence of phosphorus promote the reduction of graphene oxide. The electrochemical performance of P @rGO nanohybrid as an anode material was investigated by galvanostatic charge/discharge, rate performance, cyclic voltammetry and AC impedance test. With increasing the mass of rGO, the electrochemical performance of P @rGO nanohybrid was significantly enhanced. The first discharge/charge specific capacity of the nanohybrid prepared at optimum condition (P:GO = 7:3) could achieve approximately 2400 mAh/g and 1600 mAh/g respectively and still retained ∼1000 mAh/g after 80 cycles and the coulombic efficiency maintained almost 100%. The enhancement in P @rGO nanohybrid was attributed to the introduction of graphene, which led to the elimination of volume effect and the enhancement of conductively of pure red phosphorus.

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.

Layer Control of WSe2 via Selective Surface Layer Oxidation.

PubMed

Li, Zhen; Yang, Sisi; Dhall, Rohan; Kosmowska, Ewa; Shi, Haotian; Chatzakis, Ioannis; Cronin, Stephen B

2016-07-26

We report Raman and photoluminescence spectra of mono- and few-layer WSe2 and MoSe2 taken before and after exposure to a remote oxygen plasma. For bilayer and trilayer WSe2, we observe an increase in the photoluminescence intensity and a blue shift of the photoluminescence peak positions after oxygen plasma treatment. The photoluminescence spectra of trilayer WSe2 exhibit features of a bilayer after oxygen plasma treatment. Bilayer WSe2 exhibits features of a monolayer, and the photoluminescence of monolayer WSe2 is completely absent after the oxygen plasma treatment. These changes are observed consistently in more than 20 flakes. The mechanism of the changes observed in the photoluminescence spectra of WSe2 is due to the selective oxidation of the topmost layer. As a result, N-layer WSe2 is reduced to N-1 layers. Raman spectra and AFM images taken from the WSe2 flakes before and after the oxygen treatment corroborate these findings. Because of the low kinetic energy of the oxygen radicals in the remote oxygen plasma, the oxidation is self-limiting. By varying the process duration from 1 to 10 min, we confirmed that the oxidation will only affect the topmost layer of the WSe2 flakes. X-ray photoelectron spectroscopy shows that the surface layer WOx of the sample can be removed by a quick dip in KOH solution. Therefore, this technique provides a promising way of controlling the thickness of WSe2 layer by layer.

Will the Oxygen-Phosphorus Paradigm Persist? - Expert Views of the Future of Management and Restoration of Eutrophic Lakes

NASA Astrophysics Data System (ADS)

Nygrén, Nina A.; Tapio, Petri; Horppila, Jukka

2017-11-01

In the age of climate change, the demand and lack of pure water challenges many communities. Substantial amount of effort is put in every year to manage and restore degraded lakes while the long-term effects of those efforts are only poorly known or monitored. Oxygenation, or aeration, is used extensively for the restoration of eutrophic lakes, although many studies question whether this process improves the status of the lakes in the long-term. The desired effect of oxygenation is based on paradigmatic theories that, in the light of recent literature, might not be adequate when long-term improvements are sought. This article canvasses expert views on the feasibility of the `oxygen-phosphorus paradigm' as well as the future of the management and restoration of eutrophic lakes, based on an international, two-rounded, expert panel survey (Delphi study), employing 200 freshwater experts from 33 nationalities, contacted at three conferences on the topic. The conclusion is that the oxygen-phosphorus paradigm seems to be rather persistent. The experts considered oxygenation to be a valid short-term lake restoration method, but not without harmful side-effects. In addition, experts' low level of trust in the adequacy of the scientific knowledge on the effects of restorations and in the use of the scientific knowledge as a basis of choice of restoration methods, could be signs of a paradigm shift towards an outlook emphasizing more effective catchment management over short-term restorations. The expert panel also anticipated that reducing external nutrient loads from both point and diffuse sources will succeed in the future.

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.

Oxygen potential of uranium--plutonium oxide as determined by controlled- atmosphere thermogravimetry

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

Swanson, Gerald C.

1975-10-01

The oxygen-to-metal atom ratio, or O/M, of solid solution uranium- plutonium oxide reactor fuel is a measure of the concentration of crystal defects in the oxide which affect many fuel properties, particularly, fuel oxygen potential. Fabrication of a high-temperature oxygen electrode, employing an electro-active tip of oxygen-deficient solid-state electrolyte, intended to confirm gaseous oxygen potentials is described. Uranium oxide and plutonium oxide O/M reference materials were prepared by in situ oxidation of high purity metals in the thermobalance. A solid solution uranium-plutonium oxide O/M reference material was prepared by alloying the uranium and plutonium metals in a yttrium oxide cruciblemore » at 1200°C and oxidizing with moist He at 250°C. The individual and solid solution oxides were isothermally equilibrated with controlled oxygen potentials between 800 and 1300°C and the equilibrated O/ M ratios calculated with corrections for impurities and buoyancy effects. Use of a reference oxygen potential of -100 kcal/mol to produce an O/M of 2.000 is confirmed by these results. However, because of the lengthy equilibration times required for all oxides, use of the O/M reference materials rather than a reference oxygen potential is recommended for O/M analysis methods calibrations.« less

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.

Nitrite oxidation in the Namibian oxygen minimum zone

PubMed Central

Füssel, Jessika; Lam, Phyllis; Lavik, Gaute; Jensen, Marlene M; Holtappels, Moritz; Günter, Marcel; Kuypers, Marcel MM

2012-01-01

Nitrite oxidation is the second step of nitrification. It is the primary source of oceanic nitrate, the predominant form of bioavailable nitrogen in the ocean. Despite its obvious importance, nitrite oxidation has rarely been investigated in marine settings. We determined nitrite oxidation rates directly in 15N-incubation experiments and compared the rates with those of nitrate reduction to nitrite, ammonia oxidation, anammox, denitrification, as well as dissimilatory nitrate/nitrite reduction to ammonium in the Namibian oxygen minimum zone (OMZ). Nitrite oxidation (⩽372 nM NO2− d−1) was detected throughout the OMZ even when in situ oxygen concentrations were low to non-detectable. Nitrite oxidation rates often exceeded ammonia oxidation rates, whereas nitrate reduction served as an alternative and significant source of nitrite. Nitrite oxidation and anammox co-occurred in these oxygen-deficient waters, suggesting that nitrite-oxidizing bacteria (NOB) likely compete with anammox bacteria for nitrite when substrate availability became low. Among all of the known NOB genera targeted via catalyzed reporter deposition fluorescence in situ hybridization, only Nitrospina and Nitrococcus were detectable in the Namibian OMZ samples investigated. These NOB were abundant throughout the OMZ and contributed up to ∼9% of total microbial community. Our combined results reveal that a considerable fraction of the recently recycled nitrogen or reduced NO3− was re-oxidized back to NO3− via nitrite oxidation, instead of being lost from the system through the anammox or denitrification pathways. PMID:22170426

Nitrite oxidation in the Namibian oxygen minimum zone.

PubMed

Füssel, Jessika; Lam, Phyllis; Lavik, Gaute; Jensen, Marlene M; Holtappels, Moritz; Günter, Marcel; Kuypers, Marcel M M

2012-06-01

Nitrite oxidation is the second step of nitrification. It is the primary source of oceanic nitrate, the predominant form of bioavailable nitrogen in the ocean. Despite its obvious importance, nitrite oxidation has rarely been investigated in marine settings. We determined nitrite oxidation rates directly in (15)N-incubation experiments and compared the rates with those of nitrate reduction to nitrite, ammonia oxidation, anammox, denitrification, as well as dissimilatory nitrate/nitrite reduction to ammonium in the Namibian oxygen minimum zone (OMZ). Nitrite oxidation (≤372 nM NO(2)(-) d(-1)) was detected throughout the OMZ even when in situ oxygen concentrations were low to non-detectable. Nitrite oxidation rates often exceeded ammonia oxidation rates, whereas nitrate reduction served as an alternative and significant source of nitrite. Nitrite oxidation and anammox co-occurred in these oxygen-deficient waters, suggesting that nitrite-oxidizing bacteria (NOB) likely compete with anammox bacteria for nitrite when substrate availability became low. Among all of the known NOB genera targeted via catalyzed reporter deposition fluorescence in situ hybridization, only Nitrospina and Nitrococcus were detectable in the Namibian OMZ samples investigated. These NOB were abundant throughout the OMZ and contributed up to ~9% of total microbial community. Our combined results reveal that a considerable fraction of the recently recycled nitrogen or reduced NO(3)(-) was re-oxidized back to NO(3)(-) via nitrite oxidation, instead of being lost from the system through the anammox or denitrification pathways.

Production of Oxygen from Lunar Regolith by Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Curreri, Peter A.

2009-01-01

This paper describes the use of the molten oxide electrolysis (MOE) process for the extraction of oxygen for life support and propellant, and silicon and metallic elements for use in fabrication on the Moon. The Moon is rich in mineral resources, but it is almost devoid of chemical reducing agents, therefore, molten oxide electrolysis is ideal for extraction, since the electron is the only practical reducing agent. MOE has several advantages over other extraction methods. First, electrolytic processing offers uncommon versatility in its insensitivity to feedstock composition. Secondly, oxide melts boast the twin key attributes of highest solubilizing capacity for regolith and lowest volatility of any candidate electrolytes. The former is critical in ensuring high productivity since cell current is limited by reactant solubility, while the latter simplifies cell design by obviating the need for a gas-tight reactor to contain evaporation losses as would be the case with a gas or liquid phase fluoride reagent operating at such high temperatures. Alternatively, MOE requires no import of consumable reagents (e.g. fluorine and carbon) as other processes do, and does not rely on interfacing multiple processes to obtain refined products. Electrolytic processing has the advantage of selectivity of reaction in the presence of a multi-component feed. Products from lunar regolith can be extracted in sequence according to the stabilities of their oxides as expressed by the values of the free energy of oxide formation (e.g. chromium, manganese, Fe, Si, Ti, Al, magnesium, and calcium). Previous work has demonstrated the viability of producing Fe and oxygen from oxide mixtures similar in composition to lunar regolith by molten oxide electrolysis (electrowinning), also called magma electrolysis having shown electrolytic extraction of Si from regolith simulant. This paper describes recent advances in demonstrating the MOE process by a joint project with participation by NASA KSC and

[The evaluation of selected oxidative stress parameters in patients with hyperthyroidism].

PubMed

Andryskowski, Grzegorz; Owczarek, Tomasz

2007-07-01

Hyperthyroidism induces the acceleration of the basic metabolism and increases cellular oxygen utilization, consequently intensifies reactive oxygen species production and disturbs the oxidant-antioxidant balance. The objective of this study was to evaluate the selected oxidative stress parameters in patients with hyperthyroidism by analysis of the reactive oxygen species neutralizing enzymes activity--superoxide dismutase (SOD), glutathione peroxidase (GSHPx) and catalase (CAT), the estimation of free radical processes intensity--concentration of malondialdehyde (MDA), sulfhydryl groups (SH) in proteins and by quantification of the serum total antioxidant status (TAS). . Twenty-seven patients treated for hyperthyroidism and 12 healthy individuals were enrolled in the study. Enzyme activity (SOD, GSHPx, CAT), MDA and concentration of SH groups were analysed in erythrocytes, while TAS was measured in serum. Patients with hyperthyroidism compared with healthy subjects were characterized by a higher GSHPx activity in erythrocytes, lower serum TAS, the lower content of SH groups in proteins and the lower MDA concentration in erythrocytes. Our results suggest that hyperthyroidism increases oxidative stress and disturbs oxidant-antioxidant balance in the body. Thyreostatic treatment, if not leads to whole metabolic compensation, may only reduce oxidant-antioxidant disorders, however is not able to eliminate them entirely.

Amphiphilic block copolymer membrane for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wang, Fei; Sylvia, James M.; Jacob, Monsy M.; Peramunage, Dharmasena

2013-11-01

An amphiphilic block copolymer comprised of hydrophobic polyaryletherketone (PAEK) and hydrophilic sulfonated polyaryletherketone (SPAEK) blocks has been synthesized and characterized. A membrane prepared from the block copolymer is used as the separator in a single cell vanadium redox flow battery (VRB). The proton conductivity, mechanical property, VO2+ permeability and single VRB cell performance of this block copolymer membrane are investigated and compared to Nafion™ 117. The block copolymer membrane showed significantly improved vanadium ion selectivity, higher mechanical strength and lower conductivity than Nafion™ 117. The VRB containing the block copolymer membrane exhibits higher coulombic efficiency and similar energy efficiency compared to a VRB using Nafion™ 117. The better vanadium ion selectivity of the block copolymer membrane has led to a much smaller capacity loss during 50 charge-discharge cycles for the VRB.

Oxygen concentrators performance with nitrous oxide at 50:50 volume.

PubMed

Moll, Jorge Ronaldo; Vieira, Joaquim Edson; Gozzani, Judymara Lauzi; Mathias, Lígia Andrade Silva Telles

2014-01-01

Few investigations have addressed the safety of oxygen from concentrators for use in anesthesia in association with nitrous oxide. This study evaluated the percent of oxygen from a concentrator in association with nitrous oxide in a semi-closed rebreathing circuit. Adult patients undergoing low risk surgery were randomly allocated into two groups, receiving a fresh gas flow of oxygen from concentrators (O293) or of oxygen from concentrators and nitrous oxide (O293N2O). The fraction of inspired oxygen and the percentage of oxygen from fresh gas flow were measured every 10 min. The ratio of FiO2/oxygen concentration delivered was compared at various time intervals and between the groups. Thirty patients were studied in each group. There was no difference in oxygen from concentrators over time for both groups, but there was a significant improvement in the FiO2 (p<0.001) for O293 group while a significant decline (p<0.001) for O293N2O. The FiO2/oxygen ratio varied in both groups, reaching a plateau in the O293 group. Pulse oximetry did not fall below 98.5% in either group. The FiO2 in the mixture of O293 and nitrous oxide fell during the observation period although oxygen saturation was higher than 98.5% throughout the study. Concentrators can be considered a stable source of oxygen for use during short anesthetic procedures, either pure or in association with nitrous oxide at 50:50 volume. Copyright © 2013 Sociedade Brasileira de Anestesiologia. Published by Elsevier Editora Ltda. All rights reserved.

Gradually Increased Oxygen Administration Improved Oxygenation and Mitigated Oxidative Stress after Resuscitation from Severe Hemorrhagic Shock.

PubMed

Luo, Xin; Yin, Yujing; You, Guoxing; Chen, Gan; Wang, Ying; Zhao, Jingxiang; Wang, Bo; Zhao, Lian; Zhou, Hong

2015-11-01

The optimal oxygen administration strategy during resuscitation from hemorrhagic shock (HS) is still controversial. Improving oxygenation and mitigating oxidative stress simultaneously seem to be contradictory goals. To maximize oxygen delivery while minimizing oxidative damage, the authors proposed the notion of gradually increased oxygen administration (GIOA), which entails making the arterial blood hypoxemic early in resuscitation and subsequently gradually increasing to hyperoxic, and compared its effects with normoxic resuscitation, hyperoxic resuscitation, and hypoxemic resuscitation in severe HS. Rats were subjected to HS, and on resuscitation, the rats were randomly assigned to four groups (n = 8): the normoxic, the hyperoxic, the hypoxemic, and the GIOA groups. Rats were observed for an additional 1 h. Hemodynamics, acid-base status, oxygenation, and oxidative injury were observed and evaluated. Central venous oxygen saturation promptly recovered only in the hyperoxic and the GIOA groups, and the liver tissue partial pressure of oxygen was highest in the GIOA group after resuscitation. Oxidative stress in GIOA group was significantly reduced compared with the hyperoxic group as indicated by the reduced malondialdehyde content, increased catalase activity, and the lower histologic injury scores in the liver. In addition, the tumor necrosis factor-α and interleukin-6 expressions in the liver were markedly decreased in the GIOA group than in the hyperoxic and normoxic groups as shown by the immunohistochemical staining. GIOA improved systemic/tissue oxygenation and mitigated oxidative stress simultaneously after resuscitation from severe HS. GIOA may be a promising strategy to improve resuscitation from HS and deserves further investigation.

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3.

PubMed

Lee, Sang Moon; Park, Kwang Hee; Kim, Sung Su; Kwon, Dong Wook; Hong, Sung Chang

2012-09-01

TiO2-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH3 with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn4+ displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO2 catalysts were important for the low-temperature SCR at 80-160 and 200-350 degrees C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO2 oxidation at low temperatures. Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO(x)). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO2 catalysts.

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.

Two Catalysts for Selective Oxidation of Contaminant Gases

NASA Technical Reports Server (NTRS)

Wright, John D.

2011-01-01

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to

Dynamics and Thermochemistry of Oxygen Uptake by a Mixed Ce-Pr Oxide

NASA Astrophysics Data System (ADS)

Sinev, M. Yu.; Fattakhova, Z. T.; Bychkov, V. Yu.; Lomonosov, V. I.; Gordienko, Yu. A.

2018-03-01

The dynamics of oxygen uptake by mixed Ce0.55Pr0.45O2-x oxide is studied in a pulsed oxygen supply mode using in situ high-temperature heat flow differential scanning calorimetry. It is stated that the oxidation proceeds in two regimes: a fast one at the beginning of the oxidation process, and a slow one, which is controlled by the diffusion of oxygen through the bulk of the solid at the later stages of the process. Analysis of the shape of calorimetric profiles reveals some processes, accompanied by heat release, that occur in the sample in the absence of oxygen in the gas phase. These could be due to both the redistribution of consumed oxygen in the oxide lattice and the lattice relaxation associated with the transformation of phases with different arrangements of oxygen vacancies in them. The heat effect (which diminishes from 60 to 40 kJ/mol in the course of oxygen uptake) associated with the oxidation of the reduced form of mixed Ce-Pr oxide, corresponds to the oxidation of praseodymium ions from (3+) to (4+).

Study of the long-term operation of a vanadium/oxygen fuel cell

NASA Astrophysics Data System (ADS)

Noack, Jens; Cognard, Gwenn; Oral, Meryem; Küttinger, Michael; Roznyatovskaya, Nataliya; Pinkwart, Karsten; Tübke, Jens

2016-09-01

A vanadium/oxygen fuel cell (VOFC) with a geometrically active area of 51 cm2 and two membranes was discontinuously operated over a period of over 676 h with 47 successive tests at room temperature with a current density of 19.6 mA/cm2 in order to investigate signs of ageing. As well as measuring cell voltages, the test setup was also used to measure anode and redox potentials as well as cell and half-cell impedances. The performance data of the VOFC fluctuated widely over the course of the test period, due to different V2+ concentrations and instabilities of the starting solutions on the one hand and complex changes in cathode conditions on the other. The desired behaviour of the anode reactions was achieved primarily through improved methods for producing the V2+ solutions, and remained stable at the end of the experiments. The kinetics of the cathode reactions were temporarily increased by purging with 2 M H2SO4, however their performance decreased over time. The VOFC had symptoms of ageing by complex and overlaid changes in the cathode's triple phase boundary layer and in the special conditions between the two electrodes and membranes.

Workshop on Oxygen in the Terrestrial Planets

NASA Technical Reports Server (NTRS)

2004-01-01

Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe

Functionalized Cobalt Triarylcorrole Covalently Bonded with Graphene Oxide: A Selective Catalyst for the Two- or Four-Electron Reduction of Oxygen.

PubMed

Tang, Jijun; Ou, Zhongping; Guo, Rui; Fang, Yuanyuan; Huang, Dong; Zhang, Jing; Zhang, Jiaoxia; Guo, Song; McFarland, Frederick M; Kadish, Karl M

2017-08-07

A cobalt triphenylcorrole (CorCo) was covalently bonded to graphene oxide (GO), and the resulting product, represented as GO-CorCo, was characterized by UV-vis, FT-IR, and micro-Raman spectroscopy as well as by HRTEM, TGA, XRD, XPS, and AFM. The electrocatalytic activity of GO-CorCo toward the oxygen reduction reaction (ORR) was then examined in air-saturated 0.1 M KOH and 0.5 M H 2 SO 4 solutions by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and/or a rotating ring-disk electrode. An overall 4-electron reduction of O 2 is obtained in alkaline media while under acidic conditions a 2-electron process is seen. The ORR results thus indicate that covalently bonded GO-CoCor can be used as a selective catalyst for either the 2- or 4-electron reduction of oxygen, the prevailing reaction depending upon the acidity of the solution.

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

Sequential extraction of chromium, molybdenum, and vanadium in basic oxygen furnace slags.

PubMed

Spanka, Marina; Mansfeldt, Tim; Bialucha, Ruth

2018-06-02

Basic oxygen furnace slags (BOS) are by-products of basic oxygen steel production. Whereas the solubility of some elements from these slags has been well investigated, information about the mineralogy and related leaching, i.e., availability of the environmentally relevant elements chromium (Cr), molybdenum (Mo), and vanadium (V), is still lacking. The aim of this study was to investigate these issues with a modified, four-fraction-based, sequential extraction procedure (F1-F4), combined with X-ray diffraction, of two BOS. Extractants with increasing strength were used (F1 demineralized water, F2 CH 3 COOH + HCl, F3 Na 2 EDTA + NH 2 OH·HCl, and F4 HF + HNO 3 + H 2 O 2 ), and after each fraction, X-ray diffraction was performed. The recovery of Cr was moderate (66.5%) for one BOS, but significantly better (100.2%) for the other one. High recoveries were achieved for the other elements (Mo, 100.8-107.9% and V, 112.6-87.0%), indicating that the sequential extraction procedure was reliable when adapted to BOS. The results showed that Cr and Mo primarily occurred in F4, representing rather immobile elements under natural conditions, which were strongly bound into/onto Fe minerals (srebrodolskite, magnetite, hematite, or wustite). In contrast, V was more mobile with proportional higher findings in F2 and F3, and the X-ray diffraction results reveal that V was not solely bound into Ca minerals (larnite, hatrurite, kirschsteinite, and calcite), but also bound to Fe minerals. The results indicated that the total amount of recovery was a poor indicator of the availability of elements and did not correspond to the leaching of elements from BOS.

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.

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

In situ electrical resistivity measurements of vanadium thin films performed in vacuum during different annealing cycles

NASA Astrophysics Data System (ADS)

Pedrosa, Paulo; Cote, Jean-Marc; Martin, Nicolas; Arab Pour Yazdi, Mohammad; Billard, Alain

2017-02-01

The present study describes a sputtering and in situ vacuum electrical resistivity setup that allows a more efficient sputtering-oxidation coupling process for the fabrication of oxide compounds like vanadium dioxide, VO2. After the sputtering deposition of pure V thin films, the proposed setup enables the sample holder to be transferred from the sputtering to the in situ annealing + resistivity chamber without venting the whole system. The thermal oxidation of the V films was studied by implementing two different temperature cycles up to 550 °C, both in air (using a different resistivity setup) and vacuum conditions. Main results show that the proposed system is able to accurately follow the different temperature setpoints, presenting clean and low-noise resistivity curves. Furthermore, it is possible to identify the formation of different vanadium oxide phases in air, taking into account the distinct temperature cycles used. The metallic-like electrical properties of the annealed coatings are maintained in vacuum whereas those heated in air produce a vanadium oxide phase mixture.

In situ electrical resistivity measurements of vanadium thin films performed in vacuum during different annealing cycles.

PubMed

Pedrosa, Paulo; Cote, Jean-Marc; Martin, Nicolas; Arab Pour Yazdi, Mohammad; Billard, Alain

2017-02-01

The present study describes a sputtering and in situ vacuum electrical resistivity setup that allows a more efficient sputtering-oxidation coupling process for the fabrication of oxide compounds like vanadium dioxide, VO 2 . After the sputtering deposition of pure V thin films, the proposed setup enables the sample holder to be transferred from the sputtering to the in situ annealing + resistivity chamber without venting the whole system. The thermal oxidation of the V films was studied by implementing two different temperature cycles up to 550 °C, both in air (using a different resistivity setup) and vacuum conditions. Main results show that the proposed system is able to accurately follow the different temperature setpoints, presenting clean and low-noise resistivity curves. Furthermore, it is possible to identify the formation of different vanadium oxide phases in air, taking into account the distinct temperature cycles used. The metallic-like electrical properties of the annealed coatings are maintained in vacuum whereas those heated in air produce a vanadium oxide phase mixture.

Polyimides Containing Fluorine and Phosphorus for Potential Space Applications

NASA Technical Reports Server (NTRS)

Connell, John W.; Watson, Kent A.

2000-01-01

As part of an effort to develop low color, ultraviolet (UV) radiation and atomic oxygen resistant polyimides for potential space applications, a novel diamine containing fluorine and phosphorus was synthesized and used to prepare polyimides. The approach was to combine attributes from colorless, UV resistant polyimides and atomic oxygen (AO) resistant polymers into a single material. Preparation of colorless polyimides has focused on minimization of charge transfer complex formation by incorporation of bulky substituents and disrupting conjugation by using meta-catenated monomers. AO resistant polymer technology development has focused on placing phenylphosphine oxide groups into the backbone of aromatic polymers. However, polyimides prepared utilizing this approach thus far have all exhibited significant color. Thus in an attempt to combine these features in a polyimide a new diamine, bis(3-aminophenyl)-3,5-di(trifluoromethyl)phenylphosphine oxide (TFMDA) was synthesized and used to prepare polyimides. The polyimides were cast into films and characterized for physical and mechanical properties, optical transmission and AO and UV resistance.

Utilization of Glyphosate as Phosphate Source: Biochemistry and Genetics of Bacterial Carbon-Phosphorus Lyase

PubMed Central

Zechel, David L.; Jochimsen, Bjarne

2014-01-01

SUMMARY After several decades of use of glyphosate, the active ingredient in weed killers such as Roundup, in fields, forests, and gardens, the biochemical pathway of transformation of glyphosate phosphorus to a useful phosphorus source for microorganisms has been disclosed. Glyphosate is a member of a large group of chemicals, phosphonic acids or phosphonates, which are characterized by a carbon-phosphorus bond. This is in contrast to the general phosphorus compounds utilized and metabolized by microorganisms. Here phosphorus is found as phosphoric acid or phosphate ion, phosphoric acid esters, or phosphoric acid anhydrides. The latter compounds contain phosphorus that is bound only to oxygen. Hydrolytic, oxidative, and radical-based mechanisms for carbon-phosphorus bond cleavage have been described. This review deals with the radical-based mechanism employed by the carbon-phosphorus lyase of the carbon-phosphorus lyase pathway, which involves reactions for activation of phosphonate, carbon-phosphorus bond cleavage, and further chemical transformation before a useful phosphate ion is generated in a series of seven or eight enzyme-catalyzed reactions. The phn genes, encoding the enzymes for this pathway, are widespread among bacterial species. The processes are described with emphasis on glyphosate as a substrate. Additionally, the catabolism of glyphosate is intimately connected with that of aminomethylphosphonate, which is also treated in this review. Results of physiological and genetic analyses are combined with those of bioinformatics analyses. PMID:24600043

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.

Dual-triggered oxygen self-supply black phosphorus nanosystem for enhanced photodynamic therapy.

PubMed

Liu, Jintong; Du, Ping; Mao, Hui; Zhang, Lei; Ju, Huangxian; Lei, Jianping

2018-07-01

Nonspecific distribution of photosensitizer and the intrinsic hypoxic condition in the tumor microenvironment are two key factors limiting the efficacy of O 2 -dependent photodynamic therapy (PDT). Herein, a dual-triggered oxygen self-supported nanosystem using black phosphorus nanosheet (BPNS) as both photosensitizer and nanocarrier was developed to enhance PDT for tumors within hypoxic microenvironment. The BPNS platform was functionalized with folate and a blocker DNA duplex of 5'-Cy5-aptamer-heme/3'-heme labeled oligonucleotides. The resulting heme dimer could passivate its peroxidase activity. After specific recognition of aptamer-target, the quenched fluorescence is "turned" on by cellular adenosine triphosphate. The passivated nanosystem then activates the catalytic function towards excessive intracellular H 2 O 2 to generate O 2 essential to sustain BPNS-mediated PDT, leading to 8.7-fold and 7.5-fold increase of PDT efficacy in treating the hypoxic cell and tumor, respectively. Therefore, the dual-triggered oxygen self-supply nanosystem not only exerts tumor microenvironment-associated stimulus for enhanced PDT but also surmounts hypoxia-associated therapy resistance. Copyright © 2018 Elsevier Ltd. All rights reserved.

Selective C(sp3 )-H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow.

PubMed

Laudadio, Gabriele; Govaerts, Sebastian; Wang, Ying; Ravelli, Davide; Koolman, Hannes F; Fagnoni, Maurizio; Djuric, Stevan W; Noël, Timothy

2018-04-03

A mild and selective C(sp 3 )-H aerobic oxidation enabled by decatungstate photocatalysis has been developed. The reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture. Our method allows for the oxidation of both activated and unactivated C-H bonds (30 examples). The ability to selectively oxidize natural scaffolds, such as (-)-ambroxide, pregnenolone acetate, (+)-sclareolide, and artemisinin, exemplifies the utility of this new method. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Oxygen-producing inert anodes for SOM process

DOEpatents

Pal, Uday B

2014-02-25

An electrolysis system for generating a metal and molecular oxygen includes a container for receiving a metal oxide containing a metallic species to be extracted, a cathode positioned to contact a metal oxide housed within the container; an oxygen-ion-conducting membrane positioned to contact a metal oxide housed within the container; an anode in contact with the oxygen-ion-conducting membrane and spaced apart from a metal oxide housed within the container, said anode selected from the group consisting of liquid metal silver, oxygen stable electronic oxides, oxygen stable crucible cermets, and stabilized zirconia composites with oxygen stable electronic oxides.

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.

Effects of sustained-release composite on the oxygen levels and sediment phosphorus fractions of an urban river in Shanghai.

PubMed

Li, Yang; Zhou, Yanbo; Zhou, Zhenhua; Wang, Ningsheng; Zhou, Qiang; Wang, Fuchen

2014-01-01

The eutrophication of many rivers and lakes is attributed to the anoxia and the increasing internal loading of nutrients from sediment. A novel sustained-release composite (SRC) synthesis of stearic acid and calcium peroxide (CaO2) was applied to supply a water body with oxygen endured in this study. The influences of SRC on the dissolved oxygen (DO) level, pH and total phosphorus (TP) of an urban river in Shanghai were studied. The results show that SRC has a longer oxygen-releasing cycle and a more tender effect on pH with the comparison of CaO2 powder. Reduction of 79.6% in the concentration of TP was observed in the water column. After 35 days of SRC addition, there was a significant positive correlation between TP and DO. As a consequence, the phosphorus fractions in sediment, including loosely sorbed P (NH4Cl-P), redox-sensitive P (Fe-P), calcium bound P (Ca-P), aluminium bound P (Al-P) and residual P (organic and refractory P) were affected by the addition of SRC. The NH4Cl-P and Fe-P fractions in the sediment that could release P easily were well constrained under the positive effect of SRC.

Resuscitation with supplementary oxygen induces oxidative injury in the cerebral cortex.

PubMed

Solberg, Rønnaug; Longini, Mariangela; Proietti, Fabrizio; Vezzosi, Piero; Saugstad, Ola Didrik; Buonocore, Giuseppe

2012-09-01

Isoprostanes, neuroprostanes, isofurans, and neurofurans have all become attractive biomarkers of oxidative damage and lipid peroxidation in brain tissue. Asphyxia and subsequent reoxygenation cause a burst of oxygen free radicals. Isoprostanes and isofurans are generated by free radical attacks of esterified arachidonic acid. Neuroprostanes and neurofurans are derived from the peroxidation of docosahexanoic acid, which is abundant in neurons and could therefore more selectively represent oxidative brain injury. Newborn piglets (age 12-36 h) underwent hypoxia until the base excess reached -20 mmol/L or the mean arterial blood pressure dropped below 15 mm Hg. They were randomly assigned to receive resuscitation with 21, 40, or 100% oxygen for 30 min and then ventilation with air. The levels of isoprostanes, isofurans, neuroprostanes, and neurofurans were determined in brain tissue (ng/g) isolated from the prefrontal cortex using gas chromatography-mass spectrometry (GC/MS) with negative ion chemical ionization (NICI) techniques. A control group underwent the same procedures and observations but was not submitted to hypoxia or hyperoxia. Hypoxia and reoxygenation significantly increased the levels of isoprostanes, isofurans, neuroprostanes, and neurofurans in the cerebral cortex. Nine hours after resuscitation with 100% oxygen for 30 min, there was nearly a 4-fold increase in the levels of isoprostanes and isofurans compared to the control group (P=0.007 and P=0.001) and more than a 2-fold increase in neuroprostane levels (P=0.002). The levels of neuroprostanes and neurofurans were significantly higher in the piglets that were resuscitated with supplementary oxygen (40 and 100%) compared to the group treated with air (21%). The significance levels of the observed differences in neuroprostanes for the 21% vs 40% comparison and the 21% vs 100% comparison were P<0.001 and P=0.001, respectively. For neurofurans, the P values of the 21% vs 40% comparison and the 21% vs

Vanadium Respiration by Geobacter metallireducens: Novel Strategy for In Situ Removal of Vanadium from Groundwater

PubMed Central

Ortiz-Bernad, Irene; Anderson, Robert T.; Vrionis, Helen A.; Lovley, Derek R.

2004-01-01

Vanadium can be an important contaminant in groundwaters impacted by mining activities. In order to determine if microorganisms of the Geobacteraceae, the predominant dissimilatory metal reducers in many subsurface environments, were capable of reducing vanadium(V), Geobacter metallireducens was inoculated into a medium in which acetate was the electron donor and vanadium(V) was the sole electron acceptor. Reduction of vanadium(V) resulted in the production of vanadium(IV), which subsequently precipitated. Reduction of vanadium(V) was associated with cell growth with a generation time of 15 h. No vanadium(V) was reduced and no precipitate was formed in heat-killed or abiotic controls. Acetate was the most effective of all the electron donors evaluated. When acetate was injected into the subsurface to enhance the growth and activity of Geobacteraceae in an aquifer contaminated with uranium and vanadium, vanadium was removed from the groundwater even more effectively than uranium. These studies demonstrate that G. metallireducens can grow via vanadium(V) respiration and that stimulating the activity of Geobacteraceae, and hence vanadium(V) reduction, can be an effective strategy for in situ immobilization of vanadium in contaminated subsurface environments. PMID:15128571

Lithium Metal-Copper Vanadium Oxide Battery with a Block Copolymer Electrolyte

DOE PAGES

Devaux, Didier; Wang, Xiaoya; Thelen, Jacob L.; ...

2016-09-08

Lithium (Li) batteries comprising multivalent positive active materials such as copper vanadium oxide have high theoretical capacity. These batteries with a conventional liquid electrolyte exhibit limited cycle life because of copper dissolution into the electrolyte. In this paper, we report here on the characterization of solid-state Li metal batteries with a positive electrode based on α-Cu 6.9V 6O 18.9 (α-CuVO 3). We replaced the liquid electrolyte by a nanostructured solid block copolymer electrolyte comprising of a mixture of polystyrene-b-poly(ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. In situ X-ray diffraction was used to follow the Li insertion/de-insertion mechanism into themore » α-CuVO 3 host material and its reversibility. In situ X-ray scattering revealed that the multistep electrochemical reactions involved are similar in the presence of liquid or solid electrolyte. The capacity fade of the solid-state batteries is less rapid than that of α-CuVO 3–Li metal batteries with a conventional liquid electrolyte. Hard X-ray microtomography revealed that upon cycling, voids and Cu-rich agglomerates were formed at the interface between the Li metal and the SEO electrolyte. Finally, the void volume and the volume occupied by the Cu-rich agglomerates were independent of C-rate and cycle number.« less

[Effects of selective cutting on soil phosphorus forms and availability in Korean pine broad-leaved forest in Xiaoxing'an Mountains of China.

PubMed

Zhang, Xin; Gu, Hui Yan; Chen, Xiang Wei

2018-02-01

In order to clarify the effects of selective cutting on soil phosphorus availability in Korean pine broad-leaved forest, surface soil (0-10 cm) samples from original Korean pine broad-leaved forest and natural forests with mild, medium and intensive cutting disturbances were collected. The Sui modified Hedley phosphorus fractionation method was used to continuously extract soil samples and analyzed the differences and changes of soil phosphorus fractions from different experimental stands. The results showed that the soil total phosphorus content of Korean pine broad-leaved forest varied from 1.09 to 1.66 g·kg -1 , with the original stand and intensive cutting disturbance stand being the maximum and minimum one, respectively. The differences of soil total phosphorus content among cutting disturbance levels were significant. The Olsen phosphorus and phosphorus activation coefficients changed with an amplitude of 7.26-17.79 mg·kg -1 and 0.67%-1.07%, respectively. Both of them significantly decreased with the increase of selective cutting disturbance level. The concentrations of all P fractions except HCl-P o , i.e., H 2 O-P i , NaHCO 3 -P, NaOH-P, HCl-P i , Residual-P, decreased with increasing cutting disturbance levels compared with original forest. The correlation coefficient between H 2 O-P i and soil Olsen phosphorus was the highest (0.98), though it only accounted for 1.5%-2.2% of the total phosphorus. NaOH-P content contributed to more than 48.0% of the total phosphorus, acknowledged as the potential source of soil phosphorus. In conclusion, selective cutting disturbance could constrain phosphorus storage and soil phosphorus availabi-lity of the Korean pine broad-leaved forests by significantly reducing the content of soil inorganic phosphorus and NaOH-P o , and such trends were positively dependent on the intensity of selective cutting.

Effect of oxygen partial pressure on oxidation of Mo-metal

NASA Astrophysics Data System (ADS)

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

2018-05-01

This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

Selective C(sp3)−H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow

PubMed Central

Laudadio, Gabriele; Govaerts, Sebastian; Wang, Ying; Ravelli, Davide; Koolman, Hannes F.; Fagnoni, Maurizio; Djuric, Stevan W.

2018-01-01

Abstract A mild and selective C(sp3)−H aerobic oxidation enabled by decatungstate photocatalysis has been developed. The reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture. Our method allows for the oxidation of both activated and unactivated C−H bonds (30 examples). The ability to selectively oxidize natural scaffolds, such as (−)‐ambroxide, pregnenolone acetate, (+)‐sclareolide, and artemisinin, exemplifies the utility of this new method. PMID:29451725

USE OF OXYGEN-18 ISOTOPE LABELING FOR MEASUREMENT OF OXIDATIVE STRESS

EPA Science Inventory

Oxygen-18 (18-O) labeling provides a sensitive means for quantifying oxygen
binding that occurs during in vivo oxidations. Oxidants (ozone, nitrogen
oxides, hydrogen peroxide, etc.) are first synthesized using 18-O, then cells
or tissues are exposed to the labeled ...

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.

Metal-insulator and charge ordering transitions in oxide nanostructures

NASA Astrophysics Data System (ADS)

Singh, Sujay Kumar

. 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.

Near-Infrared Phosphorus-Substituted Rhodamine with Emission Wavelength above 700 nm for Bioimaging.

PubMed

Chai, Xiaoyun; Cui, Xiaoyan; Wang, Baogang; Yang, Fan; Cai, Yi; Wu, Qiuye; Wang, Ting

2015-11-16

Phosphorus has been successfully fused into a classic rhodamine framework, in which it replaces the bridging oxygen atom to give a series of phosphorus-substituted rhodamines (PRs). Because of the electron-accepting properties of the phosphorus moiety, which is due to effective σ*-π* interactions and strengthened by the inductivity of phosphine oxide, PR exhibits extraordinary long-wavelength fluorescence emission, elongating to the region above 700 nm, with bathochromic shifts of 140 and 40 nm relative to rhodamine and silicon-substituted rhodamine, respectively. Other advantageous properties of the rhodamine family, including high molar extinction coefficient, considerable quantum efficiency, high water solubility, pH-independent emission, great tolerance to photobleaching, and low cytotoxicity, stay intact in PR. Given these excellent properties, PR is desirable for NIR-fluorescence imaging in vivo. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Total Phosphorus Loads for Selected Tributaries to Sebago Lake, Maine

USGS Publications Warehouse

Hodgkins, Glenn A.

2001-01-01

The streamflow and water-quality datacollection networks of the Portland Water District (PWD) and the U.S. Geological Survey (USGS) as of February 2000 were analyzed in terms of their applicability for estimating total phosphorus loads for selected tributaries to Sebago Lake in southern Maine. The long-term unit-area mean annual flows for the Songo River and for small, ungaged tributaries are similar to the long-term unit-area mean annual flows for the Crooked River and other gaged tributaries to Sebago Lake, based on a regression equation that estimates mean annual streamflows in Maine. Unit-area peak streamflows of Sebago Lake tributaries can be quite different, based on a regression equation that estimates peak streamflows for Maine. Crooked River had a statistically significant positive relation (Kendall's Tau test, p=0.0004) between streamflow and total phosphorus concentration. Panther Run had a statistically significant negative relation (p=0.0015). Significant positive relations may indicate contributions from nonpoint sources or sediment resuspension, whereas significant negative relations may indicate dilution of point sources. Total phosphorus concentrations were significantly larger in the Crooked River than in the Songo River (Wilcoxon rank-sum test, p<0.0001). Evidence was insufficient, however, to indicate that phosphorus concentrations from medium-sized drainage basins, at a significance level of 0.05, were different from each other or that concentrations in small-sized drainage basins were different from each other (Kruskal-Wallis test, p= 0.0980, 0.1265). All large- and medium-sized drainage basins were sampled for total phosphorus approximately monthly. Although not all small drainage basins were sampled, they may be well represented by the small drainage basins that were sampled. If the tributaries gaged by PWD had adequate streamflow data, the current PWD tributary monitoring program would probably produce total phosphorus loading data that

Observation of oxide particles below the apparent oxygen solubility limit in tantalum

NASA Technical Reports Server (NTRS)

Stecura, S.

1973-01-01

The apparent solubility of oxygen in polycrystalline tantalum as determined by the X-ray diffraction lattice parameter technique is about 1.63 atomic percent at 820 C. However, oxide particles were identified in samples containing as low as 0.5 atomic percent of oxygen. These oxide particles were present at the grain boundaries and within the grains. The number of oxide particles increased with increasing oxygen concentration in tantalum. The presence of oxide particles suggests that the true solubility of oxygen in the polycrystalline tantalum metal is probably significantly lower than that reported in the literature.

Apparent phosphorus availabilities of selected traditional and alternative feedstuffs for channel catfish

USDA-ARS?s Scientific Manuscript database

A digestibility trial with channel catfish Ictalurus punctatus was conducted to determine apparent availability coefficients (AACs) of phosphorus for selected common feedstuffs: soybean meal, cottonseed meal, wheat middlings, corn gluten feed (CGF), and corn distillers dried grains with solubles (DD...

Atomic scale observation of oxygen delivery during silver–oxygen nanoparticle catalysed oxidation of carbon nanotubes

PubMed Central

Yue, Yonghai; Yuchi, Datong; Guan, Pengfei; Xu, Jia; Guo, Lin; Liu, Jingyue

2016-01-01

To probe the nature of metal-catalysed processes and to design better metal-based catalysts, atomic scale understanding of catalytic processes is highly desirable. Here we use aberration-corrected environmental transmission electron microscopy to investigate the atomic scale processes of silver-based nanoparticles, which catalyse the oxidation of multi-wall carbon nanotubes. A direct semi-quantitative estimate of the oxidized carbon atoms by silver-based nanoparticles is achieved. A mechanism similar to the Mars–van Krevelen process is invoked to explain the catalytic oxidation process. Theoretical calculations, together with the experimental data, suggest that the oxygen molecules dissociate on the surface of silver nanoparticles and diffuse through the silver nanoparticles to reach the silver/carbon interfaces and subsequently oxidize the carbon. The lattice distortion caused by oxygen concentration gradient within the silver nanoparticles provides the direct evidence for oxygen diffusion. Such direct observation of atomic scale dynamics provides an important general methodology for investigations of catalytic processes. PMID:27406595

Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

PubMed

Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

2017-07-01

Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO 3 , SrTiO 3 , and BaTiO 3 , together with reference oxides, MgO, CaO, SrO, BaO, and TiO 2 , were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

NASA Technical Reports Server (NTRS)

Opila, E. J.; Serra, J. L.

2007-01-01

T-300 carbon fibers and T-300 carbon fiber reinforced silicon carbide composites (C/SiC) were oxidized in flowing reduced oxygen partial pressure environments at a total pressure of one atmosphere (0.5 atm O2, 0.05 atm O2 and 0.005 atm O2, balance argon). Experiments were conducted at four temperatures (816deg, 1149deg, 1343deg, and 1538 C). The oxidation kinetics were monitored using thermogravimetric analysis. T-300 fibers were oxidized to completion for times between 0.6 and 90 h. Results indicated that fiber oxidation kinetics were gas phase diffusion controlled. Oxidation rates had an oxygen partial pressure dependence with a power law exponent close to one. In addition, oxidation rates were only weakly dependent on temperature. The C/SiC coupon oxidation kinetics showed some variability, attributed to differences in the number and width of cracks in the SiC seal coat. In general, weight losses were observed indicating oxidation of the carbon fibers dominated the oxidation behavior. Low temperatures and high oxygen pressures resulted in the most rapid consumption of the carbon fibers. At higher temperatures, the lower oxidation rates were primarily attributed to crack closure due to SiC thermal expansion, rather than oxidation of SiC since these reduced rates were observed even at the lowest oxygen partial pressures where SiC oxidation is minimal.

Phase transition kinetics in DIET of vanadium pentoxide. I. Experimental results

NASA Astrophysics Data System (ADS)

Ai, R.; Fan, H.-J.; Marks, L. D.

1993-01-01

Experimental results of the kinetics of phase transformation in vanadium pentoxide during surface loss of oxygen from electron irradiation are described. Phase transformations under three different regimes were examined: (a) low flux; (b) intermediate flux and (c) high flux. Different phase transformation routes were observed under different fluxes. In a companion paper, numerical calculations are presented demonstrating that these results are due to a mixed interface/diffusion controlled phase transition pumped by surface oxygen loss.

Vanadium(III)-l-cysteine enhances the sensitivity of murine breast adenocarcinoma cells to cyclophosphamide by promoting apoptosis and blocking angiogenesis.

PubMed

Basu, Abhishek; Bhattacharjee, Arin; Baral, Rathindranath; Biswas, Jaydip; Samanta, Amalesh; Bhattacharya, Sudin

2017-05-01

Various epidemiological and preclinical studies have already established the cancer chemopreventive potential of vanadium-based compounds. In addition to its preventive efficacy, studies have also indicated the abilities of vanadium-based compounds to induce cell death selectively toward malignant cells. Therefore, the objective of the present investigation is to improve the therapeutic efficacy and toxicity profile of an alkylating agent, cyclophosphamide, by the concurrent use of an organovanadium complex, vanadium(III)-l-cysteine. In this study, vanadium(III)-l-cysteine (1 mg/kg body weight, per os) was administered alone as well as in combination with cyclophosphamide (25 mg/kg body weight, intraperitoneal) in concomitant and pretreatment schedule in mice bearing breast adenocarcinoma cells. The results showed that the combination treatment significantly decreased the tumor burden and enhanced survivability of tumor-bearing mice through generation of reactive oxygen species in tumor cells. These ultimately led to DNA damage, depolarization of mitochondrial membrane potential, and apoptosis in tumor cells. Further insight into the molecular pathway disclosed that the combination treatment caused upregulation of p53 and Bax and suppression of Bcl-2 followed by the activation of caspase cascade and poly (ADP-ribose) polymerase cleavage. Administration of vanadium(III)-l-cysteine also resulted in significant attenuation of peritoneal vasculature and sprouting of the blood vessels by decreasing the levels of vascular endothelial growth factor A and matrix metalloproteinase 9 in the ascites fluid of tumor-bearing mice. Furthermore, vanadium(III)-l-cysteine significantly attenuated cyclophosphamide-induced hematopoietic, hepatic, and genetic damages and provided additional survival advantages. Hence, this study suggested that vanadium(III)-l-cysteine may offer potential therapeutic benefit in combination with cyclophosphamide by augmenting anticancer efficacy and

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

Leaching characteristics of vanadium in mine tailings and soils near a vanadium titanomagnetite mining site.

PubMed

Yang, Jinyan; Tang, Ya; Yang, Kai; Rouff, Ashaki A; Elzinga, Evert J; Huang, Jen-How

2014-01-15

A series of column leaching experiments were performed to understand the leaching behaviour and the potential environmental risk of vanadium in a Panzhihua soil and vanadium titanomagnetite mine tailings. Results from sequential extraction experiments indicated that the mobility of vanadium in both the soil and the mine tailings was low, with <1% of the total vanadium readily mobilised. Column experiments revealed that only <0.1% of vanadium in the soil and mine tailing was leachable. The vanadium concentrations in the soil leachates did not vary considerably, but decreased with the leachate volume in the mine tailing leachates. This suggests that there was a smaller pool of leachable vanadium in the mine tailings compared to that in the soil. Drought and rewetting increased the vanadium concentrations in the soil and mine tailing leachates from 20μgL(-1) to 50-90μgL(-1), indicating the potential for high vanadium release following periods of drought. Experiments with soil columns overlain with 4, 8 and 20% volume mine tailings/volume soil exhibited very similar vanadium leaching behaviour. These results suggest that the transport of vanadium to the subsurface is controlled primarily by the leaching processes occurring in soils. Copyright © 2013 Elsevier B.V. All rights reserved.

Elucidating anionic oxygen activity in lithium-rich layered oxides

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

Xu, Jing; Sun, Meiling; Qiao, Ruimin

Recent research has explored combining conventional transition metal redox with anionic lattice oxygen redox as a new and exciting direction to search for high-capacity lithium-ion cathodes. For this study, we probe the poorly understood electrochemical activity of anionic oxygen from a material perspective by elucidating the effect of the transition metal on oxygen redox activity. We study two lithium-rich layered oxides, specifically lithium nickel metal oxides where metal is either manganese or ruthenium, which possess similar structure and discharge characteristics, but exhibit distinctly different charge profiles. By combining X-ray spectroscopy with operando differential electrochemical mass spectrometry, we reveal completely differentmore » oxygen redox activity in each material, likely resulting from the different interaction between the lattice oxygen and transition metals. This work provides additional insights into the complex mechanism of oxygen redox and development of advanced high-capacity lithium-ion cathodes.« less

Elucidating anionic oxygen activity in lithium-rich layered oxides

DOE PAGES

Xu, Jing; Sun, Meiling; Qiao, Ruimin; ...

2018-03-05

Recent research has explored combining conventional transition metal redox with anionic lattice oxygen redox as a new and exciting direction to search for high-capacity lithium-ion cathodes. For this study, we probe the poorly understood electrochemical activity of anionic oxygen from a material perspective by elucidating the effect of the transition metal on oxygen redox activity. We study two lithium-rich layered oxides, specifically lithium nickel metal oxides where metal is either manganese or ruthenium, which possess similar structure and discharge characteristics, but exhibit distinctly different charge profiles. By combining X-ray spectroscopy with operando differential electrochemical mass spectrometry, we reveal completely differentmore » oxygen redox activity in each material, likely resulting from the different interaction between the lattice oxygen and transition metals. This work provides additional insights into the complex mechanism of oxygen redox and development of advanced high-capacity lithium-ion cathodes.« less

Phosphorus-supported ligands for the assembly of multimetal architectures.

PubMed

Chandrasekhar, Vadapalli; Murugesapandian, Balasubramanian

2009-08-18

perfectly linear manner in many cases. Incorporating an additional methoxy group into LH(3) affords the ligand (S)P[N(Me)N=CH-C(6)H(3)-2-OH-3-OMe](3) (L'H(3)), which contains nine coordination sites: three imino nitrogen atoms, three phenolate oxygen atoms, and three methoxy oxygen atoms. The reaction of L'H(3) with transition metal salts in 1:1 ratio leads to the in situ formation of a metalloligand (L'M), which on further treatment with lanthanide salts gives heterobimetallic trinuclear cationic complexes [L'(2)M(2)Ln](+) containing a M-Ln-M linear array (M = transition metal ion in a +2 oxidation state). Many of these 3d-4f compounds behave as single-molecule magnets at low temperatures. Although challenges remain in the development of synthetic methods and in the architectural control of the coordination platforms, we see opportunities for further research into coordination platforms supported by main group elements such as phosphorus. As we have shown in this Account, one potential disadvantage, sensitivity of P-N bonds to hydrolysis, can be used successfully to build larger assemblies.

Exploring Oxidative Reactions in Hemoglobin Variants Using Mass Spectrometry: Lessons for Engineering Oxidatively Stable Oxygen Therapeutics

PubMed Central

Strader, Michael Brad

2017-01-01

Abstract Significance: Worldwide demand has driven the development of hemoglobin (Hb)-based oxygen carriers (HBOCs) as potential acellular oxygen therapeutics. HBOCs have the potential to provide an oxygen bridge to patients and minimize current problems associated with supply and storage of donated blood. However, to date, safety and efficacy issues have hampered the approval of viable HBOCs in the United States. These previous efforts have underscored the need for a better molecular understanding of toxicity to design safe and oxidatively stable HBOCs. Recent Advances: High-resolution accurate mass (HRAM) mass spectrometry (MS) has recently become a versatile tool in characterizing oxidative post-translational modifications that occur in Hb. When integrated with other analytical techniques, HRAM data have been invaluable in providing mechanistic insight into the extent of oxidative modification by quantifying oxidation in amino acids near the reactive heme or at specific “oxidative hotspots.” Critical Issues: In addition to providing a deeper understanding of Hb oxidative toxicity, HRAM MS studies are currently being used toward developing suitable HBOCs using a “two-prong” strategy that involves (i) understanding the mechanism of Hb toxicity by evaluating mutant Hbs identified in patients with hemoglobinopathies and (ii) utilizing this information toward designing against (or for) these reactions in acellular oxygen therapeutics that will result in oxidatively stable protein. Future Directions: Future HRAM studies are aimed at fully characterizing engineered candidate HBOCs to determine the most oxidatively stable protein while retaining oxygen carrying function in vivo. Antioxid. Redox Signal. 26, 777–793. PMID:27626360

Ferrous Analysis.

ERIC Educational Resources Information Center

Straub, William A.

1989-01-01

Elements covered in this review include: aluminum, antimony, arsenic, bismuth, boron, calcium, carbon, chromium, cobalt, copper, hydrogen, iron, lead, magnesium, manganese, molybdenum, nickel, niobium, nitrogen, oxygen, phosphorus, platinum, rare earths, silicons, sulfur, tin, titanium, tungsten, vanadium, zinc, and zirconium. Analytical methods…

Planktonic Marine Iron-Oxidizers Drive Iron(III) Mineralization Under Low Oxygen Conditions

NASA Astrophysics Data System (ADS)

Luther, G. W., III; Field, E.; Findlay, A.; MacDonald, D. J.; Chan, C. S. Y.; Kato, S.

2016-02-01

Observations of modern microbes have led to several hypotheses on how microbes precipitated the extensive banded iron formations in the geologic record, but we have yet to resolve the exact microbial contributions. An initial hypotheses was that cyanobacteria produced oxygen that oxidized iron(II) abiotically; however, in modern environments such as microbial mats, where Fe(II) and O2 coexist, we commonly find microaerophilic chemolithotrophic iron(II)-oxidizing bacteria producing Fe(III) oxyhydroxides. This suggests that such iron-oxidizers could have inhabited niches in ancient coastal oceans where Fe(II) and O2 coexisted, and therefore contributed to iron deposits, but there is currently little evidence for planktonic marine iron-oxidizers in modern analogs. Here, we demonstrate successful cultivation of planktonic microaerophilic iron-oxidizing Zetaproteobacteria from the Chesapeake Bay during seasonal stratification. Iron-oxidizers were associated with low oxygen concentrations and active iron redox cycling in the oxic-anoxic transition zone (<3 µM O2, <0.2 µM H2S). While cyanobacteria were also detected in this transition zone, oxygen concentrations were too low to support significant rates of abiotic iron oxidation. Instead, cyanobacteria may be providing oxygen for microaerophilic iron(II) oxidation through a symbiotic relationship that promotes oxygen consumption rather than build-up. Our results suggest that once oxygenic photosynthesis evolved, microaerophilic chemolithotrophic iron(II)-oxidizers were likely important drivers of iron(III) mineralization in ancient oceans.

Aerobic sulfur-oxidizing bacteria: Environmental selection and diversification

NASA Technical Reports Server (NTRS)

Caldwell, D.

1985-01-01

Sulfur-oxidizing bacteria oxidize reduced inorganic compounds to sulfuric acid. Lithotrophic sulfur oxidizer use the energy obtained from oxidation for microbial growth. Heterotrophic sulfur oxidizers obtain energy from the oxidation of organic compounds. In sulfur-oxidizing mixotrophs energy are derived either from the oxidation of inorganic or organic compounds. Sulfur-oxidizing bacteria are usually located within the sulfide/oxygen interfaces of springs, sediments, soil microenvironments, and the hypolimnion. Colonization of the interface is necessary since sulfide auto-oxidizes and because both oxygen and sulfide are needed for growth. The environmental stresses associated with the colonization of these interfaces resulted in the evolution of morphologically diverse and unique aerobic sulfur oxidizers.

Cuprous oxide nanoparticles selectively induce apoptosis of tumor cells

PubMed Central

Wang, Ye; Zi, Xiao-Yuan; Su, Juan; Zhang, Hong-Xia; Zhang, Xin-Rong; Zhu, Hai-Ying; Li, Jian-Xiu; Yin, Meng; Yang, Feng; Hu, Yi-Ping

2012-01-01

In the rapid development of nanoscience and nanotechnology, many researchers have discovered that metal oxide nanoparticles have very useful pharmacological effects. Cuprous oxide nanoparticles (CONPs) can selectively induce apoptosis and suppress the proliferation of tumor cells, showing great potential as a clinical cancer therapy. Treatment with CONPs caused a G1/G0 cell cycle arrest in tumor cells. Furthermore, CONPs enclosed in vesicles entered, or were taken up by mitochondria, which damaged their membranes, thereby inducing apoptosis. CONPs can also produce reactive oxygen species (ROS) and initiate lipid peroxidation of the liposomal membrane, thereby regulating many signaling pathways and influencing the vital movements of cells. Our results demonstrate that CONPs have selective cytotoxicity towards tumor cells, and indicate that CONPs might be a potential nanomedicine for cancer therapy. PMID:22679374

Oxygen fugacity of mare basalts and the lunar mantle application of a new microscale oxybarometer based on the valence state of vanadium

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

Shearer, C.K.; Karner, J.; Papike, J.J.

2004-05-25

Using the valence state of vanadium on a microscale in lunar volcanic glasses we have developed another approach to estimating the oxygen fugacity of mare basalts. The ability to estimate oxygen fugacities for mare basalts and to extend these observations to the lunar mantle is limited using bulk analysis techniques based on buffering assemblages or the valence state of iron. These limitations are due to reequilibration of mineral assemblages at subsolidus conditions, deviations of mineral compositions from thermodynamic ideality, size requirements, and the limits of the iron valence at very low fO{sub 2}. Still, these approaches have been helpful andmore » indicate that mare basalts crystallized at fO{sub 2} between the iron-wuestite buffer (IW) and the ilmenite breakdown reaction (ilmenite = rutile + iron). It has also been inferred from these estimates that the lunar mantle is also highly reduced lying at conditions below IW. Generally, these data cannot be used to determine if the mare basalts become increasingly reduced during transport from their mantle source and eruption at the lunar surface and if there are differences in fO{sub 2} among mare basalts or mantle sources. One promising approach to determining the fO2 of mare basalts is using the mean valence of vanadium (2+, 3+, 4+, 5+) determined on spots of a few micrometers in diameter using synchrotron x-ray absorption fine structure (XAFS) spectroscopy. The average valence state of V in basaltic glasses is a function of fO{sub 2}, temperature, V coordination, and melt composition. Here, we report the initial results of this approach applied to lunar pyroclastic glasses.« less

Phosphorus, and nitrogen co-doped carbon dots as a fluorescent probe for real-time measurement of reactive oxygen and nitrogen species inside macrophages.

PubMed

Gong, Yunqian; Yu, Bin; Yang, Wen; Zhang, Xiaoling

2016-05-15

Phosphorus and nitrogen doped carbon dots (PN-CDs) were conveniently prepared by carbonization of adenosine-5'-triphosphate using a hydrothermal treatment. The PN-CDs with P/C atomic ratio of ca. 9.2/100 emit blue luminescence with high quantum yields of up to 23.5%. The PN-CDs were used as a novel sensing platform for live cell imaging of reactive oxygen species (ROS) and reactive nitrogen species (RNS), including ClO(-), ONOO(-), and NO in macrophages. The nanosensor design is based on our new finding that the strong fluorescence of the PN-CDs can be sensitively and selectively quenched by ROS and RNS both in vitro and in vivo. These results reveal that the PN-CDs can serve as a sensitive sensor for rapid imaging of ROS and RNS signaling with high selectivity and contrast. Copyright © 2016 Elsevier B.V. All rights reserved.

Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.

1994-01-01

The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

Bioaccumulation of Vanadium by Vanadium-Resistant Bacteria Isolated from the Intestine of Ascidia sydneiensis samea.

PubMed

Romaidi; Ueki, Tatsuya

2016-06-01

Isolation of naturally occurring bacterial strains from metal-rich environments has gained popularity due to the growing need for bioremediation technologies. In this study, we found that the vanadium concentration in the intestine of the vanadium-rich ascidian Ascidia sydneiensis samea could reach 0.67 mM, and thus, we isolated vanadium-resistant bacteria from the intestinal contents and determined the ability of each bacterial strain to accumulate vanadium and other heavy metals. Nine strains of vanadium-resistant bacteria were successfully isolated, of which two strains, V-RA-4 and S-RA-6, accumulated vanadium at a higher rate than did the other strains. The maximum vanadium absorption by these bacteria was achieved at pH 3, and intracellular accumulation was the predominant mechanism. Each strain strongly accumulated copper and cobalt ions, but accumulation of nickel and molybdate ions was relatively low. These bacterial strains can be applied to protocols for bioremediation of vanadium and heavy metal toxicity.

Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Planavsky, Noah J.; Asael, Dan; Hofmann, Axel; Reinhard, Christopher T.; Lalonde, Stefan V.; Knudsen, Andrew; Wang, Xiangli; Ossa Ossa, Frantz; Pecoits, Ernesto; Smith, Albertus J. B.; Beukes, Nicolas J.; Bekker, Andrey; Johnson, Thomas M.; Konhauser, Kurt O.; Lyons, Timothy W.; Rouxel, Olivier J.

2014-04-01

The early Earth was characterized by the absence of oxygen in the ocean-atmosphere system, in contrast to the well-oxygenated conditions that prevail today. Atmospheric concentrations first rose to appreciable levels during the Great Oxidation Event, roughly 2.5-2.3 Gyr ago. The evolution of oxygenic photosynthesis is generally accepted to have been the ultimate cause of this rise, but it has proved difficult to constrain the timing of this evolutionary innovation. The oxidation of manganese in the water column requires substantial free oxygen concentrations, and thus any indication that Mn oxides were present in ancient environments would imply that oxygenic photosynthesis was ongoing. Mn oxides are not commonly preserved in ancient rocks, but there is a large fractionation of molybdenum isotopes associated with the sorption of Mo onto the Mn oxides that would be retained. Here we report Mo isotopes from rocks of the Sinqeni Formation, Pongola Supergroup, South Africa. These rocks formed no less than 2.95 Gyr ago in a nearshore setting. The Mo isotopic signature is consistent with interaction with Mn oxides. We therefore infer that oxygen produced through oxygenic photosynthesis began to accumulate in shallow marine settings at least half a billion years before the accumulation of significant levels of atmospheric oxygen.

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.