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Sample records for surface vanadium oxide

  1. Effect of vanadium admixing on the surface structure of TiO2(110) under non-oxidizing conditions

    Science.gov (United States)

    Song, Xin; Primorac, Elena; Kuhlenbeck, Helmut; Freund, Hans-Joachim

    2016-11-01

    Single crystalline Ti + V mixed oxide layers have been prepared by doping vanadium into TiO2(110) thin films on TiO2(110) single crystal substrates with a Ti + Ta mixed oxide interlayer between the film and the substrate. The interlayer prevents the diffusion of vanadium into the substrate and also the diffusion of Ti3 + between substrate and overlayer. Mixing vanadium into the TiO2 lattice increases the reducibility of the host oxide as concluded from an appreciable degree of reduction produced by comparatively mild annealing. A high density of bridging oxygen vacancies was identified at the surface of films with a low vanadium content (2%) while a (1 × 2) reconstruction as also known for massively reduced TiO2(110) was observed for layers with 8% of vanadium. Studies of methanol adsorption indicate that the vanadium atoms are mostly located below the surface since there is no indication of a vanadium-methanol interaction. We provide evidence that the reducibility of the vanadium ions in the thin film is higher than that of the titanium ions and we suggest that this is the origin of the increased reducibility of the mixed oxide.

  2. Surface and Bulk Electronic Structure and Chemisorption Properties of Titanium and Vanadium Oxides

    Science.gov (United States)

    Smith, Kevin Eugene

    The unusual electronic properties of Ti _2O_3 and V _2O_3, in particular the metal-insulator transitions which they undergo, have produced widespread interest in the physics of these materials, while the use of titanium and vanadium oxides as catalysts and catalyst supports makes a detailed understanding of their surface properties of great importance. The electronic structure and gas adsorption properties of single crystal titanium and vanadium oxides have been studied here using ultraviolet and x-ray photoemission spectroscopy, synchrotron radiation, Auger electron spectroscopy and low energy electron diffraction. Spatially anisotropic resonant photoemission from 3d states in Ti_2O_3 and V_2O_3 was observed and shown to originate from localised molecular orbitals. This contrasts with an energy analysis of the photoemission data which revealed dispersing, delocalised d-bands in both oxides. A large resonance was observed in the O 2p emission at the cation 3p to 3d absorption edge in Ti_2O _3 which is inconsistent with hybridisation, indicating the possible existence of inter-atomic resonances. The first detailed photoemission observation of metal-insulator transitions in Cr-doped V_2O _3 is reported; large changes in the density of states at the Fermi level are seen at these transitions. The surface electronic structure of single crystal TiO_2, Ti_2O _3 and V_2O _3 was found to be indistinguishable from that of the bulk. The interaction of SO_2 with these oxides was extensively studied since sulfur is a notorious catalyst poison. SO_2 reacts vigorously with the titanium oxides, dissociating in the presence of Ti^{3+} cations to form TiO_2 and TiS _2; in their absence no reaction occurs. Surprisingly, SO_2 reacts very weakly with V _2O_3, adsorbing in both dissociated and molecular form. Additionally, only a weak reaction of H_2S and TiO _2 was found. The electronic structure of these oxides is shown to be extremely complex, displaying both localised and

  3. Surface oxidation of vanadium dioxide films prepared by radio frequency magnetron Sputtering

    Institute of Scientific and Technical Information of China (English)

    Wang Xue-Jin; Liang Chun-Jun; Guan Kang-Ping; Li De-Hua; Nie Yu-Xin; Zhu Shi-Oiu; Huang Feng; Zhang Wei-Wei; Cheng Zheng-Wei

    2008-01-01

    This paper reports that the thermochromic vanadium dioxide films were deposited on various transparent substrates by radio frequency magnetron sputtering,and then aged under circumstance for years.Samples were characterized with several different techniques such as x-ray diffraction,x-ray photoelectron spectroscopy,and Raman,when they were fresh from sputter chamber and aged after years,respectively,in order to determine their structure and composition.It finds that a small amount of sodium occurred on the surface of vanadium dioxide films,which was probably due to sodium ion diffusion from soda-lime glass when sputtering was performed at high substrate temperature.It also finds that aging for years significantly affected the noustoichiometry of vanadium dioxide films,thus inducing much change in Raman modes.

  4. Vanadium and molybdenum oxide thin films on Au(111). Growth and surface characterization

    Energy Technology Data Exchange (ETDEWEB)

    Guimond, Sebastien

    2009-06-04

    The growth and the surface structure of well-ordered V{sub 2}O{sub 3}, V{sub 2}O{sub 5} and MoO{sub 3} thin films have been investigated in this work. These films are seen as model systems for the study of elementary reaction steps occurring on vanadia and molybdena-based selective oxidation catalysts. It is shown that well-ordered V{sub 2}O{sub 3}(0001) thin films can be prepared on Au(111). The films are terminated by vanadyl groups which are not part of the V{sub 2}O{sub 3} bulk structure. Electron irradiation specifically removes the oxygen atoms of the vanadyl groups, resulting in a V-terminated surface. The fraction of removed vanadyl groups is controlled by the electron dose. Such surfaces constitute interesting models to probe the relative role of both the vanadyl groups and the undercoordinated V ions at the surface of vanadia catalysts. The growth of well-ordered V{sub 2}O{sub 5}(001) and MoO{sub 3}(010) thin films containing few point defects is reported here for the first time. These films were grown on Au(111) by oxidation under 50 mbar O{sub 2} in a dedicated high pressure cell. Contrary to some of the results found in the literature, the films are not easily reduced by annealing in UHV. This evidences the contribution of radiation and surface contamination in some of the reported thermal reduction experiments. The growth of ultrathin V{sub 2}O{sub 5} and MoO{sub 3} layers on Au(111) results in formation of interface-specific monolayer structures. These layers are coincidence lattices and they do not correspond to any known oxide bulk structure. They are assumed to be stabilized by electronic interaction with Au(111). Their formation illustrates the polymorphic character and the ease of coordination units rearrangement which are characteristic of both oxides. The formation of a second layer apparently precedes the growth of bulk-like crystallites for both oxides. This observation is at odds with a common assumption that crystals nucleate as soon as a

  5. Chemical separation of vanadium oxides in the gaseous phase. Chemische Gasphasenabscheidung von Vanadiumoxiden

    Energy Technology Data Exchange (ETDEWEB)

    Wormer, O.G.

    1993-01-01

    The report discusses the possibility of producing vanadium oxide films on ceramics by the CVD process. It was found that the reaction of VOCl[sub 3] with oxygen resulted in well-adhesive layers on the fibrous matrix although the specific surface was hardly higher than in the case of uncoated ceramic fibres. The technique promises good results in producing novel catalytic converters on the basis of oxidic ceramics coated with vanadium oxides. (orig.)

  6. Investigation on the pure and fluorine doped vanadium oxide thin films deposited by spray pyrolysis method

    Energy Technology Data Exchange (ETDEWEB)

    Margoni, Mudaliar Mahesh; Mathuri, S. [Crystal Growth and Thin Film Laboratory, Department of Physics and Nanotechnology, Faculty of Engineering and Technology, SRM University, Kattankulathur, – 603203 Kancheepuram Dt., Tamil Nadu (India); Ramamurthi, K., E-mail: krmurthin@yahoo.co.in [Crystal Growth and Thin Film Laboratory, Department of Physics and Nanotechnology, Faculty of Engineering and Technology, SRM University, Kattankulathur, – 603203 Kancheepuram Dt., Tamil Nadu (India); Babu, R. Ramesh [Crystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan University, Tiruchirappalli – 620024, Tamil Nadu (India); Sethuraman, K. [School of Physics, Madurai Kamaraj University, Madurai – 625021, Tamil Nadu (India)

    2016-05-01

    Vanadium oxide and fluorine doped vanadium oxide thin films were deposited on the micro-slide glass substrates at 400 °C by spray pyrolysis technique. Vanadium oxide films were deposited using 0.1 M ammonium meta vanadate aqua solution. Precursor solution used to deposit fluorine doped vanadium oxide films was prepared adding separately 5 wt.%, 10 wt.%, 15 wt.% and 20 wt.% of ammonium fluoride with the 0.1 M ammonium meta vanadate aqua solution. X-ray diffraction results showed that the films are in mixed phases of β-V{sub 2}O{sub 5}, V{sub 2}O{sub 5} and V{sub 3}O{sub 7}. Surface morphology and band gap of these films were modified due to different levels of fluorine doping. The average visible transmittance (500–800 nm) of vanadium oxide films is decreased due to low level concentration of fluorine doping. - Highlights: • Addition of a few ml HCl yielded clear precursor aqua solution. • F doped vanadium oxide films were deposited for less concentration of fluorine. • Low level fluorine doping modified the surface morphology of the thin films. • Direct band gap of vanadium oxide film is slightly increased by fluorine doping.

  7. Structure, properties, and MEMS and microelectronic applications of vanadium oxides

    Indian Academy of Sciences (India)

    Robert B Darling; Shiho Iwanaga

    2009-08-01

    Vanadium oxides have for many decades attracted much attention for their rich and unique physical properties which pose intriguing questions as to their fundamental origins as well as offering numerous potential applications for microelectronics, sensors, and microelectromechanical systems (MEMS). This paper reviews the unique structure and properties of the two most common vanadium oxides which have entered into microfabricated devices, VO2 and V25, and some of the past and future device applications which can be realized using these materials. Two emerging new materials, sodium vanadium bronzes and vanadium oxide nanotubes are also discussed for their potential use in new microelectronic devices.

  8. Vanadium Trineodecanoate Promoter for Fiberglass-Polyester Soil Surfacings.

    Science.gov (United States)

    1980-06-01

    surfaces for soils consists of a polyester resin, cumene hydroperoxide catalyst and a promoter solution containing a vanadium salt and N,N-dimethyl-p-tolui...4 Synthesis of Vanadium Trineodecanoate .. .... ......... 4 Reactions Using Various Reagents. ..... ........... 4 Analysis of Vanadium...polymer system consists of a polyester resin, a peroxide cata- lyst ( cumene hydroperoxide) and a two-part, premixed, promoter solution. The promoter

  9. The Oxidation Behavior of Vanadium Alloys in Air at Elevated Temperature

    Institute of Scientific and Technical Information of China (English)

    CHENJiming; XUYing; XUZengyu

    2001-01-01

    Vanadium alloy is one of the most important candidate structural materials for a fusion reactor. Its main advantages over other candidates are its low activity feature and feasible properties at high temperature. However, vanadium is easily oxidized at high temperature to form a non-protective surface film of V2O5. Oxygen concentration would thus get high and the properties get worse in not only the loss of the ductility but also the enhanced hydrogen embrittlement by the oxidation.

  10. Lithium insertion in sputtered vanadium oxide film

    DEFF Research Database (Denmark)

    West, K.; Zachau-Christiansen, B.; Skaarup, S.V.

    1992-01-01

    were oxygen deficient compared to V2O5. Films prepared in pure argon were reduced to V(4) or lower. The vanadium oxide films were tested in solid-state lithium cells. Films sputtered in oxygen showed electrochemical properties similar to crystalline V2O5. The main differences are a decreased capacity...... above 3.0 V, showing that V is partially reduced, and a broadening of the capacity peaks, showing that the crystallinity of these films is rather low. The film sputtered in argon behaved differently, discharging at a very low potential, 1.9 V versus Li, in the first cycle. In subsequent cycles...

  11. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, Michael; Baik, Seungyun [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany); Jeon, Hojeong; Kim, Yuchan [Center for Biomaterials, Biomedical Research Institute Korea Institute of Science and Technology (KIST), Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Kim, Jungtae [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany); Kim, Young Jun, E-mail: youngjunkim@kist-europe.de [Environmental Safety Group, Korea Institute of Science and Technology Europe (KIST-Europe) Forschungsgesellschaft mbH, Campus E 7 1, Saarbruecken (Germany)

    2015-05-15

    Highlights: • Phage is an excellent seeding for bio-templates for environmentally benign vanadium oxide nanocomposite synthesis. • The synthesized bio-inorganic vanadium oxide showed photodegradation activities. • The fabricated wt phage/vanadium oxide composite exhibited bundle-like structure. • The fabricated RSTB-phage/vanadium oxide composite exhibited a ball with a fiber-like nanostructure. • The virus/vanadium oxide composite could be applied in photocatalysts, sensors and nanoelectronic applications. - Abstract: The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V{sub 2}O{sub 5} 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 V{sub 2}O{sub 5} 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 V{sub 2}O{sub 5} precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/V{sub x}O{sub x} composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V{sub 2}O{sub 5} composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure

  13. Facile synthesis of vanadium oxide nanowires

    Science.gov (United States)

    Kysar, Jesse; Sekhar, Praveen Kumar

    2016-10-01

    A simple growth process is reported for the synthesis of vanadium (II) oxide nanowires with an average width of 65 nm and up to 5 μm in length for growth at 1000 °C for 3 h. The vanadium (II) oxide nanowires were grown on a gold-coated silicon substrate at ambient pressure using a single heat zone furnace with Ar as the carrier gas. Gold was utilized as a catalyst for the growth of the nanowires. The growth temperature and heating time were varied to observe the nanowire morphology. An increase in nanowire width was observed with an increase in the heating temperature. A ninefold increase in the number density of the nanowires was observed when the heating time was changed from 30 min to 3 h. This is the first time a simple growth process for producing VO nanowires at ambient pressure has been demonstrated. Such a scheme enables wider use of VO nanowires in critical applications such as energy storage, gas sensors, and optical devices.

  14. Theoretical study of the interaction between vanadium oxide and HY-Zeolite elucidating loss activity of the catalyst

    Directory of Open Access Journals (Sweden)

    Irineo Pedro Zaragoza

    2017-01-01

    Full Text Available The study of the interaction between vanadium oxide and the HY-zeolite using molecular dynamics interaction was carried out for two systems: i when vanadium oxide penetrates a zeolite ring at its center, and ii when vanadium oxide impacts the zeolite surface model. The dynamical effects are used to investigate the reduced activity and eventual degradation of the catalyst for the vanadium oxide presence. In the first case, we observe the breaking of an OH-bond that belongs to the acid site. This is related to an initial loss activity stage of the catalyst. In the second case, vanadium oxide is weakly adsorbed onto the zeolite surface velocity depending. Density functional theory, with nonlocal exchange and correlation functional and the basis set of double numerical accuracy, is used to analyze the electronic structure. It was used in combination with Born-Oppenheimer dynamics to perform calculations.

  15. Study of propane partial oxidation on vanadium-containing catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Komashko, G.A.; Khalamejda, S.V.; Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    The present results indicate that maximum selectivity to acrylic acid can be reached over V-P-Zr-O catalysts. When the hydrocarbon concentration is 5.1 vol.% the selectivity is about 30% at quite high paraffin conversion. Conclusively, some explanations to the observed facts can be given. The V-P-O catalyst promotion with lanthanum by means of mechanochemical treatment is distinguished by the additive uniform spreading all over the matrix surface. Such twophase system is highly active in propane conversion (lanthanum oxide) and further oxidation of the desired products. The similar properties are attributed to V-P-Bi-La-O catalyst. Bismuth, tellurium and zirconium additives having clearly defined acidic properties provoke the surface acidity strengthening and make easier desorption of the acidic product (acrylic acid) from the surface lowering its further oxidation. Additionally, since bismuth and zirconium are able to form phosphates and, according to, to create space limitations for the paraffin molecule movement out of the active group boundaries, this can be one more support in favour of the selectivity increase. With this point of view very interesting results were obtained. It has been shown that the more limited the size of the vanadium unit, the higher the selectivity is. Monoclinic phase AV{sub 2}P{sub 2}O{sub 10} which consists in clusters of four vanadium atoms is sensibly more reactive than the orthorhombic phase consists in V{sub {infinity}} infinite chains. (orig.)

  16. Platinum–Vanadium Oxide Nanotube Hybrids

    Directory of Open Access Journals (Sweden)

    Hernández EduardoPadrón

    2010-01-01

    Full Text Available Abstract The present contribution reports on the features of platinum-based systems supported on vanadium oxide nanotubes. The synthesis of nanotubes was carried out using a commercial vanadium pentoxide via hydrothermal route. The nanostructured hybrid materials were prepared by wet impregnation using two different platinum precursors. The formation of platinum nanoparticles was evaluated by applying distinct reduction procedures. All nanostructured samples were essentially analysed by X-ray diffraction and transmission electron microscopy. After reduction, transmission electron microscopy also made it possible to estimate particle size distribution and mean diameter calculations. It could be seen that all reduction procedures did not affect the nanostructure of the supports and that the formation of metallic nanoparticles is quite efficient with an indistinct distribution along the nanotubes. Nevertheless, the reduction procedure determined the diameter, dispersion and shape of the metallic particles. It could be concluded that the use of H2PtCl6 is more suitable and that the use of hydrogen as reducing agent leads to a nanomaterial with unagglomerated round-shaped metallic particles with mean size of 6–7 nm.

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

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, William David [Iowa State Univ., Ames, IA (United States)

    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 m2/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO3/(MoO3 + V2O5). 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 water 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 V2O5-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 V2O5, solid solutions of Mo in V2O5, V9Mo6O40, 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% MoO3/(V2O5 + MoO3), determined by EDS analysis.

  18. Oxidation of vanadium metal in oxygen plasma and their characterizations

    Directory of Open Access Journals (Sweden)

    Rabindar Kumar Sharma

    2015-09-01

    Full Text Available In this report, the role of oxygen plasma on oxidation of vanadium (V metal and the volatilization of its oxides has been studied as a function of source (V metal strip temperature (Tss and oxygen partial pressure (PO2. The presence of O2-plasma not only enhances the oxidation rate but also ficilitates in transport of oxide molecules from metal to substrate, as confirmed by the simultanous deposition of oxide film onto substrate. Both the oxidized metal strips and oxide films deposited on substrates are characterized separately. The structural and vibrational results evidence the presence of two different oxide phases (i.e. orthorhombic V2O5 and monocilinic V O2 in oxide layers formed on V metal strips, whereas the oxide films deposited on substrates exhibit only orthorhombic phase (i.e. V2O5. The decrease in peak intensities recorded from heated V metal strips on increasing Tss points out the increment in the rate of oxide volatilization, which also confirms by the oxide layer thickness measurements. The SEM results show the noticeable surface changes on V-strips as the function of Tss and PO2 and their optimum values are recorded to be 500   ˚ C and 7.5 × 10−2 Torr, respectively to deposit maximum thick oxide film on substrate. The formation of microcracks on oxidized V-strips, those responsible to countinue oxidation is also confirmed by SEM results. The compositional study of oxide layers formed on V-strips, corroborates their pureness and further assures about the existence of mixed oxide phases. The effect of oxygen partial pressure on oxidation of V-metal has also been discussed in the present report. All the results are well in agreement to each other.

  19. Oxidation of methanol to formaldehyde on supported vanadium oxide catalysts compared to gas phase molecules.

    Science.gov (United States)

    Döbler, Jens; Pritzsche, Marc; Sauer, Joachim

    2005-08-10

    The oxidation of methanol to formaldehyde on silica supported vanadium oxide is studied by density functional theory. For isolated vanadium oxide species silsesquioxane-type models are adopted. The first step is dissociative adsorption of methanol yielding CH3O(O=)V(O-)2 surface complexes. This makes the O=V(OCH3)3 molecule a suited model system. The rate-limiting oxidation step involves hydrogen transfer from the methoxy group to the vanadyl oxygen atom. The transition state is biradicaloid and needs to be treated by the broken-symmetry approach. The activation energies for O=V(OCH3)3 and the silsesquioxane surface model are 147 and 154 kJ/mol. In addition, the (O=V(OCH3)3)(2) dimer (a model for polymeric vanadium oxide species) and the O=V(OCH3)3(*+) radical cation are studied. For the latter the barrier is only 80 kJ/mol, indicating a strong effect of the charge on the energy profile of the reaction and questioning the significance of gas-phase cluster studies for understanding the activity of supported oxide catalysts.

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

    Directory of Open Access Journals (Sweden)

    Juan M. Salazar

    2013-01-01

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

  1. Novel hybrid materials based on the vanadium oxide nanobelts

    Science.gov (United States)

    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.

  2. Conceptual chemistry approach towards the support effect in supported vanadium oxides : Valence bond calculations on the ionicity of vanadium catalysts

    NARCIS (Netherlands)

    Fievez, Tim; De Proft, Frank; Geerlings, Paul; Weckhuysen, Bert M.; Havenith, Remco W. A.

    2011-01-01

    The concept of bond ionicity, obtained via a valence bond analysis, is invoked in the interpretation of the catalytic activity of supported vanadium oxides, in analogy with previous work conducted within the framework of conceptual DFT. For a set of model clusters representing the vanadium oxide sup

  3. Preparation and characterization of vanadium(Ⅳ) oxide supported on SBA-15 and its catalytic performance in benzene hydroxylation to phenol using molecular oxygen

    Institute of Scientific and Technical Information of China (English)

    Xing Chen; Wenguang Zhao; Feng Wang; Jie Xu

    2012-01-01

    Preparation of dispersed transition metal oxides catalyst with low oxidation state still remains a challenging task in heterogeneous catalysis.In this study,vanadium oxides supported on zeolite SBA-15 have been prepared under hydrothermal condition using V2O5 and oxalic acid as sources of vanadium and reductant,respectively.The structures of samples,especially the oxidation state of vanadium,and the surface distribution of vanadium oxide species,have been thoroughly characterized using various techniques,including N2-physisorption,X-ray diffraction (XRD),transmission electron microscopy (TEM),X-ray photoelectron spectroscopy (XPS),UV-visible spectra (UV-Vis) and UV-visible-near infrared spectra (UV-Vis-NIR).It is found that the majority of supported vanadium was in the form of vanadium(Ⅳ) oxide species with the low valence of vanadium.By adjusting hydrothermal treatment time,the surface distribution of vanadium(Ⅳ) oxide species can be tuned from vanadium(Ⅳ) oxide cluster to crystallites.These materials have been tested in the hydroxylation of benzene to phenol in liquid-phase with molecular oxygen in the absence of reductant.The catalyst exhibits high selectivity for phenol (61%) at benzene conversion of 4.6%,which is a relatively good result in comparison with other studies employing molecular oxygen as the oxidant.

  4. Silver vanadium oxide cathode material and method of preparation

    Energy Technology Data Exchange (ETDEWEB)

    Crespi, A.M.

    1993-06-22

    A method for making an electrochemical cell having the steps of admixing silver vanadium oxide with a conductive material and a binder and forming the admixture into a cathode, combining the cathode with a lithium metal anode; and combining an electrolyte with the anode and cathode, the method is described consisting of preparing the silver vanadium oxide by a chemical addition reaction consisting of admixing AgVO[sub 3] and V[sub 2]O[sub 5] in a 2:1 mole ratio heating the admixed AgVO[sub 3] and V[sub 3]O[sub 5] at a reaction temperature in the range of 300 C to 700 C for 5 to 24 hours. An electrochemical cell having a lithium metal anode, cathode and an electrolyte having a metal salt in a nonaqueous solvent comprising: the cathode including a crystalline silver vanadium oxide prepared by a chemical addition reaction.

  5. THE INFLUENCE OF NIOBIUM ON THE ACIDITY AND STRUCTURE OF GAMMA-ALUMINA-SUPPORTED VANADIUM OXIDES

    Directory of Open Access Journals (Sweden)

    M.N.B. Sathler

    1998-06-01

    Full Text Available Gamma-alumina-supported niobium oxide was used as a support for vanadium oxides. The influence of the addition of niobium oxide was studied by looking for changes in the structure and acid-base character of superficial species. Vanadium oxide was deposited using the continuous adsorption method; niobium oxide was impregnated using the incipient wetness method. The catalysts were characterized by XPS, UV-visible and IR spectroscopy. Catalytic tests were performed using propane oxidation reaction at 400oC. For coverage below the monolayer, both vanadium and niobium oxides were observed in slightly condensed superficial species. The presence of vanadium oxide on the support was found to increase the Lewis acidity and create some Bronsted acidity. Higher catalytic activity and selectivity for propene were associated with vanadium oxides. The presence of niobium did not contribute to the modification of the chemical properties of superficial vanadium but did decrease the adsorption of vanadium on the alumina.

  6. Novel hybrid materials based on the vanadium oxide nanobelts

    Energy Technology Data Exchange (ETDEWEB)

    Zabrodina, G.S., E-mail: kudgs@mail.ru [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation); Makarov, S.G.; Kremlev, K.V. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation); Yunin, P.A.; Gusev, S.A. [Institute for Physics of Microstructures Russian Academy of Sciences, Nizhny Novgorod 603087 (Russian Federation); Kaverin, B.S.; Kaverina, L.B. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Ketkov, S.Yu. [G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Nizhny Novgorod 603950 (Russian Federation); Lobachevsky State University, Nizhny Novgorod 603950 (Russian Federation)

    2016-04-15

    Graphical abstract: - Highlights: • Flat and curved vanadium oxide nanobelts have been synthesized. • Hybrid material was prepared via decoration of flexible nanobelts with zinc phthalocyanine. • Investigations of the thermal stability, morphologies and structures were carried out. - Abstract: 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 V{sub 2}O{sub 5}·nH{sub 2}O gel with surfactants (TBAB, CTAB) used as structure-directing agents, where CTAB – cetyltrimethylammonium bromide, TBAB – tetrabutylammonium bromide. Hybrid materials were prepared decoration of (CTA){sub 0.33}V{sub 2}O{sub 5} flexible nanobelts with cationic zinc phthalocyanine by the ion-exchange route. Investigations of the thermal stability, morphologies and structures of the (CTA){sub 0.33}V{sub 2}O{sub 5}, (TBA){sub 0.16}V{sub 2}O{sub 5} 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.

  7. Nature of active vanadium nanospecies in MCM-41 type catalysts for olefins oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Chanquía, Corina M., E-mail: cchanquia@cab.cnea.gov.ar [Centro Atómico Bariloche, Comisión Nacional de Energía Atómica (CAB-CNEA). Av. Bustillo 9500, R8402AGP, San Carlos de Bariloche, Río Negro (Argentina); Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Avenida Rivadavia 1917, C1033AAJ, Ciudad Autónoma de Buenos Aires (Argentina); Cánepa, Analía L. [Centro de Investigación y Tecnología Química (CITeQ), Universidad Tecnológica Nacional, Facultad Regional Córdoba (UTN-FRC), Maestro López esq. Cruz Roja Argentina, Ciudad Universitaria, 5016, Córdoba Capital (Argentina); Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Avenida Rivadavia 1917, C1033AAJ, Ciudad Autónoma de Buenos Aires (Argentina); Winkler, Elin L. [Centro Atómico Bariloche, Comisión Nacional de Energía Atómica (CAB-CNEA). Av. Bustillo 9500, R8402AGP, San Carlos de Bariloche, Río Negro (Argentina); Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). Avenida Rivadavia 1917, C1033AAJ, Ciudad Autónoma de Buenos Aires (Argentina); and others

    2016-06-01

    A multi-technique physicochemical investigation including UV–Vis-DRS, Raman spectroscopy, XPS, ESR and FTIRS with pyridine adsorption was performed to analyze the nature of different vanadium nanospecies present on MCM-41 type catalysts. By employing a direct hydrothermal synthesis, vanadium species were incorporated into siliceous structure mainly as tetrahedrally coordinated isolated V{sup δ+} ions, which would be located inside the wall and on the wall surface of the mesoporous channels. The coexistence of both vanadium oxidation states V{sup 4+} and V{sup 5+} was also revealed. Acidity measurements permitted to infer about the majority presence of Lewis acid sites, which increase with vanadium content. The catalytic performance of these materials was evaluated in the reaction of α-pinene oxidation with H{sub 2}O{sub 2}. The highest intrinsic activity of the sample with lower V loading was attributed to the high dispersion and efficiency of the isolated V{sup δ+} species that actuate as active sites. A mixture of reaction products arising from competitive processes of epoxidation and allylic oxidation was found. - Highlights: • Nature of vanadium nanospecies in mesoporous silicates was investigated. • From hydrothermal sol–gel synthesis, isolated V{sup δ+} sites were mainly generated. • The coexistence of both vanadium oxidation states V{sup 4+} and V{sup 5+} was revealed. • The catalytic performance was evaluated in α-pinene oxidation with H{sub 2}O{sub 2}. • The high catalytic activity is attributed to high dispersion of isolated V{sup δ+} ions.

  8. Chemistry, spectroscopy and the role of supported vanadium oxides in heterogeneous catalysis

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Keller, D.E.

    2003-01-01

    Supported vanadium oxide catalysts are active in a wide range of applications. In this review, an overview is given of the current knowledge available about vanadium oxide-based catalysts. The review starts with the importance of vanadium in heterogeneous catalysis, a discussion of the molecular str

  9. Tuning surface porosity on vanadium surface by low energy He+ ion irradiation

    Science.gov (United States)

    Tripathi, J. K.; Novakowski, T. J.; Hassanein, A.

    2016-08-01

    In the present study, we report on tuning the surface porosity on vanadium surfaces using high-flux, low-energy He+ ion irradiation as function of sample temperature. Polished, mirror-finished vanadium samples were irradiated with 100 eV He+ ions at a constant ion-flux of 7.2 × 1020 ions m-2 s-1 for 1 h duration at constant sample temperatures in the wide range of 823-1173 K. Our results show that the surface porosity of V2O5 (naturally oxidized vanadium porous structure, after taking out from UHV) is strongly correlated to the sample temperature and is highly tunable. In fact, the surface porosity significantly increases with reducing sample temperature and reaches up to ∼87%. Optical reflectivity on these highly porous V2O5 surfaces show ∼0% optical reflectivity at 670 nm wavelength, which is very similar to that of "black metal". Combined with the naturally high melting point of V2O5, this very low optical reflectivity suggests potential application in solar power concentration technology. Additionally, this top-down approach guarantees relatively good contact between the different crystallites and avoids electrical conductivity limitations (if required). Since V2O5 is naturally a potential photocatalytic material, the resulting sub-micron-sized cube-shaped porous structures could be used in solar water splitting for hydrogen production in energy applications.

  10. Structure and properties of bimetallic titanium and vanadium oxide clusters.

    Science.gov (United States)

    Helmich, Benjamin; Sierka, Marek; Döbler, Jens; Sauer, Joachim

    2014-05-14

    By employing a genetic algorithm together with density functional theory (B3LYP), we investigate the most stable minimum structures of several bimetallic titanium and vanadium oxide clusters that contain four metal atoms. The following compositions are studied: VnTin-4O10(-) (n = 1-4), (TiO2)VOn(-) (n = 1-4), and (TiO2)VOn(+) (n = 1-3). Apart from (TiO2)3VO(-), vanadium oxo groups are always part of the most stable minimum structures when vanadium is present. Anti-ferromagnetic coupling lowers the energy substantially if spin centers are located at neighbored metal atoms rather than at distant oxygen radical sites. Vanadium-rich or oxygen-poor compositions prefer symmetric adamantane-like cage structures, some of which have already been proposed in a previous study. In contrast, vanadium-poor and oxygen-rich compositions show versatile structural motifs that cannot be intuitively derived from the symmetric cage motif. Particularly, for Ti4O10(-) there are several non-symmetric and distorted cages that have an up to 68 kJ mol(-1) lower energy than the symmetric adamantane-like cage structure. Nevertheless, for the adamantane-like cage the simulated infra-red spectrum (within the harmonic approximation) agrees best with the experimental vibrational spectrum. The oxidative power of the (TiO2)3VO3(-) and (TiO2)3VO2(+) clusters as measured by the energy of removing 1/2 O2 (297 and 227 kJ mol(-1), respectively) is less than that of the pure vanadium oxide clusters (V2O5)VO3(-) and (V2O5)VO2(+) (283 and 165 kJ mol(-1), respectively).

  11. Structure, activity and kinetics of supported molybdenum oxide and mixed molybdenum-vanadium oxide catalysts prepared by flame spray pyrolysis for propane OHD

    DEFF Research Database (Denmark)

    Høj, Martin; Kessler, Thomas; Beato, Pablo

    2013-01-01

    reflectance UV-vis spectroscopy and evaluated as catalysts for the oxidative dehydrogenation (ODH) of propane. The results show that samples with high specific surface areas between 122 and 182 m2/g were obtained, resulting in apparent MoOx and VOx surface densities from 0.7 to 7.7 nm -2 and 1.5 to 1.9 nm-2......, respectively. Raman spectroscopy, UV-vis spectroscopy and XRD confirmed the high dispersion of molybdenum and vanadia species on γ-Al2O3 as the main crystalline phase. Only at the highest loading of 15 wt% Mo, with theoretically more than monolayer coverage, some crystalline molybdenum oxide was observed....... For the mixed molybdenum-vanadium oxide catalysts the surface species were separate molybdenum oxide and vanadium oxide monomers at low loadings of molybdenum, but with increasing molybdenum loading interactions between surface molybdenum and vanadium oxide species were observed with Raman spectroscopy...

  12. Selective oxidation of 5-hydroxymethylfurfural to 2,5- diformylfuran over intercalated vanadium phosphate oxides

    OpenAIRE

    Grasset, Fabien; Katryniok, Benjamin; Paul, Sébastien; Nardello-Rataj, Veronique; Pera-Titus, Marc; Clacens, Jean-Marc; De Campo, Floryan; Dumeignil, Franck

    2013-01-01

    International audience; The selective oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF) was studied over vanadium phosphate oxide (VPO)-based heterogeneous catalysts in the liquid phase. The selectivity to DFF was highly increased when using intercalated vanadium phosphate oxides under mild conditions (1 atm of oxygen, 110 uC) in an aromatic solvent. We found that the length of the intercalated ammonium alkyl chain had no clear influence on the catalytic performances, an...

  13. X-Ray Absorption Studies of Vanadium-Containing Metal Oxide Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Hohn, Keith, L.

    2006-01-09

    Metal oxide nanocrystals offer significant potential for use as catalysts or catalyst supports due to their high surface areas and unique chemical properties that result from the high number of exposed corners and edges. However, little is known about the catalytic activity of these materials, especially as oxidation catalysts. This research focused on the preparation, characterization and use of vanadium-containing nanocrystals as selective oxidation catalysts. Three vanadium-containing nanocrystals were prepared using a modified sol-gel procedure: V/MgO, V/SiO2, and vanadium phosphate (VPO). These represent active oxidation catalysts for a number of industrially relevant reactions. The catalysts were characterized by x-ray diffraction and Raman, UV-VIS, infrared and x-ray absorption spectroscopies with the goal of determining the primary structural and chemical differences between nanocrystals and microcrystals. The catalytic activity of these catalysts was also studied in oxidative dehydrogenation of butane and methanol oxidation to formaldehyde. V/MgO nanocrystals were investigated for activity in oxidative dehydrogenation of butane and compared to conventional V/MgO catalysts. Characterization of V/MgO catalysts using Raman spectroscopy and x-ray absorption spectroscopy showed that both types of catalysts contained magnesium orthovanadate at vanadium loadings below 15 weight%, but above that loading, magnesium pyrovanadate may have been present. In general, MgO nanocrystals had roughly half the crystal size and double the surface area of the conventional MgO. In oxidative dehydrogenation of butane, nanocrystalline V/MgO gave higher selectivity to butene than conventional V/MgO at the same conversion. This difference was attributed to differences in vanadium domain size resulting from the higher surface areas of the nanocrystalline support, since characterization suggested that similar vanadium phases were present on both types of catalysts. Experiments in

  14. Gas-Phase Partial Oxidation of Lignin to Carboxylic Acids over Vanadium Pyrophosphate and Aluminum-Vanadium-Molybdenum.

    Science.gov (United States)

    Lotfi, Samira; Boffito, Daria C; Patience, Gregory S

    2015-10-26

    Lignin is a complex polymer that is a potential feedstock for aromatic compounds and carboxylic acids by cleaving the β-O-4 and 5-5' linkages. In this work, a syringe pump atomizes an alkaline solution of lignin into a catalytic fluidized bed operating above 600 K. The vanadium heterogeneous catalysts convert all the lignin into carboxylic acids (up to 25 % selectivity), coke, carbon oxides, and hydrogen. Aluminum-vanadium-molybdenum mostly produced lactic acid (together with formic acid, acrylic acid, and maleic anhydride), whereas the vanadium pyrophosphate catalyst produced more maleic anhydride.

  15. Structure of vanadium oxide on supports as measure by the benzaldehyde-ammonia titration method

    Energy Technology Data Exchange (ETDEWEB)

    Niwa, M.; Matsuoka, Y.; Murakami, Y.

    1987-08-13

    In order to clarify the structure of vanadium oxide on supports, the benzaldehyde-ammonia titration (BAT) method was applied to various supported vanadium oxide catalysts. Prior to the measurements, an infrared study of the adsorbed benzoate ion on TiO/sub 2/, ZrO/sub 2/, and CeO/sub 2/ was carried out to justify the BAT method to measure surface cus sites. The exposed surface area of the supports Al/sub 2/O/sub 3/, TiO/sub 2/, and ZrO/sub 2/ with different crystal phases was then measured, and the surface area of vanadium oxide supported was calculated by the difference between BET and exposed surfaced areas. On the other hand, the surface area of vanadium oxide on SiO/sub 2/ was measured after reduction on 773 K, because benzaldehyde was adsorbed on the reduced V/sub 2/O/sub 3/ but not on SiO/sub 2/. Based on these measurements, the relationship between percent coverage on support and surface V/sub 2/O/sub 5/ concentration was obtained. The structure of supported V/sub 2/O/sub 5/ thus determined depended on the kind of support, but not significantly on the crystal phase. Except in small concentration on Al/sub 2/O/sub 3/ and SiO/sub 2/, vanadium oxide formed a multilayer. The support surface at Al/sub 2/O/sub 3/(..gamma..) was covered most effectively, and the average thickness of V/sub 2/O/sub 5/ in 100% of the coverage was 3 layers. To the contrary, the SiO/sub 2/ surface was not covered effectively, and the average thickness attained up to 50 layers. Furthermore, ZrO/sub 2/ and TiO/sub 2/ showed intermediate behavior between these supports. It is shown that the coverage efficiency and thickness of the formed metal oxides are correlated with the electronegativity of the cations of supports.

  16. Oxidation of sulfites on vanadium-molybdenum oxides

    Science.gov (United States)

    Matrosova, O. V.; Vishnetskaya, M. V.

    2014-01-01

    The low temperature emission of 1O2 singlet oxygen from xV2O5 · yMoO3 binary oxides is investigated by means of flash desorption. Conditions for the generation of 1O2 on their surfaces are determined, along with the correlation between the amount of 1O2 and the degree of NaHSO3 conversion in the oxidation reaction. It is shown that on the surface of oxides there are oxygen species that upon decomposition produce 1O2 involved in the oxidation of HSO{3/-}.

  17. On the validity of the electron transfer model in photon emission from ion bombarded vanadium surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ait El Fqih, M.; El Boujlaidi, A.; Jourdani, R.; Kaddouri, A. [Equipe de Spectroscopie and Imagerie Atomiques des Materiaux, Universite Cadi Ayyad, Marrakech (Morocco); Ait El Fqih, M. [Faculte Polydisciplinaire, Universite Chouaib Doukkali, B.P. 2390 El Jadida (Morocco)

    2011-06-15

    The spectral structure of the radiation (250-500 nm) emitted during sputtering of clean and oxygen-covered polycrystalline vanadium and V{sub 2}O{sub 5} by 5 keV Kr{sup +} ions is presented. The optical spectra obtained by bombarding the vanadium target consist of series of sharp lines, which are attributed to neutral and ionic excited V. The same lines are observed in the spectra of V{sub 2}O{sub 5} and vanadium when oxygen is present. The absolute intensities of VI and VII lines are measured under similar conditions for all spectra. The difference in photon yield from the clean and oxide vanadium targets is discussed in terms of the electron-transfer processes between the excited sputtered and electronic levels of the two types of surfaces. We have examined the existing models of ionisation, excitation, neutralisation and de-excitation of atomic particles in the vicinity of solid surfaces. Continuum radiation was also observed and interpreted as a result of the emission of excited molecules of the metal-oxide. (authors)

  18. On the validity of the electron transfer model in photon emission from ion bombarded vanadium surfaces

    Science.gov (United States)

    El Fqih, M. Ait; El Boujlaïdi, A.; Jourdani, R.; Kaddouri, A.

    2011-06-01

    The spectral structure of the radiation (250-500 nm) emitted during sputtering of clean and oxygen-covered polycrystalline vanadium and V2O5 by 5 keV Kr+ ions is presented. The optical spectra obtained by bombarding the vanadium target consist of series of sharp lines, which are attributed to neutral and ionic excited V. The same lines are observed in the spectra of V2O5 and vanadium when oxygen is present. The absolute intensities of VI and VII lines are measured under similar conditions for all spectra. The difference in photon yield from the clean and oxide vanadium targets is discussed in terms of the electron-transfer processes between the excited sputtered and electronic levels of the two types of surfaces. We have examined the existing models of ionisation, excitation, neutralisation and de-excitation of atomic particles in the vicinity of solid surfaces. Continuum radiation was also observed and interpreted as a result of the emission of excited molecules of the metal-oxide.

  19. Crossing points in the electronic band structure of vanadium oxide

    Directory of Open Access Journals (Sweden)

    Keshav N. Shrivastava

    2010-03-01

    Full Text Available The electronic band structures of several models of vanadium oxide are calculated. In the models 1-3, every vanadium atom is connected to 4 oxygen atoms and every oxygen atom is connected to 4 vanadium atoms. In model 1, a=b=c 2.3574 Å; in model 2, a= 4.7148 Å, b= 2.3574 Å and c= 2.3574 Å; and in model 3, a= 4.7148 Å, b= 2.3574 Å and c= 4.7148 Å. In the models 4-6, every vanadium atom is connected to 4 oxygen atoms and every oxygen atom is connected to 2 vanadium atoms. In model 4, a=b= 4.551 Å and c= 2.851 Å; in model 5, a=b=c= 3.468 Å; and in model 6, a=b=c= 3.171 Å. We have searched for a crossing point in the band structure of all the models. In model 1 there is a point at which five bands appear to meet but the gap is 7.3 meV. In model 2 there is a crossing point between G and F points and there is a point between F and Q with the gap ≈ 3.6608 meV. In model 3, the gap is very small, ~ 10-5 eV. In model 4, the gap is 5.25 meV. In model 5, the gap between Z and G points is 2.035 meV, and in model 6 the gap at Z point is 4.3175 meV. The crossing point in model 2 looks like one line is bent so that the supersymmetry is broken. When pseudopotentials are replaced by a full band calculation, the crossing point changes into a gap of 2.72 x 10-4 eV.

  20. Tuning surface porosity on vanadium surface by low energy He{sup +} ion irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Tripathi, J.K., E-mail: jtripat@purdue.edu; Novakowski, T.J.; Hassanein, A.

    2016-08-15

    Highlights: • Surface nanostructuring on vanadium surface using novel He{sup +} ion irradiation process. • Tuning surface-porosity using high-flux, low-energy He{sup +} ion irradiation at constant elevated sample temperature (823–173 K). • Presented top-down approach guarantees good contact between different crystallites. • Sequential significant enhancement in surface-pore edge size (and corresponding reduction in surface-pore density) with increasing sample temperature. - Abstract: In the present study, we report on tuning the surface porosity on vanadium surfaces using high-flux, low-energy He{sup +} ion irradiation as function of sample temperature. Polished, mirror-finished vanadium samples were irradiated with 100 eV He{sup +} ions at a constant ion-flux of 7.2 × 10{sup 20} ions m{sup −2} s{sup −1} for 1 h duration at constant sample temperatures in the wide range of 823–1173 K. Our results show that the surface porosity of V{sub 2}O{sub 5} (naturally oxidized vanadium porous structure, after taking out from UHV) is strongly correlated to the sample temperature and is highly tunable. In fact, the surface porosity significantly increases with reducing sample temperature and reaches up to ∼87%. Optical reflectivity on these highly porous V{sub 2}O{sub 5} surfaces show ∼0% optical reflectivity at 670 nm wavelength, which is very similar to that of “black metal”. Combined with the naturally high melting point of V{sub 2}O{sub 5}, this very low optical reflectivity suggests potential application in solar power concentration technology. Additionally, this top-down approach guarantees relatively good contact between the different crystallites and avoids electrical conductivity limitations (if required). Since V{sub 2}O{sub 5} is naturally a potential photocatalytic material, the resulting sub-micron-sized cube-shaped porous structures could be used in solar water splitting for hydrogen production in energy applications.

  1. Novel vanadium phosphate phases as catalysts for selective oxidation

    Indian Academy of Sciences (India)

    Arunabha Datta; Monika Agarwal; Soumen Dasgupta

    2002-08-01

    In our effort to induce novel modifications in the structure of some important vanadium phosphate phases used as selective oxidation catalysts, it has been observed that metal ions such as Zn2+, Ni2+, Pd2+ can be incorporated into the vanadyl hydrogen phosphate VOHPO4$\\cdot$0.5H2O phase in very different ways depending upon the medium of preparation. It has been found that the metal ions are either substituted into the lattice with retention of structure of the parent compound or intercalated between the layers of a new mixed-valent phase. These new metalincorporated phases are catalytically active and the palladium incorporated compound in particular displays shape selective catalysis for different oxidation and reduction reactions. In another approach, the preparation of VOHPO4$\\cdot$0.5H2O has been modified to give a novel crystalline phase containing mixed-valent vanadium and having NH3 species bound to the lattice. This phase could be a potential catalyst for ammoxidation reactions. In addition, novel mesostructured vanadium phosphate phases have been prepared using a long-chain amine as the templating agent involving a ligand templating mechanism of formation.

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

    Science.gov (United States)

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

    2015-01-21

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

  3. Vanadium Oxide in the Spectra of Mira Variables

    Science.gov (United States)

    Castelaz, M. W.; Luttermoser, D. G.; Piontek, R. A.

    1999-05-01

    Over the last three years, we have made spectroscopic measurements of twenty Mira variable stars, as a function of phase, probing their stellar atmospheres and underlying pulsation mechanisms. Measurement of variations in TiO and VO with phase can be used to help determine whether these molecular species are produced in an extended region above the layers where Balmer line emission occurs or below this shocked region. Piontek & Luttermoser (1999 IAPPPC, submitted), produce synthetic spectra for three Mira variables, R Leo, V CVn, and R CVn as a function of phase. Comparison of their synthetic spectra to our observed spectra yield the fundamental astrophysical parameters of effective temperatures and surface gravities. Spectra are synthesized with LTE stellar stmospheres code ATLAS, using the 6.6--million Indiana University atomic and molecular line dataset. Piontek & Luttermoser point out that the IU dataset does not include vanadium oxide (VO). Thus, there is a noticeable difference between the synthetic spectra and observed near-IR spectra corresponding to the B-X bands of VO (Mahanti 1935, Proc. Phys. Soc., 47, 43; Keenan & Schroeder 1952,L. W., ApJ, 115, 82). In order to incorporate the VO bands in the synthetic spectra, we need to establish tables of wavenumbers, lowest energy levels, and oscillator strengths. Producing the tables is non-trivial. Laboratory measurements of wavenumbers are used in the Just-Overlapping Line Approximation (JOLA; Tsuji 1966, PASJ, 18, 127) to calculate oscillator strengths. The JOLA technique and preliminary results will be presented. MWC greatly appreciates support from the National Science Foundation grant AST-9500756. RAP acknowledges the Southeastern Association for Research in Astronomy 1998 Summer REU program supported by the National Science Foundation and thanks DGL for being his mentor.

  4. Hysteresis Phenomena in Sulfur Dioxide Oxidation over Supported Vanadium Catalysts

    DEFF Research Database (Denmark)

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

    1997-01-01

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

  5. Electrochromic and chemochromic performance of mesoporous thin-film vanadium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ping; Lee, Se-Hee; Tracy, C. Edwin; Turner, John A.; Pitts, J. Roland; Deb, Satyen K. [National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, CO 80401 (United States)

    2003-12-01

    Mesoporous vanadium oxide thin films have been deposited electrochemically from a water/ethanol solution of vanadyl sulfate and a nonionic polymer surfactant. Aggregates of the polymer surfactant serve as templates that result in the formation of a mesoporous structure. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicate the presence of both macroporosity and mesoporosity in the electrodeposited film. Chemochromic behavior of mesoporous vanadium oxide is demonstrated in a palladium/vanadium oxide thin-film device, which colors when exposed to hydrogen gas. A comparison of results with evaporated vanadium oxide reveals that the mesoporous film displays an improved kinetic performance, which is most likely attributable to its highly porous structure. Also, the electrochemical properties have been explored in a lithium-battery configuration. Mesoporous vanadium oxide exhibits a very high lithium storage capacity and greatly enhanced charge-discharge rate. In situ optical measurements show that the film exhibits a multicolor electrochromic effect.

  6. Preparation, characterization, and electrochemical properties of lithium vanadium oxide nanoribbons

    Energy Technology Data Exchange (ETDEWEB)

    Zhuo Shujuan [Institute of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou, Jiangsu 215123 (China); Anhui Key Laboratory of Functional Molecular Solids, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000 (China); Shao Mingwang, E-mail: mwshao@suda.edu.cn [Institute of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou, Jiangsu 215123 (China); Zhou Qing; Liao Fan [Institute of Functional Nano and Soft Materials (FUNSOM) and Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou, Jiangsu 215123 (China)

    2011-07-15

    Graphical abstract: Display Omitted Highlights: > The lithium ions can easily move between the layers of lithium vanadium oxide. > It can highly increase the electron transfer between the electrode and dopamine. > The reversibility of electrochemical process was significantly improved. - Abstract: Highly uniform lithium vanadium oxide nanoribbons were successfully prepared in large quantities using a facile hydrothermal approach without employing any surfactants or templates. The as-prepared products were up to hundreds of micrometers in length, about 200 nm in width, and 20 nm in thickness. These nanoribbons and nafion composite were employed to modify glassy carbon electrode, which displayed excellent electrochemical sensitivity and rapid response in detecting dopamine in phosphate buffer solution. Lithium ions can greatly increase the electron transfer between the electrode and biological materials, and significantly increase the reversibility of electrochemical process. A linear relationship between the concentrations of dopamine and its oxidation peak currents was obtained. The linear range for the detection of dopamine was 2.0 x 10{sup -6} to 1.0 x 10{sup -4} M with a detection limit of 1.0 x 10{sup -7} M. In addition, the good reproducibility and long-term stability of the sensor make it valuable for further application.

  7. Oxidative dehydration of glycerol to acrylic acid over vanadium-impregnated zeolite beta

    Energy Technology Data Exchange (ETDEWEB)

    Pestana, Carolina F.M.; Guerra, Antonio C.O.; Turci, Cassia C. [Universidade Federal do Rio de Janeiro, RJ (Brazil). Inst. de Quimica; Ferreira, Glaucio B. [Universidade Federal Fluminense, Niteroi, RJ (Brazil). Inst. de Quimica; Mota, Claudio J.A., E-mail: cmota@iq.ufrj.br [INCT Energia e Ambiente, Universidade Federal do Rio de Janeiro, RJ (Brazil)

    2013-01-15

    The oxidative dehydration of glycerol to acrylic acid was studied over vanadium-impregnated zeolite Beta. Catalysts were prepared by wet impregnation of ammonium metavanadate over ammonium-exchanged zeolite Beta, followed by air calcination at 823 K. Impregnation reduced the specific surface area, but did not significantly affected the acidity (Bronsted and Lewis) of the zeolites. The catalytic evaluation was carried out in a fixed bed flow reactor using air as the carrier and injecting glycerol by means of a syringe pump. Acrolein was the main product, with acetaldehyde and hydroxy-acetone (acetol) being also formed. Acrylic acid was formed with approximately 25% selectivity at 548 K over the impregnated zeolites. The result can be explained by XPS (X-ray photoelectron spectroscopy) measurements, which indicated a good dispersion of the vanadium inside the pores. (author)

  8. Growth of ultrathin vanadium oxide films on Ag(100)

    Science.gov (United States)

    Nakamura, Takuya; Sugizaki, Yuichi; Ishida, Shuhei; Edamoto, Kazuyuki; Ozawa, Kenichi

    2016-07-01

    Vanadium oxide films were grown on Ag(100) by vanadium deposition in O2 and subsequent annealing at 450 °C. It was found that at least three types of ordered V oxide films, which showed (1 × 1), hexagonal, and (4 × 1) LEED patterns, were formed on Ag(100) depending on the O2 pressure during deposition and conditions during postannealing. The films with the hexagonal and (1 × 1) periodicities were characterized by photoelectron spectroscopy (PES) and near-edge X-ray absorption fine structure (NEXAFS) analysis. The film with the (1 × 1) periodicity was ascribed to a VO(100) film. On the other hand, the film with the hexagonal periodicity was found to be composed of V2O3, and the analysis of the LEED pattern revealed that the lattice parameter of the hexagonal lattice is 0.50 nm, which is very close to that of corundum V2O3(0001) (0.495 nm).

  9. Role of vanadium in Keggin heteropoly molybdate supported on titania catalysts for oxidation reactions

    Indian Academy of Sciences (India)

    A Srivani; K T Venkateswara Rao; P S Sai Prasad; N Lingaiah

    2014-03-01

    Vanadium-incorporated molybdophosporic acid catalysts supported on titania were prepared and characterized by FT-IR, X-ray diffraction and laser Raman spectroscopy. Characterization data reveals the incorporation of vanadium into the primary structure of Keggin ion of MPA. Catalysts activities were evaluated for oxidation of 1,2-benzenedimethanol using H2O2 and O2 as oxidants. Vanadium-containing catalysts showed high activity compared to their parent heteropoly acids. Oxidation ability depended on the number of V atoms present in Keggin heteropoly molybdate. Effect of reaction parameters on the oxidation ability was also evaluated.

  10. Characteristics of graphite felt electrode electrochemically oxidized for vanadium redox battery application

    Institute of Scientific and Technical Information of China (English)

    LI Xiao-gang; HUANG Ke-long; LIU Su-qin; TAN Ning; CHEN Li-quan

    2007-01-01

    The graphite felt was oxidized at a positive electrode potential in sulfuric acid solution. The electrochemical performance of the treated graphite felt served as electrode for vanadium redox battery was investigated with FT-IR, SEM, XPS, BET, cyclic voltammetry and testing VRB system, respectively. The results show that the molar ratio of O to C increases from 0.085 to 0.15 due to the increase of -COOH functional groups during electrochemical oxidation treatment, and the GF surface is eroded by electrochemical oxidation, resulting in the surface area increase from 0.33 m2/g to 0.49 m2/g. The VRB with modified GF electrode exhibits excellent performance under a current density of 30 mA/cm2. The average current efficiency reaches 94% and average voltage efficiency reaches 85%. The improvement of electrochemical activity for the electrode is ascribed to the increase of the number of -COOH group and the special surface of GF.

  11. Structural and catalytic properties of a novel vanadium containing solid core mesoporous silica shell catalysts for gas phase oxidation reaction

    Indian Academy of Sciences (India)

    N Venkatathri; Vijayamohanan K Pillai; A Rajini; M Nooka Raju; I A K Reddy

    2013-01-01

    A novel vanadium containing solid core mesoporous silica shell catalyst was synthesized with different Si/V ratios by sol-gel method under neutral conditions. The synthesized materials were characterized by various techniques and gas phase diphenyl methane oxidation reaction. The mesoporosity combined with microporosity are formed by incorporation of octadecyltrichloro silane and triethylamine in the catalyst and it was found out from E-DAX and BET—surface area analysis. The material was found to be nanocrystalline. Vanadium is present as V4+ species in as-synthesized samples and convert to V5+ on calcination. Most of the vanadium is present in tetrahedral or square pyramidal environment. Incorporation of vanadium in silica framework was confirmed by 29Si MAS NMR analysis. Among the various vanadium containing solid core mesoporous silica shell catalysts, the Si/V =100 ratio exhibited maximum efficiency towards diphenyl methane to benzophenone gas phase reaction. The optimum condition required for maximum conversion and selectivity was found out from the catalytic studies.

  12. Unusual phase transition in a natural heterostructure of iron pnictides and vanadium oxides

    Science.gov (United States)

    Ok, Jong Mok; Baek, S.-H.; Eom, Man Jin; Hoch, C.; Kremer, R. K.; Kim, Dong-Hwan; Chang, Chun-Fu; Ko, Kyung-Tae; Park, Sang-Youn; Ji, Sung Dae; Büchner, B.; Park, Jae-Hoon; Shim, J. H.; Mazin, I. I.; Kim, Jun Sung

    We report the unusual phase transition in Sr2VO3FeAs single crystal, where the Mott-insulating vanadium oxides and the high-Tc superconducting iron pnictides form a natural heterostructure. Clear evidence of the phase transition at T0 = 155 K was observed in the iron pnictide layer, not in the vanadium oxide layer, using bulk and NMR measurements. Neither magnetic ordering with sufficient spin moment nor symmetry change in the crystal structure has been detected at T0. At Tmag ~ 45 K, far below T0, magnetic transition occurs in the iron pnictide layer, while the vanadium oxide layer remains nonmagnetic at low temperatures. The complex evolution of various phases in Sr2VO3FeAs is drastically distinct from the phase transitions found in other iron pnictides or vanadium oxides, highlighting the importance of the additional interlayer coupling between the layers. Equal contribution, corresponding author.

  13. Selective Oxidation of Propane by Lattice Oxygen of Vanadium-Phosphorous Oxide in a Pulse Reactor

    Institute of Scientific and Technical Information of China (English)

    Rusong Zhao; Jian Wang; Qun Dong; Jianhong Liu

    2005-01-01

    Selective oxidation of propane by lattice oxygen of vanadium-phosphorus oxide (VPO) catalysts was investigated with a pulse reactor in which the oxidation of propane and the re-oxidation of catalyst were implemented alternately in the presence of water vapor. The principal products are acrylic acid (AA),acetic acid (HAc), and carbon oxides. In addition, small amounts of C1 and C2 hydrocarbons were also found, molar ratio of AA to HAc is 1.4-2.2. The active oxygen species are those adsorbed on catalyst surface firmly and/or bound to catalyst lattice, i.e. lattice oxygen; the selective oxidation of propane on VPO catalysts can be carried out in a circulating fluidized bed (CFB) riser reactor. For propane oxidation over VPO catalysts, the effects of reaction temperature in a pulse reactor were found almost the same as in a steady-state flow reactor. That is, as the reaction temperature increases, propane conversion and the amount of C1+C2 hydrocarbons in the product increase steadily, while selectivity to acrylic acid and to acetic acid increase prior to 350 ℃ then begin to drop at temperatures higher than 350 ℃, and yields of acrylic acid and of acetic acid attained maximum at about 400 ℃. The maximum yields of acrylic acid and of acetic acid for a single-pass are 7.50% and 4.59% respectively, with 38.2% propane conversion. When the amount of propane pulsed decreases or the amount of catalyst loaded increases, the conversion increases but the selectivity decreases. Increasing the flow rate of carrier gases causes the conversion pass through a minimum but selectivity and yields pass through a maximum. In a fixed bed reactor, it is hard to obtain high selectivity at a high reaction conversion due to the further degradation of acrylic acid and acetic acid even though propane was oxidized by the lattice oxygen. The catalytic performance can be improved in the presence of excess propane. Propylene can be oxidized by lattice oxygen of VPO catalyst at 250

  14. Hydrocarbon oxidation catalyzed by vanadium polyoxometalate supported on mesoporous MCM-41 under ultrasonic irradiation.

    Science.gov (United States)

    Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Shams, Esmaeil; Salavati, Hossein

    2008-04-01

    Vanadium polyoxometalate (PVMo) supported on mesoporous MCM-41, MCM-41-NH(2), as efficient and heterogeneous catalysts, with large surface area, for hydrocarbon oxidation with hydrogen peroxide is reported. Oxidation of the alkenes and alkanes gave product selectivities, which are similar to those observed for corresponding homogeneous catalyst. PVMo-MCM was prepared by introduction of PVMo into the mesoporous molecule sieves of MCM-41 by impregnation and adsorption techniques. The samples were characterized by X-ray diffraction (XRD), thermal gravimetric-differential thermal analysis (TG-DTA), FT-IR, scanning electron microscopy (SEM), UV-Vis and cyclic voltametry (CV). Ultrasonic irradiation has a particular effect on MCM-41 structural uniformity and reduced the reaction times and improved the product yields. In addition, the solid catalysts could be recovered and reused several times without loss of its activity.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-22

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

  16. High-Temperature Oxidation Behavior of Vanadium, Titanium-Bearing Magnetite Pellet%High-Temperature Oxidation Behavior of Vanadium, Titanium-Bearing Magnetite Pellet

    Institute of Scientific and Technical Information of China (English)

    HAN Gui-hong; JIANG Tao; ZHANG Yuan-bo; HUANG Yan-fang; LI Guang-hui

    2011-01-01

    By means of isothermal oxidation and chemical analysis, great importance was attached to the parameters that made effects on the oxidation degree of vanadium, titanium-bearing magnetite pellet in high-temperature processing (1 073- 1 323 K). Based on the experimental data, oxidation kinetics of pellet was analyzed according to shrinking unreacted-core model subsequently. Experiment results display that the oxidation degree of pellet increases with increasing of oxidation time, oxidation temperature and oxygen content, as well as shrinking of pellet diameter. Under the condition of oxidation time 20 min, oxidation temperature 1223 K, oxygen content 15%, and pellet diameter 12 mm, oxidation degree of pellet reaches 92.92%. The analysis of oxidation kinetics indicates that oxidation process of pellet is controlled by chemical reaction with activation energy 68.64 kJ/mol at a relatively lower temperature (1073-1 173 K). Oxidation process of pellet is mixed-controlled by chemistry reaction and diffusion with activation energy 39.66 kJ/mol in the temperature range of 1 173-1 273 K. When oxidation temperature is higher than 1 273 K, the limited link of oxidation reaction is the diffusion control with the activation energy 20.85 kJ/mol. These results can serve as a reference to the production of vanadium, titanium-hearing magnetite pellet.

  17. Synthesis, investigation and practical application in lithium batteries of some compounds based on vanadium oxides

    Science.gov (United States)

    Shembel, E.; Apostolova, R.; Nagirny, V.; Aurbach, D.; Markovsky, B.

    In this paper, we investigate the inter-relationship between the conditions of the electrochemical synthesis of vanadium oxide compounds, their structural and morphological characteristics, kinetic parameters of the redox processes, and charge-discharge performance of lithium batteries with vanadium oxide cathodes. The materials studied were V 2O 5- y oxides and those with inserted sodium ions (Na-vanadium oxide compounds, Na-VOC) obtained electrochemically in the form of compact deposits on a metal substrate. The electrochemical synthesis of the oxides has been performed from aqueous vanadyl sulphate solutions. Optimal synthesis conditions (current density, pH, temperature, vanadyl sulphate and sodium sulphate concentrations), and subsequent optimal thermal treatment of the oxides, which provide high electrochemical activity of the cathode material and good adhesion of the oxide to the metal substrate, have been elucidated. A correlation between the structure of the vanadium oxides and Na-VOC, their morphology, impedance characteristics of the cathode, and lithium-ion solid state diffusion in the host cathode bulk has been established and discussed. A combination of analytical techniques (XRD, IR spectroscopy, TGA, BET, SEM) and electrochemical methods (cyclic voltammetry, chronopotentiometry, GITT, EIS) has been used in this study.

  18. Dissolution kinetics and thermodynamic analysis of vanadium trioxide during pressure oxidation

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The dissolution kinetics of vanadium trioxide in sulphuric acid-oxygen medium was examined. It was determined that the concentration of sulphuric acid and stirring speed above 800 r min 1 did not significantly affect vanadium extraction. The dissolution rate increased with increasing temperature and oxygen partial pressure, but decreased with increasing particle size. The dissolution kinetics was controlled by the chemical reaction at the surface with the estimated activation energy of 43.46 kJ·mol-1. The l...

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

    Science.gov (United States)

    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.

  20. Facile embedding of single vanadium atoms at the anatase TiO2(101) surface.

    Science.gov (United States)

    Koust, Stig; Arnarson, Logi; Moses, Poul G; Li, Zheshen; Beinik, Igor; Lauritsen, Jeppe V; Wendt, Stefan

    2017-04-05

    To understand the structure-reactivity relationships for mixed-metal oxide catalysts, well-defined systems are required. Mixtures of vanadia and titania (TiO2) are of particular interest for application in heterogeneous catalysis, with TiO2 often acting as the support. By utilizing high-resolution scanning tunneling microscopy, we studied the interaction of vanadium (V) with the anatase TiO2(101) surface in the sub-monolayer regime. At 80 K, metallic V nucleates into homogeneously distributed clusters onto the terraces with no preference for nucleation at the step edges. However, embedding of single V atoms into TiO2 occurs following annealing at room temperature. In conjunction with X-ray photoelectron spectroscopy data and density functional theory calculations, we propose that monomeric V atoms occupy positions of regular surface Ti sites, i.e., Ti atoms are substituted by V atoms.

  1. Vanadium oxide nanotubes as cathode material for Mg-ion batteries

    DEFF Research Database (Denmark)

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

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

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

    Science.gov (United States)

    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., 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.

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

    Science.gov (United States)

    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.

  4. First nucleation steps of vanadium oxide thin films studied by XPS inelastic peak shape analysis

    Energy Technology Data Exchange (ETDEWEB)

    Gracia, F. [Instituto de Ciencia de Materiales de Sevilla (CSIC-U. Sevilla) and Dpt. Q. Inorganica, c/Americo Vespucio s/n, E-41092 Sevilla (Spain)]. E-mail: torres@icmse.isic.es; Yubero, F. [Instituto de Ciencia de Materiales de Sevilla (CSIC-U. Sevilla) and Dpt. Q. Inorganica, c/Americo Vespucio s/n, E-41092 Sevilla (Spain); Espinos, J.P. [Instituto de Ciencia de Materiales de Sevilla (CSIC-U. Sevilla) and Dpt. Q. Inorganica, c/Americo Vespucio s/n, E-41092 Sevilla (Spain); Gonzalez-Elipe, A.R. [Instituto de Ciencia de Materiales de Sevilla (CSIC-U. Sevilla) and Dpt. Q. Inorganica, c/Americo Vespucio s/n, E-41092 Sevilla (Spain)

    2005-09-30

    The initial states of deposition of vanadium oxide thin films have been studied by analysis of the peak shape (both inelastic background and elastic contributions) of X-ray photoemission spectra (XPS) after successive deposition experiments. This study has permitted to assess the type of nucleation and growth mechanisms of the films. The experiments have been carried out in situ in the preparation chamber of a XPS spectrometer. Thin films of vanadium oxide have been prepared on Al{sub 2}O{sub 3} and TiO{sub 2} by means of thermal evaporation, ion beam assisted deposition and plasma enhanced chemical vapour deposition. The thin films prepared by the first two procedures consisted of V{sub 2}O{sub 4}, while those prepared by the latter had a V{sub 2}O{sub 5} stoichiometry. The analysis of the inelastic background of the photoemission spectra has shown that the films prepared by thermal evaporation on Al{sub 2}O{sub 3} are formed by big particles that only cover completely the surface of the substrate when their height reaches 16 nm. By contrast, the thin films prepared with assistance of ions on Al{sub 2}O{sub 3} or with plasma on TiO{sub 2} consist of smaller particles that succeed in covering the substrate surface already for a height of approximately 4 nm. Thin films prepared by plasma-assisted deposition on Al{sub 2}O{sub 3} depict an intermediate situation where the substrate is completely covered when the particles have a height of approximately 6 nm. The type of substrates, differences in the deposition procedure or the activation of the adatoms by ion bombardment are some of the factors that are accounted for by to explain the different observed behaviours.

  5. Vanadium Oxide Electrochemical Capacitors: An Investigation into Aqueous Capacitive Degradation, Alternate Electrolyte-Solvent Systems, Whole Cell Performance and Graphene Oxide Composite Electrodes

    Science.gov (United States)

    Engstrom, Allison Michelle

    Vanadium oxide has emerged as a potential electrochemical capacitor material due to its attractive pseudocapacitive performance; however, it is known to suffer from capacitive degradation upon sustained cycling. In this work, the electrochemical cycling behavior of anodically electrodeposited vanadium oxide films with various surface treatments in aqueous solutions is investigated at different pH. Quantitative compositional analysis and morphological studies provide additional insight into the mechanism responsible for capacitive degradation. Furthermore, the capacitance and impedance behavior of vanadium oxide electrochemical capacitor electrodes is compared for both aqueous and nonaqueous electrolyte-solvent systems. Alkali metal chloride and bromide electrolytes were studied in aqueous systems, and nonaqueous systems containing alkali metal bromides were studied in polar aprotic propylene carbonate (PC) or dimethyl sulfoxide (DMSO) solvents. The preferred aqueous and nonaqueous systems identified in the half-cell studies were utilized in symmetric vanadium oxide whole-cells. An aqueous system utilizing a 3.0 M NaCl electrolyte at pH 3.0 exhibited an excellent 96% capacitance retention over 3000 cycles at 10 mV s-1. An equivalent system tested at 500 mV s-1 displayed an increase in capacitance over the first several thousands of cycles, and eventually stabilized over 50,000 cycles. Electrodes cycled in nonaqueous 1.0 M LiBr in PC exhibited mostly non-capacitive charge-storage, and electrodes cycled in LiBr-DMSO exhibited a gradual capacitive decay over 10,000 cycles at 500 mV s-1. Morphological and compositional analyses, as well as electrochemical impedance modeling, provide additional insight into the cause of the cycing behavior. Lastly, reduced graphene oxide and vanadium oxide nanowire composites have been successfully synthesized using electrophoretic deposition for electrochemical capacitor electrodes. The composite material was found to perform with a

  6. Component effects on the vanadium oxide thin films phase transition character phenomenon observed

    Science.gov (United States)

    Tian, X. S.; Liu, J. C.; Wang, Q.

    2008-10-01

    We present what is, to the best of our knowledge, how the components affect the phase transition character of the vanadium oxide thin films. The vanadium oxide thin films are prepared on zinc selenide by a DC magnet sputtering method for the first time; the components are achieved by the x-ray photoelectron spectroscopy (XPS). The films are annealed to tune their components. A spectral transmittance study has been made from 2.5 to 25.0 μm. We can see that, except for doping, different components can change the phase transition characters of the films. The components can affect the phase transition temperature, hysteresis cycle, and the transmittance.

  7. Application of AXAFS Spectroscopy to Transition-Metal Oxides: Influence of the Nearest and Next Nearest Neighbour Shells in Vanadium Oxides

    NARCIS (Netherlands)

    Keller, D.E.; Weckhuysen, B.M.; Koningsberger, D.C.

    2007-01-01

    The influence of changes in coordination number, interatomic distances, and oxidation state on the intensity and centroid position of the Fourier transform (FT) of the atomic X-ray absorption fine structure (AXAFS) peak of vanadium oxide bulk model compounds and alumina-supported vanadium oxide clus

  8. Incorporation of Vanadium Oxide in Silica Nanofiber Mats via Electrospinning and Sol-Gel Synthesis

    Directory of Open Access Journals (Sweden)

    Jeanne E. Panels

    2006-01-01

    Full Text Available Submicron scale vanadia/silica hybrid nanofiber mats have been produced by electrospinning silica sol-gel precursor containing vanadium oxytriisopropoxide (VOTIP, followed by calcinations at high temperature. The properties of the resulting inorganic hybrid nanofiber mats are compared to those of electrospun pure silica nanofibers. SEM images show fibers are submicron in diameter and their morphology is maintained after calcination. Physisorption experiments reveal that silica nanofiber mats have a high specific surface area of 63 m2/g. FT-IR spectra exhibit Si—O vibrations and indicate the presence of V2O5 in the fibers. XPS studies reveal that the ratio of Si to O is close to 0.5 on the surface of fibers and the amount of vanadium on the surface of fibers increases with calcination. XRD diffraction patterns show that silica nanofibers are amorphous and orthorhombic V2O5 crystals have formed after calcination. EFTEM images demonstrate the growth of crystals on the surface of fibers containing vanadium after calcination. SEM images of fibers with high-vanadium content (50 mol% V: Si show that vanadia crystals are mostly aligned along the fiber axis. XPS shows an increase in vanadium contents at the surface, and XRD patterns exhibit an increase in the degree of crystallinity. A coaxial electrospinning scheme has successfully been employed to selectively place V2O5 in the skin layer.

  9. Investigation on vanadium oxide thin films deposited by spray pyrolysis technique

    Energy Technology Data Exchange (ETDEWEB)

    Margoni, Mudaliar Mahesh; Mathuri, S.; Ramamurthi, K., E-mail: krmurthin@yahoo.co.in, E-mail: ramamurthi.k@ktr.srmuniv.ac.in [Crystal Growth and Thin Film Laboratory, Department of Physics and Nanotechnology, Faculty of Engineering and Technology, SRM University, Kattankulathur – 603 203, Kancheepuram Dt., Tamil Nadu (India); Babu, R. Ramesh [Crystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan University, Tiruchirappalli – 620024, Tamil Nadu (India); Sethuraman, K. [School of Physics, Madurai Kamaraj University, Madurai – 625 021, Tamil Nadu (India)

    2016-05-06

    Vanadium oxide thin films were deposited at 400 °C by spray pyrolysis technique using 0.1 M aqueous precursor solution of ammonium meta vanadate (AMV) with two different pH values. X-ray diffraction results showed that the film prepared using aqueous precursor AMV solution (solution A; pH 7) is amorphous in nature and the film prepared by adding HNO{sub 3} in the AMV aqua solution A (solution B; pH 3) is polycrystalline in nature. Vanadium oxide film prepared from the precursor solution B is in the mixed phases of V{sub 2}O{sub 5} and V{sub 4}O{sub 7}. Crystallinity is improved for the film prepared using solution B when compared to film prepared from solution A. Crystallite size, strain and dislocation density calculated for the film prepared from solution B is respectively 72.1 nm, 0.4554 × 10{sup −3} lin.{sup −2}m{sup −4} and 1.7263 × 10{sup 14} lin.m{sup −2}. Morphology study revealed that the size of the flakes formed on the surface of the films is influenced by the pH of the precursor solution. Average Visible Transmittance and maximum transmittance of the deposited films exceed 70% and the direct optical band gap value calculated for the films deposited from A and B solution is 1.91 eV and 2.08 eV respectively.

  10. Results on the electrochromic and photocatalytic properties of vanadium doped tungsten oxide thin films prepared by reactive dc magnetron sputtering technique

    Science.gov (United States)

    Muthu Karuppasamy, K.; Subrahmanyam, A.

    2008-02-01

    In this investigation, vanadium doped tungsten oxide (V : WO3) thin films are prepared at room temperature by reactive dc magnetron sputtering employing a tungsten-vanadium 'inlay' target. In comparison with pure sputtered tungsten oxide thin films, 11% vanadium doping is observed to decrease the optical band gap, enhance the colour neutral property, decrease the coloration efficiency (from 121 to 13 cm2 C-1), increase the surface work function (4.68-4.83 eV) and significantly enhance the photocatalytic efficiency in WO3 thin films. These observations suggest that (i) vanadium creates defect levels that are responsible for optical band gap reduction, (ii) multivalent vanadium bonding with terminal oxygen in the WO3 lattice gives rise to localized covalent bonds and thus results in an increase in the work function, and (iii) a suitable work function of V : WO3 with ITO results in an enhancement of the photocatalytic activity. These results on electrochromic and photocatalytic properties of V : WO3 thin films show good promise in the low maintenance window application.

  11. Results on the electrochromic and photocatalytic properties of vanadium doped tungsten oxide thin films prepared by reactive dc magnetron sputtering technique

    Energy Technology Data Exchange (ETDEWEB)

    Karuppasamy, K Muthu; Subrahmanyam, A [Semiconductor Laboratory, Department of Physics, Indian Institute of Technology Madras, Chennai 600036 (India)

    2008-02-07

    In this investigation, vanadium doped tungsten oxide (V : WO{sub 3}) thin films are prepared at room temperature by reactive dc magnetron sputtering employing a tungsten-vanadium 'inlay' target. In comparison with pure sputtered tungsten oxide thin films, 11% vanadium doping is observed to decrease the optical band gap, enhance the colour neutral property, decrease the coloration efficiency (from 121 to 13 cm{sup 2} C{sup -1}), increase the surface work function (4.68-4.83 eV) and significantly enhance the photocatalytic efficiency in WO{sub 3} thin films. These observations suggest that (i) vanadium creates defect levels that are responsible for optical band gap reduction, (ii) multivalent vanadium bonding with terminal oxygen in the WO{sub 3} lattice gives rise to localized covalent bonds and thus results in an increase in the work function, and (iii) a suitable work function of V : WO{sub 3} with ITO results in an enhancement of the photocatalytic activity. These results on electrochromic and photocatalytic properties of V : WO{sub 3} thin films show good promise in the low maintenance window application.

  12. A comprehensive model for the supported vanadium oxide catalyst: The umbrella model

    NARCIS (Netherlands)

    Lingen, J.N.J. van

    2006-01-01

    Supported vanadium oxide catalysts are widely used in industry. However, the molecular structure of the active species, responsible for the actual catalysis, is for a large part still unknown. This thesis describes four years study on the elucidation of this molecular structure. It mainly focuses on

  13. Selective Oxidative Decarboxylation of Amino Acids to Produce Industrially Relevant Nitriles by Vanadium Chloroperoxidase

    NARCIS (Netherlands)

    But, A.; Notre, le J.E.L.; Scott, E.L.; Wever, R.; Sanders, J.P.M.

    2012-01-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative

  14. Selective Oxidative Decarboxylation of Amino Acids to Produce Industrially Relevant Nitriles by Vanadium Chloroperoxidase

    NARCIS (Netherlands)

    But, A.; Notre, le J.E.L.; Scott, E.L.; Wever, R.; Sanders, J.P.M.

    2012-01-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative dec

  15. Selective Oxidative Decarboxylation of Amino Acids to Produce Industrially Relevant Nitriles by Vanadium Chloroperoxidase

    NARCIS (Netherlands)

    But, A.; Notre, le J.E.L.; Scott, E.L.; Wever, R.; Sanders, J.P.M.

    2012-01-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative dec

  16. Polyaniline/Vanadium oxide composites: An effective control in morphology by varying reactant concentrations

    Energy Technology Data Exchange (ETDEWEB)

    Goswami, S. [Thin Film and Nanoscience Laboratory, Department of Physics, Jadavpur University, Kolkata 700 032 (India); School of Materials Science and Nanotechnology, Jadavpur University, Kolkata 700 032 (India); Maiti, U.N.; Maiti, S. [Thin Film and Nanoscience Laboratory, Department of Physics, Jadavpur University, Kolkata 700 032 (India); Mitra, M.K. [School of Materials Science and Nanotechnology, Jadavpur University, Kolkata 700 032 (India); Chattopadhyay, K.K., E-mail: kalyan_chattopadhyay@yahoo.com [Thin Film and Nanoscience Laboratory, Department of Physics, Jadavpur University, Kolkata 700 032 (India); School of Materials Science and Nanotechnology, Jadavpur University, Kolkata 700 032 (India)

    2013-02-15

    A one pot synthesis protocol is presented for the realization of organic/inorganic hybrid nanostructures comprised of polyaniline and vanadium oxide. The polyaniline/vanadium oxide hybrid morphology is tailored by controlling the relative concentration of reactants which resulted in diverse morphologies ranging from nanorods, combined nano/microrods to porous nano/microspheres. Temporal evolution of morphology is investigated to elucidate the formation mechanism in detail. The prepared composites exhibit enhanced thermal stability in comparison to pure polyaniline which may be attributed to the strong chemical combination of vanadium oxide and polyaniline within the composites as prevailed by FTIR and TGA analysis of the products. This simple and controllable approach for synthesizing the organic/inorganic hybrid material should have future applications in energy storage devices, sensors and many more. Highlights: ► Polyaniline/Vanadium oxide composite was tailored by a simple route. ► Morphology control by varying reagent concentrations. ► Possible growth mechanism for rods and hollow spheres. ► Exhibited enhanced thermal stability in comparison to pure polyaniline.

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

    Science.gov (United States)

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

    2011-08-15

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

  18. Mechanism of SO2 Promotion for NO Reduction With NH3 over Activaed Carbon—Supported Vanadium Oxide Catalyst

    Institute of Scientific and Technical Information of China (English)

    ZhenpingZhu; ZhenyuLiu; HongxianNiu; ShoujunLiu; TiandouHu; TaoLiu

    2001-01-01

    SO2 shows a significant promoting effect on the activity of V2O5/AC catlayst for No reduction with ammonia at low temperatrures (180-250℃).In the present study,the mechanism of the SO2 promotion was studied.It was found that the promoting effect of SO2 on the catalytic activity is due to the formation of a sulfate species on the catalyst surace.The sulfate species is linked to carbon surfaces other the vanadium or mineral surfaces.There is a synergetic role between carbon and V2O5 for the formation of surface sulfate species.A possilbe mechanism is proposed.SO2 is adsorbed and oxidized by oxygen to SO3 on the vanadium surface, and the formed SO3 shifts to the carbon surface and converts into sulfate species.The formed sulfate species acts as a new acid site,improves significantly the NH3 adsorption,and hence promotes the activity of the catalyst.During the reaction in the presence of SO2 at low temperatures,the sulfate species stays on the catalyst surface,while the ammonium ions react with NO continuously to avoid the formation and deposition of excess ammonium sulfate salts on the catalyst surface.

  19. Characterization of silver vanadium oxide cathode material by high-resolution electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Crespi, A.M. [Medtronic, Inc., Minneapolis, MN (United States); Skarstad, P.M. [Medtronic, Inc., Minneapolis, MN (United States); Zandbergen, H.W. [National Centre for HREM, Lab. of Materials Science, Delft Univ. of Technology (Netherlands)

    1995-03-01

    The nature of the discharge reaction of lithium/silver vanadium oxide batteries was investigated. The lithiation of silver vanadium oxide, which has the formula Ag{sub 2-y}V{sub 4}O{sub 11}, proceeds by a multistep reaction, as indicated by the open-circuit voltage curve. The first step in the discharge reaction involves reduction of silver and separation of the oxide into two phases of differing composition. Electron diffraction of lithiated materials of various compositions suggests that the layered structure of the oxide is maintained, but with an increased amount of stacking disorder. High-resolution electron micrographs of lithiated Ag{sub 2-y}V{sub 4}O{sub 11} at atomic resolution could not be obtained because of sample decomposition in the electron beam. (orig.)

  20. Tunable Oxygen Functional Groups as Electrocatalysts on Graphite Felt Surfaces for All-Vanadium Flow Batteries.

    Science.gov (United States)

    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.

  1. Nickel-vanadium monolayer double hydroxide for efficient electrochemical water oxidation

    Science.gov (United States)

    Fan, Ke; Chen, Hong; Ji, Yongfei; Huang, Hui; Claesson, Per Martin; Daniel, Quentin; Philippe, Bertrand; Rensmo, Håkan; Li, Fusheng; Luo, Yi; Sun, Licheng

    2016-06-01

    Highly active and low-cost electrocatalysts for water oxidation are required due to the demands on sustainable solar fuels; however, developing highly efficient catalysts to meet industrial requirements remains a challenge. Herein, we report a monolayer of nickel-vanadium-layered double hydroxide that shows a current density of 27 mA cm-2 (57 mA cm-2 after ohmic-drop correction) at an overpotential of 350 mV for water oxidation. Such performance is comparable to those of the best-performing nickel-iron-layered double hydroxides for water oxidation in alkaline media. Mechanistic studies indicate that the nickel-vanadium-layered double hydroxides can provide high intrinsic catalytic activity, mainly due to enhanced conductivity, facile electron transfer and abundant active sites. This work may expand the scope of cost-effective electrocatalysts for water splitting.

  2. Nickel–vanadium monolayer double hydroxide for efficient electrochemical water oxidation

    Science.gov (United States)

    Fan, Ke; Chen, Hong; Ji, Yongfei; Huang, Hui; Claesson, Per Martin; Daniel, Quentin; Philippe, Bertrand; Rensmo, Håkan; Li, Fusheng; Luo, Yi; Sun, Licheng

    2016-01-01

    Highly active and low-cost electrocatalysts for water oxidation are required due to the demands on sustainable solar fuels; however, developing highly efficient catalysts to meet industrial requirements remains a challenge. Herein, we report a monolayer of nickel–vanadium-layered double hydroxide that shows a current density of 27 mA cm−2 (57 mA cm−2 after ohmic-drop correction) at an overpotential of 350 mV for water oxidation. Such performance is comparable to those of the best-performing nickel–iron-layered double hydroxides for water oxidation in alkaline media. Mechanistic studies indicate that the nickel–vanadium-layered double hydroxides can provide high intrinsic catalytic activity, mainly due to enhanced conductivity, facile electron transfer and abundant active sites. This work may expand the scope of cost-effective electrocatalysts for water splitting. PMID:27306541

  3. CeO_2-supported vanadium oxide catalysts for soot oxidation:the roles of molecular structure and nanometer effect

    Institute of Scientific and Technical Information of China (English)

    刘坚; 赵震; 徐春明; 段爱军; 姜桂元

    2010-01-01

    The nanometer CeO2 powder was prepared by the method of microwave-assisted heating hydrolysis,and the nanometer CeO2-supported or ordinary CeO2-supported vanadia catalysts with different vanadium loadings(atomic ratios:100V/Ce=0.1,1,4,10,and 20) were prepared by an incipient-wetness impregnation method.Spectroscopic techniques(XRD,FT-IR,Raman and UV-Vis DRS) were utilized to characterize the structures of VOx/CeO2 catalysts.The results showed that the structures of CeO2-supported vanadium oxide catalysts de...

  4. Electrochromic properties of inkjet printed vanadium oxide gel on flexible polyethylene terephthalate/indium tin oxide electrodes.

    Science.gov (United States)

    Costa, Cláudia; Pinheiro, Carlos; Henriques, Inês; Laia, César A T

    2012-10-24

    Vanadium oxide gel was synthesized and formulated for the assembly of solid-state electrochromic cells on flexible and transparent electrodes using inkjet printing. FTIR, Raman, and X-ray diffraction spectroscopic measurements showed that the vanadium oxide gel here synthesized consisted of V(2)O(5)·6H(2)O, microstructures similar to orthorhombic V(2)O(5), while Raman spectroscopy also shows the presence of amorphous domains. Atomic force microscopy (AFM) images of the thin films printed using an inkjet shows a ribbonlike structure, which is in accordance with previous results of the vanadium oxide gels in solution. Solid-state electrochromic devices were assembled at room temperature using the inkjet printed films, without any sinterization step. The electrochemical properties of the vanadium oxide gel were characterized by cyclic voltammetry and spectroelectrochemistry by visible/NIR absorption spectroscopy (in both liquid and solid-state). Several redox steps are observed, which gives rise to a variety of color transitions as a function of the applied voltage. The different optical properties of the vanadium oxide gel are assigned to different intercalation steps of Li(+), leading to different crystalline phases of the gel. The final result is a solid-state electrochromic cell showing excellent contrast between the redox states, giving rise to colors such as yellow, green, or blue. Color space analysis was used to characterize the electrochromic transitions, and while absorption spectra showed rather long switching times (up to 100 s), in L*a*b* color space coordinates, the switching time is smaller than 30 s. These electrochromic cells also have an excellent cycling stability showing high reversibility and a cyclability up to more than 30,000 cycles with a degradation of 18%.

  5. Sol-gel synthesis and XPS study of vanadium-hydroquinone oxide bronze films

    Energy Technology Data Exchange (ETDEWEB)

    Bondarenka, V. [Semiconductor Physics Institute, A. Gostauto 11, 01108 Vilnius (Lithuania); Vilnius Pedagogical University, Studentu 39, 08106 Vilnius (Lithuania); Tvardauskas, H.; Grebinskij, S.; Senulis, M.; Pasiskevicius, A. [Semiconductor Physics Institute, A. Gostauto 11, 01108 Vilnius (Lithuania); Volkov, V.; Zakharova, G. [Institute of Solid State Chemistry, Pervomaiskaia 91, 620219 Yekaterinburg (Russian Federation)

    2009-12-15

    A vanadium - hydroquinone oxide bronze has been synthesized by using a sol gel technology. The V{sub 2}O{sub 5} powder, hydrogen peroxide, and hydroquinone C{sub 6}H{sub 4}(OH){sub 2} were used as the starting materials to produce the bronze. At first the vanadium gel was made by the dissolving of vanadium pentoxide powder in hydrogen peroxide at 273 K. Then the solution was heated up to 350 K for the dissociation of peroxide complexes. An aqueous solution of hydroquinone was mixed with the formed gel in molar ratio 0.33:1. In this way the V{sub 2}O{sub 5{+-}}{sub {delta}}.nH{sub 2}O/HQ (HQ-hydroquinone) gel was synthesized. These gels are applied on the Ni pad and dried in an air (wet gel synthesis) or heated up to 580 K in air for 1 h for the water removal from gel (bronze production). The wet gel, as well as a bronze, was investigated by means of XPS method. Analysis of V-O region of XPS spectra shows that vanadium in both cases (wet gel and bronze) is in stable V{sup 5+} state. Oxygen in wet gel can be associated with V ions, hydroxide group and water. In bronze oxygen is connected with V and hydrogen (hydroxide). (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  6. Influence of the C/O ratio on titanium and vanadium oxides in protoplanetary disks

    CERN Document Server

    Ali-Dib, M; Pekmezci, G S; Lunine, J I; Madhusudhan, N; Petit, J -M

    2013-01-01

    Context. The observation of carbon-rich disks have motivated several studies questioning the influence of the C/O ratio on their gas phase composition in order to establish the connection between the metallicity of hot-Jupiters and that of their parent stars. Aims. We to propose a method that allows the characterization of the adopted C/O ratio in protoplanetary disks independently from the determination of the host star composition. Titanium and vanadium chemistries are investigated because they are strong optical absorbers and also because their oxides are known to be sensitive to the C/O ratio in some exoplanet atmospheres. Methods. We use a commercial package based on the Gibbs energy minimization technique to compute the titanium and vanadium equilibrium chemistries in protoplanetary disks for C/O ratios ranging from 0.05 to 10. Our calculations are performed for pressures ranging from 1e-6 to 1e-2 bar, and for temperatures ranging from 50 to 2000 K. Results. We find that the vanadium nitride/vanadium ox...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-06-24

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

  8. Reaction Mechanism of Thiophene on Vanadium Oxides under FCC Operating Conditions

    Institute of Scientific and Technical Information of China (English)

    Wang Peng; Zheng Aiguo; Tian Huiping; Long Jun

    2004-01-01

    The reaction mechanism of thiophene on vanadium oxides under FCC operating conditions had been preliminary studied using in-situ FT-IR analysis of thiophene and atmospheric pressure continuous fixed-bed reaction, followed by characterization via pyridine adsorption-temperature programmed desorption method, and FT-IR and XPS spectra. The research had discovered that, under 500C thiophene could undergo the redox reaction with V2O5, while being converted into CO, CO2 as well as SO2 with its conversion rate reaching 41.2%. At the same time the oxidation number of vanadium decreased. The existence of a few Bronsted acid centers on V2O5 could lead to an increase of H2S yield among the products derived from the reaction with thiophene.

  9. Selective oxidative decarboxylation of amino acids to produce industrially relevant nitriles by vanadium chloroperoxidase.

    Science.gov (United States)

    But, Andrada; Le Nôtre, Jérôme; Scott, Elinor L; Wever, Ron; Sanders, Johan P M

    2012-07-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative decarboxylation can be applied to mixtures of amino acids obtained from plant waste streams, leading to easily separable nitriles. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Controlled synthesis and electrochemical properties of vanadium oxides with different nanostructures

    Indian Academy of Sciences (India)

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

    2012-06-01

    Vanadium oxides (V3O7.H2O and VO2) with different morphologies have been selectively synthesized by a facile hydrothermal approach using glucose as the reducing and structure-directing reagent. The as-obtained V3O7.H2O nanobelts have a length up to several tens of micrometers, width of about 60–150 nm and thickness of about 5–10 nm, while the as-prepared VO2(B) nanobelts have a length of about 1.0–2.7 m, width, 80–140 nm and thickness, 2–8 nm. It was found that the quantity of glucose, the reaction temperature and the reaction time had significant influence on the compositions and morphologies of final products. Vanadium oxides with different morphologies were easily synthesized by controlling the concentration of glucose. The formation mechanism was also briefly discussed, indicating that glucose played different roles in synthesizing various vanadium oxides. The phase transition from VO2(B) to VO2(M) were investigated and the phase transition temperature of the VO2(M) appeared at around 68 °C. Furthermore, the electrochemical properties of V3O7.H2O nanobelts, VO2(B) nanobelts and VO2(B) nanosheets were investigated and they exhibited a high initial discharge capacity of 296, 247 and 227 mAh/g, respectively.

  11. Resistance repeatability study of ion-beam deposited vanadium oxide thin films

    Science.gov (United States)

    Alvarez, P.; Pearson, D. I. C.; Pochon, S.; Thomas, O.; Cooke, M.; Gunn, R.

    2016-09-01

    Ion Beam Sputter Deposition (IBSD) is a versatile technique particularly suited to applications requiring high quality, high performance layer materials as it allows independent and accurate control of the process parameters. Vanadium oxides, used for example in the fabrication of microbolometers, optical switches or optical storage, exhibit interesting properties such as a high Temperature Coefficient of Resistance (TCR), relatively low 1/f noise and a semiconductormetal phase transition close to room temperature. However, it is very challenging to control the stoichiometry of the deposited film as there are at least 25 different oxidation states of vanadium, few of which display the required electrical characteristics. In the present study, vanadium oxide thin layers were deposited by IBSD using an Oxford Ionfab300+ and analyzed with regard to their electrical properties. The impact of the system parameters on the resistance repeatability, wafer-to-wafer and batch-to-batch, was thoroughly investigated to provide the end user with a clear understanding of the factors affecting film resistivity while ensuring at the same time a steep variation of resistance with temperature, as notably required for uncooled bolometers. These parameters were balanced to also achieve a good deposition rate, throughput and uniformity over large device areas, compatible with the requirements of industrial applications.

  12. Role of chromium and vanadium in the atmospheric oxidation of sulfur(IV)

    Science.gov (United States)

    Brandt, Christian; Elding, Lars I.

    Oxidation of HSO 3- in aqueous solution has been studied in the presence of vanadium(V), chromium(III) and chromium(VI). Based on spectrophotometric kinetics data and product analysis it is concluded that the autoxidation rate of sulfur(IV) in slightly acidic solution is unaffected by the presence of vanadium(V) and chromium(III). Chromate(VI), on the other hand, oxidizes sulfur(IV) in a direct redox process in acidic solution. The overall rate of this reaction decreases with increasing pH and it becomes relatively slow in the atmospherically relevant pH range 4-6. Moreover, chromium(III) dominates strongly over chromium(VI) in the atmospheric aqueous phase. Hence, it is concluded that cations of vanadium and chromium have no significant influence on the atmospheric aqueous-phase oxidation of sulfur(IV) under most ambient atmospheric conditions. Only in very acidic droplets, direct redox between chromium(VI) and sulfite might be of some importance.

  13. Synthesis, characterization and study of band gap variations of vanadium doped indium oxide nanoparticles

    Science.gov (United States)

    Parhoodeh, Saeed; Kowsari, Mohammad

    2016-10-01

    In this study, effects of vanadium doping in crystal lattice structure of indium oxide (In2O3) were investigated. Indium oxide nanoparticles with different amounts of dopant concentrations were fabricated by a facile and cost effective method. X-ray diffraction (XRD) analysis revealed the formation of cubic phase for doped and undoped samples. It was observed that the lattice parameters of doped samples were decreased respect to the pure indium oxide, but the crystallite sizes and the particles' sizes of doped samples were increased in result of substitution of vanadium in crystal lattice of In2O3. The scanning electron microscope (SEM) images of samples showed that all samples have spherical shapes, and their distribution sizes are between 10 and 70 nm. It was found that the average sizes of nanoparticles were increased linearly with the amounts of dopant concentration. A red shift was founded in the band gap of vanadium doped samples respect to pure In2O3. The maximum of the band gap shift was observed for samples with 0.025 M concentration of dopant. Based on impedance spectroscopy data, it was found that impedances of samples are increased by increasing of dopant concentration for all frequencies which were tested in this study.

  14. Synthesis, characterization and study of band gap variations of vanadium doped indium oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Parhoodeh, Saeed, E-mail: saeed.parhoodeh@gmail.com [Physics Department, Shiraz branch, Islamic Azad University, Shiraz (Iran, Islamic Republic of); Kowsari, Mohammad [Department of Electronics, Sepidan branch, Islamic Azad University, Sepidan (Iran, Islamic Republic of)

    2016-10-01

    In this study, effects of vanadium doping in crystal lattice structure of indium oxide (In{sub 2}O{sub 3}) were investigated. Indium oxide nanoparticles with different amounts of dopant concentrations were fabricated by a facile and cost effective method. X-ray diffraction (XRD) analysis revealed the formation of cubic phase for doped and undoped samples. It was observed that the lattice parameters of doped samples were decreased respect to the pure indium oxide, but the crystallite sizes and the particles’ sizes of doped samples were increased in result of substitution of vanadium in crystal lattice of In{sub 2}O{sub 3}. The scanning electron microscope (SEM) images of samples showed that all samples have spherical shapes, and their distribution sizes are between 10 and 70 nm. It was found that the average sizes of nanoparticles were increased linearly with the amounts of dopant concentration. A red shift was founded in the band gap of vanadium doped samples respect to pure In{sub 2}O{sub 3}. The maximum of the band gap shift was observed for samples with 0.025 M concentration of dopant. Based on impedance spectroscopy data, it was found that impedances of samples are increased by increasing of dopant concentration for all frequencies which were tested in this study.

  15. The microstructures and electrical properties of Y-doped amorphous vanadium oxide thin films

    Science.gov (United States)

    Gu, Deen; Zhou, Xin; Guo, Rui; Wang, Zhihui; Jiang, Yadong

    2017-03-01

    One of promising approaches for further improving the sensitivity of microbolometer arrays with greatly-reduced pixel size is using the thermal-sensitive materials with higher performance. In this paper, Y-doped vanadium oxide (VOx) thin films prepared by a reactively sputtering process exhibit enhanced performance for the microbolometer application compared with frequently-applied VOx thin films. Both undoped and Y-doped VOx thin films are amorphous due to the relatively low deposition temperature. Y-doped VOx thin films exhibit smoother surface morphology than VOx due to the restrained expansion of particles during depositions. Y-doping increases the temperature coefficient of resistivity by over 20% for the doping level of 1.30 at%. The change rate of resistivity, after aging for 72 h, of thin films was reduced from about 15% for undoped VOx to 2% due to the introduction of Y. Moreover, Y-doped VOx thin films have a low 1/f noise level as VOx ones. Y-doping provides an attractive approach for preparing VOx thermal-sensitive materials with enhanced performance for microbolometers.

  16. Spontaneous electrochemical treatment for sulfur recovery by a sulfide oxidation/vanadium(V) reduction galvanic cell.

    Science.gov (United States)

    Kijjanapanich, Pimluck; Kijjanapanich, Pairoje; Annachhatre, Ajit P; Esposito, Giovanni; Lens, Piet N L

    2015-02-01

    Sulfide is the product of the biological sulfate reduction process which gives toxicity and odor problems. Wastewaters or bioreactor effluents containing sulfide can cause severe environmental impacts. Electrochemical treatment can be an alternative approach for sulfide removal and sulfur recovery from such sulfide rich solutions. This study aims to develop a spontaneous electrochemical sulfide oxidation/vanadium(V) reduction cell with a graphite electrode system to recover sulfide as elemental sulfur. The effects of the internal and external resistance on the sulfide removal efficiency and electrical current produced were investigated at different pH. A high surface area of the graphite electrode is required in order to have as less internal resistance as possible. In this study, graphite powder was added (contact area >633 cm(2)) in order to reduce the internal resistance. A sulfide removal efficiency up to 91% and electrical charge of more than 400 C were achieved when using five graphite rods supplemented with graphite powder as the electrode at an external resistance of 30 Ω and a sulfide concentration of 250 mg L(-1). Copyright © 2014 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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.

  18. 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}

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Xinbo [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Wang, Danjun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Li, Kebin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Zhen, Yanzhong [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Hu, Huaiming [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Xue, Ganglin, E-mail: xglin707@163.com [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China)

    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 catalyst 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}.

  19. Improved performance of organic light-emitting diode with vanadium pentoxide layer on the FTO surface

    Science.gov (United States)

    Saikia, D.; Sarma, R.

    2017-06-01

    Vanadium pentoxide layer deposited on the fluorine-doped tin oxide (FTO) anode by vacuum deposition has been investigated in organic light-emitting diode (OLED). With 12 nm optimal thickness of V2O5, the luminance efficiency is increased by 1.66 times compared to the single FTO-based OLED. The improvement of current efficiency implies that there is a better charge injection and better controlling of hole current. To investigate the performance of OLED by the buffer layer, V2O5 films of different thicknesses were deposited on the FTO anode and their J- V and L- V characteristics were studied. Further analysis was carried out by measuring sheet resistance, optical transmittance and surface morphology with the FE-SEM images. This result indicates that the V2O5 (12 nm) buffer layer is a good choice for increasing the efficiency of FTO-based OLED devices within the tunnelling region. Here the maximum value of current efficiency is found to be 2.83 cd / A.

  20. Improved performance of organic light-emitting diode with vanadium pentoxide layer on the FTO surface

    Indian Academy of Sciences (India)

    D SAIKIA; R SARMA

    2017-06-01

    Vanadium pentoxide layer deposited on the fluorine-doped tin oxide (FTO) anode by vacuum deposition has been investigated in organic light-emitting diode (OLED).With 12nm optimal thickness of $V_{2}O_{5}$, the luminance efficiency is increased by 1.66 times compared to the single FTO-based OLED. The improvement of current efficiency implies that there is a better charge injection and better controlling of hole current. To investigate the performance of OLED by the buffer layer, $V_{2}O_{5}$ films of different thicknesses were deposited on the FTO anode and their $J–V$ and $L–V$ characteristics were studied. Further analysis was carried out by measuring sheet resistance, optical transmittance and surface morphology with the FE-SEM images. This result indicates that the $V_{2}O_{5}$ (12 nm) buffer layer is a good choice for increasing the efficiency of FTO-based OLED devices within the tunnelling region. Here the maximum value of current efficiency is found to be 2.83 cd/A.

  1. Synthesis, characterization, and transport properties of single-layer pure and molybdenum-doped vanadium oxide thin films on metallic conductive substrates

    Energy Technology Data Exchange (ETDEWEB)

    Karthikeyan, Muthukkumaran; Um, Sukkee, E-mail: sukkeeum@hanyang.ac.kr

    2016-05-01

    Single-layer undoped and 10 mol% molybdenum (Mo)-doped vanadium oxide (V{sub 2}O{sub 3}) thin films with thicknesses of approximately 342 nm are fabricated by an aqueous sol–gel method and then deposited onto 316L stainless steel conductive substrates. The influence of various annealing temperatures (in a nitrogen atmosphere) on the structural and electrical properties of undoped and Mo-doped vanadium oxide thin films is investigated. Through a controlled annealing process, the electrical resistances of the single-layer thin films are optimized to attain the required amount of Joule heating for cold-start fuel cell applications within an ambient temperature range (273.15 to 253.15 K). The films show a negative temperature coefficient (NTC) behavior and a transition from a metal to an insulator at sub-zero temperatures. The highest electrical resistivities are measured to be 0.032 Ω·cm and 0.071 Ω·cm for undoped and Mo-doped vanadium oxide films, respectively, after annealing under 20 sccm N{sub 2} at 673.15 K. Consequently, the equilibrium surface temperature of the single-layer Mo-doped vanadium oxide thin film increases from 253.15 K to 299.46 K upon induced Joule heating at a current density of 0.1 A·cm{sup −2}. Thus, it is concluded that single-layer NTC Mo-doped vanadium oxides can be effectively used for cold-start fuel cell applications. - Highlights: • Single-layer undoped and 10 mol% Mo-doped vanadium oxide films were fabricated. • Mo-doped V{sub 2}O{sub 3} thin films showed am enhanced NTC behavior through annealing. • Mo-doped V{sub 2}O{sub 3} thin films revealed the high resistivity of 0.071 Ω·cm at 253.15 K. • Remarkable temperature rise of a Mo-doped V{sub 2}O{sub 3} film was achieved by Joule heating. • Mo-doped V{sub 2}O{sub 3} films can be effectively used for cold-start fuel cell applications.

  2. Imaging metal-like monoclinic phase stabilized by surface coordination effect in vanadium dioxide nanobeam

    Science.gov (United States)

    Li, Zejun; Wu, Jiajing; Hu, Zhenpeng; Lin, Yue; Chen, Qi; Guo, Yuqiao; Liu, Yuhua; Zhao, Yingcheng; Peng, Jing; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

    2017-06-01

    In correlated systems, intermediate states usually appear transiently across phase transitions even at the femtosecond scale. It therefore remains an open question how to determine these intermediate states--a critical issue for understanding the origin of their correlated behaviour. Here we report a surface coordination route to successfully stabilize and directly image an intermediate state in the metal-insulator transition of vanadium dioxide. As a prototype metal-insulator transition material, we capture an unusual metal-like monoclinic phase at room temperature that has long been predicted. Coordinate bonding of L-ascorbic acid molecules with vanadium dioxide nanobeams induces charge-carrier density reorganization and stabilizes metallic monoclinic vanadium dioxide, unravelling orbital-selective Mott correlation for gap opening of the vanadium dioxide metal-insulator transition. Our study contributes to completing phase-evolution pathways in the metal-insulator transition process, and we anticipate that coordination chemistry may be a powerful tool for engineering properties of low-dimensional correlated solids.

  3. Importance of Vanadium-Catalyzed Oxidation of SO2to SO3in Two-Stroke Marine Diesel Engines

    DEFF Research Database (Denmark)

    Colom, Juan M.; Alzueta, María U.; Christensen, Jakob Munkholt

    2016-01-01

    Low-speed marine diesel engines are mostly operated on heavy fuel oils, which have a high content of sulfur andash, including trace amounts of vanadium, nickel, and aluminum. In particular, vanadium oxides could catalyze in-cylinderoxidation of SO2 to SO3, promoting the formation of sulfuric acid...... of the catalyticspecies within the engine. Experiments with different particle compositions (vanadium/sodium ratio) and temperatures (300−800 °C) show that both the temperature and sodium content have a major impact on the oxidation rate. Kinetic parameters forthe catalyzed reaction are determined, and the proposed...... kinetic model fits well with the experimental data. The impact of thecatalytic reaction is studied with a phenomenological zero-dimensional (0D) engine model, where fuel oxidation and SOxformation is modeled with a comprehensive gas-phase reaction mechanism. Results indicate that the oxidation of SO2...

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

    Science.gov (United States)

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

    2017-07-01

    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.

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

    Science.gov (United States)

    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.

  6. Synthesis and Characterization of Vanadium Doped Zinc Oxide Thick Film for Chemical Sensor Application

    Directory of Open Access Journals (Sweden)

    Rayees Ahmad Zargar

    2015-01-01

    Full Text Available Zinc oxide and vanadium pentoxide nanoparticles derived by chemical coprecipitation route were used to cast Zn0.96V0.04O thick film by screen printing method. The structural, morphological, optical, and electrical properties of the film were characterized by powder XRD, SEM, Raman, UV-VIS, and DC conductivity techniques. XRD pattern, SEM image, and Raman spectrum of the film confirm the single phase formation of Wurtzite structure with preferential orientation along [101] plane, minor variation in lattice parameters, and vanadium ions substitution at zinc sites. Zn0.96V0.04O pellet has been used for sensing ammonia vapor concentrations in 20–50°C temperature range which exhibits maximum responsiveness and sensitivity at 30°C. The minor variations in resistance are observed with ammonia vapor concentration. The adsorption of ammonia vapors through weak hydrogen bonding and its insertion into lattice by nitrogen lone pairs donation at vacant/defect sites in lattice caused by vanadium doping are considered to explain gas sensing mechanism.

  7. Vanadium distribution, lipid peroxidation and oxidative stress markers upon decavanadate in vivo administration.

    Science.gov (United States)

    Soares, S S; Martins, H; Duarte, R O; Moura, J J G; Coucelo, J; Gutiérrez-Merino, C; Aureliano, M

    2007-01-01

    The contribution of decameric vanadate species to vanadate toxic effects in cardiac muscle was studied following an intravenous administration of a decavanadate solution (1mM total vanadium) in Sparus aurata. Although decameric vanadate is unstable in the assay medium, it decomposes with a half-life time of 16 allowing studying its effects not only in vitro but also in vivo. After 1, 6 and 12h upon decavanadate administration the increase of vanadium in blood plasma, red blood cells and in cardiac mitochondria and cytosol is not affected in comparison to the administration of a metavanadate solution containing labile oxovanadates. Cardiac tissue lipid peroxidation increases up to 20%, 1, 6 and 12h after metavanadate administration, whilst for decavanadate no effects were observed except 1h after treatment (+20%). Metavanadate administration clearly differs from decavanadate by enhancing, 12h after exposure, mitochondrial superoxide dismutase (SOD) activity (+115%) and not affecting catalase (CAT) activity whereas decavanadate increases SOD activity by 20% and decreases (-55%) mitochondrial CAT activity. At early times of exposure, 1 and 6h, the only effect observed upon decavanadate administration was the increase by 20% of SOD activity. In conclusion, decavanadate has a different response pattern of lipid peroxidation and oxidative stress markers, in spite of the same vanadium distribution in cardiac cells observed after decavanadate and metavanadate administration. It is suggested that once formed decameric vanadate species has a different reactivity than vanadate, thus, pointing out that the differential contribution of vanadium oligomers should be taken into account to rationalize in vivo vanadate toxicity.

  8. Synthesis and characterization of alumina-supported vanadium oxide catalysts prepared by the molecular designed dispersion of VO(acac)2 complexes

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Baltes, M.; Voort, P. van der; Ramachandra Rao, R.; Catana, Gabriela; Schoonheydt, R.A.; Vansant, E.F.

    2000-01-01

    Alumina-supported vanadium oxide catalysts have been prepared by the molecular designed dispersion method, using the vanadyl acetylacetonate complex (VO(acac)2). The complex has been adsorbed on the support from solution, followed by thermal conversion into the corresponding supported vanadium oxide

  9. In-situ UV-Raman study on soot combustion over TiO2 or ZrO2-supported vanadium oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    WACHS; Israel; E.

    2008-01-01

    UV-Raman spectroscopy was used to study the molecular structures of TiO2 or ZrO2-supported vana-dium oxide catalysts.The real time reaction status of soot combustion over these catalysts was de-tected by in-situ UV-Raman spectroscopy.The results indicate that TiO2 undergoes a crystalline phase transformation from anatase to rutile phase with the increasing of reaction temperature.However,no obvious phase transformation process is observed for ZrO2 support.The structures of supported va-nadium oxides also depend on the V loading.The vanadium oxide species supported on TiO2 or ZrO2 attain monolayer saturation when V loading is equal to 4(4 is the number of V atoms per 100 support metal ions).Interestingly,this loading ratio(V4/TiO2 and V4/ZrO2) gave the best catalytic activities for soot combustion reaction on both supports(TiO2 and ZrO2).The formation of surface oxygen com-plexes(SOC) is verified by in-situ UV Raman spectroscopy and the SOC mainly exist as carboxyl groups during soot combustion.The presence of NO in the reaction gas stream can promote the pro-duction of SOC.

  10. Controlled three-dimensional manipulation of vanadium oxide nanotubes with optical tweezers

    Science.gov (United States)

    Hernández-Pozos, Jose Luis; Lee, Woei Ming; Vera-Robles, Liliana Irais; Campero, Antonio; Dholakia, Kishan

    2008-12-01

    We present a direct nanotube-microsphere tagging technique for the controlled three-dimensional (3D) manipulation and transportation of vanadium oxide nanotubes (VOx-NTs) with optical tweezers. The high scattering and absorptive nature of the VOx-NTs preclude the 3D optical trapping of such nanostructures. VOx-NTs are adhered to 3-aminopropyl-triethoxysilane functionalized silica microspheres, which act as handles for indirectly manipulating and transporting the nanotubes in three dimensions with optical tweezers. The optical tweezers can also operate as optical scissors that can remove the dielectric handles and trim these nanotubes. This technique may be extended to the optical manipulation of nanotubes of any material.

  11. Experimental and theoretical studies of the reaction between cationic vanadium oxide clusters and acetylene

    Institute of Scientific and Technical Information of China (English)

    YIN Shi; MA YanPing; DU Lin; HE ShengGui; GE MaoFa

    2008-01-01

    The time of flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source and a fast flow reactor was adopted to study the reactivity of cationic vanadium oxide clusters (VmO+n) toward acetylene (C2H2) molecules under gas phase (P, ~ 1.14 kPa), under near room temperature (T, ~ 350 K) conditions. Association products, VmOnC2H+2 (m,n = 2,4; 2,6; 3,7-8; 4,9-11; 5,12-13;6,13-16, and 7,17), are observed. The oxidation of C2H2 by (V2O5)+n, (n = 1-3) is experimentally identified.The reactivity of (V2O5)+n decreases as n increases. Density functional theory (DFT) calculations were carried out to interpret the reaction mechanisms. The DFT results indicate that a terminal oxygen atom from V2O+5 can transfer overall barrierlessly to C2H2 at room temperature, which is in agreement with the experimental observation. Other experimental results such as the observation of V2O6C2H+2 and nonobservation of V2O7,8C2H+2 in the experiments are also well interpreted based on the DFT calculations.The reactivity of vanadium oxide clusters toward acetylene and other hydrocarbons may be considered in identifying molecular level mechanisms for related heterogeneous catalysis.

  12. Reactivity control of C-H bond activation over vanadium-silver bimetallic oxide cluster cations.

    Science.gov (United States)

    Li, Xiao-Na; Wu, Xiao-Nan; Ding, Xun-Lei; Xu, Bo; He, Sheng-Gui

    2012-08-27

    Vanadium-silver bimetallic oxide cluster ions (V(x)Ag(y)O(z)(+); x=1-4, y=1-4, z=3-11) are produced by laser ablation and reacted with ethane in a fast-flow reactor. A reflectron time of flight (Re-TOF) mass spectrometer is used to detect the cluster distribution before and after the reactions. Hydrogen atom abstraction (HAA) reactions are identified over VAgO(3)(+), V(2)Ag(2)O(6)(+), V(2)Ag(4)O(7)(+), V(3)AgO(8)(+), V(3)Ag(3)O(9)(+), and V(4)Ag(2)O(11)(+) ions, in which the oxygen-centered radicals terminally bonded on V atoms are active sites for the facile HAA reactions. DFT calculations are performed to study the structures, bonding, and reactivity. The reaction mechanisms of V(2)Ag(2)O(6)(+) +C(2)H(6) are also given. The doped Ag atoms with a valence state of +1 are highly dispersed at the periphery of the V(x)Ag(y)O(z)(+) cluster ions. The reactivity can be well-tuned gradually by controlling the number of Ag atoms. The steric protection due to the peripherally bonded Ag atoms greatly enhances the selectivity of the V-Ag bimetallic oxide clusters with respect to the corresponding pure vanadium oxide systems. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Adsorption of ammonia on vanadium-antimony mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Hernan; German, Estefania [Departamento e Instituto de Fisica del Sur, Universidad Nacional del Sur-CONICET, Avda. Alem 1253, (8000) Bahia Blanca (Argentina); Juan, Alfredo, E-mail: cajuan@uns.edu.ar [Departamento e Instituto de Fisica del Sur, Universidad Nacional del Sur-CONICET, Avda. Alem 1253, (8000) Bahia Blanca (Argentina); Irigoyen, Beatriz [Departamento de Ingenieria Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Pabellon de Industrias, Ciudad Universitaria, (1428) Ciudad Autonoma de Buenos Aires (Argentina)

    2012-02-01

    We analyzed the adsorption of ammonia (NH{sub 3}) on the VSbO{sub 4}(1 1 0) catalyst surface using density functional theory (DFT) calculations. We followed the evolution of the chemical bonds between different atoms of the resulting NH{sub 3}/VSbO{sub 4} system and the changes in the electronic structure of the catalyst. NH{sub 3} preferential adsorption geometries were analyzed through the crystal orbital overlap population (COOP) concept and the density of states (DOS) curves. The VSbO{sub 4}(1 1 0) surface exhibits Lewis and Bronsted acid sites on which the ammonia molecule can interact. On the Lewis acid site, NH{sub 3} adsorption resulted in the interaction between the N and a surface V-isolated cation. On Bronsted acid site, N interacted with a surface H coming from the chemical dissociation of water. The COOP analysis indicate that NH{sub 3} interaction on the VSbO{sub 4}(1 1 0) surface is weak. In addition, the DOS curves show more developed electronic interactions for NH{sub 3} adsorption on Lewis acid site than over Bronsted acid site.

  14. The ability of silicide coating to delay the catastrophic oxidation of vanadium under severe conditions

    Science.gov (United States)

    Chaia, N.; Mathieu, S.; Rouillard, F.; Vilasi, M.

    2015-02-01

    V-4Cr-4Ti vanadium alloy is a potential cladding material for sodium-cooled fast-neutron reactors (SFRs). However, its affinity for oxygen and the subsequent embrittlement that oxygen induces causes a need for an oxygen diffusion barrier, which can be obtained by manufacturing a multi-layered silicide coating. The present work aims to evaluate the effects of thermal cycling (using a cyclic oxidation device) and tensile and compressive stresses (using the three-point flexure test) on the coated alloy system. Tests were performed in air up to 1100 °C, which is 200 °C higher than the accidental temperature for SFR applications. The results showed that the VSi2 coating was able to protect the vanadium substrate from oxidation for more than 400 1-h cycles between 1100 °C and room temperature. The severe bending applied to the coated alloy at 950 °C using a load of 75 MPa did not lead to specimen breakage. It can be suggested that the VSi2 coating has mechanical properties compatible with the V-4Cr-4Ti alloy for SFR applications.

  15. Nano-vanadium oxide thin films in mixed phase for microbolometer applications

    Energy Technology Data Exchange (ETDEWEB)

    Subrahmanyam, A; Bharat Kumar Reddy, Y [Department of Physics, Indian Institute of Technology Madras, Chennai 600036 (India); Nagendra, C L [LEOS, ISRO, Peenya Industrial Estate, Bangalore 560060 (India)], E-mail: manu@iitm.ac.in

    2008-10-07

    Among the several phases of vanadium oxide, mixed phases of VO{sub 2} and V{sub 2}O{sub 5} are preferred for uncooled micro-bolometers with low noise. The aim of this investigation is to achieve mixed phase VO{sub 2} and V{sub 2}O{sub 5} thin films with nanometre grain sizes and high temperature coefficient of resistance (TCR). Since the phase depends upon the oxygen reactivity, these vanadium oxide thin films are prepared by reactive electron beam evaporation at different oxygen flow rates and substrate temperatures. The mixed phases have been evaluated through x-ray diffraction and x-ray photo emission studies. The temperature dependence of resistance has shown that the films grown at 473 K with 2.8 x 10{sup -5} mbar chamber pressure of oxygen (VO{sub 2} : V{sub 2}O{sub 5} ratio of 36 : 64) have the highest TCR of -3.2 K{sup -1} with a reasonable low resistance (120 {omega}/square)

  16. Target voltage behaviour of a vanadium-oxide thin film during reactive magnetron sputtering

    Institute of Scientific and Technical Information of China (English)

    Wang Tao; Jiang Ya-Dong; Yu He; Wu Zhi-Ming; Zhao He-Nan

    2011-01-01

    This paper simulates reactive magnetron-sputtering in constant current mode in a Vanadium-O2/Ar system equipped with a DC power supply by adopting both kinetics model and Berg's model. The target voltage during the reactive sputtering has been investigated as a function of reactive gas flow. Both experiments and simulations demonstrate a hysteresis curve with respect to the oxygen supply. The time-dependent variation of the target mode is studied by measuring the target voltage for various reactive oxygen gas flows and pre-sputtering times. The presputtering time increases with the increased initial target voltage. Furthermore, a corresponding time-dependent model simulating target voltage changes is also proposed. Based on these simulations, we find some relationships between the discharge voltage behaviour and the properties of the formed oxide. In this way, a better understanding of the target voltage changes during reactive sputtering can be achieved. We conclude that the presented theoretical models for parameter-dependent case and time-dependent case are in qualitative agreement with the experimental results and can be used to comprehend the target voltage behaviour in the deposition of vanadium oxide thin films.

  17. Zirconium oxide nanotube-Nafion composite as high performance membrane for all vanadium redox flow battery

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    1996-08-01

    respectively; Lehninger , 1965); by comparison, the E0 for one-electron reduction of V(v) is about +1.0 V, but may be further affected by chelation...vanadium compounds in fuel oil ash. Br. J. Ind. Med. 37:253-256. Lehninger , A.L. 1965. The Mitochondrion: Molecular Basis of Structure and Function. W.A

  19. Mesoporous vanadium nitride as a high performance catalyst support for formic acid electrooxidation.

    Science.gov (United States)

    Yang, Minghui; Cui, Zhiming; DiSalvo, Francis J

    2012-11-04

    Mesoporous vanadium nitride (VN) with high surface area and good electrical conductivity was prepared by a solid-solid phase separation method from a Zn containing vanadium oxide, Zn(3)V(2)O(8). The VN supported Pd catalyst exhibited significant catalytic activity for formic acid oxidation.

  20. Vanadium and cadmium in vivo effects in teleost cardiac muscle: metal accumulation and oxidative stress markers.

    Science.gov (United States)

    Soares, S S; Martins, H; Gutiérrez-Merino, C; Aureliano, M

    2008-03-01

    Several biological studies associate vanadium and cadmium with the production of reactive oxygen species (ROS), leading to lipid peroxidation and antioxidant enzymes alterations. The present study aims to analyse and compare the oxidative stress responses induced by an acute intravenous exposure (1 and 7 days) to a sub-lethal concentration (5 mM) of two vanadium solutions, containing different vanadate n-oligomers (n=1-5 or n=10), and a cadmium solution on the cardiac muscle of the marine teleost Halobatrachus didactylus (Lusitanian toadfish). It was observed that vanadium is mainly accumulated in mitochondria (1.33+/-0.26 microM), primarily when this element was administrated as decameric vanadate, than when administrated as metavanadate (432+/-294 nM), while the highest content of cadmium was found in cytosol (365+/-231 nM). Indeed, decavanadate solution promotes stronger increases in mitochondrial antioxidant enzymes activities (catalase: +120%; superoxide dismutase: +140%) than metavanadate solution. On contrary, cadmium increases cytosolic catalase (+111%) and glutathione peroxidases (+50%) activities. It is also observed that vanadate oligomers induce in vitro prooxidant effects in toadfish heart, with stronger effects induced by metavanadate solution. In summary, vanadate and cadmium are differently accumulated in blood and cardiac subcellular fractions and induced different responses in enzymatic antioxidant defence mechanisms. In the present study, it is described for the first time the effects of equal doses of two different metals intravenously injected in the same fish species and upon the same exposure period allowing to understand the mechanisms of vanadate and cadmium toxicity in fish cardiac muscle.

  1. Nanorod niobium oxide as powerful catalysts for an all vanadium redox flow battery.

    Science.gov (United States)

    Li, Bin; Gu, Meng; Nie, Zimin; Wei, Xiaoliang; Wang, Chongmin; Sprenkle, Vincent; Wang, Wei

    2014-01-01

    A powerful low-cost electrocatalyst, nanorod Nb2O5, is synthesized using the hydrothermal method with monoclinic phases and simultaneously deposited on the surface of a graphite felt (GF) electrode in an all vanadium flow battery (VRB). Cyclic voltammetry (CV) study confirmed that Nb2O5 has catalytic effects toward redox couples of V(II)/V(III) at the negative side and V(IV)/V(V) at the positive side to facilitate the electrochemical kinetics of the vanadium redox reactions. Because of poor conductivity of Nb2O5, the performance of the Nb2O5 loaded electrodes is strongly dependent on the nanosize and uniform distribution of catalysts on GF surfaces. Accordingly, an optimal amount of W-doped Nb2O5 nanorods with minimum agglomeration and improved distribution on GF surfaces are established by adding water-soluble compounds containing tungsten (W) into the precursor solutions. The corresponding energy efficiency is enhanced by ∼10.7% at high current density (150 mA·cm(-2)) as compared with one without catalysts. Flow battery cyclic performance also demonstrates the excellent stability of the as prepared Nb2O5 catalyst enhanced electrode. These results suggest that Nb2O5-based nanorods, replacing expensive noble metals, uniformly decorating GFs holds great promise as high-performance electrodes for VRB applications.

  2. Partial oxidation of n- and i-pentane over promoted vanadium-phosphorus oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A.; Mikhajluk, B.D.; Komashko, G.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    It is known, that the cost of raw materials for catalytic oxidation processes is about 60% of the product price. Cheap initial compounds to produce variety of products and to replace olefins and aromatic hydrocarbons are paraffins. That is why catalytic systems which could be possibly rather efficient in selective oxidation of paraffin hydrocarbons are under very close investigation now. One of such processes in n-pentane oxidation. The obtained results on n-pentane oxidation over VPO catalysts were quite encouraging in respect of possible reach high selectivity and yield of phthalic anhydride. However, in our work it was shown that the main product of n-pentane oxidation in the presence of VPO catalytic system as well as VPMeO was maleic anhydride. Some later our results were confirmed in, where to grow the selectivity towards phthalic anhydride the Co-additive was introduced. On the basis of the proposal made before on the mechanism of paraffins conversion over the vanadyl pyrophosphate surface with their activation at the first and fourth carbon atoms, we assumed possible methylmaleic (citraconic) anhydride forming at n- and i-pentane oxidation. This assumption has been recently supported by both our and other researchers` experimental results. In it was also hypothized possible mechanistic features for phthalic anhydride forming from n-pentane. The present work deals with the results of n- and i-pentane oxidation over VPO catalysts promoted with Bi, Cs, Te, Zr. (orig.)

  3. Catalytic Spectrophotometry for Vanadium Determination Based on Oxidation of Arsenazo Ⅲ by Bichromate

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    A catalytic spectrophotometry for the determination of trace amount of vanadium was developed based on its catalytic effect on the oxidation of arsenazo Ⅲ by potassium bichromate in weak acidic medium. The optimized conditions for determinations are: cK2Cr2O7=3.0×10-5 mol·L-1, carsenazo Ⅲ=3.0×10-5 mol·L-1, pH=4.0, t=90℃. The calibration graph is linear for 0.02~0.2 μg·ml-1, and the detection limit is 0.02 μg·ml-1 V. The apparent active energy of this catalytic reaction is 21.72 kJ·mol-1. Most foreign ions do not interfere with the determination of vadadium, except for Fe(Ⅱ) and Co(Ⅱ), and their interferences could be eliminated by ion exchange. The present method has been used to make the determination of vanadium in human hair, tea, potato and wastewater, and the results were satisfactory.

  4. CHEMILUMINESCENCE ON OXIDE SURFACE

    OpenAIRE

    L. I. IVANKIV; O. V. DZYUPYN; O.A. Balitskii

    2008-01-01

    This paper describes the oxygen adsorption properties on magnesium oxide surface. The results are compared with theoretical adsorption kinetics. Temperature and time dependences of adsorption mechanisms and chemiluminescence are discussed.

  5. Vanadium-catalyzed oxidative Strecker reaction: α-C-H cyanation of para-methoxyphenyl (PMP)-protected primary amines.

    Science.gov (United States)

    Zhu, Chen; Xia, Ji-Bao; Chen, Chuo

    2014-01-01

    We describe an oxidative Strecker reaction that allows for direct cyanation of para-methoxyphenyl (PMP)-protected primary amines. A vanadium(V) complex was used as the catalyst and TBHP as the oxidant. The cyanation occurs at the α-C position bearing either an alkyl or an aromatic group. This method provides a direct access to α-aminonitrile from amines with one-carbon extension.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Hye-Mi; Um, Sukkee, E-mail: sukkeeum@hanyang.ac.kr

    2016-05-01

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

  7. Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

    Science.gov (United States)

    Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

    2010-01-01

    Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re

  8. Vanadium dioxide - Reduced graphene oxide composite as cathode materials for rechargeable Li and Na batteries

    Science.gov (United States)

    Mahadi, Nurulhuda Binti; Park, Jae-Sang; Park, Jae-Ho; Chung, Kyung Yoon; Yi, Su Youl; Sun, Yang-Kook; Myung, Seung-Taek

    2016-09-01

    In this study, a metastable form of vanadium dioxide, denoted as VO2(B), has been successfully synthesized under solvothermal condition. However, the as-received VO2(B) suffers from fast capacity fading and poor high-rate performance. In order to overcome these problems, the as-received VO2(B) is solvothermally treated with reduced graphene oxide (rGO) to produce VO2(B)/rGO composite. As a result, the resulting electric conductivity of the VO2(B)/rGO composite is improved to ∼10-4 cm S-1 (from ∼10-7 S cm-1 for the as-received VO2(B)). Electrochemical data of the VO2(B)/rGO composite, tested in both Li and Na cells, shows markedly enhanced electrochemical performance compared to bare VO2(B). The effect of electro-conducting rGO is more evident at high rates.

  9. Sonochemical synthesis of silver vanadium oxide micro/nanorods: solvent and surfactant effects.

    Science.gov (United States)

    Mohandes, Fatemeh; Salavati-Niasari, Masoud

    2013-01-01

    In this investigation, a facile sonochemical route has been developed for the preparation of silver vanadium oxide (SVO) micro/nanorods by using silver salicylate and ammonium metavanadate as silver and vanadate precursor, respectively. Here, silver salicylate, [Ag(HSal)], is introduced as a new silver precursor to fabricate AgVO(3) nanorods. The effect of numerous solvents and surfactants on the morphology and sonochemical formation mechanism of AgVO(3) nanorods was studied. AgVO(3) nanorods were characterized by SEM and TEM images, XRD patterns, FT-IR, XPS, and EDS spectroscopy. SEM, TEM, and XRD results showed that AgO nanoparticles were formed onto AgVO(3) nanorods in the presence of ethanol, cyclohexanol, dimethylsulfoxide (DMSO), and acetone. By using polyethylene glycol (PEG-6000) and N,N-dimethylformamide (DMF) as organic additives, the thickness of AgVO(3) nanorods decreased.

  10. Role of vanadium and pyridine in heteropolycompounds for selective oxidation of alcohols with hydrogen peroxide

    Indian Academy of Sciences (India)

    Valeria Palermo; Paula I Villabrille; Patricia G Vázquez; Carmen V Cáceres; Pietro Tundo; Gustavo P Romanelli

    2013-11-01

    This study describes the application of heteropolyacids H3PMo12O40,H4SiMo12O40, H4PMo11VO40, H5PMo10V2O40, H9PMo6V6O40, and a hybrid pyridine-modified heteropolyacid with Keggin structure for selective oxidation of alcohols to ketones or aldehydes using aqueous hydrogen peroxide and acetonitrile as solvent. Performance of these different catalysts in 1-phenylethanol oxidation was studied. Influence of reaction temperature, amount of catalyst and hydrogen peroxide and reaction time on the yield of acetophenone was investigated to obtain optimal reaction conditions. Oxidation ability of the catalyst depended on the number of vanadium atoms present in the Keggin ion and to a lesser extent on pyridine substitution in the Keggin secondary structure. In order to explore the applicability of the method for selective oxidation of alcohols to ketones or aldehydes, various alcohols were investigated according to the general procedure using hybrid pyridine-modified heteropolyacid.

  11. Samarium-modified vanadium phosphate catalyst for the selective oxidation of n-butane to maleic anhydride

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Hua-Yi [State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Wang, Hai-Bo [Fushun Res InstPetr& Petrochem, Fushun, 113001 (China); Liu, Xin-Hua; Li, Jian-Hui; Yang, Mei-Hua [State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Huang, Chuan-Jing, E-mail: huangcj@xmu.edu.cn [State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Weng, Wei-Zheng [State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China); Wan, Hui-Lin, E-mail: hlwan@xmu.edu.cn [State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)

    2015-10-01

    Graphical abstract: The addition of a small amount of Sm into VPO catalyst brought about great changes in its physicochemical properties such as surface area, surface morphology, phase composition and redox property, thus leading to a higher catalytic performance in the selective oxidation of n-butane to maleic anhydride, as compared to the undoped VPO catalyst. - Highlights: • The addition of Sm leads to great changes in the structure of VPO catalyst. • Sm improves performance of VPO for oxidation of n-butane to maleic anhydride. • Catalytic performance is closely related to structure of VPO catalyst. - Abstract: A series of samarium-modified vanadium phosphate catalysts were prepared and studied in selective oxidation of n-butane to maleic anhydride. The catalytic evaluation showed that Sm modification significantly increased the overall n-butane conversion and intrinsic activity. N{sub 2}-adsorption, XRD, SEM, Raman, XPS, EPR and H{sub 2}-TPR techniques were used to investigate the intrinsic difference among these catalysts. The results revealed that the addition of Sm to VPO catalyst can increase the surface area of the catalyst, lead to a significant change in catalyst morphology from plate-like structure into rosette-shape clusters, and largely promote the formation of (VO){sub 2}P{sub 2}O{sub 7}. All of these were related to the different catalytic performance of Sm-doped and undoped VPO catalysts. The roles of the different VOPO{sub 4} phases and the influence of Sm were also described and discussed.

  12. Kinetics and mechanism of the oxidation of D-fructose by vanadium(V) in H2SO4 medium.

    Science.gov (United States)

    Khan, Zaheer; Babu, P S S; Kabir-ud-Din

    2004-01-02

    The oxidative degradation of D-fructose by vanadium(V) in the presence of H(2)SO(4) has an induction period followed by autoacceleration. The kinetics and mechanism of the induction period have been studied at constant ionic strength. The reaction was followed spectrophotometrically by measuring the changes in absorbance at 350 nm. Evidence of induced polymerization of acrylonitrile and of reduction of mercuric chloride indicates that a free-radical mechanism operates during the course of reaction. Vanadium(V) is only reduced to vanadium(IV). The reaction is first and fractional order in [V(V)] and [D-fructose], respectively; but dependence on [H+] is complex, that is, [equation: see text]. At constant [H2SO4], sodium hydrogensulfate accelerates the reaction. The effect of added sodium sulfate on the H2SO4 and HSO4-catalyzed reaction is also reported. The activation parameters Ea=118 kJ mol(-1), DeltaH#=116 kJ mol(-1), DeltaS#=-301 J K(-1) mol(-1), and DeltaG#=213 kJ mol(-1) are calculated and discussed. Reaction products are also examined, and it is concluded that oxidation of D-fructose by vanadium(V) involves consecutive one-electron abstraction steps.

  13. Defects at oxide surfaces

    CERN Document Server

    Thornton, Geoff

    2015-01-01

    This book presents the basics and characterization of defects at oxide surfaces. It provides a state-of-the-art review of the field, containing information to the various types of surface defects, describes analytical methods to study defects, their chemical activity and the catalytic reactivity of oxides. Numerical simulations of defective structures complete the picture developed. Defects on planar surfaces form the focus of much of the book, although the investigation of powder samples also form an important part. The experimental study of planar surfaces opens the possibility of applying the large armoury of techniques that have been developed over the last half-century to study surfaces in ultra-high vacuum. This enables the acquisition of atomic level data under well-controlled conditions, providing a stringent test of theoretical methods. The latter can then be more reliably applied to systems such as nanoparticles for which accurate methods of characterization of structure and electronic properties ha...

  14. Surface and bulk aspects of mixed oxide catalytic nanoparticles: oxidation and dehydration of CH(3)OH by polyoxometallates.

    Science.gov (United States)

    Nakka, Lingaiah; Molinari, Julie E; Wachs, Israel E

    2009-10-28

    The molecular structures and surface chemistry of mixed metal oxide heteropolyoxo vanadium tungstate (H(3+x)PW(12-x)V(x)O(40) with x = 0, 1, 2, and 3) Keggin nanoparticles (NPs), where vanadium is incorporated into the primary Keggin structure, and supported VO(x) on tungstophosphoric acid (TPA, H(3)PW(12)O(40)), where vanadium is present on the surface of the Keggin unit, were investigated with solid-state magic angle spinning (51)V NMR, FT-IR, in situ Raman, in situ UV-vis, CH(3)OH temperature-programmed surface reaction (TPSR), and steady-state methanol oxidation. The incorporated VO(x) unit possesses one terminal V horizontal lineO bond, four bridging V-O-W/V bonds, and one long V-O-P bond in the primary Keggin structure, and the supported VO(x) unit possesses a similar coordination in the secondary structure under ambient conditions. The specific redox reaction rate for VO(x) in the Keggin primary structure is comparable to that of bulk V(2)O(5) and the more active supported vanadium oxide catalysts. The specific acidic reaction rate for the WO(x) in the TPA Keggin, however, is orders of magnitude greater than found for bulk WO(3), supported tungsten oxide catalysts, and even the highly acidic WO(3)-ZrO(2) catalyst synthesized by coprecipitation of ammonium metatungstate and ZrO(OH)(2). From CH(3)OH-TPSR and in situ Raman spectroscopy it was found that incorporation of vanadium oxide into the primary Keggin structure is also accompanied by the formation of surface VO(x) species at secondary sites on the Keggin outer surface. Both CH(3)OH-TPSR and steady-state methanol oxidation studies demonstrated that the surface VO(x) species on the Keggin outer surface are significantly less active than the VO(x) species incorporated into the primary Keggin structure. The presence of the less active surface VO(x) sites in the Keggins, thus, decreases the specific reaction rates for both methanol oxidation and methanol dehydration. During methanol oxidation/dehydration (O(2

  15. Visible light photooxidative performance of a high-nuclearity molecular bismuth vanadium oxide cluster

    Directory of Open Access Journals (Sweden)

    Johannes Tucher

    2014-05-01

    Full Text Available The visible light photooxidative performance of a new high-nuclearity molecular bismuth vanadium oxide cluster, H3[{Bi(dmso3}4V13O40], is reported. Photocatalytic activity studies show faster reaction kinetics under anaerobic conditions, suggesting an oxygen-dependent quenching of the photoexcited cluster species. Further mechanistic analysis shows that the reaction proceeds via the intermediate formation of hydroxyl radicals which act as oxidant. Trapping experiments using ethanol as a hydroxyl radical scavenger show significantly decreased photocatalytic substrate oxidation in the presence of EtOH. Photocatalytic performance analyses using monochromatic visible light irradiation show that the quantum efficiency Φ for indigo photooxidation is strongly dependent on the irradiation wavelength, with higher quantum efficiencies being observed at shorter wavelengths (Φ395nm ca. 15%. Recycling tests show that the compound can be employed as homogeneous photooxidation catalyst multiple times without loss of catalytic activity. High turnover numbers (TON ca. 1200 and turnover frequencies up to TOF ca. 3.44 min−1 are observed, illustrating the practical applicability of the cluster species.

  16. Study of the performance of vanadium based catalysts prepared by grafting in the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Santacesaria, E.; Carotenuto, G.; Tesser, R.; Di Serio, M. [Naples Univ. (Italy). Dept. of Chemistry

    2011-07-01

    The oxidative dehydrogenation (ODH) of propane has been investigated by using many different vanadia based catalysts, prepared by grafting technique and containing variable amounts of active phase supported on SiO{sub 2} previously coated, by grafting in three different steps, with multilayer of TiO{sub 2}. A depth catalytic screening, conducted in a temperature range of 400-600 C, at atmospheric pressure and in a range of residence time W/F=0.08-0.33 ghmol{sub -1}, has shown that the vanadium oxide catalysts on TiO{sub 2}-SiO{sub 2} support, prepared by grafting have good performances in the ODH of propane. In particular, a preliminary study has demonstrated that higher selectivities can be obtained employing catalysts having a well dispersed active phase that can be achieved with a V{sub 2}O{sub 5} content lower than 10%{sub w}t. It is well known that, in the case of redox catalysts, an increase of the selectivity can be achieved not only by using an adequate catalytic system but also via engineering routes like decoupling catalytic steps of reduction and re-oxidation. In fact it has been observed that by operating in dehydrogenating mode, on the same catalysts, a higher selectivity is obtained although the catalyst is poisoned by the formation of coke on the surface. As consequence of the results obtained in dehydrogenation, in this work has been explored the possibility to feed low amounts of oxygen, below the stoichiometric level with the aim to keep clean the surface from coke but maintaining high the selectivity, because, dehydrogenation reaction prevails. In this work, the behavior of catalysts containing different amounts of V2O5 has been studied in the propane-propene reaction by using different ratios C{sub 3}H{sub 8}/O{sub 2} included in the range 0-2. (orig.)

  17. [Vanadium: threat and hope].

    Science.gov (United States)

    Urban, J; Antonowicz-Juchniewicz, J; Andrzejak, R

    2001-01-01

    Vanadium is an element classified in the group of heavy metals, very common in the natural environment and widely used in industry. It is mainly used in the production of nonferrous alloys, most resistant carbon steel, as well as in chemical, glass, paint and varnish, ceramic, and photographic industries. In the atmosphere, two second of vanadium originates from anthropogenic sources, sea-born aerosols and volcanic eruptions. Municipal waste is the major source of vanadium in surface water. It is one of the components of live organisms and participates in many biochemical processes essential for their proper functioning, but in higher concentrations it may induce acute or chronic intoxication that damage biological structures and disorder biochemical systems. The mechanism of vanadium toxic effect has not as yet been elucidated, however, it is already known that this mechanism is rooted among others in vanadium properties able to hinder a number of enzymatic systems. For vanadium the most "critical" systems are respiratory, urinary and hemopoietic. Vanadium salts may also be genotoxic and harmful at different phases of reproduction and development. Numerous studies of a possible use of vanadium in treatment of certain diseases, e.g., diabetes, have been carried out. Some findings on a potential antineoplastic or contraceptive effect of vanadium compounds have recently been reported. To sum up, there are numerous hazards associated with the wide industrial use of vanadium, nevertheless, the number of findings highlighting its nutritive and therapeutic properties is growing.

  18. In-situ UV-Raman study on soot combustion over TiO2 or ZrO2-supported vanadium oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    LIU Jian; ZHAO Zhen; XU ChunMing; DUAN AiJun; JIANG GuiYuan; GAO JinSen; LIN WenYong; WACHS Israel E.

    2008-01-01

    UV-Raman spectroscopy was used to study the molecular structures of TiO2 or ZrO2-supported vana- dium oxide catalysts. The real time reaction status of soot combustion over these catalysts was de-tected by in-situ UV-Raman spectroscopy. The results indicate that TiO= undergoes a crystalline phase transformation from anatase to futile phase with the increasing of reaction temperature. However, no obvious phase transformation process is observed for ZrO2 support. The structures of supported va-nadium oxides also depend on the V loading. The vanadium oxide species supported on TiO2 or ZrO2 attain monolayer saturation when V loading is equal to 4 (4 is the number of V atoms per 100 support metal ions). Interestingly, this loading ratio (V4/TiO2 and V4/ZrO2) gave the best catalytic activities for soot combustion reaction on both supports (TiO2 and ZrO2). The formation of surface oxygen com-plexes (SOC) is verified by in-situ UV Raman spectroscopy and the SOC mainly exist as carboxyl groups during soot combustion. The presence of NO in the reaction gas stream can promote the pro-duction of SOC.

  19. Self-organized homo-epitaxial growth of (001) vanadium assisted by oxygen surface reconstruction

    Science.gov (United States)

    Andrieu, S.; Turban, P.; Kierren, B.

    2016-09-01

    In this paper the effect of oxygen on the vanadium homoepitaxial growth process is analyzed by using Auger spectroscopy, electron diffraction and scanning tunneling microscopy. As the oxygen induced 1 × 5 surface structure got a lattice spacing 6% different from the pure V lattice, relaxation is observed by electron diffraction during the growth. The average in-plane lattice spacing is thus shown to be proportional to the oxygen surface concentration. The surface lattice relaxation is observed to exponentially vary with the number of deposited atomic planes. A kinetic model is proposed and allows us to explain these observations. Furthermore, it helps us to distinguish two regimes depending on growth temperature. At high temperature, the oxygen surface concentration during growth is due to oxygen upward diffusion from the underneath V layer. For lower temperature however, this upward diffusion is not efficient and another source of oxygen contamination is evidenced. When the oxygen surface concentration is sufficient, a spectacular self-organization is observed at the surface by surface microscopy. Ribbons shape islands are observed and are tentatively explained as a consequence of oxygen surface concentration and stress induced by the surface reconstruction.

  20. Iron oxide surfaces

    Science.gov (United States)

    Parkinson, Gareth S.

    2016-03-01

    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  1. 熔融钒渣直接氧化钠化提钒新工艺研究%A New Process for Vanadium Extraction from Molten Vanadium Slag by Direct Oxidation and Sodium Activating Method

    Institute of Scientific and Technical Information of China (English)

    宋文臣; 李宏

    2012-01-01

    To address the problem of heat waste of vanadium slag in the existing vanadium extraction process, a new process is proposed in this paper to extract vanadium from molten vanadium slag by direct oxidation and sodium activating method. On the basis of current vanadium extraction process, the new process was verified by thermodynamic and kinetic calculation and analysis, and then simulation tests were carried out in the laboratory. The results show that with enough heat, vanadium slag can be kept in molten state during the vanadium extraction process. The dynamic conditions of the new process are noticeably better than the existing process. The oxidization rate of vanadium slag is about 90% and vanadium leaching rate can reach 82% or above with enough oxygen and Na2CO3 content at 20% ~ 30% of vanadium slag' weight. Thus, the feasibility of the new process is confirmed by the results.%针对现行钒渣焙烧工艺中存在的钒渣高温物理热的浪费问题,提出“熔融钒渣直接氧化钠化提钒”新工艺.在现行工艺基础上,对新工艺进行了热力学和动力学的计算与分析,最后进行了新工艺的实验室模拟试验.研究结果表明:新工艺条件下,钒渣在反应过程中热量充足会保持良好的熔融状态;新工艺的动力学条件明显优越于现行工艺;实验室试验结果验证了新工艺的可行性,在供氧充足,Na2CO3用量为20%~30%的条件下,钒渣氧化率约为90%,钒浸出率在82%以上.

  2. Vanadium oxides supported on hydrotalcite-type precursors: the effect of acid base properties on the oxidation of isopropanol

    Energy Technology Data Exchange (ETDEWEB)

    Meira, D.M.; Cortez, G.G. [Faculdade de Engenharia Quimica de Lorena, Lorena, SP (Brazil). Dept. de Engenharia Quimica. Lab. de Catalise II]. E-mail: cortez@dequi.faenquil.br; Monteiro, W.R.; Rodrigues, J.A.J. [Instituto Nacional de Pesquisas Espaciais (INPE), Sao Jose dos Campos, SP (Brazil). Lab. Associado de Combustao e Propulsao]. E-mail: jajr@lcp.inpe.br

    2006-07-15

    Vanadium oxide supported on hydrotalcite-type precursors was studied in the oxidation of isopropanol. Hydrotalcites with different y = Mg/Al ratios were synthesized by the method of coprecipitation nitrates of Mg and Al cations with K{sub 2}CO{sub 3} as precipitant. The decomposition of these hydrotalcite precursors at 450 deg C yielded homogeneous MgyAlOx mixed oxides that contain the Al{sup +3} cations totally incorporated into the MgO framework. The materials were characterized by chemical analysis, BET superficial area, X-ray diffraction, temperature-programmed reduction (TPR) and the reaction of isopropanol, a probe molecule used to evaluate the acid-base properties. The results of TPR showed that the reducibility of V{sup +5} decreased with the increase in magnesium loading in catalysts. The X-ray diffraction patterns of Al-rich hydrotalcite precursors showed the presence of crystalline phases of brucite and gibbsite. It was shown that chemical composition, texture, acid-base properties of the active sites and also Mg/Al ratio strongly affect the formation of the products in the oxidation of isopropanol. The Al-rich catalysts were much more active than the Mg-rich ones, converting isopropanol mainly to propylene. (author)

  3. Vanadium oxides supported on hydrotalcite-type precursors: the effect of acid-base properties on the oxidation of isopropanol

    Directory of Open Access Journals (Sweden)

    D. M. Meira

    2006-09-01

    Full Text Available Vanadium oxide supported on hydrotalcite-type precursors was studied in the oxidation of isopropanol. Hydrotalcites with different y = Mg/Al ratios were synthesized by the method of coprecipitation nitrates of Mg and Al cations with K2CO3 as precipitant. The decomposition of these hydrotalcite precursors at 450°C yielded homogeneous MgyAlOx mixed oxides that contain the Al+3 cations totally incorporated into the MgO framework. The materials were characterized by chemical analysis, BET superficial area, X-ray diffraction, temperature-programmed reduction (TPR and the reaction of isopropanol, a probe molecule used to evaluate the acid-base properties. The results of TPR showed that the reducibility of V+5 decreased with the increase in magnesium loading in catalysts. The X-ray diffraction patterns of Al-rich hydrotalcite precursors showed the presence of crystalline phases of brucite and gibbsite. It was shown that chemical composition, texture, acid-base properties of the active sites and also Mg/Al ratio strongly affect the formation of the products in the oxidation of isopropanol. The Al-rich catalysts were much more active than the Mg-rich ones, converting isopropanol mainly to propylene.

  4. n-Butane Oxidation over γ-Al2O3 Supported Vanadium Phosphate Catalysts

    Institute of Scientific and Technical Information of China (English)

    Y.H.Taufiq-Yap; L.K.Leong; R.Irmawati

    2007-01-01

    Four vanadium phosphate catalysts supported on γ-Al2O3(20 wt%)were synthesized via 75 h)at 673 K in a reaction flow of n-butane/air mixture.The samples calcined for 6 and 10 h produced only a single phase of(VO)2P2O7.However,the VOPO4 phase(β-VOPO4)was detected and became more prominent with only a minor pyrophosphate peaks were found after 30 h of calcination.All these pyrophosphate peaks disappeared after 75 h of calcination.The formation of V5+ phase Was also observed in the SEM micrographs.The redox properties and the nature of oxidants of the catalysts employed in this study were investigated by H2-TPR analysis.Selective oxidation of n-butane to maleic anhydride (MA) over these catalysts shows that the percentage of n-butane conversion decreases with the transformation of the catalysts from V4+ to V5+ phases.An appropriate ratio of V5+/V4+ can enhance the performance of the VPO catalyst.However,a higher amount of V5+ and its associated oxygen species are responsible to promote the MA selectivity.

  5. Influence of Concentration of Vanadium in Zinc Oxide on Structural and Optical Properties with Lower Concentration

    Institute of Scientific and Technical Information of China (English)

    WANG Li-Wei; XU Zheng; MENG Li-Jian; Vasco Teixeira; SONG Shi-Geng; XU Xu-Rong

    2009-01-01

    ZnO films doped with different vanadium concentrations are deposited onto glass substrates by dc reactive magnetron sputtering using a zinc target doped with vanadium. The vanadium concentrations are examined by energy dispersive spectroscopy (EDS) and the charge state of vanadium in ZnO thin films is characterized by x-ray photoelectron spectroscopy. The results of x-ray diffraction (XRD) show that all the films have a wurtzite structure and grow mainly in the c-axis orientation. The grain size and residual stress in the deposited films are estimated by fitting the XRD results. The optical properties of the films are studied by measuring the transmittance. The optical constants (refractive index and extinction coefficient) and the film thickness are obtained by fitting the transmittance. All the results are discussed in relation with the doping of the vanadium.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-15

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

  7. Influence of concentration and volume of precursor on the electrochemical properties of vanadium oxide thin films prepared by spray pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Ingole, R. S.; Fugare, B. Y.; Lokhande, B. J., E-mail: bjlokhande@yahoo.com [School of Physical Sciences, Solapur University, Solapur 413 255, M.S. (India)

    2016-04-13

    Vanadium oxide (V{sub 2}O{sub 5}) thin films have been prepared by spray pyrolysis using different concentrations and volumes of precursor solution via aqueous route at 673K deposition temperature. The influences of concentration and volume on the structural, morphological and electrochemical properties of the deposited samples are studied well. X - ray diffraction study shows orthorhombic crystal structure with V{sub 2}O{sub 5} phase, confirmed by FTIR spectroscopy. Scanning electron microscopy shows granular, homogeneous and dense surface morphology. Cyclic voltammetery of all samples carried at all scan rates. Samples prepared using 0.05M, 40 ml of precursor solution shows highest specific capacitance 428.25 F/gm at 5 mV/s, Charge discharge behavior exhibits specific energy 18.73 Wh/kg, specific power 36.00 kW/kg, columbic efficiency 87.50 %. Impedance spectroscopy study was carried in the frequency range 1mHz – 1MHz, reveals pseudocapacitive behavior of the electrode exhibiting internal resistance 1.34 ohm.

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

    Science.gov (United States)

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

    2015-06-01

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

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

    Science.gov (United States)

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

    2008-02-13

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

  10. Arsenic, Fluoride and Vanadium in surface water (Chasicó Lake, Argentina

    Directory of Open Access Journals (Sweden)

    Maria laura ePuntoriero

    2014-06-01

    Full Text Available Chasicó Lake is the main water body in the southwest of the Chaco-Pampean plain. It shows some differences from the typical Pampean shallow lakes, such as high salinity and high arsenic and fluoride levels. The aim of this paper is to analyze the trace elements [arsenic (As, fluoride (F- and vanadium (V] present in Chasicó Lake. Surface and groundwater were sampled in dry and wet periods, during 2010 and 2011. Fluoride was determined with a selective electrode. As and V were determined by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES. Significant correlation in surface water was only found for As and F- (r=0.978, p<0.01. The As, F- and V concentration values were higher and more widely dispersed in surface water than in groundwater, as a consequence of evaporation. The fact that these elements do not correlate in surface water may also indicates that groundwater would not be the main source of origin of As, F- and V in surface water. The origin of these trace elements is from volcanic glass from Pampean loess. As, F- and V concentration were higher than in national and international guideline levels for the protection of aquatic biota. Hence, this issue is relevant since the silverside (Odontesthes bonariensis is the most important commercial species in Chasicó Lake. This fish is both consumed locally and exported to other South-American countries through commercial and sport fishing.

  11. Properties of Vanadium-Doped Indium Oxide Deposited at Room Temperature as Transparent Conductor for Inverted Polymer Solar Cells

    Science.gov (United States)

    Choi, Min-Jun; Lim, Keun Yong; Park, Hyun-Woo; Kim, Han-Ki; Hwang, Do Kyung; Lim, Sung-Jin; Shim, Jae Won; Chung, Kwun-Bum

    2017-10-01

    The properties of vanadium-doped indium oxide (IVO) deposited at room temperature as a transparent conductor for inverted polymer solar cells have been investigated as a function of the vanadium doping concentration. IVO film prepared with V doping concentration of 0.03% showed optimal properties for use as a transparent conductor with figure of merit of 4.35 × 10-3 Ohm-1, related to altered band alignment between the Fermi level and conduction-band minimum. In the optimal optoelectrical conditions for the IVO film, performance optimization of PTB7:PC70BM inverted polymer solar cells resulted in maximum power conversion efficiency of 4.7 ± 0.4% under simulated air mass 1.5 global illumination at 100 mW/cm2.

  12. The mechanism of cysteine detection in biological media by means of vanadium oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Bezerra, A. G. [Universidade Tecnologica Federal do Parana, Departamento Academico de Fisica (Brazil); Barison, A. [Universidade Federal do Parana, Departamento de Quimica (Brazil); Oliveira, V. S. [Universidade Federal do Parana, Departamento de Fisica (Brazil); Foti, L.; Krieger, M. A. [Fundacao Oswaldo Cruz, Instituto de Biologia Molecular do Parana (Brazil); Dhalia, R.; Viana, I. F. T. [Fundacao Oswaldo Cruz, Centro de Pesquisas Aggeu Magalhaes (Brazil); Schreiner, W. H., E-mail: wido@fisica.ufpr.br [Universidade Federal do Parana, Departamento de Fisica (Brazil)

    2012-09-15

    We report on the interaction of vanadate nanoparticles, produced using the laser ablation in liquids synthesis, with cysteine in biological molecules. Cysteine is a very important amino acid present in most proteins, but also because cysteine and the tripeptide glutathione are the main antioxidant molecules in our body system. Detailed UV-Vis absorption spectra and dynamic light scattering measurements were done to investigate the detection of cysteine in large biological molecules. The intervalence band of the optical absorption spectra shows capability for quantitative cysteine sensing in the {mu}M range in biological macromolecules. Tests included cytoplasmic repetitive antigen and flagellar repetitive antigen proteins of the Trypanosoma cruzi protozoa, as well as the capsid p24 proteins from Human Immunodeficiency Virus type 1 and type 2. Detailed NMR measurements for hydrogen, carbon, and vanadium nuclei show that cysteine in contact with the vanadate looses hydrogen of the sulphydryl side chain, while the vanadate is reduced. The subsequent detachment of two deprotonated molecules to form cystine and the slow return to the vanadate complete the oxidation-reduction cycle. Therefore, the vanadate acts as a charge exchanging catalyst on cysteine to form cystine. The NMR results also indicate that the nanoparticles are not formed by the common orthorhombic V{sub 2}O{sub 5} form.

  13. Vanadium oxide-carbon nanotube composite films characterized by spectroscopic ellipsometry

    Science.gov (United States)

    He, Qiong; Xu, Xiangdong; Gu, Yu; Wang, Meng; Yao, Jie; Jiang, Yadong; Sun, Minghui; Ao, Tianhong; Lian, Yuxiang; Wang, Fu; Li, Xinrong

    2016-10-01

    Spectroscopic ellipsometry (SE) is utilized to characterize the vanadium oxide (VO x )-single walled carbon nanotube (SWCNT) composite films prepared by sol-gel. Five Tauc-Lorentz oscillators model is employed to describe the dispersions in the optical responses of VO x and VO x -SWCNT thin films. Results reveal that if the SWCNT concentration in the composite film is increased, the refractive index is decreased, while the extinction coefficient is increased. Moreover, higher SWCNT content leads to lower optical band gap (E g) but larger localized state (E e). Interestingly, both E g and E e values reach saturated at a SWCNT content of ~8 wt%. Particularly, the peak transition energies of the 5 Tauc-Lorentz oscillators have been assigned to the specific transitions according to the band structures of VO x . This work reveals the feasibility of investigating the optical properties and microstructures of VO x -SWCNT composite films by SE. These experimental results will be helpful for better understanding the VO x -SWCNT composite films, and promoting future characterizations of other SWCNT-based composites by SE.

  14. Oriented free-standing ammonium vanadium oxide nanobelt membranes: highly selective absorbent materials.

    Science.gov (United States)

    Zou, Rujia; Zhang, Zhenyu; Yu, Li; Tian, Qiwei; Wu, Jianghong; Sun, Yangang; Chen, Zhigang; Hu, Junqing

    2010-12-27

    Highly selective, absorbent, free-standing, paper-like membranes made of ammonium vanadium oxide (NH(4)V(4)O(14)) nanobelts have been engineered by taking advantage of the nanoscaled self-assembly of architectures that display a mesh structure with an average periodic pore size of about 5 to 10 nm. The NH(4)V(4)O(14) nanobelts are synthesized by using a simple hydrothermal process, and exhibit the same orientation and assemble into bundles, each about 40 to 80 nm in width, 3 to 5 nm in thickness, and up to several millimeters in length. Importantly, the as-obtained NH(4)V(4)O(14) nanobelt membranes can highly selectively absorb a variety of organic solvents, covering both polar and non-polar solvents, for example, the absorbent capacity of glycol is 28 times as high as the initial weight of the membrane, and it can even separate organic solvents with similar polarities and absorb solid contaminants in organic solvents. These highly selective, absorbent membrane materials can be an ideal candidate for the separation and removal of pollution in industrial and environmental applications.

  15. Activity Enhancement of Vanadium Catalysts with Ultrasonic Preparation Process for the Oxidation of Sulfur Dioxide

    Institute of Scientific and Technical Information of China (English)

    Zhenxing Chen; Honggui Li; Lingsen Wang

    2003-01-01

    The effect of ultrasonic cavitations on the activity of vanadium catalysts at low temperatures for the oxidation of sulfur dioxide, in which refined carbonized mother liquor had been added, was investigated.Twenty minutes were needed to produce obvious cavitations when the catalyst raw material was treated in the 50 W ultrasonic generator. However, only 10 minutes would be needed in a 150 W ultrasonic generator.The higher the temperature of the wet material, the less time was needed to produce cavitations, and the optimal temperature was 60 ℃. The water content in the wet material mainly affected the quantity of cavitations. Ls-8 catalyst was prepared using ultrasonic. Its activity for conversion of SO2 reached to 52.5% at 410 ℃ and 4.2% at 350 ℃. The differential thermal analyses indicate that both endothermic peaks and exothermic peaks noticeably shifted forward compared with Ls catalyst prepared without ultrasonic, and SEM results show a uniform pore size distribution for Ls-8 catalyst.

  16. Carbon nanotubes loaded with vanadium oxide for reduction NO with NH3 at low temperature☆

    Institute of Scientific and Technical Information of China (English)

    Shuli Bai; Shengtao Jiang; Huanying Li; Yujiang Guan

    2015-01-01

    The catalytic activity of carbon nanotubes-supported vanadium oxide (V2O5/CNTs) catalysts in the selective catalytic reduction (SCR) of NO with NH3 at low temperatures (≤250 °C) was investigated. The effects of V2O5 loading, reaction temperature, and presence of SO2 on the SCR activity were evaluated. The results show that V2O5/CNTs catalysts exhibit high activity for NO reduction with NH3 at low-temperatures. The catalysts also show very high stability in the presence of SO2. More interestingly, their activities are significantly promoted in-stead of being poisoned by SO2. The promoting effect of SO2 is distinctly associated with V2O5 loading, particularly maximized at low V2O5 loading, which indicated the role of CNTs support in this effect. The promoting effect of SO2 at low temperatures suggests that V2O5/CNTs catalysts are promising catalytic materials for low-temperature SCR reactions.

  17. Observation of in situ oxidation dynamics of vanadium thin film with ambient pressure X-ray photoemission spectroscopy

    Science.gov (United States)

    Kim, Geonhwa; Yoon, Joonseok; Yang, Hyukjun; Lim, Hojoon; Lee, Hyungcheol; Jeong, Changkil; Yun, Hyungjoong; Jeong, Beomgyun; Crumlin, Ethan; Lee, Jouhahn; Lee, Jaeyoung; Ju, Honglyoul; Mun, Bongjin Simon

    2016-11-01

    The evolution of oxidation/reduction states of vanadium oxide thin film was monitored in situ as a function of oxygen pressure and temperature via ambient pressure X-ray photoemission spectroscopy. Spectra analysis showed that VO2 can be grown at a relatively low temperature, T ˜ 523 K, and that V2O5 oxide develops rapidly at elevated oxygen pressure. Raman spectroscopy was applied to confirm the formation of VO2 oxide inside of the film. In addition, the temperature-dependent resistivity measurement on the grown thin film, e.g., 20 nm exhibited a desirable metal-insulator transition of VO2 with a resistivity change of ˜1.5 × 103 times at 349.3 K, displaying typical characteristics of thick VO2 film, e.g., 100 nm thick. Our results not only provide important spectroscopic information for the fabrication of vanadium oxides, but also show that high quality VO2 films can be formed at relatively low temperature, which is highly critical for engineering oxide film for heat-sensitive electronic devices.

  18. Lithium insertion into silver vanadium oxide, Ag{sub 2}V{sub 4}O{sub 11}

    Energy Technology Data Exchange (ETDEWEB)

    West, K. [Dept. of Physical Chemistry, Technical Univ. of Denmark, Lyngby (Denmark); Crespi, A.M. [Medtronic, Inc., Minneapolis, MN (United States)

    1995-04-01

    Lithium insertion into the silver vanadium oxide, Ag{sub 2}V{sub 4}O{sub 11}, was investigated at 25 and 100 C, and was found to be reversible throughout the composition interval 0 < x < 7, x being the composition parameter in Li{sub x}Ag{sub 2}V{sub 4}O{sub 11}. Silver was found to be mobile in the oxide, and for 0 < x < 2 insertion of lithium is associated with reduction of silver ions to metallic silver. When lithium is extracted, silver ions re-enter the structure. (orig.)

  19. A highly permeable and enhanced surface area carbon-cloth electrode for vanadium redox flow batteries

    Science.gov (United States)

    Zhou, X. L.; Zhao, T. S.; Zeng, Y. K.; An, L.; Wei, L.

    2016-10-01

    In this work, a high-performance porous electrode, made of KOH-activated carbon-cloth, is developed for vanadium redox flow batteries (VRFBs). The macro-scale porous structure in the carbon cloth formed by weaving the carbon fibers in an ordered manner offers a low tortuosity (∼1.1) and a broad pore distribution from 5 μm to 100 μm, rendering the electrode a high hydraulic permeability and high effective ionic conductivity, which are beneficial for the electrolyte flow and ion transport through the porous electrode. The use of KOH activation method to create nano-scale pores on the carbon-fiber surfaces leads to a significant increase in the surface area for redox reactions from 2.39 m2 g-1 to 15.4 m2 g-1. The battery assembled with the present electrode delivers an energy efficiency of 80.1% and an electrolyte utilization of 74.6% at a current density of 400 mA cm-2, as opposed to an electrolyte utilization of 61.1% achieved by using a conventional carbon-paper electrode. Such a high performance is mainly attributed to the combination of the excellent mass/ion transport properties and the high surface area rendered by the present electrode. It is suggested that the KOH-activated carbon-cloth electrode is a promising candidate in redox flow batteries.

  20. Effect of low temperature vacuum annealing on microstructural, optical, electronic, electrical, nanomechanical properties and phase transition behavior of sputtered vanadium oxide thin films

    Science.gov (United States)

    Porwal, Deeksha; Esther, A. Carmel Mary; Dey, Arjun; Gupta, A. K.; Raghavendra Kumar, D.; Bera, Parthasarathi; Barshilia, Harish C.; Bhattacharya, Manjima; Mukhopadhyay, Anoop Kumar; Khan, Kallol; Sharma, Anand Kumar

    2016-10-01

    Vanadium oxide thin films were deposited on quartz substrate by pulsed RF magnetron sputtering technique at 400-600 W and subsequently annealed at 100 °C in vacuum (1.5 × 10-5 mbar). Phase analysis, surface morphology and topology of the films e.g., both as-deposited and annealed were investigated by x-ray diffraction, field emission scanning electron microscopy and atomic force microscopy techniques. X-ray photoelectron spectroscopy (XPS) was employed to understand the elemental oxidation of the films. Transmittance of the films was evaluated by UV-vis-NIR spectrophotometer in the wavelength range of 200-1600 nm. Sheet resistance of the films was measured by two-probe method both for as-deposited and annealed conditions. XPS study showed the existence of V5+ and V4+ species. Metal to insulator transition temperature of the as-deposited film decreased from 339 °C to 326 °C after annealing as evaluated by differential scanning calorimetric technique. A significant change in transmittance was observed in particular at near infrared region due to alteration of surface roughness and grain size of the film after annealing. Sheet resistance values of the annealed films decreased as compared to the as-deposited films due to the lower in oxidation state of vanadium which led to increase in carrier density. Combined nanoindentation and finite element modeling were applied to evaluate nanohardness (H), Young’s modulus (E), von Mises stress and strain distribution. Both H and E were improved after annealing due to increase in crystallinity of the film.

  1. Nanorod Niobium Oxide as Powerful Catalysts for an All Vanadium Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bin; Gu, Meng; Nie, Zimin; Wei, Xiaoliang; Wang, Chong M.; Sprenkle, Vincent L.; Wang, Wei

    2014-01-01

    Graphite felts (GFs), as typical electrode materials for all vanadium redox flow batteries (VRBs), limit the cell operation to low current density because of their poor kinetic reversibility and electrochemical activity. Here, in order to address this issue we report an electrocatalyst, Nb2O5, decorating the surface of GFs to reduce the activation barrier for redox conversion. Nb2O5 nanofibers with monoclinic phases are synthesized by hydrothermal method and deposited on GFs, which is confirmed to have catalytic effects towards redox couples of V(II)/V(III) at the negative side and V(IV)/V(V) at the positive side, and thus applied in both electrodes of VRB cells. Due to the low conductivity of Nb2O5, the performance of electrodes heavily depends on the nano size and uniform distribution of catalysts on GFs surfaces. The addition of the water-soluble compounds containing W element into the precursor solutions facilitates the precipitation of nanofibers on the GFs. Accordingly, an optimal amount of W-doped Nb2O5 nanofibers with weaker agglomeration and better distribution on GFs surfaces are obtained, leading to significant improvement of the electrochemical performances of VRB cells particularly under the high power operation. The corresponding energy efficiency is enhanced by 10.7 % under the operation of high charge/discharge current density (150 mA•cm-2) owing to faster charge transfer as compared with that without catalysts. These results suggest that Nb2O5 based nanofibers-decorating GFs hold great promise as high-performance electrodes for VRB applications.

  2. The dynamics of the surface layer of lipid membranes doped by vanadium complex: computer modeling and EPR studies

    Directory of Open Access Journals (Sweden)

    Olchawa Ryszard

    2015-07-01

    Full Text Available Penetration of the liposome membranes doped with vanadium complex formed in the liquid-crystalline phase from egg yolk lecithin (EYL by the TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl spin probes has been investigated. The penetration process was followed by 360 hours at 24°C, using the electron spin resonance (EPR method. The spectroscopic parameter of the partition (F of this probe indicated that a maximum rigidity of the membrane was at 3% concentration of the vanadium complex. Computer simulations showed that the increase in the rigidity of the membrane corresponds to the closure of gaps in the surface layer of the membrane, and indicates the essential role of the membrane surface in transport processes.

  3. Structure and reactivity of titania-supported oxides. Part 1: vanadium oxide on titania in the sub- and super-monolayer regions

    NARCIS (Netherlands)

    Bond, Geoffrey C.; Perez Zurita, Josefina; Flamerz, Saad; Gellings, Paul J.; Bosch, Hans; Ommen, van Jan G.; Kip, Bert J.

    1986-01-01

    Vanadium oxide has been deposited on TiO2 (washed anatase, 10 m2g−1; Degussa P-25, 55 ±3 m2g−1; Eurotitania, 46 m2g−1) by aqueous impregnation of (NH4)2[VO(C2O4)2] and by reaction with VOCl3, VO(OR)3 (R=iBu) and VO(acac)2 in organic solvents. Single applications of the last tree reagents form not mo

  4. General synthesis of vanadium-based mixed metal oxides hollow nanofibers for high performance lithium-ion batteries

    Science.gov (United States)

    Xiang, Juan; Yu, Xin-Yao; Paik, Ungyu

    2016-10-01

    Hollow nanostructured mixed metal oxides have recently been intensively investigated as electrode materials for energy storage and conversion due to their remarkable electrochemical properties. Although great efforts have been made, the synthesis of hollow nanostructured vanadium-based mixed metal oxides especially those with one dimensional structure is rarely reported. Vanadium-based mixed metal oxides are promising electrode materials for lithium-ion batteries with high capacity and good rate capability. Here, we develop a facile and general method for the synthesis of one dimensional MxV2O8 (M = Co, Ni, Fe) tubular structure through a simple single-spinneret electrospinning technique followed by a calcination process. As a demonstration, Co3V2O8 hollow nanofibers are evaluated as anode materials for lithium-ion batteries. As expected, benefiting from their unique one dimensional tubular structure, the as-synthesized Co3V2O8 exhibits excellent electrochemical properties for lithium storage. To be specific, it can deliver a high specific capacity of 900 mAh g-1 at 5 A g-1, and long cycling stability up to 2000 cycles. The present work makes a significant contribution to the design and synthesis of mixed metal oxides with one dimensional tubular structure, as well as their potential applications in electrochemical energy storage.

  5. Two-dimensional recrystallisation processes of nanometric vanadium oxide thin films grown by atomic layer chemical vapor deposition (ALCVD) evidenced by AFM

    Energy Technology Data Exchange (ETDEWEB)

    Groult, H. [Laboratoire Liquides Ioniques et Interfaces Chargees (CNRS-UMR 7612), Universite P and M Curie, 4 Place Jussieu, 75252 Paris Cedex 05 (France)]. E-mail: groult@ccr.jussieu.fr; Balnois, E. [Laboratoire Liquides Ioniques et Interfaces Chargees (CNRS-UMR 7612), Universite P and M Curie, 4 Place Jussieu, 75252 Paris Cedex 05 (France); Laboratoire Polymeres, Proprietes aux Interfaces et Composites, Universite de Bretagne Sud, rue de St. Maude, BP92116, 56321 Lorient Cedex (France); Mantoux, A. [Laboratoire Liquides Ioniques et Interfaces Chargees (CNRS-UMR 7612), Universite P and M Curie, 4 Place Jussieu, 75252 Paris Cedex 05 (France); Le Van, K. [Laboratoire Liquides Ioniques et Interfaces Chargees (CNRS-UMR 7612), Universite P and M Curie, 4 Place Jussieu, 75252 Paris Cedex 05 (France); Lincot, D. [Laboratoire d' Electrochimie et de Chimie Analytique (UMR CNRS 7575), ENSCP, 11 rue P and M Curie, 75231 Paris Cedex 05 (France)

    2006-06-15

    The influence of thermal annealing on the morphology and structure of nanometer range thickness vanadium oxide films deposited by ALCVD on silicon substrate was investigated by AFM. The appearance of crystalline centres with typical rectangular V{sub 2}O{sub 5} plates was clearly observed from 400 deg. C. Furthermore, spectacular 2D-reorganisation phenomenon with increasing temperature was pointed out since, initial circular particles change to elongated ones with a rectangular shape with increasing temperature. This reorganisation process results from an increase in the high surface atomic mobilities with increasing temperature. The growth of V{sub 2}O{sub 5} particles in the ab-plane occurs preferentially along the b-direction for which the atoms density is higher, in good agreement with results previously deduced from XRD analyses. The latter show limitation of the coherence domains values along the a-axis for temperatures higher than 450 deg. C.

  6. Zero-Thermal Expansion and Heat Capacity of Zirconium Pyrovanadate Doped with Zirconia and Vanadium (V) Oxide

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The dominant phase ZrV2O7 material, doped with zirconia and vanadium (V) oxide, was synthesized by solid state reaction and sol-gel methods. X-ray power diffraction patterns show that it is cubic structure. Thermal mechanic analysis measurements exhibit a zero-thermal expansion of this material above 150 ℃. Meanwhile, the heat capacity dependent on temperature, determined by differential scanning calorimetry, keeps in constant almost in the same temperature range. The relationship between unusual thermal expansion and abnormal heat capacity is discussed with Gr€黱eisen parameter.

  7. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane. Quarterly technical progress report 10, July 1, 1995--September 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L.

    1995-12-07

    This document is the tenth quarterly technical progress report under Contract No. DE-AC22-92PC92110 {open_quotes}Development of Vanadium-Phosphate Catalysts for Methanol Production by Selective Oxidation of Methane{close_quotes}. Activities focused on testing of additional modified and promoted catalysts and characterization of these materials. Attempts at improving the sensitivity of our GC based analytical systems were also made with some success. Methanol oxidation studies were initiated. These results are reported. Specific accomplishments include: (1) Methane oxidation testing of a suite of catalysts promoted with most of the first row transition metals was completed. Several of these materials produced low, difficult to quantify yields of formaldehyde. (2) Characterization of these materials by XRD and FTIR was performed with the goal of correlating activity and selectivity with catalyst properties. (3) We began to characterize catalysts prepared via modified synthesis methods designed to enhance acidity using TGA measurements of acetonitrile chemisorption and methanol dehydration to dimethyl ether as a test reaction. (4) A catalyst prepared in the presence of naphthalene methanol as a structural disrupter was tested for activity in methane oxidation. It was found that this material produced low yields of formaldehyde which were difficult to quantify. (5) Preparation of catalysts with no Bronsted acid sites. This was accomplished by replacement of exchangeable protons with potassium, and (6) Methanol oxidation studies were initiated to provide an indication of catalyst activity for decomposition of this desired product and as a method of characterizing the catalyst surface.

  8. The Significance of Lewis Acid Sites for the Selective Catalytic Reduction of Nitric Oxide on Vanadium-Based Catalysts.

    Science.gov (United States)

    Marberger, Adrian; Ferri, Davide; Elsener, Martin; Kröcher, Oliver

    2016-09-19

    The long debated reaction mechanisms of the selective catalytic reduction (SCR) of nitric oxide with ammonia (NH3 ) on vanadium-based catalysts rely on the involvement of Brønsted or Lewis acid sites. This issue has been clearly elucidated using a combination of transient perturbations of the catalyst environment with operando time-resolved spectroscopy to obtain unique molecular level insights. Nitric oxide reacts predominantly with NH3 coordinated to Lewis sites on vanadia on tungsta-titania (V2 O5 -WO3 -TiO2 ), while Brønsted sites are not involved in the catalytic cycle. The Lewis site is a mono-oxo vanadyl group that reduces only in the presence of both nitric oxide and NH3 . We were also able to verify the formation of the nitrosamide (NH2 NO) intermediate, which forms in tandem with vanadium reduction, and thus the entire mechanism of SCR. Our experimental approach, demonstrated in the specific case of SCR, promises to progress the understanding of chemical reactions of technological relevance.

  9. Preparation of graphene/vanadium oxide nanocomposite monolith and its electrochemical performance

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Lingjuan; Ma, Zhanying; Li, Xiaobo; Fan, Guang, E-mail: Chemfang@163.com

    2015-10-15

    Graphical Abstract: Graphene/V{sub 2}O{sub 5}(G/V{sub 2}O{sub 5}) nanocomposite monolith is prepared in a mixture of ammonium vanadate, acetic acid and graphite oxide by one-step hydrothermal technology. Owing to the novel structure of ultralong V{sub 2}O{sub 5} nanobelts interpenetrated between the G nanosheets, the G/V{sub 2}O{sub 5} nanocomposite electrode shows higher specific capacitances and better cycle stability than those of G and V{sub 2}O{sub 5} electrodes for supercapaciors and lithium ion battaries. - Highlights: • G/V{sub 2}O{sub 5} nanocomposite monolith is prepared by one-step hydrothermal technology. • G/V{sub 2}O{sub 5} nanocomposite electrode shows much excellent capacitive property. • G/V{sub 2}O{sub 5} nanocomposite exhibits more stable cycle performance. - Abstract: Graphene/vanadium oxide nanocomposite (G/V{sub 2}O{sub 5}) monolith is prepared via a simple hydrothermal process. Owing to the intimate contact between the V{sub 2}O{sub 5} nanobelts and graphene nanosheets in the monolith, the nanocomposite shows excellent electric conductivity, and therefore makes the electrode–electrolyte contact better and Li{sup +} diffusion faster. A high specific capacitance of 163 F g{sup −1} has been achieved for G/V{sub 2}O{sub 5} electrode in 0.5 mol L{sup −1} K{sub 2}SO{sub 4} solution. The G/V{sub 2}O{sub 5} nanocomposite exhibits excellent cyclic performance with nearly 80% capacity retention at a current density of 5 A g{sup −1} in a testing range of 1000 cycles. Moreover, G/V{sub 2}O{sub 5} nanocomposite exhibits excellent discharge properties and cycle stability as an anode material for lithium ion batteries. The initial capacity is 1100 mAh g{sup −1} and the reversible capacity of 530 mAh g{sup −1} is maintained after 100 cycles at a current density of 50 mA g{sup −1}.

  10. Thermal oxidation of vanadium-free Ti alloys: An X-ray photoelectron spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, Maria Francisca, E-mail: mflopez@icmm.csic.es [Department of Surfaces and Coatings, ICMM-CSIC, Sor Juana Ines de la Cruz, 3, Cantoblanco, 28049 Madrid (Spain); Gutierrez, Alejandro [Departamento de Fisica Aplicada and Instituto Nicolas Cabrera, Universidad Autonoma de Madrid, Cantoblanco, E-28049 Madrid (Spain); Jimenez, Jose Antonio [Centro Nacional de Investigaciones Metalurgicas, CSIC, Avda. Gregorio del Amo 8, E-28040 Madrid (Spain); Martinesi, Maria; Stio, Maria; Treves, Cristina [Department of Biochemical Sciences of University of Florence, Viale Morgagni 50, 50134 Florence (Italy)

    2010-04-06

    In the present work, X-ray photoelectron spectroscopy (XPS) was used to study the surface chemical composition of three alloys for biomedical applications: Ti-7Nb-6Al, Ti-13Nb-13Zr and Ti-15Zr-4Nb. The surface of these alloys was modified by annealing in air at 750 deg. C for different times with the aim of developing an oxide thick layer on top. The evolution of surface composition with annealing time was studied by XPS, and compared with the composition of the native oxide layer present on the samples before annealing. Two different oxidation trends were observed depending on the alloying elements and their corresponding diffusion kinetics, which give rise to different chemical species at the topmost layers. These results were linked with an evaluation of the biological response of the alloys by bringing them in contact with human peripheral blood mononuclear cells (PBMC).

  11. Annealing effects on the structural and optical properties of vanadium oxide film obtained by the hot-filament metal oxide deposition technique (HFMOD)

    Energy Technology Data Exchange (ETDEWEB)

    Scarminio, Jair; Silva, Paulo Rogerio Catarini da, E-mail: scarmini@uel.br, E-mail: prcsilva@uel.br [Universidade Estadual de Londrina (UEL), PR (Brazil). Departamento de Fisica; Gelamo, Rogerio Valentim, E-mail: rogelamo@gmail.com [Universidade Federal do Triangulo Mineiro (UFTM), Uberaba, MG (Brazil); Moraes, Mario Antonio Bica de, E-mail: bmoraes@mailhost.ifi.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil)

    2017-01-15

    Vanadium oxide films amorphous, nonstoichiometric and highly absorbing in the optical region were deposited on ITO-coated glass and on silicon substrates, by the hot-filament metal oxide deposition technique (HFMOD) and oxidized by ex-situ annealing in a furnace at 200, 300, 400 and 500 deg C, under an atmosphere of argon and rarefied oxygen. X-ray diffraction, Raman and Rutherford backscattering spectroscopy as well as optical transmission were employed to characterize the amorphous and annealed films. When annealed at 200 and 300 deg C the as-deposited opaque films become transparent but still amorphous. Under treatments at 400 and 500 deg C a crystalline nonstoichiometric V{sub 2}O{sub 5} structure is formed. All the annealed films became semiconducting, with their optical absorption coefficients changing with the annealing temperature. An optical gap of 2.25 eV was measured for the films annealed at 400 and 500 deg C. The annealing in rarefied oxygen atmosphere proved to be a useful and simple ex-situ method to modulate the structural and optical properties of vanadium oxide films deposited by HFMOD technique. This technique could be applied to other amorphous and non-absorbing oxide films, replacing the conventional and sometimes expensive method of modulate desirable film properties by controlling the film deposition parameters. Even more, the HFMOD technique can be an inexpensive alternative to deposit metal oxide films. (author)

  12. Optimisation study of the synthesis of vanadium oxide nanostructures using pulsed laser deposition

    CSIR Research Space (South Africa)

    Masina, BN

    2014-02-01

    Full Text Available Fast imaging plasma plume study have been carried out on vanadium-oxygen plasma generated using 248 nm, 25 ns pulses from an excimer KrF laser under oxygen atmosphere. The plume expansion dynamics of an ablated VO(sub2) target was investigated using...

  13. Electrodeposition of Vanadium Oxides at Room Temperature as Cathodes in Lithium-Ion Batteries

    Directory of Open Access Journals (Sweden)

    Michalis Rasoulis

    2017-07-01

    Full Text Available Electrodeposition of vanadium pentoxide coatings was performed at room temperature and a short growth period of 15 min based on an alkaline solution of methanol and vanadyl (III acetyl acetonate. All samples were characterized by X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The current density and electrolyte concentration were found to affect the characteristics of the as-grown coatings presenting enhanced crystallinity and porous structure at the highest values employed in both cases. The as-grown vanadium pentoxide at current density of 1.3 mA·cm−2 and electrolyte concentration of 0.5 M indicated the easiest charge transfer of Li+ across the vanadium pentoxide/electrolyte interface presenting a specific discharge capacity of 417 mAh·g−1, excellent capacitance retention of 95%, and coulombic efficiency of 94% after 1000 continuous Li+ intercalation/deintercalation scans. One may then suggest that this route is promising to prepare large area vanadium pentoxide electrodes with excellent stability and efficiency at very mild conditions.

  14. Rf-sputtered vanadium oxide thin films: effect of oxygen partial pressure on structural and electrochemical properties

    CERN Document Server

    Park, Y J; Ryu, K S; Chang, S H; Park, S C; Yoon, S M; Kim, D K

    2001-01-01

    Vanadium oxide thin films with thickness of about 2000 A have been prepared by radio frequency sputter deposition using a V sub 2 O sub 5 target in a mixed argon and oxygen atmosphere with different Ar/O sub 2 ratio ranging from 99/1 to 90/10. X-ray diffraction and X-ray absorption near edge structure spectroscopic studies show that the oxygen content higher than 5% crystallizes a stoichiometric V sub O sub 5 phase, while oxygen deficient phase is formed in the lower oxygen content. The oxygen content in the mixed Ar + O sub 2 has a significant influence on electrochemical lithium insertion/deinsertion property. The discharge-charge capacity of vanadium oxide film increases with increasing the reactive oxygen content. The V sub O sub 5 film deposited at the Ar/O sub 2 ratio of 90/10 exhibits high discharge capacity of 100 mu Ah/cm sup 2 -mu m along with good cycle performance.

  15. Structural and electrochemical behaviour of sputtered vanadium oxide films: oxygen non-stoichiometry and lithium ion sequestration

    Indian Academy of Sciences (India)

    K J Rao; B Pecquenard; A Gies; A Levasseur; J Etourneau

    2006-10-01

    Structural and electrochemical aspects of vanadium oxide films recently reported from ICMCB/ENSCPB have been examined using appropriate structural models. It is shown that amorphous films are nonstoichiometric as a result of pre-deposition decomposition of V2O5. It is proposed that the structure of amorphous films corresponds to a nanotextured mosaic of V2O5 and V2O4 regions. Lithium intercalation into these regions is considered to occur sequentially and determined by differences in group electronegativities. Open circuit voltages (OCV) have been calculated for various stoichiometric levels of lithiation using available thermodynamic data with approximate corrections. Sequestration of lithium observed in experiments is shown to be an interfacial phenomenon. X-ray photoelectron spectroscopic observation of the formation of V3+ even when V5+ has not been completely reduced to V4+ is shown to be entirely consistent with the proposed structural model and a consequence of initial oxygen nonstoichiometry. Based on the structural data available on V2O5 and its lithiated products, it is argued that the geometry of VO polyhedron changes from square pyramid to trigonal bipyramid to octahedron with increase of lithiation. A molecular orbital based energy band diagram is presented which suggests that lithiated vanadium oxides, Li V2O5, become metallic for high values of .

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

    Science.gov (United States)

    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.

  17. Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}): Peroxovanadate sol gel synthesis and structural study

    Energy Technology Data Exchange (ETDEWEB)

    Langie da Silva, Douglas, E-mail: douglas.langie@ufpel.edu.br [Departamento de Física, Universidade Federal de Pelotas, Caixa Postal 354, Pelotas 96010-900 (Brazil); Moreira, Eduardo Ceretta [Laboratório de Espectroscopia, Universidade Federal do Pampa, Campus Bagé, Bagé 96400-970 (Brazil); Dias, Fábio Teixeira; Neves Vieira, Valdemar das [Departamento de Física, Universidade Federal de Pelotas, Caixa Postal 354, Pelotas 96010-900 (Brazil); Brandt, Iuri Stefani; Cas Viegas, Alexandre da; Pasa, André Avelino [Laboratório de Filmes Finos e Superfícies, Universidade Federal de Santa Catarina, Caixa Postal 476, Florianópolis 88.040-900 (Brazil)

    2015-01-15

    Nanostructured cobalt vanadium oxide (V{sub 2}O{sub 5}) xerogels spread onto crystalline Si substrates were synthesized via peroxovanadate sol gel route. The resulting products were characterized by distinct experimental techniques. The surface morphology and the nanostructure of xerogels correlate with Co concentration. The decrease of the structural coherence length is followed by the formation of a loose network of nanopores when the concentration of intercalated species was greater than 4 at% of Co. The efficiency of the synthesis route also drops with the increase of Co concentration. The interaction between the Co(OH{sub 2}){sub 6}{sup 2+} cations and the (H{sub 2}V{sub 10}O{sub 28}){sup 4−} anions during the synthesis was suggested as a possible explanation for the incomplete condensation of the V{sub 2}O{sub 5} gel. Finally the experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5}. In this scenario two possible preferential occupation sites for the metallic atoms in the framework of the xerogel were proposed. - Graphical abstract: Quasi-one-dimensional nanostructured cobalt (Co) intercalated vanadium oxide (V{sub 2}O{sub 5}) nanoribbons synthesized by peroxovanadate sol gel route. - Highlights: • Nanostructured cobalt V{sub 2}O{sub 5} gel spread onto c{sub S}i were synthesized via peroxovanadate sol gel route. • The micro and nanostructure correlates with the cobalt content. • The efficiency of the synthesis route shows to be also dependent of Co content. • The experimental results points for the intercalation of Co between the bilayers of the V{sub 2}O{sub 5} xerogel.

  18. On the structural and electronic properties of hexanuclear vanadium oxide clusters V6On-/0 (n = 12-15): Is V6O12 cluster planar or cage-like?

    Science.gov (United States)

    Wang, Ling-Fei; Xie, Lu; Fang, Hong-Ling; Li, Yun-Fei; Zhang, Xiao-Bin; Wang, Bin; Zhang, Yong-Fan; Huang, Xin

    2014-10-01

    Density functional theory (DFT) calculations are carried out to investigate the structural and electronic properties of a series of hexanuclear vanadium oxide clusters V6On-/0 (n = 12-15). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES) for V6On- (n = 12-15) clusters. Extensive DFT calculations are performed in search of the lowest-energy structures for both the anions and neutrals. All of these clusters appear to prefer the polyhedral cage structures, in contrast to the planar star-like structures observed in prior model surface studies for the V6O12 cluster. Molecular orbitals are performed to analyze the chemical bonding in the hexanuclear vanadium oxide clusters and provide insights into the sequential oxidation of V6On- (n = 12-15) clusters. The V6On- (n = 12-15) clusters possess well-defined V5+ and V3+ sites, and may serve as molecular models for surface defects. Electron spin density analyses show that the unpaired electrons in V6On- (n = 12-14) clusters are primarily localized on the V3+ sites rather than on the V5+ sites. The difference gas phase versus model surface structures of V6O12 hints the critical roles of cluster-substrate interactions in stabilizing the planar V6O12 cluster on model surfaces.

  19. On the structural and electronic properties of hexanuclear vanadium oxide clusters V6On(-/0) (n=12-15): is V6O12 cluster planar or cage-like?

    Science.gov (United States)

    Wang, Ling-Fei; Xie, Lu; Fang, Hong-Ling; Li, Yun-Fei; Zhang, Xiao-Bin; Wang, Bin; Zhang, Yong-Fan; Huang, Xin

    2014-10-15

    Density functional theory (DFT) calculations are carried out to investigate the structural and electronic properties of a series of hexanuclear vanadium oxide clusters V6On(-/0) (n=12-15). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES) for V6On(-) (n=12-15) clusters. Extensive DFT calculations are performed in search of the lowest-energy structures for both the anions and neutrals. All of these clusters appear to prefer the polyhedral cage structures, in contrast to the planar star-like structures observed in prior model surface studies for the V6O12 cluster. Molecular orbitals are performed to analyze the chemical bonding in the hexanuclear vanadium oxide clusters and provide insights into the sequential oxidation of V6On(-) (n=12-15) clusters. The V6On(-) (n=12-15) clusters possess well-defined V(5+) and V(3+) sites, and may serve as molecular models for surface defects. Electron spin density analyses show that the unpaired electrons in V6On(-) (n=12-14) clusters are primarily localized on the V(3+) sites rather than on the V(5+) sites. The difference gas phase versus model surface structures of V6O12 hints the critical roles of cluster-substrate interactions in stabilizing the planar V6O12 cluster on model surfaces. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Intramolecular Biaryl Oxidative Coupling of Stilbene Substrates by Vanadium Oxytrichloride (VOCl3):Facile Synthesis of Substituted Phenanthrene Derivatives

    Institute of Scientific and Technical Information of China (English)

    JIN,Zhong; WANG,Qing-Min; HUANG,Run-Qiu; LIU,Yu-Xiu; LI,Hao; LI,Shi-Pu

    2004-01-01

    @@ The biaryl unit is extensively presented in many classes of natural products, such as polyketides, terpenes, lignanes,coumarins, flavonoids, tannins, and many alkaloids.[1] It has long been recognized that an intramolecular oxidative phenolic or nonphenolic coupling reaction serves as the key step in the biosynthesis of these natural products, and the non-enzymic analogue of this transformation can lead the elegantly simple syntheses of these compounds.[2] During the last decade, a large number of oxidative coupling reagents, such as ferric chloride (FeCl3), phenyliodine(Ⅲ)bis(trifluoroacetate) (PIFA), lead(Ⅳ) tetraacetate [Pb(OAc)4], thallium(Ⅲ) triflouroacetate (TTFA), as well as vanadium oxytrifluoride (VOF3),[3,4] have been developed for this target. However, extensive application of this synthetic potential has been limited by low yields and unexpected side reactions usually encountered.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  3. Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study

    NARCIS (Netherlands)

    Keller, D.E.; Visser, T.; Soulimani, F.; Koningsberger, D.C.; Weckhuysen, B.M.

    2007-01-01

    The effect of hydration on the molecular structure of silica-supported vanadium oxide catalysts with loadings of 1–16 wt.% V has been systematically investigated by infrared, Raman, UV–vis and EXAFS spectroscopy. IR and Raman spectra recorded during hydration revealed the formation of V–OH groups, c

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

    DEFF Research Database (Denmark)

    Martinez, Nieves Espinosa; Dam, Henrik Friis; Tanenbaum, David M.

    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...

  5. Synthesis, structural and optical properties of nanocrystalline vanadium doped zinc oxide aerogel

    Science.gov (United States)

    El Ghoul, J.; Barthou, C.; El Mir, L.

    2012-06-01

    We report the synthesis of vanadium-doped ZnO nanoparticles prepared by a sol-gel processing technique. In our approach, the water for hydrolysis was slowly released by esterification reaction followed by a supercritical drying in ethyl alcohol. Vanadium doping concentration of 10 at% has been investigated. After treatment in air at different temperatures, the obtained nanopowder was characterized by various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence (PL). Analysis by scanning electron microscopy at high resolution shows that the grain size increases with increasing temperature. Thus, in the case of thermal treatment at 500 °C in air, the powder with an average particle size of 25 nm shows a strong luminescence band in the visible range. The intensity and energy position of the obtained PL band depends on the temperature measurement increase. The mechanism of this emission band is discussed.

  6. Synthesis and luminescence properties of vanadium-doped nanosized zinc oxide aerogel

    Science.gov (United States)

    El Mir, L.; El Ghoul, J.; Alaya, S.; Ben Salem, M.; Barthou, C.; von Bardeleben, H. J.

    2008-05-01

    We report the elaboration of vanadium-doped ZnO nanoparticles prepared by a sol-gel processing technique. In our approach, the water for hydrolysis was slowly released by esterification reaction followed by a supercritical drying in ethyl alcohol. Vanadium doping concentration of 10 at% has been investigated. The obtained nanopowder was characterised by various techniques such as particle size analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence (PL). In the as-prepared state, the powder with an average particle size of 25 nm presents a strong luminescence band in the visible range after thermal treatment at 500 °C in air. The energy position of the obtained PL band depends on the wavelength excitation and presents a blue shift with measurement temperature increase. Different possible attributions of this emission band will be discussed.

  7. Selective nano alumina supported vanadium oxide catalysts for oxidative dehydrogenation of ethylbenzene to styrene using CO2 as soft oxidant

    Directory of Open Access Journals (Sweden)

    A.M. Elfadly

    2013-12-01

    Full Text Available Nano alumina-supported V2O5 catalysts with different loadings have been tested for the dehydrogenation of ethylbenzene with CO2 as an oxidant. High surface area nano-alumina was prepared and used as support for V2O5 as the catalyst. The catalysts were synthesized by impregnation techniques followed by calcinations and microwave treatment, denoted as V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW, respectively. The V2O5 loading was varied on nano-alumina from 5 to 30 wt%. The support and catalysts were characterized by X-ray diffraction (XRD, Barett–Joyner–Halenda (BJH pore-size distribution, N2-adsorption isotherms, Fourier transform infrared (FT-IR, scanning electron microscopy (SEM, transmission electron microscopy (TEM and temperature programed desorption (TPD-NH3. The characterization results indicated that V2O5 is highly dispersed on alumina up to 30%-V2O5/γ-Al2O3-MW prepared by MW method. The TPD studies indicated that there are significant differences in acid amount and strength for V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW-catalysts. The catalytic activity of the prepared catalysts was evaluated in the temperature range 450–600 °C in relation to the physicochemical properties and surface acidity. The results revealed that optimum catalytic activity and selectivity (∼100% toward styrene production were obtained using 10% V2O5/γ-Al2O3-MW catalyst treated with microwave.

  8. Investigation of the Electrolyte Effects on Formation of Vanadium Carbide via Plasma Electrolytic Saturation Method (pes)

    Science.gov (United States)

    Ghorbanian, Babak; Khoie, Seyed Mohammad Mousavi; Rasouli, Mahmood; Doodran, Ramona Javadi

    2016-02-01

    One of the most important hardening methods of tool steel is the use of carbide coatings. During this process, vanadium atoms diffuse the specimen’s surface at high temperature and reacts with the available carbon in steel and create vanadium carbide with high hardness. During the plasma electrolytic saturation (PES) process, the vanadium element diffuses with the help of plasma and increases up to around 950∘ as a result of the temperature, providing conditions for the creation of vanadium carbide. The best combination of electrolyte is 4g vanadium oxide and 50mL hydrochloric acid and different concern of sodium hydroxide. The results indicate that the formed coating is about 30μm. As the conductivity increases, the condition for diffusion is provided; however, with increase in the temperature, the diffusion decreases. The coating formation is observed in the current at 9-11 A and hardness of this coating is about 1400vickers.

  9. Multi-scale cell/surface interaction on modified titanium aluminum vanadium surfaces

    Science.gov (United States)

    Chen, Jianbo

    This dissertation presents a series of experimental studies of the effects of multi-scale cell/surface interactions on modified Ti-6Al-4V surfaces. These include laser-grooved surfaces; porous structures and RGD-coated laser-grooved surfaces. A nano-second DPSS UV lasers with a Gaussian pulse energy profile was used to introduce the desired micro-groove geometries onto Ti-6Al-4V surfaces. This was done without inducing micro-cracks or significant changes in surface chemistry within the heat affected zones. The desired 8-12 mum groove depths and widths were achieved by the control of pulse frequency, scan speed, and the lens focal length that controls spot size. The interactions between human osteosarcoma (HOS) cells and laser-grooved Ti-6Al-4V surfaces were investigated after 48 hours of cell culture. The cell behavior, including cell spreading, alignment and adhesion, was elucidated using scanning electronic microscopy (SEM), immuno-fluorescence staining and enzymatic detachment. Contact guidance was shown to increase as grooved spacing decreased. For the range of micro-groove geometries studied, micro-grooves with groove spacings of 20 mum provided the best combination of cell orientation and adhesion. Short-term adhesion experiments (15 mins to 1 day) also revealed that there is a positive correlation between cell orientation and cell adhesion. Contact guidance on the micro-grooved surfaces is shown to be enhanced by nano- and micro-scale asperities that provide sites for the attachment of lamellopodia during cell locomotion and spreading. Contact guidance is also promoted by the geometrical confinement provided by laser grooves. An experimental study of initial cell spreading and ingrowth into Ti-6Al-4V porous structures was also carried out on porous structures with different pore sizes and geometries. A combination of SEM, the tetrazolium salt (MTT) colorimetric assay and enzymatic detachment were used to study cell spreading and adhesion. The extent of cell

  10. Simultaneous recovery of vanadium and nickel from power plant fly-ash: Optimization of parameters using response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Nazari, E.; Rashchi, F., E-mail: rashchi@ut.ac.ir; Saba, M.; Mirazimi, S.M.J.

    2014-12-15

    Highlights: • Leaching of vanadium and nickel from fly ash (14.43% V and 5.19% Ni) in sulfuric acid was performed. • Optimization of leaching parameters was carried out using a response surface methodology. • Using optimum conditions, 94.28% V and 81.01% Ni “actual recovery” was obtained. - Abstract: Simultaneous recovery of vanadium (V) and nickel (Ni), which are classified as two of the most hazardous metal species from power plant heavy fuel fly-ash, was studied using a hydrometallurgical process consisting of acid leaching using sulfuric acid. Leaching parameters were investigated and optimized in order to maximize the recovery of both vanadium and nickel. The independent leaching parameters investigated were liquid to solid ratio (S/L) (5–12.5 wt.%), temperature (45–80 °C), sulfuric acid concentration (5–25 v/v%) and leaching time (1–5 h). Response surface methodology (RSM) was used to optimize the process parameters. The most effective parameter on the recovery of both elements was found to be temperature and the least effective was time for V and acid concentration for Ni. Based on the results, optimum condition for metals recovery (actual recovery of ca.94% for V and 81% for Ni) was determined to be solid to liquid ratio of 9.15 wt.%, temperature of 80 °C, sulfuric acid concentration of 19.47 v/v% and leaching time of 2 h. The maximum V and Ni predicted recovery of 91.34% and 80.26% was achieved.

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

    Directory of Open Access Journals (Sweden)

    Sanju Gupta

    2016-07-01

    Full Text Available Graphene nanosheets and graphene nanoribbons, G combined with vanadium pentoxide (VO nanobelts (VNBs and VNBs forming GVNB composites with varying compositions were synthesized via a one-step low temperature facile hydrothermal decomposition method as high-performance electrochemical pseudocapacitive electrodes. VNBs from vanadium pentoxides (VO are formed in the presence of graphene oxide (GO, a mild oxidant, which transforms into reduced GO (rGOHT, assisting in enhancing the electronic conductivity coupled with the mechanical robustness of VNBs. From electron microscopy, surface sensitive spectroscopy and other complementary structural characterization, hydrothermally-produced rGO nanosheets/nanoribbons are decorated with and inserted within the VNBs’ layered crystal structure, which further confirmed the enhanced electronic conductivity of VNBs. Following the electrochemical properties of GVNBs being investigated, the specific capacitance Csp is determined from cyclic voltammetry (CV with a varying scan rate and galvanostatic charging-discharging (V–t profiles with varying current density. The rGO-rich composite V1G3 (i.e., VO/GO = 1:3 showed superior specific capacitance followed by VO-rich composite V3G1 (VO/GO = 3:1, as compared to V1G1 (VO/GO = 1:1 composite, besides the constituents, i.e., rGO, rGOHT and VNBs. Composites V1G3 and V3G1 also showed excellent cyclic stability and a capacitance retention of >80% after 500 cycles at the highest specific current density. Furthermore, by performing extensive simulations and modeling of electrochemical impedance spectroscopy data, we determined various circuit parameters, including charge transfer and solution resistance, double layer and low frequency capacitance, Warburg impedance and the constant phase element. The detailed analyses provided greater insights into physical-chemical processes occurring at the electrode-electrolyte interface and highlighted the comparative performance of

  12. Surface properties and graphitization of polyacrylonitrile based fiber electrodes affecting the negative half-cell reaction in vanadium redox flow batteries

    Science.gov (United States)

    Langner, J.; Bruns, M.; Dixon, D.; Nefedov, A.; Wöll, Ch.; Scheiba, F.; Ehrenberg, H.; Roth, C.; Melke, J.

    2016-07-01

    Carbon felt electrodes for vanadium redox flow batteries are obtained by the graphitization of polyacrylonitrile based felts at different temperatures. Subsequently, the surface of the felts is modified via thermal oxidation at various temperatures. A single-cell experiment shows that the voltage efficiency is increased by this treatment. Electrode potentials measured with reference electrode setup show that this voltage efficiency increase is caused mainly by a reduction of the overpotential of the negative half-cell reaction. Consequently, this reaction is investigated further by cyclic voltammetry and the electrode activity is correlated with structural and surface chemical properties of the carbon fibers. By Raman, X-ray photoelectron and near edge X-ray absorption fine structure spectroscopy the role of edge sites and oxygen containing functional groups (OCFs) for the electrochemical activity are elucidated. A significant activity increase is observed in correlation with these two characteristics. The amount of OCFs is correlated with structural defects (e.g. edge sites) of the carbon fibers and therefore decreases with an increasing graphitization degree. Thus, for the same thermal oxidation temperature carbon fibers graphitized at a lower temperature show higher activities than those graphitized at a higher temperature.

  13. Effect of tellurium promoter on vanadium phosphate catalyst for partial oxidation of n-butane

    Institute of Scientific and Technical Information of China (English)

    Y. H. Taufiq-Yap; S. Nor Asrina; G. J. Hutchings; N. F. Dummer; J. K. Bartley

    2011-01-01

    Te-promoted (1%) vanadium phosphate catalyst (VPDTe) was prepared via VOPO4·2H2O by calcining its precursor VOHPO4·0·5H2O in a flow of n-b(u)ane/air.VPDTe catalyst has resulted a higher existence of V5+ phase with V5+/V4+ ratio of 0.23.SEM micrographs show that Te addition altered the arrangement of the platelets from "rose-like" clusters to layer with irregular shape.Te addition has also markedly lowered the reduction activation energies of the vanadium phosphate catalyst as revealed by TPR profile.The amount of active oxygen species associated with V4+ phase of the Te promoted catalyst was significantly higher than those of the unpromoted catalyst.These observations suggest that high mobility and availability of reactive oxygen species contributed to the enhancement of n-butane conversion up to 80% at 673 K,while only 47% over unpromoted catalyst (2400 h-1,1.7% n-butane in air).

  14. Structural characterization of vanadium oxide catalysts supported on nanostructured silica SBA-15 using X-ray absorption spectroscopy

    Directory of Open Access Journals (Sweden)

    Walter Anke

    2010-02-01

    Full Text Available Abstract 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.

  15. Simultaneous recovery of vanadium and nickel from power plant fly-ash: optimization of parameters using response surface methodology.

    Science.gov (United States)

    Nazari, E; Rashchi, F; Saba, M; Mirazimi, S M J

    2014-12-01

    Simultaneous recovery of vanadium (V) and nickel (Ni), which are classified as two of the most hazardous metal species from power plant heavy fuel fly-ash, was studied using a hydrometallurgical process consisting of acid leaching using sulfuric acid. Leaching parameters were investigated and optimized in order to maximize the recovery of both vanadium and nickel. The independent leaching parameters investigated were liquid to solid ratio (S/L) (5-12.5 wt.%), temperature (45-80 °C), sulfuric acid concentration (5-25 v/v%) and leaching time (1-5h). Response surface methodology (RSM) was used to optimize the process parameters. The most effective parameter on the recovery of both elements was found to be temperature and the least effective was time for V and acid concentration for Ni. Based on the results, optimum condition for metals recovery (actual recovery of ca.94% for V and 81% for Ni) was determined to be solid to liquid ratio of 9.15 wt.%, temperature of 80 °C, sulfuric acid concentration of 19.47 v/v% and leaching time of 2h. The maximum V and Ni predicted recovery of 91.34% and 80.26% was achieved.

  16. Dehydrogenation of Isobutane with Carbon Dioxide over SBA-15-Supported Vanadium Oxide Catalysts

    Directory of Open Access Journals (Sweden)

    Chunling Wei

    2016-10-01

    Full Text Available A series of vanadia catalysts supported on SBA-15 (V/SBA with a vanadia (V content ranging from 1% to 11% were prepared by an incipient wetness method. Their catalytic behavior in the dehydrogenation of isobutane to isobutene with CO2 was examined. The catalysts were characterized by N2 adsorption, X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy, and temperature-programmed reduction (TPR. It was found that these catalysts were effective for the dehydrogenation reaction, and the catalytic activity is correlated with the amount of dispersed vanadium species on the SBA-15 support. The 7% V/SBA catalyst shows the highest activity, which gives 40.8% isobutane conversion and 84.8% isobutene selectivity. The SBA-15-supported vanadia exhibits higher isobutane conversion and isobutene selectivity than the MCM-41-supported one.

  17. Charge transfer in Li/CFx-silver vanadium oxide hybrid cathode batteries revealed by solid state 7Li and 19F nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Sideris, Paul J.; Yew, Rowena; Nieves, Ian; Chen, Kaimin; Jain, Gaurav; Schmidt, Craig L.; Greenbaum, Steve G.

    2014-05-01

    Solid state 7Li and 19F magic angle spinning nuclear magnetic resonance (MAS NMR) experiments are conducted on several cathodes containing CFx-Silver vanadium oxide (CFx-Ag2V4O11) hybrid cathodes discharged to 50% depth of discharge (DoD) and stored at their open-circuit voltage for a period of one and three months. Three carbonaceous sources for the CFx phase are investigated: petroleum coke-based, fibrous, and mixed fibrous. For each hybrid cathode, a measurable increase in the relative amount of lithium fluoride is observed after a three month resting period in both the 7Li and 19F NMR spectra. These changes are attributed to lithium ion migration from the silver vanadium oxide to the CFx phase during the resting period, and help clarify the mechanism behind high power handling capability of this cathode.

  18. Effect of Cr and Co Promoters Addition on Vanadium Phosphate Catalysts for Mild Oxidation of n-Butane

    Institute of Scientific and Technical Information of China (English)

    Yun Hin Taufiq-Yap

    2006-01-01

    In this study, Cr and Co promoted, as well as unpromoted vanadium phosphate (VPO)catalysts were synthesized by the reaction of V2O5 and o-H3PO4 in organic medium followed by calcination in n-butane/air environment at 673 K. The physico-chemical properties and the catalytic behavior were affected by the addition of Cr and Co dopants. H2-TPR was used to investigate the nature of oxidants in the unpromoted and promoted catalysts. The results showed that both the Cr and Co promoters remarkably lowered the temperature of the reduction peak associated with V5+. The amount of oxygen species originated from the active phase, V4+, removed was significantly increased for Co and Cr-promoted catalysts. Both Cr and Co dopants improve strongly the n-butane conversion without sacrificing the MA selectivity. A good correlation was observed between the amount of oxygen species removed from V4+ phase and the activity for n-butane oxidation to maleic anhydride. This suggested that V4+-O was the center for the activation of n-butane.

  19. Electro-optical evaluation of tungsten oxide and vanadium pentoxide thin films for modeling an electrochromic device

    Directory of Open Access Journals (Sweden)

    H Najafi Ashtiani

    2015-01-01

    Full Text Available In this study, tungsten oxide and vanadium oxide electrochromic thin films were placed in vacuum and in a thickness of 200 nm on a transparent conductive substrate of SnO2:F using the physical method of thermal evaporation. Then they were studied for the optical characteristics in the wavelength range from 400 to 700 nm and for their electrical potentials in the range form +1.5 to -1.5 volts. The films were post heated in order to assess changes in energy gap with temperature, at temperatures120 , 300 and 500°C. Refractive and extinction coefficients and the transition type of films in the visible light range and in the thickness of 200 nm were determined and measured. X-ray diffraction pattern and SEM images and cyclic Voltammetry of layers were also studied. The results of this study due to the deposition of layers, the layer thickness selected, the type of substrate, the range of annealing temperatures and selected electrolyte were in full compliance with the works of other researchers [1,2,3]. Therefore, these layers with features such as crystal structure, refractive and even extinction coefficients in the range of visible light, the appropriate response of chromic switch in the replication potential, good adhesion to the substrate, and the high amount of optical transmition and so on, prove useful to be used in an electrochromic device

  20. Effects of synthetic conditions on the structure and morphology of open-ended vanadium oxide nanotubes and study of their growth mechanism

    Institute of Scientific and Technical Information of China (English)

    WEI Jia; ZHU Ying; ZHANG JingChang

    2007-01-01

    Vanadium oxide nanotubes (Vox-NTs) have been synthesized by using n-butylamine as structure- directing template and V2O5 as precursor under hydrothermal conditions. XRD, FTIR, SEM, TEM, BET and TG-DTA characterizations have been performed to both optimize the synthetic conditions and understand the growth mechanism of Vox-NTs. The results showed that open-ended Vox-NTs were obtained under the optimized conditions (hydrothermal temperature: 150-160°C, hydrothermal time: 5-7 d, the molar ratio of V2O5 to n-butylamine is 1:1) with diameters ranging from about 30 to 100 nm and several micrometers in length. The BET surface area and the desorption cumulative pore volume of pores of the as-synthesized sample were about 27.4609 m2/g and 0.191087 cm3/g, respectively. The result presents that the synthesis of Vox-NTs is controlled by the "rolling" mechanism and temperature is primary driving force for rolling.

  1. Effects of vanadium(V)-substitution on the oxidative properties of α-Keggin-type heteropolyanion clusters——progress in DFT theoretical studies

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The redox properties of α-Keggin-type heteropolyanion clusters [XM12O40]n-(X = Si,P; M = Mo,W) mainly depend on their constituent outer metal-oxygen cages {M12O36}. They act as "reservoirs",through which the transfer and transition of electrons and protons may occur. At the atomic and molecular level,the redox properties of these clusters can be controlled and also tuned by modifying the metal M in the cages and the central heteroatom X of the clusters. Combined with relevant experimental results,this review summarizes our recent theoretical investigations of the effect of vanadium substitution on the redox properties of Keggin anion clusters. Theoretical modeling and calculation results showed that the oxidative ability of the modified species was increased by partial substitution of the cage M atoms of the Keggin clusters by vanadium atoms which have lower electronegativity. A linear correlation between the catalytic efficiency per vanadium atom and the microstructures of the vanadium(V)-substituted heteropolyanions [PVnMo12-nO40](3+n)-(n = 1-3) was established for the first time. This relationship may be suitable to interpret the catalytic behavior of the title compounds in the hydroxylation of benzene to phenol,and may also be used in understanding other reactions such as the oxidative dehydrogenation of isobutyric acid and the nitration of adamantine. The establishment of this nearly linear structure-property relationship may lay the foundations of understanding the behavior of the title compounds in homogeneous catalytic oxidation reactions,and may direct the design of future catalysts and the choice of other catalytic reactions.

  2. Vanadium-Doped Magnesium Oxide Nanoparticles Formation in Presence of Ionic Liquids and Their Use in Photocatalytic Degradation of Methylene Blue

    Institute of Scientific and Technical Information of China (English)

    Harshad R.Patil; Z.V.P.Murthy

    2016-01-01

    Magnesium oxide (MgO) is one of the metal oxides having unique properties with numerous potential industrial applications.In this study,MgO and vanadium-doped MgO nanoparticles were synthesized by sol-gel method in 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] and 1-octyl-3-methylimidazolium tetrafluoroborate [OMIM][BF4] ionic liquids.Vanadium-doped MgO nanoparticles exhibited nanosphere and nanorod morphologies with 40-80 nm in particle size,primarily due to the influence of ionic liquids as demonstrated by high-resolution scanning electron microscopy and transmission electron microscopy.Characteristics of nanoparticles were also studied by thermal gravimetric analysis,X-ray diffraction and energy-dispersive X-ray spectroscopy.Photodegradation ability of synthesized nanoparticles was evaluated for methylene blue (MB) in specially designed UV reactor.Photodegradation is found to be dependent on doping,and particle characteristics change due to the influence of ionic liquid.The ionic liquid-assisted vanadium-doped MgO nanoparticles showed good reusability under UV irradiation and MB degradation ability under visible light.

  3. Controlling interlayer interactions in vanadium pentoxide-poly(ethylene oxide) nanocomposites for enhanced magnesium-ion charge transport and storage

    Science.gov (United States)

    Perera, Sanjaya D.; Archer, Randall B.; Damin, Craig A.; Mendoza-Cruz, Rubén; Rhodes, Christopher P.

    2017-03-01

    Rechargeable magnesium batteries provide the potential for lower cost and improved safety compared with lithium-ion batteries, however obtaining cathode materials with highly reversible Mg-ion capacities is hindered by the high polarizability of divalent Mg-ions and slow solid-state Mg-ion diffusion. We report that incorporating poly(ethylene oxide) (PEO) between the layers of hydrated vanadium pentoxide (V2O5) xerogels results in significantly improved reversible Mg-ion capacities. X-ray diffraction and high resolution transmission electron microscopy show that the interlayer spacing between V2O5 layers was increased by PEO incorporation. Vibrational spectroscopy supports that the polymer interacts with the V2O5 lattice. The V2O5-PEO nanocomposite exhibited a 5-fold enhancement in Mg-ion capacity, improved stability, and improved rate capabilities compared with V2O5 xerogels. The Mg-ion diffusion coefficient of the nanocomposite was increased compared with that of V2O5 xerogels which is attributed to enhanced Mg-ion mobility due to the shielding interaction of PEO with the V2O5 lattice. This study shows that beyond only interlayer spacing, the nature of interlayer interactions of Mg-ions with V2O5, PEO, and H2O are key factors that affect Mg-ion charge transport and storage in layered materials. The design of layered materials with controlled interlayer interactions provides a new approach to develop improved cathodes for magnesium batteries.

  4. Enhanced Lithium Storage in Reduced Graphene Oxide-supported M-phase Vanadium(IV) Dioxide Nanoparticles

    Science.gov (United States)

    Song, Hee Jo; Choi, Mingu; Kim, Jae-Chan; Park, Sangbaek; Lee, Chan Woo; Hong, Seong-Hyeon; Kim, Byung-Kook; Kim, Dong-Wan

    2016-07-01

    Vanadium(IV) dioxide (VO2) has drawn attention as one of the most attractive electrode materials for lithium-ion batteries (LIBs), hence, much research has been conducted in various sectors in this field. However, to date, most of this research has focused on the VO2(B) polymorph, whereas electrochemical information on the use of VO2(M) in LIB electrodes is insufficient. Thus, it is worthwhile to explore the possibility of using VO2(M) for LIB electrode application, and to investigate whether its electrochemical properties can be improved. In this study, VO2(M) nanoparticles, incorporated with a reduced graphene oxide composite (NP-VO2/rGO), were successfully synthesized via a sol-gel assisted hydrothermal process by the chemical reduction of V2O5 gel, using hydrazine as the reducing agent. The particle size was less than 50 nm regardless of the presence of rGO. Also, NP-VO2/rGO exhibited a specific capacity of 283 mA h g-1 up to the 200th cycle at a current density of 60 mA g-1, indicating its potential to be used in LIBs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Majid, S. S., E-mail: suhailphy276@gmail.com; Rahman, F. [Department of Physics, Aligarh Muslim University, Aligarh-202002 (India); Shukla, D. K.; Choudhary, R. J.; Phase, D. M. [UGC-DAE Consortium for Scientific Research, Indore-452001 (India)

    2015-06-24

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

  6. Effect of citric acid dosage and sintered temperature on the composition, morphology and electrochemical properties of lithium vanadium oxide prepared by a sol–gel method

    Science.gov (United States)

    Zhong, C. R.; Su, X. J.; Hou, G. L.; Liu, Z. H.; Yu, F. S.; Bi, S.; Li, H.

    2017-03-01

    A lithium vanadium oxide cathode material was synthesized via sol-gel processing using citric acid as the chelating agent. Different dosage of citric acid and sintered temperature were introduced to investigate their effects on the products composition, morphology and electrochemical properties. The results showed that the V2O3 yield was inhibited and the crystallization of grain was accelerated with the increasing dosage of citric acid. Furthermore, V2O3 was oxidized to LiV3O8 and Li0.3V2O5 with the increase of sintered temperature.

  7. Oxidation Catalysts in the Dark and the Light

    Science.gov (United States)

    2010-01-01

    xerogel synthetic methods to high surface area titanium oxide, silicon oxide, and mixed TiO2 -SiO2 were used. Metal ions of chromium, vanadium, manganese...Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 15. SUBJECT TERMS photocatalysis , destruction, toxic chemicals, visible light...and xerogel synthetic methods to high surface area titanium oxide, silicon oxide, and mixed TiO2 -SiO2 were used. Metal ions of chromium, vanadium

  8. The metal-insulator transition in vanadium dioxide: A view at bulk and surface contributions for thin films and the effect of annealing

    Science.gov (United States)

    Yin, W.; West, K. G.; Lu, J. W.; Pei, Y.; Wolf, S. A.; Reinke, P.; Sun, Y.

    2009-06-01

    Vanadium dioxide is investigated as potential oxide barrier in spin switches, and in order to incorporate VO2 layers in complex multilayer devices, it is necessary to understand the relation between bulk and surface/interface properties. Highly oriented VO2 thin films were grown on (0001) sapphire single crystal substrates with reactive bias target ion beam deposition. In the analysis of the VO2 films, bulk-sensitive methods [x-ray diffraction (XRD) and transport measurements] and surface sensitive techniques [photoelectron spectroscopy (PES) and scanning tunneling microscopy and spectroscopy] were employed. The samples were subjected to heating cycles with annealing temperatures of up to 425 and 525K. Prior to annealing the VO2 films exhibit the transition from the monoclinic to the tetragonal phase with the concurrent change in conductivity by more than a factor of 103 and their phase purity is confirmed by XRD. Annealing to 425K and thus cycling across the metal-insulator transition (MIT) temperature has no impact on the bulk properties of the VO2 film but the surface undergoes irreversible electronic changes. The observation of the valence band with PES during the annealing illustrates that the surface adopts a partially metallic character, which is retained after cooling. Annealing to a higher temperature (525K ) triggers a modification of the bulk, which is evidenced by a considerable reduction in the MIT characteristics, and a degradation in crystallite morphology. The local measurement of the conductivity with scanning tunneling spectroscopy shows the transition of the surface from predominantly semiconducting surface prior to annealing to a surface with an overwhelming contribution from metallic sections afterward. The spatial distribution of metallic regions cannot be linked in a unique manner to the crystallite size or location within the crystallites. The onset of oxygen depletion at the surface is held responsible for this behavior. The onset of bulk

  9. Surface cracking of tungsten-vanadium alloys under transient heat loads

    Directory of Open Access Journals (Sweden)

    Kameel Arshad

    2015-07-01

    Full Text Available To evaluate high heat load performance of tungsten-vanadium (W-V alloys as a potential candidate for plasma facing materials of fusion devices, the target materials with three different V concentrations (1, 5 and 10 wt% are exposed to thermal shock loading. The alloys are fabricated by cold isostatic pressing and subsequently sintered in a vacuum furnace. Thereafter, they are exposed to different high heat flux densities ranging from 340 to 675 MW/m2 for single shot of 5 ms duration in an intense electron beam test facility. The alloys with lowest V concentration (1 wt% are highly damaged in form of seriously cracking. The ones with intermediate V content (5 wt% has shown comparatively better performance than both highest and lowest V contents alloys. The results indicate that improved mechanical properties and reduced thermal conductivity due to V addition comprehensively affect the cracking behavior of W-V alloy under transient thermal shock.

  10. Vanadium(IV/V) speciation of pyridine-2,6-dicarboxylic acid and 4-hydroxy-pyridine-2,6-dicarboxylic acid complexes: potentiometry, EPR spectroscopy and comparison across oxidation states.

    Science.gov (United States)

    Jakusch, Tamás; Jin, Wenzheng; Yang, Luqin; Kiss, Tamás; Crans, Debbie C

    2003-05-01

    Evaluation of stability of vanadium(IV) and (V) complexes under similar conditions is critical for the interpretation and assessment of bioactivity of various vanadium species. Detailed understanding of the chemical properties of these complexes is necessary to explain differences observed their activity in biological systems. These studies are carried out to link the chemistry of both vanadium(IV) and (V) complexes of two ligands, 2,6-pyridinedicarboxylic acid (dipicolinic acid, H(2)dipic) and 4-hydroxy-2,6-pyridinedicarboxylic acid (H(2)dipic-OH). Solution speciation of the two 2,6-pyridinedicarboxylic acids with vanadium(IV) and vanadium(V) ions was determined by pH-potentiometry at I=0.2 M (KCl) ionic strength and at T=298 K. The stability and the metal affinities of the ligands were compared. Vanadium(V) complexes were found to form only tridentate coordinated 1:1 complexes, while vanadium(IV) formed complexes with both 1:1 and 1:2 stoichiometries. The formation constant reflects hindered coordination of a second ligand molecule, presumably because of the relatively small size of the metal ion. The most probable binding mode of the complexes was further explored using ambient and low temperature EPR spectroscopy for vanadium(IV) and 51V NMR spectroscopy for vanadium(V) systems. Upon complex formation the pyridinol-OH in position 4 deprotonates with pK approximately 3.7-4.1, which is approximately 6 orders of magnitude lower than that of the free ligand. The deprotonation enhances the ligand metal ion affinity compared to the parent ligand dipicolinic acid. In the light of the speciation and stability data of the metal complexes, the efficiency of the two ligands in transporting the metal ion in the two different oxidation states are assessed and discussed.

  11. High surface area bio-waste based carbon as a superior electrode for vanadium redox flow battery

    Science.gov (United States)

    Maharjan, Makhan; Bhattarai, Arjun; Ulaganathan, Mani; Wai, Nyunt; Oo, Moe Ohnmar; Wang, Jing-Yuan; Lim, Tuti Mariana

    2017-09-01

    Activated carbon (AC) with high surface area (1901 m2 g-1) is synthesized from low cost bio-waste orange (Citrus sinensis) peel for vanadium redox flow battery (VRB). The composition, structure and electrochemical properties of orange peel derived AC (OP-AC) are characterized by elemental analyzer, field emission-scanning electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy. CV results show that OP-AC coated bipolar plate demonstrates improved electro-catalytic activity in both positive and negative side redox couples than the pristine bipolar plate electrode and this is ascribed to the high surface area of OP-AC which provides effective electrode area and better contact between the porous electrode and bipolar plate. Consequently, the performance of VRB in a static cell shows higher energy efficiency for OP-AC electrode than the pristine electrode at all current densities tested. The results suggest the OP-AC to be a promising electrode for VRB applications and can be incorporated into making conducting plastics electrode to lower the VRB cell stack weight and cost.

  12. Exploring a novel approach to fabricate vanadium carbide encapsulated into carbon nanotube (VC@C) with large specific surface area

    Indian Academy of Sciences (India)

    Yifu Zhang; Juecheng Zhang; Meijuan Fan; Yan’an Long; Yalan Zhong; Xinghai Liu; Chi Huang

    2013-06-01

    A novel approach to the fabrication of vanadium carbide encapsulated into carbon nanotube (VC@C) core-shell structured composite by thermal treatment with the precursor V3O7.H2O@C was developed for the first time. The as-obtained VC@C were characterized by X-ray powder diffraction (XRD), Raman spectrum, energydispersive X-ray spectrometer (EDX), elemental analysis (EA), Fourier transform infrared spectroscopy (FT)–(IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer–Emmett–Teller (BET). The results showed that VC@C with core-shell structures could be successfully synthesized at 1000 °C for 2 h. The specific surface area, average pore size and measured pore volume of VC@C were 135.46 m2/g, 4.443 nm and 0.180 cm3/g, respectively indicating that the as-obtained VC@C composite could be used as a mesoporous material. Furthermore, thermal behaviour of the as-obtained VC@C composite in air was investigated by thermogravimetric/differential thermal analyser (TG/DTA). The experimental result revealed that the carbon coated on the surface of VC has high activity with O2 in air atmosphere.

  13. Melt quenched vanadium oxide embedded in graphene oxide sheets as composite electrodes for amperometric dopamine sensing and lithium ion battery applications

    Science.gov (United States)

    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.

  14. Mechanosynthesis and mechanochemical treatment of bismuth doped vanadium phosphorus oxide catalysts for the partial oxidation of n-butane to maleic anhydride

    Institute of Scientific and Technical Information of China (English)

    Y H.Taufiq-Yap; Y C.Wong; Y Kamiya; W.J.Tang

    2008-01-01

    Three Bi-doped vanadyl pyrophosphate catalysts were prepared via dihydrate route(VPD method),which consisted of different preparation methods including mechanosvnthesis,mechanochemical treatment,and the conventional reflux method.The catalysts produced by the above three methods were characterized by x-ray diffraction(XRD),scanning electron microscopy(SEM),and temperature programmed reduction(TPR).Catalytic evaluation for the partial oxidation of n-butane to maleic anhydride (MA) was also carried out.The XRD patterns of all the Bi-doped catalysts showed the main peaks of pyrophosphate phase.Lower intensity peaks were observed for the mechanochemically treated Bi-doped catalyst(VPDBiMill)with two additional small DeakS corresponding to the presence of a small amount of V5+ phase.The TPR profiles showed that the highest amount of active oxygen species.i.e.V4+-O- pair,responsible for n-butane activation,was removed from VPDBiMill.Furthermore.from the catalytic test results.the graph of selectivity to MA as a function of the conversion of n-butane demonstrated that VPDBiMill was the most selective catalyst.This suggests that the mechanochemical treatment of vanadium phosphate catalyst(VPDBiMill)is a potential method to improve the catalytic properties for the partial oxidation of n-butane to maleic anhydride.

  15. Kinetics of oxidation of D-arabinose and D-xylose by vanadium (V in the presence of manganese II as homogeneous catalyst

    Directory of Open Access Journals (Sweden)

    Ezekiel O. Odebunmi

    2010-12-01

    Full Text Available Kinetics of oxidation of D-arabinose and D-xylose by acidic solution of vanadium (V ions in the presence of manganese (II has been reported. First-order dependence of the reaction rate was observed on [sugars] and [H+] at low concentrations throughout the oxidation reaction and a zero-order dependence on [sugar] and [H+] was observed at high concentrations. First-order kinetics with respect to [Mn (II] was also observed throughout the oxidation for both sugars. The results indicate the effect of Cl- concentration is negligible. The reaction rates increase with the ionic strength of the medium. Various activation parameters were evaluated and provide further support to the proposed mechanism. Formic acid was reported as one of the oxidation products of these sugars.

  16. Direct oxidation of benzene to phenol in liquid phase by H2O2 over vanadium catalyst supported on highly ordered nanoporous silica

    Directory of Open Access Journals (Sweden)

    A. R. Badiei

    2011-01-01

    Full Text Available Vanadium supported on highly ordered nanoporous silica (VOx-LUS-1 was synthesized and characterized by XRD, Nitrogen adsorption‑desorption isotherms and UV-visible spectrophotometer. Direct oxidation of benzene to phenol in liquid phase by H2O2 peroxide were examined by using various solvents (methanol, acetone, acetic acid, acetonitryl. The maximum yield (25% and selectivity (73% of the phenol  produced were obtained in the presence of acetic acid. The catalyst can be reused for  several times without any appreciable loss of activity.

  17. Vanadium Oxide Nanomaterials for Sodium-Ion Battery%钒氧化物纳米材料在钠离子电池中的应用

    Institute of Scientific and Technical Information of China (English)

    魏湫龙; 蒋周阳; 谭双双; 李启东; 麦立强

    2016-01-01

    Sodium-ion batteries (SIBs) as next-generation energy storage technology, especially for the large scale energy storage systems, have attracted recent attentions due to their abundant resource and low cost of sodium. It is important to develop high performance SIB cathodes and realize safe, efficient and commercialized applications. Vanadium oxides with various valence states, layered structures and compounds with multi-electron reaction exhibit a high storage capacity for SIBs. The design and optimization of vanadium oxide nanostructure can largely improve the electrochemical performance. This review summarizes recent development and their optimization strategies of vanadium oxide nanomaterials for SIBs. Combining with previous work by our group, we discuss the future directions in the application of vanadium oxides for high performance SIBs.%钠离子电池具有资源广、成本低等优势,是新一代储能技术,更是大规模储能的发展前沿与热点。为获得安全、高效、可商业化的钠离子电池,其正极材料的开发是研究者们面临的难题之一。钒氧化物具有多变的价态与化合物,通过多电子反应可获得高的存储容量,丰富的层状结构为高容量的钠离子存储提供了可能。通过对钒氧化物纳米结构的设计与优化可有效改善电极材料的储钠性能。本文主要综述了最近钒氧化物纳米结构的储钠机理与性能优化的研究进展,并结合本课题组的研究工作讨论了相关的发展方向。

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

    Science.gov (United States)

    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.

  19. Plasma assisted synthesis of vanadium pentoxide nanoplates

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Megha; Sharma, Rabindar Kumar; Kumar, Prabhat, E-mail: prabhat89k@gmail.com; Reddy, G. B. [Thin film laboratory, Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi-110016 (India)

    2015-08-28

    In this work, we report the growth of α-V{sub 2}O{sub 5} (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 V{sub 2}O{sub 5} to take place. Samples grown have been studied using XPS, XRD and HRTEM to confirm the growth of α-phase of V{sub 2}O{sub 5}, which revealed pure single crystal of α- V{sub 2}O{sub 5} 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 V{sub 2}O{sub 5} have been deposited.

  20. Adsorption of a single gold or silver atom on vanadium oxide clusters.

    Science.gov (United States)

    Ding, Xun-Lei; Wang, Dan; Li, Rui-Jie; Liao, Heng-Lu; Zhang, Yan; Zhang, Hua-Yong

    2016-04-14

    The bonding properties between a single atom and its support have a close relationship with the stability and reactivity of single-atom catalysts. As a model system, the structural and electronic properties of bimetallic oxide clusters MV3Oy(q) (M = Au or Ag, q = 0, ±1, and y = 6-8) are systematically studied using density functional theory. The single noble metal atom Au or Ag tends to be adsorbed on the periphery of the V oxide clusters. Au prefers V sites for oxygen-poor clusters and O sites for oxygen-rich clusters, while Ag prefers O sites for most cases. According to natural population analysis, Au may possess positive or negative charges in the bimetallic oxide clusters, while Ag usually possesses positive charges. The bonding between Au and V has relatively high covalent character according to the bond order analysis. This work may provide some clues for understanding the bonding properties of single noble metal atoms on the support in practical single-atom catalysts, and serve as a starting point for further theoretical studies on the reaction mechanisms of related catalytic systems.

  1. Speciation of vanadium in soil.

    Science.gov (United States)

    Połedniok, Justyna; Buhl, Franciszek

    2003-01-02

    A method for speciation of vanadium in soil is presented in this work. The sequential extraction analysis procedure of Tessier et al. for heavy metals was used for the vanadium separation. The method consists of sequential leaching of the soil samples to separate five fractions of metals: (1) exchangeable, (2) bound to carbonates, (3) bound to Fe-Mn oxides, (4) bound to organic matter and (5) residual. The leaching solutions of Tessier were used for the vanadium extraction, only for the residual fraction the HClO(4) was replaced with H(2)SO(4). The optimum conditions for leaching of vanadium from soil (weight of sample, concentration and volume of extractants, time of extraction) were chosen for each fraction. A sensitive, spectrophotometric method based on the ternary complex V(IV) with Chrome Azurol S and benzyldodecyldimethylammonium bromide (epsilon=7.1x10(4) l mol(-1) cm(-1)) was applied for the vanadium determination after separation of V(V) by solvent extraction using mesityl oxide and reduction of V(V) using ascorbic acid. This method was applied for vanadium speciation in soil from two different regions of Poland: Upper Silesia (industrial region) and Podlasie (agricultural region). The content of vanadium in the fractions of Upper Silesia soil was respectively (in 10(-3)%): I, 3.39; III, 4.53; IV, 10.70; V, 8.70 and it was the highest in the organic fraction, indicating input by anthropogenic activities. The content of vanadium in Podlasie soil was clearly lower and it was (in 10(-3)%): I, 2.07; III, 0.92; IV, 0.69; V, 1.23. The concentration of vanadium in fraction 2 of both soils was less than detection limit of applied method. The total content of vanadium in the five soil fractions was in good correlation with the total content of this element in both soils found after HF-H(2)SO(4) digestion. Analysis using the ICP-AES method gave comparable results.

  2. Titanium–vanadium oxide nanocomposite thin films: Synthesis, characterization and antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Wren, A.W.; Adams, B.M.; Pradhan, D.; Towler, M.R.; Mellott, N.P., E-mail: mellott@alfred.edu

    2014-04-01

    A sol–gel based deposition method was successfully developed to produce a series of crack-free, spatially homogeneous undoped/silver doped titania–vanadia oxide nanocomposite thin films. Thin films were characterized using Glancing Incidence X-ray Diffraction (GIXRD), X-ray Photoelectron Spectroscopy (XPS), and Ultraviolet Visible Spectroscopy (UV–Vis). It was determined via both XRD and XPS that when calcined at 450 °C the nanocomposite crystallinity was a function of sol composition. Additionally, it was determined via GIXRD that upon silver doping, silver was incorporated into the vanadia structure or present in silver oxide form in crystalline films. A red shift within the UV–Vis spectra was observed with an increase of vanadia concentration from 0 to 100% respectively. Antibacterial analysis conducted on Escherichia coli and Staphylococcus epidermidis demonstrated that films exposed to light showed greater antibacterial properties. - Highlights: • Nanocomposite crystallinity was a function of sol composition. • Silver was incorporated into the vanadia structure. • A red shift was observed with an increase of vanadia concentration. • Antibacterial analysis conducted on Escherichia coli and Staphylococcus epidermidis.

  3. OXIDATION OF METHANOL USING OZONE ON TITANIA-SUPPORTED VANADIUM CATALYST

    Science.gov (United States)

    Catalytic ozone decomposition of methanol has been conducted at mild temperatures of 100 to 250°C using V2O5/TiO2 catalyst prepared by either sol-gel or wet impregnation methods. The catalysts were characterized using XRD, surface area measurements, and desorption of CH3OH. Gas p...

  4. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L. [Colorado School of Mines, Golden, CO (United States)

    1995-12-31

    The United States has vast natural gas reserves which could contribute significantly to our energy security if economical technologies for conversion to liquid fuels and chemicals were developed. Many of these reserves are small scale or in remote locations and of little value unless they can be transported to consumers. Transportation is economically performed via pipeline, but this route is usually unavailable in remote locations. Another option is to convert the methane in the gas to liquid hydrocarbons, such as methanol, which can easily and economically be transported by truck. Therefore, the conversion of methane to liquid hydrocarbons has the potential to decrease our dependence upon oil imports by opening new markets for natural gas and increasing its use in the transportation and chemical sectors of the economy. In this project, we are attempting to develop, and explore new catalysts capable of direct oxidation of methane to methanol. The specific objectives of this work are discussed.

  5. Vaporization Studies from Slag Surfaces Using a Thin Film Technique

    Science.gov (United States)

    Seetharaman, Seshadri; Shyrokykh, Tetiana; Schröder, Christina; Scheller, Piotr R.

    2013-08-01

    The investigations of vanadium vaporization from CaO-SiO2-FeO-V2O5 thin film slags were conducted using the single hot thermocouple technique (SHTT) with air as the oxidizing atmosphere. The slag samples were analyzed after the experiments by SEM/EDX. The vanadium content was found to decrease as a function of time. The loss of vanadium from the slag film after 30 minutes of oxidation was approximately 18 pct and after 50 minutes, it was nearly 56 pct. The possible mechanism of vanadium loss would be the surface oxidation of vanadium oxide in the slag, VO x to V5+, followed by surface evaporation of V2O5, which has a high vapor pressure at the experimental temperature.

  6. In situ vibrational spectroscopic investigation of C4 hydrocarbon selective oxidation over vanadium-phosphorus-oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Zhi -Yang [Iowa State Univ., Ames, IA (United States)

    1999-05-10

    n-Butane selective oxidation over the VPO catalyst to maleic anhydride is the first and only commercialized process of light alkane selective oxidation. The mechanism of this reaction is still not well known despite over twenty years of extensive studies, which can partially be attributed to the extreme difficulties to characterize catalytic reactions real-time under typical reaction conditions. In situ spectroscopic characterization techniques such as Infrared spectroscopy and laser Raman spectroscopy were used in the current mechanistic investigations of n-butane oxidation over VPO catalysts. To identify the reaction intermediates, oxidation of n-butane, 1,3-butadiene and related oxygenates on the VPO catalyst were monitored using FTIR spectroscopy under transient conditions. n-Butane was found to adsorb on the VPO catalyst to form olefinic species, which were further oxidized to unsaturated, noncyclic carbonyl species. The open chain dicarbonyl species then experienced cycloaddition to form maleic anhydride. VPO catalyst phase transformations were investigated using in situ laser Raman spectroscopy. This report contains Chapter 1: General introduction; Chapter 2: Literature review; and Chapter 5: Conclusion and recommendations.

  7. In situ vibrational spectroscopic investigation of C{sub 4} hydrocarbon selective oxidation over vanadium-phosphorus-oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Xue, Z.Y.

    1999-05-10

    n-Butane selective oxidation over the VPO catalyst to maleic anhydride is the first and only commercialized process of light alkane selective oxidation. The mechanism of this reaction is still not well known despite over twenty years of extensive studies, which can partially be attributed to the extreme difficulties to characterize catalytic reactions real-time under typical reaction conditions. In situ spectroscopic characterization techniques such as Infrared spectroscopy and laser Raman spectroscopy were used in the current mechanistic investigations of n-butane oxidation over VPO catalysts. To identify the reaction intermediates, oxidation of n-butane, 1,3-butadiene and related oxygenates on the VPO catalyst were monitored using FTIR spectroscopy under transient conditions. n-Butane was found to adsorb on the VPO catalyst to form olefinic species, which were further oxidized to unsaturated, noncyclic carbonyl species. The open chain dicarbonyl species then experienced cycloaddition to form maleic anhydride. VPO catalyst phase transformations were investigated using in situ laser Raman spectroscopy. This report contains Chapter 1: General introduction; Chapter 2: Literature review; and Chapter 5: Conclusion and recommendations.

  8. Small cluster models of the surface electronic structure and bonding properties of titanium carbide, vanadium carbide, and titanium nitride.

    Science.gov (United States)

    Didziulis, Stephen V; Butcher, Kristine D; Perry, Scott S

    2003-12-01

    Density functional theory (DFT) calculations on stoichiometric, high-symmetry clusters have been performed to model the (100) and (111) surface electronic structure and bonding properties of titanium carbide (TiC), vanadium carbide (VC), and titanium nitride (TiN). The interactions of ideal surface sites on these clusters with three adsorbates, carbon monoxide, ammonia, and the oxygen atom, have been pursued theoretically to compare with experimental studies. New experimental results using valence band photoemission of the interaction of O(2) with TiC and VC are presented, and comparisons to previously published experimental studies of CO and NH(3) chemistry are provided. In general, we find that the electronic structure of the bare clusters is entirely consistent with published valence band photoemission work and with straightforward molecular orbital theory. Specifically, V(9)C(9) and Ti(9)N(9) clusters used to model the nonpolar (100) surface possess nine electrons in virtually pure metal 3d orbitals, while Ti(9)C(9) has no occupation of similar orbitals. The covalent mixing of the valence bonding levels for both VC and TiC is very high, containing virtually 50% carbon and 50% metal character. As expected, the predicted mixing for the Ti(9)N(9) cluster is somewhat less. The Ti(8)C(8) and Ti(13)C(13) clusters used to model the TiC(111) surface accurately predict the presence of Ti 3d-based surface states in the region of the highest occupied levels. The bonding of the adsorbate species depends critically on the unique electronic structure features present in the three different materials. CO bonds more strongly with the V(9)C(9) and Ti(9)N(9) clusters than with Ti(9)C(9) as the added metal electron density enables an important pi-back-bonding interaction, as has been observed experimentally. NH(3) bonding with Ti(9)N(9) is predicted to be somewhat enhanced relative to VC and TiC due to greater Coulombic interactions on the nitride. Finally, the interaction with

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

    Science.gov (United States)

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

    2016-12-01

    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.

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

    Science.gov (United States)

    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.

  11. Formation of graded vanadium oxide (V–O compound) under strong gravitational field

    Energy Technology Data Exchange (ETDEWEB)

    Khandaker, Jahirul Islam; Tokuda, Makoto; Ogata, Yudai; Januszko, Kamila; Mashimo, Tsutomu, E-mail: mashimo@gpo.kumamoto-u.ac.jp [Institute of Pulsed Power Science, Kumamoto University, Kumamoto 860-8555 (Japan); Nishiyama, Tadao; Yoshiasa, Akira [Faculty of Science, Kumamoto University, Kumamoto 860-8555 (Japan)

    2015-05-14

    Sedimentation of atoms induced under strong gravitational field gives a tool for controlling elemental compositions in condensed matter. We performed a strong-gravity experiment (0.397 × 10{sup 6 }G at 400 °C for 24 h) on a V{sub 2}O{sub 5} polycrystal using the high-temperature ultracentrifuge to examine the composition change and further the structure change. The graded composition structure of V and O was formed along gravity direction, where V increases and O decreases with gravity. It was found by the x-ray diffraction and Raman scattering method that VO{sub 2} and V{sub 2}O{sub 3} phases appeared and the amounts increased, while one of the V{sub 2}O{sub 5} phase decreased gradually along gravity direction. The X-ray absorption near edge structure spectra analysis identified the chemical valency decrease (+5 to +3). The UV-Vis absorption spectroscopy addressed the shifting in center of major absorption peak to longer wavelength (red shift) with the increase in gravitational field. The tail absorption peak (band gap 2.09 eV) at strong gravity region in the graded structure showed transparent conductive oxide.

  12. Vanadium Sulfide on Reduced Graphene Oxide Layer as a Promising Anode for Sodium Ion Battery.

    Science.gov (United States)

    Sun, Ruimin; Wei, Qiulong; Li, Qidong; Luo, Wen; An, Qinyou; Sheng, Jinzhi; Wang, Di; Chen, Wei; Mai, Liqiang

    2015-09-23

    As an alternative system of rechargeable lithium ion batteries, sodium ion batteries revitalize researchers' interest due to the low cost, abundant sodium resources, and similar storage mechanism to lithium ion batteries. VS4 has emerged as a promising anode material for SIBs due to low cost and its unique linear chains structure that can offer potential sites for sodium storage. Herein, we present the growth of VS4 on reduced graphene oxide (rGO) as SIBs anode for the first time. The VS4/rGO anode exhibits promising performance in SIBs. It delivers a reversible capacity of 362 mAh g(-1) at 100 mA g(-1) and a good rate performance. We also investigate the sodium storage behavior of the VS4/rGO. Different than most transition metal sulfides, the VS4/rGO composite experiences a three-step separation mechanism during the sodiation process (VS4 to metallic V and Na2S, then the electrochemical mechanism is akin to Na-S). The VS4/rGO composite proves to be a promising material for rechargeable SIBs.

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

    Science.gov (United States)

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

    2016-07-01

    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.

  14. Vanadium based amorphous mixed oxides used as negative electrodes of lithium batteries; Oxydes mixtes amorphes a base de vanadium comme electrodes negatives de batteries au lithium

    Energy Technology Data Exchange (ETDEWEB)

    Guyomard, D.; Leroux, F.; Sigala, C.; Le Gal La Salle, A.; Piffard, Y. [Institut des Materiaux de Nantes, 44 (France). Laboratoire de Chimie des Solides

    1996-12-31

    This paper presents recent results concerning the chemical and electrochemical synthesis, the electrochemical properties and the characterization of two new families of amorphous oxides of formula Li{sub x}MVO{sub 4} (1oxides allows the low potential reversible insertion of lithium and can be used as negative electrodes in high performance lithium-ion batteries. (J.S.) 19 refs.

  15. Reaction mechanism and optimal conditions for preparation of high-quality vanadium oxide films by organic sol-gel for optoelectronic applications

    Science.gov (United States)

    Sun, Minghui; Wen, Yuejiang; Xu, Xiangdong; Wang, Meng; He, Qiong; Jiang, Yadong; Dai, Zelin; Gu, Yu; Chen, Zhegeng

    2016-03-01

    Although vanadium oxides (VO x ) are important functional materials for academic research and industrial applications, the reaction mechanism of VO x prepared by organic sol-gel remains unclear. In order to investigate this mechanism, VO x organic sols were reacted at different temperatures, by which various VO x thin films were prepared. The products were systematically characterized by infrared spectroscopy, Raman spectroscopy, UV-vis spectroscopy, thermogravimetric analysis, scanning electron microscopy, x-ray diffraction, and a high resistance meter. Results reveal that vanadium alkoxides are created through an alcoholysis reaction of V2O5 powder and isobutyl alcohol, and then a condensation reaction of the vanadium alkoxides leads to the formation of VO x networks. The as-prepared sols are strongly temperature-dependent, causing different chemical structures and physical properties for the resulting VO x films. Particularly, a moderate temperature of 110 °C prompts both alcoholysis and condensation reactions, and thus the VO x films that are produced by the sol reacted at 110 °C possess a low resistivity of 23 Ω cm, a high temperature coefficient resistance (TCR) of  -3.2% K-1, and a low average transmittance of 54% in 580-1100 nm, compared with those prepared by the sols reacted at lower or higher temperatures. Therefore, 110 °C is a desirable sol temperature for producing VO x films serving as high-quality bolometric materials for uncooled infrared detectors. This work discloses not only the reaction mechanism of VO x films prepared by organic sol-gel, but also the route to yield desirable VO x films for optoelectronic applications.

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

    Science.gov (United States)

    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.

  17. Thermodynamic and experimental study of corrosion behavior of vanadium-based alloy in liquid sodium-potassium coolant

    Science.gov (United States)

    Krasin, V. P.; Lyublinski, I. E.; Soyustova, S. I.

    2016-11-01

    A preliminary assessment of oxygen effect on vanadium solubility in Na-K melt eutectic composition has been carried out using mathematical framework of the subregular solution model and equations of coordination-cluster model. The effect of oxygen on the solubility of vanadium in the Na-K alloy can be considered as the result of short-range ordering in liquid metal solution. The negative deviations from the ideality for dilute oxygen solutions in Na-K solvent is one reason that explains the quantitative differences between Na and Na-K coolants, when we need to estimate the threshold oxygen concentration for the formation of ternary oxide NaVO2 on the surface of the solid vanadium in liquid sodium and in Na-K alloy. Isothermal capsule experiments qualitatively confirmed the results of calculations of vanadium solubility in Na0.32K0.68 alloy.

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

    Science.gov (United States)

    Chatterjee, Pabitra B; Crans, Debbie C

    2012-09-03

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

  19. Synthesis by sol-gel process, structural and optical properties of nanoparticles of zinc oxide doped vanadium

    Science.gov (United States)

    El Ghoul, J.; Barthou, C.; El Mir, L.

    2012-06-01

    We report the elaboration of vanadium-doped ZnO nanoparticles prepared by a sol-gel processing technique. In our approach, the water for hydrolysis was slowly released by esterification reaction followed by a supercritical drying in ethyl alcohol. Vanadium doping concentration of 10 at.% has been investigated. After treatment in air at different temperatures, the obtained nanopowder was characterised by various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence (PL). Analysis by scanning electron microscopy at high resolution shows that the grain size increases with increasing temperature. Thus, in the case of thermal treatment at 500 °C in air, the powder with an average particle size of 25 nm shows a strong luminescence band in the visible range. The intensity and energy position of the obtained PL band depends on the temperature measurement increase. The mechanism of this emission band is discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-01

    resulted in less structural deformation in the final solid. Loading of the vanadyl sulfate hydrate (VOSO{sub 4}·H{sub 2}O) resulted in a higher V/Si ratio in the solid since both settling and ion exchange mechanism occured. The vanadium was usually bonded in the +5 oxide form, and the particles were settled between these layers and onto the outer surface of the clay particles. The existence of V–O structural bonds and Bronsted and Lewis acid sites were observed in the Fourier transform infrared spectroscopy (FTIR) results. Up to 300 °C dehydration with high mass loss was observed, followed by the decreases in mass loss, and finally, at around 900 °C, hydroxylation reactions were observed in the TGA/DTA analyses.

  1. Experimental and theoretical studies on the vibrational structure on disperse vanadium and titanium oxide; Experimentelle und theoretische Untersuchungen zur Schwingungsstruktur an dispersem Vanadium- und Titanoxid

    Energy Technology Data Exchange (ETDEWEB)

    Nitsche, David

    2014-10-20

    By combination of FT-IR- and UV-Raman spectroscopy with normal mode analysis, this study analyzes the vibrational structure of silica supported vanadia and titania. Based on these results, structural models are developed for vanadia species under hydrated and dehydrated conditions as well as for titania species under dehydrated conditions. To this end, a novel UV-Raman setup has been developed allowing for resonance enhancement of the silica supported vanadia and titania systems. The use of a tunable solid-state laser (193-420 nm) and a triple spectrometer enables the flexibility necessary for selective resonance enhancement. In accordance with the selection rules of Raman theory the sensitivity of the method was significantly increased and made it possible, for the first time, to measure solid-state systems with a loading density of 0.00001-0.7 V nm{sup -2} and 0.0001-0.7 Ti nm{sup -2} under hydrated and dehydrated conditions. The investigated samples are based on nanostructured silicon dioxide (SBA-15), which was functionalized using an ion-exchange method and incipient wetness impregnation. UV-Vis analysis of silica supported vanadia indicated the presence of both monomeric and oligomeric surface species under hydrated and dehydrated conditions. In contrast, UV-Vis analysis of silica supported titania revealed the presence of monomeric species with both a tetrahedral and octahedral koordination. FT-IR measurements of silica supported vanadia and titania samples under dehydrated conditions showed absorption signals at 3660 and 3658 cm{sup -1}, which are consistent with stretch vibrations of hydroxylated surface species. Previous literature on silica supported vanadia has described a signal at 1020 cm{sup -1}, which could be verified by the UV-Raman method. It can be attributed to a totally symmetrical V=O stretch vibration due to the occurance of the corresponding overtone at 2039-2045 cm{sup -1}. Furthermore, under hydrated conditions at low loadings signals at

  2. Oxide driven strength evolution of silicon surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Grutzik, Scott J.; Zehnder, Alan T., E-mail: atz2@cornell.edu [Field of Theoretical and Applied Mechanics, Cornell University, Ithaca, New York 14853 (United States); Milosevic, Erik [Department of Nanoengineering, SUNY Polytechnic University, Albany, New York 12203 (United States); Boyce, Brad L. [Sandia National Laboratories, Albuquerque, New Mexico 87185-0889 (United States)

    2015-11-21

    Previous experiments have shown a link between oxidation and strength changes in single crystal silicon nanostructures but provided no clues as to the mechanisms leading to this relationship. Using atomic force microscope-based fracture strength experiments, molecular dynamics modeling, and measurement of oxide development with angle resolved x-ray spectroscopy we study the evolution of strength of silicon (111) surfaces as they oxidize and with fully developed oxide layers. We find that strength drops with partial oxidation but recovers when a fully developed oxide is formed and that surfaces intentionally oxidized from the start maintain their high initial strengths. MD simulations show that strength decreases with the height of atomic layer steps on the surface. These results are corroborated by a completely separate line of testing using micro-scale, polysilicon devices, and the slack chain method in which strength recovers over a long period of exposure to the atmosphere. Combining our results with insights from prior experiments we conclude that previously described strength decrease is a result of oxidation induced roughening of an initially flat silicon (1 1 1) surface and that this effect is transient, a result consistent with the observation that surfaces flatten upon full oxidation.

  3. Photochemical transformation of vanadium(5) acetylacetonate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kuchmij, S.Ya.; Turchaninov, A.M.; Kryukov, A.I. (AN Ukrainskoj SSR, Kiev. Inst. Fizicheskoj Khimii)

    1980-08-01

    Photochemical transformations of mixed vanadium (5) complex formed as a result of interaction between ethylorthovanadate and acetylacetone which includes in the first coordination sphere vanadyl oxygen, two enolate-ions and enthoxygroup are studied spectrophotometrically and using ESR method. During irradiation of ethanol solutions of the complex a successive reduction of central atom with formation of acetyl-acetonate complexes of vanadium (4) and (3) takes place. At that the solvent is oxidated. In CCl/sub 4/ solution under the effect of UV irradiation ethoxygroup is replaced by chlorine ion with the formation of new mixed vanadium (5) complex, sensible to visible and UV radiation.

  4. Surface modification to prevent oxide scale spallation

    Science.gov (United States)

    Stephens, Elizabeth V; Sun, Xin; Liu, Wenning; Stevenson, Jeffry W; Surdoval, Wayne; Khaleel, Mohammad A

    2013-07-16

    A surface modification to prevent oxide scale spallation is disclosed. The surface modification includes a ferritic stainless steel substrate having a modified surface. A cross-section of the modified surface exhibits a periodic morphology. The periodic morphology does not exceed a critical buckling length, which is equivalent to the length of a wave attribute observed in the cross section periodic morphology. The modified surface can be created using at least one of the following processes: shot peening, surface blasting and surface grinding. A coating can be applied to the modified surface.

  5. Synthesis of vanadium oxides 5 wt.%VO2–MO by sol–gel process and application in cyclohexene epoxidation

    Indian Academy of Sciences (India)

    S El-Korso; I Rekkab; A Choukchou-Braham; S Bedrane; L Pirault-Roy; C Kappenstein

    2012-12-01

    A series of SiO2, Al2O3 and TiO2 mixed vanadium materials have been prepared from inorganic precursors via the sol–gel process and subsequently dried, calcined and reduced at elevated temperatures. Structural characterization of these materials was carried out by X-ray diffraction (XRD), N2 adsorption at 77 K, thermal analysis (TGA/DTA), UV-vis diffused reflectance spectroscopy (DR UV-vis) and scanning electron microscopy (SEM) with energy dispersive X-ray (EDX). Their catalytic activities in the epoxidation of cyclohexene with TBHP as oxidant were also examined. Results of XRD and DR UV-visible diffused revealed that VO2 species are predominant in all samples and no formation of V2O5 was detected. Experimental results indicated that the VO2–SiO2 catalysts performed excellently for the epoxidation of cyclohexene by tertiobutyl hydroperoxide.

  6. Vanadium recycling in the United States in 2004

    Science.gov (United States)

    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).

  7. Surface wrinkling on polydimethylsiloxane microspheres via wet surface chemical oxidation.

    Science.gov (United States)

    Yin, Jian; Han, Xue; Cao, Yanping; Lu, Conghua

    2014-07-16

    Here we introduce a simple low-cost yet robust method to realize spontaneously wrinkled morphologies on spherical surfaces. It is based on surface chemical oxidation of aqueous-phase-synthesized polydimethylsiloxane (PDMS) microspheres in the mixed H2SO4/HNO3/H2O solution. Consequently, curvature and overstress-sensitive wrinkles including dimples and labyrinth patterns are successfully induced on the resulting oxidized PDMS microspheres. A power-law dependence of the wrinkling wavelength on the microsphere radius exists. The effects of experimental parameters on these tunable spherical wrinkles have been systematically investigated, when the microspheres are pre-deposited on a substrate. These parameters include the radius and modulus of microspheres, the mixed acid solution composition, the oxidation duration, and the water washing post-treatment. Meanwhile, the complicated chemical oxidation process has also been well studied by in-situ optical observation via the microsphere system, which represents an intractable issue in a planar system. Furthermore, we realize surface wrinkled topographies on the whole microspheres at a large scale, when microspheres are directly dispersed in the mixed acid solution for surface oxidation. These results indicate that the introduced wet surface chemical oxidation has the great potential to apply to other complicated curved surfaces for large-scale generation of well-defined wrinkling patterns, which endow the solids with desired physical properties.

  8. CO oxidation on PdO surfaces

    DEFF Research Database (Denmark)

    Hirvi, Janne T.; Kinnunen, Toni-Jani J.; Suvanto, Mika;

    2010-01-01

    , the reaction with the site blocking molecular oxygen is slightly more favorable, enabling also possible formation of carbonate surface species at low temperatures. The extreme activity of strongly bonded surface oxygen atoms is more greatly emphasized on the PdO(100)–O surface. The direct reaction without...... adsorption, following the Eley–Rideal mechanism and taking advantage of the reaction tunnel provided by the adjacent palladium atom, has an activation energy of only 0.24 eV. The reaction mechanism and activation energy for the palladium activated CO oxidation on the most stable PdO(100)–O surface......Density functional calculations were performed in order to investigate CO oxidation on two of the most stable bulk PdO surfaces. The most stable PdO(100) surface, with oxygen excess, is inert against CO adsorption, whereas strong adsorption on the stoichiometric PdO(101) surface leads to favorable...

  9. Surface protected lithium-metal-oxide electrodes

    Science.gov (United States)

    Thackeray, Michael M.; Kang, Sun-Ho

    2016-04-05

    A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

  10. Effect of vanadium substitution on structural and electrical properties of sol-gel grown nanostructured zinc oxide

    Science.gov (United States)

    Boricha, Hetal; Rajyaguru, Bhargav; Gadani, Keval; Rathod, K. N.; Shrimali, V. G.; Udeshi, Bhagyashree; Keshvani, M. J.; Joshi, A. D.; Pandya, D. D.; Solanki, P. S.; Shah, N. A.

    2017-05-01

    In the present communication, we report the results on the structural and electrical studies on nanostructured pure (ZnO) and Vanadium (V) doped Zn0.95V0.05O samples synthesized using low cost Sol-Gel technique. To understand the structural properties and their dependence on V substitution, X-Ray diffraction (XRD) measurement was carried out for both the samples understudy. XRD results reveal the single phasic wurtzite nature of both the samples showing hexagonal unit cell structure. A minor phase of ZnV2O6 is observed in V doped ZnO sample. Improved dielectric permittivity, enhanced ac conductivity (σac) and suppression in impedance have been discussed on the basis of structural modifications by the substitution of V in ZnO, enhanced charge carrier concentration, charge carrier polarization and correlated barrier hopping due to the localized state.

  11. Surface studies of gas sensing metal oxides.

    Science.gov (United States)

    Batzill, Matthias; Diebold, Ulrike

    2007-05-21

    The relation of surface science studies of single crystal metal oxides to gas sensing applications is reviewed. Most metal oxide gas sensors are used to detect oxidizing or reducing gases and therefore this article focuses on surface reduction processes and the interaction of oxygen with these surfaces. The systems that are discussed are: (i) the oxygen vacancy formation on the surface of the ion conductor CeO(2)(111); (ii) interaction of oxygen with TiO(2) (both adsorption processes and the incorporation of oxygen into the TiO(2)(110) lattice are discussed); (iii) the varying surface composition of SnO(2)(101) and its consequence for the adsorption of water; and (iv) Cu modified ZnO(0001)-Zn surfaces and its interaction with oxygen. These examples are chosen to give a comprehensive overview of surface science studies of different kinds of gas sensing materials and to illustrate the potential that surface science studies have to give fundamental insight into gas sensing phenomena.

  12. Hierarchical nanocomposites of vanadium oxide thin film anchored on graphene as high-performance cathodes in li-ion batteries.

    Science.gov (United States)

    Li, Zhe-Fei; Zhang, Hangyu; Liu, Qi; Liu, Yadong; Stanciu, Lia; Xie, Jian

    2014-11-12

    Hierarchical nanocomposites of V2O5 thin film anchored on graphene sheets were prepared by slow hydrolysis of vanadyl triisobutoxide on graphene oxide followed by thermal treatment. The nanocomposite possessed a hierarchical structure of thin V2O5 film uniformly grown on graphene, leading to a high specific surface area and a good electronic/ionic conducting path. When used as the cathode material, the graphene/V2O5 nanosheet nanocomposites exhibit higher specific capacity, better rate performance, and longer cycle life, as compared to the pure V2O5. The nanocomposite cathode was able to deliver a specific capacity of 243 mAh/g, 191 mAh/g, and 86 mAh/g at a current density of 50 mA/g, 500 mA/g, and 15 A/g, respectively. Even after 300 cycles at 500 mA/g, the composite electrode still exhibited a specific capacity of ∼ 122 mAh/g, which corresponds to ∼ 64% of its initial capacity. This enhanced electrochemical performance can be attributed to facile electron transport between graphene and V2O5, fast Li-ion diffusion within the electrode, the high surface area of the composites, and a pore structure that can accommodate the volume change during lithiation/delithiation, which results from the unique hierarchical nanostructure of the V2O5 anchored on graphene.

  13. Atomically flat single terminated oxide substrate surfaces

    Science.gov (United States)

    Biswas, Abhijit; Yang, Chan-Ho; Ramesh, Ramamoorthy; Jeong, Yoon H.

    2017-05-01

    Scientific interest in atomically controlled layer-by-layer fabrication of transition metal oxide thin films and heterostructures has increased intensely in recent decades for basic physics reasons as well as for technological applications. This trend has to do, in part, with the coming post-Moore era, and functional oxide electronics could be regarded as a viable alternative for the current semiconductor electronics. Furthermore, the interface of transition metal oxides is exposing many new emergent phenomena and is increasingly becoming a playground for testing new ideas in condensed matter physics. To achieve high quality epitaxial thin films and heterostructures of transition metal oxides with atomically controlled interfaces, one critical requirement is the use of atomically flat single terminated oxide substrates since the atomic arrangements and the reaction chemistry of the topmost surface layer of substrates determine the growth and consequent properties of the overlying films. Achieving the atomically flat and chemically single terminated surface state of commercially available substrates, however, requires judicious efforts because the surface of as-received substrates is of chemically mixed nature and also often polar. In this review, we summarize the surface treatment procedures to accomplish atomically flat surfaces with single terminating layer for various metal oxide substrates. We particularly focus on the substrates with lattice constant ranging from 4.00 Å to 3.70 Å, as the lattice constant of most perovskite materials falls into this range. For materials outside the range, one can utilize the substrates to induce compressive or tensile strain on the films and explore new states not available in bulk. The substrates covered in this review, which have been chosen with commercial availability and, most importantly, experimental practicality as a criterion, are KTaO3, REScO3 (RE = Rare-earth elements), SrTiO3, La0.18Sr0.82Al0.59Ta0.41O3 (LSAT), Nd

  14. The effect of vanadium-carbon monolayer on the adsorption of tungsten and carbon atoms on tungsten-carbide (0001 surface

    Directory of Open Access Journals (Sweden)

    Moitra A.

    2011-01-01

    Full Text Available We report a first-principles calculations to study the effect of a vanadium-carbon (VC monolayer on the adsorption process of tungsten (W and carbon (C atoms onto tungsten-carbide (WC (0001 surface. The essential configuration for the study is a supercell of hexagonal WC with a (0001 surface. When adding the VC monolayer, we employed the lowest energy configuration by examining various configurations. The total energy of the system is computed as a function of the W or C adatoms’ height from the surface. The adsorption of a W and C adatom on a clean WC (0001 surface is compared with that of a W and C adatom on a WC (0001 surface with VC monolayer. The calculations show that the adsorption energy increased for both W and C adatoms in presence of the VC monolayer. Our results provide a fundamental understanding that can explain the experimentally observed phenomena of inhibited grain growth during sintering of WC or WC-Co powders in presence of VC.

  15. Inverted organic solar cells with sol-gel processed high work-function vanadium oxide hole-extraction layers

    Energy Technology Data Exchange (ETDEWEB)

    Zilberberg, Kirill; Trost, Sara; Riedl, Thomas [Institute of Electronic Devices, University of Wuppertal, Rainer-Gruenter-Str. 21, 42119 Wuppertal (Germany); Meyer, Jens; Kahn, Antoine [Department of Electrical Engineering, Princeton University, Princeton, NJ (United States); Behrendt, Andreas; Luetzenkirchen-Hecht, Dirk; Frahm, Ronald [Physics of Condensed Matter, University of Wuppertal (Germany)

    2011-12-20

    For large-scale and high-throughput production of organic solar cells (OSCs), liquid processing of the functional layers is desired. We demonstrate inverted bulk-heterojunction organic solar cells (OSCs) with a sol-gel derived V{sub 2}O{sub 5} hole-extraction-layer on top of the active organic layer. The V{sub 2}O{sub 5} layers are prepared in ambient air using Vanadium(V)-oxitriisopropoxide as precursor. Without any post-annealing or plasma treatment, a high work function of the V{sub 2}O{sub 5} layers is confirmed by both Kelvin probe analysis and ultraviolet photoelectron spectroscopy (UPS). Using UPS and inverse photoelectron spectroscopy (IPES), we show that the electronic structure of the solution processed V{sub 2}O{sub 5} layers is similar to that of thermally evaporated V{sub 2}O{sub 5} layers which have been exposed to ambient air. Optimization of the sol gel process leads to inverted OSCs with solution based V{sub 2}O{sub 5} layers that show power conversion efficiencies similar to that of control devices with V{sub 2}O{sub 5} layers prepared in high-vacuum. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. A chemical approach to understanding oxide surfaces

    Science.gov (United States)

    Enterkin, James A.; Becerra-Toledo, Andres E.; Poeppelmeier, Kenneth R.; Marks, Laurence D.

    2012-02-01

    Chemical bonding has often been ignored in favor of physics based energetic considerations in attempts to understand the structure, stability, and reactivity of oxide surfaces. Herein, we analyze the chemical bonding in published structures of the SrTiO3, MgO, and NiO surfaces using bond valence sum (BVS) analysis. These simple chemical bonding theories compare favorably with far more complex quantum mechanical calculations in assessing surface structure stability. Further, the coordination and bonding of surface structures explains the observed stability in a readily comprehensible manner. Finally, we demonstrate how simple chemical bonding models accurately predict the adsorption of foreign species onto surfaces, and how such models can be used to predict changes in surface structures.

  17. 低品位钒渣在碳酸钠存在下的氧化过程%Oxidation process of low-grade vanadium slag in presence of Na2CO3

    Institute of Scientific and Technical Information of China (English)

    李新生; 谢兵; 王广恩; 李晓军

    2011-01-01

    The oxidation process of low-grade vanadium slag in the presence of Na2CO3 was investigated by XRD,SEM/EDS and TG-DSC techniques.The results show that the vanadium slag is oxidized in a temperature range from 273 to 700 ℃.Olivine phases and spinel phases are completely decomposed at 500 and 600 ℃,respectively.Most of water-soluble sodium vanadates are formed between 500 and 600 ℃.When roasting temperature reaches above 700 ℃,the vanadium-rich phases of sodium vanadates can be obviously observed.However,at temperature above 800 ℃,the samples are sintered.Most of the vanadium is enwrapped by glassy phase compounds which lead to the decrease of the leaching rate of vanadium.At the same time,the effect of roasting temperature on extraction of vanadium and characterization of leach residues were discussed.%利用XRD,SEM/EDS和TG-DSC等手段对低品位钒渣在Na2CO3存在条件下的氧化过程进行检测.结果表明:钒渣的氧化温度范围为273至700℃,橄榄石相与尖晶石相彻底分解的温度分别是500和600℃,大部分水溶性的钒酸盐在500与600℃之间形成.当温度达到700℃以上时,钒酸盐富集相明显可见,但焙烧温度在800℃以上时,样品发生烧结,并且钒被形成的玻璃相包裹,导致其浸出率下降.同时,研究不同焙烧温度对钒浸出率的影响,并对浸出残渣进行分析.

  18. Electrolysis of water on (oxidized) metal surfaces

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Logadottir, Ashildur; Nørskov, Jens Kehlet

    2005-01-01

    directly from the electronic structure calculations. We consider electrodes of Pt(111) and Au(111) in detail and then discuss trends for a series of different metals. We show that the difficult step in the water splitting process is the formation of superoxy-type (OOH) species on the surface...... by the splitting of a water molecule on top an adsorbed oxygen atom. One conclusion is that this is only possible on metal surfaces that are (partly) oxidized. We show that the binding energies of the different intermediates are linearly correlated for a number of metals. In a simple analysis, where the linear...... relations are assumed to be obeyed exactly, this leads to a universal relationship between the catalytic rate and the oxygen binding energy. Finally, we conclude that for systems obeying these relations, there is a limit to how good a water splitting catalyst an oxidized metal surface can become. (c) 2005...

  19. Strengthening of Ceramic-based Artificial Nacre via Synergistic Interactions of 1D Vanadium Pentoxide and 2D Graphene Oxide Building Blocks

    Science.gov (United States)

    Knöller, Andrea; Lampa, Christian P.; Cube, Felix von; Zeng, Tingying Helen; Bell, David C.; Dresselhaus, Mildred S.; Burghard, Zaklina; Bill, Joachim

    2017-01-01

    Nature has evolved hierarchical structures of hybrid materials with excellent mechanical properties. Inspired by nacre’s architecture, a ternary nanostructured composite has been developed, wherein stacked lamellas of 1D vanadium pentoxide nanofibres, intercalated with water molecules, are complemented by 2D graphene oxide (GO) nanosheets. The components self-assemble at low temperature into hierarchically arranged, highly flexible ceramic-based papers. The papers’ mechanical properties are found to be strongly influenced by the amount of the integrated GO phase. Nanoindentation tests reveal an out-of-plane decrease in Young’s modulus with increasing GO content. Furthermore, nanotensile tests reveal that the ceramic-based papers with 0.5 wt% GO show superior in-plane mechanical performance, compared to papers with higher GO contents as well as to pristine V2O5 and GO papers. Remarkably, the performance is preserved even after stretching the composite material for 100 nanotensile test cycles. The good mechanical stability and unique combination of stiffness and flexibility enable this material to memorize its micro- and macroscopic shape after repeated mechanical deformations. These findings provide useful guidelines for the development of bioinspired, multifunctional systems whose hierarchical structure imparts tailored mechanical properties and cycling stability, which is essential for applications such as actuators or flexible electrodes for advanced energy storage. PMID:28102338

  20. Brannerite-Type Vanadium-Molybdenum Oxide LiVMoO₆ as a Promising Anode Material for Lithium-Ion Batteries with High Capacity and Rate Capability.

    Science.gov (United States)

    Chen, Nan; Wang, Chunzhong; Hu, Fang; Bie, Xiaofei; Wei, Yingjin; Chen, Gang; Du, Fei

    2015-07-29

    Brannerite-type vanadium-molybdenum oxide LiVMoO6 is prepared by a facile liquid-phase method, and its electrochemical properties as anode of lithium-ion batteries are comprehensively studied by means of galvanostatic charge-discharge profiles, rate performance, and cyclic voltammetry. In the working voltage between 3.0 and 0.01 V, LiVMoO6 delivers a high reversible capacity of more than 900 mAh g(-1) at the current density of 100 mA g(-1) and a superior rate capability with discharge capacity of ca. 584 and 285 mAh g(-1) under the high current densities of 2 and 5 A g(-1), respectively. Moreover, ex situ X-ray diffraction and X-ray photoelectron spectroscopy are utilized to examine the phase evolution and valence changes during the first lithiated process. A small amount of inserted Li(+) induces a decomposition of LiVMoO6 into Li2Mo2O7 and V2O5, which play the host during further lithiated processes. When being discharged to 0.01 V, most V(5+) change into V(3+)/V(2+), suggesting intercalation/deintercalation processes, whereas Mo(6+) are reduced into a metallic state on the basis of the conversion reaction. The insights obtained from this study will benefit the design of novel anode materials for lithium-ion batteries.

  1. Strengthening of Ceramic-based Artificial Nacre via Synergistic Interactions of 1D Vanadium Pentoxide and 2D Graphene Oxide Building Blocks

    Science.gov (United States)

    Knöller, Andrea; Lampa, Christian P.; Cube, Felix Von; Zeng, Tingying Helen; Bell, David C.; Dresselhaus, Mildred S.; Burghard, Zaklina; Bill, Joachim

    2017-01-01

    Nature has evolved hierarchical structures of hybrid materials with excellent mechanical properties. Inspired by nacre’s architecture, a ternary nanostructured composite has been developed, wherein stacked lamellas of 1D vanadium pentoxide nanofibres, intercalated with water molecules, are complemented by 2D graphene oxide (GO) nanosheets. The components self-assemble at low temperature into hierarchically arranged, highly flexible ceramic-based papers. The papers’ mechanical properties are found to be strongly influenced by the amount of the integrated GO phase. Nanoindentation tests reveal an out-of-plane decrease in Young’s modulus with increasing GO content. Furthermore, nanotensile tests reveal that the ceramic-based papers with 0.5 wt% GO show superior in-plane mechanical performance, compared to papers with higher GO contents as well as to pristine V2O5 and GO papers. Remarkably, the performance is preserved even after stretching the composite material for 100 nanotensile test cycles. The good mechanical stability and unique combination of stiffness and flexibility enable this material to memorize its micro- and macroscopic shape after repeated mechanical deformations. These findings provide useful guidelines for the development of bioinspired, multifunctional systems whose hierarchical structure imparts tailored mechanical properties and cycling stability, which is essential for applications such as actuators or flexible electrodes for advanced energy storage.

  2. Theoretical study of the influence of cation vacancies on the catalytic properties of vanadium antimonate

    Energy Technology Data Exchange (ETDEWEB)

    Messina, S. [Laboratorio de Procesos Cataliticos, Departamento de Ingenieria Quimica, FIUBA, Pabellon de Industrias, Ciudad Universitaria, (1428) Capital Federal (Argentina); Juan, A. [Departamento de Fisica, UNS, Av. Alem 1253, (8000) Bahia Blanca (Argentina)], E-mail: cajuan@uns.edu.ar; Larrondo, S.; Irigoyen, B.; Amadeo, N. [Laboratorio de Procesos Cataliticos, Departamento de Ingenieria Quimica, FIUBA, Pabellon de Industrias, Ciudad Universitaria, (1428) Capital Federal (Argentina)

    2008-07-15

    We have theoretically studied the influence of antimony and vanadium cation vacancies in the electronic structure and reactivity of vanadium antimonate, using molecular orbital methods. From the analysis of the electronic properties of the VSbO{sub 4} crystal structure, we can infer that both antimony and vanadium vacancies increase the oxidation state of closer V cations. This would indicate that, in the rutile-type VSbO{sub 4} phase the Sb and V cations defects stabilize the V in a higher oxidation state (V{sup 4+}). Calculations of the adsorption energy for different toluene adsorption geometries on the VSbO{sub 4}(1 1 0) surface have also been performed. The oxidation state of Sb, V and O atoms and the overlap population of metal-oxygen bonds have been evaluated. Our results indicate that the cation defects influence in the toluene adsorption reactions is slight. We have computed different alternatives for the reoxidation of the VSbO{sub 4}(1 1 0) surface active sites which were reduced during the oxygenated products formation. These calculations indicate that the V cations in higher oxidation state (V{sup 4+}) are the species, which preferentially incorporate lattice oxygen to the reduced Sb cations. Thus, the cation defects would stabilize the V{sup 4+} species in the VSbO{sub 4} structure, determining its ability to provide lattice oxygen as a reactant.

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

    Science.gov (United States)

    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

  4. Surface chemistry and catalytic properties of VO{sub X}/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

    Energy Technology Data Exchange (ETDEWEB)

    González, J. [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Chen, L.F., E-mail: lchen@ipn.mx [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Wang, J.A.; Manríquez, Ma.; Limas, R. [ESIQIE, Instituto Politécnico Nacional, Av. Instituto Politécnico Nacional s/n, 07738 Col. Zacatenco, Mexico City (Mexico); Schachat, P.; Navarrete, J. [Dirección de Investigación, Instituto Mexicano del Petróleo, Eje Lázaro Cárdenas 152, 07730 México D.F. (Mexico); Contreras, J.L. [Laboratorio de Catálisis y Polímeros, División de Ciencias Básicas e Ingeniería, Universidad Autónoma Metropolitana-A, Av. San Pablo No. 180, 02200 México D.F. (Mexico)

    2016-08-30

    Highlights: • Oxidative desulfurization of model diesel was tested in a biphasic system. • ODS activity was proportional to the V{sup 5+}/(V{sup 4+} + V{sup 5+}) values of the catalysts. • Lewis acidity was related to vanadium content and catalytic activity. • 99.9% DBT was oxidized using 25%V{sub 2}O{sub 5}/Ti-MCM-41 at 60 °C within 60 min. - Abstract: A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H{sub 2}O{sub 2} as oxidant. ODS activity was found to be proportional to the V{sup 5+}/(V{sup 4+} + V{sup 5+}) values of the catalysts, indicating that the surface vanadium pentoxide (V{sub 2}O{sub 5}) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V{sub 2}O{sub 5}) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V{sub 2}O{sub 5}/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

  5. Study on the Process of Extracting Vanadium from Stone Coal Vanadium Ore by No Pollution Oxidizer-Oxidizing-Acid Leaching%硅质石煤钒矿无污染氧化剂氧化—酸浸法提钒工艺研究

    Institute of Scientific and Technical Information of China (English)

    孙德四; 孙剑奇; 张贤珍

    2011-01-01

    The optimal technological parameters of the process of no pollution oxidizer-oxidizing were experimented by the test of single factor conditions. The results showed that the leaching rate of vanadium pentoxide is up to 72. 4% at the temperature 90℃ , manganese dioxide dosage 5% , concentration of sulfuric acid of 40% , particle size - 74 μm, leaching time 9 h, the mass ratio of liquid and solid 2. 5: 1. It is about 10% higher than the process of oxidization roasting with sodium salt%通过单因素条件试验确定了“氧化剂氧化—硫酸浸出提钒工艺”的最优工艺参数.试验结果表明,在氧化剂二氧化锰用量为5%、硫酸浓度为40%、浸出温度为90℃、矿物粒度- 74μm、浸出时间为9h、液固比为2.5:1的条件下,钒的浸出率可达72.4%.比起传统的钠化焙烧工艺高出10%以上.

  6. A new oxo-vanadium complex employing an imidazole-rich tripodal ligand: a bioinspired bromide and hydrocarbon oxidation catalyst.

    Science.gov (United States)

    Fernández, Tatiana L; Souza, Elizabeth T; Visentin, Lorenzo C; Santos, Jeniffer V; Mangrich, Antonio S; Faria, Roberto B; Antunes, O A C; Scarpellini, Marciela

    2009-04-01

    A vanadyl complex with the ligand (bis(1-methylimidazol-2-yl)methyl)(2-(pyridyl-2-yl)ethyl)amine was synthesized and fully characterized by X-ray crystallography, elemental analyses, cyclic voltammetry and infrared, electronic and electron paramagnetic resonance spectroscopies. This compound was designed under the so called hybrid concept. It shows to be able to promiscuously use hydrogen peroxide to oxidize bromide and to catalyze the oxidation of benzene and cyclohexane with very good selectivities.

  7. Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.; Schoonheydt, R.A.

    1996-01-01

    Focuses on the surface chemistry and spectroscopy of chromium in inorganic oxides. Characterization of the molecular structures of chromium; Mechanics of hydrogenation-dehydrogenation reactions; Mobility and reactivity on oxidic surfaces.

  8. Perfluorodiethoxymethane on nickel and nickel oxide surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Jacobson, Joyce [Iowa State Univ., Ames, IA (United States)

    1994-03-03

    The interaction of perfluorodiethoxymethane with a nickel single crystal, Ni(100); a nickel crystal with chemisorbed oxygen, Ni(100)-c(2x2)O; and a nickel crystal with nickel oxide crystallites, NiO(100) is investigated in an ultra high vacuum environment using thermal desorption spectroscopy and high resolution electron energy loss spectroscopy. Nickel, a component of hard disk drives and stainless steel, is used to represent metal surfaces in these "real" systems. Perfluorodiethoxymethane is used in this study as a model compound of industrial perfluoropolyether lubricants. These lubricants are known for their exceptional stability, except in the presence of metals. Perfluorodiethoxymethane contains the acetal group (-OCF2O-), believed to be particularly vulnerable to attack in the presence of Lewis acids. Since the surfaces studied show increasing Lewis acidity at the nickel atom sites, one might expect to see increasing decomposition of perfluorodiethoxymethane due to acidic attack of the acetal group. No decomposition of perfluorodiethoxymethane is observed on the clean Ni(100) surface, while more research is needed to determine whether a small decomposition pathway is observed on the oxygenated surfaces, or whether sample impurities are interfering with results. The strength of the bonding of perfluorodiethoxymethane to the surface is found to increase as the nickel atoms sites become more acidic in moving from Ni(100) to Ni (100)-c(2x2)O to NiO (100).

  9. A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state

    OpenAIRE

    Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar

    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 dimethylsulfo...

  10. Radiolysis of water with aluminum oxide surfaces

    Science.gov (United States)

    Reiff, Sarah C.; LaVerne, Jay A.

    2017-02-01

    Aluminum oxide, Al2O3, nanoparticles with water were irradiated with γ-rays and 5 MeV He ions followed by the determination of the production of molecular hydrogen, H2, and characterization of changes in the particle surface. Surface analysis techniques included: diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), nitrogen absorption with the Brunauer - Emmett - Teller (BET) methodology for surface area determination, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Production of H2 by γ-ray radiolysis was determined for samples with adsorbed water and for Al2O3 - water slurries. For Al2O3 samples with adsorbed water, the radiation chemical yield of H2 was measured as 80±20 molecules/100 eV (1 molecule/100 eV=1.04×10-7 mol/J). The yield of H2 was observed to decrease as the amount of water present in the Al2O3 - water slurries increased. Surface studies indicated that the α-phase Al2O3 samples changed phase following irradiation by He ions, and that the oxyhydroxide layer, present on the pristine sample, is removed by γ-ray and He ion irradiation.

  11. Non-conventional halide oxidation pathways : oxidation by imidazole triplet and surface specific oxidation by ozone

    Science.gov (United States)

    Ammann, Markus; Corral-Arroyo, Pablo; Aellig, Raphael; Orlando, Fabrizio; Lee, Ming-Tao; Artiglia, Luca

    2016-04-01

    Oxidation of halide ions (chloride, bromide, iodide) are the starting point of halogen release mechanisms out of sea water, marine aerosol or other halide containing continental aerosols. Slow oxidation of chloride and bromide by ozone in the bulk aqueous phase is of limited relevance. Faster surface specific oxidation has been suggested based on heterogeneous kinetics experiments. We provide first insight into very efficient bromide oxidation by ozone at the aqueous solution - air interface by surface sensitive X-ray photoelectron spectroscopy indicating significant build-up of an oxidized intermediate at the surface within millisecond time scales. The second source of oxidants in the condensed we have considered is the absorption of light by triplet forming photosensitizers at wavelengths longer than needed for direct photolysis and radical formation. We have performed coated wall flow tube experiments with mixtures of citric acid (CA) and imidazole-2-carboxaldehyde (IC) to represent secondary organic material rich marine aerosol. The halide ions bromide and iodide have been observed to act as efficient electron donors leading to their oxidation, HO2 formation and finally release of molecular halogen compounds. The photosensitization of imidazole-2-carboxaldehyde (IC) involves a well-known mechanism where the triplet excited state of IC is reduced by citric acid to a reduced ketyl radical that reacts with halide ions. A competition kinetics approach has been used to evaluate the rate limiting steps and to assess the significance of this source of halogens to the gas phase.

  12. Microstructures of the oxides on the activated AB{sub 2} and AB{sub 5} metal hydride alloys surface

    Energy Technology Data Exchange (ETDEWEB)

    Young, K., E-mail: kwo.young@BASF.com [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Chao, B. [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States); Liu, Y. [Electron Microscopy Facility, 145 Linus Pauling Science Center, 2900 SW Campus Way, Oregon State University, Corvallis, OR 97331 (United States); Nei, J. [BASF/Battery Materials-Ovonic, 2983 Waterview Drive, Rochester Hills, MI 48309 (United States)

    2014-09-01

    Highlights: • Morphologies of surface hydroxide of AB{sub 2}, AB{sub 5}, and A{sub 2}B{sub 7} alloys were compared. • Nd promotes the formation of thick rod instead of fine needles. • Both AB{sub 2} and AB{sub 5} show similar buffer oxide + surface oxide structure. • The surface oxide layers in AB{sub 2} are thicker than those from AB{sub 5}. • AB{sub 2} surface is covered by oxide with less solubility in KOH. - Abstract: The surface oxides of the activated metal hydride alloys used as the negative electrode for nickel–metal hydride battery were studied by both scanning and transmission electron microscope techniques. In transition metal based AB{sub 2} metal hydride alloys, the surface of the powder is covered with oxides as a product of oxidation from the electrolyte and protected by zirconium oxide and vanadium-rich BCC-structured secondary phase. In the rare-earth based AB{sub 5} and A{sub 2}B{sub 7} metal hydride alloys, the surface is decorated with nano-structured needles and larger-scaled rods of hydroxides from the precipitation of rare earth ions after the oxidation by the electrolyte. Further TEM studies show the existence of a buffer oxide layer sandwiched between the inclusion-embedded surface oxide and alloy bulk in both AB{sub 2} and AB{sub 5} alloys. In both cases, the inclusions are found to be metallic nanocrystals mainly composed of Ni and Co as determined by electron energy loss spectroscopy, selective area electron diffraction, transmission electron atomic image, and X-ray energy dispersive spectroscopy. The Co-to-Ni ratio in the inclusion is larger than that in the bulk due to the less corrosive nature of Co. The additions of Co and Al in the AB{sub 2} are found to reduce number of activation cycles needed to generate a surface oxide with proper catalytic capability.

  13. The oxidation and surface speciation of indium and indium oxides exposed to atmospheric oxidants

    Science.gov (United States)

    Detweiler, Zachary M.; Wulfsberg, Steven M.; Frith, Matthew G.; Bocarsly, Andrew B.; Bernasek, Steven L.

    2016-06-01

    Metallic indium and its oxides are useful in electronics applications, in transparent conducting electrodes, as well as in electrocatalytic applications. In order to understand more fully the speciation of the indium and oxygen composition of the indium surface exposed to atmospheric oxidants, XPS, HREELS, and TPD were used to study the indium surface exposed to water, oxygen, and carbon dioxide. Clean In and authentic samples of In2O3 and In(OH)3 were examined with XPS to provide standard spectra. Indium was exposed to O2 and H2O, and the ratio of O2 - to OH- in the O1s XPS region was used to monitor oxidation and speciation of the surface. HREELS and TPD indicate that water dissociates on the indium surface even at low temperature, and that In2O3 forms at higher temperatures. Initially, OH- is the major species at the surface. Pure In2O3 is also OH- terminated following water exposure. Ambient pressure XPS studies of water exposure to these surfaces suggest that high water pressures tend to passivate the surface, inhibiting extensive oxide formation.

  14. Formation of vanadium carbide precipitations at the surface of alloys: Thermodynamics and kinetics aspects; Bildung von Vanadiumcarbid-Ausscheidungen auf Legierungsoberflaechen: Thermodynamische und kinetische Aspekte

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, A.; Uebing, C. [Max-Planck-Institut fuer Eisenforschung GmbH, Duesseldorf (Germany)

    1998-12-31

    The paper describes the formation of vanadium carbides on the surface layers of Fe-3%V-C(100) alloys. The phase diagram calculated for this alloyed material using the ThermoCalc program package reveals a co-existence of ferritic matrix and V{sub 3}C{sub 2} at temperatures of T{<=}650 C. This carbide is instable at elevated temperatures, leading to co-existence of ferrite and the cubic VC{sub 1-x}. Experimental analyses revealed the formation of a 2D VC compound in the top layers of the surface of Fe-3%V-C(100) alloys, induced by equilibrium segregation. The paper explains the usefulness of thermodynamic and kinetic calculations for interpretation of precipitation phenomena in steels. Mathematically derived and experimental results of analyses for the case of non-equilibrium segregation showed excellent agreement in the determination of carbide thickness (nanometer scale) and time dependence of segregation under fast cooling conditions. (orig./CB) [Deutsch] In der vorliegenden Arbeit wurde die Bildung von Vanadiumcarbiden auf Fe-3%V-C(100)-Legierungsoberflaechen beschrieben. Das anhand des ThermoCalc-Programmpakets fuer diese Legierungszusammensetzung berechnete Phasendiagramm zeigt bei niedrigen Temperaturen T{<=}650 C die Koexistenz von ferritischer Matrix und V{sub 3}C{sub 2}. Bei hoeheren Temperaturen ist dieses Carbid instabil und es liegt Koexistenz von Ferrit und dem kubischen VC{sub 1-x} vor. Die experimentellen Untersuchungen zeigen die Ausbildung einer zweidimensionalen VC-Oberflaechenverbindung auf Fe-3%V-C(100)-Legierungsoberflaechen durch Gleichgewichtssegregation. Diese Arbeit zeigt, dass thermodynamische und kinetische Rechnungen bei der Deutung von Ausscheidungsphaenomenen in Staehlen sinnvoll eingesetzt werden koennen. Bei der Nichtgleichgewichtssegregation wurde bezueglich Carbiddicke (im Nanometerbereich) und Zeitabhaengigkeit der Ausscheidung bei schneller Abkuehlung eine hervorragende Uebereinstimmung zwischen Simulation und Experiment gefunden

  15. Nuclear reactor fuel element with vanadium getter on cladding

    Science.gov (United States)

    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.

  16. Synthesis and characterization of sodium vanadium oxide gels: the effects of water (n) and sodium (x) content on the electrochemistry of Na(x)V2O5·nH2O.

    Science.gov (United States)

    Lee, Chia-Ying; Marschilok, Amy C; Subramanian, Aditya; Takeuchi, Kenneth J; Takeuchi, Esther S

    2011-10-28

    Sodium vanadium oxide gels, Na(x)V(2)O(5)·nH(2)O, of varying sodium content (0.12 n > 0.01) and interlayer spacing were found to be inversely proportional to the sodium level (x), thus control of sodium (x) content provided a direct, chimie douce approach for control of hydration level (n) and interlayer spacing, without the need for high temperature treatment to affect dehydration. Notably, the use of high temperatures to modify hydration levels can result in crystallization and collapse of the interlayer structure, highlighting the distinct advantage of our novel chimie douce synthesis strategy. Subsequent to synthesis and characterization, results from an electrochemical study of a series of Na(x)V(2)O(5)·nH(2)O samples highlight the significant impact of interlayer water on delivered capacity of the layered materials. Specifically, the sodium vanadium oxide gels with higher sodium content and lower water content provided higher capacities in lithium based cells, where capacity delivered to 2.0 V under C/20 discharge ranged from 170 mAh/g for Na(0.12)V(2)O(5)·0.23H(2)O to 300 mAh/g for Na(0.32)V(2)O(5)·0.01H(2)O. The capacity differences were maintained as the cells were cycled.

  17. Tunable oxygen functional groups as electro-catalysts on graphite felt surfaces for all vanadium flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Estevez, Luis; Reed, David M.; Nie, Zimin; Schwarz, Ashleigh M.; Nandasiri, Manjula I.; Kizewski, James P.; Wang, Wei; Thomsen, Edwin C.; Liu, Jun; Zhang, Jiguang; Sprenkle, Vincent L.; Li, Bin

    2016-06-22

    We decorated the surfaces of graphite felts with some oxygen-containing functional groups, such as C-OH, O=C and HO-C=O. And the mole ratios and amounts of these functional groups were effectively adjusted on the graphite surface by a particular method. The catalytic effects of amounts and mole ratio of different kinds of functional groups on VRB electrode performances were investigated in detail.

  18. Study of the structure of passivated vanadium-titanium alloys and their semiconductor properties.

    Science.gov (United States)

    Bachmann, T; Vonau, W; John, P

    2002-10-01

    The possibility of investigating the photocurrent behavior and structure of electrochemically prepared passive films on metallic titanium and on binary vanadium-titanium alloys has been demonstrated. The semiconductor properties were characterized by measuring the dependence of the photocurrent on the wavelength of the incident light and on the electrode potential. The results showed the oxide layers to be n-type semiconductors with a bandgap between 2.6 and 3.3 eV and a flatband potential of approximately -300 to +400 mV (relative to the SCE). The results were interpreted in terms of the corrosion characteristics of the materials. XPS measurements on pure vanadium and some alloys are presented. Several properties were used to characterize the passive surface of these materials. The V(2)O(5) and TiO(2) content decreases with increasing depth.

  19. A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state.

    Science.gov (United States)

    Krakowiak, Joanna; Lundberg, Daniel; Persson, Ingmar

    2012-09-17

    The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen-donor solvents water, dimethyl sulfoxide (DMSO), and N,N'-dimethylpropyleneurea (DMPU) has been studied in solution by extended X-ray absorption fine structure (EXAFS) and large-angle X-ray scattering (LAXS) and in the 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 DMSO-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-O(perp) bond angle is ca. 98°. In the DMPU-solvated oxovanadium(IV) ion, the space-demanding properties of the DMPU molecule leave 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, 107°, and the mean V═O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and DMSO-solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in the cis position with a mean V═O bond distance 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-02-01

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

  1. Thermodynamic analysis on the direct preparation of metallic vanadium from NaVO3 by molten salt electrolysis☆

    Institute of Scientific and Technical Information of China (English)

    Wei Weng; Mingyong Wang; Xuzhong Gong; Zhi Wang; Zhancheng Guo

    2016-01-01

    A novel and environmentally friendly route to directly prepare metallic vanadium from NaVO3 by molten salt electrolysis is proposed. The feasibility about the direct electro-reduction of NaVO3 to metallic vanadi-um is analyzed based on the thermodynamic calculations and experimental verifications. The theoretical decomposition voltage of NaVO3 to metallic vanadium is only 0.47 V at 800 °C and much lower than that of the alkali and alkali earth metal chloride salts. The value is slightly higher than that of low-valence vanadium oxides such as V2O3, V3O5 and VO. However, the low-valence vanadium oxides can be further electro-reduced to metallic vanadium thermodynamically. The thermodynamic analysis is verified by the experimental results. The direct preparation of metallic vanadium from NaVO3 by molten salt electrolysis is feasible.

  2. Reducibility, heats of re-oxidation, and structure of vanadia supported on TiO{sub 2} and TiO{sub 2}-Al{sub 2}O{sub 3} supports used as vanadium traps in FCC

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Silvia [CIEP/Facultad de Ciencias Quimicas, Universidad Autonoma de San Luis Potosi, Av. Dr. Manuel Nava 6, Zona Universitaria, CP 78210 San Luis Potosi, SLP Mexico (Mexico); Morales, Rosario [CIEP/Facultad de Ciencias Quimicas, Universidad Autonoma de San Luis Potosi, Av. Dr. Manuel Nava 6, Zona Universitaria, CP 78210 San Luis Potosi, SLP Mexico (Mexico); Cardenas-Galindo, Maria Guadalupe [CIEP/Facultad de Ciencias Quimicas, Universidad Autonoma de San Luis Potosi, Av. Dr. Manuel Nava 6, Zona Universitaria, CP 78210 San Luis Potosi, SLP Mexico (Mexico); Rodriguez, A. Gabriel [Instituto de Investigaciones en Comunicaciones y Opticas, Universidad Autonoma de San Luis Potosi, Av. Karakorum 1470, CP 78216 San Luis Potosi, SLP Mexico (Mexico); Pedraza, Francisco [Instituto Mexicano del Petroleo, Eje Centrale Lazaro Cardenas 152, Col. San Bartolo Atepehuacan, Delg. Gustavo I. Madero, Mexico DF 07730 (Mexico); Handy, Brent E. [CIEP/Facultad de Ciencias Quimicas, Universidad Autonoma de San Luis Potosi, Av. Dr. Manuel Nava 6, Zona Universitaria, CP 78210 San Luis Potosi, SLP Mexico (Mexico)]. E-mail: handy@uaslp.mx

    2005-08-15

    V/TiO{sub 2} and V/TiO{sub 2}-Al{sub 2}O{sub 3} (1:1 w/w basis) supports were characterized by TPR, Raman spectroscopy, and heats of re-oxidation of samples pre-reduced in CO at 770 K with a heat-flow calorimeter. Supports were pure anatase or rutile dispersed with hydrated aluminas (boehmite, gibbsite, bayerite) subsequently calcined at 870 K. Raman spectroscopy of fully oxidized, air-exposed samples show the presence of polymeric polyvanadate species, but not of isolated monomeric species. Sample loadings were 4 wt.% and show different reduction and structural features. During TPR, vanadia reduced to V(III) and V(IV) in V/rutile and V/anatase, respectively, and multiple reduction peaks were observed due to crystalline V{sub 2}O{sub 5} and amorphous vanadia. In V/TiO{sub 2}-Al{sub 2}O{sub 3} samples, vanadium coverages were 6-8 {mu}mol V m{sup -2} yielding well-dispersed, amorphous vanadia. Trends observed during TPR were: addition of bayerite phase to anatase or rutile increases H{sub 2} consumption by 100%, implying formation of V(III) and V(II), respectively. However, with addition of boehmite or gibbsite to either titania phase, vanadia reduces only to V(IV). Oxygen doses at 473 K of pre-reduced samples titrated about one-third of total vanadia content. Re-oxidation heat values range from 400 to 500 kJ mol{sup -1} O{sub 2} and represent oxygen-vanadium ion bond strengths within the dispersed vanadia. The heat values are higher than expected for re-oxidation of a bulk phase, and are indicative of the degree of stabilization provided by the support.

  3. Oxidation of nickel surfaces by low energy ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Saric, Iva [Faculty of Civil Engineering, University of Rijeka (Croatia); Center for Micro and Nano Sciences and Technologies, University of Rijeka (Croatia); Peter, Robert; Kavre, Ivna; Badovinac, Ivana Jelovica; Petravic, Mladen [Center for Micro and Nano Sciences and Technologies, University of Rijeka (Croatia); Department of Physics, University of Rijeka (Croatia)

    2016-03-15

    We have studied formation of oxides on Ni surfaces by low energy oxygen bombardment using X-ray photoemission spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). Different oxidation states of Ni ions have been identified in XPS spectra measured around Ni 2p and O 1s core-levels. We have compared our results with thermal oxidation of Ni and shown that ion bombardment is more efficient in creating thin oxide films on Ni surfaces. The dominant Ni-oxide in both oxidation processes is NiO (Ni{sup 2+} oxidation state), while some Ni{sub 2}O{sub 3} contributions (Ni{sup 3+} oxidation state) are still present in all oxidised samples. The oxide thickness of bombarded Ni samples, as determined by SIMS, was shown to be related to the penetration depth of oxygen ions in Ni.

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

    Science.gov (United States)

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

    2017-02-01

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

  5. Ab initio study of proton dynamics on perovskite oxide surfaces

    Directory of Open Access Journals (Sweden)

    Fuyuki Shimojo

    2007-01-01

    Full Text Available First-principles studies of the proton dynamics in perovskite oxides and the water adsorption on various oxide surfaces are briefly reviewed. Recent progress in the study of the microscopic mechanism of the proton absorption from perovskite oxide surfaces is also presented. It is shown that dopant ions on the surface and oxygen vacancies in the inside just below the surface play an important role for the proton absorption, while oxygen vacancies on the surface are influential for the dissociative adsorption of water molecules.

  6. Process development for economical processing of various vanadium bearing materials

    Science.gov (United States)

    Retelsdorf, H. J.; Rothmann, H.; Fichte, R.

    1982-06-01

    Three different vanadium bearing products were tested. It was proven feasible to recover a ferroalloy containing 73.5% of the vanadium contained in the leaching residues from blast furnace slags by reduction in an electric arc furnace. The composition of the obtained ferroalloy was 67% Fe, 2% V, 7% Cr, and 5.5% C. The vanadium recovery contained 0.5 to 6% in the fly ash, resulting from the combustion of fuel. Different fly ashes were tested by oxidation through roasting and subsequent basic leaching, or by reduction roasting with subsequent acid leaching, or bysoda roasting and leaching. The third source of vanadium tested was the waste salt, originating in alumina production, and containing about 4% V, 5% P, and 0.5% As. It was possible to produce a ferroalloy containing V2O5 and a secondary sodium phosphate, which could be applied in the phosphate processing industry.

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

    OpenAIRE

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

    2015-01-01

    Solution processed metal oxide thin films are important for modern optoelectronic devices ranging from thin film transistors to photovoltaics and for functional optical coatings. Solution processed techniques such as dip-coating, allow thin films to be rapidly deposited over a large range of surfaces including curved, flexible or plastic substrates without extensive processing of comparative vapour or physical deposition methods. To increase the effectiveness and versatility of dip-coated thi...

  8. Electrochemical properties of dip-coated vanadium pentaoxide thin films

    Indian Academy of Sciences (India)

    R S INGOLE; B J LOKHANDE

    2016-10-01

    Vanadium oxide (V$_2$O$_5$) thin films have been deposited on to the stainless-steel substrates by simple dip-coating technique using vanadium pentaoxide as an initial ingredient. Deposited samples were annealed at773 K for 3 h in air. X-ray diffraction analysis of the sample shows crystalline with orthorhombic crystal structure. Scanning electron microscopy study depicts the homogeneous and dense surface morphology. Optical study provesthe direct bandgap transition with energy $\\sim$2.25 eV. Electrochemical performance of the deposited electrode was studied in 1 M NaNO$_3$ electrolyte using cyclic voltammetery, electrochemical impedance spectroscopy and galvanostatic charge–discharge tests. Prepared V$_2$O$_5$ electrode shows 207.50 F g$^{−1}$ specific capacitance at the scan rate 5 mV s$^{−1}$, specific energy, specific power and efficiency are 41.33 Whkg$^{−1}$, 21 kW kg$^{−1}$ and 96.72%, respectively. The internal resistance observed from impedance spectroscopy is $\\sim$8.77 ohm. Electrode exhibits excellent chemicalstability up to 1000 cycles.

  9. Engineering Polarons at a Metal Oxide Surface

    Science.gov (United States)

    Yim, C. M.; Watkins, M. B.; Wolf, M. J.; Pang, C. L.; Hermansson, K.; Thornton, G.

    2016-09-01

    Polarons in metal oxides are important in processes such as catalysis, high temperature superconductivity, and dielectric breakdown in nanoscale electronics. Here, we study the behavior of electron small polarons associated with oxygen vacancies at rutile TiO2(110 ) , using a combination of low temperature scanning tunneling microscopy (STM), density functional theory, and classical molecular dynamics calculations. We find that the electrons are symmetrically distributed around isolated vacancies at 78 K, but as the temperature is reduced, their distributions become increasingly asymmetric, confirming their polaronic nature. By manipulating isolated vacancies with the STM tip, we show that particular configurations of polarons are preferred for given locations of the vacancies, which we ascribe to small residual electric fields in the surface. We also form a series of vacancy complexes and manipulate the Ti ions surrounding them, both of which change the associated electronic distributions. Thus, we demonstrate that the configurations of polarons can be engineered, paving the way for the construction of conductive pathways relevant to resistive switching devices.

  10. Surface oxidation of cobalt nanoparticles studied by Mossbauer spectroscopy

    DEFF Research Database (Denmark)

    Bødker, Franz; Mørup, Steen; Charles, S.W.

    1999-01-01

    The surface oxide formed on cobalt nanoparticles has been studied by Mossbauer emission spectroscopy. Exposure of the cobalt particles to oxygen at room temperature was found to result in the formation of a relatively well-ordered surface oxide with Mossbauer parameters similar to those of CoO....

  11. 射频磁控溅射氧化钒薄膜的结构与性能研究%Structure and Property Study on Vanadium Oxide Thin Films Deposited by Radio Frequency Magnetron Sputtering Technique

    Institute of Scientific and Technical Information of China (English)

    刘黎明; 莫镜辉; 史衍丽; 曾华荣; 杨培志

    2012-01-01

    Aimed at uncooled microbolometer infrared detector applications,vanadium oxide thin films were fabricated successfully by the radio frequency magnetron sputtering technique at low temperature of 300℃.The crystalline,microstructure and composition of the films were characterized by X-ray diffraction (XRD),atomic force microscopy (AFM),energy-dispersive spectra (EDS) and X-ray photoelectron spectroscopy (XPS).The electric properties of the film were investigated using four-point probe technique.The results show that the film is VO2 phase and exhibits amorphous structure with smooth surface morphology.Semiconductor-to-metal phase transition was not observed for such an amorphous VO2 thin film in the temperature range of 22-100℃.Moreover,excellent performances such as temperature coefficient of resistance (TCR) of -2.1%/℃ at room temperature and sheet resistance of 600 kΩ/square was obtained in the VO2 thin film with suitable thickness (100 nm),suggesting a potential application in uncooled microbolometer infrared detectors.%以非制冷微测辐射热计型红外探测器应用为需求背景,采用射频磁控溅射技术在300℃低温条件下制备了氧化钒薄膜.采用X射线衍射(XRD)、原子力显微镜(AFM)、能量色散谱(EDS)及X射线光电子能谱(XPS)技术表征了薄膜的结晶状态、微观结构与化学组成.采用四探针技术研究了薄膜的电学性能.结果表明该薄膜主要为非晶态的二氧化钒( VO2),并具有光滑的表面形貌.这种非晶VO2薄膜在22~100℃温度范围内不存在半导体-金属相变.100 nm厚的非晶VO2薄膜室温下的面电阻为600 kΩ/,同时表现出-2.1%/℃的较高电阻温度系数(TCR),这表明该薄膜有希望用于非制冷微测辐射热计型红外探测器.

  12. Oxidative dehydrogenation of n-butane over vanadium magnesium oxide catalysts supported on nano-structured MgO and ZrO2: effect of oxygen capacity of the catalyst.

    Science.gov (United States)

    Lee, Howon; Lee, Jong Kwon; Hong, Ung Gi; Song, In Kyu; Yoo, Yeonshick; Cho, Young-Jin; Lee, Jinsuk; Chang, Hosik; Jung, Ji Chul

    2012-07-01

    Vanadium-magnesium oxide catalysts supported on nano-structured MgO and ZrO2 (Mg3(VO4)2/MgO/ZrO2) were prepared by a wet impregnation method with a variation of Mg:Zr ratio (8:1, 4:1, 2:1, and 1:1). For comparison, Mg3(VO4)2/MgO and Mg3(VO4)2/ZrO2 catalysts were also prepared by a wet impregnation method. The prepared catalysts were applied to the oxidative dehydrogenation of n-butane in a continuous flow fixed-bed reactor. Mg3(VO4)2/MgO/ZrO2 (Mg:Zr = 4:1, 2:1, and 1:1) and Mg3(VO4)2/ZrO2 catalysts showed a stable catalytic activity during the whole reaction time, while Mg3(VO4)2/MgO/ZrO2 (8:1) and Mg3(VO4)2/MgO catalysts experienced a severe catalyst deactivation. Deactivation of Mg3(VO4)2/MgO/ZrO2 (8:1) and Mg3(VO4)2/MgO catalysts was due to their low oxygen mobility. Effect of oxygen capacity (the amount of oxygen in the catalyst involved in the reaction) of the supported Mg3(V04)2 catalysts on the catalytic performance in the oxidative dehydrogenation of n-butane was investigated. Experimental results revealed that oxygen capacity of the catalyst was closely related to the catalytic activity in the oxidative dehydrogenation of n-butane. A large oxygen capacity of the catalyst was favorable for obtaining a high catalytic activity in this reaction. Among the catalysts tested, Mg3(VO4)2/MgO/ZrO2 (4:1) catalyst with the largest oxygen capacity showed the best catalytic performance.

  13. Synthesis and gas-sensing prop erties of the silicon nanowires/vanadium oxide nanoro ds comp osite%硅纳米线/氧化钒纳米棒复合材料的制备与气敏性能研究∗

    Institute of Scientific and Technical Information of China (English)

    张玮祎; 胡明; 刘星; 李娜; 闫文君

    2016-01-01

    As air pollution is becoming more and more serious in recent years, gas-sensing devices have attracted intensive attention. In particular, NO2 is one of the most toxic gases in the atmosphere, which tends to produce acid rain and photochemical smog. Thus, there is a strong demand of cheap, reliable and sensitive gas sensors targeting NO2. Gas sensors fabricated on silicon substrates with room-temperature operation are very promising in power saving, integrated circuit processing and portable detectors. More important, the silicon nanowires (SiNWs)-based devices are compatible with very large scale integration processes and complementary metal oxide semiconductor technologies. In the present work, the novel nanocomposite structure of (SiNWs)/vanadium oxide (V2O5) nanorods for NO2 detection is successfully synthesized. The SiNWs are fabricated by a combination of nanosphere lithography and metal-assisted chemical etching. Vanadium films are deposited on SiNWs by DC magnetron sputtering, and then V2O5 nanorods are synthesized with subsequent thermal annealing process for full oxidation in air. The morphology and crystal structure of product obtained are characterized by field-emission scanning electron microscopy and X-ray diffraction. The characterization results indicate that V2O5 nanorods are uniformly distributed on the surfaces of SiNWs. The increased specific surface area of SiNWs/V2O5 nanocomposite provides more adsorption sites and diffusion conduits for gas molecules. Therefore, the novel structure of the nanocomposite is conducive to gas-sensing. In addition, the sputtering time has an obvious influence on the morphology of vanadium oxide. With the increase of the sputtering time, the specific surface area and the number of p-n heterojunctions formed in the nanocomposite are both less than those of nanocomposite with appropriate sputtering time. The gas-sensing properties are examined by measuring the resistance change towards 0.5–4 ppm NO2 gas at room

  14. Relationship Between Iron Oxides and Surface Charge Characteristics in Soils

    Institute of Scientific and Technical Information of China (English)

    SHAOZONG-CHEN; WANGWEI-JUN

    1991-01-01

    The relationship between iron oxides and surface charge characteristics in variable charge soils (latosol and red earth) was studied in following three ways.(1)Remove free iron oxides (Fed) and amorphous iron oxides (Feo) from the soils with sodium dithionite and acid ammonium oxalate solution respectively.(2) Add 2% glucose (on the basis of air-dry soil weight) to soils and incubate under submerged condition to activate iron oxides,and then the mixtures are dehydrated and air-dried to age iron oxides.(3) Precipitate various crystalline forms of iron oxides onto kaolinite.The results showed that free iron oxides (Fed) were the chief carrier of variable positive charges.Of which crystalline iron oxides (Fed-Feo) presented mainly as discrete particles in the soils and could only play a role of the carrier of positive charges,and did little influence on negative charges.Whereas the amorphous iron oxides (Feo),which presented mainly fas a coating with a large specific surface area,not only had positive charges,but also blocked the negative charge sites in soils.Submerged incubation activated iron oxides in the soils,and increased the amount of amorphous iron oxides and the degree of activation of iron oxide,which resulted in the increase of positive and negative charges of soils.Dehydration and air-dry aged iron oxides in soils and decreased the amount of amorphous iron oxides and the degree of activation of iron oxide,and also led to the decrease of positive and negative charges.Both the submerged incubation and the dehydration and air-dry had no significant influence on net charges.Precipitation of iron oxides onto kaolinite markedly increased positive charges and decreased negative charges.Amorphous iron oxide having a larger surface area contributed more positive charge sites and blocked more negative charge sites in kaolinite than crystalline goethite.

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

    Science.gov (United States)

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

    2012-06-01

    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.

  16. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

    National Research Council Canada - National Science Library

    Elçin Külah; Laurent Marot; Roland Steiner; Andriy Romanyuk; Thomas A Jung; Aneliia Wäckerlin; Ernst Meyer

    2017-01-01

    .... Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide...

  17. Release of Vanadium from soils by conventional leaching procedures and extractions.

    OpenAIRE

    Cappuyns, Valérie

    2013-01-01

    1. Introduction Despite the fact that vanadium (V) is among the 20 most abundant elements in the earth's crust5, with average concentrations between 50 and 150 µg g-1, this element receives relatively few attention in the scientific literature on soil and sediment geochemistry. However, the last few years, the attention for this potentially harmful element is growing. Some countries adopted threshold values for vanadium in soils, sediments, ground- or surface water, but in general vanadium...

  18. Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

    Science.gov (United States)

    Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

    2015-10-01

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

  19. Mathematical modeling taking into account of intrinsic kinetic properties of cylinder-type vanadium catalyst

    Institute of Scientific and Technical Information of China (English)

    陈振兴; 李洪桂; 王零森

    2004-01-01

    The method to calculate internal surface effective factor of cylinder-type vanadium catalyst Ls-9 was given. Based on hypothesis of subjunctive one dimension diffusion and combined shape adjustment factor with threestep catalytic mechanism model, the macroscopic kinetic model equation about SO2 oxidation on Ls-9 was deduced.With fixed-bed integral reactor and under the conditions of temperature 350 - 410 ℃, space velocity 1 800 - 5 000h-1, SO2 inlet content 7 %- 12%, the macroscopic kinetic data were detected. Through model parameter estimation,the macroscopic kinetic model equation was obtained.

  20. Magnetic Iron Oxide Nanoparticles: Synthesis and Surface Functionalization Strategies

    Directory of Open Access Journals (Sweden)

    He Quanguo

    2008-01-01

    Full Text Available Abstract Surface functionalized magnetic iron oxide nanoparticles (NPs are a kind of novel functional materials, which have been widely used in the biotechnology and catalysis. This review focuses on the recent development and various strategies in preparation, structure, and magnetic properties of naked and surface functionalized iron oxide NPs and their corresponding application briefly. In order to implement the practical application, the particles must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of iron oxide NPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The problems and major challenges, along with the directions for the synthesis and surface functionalization of iron oxide NPs, are considered. Finally, some future trends and prospective in these research areas are also discussed.

  1. Volcano Relations for Oxidation of Hydrogen Halides over Rutile Oxide Surfaces

    DEFF Research Database (Denmark)

    Toftelund, Anja; Man, Isabela C.; Hansen, Heine A.

    2012-01-01

    We investigate the heterogeneously catalysed oxidation of HX (X=Cl, Br and I) on the RuO2 (110) surface with DFT. We also solve a micro-kinetic model of HX oxidation and compare oxidation activity at different coverages. We further establish linear energy relations for the reaction intermediates ...

  2. Extraction of vanadium from athabasca tar sands fly ash

    Science.gov (United States)

    Gomez-Bueno, C. O.; Spink, D. R.; Rempel, G. L.

    1981-06-01

    The production of refinery grade oil from the Alberta tar sands deposits as currently practiced by Suncor (formally Great Canadian Oil Sands Ltd.—GCOS) generates a substantial amount of petroleum coke fly ash which contains appreciable amounts of valuable metals such as vanadium, nickel and titanium. Although the recovery of vanadium from petroleum ash is a well established commercial practice, it is shown in the present work that such processes are not suitable for recovery of vanadium from the GCOS fly ash. The fact that the GCOS fly ash behaves so differently when compared to other petroleum fly ash is attributed to its high silicon and aluminum contents which tie up the metal values in a silica-alumina matrix. Results of experiments carried out in this investigation indicate that such matrices can be broken down by application of a sodium chloride/water roast of the carbon-free fly ash. Based on results from a series of preliminary studies, a detailed investigation was undertaken in order to define optimum conditions for a vanadium extraction process. The process developed involves a high temperature (875 to 950 °C) roasting of the fly ash in the presence of sodium chloride and water vapor carried out in a rotary screw kiln, followed by dilute sodium hydroxide atmosphereic leaching (98 °C) to solublize about 85 pet of the vanadium originally present in the fly ash. It was found that the salt roasting operation, besides enhancing vanadium recovery, also inhibits silicon dissolution during the subsequent leaching step. The salt roasting treatment is found to improve vanadium recovery significantly when the fly ash is fully oxidized. This is easily achieved by burning off the carbon present in the “as received” fly ash under excess air. The basic leaching used in the new process selectively dissolves vanadium from the roasted ash, leaving nickel and titanium untouched.

  3. Uniform decoration of vanadium oxide nanocrystals on reduced graphene-oxide balls by an aerosol process for lithium-ion battery cathode material.

    Science.gov (United States)

    Choi, Seung Ho; Kang, Yun Chan

    2014-05-19

    VO2-decorated reduced graphene balls were prepared by a one-pot spray-pyrolysis process from a colloidal spray solution of well-dispersed graphene oxide and ammonium vanadate. The graphene-VO2 composite powders prepared directly by spray pyrolysis had poor electrochemical properties. Therefore, the graphene-VO2 composite powders were transformed into a reduced graphene ball (RGB)-V2O5 (RGB) composite by post-treatment at 300 °C in an air atmosphere. The TEM and dot-mapping images showed a uniform distribution of V and C components, originating from V2O5 and graphene, consisting the composite. The graphene content of the RGB-V2O5 composite, measured by thermogravimetric analysis, was approximately 5 wt %. The initial discharge and charge capacities of RGB-V2O5 composite were 282 and 280 mA h g(-1), respectively, and the corresponding Coulombic efficiency was approximately 100 %. On the other hand, the initial discharge and charge capacities of macroporous V2O5 powders were 205 and 221 mA h g(-1), respectively, and the corresponding Coulombic efficiency was approximately 93 %. The RGB-V2O5 composite showed a better rate performance than the macroporous V2O5 powders.

  4. Vanadium distribution following decavanadate administration.

    Science.gov (United States)

    Soares, S S; Martins, H; Aureliano, M

    2006-01-01

    An acute exposure of two vanadate solutions-metavanadate and decavanadate-containing different vanadate oligomers, induces different patterns of subcellular vanadium distribution in blood plasma, red blood cells (RBC), and cardiac muscle subcellular fractions of the fish Sparus aurata (gilthead seabream). The highest amount of vanadium was found in blood plasma 1 h after (5 mM) intravenous vanadate administration (295 +/- 64 and 383 +/- 104 microg V/g dry tissue, for metavanadate and decavanadate solutions, respectively), being 80-fold higher than in RBC. After 12 h of administration, the amount of vanadium in plasma, as well as in cardiac cytosol, decreased about 50%, for both vanadate solutions. During the period between 1 and 12 h, the ratio of vanadium in plasma/vanadium in RBC increased from 27 to 128 for metavanadate, whereas it remains constant (77) for decavanadate. Both vanadium solutions were primarily accumulated in the mitochondrial fraction (138 +/- 0 and 195 +/- 34 ng V/g dry tissue for metavanadate and decavanadate solutions, respectively, after 12 h exposure), rather than in cytosol. The amount of vanadium in cardiac mitochondria was twofold higher than in cytosol, earlier for metavanadate (6 h) than for decavanadate (12 h). It is concluded that, in fish cardiac muscle, the vanadium distribution is dependent on the administration of decameric vanadate, with vanadium being mainly distributed in plasma, before being accumulated into the mitochondrial fraction.

  5. Enhancement in Activity of a Vanadium Catalyst for the Oxidation of Sulfur Dioxide by Radio Frequency Plasma During the Preparation Process

    Institute of Scientific and Technical Information of China (English)

    Zhenxing Chen; Honggui Li; Lingsen Wang

    2003-01-01

    Radio frequency plasma was used to prepare a vanadium catalyst. The results showed that activating time of the catalyst could be shortened quickly and the catalytic activity was improved to some extent with the use of plasma. Catalyst Ls-9 was prepared under an optimal condition of 40 W discharge power, 10 min discharge time and 8 Pa gas pressure. The catalytic activity was up to 54.7% at 410 ℃,which was 2.2% higher than that of the Ls-8 catalyst. Only 10 min was needed to activate the catalyst with plasma, which was 1/9 of the traditional calcination time. For Ls-9, both the endothermic as well as the exothermic peaks detected by differential thermal analysis shifted to higher temperatures obviously,indicating that its crystal phase could melt easily. There existed an apparent endothermic peak at 283 ℃. SEM photographs showed a uniform size distribution. It is inferred that the quadrivalent vanadium compound may exist mainly in the form of VOSO4.

  6. Oxidation and photo-oxidation of water on TiO2 surface

    DEFF Research Database (Denmark)

    Valdes, A.; Qu, Z.W.; Kroes, G.J.

    2008-01-01

    The oxidation and photo-oxidation of water on the rutile TiO2(110) surface is investigated using density functional theory (DFT) calculations. We investigate the relative stability of different surface terminations of TiO2 interacting with H2O and analyze the overpotential needed...

  7. Interactions of graphene oxide nanomaterials with natural organic matter and metal oxide surfaces.

    Science.gov (United States)

    Chowdhury, Indranil; Duch, Matthew C; Mansukhani, Nikhita D; Hersam, Mark C; Bouchard, Dermont

    2014-08-19

    Interactions of graphene oxide (GO) nanomaterials with natural organic matter (NOM) and metal oxide surfaces were investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Three different types of NOM were studied: Suwannee River humic and fulvic acids (SRHA and SRFA) and alginate. Aluminum oxide surface was used as a model metal oxide surface. Deposition trends show that GO has the highest attachment on alginate, followed by SRFA, SRHA, and aluminum oxide surfaces, and that GO displayed higher interactions with all investigated surfaces than with silica. Deposition and release behavior of GO on aluminum oxide surface is very similar to positively charged poly-L-lysine-coated surface. Higher interactions of GO with NOM-coated surfaces are attributed to the hydroxyl, epoxy, and carboxyl functional groups of GO; higher deposition on alginate-coated surfaces is attributed to the rougher surface created by the extended conformation of the larger alginate macromolecules. Both ionic strength (IS) and ion valence (Na(+) vs Ca(2+)) had notable impact on interactions of GO with different environmental surfaces. Due to charge screening, increased IS resulted in greater deposition for NOM-coated surfaces. Release behavior of deposited GO varied significantly between different environmental surfaces. All surfaces showed significant release of deposited GO upon introduction of low IS water, indicating that deposition of GO on these surfaces is reversible. Release of GO from NOM-coated surfaces decreased with IS due to charge screening. Release rates of deposited GO from alginate-coated surface were significantly lower than from SRHA and SRFA-coated surfaces due to trapping of GO within the rough surface of the alginate layer.

  8. Impedance spectroscopy and sensors under ethanol vapors application of sprayed vanadium-doped ZnO compounds

    Energy Technology Data Exchange (ETDEWEB)

    Mhamdi, A., E-mail: mhaammar@gmail.com [Unité de physique des dispositifs à semi-conducteurs, Tunis EL MANAR University, 2092 Tunis (Tunisia); Labidi, A. [Unite de Recherche de Physique des Semiconducteurs et Capteurs, IPEST, BP 51, La Marsa 2070, Tunis (Tunisia); Souissi, B. [Unité de physique des dispositifs à semi-conducteurs, Tunis EL MANAR University, 2092 Tunis (Tunisia); Kahlaoui, M. [Laboratoire de Physique des Matériaux, Faculté des Sciences de Bizerte, Université de Carthage, Zarzouna 7021 (Tunisia); Yumak, A. [Physics Department, Faculty of Arts and Sciences, Marmara University, 34722 Göztepe, Istanbul (Turkey); Boubaker, K.; Amlouk, A.; Amlouk, M. [Unité de physique des dispositifs à semi-conducteurs, Tunis EL MANAR University, 2092 Tunis (Tunisia)

    2015-08-05

    Highlights: • Proposing an original explanation to the behavior of vanadium-doped zinc oxide structures. • Presenting an original combination of several referred and established characterization means. • Outlining average particle size changes effects along the surface of the compounds. - Abstract: Thin films of vanadium-doped zinc oxide with different vanadium-doping levels (0, 1, 2 and 3 at%) were deposited on glass substrates by employing an inexpensive, simplified spray technique using at relatively low substrate temperature (460 °C). The effect of V doping on the structural, morphological and optical properties of the films was investigated by Mhamdi et al. (2013). The X-ray diffraction analysis shows that the films were well crystallized in würtzite phase with the crystallites preferentially oriented toward (0 0 2) direction parallel c-axis. As also that the average particle size along the surface of the films decreases with increasing of concentration of vanadium. In this work we study the AC and DC conductivity and gas sensor application on ZnO:V thin films. The dielectric properties of ZnO:V thin films were studied by means of complex impedance spectroscopy and frequency dependence of conductivity measured from the impedance data at a range of frequency intervals between 10 Hz and 13 MHz with a temperature between 355 and 445 °C. The frequency dependence of the dielectric constant ε′, dielectric loss ε″, loss tangent (tan δ) and AC electrical conductivity (σ{sub AC}) of the layers was subsequently investigated. In literature, we have shown in previous papers that structural and surface morphology of ZnO thin films, prepared by spray, plays an important role in the gas detection mechanism. In this article, we have studied the response evolution of ZnO:V sensors ethanol versus time and working temperature, relative doping and the concentration of the ethanol vapor.

  9. Thermal instability of GaSb surface oxide

    Science.gov (United States)

    Tsunoda, K.; Matsukura, Y.; Suzuki, R.; Aoki, M.

    2016-05-01

    In the development of InAs/GaSb Type-II superlattice (T2SL) infrared photodetectors, the surface leakage current at the mesa sidewall must be suppressed. To achieve this requirement, both the surface treatment and the passivation layer are key technologies. As a starting point to design these processes, we investigated the GaSb oxide in terms of its growth and thermal stability. We found that the formation of GaSb oxide was very different from those of GaAs. Both Ga and Sb are oxidized at the surface of GaSb. In contrast, only Ga is oxidized and As is barely oxidized in the case of GaAs. Interestingly, the GaSb oxide can be formed even in DI water, which results in a very thick oxide film over 40 nm after 120 minutes. To examine the thermal stability, the GaSb native oxide was annealed in a vacuum and analyzed by XPS and Raman spectroscopy. These analyses suggest that SbOx in the GaSb native oxide will be reduced to metallic Sb above 300°C. To directly evaluate the effect of oxide instability on the device performance, a T2SL p-i-n photodetector was fabricated that has a cutoff wavelength of about 4 μm at 80 K. As a result, the surface leakage component was increased by the post annealing at 325°C. On the basis of these results, it is possible to speculate that a part of GaSb oxide on the sidewall surface will be reduced to metallic Sb, which acts as an origin of additional leakage current path.

  10. Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces

    DEFF Research Database (Denmark)

    Man, Isabela Costinela; Su, Hai-Yan; Vallejo, Federico Calle

    2011-01-01

    Trends in electrocatalytic activity of the oxygen evolution reaction (OER) are investigated on the basis of a large database of HO* and HOO* adsorption energies on oxide surfaces. The theoretical overpotential was calculated by applying standard density functional theory in combination...... that was the same for a wide variety of oxide catalyst materials and a universal descriptor for the oxygen evolution activity, which suggests a fundamental limitation on the maximum oxygen evolution activity of planar oxide catalysts....

  11. Functional oxide structures on a surface of metals and alloys

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    @@ The investigations of the plasma electrolytic processes in our laboratory are aimed to the development of conditions of formation of oxide layers with determined composition, structure and functional properties on the surface of valve metals (Al, Ti) and their alloys.

  12. Selective oxidations on vanadiumoxide containing amorphous mixed oxides (AMM-V) with tert.-butylhydroperoxide

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Y.; Hunnius, M.; Storck, S.; Maier, W.F. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzed reactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)

  13. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    Science.gov (United States)

    2014-10-27

    a native SiO2 oxide layer (P-type; 1 Ω·cm, SQI, San Jose, CA) were washed with persulfuric acid solution prior to use. Oxidation of Diamond... Graphene . Phys. Rep.: Rev. Sect. Phys. Lett. 2009, 473, 51−87. (34) Ferrari, A. C.; Meyer, J. C.; Scardaci, V.; Casiraghi, C.; Lazzeri, M.; Mauri, F...Piscanec, S.; Jiang, D.; Novoselov, K. S.; Roth, S.; Geim, A. K. Raman Spectrum of Graphene and Graphene Layers. Phys. Rev. Lett. 2006, 97, 187401−18740

  14. Improve oxidation resistance at high temperature by nanocrystalline surface layer.

    Science.gov (United States)

    Xia, Z X; Zhang, C; Huang, X F; Liu, W B; Yang, Z G

    2015-08-13

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content.

  15. Surface-Controlled Metal Oxide Resistive Memory

    KAUST Repository

    Ke, Jr-Jian

    2015-10-28

    To explore the surface effect on resistive random-access memory (ReRAM), the impact of surface roughness on the characteristics of ZnO ReRAM were studied. The thickness-independent resistance and the higher switching probability of ZnO ReRAM with rough surfaces indicate the importance of surface oxygen chemisorption on the switching process. Furthermore, the improvements in switching probability, switching voltage and resistance distribution observed for ReRAM with rough surfaces can be attributed to the stable oxygen adatoms under various ambience conditions. The findings validate the surface-controlled stability and uniformity of ReRAM and can serve as the guideline for developing practical device applications.

  16. 熔融钒渣直接提钒新工艺%New Process of Vanadium Extraction from Molten Vanadium Slag

    Institute of Scientific and Technical Information of China (English)

    宋文臣; 李宏; 李昆; 郑权

    2013-01-01

    现行钒渣焙烧工艺中的钒渣高温物理热被浪费,对“熔融钒渣直接氧化钠化提钒”新工艺的可行性进行分析,并进行实验室模拟试验.结果表明,新工艺条件下,试验过程中熔融钒渣流动性良好,焙烧后钒渣水浸率为50%~80%,焙烧后钒渣中的钒主要以偏钒酸钠的形式存在.新工艺是合理可行的,具有工业生产价值.%A new process of extracting vanadium from molten vanadium slag by direct oxidation and sodium salt roasting method was introduced,with the aim to address heat waste of vanadium slag existing in vanadium extraction process through vanadium slag roasting.The feasibility of the new process was analyzed,and the simulation test was carried out in laboratory.The results show that under the new process condition,molten vanadium slag can be kept with good fluidity.Water leaching rate of vanadium is 50 % ~80 %.Vanadium in roasted slag exists in form of sodium metavanadate.To conclude,the new process is feasible and can meet industrial production requirement.

  17. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  18. Surface Embedded Metal Oxide Sensors (SEMOS)

    DEFF Research Database (Denmark)

    Jespersen, Jesper Lebæk; Talat Ali, Syed; Pleth Nielsen, Lars

    complex and sensors are not easily implemented in the construction. Hence sensor interface and sensor position must therefore be chosen carefully in order to make the sensors as non-intrusive as possible. Metal Oxide Sensors (MOX) for measuring H2, O2 and CO concentration in a fuel cell environment...

  19. Electrochemical behavior of diverse vanadium ions at modified graphite felt electrode in sulphuric solution

    Institute of Scientific and Technical Information of China (English)

    LI Xiao-gang; HUANG Ke-long; LIU Su-qin; CHEN Li-quan

    2007-01-01

    PAN-based graphite feIt (PGF)treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery(VRB). Structure and characteristic of treated PAN-based graphite felt(TPGF) were determined by means of Fourier Transform Infrared Spectroscopy,Scanning Electron Microscopy, Brunauer-Einlrlett-Teller surface area analysis and VRB test system.The results show that the acid and heat synergistic effect increase the number of-COOH functional groups on the PGF surface. and the PGF is eroded by sulphuric acid oxidation.resulting in the surface area increases from 0.31 m2/g to 0.45 m2/g.The V(Ⅱ)/V(Ⅲ)redox reaction is electrochemically reversible on the TPGF electrode, while the V(Ⅳ)/V(Ⅴ)couple is a quasi reversible process.The diflusion coeffcients of the oxidation for V(Ⅳ)/V(Ⅴ)obtained from the scope of peak current Ip vs scan rate v1/2 is 4.4x10-5cm2/s. The improvement of electrochemical activity for the electrode is mainly ascribed to the increase of the number of-C00H groups on the TPGF,which behaves as active sites catalyzing the vanadium species reactions and accelerating electron transfer reaction and oxygen transfer.

  20. Environmental geochemistry and ecological risk of vanadium pollution in Panzhihua mining and smelting area, Sichuan, China

    Institute of Scientific and Technical Information of China (English)

    TENG Yanguo; NI Shijun; ZHANG Chengjiang; WANG Jinsheng; LIN Xueyu; HUANG Yi

    2006-01-01

    Vanadium is a trace element widely distributed in the Earth's crust. Naturally high levels of vanadium are recognized mainly in basic rocks and minerals, particularly in titaniferous magnetite. And the anthropogenic sources of vanadium include fossil fuel combustion and wastes including steel-industry slags. In the last few years, the authors have made investigations and assessments on the environmental geochemistry and ecological risk of vanadium in the Panzhihua mining and smelting area. In the study area, anthropogenic vanadium resulted from mining, extracting and smelting of V-Ti magnetite; vanadium pollution of topsoil and sediments occurs mainly in the mining and extracting area, smelting area, slag dumping area, tailing dam and coal mining area. In the soil, the chemical speciation of vanadium shows: insoluble residue>organically bound>Fe (amorphous) oxide-bound>Mn oxide-bound>soluble component. Vanadium pollution can cause potential harmful effects on ecological systems, and lead to animal poisoning and human disease. So vanadiam pollution should be monitored on a regular basis in the Panzhihua area.

  1. MOISTURE AND SURFACE AREA MEASUREMENTS OF PLUTONIUM-BEARING OXIDES

    Energy Technology Data Exchange (ETDEWEB)

    Crowder, M.; Duffey, J.; Livingston, R.; Scogin, J.; Kessinger, G.; Almond, P.

    2009-09-28

    To ensure safe storage, plutonium-bearing oxides are stabilized at 950 C for at least two hours in an oxidizing atmosphere. Stabilization conditions are expected to decompose organic impurities, convert metals to oxides, and result in moisture content below 0.5 wt%. During stabilization, the specific surface area is reduced, which minimizes readsorption of water onto the oxide surface. Plutonium oxides stabilized according to these criteria were sampled and analyzed to determine moisture content and surface area. In addition, samples were leached in water to identify water-soluble chloride impurity content. Results of these analyses for seven samples showed that the stabilization process produced low moisture materials (< 0.2 wt %) with low surface area ({le} 1 m{sup 2}/g). For relatively pure materials, the amount of water per unit surface area corresponded to 1.5 to 3.5 molecular layers of water. For materials with chloride content > 360 ppm, the calculated amount of water per unit surface area increased with chloride content, indicating hydration of hygroscopic salts present in the impure PuO{sub 2}-containing materials. The low moisture, low surface area materials in this study did not generate detectable hydrogen during storage of four or more years.

  2. Thermal and chemical modification of titanium-aluminum-vanadium implant materials: effects on surface properties, glycoprotein adsorption, and MG63 cell attachment.

    Science.gov (United States)

    MacDonald, D E; Rapuano, B E; Deo, N; Stranick, M; Somasundaran, P; Boskey, A L

    2004-07-01

    The microstructure, chemical composition and wettability of thermally and chemically modified Ti-6Al-4V alloy disks were characterized and correlated with the degree of radiolabeled fibronectin-alloy surface adsorption and subsequent adhesion of osteoblast-like cells. Heating either in pure oxygen or atmosphere (atm) resulted in an enrichment of Al and V within the surface oxide. Heating (oxygen/atm) and peroxide treatment both followed by butanol treatment resulted in a reduction in content of V, but not in Al. Heating (oxygen/atm) or peroxide treatment resulted in a thicker oxide layer and a more hydrophilic surface when compared with passivated controls. Post-treatment with butanol, however, resulted in less hydrophilic surfaces than heating or peroxide treatment alone. The greatest increases in the adsorption of radiolabeled fibronectin following treatment were observed with peroxide/butanol-treated samples followed by peroxide/butanol and heat/butanol, although binding was only increased by 20-40% compared to untreated controls. These experiments with radiolabeled fibronectin indicate that enhanced adsorption of the glycoprotein was more highly correlated with changes in chemical composition, reflected in a reduction in V content and decrease in the V/Al ratio, than with changes in wettability. Despite promoting only a modest elevation in fibronectin adsorption, the treatment of disks with heat or heat/butanol induced a several-fold increase in the attachment of MG63 cells promoted by a nonadhesive concentration of fibronectin that was used to coat the pretreated disks compared to uncoated disks. Therefore, results obtained with these modifications of surface properties indicate that an increase in the absolute content of Al and/or V (heat), and/or in the Al/V ratio (with little change in hydrophilicity; heat+butanol) is correlated with an increase in the fibronectin-promoted adhesion of an osteoblast-like cell line. It would also appear that the thermal

  3. Measuring Forces between Oxide Surfaces Using the Atomic Force Microscope

    DEFF Research Database (Denmark)

    Pedersen, Henrik Guldberg; Høj, Jakob Weiland

    1996-01-01

    The interactions between colloidal particles play a major role in processing of ceramics, especially in casting processes. With the Atomic Force Microscope (AFM) it is possible to measure the inter-action force between a small oxide particle (a few micron) and a surface as function of surface sep...

  4. Measuring Forces between Oxide Surfaces Using the Atomic Force Microscope

    DEFF Research Database (Denmark)

    Pedersen, Henrik Guldberg; Høj, Jakob Weiland

    1996-01-01

    The interactions between colloidal particles play a major role in processing of ceramics, especially in casting processes. With the Atomic Force Microscope (AFM) it is possible to measure the inter-action force between a small oxide particle (a few micron) and a surface as function of surface...

  5. Structure, Bonding and Surface Chemistry of Metal Oxide Nanoclusters

    Science.gov (United States)

    2015-06-23

    Characterization of these ligand- coated oxides included laser desorption mass spectrometry, infrared, Raman and UV - visible spectroscopy ...desorption and electrospray ionization mass spectrometry, optical spectroscopy methods (IR, surface-enhanced Raman, UV - visible absorption and...clusters are studied with laser desorption and electrospray ionization mass spectrometry, optical spectroscopy methods (IR, surface-enhanced Raman, UV

  6. Electron beam induced oxidation of Al–Mg alloy surfaces

    NARCIS (Netherlands)

    Palasantzas, G.; Agterveld, D.T.L. van; Hosson, J.Th.M. De

    2002-01-01

    Electron beam currents of a few nanoamperes, currently used in nanometer scale scanning Auger/electron microscopy, induces severe oxidation of Al–Mg alloy surfaces at room temperature. Auger peak-to-peak oxygen curves for Al–Mg surfaces support the hypothesis that the electron beam creates

  7. Electron beam induced oxidation of Al–Mg alloy surfaces

    NARCIS (Netherlands)

    Palasantzas, G.; Agterveld, D.T.L. van; Hosson, J.Th.M. De

    2002-01-01

    Electron beam currents of a few nanoamperes, currently used in nanometer scale scanning Auger/electron microscopy, induces severe oxidation of Al–Mg alloy surfaces at room temperature. Auger peak-to-peak oxygen curves for Al–Mg surfaces support the hypothesis that the electron beam creates additiona

  8. SBA-15介孔分子筛担载的钒基氧化物催化剂对乙烷选择氧化性能%Selective Oxidation of Ethane over SBA-15 Mesoporous Zeolite Supported Vanadium-Based Oxide Catalysts

    Institute of Scientific and Technical Information of China (English)

    刘坚; 赵震; 张哲; 徐春明; 段爱军; 姜桂元

    2009-01-01

    用等体积浸渍法制备了SBA-15担载的钒基(V/SBA-15)和钾修饰的钒基氧化物(K-V/SBA-15)催化剂,使用氮气吸附、小角X射线衍射(XRD)、紫外.可见漫反射光谱(UV-Vis DRS)和紫外激光拉曼光谱对这些催化剂的结构进行表征,并评价了这些催化剂对乙烷选择氧化的活性与选择性.实验结果表明介孔结构SBA-15对乙烷选择氧化的活性优于常规的SiO_2;对于SBA-15担载的V/SBA-15和K-V/SBA-15催化剂,极低钒担载量(nv:mso≤0.1:100)时隔离的四配位钒氧化物是乙烷选择氧化生成醛类化合物的活性物种,高钒担载量(nv:nsi≥2.5:100)时聚合的和微晶态的钒氧化物是乙烷氧化脱氢或深度氧化的活性物种.%A series of SBA-15 supported vanadium oxide (V/SBA-15) and K-modified vanadium oxide (K-V/SBA-15) catalysts with different active components were prepared by incipient-wetness impregnation. The structures of the catalysts were characterized using N_2 adsorption, low angle X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and UV-Raman spectroscopy techniques. Their catalytic performances for the selective oxidation of ethane were also investigated. The results showed that SBA-15 was a better support for the catalyst system than SiO_2 for the selective oxidation of ethane to aldehydes. The SBA-15-supported low loading catalyst was a highly dispersed catalyst system and the SBA-15 supported K-V samples with low loading (n_V:n_(Si)≤5.0:100) had ordered hexagonal mesostructures. For the V/SBA-15 and K-V/SBA-15 catalysts, isolated vanadyl species with tetrahedral coordination are determined to be the active sites for aldehyde formation at very low vanadium loading (nv:nSi≤0.1:100). The polymeric vanadyl species with octahedral coordination and the microcrystalline vanadium oxide constitute the active sites for the oxidative dehydrogenation or deep oxidation of ethane when the loading of vanadium is higher than 2.5:100.

  9. Surface oxidation and water desorption of CdS

    Institute of Scientific and Technical Information of China (English)

    陈正石; 李庆霖; 金振声

    1996-01-01

    The surface oxidation and HP desorption of powder CdS were studied by means of X-ray photoetectron spectroscopy (XPS), quadrupole mass spectrometry (QMS) and in-situ FTIR. The results show that with the changes of surface composition and the elongation of store time of CdS there are four types of H2O thermally desorbed at different temperatures. It has also been found that through high-temperature air treatment for a short time the oxidized surface layer of CdS can prevent O2 and H2O in air from further attacking the inner CdS molecules.

  10. Microbial Manganese Oxidation in Saltmarsh Surface Sediments Using a Leuco Crystal Violet Manganese Oxide Detection Technique

    Science.gov (United States)

    Spratt, Henry G.; Siekmann, Ellen C.; Hodson, Robert E.

    1994-01-01

    Microbial manganese (Mn) oxide production in surface sediments of a Georgia saltmarsh was directly measured using an assay involving the oxidation of 4,4',4″-methylidynetris (N,N-dimethylaniline), leuco crystal violet (LCV), by Mn oxides to produce crystal violet. The assay exhibits high specificity for Mn oxides without interference by Mn(II) and is sufficiently sensitive to determine rates of Mn oxidation in surface sediment or saltmarsh creek water suspensions. Sample salinity affects crystal violet absorbance in the 0-25 salinity range and must be corrected for in Mn oxide determinations for estuarine samples of variable salinity. Other oxidants found to oxidize LCV slowly included Cl(I), Cr(III), I(V), Fe(III), and Mn(III), although the sensitivity of the assay for Mn(IV) oxides was found to be seven times greater than for Mn(III), and at least 100 times greater than for any of the other oxidants. Rates of abiotic Mn oxide production in sediment suspensions treated with either sodium azide or formalin, or autoclaved, were much slower than rates determined for untreated sediments. Sodium azide (7·7 mM) inhibited Mn oxide production in these sediment suspensions to rates between 5 and 10% of the rates of Mn oxidation determined for unamended suspensions. Manganese oxidation was highly temperature dependent, with maximal rates on a dry weight basis (8·9 nmol mg dwt -1 h -1), occurring at 60°C, and negligible activity at 100 and 0°C. Rates were also dependent on sample pH, with maximal rates at pH 6·7, decreasing to near 0 as the pH was lowered to approximately 3·0. For Mn(II) concentrations ranging from 9 to 91 μM, rates of Mn oxide production were independent of Mn(II) concentration, while Mn oxide production was inhibited at concentrations greater than 91 μM (e.g. by 25-40% at 450 μM). Rates of microbial Mn oxide production in surface sediment/saltmarsh creek water suspensions incubated under natural conditions of temperature, pH, and Mn

  11. Surface and Core Electronic Structure of Oxidized Silicon Nanocrystals

    Directory of Open Access Journals (Sweden)

    Noor A. Nama

    2010-01-01

    Full Text Available Ab initio restricted Hartree-Fock method within the framework of large unit cell formalism is used to simulate silicon nanocrystals between 216 and 1000 atoms (1.6–2.65 nm in diameter that include Bravais and primitive cell multiples. The investigated properties include core and oxidized surface properties. Results revealed that electronic properties converge to some limit as the size of the nanocrystal increases. Increasing the size of the core of a nanocrystal resulted in an increase of the energy gap, valence band width, and cohesive energy. The lattice constant of the core and oxidized surface parts shows a decreasing trend as the nanocrystal increases in a size that converges to 5.28 Ǻ in a good agreement with the experiment. Surface and core convergence to the same lattice constant reflects good adherence of oxide layer at the surface. The core density of states shows highly degenerate states that split at the oxygenated (001-(1×1 surface due to symmetry breaking. The nanocrystal surface shows smaller gap and higher valence and conduction bands when compared to the core part, due to oxygen surface atoms and reduced structural symmetry. The smaller surface energy gap shows that energy gap of the nanocrystal is controlled by the surface part. Unlike the core part, the surface part shows a descending energy gap that proves its obedience to quantum confinement effects. Nanocrystal geometry proved to have some influence on all electronic properties including the energy gap.

  12. Surface structure and relaxation during the oxidation of carbon monoxide on Pt Pd bimetallic surfaces

    Science.gov (United States)

    Lucas, C. A.; Markovic, N. M.; Ball, M.; Stamenkovic, V.; Climent, V.; Ross, P. N.

    2001-05-01

    The atomic structure and surface relaxation of Pd monolayer on Pt(1 1 1) has been studied by surface X-ray scattering, in an aqueous environment under electrostatic potential control, during the adsorption and oxidation of carbon monoxide. The results show that the Pd-Pt layer spacing contracts at the onset of CO oxidation before the Pd adlayer forms an oxide structure that is incommensurate with the Pt lattice. Both the oxide formation and the lattice contraction are fully reversible over many cycles of the applied electrode potential.

  13. Oxidation of silicon surface with atomic oxygen radical anions

    Institute of Scientific and Technical Information of China (English)

    Wang Lian; Song Chong-Fu; Sun Jian-Qiu; Hou Ying; Li Xiao-Guang; Li Quan-Xin

    2008-01-01

    The surface oxidation of silicon (Si) wafers by atomic oxygen radical anions (O- anions) and the preparation of metal-oxide-semiconductor (MOS) capacitors on the O--oxidized Si substrates have been examined for the first time. The O- anions are generated from a recently developed O- storage-emission material of [Ca24Al28O64]4+.4O- (C12A7-O- for short). After it has been irradiated by an O- anion beam (0.5 μA/cm2) at 300℃ for 1-10 hours, the Si wafer achieves an oxide layer with a thickness ranging from 8 to 32 nm. X-ray photoelectron spectroscopy (XPS) results reveal that the oxide layer is of a mixture of SiO2, Si2O3, and Si2O distributed in different oxidation depths. The features of the MOS capacitor of are investigated by measuring capacitance-voltage (C - V) and current-voltage (Ⅰ - Ⅴ) curves. The oxide charge density is about 6.0×1011 cm-2 derived from the C - V curves. The leakage current density is in the order of 10-6 A/cm2 below 4 MV/cm, obtained from the Ⅰ - Ⅴ curves. The Oanions formed by present method would have potential applications to the oxidation and the surface-modification of materials together with the preparation of semiconductor devices.

  14. 水热氧化改性碳纸电极在全钒氧化还原电池中的应用%Modification of Carbon Paper Electrode via Hydrothermal Oxidation Applied in the Vanadium Redox Battery

    Institute of Scientific and Technical Information of China (English)

    苏安群; 汪南方; 刘素琴; 吴涛; 彭穗

    2012-01-01

    为了提高钒氧化还原电池电极的活性,在180℃下将碳纸电极与过氧化氢的硫酸溶液置于有聚四氟乙烯内衬的不锈钢反应釜中进行不同时间的水热酸氧化处理.水的接触角测试表明,随着处理时间从6h调整至18h,处理前后碳纸电极的接触角也从120.0°降低至100.8°,尤其是经过12h处理的样品的接触角最小,这说明在此条件下处理过的碳纸的亲水性得到了提高.而傅里叶变换红外测试表明,羰基和羧基等含氧基团被成功地引入到了碳纸电极中.使用扫描电镜,循环伏安,电化学阻抗以及充放电技术分别检测了处理前后样品的表面形貌及电化学性能.V(Ⅳ)(/V)(Ⅴ)氧化还原电对在这些处理过的样品上表现出较大的活性.用处理12h的碳纸电极组装的单电池性能优异,在30 mA· cm-2的电流密度下能量效率达到了80%,相应的电流效率和电压效率分别为96%和84%.%To improve the electrochemical activity of electrodes in the vanadium redox battery,carbon paper electrode was treated with a hydrogen peroxide and sulfuric acid solution,according to the hydrothermal acid oxidation method,in a Teflon-lined stainless steel autoclave over different time periods at 180 ℃.The water contact angle test showed that the contact angle of treated carbon paper samples changed from 120.0° to 100.8° by adjusting the treatment time from 6 to 18 h.Furthermore,a treatment time of 12 h resulted in the lowest contact angle observed,indicating that the wetting property of the carbon paper had been enhanced under these treatment conditions.Fourier transformation infrared spectroscopy results showed that oxygen-containing groups,such as the carbonyl and carboxyl groups,had been successfully introduced to the carbon papers.Scanning electron microscopy,cyclic vollammetry,electrochemical impedance spectroscopy,and charge-discharge tests were camied to characterize the surface topography and electrochemical

  15. Research and development on vanadium alloys for fusion applications

    Energy Technology Data Exchange (ETDEWEB)

    Zinkle, S.J.; Rowcliffe, A.F. [Oak Ridge National Lab., TN (United States); Matsui, H.; Abe, K. [Tohoku Univ. (Japan); Smith, D.L. [Argonne National Lab., IL (United States); Osch, E. van [NERF, Petten (Netherlands); Kazakov, V.A. [RIAR, Dimitrovgrad (Russian Federation)

    1998-03-01

    The current status of research and development on unirradiated and irradiated V-Cr-Ti alloys intended for fusion reactor structural applications is reviewed, with particular emphasis on the flow and fracture behavior of neutron-irradiated vanadium alloys. Recent progress on fabrication, joining, oxidation behavior, and the development of insulator coatings is also summarized. Fabrication of large (>500 kg) heats of V-4Cr-4Ti with properties similar to previous small laboratory heats has now been demonstrated. Impressive advances in the joining of thick sections of vanadium alloys using GTA and electron beam welds have been achieved in the past two years, although further improvements are still needed.

  16. Recent applications of liquid metals featuring nanoscale surface oxides

    Science.gov (United States)

    Neumann, Taylor V.; Dickey, Michael D.

    2016-05-01

    This proceeding describes recent efforts from our group to control the shape and actuation of liquid metal. The liquid metal is an alloy of gallium and indium which is non-toxic, has negligible vapor pressure, and develops a thin, passivating surface oxide layer. The surface oxide allows the liquid metal to be patterned and shaped into structures that do not minimize interfacial energy. The surface oxide can be selectively removed by changes in pH or by applying a voltage. The surface oxide allows the liquid metal to be 3D printed to form free-standing structures. It also allows for the liquid metal to be injected into microfluidic channels and to maintain its shape within the channels. The selective removal of the oxide results in drastic changes in surface tension that can be used to control the flow behavior of the liquid metal. The metal can also wet thin, solid films of metal that accelerates droplets of the liquid along the metal traces .Here we discuss the properties and applications of liquid metal to make soft, reconfigurable electronics.

  17. Phase evolution of vanadium oxides obtained through temperature programmed calcinations of ammonium vanadate in hydrogen atmosphere and their humidity sensing properties

    Energy Technology Data Exchange (ETDEWEB)

    Akande, A.A. [DST/CSIR National Centre for Nano-Structured Materials, P O Box 395, Pretoria, 0001 (South Africa); University of Limpopo, Department of Physics, P/Bag X1106, Sovenga, 0727 (South Africa); Linganiso, E.C.; Dhonge, B.P. [DST/CSIR National Centre for Nano-Structured Materials, P O Box 395, Pretoria, 0001 (South Africa); Rammutla, K.E. [University of Limpopo, Department of Physics, P/Bag X1106, Sovenga, 0727 (South Africa); Machatine, A.; Prinsloo, L.; Kunert, H. [School of Physics, University of Pretoria, Pretoria, 0002 (South Africa); Mwakikunga, B.W., E-mail: bmwakikunga@csir.co.za [DST/CSIR National Centre for Nano-Structured Materials, P O Box 395, Pretoria, 0001 (South Africa)

    2015-02-01

    The possibility of obtaining vanadium dioxide (VO{sub 2}) [wherein the vanadium ionic state is 4{sup +}] from a precursor of ammonium metavanadate (NH{sub 4}VO{sub 3}) bearing the ion V{sup 5+} is investigated. The reduction is carried out by calcining the NH{sub 4}VO{sub 3} powders in similar concentrations of H{sub 2} flow at varying temperatures. The resulting powders have been studied by several techniques including XRD, Raman spectroscopy, FTIR, TEM, BET and DSC. It is found that remnants of bright yellow V{sup 5+} still exist up to calcination temperatures of 100 °C after which the sky-blue VO{sub 2} dominates at calcination temperatures of 150 °C–250 °C. There is a population surge of metastable dark-blue V{sub 6}O{sub 13} (where V is in between V{sup 4+} and V{sup 5+} ionic states) between 250 °C and 300 °C. However above 350 °C the material reverts to the stable V{sup 5+} in the yellow–orange V{sub 2}O{sub 5}. XPS/EDS and VSM confirm the order of appearance to be VO{sub 2}(150 °C) → V{sub 6}O{sub 13}(200 °C) → V{sub 2}O{sub 5} (350 °C). - Highlights: • Validated the theoretical mass losses at each temperature of NH{sub 4}VO{sub 3} with TGA. • Confirmed mechanisms of formation of various stoichiometries of VO{sub x} from NH{sub 4}VO{sub 3}. • Determined the evolution of VO{sub 2}, V{sub 6}O{sub 13} and V{sub 2}O{sub 5} with temperature. • Phase diagram of VO{sub 2}, V{sub 6}O{sub 13} and V{sub 2}O{sub 5} by VSM, XPS/EDS, XRD and Raman spectra. • Comparative response of VO{sub 2}, V{sub 6}O{sub 13} and V{sub 2}O{sub 5} to humidity.

  18. The determination of vanadium in brines by atomic absorption spectroscopy

    Science.gov (United States)

    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.

  19. Vanadium-modified molecular sieves: preparation, characterization and catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Teixeira-Neto, Angela A. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental]. E-mail: gpmmm@iqm.unicamp.br; Marchese, Leonardo [Universita del Piemonte Orientale A. Avogadro, Alessandria (Italy); Pastore, Heloise O. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Inorganica

    2009-07-01

    Vanadium-containing molecular sieves are redox catalysts and are good candidates as substitutes for oxide-supported V{sub 2}O{sub 5} in a number of reactions. These materials have the advantage of presenting better dispersion of vanadium species, as well as shape-selective properties and controllable acidities. They may be prepared by one-pot synthesis or by post-synthesis methods and a number of techniques such as diffuse reflectance UV-visible spectroscopy, {sup 51}V nuclear magnetic resonance and electron paramagnetic resonance, to name but a few, have been used to characterize these materials. In this review, methods of preparation of vanadium-modified molecular sieves, their characterization and applications in catalysis are discussed. (author)

  20. Surface Properties of Photo-Oxidized Bituminous Coals: Final report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-09-01

    Natural weathering has a detrimental effect on the hydrophobic nature of coal, which in turn can influence clean-coal recovery during flotation. Few techniques are available that can establish the quality of coal surfaces and that have a short analysis time to provide input for process control. Luminescence emissions which can be quantified with an optical microscope and photometer system, are measurably influenced by degree of weathering as well as by mild storage deterioration. In addition, it has been shown that when vitrinite is irradiated with a relatively high intensity flux of violet- or ultraviolet- light in the presence of air, photo-oxidation of the surface occurs. The combination of measuring the change in luminescence emission intensity with degree of surface oxidation provided the impetus for the current investigation. The principal aim of this research was to determine whether clear correlations could be established among surface oxygen functionality, hydrophobicity induced by photo-oxidation, and measurements of luminescence intensity and alteration. If successful, the project would result in quantitative luminescence techniques based on optical microscopy that would provide a measure of the changes in surface properties as a function of oxidation and relate them to coal cleanability. Two analytical techniques were designed to achieve these goals. Polished surfaces of vitrain bands or a narrow size fraction of powdered vitrain concentrates were photo-oxidized using violet or ultraviolet light fluxes and then changes in surface properties and chemistry were measured using a variety of near-surface analytical techniques. Results from this investigation demonstrate that quantitative luminescence intensity measurements can be performed on fracture surfaces of bituminous rank coals (vitrains) and that the data obtained do reveal significant variations depending upon the level of surface oxidation. Photo-oxidation induced by violet or ultraviolet light

  1. Vanadium promotes hydroxyl radical formation by activated human neutrophils.

    Science.gov (United States)

    Fickl, Heidi; Theron, Annette J; Grimmer, Heidi; Oommen, Joyce; Ramafi, Grace J; Steel, Helen C; Visser, Susanna S; Anderson, Ronald

    2006-01-01

    This study was undertaken to investigate the effects of vanadium in the +2, +3, +4, and +5 valence states on superoxide generation, myeloperoxidase (MPO) activity, and hydroxyl radical formation by activated human neutrophils in vitro, using lucigenin-enhanced chemiluminescence (LECL), autoiodination, and electron spin resonance with 5,5-dimethyl-l-pyrroline N-oxide as the spin trap, respectively. At concentrations of up to 25 microM, vanadium, in the four different valence states used, did not affect the LECL responses of neutrophils activated with either the chemoattractant, N-formyl-l-methionyl-l-leucyl-l-phenylalanine (1 microM), or the phorbol ester, phorbol 12-myristate 12-acetate (25 ng/ml). However, exposure to vanadium in the +2, +3, and +4, but not the +5, valence states was accompanied by significant augmentation of hydroxyl radical formation by activated neutrophils and attenuation of MPO-mediated iodination. With respect to hydroxyl radical formation, similar effects were observed using cell-free systems containing either hydrogen peroxide (100 microM) or xanthine/xanthine oxidase together with vanadium (+2, +3, +4), while the activity of purified MPO was inhibited by the metal in these valence states. These results demonstrate that vanadium in the +2, +3, and +4 valence states interacts prooxidatively with human neutrophils, competing effectively with MPO for hydrogen peroxide to promote formation of the highly toxic hydroxyl radical.

  2. Can Vanadium Be Substituted into LiFePO4

    Energy Technology Data Exchange (ETDEWEB)

    Omenya F.; Nam K.; Chernova N.A.; Upreti S.; Zavalij P.Y.; Nam K.-W.; Yang X.-Q.; Whittingham M.S.

    2011-11-08

    Vanadium is shown to substitute for iron in the olivine LiFePO{sub 4} up to at least 10 mol %, when the synthesis is carried out at 550 C. In the solid solution LiFe{sub 1-3y/2}V{sub y}PO{sub 4}, the a and b lattice parameters and cell volume decrease with increasing vanadium content, while the c lattice parameter increases slightly. However, when the synthesis is performed at 650 C, a NASICON phase, Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}, is also formed, showing that solid solution is a function of the synthesis temperature. X-ray absorption near-edge structure indicates vanadium is in the 3+ oxidation state and in an octahedral environment. Magnetic studies reveal a shift of the antiferromagnetic ordering transition toward lower temperatures with increasing vanadium substitution, confirming solid solution formation. The addition of vanadium enhances the electrochemical performance of the materials especially at high current densities.

  3. Geochemical controls of vanadium accumulation in fossil fuels

    Science.gov (United States)

    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.

  4. Geochemical controls on vanadium accumulation in fossil fuels

    Science.gov (United States)

    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.

  5. Analysis and measurement of the electrolyte imbalance in a vanadium redox flow battery

    Science.gov (United States)

    Ngamsai, Kittima; Arpornwichanop, Amornchai

    2015-05-01

    Electrolyte imbalance in vanadium redox flow batteries is an important problem for its long-term operation as it leads to loss of energy. To address this problem, a modified open circuit voltage (OCV) cell is developed by adding a middle half cell between the negative and positive half cells of a conventional OCV cell and used to predict the oxidation state of vanadium in the electrolyte solution from the measured voltage in each side of the electrolyte (positive and negative). The correlation between the oxidation state of vanadium and cell voltage is explained by a basic electrochemical principle and the Nernst equation. The experimental results show that at different oxidation states of vanadium, the predicted OCV agrees reasonably with the experimental data. In addition, the effect of the state of charge (SOC) and electrolyte imbalance on the energy capacity of a cell is discussed.

  6. Facile preparation of superhydrophobic surfaces based on metal oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Bao, Xue-Mei; Cui, Jin-Feng; Sun, Han-Xue; Liang, Wei-Dong; Zhu, Zhao-Qi; An, Jin; Yang, Bao-Ping; La, Pei-Qing; Li, An, E-mail: lian2010@lut.cn

    2014-06-01

    A novel method for fabrication of superhydrophobic surfaces was developed by facile coating various metal oxide nanoparticles, including ZnO, Al{sub 2}O{sub 3} and Fe{sub 3}O{sub 4}, on various substrates followed by treatment with polydimethylsiloxane (PDMS) via chemical vapor deposition (CVD) method. Using ZnO nanoparticles as a model, the changes in the surface chemical composition and crystalline structures of the metal oxide nanoparticles by PDMS treatment were investigated by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) analysis. The results show that the combination of the improved surface roughness generated from of the nanoparticles aggregation with the low surface-energy of silicon-coating originated from the thermal pyrolysis of PDMS would be responsible for the surface superhydrophobicity. By a simple dip-coating method, we show that the metal oxide nanoparticles can be easily coated onto the surfaces of various textural and dimensional substrates, including glass slide, paper, fabric or sponge, for preparation of superhydrophobic surfaces for different purpose. The present strategy may provide an inexpensive and new route to surperhydrophobic surfaces, which would be of technological significance for various practical applications especially for separation of oils or organic contaminates from water.

  7. Facile preparation of superhydrophobic surfaces based on metal oxide nanoparticles

    Science.gov (United States)

    Bao, Xue-Mei; Cui, Jin-Feng; Sun, Han-Xue; Liang, Wei-Dong; Zhu, Zhao-Qi; An, Jin; Yang, Bao-Ping; La, Pei-Qing; Li, An

    2014-06-01

    A novel method for fabrication of superhydrophobic surfaces was developed by facile coating various metal oxide nanoparticles, including ZnO, Al2O3 and Fe3O4, on various substrates followed by treatment with polydimethylsiloxane (PDMS) via chemical vapor deposition (CVD) method. Using ZnO nanoparticles as a model, the changes in the surface chemical composition and crystalline structures of the metal oxide nanoparticles by PDMS treatment were investigated by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) analysis. The results show that the combination of the improved surface roughness generated from of the nanoparticles aggregation with the low surface-energy of silicon-coating originated from the thermal pyrolysis of PDMS would be responsible for the surface superhydrophobicity. By a simple dip-coating method, we show that the metal oxide nanoparticles can be easily coated onto the surfaces of various textural and dimensional substrates, including glass slide, paper, fabric or sponge, for preparation of superhydrophobic surfaces for different purpose. The present strategy may provide an inexpensive and new route to surperhydrophobic surfaces, which would be of technological significance for various practical applications especially for separation of oils or organic contaminates from water.

  8. Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons

    Science.gov (United States)

    Külah, Elçin; Marot, Laurent; Steiner, Roland; Romanyuk, Andriy; Jung, Thomas A.; Wäckerlin, Aneliia; Meyer, Ernst

    2017-01-01

    Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect – oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level. PMID:28327642

  9. Surface Chemistry and Properties of Oxides as Catalyst Supports

    Energy Technology Data Exchange (ETDEWEB)

    DeBusk, Melanie Moses [ORNL; Narula, Chaitanya Kumar [ORNL; Contescu, Cristian I [ORNL

    2015-01-01

    Heterogeneous catalysis relies on metal-oxides as supports for the catalysts. Catalyst supports are an indispensable component of most heterogeneous catalysts, but the role of the support is often minimized in light of the one played by the catalytically active species it supports. The active species of supported catalysts are located on the surface of the support where their contact with liquid or gas phase reactants will be greatest. Considering that support plays a major role in distribution and stability of active species, the absorption and retention of reactive species, and in some cases in catalytic reaction, the properties and chemistry that can occur at the surface of an oxide support are important for understanding their impact on the activity of a supported catalyst. This chapter examines this rich surface chemistry and properties of oxides used as catalyst supports, and explores the influence of their interaction with the active species.

  10. Structural and surface changes of copper modified manganese oxides

    Energy Technology Data Exchange (ETDEWEB)

    Gac, Wojciech, E-mail: wojciech.gac@umcs.lublin.pl; Słowik, Grzegorz; Zawadzki, Witold

    2016-05-01

    Highlights: • Formation of MnO with regular rippled-like surface patterns. • Synthesis of copper nanorods supported on MnO nanoparticles. • Hydrogen production in steam methanol reforming over supported copper nanorods. - Abstract: The structural and surface properties of manganese and copper–manganese oxides were investigated. The oxides were prepared by the redox-precipitation method. X-ray diffraction and electron microscopy studies evidenced transformation of cryptomelane-type nanoparticles with 1-D channel structure into the large MnO crystallites with regular rippled-like surface patterns under reduction conditions. The development of Cu/CuO nanorods from strongly dispersed species was evidenced. Coper-modified manganese oxides showed good catalytic performance in methanol steam reforming reaction for hydrogen production. Low selectivity to CO was observed in the wide range of temperatures.

  11. The heterogeneous oxidation of SO2 on aerosol surface

    Institute of Scientific and Technical Information of China (English)

    高会旺; 黄美元; 徐华英

    1997-01-01

    A heterogeneous chemical model is developed by coupling aerosol, gas-phase and liquid-phase chemical model. SO2 oxidation rates on the aerosol surface are calculated and the influence of some factors is discussed. Model simulations indicate that SO2 heterogeneous oxidation rates are sensitive to the mass concentration and chemical composition of aerosols, relative humidity, initial values of SO2 and H2O2. The heterogeneous chemical model is coupled with a Eulerian deposition model. Model results show that oxidation of SO2 on the aerosol surface is found to reduce SO2 levels by 5%-33%, to increase SO2-4 concentrations by 8%-50% in the surface layer.

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

    Science.gov (United States)

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

    2000-01-01

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

  13. Uptake and speciation of vanadium in the benthic invertebrate Hyalella azteca.

    Science.gov (United States)

    Jensen-Fontaine, Madeleine; Norwood, Warren P; Brown, Mitra; Dixon, D George; Le, X Chris

    2014-01-01

    Vanadium has the potential to leach into the environment from petroleum coke, an oil sands byproduct. To determine uptake of vanadium species in the biota, we exposed the benthic invertebrate Hyalella azteca with increasing concentrations of two different vanadium species, V(IV) and V(V), for seven days. The concentrations of vanadium in the H. azteca tissue increased with the concentration of vanadium in the exposure water. Speciation analysis revealed that V(IV) in the exposure water was oxidized to V(V) between renewal periods, and therefore the animals were mostly exposed to V(V). Speciation analysis of the H. azteca tissue showed the presence of V(V), V(IV), and an unidentified vanadium species. These results indicate the uptake and metabolism of vanadium by H. azteca. Because H. azteca are widely distributed in freshwater systems and are an important food supply for many fish, determining the uptake and metabolism of vanadium allows for a better understanding of the potential environmental effects on invertebrates.

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

    Science.gov (United States)

    Sepehr, Fatemeh; Paddison, Stephen J

    2015-06-01

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

  15. Process of forming catalytic surfaces for wet oxidation reactions

    Science.gov (United States)

    Jagow, R. B. (Inventor)

    1977-01-01

    A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

  16. Enhanced photothermal effect of surface oxidized silicon nanocrystals anchored to reduced graphene oxide nanosheets

    Science.gov (United States)

    Afshani, Parichehr; Moussa, Sherif; Atkinson, Garrett; Kisurin, Vitaly Y.; Samy El-Shall, M.

    2016-04-01

    We demonstrate the coupling of the photothermal effects of silicon nanocrystals and graphene oxide (GO) dispersed in water. Using laser irradiation (532 nm or 355 nm) of suspended Si nanocrystals in an aqueous solution of GO, the synthesis of surface oxidized Si-reduced GO nanocomposites (SiOx/Si-RGO) is reported. The laser reduction of GO is accompanied by surface oxidation of the Si nanocrystals resulting in the formation of the SiOx/Si-RGO nanocomposites. The SiOx/Si-RGO nanocomposites are proposed as promising materials for photothermal therapy and for the efficient conversion of solar energy into usable heat for a variety of thermal and thermomechanical applications.

  17. Formation and characterization of infrared absorbing copper oxide surfaces

    Science.gov (United States)

    Arslan, Burcu; Demirci, Gökhan; Erdoğan, Metehan; Karakaya, İshak

    2017-04-01

    Copper oxide formation has been investigated to combine the advantages of producing different size and shapes of coatings that possess good light absorbing properties. An aqueous blackening solution was investigated and optimum composition was found as 2.5 M NaOH and 0.225 M NaClO to form velvet copper oxide films. A two-step oxidation mechanism was proposed for the blackening process by carefully examining the experimental results. Formation of Cu2O was observed until the entire copper surface was covered at first. In the second step, Cu2O surface was further oxidized to CuO until the whole Cu2O surface was covered by CuO. Therefore, blackened copper surfaces consisted of Cu2O/CuO duplex oxides. Characterization of the coatings were performed in terms of microstructure, phase analysis, chemical state, infrared specular and total reflectivity by SEM, XRD, XPS, FTIR and UV-vis spectrophotometry, respectively.

  18. Structure and surface properties of supported oxides

    Energy Technology Data Exchange (ETDEWEB)

    Leyrer, J.; Vielhaber, B.; Zaki, M.I.; Zhuang Shuxian; Weitkamp, J.; Knoezinger, H.

    1985-09-15

    Supported molybdate catalysts have been prepared on Al/sub 2/O/sub 3/,TiO/sub 2/, CeO/sub 2/, ZrO/sub 2/ and SiO/sub 2/ by impregnation from aqueous solution. The isoelectric point (IEPS) of the support surfaces determines the primary adsorption interaction of the molybdate species with the surface at a given pH. Raman spectroscopy shows monolayer formation on Al/sub 2/O/sub 3/, TiO/sub 2/ and CeO/sub 2/, while high proportions of MoO/sub 3/ are detected on SiO/sub 2/ and ZrO/sub 2/. Strong support effects influence the reducibility of the supported molybdate, which decreases in the sequence Mo/TiO/sub 2/ > Mo/ > CeO/sub 2/ > Mo/Al/sub 2/O/sub 3/ > Mo/ZrO/sub 2/. The dispersion of the monolayer on TiO/sub 2/, CeO/sub 2/ and Al/sub 2/O/sub 3/ seems to be fairly stable under reduction conditions, indicating strong chemical interaction with the supports.

  19. Vanadium based materials as electrode materials for high performance supercapacitors

    Science.gov (United States)

    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.

  20. Electron beam induced surface activation of oxide surfaces for nanofabrication

    Energy Technology Data Exchange (ETDEWEB)

    Vollnhals, Florian; Seiler, Steffen; Walz, Marie-Madeleine; Steinrueck, Hans-Peter; Marbach, Hubertus [Lehrstuhl fuer Physikalische Chemie II and Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universitaet Erlangen-Nuernberg, Erlangen (Germany); Woolcot, Tom; Thornton, Geoff [London Centre for Nanotechnology and Department of Chemistry, University College London (United Kingdom)

    2012-07-01

    The controlled fabrication of structures on the nanoscale is a major challenge in science and engineering. Direct-write techniques like Electron Beam Induced Deposition (EBID) were shown to be suitable tools in this context. Recently, Electron Beam Induced Surface Activation (EBISA) has been introduced as a new focused electron beam technique. In EBISA, a surface, e.g. SiO{sub 2}, is irradiated by a focused electron beam, resulting in an activation of the exposed area. The activated area can then react and decompose precursor gases like iron pentacarbonyl, Fe(CO){sub 5}. This leads to a primary deposit, which continues to grow autocatalytically as long as Fe(CO){sub 5} is supplied, resulting in pure (> 90 % at.), crystalline iron nanostructures. We expand the use of this concept by exploring EBISA to produce metallic nanostructures on TiO{sub 2}(110) in UHV; atomistic insight into the process is obtained via Scanning Tunneling Microscopy (STM) and chemical insight via Auger Electron Spectroscopy (AES).

  1. Surface oxide formation during corona discharge treatment of AA 1050 aluminium surfaces

    DEFF Research Database (Denmark)

    Minzari, Daniel; Møller, Per; Kingshott, Peter

    2008-01-01

    Atmospheric plasmas have traditionally been used as a non-chemical etching process for polymers, but the characteristics of these plasmas could very well be exploited for metals for purposes more than surface cleaning that is presently employed. This paper focuses on how the corona discharge...... process modifies aluminium AA 1050 surface, the oxide growth and resulting corrosion properties. The corona treatment is carried out in atmospheric air. Treated surfaces are characterized using XPS, SEM/EDS, and FIB-FESEM and results suggest that an oxide layer is grown, consisting of mixture of oxide...... and hydroxide. The thickness of the oxide layer extends to 150–300 nm after prolonged treatment. Potentiodynamic polarization experiments show that the corona treatment reduces anodic reactivity of the surface significantly and a moderate reduction of the cathodic reactivity....

  2. Oxidized Zirconium Bearing Surfaces in Total Knee Arthroplasty: Lessons Learned.

    Science.gov (United States)

    Schüttler, Karl Friedrich; Efe, Turgay; Heyse, Thomas J; Haas, Steven B

    2015-10-01

    Polyethylene wear in total knee arthroplasty is a still unsolved problem resulting in osteolysis and long-term failure of knee joint replacement. To address the problem of polyethylene wear, research aimed for an optimal implant design and for an optimal combination of bearing surfaces. Oxidized zirconium was introduced to minimize surface wear and thus potentially increase long-term implant survival. This review comprises the current literature related to in vitro and in vivo studies evaluating performance of oxidized zirconium total knee arthroplasty and results from retrieval analyses.

  3. Simultaneous removal of ethanol,acetaldehyde and nitrogen oxides over V-Pd/γ-Al2O3-TiO2 catalyst

    Institute of Scientific and Technical Information of China (English)

    Zhe Li; Jing Wang; Kai He; Xia An; Wei Huang; Kechang Xie

    2011-01-01

    V-Pd/γ-Al2O3-TiO2 catalysts with different vanadium contents were prepared by a combined sol-gel and impregnation method.X-ray diffraction(XRD),N2 adsorption-desorption(BET),X-ray photoelectron spectroscopy(XPS)and catalytic removal of ethanol,acetaldehyde and nitrogen oxides at low temperature(<300℃)were used to assess the properties of the catalysts.The results showed that the sample with 1wt% vanadium exhibited an excellent catalytic performance for simultaneous removal of ethanol,acetaldehyde and nitrogen oxides.The conversions of ethanol,acetaldehyde and nitrogen oxides at 250℃ were 100%,74.4% and 98.7%,respectively.V-Pd/γ-Al2O3-TiO2 catalyst with 1 wt% vanadium showed the largest surface area and higher dispersion of vanadium oxide on the catalyst surface,and possessed a larger mole fraction of V4+species and unique PdO species on the surface,which can be attributed to the strong synergistic effect among palladium,vanadium and the carriers.The higher activity of V-Pd/γ-Al2O3-TiO2 catalyst is related to the V4+and Pd2+species on the surface,which might be favorable for the formation of active sites.

  4. Surface chemistry of black phosphorus under a controlled oxidative environment

    Science.gov (United States)

    Luo, Wei; Zemlyanov, Dmitry Y.; Milligan, Cory A.; Du, Yuchen; Yang, Lingming; Wu, Yanqing; Ye, Peide D.

    2016-10-01

    Black phosphorus (BP), the bulk counterpart of monolayer phosphorene, is a relatively stable phosphorus allotrope at room temperature. However, monolayer phosphorene and ultra-thin BP layers degrade in ambient atmosphere. In this paper, we report the investigation of BP oxidation and discuss the reaction mechanism based on the x-ray photoelectron spectroscopy (XPS) data. The kinetics of BP oxidation was examined under various well-controlled conditions, namely in 5% O2/Ar, 2.3% H2O/Ar, and 5% O2 and 2.3% H2O/Ar. At room temperature, the BP surface is demonstrated not to be oxidized at a high oxidation rate in 5% O2/Ar nor in 2.3% H2O/Ar, according to XPS, with the thickness of the oxidized phosphorus layer <5 Å for 5 h. On the other hand, in the O2/H2O mixture, a 30 Å thickness oxide layer was detected already after 2 h of the treatment. This result points to a synergetic effect of water and oxygen in the BP oxidation. The oxidation effect was also studied in applications to the electrical measurements of BP field-effect transistors (FETs) with or without passivation. The electrical performance of BP FETs with atomic layer deposition (ALD) dielectric passivation or h-BN passivation formed in a glove-box environment are also presented.

  5. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid

    Science.gov (United States)

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

    2014-10-01

    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (Ep, 1.10 ≤ Ep ≤ 1.50 V), polarization time (tp, 100 ≤ tp ≤ 104 s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (dox). Because X1 > dox for the entire range of Ep, tp, and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Ptδ+-Oδ- surface dipole (μPtO), and the potential drop (Vox) and electric field (Eox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

  6. Interactions of Graphene Oxide Nanomaterials with Natural Organic Matter and Metal Oxide Surfaces

    Science.gov (United States)

    Interactions of graphene oxide (GO) with silica surfaces were investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Both GO deposition and release were monitored on silica- and poly-l-lysine (PLL) coated surfaces as a function of GO concentration a...

  7. Modification of platinum surfaces by spontaneous deposition: Methanol oxidation electrocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    MacDonald, J.P.; Gualtieri, B.; Runga, N.; Teliz, E.; Zinola, C.F. [Fundamental Electrochemistry Laboratory, School of Sciences, Universidad de la Republica, Igua Street No. 4225, CP 11400, Montevideo (Uruguay)

    2008-12-15

    The presence of a second metal on platinum surfaces affects the performance of methanol oxidation. However, most of the electrocatalytic reactions are studied by using electrochemically deposited platinum alloys, but in the case of spontaneous deposition the situation is not so clear since the surface distribution, stability and morphology are usually not well documented. The formation of surface decorated samples on mono- and poly-crystalline platinum is followed by electrochemical and spectroscopic techniques and analysis of their performance towards methanol adsorption and oxidation compared with that on pure platinum. Pt/Sn and Pt/Ru are of special interest because of their well-known performance in methanol fuel cells. Methanol oxidation on Pt(111)/Ru, Pt(111)/Sn and Pt(111) shows that ruthenium is the only one able to promote the reaction since the simultaneous dissolution of tin occurs and competes with the process of interest. The in situ infrared spectroscopy is used to compare methanol oxidation on Pt(111)/Ru and Pt(111) in acid media using p-polarized light. The formation of bridge bound carbon monoxide is inhibited in the presence of ruthenium ad-species, whereas on Pt(111) the three adsorption configurations are observed. Linear sweep polarization curves and Tafel slopes (calculated from steady state potentiostatic plots) for methanol oxidation are compared on polycrystalline surfaces modified by tin or ruthenium at different coverages. There is almost no change in the Tafel slopes due to the presence of the foreign metal except for Pt/Ru, where a 0.09 V decade{sup -1} slope was calculated below 0.55 V due to hydroxyl adsorbates on ruthenium islands. The anodic stripping of methanol residues on the three surfaces indicates a lower amount of carbon monoxide-type adsorbates on Pt/Ru, and the simultaneous tin dissolution process leading to residues oxidation on Pt/Sn electrodes. (author)

  8. The Role of Oxygen Uptake and Scale Formation on the Embrittlement of Vanadium Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Pint, Bruce A [ORNL; Distefano, James R [ORNL

    2005-01-01

    Vanadium alloys are of interest in fusion energy systems, however, their environmental durability is a major concern. Specimens of V-4Cr-4Ti were exposed to air and oxygen (10{sup 5},Pa), low pressure (10{sup -3}-10{sup -6} Pa) oxygen and high purity He environments (10{sup 5}-10{sup 1} Pa) it at 500-700 C in order to characterize the surface oxide, determine oxidation kinetics and quantify effects on mechanical properties at 25 and 600 C. At low oxygen pressures (P{sub O{sub 2}}.10{sup -5} Pa), linear reaction kinetics were measured for exposures up to 2000 hr and the data were used to develop a mathematical expression for the oxidation rate as a function of temperature and oxygen pressure. At higher pressures, linear-parabolic reaction kinetics were associated with high oxygen uptake and the formation of an external oxide layer. Room-temperature and 600 C tensile ductility was reduced by these exposures, but specimens which formed an external oxide were found to retain some tensile ductility after exposure. However, similar specimens with an external oxide that were subsequently annealed for 2000 hr at 700 C became severely embrittled demonstrating that a surface oxide will not prevent degradation of this refractory alloy. Exposures in He were performed to determine the effect of total gas pressure on oxygen uptake.

  9. Influence of mineral oil and additives on microhardness and surface chemistry of magnesium oxide (001) surface

    Science.gov (United States)

    Miyoshi, K.; Shigaki, H.; Buckley, D. H.

    1982-01-01

    X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.

  10. Accumulation-layer surface plasmons in transparent conductive oxides.

    Science.gov (United States)

    Fardad, Shima; Alexander Ramos, E; Salandrino, Alessandro

    2017-05-15

    A rigorous analytical study of the eigenmodes supported by a charge accumulation layer within a transparent conductive oxide (TCO) is presented. The new class of surface plasmons termed accumulation-layer surface plasmons (ASPs) is introduced. Near resonance ASPs are tightly bound and display a vast effective index tunability that could be of great practical interest. The suppression of ASPs in the presence of epsilon-near zero regions is discussed.

  11. Single-Site VO x Moieties Generated on Silica by Surface Organometallic Chemistry: A Way To Enhance the Catalytic Activity in the Oxidative Dehydrogenation of Propane

    KAUST Repository

    Barman, Samir

    2016-07-26

    We report here an accurate surface organometallic chemistry (SOMC) approach to propane oxidative dehydrogenation (ODH) using a μ2-oxo-bridged, bimetallic [V2O4(acac)2] (1) (acac = acetylacetonate anion) complex as a precursor. The identity and the nuclearity of the product of grafting and of the subsequent oxidative treatment have been systematically studied by means of FT-IR, Raman, solid-state (SS) NMR, UV-vis DRS, EPR and EXAFS spectroscopies. We show that the grafting of 1 on the silica surface under a rigorous SOMC protocol and the subsequent oxidative thermal treatment lead exclusively to well-defined and isolated monovanadate species. The resulting material has been tested for the oxidative dehydrogenation of propane in a moderate temperature range (400-525 °C) and compared with that of silica-supported vanadium catalysts prepared by the standard impregnation technique. The experimental results show that the catalytic activity in propane ODH is strongly upgraded by the degree of isolation of the VOx species that can be achieved by employing the SOMC protocol. © 2016 American Chemical Society.

  12. Surface functionalization of dopamine coated iron oxide nanoparticles for various surface functionalities

    Science.gov (United States)

    Sherwood, Jennifer; Xu, Yaolin; Lovas, Kira; Qin, Ying; Bao, Yuping

    2017-04-01

    We present effective conjugation of four small molecules (glutathione, cysteine, lysine, and Tris(hydroxymethyl)aminomethane) onto dopamine-coated iron oxide nanoparticles. Conjugation of these molecules could improve the surface functionality of nanoparticles for more neutral surface charge at physiological pH and potentially reduce non-specific adsorption of proteins to nanoparticles surfaces. The success of conjugation was evaluated with dynamic light scattering by measuring the surface charge changes and Fourier transform infrared spectroscopy for surface chemistry analysis. The stability of dopamine-coated nanoparticles and the ability of conjugated nanoparticles to reduce the formation of protein corona were evaluated by measuring the size and charge of the nanoparticles in biological medium. This facile conjugation method opens up possibilities for attaching various surface functionalities onto iron oxide nanoparticle surfaces for biomedical applications.

  13. Covalent Attachment of 1-Alkenes to Oxidized Platinum Surfaces

    NARCIS (Netherlands)

    Alonso Carnicero, J.M.; Fabre, B.; Trilling, A.K.; Scheres, L.M.W.; Franssen, M.C.R.; Zuilhof, H.

    2015-01-01

    We report the formation of covalently bound alkyl layers onto oxidized Pt (PtOx) substrates by reaction with 1-alkenes as a novel way to bind organic molecules to metal surfaces. The organic layers were characterized by static contact angle, infrared reflection absorption spectroscopy (IRRAS), X-ray

  14. Functional oxide structures on a surface of metals and alloys

    Institute of Scientific and Technical Information of China (English)

    Rudnev; V.; S.; Yarovaya; T.; P.; Boguta; D.; L.; Lukiyanchuk; I.; V.; Tyrina; L.; M.; Morozova; V.; P.; Nedozorov; P.; M.; Vasilyeva; M.; S.; Kondrikov; N.; B.

    2005-01-01

    The investigations of the plasma electrolytic processes in our laboratory are aimed to the development of conditions of formation of oxide layers with determined composition, structure and functional properties on the surface of valve metals (Al, Ti) and their alloys.……

  15. Stability and morphology of cerium oxide surfaces in an oxidizing environment: A first-principles investigation

    Science.gov (United States)

    Fronzi, Marco; Soon, Aloysius; Delley, Bernard; Traversa, Enrico; Stampfl, Catherine

    2009-09-01

    We present density functional theory investigations of the bulk properties of cerium oxides (CeO2 and Ce2O3) and the three low index surfaces of CeO2, namely, (100), (110), and (111). For the surfaces, we consider various terminations including surface defects. Using the approach of "ab initio atomistic thermodynamics," we find that the most stable surface structure considered is the stoichiometric (111) surface under "oxygen-rich" conditions, while for a more reducing environment, the same (111) surface, but with subsurface oxygen vacancies, is found to be the most stable one, and for a highly reducing environment, the (111) Ce-terminated surface becomes energetically favored. Interestingly, this latter surface exhibits a significant reconstruction in that it becomes oxygen terminated and the upper layers resemble the Ce2O3(0001) surface. This structure could represent a precursor to the phase transition of CeO2 to Ce2O3.

  16. Effect of Surface Modification on Behaviors of Cerium Oxide Nanopowders

    Institute of Scientific and Technical Information of China (English)

    Li Mei; Shi Zhenxue; Liu Zhaogang; Hu Yanhong; Wang Mitang; Li Hangquan

    2007-01-01

    Study was made on the effect of surface modification on the behaviors of cerium oxide nanopowders. A surfactant-sodium dodecyl sulfate(C12H25SO4Na) was used to modify the surface of CeO2 powder particles. The unmodified and modified CeO2 powders were characterized by using a powder comprehensive characteristic tester, laser particle size analyzer, specific surface area tester, X-ray diffraction tester, and a scanning electron microscope. The testing and analysis results showed that C12H25SO4Na surface modification might increase the flowability and dispersity, and decrease the specific surface area and agglomeration of CeO2 powders. The mechanism of the surface modification of CeO2 powder particles was also discussed.

  17. Oxidation of clean silicon surfaces studied by four-point probe surface conductance measurements

    DEFF Research Database (Denmark)

    Petersen, Christian Leth; Grey, Francois; Aono, M.

    1997-01-01

    We have investigated how the conductance of Si(100)-(2 x 1) and Si(111)-(7 x 7) surfaces change during exposure to molecular oxygen. A monotonic decrease in conductance is seen as the (100) surfaces oxidizes. In contract to a prior study, we propose that this change is caused by a decrease in sur...

  18. First principles investigation of heterogeneous catalysis on metal oxide surfaces

    Science.gov (United States)

    Ghoussoub, Mireille

    Metal oxides possess unique electronic and structural properties that render them highly favourable for applications in heterogeneous catalysis. In this study, computational atomistic modelling based on Density Functional Theory was used to investigate the reduction of carbon dioxide over hydroxylated indium oxide nanoparticles, as well at the activation of methane over oxygen-covered bimetallic surfaces. The first study employed metadynamics-biased ab initio molecular dynamics to obtain the free energy surface of the various reaction steps at finite temperature. In the second study, the nudged elastic band method was used to probe the C-H activation mechanisms for different surface configurations. In both cases, activation energies, reaction energies, transition state structures, and charge analysis results are used to explain the underlying mechanistic pathways.

  19. Reversible Compositional Control of Oxide Surfaces by Electrochemical Potentials

    KAUST Repository

    Mutoro, Eva

    2012-01-05

    Perovskite oxides can exhibit a wide range of interesting characteristics such as being catalytically active and electronically/ionically conducting, and thus, they have been used in a number of solid-state devices such as solid oxide fuel cells (SOFCs) and sensors. As the surface compositions of perovskites can greatly influence the catalytic properties, knowing and controlling their surface compositions is crucial to enhance device performance. In this study, we demonstrate that the surface strontium (Sr) and cobalt (Co) concentrations of perovskite-based thin films can be controlled reversibly at elevated temperatures by applying small electrical potential biases. The surface compositional changes of La 0.8Sr 0.2CoO 3-δ (LSC 113), (La 0.5Sr 0.5) 2CoO 4±δ (LSC 214), and LSC 214-decorated LSC 113 films (LSC 113/214) were investigated in situ by utilizing synchrotron-based X-ray photoelectron spectroscopy (XPS), where the largest changes of surface Sr were found for the LSC 113/214 surface. These findings offer the potential of reversibly controlling the surface functionality of perovskites. © 2011 American Chemical Society.

  20. Surface State of Carbon Fibers Modified by Electrochemical Oxidation

    Institute of Scientific and Technical Information of China (English)

    Yunxia GUO; Jie LIU; Jieying LIANG

    2005-01-01

    Surface of polyacrylonitrile (PAN)-based carbon fibers was modified by electrochemical oxidation. The modification effect on carbon fibers surface was explored using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Results showed that on the modified surface of carbon fibers, the carbon contents decreased by 9.7% and the oxygen and nitrogen contents increased by 53.8% and 7.5 times, respectively. The surface roughness and the hydroxyl and carbonyl contents also increased. The surface orientation index was reduced by 1.5%which decreased tensile strength of carbon fibers by 8.1%, and the microcrystalline dimension also decreased which increased the active sites of carbon fiber surface by 78%. The physical and chemical properties of carbon fibers surface were modified through the electrochemical oxidative method, which improved the cohesiveness between the fibers and resin matrix and increased the interlaminar shear strength (ILSS) of carbon fibers reinforced epoxy composite (CFRP) over 20%.

  1. Bacterial adhesion to glass and metal-oxide surfaces.

    Science.gov (United States)

    Li, Baikun; Logan, Bruce E

    2004-07-15

    Metal oxides can increase the adhesion of negatively-charged bacteria to surfaces primarily due to their positive charge. However, the hydrophobicity of a metal-oxide surface can also increase adhesion of bacteria. In order to understand the relative contribution of charge and hydrophobicity to bacterial adhesion, we measured the adhesion of 8 strains of bacteria, under conditions of low and high-ionic strength (1 and 100 mM, respectively) to 11 different surfaces and examined adhesion as a function of charge, hydrophobicity (water contact angle) and surface energy. Inorganic surfaces included three uncoated glass surfaces and eight metal-oxide thin films prepared on the upper (non-tin-exposed) side of float glass by chemical vapor deposition. The Gram-negative bacteria differed in lengths of lipopolysaccharides on their outer surface (three Escherichia coli strains), the amounts of exopolysaccharides (two Pseudomonas aeruginosa strains), and their known relative adhesion to sand grains (two Burkholderia cepacia strains). One Gram positive bacterium was also used that had a lower adhesion to glass than these other bacteria (Bacillus subtilis). For all eight bacteria, there was a consistent increase in adhesion between with the type of inorganic surface in the order: float glass exposed to tin (coded here as Si-Sn), glass microscope slide (Si-m), uncoated air-side float glass surface (Si-a), followed by thin films of (Co(1-y-z)Fe(y)Cr(z))3O4, Ti/Fe/O, TiO2, SnO2, SnO2:F, SnO2:Sb, A1(2)O3, and Fe2O3 (the colon indicates metal doping, a slash indicates that the metal is a major component, while the dash is used to distinguish surfaces). Increasing the ionic strength from 1 to 100 mM increased adhesion by a factor of 2.0 +/- 0.6 (73% of the sample results were within the 95% CI) showing electrostatic charge was important in adhesion. However, adhesion was not significantly correlated with bacterial charge and contact angle. Adhesion (A) of the eight strains was

  2. Reactions of metal ions at surfaces of hydrous iron oxide

    Science.gov (United States)

    Hem, J.D.

    1977-01-01

    Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

  3. New perspectives on thermal and hyperthermal oxidation of silicon surfaces

    Science.gov (United States)

    Khalilov, Umedjon

    The growth of (ultra)thin silica (SiO2) layers on crystalline silicon (c-Si) and controlling the thickness of SiO2 is an important issue in the fabrication of microelectronics and photovoltaic devices (e.g., MOSFETs, solar cells, optical fibers etc.). Such ultrathin oxide can be grown and tuned even at low temperature (including room temperature), by hyperthermal oxidation or when performed on non-planar Si surfaces (e.g., Si nanowires or spheres). However, hyperthermal silica growth as well as small Si-NW oxidation in general and the initial stages in particular have not yet been investigated in full detail. This work is therefore devoted to controlling ultrathin silica thickness on planar and non-planar Si surfaces, which can open new perspectives in nanodevice fabrication. The simulation of hyperthermal (1-100 eV) Si oxidation demonstrate that at low impact energy (nanotechnology. Above the transition temperature such core-shell nanowires are completely converted to a-SiO2 nanowires. It can be concluded that an accurate control over the interfacial stress by choosing a suitable oxidation temperature and Si-NW diameter can lead to precise nanoscale control over the Si-core radius. All investigations were carried out by applying molecular dynamics calculations using the ReaxFF potential, allowing a accurately study of the underpinning physical and chemical processes.

  4. The role of probe oxide in local surface conductivity measurements

    Energy Technology Data Exchange (ETDEWEB)

    Barnett, C. J.; Kryvchenkova, O.; Wilson, L. S. J.; Maffeis, T. G. G.; Cobley, R. J. [Multidisciplinary Nanotechnology Centre, College of Engineering, Swansea University, Singleton Park, Swansea SA2 8PP (United Kingdom); Kalna, K. [Electronic Systems Design Centre, College of Engineering, Swansea University, Singleton Park, Swansea SA2 8PP (United Kingdom)

    2015-05-07

    Local probe methods can be used to measure nanoscale surface conductivity, but some techniques including nanoscale four point probe rely on at least two of the probes forming the same low resistivity non-rectifying contact to the sample. Here, the role of probe shank oxide has been examined by carrying out contact and non-contact I V measurements on GaAs when the probe oxide has been controllably reduced, both experimentally and in simulation. In contact, the barrier height is pinned but the barrier shape changes with probe shank oxide dimensions. In non-contact measurements, the oxide modifies the electrostatic interaction inducing a quantum dot that alters the tunneling behavior. For both, the contact resistance change is dependent on polarity, which violates the assumption required for four point probe to remove probe contact resistance from the measured conductivity. This has implications for all nanoscale surface probe measurements and macroscopic four point probe, both in air and vacuum, where the role of probe oxide contamination is not well understood.

  5. Formation, Removal, and Reformation of Surface Coatings on Various Metal Oxide Surfaces Inspired by Mussel Adhesives.

    Science.gov (United States)

    Kang, Taegon; Oh, Dongyeop X; Heo, Jinhwa; Lee, Han-Koo; Choy, Seunghwan; Hawker, Craig J; Hwang, Dong Soo

    2015-11-11

    Mussels survive by strongly attaching to a variety of different surfaces, primarily subsurface rocks composed of metal oxides, through the formation of coordinative interactions driven by protein-based catechol repeating units contained within their adhesive secretions. From a chemistry perspective, catechols are known to form strong and reversible complexes with metal ions or metal oxides, with the binding affinity being dependent on the nature of the metal ion. As a result, catechol binding with metal oxides is reversible and can be broken in the presence of a free metal ion with a higher stability constant. It is proposed to exploit this competitive exchange in the design of a new strategy for the formation, removal, and reformation of surface coatings and self-assembled monolayers (SAM) based on catechols as the adhesive unit. In this study, catechol-functionalized tri(ethylene oxide) (TEO) was synthesized as a removable and recoverable self-assembled monolayer (SAM) for use on oxides surfaces. Attachment and detachment of these catechol derivatives on a variety of surfaces was shown to be reversible and controllable by exploiting the high stability constant of catechol to soluble metal ions, such as Fe(III). This tunable assembly based on catechol binding to metal oxides represents a new concept for reformable coatings with applications in fields ranging from friction/wettability control to biomolecular sensing and antifouling.

  6. Optimum conditions for fabricating superhydrophobic surface on copper plates via controlled surface oxidation and dehydration processes

    Science.gov (United States)

    Zhang, Yan; Li, Wen; Ma, Fumin; Yu, Zhanlong; Ruan, Min; Ding, Yigang; Deng, Xiangyi

    2013-09-01

    The superhydrophobic surfaces on copper substrate were fabricated by direct oxidation and dehydration processes, and the reaction and modification conditions were optimized. Firstly, the oxidation conditions including the concentrations of K2S2O8 and NaOH, the oxidation time were studied. It is found that the superhydrophobicity would be better if the copper plates were oxidized in 0.06 M K2S2O8 and 3.0 M NaOH solution at 65 °C for 35 min. Then, the modification conditions including modifier concentration and modification time were investigated. The results showed that 5 wt% lauric acid and 1 h modification time were suitable modification conditions for preparing copper-based superhydrophobic surfaces. The surface fabricated under optimized conditions displayed excellent superhydrophobicity of high water contact angle of 161.1° and a low contact angle hysteresis of 2.5°. The surface microstructure and composition of the superhydrophobic surfaces were also characterized by SEM and FT-IR. It is found that the highly concentrated micro/nanostructured sheets and the low surface energy materials on the surface should be responsible for the high superhydrophobicity.

  7. Macromolecular surface design: photopatterning of functional stable nitrile oxides.

    Science.gov (United States)

    Altintas, Ozcan; Glassner, Mathias; Rodriguez-Emmenegger, Cesar; Welle, Alexander; Trouillet, Vanessa; Barner-Kowollik, Christopher

    2015-05-04

    The efficient trapping of photogenerated thioaldehydes with functional shelf-stable nitrile oxides in a 1,3-dipolar cycloaddition is a novel and versatile photochemical strategy for polymer end-group functionalization and surface modification under mild and equimolar conditions. The modular ligation in solution was followed in detail by electrospray ionization mass spectrometry (ESI-MS). X-ray photoelectron spectroscopy (XPS) was employed to analyze the functionalized surfaces, whereas time-of-flight secondary-ion mass spectrometry (ToF-SIMS) confirmed the spatial control of the surface functionalization using a micropatterned shadow mask. Polymer brushes were grown from the surface in a spatially confined regime by surface-initiated atom transfer radical polymerization (SI-ATRP) as confirmed by TOF-SIMS, XPS as well as ellipsometry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Trends in Metal Oxide Stability for Nanorods, Nanotubes, and Surfaces

    DEFF Research Database (Denmark)

    Mowbray, Duncan; Martinez, Jose Ignacio; Vallejo, Federico Calle;

    2011-01-01

    The formation energies of nanostructures play an important role in determining their properties, including their catalytic activity. For the case of 15 different rutile and 8 different perovskite metal oxides, we used density functional theory (DFT) to calculate the formation energies of (2......,2) nanorods, (3,3) nanotubes, and the (110) and (100) surfaces. These formation energies can be described semiquantitatively (mean absolute error ≈ 0.12 eV) by the fraction of metal−oxygen bonds broken and the metal d-band and p-band centers in the bulk metal oxide....

  9. Mechanical Properties of Glass Surfaces Coated with Tin Oxide

    DEFF Research Database (Denmark)

    Swindlehurst, W. E.; Cantor, B.

    1978-01-01

    of tin tetrachloride on industrial soda glass at ~800K to thicknesses of ~3×10-8 and 3×10 -7 m, commercially by the `titanising' process on industrial soda glass at ~800K to a thickness of ~3.10-9 m, and in the laboratory by radio frequency sputtering from tin oxide powder over a range of glass......The effect of tin oxide coatings on the coefficient of friction and fracture strength of glass surfaces is studied. Experiments were performed partly on commercially treated glass bottles and partly on laboratory prepared microscope slides. Coatings were applied in the laboratory by decomposition...

  10. Role of oxidation on surface conductance of the topological insulator Bi2Te2Se

    Science.gov (United States)

    Hwang, Jin Heui; Park, Joonbum; Kwon, Sangku; Kim, Jun Sung; Park, Jeong Young

    2014-12-01

    We investigated the effect of surface oxides on charge transport properties in a topological insulator (Bi2Te2Se) using conductive probe atomic force microscopy in an ultrahigh vacuum environment. Uniform distribution of the measured friction and current were observed over a single quintuple layer terrace after exposure to the ambient environment, which is an indication of uniform surface oxide coverage. An oxide-free topological insulator surface was exposed using tip-induced etching. By comparing surface conduction on a fresh surface versus a surface exposed to air, we observed a minor change in resistance when surface oxide was present. The current density varied with applied load on the oxidized surface, which implies that the topological surface states respond to tip-induced pressure even though surface oxide is present. From these results, we conclude that surface oxidation in air has a negligible effect on surface conductance in topological insulators.

  11. Molecularly imprinted Ru complex catalysts integrated on oxide surfaces.

    Science.gov (United States)

    Muratsugu, Satoshi; Tada, Mizuki

    2013-02-19

    Selective catalysis is critical for the development of green chemical processes, and natural enzymes that possess specialized three-dimensional reaction pockets with catalytically active sites represent the most sophisticated systems for selective catalysis. A reaction space in an enzyme consists of an active metal center, functional groups for molecular recognition (such as amino acids), and a surrounding protein matrix to prepare the reaction pocket. The artificial design of such an integrated catalytic unit in a non-enzymatic system remains challenging. Molecular imprinting of a supported metal complex provides a promising approach for shape-selective catalysis. In this process, an imprinted cavity with a shape matched to a template molecule is created in a polymer matrix with a catalytically active metal site. In this Account, we review our studies on molecularly imprinted metal complex catalysts, focusing on Ru complexes, on oxide surfaces for shape-selective catalysis. Oxide surface-attached transition metal complex catalysts not only improve thermal stability and catalyst dispersion but also provide unique catalytic performance not observed in homogeneous precursors. We designed molecularly imprinted Ru complexes by using surface-attached Ru complexes with template ligands and inorganic/organic surface matrix overlayers to control the chemical environment around the active metal complex catalysts on oxide surfaces. We prepared the designed, molecularly imprinted Ru complexes on SiO(2) surfaces in a step-by-step manner and characterized them with solid-state (SS) NMR, diffuse-reflectance (DR) UV-vis, X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller isotherm (BET), X-ray fluorescence (XRF), and Ru K-edge extended X-ray absorption fine structure (EXAFS). The catalytic performances of these Ru complexes suggest that this process of molecular imprinting facilitates the artificial integration of catalytic functions at surfaces. Further advances such

  12. Sorption, desorption, and surface oxidative fate of nicotine.

    Science.gov (United States)

    Petrick, Lauren; Destaillats, Hugo; Zouev, Irena; Sabach, Sara; Dubowski, Yael

    2010-09-21

    Nicotine dynamics in an indoor environment can be greatly affected by building parameters (e.g. relative humidity (RH), air exchange rate (AER), and presence of ozone), as well as surface parameters (e.g. surface area (SA) and polarity). To better understand the indoor fate of nicotine, these parameter effects on its sorption, desorption, and oxidation rates were investigated on model indoor surfaces that included fabrics, wallboard paper, and wood materials. Nicotine sorption under dry conditions was enhanced by higher SA and higher polarity of the substrate. Interestingly, nicotine sorption to cotton and nylon was facilitated by increased RH, while sorption to polyester was hindered by it. Desorption was affected by RH, AER, and surface type. Heterogeneous nicotine-ozone reaction was investigated by Fourier transform infrared spectrometry with attenuated total reflection (FTIR-ATR), and revealed a pseudo first-order surface reaction rate of 0.035 +/- 0.015 min(-1) (at [O(3)] = 6 +/- 0.3 x 10(15) molecules cm(-3)) that was partially inhibited at high RH. Extrapolation to a lower ozone level ([O(3)] = 42 ppb) showed oxidation on the order of 10(-5) min(-1) corresponding to a half-life of 1 week. In addition, similar surface products were identified in dry and high RH using gas chromatography-mass spectrometry (GC-MS). However, FTIR analysis revealed different product spectra for these conditions, suggesting additional unidentified products and association with surface water. Knowing the indoor fate of condensed and gas phase nicotine and its oxidation products will provide a better understanding of nicotine's impact on personal exposures as well as overall indoor air quality.

  13. Ammonia modification of oxide-free Si(111) surfaces

    Science.gov (United States)

    Chopra, Tatiana Peixoto; Longo, Roberto C.; Cho, Kyeongjae; Chabal, Yves J.

    2016-08-01

    Amination of surfaces is useful in a variety of fields, ranging from device manufacturing to biological applications. Previous studies of ammonia reaction on silicon surfaces have concentrated on vapor phase rather than wet chemical processes, and mostly on clean Si surfaces. In this work, the interaction of liquid and vapor-phase ammonia is examined on three types of oxide-free surfaces - passivated by hydrogen, fluorine (1/3 monolayer) or chlorine - combining infrared absorption spectroscopy, X-ray photoelectron spectroscopy, and first-principles calculations. The resulting chemical composition highly depends on the starting surface; there is a stronger reaction on both F- and Cl-terminated than on the H-terminated Si surfaces, as evidenced by the formation of Si-NH2. Side reactions can also occur, such as solvent reaction with surfaces, formation of ammonium salt by-products (in the case of 0.2 M ammonia in dioxane solution), and nitridation of silicon (in the case of neat and gas-phase ammonia reactions for instance). Unexpectedly, there is formation of Si-H bonds on hydrogen-free Cl-terminated Si(111) surfaces in all cases, whether vapor phase of neat liquid ammonia is used. The first-principles modeling of this complex system suggests that step-edge surface defects may play a key role in enabling the reaction under certain circumstances, despite the endothermic nature for Si-H bond formation.

  14. Mechanism of glucose electrochemical oxidation on gold surface

    KAUST Repository

    Pasta, Mauro

    2010-08-01

    The complex oxidation of glucose at the surface of gold electrodes was studied in detail in different conditions of pH, buffer and halide concentration. As observed in previous studies, an oxidative current peak occurs during the cathodic sweep showing a highly linear dependence on glucose concentration, when other electrolyte conditions are unchanged. The effect of the different conditions on the intensity of this peak has stressed the limitations of the previously proposed mechanisms. A mechanism able to explain the presence of this oxidative peak was proposed. The mechanism takes into account ion-sorption and electrochemical adsorption of OH-, buffer species (K2HPO4/KH2PO4) and halides. © 2010 Elsevier Ltd. All rights reserved.

  15. Solubility of vanadium from manganese vanadates in aqueous solutions of soda ash

    Science.gov (United States)

    Khalezov, B. D.; Krasheninin, A. G.; Vatolin, N. A.; Ovchinnikova, L. A.

    2016-05-01

    It is shown that, in the course of developing the technology of pure vanadium pentoxide preparation from manganic vanadium-containing metallurgical slags, their oxidative roasting and cinder formation without alkaline additives are accompanied by the decomposition of spinelides with the formation of manganese meta- and pyrovanadates. Concentrated aqueous solutions of soda ash with an Na2CO3 concentration of 120-150 g/dm3 are accepted as a selective leaching reagent for vanadium from a cinder. Manganese metaand pyrovanadates are synthesized, and the procedure of their preparation is presented. The solubility of vanadium from manganese vanadates in aqueous solutions of soda ash at C_{Na_2 CO_3 } = 150 g/dm^3 is studied at 20-95°C for pyrovanadate and at 85-95°C for metavanadate. It is shown that vanadium should be leached from converter manganic slags roasted without alkaline metal additives at a leaching solution temperature higher than 95°C. There is a possibility to increase the vanadium content in a leaching solution to 60-80 g/dm3. The results obtained are used in the development of the technology of vanadium leaching.

  16. Oxide cathode mechanisms: Electronic and structural features of oxide cathode surfaces

    Science.gov (United States)

    Cunningham, J.; Nunan, J.

    1985-01-01

    This report describes studies made upon systems selected for their ability to model various important features of oxide cathodes and the mechanisms which enable them to function as efficient thermionic emitters at moderate temperatures. An account is given of experiments which aimed to simulate conditions upon the surfaces of polycrystalline samples of alkaline earth oxides (e.g., SrO and BaO/SrO or MgO and BaO/MgO) at various stages of their preparation in similiar fashion to that used in the thermal activation of oxide cathodes. Accounts are given of experiments which examined the interaction between the gases O2, N2O, H2 or Ch4 and appropriately preactivated surface of pure and mixed alkaline earth oxide samples. Accounts are given of experiments involving the controlled deposition in UHV conditions of zero-valent Ba ad-atoms-in amounts ranging from submonolayer to multilayer coverage - upon layers of SrO or BaO previously prepared in UHV conditions by evaporation of the corresponding metal and its subsequent oxidation. UPS spectra have been undertaken in order to examine surfaces of samples prepared by evaporation of barium metal or strontium metal and to study effects upon the UPS spectra by exposures to the gases N20, O2 and CH4.

  17. Kinetics and Mechanisms of Ciprofloxacin Oxidation on Hematite Surfaces.

    Science.gov (United States)

    Martin, Sébastien; Shchukarev, Andrey; Hanna, Khalil; Boily, Jean-François

    2015-10-20

    Adsorption of antibiotics at mineral surfaces has been extensively studied over the past 20 years, yet much remains to be learned on their interfacial properties and transformation mechanisms. In this study, interactions of Ciprofloxacin (CIP), a fluoroquinolone antibiotic with two sets of synthetic nanosized hematite particles, with relatively smooth (H10, 10-20 nm in diameter) and roughened (H80, 80-90 nm in diameter) surfaces, were studied by means of liquid chromatography (LC), mass spectrometry (MS), and spectroscopy (vibration and X-ray photoelectron). Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy provides evidence for inner-sphere bidentate complex formation of CIP at hematite surfaces in 0.01 M NaCl, irrespective of pH and particle size. ATR-FTIR spectroscopy also revealed that the sorbed mother CIP molecule decayed to other surface species over a period of at least 65 h. This was supported by the detection of three daughter products in the aqueous phase by LC/MS. The appearance of NH3(+) groups during the course of these experiments, revealed by cryogenic XPS, provides further evidence that CIP oxidation proceeds through an opening of piperazine ring via N-dealkylation. Additional in vacuo FTIR experiments under temperature-programmed desorption also showed that oxidation of sorbed byproducts were effectively degraded beyond 450 °C, a result denoting considerably strong (inter)molecular bonds of both mother and daughter products. This work also showed that rougher, possibly multidomainic particles (H80) generated slower rates of CIP decomposition but occurring through more complex schemes than at smoother particle surfaces (H10). This work thus uncovered key aspects of the binding of an important antibiotic at iron oxide surfaces, and therefore provided additional constraints to our growing understanding of the fate of emerging contaminants in the environment.

  18. Band energy control of molybdenum oxide by surface hydration

    Energy Technology Data Exchange (ETDEWEB)

    Butler, Keith T., E-mail: k.t.butler@bath.ac.uk; Walsh, Aron [Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Crespo-Otero, Rachel [School of Biological and Chemical Sciences, Queen Mary University London, Mile End Road, London E1 4NS (United Kingdom); Buckeridge, John; Scanlon, David O. [University College London, Kathleen Lonsdale Materials Chemistry, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Bovill, Edward; Lidzey, David [Department of Physics and Astronomy, University of Sheffield, Hicks Building, Hounsfield Road, Sheffield S3 7RH (United Kingdom)

    2015-12-07

    The application of oxide buffer layers for improved carrier extraction is ubiquitous in organic electronics. However, the performance is highly susceptible to processing conditions. Notably, the interface stability and electronic structure is extremely sensitive to the uptake of ambient water. In this study we use density functional theory calculations to asses the effects of adsorbed water on the electronic structure of MoO{sub x}, in the context of polymer-fullerene solar cells based on PCDTBT. We obtain excellent agreement with experimental values of the ionization potential for pristine MoO{sub 3} (010). We find that IP and EA values can vary by as much as 2.5 eV depending on the oxidation state of the surface and that adsorbed water can either increase or decrease the IP and EA depending on the concentration of surface water.

  19. Designing porous metallic glass compact enclosed with surface iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Jae Young; Park, Hae Jin; Hong, Sung Hwan; Kim, Jeong Tae; Kim, Young Seok; Park, Jun-Young; Lee, Naesung [Hybrid Materials Center (HMC), Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul 143-747 (Korea, Republic of); Seo, Yongho [Graphene Research Institute (GRI) & HMC, Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul 143-747 (Korea, Republic of); Park, Jin Man, E-mail: jinman_park@hotmail.com [Global Technology Center, Samsung Electronics Co., Ltd, 129 Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do 443-742 (Korea, Republic of); Kim, Ki Buem, E-mail: kbkim@sejong.ac.kr [Hybrid Materials Center (HMC), Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul 143-747 (Korea, Republic of)

    2015-06-25

    Highlights: • Porous metallic glass compact was developed using electro-discharge sintering process. • Uniform PMGC can only be achieved when low electrical input energy was applied. • Functional iron-oxides were formed on the surface of PMGCs by hydrothermal technique. - Abstract: Porous metallic glass compact (PMGC) using electro-discharge sintering (EDS) process of gas atomized Zr{sub 41.2}Ti{sub 13.8}Cu{sub 12.5}Ni{sub 10}Be{sub 22.5} metallic glass powder was developed. The formation of uniform PMGC can only be achieved when low electrical input energy was applied. Functional iron-oxides were formed on the surface of PMGCs by hydrothermal technique. This finding suggests that PMGC can be applied in the new area such as catalyst via hydrothermal technique and offer a promising guideline for using the metallic glasses as a potential functional application.

  20. SURFACE-MODIFICATION OF FINE RED IRON OXIDE PIGMENT

    Institute of Scientific and Technical Information of China (English)

    Shuilin Zheng; Qinghui Zhang

    2003-01-01

    Surface-modification of fine red iron oxide pigment was carried out in an aqueous solution of sodium polyacrylate. The sedimentation time of modified samples in water increased from 1.05 to 264.4 hours while the particle size (d50) decreased from 1.09 to 0.85 μm, and the tinting strength increased from 100 to 115. The surface-modification as well as the dispersing and stabilizing mechanisms in aqueous solution of the samples were studied by means of IR,Thermal analysis and Zeta potential. The results showed that the modifier molecules acted on the surface of the particles by chemical and physical adsorption, and after the particles were dispersed in aqueous solution, endowing the particle surface with a relatively high negative Zeta potential, thus enhancing electrostatic and steric repulsion between particles for their effective stabilization.

  1. In Situ Atomic Scale Visualization Of Surface Kinetics Driven Dynamics Of Oxide Growth On A Ni–Cr Surface

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Langli; Zou, Lianfeng; Schreiber, Daniel K.; Olszta, Matthew J.; Baer, Donald R.; Bruemmer, Stephen M.; Zhou, Guangwen; Wang, Chong M.

    2016-01-20

    We report in situ atomic-scale visualization of the dynamical three-dimensional (3D) growth of NiO during initial oxidation of Ni-10at%Cr using environmental transmission electron microscopy (ETEM). Despite the thermodynamic preference for Cr2O3 formation, cubic NiO oxides nucleated and grew epitaxially as the dominating oxide phase on the Ni-Cr (100) surface during initial oxidation. The growth of NiO islands proceeds through step-by-step adatom mechanism in 3D, which is sustained by surface diffusion of Ni and O atoms. Although the shapes of oxide islands are controlled by strain energy between oxide and alloy substrate, local surface kinetic variations can lead to the change of surface planes of oxide islands. These results demonstrate that surface diffusion dominates initial oxidation of Ni-Cr in these test conditions.

  2. Effect of Surface Treatments on Leakage of Zirconium Oxide Ceramics

    OpenAIRE

    Göknil Alkan Demetoğlu; Mustafa Zortuk

    2016-01-01

    Objective: The aim of this pilot study was to compare the effects of pretreatments on leakage of zirconia ceramics. Materials and Methods: The speciments divided into 6 groups that were subsequently treated as follows: group 1, no treatment (control); group 2, the ceramic surfaces were airborne-particle abraded with 110 μm aluminum-oxide (Al2O3) particles; group 3, after abrasion of the surfaces with 110 μm Al2O3 particles, silica coating using 30 μm (Al2O3) particles modified by silica (r...

  3. Adsorption and surface oxidation of Fe(II) on metal (hydr)oxides.

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.

    2007-01-01

    The Fe(II) adsorption by non-ferric and ferric (hydr)oxides has been analyzed with surface complexation modeling. The CD model has been used to derive the interfacial distribution of charge. The fitted CD coefficients have been linked to the mechanism of adsorption. The Fe(II) adsorption is

  4. Effect of surface oxidation on the surface condition and deuterium permeability of a palladium membrane

    Energy Technology Data Exchange (ETDEWEB)

    Feng Wei [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China); Chengdu University, Chengdu, 610106 (China); Liu Ying, E-mail: liuying5536@163.com [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China); Lian Lixian [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China); Peng Lixia [National Key Laboratory for Surface Physics and Chemistry, Mianyang, 621907 (China); Li Jun [School of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China)

    2011-09-15

    Oxidation and deoxidation of a Pd membrane was conducted in a quartz tube oven in a temperature range of 23-500 deg. C. The micromorphology and chemical composition of the Pd membrane surface was characterized using scanning electronic microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Micropores and PdO began to form on the Pd membrane surface after oxidation at 240 deg. C for 1 h and their quantity increased gradually with increasing temperature. A rough Pd membrane surface was obtained when the temperature rose to 500 deg. C. The PdO on the Pd membrane surface was completely deoxidized once more using H{sub 2} at room temperature, but the rough surface morphology caused by oxidation remained. The deuterium permeability of the Pd membrane was tested using special equipment in the China National Key Laboratory and the results indicated that the rough Pd membrane surface had higher deuterium permeability than the original membrane. The improved deuterium permeability could be attributed to the higher Pd membrane surface area, which provided deuterium atoms with more adsorption sites and dissociation sites.

  5. Surface composition and catalytic activity of La-Fe mixed oxides for methane oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Fengxiang [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China); Li, Zhanping [Analysis Center, Tsinghua University, Beijing 100084 (China); Ma, Hongwei [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China); Gao, Zhiming, E-mail: zgao@bit.edu.cn [School of Chemistry, Beijing Institute of Technology, Liangxiang East Road, Beijing 102488 (China)

    2015-10-01

    Graphical abstract: - Highlights: • The sample with La/Fe atomic ratio of 0.94 is single phase perovskite La{sub 0.94}FeO{sub 3−d}. • The excess ironic oxide exists on the surface of the perovskite crystallites. • La{sup 3+} ions are enriched on surface of the oxides even for the La{sub 0.68}Fe sample. - Abstract: Four La-Fe oxide samples with La/Fe atomic ratio y = 1.02 ∼ 0.68 (denoted as LayFe) were prepared by the citrate method. The samples had a decreased specific surface area with the La/Fe atomic ratio decreasing. XRD pattern proved that the sample La{sub 0.94}Fe is single phase perovskite La{sub 0.94}FeO{sub 3−d}. Phase composition of the samples was estimated by the Rietveld refinement method. XPS analyses indicate that La{sup 3+} ions are enriched on surface of crystallites for all the samples, and surface carbonate ions are relatively abundant on the samples La{sub 1.02}Fe and La{sub 0.94}Fe. Catalytic activity for methane oxidation per unit surface area of the samples is in the order of La{sub 0.68}Fe > La{sub 0.76}Fe > La{sub 0.94}Fe > La{sub 1.02}Fe both in the presence and in the absence of gaseous oxygen. A reason for this order would be the higher concentration of Fe{sup 3+} ion on the surface of the samples La{sub 0.68}Fe and La{sub 0.76}Fe.

  6. Adsorption of T4 bacteriophages on planar indium tin oxide surface via controlled surface tailoring.

    Science.gov (United States)

    Liana, Ayu Ekajayanthi; Chia, Ed Win; Marquis, Christopher P; Gunawan, Cindy; Gooding, J Justin; Amal, Rose

    2016-04-15

    The work investigates the influence of surface physicochemical properties of planar indium tin oxide (ITO) as a model substrate on T4 bacteriophage adsorption. A comparative T4 bacteriophage adsorption study shows a significant difference in bacteriophage adsorption observed on chemically modified planar ITO when compared to similarly modified particulate ITO, which infers that trends observed in virus-particle interaction studies are not necessarily transferrable to predict virus-planar surface adsorption behaviour. We also found that ITO surfaces modified with methyl groups, (resulting in increased surface roughness and hydrophobicity) remained capable of adsorbing T4 bacteriophage. The adsorption of T4 onto bare, amine and carboxylic functionalised planar ITO suggests the presence of a unique binding behaviour involving specific functional groups on planar ITO surface beyond the non-specific electrostatic interactions that dominate phage to particle interactions. The paper demonstrates the significance of physicochemical properties of surfaces on bacteriophage-surface interactions.

  7. Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

    Science.gov (United States)

    Choi, J.; Ji, M. K.; Yun, H. S.; Park, Y. T.; Gee, E. D.; Lee, W. R.; Jeon, B.-H.

    2012-04-01

    Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to

  8. Separation of Impurity Vanadium from TiCl4 by Means of Adsorption

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The possibility and extent of the separation of impurity vanadium in titanium tetrachloride by means of adsorption with molecular sieves were studied. As ascertained by the experimental results, the adsorption of VOCl3 onto molecular sieve internal surface was controlled by the intraparticle diffusion of the molecules. Although all of the three kinds of molecular sieves used are competent for removing vanadium from titanium tetrachloride, type 4 A behaves more effectively than the others under the same conditions. After adsorption for nine stages, the concentration of vanadium in the product becomes as less as that of industrial standard level.

  9. Surface modification of promising cerium oxide nanoparticles for nanomedicine applications

    KAUST Repository

    Nanda, Himansu Sekhar

    2016-11-14

    Cerium oxide nanoparticles (CNPs) or nanoceria have emerged as a potential nanomedicine for the treatment of several diseases such as cancer. CNPs have a natural tendency to aggregate or agglomerate in their bare state, which leads to sedimentation in a biological environment. Since the natural biological environment is essentially aqueous, nanoparticle surface modification using suitable biocompatible hydrophilic chemical moieties is highly desirable to create effective aqueous dispersions. In this report, (6-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-hexyl)triethoxysilane was used as a functional, biocompatible organosilane to modify the surface of CNPs to produce promising nanoparticles which open substantial therapeutic avenues. The surface modified nanoparticles were produced in situ via an ammonia-induced ethylene glycol-assisted precipitation method and were characterized using complimentary characterization techniques. The interaction between the functional moiety and the nanoparticle was studied using powerful cross polarization/magic angle sample spinning solid state nuclear magnetic resonance spectroscopy. The surface-modified nanoparticles were extremely small and demonstrated a significant improvement in aqueous dispersibility. Moreover, the existence of a strong ionic coordination between the functional moiety and the surface of the nanoparticle was realised, indicating that the surface modified nanoceria are stable and that the nanoparticles should demonstrate an enhanced circulation time in a biological environment. The surface modification approach should be promising for the production of CNPs for nanomedicine applications. © The Royal Society of Chemistry.

  10. Microarc Oxidation of Product Surfaces without Using a Bath

    Directory of Open Access Journals (Sweden)

    V. K. Shatalov

    2015-01-01

    Full Text Available While using an electrochemical method to cover the large-sized work-pieces, units, and products up to 6 м3 by protective coating, there is a certain difficulty to apply traditional anodizing techniques in a plating vat, and it is necessary to find various processing techniques.To use the existing micro-arc oxide coating (MOC methods for work-pieces of various forms and sizes in a plating vat is complicated in case it is required to provide oxide layers in separate places rather than over entire surface of a work-piece. The challenge is to treat flat surfaces in various directions, external and internal surfaces of rotation bodies, profiled surfaces, intersections, closed and through holes, pipes, as well as spline and thread openings for ensuring anti-seize properties in individual or small-scale production to meet technical requirements and operational properties of products.A design of tools to provide MOC-process of all possible surfaces of various engineering box-type products depends on many factors and can be considerably different even when processing the surfaces of the same forms. An attachment to be used is fixed directly on a large-sized design (a work-piece, a product or fastened in the special tool. The features of technological process, design shape, and arrangement of the processed surfaces define a fastening method of the attachment. Therefore it is necessary to pay much attention to a choice of the processing pattern and a design of tools.The Kaluga-branch of Bauman Moscow State Technical University is an original proposer of methods to form MOC-coatings on the separate surfaces of large-sized work-pieces using the moved and stationary electrodes to solve the above listed tasks.The following results of work will have an impact on development of the offered processing methods and their early implementation in real production:1. To provide oxide coatings on the surfaces of large-sized products or assemblies in a single or small

  11. Fabrication of anodic aluminium oxide templates on curved surfaces.

    Science.gov (United States)

    Yin, Aijun; Guico, Rodney S; Xu, Jimmy

    2007-01-24

    Aluminium anodization provides a simple and inexpensive way to obtain nanoporous templates with uniform and controllable pore diameters and periods over a wide range. Moreover, one of the interesting possibilities afforded by the anodization process is that the anodization can take place on arbitrary surfaces, such as curved surfaces, which has not yet been well studied or applied in nanofabrication. In this paper, we characterize the anodization of Al films on silicon substrates with a curved top surface. The structures of the resultant anodic aluminium oxide (AAO) films are examined by scanning electron microscopy. Unique features including cessation, bending, and branching of pore channels are observed in the curved area. Possible growth mechanisms are proposed, which can also contribute to the understanding of the self-organization mechanism in the formation of porous AAO membranes. The new structures may open new opportunities in optical, electronic and electrochemical applications.

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

    Directory of Open Access Journals (Sweden)

    Keisuke Shibuya

    2015-10-01

    Full Text Available We systematically examined the effects of the substrate temperature (TS and the oxygen pressure (PO2 on the structural and optical properties polycrystalline V O2 films grown directly on Si(100 substrates by pulsed-laser deposition. A rutile-type V O2 phase was formed at a TS ≥ 450 °C at PO2 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 O2 films significantly increased at growth temperatures of 550 °C or more due to agglomeration of V O2 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 O2 films grown at a TS 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 TS and PO2, and was maximal for a V O2 film grown at 450 °C under 20 mTorr. Based on the results, we derived the PO2 versus 1/TS phase diagram for the films of vanadium oxides, which will provide a guide to optimizing the conditions for growth of V O2 films on silicon platforms.

  13. Nonuniform Oxidation on the Surface of Fuel Element in HTR

    Directory of Open Access Journals (Sweden)

    Peng Liu

    2016-01-01

    Full Text Available The graphite oxidation of fuel element has obtained high attention in air ingress accident analysis of high temperature gas-cooled reactor (HTR. The shape function, defined as the relationship between the maximum and the average of the oxidation, is an important factor to estimate the consequence of the accident. There are no detailed studies on the shape function currently except two experiments several decades ago. With the development of computer technology, CFD method is used in the numerical experiment about graphite oxidation in pebble bed of HTR in this paper. Structured packed beds are used in the calculation instead of random packed beds. The result shows the nonuniform distribution of oxidation on the sphere surface and the shape function in the condition of air ingress accident. Furthermore, the sensitive factors of shape function, such as temperature and Re number, are discussed in detail and the relationship between the shape function and sensitive factors is explained. According to the results in this paper, the shape function ranges from 1.05 to 4.7 under the condition of temperature varying from 600°C to 1200°C and Re varying from 16 to 1600.

  14. Ozone Decomposition on the Surface of Metal Oxide Catalyst

    Directory of Open Access Journals (Sweden)

    Batakliev Todor Todorov

    2014-12-01

    Full Text Available The catalytic decomposition of ozone to molecular oxygen over catalytic mixture containing manganese, copper and nickel oxides was investigated in the present work. The catalytic activity was evaluated on the basis of the decomposition coefficient which is proportional to ozone decomposition rate, and it has been already used in other studies for catalytic activity estimation. The reaction was studied in the presence of thermally modified catalytic samples operating at different temperatures and ozone flow rates. The catalyst changes were followed by kinetic methods, surface measurements, temperature programmed reduction and IR-spectroscopy. The phase composition of the metal oxide catalyst was determined by X-ray diffraction. The catalyst mixture has shown high activity in ozone decomposition at wet and dry O3/O2 gas mixtures. The mechanism of catalytic ozone degradation was suggested.

  15. Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

    Science.gov (United States)

    Ishigaki, H.; Miyoshi, K.; Buckley, D. H.

    1982-01-01

    X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

  16. Multifunctional Indium Tin Oxide Electrode Generated by Unusual Surface Modification

    Science.gov (United States)

    Bouden, Sarra; Dahi, Antoine; Hauquier, Fanny; Randriamahazaka, Hyacinthe; Ghilane, Jalal

    2016-11-01

    The indium tin oxide (ITO) material has been widely used in various scientific fields and has been successfully implemented in several devices. Herein, the electrochemical reduction of ITO electrode in an organic electrolytic solution containing alkali metal, NaI, or redox molecule, N-(ferrocenylmethyl) imidazolium iodide, was investigated. The reduced ITO surfaces were investigated by X-ray photoelectron spectroscopy and grazing incident XRD demonstrating the presence of the electrolyte cation inside the material. Reversibility of this process after re-oxidation was evidenced by XPS. Using a redox molecule based ionic liquid as supporting electrolyte leads to fellow electrochemically the intercalation process. As a result, modified ITO containing ferrocenyl imidazolium was easily generated. This reduction process occurs at mild reducing potential around -1.8 V and causes for higher reducing potential a drastic morphological change accompanied with a decrease of the electrode conductivity at the macroscopic scale. Finally, the self-reducing power of the reduced ITO phase was used to initiate the spontaneous reduction of silver ions leading to the growth of Ag nanoparticles. As a result, transparent and multifunctional active ITO surfaces were generated bearing redox active molecules inside the material and Ag nanoparticles onto the surface.

  17. Ultralyophobic oxidized aluminum surfaces exhibiting negligible contact angle hysteresis.

    Science.gov (United States)

    Hozumi, Atsushi; McCarthy, Thomas J

    2010-02-16

    Ultralyophobic oxidized aluminum surfaces exhibiting negligible contact angle hysteresis for probe liquids were prepared by chemical vapor deposition (CVD) of bis((tridecafluoro-1,1,2,2,-tetrahydrooctyl)-dimethylsiloxy)methylsilane (CF(3)(CF(2))(5)CH(2)CH(2)Si(CH(3))(2)O)(2)SiCH(3)H, (R(F)Si(Me)(2)O)(2)SiMeH). Oxidized aluminum surfaces were prepared by photooxidation/cleaning of sputter-coated aluminum on silicon wafers (Si/Al(Al(2)(O(3)))) using oxygen plasma. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) confirmed that this facile CVD method produces a monolayer with a thickness of 1.1 nm on the Si/Al(Al(2)(O(3))) surface without a discernible change in surface morphology. After monolayer deposition, the hydrophilic Si/Al(Al(2)(O(3))) surface became both hydrophobic and oleophobic and exhibited essentially no contact angle hysteresis for water and n-hexadecane (advancing/receding contact angles (theta(A)/theta(R)) = 110 degrees/109 degrees and 52 degrees/50 degrees, respectively). Droplets move very easily on this surface and roll off of slightly tilted surfaces, independently of the contact angle (which is a practical definition of ultralyophobic). A conventional fluoroalkylsilane monolayer was also prepared from 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (CF(3)(CF(2))(7)CH(2)CH(2)Si(OCH(3))(3), R(F)Si(OMe)(3)) for comparison. The theta(A)/theta(R) values for water and n-hexadecane are 121 degrees/106 degrees and 76 degrees/71 degrees, respectively. The larger hysteresis values indicate the "pinning" of probe liquids, even though advancing contact angles are larger than those of the (R(F)Si(Me)(2)O)(2)SiMeH-derived monolayers. The (R(F)Si(Me)(2)O)(2)SiMeH-derived monolayers have excellent hydrolytic stability in water. We propose that the (R(F)Si(Me)(2)O)(2)SiMeH-derived monolayers are flexible and liquidlike and that drops in contact with these surfaces experience very low energy barriers between metastable states, leading to the

  18. Characterization of vanadium flow battery

    Energy Technology Data Exchange (ETDEWEB)

    Bindner, H.; Ekman, C.; Gehrke, O.; Isleifsson, F.

    2010-10-15

    This report summarizes the work done at Risoe DTU testing a vanadium flow battery as part of the project 'Characterisation of Vanadium Batteries' (ForskEl project 6555) with the partners PA Energy A/S and OI Electric A/S under the Danish PSO energy research program. A 15kW/120kWh vanadium battery has been installed as part of the distributed energy systems experimental facility, SYSLAB, at Risoe DTU. A test programme has been carried out to get hands-on experience with the technology, to characterize the battery from a power system point of view and to assess it with respect to integration of wind energy in the Danish power system. The battery has been in operation for 18 months. During time of operation the battery has not shown signs of degradation of performance. It has a round-trip efficiency at full load of approximately 60% (depending on temperature and SOC). The sources of the losses are power conversion in cell stacks/electrolyte, power converter, and auxiliary power consumption from pumps and controller. The response time for the battery is limited at 20kW/s by the ramp rate of the power converter. The battery can thus provide power and frequency support for the power system. Vanadium battery is a potential technology for storage based services to the power system provided investment and O and M cost are low enough and long term operation is documented. (Author)

  19. Positive Biomechanical Effects of Titanium Oxide for Sandblasting Implant Surface as an Alternative to Aluminium Oxide.

    Science.gov (United States)

    Gehrke, Sergio Alexandre; Taschieri, Silvio; Del Fabbro, Massimo; Coelho, Paulo Guilherme

    2015-10-01

    The aim of this study was to evaluate the physico-chemical properties and the in vivo host response of a surface sandblasted with particles of titanium oxide (TiO2) followed by acid etching as an alternative to aluminium oxide. Thirty titanium disks manufactured in the same conditions as the implants and 24 conventional cylindrical implants were used. Half of the implants had a machined surface (Gcon) while in the other half; the surface was treated with particles of TiO2 followed by acid etching (Gexp). Surface characterization was assessed by scanning electron microscope (SEM), energy dispersive X-ray spectrometry (EDS), profilometry, and wettability. For the in vivo test, 12 implants of each group were implanted in the tibia of 6 rabbits, and were reverse torque tested after periods of 30 or 60 days after implantation. Following torque, SEM was utilized to assess residual bone-implant contact. The surface characterization by SEM showed a very homogeneous surface with uniform irregularities for Gexp and a small amount of residues of the blasting procedure, while Gcon presented a surface with minimal irregularities from the machining tools. Wettability test showed decreased contact angle for the Gcon relative to the Gexp. The Gexp removal torque at 30 and 60 days was 28.7%, and 33.2% higher relative to the Gcon, respectively. Blasting the surface with particles of TiO2 represents an adequate option for the surface treatment of dental implants, with minimal risk of contamination by the residual debris from the blasting procedure.

  20. Infrared study of lower sulfur oxides on Io's surface

    Science.gov (United States)

    Baklouti, D.; Schmitt, B.; Brissaud, O.

    2004-11-01

    Sulfur dioxide, SO2, and sulfur monoxide, SO, are the only sulfur oxides that have been firmly identified in Io's atmosphere. While SO2, according to infrared observations, is ubiquitous on Io's surface and seems to widely dominate it, SO has never been found on the surface. In fact, contrary to SO2, SO is extremely reactive and unstable. It decomposes by disproportionation forming SO2 and S2O. This latter molecule, disulfur monoxide, is much more stable than SO and, depending on temperature and pressure conditions, it can, either, directly condense on the "cold" surface, or polymerize forming polysulfuroxides, or even, thermally decompose to SO2 and sulfur. Hapke (1989, Icarus 79, 47-74) measured the spectral reflectance of S2O and its resulting polymer over the range 200-1700 nm. Using Voyager observations, he tried to show that the spectral properties of Io can be matched by combinations of SO2, S2O, polysulfuroxide and basalt, but his model was controversial and since then, no experimental data on S2O and its polymer were added to confirm or definitely reject the possibility of the presence of these molecules on Io's surface. Thus, we have undertaken series of laboratory experiments to synthesize and measure the infrared spectra of S2O and its resulting polymeric sulfuroxides, under different temperature conditions and very low pressures. The results of these experiments will be presented and compared to NIMS/Galileo data. Then, the way of formation and possible presence of these lower sulfur oxides on Io's surface will be discussed.

  1. The Reduction of Aqueous Metal Species on the Surfaces of Fe(II)-Containing Oxides: The Role of Surface Passivation

    Science.gov (United States)

    White, A.F.; Peterson, M.L.

    1998-01-01

    The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

  2. An improved method of preparation of nanoparticular metal oxide catalysts

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...... combustible crystallization seeds upon which the catalyst metal oxide is coprecipitated with the carrier metal oxide, which crystallization seeds are removed by combustion in a final calcining step.......The present invention concerns an improved method of preparation of nanoparticular vanadium oxide/anatase titania catalysts having a narrow particle size distribution. In particular, the invention concerns preparation of nanoparticular vanadium oxide/anatase titania catalyst precursors comprising...

  3. Swelling and tensile properties of neutron-irradiated vanadium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Loomis, B.A.; Smith, D.L.

    1990-07-01

    Vanadium-base alloys are candidates for use as structural material in magnetic fusion reactors. In comparison to other candidate structural materials (e.g., Type 316 stainless and HT-9 ferritic steels), vanadium-base alloys such as V-15Cr-5Ti and V-20Ti have intrinsically lower long-term neutron activation, neutron irradiation after-heat, biological hazard potential, and neutron-induced helium and hydrogen transmutation rates. Moreover, vanadium-base alloys can withstand a higher surface-heat, flux than steels because of their lower thermal stress factor. In addition to having these favorable neutronic and physical properties, a candidate alloy for use as structural material in a fusion reactor must have dimensional stability, i.e., swelling resistance, and resistance to embrittlement during the reactor lifetime at a level of structural strength commensurate with the reactor operating temperature and structural loads. In this paper, we present experimental results on the swelling and tensile properties of several vanadium-base alloys after irradiation at 420, 520, and 600{degree}C to neutron fluences ranging from 0.3 to 1.9 {times} 10{sup 27} neutrons/m{sup 2} (17 to 114 atom displacements per atom (dpa)).

  4. Covalent attachment of 1-alkenes to oxidized platinum surfaces.

    Science.gov (United States)

    Alonso, Jose Maria; Fabre, Bruno; Trilling, Anke K; Scheres, Luc; Franssen, Maurice C R; Zuilhof, Han

    2015-03-10

    We report the formation of covalently bound alkyl layers onto oxidized Pt (PtOx) substrates by reaction with 1-alkenes as a novel way to bind organic molecules to metal surfaces. The organic layers were characterized by static contact angle, infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The grafted alkyl layers display a hydrolytic stability that is comparable to that of alkyl thiols on Au. PtOx-alkene attachment is compatible with terminal ester moieties enabling further anchoring of functional groups, such as redox-active ferrocene, and thus has great potential to extend monolayer chemistry on noble metals.

  5. Synthesis, characterisation and antioxidant activity of luteolin-vanadium(II) complex.

    Science.gov (United States)

    Roy, Souvik; Mallick, Sougata; Chakraborty, Tania; Ghosh, Nilanjan; Singh, Amit Kumar; Manna, Subhadip; Majumdar, Sumana

    2015-04-15

    The complex formation between luteolin (L) and vanadium(IV) oxide sulphate monohydrate (VOSO4·H2O) was examined under UV-visible, infra-red spectroscopy, mass spectroscopy and NMR techniques. The spectroscopic data indicated that luteolin reacts with vanadium oxide cation (VO(+2)) through 4-carbonyl-5-hydroxy chelation site in the two luteolin molecule. The free radical antioxidant activity of the complex with respect to the parent molecule was evaluated using 1,1-diphenyl-2-picrylhydrazyl (DPPH), ferric reducing antioxidant power (FRAP) and 2,2'-azinobis 3-ethylbenzothiazoline-6-sulphonic acid diammonium salt (ABTS) methods. It was observed that the free radical scavenging activity and ferric ion reducing potential of luteolin was increased after the formation of complex with vanadium oxide (VO(+2)) cation.

  6. Diel cycles in dissolved barium, lead, iron, vanadium, and nitrite in a stream draining a former zinc smelter site near Hegeler, Illinois

    Science.gov (United States)

    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

  7. Surface Preparation and Deposited Gate Oxides for Gallium Nitride Based Metal Oxide Semiconductor Devices

    Directory of Open Access Journals (Sweden)

    Paul C. McIntyre

    2012-07-01

    Full Text Available The literature on polar Gallium Nitride (GaN surfaces, surface treatments and gate dielectrics relevant to metal oxide semiconductor devices is reviewed. The significance of the GaN growth technique and growth parameters on the properties of GaN epilayers, the ability to modify GaN surface properties using in situ and ex situ processes and progress on the understanding and performance of GaN metal oxide semiconductor (MOS devices are presented and discussed. Although a reasonably consistent picture is emerging from focused studies on issues covered in each of these topics, future research can achieve a better understanding of the critical oxide-semiconductor interface by probing the connections between these topics. The challenges in analyzing defect concentrations and energies in GaN MOS gate stacks are discussed. Promising gate dielectric deposition techniques such as atomic layer deposition, which is already accepted by the semiconductor industry for silicon CMOS device fabrication, coupled with more advanced physical and electrical characterization methods will likely accelerate the pace of learning required to develop future GaN-based MOS technology.

  8. Surface potential determination in metal-oxide-semiconductor capacitors

    Science.gov (United States)

    Moragues, J. M.; Ciantar, E.; Jerisian, R.; Sagnes, B.; Oualid, J.

    1994-11-01

    Different methods using the relationship between surface potential Psi(sub S) and gate bias V(sub G) in metal-oxide-semiconductor (MOS) capacitors have been compared. These methods can be applied even if the doping profile is very abrupt and the interface state density very high. The shifts of midgap, flatband, and threshold voltages, observed after Fowler-Nordheim electron injection, and deduced from the various Psi(sub S(V (sub G)) relationships obtained by these different methods, are in good agreement. These shifts give the number of effective oxide trapped charges (N(sub ox)) per unit area and acceptor-like and donor-like interface states (N(sub SS)A and N(sub SS)D) which are created during the electron injection. We reveal that the number of positive charges created in the gate oxide, unlike the number of generated interface states, strongly depends on the position of the post-metallization annealing step in the process. After relaxation of the stressed MOS capacitors, most of the generated positive charges can be attributed, in the MOS capacitors studied, to hydrogen-related species. It seems that the interface states are essentially created by the recombination of holes generated by electron impact.

  9. Effect of Surface Treatments on Leakage of Zirconium Oxide Ceramics

    Directory of Open Access Journals (Sweden)

    Göknil Alkan Demetoğlu

    2016-08-01

    Full Text Available Objective: The aim of this pilot study was to compare the effects of pretreatments on leakage of zirconia ceramics. Materials and Methods: The speciments divided into 6 groups that were subsequently treated as follows: group 1, no treatment (control; group 2, the ceramic surfaces were airborne-particle abraded with 110 μm aluminum-oxide (Al2O3 particles; group 3, after abrasion of the surfaces with 110 μm Al2O3 particles, silica coating using 30 μm (Al2O3 particles modified by silica (rocatec system and application of the silane coupling agent (espe-sil; group 4, ceramic surfaces irritated with neodymium-doped yttrium aluminium garnet (Nd:YAG laser [fidelis plus 3 foton (Ljubljana, Slovenia] at 20 hz, 100 mj, 2 w, 100 μs; group 5, ceramic surfaces irritated with Nd:YAG laser at fidelis plus 3 fotona (Ljubljana, Slovenia at 20 hz, 100 mj, 2 w, 100 μs; group 6; application of a zirconia primer (z-prime plus bisco, IL, USA agent. And all ceramics tested for leakage. Results: For marginal leakage, score 0 was found in all groups. Conclusion: No significant differences were found in marginal leakage under all conditions.

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

    Science.gov (United States)

    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.

  11. Giant and switchable surface activity of liquid metal via surface oxidation

    OpenAIRE

    Khan, Mohammad Rashed; Eaker, Collin B.; Bowden, Edmond F.; Dickey, Michael D.

    2014-01-01

    We present a method to control the interfacial energy of a liquid metal via electrochemical deposition (or removal) of an oxide layer on its surface. Unlike conventional surfactants, this approach can tune the interfacial tension of a metal significantly (from ∼7× that of water to near zero), rapidly, and reversibly using only modest voltages. These properties can be harnessed to induce previously unidentified electrohydrodynamic phenomena for manipulating liquid metal alloys based on gallium...

  12. Rapid Surface Oxidation as a Source of Surface Degradation Factor for Bi 2 Se 3

    KAUST Repository

    Kong, Desheng

    2011-06-28

    Bismuth selenide (Bi2Se3) is a topological insulator with metallic surface states (SS) residing in a large bulk bandgap. In experiments, synthesized Bi2Se3 is often heavily n-type doped due to selenium vacancies. Furthermore, it is discovered from experiments on bulk single crystals that Bi2Se3 gets additional n-type doping after exposure to the atmosphere, thereby reducing the relative contribution of SS in total conductivity. In this article, transport measurements on Bi2Se3 nanoribbons provide additional evidence of such environmental doping process. Systematic surface composition analyses by X-ray photoelectron spectroscopy reveal fast formation and continuous growth of native oxide on Bi2Se3 under ambient conditions. In addition to n-type doping at the surface, such surface oxidation is likely the material origin of the degradation of topological SS. Appropriate surface passivation or encapsulation may be required to probe topological SS of Bi2Se3 by transport measurements. © 2011 American Chemical Society.

  13. Cation-Induced Coiling of Vanadium Pentoxide Nanobelts

    Directory of Open Access Journals (Sweden)

    Liu Jun

    2010-01-01

    Full Text Available Abstract Single-crystalline V2O5·xH2O nanorings and microloops were chemically assembled via an ion-induced chemical spinning route in the designed hydrothermal system. The morphology and structure of products were investigated by means of scanning electron microscopy (SEM and transmission electron microscopy (TEM. X-ray powder diffraction (XRD measurement, energy-dispersive X-ray spectroscopy (EDS microanalysis and thermal gravimetric analysis (TGA revealed that the composition of nanorings and microloops is V2O5·1·1H2O. For these oxide nanorings and microloops, the cation-induced coiling growth mechanism of vanadium pentoxide nanobelts has been proposed on the basis of crystallographic structure of vanadium pentoxide. Our proposed chemical spinning process and the rational solution-phase synthesis route can also be extended to prepare novel 1D materials with layered or more complex structures.

  14. Biochemical and medical importance of vanadium compounds.

    Science.gov (United States)

    Korbecki, Jan; Baranowska-Bosiacka, Irena; Gutowska, Izabela; Chlubek, Dariusz

    2012-01-01

    Vanadium belongs to the group of transition metals and is present in the air and soil contaminants in large urban agglomerations due to combustion of fossil fuels. It forms numerous inorganic compounds (vanadyl sulfate, sodium metavanadate, sodium orthovanadate, vanadium pentoxide) as well as complexes with organic compounds (BMOV, BEOV, METVAN). Depending on the research model, vanadium compounds exhibit antitumor or carcinogenic properties. Vanadium compounds generate ROS as a result of Fenton's reaction or of the reaction with atmospheric oxygen. They inactivate the Cdc25B(2) phosphatase and lead to degradation of Cdc25C, which induces G(2)/M phase arrest. In cells, vanadium compounds activate numerous signaling pathways and transcription factors, including PI3K-PKB/Akt-mTOR, NF-κB, MEK1/2-ERK, that cause cell survival or increased expression and release of VEGF. Vanadium compounds inhibit p53-dependent apoptosis and promote entry into the S phase of cells containing functional p53 protein. In addition, vanadium compounds, in particular organic derivatives, have insulin-mimetic and antidiabetic properties. Vanadium compounds lower blood glucose levels in animals and in clinical trials. They also inhibit the activity of protein tyrosine phosphatase 1B. By activating the PI3K-PKB/Akt pathway, vanadium compaunds increase the cellular uptake of glucose by the GLUT4 transporter. The PKB/Akt pathway is also used to inactivate glycogen synthase kinase-3. The impact of vanadium compounds on inflammatory reactions has not been fully studied. Vanadium pentoxide causes expression of COX-2 and the release of proinflammatory cytokines in a human lung fibroblast model. Other vanadium compounds activate NF-κB in macrophages by activating IKKβ.

  15. Mineral resource of the month: vanadium

    Science.gov (United States)

    Magyar, Michael J.

    2007-01-01

    Vanadium, the name of which comes from Vanadis, a goddess in Scandinavian mythology, is one of the most important ferrous metals. Vanadium has many uses, but the metal’s metallurgical applications, such as an alloying element in iron and steel, account for more than 85 percent of U.S. consumption. The dominant nonmetallurgical use of the metal is as a catalyst for the production of maleic anhydride and sulfuric acid, ceramics, vanadium chemicals and electronics.

  16. Effects of a vanadium post-metallocene catalyst-induced polymer backbone inhomogeneity on UV oxidative degradation of the resulting polyethylene film

    KAUST Repository

    Atiqullah, M.

    2012-07-01

    A Group 5 post-metallocene precatalyst, (ONO)VCl(THF) 2 (ONO = a bis(phenolate)pyridine LX 2 pincer ligand), activated with modified methylaluminoxane (MMAO-3A) produced a linear ethylene homopolymer (nm-HomoPE)and an unusual inhomogeneous copolymer (nm-CopolyPE) with 1-hexene having very low backbone unsaturation. The nm-CopolyPE inhomogeneity was reflected in the distributions of short chain branches, 1-hexene composition, and methylene sequence length. The 1-hexene incorporation into the polyethylene backbone strongly depended on the molecular weight of the growing polymer chain. (ONO)VCl(THF) 2, because of site diversity and easier removal of a tertiary (vs. a secondary) hydrogen, produced a skewed short chain branching (SCB) profile, incorporating 1-hexene more efficiently in the low molecular weight region than in the high molecular weight region. The significant decrease in molecular weight by 1-hexene showed that the (ONO)VCl(THF) 2 catalytic sites were also highly responsive to chain-transfer directly to 1-hexene itself, producing vinyl and trans-vinylene termini. Subsequently, the effect of backbone inhomogeneity on the UV oxidative degradation of films made from both polyethylenes was investigated. The major functional group accumulated in the branched nm-CopolyPE film was carbonyl followed by carboxyl, then vinyl/ester, whereas that in the linear nm-HomoPE film was carboxyl. However, (carbonyl, carboxyl, vinyl, and ester) nm-CopolyPE film >> (carboxyl) nm-HomoPE film). The distributions of the tertiary C-H sites and methylene sequence length in the branched nm-CopolyPE film enhanced abstraction of H, decomposition of hydroperoxide group ROOH, and generation of carbonyl compounds as compared with those in the linear nm-HomoPE film. This clearly establishes the role played by the backbone inhomogeneity. The effect of short chain branches and sequence length distributions on peak melting temperature T pm, and most probably lamellar thickness L o, was

  17. Vanadium irradiation at ATR - neutronics aspects

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, I.C.; Smith, D.L. [Argonne National Laboratory, Chicago, IL (United States)

    1995-04-01

    Calculations were performed to estimate damage and transmutation rates in vanadium irradiated in the ATR (Advanced Test Reactor) located in Idaho. The main focuses of the study are to evaluate the transmutation of vanadium to chromium and to explore ways to design the irradiation experiment to avoid excessive transmutation. It was found that the A-hole of ATR produces damage rate of {approximately} 0.2%/dpa of vanadium to chromium. A thermal neutron filter can be incorporated into the design to reduce the vanadium-to-chromium transmutation rate to low levels. A filter 1-2 mm thick of gadolinium or hafnium can be used.

  18. 钒新技术及钒产业发展前景分析%Analysis on New Vanadium Technologies and Prospects of Vanadium Industry

    Institute of Scientific and Technical Information of China (English)

    孙朝晖

    2012-01-01

    Vanadium resources in domestic and international markets and their current utilization as well as major achievements in this field are analyzed in the present work. It is suggested that efforts should be made in China for a better and stronger vanadium industry based on rich vanadium resources, encouragement from Chinese government and relatively stable market demand for vanadium products. In the paper, it is pointed out that waste water and tailings from vanadium extraction can be recycled in the cleaner production process of vanadium oxide using vanadium-bearing titaniferous magnetite as raw material, which can solve the potential pollution problems caused by waste water with high ammonia nitrogen and sodium salt from the extraction. Cleaner and high efficient vanadium oxide production technology will be a prevailing technology in the future and the success of this project is a revolutionary technical innovation for the global vanadium industry.%简要分析了国内外钒资源的情况与利用状况以及当前该领域已经取得的主要成绩.认为中国有比较丰富的钒资源,国家鼓励钒产业的发展,钒产品有比较稳定的市场需求,应该做好、做强钒产业.指出利用钒钛磁铁矿为原料提取氧化钒的清洁生产工艺可实现提钒废水和提钒尾渣闭路循环使用,解决了潜在的高氨氮-高钠盐提钒废水的污染问题,该项目的开发成功对全球钒产业将是一次革命性的技术创新,清洁、高效钒生产新技术是今后的发展方向.

  19. 油酸表面修饰的Ce2O3纳米微粒的制备和钝钒研究%PREPARATION AND VANADIUM PASSIVATION EFFECT OF SURFACE MODIFIED Ce2O3 NANOPARTICLES

    Institute of Scientific and Technical Information of China (English)

    王国良

    2001-01-01

    以硝酸铈为原料,在水-乙醇混合溶剂中制备出油酸修饰的Ce2O3纳米微粒,并用FT-IR、TEM对其进行了表征。结果表明:油酸修饰Ce2O3纳米微粒在四氢呋喃、石油醚、氯仿、苯和甲苯等有机溶剂中具有良好的分散性,说明油酸修饰的Ce2O3纳米微粒表面存在疏水有机基团,修饰剂油酸与Ce2O3纳米核之间存在着化学键合作用。用Ce2O3纳米微粒浸渍钒中毒催化裂化催化剂进行实验,结果表明,可使其比表面积、孔体积和微反活性得到不同程度的恢复。%Olelic acid surface modified Ce2O3 nanoparticles were prepared in the water-alcohol solvent.Such Ce2O3 nanoparticles were analyzed by means of various characterization approaches,including TEM and FT-IR.It was found that the olelic acid modified Ce2O3 nanoparticles can be well dispersed in such organic solvents as tetrahydrofuran,petroleum ether,trichloromethane,benzene and toluene.The dispersancy test showed that some hydrophobic groups exist at the surface of olelic acid modified Ce2O3 nanoparticles and olelic acid chemically bonds Ce2O3 nanonuclear with each other.By impregnation of Ce2O3 nanoparticles on vanadium contaminated FCC catalyst,the specific surface area,pore volume and microactivity of the catalyst can be restored partially.

  20. High surface area, electrically conductive nanocarbon-supported metal oxide

    Energy Technology Data Exchange (ETDEWEB)

    Worsley, Marcus A.; Han, Thomas Yong-Jin; Kuntz, Joshua D.; Cervantes, Octavio; Gash, Alexander E.; Baumann, Theodore F.; Satcher, Jr., Joe H.

    2015-07-14

    A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust.

  1. Characterization of Vanadium Flow Battery

    DEFF Research Database (Denmark)

    Bindner, Henrik W.; Krog Ekman, Claus; Gehrke, Oliver;

    of wind energy in the Danish power system. The battery has been in operation for 18 months. During time of operation the battery has not shown signs of degradation of performance. It has a round-trip efficiency at full load of approximately 60% (depending on temperature and SOC). The sources of the losses......This report summarizes the work done at Risø-DTU testing a vanadium flow battery as part of the project “Characterisation of Vanadium Batteries” (ForskEl project 6555) with the partners PA Energy A/S and OI Electric A/S under the Danish PSO energy research program. A 15kW/120kWh vanadium battery...... has been installed as part of the distributed energy systems experimental facility, SYSLAB, at Risø DTU. A test programme has been carried out to get hands-on experience with the technology, to characterize the battery from a power system point of view and to assess it with respect to integration...

  2. Characterization of Vanadium Flow Battery

    DEFF Research Database (Denmark)

    Bindner, Henrik W.; Krog Ekman, Claus; Gehrke, Oliver

    This report summarizes the work done at Risø-DTU testing a vanadium flow battery as part of the project “Characterisation of Vanadium Batteries” (ForskEl project 6555) with the partners PA Energy A/S and OI Electric A/S under the Danish PSO energy research program. A 15kW/120kWh vanadium battery...... has been installed as part of the distributed energy systems experimental facility, SYSLAB, at Risø DTU. A test programme has been carried out to get hands-on experience with the technology, to characterize the battery from a power system point of view and to assess it with respect to integration...... of wind energy in the Danish power system. The battery has been in operation for 18 months. During time of operation the battery has not shown signs of degradation of performance. It has a round-trip efficiency at full load of approximately 60% (depending on temperature and SOC). The sources of the losses...

  3. Zinc Oxide Surface Flashover Triggering of Pseudospark Switch

    Institute of Scientific and Technical Information of China (English)

    谢建民; 邱毓昌

    2003-01-01

    Accurate and reliable triggering is one of the most important issues with high powerpseudospark switch, because it not only has an impact on the design of discharge chamber ofswitch, but also has an influence on the dynamic range of operation voltage, repetition frequenciesand lifetime of switch. The unique feature of pseudospark switch is its hollow cathode geometry.The hollow cathode effect produced by the hollow cathode provides the protection of the switchfor the triggering unit from erosion by high discharge plasma. In this paper, a zinc oxide (ZnO)surface flashover triggering is presented. This trigger unit possesses an excellent time delay (80 ns~ 360 ns) and jitter (20 ns ~ 50 ns) at the switch voltage of 30 kV ~ 2 kV. The emitted plasmaelectron density is high enough to trigger switch reliably down to switch voltage of 440 V.

  4. Mechanisms of Mn(II) catalytic oxidation on ferrihydrite surfaces and the formation of manganese (oxyhydr)oxides

    Science.gov (United States)

    Lan, Shuai; Wang, Xiaoming; Xiang, Quanjun; Yin, Hui; Tan, Wenfeng; Qiu, Guohong; Liu, Fan; Zhang, Jing; Feng, Xionghan

    2017-08-01

    Oxidation of Mn(II) is an important process that controls the mobility and bioavailability of Mn, as well as the formation of Mn (oxyhydr)oxides in natural systems. It was found that the surfaces of minerals, such as iron (oxyhydr)oxides, can accelerate Mn(II) oxidation to a certain degree, but the underlying mechanism has not been clearly understood. This study explores the reaction pathways and mechanisms of Mn(II) oxidation on ferrihydrite surfaces at neutral pH, commonly found in natural environments, by comparisons with montmorillonite, amorphous Al(OH)3, goethite, and magnetite using macroscopic experiments and spectroscopic analyses. Results show that when Mn(II) concentrations are below 4 mM, macroscopic Mn(II) adsorption on the three iron (oxyhydr)oxide surfaces conforms well to the Langmuir equation, with ferrihydrite showing the highest adsorption capacity. With Mn(II) concentrations ranging within 6-24 mM, the adsorbed Mn(II) is mainly oxidized into manganite (γ-MnOOH) and/or feitknechtite (β-MnOOH) by dissolved O2, and Mn(II) removal on a unit mass basis in the presence of magnetite is the highest compared with ferrihydrite and goethite. Ferrihydrite, a semiconductor material, shows stronger catalytic ability for Mn(II) oxidation on the same surface area than insulator minerals (i.e., montmorillonite and amorphous Al(OH)3). Additionally, the products of Mn(II) oxidation in the presence of semiconductor iron (oxyhydr)oxides (i.e., ferrihydrite, goethite, or magnetite) at the same Fe/Mn molar ratio include both manganite and a small amount of Mn(IV) minerals, and the Mn average oxidation states (Mn AOSs) of these products follow the order: magnetite > goethite > ferrihydrite. Magnetite and goethite, with relatively smaller SSAs and lower band gap energies, exhibit greater catalysis for Mn(II) oxidation than ferrihydrite at the same Fe/Mn ratio, which goes against the conventional interfacial effect and is related to the electrochemical properties. Thus

  5. PEGylated graphene oxide elicits strong immunological responses despite surface passivation

    Science.gov (United States)

    Luo, Nana; Weber, Jeffrey K.; Wang, Shuang; Luan, Binquan; Yue, Hua; Xi, Xiaobo; Du, Jing; Yang, Zaixing; Wei, Wei; Zhou, Ruhong; Ma, Guanghui

    2017-02-01

    Engineered nanomaterials promise to transform medicine at the bio-nano interface. However, it is important to elucidate how synthetic nanomaterials interact with critical biological systems before such products can be safely utilized in humans. Past evidence suggests that polyethylene glycol-functionalized (PEGylated) nanomaterials are largely biocompatible and elicit less dramatic immune responses than their pristine counterparts. We here report results that contradict these findings. We find that PEGylated graphene oxide nanosheets (nGO-PEGs) stimulate potent cytokine responses in peritoneal macrophages, despite not being internalized. Atomistic molecular dynamics simulations support a mechanism by which nGO-PEGs preferentially adsorb onto and/or partially insert into cell membranes, thereby amplifying interactions with stimulatory surface receptors. Further experiments demonstrate that nGO-PEG indeed provokes cytokine secretion by enhancing integrin β8-related signalling pathways. The present results inform that surface passivation does not always prevent immunological reactions to 2D nanomaterials but also suggest applications for PEGylated nanomaterials wherein immune stimulation is desired.

  6. Chemical oscillation in electrochemical oxidation of methanol on Pt surface

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode potential (e), the surface coverage of carbon monoxide (x), and adsorbed water (y). The chemical reactions and electrode potential were coupled together through the rate constant ki = exp(ai(e ? ei)). The analysis to the established model discloses the following: there are different kinetics be- haviors in different ranges of current densities. The chemical oscillation in methanol electrooxidation is assigned to two aspects, one from poison mediate CO of methanol electrooxidation, which is the in- duced factor of the chemical oscillation, and the other from the oxygen-containing species, such as H2Oa. The formation and disappearance of H2Oa deeply depend on the electrode potential, and directly cause the chemical oscillation. The established model makes clear that the potential oscillation in methanol electrooxidation is the result of the feedback of electrode potential e on the reactions in- volving poison mediates CO and oxygen-containing species H2Oa. The numerical analysis of the estab- lished model successfully explains why the potential oscillation in methanol galvanostatic oxidation on a Pt electrode only happens in a certain range of current densities but not at any current density.

  7. PEGylated graphene oxide elicits strong immunological responses despite surface passivation

    Science.gov (United States)

    Luo, Nana; Weber, Jeffrey K.; Wang, Shuang; Luan, Binquan; Yue, Hua; Xi, Xiaobo; Du, Jing; Yang, Zaixing; Wei, Wei; Zhou, Ruhong; Ma, Guanghui

    2017-01-01

    Engineered nanomaterials promise to transform medicine at the bio–nano interface. However, it is important to elucidate how synthetic nanomaterials interact with critical biological systems before such products can be safely utilized in humans. Past evidence suggests that polyethylene glycol-functionalized (PEGylated) nanomaterials are largely biocompatible and elicit less dramatic immune responses than their pristine counterparts. We here report results that contradict these findings. We find that PEGylated graphene oxide nanosheets (nGO-PEGs) stimulate potent cytokine responses in peritoneal macrophages, despite not being internalized. Atomistic molecular dynamics simulations support a mechanism by which nGO-PEGs preferentially adsorb onto and/or partially insert into cell membranes, thereby amplifying interactions with stimulatory surface receptors. Further experiments demonstrate that nGO-PEG indeed provokes cytokine secretion by enhancing integrin β8-related signalling pathways. The present results inform that surface passivation does not always prevent immunological reactions to 2D nanomaterials but also suggest applications for PEGylated nanomaterials wherein immune stimulation is desired. PMID:28233871

  8. Chemical oscillation in electrochemical oxidation of methanol on Pt surface

    Institute of Scientific and Technical Information of China (English)

    LI LanLan; WEI ZiDong; QI XueQiang; SUN CaiXin; YIN GuangZhi

    2008-01-01

    Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla-tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode potential (e), the surface coverage of carbon monoxide (x), and adsorbed water (y). The chemical reactions and electrode potential were coupled together through the rate constant k1= exp(a e-e1)). The analysis to the established model discloses the following: there are different kinetics be-haviors in different ranges of current densities. The chemical oscillation in methanol electrooxidation is assigned to two aspects, one from poison mediate CO of methanol electrooxidallon, which is the in-duced factor of the chemical oscillation, and the other from the oxygen-containing species, such as H2Oa. The formation and disappearance of H2Oa deeply depend on the electrode potential, and directly cause the chemical oscillation. The established model makes clear that the potential oscillation in methanol electrooxidation is the result of the feedback of electrode potential e on the reactions in-volving poison mediates CO and oxygen-containing species H2Oa. The numerical analysis of the estab-lished model successfully explains why the potential oscillation in methanol galvanostatic oxidation on a Pt electrode only happens in a certain range of current densities but not at any current density.

  9. Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

    KAUST Repository

    Crumlin, Ethan J.

    2010-11-04

    Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

  10. Phonon triggered rhombohedral lattice distortion in vanadium at high pressure

    Science.gov (United States)

    Antonangeli, Daniele; Farber, Daniel L.; Bosak, Alexei; Aracne, Chantel M.; Ruddle, David G.; Krisch, Michael

    2016-01-01

    In spite of the simple body-centered-cubic crystal structure, the elements of group V, vanadium, niobium and tantalum, show strong interactions between the electronic properties and lattice dynamics. Further, these interactions can be tuned by external parameters, such as pressure and temperature. We used inelastic x-ray scattering to probe the phonon dispersion of single-crystalline vanadium as a function of pressure to 45 GPa. Our measurements show an anomalous high-pressure behavior of the transverse acoustic mode along the (100) direction and a softening of the elastic modulus C44 that triggers a rhombohedral lattice distortion occurring between 34 and 39 GPa. Our results provide the missing experimental confirmation of the theoretically predicted shear instability arising from the progressive intra-band nesting of the Fermi surface with increasing pressure, a scenario common to all transition metals of group V. PMID:27539662

  11. High power density self-cooled lithium-vanadium blanket.

    Energy Technology Data Exchange (ETDEWEB)

    Gohar, Y.; Majumdar, S.; Smith, D.

    1999-07-01

    A self-cooled lithium-vanadium blanket concept capable of operating with 2 MW/m{sup 2} surface heat flux and 10 MW/m{sup 2} neutron wall loading has been developed. The blanket has liquid lithium as the tritium breeder and the coolant to alleviate issues of coolant breeder compatibility and reactivity. Vanadium alloy (V-4Cr-4Ti) is used as the structural material because it can accommodate high heat loads. Also, it has good mechanical properties at high temperatures, high neutron fluence capability, low degradation under neutron irradiation, good compatibility with the blanket materials, low decay heat, low waste disposal rating, and adequate strength to accommodate the electromagnetic loads during plasma disruption events. Self-healing electrical insulator (CaO) is utilized to reduce the MHD pressure drop. A poloidal coolant flow with high velocity at the first wall is used to reduce the peak temperature of the vanadium structure and to accommodate high surface heat flux. The blanket has a simple blanket configuration and low coolant pressure to reduce the fabrication cost, to improve the blanket reliability, and to increase confidence in the blanket performance. Spectral shifter, moderator, and reflector are utilized to improve the blanket shielding capability and energy multiplication, and to reduce the radial blanket thickness. Natural lithium is used to avoid extra cost related to the lithium enrichment process.

  12. High power density self-cooled lithium-vanadium blanket.

    Energy Technology Data Exchange (ETDEWEB)

    Gohar, Y.; Majumdar, S.; Smith, D.

    1999-07-01

    A self-cooled lithium-vanadium blanket concept capable of operating with 2 MW/m{sup 2} surface heat flux and 10 MW/m{sup 2} neutron wall loading has been developed. The blanket has liquid lithium as the tritium breeder and the coolant to alleviate issues of coolant breeder compatibility and reactivity. Vanadium alloy (V-4Cr-4Ti) is used as the structural material because it can accommodate high heat loads. Also, it has good mechanical properties at high temperatures, high neutron fluence capability, low degradation under neutron irradiation, good compatibility with the blanket materials, low decay heat, low waste disposal rating, and adequate strength to accommodate the electromagnetic loads during plasma disruption events. Self-healing electrical insulator (CaO) is utilized to reduce the MHD pressure drop. A poloidal coolant flow with high velocity at the first wall is used to reduce the peak temperature of the vanadium structure and to accommodate high surface heat flux. The blanket has a simple blanket configuration and low coolant pressure to reduce the fabrication cost, to improve the blanket reliability, and to increase confidence in the blanket performance. Spectral shifter, moderator, and reflector are utilized to improve the blanket shielding capability and energy multiplication, and to reduce the radial blanket thickness. Natural lithium is used to avoid extra cost related to the lithium enrichment process.

  13. Perspectives for vanadium in health issues.

    Science.gov (United States)

    Rehder, Dieter

    2016-01-01

    Vanadium is omnipresent in trace amounts in the environment, in food and also in the human body, where it might serve as a regulator for phosphate-dependent proteins. Potential vanadium-based formulations--inorganic and coordination compounds with organic ligands--commonly underlie speciation in the body, that is, they are converted to vanadate(V), oxidovanadium(IV) and to complexes with the body's own ligand systems. Vanadium compounds have been shown to be potentially effective against diabetes Type 2, malign tumors including cancer, endemic tropical diseases (such as trypanosomiasis, leishmaniasis and amoebiasis), bacterial infections (tuberculosis and pneumonia) and HIV infections. Furthermore, vanadium drugs can be operative in cardio- and neuro-protection. So far, vanadium compounds have not yet been approved as pharmaceuticals for clinical use.

  14. The Thickness Distribution of Oxidation Film on Tapered Pipe Surface in Dieless Drawing

    Directory of Open Access Journals (Sweden)

    Fang Qin

    2011-01-01

    Full Text Available The thickness distribution of oxidation film on the surface of AISI304 stainless steel tapered pipe, its influence factors, and the effect of metal matrix deformation on oxidation behavior during dieless drawing were studied in this paper. The results showed that oxidation rate was affected strongly by induction heating temperature and deformation degree. The thickness distribution of oxidation film was uneven and increased from the larger diameter end to the smaller diameter end along the axial direction of tapered pipe. When induction heating temperature raised or the distance between heat and cold sources was increased, or feed speed was decreased, oxidation rate was accelerated and oxidation film on the tapered pipe surface thickened significantly, due to massive cracks in oxidation film induced by deformation of metal matrix. The density and width of cracks in oxidation film were enlarged, and the thickness of oxidation film increased with the increase in deformation degree.

  15. The surface treatment on oxide film of pure titanium Part 1. The effect of Anodic oxidation

    Institute of Scientific and Technical Information of China (English)

    Ge Wang; Xiangrong Cheng

    2006-01-01

    that the open circuit potential (OCP) of the anodic oxide was very stable at 0mV. Natural oxide increased quickly from -50 mV to -40mV and plateaued 350s later at -40mV. The curve of anodic polarization in the same liquid showed that the polarized current was 100 times lower than that of natural oxide film. In artificial seawater (ASW) the OCP of the anodic oxide was stable at -90mV. Natural oxide in ASW did not stop rising from -480mV to -310mV during 1000s. The active current appeared to be much greater than that of the anodic oxide film. Conclusion: The color of the oxide film may be related to the thickness and influenced the future prosthetics as an implant. So gold was chosen as the ideal color. The reason was not clear why the rule of altering at peak 2.55 and 2.34 below the surface titanium oxides. The stability and corrosive-resistance of the anodic oxide film was much higher than that of natural oxide film. Anodic oxidation was a good way to enhance the pure titanium corrosive-resistance in vitro.

  16. First-principles study on initial stage of oxidation on Si(110) surface

    Energy Technology Data Exchange (ETDEWEB)

    Nagasawa, Takahiro; Shiba, Seiji; Sueoka, Koji [Department of System Engineering, Okayama Prefectural University, 111 Kuboki, Soja, Okayama 719-1197 (Japan)

    2011-03-15

    There is a great deal of engineering interest in Si (110) wafers as the substrates of large scale integrations (LSIs) in the next generation. However, few studies on Si (110) surface have been reported in comparison with those on other low-index surfaces, still less the mechanism of surface oxidation. We analyzed the surface structure and the initial stage of oxidation on the Si (110)-(16 x 2) clean surface with first-principles calculation. The results of our calculations showed that first, the stable structure of the Si (110) clean surface was the adatom-tetramer-interstitial (ATI) reconstruction. Second, pairs of pentagon (PPs) were preferentially oxidized in the initial stage of the oxidation. Third, the oxidation growth should progress with the clustering of O atoms. (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    CSIR Research Space (South Africa)

    Masina, BN

    2013-10-01

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

  18. Hydrophobic cotton textile surfaces using an amphiphilic graphene oxide (GO) coating

    Science.gov (United States)

    Tissera, Nadeeka D.; Wijesena, Ruchira N.; Perera, J. Rangana; de Silva, K. M. Nalin; Amaratunge, Gehan A. J.

    2015-01-01

    We report for the first time hydrophobic properties on cotton fabric successfully achieved by grafting graphene oxide on the fabric surface, using a dyeing method. Graphite oxide synthesized by oxidizing natural flake graphite employing improved Hummer's method showed an inter layer spacing of ∼1 nm from XRD. Synthesized graphite oxide was exfoliated in water using ultrasound energy to obtain graphene oxide (GO). AFM data obtained for the graphene oxide dispersed in an aqueous medium revealed a non-uniform size distribution. FTIR characterization of the synthesized GO sheets showed both hydrophilic and hydrophobic functional groups present on the nano sheets giving them an amphiphilic property. GO flakes of different sizes were successfully grafted on to a cotton fabric surface using a dip dry method. Loading different amounts of graphene oxide on the cotton fiber surface allowed the fabric to demonstrate different degrees of hydrophobicity. The highest observed water contact angle was at 143° with the highest loading of graphene oxide. The fabric surfaces grafted with GO also exhibits adhesive type hydrophobicity. Microscopic characterization of the fiber surface using SEM and AFM reveals the deposition of GO sheets on the fiber surface as a conformal coating. Analysis of the fabric surface using UV-vis absorption allowed identification of the ratio of hydrophobic to hydrophilic domains present on the GO coated cotton fabric surface. Hydrophobic properties on cotton fabric are ascribed to two dimensional amphiphilic properties of deposited GO nano sheets, which successfully lower the interfacial energy of the fabric surface.

  19. Resistance given by tiling grain surface with micro surface structures in polycrystalline metal oxide

    Science.gov (United States)

    Moriyama, T.; Yamasaki, T.; Ohno, T.; Kishida, S.; Kinoshita, K.

    2016-12-01

    Practical use of Resistive Random Access Memory (ReRAM) depends on thorough understanding of the resistive switching (RS) mechanism in transition metal oxides. Although most of ReRAM samples have polycrystalline structures, both experimental studies and theoretical calculations do not often consider the effects that grain boundaries have on the RS mechanism. This paper discusses what determines resistance values in a Pt/polycrystalline NiO/Pt ReRAM structures by using both experiments and first-principles calculations. Electrical measurements suggest that the RS is caused in the grain boundaries of NiO films. First-principles calculations indicate that slight displacements of atoms with a small energy change of 0.04 eV per atom on the surfaces exposed in the grain boundaries can drastically change conductivities. We propose the tiling model, in which grain surfaces are composed by insulating and conductive micro surface structures, and the surface resistances are determined by the tiling patterns.

  20. Chemistry and biochemistry of vanadium.

    Science.gov (United States)

    Meisch, H U; Bielig, H J

    1980-01-01

    The transition metal vanadium is considered to be essential for plants and animals. In order to understand its physiological function, some important chemical properties of V are reviewed, e.g. its redox activity and the tendency of V3+, VO2+, and VO3- ions to form chelates with numerous ligands. A survey of the occurrence and distribution of kV in geochemistry and in living organisms is followed by a consideration of the V influence on several metabolic events such as microbial nitrogen metabolism, chlorophyll biosynthesis, and activation or inhibition of regulatory enzymes.

  1. Absorption of hydrogen in vanadium, enhanced by ion bombardment; Ionenbeschussunterstuetzte Absorption des Wasserstoffs in Vanadium

    Energy Technology Data Exchange (ETDEWEB)

    Paulus, H.; Lammers, M. [Inst. fuer Technologie- und Wissenstransfer, Soest (Germany); Mueller, K.H. [Inst. fuer Technologie- und Wissenstransfer, Soest (Germany)]|[Paderborn Univ. (Gesamthochschule), Soest (Germany). Fachbereich 16 - Elektrische Energietechnik; Kiss, G.; Kemeny, Z. [Technical Univ. Budapest (Hungary)

    1998-12-31

    Prior to hydrogen implantation into vanadium, the vanadium specimen usually is exposed to an activation process and is then heated at 1 atm hydrogen to temperatures between 500 and 600 C, subsequently cooled down in several steps. Within this temperature range, hydrogen solubility increases with declining temperature. A decisive factor determining hydrogen absorption is the fact that at temperatures above 250 C, oxygen desorbs from the material surface and thus no longer inhibits hydrogen absorption. Therefore a different approach was chosen for the experiments reported: Hydrogen absorption under UHV conditions at room temperature. After the usual activation process, the vanadium surface was cleaned by 5 keV Ar{sup +} ion bombardment. Thus oxygen absorption at the specimen surface (and new reactions with oxygen from the remaining gas) could be avoided, or removed. By means of thermal desorption mass spectrometry (TDMS), hydrogen absorption as a function of argon ion dose was analysed. TDMS measurements performed for specimens treated by ion bombardment prior to H{sup 2} exposure showed two H{sup 2} desorption peaks, in contrast to the profiles measured with specimens not exposed to ion bombardment. It is assumed that the ion bombardment disturbs the crystal structure so that further sites for hydrogen absorption are produced. (orig./CB) [Deutsch] Bei der Beladung von Vandium mit Wasserstoff wird ueblicherweise die Probe nach einer Aktivierungsprozedur bei 1 atm Wasserstoff auf Temperaturen im Bereich von 500 bis 600 C hochgeheizt und danach schrittweise abgekuehlt. In diesem Temperaturbereich nimmt die Wasserstoffloeslichkeit mit abnehmender Temperatur zu. Entscheidend fuer die Beladung ist aber auch die Tatsache, dass bei Temperaturen groesser 250 C Sauerstoff von der Oberflaeche desorbiert und dadurch die Absorption von Wasserstoff nicht mehr blockieren kann. Im Rahmen der hier beschriebenen Untersuchungen sollte die Wasserstoffbeladung unter UHV-Bedingungen bei

  2. Electrospun nickel oxide nanofibers: Microstructure and surface evolution

    Science.gov (United States)

    Khalil, Abdullah; Hashaikeh, Raed

    2015-12-01

    Nickel oxide (NiO) nanofibers with controlled microstructure were synthesized through the electrospinning technique using a solution composed of nickel acetate and polyvinyl alcohol. The microstructure of NiO nanofibers was found to be highly dependent on nickel acetate concentration in the solution and the post-heat treatment. As the nickel acetate concentration increases, the crystallinity index of NiO nanofibers increases from nearly 50 percent to 90 percent and the average crystallite size in the nanofibers increases from about 20 nm to 30 nm. Further, it was found that annealing the nanofibers at 1000 °C for 2 h leads to nearly full crystallization of nanofibers with significant increase in the crystallite size to about 50 nm while maintaining the fibrous shape. For low nickel acetate concentration, and because of the small nanofibers size, the surface of the calcined nanofibers showed oxygen deficiency which promises a superior activity of these NiO nanofibers for catalytic and sensing applications.

  3. Soot Surface Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix I

    Science.gov (United States)

    Xu, F.; El-Leathy, A. M.; Kim, C. H.; Faeth, G. M.; Yuan, Z.-G. (Technical Monitor); Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2003-01-01

    Soot surface oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round fuel jets burning in coflowing dry air considering acetylene-nitrogen, ethylene, propyiene-nitrogen, propane and acetylene-benzene-nitrogen in the fuel stream. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of major stable gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2, C2H6, C3H6, C3H8, and C6H6) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by deconvoluted Li/LiOH atomic absorption and flow velocities by laser velocimetry. For present test conditions, it was found that soot surface oxidation rates were not affected by fuel type, that direct rates of soot surface oxidation by O2 estimated from Nagle and Strickland-Constable (1962) were small compared to observed soot surface oxidation rates because soot surface oxidation was completed near the flame sheet where O2 concentrations were less than 3% by volume, and that soot surface oxidation rates were described by the OH soot surface oxidation mechanism with a collision efficiency of 0.14 and an uncertainty (95% confidence) of +/- 0.04 when allowing for direct soot surface oxidation by O2, which is in reasonably good agreement with earlier observations of soot surface oxidation rates in both premixed and diffusion flames at atmospheric pressure.

  4. Comparative temporal analysis of multiwalled carbon nanotube oxidation reactions: Evaluating chemical modifications on true nanotube surface

    Science.gov (United States)

    Pacheco, Flávia G.; Cotta, Alexandre A. C.; Gorgulho, Honória F.; Santos, Adelina P.; Macedo, Waldemar A. A.; Furtado, Clascídia A.

    2015-12-01

    The influence of extensive purification on oxidized multiwalled carbon nanotube surface composition was studied through the characterization and differentiation of the actual surface submitted to three oxidation methods: microwave-assisted acid oxidation, hydrogen peroxide reflux, and Fenton reaction. The oxidized samples were purified by a multi-step procedure including the sequential use of basic reflux and dispersion in dimethylformamide (DMF). The results showed a significant increase in the amount of oxidation debris with hydrogen peroxide and Fenton reaction times longer than 8 h and strong surface characteristic modification. With regard to sample purification, basic reflux led to a reduction in oxygenated group concentration of only 10% in the samples treated by acid oxidation. On the other hand, the subsequent use of DMF led to a further decrease in concentration of 39%, proving to be a more efficient method for the removal of oxidation debris.

  5. Characterization of Different on the Oxidation Behaviours Surface States and Its Effects of Alloy 690TT

    Institute of Scientific and Technical Information of China (English)

    Zhiming Zhang; Jianqiu Wang; En-Hou Han; Wei Ke

    2012-01-01

    Alloy 690TT samples with four kinds of surface states were prepared: 1) ground to 400 grit; 2) ground to 1500 grit; 3) mechanically polished (MP) and 4) electro-polished (EP). The surface morphologies and the surface skin layers' microstructures of these samples were characterized systematically using various methods and the effects of surface states on the oxidation behaviours of Alloy 690TT were also discussed. The results showed that surface roughness and micro-hardness decreased gradually from the ground to EP surfaces. The grains in the near-surface layers of the ground and MP surfaces had been refined and the residual strains were also very high. The dislocations on the ground surfaces were mainly parallel dislocation lines. The thickness of the superficial cold-worked layers decreased gradually from the ground surfaces to polished surfaces. The oxide morphologies and oxidation rate depended greatly on the surface states of samples. Cold-working by grinding treatments could benefit the outward diffusion of metallic atoms and the nucleation of surface oxides and then accelerate the growth of surface oxide films.

  6. Surface morphology and structure of ultra-thin magnesium oxide grown on (100) silicon by atomic layer deposition oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Rochdi, N., E-mail: rochdi.nabil@gmail.com [Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), CNRS UPR 3118, Aix-Marseille Universite, Case 913, Campus de Luminy, 13288 Marseille cedex 9 (France); Liudvikouskaya, K. [Belarusian State University of Informatics and Radioelectronics, P. Browka 6, 220013 Minsk (Belarus); Descoins, M.; Raissi, M.; Coudreau, C.; Lazzari, J.-L. [Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), CNRS UPR 3118, Aix-Marseille Universite, Case 913, Campus de Luminy, 13288 Marseille cedex 9 (France); Oughaddou, H. [Commissariat a l' Energie Atomique, DSM-IRAMIS-SPCSI, Bat. 462, Saclay, 91191, Gif-sur-Yvette cedex (France); Universite de Cergy-Pontoise, LAMAp, 95000 Cergy-Pontoise cedex (France); D' Avitaya, F. Arnaud [Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), CNRS UPR 3118, Aix-Marseille Universite, Case 913, Campus de Luminy, 13288 Marseille cedex 9 (France)

    2011-07-29

    Ultra-thin magnesium oxide layers were elaborated by atomic layer deposition and oxidation process on silicon (100) starting from (2 x 1) thermally-reconstructed or hydrogen-terminated Si surfaces. Low-energy electron diffraction experiments show (2 x 3) and (3 x 3) reconstructions while depositing a magnesium monolayer on Si clean surfaces, and a 3-dimentional growth of the oxide as confirmed by ex-situ atomic force microscopy. For hydrogen-terminated or clean surfaces previously physisorbed by oxygen, uniform cobalt/magnesium-oxide/silicon stacks of layers are observed by transmission electron microscopy. Annealing above 150 deg. C leads to MgO dissolution and formation of an interfacial complex compound by inter-diffusion of Si and Co.

  7. Influence of additive element on surface oxide film of A356 alloy

    Institute of Scientific and Technical Information of China (English)

    OUYANG Zhi-ying; LIANG Hong-yu; MAO Xie-min; HONG Mei

    2006-01-01

    The influences of RE-modification and Sr-modification on the hydrogen content and surface oxide film of A356 aluminum alloy melt were investigated. The hydrogen content of the melt was measured by reduce pressure test. The phases in the surface oxide film were analyzed by X-ray diffractometry (XRD), and the morphology of the surface oxide film was observed by scanning electronic microscopy (SEM). The results show that RE-modification reduces the hydrogen content of A356 aluminum alloy greatly.Contrarily, Sr-modification increases the hydrogen content remarkably. After being treated with RE, a large number of LaAl11O18 consisting of Al2O3 and La2O3, are generated in the surface oxide film of A356 alloy. The surface oxide film of Sr-modification is almost composed of Al2SrO4. According to the results of SEM, the surface oxide film of Sr-modification is very easy to crack,destroy the continuity and compactness of surface oxide film, accelerate the vapor diffusing into the melt, consequently, increase the hydrogen content of A356 alloy melt significantly. But RE-modification makes the surface oxide film compact, and restrains the aluminum exposed to water, so reduces the hydrogen content of A356 alloy melt.

  8. RF Magnetron Sputtering Aluminum Oxide Film for Surface Passivation on Crystalline Silicon Wafers

    Directory of Open Access Journals (Sweden)

    Siming Chen

    2013-01-01

    Full Text Available Aluminum oxide films were deposited on crystalline silicon substrates by reactive RF magnetron sputtering. The influences of the deposition parameters on the surface passivation, surface damage, optical properties, and composition of the films have been investigated. It is found that proper sputtering power and uniform magnetic field reduced the surface damage from the high-energy ion bombardment to the silicon wafers during the process and consequently decreased the interface trap density, resulting in the good surface passivation; relatively high refractive index of aluminum oxide film is benefic to improve the surface passivation. The negative-charged aluminum oxide film was then successfully prepared. The surface passivation performance was further improved after postannealing by formation of an SiOx interfacial layer. It is demonstrated that the reactive sputtering is an effective technique of fabricating aluminum oxide surface passivation film for low-cost high-efficiency crystalline silicon solar cells.

  9. Superhydrophilicity and antibacterial property of a Cu-dotted oxide coating surface

    Directory of Open Access Journals (Sweden)

    Nie Yining

    2010-09-01

    Full Text Available Abstract Background Aluminum-made settings are widely used in healthcare, schools, public facilities and transit systems. Frequently-touched surfaces of those settings are likely to harbour bacteria and be a potential source of infection. One method to utilize the effectiveness of copper (Cu in eliminating pathogens for these surfaces would be to coat the aluminum (Al items with a Cu coating. However, such a combination of Cu and Al metals is susceptible to galvanic corrosion because of their different electrochemical potentials. Methods In this work, a new approach was proposed in which electrolytic plasma oxidation (EPO of Al was used to form an oxide surface layer followed by electroplating of Cu metal on the top of the oxide layer. The oxide was designed to function as a corrosion protective and biocompatible layer, and the Cu in the form of dots was utilized as an antibacterial material. The antibacterial property enhanced by superhydrophilicity of the Cu-dotted oxide coating was evaluated. Results A superhydrophilic surface was successfully prepared using electrolytic plasma oxidation of aluminum (Al followed by electroplating of copper (Cu in a Cu-dotted form. Both Cu plate and Cu-dotted oxide surfaces had excellent antimicrobial activities against E. coli ATCC 25922, methicillin-resistant Staphylococcus aureus (MRSA ATCC 43300 and vancomycin-resistant Enterococcus faecium (VRE ATCC 51299. However, its Cu-dotted surface morphology allowed the Cu-dotted oxide surface to be more antibacterial than the smooth Cu plate surface. The enhanced antibacterial property was attributed to the superhydrophilic behaviour of the Cu-dotted oxide surface that allowed the bacteria to have a more effective killing contact with Cu due to spreading of the bacterial suspension media. Conclusion The superhydrophilic Cu-dotted oxide coating surface provided an effective method of controlling bacterial growth and survival on contact surfaces and thus reduces the

  10. Trends in CO Oxidation Rates for Metal Nanoparticles and Close-Packed, Stepped, and Kinked Surfaces

    DEFF Research Database (Denmark)

    Jiang, Tao; Mowbray, Duncan; Dobrin, Sergey;

    2009-01-01

    Using density functional theory calculations, we study trends in the CO oxidation activity for different metals and surfaces. Specifically, we show how the activity of (111) close-packed surfaces, (211) stepped surfaces, (532) kinked surfaces, 55 atom cuboctahedral clusters, and 12 atom cluster...

  11. The Effect of Anodic Surface Treatment on the Oxidation of Catechols at Ultrasmall Carbon Ring Electrodes

    Science.gov (United States)

    1991-07-09

    selectivity. A model of the surface formed following anodic oxidation is consistent with previous models involving both surface cleanliness and carbon...involving both surface cleanliness and carbon structure orientation. 2 INTRODUCTION Because of the vast electroanalytical utility of carbon electrodes...of the electron transfer rate following treatment are a function of the surface cleanliness and the orientation of the carbon structure

  12. Surface Catalysis and Oxidation on Stagnation Point Heat Flux Measurements in High Enthalpy Arc Jets

    Science.gov (United States)

    Nawaz, Anuscheh; Driver, David M.; Terrazas-Salinas

    2013-01-01

    Heat flux sensors are routinely used in arc jet facilities to determine heat transfer rates from plasma plume. The goal of this study is to assess the impact of surface composition changes on these heat flux sensors. Surface compositions can change due to oxidation and material deposition from the arc jet. Systematic surface analyses of the sensors were conducted before and after exposure to plasma. Currently copper is commonly used as surface material. Other surface materials were studied including nickel, constantan gold, platinum and silicon dioxide. The surfaces were exposed to plasma between 0.3 seconds and 3 seconds. Surface changes due to oxidation as well as copper deposition from the arc jets were observed. Results from changes in measured heat flux as a function of surface catalycity is given, along with a first assessment of enthalpy for these measurements. The use of cupric oxide is recommended for future heat flux measurements, due to its consistent surface composition arc jets.

  13. Research of oxidation processes of a cadmium telluride film surface by ellipsometric method

    Science.gov (United States)

    Zabashta, Lubov A.; Opanasyuk, A. S.; Kharchenko, V. I.

    1997-04-01

    Kinetics of formation of an oxide on the CdTe surface was investigated during a sample exposition in air at temperatures Th equals 20 degrees C, 260 degrees C, 340 degrees C, 420 degrees C, for 200 hours. For nonoxide CdTe surface the following values of optical constants ns equals 2.6 and ks equals 0.6 are received. At a exposition of samples at room temperature a refractive index of an oxide film changed from nf equals 1.7 at initial stages of growth up to nf equals 2.37 after 200 hours oxidation. At all stages of oxidation process the monotone reduction of a refractive index of oxide layers at an increase of heating temperature is found out. During natural oxidation oxide layer thickness reaches 1.8 nm in the course of 20 hours. Hereafter oxide formation speed decreases that results in stabilization of its thickness. It is shown that the growth of the oxide phase is descried with the parabolic law and is checked with diffusion processes. To determine the energy of oxidation process activation the charts of dependence of logarithm of oxide film thickness upon inverse temperature at constant oxidation time were built. The presence of two areas of heating temperatures with different energy of oxidation process activation is established. The parameters of kinetic equation are determined which describe oxide film growth in low temperature and high temperature fields.

  14. Oxidation behavior and thermal stability of a NiAl-Veutectic alloy

    Energy Technology Data Exchange (ETDEWEB)

    Milenkovic, Srdjan [IMDEA Materials Institute, Eric Kandel 2, 28906 Getafe, Madrid (Spain); Caram, Rubens [Department of Materials Science and Engineering, State University of Campinas, P.O. 6122, 13083-970 Campinas, SP (Brazil)

    2013-05-15

    Oxidation behavior and thermal stability of a NiAl-V alloy with eutectic composition processed by directional solidification technique has been investigated. The surface analysis at the elevated temperature indicated that the investigated microstructures are stable at the isothermal conditions and an inert atmosphere. The oxidation testing in the synthetic air showed that the temperature of 400 C is critical. In addition, the oxidation of the NiAl-V eutectic alloy is characterized by: (a) alteration of composition immediately below the surface substrate/oxide; (b) formation of the oxide layer rich in V, adherent to the substrate; and (c) formation of external oxide layer that presents oxide mixture formed by vanadium, nickel, and aluminum. Microstructure of the substrate/oxide interface of NiAl-V alloy oxidized at 900 C for 24 h. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Designed synthesis and surface engineering strategies of magnetic iron oxide nanoparticles for biomedical applications.

    Science.gov (United States)

    Wu, Wei; Jiang, Chang Zhong; Roy, Vellaisamy A L

    2016-12-01

    Iron oxide nanoparticles (NPs) hold great promise for future biomedical applications because of their magnetic properties as well as other intrinsic properties such as low toxicity, colloidal stability, and surface engineering capability. Numerous related studies on iron oxide NPs have been conducted. Recent progress in nanochemistry has enabled fine control over the size, crystallinity, uniformity, and surface properties of iron oxide NPs. This review examines various synthetic approaches and surface engineering strategies for preparing naked and functional iron oxide NPs with different physicochemical properties. Growing interest in designed and surface-engineered iron oxide NPs with multifunctionalities was explored in in vitro/in vivo biomedical applications, focusing on their combined roles in bioseparation, as a biosensor, targeted-drug delivery, MR contrast agents, and magnetic fluid hyperthermia. This review outlines the limitations of extant surface engineering strategies and several developing strategies that may overcome these limitations. This study also details the promising future directions of this active research field.

  16. Infrared Photodissociation Spectroscopy of Vanadium-Carbon Dioxide Cations: Evidence for AN Intracluster Reaction.

    Science.gov (United States)

    Brathwaite, Antonio D.; Ricks, Allen M.; Duncan, Michael A.

    2012-06-01

    Cationic vanadium-carbon dioxide clusters, consisting of up to ten carbon dioxide ligands, are produced in a molecular beam via laser vaporization in a pulsed nozzle source. The cations are mass selected and studied via infrared photodissociation spectroscopy in the 600-4000 cm1 region. The number of infrared active bands, their frequency positions and their relative intensities, allows us to gain insight into the structure and bonding of these species. The sudden appearance of new infrared bands in the spectra of complexes having seven or more ligands provides evidence for an intracluster reaction. We explore possible reaction products by comparing these spectra to those of vanadium and vanadium oxide-carbonyls. Low frequency measurements and DFT calculations have allowed us to identify complexes containing a metal atom bonded to an oxalate-like structure as the product of these reactions.

  17. The influence of calcium, magnesium, phosphorus and silica in vanadium precipitation in acidic sulfate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Martins, A.H. [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Dept. de Engenharia Metalurgica e de Materiais. E-mail: ahmartin@demet.ufmg.br

    2000-06-01

    The experimental research work was carried out in accordance with the Factorial Design Statistical Method to evaluate and analyze the influence of calcium, magnesium, silica and phosphorus on the precipitation of vanadates. precipitation was performed by neutralization with H{sub 2} SO{sub 4} of alkaline aqueous solutions containing vanadium pentoxide (V{sub 2} O{sub 5}) at 60 {+-} 2 deg C. The experimental responses measured were percent of vanadium recovery and vanadium pentoxide content in the precipitate. These impurities are considered representative of those present in a leach liquor from the ore obtained at Campo Alegre de Lourdes (Brazil). The operational variables in this work were used optimum conditions as determined by the statistical approach. Among the impurities under study, phosphorus exhibited the highest negative influence on the experimental responses. Phosphorus diminished the percent of vanadium recovered from 98.9 to 34.5 and the vanadium oxide content in the precipitate from 91.2% to 39.3%. (author)

  18. Can Vanadium Be Substituted into LiFePO[subscript 4]?

    Energy Technology Data Exchange (ETDEWEB)

    Omenya, Fredrick; Chernova, Natasha A.; Upreti, Shailesh; Zavalij, Peter Y.; Nam, Kyung-Wan; Yang, Xiao-Qing; Whittingham, M. Stanley (Binghamton); (BNL); (Maryland)

    2015-10-15

    Vanadium is shown to substitute for iron in the olivine LiFePO{sub 4} up to at least 10 mol %, when the synthesis is carried out at 550 C. In the solid solution LiFe{sub 1-3y/2}V{sub y}PO{sub 4}, the a and b lattice parameters and cell volume decrease with increasing vanadium content, while the c lattice parameter increases slightly. However, when the synthesis is performed at 650 C, a NASICON phase, Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}, is also formed, showing that solid solution is a function of the synthesis temperature. X-ray absorption near-edge structure indicates vanadium is in the 3+ oxidation state and in an octahedral environment. Magnetic studies reveal a shift of the antiferromagnetic ordering transition toward lower temperatures with increasing vanadium substitution, confirming solid solution formation. The addition of vanadium enhances the electrochemical performance of the materials especially at high current densities.

  19. The influence of calcium, magnesium, phosphorus and silica on vanadium precipitation in acidic sulfate solutions

    Directory of Open Access Journals (Sweden)

    A. H. Martins

    2000-06-01

    Full Text Available The experimental research work was carried out in accordance with the Factorial Design Statistical Method to evaluate and analyze the influence of calcium, magnesium, silica and phosphorus on the precipitation of vanadates. Precipitation was performed by neutralization with H2SO4 of alkaline aqueous solutions containing vanadium pentoxide (V2O5 at 60± 2ºC. The experimental responses measured were percent of vanadium recovery and vanadium pentoxide content in the precipitate. These impurities are considered representative of those present in a leach liquor from the ore obtained at Campo Alegre de Lourdes (Brazil. The operational variables in this work were used under optimum conditions as determined by the statistical approach. Among the impurities under study, phosphorus exhibited the highest negative influence on the experimental responses. Phosphorus diminished the percent of vanadium recovered from 98.9 to 34.5 and the vanadium oxide content in the precipitate from 91.2 % to 39.3 %.

  20. Dissociative adsorption of methane on surface oxide structures of Pd-Pt alloys

    CERN Document Server

    Dianat, Arezoo; Ciacchi, Lucio Colombi; Pompe, Wolfgang; Cuniberti, Gianaurelio; Bobeth, Manfred; 10.1021/jp905689t

    2010-01-01

    The dissociative adsorption of methane on variously oxidized Pd, Pt and Pd-Pt surfaces is investigated using density-functional theory, as a step towards understanding the combustion of methane on these materials. For Pd-Pt alloys, models of surface oxide structures are built on the basis of known oxides on Pd and Pt. The methane adsorption energy presents large variations depending on the oxide structure and composition. Adsorption is endothermic on the bare Pd(111) metal surface as well as on stable thin layer oxide structures such as the ($\\sqrt{5}\\times\\sqrt{5}$) surface oxide on Pd(100) and the PtO$_2$-like oxide on Pt(111). Instead, large adsorption energies are obtained for the (100) surface of bulk PdO, for metastable mixed Pd$_{1-x}$Pt$_x$O$_{4/3}$ oxide layers on Pt(100), and for Pd-Pt(111) surfaces covered with one oxygen monolayer. In the latter case, we find a net thermodynamic preference for a direct conversion of methane to methanol, which remains adsorbed on the oxidized metal substrates via w...

  1. Plasma Niobium Surface Alloying of Pure Titanium and its Oxidation at 900 ℃

    Institute of Scientific and Technical Information of China (English)

    WANG Wen-bo; ZHONG Xu; HE Zhi-yong; WANG Zhen-xia; ZHANG Ping-ze

    2007-01-01

    A niobium-modified layer on pure titanium surface was obtained by means of double glow plasma surface alloying technique. The modified layer was uniform, continuous, compact and well adhered to the substrate. The niobium composition in the modified layer decreased gradually from the surface to the substrate. The oxidation behavior of the niobium-modified layer was investigated and compared with the untreated surface at 900 ℃ for 100 h. Characterization of the layers was performed using X-ray diffraction and scanning electron microscope, respectively. The test results show that the oxidation behavior of pure titanium was improved by niobium alloying process. Niobium has a positive influence on the oxidation resistance.

  2. Method of defence of solder surface from oxidization

    Directory of Open Access Journals (Sweden)

    Kurmashev Sh. D.

    2010-02-01

    Full Text Available Compositions are developed for defence of fusion solder from oxidization on the basis of mixture of glycerin, urea and powders of refractory oxides, carbides (Al2O3, TiO2, SIC, graphite. The offered compositions can be used for defence of fusion of solder from oxidization in the process of soludering and tinning of explorers, and also electric conclusions of elements of radio electronic apparatus by the method of immersion in stationary baths.

  3. Robust hybrid elastomer/metal-oxide superhydrophobic surfaces.

    Science.gov (United States)

    Hoshian, S; Jokinen, V; Franssila, S

    2016-08-21

    We introduce a new type of hybrid material: a nanostructured elastomer covered by a hard photoactive metal-oxide thin film resembling the exoskeleton of insects. It has extreme water repellency and fast self-recovery after damage. A new fabrication method for replicating high aspect ratio, hierarchical re-entrant aluminum structures into polydimethylsiloxane (PDMS) is presented. The method is based on a protective titania layer deposited by atomic layer deposition (ALD) on the aluminum template. The ALD titania transfers to the elastomeric scaffold via sacrificial release etching. The sacrificial release method allows for high aspect ratio, even 100 μm deep and successful release of overhanging structures, unlike conventional peeling. The ALD titania conformally covers the 3D multihierarchical structures of the template and protects the polymer during the release etch. Afterwards it prevents the high aspect ratio nanostructures from elasticity based collapse. The resulting nanostructured hybrid PDMS/titania replicas display robust superhydrophobicity without any further fluoro-coating or modification. Their mechanical and thermal robustness results from a thick nanostructured elastomeric layer which is conformally covered by ceramic titania instead of a monolayer hydrophobic coating. We have demonstrated the durability of these replicas against mechanical abrasion, knife scratches, rubbing, bending, peel tape test, high temperature annealing, UV exposure, water jet impingement and long term underwater storage. Though the material loses its superhydrophobicity in oxygen plasma exposure, a fast recovery from superhydrophilic to superhydrophobic can be achieved after 20 min UV irradiation. UV-assisted recovery is correlated with the high photoactivity of ALD titania film. This novel hybrid material will be applicable to the large area superhydrophobic surfaces in practical outdoor applications.

  4. Effects of Basicity and MgO in Slag on the Behaviors of Smelting Vanadium Titanomagnetite in the Direct Reduction-Electric Furnace Process

    Directory of Open Access Journals (Sweden)

    Tao Jiang

    2016-05-01

    Full Text Available The effects of basicity and MgO content on reduction behavior and separation of iron and slag during smelting vanadium titanomagnetite by electric furnace were investigated. The reduction behaviors affect the separation of iron and slag in the direct reduction-electric furnace process. The recovery rates of Fe, V, and Ti grades in iron were analyzed to determine the effects of basicity and MgO content on the reduction of iron oxides, vanadium oxides, and titanium oxides. The chemical compositions of vanadium-bearing iron and main phases of titanium slag were detected by XRF and XRD, respectively. The results show that the higher level of basicity is beneficial to the reduction ofiron oxides and vanadium oxides, and titanium content dropped in molten iron with the increasing basicity. As the content of MgO increased, the recovery rate of Fe increased slightly but the recovery rate of V increased considerably. The grades of Ti in molten iron were at a low level without significant change when MgO content was below 11%, but increased as MgO content increased to 12.75%. The optimum conditions for smelting vanadium titanomagnetite were about 11.38% content of MgO and quaternary basicity was about 1.10. The product, vanadium-bearing iron, can be applied in the converter steelmaking process, and titanium slag containing 50.34% TiO2 can be used by the acid leaching method.

  5. Fenton Redox Chemistry: Arsenite Oxidation by Metallic Surfaces

    NARCIS (Netherlands)

    Borges Freitas, S.C.; Van Halem, D.; Badruzzaman, A.B.M.; Van der Meer, W.G.J.

    2014-01-01

    Pre-oxidation of As(III) is necessary in arsenic removal processes in order to increase its efficiency. Therefore, the Fenton Redox Chemistry is defined by catalytic activation of H2O2 and currently common used for its redox oxidative properties. In this study the effect of H2O2 production catalysed

  6. Effect of Surface Oxidation on Interfacial Water Structure at a Pyrite (100) Surface as Studied by Molecular Dynamics Simulation

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Jiaqi; Miller, Jan D.; Dang, Liem X.; Wick, Collin D.

    2015-06-01

    In the first part of this paper, a Scanning Electron Microscopy and contact angle study of a pyrite surface (100) is reported describing the relationship between surface oxidation and the hydrophilic surface state. In addition to these experimental results, the following simulated surface states were examined using Molecular Dynamics Simulation (MDS): fresh unoxidized (100) surface; polysulfide at the (100) surface; elemental sulfur at the (100) surface. Crystal structures for the polysulfide and elemental sulfur at the (100) surface were simulated using Density Functional Theory (DFT) quantum chemical calculations. The well known oxidation mechanism which involves formation of a metal deficient layer was also described with DFT. Our MDS results of the behavior of interfacial water at the fresh and oxidized pyrite (100) surfaces without/with the presence of ferric hydroxide include simulated contact angles, number density distribution for water, water dipole orientation, water residence time, and hydrogen-bonding considerations. The significance of the formation of ferric hydroxide islands in accounting for the corresponding hydrophilic surface state is revealed not only from experimental contact angle measurements but also from simulated contact angle measurements using MDS. The hydrophilic surface state developed at oxidized pyrite surfaces has been described by MDS, on which basis the surface state is explained based on interfacial water structure. The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the DOE funded work performed by Liem X. Dang. Battelle operates the Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES.

  7. Ab initio atomistic thermodynamics study on the oxidation mechanism of binary and ternary alloy surfaces

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    Liu, Shi-Yu, E-mail: buaasyliu@gmail.com [College of Physics and Electronic Information Science, Tianjin Normal University, Tianjin 300387 (China); Department of Mechanical and Biomedical Engineering, City University of Hong Kong, Kowloon, Hong Kong (China); Liu, Shiyang [Institute of Information Optics, Zhejiang Normal University, Jinhua, Zhejiang 321004 (China); Li, De-Jun [College of Physics and Electronic Information Science, Tianjin Normal University, Tianjin 300387 (China); Wang, Sanwu, E-mail: sanwu-wang@utulsa.edu [Department of Physics a