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Sample records for cobalt oxide films

  1. Electrosynthesis of highly transparent cobalt oxide water oxidation catalyst films from cobalt aminopolycarboxylate complexes.

    PubMed

    Bonke, Shannon A; Wiechen, Mathias; Hocking, Rosalie K; Fang, Xi-Ya; Lupton, David W; MacFarlane, Douglas R; Spiccia, Leone

    2015-04-24

    Efficient catalysis of water oxidation represents one of the major challenges en route to efficient sunlight-driven water splitting. Cobalt oxides (CoOx ) have been widely investigated as water oxidation catalysts, although the incorporation of these materials into photoelectrochemical devices has been hindered by a lack of transparency. Herein, the electrosynthesis of transparent CoOx catalyst films is described by utilizing cobalt(II) aminopolycarboxylate complexes as precursors to the oxide. These complexes allow control over the deposition rate and morphology to enable the production of thin, catalytic CoOx films on a conductive substrate, which can be exploited in integrated photoelectrochemical devices. Notably, under a bias of 1.0 V (vs. Ag/AgCl), the film deposited from [Co(NTA)(OH2 )2 ](-) (NTA=nitrilotriacetate) decreased the transmission by only 10 % at λ=500 nm, but still generated >80 % of the water oxidation current produced by a [Co(OH2 )6 ](2+) -derived oxide film whose transmission was only 40 % at λ=500 nm.

  2. Fabrication of highly textured lithium cobalt oxide films by rapid thermal annealing

    DOEpatents

    Bates, John B.

    2003-05-13

    Systems and methods are described for fabrication of highly textured lithium cobalt oxide films by rapid thermal annealing. A method of forming a lithium cobalt oxide film includes depositing a film of lithium cobalt oxide on a substrate; rapidly heating the film of lithium cobalt oxide to a target temperature; and maintaining the film of lithium cobalt oxide at the target temperature for a target annealing time of at most, approximately 60 minutes. The systems and methods provide advantages because they require less time to implement and are, therefore less costly than previous techniques.

  3. Fabrication of highly textured lithium cobalt oxide films by rapid thermal annealing

    DOEpatents

    Bates, John B.

    2002-01-01

    Systems and methods are described for fabrication of highly textured lithium cobalt oxide films by rapid thermal annealing. A method of forming a lithium cobalt oxide film includes depositing a film of lithium cobalt oxide on a substrate; rapidly heating the film of lithium cobalt oxide to a target temperature; and maintaining the film of lithium cobalt oxide at the target temperature for a target annealing time of at most, approximately 60 minutes. The systems and methods provide advantages because they require less time to implement and are, therefore less costly than previous techniques.

  4. Fabrication of highly textured lithium cobalt oxide films by rapid thermal annealing

    DOEpatents

    Bates, John B.

    2003-04-29

    Systems and methods are described for fabrication of highly textured lithium cobalt oxide films by rapid thermal annealing. A method of forming a lithium cobalt oxide film includes depositing a film of lithium cobalt oxide on a substrate; rapidly heating the film of lithium cobalt oxide to a target temperature; and maintaining the film of lithium cobalt oxide at the target temperature for a target annealing time of at most, approximately 60 minutes. The systems and methods provide advantages because they require less time to implement and are, therefore less costly than previous techniques.

  5. Cobalt deposition in oxide films on reactor pipework. Final report

    SciTech Connect

    Bridle, D.A.; Bird, E.J.; Mitchell, C.R.

    1986-03-01

    This report details results of a program carried out by the UKAEA on the Winfrith SGHWR, to study the incorporation of cobalt into the corrosion product films formed on PWR primary circuit materials (stainless steel 304L, Inconel-600 and Zircaloy-4). An electromagnetic filter has been operated on a once through basis directly on the primary coolant blowdown line to remove particulate impurities. This has permitted an examination of the relative importance of soluble and insoluble species in the formation of corrosion product films. The selected alloys have been exposed to coolant up and downstream from the filter unit and data are presented which provide a detailed analysis of the coolant at these situations, with respect to soluble and insoluble, chemical and radiochemical species. Characterization of the corrosion product films has been carried out using scanning electron microscopy coupled with energy dispersive analysis using x-rays. Radiochemical analyses have been carried out using ..gamma..-spectrometry. The effectiveness of decontamination using Low Oxidation state Metal Ion (LOMI) reagent has been studied and data are presented on decontamination rates. 21 tabs.

  6. Boron-doped cobalt oxide thin films and its electrochemical properties

    NASA Astrophysics Data System (ADS)

    Kerli, S.

    2016-09-01

    The cobalt oxide and boron-doped cobalt oxide thin films were produced by spray deposition method. All films were obtained onto glass and fluorine-doped tin oxide (FTO) substrates at 400∘C and annealed at 550∘C. We present detailed analysis of the morphological and optical properties of films. XRD results show that boron doping disrupts the structure of the films. Morphologies of the films were investigated by using a scanning electron microscopy (SEM). Optical measurements indicate that the band gap energies of the films change with boron concentrations. The electrochemical supercapacitor performance test has been studied in aqueous 6 M KOH electrolyte and with scan rate of 5 mV/s. Measurements show that the largest capacitance is obtained for 3% boron-doped cobalt oxide film.

  7. Synthesis of Cobalt Oxides Thin Films Fractal Structures by Laser Chemical Vapor Deposition

    PubMed Central

    Haniam, P.; Kunsombat, C.; Chiangga, S.; Songsasen, A.

    2014-01-01

    Thin films of cobalt oxides (CoO and Co3O4) fractal structures have been synthesized by using laser chemical vapor deposition at room temperature and atmospheric pressure. Various factors which affect the density and crystallization of cobalt oxides fractal shapes have been examined. We show that the fractal structures can be described by diffusion-limited aggregation model and discuss a new possibility to control the fractal structures. PMID:24672354

  8. Synthesis of cobalt oxides thin films fractal structures by laser chemical vapor deposition.

    PubMed

    Haniam, P; Kunsombat, C; Chiangga, S; Songsasen, A

    2014-01-01

    Thin films of cobalt oxides (CoO and Co3O4) fractal structures have been synthesized by using laser chemical vapor deposition at room temperature and atmospheric pressure. Various factors which affect the density and crystallization of cobalt oxides fractal shapes have been examined. We show that the fractal structures can be described by diffusion-limited aggregation model and discuss a new possibility to control the fractal structures.

  9. High quality thin films of thermoelectric misfit cobalt oxides prepared by a chemical solution method

    PubMed Central

    Rivas-Murias, Beatriz; Manuel Vila-Fungueiriño, José; Rivadulla, Francisco

    2015-01-01

    Misfit cobaltates ([Bi/Ba/Sr/Ca/CoO]nRS[CoO2]q) constitute the most promising family of thermoelectric oxides for high temperature energy harvesting. However, their complex structure and chemical composition makes extremely challenging their deposition by high-vacuum physical techniques. Therefore, many of them have not been prepared as thin films until now. Here we report the synthesis of high-quality epitaxial thin films of the most representative members of this family of compounds by a water-based chemical solution deposition method. The films show an exceptional crystalline quality, with an electrical conductivity and thermopower comparable to single crystals. These properties are linked to the epitaxial matching of the rock-salt layers of the structure to the substrate, producing clean interfaces free of amorphous phases. This is an important step forward for the integration of these materials with complementary n-type thermoelectric oxides in multilayer nanostructures. PMID:26153533

  10. High quality thin films of thermoelectric misfit cobalt oxides prepared by a chemical solution method

    NASA Astrophysics Data System (ADS)

    Rivas-Murias, Beatriz; Manuel Vila-Fungueiriño, José; Rivadulla, Francisco

    2015-07-01

    Misfit cobaltates ([Bi/Ba/Sr/Ca/CoO]nRS[CoO2]q) constitute the most promising family of thermoelectric oxides for high temperature energy harvesting. However, their complex structure and chemical composition makes extremely challenging their deposition by high-vacuum physical techniques. Therefore, many of them have not been prepared as thin films until now. Here we report the synthesis of high-quality epitaxial thin films of the most representative members of this family of compounds by a water-based chemical solution deposition method. The films show an exceptional crystalline quality, with an electrical conductivity and thermopower comparable to single crystals. These properties are linked to the epitaxial matching of the rock-salt layers of the structure to the substrate, producing clean interfaces free of amorphous phases. This is an important step forward for the integration of these materials with complementary n-type thermoelectric oxides in multilayer nanostructures.

  11. Facile synthesis of cobalt-doped zinc oxide thin films for highly efficient visible light photocatalysts

    NASA Astrophysics Data System (ADS)

    Altintas Yildirim, Ozlem; Arslan, Hanife; Sönmezoğlu, Savaş

    2016-12-01

    Cobalt-doped zinc oxide (Co:ZnO) thin films with dopant contents ranging from 0 to 5 at.% were prepared using the sol-gel method, and their structural, morphological, optical, and photocatalytic properties were characterized. The effect of the dopant content on the photocatalytic properties of the films was investigated by examining the degradation behavior of methylene blue (MB) under visible light irradiation, and a detailed investigation of their photocatalytic activities was performed by determining the apparent quantum yields (AQYs). Co2+ ions were observed to be substitutionally incorporated into Zn2+ sites in the ZnO crystal, leading to lattice parameter constriction and band gap narrowing due to the photoinduced carriers produced under the visible light irradiation. Thus, the light absorption range of the Co:ZnO films was improved compared with that of the undoped ZnO film, and the Co:ZnO films exhibited highly efficient photocatalytic activity (∼92% decomposition of MB after 60-min visible light irradiation for the 3 at.% Co:ZnO film). The AQYs of the Co:ZnO films were greatly enhanced under visible light irradiation compared with that of the undoped ZnO thin film, demonstrating the effect of the Co doping level on the photocatalytic activity of the films.

  12. Conduction and Reactivity in Heterogeneous-Molecular Catalysis: New Insights in Water Oxidation Catalysis by Phosphate Cobalt Oxide Films.

    PubMed

    Costentin, Cyrille; Porter, Thomas R; Savéant, Jean-Michel

    2016-05-04

    Cyclic voltammetry of phosphate cobalt oxide (CoPi) films catalyzing O2-evolution from water oxidation as a function of scan rate, phosphate concentration and film thickness allowed for new insights into the coupling between charge transport and catalysis. At pH = 7 and low buffer concentrations, the film is insulating below 0.8 (V vs SHE) but becomes conductive above 0.9 (V vs SHE). Between 1.0 to 1.3 (V vs SHE), the mesoporous structure of the film gives rise to a large thickness-dependent capacitance. At higher buffer concentrations, two reversible proton-coupled redox couples appear over the capacitive response with 0.94 and 1.19 (V vs SHE) pH = 7 standard potentials. The latter is, at most, very weakly catalytic and not responsible for the large catalytic current observed at higher potentials. CV-response analysis showed that the amount of redox-active cobalt-species in the film is small, less than 10% of total. The catalytic process involves a further proton-coupled-electron-transfer and is so fast that it is controlled by diffusion of phosphate, the catalyst cofactor. CV-analysis with newly derived relationships led to a combination of the catalyst standard potential with the catalytic rate constant and a lower-limit estimation of these parameters. The large currents resulting from the fast catalytic reaction result in significant potential losses related to charge transport through the film. CoPi films appear to combine molecular catalysis with semiconductor-type charge transport. This mode of heterogeneous molecular catalysis is likely to occur in many other catalytic films.

  13. Tuning the magnetism of epitaxial cobalt oxide thin films by electron beam irradiation

    NASA Astrophysics Data System (ADS)

    Lan, Q. Q.; Zhang, X. J.; Shen, X.; Yang, H. W.; Zhang, H. R.; Guan, X. X.; Wang, W.; Yao, Y.; Wang, Y. G.; Peng, Y.; Liu, B. G.; Sun, J. R.; Yu, R. C.

    2017-07-01

    Tuning magnetic properties of perovskite thin films is a central topic of recent studies because of its fundamental significance. In this work, we demonstrated the modification of the magnetism of L a0.9C a0.1Co O3 (LCCO) thin films by introducing a stripelike superstructure in a controllable manner using electron beam irradiation (EBI) in a transmission electron microscope. The microstructure, electronic structure, strain change, and origin of magnetism of the LCCO thin films were studied in detail using aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and ab initio calculations based on density functional theory. The results indicate that the EBI-induced unit cell volume expansion accompanies the formation of oxygen vacancies and leads to the spin state transition of Co ions. The low spin state of C o4 + ions depress the stripelike superstructure, while higher spin states of Co ions with lower valences are conductive to the formation of "dark stripes". Our work clarifies the origin of magnetism of epitaxial LCCO thin films, benefiting a comprehensive understanding of correlated physics in cobalt oxide thin films.

  14. Pulsed laser deposition of porous N-carbon supported cobalt (oxide) thin films for highly efficient oxygen evolution.

    PubMed

    Bayatsarmadi, Bita; Zheng, Yao; Casari, Carlo Spartaco; Russo, Valeria; Qiao, Shi-Zhang

    2016-09-29

    Identification of efficient non-precious metal catalysts for the oxygen evolution reaction (OER) remains a great challenge. Here we report robust cobalt (oxide) nanoparticles deposited on a porous nitrogen-doped carbon (N-carbon) film prepared by pulsed laser deposition under a reactive background gas, which exhibit highly efficient OER performance with a low overpotential and high stability.

  15. The solid state conversion reaction of cobalt oxide and iron fluoride thin films

    NASA Astrophysics Data System (ADS)

    Thorpe, Ryan

    Iron (II) fluoride and cobalt (II) oxide are candidate electrode materials for a new class of rechargeable lithium ion batteries known as conversion batteries. Although the energy storage capacity of these materials represents a significant improvement over that of conventional electrode materials, many challenges must be overcome before conversion batteries can become commercially viable. Chief among these challenges is a loss of energy storage capacity as a function of the number of charge-discharge cycles. In this study, FeF2 and CoO thin films have been studied as solid state analogues for lithium ion battery electrodes. These films were grown with different crystalline orientations and exposed to lithium in an ultra high vacuum chamber in order to simulate the discharge of a conversion electrode. The electronic structure and chemical phase of the films before and after exposure to lithium were characterized using x-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), and inverse photoemission spectroscopy (IPS). The depth and homogeneity of the conversion reaction in the thin films was measured as a function of lithium exposure using angle-resolved XPS (ARXPS). The crystalline structure and morphology were studied using scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). For polycrystalline FeF2 and CoO films, the products of the solid state conversion reactions were similar to those observed in electrochemical measurements. However, parasitic reaction pathways were identified for both reactions. The products of these reaction were found to inhibit the full conversion of the thin films, and are possibly responsible for the poor reaction kinetics in electrochemical cells. Furthermore, the diffusion of lithium into the FeF2 and CoO surfaces, and the concomitant conversion reaction, was found to depend strongly on the orientation of the surface. These differences in diffusivity could partially be

  16. Cobalt (II) β-diketonate adducts as new precursors for the growth of cobalt oxide films by liquid injection MOCVD

    NASA Astrophysics Data System (ADS)

    Pasko, S.; Abrutis, A.; Hubert-Pfalzgraf, L. G.; Kubilius, V.

    2004-02-01

    New metalorganic compounds—adducts of cobalt(II) acetylacetonate (acac) and cobalt(II) 2,2,6,6-tetramethyl-3,5-heptanedionate (thd) with N,N,N',N'-tetramethyl-1,2-diaminoethane have been synthesized and studied as potential precursors for liquid injection metalorganic chemical vapor deposition of Co 3O 4 films. The properties of the films were compared with those deposited using standard [Co(acac) 2] 4 and Co(thd) 2 precursors. Depositions were carried out at 350-600°C on LaAlO 3 (1 0 0), sapphire (R-plane), MgO (1 0 0) and Si (1 0 0) substrates. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and atomic force microscopy. Depending on substrate material, highly (1 1 0) or (1 0 0) textured Co 3O 4 films have been deposited; moreover, films exhibited preferential in-plane orientation. No significant difference has been found in the quality of Co 3O 4 films deposited from different precursors.

  17. Exchange Bias Optimization by Controlled Oxidation of Cobalt Nanoparticle Films Prepared by Sputter Gas Aggregation.

    PubMed

    Antón, Ricardo López; González, Juan A; Andrés, Juan P; Normile, Peter S; Canales-Vázquez, Jesús; Muñiz, Pablo; Riveiro, José M; De Toro, José A

    2017-03-11

    Porous films of cobalt nanoparticles have been obtained by sputter gas aggregation and controllably oxidized by air annealing at 100 °C for progressively longer times (up to more than 1400 h). The magnetic properties of the samples were monitored during the process, with a focus on the exchange bias field. Air annealing proves to be a convenient way to control the Co/CoO ratio in the samples, allowing the optimization of the exchange bias field to a value above 6 kOe at 5 K. The occurrence of the maximum in the exchange bias field is understood in terms of the density of CoO uncompensated spins and their degree of pinning, with the former reducing and the latter increasing upon the growth of a progressively thicker CoO shell. Vertical shifts exhibited in the magnetization loops are found to correlate qualitatively with the peak in the exchange bias field, while an increase in vertical shift observed for longer oxidation times may be explained by a growing fraction of almost completely oxidized particles. The presence of a hummingbird-like form in magnetization loops can be understood in terms of a combination of hard (biased) and soft (unbiased) components; however, the precise origin of the soft phase is as yet unresolved.

  18. Exchange Bias Optimization by Controlled Oxidation of Cobalt Nanoparticle Films Prepared by Sputter Gas Aggregation

    PubMed Central

    Antón, Ricardo López; González, Juan A.; Andrés, Juan P.; Normile, Peter S.; Canales-Vázquez, Jesús; Muñiz, Pablo; Riveiro, José M.; De Toro, José A.

    2017-01-01

    Porous films of cobalt nanoparticles have been obtained by sputter gas aggregation and controllably oxidized by air annealing at 100 °C for progressively longer times (up to more than 1400 h). The magnetic properties of the samples were monitored during the process, with a focus on the exchange bias field. Air annealing proves to be a convenient way to control the Co/CoO ratio in the samples, allowing the optimization of the exchange bias field to a value above 6 kOe at 5 K. The occurrence of the maximum in the exchange bias field is understood in terms of the density of CoO uncompensated spins and their degree of pinning, with the former reducing and the latter increasing upon the growth of a progressively thicker CoO shell. Vertical shifts exhibited in the magnetization loops are found to correlate qualitatively with the peak in the exchange bias field, while an increase in vertical shift observed for longer oxidation times may be explained by a growing fraction of almost completely oxidized particles. The presence of a hummingbird-like form in magnetization loops can be understood in terms of a combination of hard (biased) and soft (unbiased) components; however, the precise origin of the soft phase is as yet unresolved. PMID:28336895

  19. Anisotropy, band-to-band transitions, phonon modes, and oxidation properties of cobalt-oxide core-shell slanted columnar thin films

    SciTech Connect

    Mock, Alyssa Korlacki, Rafał; Briley, Chad; Sekora, Derek; Schubert, Eva; Schubert, Mathias; Hofmann, Tino; Wilson, Peter; Sinitskii, Alexander

    2016-02-01

    Highly ordered and spatially coherent cobalt slanted columnar thin films (SCTFs) were deposited by glancing angle deposition onto silicon substrates, and subsequently oxidized by annealing at 475 °C. Scanning electron microscopy, Raman scattering, generalized ellipsometry, and density functional theory investigations reveal shape-invariant transformation of the slanted nanocolumns from metallic to transparent metal-oxide core-shell structures with properties characteristic of spinel cobalt oxide. We find passivation of Co-SCTFs yielding Co-Al{sub 2}O{sub 3} core-shell structures produced by conformal deposition of a few nanometers of alumina using atomic layer deposition fully prevents cobalt oxidation in ambient and from annealing up to 475 °C.

  20. Electronic structure at transition metal phthalocyanine-transition metal oxide interfaces: Cobalt phthalocyanine on epitaxial MnO films

    SciTech Connect

    Glaser, Mathias; Peisert, Heiko Adler, Hilmar; Aygül, Umut; Ivanovic, Milutin; Chassé, Thomas; Nagel, Peter; Merz, Michael; Schuppler, Stefan

    2015-03-14

    The electronic structure of the interface between cobalt phthalocyanine (CoPc) and epitaxially grown manganese oxide (MnO) thin films is studied by means of photoemission (PES) and X-ray absorption spectroscopy (XAS). Our results reveal a flat-lying adsorption geometry of the molecules on the oxide surface which allows a maximal interaction between the π-system and the substrate. A charge transfer from MnO, in particular, to the central metal atom of CoPc is observed by both PES and XAS. The change of the shape of N-K XAS spectra at the interface points, however, to the involvement of the Pc macrocycle in the charge transfer process. As a consequence of the charge transfer, energetic shifts of MnO related core levels were observed, which are discussed in terms of a Fermi level shift in the semiconducting MnO films due to interface charge redistribution.

  1. Pulsed Laser Deposition of Nanoporous Cobalt Thin Films

    PubMed Central

    Jin, Chunming; Nori, Sudhakar; Wei, Wei; Aggarwal, Ravi; Kumar, Dhananjay; Narayan, Roger J.

    2013-01-01

    Nanoporous cobalt thin films were deposited on anodized aluminum oxide (AAO) membranes at room temperature using pulsed laser deposition. Scanning electron microscopy demonstrated that the nanoporous cobalt thin films retained the monodisperse pore size and high porosity of the anodized aluminum oxide substrates. Temperature- and field-dependent magnetic data obtained between 10 K and 350 K showed large hysteresis behavior in these materials. The increase of coercivity values was larger for nanoporous cobalt thin films than for multilayered cobalt/alumina thin films. The average diameter of the cobalt nanograins in the nanoporous cobalt thin films was estimated to be ~5 nm for blocking temperatures near room temperature. These results suggest that pulsed laser deposition may be used to fabricate nanoporous magnetic materials with unusual properties for biosensing, drug delivery, data storage, and other technological applications. PMID:19198344

  2. Pulsed laser deposition of nanoporous cobalt thin films.

    PubMed

    Jin, Chunming; Nori, Sudhakar; Wei, Wei; Aggarwal, Ravi; Kumar, Dhananjay; Narayan, Roger J

    2008-11-01

    Nanoporous cobalt thin films were deposited on anodized aluminum oxide (AAO) membranes at room temperature using pulsed laser deposition. Scanning electron microscopy demonstrated that the nanoporous cobalt thin films retained the monodisperse pore size and high porosity of the anodized aluminum oxide substrates. Temperature- and field-dependent magnetic data obtained between 10 K and 350 K showed large hysteresis behavior in these materials. The increase of coercivity values was larger for nanoporous cobalt thin films than for multilayered cobalt/alumina thin films. The average diameter of the cobalt nanograins in the nanoporous cobalt thin films was estimated to be approsimately 5 nm for blocking temperatures near room temperature. These results suggest that pulsed laser deposition may be used to fabricate nanoporous magnetic materials with unusual properties for biosensing, drug delivery, data storage, and other technological applications.

  3. Photocatalytic activity of cobalt-doped zinc oxide thin film prepared using the spray coating technique

    NASA Astrophysics Data System (ADS)

    Sutanto, Heri; Wibowo, Singgih; Hadiyanto; Arifin, Mohammad; Hidayanto, Eko

    2017-07-01

    We report on the synthesis, characterization and photocatalytic activity of ZnO: Co thin films coated onto amorphous glass substrates by sol-gel spray coating technique. Structural and optical properties of the films were evaluated using x-ray diffractometer (XRD) and uv-vis spectrophotometer (UV-Vis), respectively. XRD patterns showed that the samples exhibited hexagonal wurtzite structure. The addition of cobalt reduced the (0 0 2) peak. This doping also reduces transparency and optical band gap. The band gap (E g) markedly decreased from 3.20 eV to 3.00 eV for undoped ZnO and ZnO: Co with 10 mol% of doping concentration, respectively. Our thin films exhibited good structural, optical and photo cataytic properties. In this study, ZnO with 4 mol% of Co was observed to have the highest photocatalytic activity with methylene blue (MB) degradation of about 76.31% for 2 h under UV irradiation.

  4. Microstructure and Thermoelectric Properties of Screen-Printed Thick Films of Misfit-Layered Cobalt Oxides with Ag Addition

    NASA Astrophysics Data System (ADS)

    Van Nong, Ngo; Samson, Alfred Junio; Pryds, Nini; Linderoth, Søren

    2012-06-01

    Thermoelectric properties of thick (~60 μm) films prepared by a screen-printing technique using p-type misfit-layered cobalt oxide Ca3Co4O9+ δ with Ag addition have been studied. The screen-printed films were sintered in air at various temperatures ranging from 973 K to 1223 K. After each sintering process, crystal and microstructure analyses were carried out to determine the optimal sintering condition. The results show that the thermoelectric properties of pure Ca3Co4O9+ δ thick film are comparable to those of cold isostatic pressing (CIP) samples. We found that the maximum power factor was improved by about 67% (to 0.3 mW/m K2) for film with proper silver (Ag) metallic inclusions as compared with 0.18 mW/m K2 for pure Ca3Co4O9+ δ film under the same sintering condition of 1223 K for 2 h in air.

  5. Photoinduced electron transfer in layer-by-layer thin solid films containing cobalt oxide nanosheets, porphyrin, and methyl viologen.

    PubMed

    Sasai, R; Kato, Y; Soontornchaiyakul, W; Usami, H; Masumori, A; Norimatsu, W; Fujimura, T; Takagi, S

    2017-02-15

    The well-known layer-by-layer (LbL) method can be used to prepare solid thin films with a controlled electron transfer direction by appropriately stacking metal oxide nanosheets and functional organic ions. In this study, we prepared thin solid films consisting of cobalt oxide nanosheets (CoNSs) as the electron transfer medium, α,β,γ,δ-tetrakis(1-methylpyridinium-4-yl)porphyrin (TMPyP) as the electron donor, and 1,1'-dimethyl-4,4'-bipyridinium or methyl viologen (MV) as the electron acceptor. We investigated the photoinduced electron transfer phenomenon in these films by irradiating them with 450 nm light. Irradiating the LbL thin solid films prepared with the CoNS/TMPyP/CoNS/MV/CoNS sequence under reduced pressure led to the production of a one-electron reduction compound of MV. Hence, photoinduced electron transfer from TMPyP to MV bound to CoNSs occurred in these LbL thin solid films. However, the conduction band of CoNSs, as determined by the photoabsorption spectral and photoelectrochemical measurements, was much higher than the lowest unoccupied molecular orbital level of TMPyP. Our findings indicate that the observed equipotential photoinduced electron transfer was caused by the metallic electron conductivity of CoNSs, which show a unique charge arrangement of Co(3+) and Co(4+). Moreover, it was also found that the observed photoinduced charge separation state has a longer life-time (>5 h) under the reduced conditions.

  6. Stabilized CdSe-CoPi composite photoanode for light-assisted water oxidation by transformation of a CdSe/cobalt metal thin film.

    PubMed

    Costi, Ronny; Young, Elizabeth R; Bulović, Vladimir; Nocera, Daniel G

    2013-04-10

    Integration of water splitting catalysts with visible-light-absorbing semiconductors would enable direct solar-energy-to-fuel conversion schemes such as those based on water splitting. A disadvantage of some common semiconductors that possess desirable optical bandgaps is their chemical instability under the conditions needed for oxygen evolution reaction (OER). In this study, we demonstrate the dual benefits gained from using a cobalt metal thin-film as the precursor for the preparation of cobalt-phosphate (CoPi) OER catalyst on cadmium chalcogenide photoanodes. The cobalt layer protects the underlying semiconductor from oxidation and degradation while forming the catalyst and simultaneously facilitates the advantageous incorporation of the cadmium chalcogenide layer into the CoPi layer during continued processing of the electrode. The resulting hybrid material forms a stable photoactive anode for light-assisted water splitting.

  7. Fabrication of Co3O4 mesoporous thin films by using cobalt/chitosan precursor on fluorine-doped tin oxide glass

    NASA Astrophysics Data System (ADS)

    Yang, Hui-Chia; Tsai, Jung-Che

    2017-06-01

    For the development of high-performance and low-cost electrode materials, many alternative materials have been fabricated by various groups. Among these materials, Co3O4 has been demonstrated to be a promising candidate for pseudocapacitors because of its low potential environmental pollution, low cost, and extremely high theoretical specific capacitance. Chitosan, a linear polysaccharide produced by the deacetylation of chitin, is a nontoxic, tissue-compatible polymeric biomaterial. It is usually used to eliminate or filter the heavy metals in wastewater. That is, chitosan can act as a deliverer of metal ions and a nanostructure constructer of metals (or metal oxides). In this study, a facile approach is developed to synthesize mesoporous cobalt oxide thin films on fluorine-doped tin oxide (FTO)-coated glass with environmentally friendly chitosan, which chelates cobalt ions.

  8. Sputter deposition and characterization of lithium cobalt oxide thin films and their applications in thin-film rechargeable lithium batteries

    SciTech Connect

    Wang, B.; Bates, J.B.; Luck, C.F.; Sales, B.C.; Zuhr, R.A.; Robertson, J.D.

    1996-01-01

    Li Co oxide thin films were deposited by rf magnetron sputtering of a LiCoO{sub 2} target in a 3:1 Ar/O{sub 2} mixture gas. From proton-induced gamma-ray emission analysis and Rutherford backscattering spectrometry, the average composition of these films was determined to be Li{sub 1.15}CoO{sub 2.16}. X-ray powder diffraction patterns of films annealed in air at 500-700 C were consistent with regular rhombohedral structure of crystalline LiCoO{sub 2}. Discharge curves of thin film lithium cells with amoprohous LiCoO{sub 2} showed no obvious structural transition between 4.2 and 1.5 V. Shape of discharge curves of cells with polycrystalline cathodes were consistent with a two-phase voltage plateau at {similar_to}3.9 V with a relatively large capacity and two additional smaller plateaus at higher voltages. Cells with the 700 C annealed cathodes showed a capacity loss of {similar_to} after 1000 cycles between 4.2 and 3.0 V.

  9. The role of cobalt doping on magnetic and optical properties of indium oxide nanostructured thin film prepared by sol–gel method

    SciTech Connect

    Baqiah, H.; Ibrahim, N.B.; Halim, S.A.; Flaifel, Moayad Husein; Abdi, M.H.

    2015-03-15

    Highlights: • Cobalt doped indium oxide thin films have been prepared by a sol–gel method. • The films have a thickness less than 100 nm and grain size less than 10 nm. • The lattice parameters and grain size of films decrease as Co content increase. • The optical band gap of films increases as the grain size decrease. • The films' magnetic behaviour is sensitive to ratio of oxygen defects per Co ions. - Abstract: The effect of Co doping concentration, (x = 0.025–0.2), in In{sub 2−x}Co{sub x}O{sub 3} thin film was investigated by X-rays diffraction (XRD), transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), Ultraviolet visible spectrophotometer (UV–vis) and vibrating sample magnetometer (VSM). All films were prepared by sol–gel technique followed by spin coating process. The XRD and XPS measurements indicate that Co{sup +2} has been successfully substituted in In{sup +3} site. The TEM measurement shows nanostructure morphology of the films. The doping of Co in indium oxide resulted in a decrease in the lattice parameters and grain size while the band gap increased with increasing Co concentration. Further, by comparing VSM and XPS results, the magnetic behaviour of the films were found to be sensitive to Co concentrations, oxygen vacancies and ratio of oxygen defects to Co concentrations. The magnetic behaviour of the prepared films was explained using bound magnetic polaron (BMP) model.

  10. Tuning the structural, electrical and optical properties of tin oxide thin films via cobalt doping and annealing

    NASA Astrophysics Data System (ADS)

    El Sayed, A. M.; Taha, S.; Shaban, Mohamed; Said, G.

    2016-07-01

    Pure and cobalt-doped SnO2 (Sn1-xCoxO2, 0 ≤ x ≤ 0.09) thin films were grown by dissolving SnCl2·2H2O in ethanol and spin coating on glass substrates. The X-ray diffraction and Raman analysis show that the films are polycrystalline and correspond to the rutile phase with a preferred orientation along (110) direction. The grain size and crystallinity of the films that annealed at 450 °C for 1.0 h are enhanced after annealing at 500 °C for 2.0 h. According to atomic force microscopy (AFM), the films consist of grains influenced by doping and annealing temperature and time. I-V measurements reveal non-Ohmic contacts of the films with the electrodes. Transmittance spectra, optical band gap (Eg), Urbach energy (EU), refractive index, film thickness, and the optical constants of the films are dependent on the Co content and annealing conditions. The obtained results illustrate the possibility of controlling the film's physical properties for the optoelectronic devices and applications.

  11. Oxidation of low cobalt alloys

    NASA Technical Reports Server (NTRS)

    Barrett, C. A.

    1982-01-01

    Four high temperature alloys: U-700, Mar M-247, Waspaloy and PM/HIP U-700 were modified with various cobalt levels ranging from 0 percent to their nominal commercial levels. The alloys were then tested in cyclic oxidation in static air at temperatures ranging from 1000 to 1150 C at times from 500 to 100 1 hour cycles. Specific weight change with time and X-ray diffraction analyses of the oxidized samples were used to evaluate the alloys. The alloys tend to be either Al2O3/aluminate spinel or Cr2O3/chromite spinel formers depending on the Cr/Al ratio in the alloy. Waspaloy with a ratio of 15:1 is a strong Cr2O3 former while this U-700 with a ratio of 3.33:1 tends to form mostly Cr2O3 while Mar M-247 with a ratio of 1.53:1 is a strong Al2O3 former. The best cyclic oxidation resistance is associated with the Al2O3 formers. The cobalt levels appear to have little effect on the oxidation resistance of the Al2O3/aluminate spinel formers while any tendency to form Cr2O3 is accelerated with increased cobalt levels and leads to increased oxidation attack.

  12. Metal oxide films on metal

    DOEpatents

    Wu, Xin D.; Tiwari, Prabhat

    1995-01-01

    A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

  13. Degradation mechanisms of lithium-rich nickel manganese cobalt oxide cathode thin films

    SciTech Connect

    Baggetto, Loïc; Mohanty, Debasish; Meisner, Roberta A.; Bridges, Craig A.; Daniel, Claus; Wood III, David L.; Dudney, Nancy J.; Veith, Gabriel M.

    2014-05-14

    We demonstrate a confinement effect where gold nanoparticles trapped within N-functionalized carbon nanofibers (N-CNFs) are more active for polyol oxidation and promote selectivity towards di-acid products, whereas AuNPs trapped on the surface produce as a major by-product the one derived from C C cleavage. As a result, the behavior of NPs confined inside the N-CNF channels can be attributed to a different, possibly multiple, coordination of glycerol on the active site

  14. Degradation mechanisms of lithium-rich nickel manganese cobalt oxide cathode thin films

    DOE PAGES

    Baggetto, Loïc; Mohanty, Debasish; Meisner, Roberta A.; ...

    2014-05-14

    We demonstrate a confinement effect where gold nanoparticles trapped within N-functionalized carbon nanofibers (N-CNFs) are more active for polyol oxidation and promote selectivity towards di-acid products, whereas AuNPs trapped on the surface produce as a major by-product the one derived from C C cleavage. As a result, the behavior of NPs confined inside the N-CNF channels can be attributed to a different, possibly multiple, coordination of glycerol on the active site

  15. Thermal oxidation of cobalt disilicide

    NASA Astrophysics Data System (ADS)

    Bartur, M.; Nicolet, M.-A.

    1982-10-01

    The thermal oxidation kinetics of cobalt disilicide on Si substrates have been investigated in the temperature range of 650 1100 °C in dry oxygen and wet oxygen. A surface layer of SiO2 grows parabolically with time. The growth rate is independent of the substrate orientation (<111> or <100>) and thickness of the CoSi2 layer. We surmize that the oxidation mechanism is dominated by the diffusion of an oxidant through the growing SiO2. Activation energies for the dry and wet oxidation are 1.49±0.05 eV and 1.05±0.05 eV, respectively. The kinetics is exactly the same as for NiSi2 oxidation which suggest that the same mechanism controls the oxidation of these two similar suicides.

  16. Addressing the selectivity issue of cobalt doped zinc oxide thin film iso-butane sensors: Conductance transients and principal component analyses

    NASA Astrophysics Data System (ADS)

    Ghosh, A.; Majumder, S. B.

    2017-07-01

    Iso-butane (i-C4H10) is one of the major components of liquefied petroleum gas which is used as fuel in domestic and industrial applications. Developing chemi-resistive selective i-C4H10 thin film sensors remains a major challenge. Two strategies were undertaken to differentiate carbon monoxide, hydrogen, and iso-butane gases from the measured conductance transients of cobalt doped zinc oxide thin films. Following the first strategy, the response and recovery transients of conductances in these gas environments are fitted using the Langmuir adsorption kinetic model to estimate the heat of adsorption, response time constant, and activation energies for adsorption (response) and desorption (recovery). Although these test gases have seemingly different vapor densities, molecular diameters, and reactivities, analyzing the estimated heat of adsorption and activation energies (for both adsorption and desorption), we could not differentiate these gases unequivocally. However, we have found that the lower the vapor density, the faster the response time irrespective of the test gas concentration. As a second strategy, we demonstrated that feature extraction of conductance transients (using fast Fourier transformation) in conjunction with the pattern recognition algorithm (principal component analysis) is more fruitful to address the cross-sensitivity of Co doped ZnO thin film sensors. We have found that although the dispersion among different concentrations of hydrogen and carbon monoxide could not be avoided, each of these three gases forms distinct clusters in the plot of principal component 2 versus 1 and therefore could easily be differentiated.

  17. Structural, morphological, and electrical characteristics of the electrodeposited cobalt oxide electrode for supercapacitor applications

    SciTech Connect

    Kandalkar, Sunil G.; Lee, Hae-Min; Chae, Heeyeop; Kim, Chang-Koo

    2011-01-15

    Cobalt oxide (Co{sub 3}O{sub 4}) thin films were prepared through electrodeposition on copper substrates using an ammonia-complexed cobalt chloride solution. The structural and morphological properties of the film were studied using an X-ray diffractometer and scanning electron microscopy, and the results showed that the electrodeposited cobalt oxide film had a nanocrystalline and porous structure. The electrochemical behavior of the electrodeposited cobalt oxide electrode was evaluated in a KOH solution using cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge tests. The electrodeposited cobalt oxide electrode exhibited a specific capacitance of 235 F/g at a scan rate of 20 mV/s. The specific energy and the specific power of the electrode were 4.0 Wh/kg and 1.33 kW/kg, respectively.

  18. Preparation and characterization of copper-doped cobalt oxide electrodes.

    PubMed

    Rosa-Toro, A La; Berenguer, R; Quijada, C; Montilla, F; Morallón, E; Vazquez, J L

    2006-11-30

    Cobalt oxide (Co3O4) and copper-doped cobalt oxide (CuxCo(3-x)O4) films have been prepared onto titanium support by the thermal decomposition method. The electrodes have been characterized by different techniques such as cyclic voltammetry, scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The effect on the electrochemical and crystallographic properties and surface morphology of the amount of copper in the oxide layer has been analyzed. The XPS spectra correspond to a characteristic monophasic Cu-Co spinel oxides when x is below 1. However, when the copper content exceeds that for the stoichiometric CuCo2O4 spinel, a new CuO phase segregates at the surface. The analysis of the surface cation distribution indicates that Cu(II) has preference for octahedral sites.

  19. Solvothermal synthesis of cobalt oxides nanocrystals

    NASA Astrophysics Data System (ADS)

    Shao, Wenyao; Yan, Mengwen

    2017-05-01

    CoO and Co3O4 nanocrystals (NCs) were synthesized by a one-pot solvothermal reaction in the presence of the oxidant NaOH and the surfactant cetyltrimethyl ammonium bromide (CTAB). The as-prepared cobalt oxide nanoparticles are size uniformed and have good dispersibility and good crystallinity.

  20. Cobalt

    SciTech Connect

    1993-02-01

    Cobalt is typical a by- or co-product with copper or nickel. The average crustal abundance of cobalt is 23 pans per million. Cobalt-containing minerals include cobaltite, skutterudite, and linnaeite. Due to the diversity of cobalt deposits, several techniques are used to extract the ore. The copper/cobalt-bearing ores of Zaire are extracted by open pit and underground methods. In Zambia, similar deposits are mined using modified sublevel, and cut-and-fill underground stoping methods. The sulfide and oxide ore concentrates mined in Zaire are roasted and leached in sulfuric acid. Copper is subsequently recovered by electrolysis, and cobalt is precipitated in the form of a hydrate. Finally, the hydrate is dissolved in acid and cobalt is recovered by electrolysis.

  1. THE BEHAVIOR OF SUPERALLOY OXIDE FILMS IN MOLTEN SALTS.

    DTIC Science & Technology

    NICKEL ALLOYS , CORROSION), (*FILMS, OXIDES), CORROSION RESISTANT ALLOYS , SALTS, CORROSIVE LIQUIDS, HIGH TEMPERATURE, NICKEL COMPOUNDS, SODIUM...COMPOUNDS, SULFATES, CHLORIDES, CHROMIUM COMPOUNDS, CHROMIUM ALLOYS , MOLYBDENUM ALLOYS , COBALT ALLOYS , ALUMINUM ALLOYS , TITANIUM ALLOYS , IRON ALLOYS , NICKEL, OXIDATION

  2. Colloidal polymerization of polymer-coated ferromagnetic nanoparticles into cobalt oxide nanowires.

    PubMed

    Keng, Pei Yuin; Kim, Bo Yun; Shim, In-Bo; Sahoo, Rabindra; Veneman, Peter E; Armstrong, Neal R; Yoo, Heemin; Pemberton, Jeanne E; Bull, Mathew M; Griebel, Jared J; Ratcliff, Erin L; Nebesny, Kenneth G; Pyun, Jeffrey

    2009-10-27

    The preparation of polystyrene-coated cobalt oxide nanowires is reported via the colloidal polymerization of polymer-coated ferromagnetic cobalt nanoparticles (PS-CoNPs). Using a combination of dipolar nanoparticle assembly and a solution oxidation of preorganized metallic colloids, interconnected nanoparticles of cobalt oxide spanning micrometers in length were prepared. The colloidal polymerization of PS-CoNPs into cobalt oxide (CoO and Co(3)O(4)) nanowires was achieved by bubbling O(2) into PS-CoNP dispersions in 1,2-dichlorobenzene at 175 degrees C. Calcination of thin films of PS-coated cobalt oxide nanowires afforded Co(3)O(4) metal oxide materials. Transmission electron microscopy (TEM) revealed the formation of interconnected nanoparticles of cobalt oxide with hollow inclusions, arising from a combination of dipolar assembly of PS-CoNPs and the nanoscale Kirkendall effect in the oxidation reaction. Using a wide range of spectroscopic and electrochemical characterization techniques, we demonstrate that cobalt oxide nanowires prepared via this novel methodology were electroactive with potential applications as nanostructured electrodes for energy storage.

  3. Fabrication of iron-doped cobalt oxide nanocomposite films by electrodeposition and application as electrocatalyst for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Zhang, Jingxuan; Wang, Xuemei; Qin, Dongdong; Xue, Zhonghua; Lu, Xiaoquan

    2014-11-01

    In this work, Fe-doped Co3O4 nanofilms were fabricated by electrodeposition on FTO glass substrates for the first time. The structures of the as-prepared nanofilms were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Characterization results demonstrate that Fe was doped homogeneously in the nanofilms. As the different concentration ratios of Fe2+/Co2+ were explored, nanofilm with the ratio of 1:5 exhibits the optimal performance in electrochemical properties assessments. It is considered that the difference in the catalytic activities for the ORR of the samples may be due to the fact that the joining of iron changed the catalyst surface's electric state and enhanced the acidity of cobalt centers, on the other hand, the doping process probably modified the absorption property of the nanofilms. The experimental results suggest that the Fe-doped Co3O4 nanofilms in this work exhibit favorable electrocatalytic activity toward ORR and appear to be promising cathodic electrocatalyst in alkaline fuel cells.

  4. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium manganese...

  5. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium manganese...

  6. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium manganese...

  7. On the cobalt and cobalt oxide electrodeposition from a glyceline deep eutectic solvent.

    PubMed

    Sakita, Alan M P; Della Noce, Rodrigo; Fugivara, Cecílio S; Benedetti, Assis V

    2016-09-14

    The electrodeposition of cobalt and cobalt oxides from a glyceline deep eutectic solvent is reported. Cyclic voltammetry, chronoamperometry, scanning electron microscopy, and Raman spectroscopy are employed to study the Co deposition processes. Surface analysis reveals that metallic cobalt is deposited at potentials less negative than the current peak potential whereas cobalt oxides are detected and electrochemically observed when the deposition is done at more negative potentials. i-t transients are analyzed by applying the Scharifker and Hills (SH) theoretical model. It is concluded that cobalt deposition occurs via a progressive nucleation and growth mechanism for concentrations higher than 0.05 mol L(-1) cobalt ions. For concentrations ≤0.025 mol L(-1) cobalt ions and low overpotentials, the mechanism changes to instantaneous nucleation. The im-tm relationships of the SH model are used to determine the values of the kinetic parameters and the cobalt ion diffusion coefficient.

  8. Effect of cobalt on the electrochromic properties of NiO films deposited by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Martinez-Luevanos, A.; Oliva, J.; Garcia, C. R.; Avalos-Belmontes, F.; Garcia-Lobato, M. A.

    2017-05-01

    In this work, the morphological, optical and electrochromic properties of NiO and Ni-Co oxides films are reported. Those films were deposited on FTO glass substrates using a simple spray pyrolysis method. SEM images indicated that the size of particles that formed the Ni-Co oxide films decreased from 18 to 6 nm as the content of Co increases. In addition, the thickness of the films decreased from 378 to 310 nm as the content of cobalt augments from 0 to 10 mol%. This reduction of thickness also produced a diminution of the band gap of the films, which benefited the electrochromic properties. Electrochemical measurements were carried out and found that the diffusion coefficient, reversibility and coloration efficiency were enhanced in samples with cobalt with respect to the sample with pure NiO. Thus, the results suggest that our films could be useful for electrochromic applications.

  9. Fabrication and characterization of high energy density lithium-rich nickel manganese cobalt oxide cathode thin films

    SciTech Connect

    Baggetto, Loic; Mohanty, Debasish; Meisner, Roberta Ann; Daniel, Claus; Wood III, David L; Dudney, Nancy J; Veith, Gabriel M

    2014-01-01

    This paper reports a method to prepare Li-rich NMC (Li1.2Mn0.55Ni0.15Co0.1O2) thin film cathodes for Li-ion batteries using magnetron sputtering and post-annealing in O2. The use of thin films with no binder and conductive additives enables to study in detail the surface reaction chemistry upon cycling as well as the microstructural changes in the bulk. We show that it is essential to control the deposition pressure to obtain the expected layered(R-3m)-layered(C2/m) structure, thus providing large reversible capacities up to 270 mAh g-1 and voltage profiles close to those expected. This is substantiated by TEM/SAED results showing that the films consist of a layered structure with trigonal symmetry in which Li/TM ordering is achieved. The study of various XPS core levels determines that the surface is comprised of Mn4+, Co3+ and Ni2+ cations inside an O2- framework. The losses mechanisms are studied during long cycling. After 184 cycles, the microstructure does not reveal the presence of Li/TM ordering, which supports that Li2MnO3 conversion is irreversible. In addition, we characterize that the surface chemistry evolves significantly upon cycling. The surface of cycled discharged electrodes is mostly made of inorganic species (LiF, Lix POy Fz , LixPFy), along with small amounts of organic species with C-O and O-C=O groups such as PEO, LiOR and LiCO2R. Moreover, the results support that Ni and Co migrate into the bulk whereas Mn is enriched at the surface. In the case of Mn, the reduction of Mn4+ into Mn3+ is clearly evidenced, as expected from the activation of Li2MnO3 domains.

  10. Oxygenation of Cobalt Porphyrinates: Coordination or Oxidation?

    PubMed Central

    Li, Jianfeng; Noll, Bruce C.; Oliver, Allen G.; Ferraudi, Guillermo; Lappin, A. Graham; Scheidt, W. Robert

    2010-01-01

    The X-ray characterization of the five-coordinate picket-fence porphyrin complex, [Co(TpivPP)(2-MeHim)], is reported. The complex has the displacement of cobalt from the porphyrin plane = 0.15 Å, and Co–NIm = 2.145 (3) and (Co–Np)av = 1.979(3) Å. This five-coordinate complex, in the presence of dioxygen and excess 2-methylimidazole, undergoes an unanticipated, photoinitiated atropisomerization of the porphyrin ligand, oxidation of cobalt(II) and the formation of the neutral cobalt(III) complex [Co(α,α,β,β-TpivPP)(2-MeHim)(2-MeIm−]. Two distinct examples of this complex have been structurally characterized, both have structural parameters consistent with cobalt(III). The two new Co(III) porphyrin complexes have axial Co–NIm distances ranging from 1.952 to 1.972 Å, but which allow for the distinction between imidazole and imidazolate. An interesting intermolecular hydrogen bonding network is observed that leads to infinite helical chains. UV-vis spectroscopic study suggests that [Co(TpivPP)(2-MeHIm)(O2)] is an intermediate state for the oxidation reaction and the atropisomerization process is photocatalyzed. A reaction route is proposed based on the spectroscopic studies. PMID:20104874

  11. Magnetoelastic properties of cobalt-nickel thin films

    NASA Astrophysics Data System (ADS)

    Anapolsky, Abraham

    Cobalt-nickel alloys show large values of magnetostriction, magnetocrystalline anisotropy, and a martensitic phase transformation at temperatures around 0 K. Collectively, these properties make Co-Ni alloys good candidates for the so-called giant magnetostrictive effect. Magnetostrictive (and giant magnetostrictive) alloys can be used to replace complex machinery (such as actuators) in micro-electromechanical systems (MEMS). For this reason, researchers have been investigating the magnetostrictive properties of thin films. I grew and characterized films in the composition range Co: 10 wt% Ni to Co: 35 wt% Ni. Films were grown by electron beam evaporation and a variety of techniques including SEM, TEM, x-ray diffraction, and SQUID magnetometry were used to characterize the films. A thorough background in elastic and non-elastic mechanisms of deformation (in relation to magnetostriction) is discussed. These topics include a semi-classical treatment of magnetoelasticity, superelasticity, and martensitic transformations. An important result of this thesis is the complete magnetic and physical characterization for the entire range of Co-Ni thin films that undergo martensitic transformation. Extensive analysis of morphology, microstructure, phase, and magnetic data, developed a consistent picture of Co-Ni polycrystalline thin films in the composition range mentioned above. Another important result was the development of a novel technique for measuring the value of the magnetostriction coefficient in thin films. The in-plane component of magnetostriction ( lips ) is determined by fitting a theoretical model (based on the Stoner-Wohlforth theory for uniaxial systems) to magnetization vs temperature (M vs T) data for cobalt-nickel thin films. My theoretical model predicts the effect of an imposed stress (or strain) on the in-plane component of saturation magnetization ( Mips ). The imposed stress (or strain) is due to a mismatch in the coefficient of thermal expansion

  12. Investigation of nanocrystalline thin cobalt films thermally evaporated on Si(100) substrates

    NASA Astrophysics Data System (ADS)

    Kozłowski, W.; Balcerski, J.; Szmaja, W.; Piwoński, I.; Batory, D.; Miękoś, E.; Cichomski, M.

    2017-03-01

    We have made a quantitative study of the morphological and magnetic domain structures of 100 nm thick nanocrystalline cobalt films thermally evaporated on naturally oxidized Si(100) substrates. The morphological structure is composed of densely packed grains with the average grain size (35.6±0.8) nm. The grains exhibit no geometric alignment and no preferred elongation on the film surface. In the direction perpendicular to the film surface, the grains are aligned in columns. The films crystallize mainly in the hexagonal close-packed phase of cobalt and possess a crystallographic texture with the hexagonal axis perpendicular to the film surface. The magnetic domain structure consists of domains forming a maze stripe pattern with the average domain size (102±6) nm. The domains have their magnetizations oriented almost perpendicularly to the film surface. The domain wall energy, the domain wall thickness and the critical diameter for single-domain particle were determined.

  13. Cobalt-free polycrystalline Ba0.95La0.05FeO3-δ thin films as cathodes for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Chen, Dengjie; Chen, Chi; Dong, Feifei; Shao, Zongping; Ciucci, Francesco

    2014-03-01

    Ba0.95La0.05FeO3-δ (BLF) thin films as electrodes for intermediate-temperature solid oxide fuel cells are prepared on single-crystal yttria-stabilized zirconia (YSZ) substrates by pulsed laser deposition. The phase structure, surface morphology and roughness of the BLF thin films are characterized by X-ray diffraction, scanning electron microscopy and atomic force microscopy. X-ray photoelectron spectroscopy is used to analyze the compositions of the deposited thin film and the chemical state of transition metal. The dense thin film exhibits a polycrystalline perovskite structure with a low surface roughness and a high oxygen vacancy concentration on the surface. Ag (paste or strip) and Au (strip) are applied on both surfaces of the symmetric cells as current collectors to evaluate electrochemical performance of the thin films. The electrode polarization resistances of the symmetric cells are found to be lower than those of most cobalt-free thin-film electrodes, e.g., 0.437 Ω cm2 at 700 °C and 0.21 atm. The oxygen reduction reaction mechanism of the BLF cathode in symmetric cells is studied by electrochemical impedance spectroscopy thanks to the equivalent fitting analysis. Both the oxygen surface exchange reaction and charge transfer are shown to determine the overall oxygen reduction reaction.

  14. Photoeffects in cobalt doped pyrite (FeS 2) films

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Ellmer, K.; Bohne, W.; Röhrich, J.; Kunst, M.; Tributsch, H.

    1999-07-01

    By indiffusion of a thin metallic cobalt layer into a pyrite film deposited by metal organic chemical vapour deposition (MOCVD), cobalt doped pyrite (FeS 2) films have been prepared. The cobalt in these films acts as a donor and transforms the originally p-type into n-type conductivity. To our knowledge this is the first time that n-type pyrite films have been prepared. Compared to the undoped p-type pyrite films, the cobalt-diffused films exhibit a much higher photoconductivity, as revealed by time resolved microwave conductivity analysis. From Hall and conductivity measurements a charge carrier concentration of about 10 20 cm -3 and a Hall mobility of about 1.5 cm 2/(V s) was calculated. This has to be compared with p-type pyrite films which do not show a Hall mobility above 0.1 cm 2/(V s), the detection limit of our Hall system. By analytical techniques (Rutherford backscattering and photoelectron spectroscopy) it was confirmed that the increase of the photoactivity is a bulk property of the pyrite films and not merely due to a surface passivation (for instance, due to metallic CoS 2). The presented results stimulate further experiments on in-situ-doping of pyrite by MOCVD and open the opportunity for the preparation of pn-junctions and pn-solar cells with pyrite.

  15. Nitrogen oxides storage catalysts containing cobalt

    DOEpatents

    Lauterbach, Jochen; Snively, Christopher M.; Vijay, Rohit; Hendershot, Reed; Feist, Ben

    2010-10-12

    Nitrogen oxides (NO.sub.x) storage catalysts comprising cobalt and barium with a lean NO.sub.x storage ratio of 1.3 or greater. The NO.sub.x storage catalysts can be used to reduce NO.sub.x emissions from diesel or gas combustion engines by contacting the catalysts with the exhaust gas from the engines. The NO.sub.x storage catalysts can be one of the active components of a catalytic converter, which is used to treat exhaust gas from such engines.

  16. Microstructure and Magnetic Properties of Electrodeposited Cobalt Film

    SciTech Connect

    Bhuiyan, Md S; Taylor, B. J.; Paranthaman, Mariappan Parans; Thompson, James R; Sinclair, J.

    2008-01-01

    Cobalt films were electrodeposited onto both iron and copper substrates from an aqueous solution containing a mixture of cobalt sulfate, boric acid, sodium citrate, and vanadyl sulfate. The structural, intermetallic diffusion and magnetic properties of the electrodeposited films were studied. Cobalt electrodeposition was carried out in a passively divided cell aided by addition of vanadyl sulfate to keep the counter electrode clean. The divided electrolytic cell with very negative current densities cause the electrodeposited Co to adopt a face-centered cubic (fcc) structure, which is more magnetically reversible than the hexagonally close-packed (hcp) structured Co. The coercive field is also significantly less in the fcc-electrodeposited cobalt than in the hcp. SEM images show dense, uniform Co films without any cracks or porosity. Beside the deposition current, thickness of the film was also found to affect the crystal orientation particularly on iron substrates. Diffusion of cobalt film into the iron substrate was studied under reduced environment and a fast process was observed.

  17. Synergetic interactions improve cobalt leaching from lithium cobalt oxide in microbial fuel cells.

    PubMed

    Huang, Liping; Li, Tianchi; Liu, Chuan; Quan, Xie; Chen, Lijie; Wang, Aijie; Chen, Guohua

    2013-01-01

    Cobalt leaching from lithium cobalt oxide is a promising reduction process for recovery of cobalt and recycle of spent lithium ion batteries, but suffers from consumption of large amount of reductants and energy, and generation of excess secondary polluted sludge. Thus, effective and environmental friendly processes are needed to improve the existing process limitations. Here we reported microbial fuel cells (MFCs) to effectively reduce Co(III) in lithium cobalt oxide with concomitant energy generation. There was a synergetic interaction in MFCs, leading to a more rapid Co(III) leaching at a rate 3.4 times the sum of rates by conventional chemical processes and no-acid controls. External resistor, solid/liquid ratio, solution conductivity, pH and temperature affected system performance. This study provides a new process for recovery of cobalt and recycle of spent lithium ion batteries with concomitant energy generation from MFCs.

  18. Improved adhesion of ultra-hard carbon films on cobalt-chromium orthopaedic implant alloy.

    PubMed

    Catledge, Shane A; Vaid, Rishi; Diggins, Patrick; Weimer, Jeffrey J; Koopman, Mark; Vohra, Yogesh K

    2011-02-01

    While interfacial graphite formation and subsequent poor film adhesion is commonly reported for chemical vapor deposited hard carbon films on cobalt-based materials, we find the presence of O(2) in the feedgas mixture to be useful in achieving adhesion on a CoCrMo alloy. Nucleation studies of surface structure before formation of fully coalesced hard carbon films reveal that O(2) feedgas helps mask the catalytic effect of cobalt with carbon through early formation of chromium oxides and carbides. The chromium oxides, in particular, act as a diffusion barrier to cobalt, minimizing its migration to the surface where it would otherwise interact deleteriously with carbon to form graphite. When O(2) is not used, graphitic soot forms and films delaminate readily upon cooling to room temperature. Continuous 1 μm-thick nanostructured carbon films grown with O(2) remain adhered with measured hardness of 60 GPa and show stable, non-catastrophic circumferential micro-cracks near the edges of indent craters made using Rockwell indentation.

  19. Development of hierarchically porous cobalt oxide for enhanced photo-oxidation of indoor pollutants

    NASA Astrophysics Data System (ADS)

    Cheng, J. P.; Shereef, Anas; Gray, Kimberly A.; Wu, Jinsong

    2015-03-01

    Porous cobalt oxide was successfully prepared by precipitation of cobalt hydroxide followed by low temperature thermal decomposition. The morphologies of the resultant oxides remained as the corresponding hydroxides, although the morphology of cobalt hydroxides was greatly influenced by the precursor salts. The cobalt oxides with average crystal size less than 20 nm were characterized by X-ray diffraction, scanning electron microscope, BET surface area, and XPS analysis. The photocatalytic activities of the various cobalt oxides morphologies were investigated by comparing the photo-degradation of acetaldehyde under simulated solar illumination. Relative to their low order structures and reference titania samples, the hierarchical nanostructures of cobalt oxide showed excellent abilities to rapidly degrade acetaldehyde, a model air pollutant. This was attributed to the unique nature of these hierarchical cobalt oxide nanoassemblies, which contained many catalytically active reaction sites and open pores.

  20. Mixed alumina and cobalt containing plasma electrolytic oxide coatings

    NASA Astrophysics Data System (ADS)

    Yar-Mukhamedova, G. Sh; Ved', M. V.; Karakurkchi, A. V.; Sakhnenko, N. D.

    2017-06-01

    Principles of plasma electrolytic oxidation of the AL25 aluminum alloy in diphosphate alkali solutions containing cobalt(2+) cations are discussed. It has been established that a variation in the concentration of the electrolyte components provides the formation of mixed-oxide coatings consisting of the basic matrix materials and the cobalt oxides of different content. An increase in the cobalt oxide content in the coating is achieved by the variation in electrolysis current density as well as the treatment time due to both the electrochemical and thermo-chemical reactions at substrate surface and in spark region. Current density intervals that provide micro-globular surface formation and uniform cobalt distribution in the coating are determined. The composition and morphology of the surface causes high catalytic properties of synthesized materials, which confirmed the results of testing in model reaction CO and benzene oxidation as well as fuel combustion for various modes of engine operation.

  1. Room temperature deposited oxide p-n junction using p-type zinc-cobalt-oxide

    NASA Astrophysics Data System (ADS)

    Kim, SeonHoo; Cianfrone, J. A.; Sadik, P.; Kim, K.-W.; Ivill, M.; Norton, D. P.

    2010-05-01

    Oxide semiconductors are attractive materials for thin-film electronics and optoelectronics due to compatibility with synthesis on large-area, inexpensive glass and flexible plastic substrate. However, development of thin-film electronics has been hampered by the limited number of semiconducting oxides that are p-type. Here, we report on the properties of zinc-cobalt-oxide (Zn-Co-O) films, deposited at room temperature using pulsed laser deposition, that exhibit p-type conduction. Films are deposited at room temperature in a background of oxygen using a polycrystalline ZnCo2O4 ablation target. The p-type conduction is confirmed by positive Seebeck coefficient and positive Hall coefficient. Both electrical resistivity and carrier density are dependent on oxygen background pressure used during deposition. Zn-Co-O films deposited in 50 mTorr oxygen pressure appear to be amorphous based on x-ray diffraction, and show an electrical conductivity as high as 21 S cm-1. Distinct rectifying current-voltage characteristics are observed for junctions between Zn-Co-O and n-type InGaZnO films, exhibiting a threshold voltage of ˜2.5 V. P-type Zn-Co-O appears promising for thin-film electronic device technology.

  2. Thin films of tetrafluorosubstituted cobalt phthalocyanine: Structure and sensor properties

    NASA Astrophysics Data System (ADS)

    Klyamer, Darya D.; Sukhikh, Aleksandr S.; Krasnov, Pavel O.; Gromilov, Sergey A.; Morozova, Natalya B.; Basova, Tamara V.

    2016-05-01

    In this work, thin films of tetrafluorosubstituted cobalt phthalocyanine (CoPcF4) were prepared by organic molecular beam deposition and their structure was studied using UV-vis, polarization dependent Raman spectroscopy, XRD and atomic force microscopy. Quantum chemical calculations (DFT) have been employed in order to determine the detailed assignment of the bands in the CoPcF4 IR and Raman spectra. The electrical sensor response of CoPcF4 films to ammonia vapours was investigated and compared with that of unsubstituted cobalt phthalocyanine films. In order to explain the difference in sensitivity of the unsubstituted and fluorinated phthalocyanines to ammonia, the nature and properties of chemical binding between CoPc derivatives and NH3 were described by quantum-chemical calculations utilizing DFT method. The effect of post-deposition annealing on surface morphology and gas sensing properties of CoPcF4 films was also studied.

  3. Cobalt nanoparticles growth on a block copolymer thin film: a time-resolved GISAXS study.

    PubMed

    Metwalli, Ezzeldin; Körstgens, Volker; Schlage, Kai; Meier, Robert; Kaune, Gunar; Buffet, Adeline; Couet, Sebastien; Roth, Stephan V; Röhlsberger, Ralf; Müller-Buschbaum, Peter

    2013-05-28

    Cobalt sputter deposition on a nanostructured polystyrene-block-poly(ethylene oxide), P(S-b-EO), template is followed in real time with grazing incidence small-angle X-ray scattering (GISAXS). The polymer template consists of highly oriented parallel crystalline poly(ethylene oxide) (PEO) domains that are sandwiched between two polystyrene (PS) domains. In-situ GISAXS shows that cobalt atoms selectively decorate the PS domains of the microphase-separated polymer film and then aggregate to form surface metal nanopatterns. The polymer template is acting as a directing agent where cobalt metal nanowires are formed. At high metal load, the characteristic selectivity of the template is lost, and a uniform metal layer forms on the polymer surface. During the early stage of cobalt metal deposition, a highly asymmetric nanoparticles agglomeration is dominating structure formation. The cobalt nanoparticles mobility in combination with the high tendency of the nanoparticles to coalescence and to form immobile large-sized particles at the PS domains are discussed as mechanisms of structure formation.

  4. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... the solution obtained by boiling 10 grams of the chromium-cobalt-aluminum oxide for 15 minutes in 50..., and set by annealing. (2) The quantity of the color additive does not exceed 2 percent by weight of...

  5. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... the solution obtained by boiling 10 grams of the chromium-cobalt-aluminum oxide for 15 minutes in 50..., and set by annealing. (2) The quantity of the color additive does not exceed 2 percent by weight of...

  6. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... the solution obtained by boiling 10 grams of the chromium-cobalt-aluminum oxide for 15 minutes in 50..., and set by annealing. (2) The quantity of the color additive does not exceed 2 percent by weight of...

  7. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... the solution obtained by boiling 10 grams of the chromium-cobalt-aluminum oxide for 15 minutes in 50..., and set by annealing. (2) The quantity of the color additive does not exceed 2 percent by weight of...

  8. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... the solution obtained by boiling 10 grams of the chromium-cobalt-aluminum oxide for 15 minutes in 50..., and set by annealing. (2) The quantity of the color additive does not exceed 2 percent by weight of...

  9. Cobalt Oxide Hollow Nanoparticles Derived by Bio-Templating

    NASA Technical Reports Server (NTRS)

    Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; Chu, Sang-Hyon; King, Glen C.; Watt, Gerald D.

    2005-01-01

    We present here the first fabrication of hollow cobalt oxide nanoparticles produced by a protein-regulated site-specific reconstitution process in aqueous solution and describe the metal growth mechanism in the ferritin interior.

  10. Cobalt Oxide Hollow Nanoparticles Derived by Bio-Templating

    NASA Technical Reports Server (NTRS)

    Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; Chu, Sang-Hyon; King, Glen C.; Watt, Gerald D.

    2005-01-01

    We present here the first fabrication of hollow cobalt oxide nanoparticles produced by a protein-regulated site-specific reconstitution process in aqueous solution and describe the metal growth mechanism in the ferritin interior.

  11. Annealing effects on microstrain of cobalt oxide nanoparticles

    SciTech Connect

    Deotale, Anjali Jain Nandedkar, R. V.; Sinha, A. K.; Singh, M. N.; Upadhyay, Anuj

    2014-04-24

    Cobalt oxide nanoparticles in different phases have been synthesized using ash supported method. The effect of isochronal annealing on micro-strain of cobalt oxide nanoparticles has been studied. The lattice strain contribution to the x-ray diffraction line broadening in the nanoparticles was analyzed using Williamson Hall (W-H) plot. It is observed that micro-strain was released at higher annealing temperature.

  12. Pulsed laser deposited cobalt-doped ZnO thin film

    NASA Astrophysics Data System (ADS)

    Wang, Li; Su, Xue-qiong; Lu, Yi; Chen, Jiang-bo

    2013-09-01

    To realize the room-temperature ferromagnetism (RTFM) in diluted magnetic semiconductors (DMS), we prepared a series of Cobalt-doped ZnO thin films using pulsed laser deposition (PLD) at deposition temperatures 500°C under oxygen pressure from 2.5×10-4 Pa to 15 Pa. To elucidate the physical origin of RTFM, Co 2p spectra of cobalt-doped ZnO thin films was measured by X-ray photoelectron spectroscopy (XPS). The magnetic properties of films were measured by an alternating gradient magnetometer (AGM), and the electrical properties were detected by a Hall Effect instrument using the Van der Pauw method. XPS analysis shows that the Co2+ exists and Co clusters and elemental content change greatly in samples under various deposition oxygen pressures. Not only the valence state and elemental content but also the electrical and magnetic properties were changed. In the case of oxygen pressure 10 Pa, an improvement of saturation magnetic moment about one order of magnitude over other oxygen pressure experiments, and the film exhibits ferromagnetism with a curie temperature above room temperature. It was found that the value of carrier concentration in the Co-doped ZnO film under oxygen pressure 10Pa increases about one order of magnitude than the values of other samples under different oxygen pressure. Combining XPS with AGM measurements, we found that the ferromagnetic signals in cobalt-doped ZnO thin film deposited at 500 °C under oxygen pressure 10 Pa only appear with the detectable Co2+ spectra from incompletely oxidized Co metal or Co cluster. So oxygen pressure 10 Pa can be thought the best condition to obtain room-temperature dilute magnetic semiconductor about cobalt-doped ZnO thin films.

  13. Synthesis of cobalt stearate as oxidant additive for oxo-biodegradable polyethylene

    SciTech Connect

    Asriza, Ristika O.; Arcana, I Made

    2015-09-30

    Cobalt stearate is an oxidant additives that can initiate a process of degradation in high density polyethylene (HDPE). To determine the effect of cobalt stearate in HDPE, oxo-biodegradable polyethylene film was given an irradiation with UV light or heating at various temperature. After given a heating, the FTIR spectra showed a new absorption peak at wave number 1712 cm{sup −1} indicating the presence of carbonyl groups in polymers, whereas after irradiation with UV light is not visible the presence of this absorption peak. The increase concentration of cobalt stearate added in HDPE and the higher heating temperature, the intensity of the absorption peak of the carbonyl group increased. The increasing intensity of the carbonyl group absorption is caused the presence of damage in the film surface after heating, and this result is supported by analysis the surface properties of the film with using SEM. Biodegradation tests were performed on oxo-biodegradable polyethylene film which has been given heating or UV light with using activated sludge under optimal conditions the growth of microorganisms. After biodegradation, the maximum weight decreased by 23% in the oxo-biodegradable polyethylene film with a cobalt stearate concentration of 0.2% and after heating at a temperature of 75 °C for 10 days, and only 0.69% in the same film after irradiation UV light for 10 days. Based on the results above, cobalt stearate additive is more effective to initiate the oxidative degradation of HDPE when it is initiated by heating compared to irradiation with UV light.

  14. Pulsed Laser Synthesized Magnetic Cobalt Oxide Nanoparticles for Biomedical Applications

    NASA Astrophysics Data System (ADS)

    Bhatta, Hari; Gupta, Ram; Ghosh, Kartik; Kahol, Pawan; Delong, Robert; Wanekawa, Adam

    2011-03-01

    Nanomaterials research has become a major attraction in the field of advanced materials research in the area of Physics, Chemistry, and Materials Science. Biocompatible and chemically stable magnetic metal oxide nanoparticles have biomedical applications that includes drug delivery, cell and DNA separation, gene cloning, magnetic resonance imaging (MRI). This research is aimed at the fabrication of magnetic cobalt oxide nanoparticles using a safe, cost effective, and easy to handle technique that is capable of producing nanoparticles free of any contamination. Cobalt oxide nanoparticles have been synthesized at room temperature using cobalt foil by pulsed laser ablation technique. These cobalt oxide nanoparticles were characterized using UV-Visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and dynamic laser light scattering (DLLS). The magnetic cobalt oxides nanoparticles were stabilized in glucose solutions of various concentrations in deionized water. The presence of UV-Vis absorption peak at 270 nm validates the nature of cobalt oxide nanoparticles. The DLLS size distributions of nanoparticles are in the range of 110 to 300 nm, which further confirms the presence nanoparticles. This work is partially supported by National Science Foundation (DMR- 0907037).

  15. Investigation of thermally evaporated nanocrystalline thin cobalt films

    NASA Astrophysics Data System (ADS)

    Kozłowski, W.; Balcerski, J.; Kowalczyk, P. J.; Cichomski, M.; Szmaja, W.

    2017-03-01

    In this paper, a study has been made of nanocrystalline thin cobalt films with thicknesses in the range from 10 to 60 nm. The films were thermally evaporated at incidence angle of 0° in a vacuum of about 10- 5 mbar. The morphological structure of the films consists of nanocrystalline grains regular in shape and densely packed. As the film thickness is increased from 10 to 60 nm, the average grain size increases from 22.0 to 28.9 nm. The films crystallize mainly in the hexagonal close-packed phase of cobalt. The magnetic structure is composed of domains. In films with thicknesses in the range from 10 to 40 nm, the domains are magnetized in the plane of the film, while films with thicknesses of 50 and 60 nm possess both inplane and perpendicular magnetization components. The domains with inplane magnetization are irregular in shape and typically from a few to 10 mm in size, whereas the domains with perpendicular magnetization form a fine maze stripe pattern of the order of 100 nm in width.

  16. Ferromagnetism of zinc oxide nanograined films

    NASA Astrophysics Data System (ADS)

    Straumal, B. B.; Protasova, S. G.; Mazilkin, A. A.; Schütz, G.; Goering, E.; Baretzky, B.; Straumal, P. B.

    2013-05-01

    The reasons for the appearance of ferromagnetic properties of zinc oxide have been reviewed. It has been shown that ferromagnetism appears only in polycrystals at a quite high density of grain boundaries. The critical size of grains is about 20 nm for pure ZnO and more than 40 μm for iron-doped zinc oxide. The solubility of manganese and cobalt in zinc oxide increases significantly with a decrease in the size of grains. The dependences of the saturation magnetization on the concentrations of cobalt, manganese, and ion are nonmonotonic. Even if the size of grains is below the critical value, the ferromagnetic properties of zinc oxide depend significantly on the texture of films and the structure of amorphous intercrystallite layers.

  17. Stabilized chromium oxide film

    DOEpatents

    Garwin, Edward L.; Nyaiesh, Ali R.

    1988-01-01

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150.ANG. are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  18. Stabilized chromium oxide film

    DOEpatents

    Nyaiesh, A.R.; Garwin, E.L.

    1986-08-04

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150A are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  19. Coordination tuning of cobalt phosphates towards efficient water oxidation catalyst

    PubMed Central

    Kim, Hyunah; Park, Jimin; Park, Inchul; Jin, Kyoungsuk; Jerng, Sung Eun; Kim, Sun Hee; Nam, Ki Tae; Kang, Kisuk

    2015-01-01

    The development of efficient and stable water oxidation catalysts is necessary for the realization of practically viable water-splitting systems. Although extensive studies have focused on the metal-oxide catalysts, the effect of metal coordination on the catalytic ability remains still elusive. Here we select four cobalt-based phosphate catalysts with various cobalt- and phosphate-group coordination as a platform to better understand the catalytic activity of cobalt-based materials. Although they exhibit various catalytic activities and stabilities during water oxidation, Na2CoP2O7 with distorted cobalt tetrahedral geometry shows high activity comparable to that of amorphous cobalt phosphate under neutral conditions, along with high structural stability. First-principles calculations suggest that the surface reorganization by the pyrophosphate ligand induces a highly distorted tetrahedral geometry, where water molecules can favourably bind, resulting in a low overpotential (∼0.42 eV). Our findings emphasize the importance of local cobalt coordination in the catalysis and suggest the possible effect of polyanions on the water oxidation chemistry. PMID:26365091

  20. Synthesis of silicon oxide nanowires and nanotubes with cobalt-palladium or palladium catalysts

    NASA Astrophysics Data System (ADS)

    Esterina, Ria; Liu, X. M.; Ross, C. A.; Adeyeye, A. O.; Choi, W. K.

    2012-07-01

    The dewetting behaviors of cobalt (Co), cobalt palladium (CoPd), and palladium (Pd) thin films on oxidized silicon substrates were examined. We observed the formation of craters in the oxide layer and pits in the Si substrate for larger CoPd or Pd catalyst particles and thinner oxide. Nanowires and nanotubes were observed near the Si pits. The nanowires and nanotubes grow via a vapor-solid-solid or vapor-liquid-solid mechanism with the silicon vapor source provided from the substrate. The original Si atoms that form the nanowires or nanotubes were oxidized in situ by the residual oxygen atoms present in the chamber. Some of the nanotubes had a series of embedded sub-catalysts that formed branches from the primary nanotube.

  1. Copper nanofiber-networked cobalt oxide composites for high performance Li-ion batteries

    PubMed Central

    2011-01-01

    We prepared a composite electrode structure consisting of copper nanofiber-networked cobalt oxide (CuNFs@CoOx). The copper nanofibers (CuNFs) were fabricated on a substrate with formation of a network structure, which may have potential for improving electron percolation and retarding film deformation during the discharging/charging process over the electroactive cobalt oxide. Compared to bare CoOxthin-film (CoOxTF) electrodes, the CuNFs@CoOxelectrodes exhibited a significant enhancement of rate performance by at least six-fold at an input current density of 3C-rate. Such enhanced Li-ion storage performance may be associated with modified electrode structure at the nanoscale, improved charge transfer, and facile stress relaxation from the embedded CuNF network. Consequently, the CuNFs@CoOxcomposite structure demonstrated here can be used as a promising high-performance electrode for Li-ion batteries. PMID:21711839

  2. Cobalt promoted copper manganese oxide catalysts for ambient temperature carbon monoxide oxidation.

    PubMed

    Jones, Christopher; Taylor, Stuart H; Burrows, Andrew; Crudace, Mandy J; Kiely, Christopher J; Hutchings, Graham J

    2008-04-14

    Low levels of cobalt doping (1 wt%) of copper manganese oxide enhances its activity for carbon monoxide oxidation under ambient conditions and the doped catalyst can display higher activity than current commercial catalysts.

  3. Substrate selectivity in the low temperature atomic layer deposition of cobalt metal films from bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and formic acid

    NASA Astrophysics Data System (ADS)

    Kerrigan, Marissa M.; Klesko, Joseph P.; Rupich, Sara M.; Dezelah, Charles L.; Kanjolia, Ravindra K.; Chabal, Yves J.; Winter, Charles H.

    2017-02-01

    The initial stages of cobalt metal growth by atomic layer deposition are described using the precursors bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and formic acid. Ruthenium, platinum, copper, Si(100), Si-H, SiO2, and carbon-doped oxide substrates were used with a growth temperature of 180 °C. On platinum and copper, plots of thickness versus number of growth cycles were linear between 25 and 250 cycles, with growth rates of 0.98 Å/cycle. By contrast, growth on ruthenium showed a delay of up to 250 cycles before a normal growth rate was obtained. No films were observed after 25 and 50 cycles. Between 100 and 150 cycles, a rapid growth rate of ˜1.6 Å/cycle was observed, which suggests that a chemical vapor deposition-like growth occurs until the ruthenium surface is covered with ˜10 nm of cobalt metal. Atomic force microscopy showed smooth, continuous cobalt metal films on platinum after 150 cycles, with an rms surface roughness of 0.6 nm. Films grown on copper gave rms surface roughnesses of 1.1-2.4 nm after 150 cycles. Films grown on ruthenium, platinum, and copper showed resistivities of <20 μ Ω cm after 250 cycles and had values close to those of the uncoated substrates at ≤150 cycles. X-ray photoelectron spectroscopy of films grown with 150 cycles on a platinum substrate showed surface oxidation of the cobalt, with cobalt metal underneath. Analogous analysis of a film grown with 150 cycles on a copper substrate showed cobalt oxide throughout the film. No film growth was observed after 1000 cycles on Si(100), Si-H, and carbon-doped oxide substrates. Growth on thermal SiO2 substrates gave ˜35 nm thick layers of cobalt(ii) formate after ≥500 cycles. Inherently selective deposition of cobalt on metallic substrates over Si(100), Si-H, and carbon-doped oxide was observed from 160 °C to 200 °C. Particle deposition occurred on carbon-doped oxide substrates at 220 °C.

  4. Substrate selectivity in the low temperature atomic layer deposition of cobalt metal films from bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and formic acid.

    PubMed

    Kerrigan, Marissa M; Klesko, Joseph P; Rupich, Sara M; Dezelah, Charles L; Kanjolia, Ravindra K; Chabal, Yves J; Winter, Charles H

    2017-02-07

    The initial stages of cobalt metal growth by atomic layer deposition are described using the precursors bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and formic acid. Ruthenium, platinum, copper, Si(100), Si-H, SiO2, and carbon-doped oxide substrates were used with a growth temperature of 180 °C. On platinum and copper, plots of thickness versus number of growth cycles were linear between 25 and 250 cycles, with growth rates of 0.98 Å/cycle. By contrast, growth on ruthenium showed a delay of up to 250 cycles before a normal growth rate was obtained. No films were observed after 25 and 50 cycles. Between 100 and 150 cycles, a rapid growth rate of ∼1.6 Å/cycle was observed, which suggests that a chemical vapor deposition-like growth occurs until the ruthenium surface is covered with ∼10 nm of cobalt metal. Atomic force microscopy showed smooth, continuous cobalt metal films on platinum after 150 cycles, with an rms surface roughness of 0.6 nm. Films grown on copper gave rms surface roughnesses of 1.1-2.4 nm after 150 cycles. Films grown on ruthenium, platinum, and copper showed resistivities of <20 μΩ cm after 250 cycles and had values close to those of the uncoated substrates at ≤150 cycles. X-ray photoelectron spectroscopy of films grown with 150 cycles on a platinum substrate showed surface oxidation of the cobalt, with cobalt metal underneath. Analogous analysis of a film grown with 150 cycles on a copper substrate showed cobalt oxide throughout the film. No film growth was observed after 1000 cycles on Si(100), Si-H, and carbon-doped oxide substrates. Growth on thermal SiO2 substrates gave ∼35 nm thick layers of cobalt(ii) formate after ≥500 cycles. Inherently selective deposition of cobalt on metallic substrates over Si(100), Si-H, and carbon-doped oxide was observed from 160 °C to 200 °C. Particle deposition occurred on carbon-doped oxide substrates at 220 °C.

  5. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt iron manganese oxide... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35) is...

  6. 21 CFR 73.3110a - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Chromium-cobalt-aluminum oxide. 73.3110a Section... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3110a Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide (Pigment Blue 36) (CAS Reg. No...

  7. 21 CFR 73.3110a - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium-cobalt-aluminum oxide. 73.3110a Section... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3110a Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide (Pigment Blue 36) (CAS Reg. No...

  8. 21 CFR 73.3110a - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Chromium-cobalt-aluminum oxide. 73.3110a Section... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3110a Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide (Pigment Blue 36) (CAS Reg. No...

  9. 21 CFR 73.3110a - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Chromium-cobalt-aluminum oxide. 73.3110a Section... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3110a Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide (Pigment Blue 36) (CAS Reg. No...

  10. 21 CFR 73.3110a - Chromium-cobalt-aluminum oxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Chromium-cobalt-aluminum oxide. 73.3110a Section... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3110a Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide (Pigment Blue 36) (CAS Reg. No...

  11. 75 FR 70583 - Cobalt Lithium Manganese Nickel Oxide; Withdrawal of Significant New Use Rule

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-18

    ... AGENCY 40 CFR Parts 9 and 721 RIN 2070-AB27 Cobalt Lithium Manganese Nickel Oxide; Withdrawal of... Control Act (TSCA) for the chemical substance identified as cobalt lithium manganese nickel oxide (CAS No... cobalt lithium manganese nickel oxide (PMN P-04-269; CAS No. 182442-95-1) at 40 CFR 721.10201 because the...

  12. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  13. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  14. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  15. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  16. 40 CFR 721.5315 - Nickel, cobalt mixed metal oxide (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Nickel, cobalt mixed metal oxide... Specific Chemical Substances § 721.5315 Nickel, cobalt mixed metal oxide (generic). (a) Chemical substance... nickel, cobalt mixed metal oxide. (PMN P-02-90) is subject to reporting under this section for...

  17. Structural changes in iron-cobalt oxide nanosystems

    NASA Astrophysics Data System (ADS)

    Nishchev, K. N.; Golub'ev, M. A.; Maksimov, Yu. V.; Beglov, V. I.; Kyashkin, V. M.; Panov, A. A.

    2015-05-01

    The structure of binary iron-cobalt oxide nanosystems—precursors of bimetallic catalysts—is studied by Mössbauer spectroscopy, X-ray diffraction, and small-angle X-ray scattering. The oxide system under study represents a promising material for creating new metallic nanocatalysts for ammonia synthesis. The structural evolution in the composition range 100Fe/0Co-5Fe/95Co is found to correspond to the transition from fine-grained α-Fe2O3 to mixed iron-cobalt spinels of various compositions and degrees of dispersity.

  18. Cobalt silicon mixed oxide nanocomposites by modified sol gel method

    NASA Astrophysics Data System (ADS)

    Esposito, Serena; Turco, Maria; Ramis, Gianguido; Bagnasco, Giovanni; Pernice, Pasquale; Pagliuca, Concetta; Bevilacqua, Maria; Aronne, Antonio

    2007-12-01

    Cobalt-silicon mixed oxide materials (Co/Si=0.111, 0.250 and 0.428) were synthesised starting from Co(NO 3) 2·6H 2O and Si(OC 2H 5) 4 using a modified sol-gel method. Structural, textural and surface chemical properties were investigated by thermogravimetric/differential thermal analyses (TG/DTA), XRD, UV-vis, FT-IR spectroscopy and N 2 adsorption at -196 °C. The nature of cobalt species and their interactions with the siloxane matrix were strongly depending on both the cobalt loading and the heat treatment. All dried gels were amorphous and contained Co 2+ ions forming both tetrahedral and octahedral complexes with the siloxane matrix. After treatment at 400 °C, the sample with lowest Co content appeared amorphous and contained only Co 2+ tetrahedral complexes, while at higher cobalt loading Co 3O 4 was present as the only crystalline phase, besides Co 2+ ions strongly interacting with siloxane matrix. At 850 °C, in all samples crystalline Co 2SiO 4 was formed and was the only crystallising phase for the nanocomposite with the lowest cobalt content. All materials retained high surface areas also after treatments at 600 °C and exhibited surface Lewis acidity, due to cationic sites. The presence of cobalt affected the textural properties of the siloxane matrix decreasing microporosity and increasing mesoporosity.

  19. Water Oxidation and Oxygen Monitoring by Cobalt-Modified Fluorine-Doped Tin Oxide Electrodes

    SciTech Connect

    Kent, CA; Concepcion, JJ; Dares, CJ; Torelli, DA; Rieth, AJ; Miller, AS; Hoertz, PG; Meyer, TJ

    2013-06-12

    Electrocatalytic water oxidation occurs at fluoride-doped tin oxide (FTO) electrodes that have been surface-modified by addition of Co(II). On the basis of X-ray photoelectron spectroscopy and transmission electron microscopy measurements, the active surface site appears to be a single site or small-molecule assembly bound as Co(II), with no evidence for cobalt oxide film or cluster formation. On the basis of cyclic voltammetry measurements, surface-bound Co(II) undergoes a pH-dependent 1e(-)/1H(+) oxidation to Co(III), which is followed by pH-dependent catalytic water oxidation. O-2 reduction at FTO occurs at -0.33 V vs NHE, allowing for in situ detection of oxygen as it is formed by water oxidation on the surface. Controlled-potential electrolysis at 1.61 V vs NHE at pH 7.2 resulted in sustained water oxidation catalysis at a current density of 0.16 mA/cm(2) with 29 000 turnovers per site over an electrolysis period of 2 h. The turnover frequency for oxygen production per Co site was 4 s(-1) at an overpotential of 800 mV at pH 7.2. Initial experiments with Co(II) on a mesoporous, high-surface-area nanoFTO electrode increased the current density by a factor of similar to 5

  20. Magnetization reversal in cobalt-phosphorus films

    NASA Astrophysics Data System (ADS)

    Hughes, Gordon F.

    1983-09-01

    A brief review is given of preparation, structure, and magnetization reversal in Co-P thin films for digital recording. From this, a magnetization reversal theory is developed which correctly predicts a number of observed facts about Co-P. Among these are &mA0.1 (conventional theory predicts 0.64 and 0.51, respectively), avalanche and cluster reversal mechanisms, transverse ripple, and sawtooth structure in recorded bits. Limitations to high bit and track density recording are discussed. It is suggested that lower Mr/Ms remanent squareness values may alleviate these density limiting mechanisms.

  1. High performance of inverted polymer solar cells with cobalt oxide as hole-transporting layer

    NASA Astrophysics Data System (ADS)

    Wang, Xiangdong; Peng, Qing; Zhu, Weiguo; Lei, Gangtie

    2015-05-01

    Cobalt oxide (II, III) (CoOx) was inserted as efficient hole-transporting interlayer between the active layer and top electrode in inverted polymer solar cells (PSCs) with titanium (diisopropoxide) bis(2, 4-pentanedionate) (TIPD) as an electron selective layer. The work function of CoOx was measured by Kelvin probe and the device performances with different thicknesses of cobalt oxide were studied. The device with CoOx exhibited a remarkable improvement in power conversion efficiency compared with that without CoOx, which indicated that CoOx efficiently prevented the recombination of charge carriers at the organic/top electrode interface. The performance improvement was attributed to the fact that the CoOx thin film can module the Schottky barrier and form an ohmic contact at the organic/metal interface, which makes it a promising hole-transporting layer.

  2. Maintaining structural integrity of 4.5 V lithium cobalt oxide cathode with fumaronitrile as a novel electrolyte additive

    NASA Astrophysics Data System (ADS)

    Wang, Xianshu; Zheng, Xiongwen; Liao, Youhao; Huang, Qiming; Xing, Lidan; Xu, Mengqing; Li, Weishan

    2017-01-01

    The specific capacity of lithium-ion battery with lithium cobalt oxide as cathode depends on the upper limitation voltage for charge/discharge cycling, but this oxide tends to be destructed structurally when it is cycled in carbonate-based electrolyte under high voltage. We report a novel electrolyte additive, fumaronitrile (FN, CNsbnd CHdbnd CHsbnd CN), which can maintain the structural integrity of lithium cobalt oxide. Electrochemical measurements indicate that lithium cobalt oxide exhibits poor cyclic stability when it is cycled under 4.5 V (vs. Li/Li+) and the charged cathode suffers serious self-discharge in a base electrolyte, 1.0 mol L-1 LiPF6 in EC/EMC/DEC (3:5:2, by weight). These issues can be overcome effectively by adding 0.5% FN into the base electrolyte. Physical and chemical characterizations demonstrate that the poor cyclic stability and self-discharge of lithium cobalt oxide result from its structural destruction caused by HF formed from electrolyte decomposition, and FN yields a protective cathode interphase film which maintains the structural integrity of lithium cobalt oxide.

  3. 40 CFR 721.10599 - Calcium cobalt lead titanium tungsten oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Calcium cobalt lead titanium tungsten... Specific Chemical Substances § 721.10599 Calcium cobalt lead titanium tungsten oxide. (a) Chemical... cobalt lead titanium tungsten oxide (PMN P-11-271; CAS No. 1262279-31-1) is subject to reporting...

  4. 40 CFR 721.10599 - Calcium cobalt lead titanium tungsten oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Calcium cobalt lead titanium tungsten... Specific Chemical Substances § 721.10599 Calcium cobalt lead titanium tungsten oxide. (a) Chemical... cobalt lead titanium tungsten oxide (PMN P-11-271; CAS No. 1262279-31-1) is subject to reporting...

  5. 40 CFR 721.10600 - Calcium cobalt lead strontium titanium tungsten oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Calcium cobalt lead strontium titanium... Specific Chemical Substances § 721.10600 Calcium cobalt lead strontium titanium tungsten oxide. (a... calcium cobalt lead strontium titanium tungsten oxide (PMN P-11-272; CAS No. 1262279-30-0) is subject to...

  6. 40 CFR 721.10600 - Calcium cobalt lead strontium titanium tungsten oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Calcium cobalt lead strontium titanium... Specific Chemical Substances § 721.10600 Calcium cobalt lead strontium titanium tungsten oxide. (a... calcium cobalt lead strontium titanium tungsten oxide (PMN P-11-272; CAS No. 1262279-30-0) is subject to...

  7. Cobalt.

    PubMed

    Fowler, Joseph F

    2016-01-01

    Cobalt has been a recognized allergen capable of causing contact dermatitis for decades. Why, therefore, has it been named 2016 "Allergen of the Year"? Simply put, new information has come to light in the last few years regarding potential sources of exposure to this metallic substance. In addition to reviewing some background on our previous understanding of cobalt exposures, this article will highlight the recently recognized need to consider leather as a major site of cobalt and the visual cues suggesting the presence of cobalt in jewelry. In addition, a chemical spot test for cobalt now allows us to better identify its presence in suspect materials.

  8. Oxide Films RF Applications

    DTIC Science & Technology

    2006-06-01

    AUTHOR(S) 5d. PROJECT NUMBER SKOWRONSKI , Marek 5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING...Report Title: Oxide Films RF applications University: Carnegie Mellon University PIs: M. Skowronski & P. Salvador Agency: Office of Naval Research Award

  9. Water-induced Formation of Cobalt Oxides Over Supported Cobalt/Ceria-Zirconia Catalysts under Ethanol-Steam Conditions

    SciTech Connect

    Lin, Sean S.-Y.; Kim, Do Heui; Engelhard, Mark H.; Ha, Su Y.

    2010-07-28

    The formation of water-induced cobalt oxides by re-oxidizing the metallic cobalt in the pre-reduced 10% Co/CeO2-ZrO2 catalyst was verified by in-situ TPR and in-situ XPS studies under various ethanol-steam conditions. The formation and transformation of water-induced cobalt oxide species were affected by the pre-reduction conditions used for the catalysts and the feed stream composition used in the reaction. This result suggests that the surface composition of the cobalt species in 10% Co-CZ catalyst, initially governed by the catalyst pre-treatment, was changed toward an equilibrium state that governed by the feed stream composition as the reaction proceeds. In addition, the reducibility of the ceria sites may play a significant role in the redox process involved both cobalt and ceria sites under ethanol-steam environment. Finally, the effect of the water-induced cobalt oxides on the catalytic performance, in particular for the carbon-carbon bond cleavage of ethanol, is negligible. However, these water-induced oxides may show importance for the subsequent reaction steps that determine the product selectivity during ethanol steam reforming, as their coexistence with the metallic cobalt species was revealed by the in-situ study under ethanol-steam conditions.

  10. Chemical Mechanical Polishing of Ruthenium, Cobalt, and Black Diamond Films

    NASA Astrophysics Data System (ADS)

    Peethala, Brown Cornelius

    Ta/TaN bilayer serves as the diffusion barrier as well as the adhesion promoter between Cu and the dielectric in 32 nm technology devices. A key concern of future technology devices (<32 nm) for Cu interconnects is the extendibility of TaN/Ta/Cu-seed to sustain the diffusion barrier performance without forming voids and meeting the requirements of low resistivity. These are very challenging requirements for the Ta/TaN bilayer at a thickness of < 5 nm. Hence, ruthenium (Ru) and cobalt (Co), among these, are being considered for replacing Ta/TaN as barrier materials for Cu interconnects in future technology devices. Both are very attractive for reasons such as the capability of direct electroplating of Cu, lower resistivity and for a single layer (vs. a bilayer of Ta/TaN) to act as a barrier. During patterning, they need to be planarized using conventional chemical mechanical polishing (CMP) to achieve a planar surface. However, CMP of these new barrier materials requires novel slurry compositions that provide adequate selectivity towards Cu and dielectric films, and minimize galvanic corrosion. Apart from the application as a barrier, Ru also has been proposed as a lower electrode material in metal-insulator-metal capacitors where high (> 50 nm/min) Ru removal rates (RRs) are required and as a stop layer in magnetic recording head fabrication where low (< 1 nm/min) Ru RRs are desired. A Ru removal rate of ˜60 nm/min was achieved with a colloidal silica-based slurry at pH 9 using potassium periodate (KIO4) as the oxidizer. At this pH, toxic RuO4 does not form eliminating a major challenge in Ru CMP. This removal rate was obtained by increasing the solubility of KIO4 by adding potassium hydroxide (KOH). It was also determined that increased the ionic strength is not responsible for the observed increase in Ru removal rate. Benzotirazole (BTA) and ascorbic acid were added to the slurry to reduce the open circuit potential (Eoc) difference between Cu and Ru to ˜20 m

  11. Dynamic Measurements of Hydrogen and Lithium Distributions in Lithium-Cobalt-Oxide Films with Charging and Heating Using Elastic Recoil Detection Techniques

    NASA Astrophysics Data System (ADS)

    Tsuchiya, B.; Morita, K.; Iriyama, Y.; Majima, T.; Tsuchida, H.

    The migrations of lithium (Li) as well as hydrogen (H) in multi-layers thin films of Au/LiCoO2 (thickness: approximately 42 nm/80 nm), deposited onto one face of Li1.4Ti2Si0.4P2.6O12-AlPO4 (LATP) substrates, were dynamically observed with electric charging as well as isochronal annealing in vacuum by combining elastic recoil detection (ERD) analysis with Rutherford backscattering spectrometry (RBS)with 9.0-MeV O4+ ion-probe beams. The ERD spectra clearly revealed that Li atoms of approximately 9.4 at% migrated from the LiCoO2 surface to the LiCoO2/LATP interface with H absorption by a charge of approximately 0.48 e/cm2, which the acquiredvoltage was1.65 V. In addition, the diffusion of Li atoms to the LATP bulk occurred with H release by isochronal annealing at only 323 K for 10 min.The presence of H significantly influences the Li+ ion conduction for the Li-battery systems.

  12. Unipolar resistive switching in cobalt titanate thin films

    NASA Astrophysics Data System (ADS)

    Thakre, Atul; Shukla, A. K.; Katiyar, R. S.; Kumar, Ashok

    2017-02-01

    We report giant resistive switching of the order of 104, long-time charge retention characteristics up to 104 s, non-overlapping SET and RESET voltages, Ohmic in low-resistance state (LRS) and space charge limited current (SCLC) mechanism in high-resistance state (HRS) properties in polycrystalline perovskite cobalt titanate (\\text{CoTiO}3∼ \\text{CTO}) thin films. Impedance spectroscopy study was carried out for both LRS and HRS states which illustrates that only bulk resistance changes after resistance switching, however, there is a small change (<10% which is in the pF range) in the bulk capacitance value in both states. These results suggest that in the LRS state current filaments break the capacitor in many small capacitors in a parallel configuration which, in turn, provides the same capacitance in both states even if there was a 90-degree change in phase angle and an order of change in the tangent loss.

  13. In situ oxidation of carbon-encapsulated cobalt nanocapsules creates highly active cobalt oxide catalysts for hydrocarbon combustion

    NASA Astrophysics Data System (ADS)

    Wang, Han; Chen, Chunlin; Zhang, Yexin; Peng, Lixia; Ma, Song; Yang, Teng; Guo, Huaihong; Zhang, Zhidong; Su, Dang Sheng; Zhang, Jian

    2015-06-01

    Combustion catalysts have been extensively explored to reduce the emission of hydrocarbons that are capable of triggering photochemical smog and greenhouse effect. Palladium as the most active material is widely applied in exhaust catalytic converter and combustion units, but its high capital cost stimulates the tremendous research on non-noble metal candidates. Here we fabricate highly defective cobalt oxide nanocrystals via a controllable oxidation of carbon-encapsulated cobalt nanoparticles. Strain gradients induced in the nanoconfined carbon shell result in the formation of a large number of active sites featuring a considerable catalytic activity for the combustion of a variety of hydrocarbons (methane, propane and substituted benzenes). For methane combustion, the catalyst displays a unique activity being comparable or even superior to the palladium ones.

  14. Complete cobalt recovery from lithium cobalt oxide in self-driven microbial fuel cell - Microbial electrolysis cell systems

    NASA Astrophysics Data System (ADS)

    Huang, Liping; Yao, Binglin; Wu, Dan; Quan, Xie

    2014-08-01

    Complete cobalt recovery from lithium cobalt oxide requires to firstly leach cobalt from particles LiCoO2 and then recover cobalt from aqueous Co(II). A self-driven microbial fuel cell (MFC)-microbial electrolysis cell (MEC) system can completely carry out these two processes, in which Co(II) is firstly released from particles LiCoO2 on the cathodes of MFCs and then reduced on the cathodes of MECs which are powered by the cobalt leaching MFCs. A cobalt leaching rate of 46 ± 2 mg L-1 h-1 with yield of 1.5 ± 0.1 g Co g-1 COD (MFCs) and a Co(II) reduction rate of 7 ± 0 mg L-1 h-1 with yield of 0.8 ± 0.0 g Co g-1 COD (MECs), as well as a overall system cobalt yield of 0.15 ± 0.01 g Co g-1 Co can be achieved in this self-driven MFC-MEC system. Coulombic efficiencies reach 41 ± 1% (anodic MFCs), 75 ± 0% (anodic MECs), 100 ± 2% (cathodic MFCs), and 29 ± 1% (cathodic MECs) whereas overall system efficiency averages 34 ± 1%. These results provide a new process of linking MFCs to MECs for complete recovery of cobalt and recycle of spent lithium ion batteries with no external energy consumption.

  15. Poorly soluble cobalt oxide particles trigger genotoxicity via multiple pathways.

    PubMed

    Uboldi, Chiara; Orsière, Thierry; Darolles, Carine; Aloin, Valérie; Tassistro, Virginie; George, Isabelle; Malard, Véronique

    2016-02-03

    Poorly soluble cobalt (II, III) oxide particles (Co3O4P) are believed to induce in vitro cytotoxic effects via a Trojan-horse mechanism. Once internalized into lysosomal and acidic intracellular compartments, Co3O4P slowly release a low amount of cobalt ions (Co(2+)) that impair the viability of in vitro cultures. In this study, we focused on the genotoxic potential of Co3O4P by performing a comprehensive investigation of the DNA damage exerted in BEAS-2B human bronchial epithelial cells. Our results demonstrate that poorly soluble Co3O4P enhanced the formation of micronuclei in binucleated cells. Moreover, by comet assay we showed that Co3O4P induced primary and oxidative DNA damage, and by scoring the formation of γ-H2Ax foci, we demonstrated that Co3O4P also generated double DNA strand breaks. By comparing the effects exerted by poorly soluble Co3O4P with those obtained in the presence of soluble cobalt chloride (CoCl2), we demonstrated that the genotoxic effects of Co3O4P are not simply due to the released Co(2+) but are induced by the particles themselves, as genotoxicity is observed at very low Co3O4P concentrations.

  16. Water oxidation using a cobalt monolayer prepared by underpotential deposition.

    PubMed

    Marsh, David A; Yan, Wenbo; Liu, Yu; Hemminger, John C; Penner, Reginald M; Borovik, A S

    2013-11-26

    Development of electrocatalysts for the conversion of water to dioxygen is important in a variety of chemical applications. Despite much research in this field, there are still several fundamental issues about the electrocatalysts that need to be resolved. Two such problems are that the catalyst mass loading on the electrode is subject to large uncertainties and the wetted surface area of the catalyst is often unknown and difficult to determine. To address these topics, a cobalt monolayer was prepared on a gold electrode by underpotential deposition and used to probe its efficiency for the oxidation of water. This electrocatalyst was characterized by atomic force microscopy, grazing-incidence X-ray diffraction, and X-ray photoelectron spectroscopy at various potentials to determine if changes occur on the surface during catalysis. An enhancement of current was observed upon addition of PO4(3-) ions, suggesting an effect from surface-bound ligands on the efficiency of water oxidation. At 500 mV overpotential, current densities of 0.20, 0.74, and 2.4 mA/cm(2) for gold, cobalt, and cobalt in PO4(3-) were observed. This approach thus provided electrocatalysts whose surface areas and activity can be accurately determined.

  17. Cobalt Oxide Nanosheet and CNT Micro Carbon Monoxide Sensor Integrated with Readout Circuit on Chip

    PubMed Central

    Dai, Ching-Liang; Chen, Yen-Chi; Wu, Chyan-Chyi; Kuo, Chin-Fu

    2010-01-01

    The study presents a micro carbon monoxide (CO) sensor integrated with a readout circuit-on-a-chip manufactured by the commercial 0.35 μm complementary metal oxide semiconductor (CMOS) process and a post-process. The sensing film of the sensor is a composite cobalt oxide nanosheet and carbon nanotube (CoOOH/CNT) film that is prepared by a precipitation-oxidation method. The structure of the CO sensor is composed of a polysilicon resistor and a sensing film. The sensor, which is of a resistive type, changes its resistance when the sensing film adsorbs or desorbs CO gas. The readout circuit is used to convert the sensor resistance into the voltage output. The post-processing of the sensor includes etching the sacrificial layers and coating the sensing film. The advantages of the sensor include room temperature operation, short response/recovery times and easy post-processing. Experimental results show that the sensitivity of the CO sensor is about 0.19 mV/ppm, and the response and recovery times are 23 s and 34 s for 200 ppm CO, respectively. PMID:22294897

  18. Cobalt oxide nanosheet and CNT micro carbon monoxide sensor integrated with readout circuit on chip.

    PubMed

    Dai, Ching-Liang; Chen, Yen-Chi; Wu, Chyan-Chyi; Kuo, Chin-Fu

    2010-01-01

    The study presents a micro carbon monoxide (CO) sensor integrated with a readout circuit-on-a-chip manufactured by the commercial 0.35 μm complementary metal oxide semiconductor (CMOS) process and a post-process. The sensing film of the sensor is a composite cobalt oxide nanosheet and carbon nanotube (CoOOH/CNT) film that is prepared by a precipitation-oxidation method. The structure of the CO sensor is composed of a polysilicon resistor and a sensing film. The sensor, which is of a resistive type, changes its resistance when the sensing film adsorbs or desorbs CO gas. The readout circuit is used to convert the sensor resistance into the voltage output. The post-processing of the sensor includes etching the sacrificial layers and coating the sensing film. The advantages of the sensor include room temperature operation, short response/recovery times and easy post-processing. Experimental results show that the sensitivity of the CO sensor is about 0.19 mV/ppm, and the response and recovery times are 23 s and 34 s for 200 ppm CO, respectively.

  19. Cobalt-based nanocatalysts for green oxidation and hydrogenation processes.

    PubMed

    Jagadeesh, Rajenahally V; Stemmler, Tobias; Surkus, Annette-Enrica; Bauer, Matthias; Pohl, Marga-Martina; Radnik, Jörg; Junge, Kathrin; Junge, Henrik; Brückner, Angelika; Beller, Matthias

    2015-06-01

    This protocol describes the preparation of cobalt-based nanocatalysts and their applications in environmentally benign redox processes for fine chemical synthesis. The catalytically active material consists of nanoscale Co3O4 particles surrounded by nitrogen-doped graphene layers (NGrs), which have been prepared by pyrolysis of phenanthroline-ligated cobalt acetate on carbon. The resulting materials have been found to be excellent catalysts for the activation of both molecular oxygen and hydrogen; in all tested reactions, water was the only by-product. By applying these catalysts, green oxidations of alcohols and hydrogenation of nitroarenes for the synthesis of nitriles, esters and amines are demonstrated. The overall time required for catalyst preparation and for redox reactions is 35 h and 10-30 h, respectively.

  20. Laser induced structural phase transformation of cobalt oxides nanostructures.

    PubMed

    Ravindra, A V; Behera, B C; Padhan, P

    2014-07-01

    Face-centered-cubic (fcc) and hexagonal-close-packed (hcp) phases of cobalt monoxide (CoO) nanostructures are prepared using thermolysis route at the same reaction temperature 296 degrees C with synthetic approach conditions. These nanostructures show mixture of nearly spherical and nanoflake morphologies. The structural phases of these nanostructures transform to spinel-Co3O4 by application of heat or Raman excitation laser beam power. The absorbance spectra of fcc and hcp-CoO and Co3O4 nanostructures yield significantly higher values of band gap which can be explained by electron confinement. Such results provide new opportunities for optimizing and enhancing the properties and performance of cobalt oxide nanomaterial.

  1. Pulsed-laser deposition of crystalline cobalt ferrite thin films at lower temperatures

    NASA Astrophysics Data System (ADS)

    Jiles, David; Raghunathan, Arun; Nlebedim, Ikenna; Snyder, John

    2010-03-01

    Cobalt ferrite thin films have been proposed for various engineering applications due to their exceptional magnetic, magnetoelastic, magnetotransport, magnetooptical properties. In this research, cobalt ferrite thin films were grown on SiO2/Si(100) substrates using pulsed-laser deposition (PLD) technique at substrate temperatures ranging from 250 C to 600 C. It has been shown in this study, that polycrystalline films with (111)-preferred orientation can be prepared at substrate temperatures as low as 250 C, as opposed to a report of optimum 600 C substrate temperature [1]. Thermal expansion mismatch between the film and substrate was found to have a substantial effect on the magnetic properties of the cobalt ferrite films, due to the large magnetoelastic coupling of cobalt ferrite. The growth of crystalline cobalt ferrite films at such low temperatures indicates the potential to use cobalt ferrite for MEMS devices and sensor applications [2] including integration with a wider range of multilayered device structures. This research was supported by the UK EPSRC (EP/D057094) and the US NSF (DMR-0402716). [1] J. Zhou et. al, Applied Surface Sciences, 253 (2007), p. 7456. [2] J. A. Paulsen et. al., Journal of Applied Physics, 97 (2005), p. 044502.

  2. Cobalt

    SciTech Connect

    Fox, G.J.

    1994-12-01

    Traditionally, cobalt has been well-known for its chemical uses, including pigments used in ceramic glazes that create the popular cobalt blue color derived from cobalt aluminate. Because of its diverse physical properties, the element is linked to many other applications, including superalloys, permanent magnets, and chemical catalysts. Cobalt 60, a radioisotope of cobalt, continues to be a contributor to the success of high-technology advancements, including innovations in medical treatments. Typically a by-product of copper and nickel production, significant cobalt reserves are found in only a few countries. The African countries of Zaire and Zambia, as well as Canada, are leading cobalt producers. Although the USA is the world's largest consumer, accounting for about one-third of total consumption, it has no domestic production and relies solely upon foreign imports to satisfy demand. The world market has been plagued with the effects of economic and political factors throughout the years, and consequently, price instability has been common. Presently, supply and demand are moving toward a closer balance, and lower market prices are expected within the next year.

  3. Catalysis on cobalt oxide-based nanocatalysts

    NASA Astrophysics Data System (ADS)

    Zhang, Shiran

    Heterogeneous catalysis, being the focus of attention in the realm of catalysis, plays a vital role in modern chemical and energy industries. A prototype of heterogeneous catalyst consists of metal nanoparticles dispersed and supported on a substrate. Transition metal oxide is one of the key components of heterogeneous catalyst and is frequently used as catalyst support for noble metal nanoparticle catalysts due to low cost. As a result of the high cost of noble metal elements, it is particularly favorable to design and develop transition metal oxide-based nanocatalysts mainly made of earthabundant elements with no or less noble metal with comparable or better catalytic performance than noble metal-based nanocatalysts in a catalytic reaction. In some cases, surface chemistry and structure of nanocatalysts are not invariable during catalysis. They evolve in terms of surface restructuring or phase change, which contributes to the complexity of catalyst surface under different catalytic conditions. Transition metal oxides, especially reducible transition metal oxides, have multiple cationic valence states and crystallographic structures. New catalytic active phases or sites could be formed upon surface restructuring under certain catalytic conditions while they may not be preserved if exposed to ambient conditions. Thus, it is essential to characterize catalyst surface under reaction conditions so that chemistry and structure of catalyst surface could be correlated with the corresponding catalytic performance. It also suggests a new route to design nanocatalysts through restructuring catalyst precursor under certain catalytic conditions tracked with in-situ analytical techniques. Catalysis occurs on catalyst surface. For noble metal nanoparticle catalysts, only atoms exposed on surface participate in catalytic processes, while atoms in bulk do not. In order to make full use of noble metal atoms, it is crucial to maximize the dispersion. A configuration of noble metal

  4. Dielectric properties of cobalt ferrite nanoparticles in ultrathin nanocomposite films.

    PubMed

    Alcantara, Gustavo B; Paterno, Leonardo G; Fonseca, Fernando J; Pereira-da-Silva, Marcelo A; Morais, Paulo C; Soler, Maria A G

    2013-12-07

    Multilayered nanocomposite films (thickness 50-90 nm) of cobalt ferrite nanoparticles (np-CoFe2O4, 18 nm) were deposited on top of interdigitated microelectrodes by the layer-by-layer technique in order to study their dielectric properties. For that purpose, two different types of nanocomposite films were prepared by assembling np-CoFe2O4 either with poly(3,4-ethylenedioxy thiophene):poly(styrene sulfonic acid) or with polyaniline and sulfonated lignin. Despite the different film architectures, the morphology of both was dominated by densely-packed layers of nanoparticles surrounded by polyelectrolytes. The dominant effect of np-CoFe2O4 was also observed after impedance spectroscopy measurements, which revealed that dielectric behavior of the nanocomposites was largely influenced by the charge transport across nanoparticle-polyelectrolyte interfaces. For example, nanocomposites containing np-CoFe2O4 exhibited a single low-frequency relaxation process, with time constants exceeding 15 ms. At 1 kHz, the dielectric constant and the dissipation factor (tan δ) of these nanocomposites were 15 and 0.15, respectively. These values are substantially inferior to those reported for pressed pellets made exclusively of similar nanoparticles. Impedance data were further fitted with equivalent circuit models from which individual contributions of particle's bulk and interfaces to the charge transport within the nanocomposites could be evaluated. The present study evidences that such nanocomposites display a dielectric behavior dissimilar from that exhibited by their individual counterparts much likely due to enlarged nanoparticle-polyelectrolyte interfaces.

  5. Tailoring the properties and the reactivity of the spinel cobalt oxide.

    PubMed

    Bahlawane, Naoufal; Ngamou, Patrick Herve Tchoua; Vannier, Vincent; Kottke, Tilman; Heberle, Joachim; Kohse-Höinghaus, Katharina

    2009-10-28

    Pulsed spray evaporation chemical vapor deposition (PSE-CVD) was employed for the synthesis of cobalt-based spinel oxide thin films, Co(3-x)Fe(x)O4 with x = 0-1.56. XRD, Raman scattering and FTIR emission spectroscopy show that the normal spinel structure was retained for 0 < or = x < or = 0.65 by the selective insertion of Fe3+ in the octahedral sites. The spinel inversion was noticed above this range, whereas the insertion of Fe2+ was first indicated with x > or = 1. The room-temperature electrical resistivity of the thin films was controlled between 9 and 0.007 Omega cm by the adjustment of iron doping concentration. Furthermore an improvement of the thermal stability of the spinel was noticed upon doping by iron. The reducibility of the spinel in the presence of molecular hydrogen was efficiently adjusted by a shift of the reduction temperature by up to 110 degrees C upon the controlled insertion of iron in the octahedral sites of the spinel. The investigation of the catalytic oxidation of CO and ethanol over Co(3-x)Fe(x)O4 films with controlled structural modification enabled the confirmation of the Mars-van Krevelen mechanism for the oxidation of CO and the tight correlation between the selectivity of the conversion of ethanol to acetaldehyde and the abundance of surface basic sites. The controlled iron doping was demonstrated to be an efficient strategy to tune the reactivity and the selectivity of the cobalt-based spinel oxide. The doping-induced transition from normal to inverse spinel was observed to induce a clear discontinuity in the trend of all investigated physicochemical properties.

  6. Unusual dielectric response in cobalt doped reduced graphene oxide

    SciTech Connect

    Akhtar, Abu Jahid; Gupta, Abhisek; Kumar Shaw, Bikash; Saha, Shyamal K.

    2013-12-09

    Intensive research on cobalt doped reduced graphene oxide (Co-RGO) to investigate the modification in graphene magnetism and spin polarization due to presence of transition metal atom has been carried out, however, its dielectric spectroscopy, particularly, how capacitance changes with impurity levels in graphene is relatively unexplored. In the present work, dielectric spectroscopy along with magneto-dielectric effect are investigated in Co-RGO. Contrary to other materials, here permittivity increases abruptly with frequency in the low frequency region and continues to increase till 10{sup 7} Hz. This unusual behavior is explained on the basis of trap induced capacitance created due to impurity levels.

  7. Direct evidence for charge stripes in a layered cobalt oxide

    NASA Astrophysics Data System (ADS)

    Babkevich, P.; Freeman, P. G.; Enderle, M.; Prabhakaran, D.; Boothroyd, A. T.

    2016-05-01

    Recent experiments indicate that static stripe-like charge order is generic to the hole-doped copper oxide superconductors and competes with superconductivity. Here we show that a similar type of charge order is present in La5/3Sr1/3CoO4, an insulating analogue of the copper oxide superconductors containing cobalt in place of copper. The stripe phase we have detected is accompanied by short-range, quasi-one-dimensional, antiferromagnetic order, and provides a natural explanation for the distinctive hourglass shape of the magnetic spectrum previously observed in neutron-scattering measurements of La2-xSrxCoO4 and many hole-doped copper oxide superconductors. The results establish a solid empirical basis for theories of the hourglass spectrum built on short-range, quasi-static, stripe correlations.

  8. Direct evidence for charge stripes in a layered cobalt oxide

    PubMed Central

    Babkevich, P.; Freeman, P. G.; Enderle, M.; Prabhakaran, D.; Boothroyd, A. T.

    2016-01-01

    Recent experiments indicate that static stripe-like charge order is generic to the hole-doped copper oxide superconductors and competes with superconductivity. Here we show that a similar type of charge order is present in La5/3Sr1/3CoO4, an insulating analogue of the copper oxide superconductors containing cobalt in place of copper. The stripe phase we have detected is accompanied by short-range, quasi-one-dimensional, antiferromagnetic order, and provides a natural explanation for the distinctive hourglass shape of the magnetic spectrum previously observed in neutron-scattering measurements of La2−xSrxCoO4 and many hole-doped copper oxide superconductors. The results establish a solid empirical basis for theories of the hourglass spectrum built on short-range, quasi-static, stripe correlations. PMID:27212023

  9. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., carboxylic acid-modified (generic). 721.10529 Section 721.10529 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35) is...

  10. Physical and electrochemical study of cobalt oxide nano- and microparticles

    SciTech Connect

    Alburquenque, D.; Vargas, E.; Denardin, J.C.; Escrig, J.; Marco, J.F.; Gautier, J.L.

    2014-07-01

    Cobalt oxide nanocrystals of size 17–21 nm were synthesized by a simple reaction between cobalt acetate (II) and dodecylamine. On the other hand, micrometric Co{sub 3}O{sub 4} was prepared using the ceramic method. The structural examination of these materials was performed using powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM and HRTEM). XRD studies showed that the oxides were pure, well-crystallized, spinel cubic phases with a-cell parameter of 0.8049 nm and 0.8069 nm for the nano and micro-oxide, respectively. The average particle size was 19 nm (nano-oxide) and 1250 μm (micro-oxide). Morphological studies carried out by SEM and TEM analyses have shown the presence of octahedral particles in both cases. Bulk and surface properties investigated by X-ray photoelectron spectroscopy (XPS), point zero charge (pzc), FTIR and cyclic voltammetry indicated that there were no significant differences in the composition on both materials. The magnetic behavior of the samples was determined using a vibrating sample magnetometer. The compounds showed paramagnetic character and no coercivity and remanence in all cases. Galvanostatic measurements of electrodes formed with nanocrystals showed better performance than those built with micrometric particles. - Highlights: • Spinel Co{sub 3}O{sub 4} nanoparticles and microparticles with same structure but with different cell parameters, particle size and surface area were synthesized. • Oxide nanoparticles showed better electrochemical behavior than micrometric ones due to area effect.

  11. Nitrous oxide activation by a cobalt(ii) complex for aldehyde oxidation under mild conditions.

    PubMed

    Corona, Teresa; Company, Anna

    2016-10-07

    Nitrous oxide (N2O) is a waste gas produced in many industrial processes with an important environmental impact. Thus, its application as an oxidant is highly desirable because it produces innocuous N2 as a by-product. In this work we report a new cobalt(ii) complex that reacts with N2O under mild conditions and the catalytic application of this system to carry out the oxidation of aldehydes.

  12. Sputtering of cobalt film with perpendicular magnetic anisotropy on disorder-free graphene

    SciTech Connect

    Jamali, Mahdi; Lv, Yang; Zhao, Zhengyang; Wang, Jian-Ping

    2014-10-15

    Growth of thin cobalt film with perpendicular magnetic anisotropy has been investigated on pristine graphene for spin logic and memory applications. By reduction of the kinetic energy of the sputtered atoms using indirect sputtered deposition, deposition induced defects in the graphene layer have been controlled. Cobalt film on graphene with perpendicular magnetic anisotropy has been developed. Raman spectroscopy of the graphene surface shows very little disorder induced in the graphene by the sputtering process. In addition, upon increasing the cobalt film thickness, the disorder density increases on the graphene and saturates for thicknesses of Co layers above 1 nm. The AFM image indicates a surface roughness of about 0.86 nm. In addition, the deposited film forms a granular structure with a grain size of about 40 nm.

  13. Characterization of cobalt(II) chloride-modified condensation polyimide films

    NASA Technical Reports Server (NTRS)

    Rancourt, J. D.; Taylor, L. T.

    1988-01-01

    The effect of solvent extraction on the properties of cobalt(II) chloride-modified polyimide films was investigated. Solvent-cast films were prepared from solutions of cobalt chloride in poly(amide acid)/N,N-dimethylacetamide (DMAc) and were subsequently dried and cured in static air, forced air, or inert gas ovens with controlled humidity. The films were extracted by either of the three processes (1) soaking in a tray with distilled water at room temperature, (2) soxhlett extraction with distilled water, or (3) soxhell extraction with DMAc. Extraction with DMAc was found to remove both cobalt and chlorine from the films and to slightly increase bulk thermal stability and both surface resistivity and electrical resistivity.

  14. Characterization of cobalt(II) chloride-modified condensation polyimide films

    NASA Technical Reports Server (NTRS)

    Rancourt, J. D.; Taylor, L. T.

    1988-01-01

    The effect of solvent extraction on the properties of cobalt(II) chloride-modified polyimide films was investigated. Solvent-cast films were prepared from solutions of cobalt chloride in poly(amide acid)/N,N-dimethylacetamide (DMAc) and were subsequently dried and cured in static air, forced air, or inert gas ovens with controlled humidity. The films were extracted by either of the three processes (1) soaking in a tray with distilled water at room temperature, (2) soxhlett extraction with distilled water, or (3) soxhell extraction with DMAc. Extraction with DMAc was found to remove both cobalt and chlorine from the films and to slightly increase bulk thermal stability and both surface resistivity and electrical resistivity.

  15. Nano-Web Cobalt Modified Silica Nanoparticles Catalysts for Water Oxidation and MB Oxidative Degradation.

    PubMed

    Wang, Li; Chen, Qiuyun; Li, Chenghao; Fang, Fang

    2016-05-01

    Dioxygen generating materials, using water as oxygen source, can be used as catalysts in hypoxic environments. Cobalt(II) modified silica (SiO2@NPCo) nanoparticles were synthesized through coordination of cobalt(II) ions with nitrogen atoms from 2-acetylpyridine modified silica (SiO2@NP). The SiO2@NPCo nanoparticles further reacted with 1,3,5-benzenetricarboxylic acids, forming porous nano-web nanoparticles (SiO2@NPCoCOOH). The synthesized SiO2@NPCoCOOH nanoparticles were demonstrated as better white LED light driven photochemical catalysts for oxidation of water than individual nanoparticles (SiO2@NPCo). Moreover, the SiO2@NPCoCOOH/water system could decrease the content of methylene blue (MB) in solution and therefore, the nanoweb cobalt(II) modified silica nanoparticles can be environmentally friendly catalysts for oxidative degradation of MB, using water as the oxygen source.

  16. Advantageous use of metallic cobalt in the target for pulsed laser deposition of cobalt-doped ZnO films

    SciTech Connect

    Ying, Minju E-mail: g.gehring@sheffield.ac.uk; Blythe, Harry J.; Gerriu, Fatma M.; Fox, A. Mark; Gehring, Gillian A. E-mail: g.gehring@sheffield.ac.uk; Dizayee, Wala; Heald, Steve M.

    2016-08-15

    We investigate the magnetic properties of ZnCoO thin films grown by pulsed laser deposition (PLD) from targets made containing metallic Co or CoO precursors instead of the usual Co{sub 3}O{sub 4}. We find that the films grown from metallic Co precursors in an oxygen rich environment contain negligible amounts of Co metal and have a large magnetization at room temperature. Structural analysis by X-ray diffraction and magneto-optical measurements indicate that the enhanced magnetism is due, in part, from Zn vacancies that partially compensate the naturally occurring n-type defects. We conclude that strongly magnetic films of Zn{sub 0.95}Co{sub 0.05}O that do not contain metallic cobalt can be grown by PLD from Co-metal-precursor targets if the films are grown in an oxygen atmosphere.

  17. Atomic layer deposition of nickel-cobalt spinel thin films.

    PubMed

    Hagen, D J; Tripathi, T S; Karppinen, M

    2017-04-05

    We report the atomic layer deposition (ALD) of high-quality crystalline thin films of the spinel-oxide system (Co1-xNix)3O4. These spinel oxides are ferrimagnetic p-type semiconductors, and promising material candidates for several applications ranging from photovoltaics and spintronics to thermoelectrics. The spinel phase is obtained for Ni contents exceeding the x = 0.33 limit for bulk samples. It is observed that the electrical resistivity decreases continuously with x while the magnetic moment increases up to x = 0.5. This is in contrast to bulk samples where a decrease of resistivity is not observed for x > 0.33 due to the formation of a rock-salt phase. From UV-VIS-NIR absorption measurements, a change from distinct absorption edges for the parent oxide Co3O4 to a continuous absorption band ranging deep into the near infrared for 0 < x ≤ 0.5 was observed. The conformal deposition of dense films on high-aspect-ratio patterns is demonstrated.

  18. Magnetic properties of thin films of samarium-cobalt alloy prepared by magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Panchal, Gyanendra; Gupta, Mukul; Choudhary, R. J.; Phase, D. M.

    2016-10-01

    We examine the magnetic properties of samarium-cobalt thin films on quartz and Si(111) substrates grown by dc magnetron sputtering. Both films are deposited on Cr buffer layer and subsequently a capping layer of Cr was also deposited. Secondary ion mass spectroscopy results reveal that Cr diffused in to Sm-Co layer.This lead to local change in magnetocrystalline anisotropy. As the result of this we observed the two coercive behaviors in magnetization of thin film.

  19. Unconventional magneto-transport in novel layered cobalt oxides

    NASA Astrophysics Data System (ADS)

    Terasaki, Ichiro

    2008-03-01

    Among strongly correlated transition-metal oxides, cobalt oxides are known to have unique features arising from the spin-state degree of freedom tightly coupled with Co valence. The Co^4+ ion in the low spin-state is responsible for anomalous metallic states such as large thermopower in NaxCoO2 and unconventional superconductivity in hydrated NaxCoO2. The Co^2+ ion favors the high-spin state, which makes magnetic insulators. The Co^3+ ion is most interesting in the sense that the low-, intermediate- and high-spin states are nearly degenerate, where a spin-state crossover/transition occurs with temperature or pressure. Recently we have discovered two complex layered cobalt oxides, which exhibit unprecedented transport originated from interplay between charge, orbital and spin-states. The first one is SrCo6O11, in which the Co-O Kagome lattice and two-types of Co-O pillars are stacked along the c axis [1]. The conduction electrons in the Kagome lattice interact with Ising spins in the pillars, and shows two-step plateau in the magnetoresistance along the c axis. The second one is Sr3YCo4O10.5, which exhibits a ferromagnetic insulating state below 340 K. Various substitutions of Sr, Y and Co sites dramatically suppress this ferromagnetic state, and concomitantly modify the magneto- and thermoelectric transport. We will discuss the structure-property relationship based on structure analyses. The main part of this work was done in collaboration with S. Ishiwata, W. Kobayashi, and M. Takano. [1] S. Ishiwata et al., Chem. Mater. 17, 2789 (2005) ; Phys. Rev. Lett. 98, 217201 (2007) [2] W. Kobayashi et al. Phys. Rev. B 72, 104408 (2005) ; S. Ishiwata et al. Phys. Rev. B75, 220406(R) (2002)

  20. In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution.

    PubMed

    Jin, Haiyan; Wang, Jing; Su, Diefeng; Wei, Zhongzhe; Pang, Zhenfeng; Wang, Yong

    2015-02-25

    Remarkable hydrogen evolution reaction (HER) or superior oxygen evolution reaction (OER) catalyst has been applied in water splitting, however, utilizing a bifunctional catalyst for simultaneously generating H2 and O2 is still a challenging issue, which is crucial for improving the overall efficiency of water electrolysis. Herein, inspired by the superiority of carbon conductivity, the propitious H atom binding energy of metallic cobalt, and better OER activity of cobalt oxide, we synthesized cobalt-cobalt oxide/N-doped carbon hybrids (CoOx@CN) composed of Co(0), CoO, Co3O4 applied to HER and OER by simple one-pot thermal treatment method. CoOx@CN exhibited a small onset potential of 85 mV, low charge-transfer resistance (41 Ω), and considerable stability for HER. Electrocatalytic experiments further indicated the better performance of CoOx@CN for HER can be attributed to the high conductivity of carbon, the synergistic effect of metallic cobalt and cobalt oxide, the stability of carbon-encapsulated Co nanoparticles, and the introduction of electron-rich nitrogen. In addition, when used as catalysts of OER, the CoOx@CN hybrids required 0.26 V overpotential for a current density of 10 mA cm(-2), which is comparable even superior to many other non-noble metal catalysts. More importantly, an alkaline electrolyzer that approached ∼20 mA cm(-2) at a voltage of 1.55 V was fabricated by applying CoOx@CN as cathode and anode electrocatalyst, which opened new possibilities for exploring overall water splitting catalysts.

  1. Study of nanocrystalline thin cobalt films with perpendicular magnetic anisotropy obtained by thermal evaporation

    NASA Astrophysics Data System (ADS)

    Kozłowski, Witold; Balcerski, Józef; Szmaja, Witold

    2017-02-01

    We have performed a detailed investigation of the morphological and magnetic domain structures of nanocrystalline thin cobalt films with perpendicular magnetic anisotropy. The films were thermally evaporated at an incidence angle of 0° in a vacuum of about 10-5 mbar and possessed thicknesses in the range from 60 nm to 100 nm. The films were studied by X-ray photoelectron spectroscopy (XPS), electron diffraction of transmission electron microscopy (TEM), atomic force microscopy (AFM), magnetic force microscopy (MFM) and the Fresnel mode of TEM. The films are polycrystalline and consist of very densely packed grains with sizes at the nanometer range. The grains are roundish in shape and generally exhibit no geometric alignment. The films are mainly composed of the hexagonal close-packed (HCP) phase of cobalt and possess preferential orientation of the cobalt grains with the hexagonal axis perpendicular to the film surface. 70 nm thick films and thicker have fully perpendicular magnetization, while 60 nm thick films possess clearly dominating perpendicular magnetization component. The magnetic domain structure is in the form of stripe domains forming a maze pattern. When the film thickness increases from 60 nm to 100 nm, the average grain size increases from 28.9 nm to 31.5 nm and the average domain width increases from 79.4 nm to 98.7 nm.

  2. In situ formation of cobalt oxide nanocubanes as efficient oxygen evolution catalysts.

    PubMed

    Hutchings, Gregory S; Zhang, Yan; Li, Jian; Yonemoto, Bryan T; Zhou, Xinggui; Zhu, Kake; Jiao, Feng

    2015-04-01

    Oxygen evolution from water poses a significant challenge in solar fuel production because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen evolution reaction (OER). Here, a new strategy was developed to synthesize nonsupported ultrasmall cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.023 per second per cobalt in photocatalytic water oxidation. X-ray absorption results suggested a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen in an octahedral arrangement to form 8 Co4O4 cubanes, which may be responsible for the exceptionally high OER activity.

  3. Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water.

    PubMed

    Bajdich, Michal; García-Mota, Mónica; Vojvodic, Aleksandra; Nørskov, Jens K; Bell, Alexis T

    2013-09-11

    The presence of layered cobalt oxides has been identified experimentally in Co-based anodes under oxygen-evolving conditions. In this work, we report the results of theoretical investigations of the relative stability of layered and spinel bulk phases of Co oxides, as well as the stability of selected surfaces as a function of applied potential and pH. We then study the oxygen evolution reaction (OER) on these surfaces and obtain activity trends at experimentally relevant electro-chemical conditions. Our calculated volume Pourbaix diagram shows that β-CoOOH is the active phase where the OER occurs in alkaline media. We calculate relative surface stabilities and adsorbate coverages of the most stable low-index surfaces of β-CoOOH: (0001), (0112), and (1014). We find that at low applied potentials, the (1014) surface is the most stable, while the (0112) surface is the more stable at higher potentials. Next, we compare the theoretical overpotentials for all three surfaces and find that the (1014) surface is the most active one as characterized by an overpotential of η = 0.48 V. The high activity of the (1014) surface can be attributed to the observation that the resting state of Co in the active site is Co(3+) during the OER, whereas Co is in the Co(4+) state in the less active surfaces. Lastly, we demonstrate that the overpotential of the (1014) surface can be lowered further by surface substitution of Co by Ni. This finding could explain the experimentally observed enhancement in the OER activity of Ni(y)Co(1-y)O(x) thin films with increasing Ni content. All energetics in this work were obtained from density functional theory using the Hubbard-U correction.

  4. Formation of Semimetallic Cobalt Telluride Nanotube Film via Anion Exchange Tellurization Strategy in Aqueous Solution for Electrocatalytic Applications.

    PubMed

    Patil, Supriya A; Kim, Eun-Kyung; Shrestha, Nabeen K; Chang, Jinho; Lee, Joong Kee; Han, Sung-Hwan

    2015-11-25

    Metal telluride nanostructures have demonstrated several potential applications particularly in harvesting and storing green energy. Metal tellurides are synthesized by tellurization process performed basically at high temperature in reducing gas atmosphere, which makes the process expensive and complicated. The development of a facile and economical process for desirable metal telluride nanostructures without complicated manipulation is still a challenge. In an effort to develop an alternative strategy of tellurization, herein we report a thin film formation of self-standing cobalt telluride nanotubes on various conducting and nonconducting substrates using a simple binder-free synthetic strategy based on anion exchange transformation from a thin film of cobalt hydroxycarbonate nanostructures in aqueous solution at room temperature. The nanostructured films before and after ion exchange transformation reaction are characterized using field emission scanning electron microscope, energy dispersive X-ray analyzer, X-ray photoelectron spectroscopy, thin film X-ray diffraction technique, high resolution transmission electron microscope, and selected area electron diffraction analysis technique. After the ion exchange transformation of nanostructures, the film shows conversion from insulator to highly electrical conductive semimetallic characteristic. When used as a counter electrode in I3(-)/I(-) redox electrolyte based dye-sensitized solar cells, the telluride film exhibits an electrocatalytic reduction activity for I3(-) with a demonstration of solar-light to electrical power conversion efficiency of 8.10%, which is highly competitive to the efficiency of 8.20% exhibited by a benchmarked Pt-film counter electrode. On the other hand, the telluride film electrode also demonstrates electrocatalytic activity for oxygen evolution reaction from oxidation of water.

  5. Precipitation method and characterization of cobalt oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Prabaharan, D. Durai Manoharadoss; Sadaiyandi, K.; Mahendran, M.; Sagadevan, Suresh

    2017-04-01

    Cobalt oxide (Co3O4) nanoparticles were synthesized using precipitation method. The X-ray diffraction (XRD) pattern was used to determine the structure of Co3O4 nanoparticles. The presence of Co3O4 nanoparticles was confirmed by the FTIR spectrum. The fact about the surface morphology of Co3O4 nanoparticles was revealed by scanning electron microscopic analysis. Transmission electron microscopy was used to measure the particle size of the Co3O4 nanoparticles. The absorption spectrum made it possible to analyze the optical properties of Co3O4 nanoparticles. This work contributes to the study of dielectric properties such as the dielectric loss and the dielectric constant of Co3O4 nanoparticles, at varied frequencies and temperatures. The magnetic properties of the Co3O4 nanoparticles were also investigated.

  6. Atomic layer deposited cobalt oxide: An efficient catalyst for NaBH{sub 4} hydrolysis

    SciTech Connect

    Nandi, Dip K.; Manna, Joydev; Dhara, Arpan; Sharma, Pratibha; Sarkar, Shaibal K.

    2016-01-15

    Thin films of cobalt oxide are deposited by atomic layer deposition using dicobalt octacarbonyl [Co{sub 2}(CO){sub 8}] and ozone (O{sub 3}) at 50 °C on microscope glass substrates and polished Si(111) wafers. Self-saturated growth mechanism is verified by x-ray reflectivity measurements. As-deposited films consist of both the crystalline phases; CoO and Co{sub 3}O{sub 4} that gets converted to pure cubic-Co{sub 3}O{sub 4} phase upon annealing at 500 °C under ambient condition. Elemental composition and uniformity of the films is examined by x-ray photoelectron spectroscopy and secondary ion-mass spectroscopy. Both as-deposited and the annealed films have been successfully tested as a catalyst for hydrogen evolution from sodium borohydride hydrolysis. The activation energy of the hydrolysis reaction in the presence of the as-grown catalyst is found to be ca. 38 kJ mol{sup −1}. Further implementation of multiwalled carbon nanotube, as a scaffold layer, improves the hydrogen generation rate by providing higher surface area of the deposited catalyst.

  7. Combinatorial studies for determining properties of thin-film gold-cobalt alloys

    NASA Astrophysics Data System (ADS)

    Ramirez, Ainissa G.; Saha, Ranjana

    2004-11-01

    A library of gold-cobalt alloys was synthesized by combinatorial methods to explore potential contact materials for microfabricated microrelays. After a compositionally graded film was deposited, it was subjected to heat treatments to create precipitates and to promote precipitation hardening. Using a high-throughput screening method, the film was then characterized for mechanical hardness, sheet resistance, composition, and microstructure by using nanoindentation, four-point probe, x-ray photoelectron spectroscopy, and transmission electron microscopy. The hardness exhibited a linear behavior from pure gold to pure cobalt from 2 to 9 GPa. The microstructure included a metastable gold-silicide with a grain size that seems dependent on the amount of cobalt. From this combinatorial method, we gain an understanding of the material's structure-property relationship and can illuminate the link between mechanical and electrical properties to composition. This work presents the experiments and techniques for mapping material properties.

  8. Corrosion inhibition of cobalt with a thin film of Cu-BTA

    SciTech Connect

    Brusic, V.; Frankel, G.S.; Schrott, A.G.; Petersen, T.A. . IBM Research Division); Rush, B.M. . Dept. of Chemical Engineering)

    1993-09-01

    Electrochemical techniques, ellipsometry and X-ray photoelectron spectroscopy were used to evaluate the use of benzotriazole, alone or in combination with boric acid/borate buffer and dilute copper sulfate for the protection of cobalt. The data indicate that in slightly alkaline solutions benzotriazole is a strong inhibitor for cobalt corrosion, whereas in water and neutral solutions it produces a barely measurable effect. In the presence of benzotriazole and Cu[sup +2] ions, spontaneous reduction of copper ions leads to the formation of a thin film of Cu-BTA on the cobalt surface. This film acts as a corrosion protector that is better than benzotriazole, with a significant reduction of the corrosion rate even during subsequent exposure to solutions without inhibitors.

  9. Oxide Films for RF Applications

    DTIC Science & Technology

    2008-07-01

    structured thin film superlattices of (AEO)m( TiO2 )n - type with varying m and n numbers in order to generate a homologous series of materials having...mechanisms in MBE oxide films The proposed goal was to identify, isolate, and reduce sources of loss in thin film dielectrics. It is important to note...that the loss in bulk single crystals is often orders of magnitude below that of their thin film counterparts. It is believed that defects in thin

  10. Light driven water oxidation by a single site cobalt salophen catalyst.

    PubMed

    Pizzolato, Erica; Natali, Mirco; Posocco, Bianca; Montellano López, Alejandro; Bazzan, Irene; Di Valentin, Marilena; Galloni, Pierluca; Conte, Valeria; Bonchio, Marcella; Scandola, Franco; Sartorel, Andrea

    2013-11-04

    A salophen cobalt(II) complex enables water oxidation at neutral pH in photoactivated sacrificial cycles under visible light, thus confirming the high appeal of earth abundant single site catalysis for artificial photosynthesis.

  11. Tunable growth of perpendicular cobalt ferrite nanosheets on reduced graphene oxide for energy storage.

    PubMed

    Dong, Bitao; Li, Mingyan; Xiao, Chunhui; Ding, Dawei; Gao, Guoxin; Ding, Shujiang

    2017-02-03

    Ultrathin cobalt ferrite nanosheets have been successfully assembled on the surface of reduced graphene oxide (rGO) via only adjusting the volume ratio of ethanol and deionized (DI) water and a post calcination treatment. The perpendicular ultrathin cobalt ferrite nanosheets supported by rGO sheets (CoFe2O4 NSs@rGO) can be obtained when the volume ratio of ethanol and DI water is 10:30. Correspondingly, the hierarchical porous films covering the total rGO sheets will be formed nanosheets. When evaluated as the electrodes for lithium ion batteries (LIBs) and supercapacitors (SCs), the resultant CoFe2O4 NSs@rGO hybrids exhibit highly enhanced electrochemical performance. Even after 200 charge-discharge cycles at 400 mA g(-1), the electrodes as the anode material for LIBs still exhibit a reversible discharge capacity of 835.6 mAh g(-1). In addition, this electrode for SCs also exhibits specific capacitance of ca 1120 F g(-1) after 3000 cycles. These superior results imply that CoFe2O4 NSs with novel hybrid structure of rGO could potentially lead to an excellent electrochemical performance for energy storage.

  12. Tunable growth of perpendicular cobalt ferrite nanosheets on reduced graphene oxide for energy storage

    NASA Astrophysics Data System (ADS)

    Dong, Bitao; Li, Mingyan; Xiao, Chunhui; Ding, Dawei; Gao, Guoxin; Ding, Shujiang

    2017-02-01

    Ultrathin cobalt ferrite nanosheets have been successfully assembled on the surface of reduced graphene oxide (rGO) via only adjusting the volume ratio of ethanol and deionized (DI) water and a post calcination treatment. The perpendicular ultrathin cobalt ferrite nanosheets supported by rGO sheets (CoFe2O4 NSs@rGO) can be obtained when the volume ratio of ethanol and DI water is 10:30. Correspondingly, the hierarchical porous films covering the total rGO sheets will be formed nanosheets. When evaluated as the electrodes for lithium ion batteries (LIBs) and supercapacitors (SCs), the resultant CoFe2O4 NSs@rGO hybrids exhibit highly enhanced electrochemical performance. Even after 200 charge-discharge cycles at 400 mA g-1, the electrodes as the anode material for LIBs still exhibit a reversible discharge capacity of 835.6 mAh g-1. In addition, this electrode for SCs also exhibits specific capacitance of ca 1120 F g-1 after 3000 cycles. These superior results imply that CoFe2O4 NSs with novel hybrid structure of rGO could potentially lead to an excellent electrochemical performance for energy storage.

  13. Supported, Alkali-Promoted Cobalt Oxide Catalysts for NOx Removal from Coal Combustion Flue Gases

    SciTech Connect

    Morris D. Argyle

    2005-12-31

    A series of cobalt oxide catalysts supported on alumina ({gamma}-Al{sub 2}O{sub 3}) were synthesized with varying contents of cobalt and of added alkali metals, including lithium, sodium, potassium, rubidium, and cesium. Unsupported cobalt oxide catalysts and several cobalt oxide catalysts supported ceria (CeO{sub 2}) with varying contents of cobalt with added potassium were also prepared. The catalysts were characterized with UV-visible spectroscopy and were examined for NO{sub x} decomposition activity. The CoO{sub x}/Al{sub 2}O{sub 3} catalysts and particularly the CoO{sub x}/CeO{sub 2} catalysts show N{sub 2}O decomposition activity, but none of the catalysts (unsupported Co{sub 3}O{sub 4} or those supported on ceria or alumina) displayed significant, sustained NO decomposition activity. For the Al{sub 2}O{sub 3}-supported catalysts, N{sub 2}O decomposition activity was observed over a range of reaction temperatures beginning about 723 K, but significant (>50%) conversions of N{sub 2}O were observed only for reaction temperatures >900 K, which are too high for practical commercial use. However, the CeO{sub 2}-supported catalysts display N{sub 2}O decomposition rates similar to the Al{sub 2}O{sub 3}-supported catalysts at much lower reaction temperatures, with activity beginning at {approx}573 K. Conversions of >90% were achieved at 773 K for the best catalysts. Catalytic rates per cobalt atom increased with decreasing cobalt content, which corresponds to increasing edge energies obtained from the UV-visible spectra. The decrease in edge energies suggests that the size and dimensionality of the cobalt oxide surface domains increase with increasing cobalt oxide content. The rate data normalized per mass of catalyst that shows the activity of the CeO{sub 2}-supported catalysts increases with increasing cobalt oxide content. The combination of these data suggest that supported cobalt oxide species similar to bulk Co{sub 3}O{sub 4} are inherently more active than

  14. Peculiar surface-interface properties of nanocrystalline ceria-cobalt oxides with enhanced oxygen storage capacity.

    PubMed

    Qiu, Nan; Zhang, Jing; Wu, Ziyu

    2014-11-07

    Peculiar surface-interface properties of nanocrystalline ceria-cobalt oxides were evidenced by X-ray diffraction, transmission electron microscopy and X-ray absorption spectroscopy. It was found that cobalt foreign cations modify the surface oxygen vacancies of ceria at the atomic level, inducing the exposure of well-defined reactive faces between the ceria-host and the cobalt oxide interface. These modifications of the surface-interface structure promoted a remarkable increase in the oxygen storage capacity of ceria nanocrystals.

  15. Effect of deposition pressure on the structural and magnetic properties of cobalt ferrite thin films

    SciTech Connect

    Nongjai, R.; Khan, S.; Ahmad, H.; Khan, I.; Asokan, K.

    2013-06-03

    We present the influence of deposition pressure on the structural and magnetic properties of cobalt ferrite thin films. Thin films of Co ferrite were deposited by rf sputtering on Si (100) substrate and characterized by X - Ray Diffraction (XRD), Atomic Force Microscopy (AFM) and Vibrating Sample Magnetometer (VSM). The XRD patterns showed the formation of crystalline single phase of the films. The particle size and surface roughness of the films were strongly influence by gas pressure. Hysteresis loops measured at room temperature showed the enhancement of magnetic properties with the increase of gas pressure which is attributed to the decrease of particle size.

  16. Characterization of the growth processes and magnetic properties of thin ferromagnetic cobalt films on Cu(100)

    NASA Astrophysics Data System (ADS)

    De Miguel, J. J.; Cebollada, A.; Gallego, J. M.; Ferrer, S.; Miranda, R.; Schneider, C. M.; Bressler, P.; Garbe, J.; Bethke, K.; Kirschner, J.

    1989-04-01

    The growth of thin films of fcc cobalt on Cu(100) has been characterized with medium energy electron diffraction (MEED) and thermal energy atom scattering (TEAS) in order to prepare films of reproducible structural perfection, interdiffusion profile and atomic concentration. The magnetic properties of thin films are shown to be strongly affected by these — usually difficult to control — parameters providing a clue to the possible origin of contradictory reports in this field. In particular, for carefully grown films, a clear thickness dependence of the Curie temperature, not previously reported for this system, has been found.

  17. Cobalt Oxide Nanoflowers for Electrochemical Determination of Glucose

    NASA Astrophysics Data System (ADS)

    Balouch, Quratulain; Ibupoto, Zafar Hussain; Khaskheli, Ghulam Qadir; Soomro, Razium Ali; Sirajuddin; Samoon, Muhammad Kashif; Deewani, Vinod Kumar

    2015-10-01

    This study reports a simple, economic, and efficient approach for synthesis of cobalt oxide (Co3O4) nanostructures by a low-temperature aqueous chemical growth method. The synthesized Co3O4 nanostructures were characterized by various techniques such as x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy. The synthesized nanostructures exhibited flower-shaped morphology with thickness of each pellet in the range of 200 to 300 nm. The synthesized Co3O4 nanostructures with excellent structural features exhibited high electrocatalytic activity towards the oxidation of glucose in alkaline solution. This enabled development of a highly sensitive (1618.71 µA mM-1 cm-2), stable and reproducible non-enzymatic glucose sensor. The developed sensor demonstrated high anti-interference capability against common interferents such as dopamine, ascorbic acid and uric acid. Furthermore, the applicability of the developed sensor for the determination of glucose from human blood serum provides an alternative approach for the routine glucose analysis.

  18. Magnetic Transparent Conducting Oxide Film And Method Of Making

    DOEpatents

    Windisch, Jr., Charles F.; Exarhos, Gregory J.; Sharma, Shiv K.

    2006-03-14

    Cobalt-nickel oxide films of nominal 100 nm thickness, and resistivity as low as 0.06 O·cm have been deposited by spin-casting from both aqueous and organic precursor solutions followed by annealing at 450° C. in air. An increase in film resistivity was found upon substitution of other cations (e.g., Zn2+, Al3+) for Ni in the spinel structure. However, some improvement in the mechanical properties of the films resulted. On the other hand, addition of small amounts of Li decreased the resistivity. A combination of XRD, XPS, UV/Vis and Raman spectroscopy indicated that NiCo2O4 is the primary conducting component and that the conductivity reaches a maximum at this stoichiometry. When x<0.67, NiO forms leading to an increase in resistivity; when x>0.67, the oxide was all spinel but the increased Co content lowered the conductivity.

  19. Dual-Templated Cobalt Oxide for Photochemical Water Oxidation.

    PubMed

    Deng, Xiaohui; Bongard, Hans-Josef; Chan, Candace K; Tüysüz, Harun

    2016-02-19

    Mesoporous Co3 O4 was prepared using a dual templating approach whereby mesopores inside SiO2 nanospheres, as well as the void spaces between the nanospheres, were used as templates. The effect of calcination temperature on the crystallinity, morphology, and textural parameters of the Co3 O4 replica was investigated. The catalytic activity of Co3 O4 for photochemical water oxidation in a [Ru(bpy)3 ](2+) [S2 O8 ](2-) system was evaluated. The Co3 O4 replica calcined at the lowest temperature (150 °C) exhibited the best performance as a result of the unique nanostructure and high surface area arising from the dual templating. The performance of Co3 O4 with highest surface area was further examined in electrochemical water oxidation. Superior activity over high temperature counterpart and decent stability was observed. Furthermore, CoO with identical morphology was prepared from Co3 O4 using an ethanol reduction method and a higher turnover-frequency number for photochemical water oxidation was obtained.

  20. Modification of Wide-Band-Gap Oxide Semiconductors with Cobalt Hydroxide Nanoclusters for Visible-Light Water Oxidation.

    PubMed

    Maeda, Kazuhiko; Ishimaki, Koki; Tokunaga, Yuki; Lu, Daling; Eguchi, Miharu

    2016-07-11

    Cobalt-based compounds, such as cobalt(II) hydroxide, are known to be good catalysts for water oxidation. Herein, we report that such cobalt species can also activate wide-band-gap semiconductors towards visible-light water oxidation. Rutile TiO2 powder, a well-known wide-band-gap semiconductor, was capable of harvesting visible light with wavelengths of up to 850 nm, and thus catalyzed water oxidation to produce molecular oxygen, when decorated with cobalt(II) hydroxide nanoclusters. To the best of our knowledge, this system constitutes the first example that a particulate photocatalytic material that is capable of water oxidation upon excitation by visible light can also operate at such long wavelengths, even when it is based on earth-abundant elements only.

  1. Impedance spectroscopy studies in cobalt ferrite-reduced graphene oxide nanocomposite

    SciTech Connect

    Supriya, Sweety Kumar, Sunil Kar, Manoranjan

    2016-05-06

    (1-x)Cobalt ferrite-(x)reduced graphene oxidenanocomposites with x=0, 0.1, 0.2 and 0.3 were prepared by the ultrasonic method. The crystal symmetry modification due to reduced graphene oxide and cobalt ferrite interaction has been studied by employing the X-ray diffraction technique. Morphology of the samples was studied by the Field emission scanning electron microscopy (FE-SEM). Study on electrical properties of the cobalt ferrite-reduced graphene oxide nanocomposites explores the possible application of these composites as anode material. Impedance decreases with an increase in frequency as well as temperature, which supports an increase in ac electrical conductivity. The modified Debye relaxation model can explain the behavior of impedance in cobalt ferrite-reduced graphene oxide nanocomposites.

  2. Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands

    NASA Astrophysics Data System (ADS)

    Fester, J.; García-Melchor, M.; Walton, A. S.; Bajdich, M.; Li, Z.; Lammich, L.; Vojvodic, A.; Lauritsen, J. V.

    2017-01-01

    Transition metal oxides show great promise as Earth-abundant catalysts for the oxygen evolution reaction in electrochemical water splitting. However, progress in the development of highly active oxide nanostructures is hampered by a lack of knowledge of the location and nature of the active sites. Here we show, through atom-resolved scanning tunnelling microscopy, X-ray spectroscopy and computational modelling, how hydroxyls form from water dissociation at under coordinated cobalt edge sites of cobalt oxide nanoislands. Surprisingly, we find that an additional water molecule acts to promote all the elementary steps of the dissociation process and subsequent hydrogen migration, revealing the important assisting role of a water molecule in its own dissociation process on a metal oxide. Inspired by the experimental findings, we theoretically model the oxygen evolution reaction activity of cobalt oxide nanoislands and show that the nanoparticle metal edges also display favourable adsorption energetics for water oxidation under electrochemical conditions.

  3. Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands

    DOE PAGES

    Fester, J.; García-Melchor, M.; Walton, A. S.; ...

    2017-01-30

    Here, transition metal oxides show great promise as Earth-abundant catalysts for the oxygen evolution reaction in electrochemical water splitting. However, progress in the development of highly active oxide nanostructures is hampered by a lack of knowledge of the location and nature of the active sites. Here we show, through atom-resolved scanning tunnelling microscopy, X-ray spectroscopy and computational modelling, how hydroxyls form from water dissociation at under coordinated cobalt edge sites of cobalt oxide nanoislands. Surprisingly, we find that an additional water molecule acts to promote all the elementary steps of the dissociation process and subsequent hydrogen migration, revealing the importantmore » assisting role of a water molecule in its own dissociation process on a metal oxide. Inspired by the experimental findings, we theoretically model the oxygen evolution reaction activity of cobalt oxide nanoislands and show that the nanoparticle metal edges also display favourable adsorption energetics for water oxidation under electrochemical conditions.« less

  4. Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands

    PubMed Central

    Fester, J.; García-Melchor, M.; Walton, A. S.; Bajdich, M.; Li, Z.; Lammich, L.; Vojvodic, A.; Lauritsen, J. V.

    2017-01-01

    Transition metal oxides show great promise as Earth-abundant catalysts for the oxygen evolution reaction in electrochemical water splitting. However, progress in the development of highly active oxide nanostructures is hampered by a lack of knowledge of the location and nature of the active sites. Here we show, through atom-resolved scanning tunnelling microscopy, X-ray spectroscopy and computational modelling, how hydroxyls form from water dissociation at under coordinated cobalt edge sites of cobalt oxide nanoislands. Surprisingly, we find that an additional water molecule acts to promote all the elementary steps of the dissociation process and subsequent hydrogen migration, revealing the important assisting role of a water molecule in its own dissociation process on a metal oxide. Inspired by the experimental findings, we theoretically model the oxygen evolution reaction activity of cobalt oxide nanoislands and show that the nanoparticle metal edges also display favourable adsorption energetics for water oxidation under electrochemical conditions. PMID:28134335

  5. Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica

    PubMed Central

    Olguin, Gianni; Yacou, Christelle; Smart, Simon; Diniz da Costa, João C.

    2013-01-01

    The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications. PMID:24022785

  6. Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica.

    PubMed

    Olguin, Gianni; Yacou, Christelle; Smart, Simon; da Costa, João C Diniz

    2013-01-01

    The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications.

  7. Mechanism of Charge Transport in Cobalt and Iron Phthalocyanine Thin Films Grown by Molecular Beam Epitaxy

    SciTech Connect

    Kumar, Arvind; Samanta, Soumen; Singh, Ajay; Debnath, A. K.; Aswal, D. K.; Gupta, S. K.

    2011-12-12

    Cobalt phthalocyanine (CoPc), iron phthalocyanine (FePc) and their composite (CoPc-FePc) films have been grown by molecular beam epitaxy (MBE). Grazing incidence X-ray diffraction (GIXRD) and scanning electron microscope (SEM) studies showed that composite films has better structural ordering compared to individual CoPc and FePc films. The temperature dependence of resistivity (in the temperature range 25 K- 100 K) showed that composite films are metallic, while individual CoPc and FePc films are in the critical regime of metal-to-insulator (M-I) transition The composite films show very high mobility of 110 cm{sup 2} V{sup -1} s{sup -1} at room temperature i.e. nearly two order of magnitude higher compared to pure CoPc and FePc films.

  8. High-purity cobalt thin films with perpendicular magnetic anisotropy prepared by chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Ootera, Yasuaki; Shimada, Takuya; Kado, Masaki; Quinsat, Michael; Morise, Hirofumi; Nakamura, Shiho; Kondo, Tsuyoshi

    2015-11-01

    A study of the chemical vapor deposition (CVD) of high-purity cobalt thin films is described. The Co layer prepared by a thermal CVD technique with a Pt/Ta underlayer and a Pt cap layer shows a saturation magnetization (Ms) of ∼1.8 T and perpendicular magnetic anisotropy (PMA) with an anisotropy energy (Ku) of ∼105 J/m3. The cobalt thickness dependence of Ku reveals that the interfacial anisotropy at the Pt/Co interface is most likely the origin of the obtained PMA.

  9. Preparation of perovskite-type oxides of cobalt by the malic acid aided process and their electrocatalytic surface properties in relation to oxygen evolution

    SciTech Connect

    Tiwari, S.K.; Chartier, P.; Singh, R.N. . Electrochemical Lab.)

    1995-01-01

    The electrocatalytic properties of perovskite-type cobalt oxides (La[sub 1[minus]x]Sr[sub x]CoO[sub 3], where x = 0, 0.2, 0.4), in the form of thin films on conductive supports, were studied by cyclic voltammetry and Tafel polarization techniques. The films had conductive and satisfactory adherent properties. The oxides were synthesized by a low temperature malic acid aided method. The cyclic voltammetry showed a pair of redox peaks prior to the onset of oxygen evolution on the oxide film with nickel support, while similar peaks were absent in the same oxide film on Pt and Ti. The anodic polarization studies indicated two Tafel slopes: 57 to 64 mV/decade at low and 100 to 130 mV/decade at high overpotentials, and first-order kinetics with respect to OH[sup [minus

  10. Microanalysis of an oxidized cobalt oxide: Zirconia eutectic

    SciTech Connect

    Bentley, J.; McKernan, S.; Carter, C.B.; Revcolevschi, A.

    1993-12-31

    The compositions of CoO, Co{sub 3}O{sub 4}, and Ca-stabilized cubic ZrO{sub 2} in an oxidized directionally solidified CoO-ZrO{sub 2} eutectic were determined by PEELS and EDS. An oxygen gradient exists across the Co{sub 3}O{sub 4} with highest levels near the ZrO{sub 2} interface. Oxygen ELNES for CoO and Co{sub 3}O{sub 4} are quite different; published oxygen ELNES have been incorrectly attributed to CoO. Normalized Co-L{sub 23} white line intensity (WLI) ratios for CoO and Co{sub 3}O{sub 4} are similar (0.53 {plus_minus} 0.02) but L{sub 3}/L{sub 2} WLI ratios are 3.88 and 2.58, respectively. ELCE data suggest Co{sub 3}O{sub 4} has the inverse spinel structure.

  11. Kinetic phase evolution of spinel cobalt oxide during lithiation

    SciTech Connect

    Li, Jing; He, Kai; Meng, Qingping; Li, Xin; Zhu, Yizhou; Hwang, Sooyeon; Sun, Ke; Gan, Hong; Zhu, Yimei; Mo, Yifei; Stach, Eric A.; Su, Dong

    2016-09-15

    Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalation reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.

  12. Kinetic phase evolution of spinel cobalt oxide during lithiation

    SciTech Connect

    Li, Jing; He, Kai; Meng, Qingping; Li, Xin; Zhu, Yizhou; Hwang, Sooyeon; Sun, Ke; Gan, Hong; Zhu, Yimei; Mo, Yifei; Stach, Eric A.; Su, Dong

    2016-09-15

    Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalation reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.

  13. Kinetic phase evolution of spinel cobalt oxide during lithiation

    DOE PAGES

    Li, Jing; He, Kai; Meng, Qingping; ...

    2016-09-15

    Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

  14. Iron-cobalt bimetal oxide nanorods as efficient and robust water oxidation catalysts.

    PubMed

    Zhou, Xichen; Huang, Jingwei; Zhang, Fuming; Zhao, Yukun; Zhang, Yan; Ding, Yong

    2017-03-15

    Cobalt-based oxides are considered as potential water oxidation catalysts for future artificial photosynthetic systems because of their high abundance, strong stability and efficient performance. Herein, a series of cobalt-based oxides, MnCo3-nO4 (M = Mn, Fe, Co) samples, were synthesized through changing the metal sources by a low-temperature coprecipitation method. These catalysts were investigated under photochemical and electrochemical water oxidation conditions. And they all exhibited efficient activity for water oxidation under alkaline, acidic and neutral conditions under visible light irradiation. An excellent O2 yield of 90.4% for Fe-Co bimetal oxide (Fe1.1Co1.9O4) nanorods was obtained under optimal conditions (photoirradiation at λ ≥ 420 nm, [Ru(bpy)3](ClO4)2 as the photosensitizer, Na2S2O8 as the oxidant in borate buffer at pH = 9.0, bpy = 2,2-bipyridine). Among MnCo3-nO4 samples, Fe1.1Co1.9O4 nanorods were proved to be the optimal electrocatalytic water oxidation catalyst as well. Multiple experiments (SEM, FT-IR, XRD, XPS, Bulk electrolysis) were used to test the stability of Fe1.1CO1.9O4 and these results indicate that Fe1.1CO1.9O4 nanorods are highly stable. Furthermore, based on Mott-Schottky and cyclic voltammetry analysis, the best balanced flat-band potential of Fe1.1CO1.9O4 nanorods is just located at the middle position between the oxidation potential of O2/H2O and the half-wave potential of [Ru(bpy)3](3+/2+), which was probably responsible for their superior photocatalytic water oxidation performance.

  15. Electroluminescence and Photoluminescence from a Fluorescent Cobalt Porphyrin Grafted on Graphene Oxide

    NASA Astrophysics Data System (ADS)

    Janghouri, Mohammad

    2017-10-01

    A new graphene oxide-cobalt porphyrin (GO-CoTPP) hybrid material has been used as an emissive layer in organic light-emitting diodes (OLEDs). Devices with fundamental structure of indium-doped tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS, 45 nm)/polyvinylcarbazole (PVK):2-(4-biphenyl)-5-(4- t-butylphenyl)-1,3,4-oxadiazole (PBD):GO-CoTPP (70 nm)/1,3,5-tris( N-phenylbenzimidazol-2-yl)-benzene (TPBI, 20 nm)/Al (150 nm) were fabricated. A red electroluminescence (EL) was obtained from thin-film PVK:PBD:CoTPP at 70 nm thickness. When CoTPP was covalently grafted on graphene oxide (GO) sheets, near-white EL was obtained. The white emission, which was composed of bluish green and red, is attributed to electroplex formation at the GO-CoTPP/PBD interface. Such electroplex emission between electrons and holes is a reason for the low turn-on voltage of the GO-CoTPP-based OLED. Maximum luminance efficiency of 1.43 cd/A with Commission International de l'Eclairage coordinates of 0.33 and 0.40 was achieved at current of 0.02 mA and voltage of 14 V.

  16. Electroluminescence and Photoluminescence from a Fluorescent Cobalt Porphyrin Grafted on Graphene Oxide

    NASA Astrophysics Data System (ADS)

    Janghouri, Mohammad

    2017-06-01

    A new graphene oxide-cobalt porphyrin (GO-CoTPP) hybrid material has been used as an emissive layer in organic light-emitting diodes (OLEDs). Devices with fundamental structure of indium-doped tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS, 45 nm)/polyvinylcarbazole (PVK):2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD):GO-CoTPP (70 nm)/1,3,5-tris(N-phenylbenzimidazol-2-yl)-benzene (TPBI, 20 nm)/Al (150 nm) were fabricated. A red electroluminescence (EL) was obtained from thin-film PVK:PBD:CoTPP at 70 nm thickness. When CoTPP was covalently grafted on graphene oxide (GO) sheets, near-white EL was obtained. The white emission, which was composed of bluish green and red, is attributed to electroplex formation at the GO-CoTPP/PBD interface. Such electroplex emission between electrons and holes is a reason for the low turn-on voltage of the GO-CoTPP-based OLED. Maximum luminance efficiency of 1.43 cd/A with Commission International de l'Eclairage coordinates of 0.33 and 0.40 was achieved at current of 0.02 mA and voltage of 14 V.

  17. Selective Area Band Engineering of Graphene using Cobalt-Mediated Oxidation.

    PubMed

    Bazylewski, Paul F; Nguyen, Van Luan; Bauer, Robert P C; Hunt, Adrian H; McDermott, Eamon J G; Leedahl, Brett D; Kukharenko, Andrey I; Cholakh, Seif O; Kurmaev, Ernst Z; Blaha, Peter; Moewes, Alexander; Lee, Young Hee; Chang, Gap Soo

    2015-10-21

    This study reports a scalable and economical method to open a band gap in single layer graphene by deposition of cobalt metal on its surface using physical vapor deposition in high vacuum. At low cobalt thickness, clusters form at impurity sites on the graphene without etching or damaging the graphene. When exposed to oxygen at room temperature, oxygen functional groups form in proportion to the cobalt thickness that modify the graphene band structure. Cobalt/Graphene resulting from this treatment can support a band gap of 0.30 eV, while remaining largely undamaged to preserve its structural and electrical properties. A mechanism of cobalt-mediated band opening is proposed as a two-step process starting with charge transfer from metal to graphene, followed by formation of oxides where cobalt has been deposited. Contributions from the formation of both CoO and oxygen functional groups on graphene affect the electronic structure to open a band gap. This study demonstrates that cobalt-mediated oxidation is a viable method to introduce a band gap into graphene at room temperature that could be applicable in electronics applications.

  18. Selective Area Band Engineering of Graphene using Cobalt-Mediated Oxidation

    PubMed Central

    Bazylewski, Paul F.; Nguyen, Van Luan; Bauer, Robert P.C.; Hunt, Adrian H.; McDermott, Eamon J. G.; Leedahl, Brett D.; Kukharenko, Andrey I.; Cholakh, Seif O.; Kurmaev, Ernst Z.; Blaha, Peter; Moewes, Alexander; Lee, Young Hee; Chang, Gap Soo

    2015-01-01

    This study reports a scalable and economical method to open a band gap in single layer graphene by deposition of cobalt metal on its surface using physical vapor deposition in high vacuum. At low cobalt thickness, clusters form at impurity sites on the graphene without etching or damaging the graphene. When exposed to oxygen at room temperature, oxygen functional groups form in proportion to the cobalt thickness that modify the graphene band structure. Cobalt/Graphene resulting from this treatment can support a band gap of 0.30 eV, while remaining largely undamaged to preserve its structural and electrical properties. A mechanism of cobalt-mediated band opening is proposed as a two-step process starting with charge transfer from metal to graphene, followed by formation of oxides where cobalt has been deposited. Contributions from the formation of both CoO and oxygen functional groups on graphene affect the electronic structure to open a band gap. This study demonstrates that cobalt-mediated oxidation is a viable method to introduce a band gap into graphene at room temperature that could be applicable in electronics applications. PMID:26486966

  19. Enhanced Magnetization of Cobalt Defect Clusters Embedded in TiO2-δ Films.

    PubMed

    Cortie, David L; Khaydukov, Yury; Keller, Thomas; Sprouster, David J; Hughes, Jacob S; Sullivan, James P; Wang, Xiaolin L; Le Brun, Anton P; Bertinshaw, Joel; Callori, Sara J; Aughterson, Robert; James, Michael; Evans, Peter J; Triani, Gerry; Klose, Frank

    2017-03-03

    High magnetizations are desirable for spintronic devices that operate by manipulating electronic states using built-in magnetic fields. However, the magnetic moment in promising dilute magnetic oxide nanocomposites is very low, typically corresponding to only fractions of a Bohr magneton for each dopant atom. In this study, we report a large magnetization formed by ion implantation of Co into amorphous TiO2-δ films, producing an inhomogeneous magnetic moment, with certain regions producing over 2.5 μB per Co, depending on the local dopant concentration. Polarized neutron reflectometry was used to depth-profile the magnetization in the Co:TiO2-δ nanocomposites, thus confirming the pivotal role of the cobalt dopant profile inside the titania layer. X-ray photoemission spectra demonstrate the dominant electronic state of the implanted species is Co(0), with a minor fraction of Co(2+). The detected magnetizations have seldom been reported before and lie near the upper limit set by Hund's rules for Co(0), which is unusual because the transition metal's magnetic moment is usually reduced in a symmetric 3D crystal-field environment. Low-energy positron annihilation lifetime spectroscopy indicates that defect structures within the titania layer are strongly modified by the implanted Co. We propose that a clustering motif is promoted by the affinity of the positively charged implanted species to occupy microvoids native to the amorphous host. This provides a seed for subsequent doping and nucleation of nanoclusters within an unusual local environment.

  20. Atomic layer deposition of cobalt carbide films and their magnetic properties using propanol as a reducing agent

    NASA Astrophysics Data System (ADS)

    Sarr, Mouhamadou; Bahlawane, Naoufal; Arl, Didier; Dossot, Manuel; McRae, Edward; Lenoble, Damien

    2016-08-01

    The investigation of highly conformal thin films using Atomic Layer Deposition (ALD) is driven by a variety of applications in modern technologies. In particular, the emergence of 3D memory device architectures requires conformal materials with tuneable magnetic properties. Here, nanocomposites of carbon, cobalt and cobalt carbide are deposited by ALD using cobalt acetylacetonate with propanol as a reducing agent. Films were grown by varying the ALD deposition parameters including deposition temperature and propanol exposure time. The morphology, the chemical composition and the crystalline structure of the cobalt carbide film were investigated. Vibrating Sample Magnetometer (VSM) measurements revealed magnetic hysteresis loops with a coercivity reaching 500 Oe and a maximal saturation magnetization of 0.9 T with a grain size less than 15 nm. Magnetic properties are shown to be tuneable by adjusting the deposition parameters that significantly affect the microstructure and the composition of the deposited films.

  1. Cobalt-containing oxide layers on titanium, their composition, morphology, and catalytic activity in CO oxidation

    NASA Astrophysics Data System (ADS)

    Vasilyeva, M. S.; Rudnev, V. S.; Ustinov, A. Yu.; Korotenko, I. A.; Modin, E. B.; Voitenko, O. V.

    2010-12-01

    In this study possibility to form the layered compositions CoO x + SiO 2/TiO 2/Ti by plasma electrolytic oxidation (PEO) method was shown. Compositions have been obtained by both one-stage PEO method (Method I) with addition of Co(CH 3COO) 2 into silicate electrolyte and impregnation of preliminary obtained by the PEO method SiO 2/TiO 2/Ti systems in aqueous solutions containing cobalt salts with their following annealing (Method II). XRD, XPS and SEM/EDX were used to investigate the phase and element composition, microstructure of the coatings prepared by the two various methods. Catalytic activity of the cobalt-containing composites was investigated in the CO oxidation reaction. Under experimental conditions, the structures obtained by impregnation and annealing method were more active, than those obtained by one-stage PEO method. The surface structures of cobalt-containing coatings obtained by the PEO method and by impregnation and annealing differ in both quantitative and qualitative relation. The cobalt content on the surface of impregnating coatings is three times as much as that for those formed by one-stage PEO method. It is found that coatings obtained by the Method II have a more developed surface. The surface of CoO x + SiO 2/TiO 2/Ti compositions obtained by the PEO method contains, presumably Co(OH) 2 and Co 3O 4. The surface of the similar compositions obtained by the Method II, possibly contains CoO, either Co 2O 3, or CoOOH. The combination of these factors, perhaps, also provides a higher activity of the compositions formed by the Method II.

  2. Synthesis, Characterization, and Electrochemistry of sigma-Bonded Cobalt Corroles in High Oxidation States.

    PubMed

    Will, Stefan; Lex, Johann; Vogel, Emanuel; Adamian, Victor A.; Van Caemelbecke, Eric; Kadish, Karl M.

    1996-09-11

    The synthesis, electrochemistry, spectroscopy, and structural characterization of two high-valent phenyl sigma-bonded cobalt corroles containing a central cobalt ion in formal +IV and +V oxidation states is presented. The characterized compounds are represented as phenyl sigma-bonded cobalt corroles, (OEC)Co(C(6)H(5)) and [(OEC)Co(C(6)H(5))]ClO(4), where OEC is the trianion of 2,3,7,8,12,13,17,18-octaethylcorrole. The electronic distribution in both molecules is discussed in terms of their NMR and EPR spectroscopic data, magnetic susceptibility, and electrochemistry.

  3. Cobalt oxide nanoparticles can enter inside the cells by crossing plasma membranes

    PubMed Central

    Bossi, Elena; Zanella, Daniele; Gornati, Rosalba; Bernardini, Giovanni

    2016-01-01

    The ability of nanoparticles (NPs) to be promptly uptaken by the cells makes them both dangerous and useful to human health. It was recently postulated that some NPs might cross the plasma membrane also by a non-endocytotic pathway gaining access to the cytoplasm. To this aim, after having filled mature Xenopus oocytes with Calcein, whose fluorescence is strongly quenched by divalent metal ions, we have exposed them to different cobalt NPs quantifying quenching as evidence of the increase of the concentration of Co2+ released by the NPs that entered into the cytoplasm. We demonstrated that cobalt oxide NPs, but not cobalt nor cobalt oxide NPs that were surrounded by a protein corona, can indeed cross plasma membranes. PMID:26924527

  4. Cobalt oxide nanoparticles can enter inside the cells by crossing plasma membranes.

    PubMed

    Bossi, Elena; Zanella, Daniele; Gornati, Rosalba; Bernardini, Giovanni

    2016-02-29

    The ability of nanoparticles (NPs) to be promptly uptaken by the cells makes them both dangerous and useful to human health. It was recently postulated that some NPs might cross the plasma membrane also by a non-endocytotic pathway gaining access to the cytoplasm. To this aim, after having filled mature Xenopus oocytes with Calcein, whose fluorescence is strongly quenched by divalent metal ions, we have exposed them to different cobalt NPs quantifying quenching as evidence of the increase of the concentration of Co(2+) released by the NPs that entered into the cytoplasm. We demonstrated that cobalt oxide NPs, but not cobalt nor cobalt oxide NPs that were surrounded by a protein corona, can indeed cross plasma membranes.

  5. Cobalt nanoparticles as recyclable catalyst for aerobic oxidation of alcohols in liquid phase

    NASA Astrophysics Data System (ADS)

    Mondal, Arijit; Mukherjee, Debkumar; Adhikary, Bibhutosh; Ahmed, Md Azharuddin

    2016-05-01

    Cobalt nanoparticles prepared at room temperature from cobalt sulphate and tetrabutyl ammonium bromide as surfactant have been found to be effective oxidation catalysts. Palladium and platinum nanoparticles (average size 4-6 nm) can also be prepared from PdCl2 and K2PtCl4, respectively, using the same surfactant but require high temperature ( 120 °C) and much longer preparation time. Agglomeration of nanoparticles prepared from metals like palladium and platinum in common solvents, however, restricts their use as catalysts. It is therefore our endeavour to find the right combination of catalyst and solvent that will be beneficial from industrial point of view. Magnetic property measurement of cobalt nanoclusters was made using SQUID to identify their reusability nature. Herein, we report the use of cobalt nanoparticles (average size 90-95 nm) in dichloromethane solvent as effective reusable catalysts for aerobic oxidation of a variety of alcohols.

  6. Synthesis and characterization of Copper/Cobalt/Copper/Iron nanostructurated films with magnetoresistive properties

    NASA Astrophysics Data System (ADS)

    Ciupinǎ, Victor; Prioteasa, Iulian; Ilie, Daniela; Manu, Radu; Petrǎşescu, Lucian; Tutun, Ştefan Gabriel; Dincǎ, Paul; MustaÅ£ǎ, Ion; Lungu, Cristian Petricǎ; Jepu, IonuÅ£; Vasile, Eugeniu; Nicolescu, Virginia; Vladoiu, Rodica

    2017-02-01

    Copper/Cobalt/Copper/Iron thin films were synthesized in order to obtain nanostructured materials with special magnetoresistive properties. The multilayer films were deposited on silicon substrates. In this respect we used Thermionic Vacuum Arc Discharge Method (TVA). The benefit of this deposition technique is the ability to have a controlled range of thicknesses starting from few nanometers to hundreds of nanometers. The purity of the thin films was insured by a high vacuum pressure and a lack of any kind of buffer gas inside the coating chamber. The morphology and structure of the thin films were analyzed using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) Techniques and Energy Dispersive X-ray Spectroscopy (EDXS). Magnetoresistive measurement results depict that thin films possess Giant Magneto-Resistance Effect (GMR). Magneto-Optic-Kerr Effect (MOKE) studies were performed to characterize the magnetic properties of these thin films.

  7. Electronic structure description of a [Co(III)3Co(IV)O4] cluster: a model for the paramagnetic intermediate in cobalt-catalyzed water oxidation.

    PubMed

    McAlpin, J Gregory; Stich, Troy A; Ohlin, C André; Surendranath, Yogesh; Nocera, Daniel G; Casey, William H; Britt, R David

    2011-10-05

    Multifrequency electron paramagnetic resonace (EPR) spectroscopy and electronic structure calculations were performed on [Co(4)O(4)(C(5)H(5)N)(4)(CH(3)CO(2))(4)](+) (1(+)), a cobalt tetramer with total electron spin S = 1/2 and formal cobalt oxidation states III, III, III, and IV. The cuboidal arrangement of its cobalt and oxygen atoms is similar to that of proposed structures for the molecular cobaltate clusters of the cobalt-phosphate (Co-Pi) water-oxidizing catalyst. The Davies electron-nuclear double resonance (ENDOR) spectrum is well-modeled using a single class of hyperfine-coupled (59)Co nuclei with a modestly strong interaction (principal elements of the hyperfine tensor are equal to [-20(±2), 77(±1), -5(±15)] MHz). Mims (1)H ENDOR spectra of 1(+) with selectively deuterated pyridine ligands confirm that the amount of unpaired spin on the cobalt-bonding partner is significantly reduced from unity. Multifrequency (14)N ESEEM spectra (acquired at 9.5 and 34.0 GHz) indicate that four nearly equivalent nitrogen nuclei are coupled to the electron spin. Cumulatively, our EPR spectroscopic findings indicate that the unpaired spin is delocalized almost equally across the eight core atoms, a finding corroborated by results from DFT calculations. Each octahedrally coordinated cobalt ion is forced into a low-spin electron configuration by the anionic oxo and carboxylato ligands, and a fractional electron hole is localized on each metal center in a Co 3d(xz,yz)-based molecular orbital for this essentially [Co(+3.125)(4)O(4)] system. Comparing the EPR spectrum of 1(+) with that of the catalyst film allows us to draw conclusions about the electronic structure of this water-oxidation catalyst.

  8. Electrochemically formed 3D hierarchical thin films of cobalt-manganese (Co-Mn) hexacyanoferrate hybrids for electrochemical applications

    NASA Astrophysics Data System (ADS)

    Alam Venugopal, Narendra Kumar; Joseph, James

    2016-02-01

    Here we report the feasibility of forming 3D nanostructured hexacyanoferates of Cobalt and Manganese (Co-MnHCF) on GC surface by a facile electrochemical method. This 3D architecture on glassy carbon electrode characterised systematically by voltammetry and other physical characterisation techniques like Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and Fourier transform Infrared spectroscopy (FTIR) etc,. Electrochemical Quartz crystal microbalance (EQCM) studies helped out to calculate the total mass change during Co-MnHCF formation. Electrochemical studies reveal that the formal redox potentials of both Co and MnHCF films remained close to that of newly formed Co-MnHCF hybrid films. These 3D modified films were successfully applied for two different electrochemical applications i) For pseudocapacitor studies in KNO3 medium ii) Investigated the electrocatalytic behaviour of redox film towards water oxidation reaction in alkaline medium. Electrochemical performances of newly formed Co-MnHCF are compared with their individual transition metal (Co, Mn) hexacyanoferrates. The resulting material shows a specific capacitance of 350 F g-1 through its fast reversible redox reaction of electrochemically formed Co-MnHCF modified film. Interestingly we showed the overpotential of 450 mV (from its thermodynamic voltage 1.2 V) to attain its optimum current density of 10 mA cm-2 for O2 evolution in alkaline medium.

  9. Stereoselective Alkane Oxidation with meta-Chloroperoxybenzoic Acid (MCPBA) Catalyzed by Organometallic Cobalt Complexes.

    PubMed

    Shul'pin, Georgiy B; Loginov, Dmitriy A; Shul'pina, Lidia S; Ikonnikov, Nikolay S; Idrisov, Vladislav O; Vinogradov, Mikhail M; Osipov, Sergey N; Nelyubina, Yulia V; Tyubaeva, Polina M

    2016-11-22

    Cobalt pi-complexes, previously described in the literature and specially synthesized and characterized in this work, were used as catalysts in homogeneous oxidation of organic compounds with peroxides. These complexes contain pi-butadienyl and pi-cyclopentadienyl ligands: [(tetramethylcyclobutadiene)(benzene)cobalt] hexafluorophosphate, [(C₄Me₄)Co(C₆H₆)]PF₆ (1); diiodo(carbonyl)(pentamethylcyclopentadienyl)cobalt, Cp*Co(CO)I₂ (2); diiodo(carbonyl)(cyclopentadienyl)cobalt, CpCo(CO)I₂ (3); (tetramethylcyclobutadiene)(dicarbonyl)(iodo)cobalt, (C₄Me₄)Co(CO)₂I (4); [(tetramethylcyclobutadiene)(acetonitrile)(2,2'-bipyridyl)cobalt] hexafluorophosphate, [(C₄Me₄)Co(bipy)(MeCN)]PF₆ (5); bis[dicarbonyl(B-cyclohexylborole)]cobalt, [(C₄H₄BCy)Co(CO)₂]₂ (6); [(pentamethylcyclopentadienyl)(iodo)(1,10-phenanthroline)cobalt] hexafluorophosphate, [Cp*Co(phen)I]PF₆ (7); diiodo(cyclopentadienyl)cobalt, [CpCoI₂]₂ (8); [(cyclopentadienyl)(iodo)(2,2'-bipyridyl)cobalt] hexafluorophosphate, [CpCo(bipy)I]PF₆ (9); and [(pentamethylcyclopentadienyl)(iodo)(2,2'-bipyridyl)cobalt] hexafluorophosphate, [Cp*Co(bipy)I]PF₆ (10). Complexes 1 and 2 catalyze very efficient and stereoselective oxygenation of tertiary C-H bonds in isomeric dimethylcyclohexanes with MCBA: cyclohexanols are produced in 39 and 53% yields and with the trans/cis ratio (of isomers with mutual trans- or cis-configuration of two methyl groups) 0.05 and 0.06, respectively. Addition of nitric acid as co-catalyst dramatically enhances both the yield of oxygenates and stereoselectivity parameter. In contrast to compounds 1 and 2, complexes 9 and 10 turned out to be very poor catalysts (the yields of oxygenates in the reaction with cis-1,2-dimethylcyclohexane were only 5%-7% and trans/cis ratio 0.8 indicated that the oxidation is not stereoselective). The chromatograms of the reaction mixture obtained before and after reduction with PPh₃ are very similar, which testifies that alkyl

  10. An hydrothermal experimental study of the cobalt-cobalt oxide redox buffer

    USGS Publications Warehouse

    Lemke, K.H.; Rosenbauer, R.J.; Bischoff, J.L.; Bird, D.K.

    2008-01-01

    Equilibrium aqueous hydrogen concentration and corresponding energies of reaction, ??Grxno(T, P), for the reaction Co(s) + H2O(l) = CoO(s) + H2(aq) have been determined at temperatures between 256 and 355 ??C and at 400 bar. Steady-state concentrations of hydrogen were approached in experiments under conditions of both H2 excess and deficiency containing the solids Co, CoO and liquid water. All experiments were carried out in flexible gold and titanium reactors with the capability of on-line fluid sampling. Measured equilibrium molal concentrations of H2(aq) at 256, 274, 300, 324 and 355 ??C are 0.81(?? 0.01) ?? 10- 3 1.11(?? 0.01) ?? 10- 3, 1.92(?? 0.01) ?? 10- 3, 3.71(?? 0.06) ?? 10- 3, 7.54(?? 0.12) ?? 10- 3, respectively, and corresponding values of ??Grxno(T, P) in units kJ ?? mol- 1 are 31.4(?? 0.1), 31.0(?? 0.1), 29.8(?? 0.1), 27.7(?? 0.5) and 25.5(?? 0.9), respectively. Using published heat capacity data for Co(s) and CoO(s) and - 79.6 J ?? mol- 1 ?? K- 1 for the entropy of formation of CoO we calculated for this study a value for ??GCoO,Tr,Pro = - 214.5(?? 0.9) kJ ?? mol- 1 and ??HCoO,Tr,Pro = - 238.3(?? 0.9) kJ ?? mol- 1 at 25 ??C and 1 bar. The value of ??HCoO,Tr,Pro determined in this study compares well with the reported calorimetric value of - 238.9(?? 1.2) kJ ?? mol- 1 [Boyle, B.J., King, E.G., Conway, K.C., 1954. Heats of formation of nickel and cobalt oxides (NiO and CoO) by combustion calorimetry. Journal of the American Chemical Society, 76, 3835-3837]. ?? 2008 Elsevier B.V. All rights reserved.

  11. Investigations of nanocomposite magnetic materials based on the oxides of iron, nickel, cobalt and silicon dioxide

    NASA Astrophysics Data System (ADS)

    Gracheva, Irina E.; Olchowik, Grazyna; Gareev, Kamil G.; Moshnikov, Vyatcheslav A.; Kuznetsov, Vladimir V.; Olchowik, Jan M.

    2013-05-01

    This paper is concerned with the study of magnetic nanocomposites containing silicon, iron, nickel, and cobalt oxides. These materials were produced in the form of thin films based on Fe-Si-O, Ni-Co-Si-O and Fe-Ni-Co-Si-O systems and powders based on Fe-Si-O, Ni-Si-O, Co-Si-O and Fe-Ni-Co-Si-O systems using sol-gel technology, through centrifugation, and deposition of ammonia solution. The morphology and magnetic properties of materials in the form of thin films were studied by using the atomic force microscopy. The phase composition, specific surface area and magnetic properties of materials in the form of powders were studied by using the X-ray phase analysis, thermal desorption, vibrational magnetometry and immittance measurements. The dependencies of the main parameters were derived for the magnetic materials from their structure and manufacturing conditions. Ways to optimise the technological processes were proposed, aimed at reducing the size of the magnetic particles in an amorphous lattice.

  12. Process for fabrication of metal oxide films

    SciTech Connect

    Tracy, C.E.; Benson, D.; Svensson, S.

    1990-07-17

    This invention is comprised of a method of fabricating metal oxide films from a plurality of reactants by inducing a reaction by plasma deposition among the reactants. The plasma reaction is effective for consolidating the reactants and producing thin films of metal oxides, e.g. electro-optically active transition metal oxides, at a high deposition rate. The presence of hydrogen during the plasma reaction enhances the deposition rate of the metal oxide. Various types of metal oxide films can be produced.

  13. Study of two-phase magnetization reversal in patterned cobalt thin film

    NASA Astrophysics Data System (ADS)

    Hussain, Zaineb; Raghavendra Reddy, V.; Kumar, Dileep; Ganesan, V.; Dhamgaye, Vishal; Khantwal, Nitin; Gupta, Ajay

    2017-10-01

    Magnetization reversal of a 5 μm wide and 10 μm grating periodic stripe-patterned cobalt thin film is investigated by Kerr microscopy. The patterned substrate and the cobalt thin film are prepared by standard UV-lithography and electron beam evaporation respectively. It is observed that magnetization reversal process strongly depends on the interplay between random magneto-crystalline anisotropy and shape-induced uniform uni-axial anisotropy. Domain wall motion is observed along easy magnetization axes (along length of stripe) while inhomogeneous rotation i.e. incoherent rotation is observed along hard magnetization axes (perpendicular to length of stripe). The angular dependence of coercivity (H C) is fitted by a two-phase model of magnetization reversal, which is corroborated with the magnetic domain images.

  14. Thermal-fatigue and oxidation resistance of cobalt-modified Udimet 700 alloy

    NASA Technical Reports Server (NTRS)

    Bizon, P. T.; Barrow, B. J.

    1986-01-01

    Comparative thermal-fatigue and oxidation resistances of cobalt-modified wrought Udimet 700 alloy (obtained by reducing the cobalt level by direct substitution of nickel) were determined from fluidized-bed tests. Bed temperatures were 1010 and 288 C (1850 and 550 C) for the first 5500 symmetrical 6-min cycles. From cycle 5501 to the 14000-cycle limit of testing, the heating bed temperature was increased to 1050 C (1922 F). Cobalt levels between 0 and 17 wt% were studied in both the bare and NiCrAlY overlay coated conditions. A cobalt level of about 8 wt% gave the best thermal-fatigue life. The conventional alloy specification is for 18.5% cobalt, and hence, a factor of 2 in savings of cobalt could be achieved by using the modified alloy. After 13500 cycles, all bare cobalt-modified alloys lost 10 to 13 percent of their initial weight. Application of the NiCrAlY overlay coating resulted in weight losses of 1/20 to 1/100 of that of the corresponding bare alloy.

  15. Effects of cobalt chloride on nitric oxide and cytokines/chemokines production in microglia.

    PubMed

    Mou, Yan Hua; Yang, Jing Yu; Cui, Nan; Wang, Ji Ming; Hou, Yue; Song, Shuang; Wu, Chun Fu

    2012-05-01

    The involvement of microglial activation in metal neurotoxicity is becoming increasingly recognized. Some metal ions, such as zinc (II) and manganese (II), have been recently reported as microglial activators to induce the release of inflammatory mediators including cytokines, chemokines and nitric oxide (NO) which are involved in the pathogenesis of neurological diseases. Cobalt is essential for human life. However, excessive cobalt is cytotoxic and neurotoxic. In the present study, we determined cobalt-induced production of NO and cytokines/chemokines in N9 cells, a murine microglial cell line. High levels of cobalt significantly up-regulated iNOS mRNA and protein expression, which resulted in the release of NO. Cobalt induced the production of tumor necrosis factor α (TNF-α) and interleukin-6 (IL-6) in a concentration- and time-dependent manner in both N9 cells and primary mouse microglia and increased lipopolysaccharides (LPS)-induced cytokine production. Further study showed that cobalt induced cytokine production by a mechanism involving both nuclear factor kappa B (NF-κB) and p38 mitogen-activated protein kinase (MAPK) signaling pathways. The involvement of reactive oxygen species (ROS) in microglial activation was also confirmed. These findings suggested that cobalt neurotoxicity should be attributed not only directly to neuronal damage but also indirectly to microglial activation which might potentiate neuronal injury via elevation of proinflammatory mediator levels.

  16. Magnetic interaction intensity in cobalt samarium thin films fabricated using DC magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Erwin

    2017-01-01

    Magnetic interaction intensity between magnetic grains was studied for as deposited cobalt samarium alloys in the form of thin films. The films were deposited onto silicon substrates using dc magnetron sputtering technique. The results showed that the magnitude of interaction intensity between magnetic grains in the films was reduced as samarium content increased until 20 at.% Sm. However, the coercivity of the films decreases with further increase in samarium concentration above 20 at. % Sm.. Thus the increase of coercivity in this range of composition (up to 20 at % of samarium) is due to the initial increase in size magnetic grains as well increase in grain separation, which reduces interaction intensity between grains. The effect of samarium content on interaction intensity between magnetic grains in the films is studied.

  17. Thermal NF3 fluorination/oxidation of cobalt, yttrium, zirconium, and selected lanthanide oxides

    SciTech Connect

    Scheele, Randall D.; McNamara, Bruce K.; Casella, Andrew M.; Kozelisky, Anne E.; Neiner, Doinita

    2013-02-01

    This paper presents results of our continuing investigation on the use of nitrogen trifluoride as a fluorination or fluorination/oxidation agent for separating valuable constituents from used nuclear fuels by exploiting the different volatilities of the constituent fission product and actinide fluorides. This article focuses on fission products that do not have volatile fluorides or oxyfluorides at expected operations temperatures. Our thermodynamic calculations show that nitrogen trifluoride has the potential to completely fluorinate fission product oxides to their fluorides. Simultaneous thermogravimetric and differential thermal analyses show that the oxides of cobalt, zirconium, and the lanthanides are fluorinated but do not form volatile fluorides when treated with nitrogen trifluoride at temperatures up to 550°C. Our studies of gadolinium-doped commercial nuclear fuel indicate that nitrogen trifluoride can extract uranium from the non-volatile gadolinium.

  18. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel

    NASA Astrophysics Data System (ADS)

    Gao, Shan; Lin, Yue; Jiao, Xingchen; Sun, Yongfu; Luo, Qiquan; Zhang, Wenhua; Li, Dianqi; Yang, Jinlong; Xie, Yi

    2016-01-01

    Electroreduction of CO2 into useful fuels, especially if driven by renewable energy, represents a potentially ‘clean’ strategy for replacing fossil feedstocks and dealing with increasing CO2 emissions and their adverse effects on climate. The critical bottleneck lies in activating CO2 into the CO2•- radical anion or other intermediates that can be converted further, as the activation usually requires impractically high overpotentials. Recently, electrocatalysts based on oxide-derived metal nanostructures have been shown to enable CO2 reduction at low overpotentials. However, it remains unclear how the electrocatalytic activity of these metals is influenced by their native oxides, mainly because microstructural features such as interfaces and defects influence CO2 reduction activity yet are difficult to control. To evaluate the role of the two different catalytic sites, here we fabricate two kinds of four-atom-thick layers: pure cobalt metal, and co-existing domains of cobalt metal and cobalt oxide. Cobalt mainly produces formate (HCOO-) during CO2 electroreduction; we find that surface cobalt atoms of the atomically thin layers have higher intrinsic activity and selectivity towards formate production, at lower overpotentials, than do surface cobalt atoms on bulk samples. Partial oxidation of the atomic layers further increases their intrinsic activity, allowing us to realize stable current densities of about 10 milliamperes per square centimetre over 40 hours, with approximately 90 per cent formate selectivity at an overpotential of only 0.24 volts, which outperforms previously reported metal or metal oxide electrodes evaluated under comparable conditions. The correct morphology and oxidation state can thus transform a material from one considered nearly non-catalytic for the CO2 electroreduction reaction into an active catalyst. These findings point to new opportunities for manipulating and improving the CO2 electroreduction properties of metal systems

  19. Facile preparation of highly-dispersed cobalt-silicon mixed oxide nanosphere and its catalytic application in cyclohexane selective oxidation

    PubMed Central

    2011-01-01

    Highly dispersed cobalt-silicon mixed oxide [Co-SiO2] nanosphere was successfully prepared with a modified reverse-phase microemulsion method. This material was characterized in detail by X-ray diffraction, transmission electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance spectra, X-ray absorption spectroscopy near-edge structure, and N2 adsorption-desorption measurements. High valence state cobalt could be easily obtained without calcination, which is fascinating for the catalytic application for its strong oxidation ability. In the selective oxidation of cyclohexane, Co-SiO2 acted as an efficient catalyst, and good activity could be obtained under mild conditions. PMID:22067075

  20. Characterization of electrochemically deposited films from aqueous and ionic liquid cobalt precursors toward hydrogen evolution reactions

    NASA Astrophysics Data System (ADS)

    Dushatinski, Thomas; Huff, Clay; Abdel-Fattah, Tarek M.

    2016-11-01

    Electrodepositions of cobalt films were achieved using an aqueous or an ethylene glycol based non-aqueous solution containing choline chloride (vitamin B4) with cobalt chloride hexahydrate precursor toward hydrogen evolution reactions from sodium borohydride (NaBH4) as solid hydrogen feedstock (SHF). The resulting cobalt films had reflectivity at 550 nm of 2.2% for aqueously deposited films (ACoF) and 1.3% for non-aqueously deposited films (NCoF). Surface morphology studied by scanning electron microscopy showed a positive correlation between particle size and thickness. The film thicknesses were tunable between >100 μm and <300 μm for each film. The roughness (Ra) value measurements by Dektak surface profiling showed that the NCoF (Ra = 165 nm) was smoother than the ACoF (Ra = 418 nm). The NCoFs and ACoFs contained only α phase (FCC) crystallites. The NCoFs were crystalline while the ACoFs were largely amorphous from X-ray diffraction analysis. The NCoF had an average Vickers hardness value of 84 MPa as compared to 176 MPa for ACoF. The aqueous precursor has a single absorption maximum at 510 nm and the non-aqueous precursor had three absorption maxima at 630, 670, and 695 nm. The hydrogen evolution reactions over a 1 cm2 catalytic surface with aqueous NaBH4 solutions generated rate constants (K) = equal to 4.9 × 10-3 min-1, 4.6 × 10-3 min-1, and 3.3 × 10-3 min-1 for ACoF, NCoF, and copper substrate respectively.

  1. Time-resolved ultrathin cobalt film growth on a colloidal polymer template.

    PubMed

    Buffet, Adeline; Abul Kashem, Mottakin M; Schlage, Kai; Couet, Sébastien; Röhlsberger, Ralph; Rothkirch, André; Herzog, Gerd; Metwalli, Ezzeldin; Meier, Robert; Kaune, Gunar; Rawolle, Monica; Müller-Buschbaum, Peter; Gehrke, Rainer; Roth, Stephan V

    2011-01-04

    Cobalt (Co) sputter deposition onto a colloidal polymer template is investigated using grazing incidence small-angle X-ray scattering (GISAXS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). SEM and AFM data picture the sample topography, GISAXS the surface and near-surface film structure. A two-phase model is proposed to describe the time evolution of the Co growth. The presence of the colloidal template results in the correlated deposition of an ultrathin Co film on the sample surface and thus in the creation of Co capped polystyrene (PS) colloids. Well below the percolation threshold, the radial growth is restricted and only height growth is observed.

  2. Epitaxial growth of cobalt oxide phases on Ru(0001) for spintronic device applications

    NASA Astrophysics Data System (ADS)

    Olanipekun, Opeyemi; Ladewig, Chad; Kelber, Jeffry A.; Randle, Michael D.; Nathawat, Jubin; Kwan, Chun-Pui; Bird, Jonathan P.; Chakraborti, Priyanka; Dowben, Peter A.; Cheng, Tao; Goddard, W. A., III

    2017-09-01

    Cobalt oxide films are of technological interest as magnetic substrates that may support the direct growth of graphene, for use in various spintronic applications. In this work, we demonstrate the controlled growth of both Co3O4(111) and CoO(111) on Ru(0001) substrates. The growth is performed by Co molecular beam epitaxy, at a temperature of 500 K and in an O2 partial pressure of 10-4 Torr for Co3O4(111), and 7.5 × 10-7 Torr for CoO(111). The films are distinguished by their dissimilar Co 2p x-ray photoemission (XPS) spectra, while XPS-derived O/Co stoichiometric ratios are 1.33 for Co3O4(111) and 1.1 for CoO(111). Electron energy loss (EELS) spectra for Co3O4(111) indicate interband transitions at ˜2.1 and 3.0 eV, while only a single interband transition near 2.0 eV is observed for CoO(111). Low energy electron diffraction (LEED) data for Co3O4(111) indicate twinning during growth, in contrast to the LEED data for CoO(111). For Co3O4(111) films of less than 20 Å average thickness, however, XPS, LEED and EELS data are similar to those of CoO(111). XPS data indicate that both Co oxide phases are hydroxylated at all thicknesses. The two phases are moreover found to be thermally stable to at least 900 K in UHV, while ex situ atomic force microscopy measurements of Co3O4(111)/Ru(0001) indicate an average surface roughness below 1 nm. Electrical measurements indicate that Co3O4(111)/Ru(0001) films exhibit dielectric breakdown at threshold voltages of ˜1 MV cm-1. Collectively, these data show that the growth procedures yield Co3O4(111) films with topographical and electrical characteristics that are suitable for a variety of advanced device applications.

  3. Electroplated thick-film cobalt platinum permanent magnets

    NASA Astrophysics Data System (ADS)

    Oniku, Ololade D.; Qi, Bin; Arnold, David P.

    2016-10-01

    The material and magnetic properties of multi-micron-thick (up to 6 μm) L10 CoPt magnetic films electroplated onto silicon substrates are investigated as candidate materials for integration in silicon-based microsystems. The influence of various process conditions on the structure and magnetic properties of electroplated CoPt thick-films is studied in order to better understand the complex process/structure/property relationships associated with the electroplated films. Process variables studied here include different seed layers, electroplating current densities (ranging from 25-200 mA/cm2), deposition times (up to 60 min), and post-deposition annealing times and temperatures. Analyses include film morphology, film thickness, composition, surface roughness, grain size, phase volume fractions, and L10 ordering parameter. Key correlations are found relating process and structure variations to the extrinsic magnetic properties (remanence, coercivity, squareness, and energy product). Strong hard magnetic properties (Br ~0.8 T, Hci ~800 kA/m, squareness close to 0.9, and BHmax of 100 kJ/m3) are obtained for films deposited on Si/TiN/Ti/Cu at current densities of 100 mA/cm2, pH of 7, and subsequently annealed at 675 °C for 30 min.

  4. Electroless (autocatalytic) nickel-cobalt thin films as solar control coatings

    SciTech Connect

    John, S.; Srinivasan, K.N.; Selvam, M.; Anuradha, S.; Rajendran, S.

    1994-12-31

    This paper describes the deposition of nickel-cobalt-phosphorus coatings by the electroless deposition technique for use as solar control coatings in architectural glazing of buildings. Electroless deposition is characterized by the autocatalytic deposition of a metal/alloy from an aqueous solution of its ions by interaction with a chemical reducing agent. The reducing agent provides electrons for the metal ions to be neutralized. The reduction is initiated by the catalyzed surface of the substrate and continued by the self catalytic activity of the deposited metal/alloy as long as the substrate is immersed in the electroless bath and operating conditions are maintained. Electroless nickel-cobalt-phosphorus thin films were deposited from a solution containing 15 g/l nickel sulphate, 5 g/l cobalt sulphate, 60 g/l ammonium citrate and 25 g/l sodium hypophosphite operating at 30 C, at a pH of 9.5 for two minutes. Electroless nickel-cobalt-phosphorus coatings are found to satisfy the basic requirements of solar control coatings. Autocatalytic deposition technique offers the possibilities of producing large area coatings with low capital investment, stability and good adhesion to glass substrates.

  5. Catalytic Decomposition of N2O at Low Temperature by Reduced Cobalt Oxides.

    PubMed

    Eom, Won-Hyun; Ayoub, Muhammad; Yoo, Kyung-Seun

    2016-05-01

    Various forms of cobalt oxide (Co3O4 and C0203) were subsequently prepared and tested for decomposition of N2O at low temperature in a fix bed differential reactor at steady state conditions. These different types of oxides were prepared by precipitation method (PM) and by calcination of commercially available CoCO3. Commercially available cobalt oxides C03O4 and C02O3 were also tested for N2O decomposition at different temperatures. All types of prepared and commercially available cobalt oxide were found inactive for N2O decomposition in the presence of oxygen at temperature less than 300 degrees C. Similar unsatisfactory results were found at low temperature N2O decomposition after impregnation of alkali metal (10% Na) and alkaline earth metal (10% Ba) over Co3O4. These catalysts were then reduced under reduction media (H2 gas). It was found that after reduction cobalt oxide catalysts became active for N2O decomposition for short time in the presence of oxygen at low temperature. The reduced form of Co3O4 catalyst showed enormous efficiency i.e., 98% at temperature (300 degrees C) under the same conditions. From results it seems that Co3O4 itself is not active for N2O decomposition but its reduced form is highly active for this reaction due to oxidation state change of C03O4 during reduction process.

  6. Angular tuning of the magnetic birefringence in rippled cobalt films

    SciTech Connect

    Arranz, Miguel A.; Colino, José M.

    2015-06-22

    We report the measurement of magnetically induced birefringence in rippled Co films. For this purpose, the magneto-optical properties of ion beam eroded ferromagnetic films were studied using Kerr magnetometry and magnetic birefringence in the transmitted light intensity. Upon sufficient ion sculpting, these ripple surface nanostructures developed a defined uniaxial anisotropy in the in-plane magnetization, finely tuning the magnetic birefringence effect. We have studied its dependence on the relative orientation between the ripple direction and the magnetic field, and found this effect to be dramatically correlated with the capability to neatly distinguish the mechanisms for the in-plane magnetization reversal, i.e., rotation and nucleation. This double refraction corresponds univocally to the two magnetization axes, parallel and perpendicular to the ripples direction. We have also observed that tuned birefringence in stack assemblies of rippled Co films, which enables us to technically manipulate the number and direction of refraction axes.

  7. Angular tuning of the magnetic birefringence in rippled cobalt films

    NASA Astrophysics Data System (ADS)

    Arranz, Miguel A.; Colino, José M.

    2015-06-01

    We report the measurement of magnetically induced birefringence in rippled Co films. For this purpose, the magneto-optical properties of ion beam eroded ferromagnetic films were studied using Kerr magnetometry and magnetic birefringence in the transmitted light intensity. Upon sufficient ion sculpting, these ripple surface nanostructures developed a defined uniaxial anisotropy in the in-plane magnetization, finely tuning the magnetic birefringence effect. We have studied its dependence on the relative orientation between the ripple direction and the magnetic field, and found this effect to be dramatically correlated with the capability to neatly distinguish the mechanisms for the in-plane magnetization reversal, i.e., rotation and nucleation. This double refraction corresponds univocally to the two magnetization axes, parallel and perpendicular to the ripples direction. We have also observed that tuned birefringence in stack assemblies of rippled Co films, which enables us to technically manipulate the number and direction of refraction axes.

  8. Catalytic Aerobic Dehydrogenation of Nitrogen Heterocycles Using Heterogeneous Cobalt Oxide Supported on Nitrogen-Doped Carbon.

    PubMed

    Iosub, Andrei V; Stahl, Shannon S

    2015-09-18

    Dehydrogenation of (partially) saturated heterocycles provides an important route to heteroaromatic compounds. A heterogeneous cobalt oxide catalyst, previously employed for aerobic oxidation of alcohols and amines, is shown to be effective for aerobic dehydrogenation of various 1,2,3,4-tetrahydroquinolines to the corresponding quinolines. The reactions proceed in good yields under mild conditions. Other N-heterocycles are also successfully oxidized to their aromatic counterparts.

  9. Surface Proton Hopping and Coupling Pathway of Water Oxidation on Cobalt Oxide Catalyst

    NASA Astrophysics Data System (ADS)

    Pham, Hieu; Cheng, Mu-Jeng; Frei, Heinz; Wang, Lin-Wang

    We propose an oxidation pathway of water splitting on cobalt oxide surface with clear thermodynamic and kinetic details. The density-functional theory studies suggest that the coupled proton-electron transfer is not necessarily sequential and implicit in every elementary step of this mechanistic cycle. Instead, the initial O-O bond could be formed by the landing of water molecule on the surface oxos, which is then followed by the dispatch of protons through the hopping manner and subsequent release of di-oxygen. Our theoretical investigations of intermediates and transition states indicate that all chemical conversions in this pathway, including the proton transfers, are possible with low activation barriers, in addition to their favorable thermodynamics. Our hypothesis is supported by recent experimental observations of surface superoxide that is stabilized by hydrogen bonding to adjacent hydroxyl group, as an intermediate on fast-kinetics catalytic site.

  10. A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.

    PubMed

    Wei, Jie; Feng, Yingying; Zhou, Panpan; Liu, Yan; Xu, Jingyin; Xiang, Rui; Ding, Yong; Zhao, Chongchao; Fan, Linyuan; Hu, Changwen

    2015-08-24

    To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts.

  11. A cobalt complex of a microbial arene oxidation product

    PubMed Central

    2011-01-01

    We report the first synthesis of a cobalt Cp diene complex wherein the diene is derived by microbial dearomatising dihydroxylation of an aromatic ring. The complex has been characterised crystallographically and its structure is compared to that of an uncomplexed diene precursor. PMID:22152033

  12. Fabrication of long-term stable superoleophobic surface based on copper oxide/cobalt oxide with micro-nanoscale hierarchical roughness

    NASA Astrophysics Data System (ADS)

    Barthwal, Sumit; Lim, Si-Hyung

    2015-02-01

    We have demonstrated a simple and cost-effective technique for the large-area fabrication of a superoleophobic surface using copper as a substrate. The whole process included three simple steps: First, the copper substrate was oxidized under hot alkaline conditions to fabricate flower-like copper oxide microspheres by heating at a particular temperature for an interval of time. Second, the copper-oxide-covered copper substrate was further heated in a solution of cobalt nitrate and ammonium nitrate in the presence of an ammonia solution to fabricate cobalt oxide nanostructures. We applied this second step to increase the surface roughness because it is an important criterion for improved superoleophobicity. Finally, to reduce the surface energy of the fabricated structures, the surfaces were chemically modified with perfluorooctyltrichlorosilane. Contact-angle measurements indicate that the micro-nano binary (MNB) hierarchical structures fabricated on the copper substrate became super-repellent toward a broad range of liquids with surface tension in the range of 21.5-72 mN/m. In an attempt to significantly improve the superoleophobic property of the surface, we also examined and compared the role of nanostructures in MNB hierarchical structures with only micro-fabricated surfaces. The fabricated MNB hierarchical structures also displays thermal stability and excellent long-term stability after exposure in air for more than 9 months. Our method might provide a general route toward the preparation of novel hierarchical films on metal substrates for various industrial applications.

  13. Enhanced Magnetization of Cobalt Defect Clusters Embedded in TiO2-δ Films

    DOE PAGES

    Cortie, David L.; Khaydukov, Yury; Keller, Thomas; ...

    2017-02-23

    High magnetizations are desirable for spintronic devices that operate by manipulating electronic states using built-in magnetic fields. However, the magnetic moment in promising dilute magnetic oxide nanocomposites is very low, typically corresponding to only fractions of a Bohr magneton for each dopant atom. In this study, we report a large magnetization formed by ion implantation of Co into amorphous TiO2-δ films, producing an inhomogeneous magnetic moment, with certain regions producing over 2.5 μB per Co, depending on the local dopant concentration. Polarized neutron reflectometry was used to depth-profile the magnetization in the Co:TiO2-δ nanocomposites, thus confirming the pivotal role ofmore » the cobalt dopant profile inside the titania layer. X-ray photoemission spectra demonstrate the dominant electronic state of the implanted species is Co0, with a minor fraction of Co2+. The detected magnetizations have seldom been reported before and lie near the upper limit set by Hund’s rules for Co0, which is unusual because the transition metal’s magnetic moment is usually reduced in a symmetric 3D crystal-field environment. Low-energy positron annihilation lifetime spectroscopy indicates that defect structures within the titania layer are strongly modified by the implanted Co. We propose that a clustering motif is promoted by the affinity of the positively charged implanted species to occupy microvoids native to the amorphous host. This provides a seed for subsequent doping and nucleation of nanoclusters within an unusual local environment.« less

  14. Electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices

    NASA Astrophysics Data System (ADS)

    He, Zhen

    The focus of this dissertation is the electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices. The electrochemical reduction of metal oxides to metals has been studied for decades as an alternative to pyrometallurgical processes for the metallurgy industry. However, the previous work was conducted on bulk polycrystalline metal oxides. Paper I in this dissertation shows that epitaxial face-centered cubic magnetite (Fe3O4 ) thin films can be electrochemically reduced to epitaxial body-centered cubic iron (Fe) thin films in aqueous solution on single-crystalline Au substrates at room temperature. This technique opens new possibilities to produce special epitaxial metal/metal oxide heterojunctions and a wide range of epitaxial metallic alloy films from the corresponding mixed metal oxides. Electrodeposition, like biomineralization, is a soft solution processing method which can produce functional materials with special properties onto conducting or semiconducting solid surfaces. Paper II in this dissertation presents the electrodeposition of cobalt-substituted magnetite (CoxFe3-xO4, 0 of cobalt-substituted magnetite (CoxFe3-xO4, 0films and superlattices on Au single-crystalline substrates, which can be potentially used in spintronics and memory devices. Paper III in this dissertation reports the electrodeposition of crystalline cobalt oxide (Co3O4) thin films on stainless steel and Au single-crystalline substrates. The crystalline Co3O4 thin films exhibit high catalytic activity towards the oxygen evolution reaction in an alkaline solution. A possible application of the electrodeposited Co 3O4 is the fabrication of highly active and low-cost photoanodes for photoelectrochemical water-splitting cells.

  15. Effect of Co/Ni ratios in cobalt nickel mixed oxide catalysts on methane combustion

    SciTech Connect

    Lim, Tae Hwan; Cho, Sung June; Yang, Hee Sung; Engelhard, Mark H.; Kim, Do Heui

    2015-07-31

    A series of cobalt nickel mixed oxide catalysts with the varying ratios of Co to Ni, prepared by co-precipitation method, were applied to methane combustion. Among the various ratios, cobalt nickel mixed oxides having the ratios of Co to Ni of (50:50) and (67:33) demonstrate the highest activity for methane combustion. Structural analysis obtained from X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) evidently demonstrates that CoNi (50:50) and (67:33) samples consist of NiCo2O4and NiO phase and, more importantly, NiCo2O4spinel structure is largely distorted, which is attributed to the insertion of Ni2+ions into octahedral sites in Co3O4spinel structure. Such structural dis-order results in the enhanced portion of surface oxygen species, thus leading to the improved reducibility of the catalysts in the low temperature region as evidenced by temperature programmed reduction by hydrogen (H2TPR) and X-ray photoelectron spectroscopy (XPS) O 1s results. They prove that structural disorder in cobalt nickel mixed oxides enhances the catalytic performance for methane combustion. Thus, it is concluded that a strong relationship between structural property and activity in cobalt nickel mixed oxide for methane combustion exists and, more importantly, distorted NiCo2O4spinel structure is found to be an active site for methane combustion.

  16. Interaction of cobalt with a stainless steel oxide surface

    SciTech Connect

    Taylor, J.B. )

    1991-01-01

    The deposition of radioactive cobalt ions from aqueous solutions in the pH range from 1 to 12 onto the internal surface of a stainless steel vessel or pipework can lead to the buildup of tenacious surface activity. For liquid streams of low specific activity (measured in becquerels per millilitre), the surface activity buildup may create a more dominant gamma radiation field than the activity suspended in the liquid. Failure to adequately predict this buildup for an operational nuclear plant can lead to an underestimate of potential gamma dose rates. This may lead to an economic penalty if additional shielding or other protective measures are necessary following plant operation. A theoretical method of determining the cobalt mass/activity deposition from aqueous liquor onto stainless steel is outlined in this paper. A validation of the method is given, and the limits of its application are discussed.

  17. Pronounced Size Dependence in Structure and Morphology of Gas-Phase Produced, Partially Oxidized Cobalt Nanoparticles under Catalytic Reaction Conditions

    SciTech Connect

    Bartling, Stephan; Yin, Chunrong; Barke, Ingo; Oldenburg, Kevin; Hartmann, Hannes; von Oeynhausen, Viola; Pohl, Marga-Martina; Houben, Kelly; Tyo, Eric C.; Seifert, Sönke; Lievens, Peter; Meiwes-Broer, Karl-Heinz; Vajda, Stefan

    2015-06-23

    It is generally accepted that optimal particle sizes are key for efficient nanocatalysis. Much less attention is paid to the role of morphology and atomic arrangement during catalytic reactions. Here we unravel the structural, stoichiometric, and morphological evolution of gas-phase produced cobalt nanoparticles in a broad size range. Particles with diameters between 1.4 nm and 22nm generated in cluster sources are size selected and deposited on amorphous alumina (Al2O3) and ultrananocrystalline diamond (UNCD) films. A combination of different techniques is employed to monitor particle properties at the stages of production, exposure to ambient conditions, and catalytic reaction, in this case the oxidative dehydrogenation of cyclohexane at elevated temperatures. A pronounced size dependence is found, naturally classifying the particles into three size regimes. While small and intermediate clusters essentially retain their compact morphology, large particles transform into hollow spheres due to the nanoscale Kirkendall effect. Depending on the substrate an isotropic (Al2O3) or anisotropic (UNCD) Kirkendall effect is observed. The latter results in dramatic lateral size changes. Our results shed light on the interplay between chemical reactions and the catalyst's structure and provide an approach to tailor the cobalt oxide phase composition required for specific catalytic schemes.

  18. Interface effects on perpendicular magnetic anisotropy for molecular-capped cobalt ultrathin films

    NASA Astrophysics Data System (ADS)

    Zhang, Xianmin; Mizukami, Shigemi; Kubota, Takahide; Oogane, Mikihiko; Naganuma, Hiroshi; Ando, Yasuo; Miyazaki, Terunobu

    2011-10-01

    The perpendicular magnetic anisotropy (PMA) of cobalt (0.5-1.8 nm) films capped separately by pentacene (Pc), fullerene (C60), and 8-hydroxyquinoline-aluminum (Alq3) are investigated. For all three series, the thickness of Co is around 0.7 nm for maximum out-of-plane coercivity. It is found that the coercivity of C60-capped films is nearly equal to that for Alq3-capped samples, although both are smaller than for Pc-capped films. The different interface effects of Co/molecules are discussed to explain this observation. This work highlights the PMA of ferromagnetic metal, which can be markedly infected depending on the nature of organic molecule.

  19. Tailoring the optical bandgap and magnetization of cobalt ferrite thin films through controlled zinc doping

    NASA Astrophysics Data System (ADS)

    Sharma, Deepanshu; Khare, Neeraj

    2016-08-01

    In this report, the tuning of the optical bandgap and saturation magnetization of cobalt ferrite (CFO) thin films through low doping of zinc (Zn) has been demonstrated. The Zn doped CFO thin films with doping concentrations (0 to 10%) have been synthesized by ultrasonic assisted chemical vapour deposition technique. The optical bandgap varies from 1.48 to 1.88 eV and saturation magnetization varies from 142 to 221 emu/cc with the increase in the doping concentration and this change in the optical and magnetic properties is attributed to the change in the relative population of the Co2+ at the tetrahedral and octahedral sites. Raman study confirms the decrease in the population of Co2+ at tetrahedral sites with controlled Zn doping in CFO thin films. A quantitative analysis has been presented to explain the observed variation in the optical bandgap and saturation magnetization.

  20. Room temperature ferromagnetism and ferroelectricity in cobalt-doped LiNbO{sub 3} film

    SciTech Connect

    Song, C.; Wang, C. Z.; Yang, Y. C.; Liu, X. J.; Zeng, F.; Pan, F.

    2008-06-30

    (5 at. %) cobalt-doped LiNbO{sub 3} (Co:LN) films were prepared by combinatorial laser molecular-beam epitaxy on Si (100). The Co:LN films with Co{sup 2+} replacing Nb exhibit room temperature ferromagnetism of 1.2{mu}{sub B}/Co and Curie temperature of {approx}540 K. Through a Ag/Co:LN/Si metal-ferroelectric-semiconductor field effect transistor configuration, ferroelectric measurements show that the films display hysteresis loops at 300 K and ferroelectric transition temperature of {approx}610 K. The hysteresis and the asymmetry in capacitance-voltage and leakage-voltage curves are ascribed to trapping/detrapping process of charges at the Co:LN/Si interface. The coexistence of room temperature ferromagnetism and ferroelectricity makes Co:LN a promising single-phase multiferroic.

  1. Lightweight polyaniline-cobalt coated fly ash cenosphere composite film for electromagnetic interference shielding

    NASA Astrophysics Data System (ADS)

    Bora, Pritom J.; Vinoy, K. J.; Ramamurthy, Praveen C.; Kishore; Madras, Giridhar

    2016-09-01

    Thermal power plant's solid environmental waste fly ash cenosphere (FAC) is cobalt coated chemically and functionalized by in situ synthesis of polyaniline (PANI) under nitrogen atmosphere at -30 ± 2 °C and characterized by various techniques. The electromagnetic interference shielding effectiveness (EMI SE) of free standing PANI/Co-FAC (PCC) films prepared by solution casting indicates an appreciable shielding. The most effective average EMI SE of ~ 30 dB was obtained for 89 ± 3 μm thicker flexible film over the frequency range of 12.4-18 GHz (Ku-band). Mechanistically, EMI shielding due to absorption was found to be dominant. The obtained shielding effectiveness due to absorbance ( SE A ) of PCC film is nearly two times higher than PC film. The microwave conductivity (σ) of PCC film (157-184 Sm-1) is much higher than PC film (118-142 Sm-1). Moreover, the high EM attenuation constant ( α) value of PCC film indicates excellent suitability of EMI shielding due to absorption.

  2. Core chemistry influences the toxicity of multicomponent metal oxide nanomaterials, lithium nickel manganese cobalt oxide, and lithium cobalt oxide to Daphnia magna.

    PubMed

    Bozich, Jared; Hang, Mimi; Hamers, Robert; Klaper, Rebecca

    2017-09-01

    Lithium intercalation compounds such as lithium nickel manganese cobalt oxide (NMC) and lithium cobalt oxide (LCO) are used extensively in lithium batteries. Because there is currently little economic incentive for recycling, chances are greater that batteries will end up in landfills or waste in the environment. In addition, the toxicity of these battery materials traditionally has not been part of the design process. Therefore, to determine the environmental impact and the possibility of alternative battery materials, representative complex battery nanomaterials, LCO and NMC, were synthesized, and toxicity was assessed in Daphnia magna. Toxicity was determined by assessing LCO and NMC at concentrations in the range of 0.1 to 25 mg/L. Acute studies (48 h) showed no effect to daphnid survival at 25 mg/L, whereas chronic studies (21 d) show significant impacts to daphnid reproduction and survival at concentrations of 0.25 mg/L for LCO and 1.0 mg/L for NMC. Dissolved metal exposures showed no effect at the amounts measured in suspension, and supernatant controls could not reproduce the effects of the particles, indicating a nanomaterial-specific impact. Genes explored in the present study were actin, glutathione-s-transferase, catalase, 18s, metallothionein, heat shock protein, and vitellogenin. Down-regulation of genes important in metal detoxification, metabolism, and cell maintenance was observed in a dose-dependent manner. The results show that battery material chemical composition can be altered to minimize environmental impacts. Environ Toxicol Chem 2017;36:2493-2502. © 2017 SETAC. © 2017 SETAC.

  3. Cobalt(II) Oxidation by the Marine Manganese(II)-Oxidizing Bacillus sp. Strain SG-1

    PubMed Central

    Lee, Yoon; Tebo, Bradley M.

    1994-01-01

    The geochemical cycling of cobalt (Co) has often been considered to be controlled by the scavenging and oxidation of Co(II) on the surface of manganese [Mn(III,IV)] oxides or manganates. Because Mn(II) oxidation in the environment is often catalyzed by bacteria, we have investigated the ability of Mn(II)-oxidizing bacteria to bind and oxidize Co(II) in the absence of Mn(II) to determine whether some Mn(II)-oxidizing bacteria also oxidize Co(II) independently of Mn oxidation. We used the marine Bacillus sp. strain SG-1, which produces mature spores that oxidize Mn(II), apparently due to a protein in their spore coats (R.A. Rosson and K. H. Nealson, J. Bacteriol. 151:1027-1034, 1982; J. P. M. de Vrind et al., Appl. Environ. Microbiol. 52:1096-1100, 1986). A method to measure Co(II) oxidation using radioactive 57Co as a tracer and treatments with nonradioactive (cold) Co(II) and ascorbate to discriminate bound Co from oxidized Co was developed. SG-1 spores were found to oxidize Co(II) over a wide range of pH, temperature, and Co(II) concentration. Leucoberbelin blue, a reagent that reacts with Mn(III,IV) oxides forming a blue color, was found to also react with Co(III) oxides and was used to verify the presence of oxidized Co in the absence of added Mn(II). Co(II) oxidation occurred optimally around pH 8 and between 55 and 65°C. SG-1 spores oxidized Co(II) at all Co(II) concentrations tested from the trace levels found in seawater to 100 mM. Co(II) oxidation was found to follow Michaelis-Menten kinetics. An Eadie-Hofstee plot of the data suggests that SG-1 spores have two oxidation systems, a high-affinity-low-rate system (Km, 3.3 × 10-8 M; Vmax, 1.7 × 10-15 M · spore-1 · h-1) and a low-affinity-high-rate system (Km, 5.2 × 10-6 M; Vmax, 8.9 × 10-15 M · spore-1 · h-1). SG-1 spores did not oxidize Co(II) in the absence of oxygen, also indicating that oxidation was not due to abiological Co(II) oxidation on the surface of preformed Mn(III,IV) oxides. These

  4. Cobalt-silicon mixed oxide nanocomposites by modified sol-gel method

    SciTech Connect

    Esposito, Serena; Turco, Maria; Ramis, Gianguido; Bagnasco, Giovanni; Pernice, Pasquale; Pagliuca, Concetta; Bevilacqua, Maria; Aronne, Antonio

    2007-12-15

    Cobalt-silicon mixed oxide materials (Co/Si=0.111, 0.250 and 0.428) were synthesised starting from Co(NO{sub 3}){sub 2}.6H{sub 2}O and Si(OC{sub 2}H{sub 5}){sub 4} using a modified sol-gel method. Structural, textural and surface chemical properties were investigated by thermogravimetric/differential thermal analyses (TG/DTA), XRD, UV-vis, FT-IR spectroscopy and N{sub 2} adsorption at -196 deg. C. The nature of cobalt species and their interactions with the siloxane matrix were strongly depending on both the cobalt loading and the heat treatment. All dried gels were amorphous and contained Co{sup 2+} ions forming both tetrahedral and octahedral complexes with the siloxane matrix. After treatment at 400 deg. C, the sample with lowest Co content appeared amorphous and contained only Co{sup 2+} tetrahedral complexes, while at higher cobalt loading Co{sub 3}O{sub 4} was present as the only crystalline phase, besides Co{sup 2+} ions strongly interacting with siloxane matrix. At 850 deg. C, in all samples crystalline Co{sub 2}SiO{sub 4} was formed and was the only crystallising phase for the nanocomposite with the lowest cobalt content. All materials retained high surface areas also after treatments at 600 deg. C and exhibited surface Lewis acidity, due to cationic sites. The presence of cobalt affected the textural properties of the siloxane matrix decreasing microporosity and increasing mesoporosity. - Graphical abstract: Highly dispersed cobalt-silicon mixed oxide nanocomposites (Co/Si=0.111, 0.250 and 0.428) were obtained by a modified sol-gel method using almost solely aqueous solutions. The nature of cobalt species and their interactions with the siloxane matrix are strongly depending on both the cobalt loading and the heat treatment. All materials retained high surface areas also after treatments at 600 deg. C and exhibited surface Lewis acidity.

  5. Cobalt-induced oxidative stress in brain, liver and kidney of goldfish Carassius auratus.

    PubMed

    Kubrak, Olha I; Husak, Viktor V; Rovenko, Bohdana M; Storey, Janet M; Storey, Kenneth B; Lushchak, Volodymyr I

    2011-10-01

    Cobalt is an essential element, but at high concentrations it is toxic. In addition to its well-known function as an integral part of cobalamin (vitamin B₁₂), cobalt has recently been shown to be a mimetic of hypoxia and a stimulator of the production of reactive oxygen species. The present study investigated the responses of goldfish, Carassius auratus, to 96 h exposure to 50, 100 or 150 mg L⁻¹ Co²⁺ in aquarium water (administered as CoCl₂). The concentrations of cobalt in aquaria did not change during fish exposure. Exposure to cobalt resulted in increased levels of lipid peroxides in brain (a 111% increase after exposure to 150 mg L⁻¹ Co²⁺) and liver (30-66% increases after exposure to 50-150 mg L⁻¹ Co²⁺), whereas the content of protein carbonyls rose only in kidney (by 112%) after exposure to 150 mg L⁻¹ cobalt. Low molecular mass thiols were depleted by 24-41% in brain in response to cobalt treatment. The activities of primary antioxidant enzymes, superoxide dismutase (SOD) and catalase, were substantially suppressed in brain and liver as a result of Co²⁺ exposure, whereas in kidney catalase activity was unchanged and SOD activity increased. The activities of glutathione-related enzymes, glutathione peroxidase and glutathione-S-transferase, did not change as a result of cobalt exposure, but glutathione reductase activity increased by ∼40% and ∼70% in brain and kidney, respectively. Taken together, these data show that exposure of fish to Co²⁺ ions results in the development of oxidative stress and the activation of defense systems in different goldfish tissues.

  6. Swift heavy ion induced changes in magnetization of cobalt thin films

    SciTech Connect

    Attri, Asha Nair, Lekha

    2016-05-06

    The effects of 45 MeV Li{sup 3+} ions and 100 MeV O{sup 7+} ions irradiation on magnetic properties of nanoparticles of 25 nm Cobalt thin films, synthesized by e-beam sputtering have been studied. Significant changes in the hysteresis loop are observed with different irradiating fluence, which may be attributed to formation of cluster of defects in the nano-crystalline samples due to swift heavy ion (SHI) irradiation along with the distortion in the lattice parameter.

  7. Electrocatalytic miRNA Detection Using Cobalt Porphyrin-Modified Reduced Graphene Oxide

    PubMed Central

    De Souza, Camille; Zrig, Samia; Wang, Dengjun; Pham, Minh-Chau; Piro, Benoit

    2014-01-01

    Metalated porphyrins have been described to bind nucleic acids. Additionally, cobalt porphyrins present catalytic properties towards oxygen reduction. In this work, a carboxylic acid-functionalized cobalt porphyrin was physisorbed on reduced graphene oxide, then immobilized on glassy carbon electrodes. The carboxylic groups were used to covalently graft amino-terminated oligonucleotide probes which are complementary to a short microRNA target. It was shown that the catalytic oxygen electroreduction on cobalt porphyrin increases upon hybridization of miRNA strand (“signal-on” response). Current changes are amplified compared to non-catalytic amperometric system. Apart from oxygen, no added reagent is necessary. A limit of detection in the sub-nanomolar range was reached. This approach has never been described in the literature. PMID:24915180

  8. Superhydrophobic honeycomb-like cobalt stearate thin films on aluminum with excellent anti-corrosion properties

    NASA Astrophysics Data System (ADS)

    Xiong, Jiawei; Sarkar, D. K.; Chen, X.-Grant

    2017-06-01

    Superhydrophobic cobalt stearate thin films with excellent anti-corrosion properties were successfully fabricated on aluminum substrates via electrodeposition process. The water-repellent properties were attributed to the honeycomb-like micro-nano structure as well as low surface energy of cobalt stearate. The correlation between the surface morphology, composition as well as wetting properties and the molar ratio of inorganic cobalt salt (Co(NO3)2) and organic stearic acid (SA) abbreviated as Co/SA, in the electrolyte were studied carefully. The optimum superhydrophobic surface obtained on the electrodeposited cathodic aluminum substrate, in the mixed ethanolic solution with Co/SA molar ratio of 0.2, was found to have a maximum contact angle of 161°. The polarization resistance of superhydrophobic aluminum substrates was calculated as high as 1591 kΩ cm2, which is determined to be two orders of magnitude larger than that of the as-received aluminum substrate as 27 kΩ cm2. Electrochemical impedance spectroscopy (EIS) was also employed to evaluate the corrosion resistance properties of these samples. Furthermore, electrical equivalent circuits (EEC) have been suggested in order to better understand the corrosion phenomena on these surfaces based on the corresponding EIS data.

  9. Differences in metal ion release following cobalt-chromium and oxidized zirconium total knee arthroplasty.

    PubMed

    Garrett, Simon; Jacobs, Neal; Yates, Piers; Smith, Anne; Wood, David

    2010-08-01

    Ions are released from all metals after implantation in the body through processes of corrosive and mechanical wear. The aim of this study was to investigate whether serum metal ion levels are raised in patients following total knee arthroplasty. Serum levels of chromium, cobalt, aluminium, molybdenum and zirconium were measured in two groups of patients at a minimum of 3 years after knee arthroplasty. Twenty three patients had a cobalt-chromium femoral component and 14 patients had an oxidized zirconium femoral component, acting as a control group as this femoral component is free from cobalt and chromium. All patients had the same titanium tibial base plates, and no patellae were resurfaced. Despite the lack of cobalt and chromium in the prostheses used in the control group, no statistically significant differences in serum cobalt and chromium ion levels were found between the groups. On the basis of these results there does not appear to be any significant rise in serum metal ion levels following total knee arthroplasty several years after implantation.

  10. Preliminary study of a solar selective coating system using black cobalt oxide for high temperature solar collectors

    NASA Technical Reports Server (NTRS)

    Mcdonald, G.

    1980-01-01

    Black cobalt oxide coatings (high solar absorptance layer) were deposited on thin layers of silver or gold (low emittance layer) which had been previously deposited on oxidized (diffusion barrier layer) stainless steel substrates. The reflectance properties of these coatings were measured at various thicknesses of cobalt for integrated values of the solar and infrared spectrum. The values of absorptance and emittance were calculated from the measured reflectance values, before and after exposure in air at 650 C for approximately 1000 hours. Absorptance and emittance were interdependent functions of the weight of cobalt oxide. Also, these cobalt oxide/noble metal/oxide diffusion barrier coatings have absorptances greater than 0.90 and emittances of approximately 0.20 even after about 1000 hours at 650 C.

  11. Hypoxic preconditioning with cobalt attenuates hypobaric hypoxia-induced oxidative damage in rat lungs.

    PubMed

    Shukla, Dhananjay; Saxena, Saurabh; Jayamurthy, Purushotman; Sairam, Mustoori; Singh, Mrinalini; Jain, Swatantra Kumar; Bansal, Anju; Ilavazaghan, Govindaswamy

    2009-01-01

    Shukla, Dhananjay, Saurabh Saxena, Purushotman Jayamurthy, Mustoori Sairam, Mrinalini, Singh, Swatantra Kumar Jain, Anju Bansal, and Govindaswamy Ilavazaghan. High Alt. Med. Biol. 10:57-69, 2009.-Hypoxic preco759nditioning (HPC) provides robust protection against injury from subsequent prolonged hypobaric hypoxia, which is a characteristic of high altitude and is known to induce oxidative injury in lung by increasing the generation of reactive oxygen species (ROS) and decreasing the effectiveness of the antioxidant defense system. We hypothesize that HPC with cobalt might protect the lung from subsequent hypobaric hypoxia-induced lung injury. HPC with cobalt can be achieved by oral feeding of CoCl(2) (12.5 mg kg(-1)) in rats for 7 days. Nonpreconditioned rats responded to hypobaric hypoxia (7619 m) by increased reactive oxygen species (ROS) generation and a decreased GSH/GSSG ratio. They also showed a marked increase in lipid peroxidation, heat-shock proteins (HSP32, HSP70), metallothionins (MT), levels of inflammatory cytokines (TNF-alpha, IFN-gamma, MCP-1), and SOD, GPx, and GST enzyme activity. In contrast, rats preconditioned with cobalt were far less impaired by severe hypobaric hypoxia, as observed by decreased ROS generation, lipid peroxidation, and inflammatory cytokine release and an inceased GSH/GSSG ratio. Increased expression of antioxidative proeins Nrf-1, HSP-32, and MT was also observed in cobalt- preconditioned animals. A marked increase in the protein expression and DNA binding activity of hypoxia-inducible transcriptional factor (HIF-1alpha) and its regulated genes, such as erythropoietin (EPO) and glucose transporter-1 (glut-1), was observed after HPC with cobalt. We conclude that HPC with cobalt enhances antioxidant status in the lung and protects from subsequent hypobaric hypoxia-induced oxidative stress.

  12. Implication of Structural Disorder in The Charge Transport Properties of Cobalt-phthalocyanine Thin Films

    SciTech Connect

    Debnath, A. K.; Kumar, A.; Samanta, S.; Singh, A.; Aswal, D. K.; Gupta, S. K.; Yakhmi, J. V.

    2011-07-15

    The charge transport properties of 100 nm thick cobalt phthalocyanine (CoPc) films grown on single crystal Al{sub 2}O{sub 3}(0001 oriented) and quartz substrates using molecular beam epitaxy, have been investigated as a function of applied bias ({+-} 50 V) at room temperature. Films grown on Al{sub 2}O{sub 3} are highly ordered and exhibited non-hysteretic current-voltage (J-V) characteristics. On the other hand, films grown on quartz substrates are highly disordered and exhibited hysteretic J-V characteristics due to charge trapping. The analysis of J-V characteristics of films on Al{sub 2}O{sub 3} substrates show that the transport is governed by shallow trap mediated space charge limited conduction (SCLC), while for the films grown on the quartz substrate transport is through the exponentially distributed traps mediated SCLC. X-ray photoelectron spectroscopy data show that charge trapping centers in the films grown on quartz substrates are created by chemisorbed oxygen.

  13. Thin film hydrous metal oxide catalysts

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.

    1995-01-01

    Thin film (<100 nm) hydrous metal oxide catalysts are prepared by 1) synthesis of a hydrous metal oxide, 2) deposition of the hydrous metal oxide upon an inert support surface, 3) ion exchange with catalytically active metals, and 4) activating the hydrous metal oxide catalysts.

  14. Phase equilibria in the iron oxide-cobalt oxide-phosphorus oxide system

    NASA Technical Reports Server (NTRS)

    De Guire, Mark R.; Prasanna, T. R. S.; Kalonji, Gretchen; O'Handley, Robert C.

    1987-01-01

    Two novel ternary compounds are noted in the present study of 1000 C solid-state equilibria in the Fe-Co-P-O system's Fe2O3-FePO4-Co3(Po4)2-CoO region: CoFe(PO4)O, which undergoes incongruent melting at 1130 C, and Co3Fe4(PO4)6, whose incongruent melting occurs at 1080 C. The liquidus behavior-related consequences of rapidly solidified cobalt ferrite formation from cobalt ferrite-phosphate melts are discussed with a view to spinel formation. It is suggested that quenching from within the spinel-plus-liquid region may furnish an alternative to quenching a homogeneous melt.

  15. Phase equilibria in the iron oxide-cobalt oxide-phosphorus oxide system

    NASA Technical Reports Server (NTRS)

    De Guire, Mark R.; Prasanna, T. R. S.; Kalonji, Gretchen; O'Handley, Robert C.

    1987-01-01

    Two novel ternary compounds are noted in the present study of 1000 C solid-state equilibria in the Fe-Co-P-O system's Fe2O3-FePO4-Co3(Po4)2-CoO region: CoFe(PO4)O, which undergoes incongruent melting at 1130 C, and Co3Fe4(PO4)6, whose incongruent melting occurs at 1080 C. The liquidus behavior-related consequences of rapidly solidified cobalt ferrite formation from cobalt ferrite-phosphate melts are discussed with a view to spinel formation. It is suggested that quenching from within the spinel-plus-liquid region may furnish an alternative to quenching a homogeneous melt.

  16. Cobalt (hydro)oxide electrodes under electrochemical conditions: a first principle study

    NASA Astrophysics Data System (ADS)

    Chen, Jia; Selloni, Annabella

    2013-03-01

    There is currently much interest in photoelectrochemical water splitting as a promising pathway towards sustainable energy production. A major issue of such photoelectrochemical devices is the limited efficiency of the anode, where the oxygen evolution reaction (OER) takes place. Cobalt (hydro)oxides, particularly Co3O4 and Co(OH)2, have emerged as promising candidates for use as OER anode materials. Interestingly, recent in-situ Raman spectroscopy studies have shown that Co3O4 electrodes undergo progressive oxidation and transform into oxyhydroxide, CoO(OH), under electrochemical working conditions. (Journal of the American Chemical Society 133, 5587 (2011))Using first principle electronic structure calculations, we provide insight into these findings by presenting results on the structural, thermodynamic, and electronic properties of cobalt oxide, hydroxide and oxydroxide CoO(OH), and on their relative stabilities when in contact with water under external voltage.

  17. Neuroprotective effect of cobalt chloride on hypobaric hypoxia-induced oxidative stress.

    PubMed

    Shrivastava, Kalpana; Shukla, Dhananjay; Bansal, Anju; Sairam, Mustoori; Banerjee, P K; Ilavazhagan, Govindaswamy

    2008-02-01

    Hypobaric hypoxia, characteristic of high altitude is known to increase the formation of reactive oxygen and nitrogen species (RONS), and decrease effectiveness of antioxidant enzymes. RONS are involved and may even play a causative role in high altitude related ailments. Brain is highly susceptible to hypoxic stress and is involved in physiological responses that follow. Exposure of rats to hypobaric hypoxia (7619 m) resulted in increased oxidation of lipids and proteins due to increased RONS and decreased reduced to oxidized glutathione (GSH/GSSG) ratio. Further, there was a significant increase in superoxide dismutase (SOD), glutathione peroxidase (GPx), and glutathione-S-transferase (GST) levels. Increase in heme oxygenase 1 (HO-1) and heat shock protein 70 (HSP70) was also noticed along with metallothionein (MT) II and III. Administration of cobalt appreciably attenuated the RONS generation, oxidation of lipids and proteins and maintained GSH/GSSH ratio similar to that of control cells via induction of HO-1 and MT offering efficient neuroprotection. It can be concluded that cobalt reduces hypoxia oxidative stress by maintaining higher cellular HO-1 and MT levels via hypoxia inducible factor 1alpha (HIF-1alpha) signaling mechanisms. These findings provide a basis for possible use of cobalt for prevention of hypoxia-induced oxidative stress.

  18. Cobalt and nickel macrocycles anchored to nanocrystalline titanium dioxide thin films: Sensitization, catalysis, and ligand association

    NASA Astrophysics Data System (ADS)

    Achey, Darren Craig

    The global demand for renewable, clean electricity and fuel has compelled efforts to utilize the immense power incident upon the Earth from the Sun. Photovoltaic systems could power the planet's electrical demands with only moderate efficiencies. However, mitigation of fossil fuels used for transportation and night-time electricity requires the storage of photon energy, for example, in the form of chemical bonds. Mesoporous, nanocrystalline TiO2 thin films provide a manifold for anchoring molecular species that absorb and utilize photons to catalyze fuel-generating reactions. The overarching theme of this thesis is to improve understanding of the semiconductor/molecule interface utilizing earth abundant first-row transition metal coordination compounds. Chapter 2 presents the non-ideal redox behavior of cobalt porphyrins anchored to semiconductor surfaces. Additionally, CoI porphyrins were utilized as photocatalysts for the 2e- reduction of organobromides to yield a CoIII-R intermediate. The cobalt-carbon bond of CoIII-R was photodissociated with visible light to yield Co II and R·. The organic radical dimerized to form R-R. Light excitation of CoI compounds was found to result in electron transfer to TiO2, Chapter 3. Cobalt porphyrins, phthalocyanines, glyoximes, and corrins were all observed to exhibit this behavior. Electron transfer was demonstrated to primarily occur via excitation into the large extinction coefficient metal-to-ligand charge transfer absorption bands of CoI complexes. Chapter 4 focuses on the unique coordination chemistry of cobalt porphyrins anchored to a TiO2 thin film. Notably, pyridine axially ligated a CoII porphyrin following excited-state electron transfer of the CoI porphyrin to the TiO2. The rate constant for recombination of an electron in the TiO2 with CoII was observed to decrease with increasing pyridine concentration, behavior attributed primarily to a negative shift of the CoII/I potential in the presence of pyridine. Finally

  19. Stability of phosphonic self assembled monolayers (SAMs) on cobalt chromium (Co-Cr) alloy under oxidative conditions

    NASA Astrophysics Data System (ADS)

    Bhure, Rahul; Abdel-Fattah, Tarek M.; Bonner, Carl; Hall, Felicia; Mahapatro, Anil

    2011-04-01

    Cobalt chromium (Co-Cr) alloys have been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and contact angle measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration.

  20. Controlled fabrication of photoactive copper oxide-cobalt oxide nanowire heterostructures for efficient phenol photodegradation.

    PubMed

    Shi, Wenwu; Chopra, Nitin

    2012-10-24

    Fabrication of oxide nanowire heterostructures with controlled morphology, interface, and phase purity is critical for high-efficiency and low-cost photocatalysis. Here, we have studied the formation of copper oxide-cobalt nanowire heterostructures by sputtering and subsequent air annealing to result in cobalt oxide (Co(3)O(4))-coated CuO nanowires. This approach allowed fabrication of standing nanowire heterostructures with tunable compositions and morphologies. The vertically standing CuO nanowires were synthesized in a thermal growth method. The shell growth kinetics of Co and Co(3)O(4) on CuO nanowires, morphological evolution of the shell, and nanowire self-shadowing effects were found to be strongly dependent on sputtering duration, air-annealing conditions, and alignment of CuO nanowires. Finite element method (FEM) analysis indicated that alignment and stiffness of CuO-Co nanowire heterostructures greatly influenced the nanomechanical aspects such as von Mises equivalent stress distribution and bending of nanowire heterostructures during the Co deposition process. This fundamental knowledge was critical for the morphological control of Co and Co(3)O(4) on CuO nanowires with desired interfaces and a uniform coating. Band gap energies and phenol photodegradation capability of CuO-Co(3)O(4) nanowire heterostructures were studied as a function of Co(3)O(4) morphology. Multiple absorption edges and band gap tailings were observed for these heterostructures, indicating photoactivity from visible to UV range. A polycrystalline Co(3)O(4) shell on CuO nanowires showed the best photodegradation performance (efficiency ~50-90%) in a low-powered UV or visible light illumination with a sacrificial agent (H(2)O(2)). An anomalously high efficiency (~67.5%) observed under visible light without sacrificial agent for CuO nanowires coated with thin (∼5.6 nm) Co(3)O(4) shell and nanoparticles was especially interesting. Such photoactive heterostructures demonstrate unique

  1. Elaboration of ammonia gas sensors based on electrodeposited polypyrrole--cobalt phthalocyanine hybrid films.

    PubMed

    Patois, Tilia; Sanchez, Jean-Baptiste; Berger, Franck; Fievet, Patrick; Segut, Olivier; Moutarlier, Virginie; Bouvet, Marcel; Lakard, Boris

    2013-12-15

    The electrochemical incorporation of a sulfonated cobalt phthalocyanine (sCoPc) in conducting polypyrrole (PPy) was done, in the presence or absence of LiClO4, in order to use the resulting hybrid material for the sensing of ammonia. After electrochemical deposition, the morphological features and structural properties of polypyrrole/phthalocyanine hybrid films were investigated and compared to those of polypyrrole films. A gas sensor consisting in platinum microelectrodes arrays was fabricated using silicon microtechnologies, and the polypyrrole and polypyrrole/phthalocyanine films were electrochemically deposited on the platinum microelectrodes arrays of this gas sensor. When exposed to ammonia, polymer-based gas sensors exhibited a decrease in conductance due to the electron exchange between ammonia and sensitive polymer-based layer. The characteristics of the gas sensors (response time, response amplitude, reversibility) were studied for ammonia concentrations varying from 1 ppm to 100 ppm. Polypyrrole/phthalocyanine films exhibited a high sensitivity and low detection limit to ammonia as well as a fast and reproducible response at room temperature. The response to ammonia exposition of polypyrrole films was found to be strongly enhanced thanks to the incorporation of the phthalocyanine in the polypyrrole matrix. © 2013 Elsevier B.V. All rights reserved.

  2. Growth Kinetics and Properties of Thin Cobalt Films Electrodeposited on n-Si(100)

    NASA Astrophysics Data System (ADS)

    Lee, Jong Duk; An, Tae Hwan; Noh, Hak Gi; Kim, Sung Gon; Choi, Young R.

    2010-08-01

    The cobalt thin films were directly grown on n-Si(100) substrates in a non-aqueous electrolyte of 0.1 M CoCl2 by using pulsed electrodeposition technique. In this paper, the growth, structural and magnetic properties of thin Co films have been investigated. Current transient experiments showed that Co nuclei in the early deposition stage forms through three dimensional (3D) instantaneous nucleation followed by diffusion-limited growth. From the atomic force microscopy (AFM) analysis, it has been found that the film surface consisted of cubic and distorted rectangular-shaped nanocrystallites with the average size of about 140 nm irrespective of the deposition voltage. X-ray diffraction (XRD) measurement indicated that Co was arranged with only a hexagonal close-packed (hcp) structure not involving face-centered cubic (fcc) Co or silicide phases. Vibrating sample magnetometer (VSM) measurements revealed that the easy magnetization axis of Co thin film is parallel to the film plane.

  3. Cobalt-phosphate-assisted photoelectrochemical water oxidation by arrays of molybdenum-doped zinc oxide nanorods.

    PubMed

    Lin, Yan-Gu; Hsu, Yu-Kuei; Chen, Ying-Chu; Lee, Bing-Wei; Hwang, Jih-Shang; Chen, Li-Chyong; Chen, Kuei-Hsien

    2014-09-01

    We report the first demonstration of cobalt phosphate (Co-Pi)-assisted molybdenum-doped zinc oxide nanorods (Zn(1-x)Mo(x)O NRs) as visible-light-sensitive photofunctional electrodes to fundamentally improve the performance of ZnO NRs for photoelectrochemical (PEC) water splitting. A maximum photoconversion efficiency as high as 1.05% was achieved, at a photocurrent density of 1.4 mA cm(-2). More importantly, in addition to achieve the maximum incident photon to current conversion efficiency (IPCE) value of 86%, it could be noted that the IPCE of Zn(1-x)Mo(x)O photoanodes under monochromatic illumination (450 nm) is up to 12%. Our PEC performances are comparable to those of many oxide-based photoanodes in recent reports. The improvement in photoactivity of PEC water splitting may be attributed to the enhanced visible-light absorption, increased charge-carrier densities, and improved interfacial charge-transfer kinetics due to the combined effect of molybdenum incorporation and Co-Pi modification, contributing to photocatalysis. The new design of constructing highly photoactive Co-Pi-assisted Zn(1-x)Mo(x)O photoanodes enriches knowledge on doping and advances the development of high-efficiency photoelectrodes in the solar-hydrogen field.

  4. Oxidation of cobalt and manganese in seawater via a common microbially catalyzed pathway

    NASA Astrophysics Data System (ADS)

    Moffett, James W.; Ho, Jackson

    1996-09-01

    Cobalt and manganese uptake onto suspended particles was studied in waters collected from Waquoit Bay, Massachusetts and the upper water column of the Sargasso Sea using radiotracers, coupled with protocols used previously for Mn and Ce to distinguish biological and redox processes. Cobalt uptake onto suspended particles in Waquiot Bay was dominated by microbial oxidation. Moreover, there was a close relationship between Mn(II) and Co(II) oxidation, with Mn(II) specific rates approximately 7-10x faster. Oxidation of each element obeys Michaelis Menten kinetics, with identifical values of K m in a given sample and values of V max are 7× higher for Mn. Lineweaver-Burk plots, generated from saturation plots for Co and Mn oxidation at different Mn and Co concentrations, demonstrated competitive inhibition between Co and Mn. The results indicate that both elements are co-oxidized via the same microbial catalytic pathway, and that this is probably an important mechanism for the incorporation of Co into marine Mn oxides. In the Sargasso Sea, by contrast, Mn and Co uptake onto suspended particles were completely decoupled. Cobalt uptake was nonoxidative, biologically mediated, and enhanced by low to moderate levels of light. It is probably due primarily to uptake by phytoplankton. Manganese uptake was almost exclusively oxidative and was inhibited by light even at low intensities. The differences probably reflect a higher biological demand for Co in the Sargasso Sea (Co is a biologically essential element), where Co concentrations are low, and lower activity of Mn oxidizing bacteria. Results suggest that higher specific uptake rates of Co than Mn by phytoplankton in oceanic regimes could result in Co having a geochemistry intermediate between Mn and a more nutrient-type element, such as Zn. Nevertheless, Co and Mn cycling are expected to be closely coupled in regions of high microbial Mn oxidizing activity.

  5. Adsorption and catalytic properties of sulfated aluminum oxide modified with cobalt ions

    NASA Astrophysics Data System (ADS)

    Lanin, S. N.; Bannykh, A. A.; Vlasenko, E. V.; Krotova, I. N.; Obrezkov, O. N.; Shilina, M. I.

    2017-01-01

    The adsorption properties of sulfated aluminum oxide (9% SO 4 2- /γ-Al2O3) and a cobalt-containing composite (0.5%Co/SO 4 2- /γ-Al2O3) based on it are studied via dynamic sorption. The adsorption isotherms of such test adsorbates as n-hydrocarbons (C6-C8), benzene, ethylbenzene, chloroform, and diethyl ether are measured, and their isosteric heats of adsorption are calculated. It is shown that the surface sulfation of aluminum oxide substantially improves its electron-accepting properties, and so the catalytic activity of SO 4 2- /γ-Al2O3 in the liquid-phase alkylation of benzene with octene-1 at temperatures of 25-120°C is one order of magnitude higher than for the initial aluminum oxide. It is established that additional modification of sulfated aluminum oxide with cobalt ions increases the activity of this catalyst by 2-4 times. It is shown that adsorption sites capable of strong specific adsorption with both donating (aromatics, diethyl ether chemosorption) and accepting molecules (chloroform) form on the surface of sulfated γ-Al2O3 promoted by cobalt salt.

  6. Nanoporous gold supported cobalt oxide microelectrodes as high-performance electrochemical biosensors.

    PubMed

    Lang, Xing-You; Fu, Hong-Ying; Hou, Chao; Han, Gao-Feng; Yang, Ping; Liu, Yong-Bing; Jiang, Qing

    2013-01-01

    Tremendous demands for electrochemical biosensors with high sensitivity and reliability, fast response and excellent selectivity have stimulated intensive research on developing versatile materials with ultrahigh electrocatalytic activity. Here we report flexible and self-supported microelectrodes with a seamless solid/nanoporous gold/cobalt oxide hybrid structure for electrochemical nonenzymatic glucose biosensors. As a result of synergistic electrocatalytic activity of the gold skeleton and cobalt oxide nanoparticles towards glucose oxidation, amperometric glucose biosensors based on the hybrid microelectrodes exhibit multi-linear detection ranges with ultrahigh sensitivities at a low potential of 0.26 V (versus Ag/AgCl). The sensitivity up to 12.5 mA mM⁻¹ cm⁻² with a short response time of less than 1 s gives rise to ultralow detection limit of 5 nM. The outstanding performance originates from a novel nanoarchitecture in which the cobalt oxide nanoparticles are incorporated into pore channels of the seamless solid/nanoporous Au microwires, providing excellent electronic/ionic conductivity and mass transport for the enhanced electrocatalysis.

  7. Dispersing molecular cobalt in graphitic carbon nitride frameworks for photocatalytic water oxidation.

    PubMed

    Zhang, Guigang; Huang, Caijin; Wang, Xinchen

    2015-03-01

    The development of water oxidation catalysts (WOCs) to cooperate with light-energy transducers for solar energy conversion by water splitting and CO2 fixation is a demanding challenge. The key measure is to develop efficient and sustainable WOCs that can support a sustainable photocatalyst to reduce over-potentials and thus to enhance reaction rate of water oxidation reaction. Cobalt has been indentified as active component of WOCs for photo/electrochemical water oxidation, and its performance relies strongly on the contact and adhesion of the cobalt species with photoactive substrates. Here, cobalt is homogeneously engineered into the framework of pristine graphitic carbon nitride (g-C3 N4 ) via chemical interaction, establishing surface junctions on the polymeric photocatalyst for the water oxidation reaction. This modification promotes the surface kinetics of oxygen evolution reaction by the g-C3 N4 -based photocatalytic system made of inexpensive substances, and further optimizations in the optical and textural structure of Co-g-C3 N4 is envisaged by considering ample choice of modification schemes for carbon nitride materials.

  8. Controllable Cobalt Oxide/Au Hierarchically Nanostructured Electrode for Nonenzymatic Glucose Sensing.

    PubMed

    Su, Yingying; Luo, Binbin; Zhang, Jin Zhong

    2016-02-02

    By electrodeposition and galvanic replacement reaction, we developed a facile, time-saving, cost-effective, and environmentally friendly, two-step synthesis route to obtain a controllable cobalt oxide/Au hierarchically nanostructured electrode for glucose sensing. The nanomaterials were characterized by transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, energy-dispersive spectrometry, and X-ray photoelectron spectroscopy, meanwhile, the sensing performance was investigated by cyclic voltammetry and amperometric response. The results revealed that this novel electrode exhibited excellent electrocatalytic performance toward glucose oxidation, with a wide double-linear range from 0.2 μM to 20 mM and a low detection limit of 0.1 μM based on a signal-to-noise ratio of 3, which was mainly attributed to the ability of loading a small amount of Au with good electron conductivity on the surface of cobalt oxide nanosheets with large active surface area and synergistic electrocatalytic activity of Au and cobalt oxide toward glucose electrooxidation. This facile, sensitive, and selective glucose sensor is also proven to be suitable for the detection of glucose in human serum.

  9. Cobalt pivalate complex as a catalyst for liquid phase oxidation of n-hexane

    NASA Astrophysics Data System (ADS)

    Moskovskaya, I. F.; Maerle, A. A.; Shvydkiy, N. V.; Romanovsky, B. V.; Ivanova, I. I.

    2015-09-01

    Catalytic properties of cobalt(II) pivalate complex as both individual and supported on mesoporous molecular sieves Si-KIT-6, Al-KIT-6, and Ce-KIT-6 were investigated in liquid-phase oxidation of n-hexane with molecular oxygen. This complex was shown to be an active and selective catalyst for the oxidation of n-C6H14 into C1-C4 carboxylic acids. The activity of Co(II) pivalate remains practically unchanged on heterogenizing the complex on molecular sieve supports. At the same time, its selectivity and resistance towards an oxidative degradation are slightly increased.

  10. Size- and support-dependent evolution of the oxidation state and structure by oxidation of subnanometer cobalt clusters.

    PubMed

    Yin, Chunrong; Zheng, Fan; Lee, Sungsik; Guo, Jinghua; Wang, Wei-Cheng; Kwon, Gihan; Vajda, Viktor; Wang, Hsien-Hau; Lee, Byeongdu; DeBartolo, Janae; Seifert, Sönke; Winans, Randall E; Vajda, Stefan

    2014-09-18

    Size-selected subnanometer cobalt clusters with 4, 7, and 27 cobalt atoms supported on amorphous alumina and ultrananocrystalline diamond (UNCD) surfaces were oxidized after exposure to ambient air. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) and near-edge X-ray absorption fine structure (NEXAFS) were used to characterize the clusters revealed a strong dependency of the oxidation state and structure of the clusters on the surface. A dominant Co(2+) phase was identified in all samples. However, XANES analysis of cobalt clusters on UNCD showed that ∼10% fraction of a Co(0) phase was identified for all three cluster sizes and about 30 and 12% fraction of a Co(3+) phase in 4, 7, and 27 atom clusters, respectively. In the alumina-supported clusters, the dominating Co(2+) component was attributed to a cobalt aluminate, indicative of a very strong binding to the support. NEXAFS showed that in addition to strong binding of the clusters to alumina, their structure to a great extent follows the tetrahedral morphology of the support. All supported clusters were found to be resistant to agglomeration when exposed to reactive gases at elevated temperatures and atmospheric pressure.

  11. Calcium- and Cobalt-doped Yttrium Chromites as an Interconnect Material for Solid Oxide Fuel Cells

    SciTech Connect

    Yoon, Kyung J.; Cramer, Carolyn N.; Thomsen, Edwin C.; Coyle, Christopher A.; Coffey, Greg W.; Marina, Olga A.

    2010-04-23

    The structural, thermal and electrical characteristics of calcium- and cobalt-doped yttrium chromites were studied for a potential use as the interconnect material in high temperature solid oxide fuel cells (SOFCs) as well as other high temperature electrochemical and thermoelectric devices. The Y0.8Ca0.2Cr1-xCoxO3±δ (x=0, 0.1, 0.2, 0.3) compositions had single phase orthorhombic perovskite structures in the wide range of oxygen pressures. Sintering behavior was remarkably enhanced upon cobalt doping and densities 95% and 97% of theoretical density were obtained after sintering at 1300oC in air, when x was 0.2 and 0.3, respectively. The electrical conductivity in both oxidizing and reducing atmospheres was significantly improved with cobalt content, and values of 49 and 10 S/cm at 850oC and 55 and 14 S/cm at 950oC in air and forming gas, respectively, were reported for x=0.2. The conductivity increase was attributed to the charge carrier density increase upon cobalt substitution for chromium confirmed with Seebeck measurements. The thermal expansion coefficient (TEC) was increased with cobalt content and closely matched to that of an 8 mol% yttria-stabilized zirconia (YSZ) electrolyte for 0.1 ≤ x ≤ 0.2. The chemical compatibility between Y0.8Ca0.2Cr1-xCoxO3±δ and YSZ was evaluated firing the two at 1400oC and no reaction products were found if x value was kept lower than 0.2.

  12. Adsorption of microbial esterases on Bacillus subtilis-templated cobalt oxide nanoparticles.

    PubMed

    Jang, Eunjin; Ryu, Bum Han; Shim, Hyun-Woo; Ju, Hansol; Kim, Dong-Wan; Kim, T Doohun

    2014-04-01

    Due to low diffusion rates and large surface areas, nanomaterials have received great interest as supporting materials for enzyme immobilization. Here, the preparation of a cobalt oxide nanoparticle using Bacillus subtilis as a biological template and use of the nanostructure for microbial esterase immobilization is described. Morphological features and size distributions were investigated using electron microscopy (EM) and dynamic light scattering (DLS). Catalytic properties of enzyme-coated nanostructures were investigated using 4-methylumbelliferyl acetate and p-nitrophenyl (PNP) acetate as model substrates. Enzyme-coated nanostructures were observed to retain ∼85% of the initial activity after 15 successive reaction cycles, and enzyme immobilization processes could be repeated four times without a loss of immobilization potential. The present work demonstrates that B. subtilis-templated cobalt oxide nanoparticles have the potential to be used as biocompatible immobilization materials, and are promising candidates for the preparation of effective nanobiocatalysts.

  13. Controllable fabrication and magnetic properties of double-shell cobalt oxides hollow particles

    PubMed Central

    Zhang, Dan; Zhu, Jianyu; Zhang, Ning; Liu, Tao; Chen, Limiao; Liu, Xiaohe; Ma, Renzhi; Zhang, Haitao; Qiu, Guanzhou

    2015-01-01

    Double-shell cobalt monoxide (CoO) hollow particles were successfully synthesized by a facile and effective one-pot solution-based synthetic route. The inner architecture and outer structure of the double-shell CoO hollow particles could be readily created through controlling experimental parameters. A possible formation mechanism was proposed based on the experimental results. The current synthetic strategy has good prospects for the future production of other transition-metal oxides particles with hollow interior. Furthermore, double-shell cobalt oxide (Co3O4) hollow particles could also be obtained through calcinating corresponding CoO hollow particles. The magnetic measurements revealed double-shell CoO and Co3O4 hollow particles exhibit ferromagnetic and antiferromagnetic behaviour, respectively. PMID:25736824

  14. Controllable fabrication and magnetic properties of double-shell cobalt oxides hollow particles

    NASA Astrophysics Data System (ADS)

    Zhang, Dan; Zhu, Jianyu; Zhang, Ning; Liu, Tao; Chen, Limiao; Liu, Xiaohe; Ma, Renzhi; Zhang, Haitao; Qiu, Guanzhou

    2015-03-01

    Double-shell cobalt monoxide (CoO) hollow particles were successfully synthesized by a facile and effective one-pot solution-based synthetic route. The inner architecture and outer structure of the double-shell CoO hollow particles could be readily created through controlling experimental parameters. A possible formation mechanism was proposed based on the experimental results. The current synthetic strategy has good prospects for the future production of other transition-metal oxides particles with hollow interior. Furthermore, double-shell cobalt oxide (Co3O4) hollow particles could also be obtained through calcinating corresponding CoO hollow particles. The magnetic measurements revealed double-shell CoO and Co3O4 hollow particles exhibit ferromagnetic and antiferromagnetic behaviour, respectively.

  15. Structural elements in the oxidation process of a single cobalt layer on Ir(100)-(1×1)

    NASA Astrophysics Data System (ADS)

    Gubo, Matthias; Ebensperger, Christina; Meyer, Wolfgang; Hammer, Lutz; Heinz, Klaus

    2011-02-01

    The ordered phases developing in sequence by oxidation of a single monolayer of cobalt deposited on Ir(100)-(1×1) were investigated by low-energy electron diffraction (LEED), scanning tunneling microscopy, and thermal desorption spectroscopy. It turns out that the structural elements of the different phases observed for increasing oxygen content and analyzed by quantitative LEED are pyramids based on squares or triangles made up by cobalt species and oxygen on top. The Co-O bond lengths are smaller than in the bulk of cobalt oxide owing to the reduced coordination of oxygen. For O:Co ratios of r=1/4, 1/2, and 5/8, the bonding of the oxide to the iridium substrate is merely by the cobalt species, and at r=1 it is via both Co and O.

  16. Synthesis of nanoporous carbon-cobalt-oxide hybrid electrocatalysts by thermal conversion of metal-organic frameworks.

    PubMed

    Chaikittisilp, Watcharop; Torad, Nagy L; Li, Cuiling; Imura, Masataka; Suzuki, Norihiro; Ishihara, Shinsuke; Ariga, Katsuhiko; Yamauchi, Yusuke

    2014-04-07

    Nanoporous carbon-cobalt-oxide hybrid materials are prepared by a simple, two-step, thermal conversion of a cobalt-based metal-organic framework (zeolitic imidazolate framework-9, ZIF-9). ZIF-9 is carbonized in an inert atmosphere to form nanoporous carbon-metallic-cobalt materials, followed by the subsequent thermal oxidation in air, yielding nanoporous carbon-cobalt-oxide hybrids. The resulting hybrid materials are evaluated as electrocatalysts for the oxygen-reduction reaction (ORR) and the oxygen-evolution reaction (OER) in a KOH electrolyte solution. The hybrid materials exhibit similar catalytic activity in the ORR to the benchmark, commercial, Pt/carbon black catalyst, and show better catalytic activity for the OER than the Pt-based catalyst. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Study of cobalt mononitride thin films prepared using DC and high power impulse magnetron sputtering

    SciTech Connect

    Gupta, Rachana; Pandey, Nidhi; Behera, Layanta; Gupta, Mukul

    2016-05-23

    In this work we studied cobalt mononitride (CoN) thin films deposited using dc magnetron sputtering (dcMS) and high power impulse magnetron sputtering (HiPIMS). A Co target was sputtered using pure N{sub 2} gas alone as the sputtering medium. Obtained long-range structural ordering was studies using x-ray diffraction (XRD), short-range structure using Co L{sub 2,3} and N K absorption edges using soft x-ray absorption spectroscopy (XAS) and the surface morphology using atomic force microscopy (AFM). It was found that HiPIMS deposited films have better long-range ordering, better stoichiometric ratio for mononitride composition and smoother texture as compared to dcMS deposited films. In addition, the thermal stability of HiPIMS deposited CoN film seems to be better. On the basis of different type of plasma conditions generated in HiPIMS and dcMS process, obtained results are presented and discussed.

  18. Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted "pH-adjusting" method: Importance of cobalt species in styrene oxidation

    NASA Astrophysics Data System (ADS)

    Li, Baitao; Zhu, Yanrun; Jin, Xiaojing

    2015-01-01

    Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted "pH-adjusting" technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co3O4 particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was more beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H2O2) at 70 °C.

  19. Electrochromism in copper oxide thin films

    SciTech Connect

    Richardson, T.J.; Slack, J.L.; Rubin, M.D.

    2000-08-15

    Transparent thin films of copper(I) oxide prepared on conductive SnO2:F glass substrates by anodic oxidation of sputtered copper films or by direct electrodeposition of Cu2O transformed reversibly to opaque metallic copper films when reduced in alkaline electrolyte. In addition, the same Cu2O films transform reversibly to black copper(II) oxide when cycled at more anodic potentials. Copper oxide-to-copper switching covered a large dynamic range, from 85% and 10% photopic transmittance, with a coloration efficiency of about 32 cm2/C. Gradual deterioration of the switching range occurred over 20 to 100 cycles. This is tentatively ascribed to coarsening of the film and contact degradation caused by the 65% volume change on conversion of Cu to Cu2O. Switching between the two copper oxides (which have similar volumes) was more stable and more efficient (CE = 60 cm2/C), but covered a smaller transmittance range (60% to 44% T). Due to their large electrochemical storage capacity and tolerance for alkaline electrolytes, these cathodically coloring films may be useful as counter electrodes for anodically coloring electrode films such as nickel oxide or metal hydrides.

  20. Magnetic transparent conducting oxide film and method of making

    DOEpatents

    Windisch, Jr., Charles F.; Exarhos, Gregory J.; Sharma, Shiv K.

    2004-07-13

    Cobalt-nickel oxide films of nominal 100 nm thickness, and resistivity as low as 0.06 .OMEGA..multidot.cm have been deposited by spin-casting from both aqueous and organic precursor solutions followed by annealing at 450.degree. C. in air. Films deposited on sapphire substrates exhibit a refractive index of about 1.7 and are relatively transparent in the wavelength region from 0.6 to 10.0 .mu.m. They are also magnetic. The electrical and spectroscopic properties of the oxides have been studied as a function of x=Co/(Co+Ni) ratio. An increase in film resistivity was found upon substitution of other cations (e.g., Zn.sup.2+, Al.sup.3+) for Ni in the spinel structure. However, some improvement in the mechanical properties of the films resulted. On the other hand, addition of small amounts of Li decreased the resistivity. A combination of XRD, XPS, UV/Vis and Raman spectroscopy indicated that NiCo.sub.2 O.sub.4 is the primary conducting component and that the conductivity reaches a maximum at this stoichiometry. When x<0.67, NiO forms leading to an increase in resistivity; when x>0.67, the oxide was all spinel but the increased Co content lowered the conductivity. The influence of cation charge state and site occupancy in the spinel structure markedly affects calculated electron band structures and contributes to a reduction of p-type conductivity, the formation of polarons, and the reduction in population of mobile charge carriers that tend to limit transmission in the infrared.

  1. Liquid-phase synthesis of cobalt oxide nanoparticles.

    PubMed

    Sinkó, Katalin; Szabó, Géza; Zrínyi, Miklós

    2011-05-01

    Various liquid-phase syntheses of CoO and Co3O4 nanoparticles have been studied. The experiments focus on two synthesis routes: the coprecipitation and the sol-gel methods combined with thermal decomposition. The effect of synthesis route, the type of precursors (cobalt nitrate/chloride) and precipitation agent (carbonate, hydroxide, oxalic acid, and ammonia), the chemical compositions, pH, application of surfactants (PDMS, Triton X-100, NaDS, NaDBS, TTAB, ethyl acetate, citric acid), and the heat treatments on the properties of particles were investigated. The particle size and distribution have been determined by dynamic light scattering (DLS). The phases and the morphology of products have been analysed by XRD and SEM. The coprecipitation technique is less able to shape the particles than sol-gel technique. PDMS can be applied efficiently as surfactant in preparation methods. The finest particles (around 85 nm) with narrow polydispersity (70-100 nm) and spherical shape could be achieved by using sol-gel technique in medium of 1-propanol and ethyl acetate.

  2. Platinum-induced structural collapse in layered oxide polycrystalline films

    SciTech Connect

    Wang, Jianlin; Liu, Changhui; Huang, Haoliang; Fu, Zhengping; Peng, Ranran E-mail: yllu@ustc.edu.cn; Zhai, Xiaofang; Lu, Yalin E-mail: yllu@ustc.edu.cn

    2015-03-30

    Effect of a platinum bottom electrode on the SrBi{sub 5}Fe{sub 1−x}Co{sub x}Ti{sub 4}O{sub 18} layered oxide polycrystalline films was systematically studied. The doped cobalt ions react with the platinum to form a secondary phase of PtCoO{sub 2}, which has a typical Delafossite structure with a weak antiferromagnetism and an exceptionally high in-plane electrical conductivity. Formation of PtCoO{sub 2} at the interface partially consumes the cobalt dopant and leads to the structural collapsing from 5 to 4 layers, which was confirmed by X-ray diffraction and high resolution transmission electron microscopy measurements. Considering the weak magnetic contribution from PtCoO{sub 2}, the observed ferromagnetism should be intrinsic of the Aurivillius compounds. Ferroelectric properties were also indicated by the piezoresponse force microscopy. In this work, the platinum induced secondary phase at the interface was observed, which has a strong impact on Aurivillius structural configuration and thus the ferromagnetic and ferroelectric properties.

  3. Optical properties and electrical transport of thin films of terbium(III) bis(phthalocyanine) on cobalt

    PubMed Central

    Robaschik, Peter; Siles, Pablo F; Bülz, Daniel; Richter, Peter; Monecke, Manuel; Fronk, Michael; Klyatskaya, Svetlana; Grimm, Daniel; Schmidt, Oliver G; Ruben, Mario; Zahn, Dietrich R T

    2014-01-01

    Summary The optical and electrical properties of terbium(III) bis(phthalocyanine) (TbPc2) films on cobalt substrates were studied using variable angle spectroscopic ellipsometry (VASE) and current sensing atomic force microscopy (cs-AFM). Thin films of TbPc2 with a thickness between 18 nm and 87 nm were prepared by organic molecular beam deposition onto a cobalt layer grown by electron beam evaporation. The molecular orientation of the molecules on the metallic film was estimated from the analysis of the spectroscopic ellipsometry data. A detailed analysis of the AFM topography shows that the TbPc2 films consist of islands which increase in size with the thickness of the organic film. Furthermore, the cs-AFM technique allows local variations of the organic film topography to be correlated with electrical transport properties. Local current mapping as well as local I–V spectroscopy shows that despite the granular structure of the films, the electrical transport is uniform through the organic films on the microscale. The AFM-based electrical measurements allow the local charge carrier mobility of the TbPc2 thin films to be quantified with nanoscale resolution. PMID:25551034

  4. CMOS-compatible synthesis of large-area, high-mobility graphene by chemical vapor deposition of acetylene on cobalt thin films.

    PubMed

    Ramón, Michael E; Gupta, Aparna; Corbet, Chris; Ferrer, Domingo A; Movva, Hema C P; Carpenter, Gary; Colombo, Luigi; Bourianoff, George; Doczy, Mark; Akinwande, Deji; Tutuc, Emanuel; Banerjee, Sanjay K

    2011-09-27

    We demonstrate the synthesis of large-area graphene on Co, a complementary metal-oxide-semiconductor (CMOS)-compatible metal, using acetylene (C(2)H(2)) as a precursor in a chemical vapor deposition (CVD)-based method. Cobalt films were deposited on SiO(2)/Si, and the influence of Co film thickness on monolayer graphene growth was studied, based on the solubility of C in Co. The surface area coverage of monolayer graphene was observed to increase with decreasing Co film thickness. A thorough Raman spectroscopic analysis reveals that graphene films, grown on an optimized Co film thickness, are principally composed of monolayer graphene. Transport properties of monolayer graphene films were investigated by fabrication of back-gated graphene field-effect transistors (GFETs), which exhibited high hole and electron mobility of ∼1600 cm(2)/V s and ∼1000 cm(2)/V s, respectively, and a low trap density of ∼1.2 × 10(11) cm(-2).

  5. Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation.

    PubMed

    Nguyen, Andy I; Ziegler, Micah S; Oña-Burgos, Pascual; Sturzbecher-Hohne, Manuel; Kim, Wooyul; Bellone, Donatela E; Tilley, T Don

    2015-10-14

    Artificial photosynthesis (AP) promises to replace society's dependence on fossil energy resources via conversion of sunlight into sustainable, carbon-neutral fuels. However, large-scale AP implementation remains impeded by a dearth of cheap, efficient catalysts for the oxygen evolution reaction (OER). Cobalt oxide materials can catalyze the OER and are potentially scalable due to the abundance of cobalt in the Earth's crust; unfortunately, the activity of these materials is insufficient for practical AP implementation. Attempts to improve cobalt oxide's activity have been stymied by limited mechanistic understanding that stems from the inherent difficulty of characterizing structure and reactivity at surfaces of heterogeneous materials. While previous studies on cobalt oxide revealed the intermediacy of the unusual Co(IV) oxidation state, much remains unknown, including whether bridging or terminal oxo ligands form O2 and what the relevant oxidation states are. We have addressed these issues by employing a homogeneous model for cobalt oxide, the [Co(III)4] cubane (Co4O4(OAc)4py4, py = pyridine, OAc = acetate), that can be oxidized to the [Co(IV)Co(III)3] state. Upon addition of 1 equiv of sodium hydroxide, the [Co(III)4] cubane is regenerated with stoichiometric formation of O2. Oxygen isotopic labeling experiments demonstrate that the cubane core remains intact during this stoichiometric OER, implying that terminal oxo ligands are responsible for forming O2. The OER is also examined with stopped-flow UV-visible spectroscopy, and its kinetic behavior is modeled, to surprisingly reveal that O2 formation requires disproportionation of the [Co(IV)Co(III)3] state to generate an even higher oxidation state, formally [Co(V)Co(III)3] or [Co(IV)2Co(III)2]. The mechanistic understanding provided by these results should accelerate the development of OER catalysts leading to increasingly efficient AP systems.

  6. High quality oxide films on substrates

    DOEpatents

    Ruckman, Mark W.; Strongin, Myron; Gao, Yong L.

    1994-01-01

    A method for providing an oxide film of a material on the surface of a substrate using a reactive deposition of the material onto the substrate surface in the presence of a solid or liquid layer of an oxidizing gas. The oxidizing gas is provided on the substrate surface in an amount sufficient to dissipate the latent heat of condensation occurring during deposition as well as creating a favorable oxidizing environment for the material.

  7. High quality oxide films on substrates

    DOEpatents

    Ruckman, M.W.; Strongin, M.; Gao, Y.L.

    1994-02-01

    A method is described for providing an oxide film of a material on the surface of a substrate using a reactive deposition of the material onto the substrate surface in the presence of a solid or liquid layer of an oxidizing gas. The oxidizing gas is provided on the substrate surface in an amount sufficient to dissipate the latent heat of condensation occurring during deposition as well as creating a favorable oxidizing environment for the material. 4 figures.

  8. Magnetic Property in large array cobalt antidot thin film using polymer-assisted nanosphere lithography

    NASA Astrophysics Data System (ADS)

    Lee, Wei-Li; Ho, Chi-Chih; Hsieh, Yung-Wu; Juan, Wen-Tau; Lin, Keng-Hui

    2010-03-01

    We have developed a new method to prepare monolayer of close- packed nanospheres (NSs) over large area onto a substrate of any kind utilizing polymer bridging effect. The NSs packing domain can be as large as 1 cmx1 cm which is demonstrated from its diffraction pattern. It was then used as a template to fabricate series of cobalt antidot thin films with different antidot diameter ranging from 100nm to 180nm. Because of the good periodicity and less defects in our nanostructured samples, we would be able to not only qualitatively study their magnetic properties but also quantitatively. As the antidot diameter increases, the surface to bulk volume fraction increases and the surface magnetism becomes more prominent. We found a systematic increase in magnetic coercivity with the antidote diameter, while the saturation magnetization drops at large antidote diameter. Detailed analysis and their implication will be discussed.

  9. Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

    NASA Astrophysics Data System (ADS)

    Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

    2013-12-01

    A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ˜550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ˜200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

  10. Sulfite oxidation catalyzed by cobalt ions in flue gas desulfurization processes.

    PubMed

    Karatza, Despina; Prisciandaro, Marina; Lancia, Amedeo; Musmarra, Dino

    2010-06-01

    This paper presents an experimental study of calcium bisulfite oxidation, a key step in the wet limestone-gypsum flue gas desulfurization (FGD) process, in the presence of catalysts (e.g., cobalt ions and a mixture of ferrous and cobalt ions). A fundamental approach is followed, by reproducing a simplified synthetic FGD liquor in which both catalyst ions, alone or mixed together, are present. A laboratory-scale apparatus is used, in which sulfurous solution is contacted with a gas phase at a fixed oxygen partial pressure (21.3 kPa) and at different temperature levels (25, 45, and 55 degrees C). The experimental results are analyzed using the theory of gas-liquid mass transfer with chemical reaction, showing that the slow reaction regime is explored and the transition from the kinetic to the diffusional subregime is identified. The experimental results are compared with those obtained in the presence of other catalytic species (manganese and ferrous ions), showing that cobalt is effective in catalyzing the oxidation of calcium bisulfite to sulfate, but to a minor extent with respect to iron and manganese.

  11. In situ observation of macroscopic phase separation in cobalt hexacyanoferrate film

    NASA Astrophysics Data System (ADS)

    Takachi, Masamitsu; Moritomo, Yutaka

    2017-02-01

    Lithium-ion secondary batteries (LIBs) store electric energy via Li+ deintercalation from cathode materials. The Li+ deintercalation frequently drives a first-order phase transition of the cathode material as a result of the Li-ordering or Li-concentration effect and causes a phase separation (PS) into the Li-rich and Li-poor phases. Here, we performed an in situ microscopic investigation of the PS dynamics in thin films of cobalt hexacyanoferrate, LixCo[Fe(CN)6]0.9, against Li+ deintercalation. The thick film (d = 1.5 μm) shows a characteristic macroscopic PS of several tens of μm into the green (Li1.6Co[Fe(CN)6]0.9) and black (Li.6Co[Fe(CN)6]0.9) phases in the x range of 1.0 < x < 1.6. Reflecting the substrate strain, the thin film (d = 0.5 μm) shows no trace of the PS in the entire x region. Our observation suggests that the macroscopic PS plays a significant role in the charge/discharge dynamics of the cathode.

  12. In situ observation of macroscopic phase separation in cobalt hexacyanoferrate film

    PubMed Central

    Takachi, Masamitsu; Moritomo, Yutaka

    2017-01-01

    Lithium-ion secondary batteries (LIBs) store electric energy via Li+ deintercalation from cathode materials. The Li+ deintercalation frequently drives a first-order phase transition of the cathode material as a result of the Li-ordering or Li-concentration effect and causes a phase separation (PS) into the Li-rich and Li-poor phases. Here, we performed an in situ microscopic investigation of the PS dynamics in thin films of cobalt hexacyanoferrate, LixCo[Fe(CN)6]0.9, against Li+ deintercalation. The thick film (d = 1.5 μm) shows a characteristic macroscopic PS of several tens of μm into the green (Li1.6Co[Fe(CN)6]0.9) and black (Li.6Co[Fe(CN)6]0.9) phases in the x range of 1.0 < x < 1.6. Reflecting the substrate strain, the thin film (d = 0.5 μm) shows no trace of the PS in the entire x region. Our observation suggests that the macroscopic PS plays a significant role in the charge/discharge dynamics of the cathode. PMID:28205619

  13. Phase formation, thermal stability and magnetic moment of cobalt nitride thin films

    SciTech Connect

    Gupta, Rachana; Pandey, Nidhi; Tayal, Akhil; Gupta, Mukul E-mail: dr.mukul.gupta@gmail.com

    2015-09-15

    Cobalt nitride (Co-N) thin films prepared using a reactive magnetron sputtering process are studied in this work. During the thin film deposition process, the relative nitrogen gas flow (R{sub N{sub 2}}) was varied. As R{sub N{sub 2}} increases, Co(N), Co{sub 4}N, Co{sub 3}N and CoN phases are formed. An incremental increase in R{sub N{sub 2}}, after emergence of Co{sub 4}N phase at R{sub N{sub 2}} = 10%, results in a linear increase of the lattice constant (a) of Co{sub 4}N. For R{sub N{sub 2}} = 30%, a maximizes and becomes comparable to its theoretical value. An expansion in a of Co{sub 4}N, results in an enhancement of the magnetic moment, to the extent that it becomes even larger than pure Co. Such larger than pure metal magnetic moment for tetra-metal nitrides (M{sub 4}N) have been theoretically predicted. Incorporation of N atoms in M{sub 4}N configuration results in an expansion of a (relative to pure metal) and enhances the itinerary of conduction band electrons leading to larger than pure metal magnetic moment for M{sub 4}N compounds. Though a higher (than pure Fe) magnetic moment for Fe{sub 4}N thin films has been evidenced experimentally, higher (than pure Co) magnetic moment is evidenced in this work.

  14. Tuning magnetic exchange interactions in crystalline thin films of substituted Cobalt Phthalocyanine

    NASA Astrophysics Data System (ADS)

    Rawat, Naveen; Manning, Lane; Hua, Kim-Ngan; Headrick, Randall; Bishop, Michael; McGill, Stephen; Waterman, Rory; Furis, Madalina

    Magnetic exchange interactions in diluted organometallic crystalline thin film alloys of Phthalocyanines (Pcs) made of a organo-soluble derivatives of Cobalt Pc and metal-free (H2Pc) molecule and is investigated. To this end, we synthesized a organosoluble CoPc and successfully employed a novel solution-based pen-writing deposition technique to fabricate long range ordered thin films of mixtures of different ratios ranging from 1:1 to 10:1 H2Pc:CoPc. Our previous magnetic circular dichroism (MCD) results on the parent CoPc crystalline thin films identified different electronic states mediating exchange interactions and indirect exchange interaction competing with superexchange interaction. This understanding of spin-dependent exchange interaction between delocalized π-electrons with unpaired d spins along with the excitonic delocalization character enabled the further tuning of these interactions by essentially varying the spatial distance between the spins. Furthermore, high magnetic field (B < 25 T) MCD and magneto-photoluminescence show evidence of spin-polarized band-edge excitons in the same materials. This work was possible due to support by the National Science Foundation, Division of Materials Research MRI, CAREER and EPM program Awards: DMR-0722451, DMR-0821268, DMR-1307017 and DMR-1056589, DMR-1229217.

  15. Influence of stoichiometry and charge state on the structure and reactivity of cobalt oxide clusters with CO.

    PubMed

    Johnson, Grant E; Reveles, J Ulises; Reilly, Nelly M; Tyo, Eric C; Khanna, Shiv N; Castleman, A W

    2008-11-13

    Cationic and anionic cobalt oxide clusters, generated by laser vaporization, were studied using guided-ion-beam mass spectrometry to obtain insight into their structure and reactivity with carbon monoxide. Anionic clusters having the stoichiometries Co2O3(-), Co2O5(-), Co3O5(-) and Co3O6(-) were found to exhibit dominant products corresponding to the transfer of a single oxygen atom to CO, indicating the formation of CO 2. Cationic clusters, in contrast, displayed products resulting from the adsorption of CO onto the cluster accompanied by the loss of either molecular O 2 or cobalt oxide units. In addition, collision induced dissociation experiments were conducted with N 2 and inert xenon gas for the anionic clusters, and xenon gas for the cationic clusters. It was found that cationic clusters fragment preferentially through the loss of molecular O 2 whereas anionic clusters tend to lose both atomic oxygen and cobalt oxide units. To further analyze how stoichiometry and ionic charge state influence the structure of cobalt oxide clusters and their reactivity with CO, first principles theoretical electronic structure studies within the density functional theory framework were performed. The calculations show that the enhanced reactivity of specific anionic cobalt oxides with CO is due to their relatively low atomic oxygen dissociation energy which makes the oxidation of CO energetically favorable. For cationic cobalt oxide clusters, in contrast, the oxygen dissociation energies are calculated to be even lower than for the anionic species. However, in the cationic clusters, oxygen is calculated to bind preferentially in a less activated molecular O 2 form. Furthermore, the CO adsorption energy is calculated to be larger for cationic clusters than for anionic species. Therefore, the experimentally observed displacement of weakly bound O 2 units through the exothermic adsorption of CO onto positively charged cobalt oxides is energetically favorable. Our joint

  16. Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes

    NASA Astrophysics Data System (ADS)

    Westerhaus, Felix A.; Jagadeesh, Rajenahally V.; Wienhöfer, Gerrit; Pohl, Marga-Martina; Radnik, Jörg; Surkus, Annette-Enrica; Rabeah, Jabor; Junge, Kathrin; Junge, Henrik; Nielsen, Martin; Brückner, Angelika; Beller, Matthias

    2013-06-01

    Molecularly well-defined homogeneous catalysts are known for a wide variety of chemical transformations. The effect of small changes in molecular structure can be studied in detail and used to optimize many processes. However, many industrial processes require heterogeneous catalysts because of their stability, ease of separation and recyclability, but these are more difficult to control on a molecular level. Here, we describe the conversion of homogeneous cobalt complexes into heterogeneous cobalt oxide catalysts via immobilization and pyrolysis on activated carbon. The catalysts thus produced are useful for the industrially important reduction of nitroarenes to anilines. The ligand indirectly controls the selectivity and activity of the recyclable catalyst and catalyst optimization can be performed at the level of the solution-phase precursor before conversion into the active heterogeneous catalyst.

  17. Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes.

    PubMed

    Westerhaus, Felix A; Jagadeesh, Rajenahally V; Wienhöfer, Gerrit; Pohl, Marga-Martina; Radnik, Jörg; Surkus, Annette-Enrica; Rabeah, Jabor; Junge, Kathrin; Junge, Henrik; Nielsen, Martin; Brückner, Angelika; Beller, Matthias

    2013-06-01

    Molecularly well-defined homogeneous catalysts are known for a wide variety of chemical transformations. The effect of small changes in molecular structure can be studied in detail and used to optimize many processes. However, many industrial processes require heterogeneous catalysts because of their stability, ease of separation and recyclability, but these are more difficult to control on a molecular level. Here, we describe the conversion of homogeneous cobalt complexes into heterogeneous cobalt oxide catalysts via immobilization and pyrolysis on activated carbon. The catalysts thus produced are useful for the industrially important reduction of nitroarenes to anilines. The ligand indirectly controls the selectivity and activity of the recyclable catalyst and catalyst optimization can be performed at the level of the solution-phase precursor before conversion into the active heterogeneous catalyst.

  18. Synthesis of silicon nanotubes with cobalt silicide ends using anodized aluminum oxide template

    NASA Astrophysics Data System (ADS)

    Zhang, Zhang; Liu, Lifeng; Shimizu, Tomohiro; Senz, Stephan; Gösele, Ulrich

    2010-02-01

    Silicon nanotubes (SiNTs) are compatible with Si-based semiconductor technology. In particular, the small diameters and controllable structure of such nanotubes are remaining challenges. Here we describe a method to fabricate SiNTs intrinsically connected with cobalt silicide ends based on highly ordered anodic aluminum oxide (AAO) templates. Size and growth direction of the SiNTs can be well controlled via the templates. The growth of SiNTs is catalyzed by the Co nanoparticles reduced on the pore walls of the AAO after annealing, with a controllable thickness at a given growth temperature and time. Simultaneously, cobalt silicide forms on the bottom side of the SiNTs.

  19. Supported cobalt oxide on graphene oxide: highly efficient catalysts for the removal of Orange II from water.

    PubMed

    Shi, Penghui; Su, Ruijing; Zhu, Shaobo; Zhu, Mincong; Li, Dengxin; Xu, Shihong

    2012-08-30

    The current paper investigated the removal of the azo dye Orange II from water using advanced oxidation processes based on sulfate radicals. The cobalt oxide catalyst immobilized on graphene oxide (GO) can activate peroxymonosulfate (PMS) for the degradation of Orange II in water. The Co(3)O(4)/GO catalyst system was characterized via X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and X-ray spectroscopy. Results showed that Co(3)O(4) was distributed on GO. The Co(3)O(4)/GO catalyst system exhibited high activity in Orange II oxidation when the Co(3)O(4)/GO catalyst has an optimum Co(3)O(4) loading. In addition, 100% decomposition could be achieved within 6 min with 0.2mM Orange II, 0.1 g L(-1) catalyst, and 2mM PMS. Meanwhile, inductively coupled plasma analysis revealed that the leach of cobalt ions was low. The catalyst also exhibited stable performance after several rounds of regeneration. Several operational parameters, such as catalyst amount, oxidant amount, pH, temperature, and oxidation rate, affected the degradation of Orange II. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Nickel hydroxide/cobalt-ferrite magnetic nanocatalyst for alcohol oxidation.

    PubMed

    Bhat, Pooja B; Inam, Fawad; Bhat, Badekai Ramachandra

    2014-08-11

    A magnetically separable, active nickel hydroxide (Brønsted base) coated nanocobalt ferrite catalyst has been developed for oxidation of alcohols. High surface area was achieved by tuning the particle size with surfactant. The surface area of 120.94 m2 g(-1) has been achieved for the coated nanocobalt ferrite. Improved catalytic activity and selectivity were obtained by synergistic effect of transition metal hydroxide (basic hydroxide) on nanocobalt ferrite. The nanocatalyst oxidizes primary and secondary alcohols efficiently (87%) to corresponding carbonyls in good yields.

  1. Scanning tunneling microscopy study of the structure and orbital-mediated tunneling spectra of cobalt(II) phthalocyanine and cobalt(II) tetraphenylporphyrin on au(111): mixed composition films.

    PubMed

    Barlow, Dan E; Scudiero, L; Hipps, K W

    2004-05-25

    Binary thin films of cobalt(II) phthalocyanine (CoPc) and cobalt(II) tetraphenylporphyrin (CoTPP) were prepared at submonolayer coverage on Au(111)/mica substrates byvapor deposition. All sample preparation and analysis were done under an ultrahigh vacuum. Scanning tunneling microscopy (STM) constant-current images of CoPc/CoTPP mixtures showed two close-packed surface structures, with different compositional percentages and some disorder. CoPc was also observed exclusively in one-dimensional chains and as single, isolated molecules below 220 K. Occupied and unoccupied orbital energy levels were identified by STM and tunnel-diode-based orbital-mediated tunneling spectroscopy. Occupied energy levels were also confirmed by ultraviolet photoelectron spectroscopy. The transient oxidation of the Co d(z2) orbital is identified in STM dI/dV(V) curves just negative of the 0 V sample bias for both molecules. Nearly identical constant-current contours are observed over the central Co2+ ions of CoTPP and CoPc, indicating that the attenuation of the d(z)2 orbital-mediated tunneling current induced by the structure of TPP relative to Pc is at most a factor of about 10. The orbital-mediated tunneling spectra of CoTPP and CoPc are distinctly different and allow these structurally similar species to be differentially identified.

  2. Perpendicular magnetic anisotropy in epitaxially strained cobalt-ferrite (001) thin films

    SciTech Connect

    Yanagihara, H. Utsumi, Y.; Niizeki, T. Inoue, J.; Kita, Eiji

    2014-05-07

    We investigated the dependencies of both the magnetization characteristics and the perpendicular magnetic anisotropy of Co{sub x}Fe{sub 3–x}O{sub 4}(001) epitaxial films (x = 0.5 and 0.75) on the growth conditions of the reactive magnetron sputtering process. Both saturation magnetization and the magnetic uniaxial anisotropy constant K{sub u} are strongly dependent on the reactive gas (O{sub 2}) flow rate, although there is little difference in the surface structures for all samples observed by reflection high-energy electron diffraction. In addition, certain dead-layer-like regions were observed in the initial stage of the film growth for all films. Our results suggest that the magnetic properties of Co{sub x}Fe{sub 3–x}O{sub 4} epitaxial films are governed by the oxidation state and the film structure at the vicinity of the interface.

  3. Sol-gel derived mesoporous cobalt silica catalyst: Synthesis, characterization and its activity in the oxidation of phenol

    NASA Astrophysics Data System (ADS)

    Andas, Jeyashelly; Adam, Farook; Rahman, Ismail Ab.

    2014-10-01

    Highly mesoporous cobalt silica rice husk catalysts with (5-15 wt.%) Co2+ loading were prepared via a simple sol-gel technique at room temperature. The successful insertion of cobalt ions into silica matrix was evidenced from FT-IR, NMR, XPS and AAS analyses. Preservation of the mesoporosity nature of silica upon incorporating Co2+ was confirmed from the N2-sorption studies. The topography and morphology viewed by TEM analysis differs as the cobalt concentration varies from 5 to 15 wt.%. Parallel pore channels and spherical nanoparticles of 9.44 nm were achieved for cobalt silica catalysts with 10 and 15 wt.% respectively. Cobalt catalysts were active in the liquid-phase oxidation of phenol with H2O2 as an oxygen source. The performances of the catalysts were greatly influenced by various parameters such as reaction temperature, catalyst amount, molar ratio of substrate to oxidant, nature of solvent, metal loading and homogeneous precursor salt. Water served as the best reaction medium for this oxidation system. The regeneration studies confirmed cobalt catalyst could be reused for five cycles without experiencing large loss in the conversion. Both leaching and reusability studies testified that the catalysts were truly heterogeneous.

  4. Size- and Support-Dependent Evolution of the Oxidation State and Structure by Oxidation of Subnanometer Cobalt Clusters

    SciTech Connect

    Yin, Chunrong; Zheng, Fan; Lee, Sungsik; Guo, Jinghua; Wang, Wei-Cheng; Kwon, Gihan; Vajda, Viktor; Wang, Hsien-Hau; Lee, Byeongdu; DeBartolo, Janae; Seifert, Sönke; Winans, Randall E.; Vajda, Stefan

    2014-09-18

    Size-selected subnanometer cobalt clusters with 4, 7 and 27 cobalt atoms supported on amorphous alumina and ultrananocrystalline diamond (UNCD) surfaces were oxidized after exposure to ambient air. Grazing incidence X-ray absorption near edge spectroscopy (GIXANES) and near edge X-ray absorption fine structure (NEXAFS) used to characterize the clusters revealed a strong dependency of the oxidation state and structure of the clusters on the surface. A dominant Co2+ phase was identified in all samples. However, form XANES analysis, on UNCD about 10% fraction of Co0 phase was identified for all three cluster sizes and about 30% and 12% fraction of Co3+ phase in 4, 7 and 27 atoms, respectively. In the alumina-supported clusters, the dominating Co2+ component was attributed to cobalt aluminate, indicative of a very strong binding to the support. NEXAFS showed that in addition to strong binding of the clusters to alumina, their structure in great extent follows the tetrahedral morphology of the support. The supported clusters of all three sizes were found resistant to agglomeration when exposed to reactive gases at elevated temperatures and atmospheric pressure.

  5. Theoretical Investigation of Supported Utra-Thin Cobalt/Nickel/Iron/Manganese Oxides

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; García Melchor, Max; Vojvodic, Alexandra

    In the last decade, a number of experiments have shown that ultra-thin layers of transition metal oxides (TMOs) can be stabilized when interfaced with precious metal supports such as Au(111) and Pt(111) or Ir(100). Moreover, gold supported Co/Ni/Mn-based catalysts have been experimentally proven to exhibit higher oxygen evolution reaction (OER) activities than other metal supported oxide catalysts. However, the synergistic effect of contact with gold support is yet to be fully understood. In this talk, I will report on our recent investigation of thermodynamic stability and and high water reactivity of ultra-thin cobalt oxide nanoislands supported on Au(111). Furthermore, the stability trends, scaling of the metal-support interaction and charge transfer of several Mn/Fe/Co/Ni supported oxides on all FCC(111) metals will be analyzed. The type and role of different edge sites for the OER activity of these nanoislands will be discussed.

  6. Template-free hydrothermal derived cobalt oxide nanopowders: Synthesis, characterization, and removal of organic dyes

    SciTech Connect

    Nassar, Mostafa Y.; Ahmed, Ibrahim S.

    2012-09-15

    Graphical abstract: XRD patterns of the products obtained by hydrothermal treatment at 160 °C for 24 h, and at different [Co{sup 2+}]/[CO{sub 3}{sup 2−}] ratios: (a) 1:6, (b) 1:3, (c) 1:1.5, (d) 1:1, (e) 1:0.5. Highlights: ► Spinel cobalt oxide nanoparticles with different morphologies were prepared by hydrothermal approach. ► The optical characteristics of the as-prepared cobalt oxide revealed the presence of two band gaps. ► Adsorption of methylene blue dye on Co{sub 3}O{sub 4} was investigated and the percent uptake was found to be >99% in 24 h. -- Abstract: Pure spinel cobalt oxide nanoparticles were prepared through hydrothermal approach using different counter ions. First, the pure and uniform cobalt carbonate (with particle size of 21.8–29.8 nm) were prepared in high yield (94%) in an autoclave in absence unfriendly organic surfactants or solvents by adjusting different experimental parameters such as: pH, reaction time, temperature, counter ions, and (Co{sup 2+}:CO{sub 3}{sup 2−}) molar ratios. Thence, the spinel Co{sub 3}O{sub 4} (with mean particle size of 30.5–47.35 nm) was produced by thermal decomposition of cobalt carbonate in air at 500 °C for 3 h. The products were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), transmission electron microscope (TEM), scanning electron microscope (SEM), and thermal analysis (TA). Also, the optical characteristics of the as-prepared Co{sub 3}O{sub 4} nanoparticles revealed the presence of two band gaps (1.45–1.47, and 1.83–1.93 eV). Additionally, adsorption of methylene blue dye on Co{sub 3}O{sub 4} nanoparticles was investigated and the uptake% was found to be >99% in 24 h.

  7. Microbially mediated cobalt oxidation in seawater revealed by radiotracer experiments

    SciTech Connect

    Lee, B.G.; Fisher, N.S. )

    1993-12-01

    The influence of microbial activity on Co and Mn oxidation in decomposing diatom cultures was determined with radiotracer techniques. Adding a consortium of microorganisms collected from coastal seawater (0.2-3-[mu]m size fraction) to the cultures increased particulate Co formation rates at 18[degrees]C by an order of magnitude (to 3.8% d[sup [minus]1]) and particulate Mn formation rates 3-fold (to 7.9% d[sup [minus

  8. Toxicity of cobalt oxide nanoparticles to normal cells; an in vitro and in vivo study.

    PubMed

    Chattopadhyay, Sourav; Dash, Sandeep Kumar; Tripathy, Satyajit; Das, Balaram; Mandal, Debasis; Pramanik, Panchanan; Roy, Somenath

    2015-01-25

    The aim of this study was to find out the intracellular signaling transduction pathways involved in cobalt oxide nanoparticles (CoO NPs) mediated oxidative stress in vitro and in vivo system. Cobalt oxide nanoparticles released excess Co++ ions which could activated the NADPH oxidase and helps in generating the reactive oxygen species (ROS). Our results showed that CoO NPs elicited a significant (p<0.05) amount of ROS in lymphocytes. In vitro pretreatment with N-acetylene cystine had a protective role on lymphocytes death induced by CoO NPs. In vitro and in vivo results showed the elevated level of TNF-α after CoO NPs treatment. This TNF-α phosphorylated the p38 mitogen-activated protein kinase followed by activation of caspase 8 and caspase 3 which could induce cell death. This study showed that CoO NPs induced oxidative stress and activated the signaling pathway of TNF-α-caspase-8-p38-caspase-3 to primary immune cells. This study suggested that bare CoO NPs are a toxic for primary human immune cells that deals directly with human health. Surface modification or surface functionalization may open the gateway for further use of CoO NPs in different industrial use or in biomedical sciences. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  9. A novel bioelectrochemical sensing platform based on covalently attachment of cobalt phthalocyanine to graphene oxide.

    PubMed

    Hosseini, Hadi; Mahyari, Mojtaba; Bagheri, Akbar; Shaabani, Ahmad

    2014-02-15

    Graphene oxide-cobalt phthalocyanine (GO-PcCo) hybrid material as a new electrocatalyst was synthesized and used successfully to fabrication of new biosensor for the electrooxidation of l-cysteine (CSH) in aqueous media. Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) images revealed that cobalt phthalocyanine is covalently attachment on graphene oxide sheets as single layers GO-PcCo. Cyclic voltammetric studies showed that the GO-PcCo/glassy carbon electrode (GO-PcCo/GCE) improves electrochemical behavior of CSH oxidation, as compared to the GO and PcCo. In addition, the results indicated that GO and PcCo have a synergic effect in the electrooxidation of CSH. The catalytic oxidation responses were studied and the reaction mechanisms were discussed. The electrocatalytic behavior is further developed as a new detection scheme for CSH by chronoamperometry method and under optimized conditions, excellent analytical features, including high sensitivity and selectivity, low detection limit and satisfactory dynamic range, were achieved.

  10. Ascorbic Acid Assisted Synthesis of Cobalt Oxide Nanostructures, Their Electrochemical Sensing Application for the Sensitive Determination of Hydrazine

    NASA Astrophysics Data System (ADS)

    Tahira, Aneela; Nafady, Ayman; Baloach, Quarratulain; Sirajuddin; Sherazi, Syed Tufail Hussain; Shaikh, Tayyaba; Arain, Munazza; Willander, Magnus; Ibupoto, Zafar Hussain

    2016-07-01

    This study describes, the synthesis of cobalt oxide nanostructures using ascorbic acid as a growth directing agent by the hydrothermal method. Ascorbic acid is used for the first time for the synthesis of cobalt oxide nanostructures and a unique morphology is prepared in the present study. The cobalt oxide nanostructures were characterized by scanning electron microcopy, x-ray diffraction, and x-ray photoelectron spectroscopy techniques. These analytical techniques demonstrated well defined morphology, good crystalline quality, and high purity of as prepared cobalt oxide nanostructures. The glassy carbon electrode was modified with cobalt oxide nanostructures for the development of a sensitive and selective electrochemical hydrazine sensor. The developed hydrazine sensor exhibits a linear range of 2-24 μM. The sensitivity and limit of detection of presented hydrazine sensors are 12,734 μA/mM/cm2 and 0.1 μM respectively. The developed hydrazine sensor is highly selective, stable, and reproducible. The proposed sensor is successfully applied for the detection of hydrazine from different water samples. The present study provides the development of an alternative tool for the reliable monitoring of hydrazine from environmental and biological samples.

  11. Activation of Molecular Oxygen: Kinetic Studies of the Oxidation of Hindered Phenols with Cobalt-Dioxygen Complexes.

    DTIC Science & Technology

    1981-07-25

    containing nucleophiles on coordinated substrates; (3) oxygen atom transfers from high oxidation state elements; (4) epoxidation of olefins using metal...or polymers, depending -2- on the choice of catalyst or reagent. The oxidation of hindered phenols by cobalt- salen -dioxygen complexes was first

  12. Comparative analysis of cobalt oxide nanoisland stability and edge structures on three related noble metal surfaces: Au(111), Pt(111) and Ag(111)

    DOE PAGES

    Fester, Jakob; Bajdich, Michal; Walton, Alex S.; ...

    2016-09-12

    Here, metal oxide nanostructures and thin films grown on metallic substrates have attracted strong attention as model catalysts and as interesting inverse catalyst systems in their own right. In this study, we investigate the role of metal support in the growth and stabilization of cobalt oxide nanostructures on the three related (111) surfaces of Au, Pt and Ag, as investigated by means of high-resolution scanning tunneling microscopy and DFT calculations. All three substrates promote the growth of crystalline CoOx (x = 1–2) islands under oxidative conditions, but we find several noteworthy differences in the occurrence and stabilization of four distinctmore » cobalt oxide island phases: Co–O bilayers, O–Co–O trilayers, Co–O–Co–O double bilayers and O–Co–O–Co–O multilayers. Using atom-resolved images combined with analysis of defect lines in bilayer islands on Au and Pt, we furthermore unambiguously determine the edge structure. Interestingly, the island shape and abundances of edge types in bilayers change radically from mixed Co/O edge terminations on Au(111) to a predominance of Co terminated edges (~91 %) on Pt(111) which is especially interesting since the Co metal edges are expected to host the most active sites for water dissociation.« less

  13. Comparative analysis of cobalt oxide nanoisland stability and edge structures on three related noble metal surfaces: Au(111), Pt(111) and Ag(111)

    SciTech Connect

    Fester, Jakob; Bajdich, Michal; Walton, Alex S.; Sun, Z.; Plessow, Philipp N.; Vojvodic, Aleksandra; Lauritsen, Jeppe V.

    2016-09-12

    Here, metal oxide nanostructures and thin films grown on metallic substrates have attracted strong attention as model catalysts and as interesting inverse catalyst systems in their own right. In this study, we investigate the role of metal support in the growth and stabilization of cobalt oxide nanostructures on the three related (111) surfaces of Au, Pt and Ag, as investigated by means of high-resolution scanning tunneling microscopy and DFT calculations. All three substrates promote the growth of crystalline CoOx (x = 1–2) islands under oxidative conditions, but we find several noteworthy differences in the occurrence and stabilization of four distinct cobalt oxide island phases: Co–O bilayers, O–Co–O trilayers, Co–O–Co–O double bilayers and O–Co–O–Co–O multilayers. Using atom-resolved images combined with analysis of defect lines in bilayer islands on Au and Pt, we furthermore unambiguously determine the edge structure. Interestingly, the island shape and abundances of edge types in bilayers change radically from mixed Co/O edge terminations on Au(111) to a predominance of Co terminated edges (~91 %) on Pt(111) which is especially interesting since the Co metal edges are expected to host the most active sites for water dissociation.

  14. Copper Zinc Cobalt Aluminium Chromium Hydroxycarbonates and Mixed Oxides

    NASA Astrophysics Data System (ADS)

    Morpurgo, Simone; Jacono, Mariano Lo; Porta, Piero

    1996-03-01

    Hydroxycarbonate precursors with different Cu/Zn/Co/Al/Cr atomic ratios were prepared by coprecipitation of the metal nitrates with a stoichiometric amount of NaHCO3under controlled conditions of temperature, stirring, and pH. Cu-Zn-Co-Al-Cr mixed oxides were obtained by decomposition of the precursors at different temperatures (623, 723, and 973 K in air). The characterization has been performed by X-ray powder diffraction (XRPD), diffuse reflectance spectroscopy in the UV-VIS-NIR region (DRS), thermal analysis (TGA/DTA), BET surface area determination, and measurements of magnetic susceptibility. The XRPD patterns show that the precursors are quasi-amorphous layered double hydroxides (LDHs or hydrotalcite-like materials with the general stoichiometric formula:MII6MIII2(OH)16CO3· 4H2O, whereMII= Cu, Zn, Co andMIII= Al, Cr) containing a variable amount of Cu2(OH)2CO3(malachite). The thermal decomposition of the precursors occurred through complete dehydration of the sample (up toT= 573 K) and further release of CO2(up toT= 773 K). The decomposition of Cu2(OH)2CO3occurred in a single step at about 653 K. The mixed oxides obtained by calcination of the precursors at 623 K were poorly crystalline materials. Crystalline oxide mixtures containing CuO, ZnO, and spinels as ZnCr2O4, ZnCo2O4, ZnAl2O4, and Co3O4in a solid solution were formed only at 973 K, after complete release of CO2.

  15. Cobalt vanadium oxide thin nanoplates: primary electrochemical capacitor application

    PubMed Central

    Zhang, Youjuan; Liu, Yuanying; Chen, Jing; Guo, Qifei; Wang, Ting; Pang, Huan

    2014-01-01

    Co3V2O8 thin nanoplates are firstly described as a kind of electrode material for supercapacitors. More importantly, from electrochemical measurements, the obtained Co3V2O8 nanoplate electrode shows a good specific capacitance (0.5 A g−1, 739 F g−1) and cycling stability (704 F g−1 retained after 2000 cycles). This study essentially offers a new kind of metal vanadium oxides as electrochemical active material for the development of supercapacitors. PMID:25023373

  16. Contrasting magnetism in dilute and supersaturated cobalt-fullerene mixture films

    NASA Astrophysics Data System (ADS)

    Lavrentiev, V.; Stupakov, A.; Pokorný, J.; Lavrentieva, I.; Vacik, J.; Dejneka, A.; Barchuk, M.; Čapková, P.

    2015-08-01

    The combination of cobalt with nanocarbons promises hybrid nanostructures that are ideal for the development of memory storage and spin-transfer electronics. Here, we report a dramatic effect of composition on the magnetic properties of the Co x C60 mixtures, whose nanostructure was organized upon simultaneous deposition and sequential exposure to air. We assert a critical change in the mixture’s organization yielding either the composite nanostructure as array of the Co/CoO core-shell nanoparticles (NPs) in the C60-based matrix at a high content of Co (a supersaturated mixture or SSM) or a coexistence of fcc-C60 and CoaC60 fulleride when the Co content x is lower than some critical value {{x}\\text{c}} (an ultradilute mixture or UDM). Magnetization of the SSM composite exhibits a superparamagnetic effect caused by the small Co/CoO NPs. Similar magnetization of the UDM with x=0.7 revealed a stable ferromagnetism and evidenced the formation of a magnetic Co2C60 fulleride. Phase composition in the UDM and SSM films was verified with the XRD and Raman spectra. The UDM and SSM films reveal great difference in content of the remaining oxygen which implies easy diffusion of O2 molecules within the C60-based phases and their splitting at the Co NP surface followed by formation of CoO shells. The results obtained indicate controlled access to a variety of promising Co-C60 magnetic nanostructures.

  17. Molecular and thin film properties of cobalt half-sandwich compounds for optoelectronic application.

    PubMed

    Reinhardt, Maxwell; Dalgleish, Simon; Shuku, Yoshiaki; Reissig, Louisa; Matsushita, Michio M; Crain, Jason; Awaga, Kunio; Robertson, Neil

    2017-03-01

    The structure and electronic properties of a novel cobalt half sandwich complex of cyclopentadiene (Cp) and diaminonaphthalene (DAnap) [CpCo(DAnap)] are described and compared to the previously reported diaminobenzene derivative [CpCo(DAbnz)] in view of their potential for (opto)electronic device application. Both complexes show stable redox processes, tunable through the diaminoacene ligand, and show strong absorption in the visible region, with additional transitions stretching into the near infrared (NIR). CpCo(DAnap) crystallises with a particularly large unit cell (9301 Å(3)), comprising 32 molecules, with a gradual rotation over 8 molecules along the long c-axis. In the solid state the balance of the optical transitions in both complexes is reversed, with a suppression of the visible band and an enhancement of the NIR band, attributed to extensive intermolecular electronic interaction. In the case of CpCo(DAnap), highly crystalline thin films could be formed under physical vapor deposition, which show a photocurrent response stretching into the NIR, and p-type semiconductor behavior in field effect transistors with mobility values of the order 1 × 10(-4) cm(2) V(-1) s(-1). The device performance is understood through investigation of the morphology of the grown films.

  18. Estimation of magnetocrystalline anisotropy of cobalt films deposited at oblique incidence

    NASA Astrophysics Data System (ADS)

    Okamoto, K.; Itoh, K.; Hashimoto, T.

    1990-07-01

    The magnetocrystalline anisotropy of obliquely deposited cobalt films prepared at a wide substrate temperature Ts range (from 94 to 473 K) was estimated on the basis of the distribution function of the c-axis which could be obtained in the process of analyzing the texture. The incidence angle was 60° and the pressure during deposition was 4.0 × 10 -3 Pa. The estimation of anisotropy was made in both the film plane and the incidence plane of the vapor beam. In both cases the maximum value of the anisotropy field is the order of 10 5 A/m. With respect to the in-plane anisotropy field the anisotropy field determined by the torque measurement was separated into the shape anisotropy part due to the columnar structure and the magnetocrystalline anisotropy part due to the texture. From the shape anisotropy part it is possible to judge the bundle formation of columnar grains along the direction perpendicular to the incidence plane in the Ts range below about 280 K.

  19. Perovskite substrates boost the thermopower of cobaltate thin films at high temperatures

    NASA Astrophysics Data System (ADS)

    Yordanov, P.; Wochner, P.; Ibrahimkutty, S.; Dietl, C.; Wrobel, F.; Felici, R.; Gregori, G.; Maier, J.; Keimer, B.; Habermeier, H.-U.

    2017-06-01

    Transition metal oxides are promising candidates for thermoelectric applications, because they are stable at high temperature and because strong electronic correlations can generate large Seebeck coefficients, but their thermoelectric power factors are limited by the low electrical conductivity. We report transport measurements on Ca3Co4O9 films on various perovskite substrates and show that reversible incorporation of oxygen into SrTiO3 and LaAlO3 substrates activates a parallel conduction channel for p-type carriers, greatly enhancing the thermoelectric performance of the film-substrate system at temperatures above 450 °C. Thin-film structures that take advantage of both electronic correlations and the high oxygen mobility of transition metal oxides thus open up new perspectives for thermopower generation at high temperature.

  20. Glutamine is highly effective in preventing in vivo cobalt-induced oxidative stress in rat liver

    PubMed Central

    Gonzales, Soledad; Polizio, Ariel H.; Erario, María A.; Tomaro, María L.

    2005-01-01

    AIM: To evaluate the in vivo effect of glutamine on cobalt-generated oxidative stress and (HO-1) induction in rat liver. METHODS: Fasted female Wistar rats received a single injection of cobalt chloride (375 µmol/kg body weight) and then were killed at different times. Lipid peroxidation and soluble and enzymatic antioxidant defense system (reduced glutathione (GSH), catalase (CAT), glutathione peroxidase (GSH-Px) and superoxide dismutase (SOD)) were measured in liver homogenates. Ferritin and ferritin iron contents as well as heme oxygenase-1 (HO-1) activity and expression were also determined. The antioxidant properties of glutamine (Gln) were also evaluated. RESULTS: Cobalt chloride increased lipid peroxidation (50% over control values) 1 h after treatment. GSH reached a minimum at 3 h (40%) increasing thereafter. Twelve hours after CoCl2 injection, the antioxidant enzymes CAT, GSH-Px and SOD also diminished by about 30%. Heme oxygenase-1 induction was observed 6 h after treatment reaching a maximum value of 14-fold over the controls, 12 h after cobalt treatment. A 1.7-fold increase in ferritin and ferritin-bound iron 24 h after treatment were also obtained. Administration of glutamine (300 mg/kg body weight) by gavage 24 h before CoCl2 treatment entirely prevented the increase in thiobarbituric acid reactive substances (TBARS) content, the decrease in GSH levels, and partially reverted heme oxygenase-1 induction. CONCLUSION: These results suggested that a natural product such as glutamine prevents glutathione depletion and consequently heme oxygenase induction. PMID:15962369

  1. The Structure and Properties of Plasma Sprayed Iron Oxide Doped Manganese Cobalt Oxide Spinel Coatings for SOFC Metallic Interconnectors

    NASA Astrophysics Data System (ADS)

    Puranen, Jouni; Lagerbom, Juha; Hyvärinen, Leo; Kylmälahti, Mikko; Himanen, Olli; Pihlatie, Mikko; Kiviaho, Jari; Vuoristo, Petri

    2011-01-01

    Manganese cobalt oxide spinel doped with Fe2O3 was studied as a protective coating on ferritic stainless steel interconnects. Chromium alloying causes problems at high operation temperatures in such oxidizing conditions where chromium compounds evaporate and poison the cathode active area, causing the degradation of the solid oxide fuel cell. In order to prevent chromium evaporation, these interconnectors need a protective coating to block the chromium evaporation and to maintain an adequate electrical conductivity. Thermal spraying is regarded as a promising way to produce dense and protective layers. In the present work, the ceramic Mn-Co-Fe oxide spinel coatings were produced by using the atmospheric plasma spray process. Coatings with low thickness and low amount of porosity were produced by optimizing deposition conditions. The original spinel structure decomposed because of the fast transformation of solid-liquid-solid states but was partially restored by using post-annealing treatment.

  2. Chemical vapor deposition of low reflective cobalt (II) oxide films

    NASA Astrophysics Data System (ADS)

    Amin-Chalhoub, Eliane; Duguet, Thomas; Samélor, Diane; Debieu, Olivier; Ungureanu, Elisabeta; Vahlas, Constantin

    2016-01-01

    Low reflective CoO coatings are processed by chemical vapor deposition from Co2(CO)8 at temperatures between 120 °C and 190 °C without additional oxygen source. The optical reflectivity in the visible and near infrared regions stems from 2 to 35% depending on deposition temperature. The combination of specific microstructural features of the coatings, namely a fractal ⿿cauliflower⿿ morphology and a grain size distribution more or less covering the near UV and IR wavelength ranges enhance light scattering and gives rise to a low reflectivity. In addition, the columnar morphology results in a density gradient in the vertical direction that we interpret as a refractive index gradient lowering reflectivity further down. The coating formed at 180 °C shows the lowest average reflectivity (2.9%), and presents an interesting deep black diffuse aspect.

  3. Influence of Cr doping on the stability and structure of small cobalt oxide clusters

    SciTech Connect

    Tung, Nguyen Thanh; Lievens, Peter; Janssens, Ewald; Tam, Nguyen Minh; Nguyen, Minh Tho

    2014-07-28

    The stability of mass-selected pure cobalt oxide and chromium doped cobalt oxide cluster cations, Co{sub n}O{sub m}{sup +} and Co{sub n−1}CrO{sub m}{sup +} (n = 2, 3; m = 2–6 and n = 4; m = 3–8), has been investigated using photodissociation mass spectrometry. Oxygen-rich Co{sub n}O{sub m}{sup +} clusters (m ⩾ n + 1 for n = 2, 4 and m ⩾ n + 2 for n = 3) prefer to photodissociate via the loss of an oxygen molecule, whereas oxygen poorer clusters favor the evaporation of oxygen atoms. Substituting a single Co atom by a single Cr atom alters the dissociation behavior. All investigated Co{sub n−1}CrO{sub m}{sup +} clusters, except CoCrO{sub 2}{sup +} and CoCrO{sub 3}{sup +}, prefer to decay by eliminating a neutral oxygen molecule. Co{sub 2}O{sub 2}{sup +}, Co{sub 4}O{sub 3}{sup +}, Co{sub 4}O{sub 4}{sup +}, and CoCrO{sub 2}{sup +} are found to be relatively difficult to dissociate and appear as fragmentation product of several larger clusters, suggesting that they are particularly stable. The geometric structures of pure and Cr doped cobalt oxide species are studied using density functional theory calculations. Dissociation energies for different evaporation channels are calculated and compared with the experimental observations. The influence of the dopant atom on the structure and the stability of the clusters is discussed.

  4. Influence of laser-generated surface structures on electrochemical performance of lithium cobalt oxide

    NASA Astrophysics Data System (ADS)

    Kohler, R.; Proell, J.; Ulrich, S.; Przybylski, M.; Seifert, H. J.; Pfleging, W.

    2012-03-01

    The further development of energy storage devices especially of lithium-ion batteries plays an important role in the ongoing miniaturization process towards lightweight, flexible mobile devices. To improve mechanical stability and to increase the power density of electrode materials while maintaining the same footprint area, a three-dimensional battery design is necessary. In this study different designs of three-dimensional cathode materials are investigated with respect to the electrochemical performance. Lithium cobalt oxide is considered as a standard cathode material, since it has been in use since the first commercialization of lithium-ion batteries. Various electrode designs were manufactured in lithium cobalt oxide electrodes via laser micro-structuring. Laser ablation experiments in ambient air were performed to obtain hierarchical and high aspect surface structures. Laser structuring using mask techniques as well as the formation of self-organized conical surface structures were studied in detail. In the latter case a density of larger than twenty million microstructures per square centimeter was obtained with a significant increase of active surface area. Laser annealing was applied for the control of the average grain size and the adjustment of a crystalline phase which exhibits electrochemical capacities in the range of the practical capacity known for lithium cobalt oxide. An investigation of cycling stability with respect to annealing parameters such as annealing time and temperature was performed using a diode laser operating at 940 nm. Information on the phase and crystalline structure were obtained using Raman spectroscopy and X-ray diffraction analysis. The electrochemical performance of the laser modified cathodes was studied via cyclic voltammetry and galvanostatic testing using a lithium anode and a standard liquid electrolyte.

  5. High-pressure and high-temperature equation of state of cobalt oxide: Implications for redox relations in Earth's mantle

    SciTech Connect

    Armentrout, Matthew M.; Rainey, Emma S.G.; Kavner, Abby

    2013-07-30

    The high-pressure and high-temperature equation of state of rock salt-structured cobalt oxide was measured up to 65 GPa and 2600 K using synchrotron X-ray diffraction in conjunction with the laser heated diamond-anvil cell. Fitting a Mie-Grüneisen-Debye model to the data we find best-fit parameters V0 = 77.4 (fixed) Å3, K0 = 190 (1) GPa, K' = 3.49 (4), γ0 = 1.54 (4), q = 2.87 (15), and θ0 = 517.8 K (fixed). We use this newly determined equation of state in conjunction with existing measurements of the thermoelastic parameters of cobalt metal to calculate the Gibbs free-energy difference between the cobalt oxide and cobalt metal phases as a function of pressure and temperature. A comparison of the energetics of the Co/CoO system with the Ni/NiO system predicts that below 58 GPa CoO+Ni is stable relative to NiO+Co, while above 58 GPa the reverse is true. This tipping point in energy can be mapped as a crossing point in the electrochemical potential of the two metal ions, suggesting that cobalt becomes more siderophile than nickel with increasing pressure. This result is in qualitative agreement with existing measurements of nickel and cobalt partition coefficients between mantle and core materials.

  6. Structure and characteristics of chitosan cobalt-containing hybrid systems, the catalysts of olefine oxidation

    NASA Astrophysics Data System (ADS)

    Mekhaev, A. V.; Pestov, A. V.; Molochnikov, L. S.; Kovaleva, E. G.; Pervova, M. G.; Yaltuk, Yu. G.; Grigor'ev, I. A.; Kirilyuk, I. A.

    2011-07-01

    Cobalt-containing hybrid organo-inorganic materials based on the chitosan-SiO2, chitosan-Al2O3, and chitosan-cellulose systems were obtained. The surface structure and processes that occur during the formation of metal-containing materials, the catalytic properties of which were studied in the oxidation reactions of alkene, were investigated by EPR spectroscopy using a stable pH-sensitive nitroxyl radical, 4-dimethylamino-2-ethyl-5,5-dimethyl-2-(pyridin-4-yl)-2,5-dihydro-1H-imidazole-1-oxyl, as the adsorbed probe molecules.

  7. Morphology control of cobalt oxide nanocrystals for promoting their catalytic performance.

    PubMed

    Xie, Xiaowei; Shen, Wenjie

    2009-10-01

    The design and fabrication of nanomaterials is a crucial issue in heterogeneous catalysis to achieve excellent performance. Traditionally, the main theme is to reduce the size of particles as small as possible mainly to increase the activity, so-called size-dependent catalytic chemistry. In recent years, the rapid developments in novel morphological and structural nanomaterials have enabled the fabrication of catalytic materials with exposing more reactive crystal planes, favoring a deep understanding of the active sites. Here, we highlight the recent progress in catalytic materials with unique performance caused by the morphology, by taking Co(3)O(4) nanomaterials as an example. Firstly, we briefly summarize the important synthetic strategies and characteristics of morphology-controlled Co(3)O(4) nanomaterials and their precursors like cobalt hydroxides, including zero- to two-dimensional and hierarchical nanostructures. Then, morphology/plane-dependent catalysis of these cobalt oxides is demonstrated, focusing on CH(4) combustion and CO oxidation in order to elaborate the intrinsic nature of morphology and surface plane. Finally, we outline our personal understanding and perspectives on the morphology-dependent nanocatalysis with metal and metal oxides. These morphology-controlled nanomaterials with more reactive crystal planes exposed are expected to be highly efficient for practical applications based on the deep understanding of the catalytically active sites.

  8. Effect of cobalt on the oxidation resistance of Pr(Nd)-Dy-Fe-Co-B materials

    NASA Astrophysics Data System (ADS)

    Kablov, E. N.; Ospennikova, O. G.; Rezchikova, I. I.; Valeev, R. A.; Piskorskii, V. P.; Sul'yanova, E. A.

    2016-07-01

    The effect of cobalt on the oxidation resistance of (Nd0.85Dy0.15)16.4(Fe0.89Co0.11)74.4Ti1.3B7.9 and (Pr0.56Dy0.39Sm0.05)14.5(Fe0.75Co0.25)78.8B6.7 alloys has been studied. The storage of magnet blanks made from these alloy in air for 200 h does not affect the magnetic properties of the sintered magnets owing to the presence of the phases (Pr, Dy)(Fe, Co)2, (Pr, Dy)(Fe, Co)2B2, (Pr, Dy)(Fe, Co)4B, (Pr, Dy)(Fe, Co)3B2, and (Pr, Dy)(Fe, Co)3, which are resistant to oxidation and ensure liquid-phase sintering of magnets. After 200-h exposure to air, oxidation of the blanks takes place, the rate of which decreases by more than two times at the expense of an increase in the cobalt content in the alloy.

  9. Electro-deposition of superconductor oxide films

    DOEpatents

    Bhattacharya, Raghu N.

    2001-01-01

    Methods for preparing high quality superconducting oxide precursors which are well suited for further oxidation and annealing to form superconducting oxide films. The method comprises forming a multilayered superconducting precursor on a substrate by providing an electrodeposition bath comprising an electrolyte medium and a substrate electrode, and providing to the bath a plurality of precursor metal salts which are capable of exhibiting superconducting properties upon subsequent treatment. The superconducting precursor is then formed by electrodepositing a first electrodeposited (ED) layer onto the substrate electrode, followed by depositing a layer of silver onto the first electrodeposited (ED) layer, and then electrodepositing a second electrodeposited (ED) layer onto the Ag layer. The multilayered superconducting precursor is suitable for oxidation at a sufficient annealing temperature in air or an oxygen-containing atmosphere to form a crystalline superconducting oxide film.

  10. Chemical routes to synthesize lithium cobalt oxide powders for rechargeable lithium batteries

    SciTech Connect

    Gallet, D.; Waghray, A.; Kumta, P.N.

    1996-12-31

    Lithium cobalt oxide (LiCoO{sub 2}) is known to be a good cathode material for high voltage (4V) rechargeable Li-ion batteries. New chemical routes based on aqueous solution chemistry have been developed to synthesize molecularly mixed precursors that transform to form LiCoO{sub 2} at temperatures as low as 400{degrees}C. The resultant oxide powders are nanocrystalline ({approx} 20-40 nm) and exhibit unique morphologies and microstructures depending on the molecular environment of the ions in solution. Cathodes fabricated from the oxide powders and tested in {open_quote}hockey-puck{close_quote} test cells exhibited specific capacities of about 135 mAh/g with a reversible range close to 0.5 Li ions. Results of the phase evolution and microstructural analysis are discussed in relation to the electrochemical performance of the cathodes.

  11. Investigation of electrodeposited cuprous oxide thin films

    NASA Astrophysics Data System (ADS)

    Mortensen, Emma L.

    This dissertation focuses on improvements to electrodeposited cuprous oxide as a candidate for the absorber layer for a thin film solar cell that could be integrated into a mechanical solar cell stack. Cuprous oxide (Cu2O) is an earth abundant material that has a bandgap of 2 eV with absorption coefficients around 102-106 cm-1. This bandgap is not optimized for use as a single-junction solar cell, but could be ideal for use in a tandem solar cell device. The theoretical efficiency of a material with a bandgap of 2.0 eV is 20%. The greatest actual efficiency that has been achieved for a Cu2O solar cell is only 8.1%. For the present work the primary focus has been on improving the microstructure of the absorber layer film. The Cu2O films were fabricated using electrodeposition. A seeding layer was developed using gold (Au); which was manipulated into nano-islands and used as the substrate for the Cu2O electrodeposition. The films were characterized and compared to determine the growth mechanism of each film using scanning electron microscopy (SEM). X-ray diffraction (XRD) was used to establish and compare the chemical phases that were present in each of the films. The crystal structure of the Cu2O film grown on gold was explored using transmission electron microscopy (TEM), and this helped confirm the effect that the gold had on the growth of Cu2O. The Tauc method was then used to determine the bandgap of the films of Cu2O grown on both substrates and this showed that the Au based Cu2O film was a superior film. Electrical tests were also completed using a solar simulator and this established that the film grown on gold exhibited photoconductivity that was not seen on the film without gold. In addition, for this thesis, a method for depositing an n-type Cu2O film, based on a Cu-metal solution-boiling process, was investigated. Three forms of copper were tested: a sheet of copper, electrodeposited copper, and sputtered copper. The chemical phases were observed using

  12. Characterisation of a water-oxidizing Co-film by XAFS

    NASA Astrophysics Data System (ADS)

    Risch, Marcel; Ringleb, Franziska; Khare, Varsha; Chernev, Petko; Zaharieva, Ivelina; Dau, Holger

    2009-11-01

    A major enterprise for scientists worldwide is the search for alternative fuels and molecular hydrogen (H2) is a promising candidate. Its large-scale technical production needs to involve water-oxidation catalysts from inexpensive and abundant materials. Here, a water-oxidizing Co-based catalyst film (CoCF) is investigated. We review and extend our previous X-ray absorption spectroscopy (XAS) measurements (at Helmholtz-Zentrum Berlin/BESSY) by comparison to LiCoO2, a CoIII compound of similar structure and composition. Further evidence is presented that the bulk oxidation state of cobalt in the CoCF is 3+. We propose that the catalyst film is composed of interconnected complete and/or incomplete Co-oxo cubanes possibly forming a disordered network of the basic Co3/4(μ-O)4 units.

  13. Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted “pH-adjusting” method: Importance of cobalt species in styrene oxidation

    SciTech Connect

    Li, Baitao Zhu, Yanrun; Jin, Xiaojing

    2015-01-15

    Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted “pH-adjusting” technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co{sub 3}O{sub 4} particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was more beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H{sub 2}O{sub 2}) at 70 °C. - Graphical abstract: Cobalt-containing mesoporous silica catalysts were developed via ultrasonic-assisted “pH-adjusting” technique. Compared with Co{sub 3}O{sub 4} in Co-MCM-41, the single-site Co(II) state in Co-SBA-15 was more efficient for the styrene oxidation. - Highlights: • Fast and cost-effective ultrasonic technique for preparing mesoporous materials. • Incorporation of Co via ultrasonic irradiation and “pH-adjusting”. • Physicochemical comparison between Co-SBA-15 and Co-MCM-41. • Correlation of styrene oxidation activity and catalyst structural property.

  14. Sprayed lanthanum doped zinc oxide thin films

    NASA Astrophysics Data System (ADS)

    Bouznit, Y.; Beggah, Y.; Ynineb, F.

    2012-01-01

    Lanthanum doped zinc oxide thin films were deposited on soda-lime glass substrates using a pneumatic spray pyrolysis technique. The films were prepared using different lanthanum concentrations at optimum deposition parameters. We studied the variations in structural, morphological and optical properties of the samples due to the change of doping concentration in precursor solutions. X-ray diffraction (XRD) patterns show that pure and La-doped ZnO thin films are highly textured along c-axis perpendicular to the surface of the substrate. Scanning electron micrographs show that surface morphology of ZnO films undergoes a significant change according to lanthanum doping. All films exhibit a transmittance higher than 80% in the visible region.

  15. Graphene oxide film as solid lubricant.

    PubMed

    Liang, Hongyu; Bu, Yongfeng; Zhang, Junyan; Cao, Zhongyue; Liang, Aimin

    2013-07-10

    As a layered material, graphene oxide (GO) film is a good candidate for improving friction and antiwear performance of silicon-based MEMS devices. Via a green electrophoretic deposition (EPD) approach, GO films with tunable thickness in nanoscale are fabricated onto silicon wafer in a water solution. The morphology, microstructure, and mechanical properties as well as the friction coefficient and wear resistance of the films were investigated. The results indicated that the friction coefficient of silicon wafer was reduced to 1/6 its value, and the wear volume was reduced to 1/24 when using GO film as solid lubricant. These distinguished tribology performances suggest that GO films are expected to be good solid lubricants for silicon-based MEMS/NEMS devices.

  16. Transferable graphene oxide films with tunable microstructures.

    PubMed

    Hasan, Saad A; Rigueur, John L; Harl, Robert R; Krejci, Alex J; Gonzalo-Juan, Isabel; Rogers, Bridget R; Dickerson, James H

    2010-12-28

    This report describes methods to produce large-area films of graphene oxide from aqueous suspensions using electrophoretic deposition. By selecting the appropriate suspension pH and deposition voltage, films of the negatively charged graphene oxide sheets can be produced with either a smooth "rug" microstructure on the anode or a porous "brick" microstructure on the cathode. Cathodic deposition occurs in the low pH suspension with the application of a relatively high voltage, which facilitates a gradual change in the colloids' charge from negative to positive as they adsorb protons released by the electrolysis of water. The shift in the colloids' charge also gives rise to the brick microstructure, as the concurrent decrease in electrostatic repulsion between graphene oxide sheets results in the formation of multilayered aggregates (the "bricks"). Measurements of water contact angle revealed the brick films (79°) to be more hydrophobic than the rug films (41°), a difference we attribute primarily to the distinct microstructures. Finally, we describe a sacrificial layer technique to make these graphene oxide films free-standing, which would enable them to be placed on arbitrary substrates.

  17. Rapid (<3 min) microwave synthesis of block copolymer templated ordered mesoporous metal oxide and carbonate films using nitrate-citric acid systems.

    PubMed

    Zhang, Yuanzhong; Bhaway, Sarang M; Wang, Yi; Cavicchi, Kevin A; Becker, Matthew L; Vogt, Bryan D

    2015-03-25

    Rapid chemical transformation from micelle templated precursors (metal nitrate and citric acid) to ordered mesoporous metal carbonates and oxides is demonstrated using microwave heating for cobalt, copper, manganese and zinc. Without aging requirements, <3 min of microwave processing yields highly ordered mesoporous films.

  18. Tailoring the energy level alignment at the Co/Alq{sub 3} interface by controlled cobalt oxidation

    SciTech Connect

    Haag, Norman; Steil, Sabine; Großmann, Nicolas; Fetzer, Roman; Cinchetti, Mirko; Aeschlimann, Martin

    2013-12-16

    We have studied the influence of oxygen exposure at the prototypical interface between cobalt and the organic semiconductor tris(8-hydroxyquinoline)aluminum (III) (Alq{sub 3}) by photoemission spectroscopy. We find that oxidation of the cobalt leads to a gradual suppression of hybrid interface states, to a progressive change in the work function and to a continuous energetic shift of the molecular orbitals towards higher binding energies. Based on these observations, we propose controlled oxidation of the ferromagnetic electrode as an easy and effective possibility to tune the performance of organic spintronics devices.

  19. Ligand contributions to the electronic structures of the oxidized cobalt(II) salen complexes.

    PubMed

    Kochem, Amélie; Kanso, Hussein; Baptiste, Benoit; Arora, Himanshu; Philouze, Christian; Jarjayes, Olivier; Vezin, Hervé; Luneau, Dominique; Orio, Maylis; Thomas, Fabrice

    2012-10-15

    Square planar cobalt(II) complexes of salen ligands N,N'-bis(3-tert-butyl-5R-salicylidene)-1,2-cyclohexanediamine), where R = OMe (1) and tert-butyl (2), were prepared. 1 and 2 were electrochemically reversibly oxidized into cations [1-H(2)O](+) and [2-H(2)O](+) in CH(2)Cl(2). The chemically generated [1-H(2)O](SbF(6))·0.68 H(2)O·0.82CH(2)Cl(2) and [2-H(2)O](SbF(6))·0.3H(2)O·0.85CH(2)Cl(2) were characterized by X-ray diffraction and NIR spectroscopy. Both complexes are paramagnetic species containing a square pyramidal cobalt ion coordinated at the apical position by an exogenous water molecule. They exhibit remarkable NIR bands at 1220 (7370 M(-1) cm(-1)) and 1060 nm (5560 M(-1) cm(-1)), respectively, assigned to a CT transition. DFT calculations and magnetic measurements confirm the paramagnetic (S = 1) ground spin state of the cations. They show that more than 70% of the total spin density in [1-H(2)O](+) and [2-H(2)O](+) is localized on the metal, the remaining spin density being distributed over the aromatic rings (30% phenoxyl character). In the presence of N-methylimidazole 1 and 2 are irreversibly oxidized by air into the genuine octahedral cobalt(III) bis(phenolate) complexes [1-im(2)](+) and [2-im(2)](+), the former being structurally characterized. Neither [1-im(2)](+) nor [2-im(2)](+) exhibits a NIR feature in its electronic spectrum. 1 and 2 were electrochemically two-electron oxidized into [1](2+) and [2](2+). The cations were identified as Co(III)-phenoxyl species by their characteristic absorption band at ca. 400 nm in the UV-vis spectrum. Coordination of the phenoxyl radical to the cobalt(III) metal ion is evidenced by the EPR signal centered at g = 2.00.

  20. Surface and redox properties of cobalt-ceria binary oxides: On the effect of Co content and pretreatment conditions

    NASA Astrophysics Data System (ADS)

    Konsolakis, Michalis; Sgourakis, Michalis; Carabineiro, Sónia A. C.

    2015-06-01

    Ceria-based transition metal catalysts have recently received considerable attention both in heterogeneous catalysis and electro-catalysis fields, due to their unique physicochemical characteristics. Their catalytic performance is greatly affected by the surface local chemistry and oxygen vacancies. The present study aims at investigating the impact of Co/Ce ratio and pretreatment conditions on the surface and redox properties of cobalt-ceria binary oxides. Co-ceria mixed oxides with different Co content (0, 20, 30, 60, 100 wt.%) were prepared by impregnation method and characterized by means of N2 adsorption at -196 °C, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The results shown the improved reducibility of Co/CeO2 mixed oxides compared to single oxides, due to a synergistic interaction between cobalt and cerium. Oxidation pretreatment results in a preferential localization of cerium species on the outer surface. In contrast, a uniform distribution of cobalt and cerium species over the entire catalyst surface is obtained by the reduction process, which facilitates the formation of oxygen vacancies though Co3+/Co2+ and Ce3+/Ce4+ redox cycles. Fundamental insights toward tuning the surface chemistry of cobalt-ceria binary oxides are provided, paving the way for real-life industrial applications.

  1. Current-direction dependence of the transport properties in single-crystalline face-centered-cubic cobalt films

    SciTech Connect

    Xiao, X.; Liang, J. H.; Chen, B. L.; Li, J. X.; Ding, Z.; Wu, Y. Z.; Ma, D. H.

    2015-07-28

    Face-centered-cubic cobalt films are epitaxially grown on insulating LaAlO{sub 3}(001) substrates by molecular beam epitaxy. Transport measurements are conducted in different current directions relative to the crystal axes. We find that the temperature dependent anisotropic magnetoresistance ratio strongly depends on the current direction. However, the anomalous Hall effect shows isotropic behavior independent of the current direction. Our results demonstrate the interplay between the current direction and the crystalline lattice in single-crystalline ferromagnetic films. A phenomenological analysis is presented to interpret the experimental data.

  2. Evidence of highly active cobalt oxide catalyst for the Fischer-Tropsch synthesis and CO2 hydrogenation.

    PubMed

    Melaet, Gérôme; Ralston, Walter T; Li, Cheng-Shiuan; Alayoglu, Selim; An, Kwangjin; Musselwhite, Nathan; Kalkan, Bora; Somorjai, Gabor A

    2014-02-12

    Hydrogenations of CO or CO2 are important catalytic reactions as they are interesting alternatives to produce fine chemical feedstock hence avoiding the use of fossil sources. Using monodisperse nanoparticle (NP) catalysts, we have studied the CO/H2 (i.e., Fischer-Tropsch synthesis) and CO2/H2 reactions. Exploiting synchrotron based in situ characterization techniques such as XANES and XPS, we were able to demonstrate that 10 nm Co NPs cannot be reduced at 250 °C while supported on TiO2 or SiO2 and that the complete reduction of cobalt can only be achieved at 450 °C. Interestingly, cobalt oxide performs better than fully reduced cobalt when supported on TiO2. In fact, the catalytic results indicate an enhancement of 10-fold for the CO2/H2 reaction rate and 2-fold for the CO/H2 reaction rate for the Co/TiO2 treated at 250 °C in H2 versus Co/TiO2 treated at 450 °C. Inversely, the activity of cobalt supported on SiO2 has a higher turnover frequency when cobalt is metallic. The product distributions could be tuned depending on the support and the oxidation state of cobalt. For oxidized cobalt on TiO2, we observed an increase of methane production for the CO2/H2 reaction whereas it is more selective to unsaturated products for the CO/H2 reaction. In situ investigation of the catalysts indicated wetting of the TiO2 support by CoO(x) and partial encapsulation of metallic Co by TiO(2-x).

  3. High quality transparent conducting oxide thin films

    DOEpatents

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

    2012-08-28

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

  4. As-grown enhancement of spinodal decomposition in spinel cobalt ferrite thin films by Dynamic Aurora pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Debnath, Nipa; Kawaguchi, Takahiko; Kumasaka, Wataru; Das, Harinarayan; Shinozaki, Kazuo; Sakamoto, Naonori; Suzuki, Hisao; Wakiya, Naoki

    2017-06-01

    Cobalt ferrite CoxFe3-xO4 thin films with composition within the miscibility gap were grown using Dynamic Aurora pulsed laser deposition. X-ray diffraction patterns reveal as-grown phase separation to Fe-rich and Co-rich phases with no post-deposition annealing. The interconnected surface microstructure of thin film shows that this phase separation occurs through spinodal decomposition enhanced by magnetic-field-induced ion-impingement. The lattice parameter variation of the thin films with the magnetic field indicates that the composition fluctuations can be enhanced further by increasing the magnetic field. Results show that spinodal decomposition enhancement by magnetic-field-induced ion-impingement is independent of the lattice-mismatch-induced strain. This approach can promote spinodal decomposition in any thin film with no post-deposition annealing process.

  5. Characteristics of the oxygen evolution reaction on synthetic copper - cobalt - oxide electrodes for water electrolysis

    NASA Astrophysics Data System (ADS)

    Park, Yoo Sei; Park, Chan Su; Kim, Chi Ho; Kim, Yang Do; Park, Sungkyun; Lee, Jae Ho

    2016-10-01

    A nano-sized Cu0.7Co2.3O4 powder was prepared using a thermal decomposition method to achieve an efficient anode catalyst for an economical water electrolysis system for high-purity hydrogen-gas production without using a noble-metal catalyst. This study showed that the calcination temperature should be maintained under 400 °C to obtain a spinel copper - cobalt oxide structure without secondary oxide phases. The powder calcined at 250 °C showed the highest current density at the oxygen evolution reaction. This was due mainly to the increased number of available active sites and the active surface area of the powders. Further systematic analyses of the electrochemical characteristics of Cu x Co3- x O4 synthesized by using the fusion method were performed to assess it as potential anode material for use in alkaline-anion-exchange-membrane water electrolysis.

  6. Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

    SciTech Connect

    Bartling, Stephan Meiwes-Broer, Karl-Heinz; Barke, Ingo; Pohl, Marga-Martina

    2015-09-21

    Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology.

  7. Incommensurate spin correlations in highly oxidized cobaltates La2−xSrxCoO4

    PubMed Central

    Li, Z. W.; Drees, Y.; Kuo, C. Y.; Guo, H.; Ricci, A.; Lamago, D.; Sobolev, O.; Rütt, U.; Gutowski, O.; Pi, T. W.; Piovano, A.; Schmidt, W.; Mogare, K.; Hu, Z.; Tjeng, L. H.; Komarek, A. C.

    2016-01-01

    We observe quasi-static incommensurate magnetic peaks in neutron scattering experiments on layered cobalt oxides La2−xSrxCoO4 with high Co oxidation states that have been reported to be paramagnetic. This enables us to measure the magnetic excitations in this highly hole-doped incommensurate regime and compare our results with those found in the low-doped incommensurate regime that exhibit hourglass magnetic spectra. The hourglass shape of magnetic excitations completely disappears given a high Sr doping. Moreover, broad low-energy excitations are found, which are not centered at the incommensurate magnetic peak positions but around the quarter-integer values that are typically exhibited by excitations in the checkerboard charge ordered phase. Our findings suggest that the strong inter-site exchange interactions in the undoped islands are critical for the emergence of hourglass spectra in the incommensurate magnetic phases of La2−xSrxCoO4. PMID:27117928

  8. Vapor Phase Hydrogenolysis of Furanics Utilizing Reduced Cobalt Mixed Metal Oxide Catalysts

    DOE PAGES

    Sulmonetti, Taylor P.; Hu, Bo; Ifkovits, Zachary; ...

    2017-03-21

    Vapor phase hydrogenolysis of both furfuryl alcohol and furfural were investigated over reduced Co based mixed metal oxides derived from the calcination of a layered double hydroxide precursor. Although a reduced cobalt aluminate sample displays promising selectivity towards 2-methylfuran (2-MF) production, the addition of an Fe dopant into the oxide matrix significantly enhances the activity and selectivity per gram of catalyst. Approximately 82% 2-MF yield is achieved at high conversion when furfuryl alcohol is fed into the reactor at 180 °C over the reduced 3Co-0.25Fe-0.75Al catalyst. Based on structural characterization studies including TPR, XPS, and in-situ XAS it is suggestedmore » that Fe facilitates the reduction of Co, allowing for formation of more metallic species. Altogether, this study demonstrates that non-precious metal catalysts offer promise for the selective conversion of a key biomass oxygenate to a proposed fuel additive.« less

  9. Cobalt-chromium spinel catalyst of exhaustive oxidation of ethyl chloride

    SciTech Connect

    Vlasenko, V.M.; Feshchenko, L.F.; Chernobrivets, V.L.

    1992-05-10

    Ethyl chloride is formed as a by-product in many plants for organochlorine synthesis and is emitted into the atmosphere with gaseous wastes, polluting the environment. Due to the toxicity of ethyl chloride, it is necessary to create methods for scrubbing this substance from waste gases. The catalytic method based on the reaction of exhaustive oxidation of the removed contaminant to carbon dioxide, water, and hydrogen chloride or chlorine, which can either be removed or used for production purposes in some cases, is a relatively effective and economical method of scrubbing toxic organochlorine contaminants from gases. Catalytic oxidation of organochlorine compounds usually takes place on catalysts containing noble metals. The shortage of catalysts resistant to aggressive media has prevented the wide use of this method. The authors present a synthesis method for a cobalt-chromium catalyst for this purpose. 6 refs., 3 figs., 3 tabs.

  10. Modeling of the liquid-phase n-octane oxidation catalyzed by cobalt

    SciTech Connect

    Garcia-Ochoa, F.; Querol, J.; Romero, A. )

    1990-10-01

    This paper reports on n-octane liquid-phase oxidation with oxygen-nitrogen mixtures homogeneously catalyzed by cobalt palmitate that has been studied. Molecular schemes of four and five reactions with two possibilities of kinetic equations used for lumping compounds are tested. Apparent rate constants are calculated by a multiresponse linear method, and discrimination among kinetic models is carried out by applying both statistical and physical criteria. Relationships of the apparent rate constants with temperature, oxygen partial pressure, and catalyst concentration are established, and parameters are optimized by nonlinear regression. The selected models are the same for catalytic and noncatalytic oxidation and describe in a suitable way the influence of temperature, oxygen partial pressure, and catalyst concentration on conversion and product selectivity. Finally, a discussion about lumping of different products based on experimental data is included.

  11. Porous cubes constructed by cobalt oxide nanocrystals with graphene sheet coatings for enhanced lithium storage properties.

    PubMed

    Geng, Hongbo; Guo, Yuanyuan; Ding, Xianguang; Wang, Huangwen; Zhang, Yufei; Wu, Xinglong; Jiang, Jiang; Zheng, Junwei; Yang, Yonggang; Gu, Hongwei

    2016-04-14

    In this manuscript, graphene-encapsulated porous cobalt oxide cubes (Co3O4@G) are fabricated through a facile precipitation reaction with subsequent calcination and a self-assembly process. The synthesized porous Co3O4 cubes anchored in the conductive graphene network can realize superior electrical conductivity, withstand volume variation upon prolonged cycling and shorten the diffusion path of lithium ions. When evaluated as anode materials, the Co3O4@G electrode shows excellent electrochemical properties in terms of both stable cycling performance and good rate capabilities. For example, a reversible discharge capacity of 980 mA h g(-1) is delivered after 80 cycles at a current density of 200 mA g(-1). Introducing a conductive graphene network to modify other metal oxides with poor electric conductivity and large volume excursions is of great interest in the development of lithium ion battery technologies.

  12. Patterning of Indium Tin Oxide Films

    NASA Technical Reports Server (NTRS)

    Immer, Christopher

    2008-01-01

    A relatively rapid, economical process has been devised for patterning a thin film of indium tin oxide (ITO) that has been deposited on a polyester film. ITO is a transparent, electrically conductive substance made from a mixture of indium oxide and tin oxide that is commonly used in touch panels, liquid-crystal and plasma display devices, gas sensors, and solar photovoltaic panels. In a typical application, the ITO film must be patterned to form electrodes, current collectors, and the like. Heretofore it has been common practice to pattern an ITO film by means of either a laser ablation process or a photolithography/etching process. The laser ablation process includes the use of expensive equipment to precisely position and focus a laser. The photolithography/etching process is time-consuming. The present process is a variant of the direct toner process an inexpensive but often highly effective process for patterning conductors for printed circuits. Relative to a conventional photolithography/ etching process, this process is simpler, takes less time, and is less expensive. This process involves equipment that costs less than $500 (at 2005 prices) and enables patterning of an ITO film in a process time of less than about a half hour.

  13. Aluminum oxide film thickness and emittance

    SciTech Connect

    Thomas, J.K.; Ondrejcin, R.S.

    1991-11-01

    Aluminum reactor components which are not actively cooled could be subjected to high temperatures due to gamma heating after the core coolant level dropped during the ECS phase of a hypothetical LOCA event. Radiative heat transfer is the dominant heat transfer process in this scenario and therefore the emittance of these components is of interest. Of particular interest are the safety rod thimbles and Mark 60B blanket assemblies; for the K Reactor, these components have been exposed to low temperature (< 55{degrees}C) moderator for about a year. The average moderator temperature was assumed to be 30{degrees}C. The Al oxide film thickness at this temperature, after one year of exposure, is predicted to be 6.4 {mu}m {plus minus} 10%; insensitive to exposure time. Dehydration of the film during the gamma heating accident would result in a film thickness of 6.0 {mu}m {plus minus} 11%. Total hemispherical emittance is predicted to be 0.69 at 96{degrees}C, decreasing to 0.45 at 600{degrees}C. Some phenomena which would tend to yield thicker oxide films in the reactor environment relative to those obtained under experimental conditions were neglected and the predicted film thickness values are therefore conservative. The emittance values predicted for a given film thickness are also conservative. The conservativisms inherent in the predicted emittance are particularly relevant for uncertainty analysis of temperatures generated using these values.

  14. Aluminum oxide film thickness and emittance

    SciTech Connect

    Thomas, J.K.; Ondrejcin, R.S.

    1991-11-01

    Aluminum reactor components which are not actively cooled could be subjected to high temperatures due to gamma heating after the core coolant level dropped during the ECS phase of a hypothetical LOCA event. Radiative heat transfer is the dominant heat transfer process in this scenario and therefore the emittance of these components is of interest. Of particular interest are the safety rod thimbles and Mark 60B blanket assemblies; for the K Reactor, these components have been exposed to low temperature (< 55{degrees}C) moderator for about a year. The average moderator temperature was assumed to be 30{degrees}C. The Al oxide film thickness at this temperature, after one year of exposure, is predicted to be 6.4 {mu}m {plus_minus} 10%; insensitive to exposure time. Dehydration of the film during the gamma heating accident would result in a film thickness of 6.0 {mu}m {plus_minus} 11%. Total hemispherical emittance is predicted to be 0.69 at 96{degrees}C, decreasing to 0.45 at 600{degrees}C. Some phenomena which would tend to yield thicker oxide films in the reactor environment relative to those obtained under experimental conditions were neglected and the predicted film thickness values are therefore conservative. The emittance values predicted for a given film thickness are also conservative. The conservativisms inherent in the predicted emittance are particularly relevant for uncertainty analysis of temperatures generated using these values.

  15. Evaluation of humidity sensing properties of TMBHPET thin film embedded with spinel cobalt ferrite nanoparticles

    NASA Astrophysics Data System (ADS)

    Zafar, Qayyum; Azmer, Mohamad Izzat; Al-Sehemi, Abdullah G.; Al-Assiri, Mohammad S.; Kalam, Abul; Sulaiman, Khaulah

    2016-07-01

    In this study, we report the enhanced sensing parameters of previously reported TMBHPET-based humidity sensor. Significant improved sensing performance has been demonstrated by coupling of TMBHPET moisture sensing thin film with cobalt ferrite nanoparticles (synthesized by eco-benign ultrasonic method). The mean size of CoFe2O4 nanoparticles has been estimated to be 6.5 nm. It is assumed that the thin film of organic-ceramic hybrid matrix (TMBHPET:CoFe2O4) is a potential candidate for humidity sensing utility by virtue of its high specific surface area and porous surface morphology (as evident from TEM, FESEM, and AFM images). The hybrid suspension has been drop-cast onto the glass substrate with preliminary deposited coplanar aluminum electrodes separated by 40 µm distance. The influence of humidity on the capacitance of the hybrid humidity sensor (Al/TMBHPET:CoFe2O4/Al) has been investigated at three different frequencies of the AC applied voltage ( V rms 1 V): 100 Hz, 1 kHz, and 10 kHz. It has been observed that at 100 Hz, under a humidity of 99 % RH, the capacitance of the sensor increased by 2.61 times, with respect to 30 % RH condition. The proposed sensor exhibits significantly improved sensitivity 560 fF/ % RH at 100 Hz, which is nearly 7.5 times as high as that of pristine TMBHPET-based humidity sensor. Further, the capacitive sensor exhibits improved dynamic range (30-99 % RH), small hysteresis ( 2.3 %), and relatively quicker response and recovery times ( 12 s, 14 s, respectively). It is assumed that the humidity response of the sensor is associated with the diffusion kinetics of water vapors and doping of the semiconductor nanocomposite by water molecules.

  16. Porous cubes constructed by cobalt oxide nanocrystals with graphene sheet coatings for enhanced lithium storage properties

    NASA Astrophysics Data System (ADS)

    Geng, Hongbo; Guo, Yuanyuan; Ding, Xianguang; Wang, Huangwen; Zhang, Yufei; Wu, Xinglong; Jiang, Jiang; Zheng, Junwei; Yang, Yonggang; Gu, Hongwei

    2016-03-01

    In this manuscript, graphene-encapsulated porous cobalt oxide cubes (Co3O4@G) are fabricated through a facile precipitation reaction with subsequent calcination and a self-assembly process. The synthesized porous Co3O4 cubes anchored in the conductive graphene network can realize superior electrical conductivity, withstand volume variation upon prolonged cycling and shorten the diffusion path of lithium ions. When evaluated as anode materials, the Co3O4@G electrode shows excellent electrochemical properties in terms of both stable cycling performance and good rate capabilities. For example, a reversible discharge capacity of 980 mA h g-1 is delivered after 80 cycles at a current density of 200 mA g-1. Introducing a conductive graphene network to modify other metal oxides with poor electric conductivity and large volume excursions is of great interest in the development of lithium ion battery technologies.In this manuscript, graphene-encapsulated porous cobalt oxide cubes (Co3O4@G) are fabricated through a facile precipitation reaction with subsequent calcination and a self-assembly process. The synthesized porous Co3O4 cubes anchored in the conductive graphene network can realize superior electrical conductivity, withstand volume variation upon prolonged cycling and shorten the diffusion path of lithium ions. When evaluated as anode materials, the Co3O4@G electrode shows excellent electrochemical properties in terms of both stable cycling performance and good rate capabilities. For example, a reversible discharge capacity of 980 mA h g-1 is delivered after 80 cycles at a current density of 200 mA g-1. Introducing a conductive graphene network to modify other metal oxides with poor electric conductivity and large volume excursions is of great interest in the development of lithium ion battery technologies. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01024e

  17. Topotactic synthesis of strontium cobalt oxyhydride thin film with perovskite structure

    SciTech Connect

    Katayama, Tsukasa; Chikamatsu, Akira Kamisaka, Hideyuki; Yokoyama, Yuichi; Hirata, Yasuyuki; Wadati, Hiroki; Fukumura, Tomoteru; Hasegawa, Tetsuya

    2015-10-15

    The substitution of hydride anions (H{sup −}) into transition metal oxides has recently become possible through topotactic reactions or high-pressure synthesis methods. However, the fabrication of oxyhydrides is still difficult because of their inherently less-stable frameworks. In this study, we successfully fabricated perovskite SrCoO{sub x}H{sub y} thin films via the topotactic hydride doping of brownmillerite SrCoO{sub 2.5} epitaxial thin films with CaH{sub 2}. The perovskite-type cation framework was maintained during the topotactic treatment owing to epitaxial stabilization. Structural and chemical analyses accompanied by X-ray absorption spectroscopy measurements revealed that the doped hydride ions form a two-dimensional network of Co-H{sup −}-Co bonds, in contrast to other reported perovskite oxyhydrides, SrMO{sub 3−x}H{sub x} (M = Cr, Ti, V). The SrCoO{sub x}H{sub y} thin film exhibited insulating behavior and had a direct band gap of 2.1 eV. Thus, topotactic hydride doping of transition-metal-oxide thin films on suitable substrates is a promising method for the synthesis of new transition metal oxyhydrides.

  18. Metal current collect protected by oxide film

    DOEpatents

    Jacobson, Craig P.; Visco, Steven J.; DeJonghe, Lutgard C.

    2004-05-25

    Provided are low-cost, mechanically strong, highly electronically conductive current collects and associated structures for solid-state electrochemical devices, techniques for forming these structures, and devices incorporating the structures. The invention provides solid state electrochemical devices having as current interconnects a ferritic steel felt or screen coated with a protective oxide film.

  19. Thin-Film Solid Oxide Fuel Cells

    NASA Technical Reports Server (NTRS)

    Chen, Xin; Wu, Nai-Juan; Ignatiev, Alex

    2009-01-01

    The development of thin-film solid oxide fuel cells (TFSOFCs) and a method of fabricating them have progressed to the prototype stage. This can result in the reduction of mass, volume, and the cost of materials for a given power level.

  20. Improved performance of quantum dot-sensitized solar cells adopting a highly efficient cobalt sulfide/nickel sulfide composite thin film counter electrode

    NASA Astrophysics Data System (ADS)

    Kim, Hee-Je; Kim, Su-Weon; Gopi, Chandu V. V. M.; Kim, Soo-Kyoung; Rao, S. Srinivasa; Jeong, Myeong-Soo

    2014-12-01

    Cobalt sulfide (CoS), nickel sulfide (NiS), and cobalt sulfide/nickel sulfide (CoS/NiS) were deposited onto fluorine-doped tin oxide (FTO) substrate using a facile chemical bath deposition method and utilized as counter electrodes (CEs) for polysulfide redox reactions in CdS/CdSe quantum dot-sensitized solar cells (QDSSCs). The thickness of 750 nm and 695 nm are optimized for NiS and CoS electrodes to prepare the CoS/NiS CE. Compared to a platinum (Pt) electrode, the CoS, NiS, and composite CoS/NiS electrodes provide higher electrocatalytic activity and lower charge-transfer resistance. The combination of a QDSSC with composite CoS/NiS CE shows an improved power conversion efficiency of 3.40% under the illumination of one sun (100 mW cm-2), which is higher than the CoS (2.53%), NiS (2.61%), and Pt (1.47%) CEs. This enhancement is mainly attributed to the NiS nanoparticles deposited on CoS film, due to which the composite structure exhibits a lower charge transfer resistance (7.61 Ω) at the interface of the CE and the electrolyte, along with superior electrochemical catalytic ability. This is well supported by the cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization measurements.

  1. Effects of Cobalt on Manganese Oxidation by Pseudomonas putida MnB1

    NASA Astrophysics Data System (ADS)

    Pena, J.; Bargar, J.; Sposito, G.

    2005-12-01

    The oxidation of Mn(II) in the environment is thought to occur predominantly through biologically mediated pathways. During the stationary phase of growth, the well-characterized freshwater and soil bacterium Pseudomonas putida MnB1 oxidizes soluble Mn(II) to a poorly crystalline layer type Mn(IV) oxide. These Mn oxide particles (2 - 5 nm thickness) are deposited in a matrix of extracellular polymeric substances (EPS) surrounding the cell, creating a multi-component system distinct from commonly studied synthetic Mn oxides. Accurate characterization of the reactivity of these biomineral assemblages is essential to understanding trace metal biogeochemistry in natural waters and sediments. Moreover, these biogenic oxides may potentially be used for the remediation of surface and ground waters impacted by mining, industrial pollution, and other anthropogenic activities. In this study, we consider the interactions between Co, P. putida MnB1, and its biogenic Mn oxide. Cobalt is a redox-active transition metal which exists in the environment as Co(II) and Co(III). While Co is not generally found in the environment at toxic concentrations, it may be released as a byproduct of mining activities (e.g. levels of up to 20 μM are found in Pinal Creek, AZ, a stream affected by copper mining). In addition, the radionuclide 60Co, formed by neutron activation in nuclear reactors, is of concern at Department of Energy sites, such as that at Hanford, and has several industrial applications, including radiotherapy. We address the following questions: Do high levels of Co inhibit enzymatic processes such as Mn(II) oxidation? Can the multicopper oxidase enzyme involved in Mn(II) oxidation facilitate Co(II) oxidation? Lastly, does the organic matter surrounding the oxides affect Co or Mn oxide reactivity? These issues were approached via wet chemical analysis, synchrotron radiation X-ray diffraction (SR-XRD), and extended X-ray absorption fine structure (EXAFS) spectroscopy. In the

  2. Total neutron scattering investigation of the structure of a cobalt gallium oxide spinel prepared by solvothermal oxidation of gallium metal

    NASA Astrophysics Data System (ADS)

    Playford, Helen Y.; Hannon, Alex C.; Tucker, Matthew G.; Lees, Martin R.; Walton, Richard I.

    2013-11-01

    A new solvothermal synthesis route to mixed-metal gallium oxides with the spinel structure has been developed for ternary oxides of ideal composition Ga3-xMxO4-y (M=Co, Zn, Ni). The structure of the novel cobalt gallate produced in this manner, Ga1.767(8)Co0.973(8)O3.752(8), has been determined from total neutron scattering to be a partially defective spinel with mixed-valent cobalt (approximately 25% Co3+ and 75% Co2+) and with vacancies on approximately 6% of oxygen sites. Pair distribution function (PDF) analysis reveals significant local deviations from the average cubic structure, which are attributed to the conflicting coordination preferences of the Co2+ (potential Jahn-Teller distortion) and Ga3+ (Ga off-centring). Reverse Monte Carlo (RMC) modelling supports this conclusion since different metal-oxygen bond-distance distributions are found for the two cations in the refined configuration. An investigation of magnetic properties shows evidence of short-range magnetic order and spin-glass-like behaviour, consistent with the structural disorder of the material.

  3. The effect of variations of cobalt content on the cyclic oxidation resistance of selected Ni-base superalloys

    NASA Technical Reports Server (NTRS)

    Barrett, Charles A.

    1987-01-01

    Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m (PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. the cobalt levels ranged from 0 wt pct to the nominal commercial content in each alloy. the alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200, and 100 hr, respectively. An oxidation attack parameter, Ka, derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the Cr/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr allys while a 5.0 wt pct Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides, perhaps due to the formation of the omnipresent trirutile Ni(Ta, Cb, Mo, W)2O6. Both scales break down as increasing amounts of NiO are formed.

  4. The effect of variations of cobalt content on the cyclic oxidation resistance of selected Ni-base superalloys

    NASA Technical Reports Server (NTRS)

    Barrett, Charles A.

    1987-01-01

    Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m (PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. the cobalt levels ranged from 0 wt pct to the nominal commercial content in each alloy. the alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200, and 100 hr, respectively. An oxidation attack parameter, Ka, derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the Cr/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr allys while a 5.0 wt pct Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides, perhaps due to the formation of the omnipresent trirutile Ni(Ta, Cb, Mo, W)2O6. Both scales break down as increasing amounts of NiO are formed.

  5. The effect of variations of cobalt content on the cyclic oxidation resistance of selected Ni-base superalloys

    NASA Technical Reports Server (NTRS)

    Barrett, C. A.

    1986-01-01

    Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m(PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. The cobalt levels ranged from 0 wt % to the nominal commercial content in each alloy. The alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200 and 100 hr respectively. An oxidation attack parameter, Ka derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the CR/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr alloys while a 5.0 wt % Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides perhaps due to the formation of the omni-present trirutile Ni(Ta,Cb,Mo,W)2O6. Both scales break down as increasing amounts of NiO is formed.

  6. Exfoliation and Reassembly of Cobalt Oxide Nanosheets into a Reversible Lithium-Ion Battery Cathode

    DTIC Science & Technology

    2012-01-01

    have been used successfully in the fabrication of nanosheet- based thin films using standard solution-processing methods such as layer- by -layer... method , which has been successfully utilized to prepare thin films from a wide variety of 2D nanoparticles including reduced graphene oxide[15] and...journal.com© 2012 Wiley-VCH Verlag GmbH & Co . KGaA, Weinheimsmall 2012, 8, No. 7, 1110–1116 4. Experimental Section Synthesis of Crystalline HCoO2

  7. Facile electrochemical co-deposition of a graphene-cobalt nanocomposite for highly efficient water oxidation in alkaline media: direct detection of underlying electron transfer reactions under catalytic turnover conditions.

    PubMed

    Guo, Si-Xuan; Liu, Yuping; Bond, Alan M; Zhang, Jie; Esakki Karthik, P; Maheshwaran, I; Senthil Kumar, S; Phani, K L N

    2014-09-21

    A facile electrochemical co-deposition method has been developed for the fabrication of graphene-cobalt nanocomposite modified electrodes that achieve exceptionally efficient water oxidation in highly alkaline media. In the method reported, a graphene-cobalt nanocomposite film was deposited electrochemically from a medium containing 1 mg ml(-1) graphene oxide, 0.8 mM cobalt nitrate and 0.05 M phytic acid (pH 7). The formation of the nanocomposite film was confirmed using electrochemical, Raman spectroscopic and scanning electron microscopic techniques. The nanocomposite film exhibits excellent activity and stability towards water oxidation to generate oxygen in 1 M NaOH aqueous electrolyte media. A turn over frequency of 34 s(-1) at an overpotential of 0.59 V and a faradaic efficiency of 97.7% were deduced from analysis of data obtained by rotating ring disk electrode voltammetry. Controlled potential electrolysis data suggests that the graphene supported catalyst exhibits excellent stability under these harsh conditions. Phytate anion acts as stabilizer for the electrochemical formation of cobalt nanoparticles. Fourier transformed ac voltammetry allowed the redox chemistry associated with catalysis to be detected directly under catalytic turnover conditions. Estimates of formal reversible potentials obtained from this method and derived from the overall reactions 3Co(OH)2 + 2OH(-) ⇌ Co3O4 + 4H2O + 2e(-), Co3O4 + OH(-) ⇌ 3CoOOH + e(-) and CoOOH + OH(-) ⇌ CoO2 + H2O + e(-) are 0.10, 0.44 and 0.59 V vs. Ag/AgCl, respectively.

  8. Nickel cobalt oxide nanowire-reduced graphite oxide composite material and its application for high performance supercapacitor electrode material.

    PubMed

    Wang, Xu; Yan, Chaoyi; Sumboja, Afriyanti; Lee, Pooi See

    2014-09-01

    In this paper, we report a facile synthesis method of mesoporous nickel cobalt oxide (NiCo2O4) nanowire-reduced graphite oxide (rGO) composite material by urea induced hydrolysis reaction, followed by sintering at 300 degrees C. P123 was used to stabilize the GO during synthesis, which resulted in a uniform coating of NiCo2O4 nanowire on rGO sheet. The growth mechanism of the composite material is discussed in detail. The NiCo2O4-rGO composite material showed an outstanding electrochemical performance of 873 F g(-1) at 0.5 A g(-1) and 512 F g(-1) at 40 A g(-1). This method provides a promising approach towards low cost and large scale production of supercapacitor electrode material.

  9. Structure and properties of Co-doped ZnO films prepared by thermal oxidization under a high magnetic field.

    PubMed

    Li, Guojian; Wang, Huimin; Wang, Qiang; Zhao, Yue; Wang, Zhen; Du, Jiaojiao; Ma, Yonghui

    2015-01-01

    The effect of a high magnetic field applied during oxidation on the structure, optical transmittance, resistivity, and magnetism of cobalt (Co)-doped zinc oxide (ZnO) thin films prepared by oxidizing evaporated Zn/Co bilayer thin films in open air was studied. The relationship between the structure and properties of films oxidized with and without an applied magnetic field was analyzed. The results show that the high magnetic field obviously changed the structure and properties of the Co-doped ZnO films. The Lorentz force of the high magnetic field suppressed the oxidation growth on nanowhiskers. As a result, ZnO nanowires were formed without a magnetic field, whereas polyhedral particles formed under a 6 T magnetic field. This morphology variation from dendrite to polyhedron caused the transmittance below 1,200 nm of the film oxidized under a magnetic field of 6 T to be much lower than that of the film oxidized without a magnetic field. X-ray photoemission spectroscopy indicated that the high magnetic field suppressed Co substitution in the ZnO lattice, increased the concentration of oxygen vacancies, and changed the chemical state of Co. The increased concentration of oxygen vacancies affected the temperature dependence of the resistivity of the film oxidized under a magnetic field of 6 T compared with that of the film oxidized without a magnetic field. The changes of oxygen vacancy concentration and Co state caused by the application of the high magnetic field also increase the ferromagnetism of the film at room temperature. All of these results indicate that a high magnetic field is an effective tool to modify the structure and properties of ZnO thin films.

  10. Weight of Polyethylene Wear Particles is Similar in TKAs with Oxidized Zirconium and Cobalt-chrome Prostheses

    PubMed Central

    Kim, Jun-Shik; Huh, Wansoo; Lee, Kwang-Hoon

    2009-01-01

    Background The greater lubricity and resistance to scratching of oxidized zirconium femoral components are expected to result in less polyethylene wear than cobalt-chrome femoral components. Questions/purposes We examined polyethylene wear particles in synovial fluid and compared the weight, size (equivalent circle diameter), and shape (aspect ratio) of polyethylene wear particles in knees with an oxidized zirconium femoral component with those in knees with a cobalt-chrome femoral component. Patients and Methods One hundred patients received an oxidized zirconium femoral component in one knee and a cobalt-chrome femoral component in the other. There were 73 women and 27 men with a mean age of 55.6 years (range, 44–60 years). The minimum followup was 5 years (mean, 5.5 years; range, 5–6 years). Polyethylene wear particles were analyzed using thermogravimetric methods and scanning electron microscopy. Results The weight of polyethylene wear particles produced at the bearing surface was 0.0223 ± 0.0054 g in 1 g synovial fluid in patients with an oxidized zirconium femoral component and 0.0228 ± 0.0062 g in patients with a cobalt-chrome femoral component. Size and shape of polyethylene wear particles were 0.59 ± 0.05 μm and 1.21 ± 0.24, respectively, in the patients with an oxidized zirconium femoral component and 0.52 ± 0.03 μm and 1.27 ± 0.31, respectively, in the patients with a cobalt-chrome femoral component. Knee Society knee and function scores, radiographic results, and complication rate were similar between the knees with an oxidized zirconium and cobalt-chrome femoral component. Conclusions The weight, size, and shape of polyethylene wear particles were similar in the knees with an oxidized zirconium and a cobalt-chrome femoral component. We found the theoretical advantages of this surface did not provide the actual advantage. Level of Evidence Level I, therapeutic study. See the guidelines for Authors for a complete

  11. In vitro assessment of cobalt oxide particle toxicity: identifying and circumventing interference.

    PubMed

    Darolles, Carine; Sage, Nicole; Armengaud, Jean; Malard, Véronique

    2013-09-01

    The continuing development of nanotechnology necessitates the reliable assessment of potential adverse health consequences associated with human exposures. The physicochemical properties of nanomaterials can be responsible for unexpected interactions with components of classical toxicity assays, which may generate erroneous interpretations. In this paper, we describe how particle interference can be observed in in vitro toxicity tests (CellTiter Blue, CyQUANT, WST-1 and CellTiter-Glo assay) and in cell biology tests using flow cytometry (cell cycle analysis). We used cobalt oxide (Co3O4) particles as an example, but these assays can be performed, in principle, regardless of the nanoparticle considered. We have shown that cobalt particles interfere with most of these tests. We adapted the protocol of the CellTiter-Glo assay to circumvent this interference and demonstrated that, using this protocol, the toxicity level is consistent with results obtained using the clonogenic assay, which is considered to be the reference test. Before assessing particle toxicity using in vitro toxicity tests, interference testing should be performed to avoid false interpretations. Furthermore, in some cases of interference, protocol adaptation can be considered to allow the reliable use of these quick and convenient in vitro tests.

  12. Mid-term survivorship and clinical outcomes of cobalt-chrome and oxidized zirconium on highly crosslinked polyethylene.

    PubMed

    Petis, Stephen M; Vasarhelyi, Edward M; Lanting, Brent A; Howard, James L; Naudie, Douglas D R; Somerville, Lyndsay E; McCalden, Richard W

    2016-02-01

    The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan-Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0-10.6) years for cobalt-chrome and 7.8 (range 2.1-10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%-97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%-99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%-98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%-99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up.

  13. Fine-Tuning the Activity of Metal-Organic Framework-Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane.

    PubMed

    Li, Zhanyong; Peters, Aaron W; Platero-Prats, Ana E; Liu, Jian; Kung, Chung-Wei; Noh, Hyunho; DeStefano, Matthew R; Schweitzer, Neil M; Chapman, Karena W; Hupp, Joseph T; Farha, Omar K

    2017-10-04

    Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal-organic framework (MOF) NU-1000, have been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 followed by Co(II) ion deposition, yielding a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Using difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the promoter ions are sited between pairs of Zr6 nodes along the MOF c axis whereas the location of the cobalt ions varies with the promoter ions. These NU-1000-supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando X-ray absorption spectroscopy at the Co K-edge. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)cobalt(III)-oxyl/propane transition state as the Lewis acidity of the promoter ions decreases. The results point to an increasing ability to fine-tune the structure-dependent activity of MOF-supported heterogeneous catalysts. Coupled with mechanistic studies-computational or experimental-this ability may translate into informed prediction of improved catalysts for propane ODH and other chemical reactions.

  14. High rate sodium ion battery anodes from block copolymer templated mesoporous nickel–cobalt carbonates and oxides

    SciTech Connect

    Bhaway, Sarang M.; Tangvijitsakul, Pattarasai; Lee, Jeongwoo; Soucek, Mark D.; Vogt, Bryan D.

    2015-09-16

    Micelle-templated ordered mesoporous nickel–cobalt carbonates and oxides are fabricated using a metal nitrate–citric acid strategy, which avoids the hydrolysis and aging requirements associated with sol–gel chemistry. A series of mesoporous NixCo(3-x)(CO3)y and NixCo(3-x)O4 films with varying Ni–Co compositions and 14 ± 4 nm mesopores are fabricated with the same block copolymer template. AFM and GISAXS analysis indicates that the mesostructure is maintained through the formation of the carbonate and oxide, while GIXD profiles confirm formation of pure spinel phases of semi-crystalline NixCo(3-x)O4. The micelle templated mesopores are interconnected and provide transport paths for the electrolyte to minimize the solid-state diffusion requirements associated with battery electrodes. These materials exhibit good performance as sodium ion battery anodes even at high current densities of 4 A g-1. Amongst the mixed-metal oxides, Ni2CoO4 exhibits the highest specific capacity of 239 mA h g-1 after galvanostatic cycling at a current density of 1 A g-1 for 10 cycles. We attribute the superior performance of Ni2CoO4 at high rates to the high surface area and short ion-diffusion paths of the nanoporous anode architecture, while the higher nickel content in the mixed metal oxide provides enhanced stability during oxide formation along with enhanced electronic conductivity, leading to improved cycling stability of the anode. This micelle template metal nitrate–citric acid method enables new possibilities for fabricating variety of ordered mesoporous mixed-metal carbonates and oxides that could be used in a wide range of applications.

  15. Low-solubility particles and a Trojan-horse type mechanism of toxicity: the case of cobalt oxide on human lung cells

    PubMed Central

    2014-01-01

    Background The mechanisms of toxicity of metal oxide particles towards lung cells are far from being understood. In particular, the relative contribution of intracellular particulate versus solubilized fractions is rarely considered as it is very challenging to assess, especially for low-solubility particles such as cobalt oxide (Co3O4). Methods This study was possible owing to two highly sensitive, independent, analytical techniques, based on single-cell analysis, using ion beam microanalysis, and on bulk analysis of cell lysates, using mass spectrometry. Results Our study shows that cobalt oxide particles, of very low solubility in the culture medium, are readily incorporated by BEAS-2B human lung cells through endocytosis via the clathrin-dependent pathway. They are partially solubilized at low pH within lysosomes, leading to cobalt ions release. Solubilized cobalt was detected within the cytoplasm and the nucleus. As expected from these low-solubility particles, the intracellular solubilized cobalt content is small compared with the intracellular particulate cobalt content, in the parts-per-thousand range or below. However, we were able to demonstrate that this minute fraction of intracellular solubilized cobalt is responsible for the overall toxicity. Conclusions Cobalt oxide particles are readily internalized by pulmonary cells via the endo-lysosomal pathway and can lead, through a Trojan-horse mechanism, to intracellular release of toxic metal ions over long periods of time, involving specific toxicity. PMID:24669904

  16. Electrodepostion of nanocrystalline cobalt iron and cobalt iron nickel soft magnetic thin films from citrate-added baths

    NASA Astrophysics Data System (ADS)

    Zhang, Yahui

    2005-11-01

    With increasing storage density of hard-disk-drives, the need for recording heads to write on high-coercivity media has raised new requirements for the write-head core material that cannot be met by traditionally employed permalloy (Ni80Fe20). Therefore, new soft magnetic materials with higher saturation flux density Bs (>>1 Tesla) such as CoFe alloys, CoFeNi alloys, and other CoFe-based alloys have been developed during the past decades. With the advantages of simplicity, cost-effectiveness and controllable patterning, electroplating processes are being employed in the fabrication of thin-film recording heads. Conventional CoFe or CoFeNi alloy plating baths, which employ low pH levels (typically 2.0-3.0), suffer from several problems that can limit commercialization. These include poor stability, i.e., precipitation occurs in plating baths rapidly with time, low current density efficiency and voids in deposited films due to the electrodeposition of hydrogen. The voids present in deposits will degenerate film uniformity and magnetic properties. Therefore, the development of stable baths with relatively high pH levels is crucial for commercial fabrication of CoFe and CoFeNi thin films with optimal soft magnetic properties. In this study, stable electrolytes, with the introduction of ammonium citrate as a complexing agent and bath stabilizer and relatively high pH levels (natural pH), have been developed for the electrodeposition of CoFe or CoFeNi alloys. Citrate can effectively improve the stability of CoFe and CoFeNi plating baths. Denser and more uniform deposits can be plated out from the citrate-added baths because of the higher pH levels. CoFe and CoFeNi thin films with preferred composition, mixed fcc-bcc phases, and 10-20nm grain sizes, which are necessary for achieving optimal soft magnetic properties, have been electroplated from the citrate-added baths. So far, the saturation magnetizations of CoFe and CoFeNi films plated from citrate-added baths can

  17. Oxidative and pro-inflammatory effects of cobalt and titanium oxide nanoparticles on aortic and venous endothelial cells.

    PubMed

    Alinovi, Rossella; Goldoni, Matteo; Pinelli, Silvana; Campanini, Marco; Aliatis, Irene; Bersani, Danilo; Lottici, Pier Paolo; Iavicoli, Sergio; Petyx, Marta; Mozzoni, Paola; Mutti, Antonio

    2015-04-01

    Ultra-fine particles have recently been included among the risk factors for the development of endothelium inflammation and atherosclerosis, and cobalt (CoNPs) and titanium oxide nanoparticles (TiNPs) have attracted attention because of their wide range of applications. We investigated their toxicity profiles in two primary endothelial cell lines derived from human aorta (HAECs) and human umbilical vein (HUVECs) by comparing cell viability, oxidative stress, the expression of adhesion molecules and the release of chemokines during NP exposure. Both NPs were very rapidly internalised, and significantly increased adhesion molecule (ICAM-1, VCAM-1, E-selectin) mRNA and protein levels and the release of monocyte chemoattractant protein-1 (MCP-1) and interleukin 8 (IL-8). However, unlike the TiNPs, the CoNPs also induced time- and concentration-dependent metabolic impairment and oxidative stress without any evident signs of cell death or the induction of apoptosis. There were differences between the HAECs and HUVECs in terms of the extent of oxidative stress-related enzyme and vascular adhesion molecule expression, ROS production, and pro-inflammatory cytokine release despite the similar rate of NP internalisation, thus indicating endothelium heterogeneity in response to exogenous stimuli. Our data indicate that NPs can induce endothelial inflammatory responses via various pathways not involving only oxidative stress.

  18. Controllable synthesis of cobalt oxide nanoflakes on three-dimensional porous cobalt networks as high-performance cathode for alkaline hybrid batteries

    SciTech Connect

    Chen, Minghua; Xia, Xinhui; Zhang, Jiawei; Qi, Meili; Yin, Jinghua; Chen, Qingguo

    2016-02-15

    Highlights: • Construct self-supported porous Co networks. • Porous Co/CoO composite films show high capacity and good cycling life. • Porous conductive metal network is favorable for fast ion/electron transfer. - Abstract: Herein we report porous three-dimensional cobalt networks supported CoO nanoflakes by the combination of successive electro-deposition methods. The electrodeposited Co networks have average large pores of ∼5 μm and all the branches are composed of interconnected nanoparticles. CoO nanoflakes with thickness of ∼15 nm are uniformly coated on the Co networks forming self-supported Co/CoO composite films. The as-prepared Co/CoO composite films possess combined properties of porous structure and strong mechanical stability. As cathode for alkaline hybrid batteries, the Co/CoO composite films exhibit good electrochemical performances with high capacity of 83.5 mAh g{sup −1} at 1 A g{sup −1} and stable high-rate cycling life (65 mAh g{sup −1} at 10 A g{sup −1} after 15,000 cycles). The hierarchical porous architecture provides positive roles in the enhancement of electrochemical properties, including fast electronic transportation path, short diffusion of ions and high contact area between the active material and the electrolyte.

  19. Oxyanion Induced Variations in Domain Structure for Amorphous Cobalt Oxide Oxygen Evolving Catalysts, Resolved by X-ray Pair Distribution Function Analysis

    DOE PAGES

    Kwon, Gihan; Kokhan, Oleksandr; Han, Ali; ...

    2015-12-01

    Amorphous thin film oxygen evolving catalysts, OECs, of first-row transition metals show promise to serve as self-assembling photoanode materials in solar-driven, photoelectrochemical `artificial leaf' devices. This report demonstrates the ability to use high-energy X-ray scattering and atomic pair distribution function analysis, PDF, to resolve structure in amorphous metal oxide catalyst films. The analysis is applied here to resolve domain structure differences induced by oxyanion substitution during the electrochemical assembly of amorphous cobalt oxide catalyst films, Co-OEC. PDF patterns for Co-OEC films formed using phosphate, Pi, methylphosphate, MPi, and borate, Bi, electrolyte buffers show that the resulting domains vary in sizemore » following the sequence Pi < MPi < Bi. The increases in domain size for CoMPi and CoBi were found to be correlated with increases in the contributions from bilayer and trilayer stacked domains having structures intermediate between those of the LiCoOO and CoO(OH) mineral forms. The lattice structures and offset stacking of adjacent layers in the partially stacked CoMPi and CoBi domains were best matched to those in the LiCoOO layered structure. The results demonstrate the ability of PDF analysis to elucidate features of domain size, structure, defect content and mesoscale organization for amorphous metal oxide catalysts that are not readily accessed by other X-ray techniques. Finally, PDF structure analysis is shown to provide a way to characterize domain structures in different forms of amorphous oxide catalysts, and hence provide an opportunity to investigate correlations between domain structure and catalytic activity.« less

  20. Oxyanion Induced Variations in Domain Structure for Amorphous Cobalt Oxide Oxygen Evolving Catalysts, Resolved by X-ray Pair Distribution Function Analysis

    SciTech Connect

    Kwon, Gihan; Kokhan, Oleksandr; Han, Ali; Chapman, Karena W.; Chupas, Peter J.; Du, Pingwu; Tiede, David M.

    2015-12-01

    Amorphous thin film oxygen evolving catalysts, OECs, of first-row transition metals show promise to serve as self-assembling photoanode materials in solar-driven, photoelectrochemical `artificial leaf' devices. This report demonstrates the ability to use high-energy X-ray scattering and atomic pair distribution function analysis, PDF, to resolve structure in amorphous metal oxide catalyst films. The analysis is applied here to resolve domain structure differences induced by oxyanion substitution during the electrochemical assembly of amorphous cobalt oxide catalyst films, Co-OEC. PDF patterns for Co-OEC films formed using phosphate, Pi, methylphosphate, MPi, and borate, Bi, electrolyte buffers show that the resulting domains vary in size following the sequence Pi < MPi < Bi. The increases in domain size for CoMPi and CoBi were found to be correlated with increases in the contributions from bilayer and trilayer stacked domains having structures intermediate between those of the LiCoOO and CoO(OH) mineral forms. The lattice structures and offset stacking of adjacent layers in the partially stacked CoMPi and CoBi domains were best matched to those in the LiCoOO layered structure. The results demonstrate the ability of PDF analysis to elucidate features of domain size, structure, defect content and mesoscale organization for amorphous metal oxide catalysts that are not readily accessed by other X-ray techniques. Finally, PDF structure analysis is shown to provide a way to characterize domain structures in different forms of amorphous oxide catalysts, and hence provide an opportunity to investigate correlations between domain structure and catalytic activity.

  1. Low-Energy Excitation Spectra in the Excitonic Phase of Cobalt Oxides

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Tomoki; Sugimoto, Koudai; Ohta, Yukinori

    2017-04-01

    We study the excitonic phase and low-energy excitation spectra of perovskite cobalt oxides. Constructing the five-orbital Hubbard model defined on the three-dimensional cubic lattice for the 3d bands of Pr0.5Ca0.5CoO3, we calculate the excitonic susceptibility in the normal state in the random-phase approximation (RPA) to show the presence of the instability toward excitonic condensation. On the basis of the excitonic ground state with a magnetic multipole obtained in the mean-field approximation, we calculate the dynamical susceptibility of the excitonic phase in the RPA and find that there appear a gapless collective excitation in the spin-transverse mode (Goldstone mode) and a gapful collective excitation in the spin-longitudinal mode (Higgs mode). The experimental relevance of our results is discussed.

  2. Light-induced water oxidation at silicon electrodes functionalized with a cobalt oxygen-evolving catalyst

    PubMed Central

    Pijpers, Joep J. H.; Winkler, Mark T.; Surendranath, Yogesh; Buonassisi, Tonio; Nocera, Daniel G.

    2011-01-01

    Integrating a silicon solar cell with a recently developed cobalt-based water-splitting catalyst (Co-Pi) yields a robust, monolithic, photo-assisted anode for the solar fuels process of water splitting to O2 at neutral pH. Deposition of the Co-Pi catalyst on the Indium Tin Oxide (ITO)-passivated p-side of a np-Si junction enables the majority of the voltage generated by the solar cell to be utilized for driving the water-splitting reaction. Operation under neutral pH conditions fosters enhanced stability of the anode as compared to operation under alkaline conditions (pH 14) for which long-term stability is much more problematic. This demonstration of a simple, robust construct for photo-assisted water splitting is an important step towards the development of inexpensive direct solar-to-fuel energy conversion technologies. PMID:21646536

  3. Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis

    PubMed Central

    Ling, Tao; Yan, Dong-Yang; Jiao, Yan; Wang, Hui; Zheng, Yao; Zheng, Xueli; Mao, Jing; Du, Xi-Wen; Hu, Zhenpeng; Jaroniec, Mietek; Qiao, Shi-Zhang

    2016-01-01

    Engineering the surface structure at the atomic level can be used to precisely and effectively manipulate the reactivity and durability of catalysts. Here we report tuning of the atomic structure of one-dimensional single-crystal cobalt (II) oxide (CoO) nanorods by creating oxygen vacancies on pyramidal nanofacets. These CoO nanorods exhibit superior catalytic activity and durability towards oxygen reduction/evolution reactions. The combined experimental studies, microscopic and spectroscopic characterization, and density functional theory calculations reveal that the origins of the electrochemical activity of single-crystal CoO nanorods are in the oxygen vacancies that can be readily created on the oxygen-terminated {111} nanofacets, which favourably affect the electronic structure of CoO, assuring a rapid charge transfer and optimal adsorption energies for intermediates of oxygen reduction/evolution reactions. These results show that the surface atomic structure engineering is important for the fabrication of efficient and durable electrocatalysts. PMID:27650485

  4. In Vivo Wear Performance of Cobalt-Chromium Versus Oxidized Zirconium Femoral Total Knee Replacements.

    PubMed

    Gascoyne, Trevor C; Teeter, Matthew G; Guenther, Leah E; Burnell, Colin D; Bohm, Eric R; Naudie, Douglas R

    2016-01-01

    This study examines the damage and wear on the polyethylene (PE) inserts from 52 retrieved Genesis II total knee replacements to identify differences in tribological performance between matched pairs of cobalt-chromium (CoCr) and oxidized zirconium (OxZr) femoral components. Observer damage scoring and microcomputed tomography were used to quantify PE damage and wear, respectively. No significant differences were found between CoCr and OxZr groups in terms of PE insert damage, surface penetration, or wear. No severe damage such as cracking or delamination was noted on any of the 52 PE inserts. Observer damage scoring did not correlate with penetrative or volumetric PE wear. The more costly OxZr femoral component does not demonstrate clear tribological benefit over the standard CoCr component in the short term with this total knee replacement design.

  5. Cobalt oxide nanosheets wrapped onto nickel foam for non-enzymatic detection of glucose

    NASA Astrophysics Data System (ADS)

    Meng, Shangjun; Wu, Meiyan; Wang, Qian; Dai, Ziyang; Si, Weili; Huang, Wei; Dong, Xiaochen

    2016-08-01

    Ultra-sensitive and highly selective detection of glucose is essential for the clinical diagnosis of diabetes. In this paper, an ultra-sensitive glucose sensor was successfully fabricated based on cobalt oxide (Co3O4) nanosheets directly grown on nickel foam through a simple hydrothermal method. Characterizations indicated that the Co3O4 nanosheets are completely and uniformly wrapped onto the surface of nickel foam to form a three-dimensional heterostructure. The resulting self-standing electrochemical electrode presents a high performance for the non-enzymatic detection of glucose, including short response time (<10 s), ultra-sensitivity (12.97 mA mM-1 cm-2), excellent selectivity and low detection limit (0.058 μM, S/N = 3). These results indicate that Co3O4 nanosheets wrapped onto nickel foam are a low-cost, practical, and high performance electrochemical electrode for bio sensing.

  6. Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis.

    PubMed

    Ling, Tao; Yan, Dong-Yang; Jiao, Yan; Wang, Hui; Zheng, Yao; Zheng, Xueli; Mao, Jing; Du, Xi-Wen; Hu, Zhenpeng; Jaroniec, Mietek; Qiao, Shi-Zhang

    2016-09-21

    Engineering the surface structure at the atomic level can be used to precisely and effectively manipulate the reactivity and durability of catalysts. Here we report tuning of the atomic structure of one-dimensional single-crystal cobalt (II) oxide (CoO) nanorods by creating oxygen vacancies on pyramidal nanofacets. These CoO nanorods exhibit superior catalytic activity and durability towards oxygen reduction/evolution reactions. The combined experimental studies, microscopic and spectroscopic characterization, and density functional theory calculations reveal that the origins of the electrochemical activity of single-crystal CoO nanorods are in the oxygen vacancies that can be readily created on the oxygen-terminated {111} nanofacets, which favourably affect the electronic structure of CoO, assuring a rapid charge transfer and optimal adsorption energies for intermediates of oxygen reduction/evolution reactions. These results show that the surface atomic structure engineering is important for the fabrication of efficient and durable electrocatalysts.

  7. Synthesis of Novel Nanostructured Lanthanum Cobalt Ferrite Mixed Metal Oxides by Sol-Gel

    NASA Astrophysics Data System (ADS)

    Teresita, V. Mary; Jeseentharani, V.; Josephine, B. Avila; Antony, S. Arul

    2013-04-01

    Properties of nanoscale materials are very interesting and these are either comparable to or superior to those of bulk. These materials are interesting due to their exciting size dependent optical, electronic, magnetic, thermal, mechanical and chemical properties. Different mole ratios of nanostructured mixed metal oxides of LaCoxFe1-xO3-δ (x = 0 to 1) were prepared by the sol-gel method by varying the mole ratios of iron and cobalt substrates. The compounds were sintered for 700°C in the tubular furnace for 8 h. The purity of the compounds was analyzed by TG-DTA. The compounds were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and scanning electron microscopy (SEM) studies were employed to study the structural phases, vibrational frequencies, surface morphology of the highest humidity sensing compounds.

  8. Water dispersible superparamagnetic Cobalt iron oxide nanoparticles for magnetic fluid hyperthermia

    NASA Astrophysics Data System (ADS)

    Salunkhe, Ashwini B.; Khot, Vishwajeet M.; Ruso, Juan M.; Patil, S. I.

    2016-12-01

    Superparamagnetic nanoparticles of Cobalt iron oxide (CoFe2O4) are synthesized chemically, and dispersed in an aqueous suspension for hyperthermia therapy application. Different parameters such as magnetic field intensity, particle concentration which regulates the competence of CoFe2O4 nanoparticle as a heating agents in hyperthermia are investigated. Specific absorption rate (SAR) decreases with increase in the particle concentration and increases with increase in applied magnetic field intensity. Highest value of SAR is found to be 91.84 W g-1 for 5 mg. mL-1 concentration. Oleic acid conjugated polyethylene glycol (OA-PEG) coated CoFe2O4 nanoparticles have shown superior cyto-compatibility over uncoated nanoparticles to L929 mice fibroblast cell lines for concentrations below 2 mg. mL-1. Present work provides the underpinning for the use of CoFe2O4 nanoparticles as a potential heating mediator for magnetic fluid hyperthermia.

  9. New misfit-layered cobalt oxide (CaOH) 1.14CoO 2

    NASA Astrophysics Data System (ADS)

    Shizuya, Mitsuyuki; Isobe, Masaaki; Baba, Yuji; Nagai, Takuro; Osada, Minoru; Kosuda, Kosuke; Takenouchi, Satoshi; Matsui, Yoshio; Takayama-Muromachi, Eiji

    2007-01-01

    We synthesized a new cobalt oxide (CaOH) 1.14CoO 2 by utilizing a high-pressure technique. X-ray and electron diffraction studies revealed that the compound has a layered structure that consists of CdI 2-type CoO 2 layers and rock-salt-type double CaOH atomic layers. The two subcells have incommensurate periodicity along the a-axis, resulting in a misfit-layered structure. From resistivity and Seebeck coefficient measurements, we have shown that the two-dimensional (2-D) variable-range hopping (VRH) regime with hole conduction is dominant at low temperature for this compound. As temperature increases, the conduction mechanism undergoes crossover from the 2-D VRH regime to a thermal activation-energy-type regime.

  10. Electronic structure of sodium cobalt oxide: Comparing mono- and bilayer hydrate

    NASA Astrophysics Data System (ADS)

    Arita, Ryotaro

    2005-04-01

    To shed light on the mechanism of superconductivity in sodium cobalt oxide bilayer-hydrate (BLH), we perform a density functional calculation with full structure optimization for BLH and its related nonsuperconducting phase, monolayer hydrate (MLH). We find that these hydrates have similar band structures, but a notable difference can be seen in the a1g band around the Fermi level. While its dispersion in the z direction is negligibly small for BLH, it is of the order of 0.1eV for MLH. This result implies that the three-dimensional feature of the a1g band may be the origin for the absence of superconductivity in MLH.

  11. In-situ fabrication of nanostructured cobalt oxide powders by spray pyrolysis technique.

    PubMed

    Zhao, Z W; Konstantinov, K; Yuan, L; Liu, H K; Dou, S X

    2004-09-01

    Nano-crystalline Co3O4 and CoO powders have been prepared by a spray pyrolysis approach. The effects of the reaction temperature and initial salts on the crystallinity and phase composition have been studied. Based on the TEM and XRD results, the crystal sizes were in the range of 1-10 nm. SEM and TEM observations also reveal that the nano-powders easily create micron-scale spherical agglomerates. The Co3O4 powders obtained by spraying nitrate solution at 500 degrees C show high specific surface area, which according to the BET method is 82.37 m2/g. The time/temperature phase diagram of cobalt oxides developed from XRD and DTA/TGA analyses shows the existence of a CoO phase at low and high temperature ranges when some specific preparation conditions are applied.

  12. Light-induced water oxidation at silicon electrodes functionalized with a cobalt oxygen-evolving catalyst.

    PubMed

    Pijpers, Joep J H; Winkler, Mark T; Surendranath, Yogesh; Buonassisi, Tonio; Nocera, Daniel G

    2011-06-21

    Integrating a silicon solar cell with a recently developed cobalt-based water-splitting catalyst (Co-Pi) yields a robust, monolithic, photo-assisted anode for the solar fuels process of water splitting to O(2) at neutral pH. Deposition of the Co-Pi catalyst on the Indium Tin Oxide (ITO)-passivated p-side of a np-Si junction enables the majority of the voltage generated by the solar cell to be utilized for driving the water-splitting reaction. Operation under neutral pH conditions fosters enhanced stability of the anode as compared to operation under alkaline conditions (pH 14) for which long-term stability is much more problematic. This demonstration of a simple, robust construct for photo-assisted water splitting is an important step towards the development of inexpensive direct solar-to-fuel energy conversion technologies.

  13. Effects of hexaammine cobalt (III) chloride on oxidative stress-related parameters and drug metabolizing enzymes in mice.

    PubMed

    Singh, Amarjit; Kalla, Natwar R; Sharma, Raj P; Sharma, Rajeshwar

    2007-01-01

    Hexaammine cobalt (III) chloride has been advocated as a potential anticarcinogenic compound. There is no information on the effects of this compound on oxidative stress-related parameters in animals. In the present study the effects of administration of hexaammine cobalt (III) chloride in drinking water to balb/c male mice at doses of 25, 50, and 100 ppm for 14 weeks were examined. The tissue distribution of the compound was seen in liver, kidney, lung, intestine, blood, and spleen. The effects of the compound were monitored on levels of lipid peroxidation, GSH content, and activities of SOD, catalase, GST, and Cyt P450, along with the liver and kidney function tests. The results show that the cobalt accumulated maximally in kidney followed by liver, intestine, blood, spleen, and lung in decreasing order, in a dose-dependent manner. GSH and GST also showed increase in a dose-dependent manner while SOD and catalase showed increase with the highest dose only. Liver and kidney function tests showed no untoward change with any dose at the end of the study. The results suggest an antioxidant potentiating effect of the hexaammine cobalt (III) chloride besides nontoxicity to liver and kidney. Since the ability to induce an increase of GSH and GST along with other detoxifying enzymes by anticarcinogenic agents has been reported to correlate with the inhibition of tumorigenesis, the cobalt complex might qualify as a potential cancer chemopreventive agent.

  14. Structural and magnetic properties of cobalt-doped iron oxide nanoparticles prepared by solution combustion method for biomedical applications

    PubMed Central

    Venkatesan, Kaliyamoorthy; Rajan Babu, Dhanakotti; Kavya Bai, Mane Prabhu; Supriya, Ravi; Vidya, Radhakrishnan; Madeswaran, Saminathan; Anandan, Pandurangan; Arivanandhan, Mukannan; Hayakawa, Yasuhiro

    2015-01-01

    Cobalt-doped iron oxide nanoparticles were prepared by solution combustion technique. The structural and magnetic properties of the prepared samples were also investigated. The average crystallite size of cobalt ferrite (CoFe2O4) magnetic nanoparticle was calculated using Scherrer equation, and it was found to be 16±5 nm. The particle size was measured by transmission electron microscope. This value was found to match with the crystallite size calculated by Scherrer equation corresponding to the prominent intensity peak (311) of X-ray diffraction. The high-resolution transmission electron microscope image shows clear lattice fringes and high crystallinity of cobalt ferrite magnetic nanoparticles. The synthesized magnetic nanoparticles exhibited the saturation magnetization value of 47 emu/g and coercivity of 947 Oe. The anti-microbial activity of cobalt ferrite nanoparticles showed better results as an anti-bacterial agent. The affinity constant was determined for the nanoparticles, and the cytotoxicity studies were conducted for the cobalt ferrite nanoparticles at different concentrations and the results are discussed. PMID:26491320

  15. Structural and magnetic properties of cobalt-doped iron oxide nanoparticles prepared by solution combustion method for biomedical applications.

    PubMed

    Venkatesan, Kaliyamoorthy; Rajan Babu, Dhanakotti; Kavya Bai, Mane Prabhu; Supriya, Ravi; Vidya, Radhakrishnan; Madeswaran, Saminathan; Anandan, Pandurangan; Arivanandhan, Mukannan; Hayakawa, Yasuhiro

    2015-01-01

    Cobalt-doped iron oxide nanoparticles were prepared by solution combustion technique. The structural and magnetic properties of the prepared samples were also investigated. The average crystallite size of cobalt ferrite (CoFe2O4) magnetic nanoparticle was calculated using Scherrer equation, and it was found to be 16±5 nm. The particle size was measured by transmission electron microscope. This value was found to match with the crystallite size calculated by Scherrer equation corresponding to the prominent intensity peak (311) of X-ray diffraction. The high-resolution transmission electron microscope image shows clear lattice fringes and high crystallinity of cobalt ferrite magnetic nanoparticles. The synthesized magnetic nanoparticles exhibited the saturation magnetization value of 47 emu/g and coercivity of 947 Oe. The anti-microbial activity of cobalt ferrite nanoparticles showed better results as an anti-bacterial agent. The affinity constant was determined for the nanoparticles, and the cytotoxicity studies were conducted for the cobalt ferrite nanoparticles at different concentrations and the results are discussed.

  16. Porous Nickel Oxide Film Sensor for Formaldehyde

    NASA Astrophysics Data System (ADS)

    Cindemir, U.; Topalian, Z.; Österlund, L.; Granqvist, C. G.; Niklasson, G. A.

    2014-11-01

    Formaldehyde is a volatile organic compound and a harmful indoor pollutant contributing to the "sick building syndrome". We used advanced gas deposition to fabricate highly porous nickel oxide (NiO) thin films for formaldehyde sensing. The films were deposited on Al2O3 substrates with prefabricated comb-structured electrodes and a resistive heater at the opposite face. The morphology and structure of the films were investigated with scanning electron microscopy and X-ray diffraction. Porosity was determined by nitrogen adsorption isotherms with the Brunauer-Emmett-Teller method. Gas sensing measurements were performed to demonstrate the resistive response of the sensors with respect to different concentrations of formaldehyde at 150 °C.

  17. Part I. Synthesis and applications of molecular sieves. Part II. The effect of temperature and support in reduction of cobalt oxide: An in situ XRD study

    NASA Astrophysics Data System (ADS)

    Garces Trujillo, Luis Javier

    Part I. Alkylation of aniline (PhNH2) with methanol (MeOH) over co-crystallized zeolite RHO-Zeolite X (FAU) and over zeolite Linde Type L (Sr,K-LTL) as catalysts has been studied. Co-crystallized zeolite RHO-Zeolite X (FAU) favors the formation of N,N-dimethylaniline (NNDMA), with high selectivity >90%, having an advantage over pure zeolite X(FAU) of staying active even after 10 h of reaction. Activity of co-crystallized RHO-Zeolite X (FAU) is higher than that for Sr,K-LTL in terms of production of NNDMA. Octahedral molecular sieves (OMS-2) have been reported as catalysts for oxidation reactions. Effects of using polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) in the synthesis of OMS-2 have been studied. Structure of OMS-2 was kept when PVA or PVP were used as indicated by XRD and FTIR data. PVA and PVP were useful to improve the film hardness of OMS-2 applied on glass surfaces as measured by the pencil hardness test, and Knoop microhardness test. By using PVA or PVP as non-chelating agents, an increase in surface area from 59 (m2/g) to 114 (m2/g), a decrease in particle size, from 29.8 nm to 12.1 nm, and a hardness value of 4H using the pencil hardness test, and 17.73 HK by Knoops micro hardness tests for OMS-2 prepared with PVA were observed. ZK-5 (KFI) molecular sieve was synthesized in the K2O: SrO: Al2O3: SiO2: 160 H2O: THF system using conventional hydrothermal heating. Products were characterized by XRD, TGA, FESEM, EDX and TPD-MS. Molar ratios of THF/Al2O3 from 0.4 to 1.0 gives best results in terms of crystallinity and purity for the prepared ZK-5. Part II. Reduction of cobalt oxide (Co 3O4) at different temperatures and in combination with different modifiers and supported on gamma-Al2O3 was monitored by in situ X-ray diffraction. Complete reduction of cobalt oxide to the (hcp) phase is observed at 250°C. Different reduction sequence can give different results in terms of crystalline phase obtained for cobalt even if the same maximum reduction

  18. Metallic oxide switches using thick film technology

    NASA Technical Reports Server (NTRS)

    Patel, D. N.; Williams, L., Jr.

    1974-01-01

    Metallic oxide thick film switches were processed on alumina substrates using thick film technology. Vanadium pentoxide in powder form was mixed with other oxides e.g., barium, strontium copper and glass frit, ground to a fine powder. Pastes and screen printable inks were made using commercial conductive vehicles and appropriate thinners. Some switching devices were processed by conventional screen printing and firing of the inks and commercial cermet conductor terminals on 96% alumina substrates while others were made by applying small beads or dots of the pastes between platinum wires. Static, and dynamic volt-ampere, and pulse tests indicate that the switching and self-oscillatory characteristics of these devices could make them useful in memory element, oscillator, and automatic control applications.

  19. Silicon oxide colloidal/polymer nanocomposite films

    SciTech Connect

    Wang Haifeng; Cao Wenwu; Zhou, Q.F.; Shung, K. Kirk; Huang, Y.H.

    2004-12-13

    The quarter-wavelength ({lambda}/4) acoustic matching layer, a vital component in medical ultrasonic transducer, can bridge the large acoustic impedance mismatch between the piezoelectric material and the human body. Composite materials are widely used as matching materials in order to cover the wide acoustic impedance range that cannot be accomplished by using a single-phase material. At high frequencies (>50 MHz), the {lambda}/4 matching layers become extremely thin so that the fabrication of homogeneous composite material matching layers becomes very challenging. A method is reported in this letter to fabricate sol-gel silicon oxide colloidal/polymer composite film on silicon substrate, in which the particle size of silicon oxide colloidal is between 10 and 40 nm. The acoustic impedance of the nanocomposite films versus aging temperature has been measured at the desired operating frequency.

  20. Silicon oxide colloidal/polymer nanocomposite films

    NASA Astrophysics Data System (ADS)

    Wang, Haifeng; Cao, Wenwu; Zhou, Q. F.; Shung, K. Kirk; Huang, Y. H.

    2004-12-01

    The quarter-wavelength (λ/4) acoustic matching layer, a vital component in medical ultrasonic transducer, can bridge the large acoustic impedance mismatch between the piezoelectric material and the human body. Composite materials are widely used as matching materials in order to cover the wide acoustic impedance range that cannot be accomplished by using a single-phase material. At high frequencies (>50MHz), the λ /4 matching layers become extremely thin so that the fabrication of homogeneous composite material matching layers becomes very challenging. A method is reported in this letter to fabricate sol-gel silicon oxide colloidal/polymer composite film on silicon substrate, in which the particle size of silicon oxide colloidal is between 10 and 40 nm. The acoustic impedance of the nanocomposite films versus aging temperature has been measured at the desired operating frequency.

  1. Enhanced Piezoelectric Response due to Polarization Rotation in Cobalt-Substituted BiFeO3 Epitaxial Thin Films.

    PubMed

    Shimizu, Keisuke; Hojo, Hajime; Ikuhara, Yuichi; Azuma, Masaki

    2016-10-01

    Polarization rotation induced by an external electric field in piezoelectric materials such as PbZr1-x Tix O3 is generally regarded as the origin of their large piezoelectric responses. Here, the piezoelectric responses of high-quality cobalt-substituted BiFeO3 epitaxial thin films with monoclinic distortions are systematically examined. It is demonstrated that polarization rotation plays a crucial role in improving the piezoelectric responses in this material. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Effect of Thermal Annealing on the Structural and Optical Properties Nanostructured Cobalt-Manganese and Cobalt-Nickel Oxides Prepared by Co-Precipitation

    NASA Astrophysics Data System (ADS)

    Indulal, C. R.; Kumar, G. Sajeev; Vaidyan, A. V.; Raveendran, R.

    2011-10-01

    Cobalt-Manganese and Cobalt-Nickel oxide (CoMnO and CoNiO) nanoparticles were synthesized via chemical co-precipitation method by decomposition of their respective metal sulfides and sodium carbonate using ethylene diamene tetra acetic acid as the capping agent. The samples were heated at 400, 600 and 800 °C. The average particle sizes were determined from the X-ray line broadening. The diffractogram were compared with JCPDS data to identify the crystallographic phase and cubic structure of the particles. The samples were characterized by XRD, FTIR and UV analyses. The internal elastic micro strains were calculated and it was seen that as the particle size increases strain decreases. The FTIR studies have been used to confirm the metal oxide formation. The chemical compositions of the samples were verified using EDX spectra. The surface morphologies of the samples were studied from the SEM images. The absorption spectra of the materials in the UV-Vis-NIR range were recorded. From the analysis of the absorption spectra, the direct band gaps of the materials were calculated.

  3. Catalytic reduction of nitric oxide with carbon monoxide on copper-cobalt oxides supported on nano-titanium dioxide.

    PubMed

    Chen, Xia; Zhang, Junfeng; Huang, Yan; Tong, Zhiquan; Huang, Ming

    2009-01-01

    A series of copper-cobalt oxides supported on nano-titanium dioxide were prepared for the reduction of nitric oxide with carbon monoxide and characterized using techniques such as XRD, BET and TPR. Catalyst CuCoOx/TiO2 with Cu/Co molar ratio of 1/2, Cu-Co total loading of 30% at the calcination temperature of 350 degrees C formed CuCo2O4 spinel and had the highest activity. NO conversion reached 98.9% at 200 degrees C. Mechanism of the reduction was also investigated, N2O was mainly yielded below 100 degrees C, while N2 was produced instead at higher temperature. O2 was supposed to accelerate the reaction between NOx and CO for its oxidation of NO to give more easily reduced NO2, but the oxidation of CO by O2 to CO2 decreased the speed of the reaction greatly. Either SO2 or H2O had no adverse impact on the activity of NO reduction; however, in the presence of both SO2 and H2O, the catalyst deactivated quickly.

  4. Water clustering on nanostructured iron oxide films.

    PubMed

    Merte, Lindsay R; Bechstein, Ralf; Peng, Guowen; Rieboldt, Felix; Farberow, Carrie A; Zeuthen, Helene; Knudsen, Jan; Lægsgaard, Erik; Wendt, Stefan; Mavrikakis, Manos; Besenbacher, Flemming

    2014-06-30

    The adhesion of water to solid surfaces is characterized by the tendency to balance competing molecule-molecule and molecule-surface interactions. Hydroxyl groups form strong hydrogen bonds to water molecules and are known to substantially influence the wetting behaviour of oxide surfaces, but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moiré-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer islands form on the bare film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous water are found to coexist at adjacent hydroxylated and hydroxyl-free domains of the moiré structure.

  5. Water Clustering on Nanostructured Iron Oxide Films

    SciTech Connect

    Merte, L. R.; Bechstein, Ralf; Peng, Guowen; Rieboldt, Felix; Farberow, Carrie A.; Zeuthen, Helene; Knudsen, Jan; Laegsgaard, E.; Wendt, Stefen; Mavrikakis, Manos; Besenbacher, Fleming

    2014-06-30

    The adhesion of water to solid surfaces is characterized by the tendency to balance competing molecule–molecule and molecule–surface interactions. Hydroxyl groups form strong hydrogen bonds to water molecules and are known to substantially influence the wetting behaviour of oxide surfaces, but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moire´-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer islands form on the are film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous water are found to coexist at adjacent hydroxylated and hydroxyl-free domains of the moire´ structure.

  6. Processes of nickel and cobalt uptake by a manganese oxide forming sediment in Pinal Creek, Globe mining district, Arizona

    USGS Publications Warehouse

    Kay, J.T.; Conklin, M.H.; Fuller, C.C.; O'Day, P. A.

    2001-01-01

    A series of column experiments was conducted using manganese oxide coated sediments collected from the hyporheic zone in Pinal Creek (AZ), a metal-contaminated stream, to study the uptake and retention of Mn, Ni, and Co. Experimental variables included the absence (abiotic) and presence (biotic) of active Mn-oxidizing bacteria, the absence and presence of dissolved Mn, and sediment manganese oxide content. Uptake of Mn under biotic conditions was between 8 and 39% higher than under abiotic conditions. Continuous uptake of Mn due to biotic oxidation was evident from extraction of column sediments. Manganese uptake is hypothesized to initially occur as adsorption, which led to subsequent surface and/or microbial oxidation. Complete breakthrough of Ni within 100 pore volumes indicated no process of continuous uptake and was modeled as an equilibrium adsorption process. Nickel uptake in the presence of dissolved Mn was 67-100% reversible. Sediment extractions suggest that Ni uptake occurred through weak and strong adsorption. Continuous uptake of cobalt increased with sediment manganese oxide content, and Co uptake was up to 75% greater under biotic than abiotic conditions. Cobalt uptake was controlled by both existing and newly formed manganese oxides. Only a small amount of Co uptake was reversible (10-25%). XANES spectral analysis indicated that most Co(II) was oxidized to Co(III) and probably incorporated structurally into manganese oxides. Although manganese oxides were the primary phase controlling uptake and retention of Mn, Ni, and Co, the mechanisms varied among the metals.

  7. Humidity Sensing Using Gelatin and Cobalt Chloride Coating on Indium Tin Oxide-Coated Long-Period Grating

    NASA Astrophysics Data System (ADS)

    Nidhi; Kaler, R. S.; Kapur, Pawan

    2014-01-01

    In this article, humidity sensing using gelatin and cobalt chloride on indium tin oxide coated long-period gratings was proposed and demonstrated. First, a thin overlay of indium tin oxide was deposited on a long-period grating by using a simple dip coating methodology. Similarly, a combination of gelatin and cobalt chloride was deposited onto the indium tin oxide layer. A field emission scanning electron microscope provided detailed evidence of the attachment of amalgamation on long-period gratings. The designed sensor showed a significant shift in the resonance wavelength when the relative humidity varied from 40% to 95%, with a sensitivity of 0.12 nm/% relative humidity and an accuracy of 98.45%.

  8. Amperometric Determination of Ascorbic Acid in Pharmaceutical Formulations by a Reduced Graphene Oxide-cobalt Hexacyanoferrate Nanocomposite

    PubMed Central

    Heli, Hossein

    2015-01-01

    Investigation of the redox properties of drugs and their determination are performed by electrochemical techniques. Data obtained from electrochemical techniques are often correlated with molecular structure and pharmacological activity of drugs. In this regard, different modified electrodes were applied as sensors for quantification of different drugs. A nanocomposite of reduced graphene oxide-cobalt hexacyanoferrate was synthesized by a simple precipitation route. Scanning electron microscopy revealed that the nanocomposite comprised nanoparticles of cobalt hexacyanoferrate attached to the reduced graphene oxide nanosheets. A nanocomposite-modified carbon paste electrode was then fabricated. It represented prominent activity toward the electrocatalytic oxidation of ascorbic acid, and the kinetics of the electrooxidation process was evaluated. Finally, an amperometric method was developed for the quantification of ascorbic acid in different pharmaceutical formulations. PMID:25901152

  9. Electron Paramagnetic Resonance Characterization of Dioxygen-Bridged Cobalt Dimers with Relevance to Water Oxidation.

    PubMed

    Stich, Troy A; McAlpin, J Gregory; Wall, Ryan M; Rigsby, Matthew L; Britt, R David

    2016-12-19

    A variety of metal oxides can catalyze the oxidation of water to molecular oxygen when polarized by a sufficiently high electrochemical potential. Minimizing the overpotential and increasing the rate of the oxygen-evolving reaction (OER) are key goals in making such materials a component of viable energy storage devices. However, the structural factors that imbue the metal oxides with their catalytic power are difficult to assess as these solids contain many distinct metal-ion sites, have a varying amount of defect sites within the lattice, and can be composed of multiple phases. In the present study, we determined the magnetic properties for a series of dimeric cobalt complexes in which the two metal centers are bridged by a dioxygen moiety. Our spectroscopically validated electronic structure description indicates that each species is best described as two Co(III) ions that are bound to a μ-η(1)η(1) superoxide ligand. Intriguingly, we found evidence that the two compounds that possess oxygen-evolving activity coordinate the superoxide ion in an unusual, nonplanar fashion. It appears as if the intermediately long Co···Co distance of 3.9 Å is responsible for the unusual superoxide binding geometry. This structural factor may be an important element in the design of solid-state OER catalysts.

  10. Cobalt-Catalyzed Oxidative C-H/C-H Cross-Coupling between Two Heteroarenes.

    PubMed

    Tan, Guangying; He, Shuang; Huang, Xiaolei; Liao, Xingrong; Cheng, Yangyang; You, Jingsong

    2016-08-22

    The first example of cobalt-catalyzed oxidative C-H/C-H cross-coupling between two heteroarenes is reported, which exhibits a broad substrate scope and a high tolerance level for sensitive functional groups. When the amount of Co(OAc)2 ⋅4 H2 O is reduced from 6.0 to 0.5 mol %, an excellent yield is still obtained at an elevated temperature with a prolonged reaction time. The method can be extended to the reaction between an arene and a heteroarene. It is worth noting that the Ag2 CO3 oxidant is renewable. Preliminary mechanistic studies by radical trapping experiments, hydrogen/deuterium exchange experiments, kinetic isotope effect, electron paramagnetic resonance (EPR), and high resolution mass spectrometry (HRMS) suggest that a single electron transfer (SET) pathway is operative, which is distinctly different from the dual C-H bond activation pathway that the well-described oxidative C-H/C-H cross-coupling reactions between two heteroarenes typically undergo. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Topotactic Synthesis of Porous Cobalt Ferrite Platelets from a Layered Double Hydroxide Precursor and Their Application in Oxidation Catalysis.

    PubMed

    Ortega, Klaus Friedel; Anke, Sven; Salamon, Soma; Özcan, Fatih; Heese, Justus; Andronescu, Corina; Landers, Joachim; Wende, Heiko; Schuhmann, Wolfgang; Muhler, Martin; Lunkenbein, Thomas; Behrens, Malte

    2017-09-12

    Monocrystalline, yet porous mosaic platelets of cobalt ferrite, CoFe2 O4 , can be synthesized from a layered double hydroxide (LDH) precursor by thermal decomposition. Using an equimolar mixture of Fe(2+) , Co(2+) , and Fe(3+) during co-precipitation, a mixture of LDH, (Fe(II) Co(II) )2/3 Fe(III)1/3 (OH)2 (CO3 )1/6 ⋅m H2 O, and the target spinel CoFe2 O4 can be obtained in the precursor. During calcination, the remaining Fe(II) fraction of the LDH is oxidized to Fe(III) leading to an overall Co(2+) :Fe(3+) ratio of 1:2 as required for spinel crystallization. This pre-adjustment of the spinel composition in the LDH precursor suggests a topotactic crystallization of cobalt ferrite and yields phase pure spinel in unusual anisotropic platelet morphology. The preferred topotactic relationship in most particles is [111]Spinel ∥[001]LDH . Due to the anion decomposition, holes are formed throughout the quasi monocrystalline platelets. This synthesis approach can be used for different ferrites and the unique microstructure leads to unusual chemical properties as shown by the application of the ex-LDH cobalt ferrite as catalyst in the selective oxidation of 2-propanol. Compared to commercial cobalt ferrite, which mainly catalyzes the oxidative dehydrogenation to acetone, the main reaction over the novel ex-LDH cobalt is dehydration to propene. Moreover, the oxygen evolution reaction (OER) activity of the ex-LDH catalyst was markedly higher compared to the commercial material. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Applications of x ray absorption fine structure to the in situ study of the effect of cobalt in nickel hydrous oxide electrodes for fuel cells and rechargeable batteries

    NASA Technical Reports Server (NTRS)

    Kim, Sunghyun; Tryk, Donald A.; Scherson, Daniel A.; Antonio, Mark R.

    1993-01-01

    Electronic and structural aspects of composite nickel-cobalt hydrous oxides have been examined in alkaline solutions using in situ X-ray absorption fine structure (XAFS). The results obtained have indicated that cobalt in this material is present as cobaltic ions regardless of the oxidation state of nickel in the lattice. Furthermore, careful analysis of the Co K-edge Extended X-ray absorption fine structure data reveals that the co-electrodeposition procedure generates a single phase, mixed metal hydrous oxide, in which cobaltic ions occupy nickel sites in the NiO2 sheet-like layers and not two intermixed phases each consisting of a single metal hydrous oxide.

  13. Anisotropy and micromagnetics in complex oxide thin films

    NASA Astrophysics Data System (ADS)

    Wynn, Thomas Andrew

    Complex oxide perovskites are a class of material with a remarkably wide range of functional properties including magnetism, superconductivity, metal-to-insulator transitions, colossal magnetoresistance, and in some cases high magnetocrystalline anisotropy. Reduction in length scales through thin film deposition and nanopatterning results in altered properties from their bulk constituents. In this work, thin films of La0.7Sr0.3CoO3 (LSCO) and LSCO/La 0.7Sr0.3MnO3 (LSMO) bilayers of varying thicknesses were deposited onto (LaAlO3)0.3(Sr2TaAlO 6)0.7 (LSAT) substrates, and their anisotropic magnetic properties were measured along the in- plane [100] and [110] directions using superconducting quantum interference device (SQUID) magnetometry and soft x-ray magnetic spectroscopy. The LSCO showed thickness dependent magnetism, and films were non-magnetic below a critical thickness of 4 nm. Magnetic LSCO films showed unique anisotropic effects on the saturation magnetization (Ms), with a lower M s in the [110] direction than the [100] direction. This potentially indicates the existence of a hard component in the [110] direction that is not being switched at fields in the SQUID magnetometer (7 T). Normalized hysteresis loops indicate the LSCO films display little magnetocrystalline anisotropy within the plane of the film. LSCO/LSMO bilayers with a fixed LSMO layer of 6 nm in thickness showed cobalt magnetism at thicknesses where single layers were non-magnetic, suggesting that the substrate/film interface is not the cause of the non-magnetic layer in the LSCO thin films. Magnetic coupling occurs in bilayers with LSCO layer thicknesses of below 4 nm, and both LSCO and LSMO layers showed a [110] easy axis. When the layer thickness of LSCO was increased above 8 nm, the LSCO layer developed a soft component at the LSCO/LSMO interface. This soft LSCO component remained coupled with the LSMO, though the easy axis changed to the [100] direction, and the harder, non-interface LSCO

  14. The local environment of cobalt in amorphous, polycrystalline and epitaxial anatase TiO{sub 2}:Co films produced by cobalt ion implantation

    SciTech Connect

    Yildirim, O.; Cornelius, S.; Hübner, R.; Potzger, K.; Smekhova, A.; Zykov, G.; Gan'shina, E. A.; Granovsky, A. B.; Bähtz, C.

    2015-05-14

    Amorphous, polycrystalline anatase and epitaxial anatase TiO{sub 2} films have been implanted with 5 at. % Co{sup +}. The magnetic and structural properties of different microstructures of TiO{sub 2}:Co, along with the local coordination of the implanted Co atoms within the host lattice are investigated. In amorphous TiO{sub 2}:Co film, Co atoms are in the (II) oxidation state with a complex coordination and exhibit a paramagnetic response. However, for the TiO{sub 2}:Co epitaxial and polycrystalline anatase films, Co atoms have a distorted octahedral (II) oxygen coordination assigned to a substitutional environment with traces of metallic Co clusters, which gives a rise to a superparamagnetic behavior. Despite the incorporation of the implanted atoms into the host lattice, high temperature ferromagnetism is absent in the films. On the other hand, it is found that the concentration and size of the implantation-induced nanoclusters and the magnetic properties of TiO{sub 2}:Co films have a strong dependency on the initial microstructure of TiO{sub 2}. Consequently, metallic nanocluster formation within ion implantation prepared transition metal doped TiO{sub 2} can be suppressed by tuning the film microstructure.

  15. Composition-induced structural, electrical, and magnetic phase transitions in AX-type mixed-valence cobalt oxynitride epitaxial thin films

    SciTech Connect

    Takahashi, Jumpei; Oka, Daichi; Hirose, Yasushi Yang, Chang; Fukumura, Tomoteru; Hasegawa, Tetsuya; Nakao, Shoichiro; Harayama, Isao; Sekiba, Daiichiro

    2015-12-07

    Synthesis of mid- to late-transition metal oxynitrides is generally difficult by conventional thermal ammonolysis because of thermal instability. In this letter, we synthesized epitaxial thin films of AX-type phase-pure cobalt oxynitrides (CoO{sub x}N{sub y}) by using nitrogen-plasma-assisted pulsed laser deposition and investigated their structural, electrical, and magnetic properties. The CoO{sub x}N{sub y} thin films with 0 ≤ y/(x + y) ≤ 0.63 grown on MgO (100) substrates showed a structural phase transition from rock salt (RS) to zinc blend at the nitrogen content y/(x + y) ∼ 0.5. As the nitrogen content increased, the room-temperature electrical resistivity of the CoO{sub x}N{sub y} thin films monotonically decreased from the order of 10{sup 5} Ω cm to 10{sup −4} Ω cm. Furthermore, we observed an insulator-to-metal transition at y/(x + y) ∼ 0.34 in the RS-CoO{sub x}N{sub y} phase, which has not yet been reported in Co{sup 2+}/Co{sup 3+} mixed-valence cobalt oxides with octahedral coordination. The low resistivity in the RS-CoO{sub x}N{sub y} phase, on the 10{sup −3} Ω cm order, may have originated from the intermediate spin state of Co{sup 3+} stabilized by the lowered crystal field symmetry of the CoO{sub 6−n}N{sub n} octahedra (n = 1, 2,…5). Magnetization measurements suggested that a magnetic phase transition occurred in the RS-CoO{sub x}N{sub y} films during the insulator-to-metal transition. These results demonstrate that low-temperature epitaxial growth is a promising approach for exploring novel electronic functionalities in oxynitrides.

  16. Synthesis and oxidation catalysis of [tris(oxazolinyl)borato]cobalt(II) scorpionates

    SciTech Connect

    Reinig, Regina R.; Mukherjee, Debabrata; Weinstein, Zachary B.; Xie, Weiwei; Albright, Toshia; Baird, Benjamin; Gray, Tristan S.; Ellern, Arkady; Miller, Gordon J.; Winter, Arthur H.; Bud'ko, Sergey L.; Sadow, Aaron D.

    2016-04-28

    The reaction of CoCl2·THF and thallium tris(4,4-dimethyl-2-oxazolinyl)phenylborate (TlToM) in tetrahydrofuran (THF) provides ToMCoCl (1) in 95 % yield; however, appropriate solvents and starting materials are required to favor 1 over two other readily formed side-products, (ToM)2Co (2) and {HToM}CoCl2 (3). ESR, NMR, FTIR, and UV/Vis spectroscopies were used to distinguish these cobalt(II) products and probe their electronic and structural properties. Even after the structures indicated by these methods were confirmed by X-ray crystallography, the spectroscopic identification of trace contaminants in the material was challenging. The recognition of possible contaminants in the synthesis of ToMCoCl in combination with the paramagnetic nature of these complexes provided impetus for the utilization of X-ray powder diffraction to measure the purity of the ToMCoCl bulk sample. Furthermore, the X-ray powder diffraction results provide support for the bulk-phase purity of ToMCoCl in preparations that avoid 2 and 3. Thus, 1 is a precursor for new [tris(oxazolinyl)borato]cobalt chemistry, as exemplified by its reactions with KOtBu and NaOAc to give ToMCoOtBu (4) and ToMCoOAc (5), respectively. Compound 5 is a catalyst for the oxidation of cyclohexane with meta-chloroperoxybenzoic acid (mCPBA), and the rate constants and selectivity for cyclohexanol versus cyclohexanone and ϵ-caprolactone were assessed.

  17. Synthesis and oxidation catalysis of [tris(oxazolinyl)borato]cobalt(II) scorpionates

    DOE PAGES

    Reinig, Regina R.; Mukherjee, Debabrata; Weinstein, Zachary B.; ...

    2016-04-28

    The reaction of CoCl2·THF and thallium tris(4,4-dimethyl-2-oxazolinyl)phenylborate (TlToM) in tetrahydrofuran (THF) provides ToMCoCl (1) in 95 % yield; however, appropriate solvents and starting materials are required to favor 1 over two other readily formed side-products, (ToM)2Co (2) and {HToM}CoCl2 (3). ESR, NMR, FTIR, and UV/Vis spectroscopies were used to distinguish these cobalt(II) products and probe their electronic and structural properties. Even after the structures indicated by these methods were confirmed by X-ray crystallography, the spectroscopic identification of trace contaminants in the material was challenging. The recognition of possible contaminants in the synthesis of ToMCoCl in combination with the paramagnetic naturemore » of these complexes provided impetus for the utilization of X-ray powder diffraction to measure the purity of the ToMCoCl bulk sample. Furthermore, the X-ray powder diffraction results provide support for the bulk-phase purity of ToMCoCl in preparations that avoid 2 and 3. Thus, 1 is a precursor for new [tris(oxazolinyl)borato]cobalt chemistry, as exemplified by its reactions with KOtBu and NaOAc to give ToMCoOtBu (4) and ToMCoOAc (5), respectively. Compound 5 is a catalyst for the oxidation of cyclohexane with meta-chloroperoxybenzoic acid (mCPBA), and the rate constants and selectivity for cyclohexanol versus cyclohexanone and ϵ-caprolactone were assessed.« less

  18. Investigation of photoelectrochemical-oxidized p-GaSb films

    SciTech Connect

    Lee, Hsin-Ying; Huang, Hung-Lin; Lee, Ching-Ting; Petrovich Pchelyakov, Oleg; Andreevich Pakhanov, Nikolay

    2012-12-17

    GaSb oxide films were directly formed on the p-GaSb films using the bias-assisted photoelectrochemical (PEC) oxidation method. X-ray photoelectron spectroscopy analysis indicated that the resulting GaSb oxide films consisted of Ga{sub 2}O{sub 3}, Sb{sub 2}O{sub 3}, and Sb{sub 2}O{sub 5}. Different from the non-PEC oxides, the PEC derived oxide contained much more Sb{sub 2}O{sub 5} than Sb{sub 2}O{sub 3}. Besides, the interface state density between the PEC oxide and p-GaSb was lower than that of the ordinary oxide/p-GaSb interface. The high quality of the PEC-oxidized GaSb films was attributed to the increase of the stable Sb{sub 2}O{sub 5} content and decrease of the elemental Sb content in the films.

  19. Mercury Adsorption and Oxidation over Cobalt Oxide Loaded Magnetospheres Catalyst from Fly Ash in Oxyfuel Combustion Flue Gas.

    PubMed

    Yang, Jianping; Zhao, Yongchun; Chang, Lin; Zhang, Junying; Zheng, Chuguang

    2015-07-07

    Cobalt oxide loaded magnetospheres catalyst from fly ash (Co-MF catalyst) showed good mercury removal capacity and recyclability under air combustion flue gas in our previous study. In this work, the Hg(0) removal behaviors as well as the involved reactions mechanism were investigated in oxyfuel combustion conditions. Further, the recyclability of Co-MF catalyst in oxyfuel combustion atmosphere was also evaluated. The results showed that the Hg(0) removal efficiency in oxyfuel combustion conditions was relative high compared to that in air combustion conditions. The presence of enriched CO2 (70%) in oxyfuel combustion atmosphere assisted the mercury oxidation due to the oxidation of function group of C-O formed from CO2. Under both atmospheres, the mercury removal efficiency decreased with the addition of SO2, NO, and H2O. However, the enriched CO2 in oxyfuel combustion atmosphere could somewhat weaken the inhibition of SO2, NO, and H2O. The multiple capture-regeneration cycles demonstrated that the Co-MF catalyst also present good regeneration performance in oxyfuel combustion atmosphere.

  20. Oxidative stress contributes to cobalt oxide nanoparticles-induced cytotoxicity and DNA damage in human hepatocarcinoma cells

    PubMed Central

    Alarifi, Saud; Ali, Daoud; Y, Al Omar Suliman; Ahamed, Maqusood; Siddiqui, Maqsood A; Al-Khedhairy, Abdulaziz A

    2013-01-01

    Background Cobalt oxide nanoparticles (Co3O4NPs) are increasingly recognized for their utility in biological applications, magnetic resonance imaging, and drug delivery. However, little is known about the toxicity of Co3O4NPs in human cells. Methods We investigated the possible mechanisms of genotoxicity induced by Co3O4NPs in human hepatocarcinoma (HepG2) cells. Cell viability, reactive oxygen species (ROS), glutathione, thiobarbituric acid reactive substance, apoptosis, and DNA damage were assessed in HepG2 cells after Co3O4NPs and Co2+ exposure. Results Co3O4NPs elicited a significant (P < 0.01) reduction in glutathione with a concomitant increase in lipid hydroperoxide, ROS generation, superoxide dismutase, and catalase activity after 24- and 48-hour exposure. Co3O4NPs had a mild cytotoxic effect in HepG2 cells; however, it induced ROS and oxidative stress, leading to DNA damage, a probable mechanism of genotoxicity. The comet assay showed a statistically significant (P < 0.01) dose- and time-related increase in DNA damage for Co3O4NPs, whereas Co2+ induced less change than Co3O4NPs but significantly more than control. Conclusion Our results demonstrated that Co3O4NPs induced cytotoxicity and genotoxicity in HepG2 cells through ROS and oxidative stress. PMID:23326189

  1. Flower-like Cobalt Hydroxide/Oxide on Graphitic Carbon Nitride for Visible-Light-Driven Water Oxidation.

    PubMed

    Zhang, Huayang; Tian, Wenjie; Guo, Xiaochen; Zhou, Li; Sun, Hongqi; Tadé, Moses O; Wang, Shaobin

    2016-12-28

    Direct water oxidation via photocatalysis is a four-electron and multiple-proton process which requires high extra energy input to produce free dioxygen gas, making it exacting, especially under visible light irradiation. To improve the oxygen evolution reaction rates (OERs) and utilize more visible light, flower-like cobalt hydroxide/oxide (Fw-Co(OH)2/Fw-Co3O4) photocatalysts were prepared and loaded onto graphitic carbon nitride (g-C3N4) by a facile coating method in this work. Influenced by the unique three-dimensional morphologies, the synthesized Fw-Co(OH)2 or Fw-Co3O4/g-C3N4 hybrids reveal favorable combination and synergism reflected by the modified photoelectric activities and the improved OER performances. Attributed to its prominent hydrotalcite structure, Fw-Co(OH)2 shows better cocatalytic activity for g-C3N4 modification compared with that of Fw-Co3O4. Specifically, 7 wt % Fw-Co(OH)2/g-C3N4 photocatalyst exhibits photocurrent density 4 times higher and OER performance 5 times better than pristine g-C3N4. This work unambiguously promotes the application of sustainable g-C3N4 in water oxidation.

  2. Sensitivity of Interfibrillar and Subsarcolemmal Mitochondria to Cobalt Chloride-induced Oxidative Stress and Hydrogen Sulfide Treatment

    PubMed Central

    Ayswarya, A.; Kurian, G. A.

    2016-01-01

    Oxidative stress plays a significant role not only in cardiovascular disease but also in non-communicable diseases, where it plays a significant role the mortality rate. Hydrogen sulfide, the biological gaseous signaling molecule that preserves mitochondria in its mode of action, is an effective cardioprotective drug. However, cardiac mitochondria comprise of two distinct populations, namely interfibrillar and subsarcolemmal mitochondria, which respond distinctly in cardiovascular disease. This study was designed to determine the direct impact of cobalt chloride-induced oxidative stress in isolated mitochondrial subpopulations with an intention to examine the efficacy of hydrogen sulfide in preserving interfibrillar and subsarcolemmal mitochondria functional activities when they were incubated as pretreated, co-treated and post-treated agent. Mitochondrial subpopulations were isolated from the heart of male Wistar rats and subjected to cobalt chloride treatment (500 μM) for 20 min, followed by incubation with 10 μM sodium hydrosulfide in three different ways (Pre, Co, and Post-cobalt chloride treatment). Mitochondrial oxidative stress was measured by the concentration of thiobarbituric acid reactive species, reduced glutathione and the activities of enzymes like superoxide dismutase, catalase and glutathione peroxidase. Mitochondrial membrane potential, swelling behavior and enzyme activities were measured to assess its function. The increased level of lipid peroxidation and the decreased level of reduced glutathione in cobalt chloride-induced group confirm the induction of oxidative stress and were more predominant in the subsarcolemmal mitochondria. Hydrogen sulfide treatment to interfibrillar and subsarcolemmal mitochondria preserved their functional activities, but the effect was prominent only with co-treated group. In conclusion, the present study demonstrated that subsarcolemmal mitochondria are more prone to oxidative stress and the co-treatment of the

  3. Sensitivity of Interfibrillar and Subsarcolemmal Mitochondria to Cobalt Chloride-induced Oxidative Stress and Hydrogen Sulfide Treatment.

    PubMed

    Ayswarya, A; Kurian, G A

    2016-01-01

    Oxidative stress plays a significant role not only in cardiovascular disease but also in non-communicable diseases, where it plays a significant role the mortality rate. Hydrogen sulfide, the biological gaseous signaling molecule that preserves mitochondria in its mode of action, is an effective cardioprotective drug. However, cardiac mitochondria comprise of two distinct populations, namely interfibrillar and subsarcolemmal mitochondria, which respond distinctly in cardiovascular disease. This study was designed to determine the direct impact of cobalt chloride-induced oxidative stress in isolated mitochondrial subpopulations with an intention to examine the efficacy of hydrogen sulfide in preserving interfibrillar and subsarcolemmal mitochondria functional activities when they were incubated as pretreated, co-treated and post-treated agent. Mitochondrial subpopulations were isolated from the heart of male Wistar rats and subjected to cobalt chloride treatment (500 μM) for 20 min, followed by incubation with 10 μM sodium hydrosulfide in three different ways (Pre, Co, and Post-cobalt chloride treatment). Mitochondrial oxidative stress was measured by the concentration of thiobarbituric acid reactive species, reduced glutathione and the activities of enzymes like superoxide dismutase, catalase and glutathione peroxidase. Mitochondrial membrane potential, swelling behavior and enzyme activities were measured to assess its function. The increased level of lipid peroxidation and the decreased level of reduced glutathione in cobalt chloride-induced group confirm the induction of oxidative stress and were more predominant in the subsarcolemmal mitochondria. Hydrogen sulfide treatment to interfibrillar and subsarcolemmal mitochondria preserved their functional activities, but the effect was prominent only with co-treated group. In conclusion, the present study demonstrated that subsarcolemmal mitochondria are more prone to oxidative stress and the co-treatment of the

  4. Quercetin and Vitamin C Mitigate Cobalt Chloride-Induced Hypertension through Reduction in Oxidative Stress and Nuclear Factor Kappa Beta (NF-Kb) Expression in Experimental Rat Model.

    PubMed

    Ajibade, Temitayo Olabisi; Oyagbemi, Ademola Adetokunbo; Omobowale, Temidayo Olutayo; Asenuga, Ebunoluwa Racheal; Adigun, Kabirat Oluwaseun

    2017-02-01

    The objective of the present work was to evaluate the toxic effects of cobalt chloride, a potent oxidative stress-inducing chemical, at 650 ppm in rats and the protective effect of quercetin and/or vitamin C against the cobalt chloride-induced toxicity. Thirty rats were randomly selected, and assigned to one of five groups: control, cobalt chloride, cobalt chloride + quercetin, cobalt chloride + vitamin C and cobalt chloride + quercetin + vitamin C. The exposure of rats to cobalt chloride led to a significant increase (p < 0.05) in malondialdehyde (MDA) and hydrogen peroxide (H2O2) generated, but decreased nitric oxide (NO) bioavailability. Also, significant (p < 0.05) reductions were observed in the activity of glutathione peroxidase (GPx) and reduced glutathione (GSH) content in the cardiac and renal tissues. Treatment with quercetin and vitamin C reversed the effect of cobalt chloride on MDA, H2O2 and NO, more potently than with either of the two antioxidants, and increased the antioxidant defence system. Further, treatment of rats with quercetin and vitamin C in combination resulted in significant (p < 0.05) decreases in the systolic, diastolic, and mean arterial blood pressure of rats, relative to those exposed to cobalt chloride alone. Immunohistochemical studies revealed a greater expression of nuclear factor kappa beta (NF-kB) in the cobalt chloride group compared with the control- and antioxidants-treated rats. The results of this study suggest a protective role for quercetin and vitamin C in the amelioration of the toxic mechanisms leading to cobalt chloride-induced hypertension and its associated cardiac and renal complications in rats.

  5. Oxidized zirconium versus cobalt-chromium against the native patella in total knee arthroplasty: Patellofemoral outcomes.

    PubMed

    Matassi, Fabrizio; Paoli, Tommaso; Civinini, Roberto; Carulli, Christian; Innocenti, Massimo

    2017-10-01

    Oxidized zirconium (OxZr) has demonstrated excellent mechanical properties in vitro when used against articular cartilage; less coefficient of friction and less chondral damage have been found when compared with cobalt-chromium (CoCr) implants. However, controversy exists as to whether implants with a zirconium femoral component articulate safely with a native patella in total knee arthroplasty (TKA). To answer this question, the clinical and radiographic results were analysed from a group of patients who underwent a TKA with patella retention; the OxZr versus CoCr femoral components were compared. The present study prospectively evaluated 83 knees of 74 patients from 2009 to 2010. Each patient was evaluated clinically (visual analogue scale, Knee Society score, patellar score) and radiographically (long leg standing radiograph, anterior-posterior and latero-lateral projections, axial view of the patella) pre-operatively and postoperatively with a mean follow-up of 4.47years. The patellar tilt and shift, and progression of patellofemoral osteoarthritis were calculated with the axial view. There were no patient reported adverse reactions and none of the evaluated prostheses failed. Both the clinical and radiographic evaluations showed no statistically significant between-group differences. No adverse events were observed clinically or radiologically. These results justify pursuing the use of oxidized zirconium as an alternative bearing surface for a femoral component associated with patellar retention in TKA. Published by Elsevier B.V.

  6. Cobalt-60 gamma radiation increased the nitric oxide generation in cultured rat vascular smooth muscle cells.

    PubMed

    Zhong, Guang Zhen; Chen, Feng Rong; Bu, Ding Fang; Wang, Shu Heng; Pang, Yong Zheng; Tang, Chao Shu

    2004-05-07

    Radiation is a promising and new treatment for restenosis following angioplasty. Nitric oxide has been proposed as a potential "anti-restenotic" molecule. We radiated the cultured rat vascular smooth muscle cells with Cobalt-60 gamma radiation at doses of 14 and 25Gy and observed nitrite production, cGMP content, L-arginine uptake, inducible nitric oxide synthase (iNOS) activity, and the gene expression of iNOS. Results showed that radiation at doses of 14 and 25Gy increased cGMP content by 92.4% and 86.4%, respectively. Radiation at the dose of 25Gy increased the iNOS activity and nitrite content, but radiation at the dose of 14Gy had no significant effect on iNOS activity and NO production. Both doses of radiation significantly decreased the L-arginine transport. Radiation at the doses of 14 and 25Gy increased iNOS gene expression significantly, which was consistent with the effect of radiation on iNOS activity. In conclusion, radiation induces the NO generation by up-regulating the iNOS activity.

  7. Synthesis of lithium cobalt oxide by single-step soft hydrothermal method

    SciTech Connect

    Kumar Bokinala, Kiran; Pollet, M.; Artemenko, A.; Miclau, M.; Grozescu, I

    2013-02-15

    Lithium cobalt double oxide LiCoO{sub 2} was synthesized at 220 Degree-Sign C by soft hydrothermal method using Co(OH){sub 2} and LiOH as precursors, LiOH/NaOH as mineralizers and H{sub 2}O{sub 2} as oxidant. The soft hydrothermal synthesis method offers the dual advantage of a much lower synthesis time and a higher purity in comparison with other synthesis methods. The compound was identified by X-ray diffraction and its purity was checked by magnetic and electron magnetic resonance measurements. The grain morphology was studied by Scanning Electron Microscopy and an exponential growth of particle size with synthesis time was observed. - Graphical abstract: Concave cuboctohedrons obtained after 60 h reaction time. Highlights: Black-Right-Pointing-Pointer An optimized soft hydrothermal method for a fast synthesis of high purity LiCoO{sub 2} compound is reported. Black-Right-Pointing-Pointer Both lamellar and cuboctahedral particles could be stabilized. Black-Right-Pointing-Pointer Secondary phases content is lower than 0.1%. Black-Right-Pointing-Pointer Close to surface defects were evidenced using EMR.

  8. Microbiological Load of Ethylene Oxide Sterilized Medical Devices and its Elimination by Cobalt 60 Source.

    PubMed

    Bashir, Rasheeda; Afroze, Bakht; Zulfiqar, Hafiza Fizza; Saleem, Resham; Altaf, Imran; Saleem, Faiza; Aslam, Farheen; Naz, Shagufta

    2016-06-01

    To determine the residing microbial flora of ethylene oxide (EtO) sterilized medical devices and optimization of safe dose of gamma radiation (Cobalt 60 source) for the complete elimination of microbial load. Experimental study. Department of Biotechnology, Lahore College for Women University, Lahore, Pakistan from September 2014 to June 2015. Thirty-six samples of EtO sterilized medical devices of same batch of three different companies were collected for this study. Isolation and enumeration of microbes were done by using different selective and differential media. Gram staining and biochemically characterization by API 20 (Bio Merieux, France) kit was done for identification of the microorganisms. The medical devices having high microbial load were sent to Pakistan Radiation Services (PARAS) for gamma irradiations at 3 different selected doses (20 KGy, 25 KGy, and 30 KGy). Different types of Gram positive bacteria (Staphylococcus epidermidis, Staphylococcus aureus andBacillus subtilis) were isolated from the EtO sterilized samples. Gram negative bacteria and fungi were not detected on these medical devices. Gamma irradiations results showed that 30 KGy was optimized dose for complete elimination of microbial flora on endotracheal, Nelaton, and tracheostomy tubes. Gamma radiations (Co 60 source) effectively decontaminate the microbial flora on the equipment previously sterilized by the ethylene oxide gas; and 30 KGy is the optimized dose for all these medical devices.

  9. Efficient electrocatalytic oxygen evolution on amorphous nickel-cobalt binary oxide nanoporous layers.

    PubMed

    Yang, Yang; Fei, Huilong; Ruan, Gedeng; Xiang, Changsheng; Tour, James M

    2014-09-23

    Nanoporous Ni-Co binary oxide layers were electrochemically fabricated by deposition followed by anodization, which produced an amorphous layered structure that could act as an efficient electrocatalyst for water oxidation. The highly porous morphologies produced higher electrochemically active surface areas, while the amorphous structure supplied abundant defect sites for oxygen evolution. These Ni-rich (10-40 atom % Co) binary oxides have an increased active surface area (roughness factor up to 17), reduced charge transfer resistance, lowered overpotential (∼325 mV) that produced a 10 mA cm(-2) current density, and a decreased Tafel slope (∼39 mV decade(-1)). The present technique has a wide range of applications for the preparation of other binary or multiple-metals or metal oxides nanoporous films. Fabrication of nanoporous materials using this method could provide products useful for renewable energy production and storage applications.

  10. Nanotoxicity of cobalt induced by oxidant generation and glutathione depletion in MCF-7 cells.

    PubMed

    Akhtar, Mohd Javed; Ahamed, Maqusood; Alhadlaq, Hisham A; Alshamsan, Aws

    2017-04-01

    There are very few studies regarding the biological activity of cobalt-based nanoparticles (NPs) and, therefore, the possible mechanism behind the biological response of cobalt NPs has not been fully explored. The present study was designed to explore the potential mechanisms of the cytotoxicity of cobalt NPs in human breast cancer (MCF-7) cells. The shape and size of cobalt NPs were characterized by scanning and transmission electron microscopy (SEM and TEM). The crystallinity of NPs was determined by X-ray diffraction (XRD). The dissolution of NPs was measured in phosphate-buffered saline (PBS) and culture media by atomic absorption spectroscopy (AAS). Cytotoxicity parameters, such as [3-(4,5-dimethyl thiazol-2-yl)-2,5-diphenyl tetrazolium bromide] (MTT), neutral red uptake (NRU), and lactate dehydrogenase (LDH) release suggested that cobalt NPs were toxic to MCF-7 cells in a dose-dependent manner (50-200μg/ml). Cobalt NPs also significantly induced reactive oxygen species (ROS) generation, lipid peroxidation (LPO), mitochondrial outer membrane potential loss (MOMP), and activity of caspase-3 enzymes in MCF-7 cells. Moreover, cobalt NPs decreased intracellular antioxidant glutathione (GSH) molecules. The exogenous supply of antioxidant N-acetyl cysteine in cobalt NP-treated cells restored the cellular GSH level and prevented cytotoxicity that was also confirmed by microscopy. Similarly, the addition of buthionine-[S, R]-sulfoximine, which interferes with GSH biosynthesis, potentiated cobalt NP-mediated toxicity. Our data suggested that low solubility cobalt NPs could exert toxicity in MCF-7 cells mainly through cobalt NP dissolution to Co(2+). Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Complex oxide thin films for microelectronics

    NASA Astrophysics Data System (ADS)

    Suvorova, Natalya

    The rapid scaling of the device dimensions, namely in metal oxide semiconductor field effect transistor (MOSFET), is reaching its fundamental limit which includes the increase in allowable leakage current due to direct tunneling with decrease of physical thickness of SiO2 gate dielectric. The significantly higher relative dielectric constant (in the range 9--25) of the gate dielectric beyond the 3.9 value of silicon dioxide will allow increasing the physical thickness. Among the choices for the high dielectric constant (K) materials for future generation MOSFET application, barium strontium titanate (BST) and strontium titanate (STO) possess one of the highest attainable K values making them the promising candidates for alternative gate oxide. However, the gate stack engineering does not imply the simple replacement of the SiO2 with the new dielectric. Several requirements should be met for successful integration of a new material. The major one is a production of high level of interface states (Dit) compared to that of SiO 2 on Si. An insertion of a thin SiO2 layer prior the growth of high-K thin film is a simple solution that helps to limit reaction with Si substrate and attains a high quality interface. However, the combination of two thin films reduces the overall K of the dielectric stack. An optimization of the SiO2 underlayer in order to maintain the interface quality yet minimize the effect on K is the focus of this work. The results from our study are presented with emphasis on the key process parameters that improve the dielectric film stack. For in-situ growth characterization of BST and STO films sputter deposited on thermally oxidized Si substrates spectroscopic ellipsometry in combination with time of flight ion scattering and recoil spectrometry have been employed. Studies of material properties have been complemented with analytical electron microscopy. To evaluate the interface quality the electrical characterization has been employed using

  12. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions.

    PubMed

    Maiyalagan, Thandavarayan; Jarvis, Karalee A; Therese, Soosairaj; Ferreira, Paulo J; Manthiram, Arumugam

    2014-05-27

    Development of efficient, affordable electrocatalysts for the oxygen evolution reaction and the oxygen reduction reaction is critical for rechargeable metal-air batteries. Here we present lithium cobalt oxide, synthesized at 400 °C (designated as LT-LiCoO2) that adopts a lithiated spinel structure, as an inexpensive, efficient electrocatalyst for the oxygen evolution reaction. The catalytic activity of LT-LiCoO2 is higher than that of both spinel cobalt oxide and layered lithium cobalt oxide synthesized at 800 °C (designated as HT-LiCoO2) for the oxygen evolution reaction. Although LT-LiCoO2 exhibits poor activity for the oxygen reduction reaction, the chemically delithiated LT-Li1-xCoO2 samples exhibit a combination of high oxygen reduction reaction and oxygen evolution reaction activities, making the spinel-type LT-Li0,5CoO2 a potential bifunctional electrocatalyst for rechargeable metal-air batteries. The high activities of these delithiated compositions are attributed to the Co4O4 cubane subunits and a pinning of the Co(3+/4+):3d energy with the top of the O(2-):2p band.

  13. Sequential oxidations of thiolates and the cobalt metallocenter in a synthetic metallopeptide: Implications for the biosynthesis of nitrile hydratase

    PubMed Central

    Dutta, Arnab; Flores, Marco; Roy, Souvik; Schmitt, Jennifer C.; Hamilton, G. Alexander; Hartnett, Hilairy E.; Shearer, Jason; Jones, Anne K.

    2013-01-01

    Cobalt nitrile hydratases (Co-NHase) contain a catalytic cobalt (III) ion coordinated in an N2S3 first coordination sphere comprised of two amidate nitrogens and three cysteine-derived sulfur donors: a thiolate (-SR), a sulfenate (-S(R)O−), and a sulfinate (-S(R)O2−). The sequence of biosynthetic reactions that leads to the post-translational oxidations of the metal and the sulfur ligands is unknown, but the process is believed to be initiated directly by oxygen. Herein we utilize cobalt bound in an N2S2 first coordination sphere by a seven amino acid peptide known as SODA (ACDLPCG) to model this oxidation process. Upon exposure to oxygen, Co-SODA is oxidized in two steps. In the first fast step (seconds), magnetic susceptibility measurements demonstrated that the metallocenter remains paramagnetic, i.e. Co2+, and sulfur K-edge X-ray absorption spectroscopy (XAS) is used to show that one of the thiolates is oxidized to sulfinate. In a second process on a longer timescale (hours), magnetic susceptibility measurements and Co K-edge XAS show that the metal is oxidized to Co3+. Unlike other model complexes, additional slow oxidation of the second thiolate in Co-SODA is not observed, and a catalytically active complex is never formed. The likely reason is the absence of the axial thiolate ligand. In essence, the reactivity of Co-SODA can be described as intermediate between previously described models which either quickly convert to final product or are stable in air, and it offers a first glimpse into a possible oxidation pathway for nitrile hydratase biosynthesis. PMID:23587023

  14. Metallic phases of cobalt-based catalysts in ethanol steam reforming: The effect of cerium oxide

    SciTech Connect

    Lin, Sean S.-Y.; Kim, Do Heui; Ha, Su Y.

    2009-02-28

    The catalytic activity of cobalt in the production of hydrogen via ethanol steam reforming has been investigated in its relation to the crystalline structure of metallic cobalt. At a reaction temperature of 350 8C, the specific hydrogen production rates show that hexagonal close-packed (hcp) cobalt possesses higher activity than face-centered cubic (fcc) cobalt. However, at typical reaction temperatures (400– 500 8C) for ethanol steam reforming, hcp cobalt is transformed to less active fcc cobalt, as confirmed by in situ X-ray diffractometry (XRD). The addition of CeO2 promoter (10 wt.%) stabilizes the hcp cobalt structure at reforming temperatures up to 600 8C. Moreover, during the pre-reduction process, CeO2 promoter prevents sintering during the transformation of Co3O4 to hcp cobalt. Both reforming experiments and in situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the surface reactions were modified by CeO2 promoter on 10% Ce–Co (hcp) to give a lower CO selectivity and a higher H2 yield as compared with the unpromoted hcp Co.

  15. Electrochromism: from oxide thin films to devices

    NASA Astrophysics Data System (ADS)

    Rougier, A.; Danine, A.; Faure, C.; Buffière, S.

    2014-03-01

    In respect of their adaptability and performance, electrochromic devices, ECDs, which are able to change their optical properties under an applied voltage, have received significant attention. Target applications are multifold both in the visible region (automotive sunroofs, smart windows, ophthalmic lenses, and domestic appliances (oven, fridge…)) and in the infrared region (Satellites Thermal Control, IR furtivity). In our group, focusing on oxide thin films grown preferentially at room temperature, optimization of ECDs performances have been achieved by tuning the microstructure, the stoichiometry and the cationic composition of the various layers. Herein, our approach for optimized ECDs is illustrated through the example of WO3 electrochromic layer in the visible and in the IR domain as well as ZnO based transparent conducting oxide layer. Targeting the field of printed electronics, simplification of the device architecture for low power ECDs is also reported.

  16. Enhanced magneto-optical Kerr effect in rare earth substituted nanostructured cobalt ferrite thin film prepared by sol-gel method

    NASA Astrophysics Data System (ADS)

    Avazpour, L.; Toroghinejad, M. R.; Shokrollahi, H.

    2016-11-01

    A series of rare-earth (RE)-doped nanocrystalline Cox RE(1-x) Fe2O4 (x = 0, 0.1, 0.2 and RE: Nd, Eu) thin films were prepared on silicon substrates by a sol-gel process, and the influences of different RE3+ ions on the microstructure, magnetism and polar magneto-optical Kerr effect of the deposited films were investigated. Also this research presents the optimization process of cobalt ferrite thin films deposited via spin coating, by studying their structural and morphological properties at different thicknesses (200, 350 nm) and various heat treatment temperatures 300-850 °C. Nanoparticulate polycrystalline thin film were formed with heat treatment above 400 °C but proper magnetic properties due to well crystallization of the film were achieved at about 650 °C. AFM results indicated that the deposited thin films were crack-free exhibiting a dense nanogranular structure. The root-mean square (RMS) roughness of the thin films was in the range of 0.2-3.2 nm. The results revealed that both of the magnetism and magneto optical Kerr (MOKE) spectra of Cox RE(1-x) Fe2O4 films could be mediated by doping with various RE ions. The Curie temperature of substituted samples was lower than pristine cobalt ferrite thin films. In MOKE spectra both dominant peaks were blue shifted with addition of RE ions. For low concentration dopant the inter-valence charge transfer related rotation was enhanced and for higher concentration dopant the crystal field rotation peak was enhanced. The MOKE enhancement for Eu3+ substituted samples was more than Nd3+ doped cobalt ferrite films. The enhanced MOKEs in nanocrystalline thin films might promise their applications for magneto-optical sensors in adopted wavelengths.

  17. Formation of double ring patterns on Co{sub 2}MnSi Heusler alloy thin film by anodic oxidation under scanning probe microscope

    SciTech Connect

    Toutam, Vijaykumar; Singh, Sandeep; Pandey, Himanshu; Budhani, R. C.

    2013-02-15

    Double ring formation on Co{sub 2}MnSi (CMS) films is observed at electrical breakdown voltage during local anodic oxidation (LAO) using atomic force microscope (AFM). Corona effect and segregation of cobalt in the vicinity of the rings is studied using magnetic force microscopy and energy dispersive spectroscopy. Double ring formation is attributed to the interaction of ablated material with the induced magnetic field during LAO. Steepness of forward bias transport characteristics from the unperturbed region of the CMS film suggest a non equilibrium spin contribution. Such mesoscopic textures in magnetic films by AFM tip can be potentially used for memory storage applications.

  18. Active and efficient Co-N/C catalysts derived from cobalt porphyrin for selective oxidation of alkylaromatics

    NASA Astrophysics Data System (ADS)

    Chen, Yuan; Jie, Shanshan; Yang, Congqiang; Liu, Zhigang

    2017-10-01

    The development of highly active and efficient heterogeneous catalytic oxidation systems has become an attractive research area. In this study, nano cobalt-coordinated nitrogen-doped carbon catalysts (Co-N/C), which were prepared by the pyrolysis of cobalt porphyrin supported on carbon black precursor, were used as highly active catalysts for the oxidation of hydrocarbons with tert-butyl hydroperoxide as the oxidant. The results showed that the catalyst was efficient in the selective oxidation of a variety of saturated (including primary, secondary, and tertiary) Csbnd H bonds. The catalyst displayed the best catalytic performance, which was comparable to those for previously reported metal oxide catalysts and even better. The resultant Co-N/C catalysts were characterized in detail by XRD, nitrogen adsorption/desorption isotherms, TEM, SEM and XPS. The homogeneous distribution of the Co species and interactions between the Co-N species could improve the synergistic effect between the Cosbnd O, Cosbnd N and Nsbnd C species, which led to their excellent catalytic performance. A first order kinetics was observed for the reaction with the apparent activation energy for ethylbenzene oxidation was 22.2 ± 2.1 kJ mol-1.

  19. Photo-catalytic Degradation and Sorption of Radio-cobalt from EDTA-Co Complexes Using Manganese Oxide Materials - 12220

    SciTech Connect

    Koivula, Risto; Harjula, Risto; Tusa, Esko

    2012-07-01

    The synthesised cryptomelane-type α-MnO{sub 2} was tested for its Co-57 uptake properties in UV-photo-reactor filled with 10 μM Co-EDTA solution with a background of 10 mM NaNO{sub 3}. High cobalt uptake of 96% was observed after 1 hour of UV irradiation. As for comparison, a well-known TiO{sub 2} (Degussa P25) was tested as reference material that showed about 92% cobalt uptake after six hours of irradiation in identical experiment conditions. It was also noted that the cobalt uptake on cryptomelane with out UV irradiation was modest, only about 10%. Decreasing the pH of the Co-EDTA solution had severe effects on the cobalt uptake mainly due to the rather high point of zero charge of the MnO{sub 2} surface (pzc at pH ∼4.5). Modifying the synthesis procedure we were able to produce a material that functioned well even in solution of pH 3 giving cobalt uptake of almost 99%. The known properties, catalytic and ion exchange, of manganese oxides were simultaneously used for the separation of EDTA complexed Co-57. Tunnel structured cryptomelane -type showed very fast and efficient Co uptake properties outperforming the well known and widely used Degussa P25 TiO{sub 2} in both counts. The layered structured manganese oxide, birnessite, reached also as high Co removal level as the reference material Degussa did but the reaction rate was considerably faster. Since the decontamination solutions are typically slightly acidic and the point of zero charge of the manganese oxides are rather high > pH 4.5 the material had to be modified. This modified material had tolerance to acidic solutions and it's Co uptake performance remained high in the solutions of lower pH (pH 3). Increasing the ion concentration of test solutions, background concentration, didn't affect the final Co uptake level; however, some changes in the uptake kinetics could be seen. The increase in EDTA/MoMO ratio was clearly reflected in the Co uptake curves. The obtained results of manganese oxide were

  20. Mid-term survivorship and clinical outcomes of cobalt-chrome and oxidized zirconium on highly crosslinked polyethylene

    PubMed Central

    Petis, Stephen M.; Vasarhelyi, Edward M.; Lanting, Brent A.; Howard, James L.; Naudie, Douglas D.R.; Somerville, Lyndsay E.; McCalden, Richard W.

    2016-01-01

    Background The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. Methods We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan–Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. Results A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0–10.6) years for cobalt-chrome and 7.8 (range 2.1–10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%–97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%–99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%–98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%–99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Conclusion Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up. PMID:26812409

  1. Dysprosium oxide and dysprosium-oxide-doped titanium oxide thin films grown by atomic layer deposition

    SciTech Connect

    Tamm, Aile Kozlova, Jekaterina; Aarik, Lauri; Aarik, Jaan; Kukli, Kaupo; Link, Joosep; Stern, Raivo

    2015-01-15

    Dysprosium oxide and dysprosium-oxide-doped titanium oxide thin films were grown by atomic layer deposition on silicon substrates. For depositing dysprosium and titanium oxides Dy(thd){sub 3}-O{sub 3} and TiCl{sub 4}-O{sub 3} were used as precursors combinations. Appropriate parameters for Dy(thd){sub 3}-O{sub 3} growth process were obtained by using a quartz crystal microbalance system. The Dy{sub 2}O{sub 3} films were deposited on planar substrates and on three-dimensional substrates with aspect ratio 1:20. The Dy/Ti ratio of Dy{sub 2}O{sub 3}-doped TiO{sub 2} films deposited on a planar silicon substrate ranged from 0.04 to 0.06. Magnetometry studies revealed that saturation of magnetization could not be observed in planar Dy{sub 2}O{sub 3} films, but it was observable in Dy{sub 2}O{sub 3} films on 3D substrates and in doped TiO{sub 2} films with a Dy/Ti atomic ratio of 0.06. The latter films exhibited saturation magnetization 10{sup −6} A cm{sup 2} and coercivity 11 kA/m at room temperature.

  2. Cobalt Phosphide Modified Titanium Oxide Nanophotocatalysts with Significantly Enhanced Photocatalytic Hydrogen Evolution from Water Splitting.

    PubMed

    Yue, Xinzheng; Yi, Shasha; Wang, Runwei; Zhang, Zongtao; Qiu, Shilun

    2017-04-01

    Production of hydrogen from photocatalytic water splitting holds promise as an alternative energy source with superiority of cleanliness, environment friendliness, low price, and sustainability. Perfectly constructing the noble-metal-free and stable hybrid structure photocatalyst is quite essential; herein, for the first time the authors aim to use cobalt phosphide as the cocatalyst on titanium oxide to form a novel hybrid structure to enhance the utilization of the photoexcited electrons in redox reactions for improved photocatalytic H2 evolution activity. Thus, the achieved significantly increased photocatalytic H2 -evolution rate on the optimized CoP/TiO2 (8350 µmol h(-1) g(-1) ) is 11 times higher than that of the pristine TiO2 . Moreover, this work is expected to spur more insight into synthesizing such novel photofunctional systems, achieving high photocatalytic H2 evolution activity and sufficient stability for solar-to-chemical conversion and utilization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Rapid removal of caffeine in aqueous solutions by peroxymonosulfate oxidant activated with cobalt ion.

    PubMed

    Guo, Yunleiyu; Shen, Tingting; Wang, Chen; Sun, Jing; Wang, Xikui

    2015-01-01

    The removal of caffeine (CAF) in aqueous solution by peroxymonosulfate oxidant activated with cobalt ion was investigated under a variety of operating conditions. The effects of various operating parameters, such as oxone and Co²⁺ concentrations, pH value, and the coexistence of dissolved organic matter and inorganic anions on the removal of CAF have been investigated. The removal efficiency increased with the increase in the concentrations of oxone and Co²⁺ ion added. The additions of chloride, bicarbonate, and sodium humate have negative effects on the removal of CAF. Near-neutral condition (5.0 < pH < 7.0) is favorable for the removal of CAF. Based on our experiments, 100% degradation of 50 mg/L CAF can be achieved within 4 minutes under the conditions of 1.00 mM oxone and 0.10 mM Co²⁺ ion at pH 5.0-7.0.

  4. Analysis of geometric and electrochemical characteristics of lithium cobalt oxide electrode with different packing densities

    DOE PAGES

    Lim, Cheolwoong; Yan, Bo; Kang, Huixiao; ...

    2016-08-06

    In order to investigate geometric and electrochemical characteristics of Li ion battery electrode with different packing densities, lithium cobalt oxide (LiCoO2) cathode electrodes were fabricated from a 94:3:3 (wt%) mixture of LiCoO2, polymeric binder, and super-P carbon black and calendered to different densities. A synchrotron X-ray nano-computed tomography system with a spatial resolution of 58.2 nm at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain three dimensional morphology data of the electrodes. The morphology data were then quantitatively analyzed to characterize their geometric properties, such as porosity, tortuosity, specific surface area, and pore size distribution.more » The geometric and electrochemical analysis reveal that high packing density electrodes have smaller average pore size and narrower pore size distribution, which improves the electrical contact between carbon-binder matrix and LiCoO2 particles. The better contact improves the capacity and rate capability by reducing the possibility of electrically isolated LiCoO2 particles and increasing the electrochemically active area. The results show that increase of packing density results in higher tortuosity, but electrochemically active area is more crucial to cell performance than tortuosity at up to 3.6 g/cm3 packing density and 4 C rate.« less

  5. Analysis of geometric and electrochemical characteristics of lithium cobalt oxide electrode with different packing densities

    SciTech Connect

    Lim, Cheolwoong; Yan, Bo; Kang, Huixiao; Song, Zhibin; Lee, Wen Chao; De Andrade, Vincent; De Carlo, Francesco; Yin, Leilei; Kim, Youngsik; Zhu, Likun

    2016-08-06

    In order to investigate geometric and electrochemical characteristics of Li ion battery electrode with different packing densities, lithium cobalt oxide (LiCoO2) cathode electrodes were fabricated from a 94:3:3 (wt%) mixture of LiCoO2, polymeric binder, and super-P carbon black and calendered to different densities. A synchrotron X-ray nano-computed tomography system with a spatial resolution of 58.2 nm at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain three dimensional morphology data of the electrodes. The morphology data were then quantitatively analyzed to characterize their geometric properties, such as porosity, tortuosity, specific surface area, and pore size distribution. The geometric and electrochemical analysis reveal that high packing density electrodes have smaller average pore size and narrower pore size distribution, which improves the electrical contact between carbon-binder matrix and LiCoO2 particles. The better contact improves the capacity and rate capability by reducing the possibility of electrically isolated LiCoO2 particles and increasing the electrochemically active area. The results show that increase of packing density results in higher tortuosity, but electrochemically active area is more crucial to cell performance than tortuosity at up to 3.6 g/cm3 packing density and 4 C rate.

  6. Efficient Removal of Cobalt from Aqueous Solution by Zinc Oxide Nanoparticles: Kinetic and Thermodynamic Studies

    NASA Astrophysics Data System (ADS)

    Khezami, L.; Taha, Kamal K.; Modwi, A.

    2017-05-01

    This article deals with the removal of cobalt ions using zinc oxide nanopowder. The nanomaterial was prepared via the sol-gel method under supercritical drying. The nanomaterial was characterised via XRD, SEM, EDX, FTIR, and BET surface area techniques. The kinetics, equilibrium, and thermodynamic studies of the metal ions adsorption on the nanomaterial were conducted in batch mode experiments by varying some parameters such as pH, contact time, initial ion concentrations, nanoparticles dose, and temperature. The data revealed significant dependence of the adsorption process on concentration, and the temperature was found to enhance the adsorption rate indicating an endothermic nature of the adsorption. The adsorption complied well with the pseudo-second-order kinetics model. The adsorption process was found to match the Langmuir adsorption isotherm. The ZnO nanoparticles could successfully remove up to 125 mg·g-1 of Co(II) ions at elevated temperature. The metal ions adsorption could be described as an endothermic, spontaneous physisorption process. A mechanism for the metal ions adsorption was proposed.

  7. Reduced Graphene Oxide Functionalized with Cobalt Ferrite Nanocomposites for Enhanced Efficient and Lightweight Electromagnetic Wave Absorption

    PubMed Central

    Ding, Yi; Liao, Qingliang; Liu, Shuo; Guo, Huijing; Sun, Yihui; Zhang, Guangjie; Zhang, Yue

    2016-01-01

    In this paper, reduced graphene oxide functionalized with cobalt ferrite nanocomposites (CoFe@rGO) as a novel type of electromagnetic wave (EW) absorbing materials was successfully prepared by a three-step chemical method including hydrothermal synthesis, annealing process and mixing with paraffin. The effect of the sample thickness and the amount of paraffin on the EW absorption properties of the composites was studied, revealing that the absorption peaks shifted toward the low frequency regions with the increasing thickness while other conditions had little or no effect. It is found that the CoFe@rGO enhanced both dielectric losses and magnetic losses and had the best EW absorption properties and the wide wavelength coverage of the hole Ku-Band when adding only 5wt% composites to paraffin. Therefore, CoFe@rGO could be used as an efficient and lightweight EW absorber. Compared with the research into traditional absorbing materials, this figures of merit are typically of the same order of magnitude, but given the lightweight nature of the material and the high level of compatibility with mass production standards, making use of CoFe@rGO as an electromagnetic absorber material shows great potential for real product applications. PMID:27587001

  8. Impact of hole doping on spin transition in perovskite-type cobalt oxides.

    PubMed

    Che, Xiangli; Li, Liping; Hu, Wanbiao; Li, Guangshe

    2016-06-28

    Series of perovskite PrCo1-xNixO3-δ (x = 0-0.4) were prepared and carefully investigated to understand the spin state transition driven by hole doping and further to reveal the effect of spin state transition on electronic conduction. It is shown that with increasing doping level, the transition temperature Ts for Co(3+) ions from low-spin (LS) to intermediate-spin (IS) reduces from 211.9 K for x = 0 to 190.5 K for x = 0.4. XPS and FT-IR spectra demonstrate that hole doping promoted this transition due to a larger Jahn-Teller distortion. Moreover, a thermal activation of spin disorder caused by thermal population of the spin states for Co ions has a great impact on the electrical transport of these perovskite samples. This work may shed light on the comprehension of spin transition in cobalt oxides through hole doping, which is promising for finding new strategies of enhancing electronic conduction, especially for energy and catalysis applications.

  9. Magnetic cobalt ferrite composite as an efficient catalyst for photocatalytic oxidation of carbamazepine.

    PubMed

    He, Yongzhen; Dai, Chaomeng; Zhou, Xuefei

    2017-01-01

    A magnetic spinel cobalt ferrite nanoparticle composite (CFO) was prepared via an ultrasonication-assisted co-precipitation method. The morphological structure and surface composition of CFO before and after reaction were investigated by using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray, and Fourier transform infrared spectroscopy, indicating the consumption of iron oxide during photodegradation. X-ray photoelectron spectroscopy and vibrating sample magnetometry confirm the preparation of the ferrite nanoparticle composite and its magnetic properties. The prepared CFO was then used for the photocatalytic degradation of carbamazepine (CBZ) as an example of pharmaceuticals and personal care products (PPCPs) from aqueous solution. The effects of the nanocomposite dosage, contact time, and solution pH on the photodegradation process were investigated. More than 96% of the CBZ was degraded within 100 min at 0.2 g·L(-1) CFO in the presence of UV light. The reactive species for CBZ degradation in the CFO/UV system was identified as hydroxyl radicals by the methanol scavenging method. Combined with the detection of leached iron ions during the process, the CBZ degradation mechanism can be presumed to be heterogeneous and homogeneous photocatalytic degradation in the CFO/UV system. Furthermore, iminostilbene and acridine were detected as intermediate products by GC-MS.

  10. In vitro evaluation of anticancer and antibacterial activities of cobalt oxide nanoparticles.

    PubMed

    Khan, Shahanavaj; Ansari, Anees A; Khan, Abdul Arif; Ahmad, Rehan; Al-Obaid, Omar; Al-Kattan, Wael

    2015-12-01

    Cobalt oxide nanoparticles (Co3O4-NPs) were synthesized using simple urea-based thermal decomposition method. Phase purity and particle size of as-synthesized nanoparticles were characterized through X-ray diffraction pattern (XRD) and transmission electron microscopy. Through XRD morphology of the Co3O4-NPs was found to be variable in size with range of 36 nm. In our present study, we explored the potential cytotoxic and antibacterial effects of Co3O4-NPs in human colorectal types of cancerous cells (HT29 and SW620) and also nine Gram-positive and Gram-negative bacteria. Co3O4-NPs showed promising anticancer activity against HT29 and SW620 cells with IC50 value of 2.26 and 394.5 μg/mL, respectively. However, no significant effect of Co3O4-NPs was observed against bacterial strains. Furthermore, a detailed study has been carried out to investigate the possible mechanism of cell death in HT29 cancer cell line through the analysis of expression level of anti-apoptotic Bcl2 and BclxL markers. Western blot analysis results suggested significant role of Co3O4-NPs exposure in cell death due to apoptosis.

  11. Boron-Doped Strontium-Stabilized Bismuth Cobalt Oxide Thermoelectric Nanocrystalline Ceramic Powders Synthesized via Electrospinning

    NASA Astrophysics Data System (ADS)

    Koçyiğit, Serhat; Aytimur, Arda; Çınar, Emre; Uslu, İbrahim; Akdemir, Ahmet

    2014-01-01

    Boron-doped strontium-stabilized bismuth cobalt oxide thermoelectric nanocrystalline ceramic powders were produced by using a polymeric precursor technique. The powders were characterized by using x-ray diffraction (XRD), scanning electron microscopy (SEM), and physical properties measurement system (PPMS) techniques. The XRD results showed that these patterns have a two-phase mixture. The phases are face-centered cubic (fcc) and body-centered cubic (bcc). Values of the crystallite size, dislocation density, and microstrain were calculated by using the Scherrer equation. The lattice parameters were calculated for fcc and bcc phases. The SEM results showed that needle-like grains are formed in boron-undoped composite materials, but the needle-like grains changed to the plate-like grains with the addition of boron. The distribution of the nanofiber diameters was calculated and the average diameter of the boron-doped sample is smaller than the boron-undoped one. PPMS values showed that the electrical resistivity values decreased, but the thermal conductivity values, the Seebeck coefficients, and figure of merit ( ZT) increased with increasing temperature for the two samples.

  12. Analysis of Geometric and Electrochemical Characteristics of Lithium Cobalt Oxide Electrode with Different Packing Densities

    SciTech Connect

    Lim, Cheolwoong; Yan, Bo; Kang, Huixiao; Song, Zhibin; Lee, Wen Chao; De Andrade, Vincent; De Carlo, Francesco; Yin, Leilei; Kim, Youngsik; Zhu, Likun

    2016-10-01

    To investigate geometric and electrochemical characteristics of Li ion battery electrode with different packing densities, lithium cobalt oxide (LiCoO2) cathode electrodes were fabricated from a 94:3:3 (wt%) mixture of LiCoO2, polymeric binder, and super-P carbon black and calendered to different densities. A synchrotron X-ray nano-computed tomography system with a spatial resolution of 58.2 nm at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain three dimensional morphology data of the electrodes. The morphology data were quantitatively analyzed to characterize their geometric properties, such as porosity, tortuosity, specific surface area, and pore size distribution. The geometric and electrochemical analysis reveal that high packing density electrodes have smaller average pore size and narrower pore size distribution, which improves the electrical contact between carbon-binder matrix and LiCoO2 particles. The better contact improves the capacity and rate capability by reducing the possibility of electrically isolated LiCoO2 particles and increasing the electrochemically active area. The results show that increase of packing density results in higher tortuosity, but electrochemically active area is more crucial to cell performance than tortuosity at up to 3.6 g/cm3 packing density and 4 C rate.

  13. Nitrite Oxidation with Copper-Cobalt Nanoparticles on Carbon Nanotubes Doped Conducting Polymer PEDOT Composite.

    PubMed

    Wang, Junjie; Xu, Guiyun; Wang, Wei; Xu, Shenghao; Luo, Xiliang

    2015-09-01

    Copper-cobalt bimetal nanoparticles (Cu-Co) have been electrochemically prepared on glassy carbon electrodes (GCEs), which were electrodeposited with conducting polymer nanocomposites of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with carbon nanotubes (CNTs). Owing to their good conductivity, high mechanical strength, and large surface area, the PEDOT/CNTs composites offered excellent substrates for the electrochemical deposition of Cu-Co nanoparticles. As a result of their nanostructure and the synergic effect between Cu and Co, the Cu-Co/PEDOT/CNTs composites exhibited significantly enhanced catalytic activity towards the electrochemical oxidation of nitrite. Under optimized conditions, the nanocomposite-modified electrodes had a fast response time within 2 s and a linear range from 0.5 to 430 μm for the detection of nitrite, with a detection limit of 60 nm. Moreover, the Cu-Co/PEDOT/CNTs composites were highly stable, and the prepared nitrite sensors could retain more than 96 % of their initial response after 30 days.

  14. Reduced Graphene Oxide Functionalized with Cobalt Ferrite Nanocomposites for Enhanced Efficient and Lightweight Electromagnetic Wave Absorption.

    PubMed

    Ding, Yi; Liao, Qingliang; Liu, Shuo; Guo, Huijing; Sun, Yihui; Zhang, Guangjie; Zhang, Yue

    2016-09-02

    In this paper, reduced graphene oxide functionalized with cobalt ferrite nanocomposites (CoFe@rGO) as a novel type of electromagnetic wave (EW) absorbing materials was successfully prepared by a three-step chemical method including hydrothermal synthesis, annealing process and mixing with paraffin. The effect of the sample thickness and the amount of paraffin on the EW absorption properties of the composites was studied, revealing that the absorption peaks shifted toward the low frequency regions with the increasing thickness while other conditions had little or no effect. It is found that the CoFe@rGO enhanced both dielectric losses and magnetic losses and had the best EW absorption properties and the wide wavelength coverage of the hole Ku-Band when adding only 5wt% composites to paraffin. Therefore, CoFe@rGO could be used as an efficient and lightweight EW absorber. Compared with the research into traditional absorbing materials, this figures of merit are typically of the same order of magnitude, but given the lightweight nature of the material and the high level of compatibility with mass production standards, making use of CoFe@rGO as an electromagnetic absorber material shows great potential for real product applications.

  15. Analysis of geometric and electrochemical characteristics of lithium cobalt oxide electrode with different packing densities

    NASA Astrophysics Data System (ADS)

    Lim, Cheolwoong; Yan, Bo; Kang, Huixiao; Song, Zhibin; Lee, Wen Chao; De Andrade, Vincent; De Carlo, Francesco; Yin, Leilei; Kim, Youngsik; Zhu, Likun

    2016-10-01

    To investigate geometric and electrochemical characteristics of Li ion battery electrode with different packing densities, lithium cobalt oxide (LiCoO2) cathode electrodes were fabricated from a 94:3:3 (wt%) mixture of LiCoO2, polymeric binder, and super-P carbon black and calendered to different densities. A synchrotron X-ray nano-computed tomography system with a spatial resolution of 58.2 nm at the Advanced Photon Source of the Argonne National Laboratory was employed to obtain three dimensional morphology data of the electrodes. The morphology data were quantitatively analyzed to characterize their geometric properties, such as porosity, tortuosity, specific surface area, and pore size distribution. The geometric and electrochemical analysis reveal that high packing density electrodes have smaller average pore size and narrower pore size distribution, which improves the electrical contact between carbon-binder matrix and LiCoO2 particles. The better contact improves the capacity and rate capability by reducing the possibility of electrically isolated LiCoO2 particles and increasing the electrochemically active area. The results show that increase of packing density results in higher tortuosity, but electrochemically active area is more crucial to cell performance than tortuosity at up to 3.6 g/cm3 packing density and 4 C rate.

  16. Cobalt oxide magnetic nanoparticles-chitosan nanocomposite based electrochemical urea biosensor

    NASA Astrophysics Data System (ADS)

    Ali, A.; Israr-Qadir, M.; Wazir, Z.; Tufail, M.; Ibupoto, Z. H.; Jamil-Rana, S.; Atif, M.; Khan, S. A.; Willander, M.

    2015-04-01

    In this study, a potentiometric urea biosensor has been fabricated on glass filter paper through the immobilization of urease enzyme onto chitosan/cobalt oxide (CS/Co3O4) nanocomposite. A copper wire with diameter of 500 µm is attached with nanoparticles to extract the voltage output signal. The shape and dimensions of Co3O4 magnetic nanoparticles are investigated by scanning electron microscopy and the average diameter is approximately 80-100 nm. Structural quality of Co3O4 nanoparticles is confirmed from X-ray powder diffraction measurements, while the Raman spectroscopy has been used to understand the chemical bonding between different atoms. The magnetic measurement has confirmed that Co3O4 nanoparticles show ferromagnetic behavior, which could be attributed to the uncompensated surface spins and/or finite size effects. The ferromagnetic order of Co3O4 nanoparticles is raised with increasing the decomposition temperature. A physical adsorption method is adopted to immobilize the surface of CS/Co3O4 nanocomposite. Potentiometric sensitivity curve has been measured over the concentration range between 1 × 10-4 and 8 × 10-2 M of urea electrolyte solution revealing that the fabricated biosensor holds good sensing ability with a linear slope curve of 45 mV/decade. In addition, the presented biosensor shows good reusability, selectivity, reproducibility and resistance against interferers along with the stable output response of 12 s.

  17. Characterization of hybrid cobalt-porous silicon systems: protective effect of the Matrix in the metal oxidation

    PubMed Central

    2012-01-01

    In the present work, the characterization of cobalt-porous silicon (Co-PSi) hybrid systems is performed by a combination of magnetic, spectroscopic, and structural techniques. The Co-PSi structures are composed by a columnar matrix of PSi with Co nanoparticles embedded inside, as determined by Transmission Electron Microscopy (TEM). The oxidation state, crystalline structure, and magnetic behavior are determined by X-Ray Absorption Spectroscopy (XAS) and Alternating Gradient Field Magnetometry (AGFM). Additionally, the Co concentration profile inside the matrix has been studied by Rutherford Backscattering Spectroscopy (RBS). It is concluded that the PSi matrix can be tailored to provide the Co nanoparticles with extra protection against oxidation. PMID:22938050

  18. Oxidation behavior of nanostructured cobalt nickel chromium aluminum yttrium and nickel cobalt chromium aluminum yttrium sprayed by HVOF

    NASA Astrophysics Data System (ADS)

    Mercier, Dominic

    In recent years, much development has been made in the world of nanotechnologies. Hence, nanomaterials, which possess unique characteristics and excellent mechanical properties, are now being used in innovative and advanced applications. Despite the incredible potential of nanomaterials, their use is still at an embryonic stage as a result of the difficulty to mass-produce them. Among the potentially viable application remains the fabrication of nanostructured powders to produce high temperature oxidation resistance coatings. Nanostructured coatings were obtained by thermally spraying cryomilled CoNiCrAlY and NiCoCrAlY feedstock using the HVOF technique. It was found that the milling process used to prepare the powder significantly altered the microstructure of the alloy. In addition to achieving grain size refinement, significant aluminum segregation at grain boundaries was observed. Upon oxidation experiments up to 96 hours in static air at 1000°C an oxide scale composed of an adherent and dense alpha-Al2O3 inner layer with a top layer of fast growing oxides such as NiO, Cr2O3, CoAl2O4 and NiAl2O4 evolved from the coatings. It was found that the formation of a two-layer scale could be prevented through surface grinding prior to oxidation. Moreover, the comparison of the oxidation results of the powders and those of the coatings revealed that the spraying process has a considerable influence on the oxidation behavior of MCrAlYs attributable to the formation of oxide seeds during the spraying process.

  19. Cobalt Oxide Nanoparticles: Behavior towards Intact and Impaired Human Skin and Keratinocytes Toxicity

    PubMed Central

    Mauro, Marcella; Crosera, Matteo; Pelin, Marco; Florio, Chiara; Bellomo, Francesca; Adami, Gianpiero; Apostoli, Piero; De Palma, Giuseppe; Bovenzi, Massimo; Campanini, Marco; Larese Filon, Francesca

    2015-01-01

    Skin absorption and toxicity on keratinocytes of cobalt oxide nanoparticles (Co3O4NPs) have been investigated. Co3O4NPs are commonly used in industrial products and biomedicine. There is evidence that these nanoparticles can cause membrane damage and genotoxicity in vitro, but no data are available on their skin absorption and cytotoxicity on keratinocytes. Two independent 24 h in vitro experiments were performed using Franz diffusion cells, using intact (experiment 1) and needle-abraded human skin (experiment 2). Co3O4NPs at a concentration of 1000 mg/L in physiological solution were used as donor phase. Cobalt content was evaluated by Inductively Coupled–Mass Spectroscopy. Co permeation through the skin was demonstrated after 24 h only when damaged skin protocol was used (57 ± 38 ng·cm−2), while no significant differences were shown between blank cells (0.92 ± 0.03 ng cm−2) and those with intact skin (1.08 ± 0.20 ng·cm−2). To further investigate Co3O4NPs toxicity, human-derived HaCaT keratinocytes were exposed to Co3O4NPs and cytotoxicity evaluated by MTT, Alamarblue® and propidium iodide (PI) uptake assays. The results indicate that a long exposure time (i.e., seven days) was necessary to induce a concentration-dependent cell viability reduction (EC50 values: 1.3 × 10−4 M, 95% CL = 0.8–1.9 × 10−4 M, MTT essay; 3.7 × 10−5 M, 95% CI = 2.2–6.1 × 10−5 M, AlamarBlue® assay) that seems to be associated to necrotic events (EC50 value: 1.3 × 10−4 M, 95% CL = 0.9–1.9 × 10−4 M, PI assay). This study demonstrated that Co3O4NPs can penetrate only damaged skin and is cytotoxic for HaCat cells after long term exposure. PMID:26193294

  20. Cobalt Oxide Nanoparticles: Behavior towards Intact and Impaired Human Skin and Keratinocytes Toxicity.

    PubMed

    Mauro, Marcella; Crosera, Matteo; Pelin, Marco; Florio, Chiara; Bellomo, Francesca; Adami, Gianpiero; Apostoli, Piero; De Palma, Giuseppe; Bovenzi, Massimo; Campanini, Marco; Filon, Francesca Larese

    2015-07-17

    Skin absorption and toxicity on keratinocytes of cobalt oxide nanoparticles (Co3O4NPs) have been investigated. Co3O4NPs are commonly used in industrial products and biomedicine. There is evidence that these nanoparticles can cause membrane damage and genotoxicity in vitro, but no data are available on their skin absorption and cytotoxicity on keratinocytes. Two independent 24 h in vitro experiments were performed using Franz diffusion cells, using intact (experiment 1) and needle-abraded human skin (experiment 2). Co3O4NPs at a concentration of 1000 mg/L in physiological solution were used as donor phase. Cobalt content was evaluated by Inductively Coupled-Mass Spectroscopy. Co permeation through the skin was demonstrated after 24 h only when damaged skin protocol was used (57 ± 38 ng·cm⁻²), while no significant differences were shown between blank cells (0.92 ± 0.03 ng cm⁻²) and those with intact skin (1.08 ± 0.20 ng·cm⁻²). To further investigate Co3O4NPs toxicity, human-derived HaCaT keratinocytes were exposed to Co3O4NPs and cytotoxicity evaluated by MTT, Alamarblue and propidium iodide (PI) uptake assays. The results indicate that a long exposure time (i.e., seven days) was necessary to induce a concentration-dependent cell viability reduction (EC50 values: 1.3 × 10-4 M, 95% CL = 0.8-1.9 × 10⁻⁴ M, MTT essay; 3.7 × 10⁻⁵ M, 95% CI = 2.2-6.1 × 10⁻⁵ M, AlamarBlue assay) that seems to be associated to necrotic events (EC50 value: 1.3 × 10⁻⁴ M, 95% CL = 0.9-1.9 × 10⁻⁴ M, PI assay). This study demonstrated that Co3O4NPs can penetrate only damaged skin and is cytotoxic for HaCat cells after long term exposure.

  1. Toxic effects of hexaammine cobalt(III) chloride on liver and kidney in mice: Implication of oxidative stress.

    PubMed

    Naura, Amarjit S; Sharma, Rajeshwar

    2009-01-01

    Hexaammine cobalt (III) chloride is a trivalent complex cation of Co(III) and amine that has previously been shown to act as an inhibitor of insulin secretion, radiosensitizing agent, and an antiviral agent. We have recently reported the anticancer potential of the compound against diethylnitrosamine-induced carcinogenesis in mice. However, there is no report on the potential toxicity of the compound. The present study was conducted to evaluate the tissue distribution of the compound and its potential toxicity following acute administration of the compound through intraperitoneal route in Balb/c mice. Our results showed that cobalt accumulated maximally in kidney, followed by liver, spleen, blood, and lung in a decreasing order and in a dose-dependent manner. Evaluation of liver and kidney function tests revealed that the compound exerted a relatively higher toxicity in kidney, as compared to liver, as evidenced by the sharp enhancement in the serum levels of urea and creatinine in a dose-dependent manner. Examination of levels of lipid peroxidation and selected oxidative stress-related parameters in kidney, liver, and lung suggest that higher accumulation of cobalt in kidney may promote higher oxidative stress in the organ, as compared to liver and lung, which may eventually impair kidney function.

  2. High carrier concentration p-type transparent conducting oxide films

    DOEpatents

    Yan, Yanfa; Zhang, Shengbai

    2005-06-21

    A p-type transparent conducting oxide film is provided which is consisting essentially of, the transparent conducting oxide and a molecular doping source, the oxide and doping source grown under conditions sufficient to deliver the doping source intact onto the oxide.

  3. Doping in zinc oxide thin films

    NASA Astrophysics Data System (ADS)

    Yang, Zheng

    Doping in zinc oxide (ZnO) thin films is discussed in this dissertation. The optimizations of undoped ZnO thin film growth using molecular-beam epitaxy (MBE) are discussed. The effect of the oxygen ECR plasma power on the growth rate, structural, electrical, and optical properties of the ZnO thin films were studied. It was found that larger ECR power leads to higher growth rate, better crystallinity, lower electron carrier concentration, larger resistivity, and smaller density of non-radiative luminescence centers in the ZnO thin films. Low-temperature photoluminescence (PL) measurements were carried out in undoped and Ga-doped ZnO thin films grown by molecular-beam epitaxy. As the carrier concentration increases from 1.8 x 1018 to 1.8 x 1020 cm-3, the dominant PL line at 9 K changes from I1 (3.368--3.371 eV), to IDA (3.317--3.321 eV), and finally to I8 (3.359 eV). The dominance of I1, due to ionized-donor bound excitons, is unexpected in n-type samples, but is shown to be consistent with the temperature-dependent Hall fitting results. We also show that IDA has characteristics of a donor-acceptor-pair transition, and use a detailed, quantitative analysis to argue that it arises from GaZn donors paired with Zn-vacancy (VZn) acceptors. In this analysis, the GaZn0/+ energy is well-known from two-electron satellite transitions, and the VZn0/- energy is taken from a recent theoretical calculation. Typical behaviors of Sb-doped p-type ZnO are presented. The Sb doping mechanisms and preference in ZnO are discussed. Diluted magnetic semiconducting ZnO:Co thin films with above room-temperature TC were prepared. Transmission electron microscopy and x-ray diffraction studies indicate the ZnO:Co thin films are free of secondary phases. The magnetization of the ZnO:Co thin films shows a free electron carrier concentration dependence, which increases dramatically when the free electron carrier concentration exceeds ˜1019 cm -3, indicating a carrier-mediated mechanism for

  4. p-type conduction in sputtered indium oxide films

    SciTech Connect

    Stankiewicz, Jolanta; Alcala, Rafael; Villuendas, Francisco

    2010-05-10

    We report p-type conductivity in intrinsic indium oxide (IO) films deposited by magnetron sputtering on fused quartz substrates under oxygen-rich ambient. Highly oriented (111) films were studied by x-ray diffraction, optical absorption, and Hall effect measurements. We fabricated p-n homojunctions on these films.

  5. Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt-Copper Complexes

    SciTech Connect

    Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.; Victor G. Young Jr.; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C.

    2016-03-04

    Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.

  6. Method of producing solution-derived metal oxide thin films

    SciTech Connect

    Boyle, T.J.; Ingersoll, D.

    2000-07-11

    A method is described for preparing metal oxide thin films by a solution method. A {beta}-metal {beta}-diketonate or carboxylate compound, where the metal is selected from groups 8, 9, 10, 11, and 12 of the Periodic Table, is solubilized in a strong Lewis base to form a homogeneous solution. This precursor solution forms within minutes and can be deposited on a substrate in a single layer or a multiple layers to form a metal oxide thin film. The substrate with the deposited thin film is heated to change the film from an amorphous phase to a ceramic metal oxide and cooled.

  7. Method of producing solution-derived metal oxide thin films

    DOEpatents

    Boyle, Timothy J.; Ingersoll, David

    2000-01-01

    A method of preparing metal oxide thin films by a solution method. A .beta.-metal .beta.-diketonate or carboxylate compound, where the metal is selected from groups 8, 9, 10, 11, and 12 of the Periodic Table, is solubilized in a strong Lewis base to form a homogeneous solution. This precursor solution forms within minutes and can be deposited on a substrate in a single layer or a multiple layers to form a metal oxide thin film. The substrate with the deposited thin film is heated to change the film from an amorphous phase to a ceramic metal oxide and cooled.

  8. Polymer-assisted aqueous deposition of metal oxide films

    DOEpatents

    Li, DeQuan [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM

    2003-07-08

    An organic solvent-free process for deposition of metal oxide thin films is presented. The process includes aqueous solutions of necessary metal precursors and an aqueous solution of a water-soluble polymer. After a coating operation, the resultant coating is fired at high temperatures to yield optical quality metal oxide thin films.

  9. Effects of oxidative treatments on human hair keratin films.

    PubMed

    Fujii, T; Ito, Y; Watanabe, T; Kawasoe, T

    2012-01-01

    The effects of hydrogen peroxide and commercial bleach on hair and human hair keratin films were examined by protein solubility, scanning electron microscopy (SEM), immunofluorescence microscopy, immunoblotting, and Fourier-transform infrared spectroscopy. Protein solubility in solutions containing urea decreased when the keratin films were treated with hydrogen peroxide or bleach. Oxidative treatments promoted the urea-dependent morphological change by turning films from opaque to transparent in appearance. Immunofluorescence microscopy and immunoblotting showed that the oxidation of amino acids and proteins occurred due to the oxidative treatments, and such occurrence was more evident in the bleach-treated films than in the hydrogen peroxide-treated films. Compared with hair samples, the formation of cysteic acid was more clearly observed in the keratin films after the oxidative treatments.

  10. Cobalt induces oxidative stress in isolated liver mitochondria responsible for permeability transition and intrinsic apoptosis in hepatocyte primary cultures.

    PubMed

    Battaglia, Valentina; Compagnone, Alessandra; Bandino, Andrea; Bragadin, Marcantonio; Rossi, Carlo Alberto; Zanetti, Filippo; Colombatto, Sebastiano; Grillo, Maria Angelica; Toninello, Antonio

    2009-03-01

    It is well established that cobalt mediates the occurrence of oxidative stress which contributes to cell toxicity and death. However, the mechanisms of these effects are not fully understood. This investigation aimed at establishing if cobalt acts as an inducer of mitochondrial-mediated apoptosis and at clarifying the mechanism of this process. Cobalt, in the ionized species Co(2+), is able to induce the phenomenon of mitochondrial permeability transition (MPT) in rat liver mitochondria (RLM) with the opening of the transition pore. In fact, Co(2+) induces mitochondrial swelling, which is prevented by cyclosporin A and other typical MPT inhibitors such as Ca(2+) transport inhibitors and bongkrekic acid, as well as anti-oxidant agents. In parallel with mitochondrial swelling, Co(2+) also induces the collapse of electrical membrane potential. However in this case, cyclosporine A and the other MPT inhibitors (except ruthenium red and EGTA) only partially prevent DeltaPsi drop, suggesting that Co(2+) also has a proton leakage effect on the inner mitochondrial membrane. MPT induction is due to oxidative stress, as a result of generation by Co(2+) of the highly damaging hydroxyl radical, with the oxidation of sulfhydryl groups, glutathione and pyridine nucleotides. Co(2+) also induces the release of the pro-apoptotic factors, cytochrome c and AIF. Incubation of rat hepatocyte primary cultures with Co(2+) results in apoptosis induction with caspase activation and increased level of expression of HIF-1alpha. All these observations allow us to state that, in the presence of calcium, Co(2+) is an inducer of apoptosis triggered by mitochondrial oxidative stress.

  11. Structures and magnetic properties of iron- and cobalt-containing oxide coatings on an aluminum alloy formed in electrolytes via plasma electrolytic oxidation

    NASA Astrophysics Data System (ADS)

    Rudnev, V. S.; Morozova, V. P.; Lukiyanchuk, I. V.; Adigamova, M. V.; Tkachenko, I. A.; Ustinov, A. Yu.; Kharitonskii, P. V.; Frolov, A. M.

    2014-05-01

    The effect of the nature of the supporting electrolyte in the composition of electrolytic suspensions containing dispersed particles of Fe(III) and Co(II) hydroxides, and of anodic and bipolar anodic-cathodic polarization on features of the formation, composition, and magnetic characteristics of oxide coatings is studied. In all cases, iron and cobalt are incorporated into the coatings and are concentrated predominantly in pores. The pores of the coatings include particles consisting of the reduced metals, presumably surrounded by oxide or hydroxide shells. The electrolyte composition affects the concentration and ratio of the metals in the particles. A correlation is observed between the ferro- or ferrimagnetism of the coatings and the content and ratio of cobalt and iron in the pores.

  12. Characterization of gadolinium and lanthanum oxide films on Si (100)

    NASA Astrophysics Data System (ADS)

    Wu, X.; Landheer, D.; Sproule, G. I.; Quance, T.; Graham, M. J.; Botton, G. A.

    2002-05-01

    High-resolution transmission electron microscopy, electron energy loss spectroscopy, and Auger electron spectroscopy, were used to study gadolinium and lanthanum oxide films deposited on Si (100) substrates using electron-beam evaporation from pressed-powder targets. As-deposited films consist of a crystalline oxide layer and an amorphous interfacial layer. A complicated distinct multilayer structure consisting of oxide layers, silicate layers, and SiO2-rich layers in thick (~30 nm) annealed films has been observed for both gadolinium and lanthanum films. For thinner annealed films (~8 nm), there is no longer a crystalline oxide layer but an amorphous gadolinium or lanthanum silicate layer and an interfacial SiO2-rich layer. The formation of the lanthanum silicate by annealing lanthanum oxide is found to be thermodynamically more favorable than the formation of gadolinium silicate.

  13. Flexible electrostatic nanogenerator using graphene oxide film

    NASA Astrophysics Data System (ADS)

    Tian, He; Ma, Shuo; Zhao, Hai-Ming; Wu, Can; Ge, Jie; Xie, Dan; Yang, Yi; Ren, Tian-Ling

    2013-09-01

    Recently, graphene oxide (GO) super capacitors with ultra-high energy densities have received significant attention. In addition to their use in energy storage, GO capacitors might also have broad applications in renewable energy engineering, such as energy harvesting. Here, a flexible nanogenerator based on GO film is designed. A multilayer structure Al/PI/GO/PI/ITO is made on a flexible PET substrate. The GO nanogenerator could generate a peak voltage of 2 V with a current of 30 nA upon the repetitive application of a 15 N force with a frequency of 1 Hz. Moreover, the output voltage was increased to 34.4 V upon increasing the frequency of force application to 10 Hz. Compared with control samples, embedding GO film with a release structure into the device could significantly enhance the output voltage from 0.1 V to 2.0 V. The mechanism of our nanogenerator can be explained by an electrostatic effect, which is fundamentally different from that of previously reported piezoelectric and triboelectric generators. In this manuscript, we demonstrate flexible nanogenerators with large-area graphene based materials, which may open up new avenues of research with regard to applications in energy harvesting.Recently, graphene oxide (GO) super capacitors with ultra-high energy densities have received significant attention. In addition to their use in energy storage, GO capacitors might also have broad applications in renewable energy engineering, such as energy harvesting. Here, a flexible nanogenerator based on GO film is designed. A multilayer structure Al/PI/GO/PI/ITO is made on a flexible PET substrate. The GO nanogenerator could generate a peak voltage of 2 V with a current of 30 nA upon the repetitive application of a 15 N force with a frequency of 1 Hz. Moreover, the output voltage was increased to 34.4 V upon increasing the frequency of force application to 10 Hz. Compared with control samples, embedding GO film with a release structure into the device could

  14. Thermoelectric misfit-layered cobalt oxides with interlayers of hydroxide and peroxide species

    SciTech Connect

    Chou, Ta-Lei; Lybeck, Jenni; Chan, Ting-Shan; Hsu, Ying-Ya; Tewari, Girish C.; Rautama, Eeva-Leena; Yamauchi, Hisao; Karppinen, Maarit

    2013-12-15

    Among the thermoelectric misfit-layered cobalt oxides, [M{sub m}A{sub 2}O{sub m+2}]{sub q}CoO{sub 2}, the parent m=0 phases exhibit divergent chemical features but are less understood than the more common m>0 members of the series. Here we synthesize Sr-for-Ca substituted [(Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2}]{sub q}CoO{sub 2} zero phases up to x=0.2 through low-temperature hydrothermal conversion of precursor powders of the m=1 misfit system, [Co(Ca{sub 1−x}Sr{sub x}){sub 2}O{sub 3}]{sub q}CoO{sub 2}. In the zero-phase [(Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2}]{sub q}CoO{sub 2} system, as the Sr content x increases the lattice expands anisotropically along the c axis such that the ab-plane dimension and the misfit parameter q remain essentially constant. X-ray absorption spectroscopy data suggest the presence of peroxide-type oxygen species in the (Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2} rock-salt block and together with infrared spectroscopy, thermogravimetric and low-temperature resistivity and thermopower measurements evidence that the isovalent Sr-for-Ca substitution controls the balance between the peroxide and hydroxide species in the (Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2} block but leaves the valence of Co essentially intact in the CoO{sub 2} block. The higher electrical conductivity of the Sr-substituted phases is explained as a consequence of increased carrier mobility. - Graphical abstract: Among the thermoelectric misfit-layered cobalt oxides, [M{sub m}A{sub 2}O{sub m+2}]{sub q}CoO{sub 2}, the parent zero (m=0) phases exhibit divergent chemical features. For [(Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2}]{sub q}CoO{sub 2}, X-ray absorption spectroscopy data suggest the presence of peroxide-type oxygen species in the (Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2} rock-salt block and together with thermogravimetric and low-temperature transport-property measurements evidence that the isovalent Sr-for-Ca substitution controls the

  15. Analysis of Gafchromic EBT3 film calibration irradiated with gamma rays from different systems: Gamma Knife and Cobalt-60 unit.

    PubMed

    Najafi, Mohsen; Geraily, Ghazale; Shirazi, Alireza; Esfahani, Mahbod; Teimouri, Javad

    2017-01-01

    In recent years, Gafchromic films are used as an advanced instrument for dosimetry systems. The EBT3 films are a new generation of Gafchromic films. Our main interest is to compare the response of the EBT3 films exposed to gamma rays provided by the Theratron 780C as a conventional radiotherapy system and the Leksell Gamma Knife as a stereotactic radiotherapy system (SRS). Both systems use Cobalt-60 sources, thus using the same energy. However, other factors such as source-to-axis distance, number of sources, dose rate, direction of irradiation, shape of phantom, the field shape of radiation, and different scatter contribution may influence the calibration curve. Calibration curves for the 2 systems were measured and plotted for doses ranging from 0 to 40 Gy at the red and green channels. The best fitting curve was obtained with the Levenberg-Marquardt algorithm. Also, the component of dose uncertainty was obtained for any calibration curve. With the best fitting curve for the EBT3 films, we can use the calibration curve to measure the absolute dose in radiation therapy. Although there is a small deviation between the 2 curves, the p-value at any channel shows no significant difference between the 2 calibration curves. Therefore, the calibration curve for each system can be the same because of minor differences. The results show that with the best fitting curve from measured data, while considering the measurement uncertainties related to them, the EBT3 calibration curve can be used to measure the unknown dose both in SRS and in conventional radiotherapy. Copyright © 2017. Published by Elsevier Inc.

  16. Thin films for micro solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Beckel, D.; Bieberle-Hütter, A.; Harvey, A.; Infortuna, A.; Muecke, U. P.; Prestat, M.; Rupp, J. L. M.; Gauckler, L. J.

    Thin film deposition as applied to micro solid oxide fuel cell (μSOFC) fabrication is an emerging and highly active field of research that is attracting greater attention. This paper reviews thin film (thickness ≤1 μm) deposition techniques and components relevant to SOFCs including current research on nanocrystalline thin film electrolyte and thin-film-based model electrodes. Calculations showing the geometric limits of μSOFCs and first results towards fabrication of μSOFCs are also discussed.

  17. Adsorption of cobalt ferrite nanoparticles within layer-by-layer films: a kinetic study carried out using quartz crystal microbalance.

    PubMed

    Alcantara, Gustavo B; Paterno, Leonardo G; Afonso, André S; Faria, Ronaldo C; Pereira-da-Silva, Marcelo A; Morais, Paulo C; Soler, Maria A G

    2011-12-28

    The paper reports on the successful use of the quartz crystal microbalance technique to assess accurate kinetics and equilibrium parameters regarding the investigation of in situ adsorption of nanosized cobalt ferrite particles (CoFe(2)O(4)--10.5 nm-diameter) onto two different surfaces. Firstly, a single layer of nanoparticles was deposited onto the surface provided by the gold-coated quartz resonator functionalized with sodium 3-mercapto propanesulfonate (3-MPS). Secondly, the layer-by-layer (LbL) technique was used to build multilayers in which the CoFe(2)O(4) nanoparticle-based layer alternates with the sodium sulfonated polystyrene (PSS) layer. The adsorption experiments were conducted by modulating the number of adsorbed CoFe(2)O(4)/PSS bilayers (n) and/or by changing the CoFe(2)O(4) nanoparticle concentration while suspended as a stable colloidal dispersion. Adsorption of CoFe(2)O(4) nanoparticles onto the 3-MPS-functionalized surface follows perfectly a first order kinetic process in a wide range (two orders of magnitude) of nanoparticle concentrations. These data were used to assess the equilibrium constant and the adsorption free energy. Alternatively, the Langmuir adsorption constant was obtained while analyzing the isotherm data at the equilibrium. Adsorption of CoFe(2)O(4) nanoparticles while growing multilayers of CoFe(2)O(4)/PSS was conducted using colloidal suspensions with CoFe(2)O(4) concentration in the range of 10(-8) to 10(-6) (moles of cobalt ferrite per litre) and for different numbers of cycles n = 1, 3, 5, and 10. We found the adsorption of CoFe(2)O(4) nanoparticles within the CoFe(2)O(4)/PSS bilayers perfectly following a first order kinetic process, with the characteristic rate constant growing with the increase of CoFe(2)O(4) nanoparticle concentration and decreasing with the rise of the number of LbL cycles (n). Additionally, atomic force microscopy was employed for assessing the LbL film roughness and thickness. We found the film

  18. An acetate bound cobalt oxide catalyst for water oxidation: role of monovalent anions and cations in lowering overpotential.

    PubMed

    Dey, Subal; Mondal, Biswajit; Dey, Abhishek

    2014-06-28

    A homogeneous solution of Co(II) in acetate buffer at pH 7 is found to be an efficient water oxidation catalyst (WOC) showing significantly greater current density than Co(II) in phosphate buffer (Co-Pi) under identical conditions owing to the higher solubility of the former. When electrodeposited on ITO/FTO electrodes it forms acetate bound cobalt(II)-oxide materials (Co-Ac-WOC) showing a catalytic current density of 0.1 mA cm(-2) at 830 mV and 1 mA cm(-2) at 1 V in a pH 7 buffer solution. The morphology of Co-Ac-WOC and its evolution with time and deposition potential is investigated with AFM, HR-TEM and SEM. The chemical composition of Co-Ac-WOC is investigated using XPS, EDX, ATR-FTIR and combustion analysis which indicate that this material has a CoO core with chloride and acetate anions bound to the Co center. Sodium is found to be integrated in the Co-Ac-WOC. The presence of the sodium and chloride ions lowers the onset potential for the oxygen evolution reaction (OER) by 240 mV relative to the classic Co-Pi at pH 7. The lower onset potential and higher OER current lowers the exchange current density to 10(-6.7) A cm(-2) in Co-Ac-WOC relative to 10(-8)-10(-10) A cm(-2) in Co-Pi and its derivatives.

  19. Synthesis, Crystal Structure, and Magnetic Properties of the Linear-Chain Cobalt Oxide Sr 5Pb 3CoO 12

    NASA Astrophysics Data System (ADS)

    Yamaura, K.; Huang, Q.; Takayama-Muromachi, E.

    2002-02-01

    The novel spin-chain cobalt oxide Sr5Pb3CoO12 [Poverline6×2m, a=10.1093(2) Å and c=3.562 51(9) Å at 295 K] is reported. A polycrystalline sample of the compound was studied by neutron diffraction (at 6 and 295 K) and magnetic susceptibility measurements (5 to 390 K). The cobalt oxide was found to be analogous to the copper oxide Sr5Pb3CuO12, which is comprised of magnetic-linear chains at an interchain distance of 10 Å. Although the cobalt oxide chains (μeff of 3.64 μB per Co) are substantially antiferromagnetic (θW=-38.8 K), neither low-dimensional magnetism nor long-range ordering has been found; a local-structure disorder in the chains might have an impact on the magnetism. This compound is highly electrically insulating.

  20. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    NASA Astrophysics Data System (ADS)

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries.

  1. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    PubMed Central

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

  2. Enhancement of the adhesion between cobalt-base alloys and veneer ceramic by application of an oxide dissolving primer.

    PubMed

    Kohorst, Philipp; Dittmer, Marc Philipp; Stiesch, Meike

    2013-12-01

    Uncontrolled formation of an oxide layer on base metal alloy surface impairs adhesion between the alloy and veneer ceramic. The aim of this study was to investigate the influence of an oxide dissolving primer on the adhesion between cobalt-base alloys and a veneer ceramic. Combinations of two cobalt-base alloys (Bärlight/BL, Cara Process/CP) and one veneering ceramic (HeraCeram) were investigated. 40 rectangular specimens of each alloy were covered with the veneer ceramic; half of the alloy samples were treated with an oxide dissolving primer (NP-Primer) prior to veneering (n=20). Subsequently, the veneering surface was ground flat and notched using the single-edge V-notched-beam method. Then specimens were loaded in a four-point bending test and the critical load to induce stable crack extension at the adhesion interface was determined, in order to calculate the strain energy release rate (G, J/m(2)). Finally, fracture surfaces of the specimens were evaluated by scanning electron microscopy (SEM). Strain energy release rates averaged between 24.1J/m(2) and 28.8 J/m(2). While application of the primer statistically significantly increased adhesion between alloy and ceramic with the BL specimens (p=0.035), no significant influence was found for the CP specimens (p=0.785). For both material combinations, SEM analysis revealed enhanced wetting of the alloy surfaces with ceramic after application of the primer. Application of an oxide dissolving primer increases the wettability of cobalt-base alloy surfaces and thus improves adhesion to veneering ceramics. This may enhance the long-term stability of bilayer restorations made from these materials. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  3. Fischer–Tropsch Synthesis at a Low Pressure on Subnanometer Cobalt Oxide Clusters: The Effect of Cluster Size and Support on Activity and Selectivity

    SciTech Connect

    Lee, Sungsik; Lee, Byeongdu; Seifert, Sönke; Winans, Randall E.; Vajda, Stefan

    2015-05-21

    In this study, the catalytic activity and changes in the oxidation state during the Fischer Tropsch (FT) reaction was investigated on subnanometer size-selected cobalt clusters deposited on oxide (Al2O3, MgO) and carbon-based (ultrananocrystalline diamond UNCD) supports by temperature programmed reaction (TPRx) combined with in-situ grazing-incidence X-ray absorption characterization (GIXAS). The activity and selectivity of ultrasmall cobalt clusters exhibits a very strong dependence on cluster size and support. The evolution of the oxidation state of metal cluster during the reaction reveals that metal-support interaction plays a key role in the reaction.

  4. Review of Zinc Oxide Thin Films

    DTIC Science & Technology

    2014-12-23

    Laboratory Air Force Materiel Command   a. REPORT U   b. ABSTRACT U   c. THIS PAGE U REPORT DOCUMENTATION PAGE Form ApprovedOMB No. 0704-0188 The public...PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ORGANIZATION. 1.  REPORT DATE (DD-MM-YYYY)      18-12-2014 2.  REPORT TYPE      Final Performance 3.  DATES...Standard Form 298 (Rev. 8/98) Prescribed by ANSI Std. Z39.18 1    Review of Zinc Oxide Thin Films   Abstract  The present review paper reports on the

  5. The chemistry of nitrogen oxides on small size-selected cobalt clusters, Co{sub n}{sup +}

    SciTech Connect

    Anderson, Marie L.; Lacz, Agnieszka; Drewello, Thomas; Derrick, Peter J.; Woodruff, D. Phil; Mackenzie, Stuart R.

    2009-02-14

    Fourier transform ion cyclotron resonance mass spectrometry has been employed to study the reactions of gas-phase cationic cobalt clusters, Co{sub n}{sup +} (n=4-30), with nitric oxide, NO, and nitrous oxide, N{sub 2}O, under single collision conditions. Isolation of the initial cluster permits detailed investigation of fragmentation channels which characterize the reactions of all but the largest clusters studied. In reaction with N{sub 2}O, most clusters generate the monoxides Co{sub n}O{sup +} without fragmentation, cobalt atom loss accompanying only subsequent reactions. By contrast, chemisorption of even a single NO molecule is accompanied by fragmentation of the cluster. The measured rate coefficients for the Co{sub n}{sup +}+N{sub 2}O reaction as a function of cluster size are significantly smaller than those calculated using the surface charge capture model, while for NO the rates are comparable. The reactions have been studied under high coverage conditions by storing clusters for extended periods to permit multiple reactions to occur. This leads to interesting chemistry on the surface of the cluster resulting in the formation of stable oxide clusters and/or the decomposition of nitric oxide on the cluster with the resulting loss of molecular nitrogen.

  6. Epitaxial Electrodeposition of Chiral Metal Oxide Films

    NASA Astrophysics Data System (ADS)

    Switzer, Jay

    2006-03-01

    Chirality is ubiquitous in Nature. One enantiomer of a molecule is often physiologically active, while the other enantiomer may be either inactive or toxic. Chiral surfaces offer the possibility of developing heterogeneous enantiospecific catalysts that can more readily be separated from the products and reused. Chiral surfaces might also serve as electrochemical sensors for chiral molecules- perhaps even implantable chiral sensors that could be used to monitor drug levels in the body. Our trick to produce chiral surfaces is to electrodeposit low symmetry metal oxide films with chiral orientations on achiral substrates (see, Nature 425, 490, 2003). The relationship between three-dimensional and two-dimensional chirality will be discussed. Chiral surfaces lack mirror or glide plane symmetry. It is possible to produce chiral surfaces of materials which do not crystallize in chiral space groups. We have deposited chiral orientations of achiral CuO onto single-crystal Au and Cu using both tartaric acid and the amino acids alanine and valine to control the handedness of the electrodeposited films. We will present results on the chiral recognition of molecules such as tartaric or malic acid and L-dopa on the chiral electrodeposited CuO. Initial work on the electrochemical biomineralization of chiral nanostructures of calcite will also be discussed.

  7. Flexible electrostatic nanogenerator using graphene oxide film.

    PubMed

    Tian, He; Ma, Shuo; Zhao, Hai-Ming; Wu, Can; Ge, Jie; Xie, Dan; Yang, Yi; Ren, Tian-Ling

    2013-10-07

    Recently, graphene oxide (GO) super capacitors with ultra-high energy densities have received significant attention. In addition to their use in energy storage, GO capacitors might also have broad applications in renewable energy engineering, such as energy harvesting. Here, a flexible nanogenerator based on GO film is designed. A multilayer structure Al/PI/GO/PI/ITO is made on a flexible PET substrate. The GO nanogenerator could generate a peak voltage of 2 V with a current of 30 nA upon the repetitive application of a 15 N force with a frequency of 1 Hz. Moreover, the output voltage was increased to 34.4 V upon increasing the frequency of force application to 10 Hz. Compared with control samples, embedding GO film with a release structure into the device could significantly enhance the output voltage from 0.1 V to 2.0 V. The mechanism of our nanogenerator can be explained by an electrostatic effect, which is fundamentally different from that of previously reported piezoelectric and triboelectric generators. In this manuscript, we demonstrate flexible nanogenerators with large-area graphene based materials, which may open up new avenues of research with regard to applications in energy harvesting.

  8. Hydrothermal synthesis of cobalt oxide porous nanoribbons anchored with reduced graphene oxide for hydrogen peroxide detection

    NASA Astrophysics Data System (ADS)

    Zhang, Xinmeng; Li, Kezhi; Li, Hejun; Lu, Jinhua; Fu, Qiangang; Zhang, Leilei

    2016-08-01

    A new Co3O4-reduced graphene oxide (Co3O4-rGO) nanostructure was successfully prepared by hydrothermal-synthesized Co3O4 porous nanoribbons with an approximate length of 6-17 μm, a width of 21-737 nm, and a thickness of 33-80 nm hybridizing with reduced graphene oxide. The electrochemical properties of the Co3O4-rGO-modified electrode were investigated by the cyclic voltammograms and amperometric current-time method. The modified electrode shows high electrochemical activity for the catalytic reduction and detection of H2O2 in alkaline medium. The nonenzymatic hydrogen peroxide sensor exhibits wide linear range of 1-18.5 mM ( R = 0.99439), high adsorption amount about 3.24 × 10-6 mol/cm2, and a low detection limit of 5.35 × 10-7 M ( S/ N = 3). In addition, the sensor has a fast response (<5 s), good long-term stability, excellent repeatability (3.22 % relative standard deviation), and high selectivity. These outstanding properties of the sensor derive from their particular hybrid structure and synergistic effects between rGO and Co3O4.

  9. Formation of cobalt disilicide films on (3×3)6H-SiC(0001)

    NASA Astrophysics Data System (ADS)

    Platow, W.; Wood, D. K.; Tracy, K. M.; Burnette, J. E.; Nemanich, R. J.; Sayers, D. E.

    2001-03-01

    This paper presents a detailed study of thin Co films grown directly, sequentially, and by codeposition with Si on the (3×3)-R30° surface of 6H-SiC(0001). The structure, chemistry, and morphology of the films were determined using x-ray absorption fine structure, x-ray photoelectron spectroscopy, Auger electron spectroscopy, and atomic force microscopy. For directly deposited Co films (1-8 nm) graphite layers form on top of the film surface during annealing, whereas Co stays mainly unreacted over a temperature range of 300-1000 °C. The formation of CoSi2 is achieved by sequential and codeposition of Co and Si. Films annealed at 550 °C are polycrystalline and further annealing to 650 °C causes no C segregation, but there is islanding of the films. Attempts to improve film morphology and homogeneity including applying a template method and varying growth temperature are also reported.

  10. Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

    DOE PAGES

    Hudak, N. S.; Davis, L. E.; Nagasubramanian, G.

    2014-12-09

    Entropy profiles of lithium cobalt oxide (LiCoO2) electrodes were measured at various stages in the cycle life to examine performance degradation and cycling-induced changes, or lack thereof, in thermodynamics. LiCoO2 electrodes were cycled at C/2 rate in half-cells (vs. lithium anodes) up to 20 cycles or C/5 rate in full cells (vs. MCMB anodes) up to 500 cycles. The electrodes were then subjected to entropy measurements (∂E/∂T, where E is open-circuit potential and T is temperature) in half-cells at regular intervals over the approximate range 0.5 ≤ x ≤ 1 in LixCoO2. Despite significant losses in capacity upon cycling, neithermore » cycling rate resulted in any change to the overall shape of the entropy profile relative to an uncycled electrode, indicating retention of the basic LiCoO2 structure, lithium insertion mechanism, and thermodynamics. This confirms that cycling-induced performance degradation in LiCoO2 electrodes is primarily caused by kinetic barriers that increase with cycling. In the case of electrodes cycled at C/5, there was a subtle, quantitative, and gradual change in the entropy profile in the narrow potential range of the hexagonal-to-monoclinic phase transition. The observed change is indicative of a decrease in the intralayer lithium ordering that occurs at these potentials, and it demonstrates that a cyclinginduced structural disorder accompanies the kinetic degradation mechanisms.« less

  11. High energy and power density asymmetric supercapacitors using electrospun cobalt oxide nanowire anode

    NASA Astrophysics Data System (ADS)

    Vidyadharan, Baiju; Aziz, Radhiyah Abd; Misnon, Izan Izwan; Anil Kumar, Gopinathan M.; Ismail, Jamil; Yusoff, Mashitah M.; Jose, Rajan

    2014-12-01

    Electrochemical materials are under rigorous search for building advanced energy storage devices. Herein, supercapacitive properties of highly crystalline and ultrathin cobalt oxide (Co3O4) nanowires (diameter ∼30-60 nm) synthesized using an aqueous polymeric solution based electrospinning process are reported. These nanowire electrodes show a specific capacitance (CS) of ∼1110 F g-1 in 6 M KOH at a current density of 1 A g-1 with coulombic efficiency ∼100%. Asymmetric supercapacitors (ASCs) (CS ∼175 F g-1 at 2 A g-1 galvanostatic cycling) are fabricated using the Co3O4 as anode and commercial activated carbon (AC) as cathode and compared their performance with symmetric electrochemical double layer capacitors (EDLCs) fabricated using AC (CS ∼31 F g-1 at 2 A g-1 galvanostatic cycling). The Co3O4//AC ASCs deliver specific energy densities (ES) of 47.6, 35.4, 20 and 8 Wh kg-1 at specific power densities (PS) 1392, 3500, 7000 and 7400 W kg-1, respectively. The performance of ASCs is much superior to the control EDLCs, which deliver ES of 9.2, 8.9, 8.4 and 6.8 Wh kg-1 at PS 358, 695, 1400 and 3500 W kg-1, respectively. The ASCs show nearly six times higher energy density (∼47.6 Wh kg-1) than EDLC (8.4 Wh kg-1) without compromising its power density (∼1400 W kg-1) at similar galvanostatic cycling conditions (2 A g-1).

  12. Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

    SciTech Connect

    Hudak, N. S.; Davis, L. E.; Nagasubramanian, G.

    2014-12-09

    Entropy profiles of lithium cobalt oxide (LiCoO2) electrodes were measured at various stages in the cycle life to examine performance degradation and cycling-induced changes, or lack thereof, in thermodynamics. LiCoO2 electrodes were cycled at C/2 rate in half-cells (vs. lithium anodes) up to 20 cycles or C/5 rate in full cells (vs. MCMB anodes) up to 500 cycles. The electrodes were then subjected to entropy measurements (∂E/∂T, where E is open-circuit potential and T is temperature) in half-cells at regular intervals over the approximate range 0.5 ≤ x ≤ 1 in LixCoO2. Despite significant losses in capacity upon cycling, neither cycling rate resulted in any change to the overall shape of the entropy profile relative to an uncycled electrode, indicating retention of the basic LiCoO2 structure, lithium insertion mechanism, and thermodynamics. This confirms that cycling-induced performance degradation in LiCoO2 electrodes is primarily caused by kinetic barriers that increase with cycling. In the case of electrodes cycled at C/5, there was a subtle, quantitative, and gradual change in the entropy profile in the narrow potential range of the hexagonal-to-monoclinic phase transition. The observed change is indicative of a decrease in the intralayer lithium ordering that occurs at these potentials, and it demonstrates that a cyclinginduced structural disorder accompanies the kinetic degradation mechanisms.

  13. Cobalt nanoparticle arrays made by templated solid-state dewetting.

    PubMed

    Oh, Yong-Jun; Ross, Caroline A; Jung, Yeon Sik; Wang, Yang; Thompson, Carl V

    2009-04-01

    Self-assembled cobalt particle arrays are formed by annealing, which cause agglomeration (dewetting) of thin Co films on oxidized silicon substrates that are topographically prepatterned with an array of 200-nm-period pits. The Co nanoparticle size and uniformity are related to the initial film thickness, annealing temperature, and template geometry. One particle per 200-nm-period pit is formed from a 15-nm film annealed at 850 degrees C; on a smooth substrate, the same annealing process forms particles with an average interparticle distance of 200 nm. Laser annealing enables templated dewetting of 5-nm-thick films to give one particle per pit. Although the as-deposited films exhibit a mixture of hexagonal close-packed and face-centered cubic (fcc) phases, the ordered cobalt particles are predominantly twinned fcc crystals with weak magnetic anisotropy. Templated dewetting is shown to provide a method for forming arrays of nanoparticles with well-controlled sizes and positions.

  14. Crystalline state and acoustic properties of zinc oxide films

    SciTech Connect

    Kal'naya, G.I.; Pryadko, I.F.; Yarovoi, Yu.A.

    1988-08-01

    We study the effect of the crystalline state of zinc oxide films, prepared by magnetron sputtering, on the efficiency of SAW transducers based on the layered system textured ZnO film-interdigital transducer (IDT)-fused quartz substrate. The crystalline perfection of the ZnO films was studied by the x-ray method using a DRON-2.0 diffractometer. The acoustic properties of the layered system fused quartz substrate-IDT-zinc oxide film were evaluated based on the squared electromechanical coupling constant K/sup 2/ for strip filters. It was found that K/sup 2/ depends on the magnitude of the mechanical stresses. When zinc oxide films are deposited by the method of magnetron deposition on fused quartz substrates, depending on the process conditions limitations can arise on the rate of deposition owing to mechanical stresses, which significantly degrade the efficiency of SAW transducers based on them, in the ZnO films.

  15. Thermal properties of rare earth cobalt oxides and of La1- x Gd x CoO3 solid solutions

    NASA Astrophysics Data System (ADS)

    Orlov, Yu. S.; Dudnikov, V. A.; Gorev, M. V.; Vereshchagin, S. N.; Solov'ev, L. A.; Ovchinnikov, S. G.

    2016-05-01

    Powder X-ray diffraction data for the crystal structure, phase composition, and molar specific heat for La1‒ x Gd x CoO3 cobaltites in the temperature range of 300-1000 K have been analyzed. The behavior of the volume thermal expansion coefficient in cobaltites with isovalent doping in the temperature range of 100-1000 K is studied. It is found that the β( T) curve exhibits two peaks at some doping levels. The rate of the change in the occupation number for the high-spin state of cobalt ions is calculated for the compounds under study taking into account the spin-orbit interaction. With the Birch-Murnaghan equation of state, it is demonstrated that the low-temperature peak in the thermal expansion shifts with the growth of the pressure toward higher temperatures and at pressure P ˜ 7 GPa coincides with the second peak. The similarity in the behavior of the thermal expansion coefficient in the La1- x Gd x CoO3 compounds with the isovalent substitution and the undoped LnCoO3 compound (Ln is a lanthanide) is considered. For the whole series of rare earth cobalt oxides, the nature of two specific features in the temperature dependence of the specific heat and thermal expansion is revealed and their relation to the occupation number for the high-spin state of cobalt ions and to the insulator-metal transition is established.

  16. Enhancing Electrode Performance by Exsolved Nanoparticles: A Superior Cobalt-Free Perovskite Electrocatalyst for Solid Oxide Fuel Cells.

    PubMed

    Yang, Guangming; Zhou, Wei; Liu, Meilin; Shao, Zongping

    2016-12-28

    The successful development of low-cost, durable electrocatalysts for oxygen reduction reaction (ORR) at intermediate temperatures is critical for broad commercialization of solid oxide fuel cells. Here, we report our findings in design, fabrication, and characterization of a cobalt-free SrFe0.85Ti0.1Ni0.05O3-δ cathode decorated with NiO nanoparticles. Exsolved from and well bonded to the parent electrode under well-controlled conditions, the NiO nanoparticles uniformly distributed on the surface of the parent electrode greatly enhance cathode performance, demonstrating ORR activity better than that of the benchmark cobalt-based Ba0.5Sr0.5Co0.8Fe0.2O3-δ. Further, a process for regeneration of the NiO nanoparticles was also developed to mitigate potential performance degradation due to coarsening of NiO particles under practical operating conditions. As a general approach, this exsolution-dissolution of electrocatalytically active nanoparticles on an electrode surface may be applicable to the development of other high-performance cobalt-free cathodes for fuel cells and other electrochemical systems.

  17. Amorphous tin-cadmium oxide films and the production thereof

    SciTech Connect

    Li, Xiaonan; Gessert, Timothy A

    2013-10-29

    A tin-cadmium oxide film having an amorphous structure and a ratio of tin atoms to cadmium atoms of between 1:1 and 3:1. The tin-cadmium oxide film may have an optical band gap of between 2.7 eV and 3.35 eV. The film may also have a charge carrier concentration of between 1.times.10.sup.20 cm.sup.-3 and 2.times.10.sup.20 cm.sup.-3. The tin cadmium oxide film may also exhibit a Hall mobility of between 40 cm.sup.2V.sup.-1 s.sup.-1 and 60 cm.sup.2V.sup.-1 s.sup.-1. Also disclosed is a method of producing an amorphous tin-cadmium oxide film as described and devices using same.

  18. Rapid Deposition of Titanium Oxide and Zinc Oxide Films by Solution Precursor Plasma Spray

    NASA Astrophysics Data System (ADS)

    Ando, Yasutaka

    In order to develop a high rate atmospheric film deposition process for functional films, as a basic study, deposition of titanium oxide film and zinc oxide film by solution precursor plasma spray (SPPS) was conducted in open air. Consequently, in the case of titanium oxide film deposition, anantase film and amorphous film as well as rutile film could be deposited by varying the deposition distance. In the case of anatase dominant film, photo-catalytic properties of the films could be confirmed by wettability test. In addition, the dye sensitized sollar cell (DSC) using the TiO2 film deposited by this SPPS technique as photo voltaic device generates 49mV in OCV. On the other hand, in the case of zinc oxide film deposition, it was proved that well crystallized ZnO films with photo catalytic properties could be deposited. From these results, this process was found to have high potential for high rate functional film deposition process conducted in the air.

  19. The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media

    DOE PAGES

    Abreu-Sepulveda, Maria A.; Dhital, Chetan; Huq, Ashfia; ...

    2016-07-30

    The effect due to systematic substitution of cobalt by iron in La0.6Ca0.4Co1-xFexO3 towards the oxygen evolution reaction(OER) in alkaline media has been investigated. We synthesized these compounds by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reaction order towards OH- near unitymore » were achieved for the unsubstituted La0.6Ca0.4CoO3. Moreover, a decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La0.6Ca0.4Co0.2Fe0.8O3 and La0.6Ca0.4Co0.1Fe0.9O3 showed higher area specific activity towards OER than La0.6Ca0.4CoO3 or La0.6Ca0.4FeO3. Finally, we believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.« less

  20. Comparative cytotoxicity and genotoxicity of cobalt (II, III) oxide, iron (III) oxide, silicon dioxide, and aluminum oxide nanoparticles on human lymphocytes in vitro.

    PubMed

    Rajiv, S; Jerobin, J; Saranya, V; Nainawat, M; Sharma, A; Makwana, P; Gayathri, C; Bharath, L; Singh, M; Kumar, M; Mukherjee, A; Chandrasekaran, N

    2016-02-01

    Despite the extensive use of nanoparticles (NPs) in various fields, adequate knowledge of human health risk and potential toxicity is still lacking. The human lymphocytes play a major role in the immune system, and it can alter the antioxidant level when exposed to NPs. Identification of the hazardous NPs was done using in vitro toxicity tests and this study mainly focuses on the comparative in vitro cytotoxicity and genotoxicity of four different NPs including cobalt (II, III) oxide (Co3O4), iron (III) oxide (Fe2O3), silicon dioxide (SiO2), and aluminum oxide (Al2O3) on human lymphocytes. The Co3O4 NPs showed decrease in cellular viability and increase in cell membrane damage followed by Fe2O3, SiO2, and Al2O3 NPs in a dose-dependent manner after 24 h of exposure to human lymphocytes. The oxidative stress was evidenced in human lymphocytes by the induction of reactive oxygen species, lipid peroxidation, and depletion of catalase, reduced glutathione, and superoxide dismutase. The Al2O3 NPs showed the least DNA damage when compared with all the other NPs. Chromosomal aberration was observed at 100 µg/ml when exposed to Co3O4 NPs and Fe2O3 NPs. The alteration in the level of antioxidant caused DNA damage and chromosomal aberration in human lymphocytes. © The Author(s) 2015.

  1. A facile route for the synthesis of nanostructured oxides and hydroxides of cobalt using laser ablation synthesis in solution (LASIS).

    PubMed

    Hu, Sheng; Melton, Chad; Mukherjee, Dibyendu

    2014-11-21

    We used a pulsed laser ablation synthesis in solution (LASIS) to produce cobalt oxide/hydroxide nanoparticles (NPs) with tailored size, morphology and structure at different laser fluences, wavelengths (532 and 1064 nm) and solvent conditions. Specifically, LASIS on bulk Co in the presence and absence of O2 in an aqueous solution initially produces cobalt monoxide (CoO) and single crystal β-cobalt hydroxide (β-Co(OH)2) nanoparticles (NPs) respectively that finally transform into cobaltosic oxide (Co3O4) through oxidation and/or thermal decomposition. Transmission electron microscopy (TEM) and scanning mobility particle sizer (SMPS) measurements on the final products reveal a bimodal size distribution of agglomerated NPs (for the 1064 and 532 nm laser) at low laser fluences, where the ablation mechanism is dominated by vaporization and normal boiling. In contrast, more efficient and predominant explosive boiling at higher laser fluences produces a mono-modal size distribution of spherically shaped primary NPs in agglomerates. Furthermore, higher absorbance of the 532 nm laser by solution-phase colloidal NPs re-ablates them into spherical shapes of larger size (∼13-22 nm) as compared to the ones from using 1064 nm LASIS (∼10-14 nm), while rendering 532 nm LASIS less productive than 1064 nm LASIS over an extended period of time. Finally, Co3O4 nanorods with enhanced localized surface plasmon resonance (LSPR) are synthesized at high pH (pH ≥ 13) and low laser fluence (<5 mJ cm(-2)) conditions. Such nanostructured materials are promising candidates as photocatalysts or additives in nanocomposite materials with enhanced light absorption properties.

  2. Immobilization of cobalt(II) Schiff base complexes on polystyrene resin and a study of their catalytic activity for the aerobic oxidation of alcohols.

    PubMed

    Jain, Suman; Reiser, Oliver

    2008-01-01

    The copper-catalyzed [3+2] azide-alkyne cycloaddition and the Staudinger ligation are readily applicable and highly efficient for the immobilization of cobalt Schiff base complexes onto polystyrene resins. Stepwise synthesis of polymer-bound Schiff bases followed by their subsequent complexation with metal ions were successfully carried out. Direct covalent attachment of preformed homogeneous cobalt Schiff base complexes to the resins was also possible. The catalytic efficiency of the so-prepared polystyrene-bound cobalt Schiff bases was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were highly efficient and even more reactive than the corresponding homogenous analogues, thus affording better yields of oxidized products within shorter reaction times. The supported catalysts could easily be recovered from the reaction mixture by simple filtration and reused for subsequent experiments with consistent catalytic activity.

  3. Active Oxygen Generator by Silent Discharge and Oxidation Power in Formation of Oxide Thin Films

    NASA Astrophysics Data System (ADS)

    Tanaka, Masaaki; Kawagoe, Yasuyuki; Tsukazaki, Hisashi; Yamanishi, Kenichiro

    We have studied the low pressure silent discharge type active oxygen generator in terms of the application to the formation of oxide thin films. In this paper the oxidation power of active oxygen in the oxide thin film formation is compared with that of oxygen and ozone by forming silicon oxide thin films. It was confirmed that the oxidation power is in turn of active oxygen > ozone > oxygen from the experimental result of the number of x in SiOx thin film. Furthermore we applied active oxygen to the formation of the thin film high temperature super conductor and active oxygen was found to be effective to the formation of the thin film with high performance.

  4. Electrocatalytic oxidation of salicylic acid by a cobalt hydrotalcite-like compound modified Pt electrode.

    PubMed

    Gualandi, Isacco; Scavetta, Erika; Zappoli, Sergio; Tonelli, Domenica

    2011-03-15

    In this paper a study of the electrocatalytic oxidation of salicylic acid (SA) at a Pt electrode coated with a Co/Al hydrotalcite-like compound (Co/Al HTLC coated-Pt) film is presented. The voltammetric behaviour of the modified electrode in 0.1M NaOH shows two different redox couples: Co(II)/Co(III) and Co(III)/Co(IV). The electrocatalysis occurs at the same potential of the latter couple, showing that Co(IV) centers act as the oxidant. The CV investigation demonstrates that the process is controlled both by mass and charge transfer and that the Co(IV) centers involved in the oxidation are two for each SA molecule. The estimated value of the catalytic constant is 4×10(4) M(-1) s(-1). The determination of salicylic acid was performed both by DPV and chronoamperometry. The linearity ranges and the LOD values resulted 1×10(-5) to 5×10(-4), 5×10(-7) to 1×10(-4), 6×10(-6) and 2×10(-7) M, respectively. The Co/Al HTLC electrode has been used for SA determination in BAYER Aspirina® and the obtained results are consistent with an independent HPLC analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Visible light-induced photocatalytic reduction of graphene oxide by tungsten oxide thin films

    NASA Astrophysics Data System (ADS)

    Choobtashani, M.; Akhavan, O.

    2013-07-01

    Tungsten oxide thin films (deposited by thermal evaporation or sol gel method) were used for photocatalytic reduction of graphene oxide (GO) platelets (synthesized through a chemical exfoliation method) on surface of the films under UV or visible light of the environment, in the absence of any aqueous ambient at room temperature. Atomic force microscopy (AFM) technique was employed to characterize surface morphology of the GO sheets and the tungsten oxide films. Moreover, using X-ray photoelectron spectroscopy (XPS), chemical state of the tungsten oxide films and the photocatalytic reduction of the GO platelets were quantitatively investigated. The better performance of the sol-gel tungsten oxide films in photocatalytic reduction of GO platelets as compared to the evaporated tungsten oxide films was assigned to lower W5+/W6+ ratio (i.e., a better stoichiometry) and higher surface water content of the sol-gel film. The GO reduction level achieved after 24 h UV-assisted photocatalytic reduction on surface of the sol-gel tungsten oxide film was comparable with the reduction level usually obtainable by hydrazine. The sol-gel tungsten oxide film even showed an efficient photocatalytic reduction of the GO platelets after exposure to the visible light of the environment for 2 days.

  6. Films based on oxidized starch and cellulose from barley.

    PubMed

    El Halal, Shanise Lisie Mello; Colussi, Rosana; Deon, Vinícius Gonçalves; Pinto, Vânia Zanella; Villanova, Franciene Almeida; Carreño, Neftali Lenin Villarreal; Dias, Alvaro Renato Guerra; Zavareze, Elessandra da Rosa

    2015-11-20

    Starch and cellulose fibers were isolated from grains and the husk from barley, respectively. Biodegradable films of native starch or oxidized starches and glycerol with different concentrations of cellulose fibers (0%, 10% and 20%) were prepared. The films were characterized by morphological, mechanical, barrier, and thermal properties. Cellulose fibers isolated from the barley husk were obtained with 75% purity and high crystallinity. The morphology of the films of the oxidized starches, regardless of the fiber addition, was more homogeneous as compared to the film of the native starch. The addition of cellulose fibers in the films increased the tensile strength and decreased elongation. The water vapor permeability of the film of oxidized starch with 20% of cellulose fibers was lower than the without fibers. However the films with cellulose fibers had the highest decomposition with the initial temperature and thermal stability. The oxidized starch and cellulose fibers from barley have a good potential for use in packaging. The addition of cellulose fibers in starch films can contribute to the development of films more resistant that can be applied in food systems to maintain its integrity.

  7. Crystallographically Oriented Cobalt Chromium Tantalum Thin-Film Media for High Areal Density Recording.

    NASA Astrophysics Data System (ADS)

    Deng, Youping

    In order to develop the techniques for increasing recording areal density, microstructural, magnetic and recording properties of crystallographically-oriented CoCrTa thin-films were investigated. The oriented films included bi-crystal and quad-crystal CoCrTa thin films, which were prepared by sputtering on (100) and (110) single crystal Cr substrates, respectively. A theoretical model was developed to calculate the in-plane torque curves of the oriented films. Based on this model, experimental investigations were conducted on the quad-crystal CoCrTa films. It was found that, by fitting the measured in-plane torque curves of the quad -crystal CoCrTa film, it was possible to determine the magnetocrystalline anisotropy constants (K_{rm u1 } and K_{rm u2}) of the CoCrTa film. The torque curves of quad -crystal films were also found to be indicative of the grain isolation and could be used to optimize the sputtering conditions. Substrate bias changed the film composition and lowered M_{rm s} and K_{rm u1}, while improving grain isolation. A more realistic micromagnetic model, which used the measured values of M_ {rm s} and K_{ rm u1} and took the film's grain-cluster microstructure into account, was developed for the bi-crystal films. The simulation results fitted well with the experimental data. A low-speed contact-recording spin-stand, which utilized a magnetoresistive head, was set up for recording studies on the oriented thin-film media and an isotropic thin-film medium prepared on a NiP/Al substrate. The readback signal from the MR head appeared to have some correlation with the medium anisotropy. The recorded patterns were imaged by magnetic force microscopy. It was found that erased bands formed on the quad-crystal and isotropic thin -film media. On the bi-crystal thin-film media, however, clear erased bands were not observed possibly due to the large head-disk distance.

  8. DC electrical, thermal, and spectroscopic properties of various condensation polyimides containing surface cobalt oxide

    NASA Technical Reports Server (NTRS)

    Rancourt, J. D.; Boggess, R. K.; Horning, L. S.; Taylor, L. T.

    1987-01-01

    Doping polyimides with cobalt ion causes the room temperature direct current electrical resistivity to decrease relative to the polymer alone, the reduction being most pronounced for the air-side of the cobalt modified polyimides. At a constant electrical field, resistivity for the volume, air-side and glass-side modes decreases yet further with an increase in temperature as expected for semiconductors and insulators. X-ray photoelectron spectroscopy indicates the air-side of the cobalt modified polyimides is predominantly Co3O4. The bulk resistivity of the air-side and activation energy of conduction for this surface are comparable to high purity sintered Co3O4. Charging characteristics at room temperature indicate a substantial polymer matrix contribution to both the glass-side and volume mode measurements but a negligible contribution to the air-side electrical properties. Volume electrical resistivity for similar additive levels is reduced by increasing the molecular flexibility of the host polymer.

  9. DC electrical, thermal, and spectroscopic properties of various condensation polyimides containing surface cobalt oxide

    NASA Technical Reports Server (NTRS)

    Rancourt, J. D.; Boggess, R. K.; Horning, L. S.; Taylor, L. T.

    1987-01-01

    Doping polyimides with cobalt ion causes the room temperature direct current electrical resistivity to decrease relative to the polymer alone, the reduction being most pronounced for the air-side of the cobalt modified polyimides. At a constant electrical field, resistivity for the volume, air-side and glass-side modes decreases yet further with an increase in temperature as expected for semiconductors and insulators. X-ray photoelectron spectroscopy indicates the air-side of the cobalt modified polyimides is predominantly Co3O4. The bulk resistivity of the air-side and activation energy of conduction for this surface are comparable to high purity sintered Co3O4. Charging characteristics at room temperature indicate a substantial polymer matrix contribution to both the glass-side and volume mode measurements but a negligible contribution to the air-side electrical properties. Volume electrical resistivity for similar additive levels is reduced by increasing the molecular flexibility of the host polymer.

  10. Surfactant-free synthesis of novel copper oxide (CuO) nanowire-cobalt oxide (Co3O4) nanoparticle heterostructures and their morphological control

    NASA Astrophysics Data System (ADS)

    Shi, Wenwu; Chopra, Nitin

    2011-02-01

    A simple and surfactant-free synthesis of novel heterostructures comprising of copper oxide (CuO) nanowires uniformly decorated with cobalt oxide (Co3O4) nanoparticles was demonstrated by combining thermal growth and wet-coating method. The heterostructures were synthesized by thermally decomposing cobalt salt (cobalt nitrate) into Co3O4 nanoparticles onto vapor-solid (VS)-grown CuO nanowires. X-ray diffraction (XRD) and high resolution transmission electron microscopy (TEM) confirmed the presence of CuO and Co3O4 phases as well as a narrow size distribution of Co3O4 nanoparticles (average diameter 7.0 ± 1.5 nm) on CuO nanowires (average diameter of nanowire tips 67.9 ± 18.6 nm). Unique interfacial lattice relationship was observed for (111) Co3O4 nanoparticles on (200) CuO nanowire surface resulting in hemispherical shape of the former. For the first time, further systematic studies were performed to understand the influence of various parameters (cobalt salt concentration and annealing temperature, atmosphere, and time) on the morphological evolution of Co3O4 nanoparticles on CuO nanowires. Interestingly, by varying these parameters, it was possible to grow Co3O4 in different shapes (spherical, triangular, rectangular, cubical, and hexagonal nanoparticles) and forms (shells and nanorods). It was observed that all these parameters play a critical role in influencing the surface migration, nucleation, and growth of Co3O4 nanoparticles on CuO nanowires and this assisted in understanding the involved growth mechanisms. Finally, UV-vis-NIR spectroscopy and band gap energies for these heterostructures were evaluated that showed higher photocatalytic degradation efficiency for Rhodamine B under low-power visible-light illumination.

  11. Low-temperature CVD of iron, cobalt, and nickel nitride thin films from bis[di(tert-butyl)amido]metal(II) precursors and ammonia

    SciTech Connect

    Cloud, Andrew N.; Abelson, John R.; Davis, Luke M.; Girolami, Gregory S.

    2014-03-15

    Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300 °C from three recently synthesized M[N(t-Bu){sub 2}]{sub 2} precursors, where M = Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200 °C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18 nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities.

  12. Self-subunit swapping chaperone needed for the maturation of multimeric metalloenzyme nitrile hydratase by a subunit exchange mechanism also carries out the oxidation of the metal ligand cysteine residues and insertion of cobalt.

    PubMed

    Zhou, Zhemin; Hashimoto, Yoshiteru; Kobayashi, Michihiko

    2009-05-29

    The incorporation of cobalt into low molecular mass nitrile hydratase (L-NHase) of Rhodococcus rhodochrous J1 has been found to depend on the alpha-subunit exchange between cobalt-free L-NHase (apo-L-NHase lacking oxidized cysteine residues) and its cobalt-containing mediator (holo-NhlAE containing Cys-SO(2)(-) and Cys-SO(-) metal ligands), this novel mode of post-translational maturation having been named self-subunit swapping, and NhlE having been recognized as a self-subunit swapping chaperone (Zhou, Z., Hashimoto, Y., Shiraki, K., and Kobayashi, M. (2008) Proc. Natl. Acad. Sci. U. S. A. 105, 14849-14854). We discovered here that cobalt was inserted into both the cobalt-free NhlAE (apo-NhlAE) and the cobalt-free alpha-subunit (apo-alpha-subunit) in an NhlE-dependent manner in the presence of cobalt and dithiothreitol in vitro. Matrix-assisted laser desorption ionization time-of-flight mass spectroscopy analysis revealed that the non-oxidized cysteine residues in apo-NhlAE were post-translationally oxidized after cobalt insertion. These findings suggested that NhlE has two activities, i.e. cobalt insertion and cysteine oxidation. NhlE not only functions as a self-subunit swapping chaperone but also a metallochaperone that includes a redox function. Cobalt insertion and cysteine oxidation occurred under both aerobic and anaerobic conditions when Co(3+) was used as a cobalt donor, suggesting that the oxygen atoms in the oxidized cysteines were derived from water molecules but not from dissolved oxygen. Additionally, we isolated apo-NhlAE after the self-subunit swapping event and found that it was recycled for cobalt transfer into L-NHase.

  13. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, Kevin C.; Kodas, Toivo T.

    1994-01-01

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said FIELD OF THE INVENTION The present invention relates to the field of film coating deposition techniques, and more particularly to the deposition of multicomponent metal oxide films by aerosol chemical vapor deposition. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

  14. Low reflectance sputtered vanadium oxide thin films on silicon

    NASA Astrophysics Data System (ADS)

    Esther, A. Carmel Mary; Dey, Arjun; Rangappa, Dinesh; Sharma, Anand Kumar

    2016-07-01

    Vanadium oxide thin films on silicon (Si) substrate are grown by pulsed radio frequency (RF) magnetron sputtering technique at RF power in the range of 100-700 W at room temperature. Deposited thin films are characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques to investigate microstructural, phase, electronic structure and oxide state characteristics. The reflectance and transmittance spectra of the films and the Si substrate are recorded at the solar region (200-2300 nm) of the spectral window. Substantial reduction in reflectance and increase in transmittance is observed for the films grown beyond 200 W. Further, optical constants viz. absorption coefficient, refractive index and extinction coefficient of the deposited vanadium oxide films are evaluated.

  15. Heterogenite vs asbolane: a mineralogical study of cobalt oxides from the DRC (Democratic Republic of the Congo)

    NASA Astrophysics Data System (ADS)

    Burlet, Christian; Vanbrabant, Yves; Decree, Sophie

    2014-05-01

    The largest cobalt ore reserves are located in DRC, the Democratic Republic of Congo. Most of cobalt is observed as black cobaltic oxide minerals: heterogenite [HCoO2] and asbolane [(Ni,Co)2-xMn(O,OH)4.nH2O] which are hardly differentiable since they exhibit similar macroscopic habit and textures. These minerals are frequently observed in similar environment (oxidized horizon of ore deposits) and they are commonly poorly-crystallized limiting their study with XRD. Their chemical composition is also not very well-constrained since they exhibit significant chemical substitutions with cations as Cu, Co, Ni, Mn. Our observations on a set of heterogenite and asbolane samples from DRC combined with samples from other localities shows that each phase, even under an amorphous form, can be readily distinguished by Raman microspectrometry. This technique is therefore attractive during ore deposit characterization campaigns or during the follow-up extraction operations where it is important to distinguish the main constituting Co-phase(s). The main advantage of this technique is its speed since no sample preparation is required during the collection Raman spectra that usually last few tens of seconds. The method provides information at a μm-scale and several points are thus required to fully characterize ore batches composed of different mineralogical phases. Our petrographical observations show also that asbolane and heterogenite mineralogical phases can coexist at a μm-scale as two distinct phases into 'heterogenite' ore. The distinction between heterogenite and asbolane from our sample set can also be conducted on a chemical base showing that heterogenite represents the richer Co-phase with variable Cu concentrations. By contrast, only Mn traces are usually observed in heterogenite minerals from DRC except in few samples, but always in lower concentration than in asbolane. The latter shows variable Mn/(Mn+Co) ratio between 0.85 and 0.3 and the decrease of this value is

  16. Altering properties of cerium oxide thin films by Rh doping

    SciTech Connect

    Ševčíková, Klára; Nehasil, Václav; Vorokhta, Mykhailo; Haviar, Stanislav; Matolín, Vladimír; and others

    2015-07-15

    Highlights: • Thin films of ceria doped by rhodium deposited by RF magnetron sputtering. • Concentration of rhodium has great impact on properties of Rh–CeO{sub x} thin films. • Intensive oxygen migration in films with low concentration of rhodium. • Oxygen migration suppressed in films with high amount of Rh dopants. - Abstract: Ceria containing highly dispersed ions of rhodium is a promising material for catalytic applications. The Rh–CeO{sub x} thin films with different concentrations of rhodium were deposited by RF magnetron sputtering and were studied by soft and hard X-ray photoelectron spectroscopies, Temperature programmed reaction and X-ray powder diffraction techniques. The sputtered films consist of rhodium–cerium mixed oxide where cerium exhibits a mixed valency of Ce{sup 4+} and Ce{sup 3+} and rhodium occurs in two oxidation states, Rh{sup 3+} and Rh{sup n+}. We show that the concentration of rhodium has a great influence on the chemical composition, structure and reducibility of the Rh–CeO{sub x} thin films. The films with low concentrations of rhodium are polycrystalline, while the films with higher amount of Rh dopants are amorphous. The morphology of the films strongly influences the mobility of oxygen in the material. Therefore, varying the concentration of rhodium in Rh–CeO{sub x} thin films leads to preparing materials with different properties.

  17. Tailoring of in-plane magnetic anisotropy in polycrystalline cobalt thin films by external stress

    NASA Astrophysics Data System (ADS)

    Kumar, Dileep; Singh, Sadhana; Vishawakarma, Pramod; Dev, Arun Singh; Reddy, V. R.; Gupta, Ajay

    2016-11-01

    Polycrystalline Co films of nominal thickness ~180 Å were deposited on intentionally curved Si substrates. Tensile and compressive stresses of 100 MPa and 150 MPa were induced in the films by relieving the curvature. It has been found that, within the elastic limit, presence of stress leads to an in-plane magnetic anisotropy in the film and its strength increases with increasing stress. Easy axis of magnetization in the films is found to be parallel/ transverse to the compressive /tensile stresses respectively. The origin of magnetic anisotropy in the stressed films is understood in terms of magneto- elastic coupling, where the stress try to align the magnetic moments in order to minimize the magneto-elastic as well as anisotropy energy. Tensile stress is also found to be responsible for the surface smoothening of the films, which is attributed to the movement of the atoms associated with the applied stress. The present work provides a possible way to tailor the magnetic anisotropy and its direction in polycrystalline and amorphous films using external stress.

  18. Method for producing high quality oxide films on substrates

    DOEpatents

    Ruckman, M.W.; Strongin, M.; Gao, Y.L.

    1993-11-23

    A method is described for providing an oxide film of a material on the surface of a substrate using a reactive deposition of the material onto the substrate surface in the presence of a solid or liquid layer of an oxidizing gas. The oxidizing gas is provided on the substrate surface in an amount sufficient to dissipate the latent heat of condensation occurring during deposition as well as creating a favorable oxidizing environment for the material. 4 figures.

  19. Method for producing high quality oxide films on substrates

    DOEpatents

    Ruckman, Mark W.; Strongin, Myron; Gao, Yong L.

    1993-01-01

    A method for providing an oxide film of a material on the surface of a substrate using a reactive deposition of the material onto the substrate surface in the presence of a solid or liquid layer of an oxidizing gas. The oxidizing gas is provided on the substrate surface in an amount sufficient to dissipate the latent heat of condensation occurring during deposition as well as creating a favorable oxidizing environment for the material.

  20. Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

    SciTech Connect

    Sato, Soshi Honjo, Hiroaki; Niwa, Masaaki; Ikeda, Shoji; Ohno, Hideo; Endoh, Tetsuo

    2015-04-06

    We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400 °C for 1 h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1 nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer. The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO{sub 2}, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.