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Sample records for spinel-type cobalt ruthenium

  1. 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

    2014-01-01

    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. PMID:24862287

  2. Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Maiyalagan, Thandavarayan; Jarvis, Karalee A.; Therese, Soosairaj; Ferreira, Paulo J.; Manthiram, Arumugam

    2014-05-01

    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 Co3+/4+:3d energy with the top of the O2-:2p band.

  3. Development of a stable cobalt-ruthenium Fisher-Tropsch catalyst. Final report

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1995-02-01

    The reverse micelle catalyst preparation method has been used to prepare catalysts on four supports: magnesium oxide, carbon, alumina- titania and steamed Y zeolite. These catalysts were not as active as a reference catalyst prepared during previous contracts to Union Carbide Corp. This catalyst was supported on steamed Y zerolite support and was impregnated by a pore-filling method using a nonaqueous solvent. Additional catalysts were prepared via pore- filling impregnation of steamed Y zeolites. These catalysts had levels of cobalt two to three and a half times as high as the original Union Carbide catalyst. On a catalyst volume basis they were much more active than the previous catalyst; on an atom by atom basis the cobalt was about of the same activity, i.e., the high cobalt catalysts` cobalt atoms were not extensively covered over and deactivated by other cobalt atoms. The new, high activity, Y zerolite catalysts were not as stable as the earlier Union Carbide catalyst. However, stability enhancement of these catalysts should be possible, for instance, through adjustment of the quantity and/or type of trace metals present. A primary objective of this work was determination whether small amounts of ruthenium could enhance the activity of the cobalt F-T catalyst. The reverse micelle catalysts were not activated by ruthenium, indeed scanning transmission electronic microscopy (STEM) analysis provided some evidence that ruthenium was not present in the cobalt crystallites. Ruthenium did not seem to activate the high cobalt Y zeolite catalyst either, but additional experiments with Y zeolite-supported catalysts are required. Should ruthenium prove not to be an effective promoter under the simple catalyst activation procedure used in this work, more complex activation procedures have been reported which are claimed to enhance the cobalt/ruthenium interaction and result in activity promotion by ruthenium.

  4. Ligand Engineering for the Efficient Dye-Sensitized Solar Cells with Ruthenium Sensitizers and Cobalt Electrolytes.

    PubMed

    Aghazada, Sadig; Gao, Peng; Yella, Aswani; Marotta, Gabriele; Moehl, Thomas; Teuscher, Joël; Moser, Jacques-E; De Angelis, Filippo; Grätzel, Michael; Nazeeruddin, Mohammad Khaja

    2016-07-01

    Over the past 20 years, ruthenium(II)-based dyes have played a pivotal role in turning dye-sensitized solar cells (DSCs) into a mature technology for the third generation of photovoltaics. However, the classic I3(-)/I(-) redox couple limits the performance and application of this technique. Simply replacing the iodine-based redox couple by new types like cobalt(3+/2+) complexes was not successful because of the poor compatibility between the ruthenium(II) sensitizer and the cobalt redox species. To address this problem and achieve higher power conversion efficiencies (PCEs), we introduce here six new cyclometalated ruthenium(II)-based dyes developed through ligand engineering. We tested DSCs employing these ruthenium(II) complexes and achieved PCEs of up to 9.4% using cobalt(3+/2+)-based electrolytes, which is the record efficiency to date featuring a ruthenium-based dye. In view of the complicated liquid DSC system, the disagreement found between different characterizations enlightens us about the importance of the sensitizer loading on TiO2, which is a subtle but equally important factor in the electronic properties of the sensitizers. PMID:27322854

  5. 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

  6. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress report No. 10, January 1, 1992--March 31, 1992

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1992-12-31

    In this report, and the three before it, progress has been reviewed toward finding a support for cobalt/ruthenium-based Fischer-Tropsch catalysts. Of the support materials investigated three have so far shown promise: magnesium oxide, carbon and 50/50 alumina/titania. However, as yet catalysts supported on these three materials have proven inferior to the reference TC 211 Y zeolite-supported catalyst with regard to both activity and selectivity. Ruthenium is considered to be a promoter of activity, however, if this effect is manifested in the experimental catalysts it is not enough to make the catalysts more active than the ruthenium-free reference catalyst. The advantages due to reverse micelle are, so far, minimal at best. When the experimental catalysts were operated at higher conversions through evaluation at Conditions 2 and 3, the magnesium oxide-supported catalysts appeared to be closest to the desired low methane selectivity of the reference catalyst at similar conversion. The catalysts prepared on the above supports were not superior to the reference catalyst TC 211. Since the main objective of the current contract is to determine whether cobalt/ruthenium catalysts can be prepared which are superior to cobalt only catalysts, the Y zeolite support will be used in the future. In this special Y zeolite-derived support crystallite size is controlled by the pore size distribution. Thus, the catalyst development objective of controlling the crystallite size will be achieved. In the following quarters, work carried out on the cobalt and cobalt/ruthenium catalysts supported on the Y zeolite-derived support will be reported.

  7. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst

    SciTech Connect

    Abrevaya, H.

    1991-01-01

    The objective of this contract is to examine the relationship between catalytic properties and the function of cobalt Fischer-Tropsch catalysts and to apply this fundamental knowledge to the development of a stable cobalt-based catalyst with a low methane-plus-ethane selectivity for use in slurry reactors. An experimental cobalt catalyst 585R2723 was tested three times in the fixed-bed reactor. The objective of the tests was to identify suitable testing conditions for screening catalyst. The {alpha}-alumina was determined to be a suitable diluent medium for controlling the catalyst bed temperature close to the inlet temperature. With 13 g of catalyst and 155 g of diluent, the catalyst maximum temperature were within 2{degree}C from the inlet temperatures. As a result of this work, 210{degree}C and 21 atm were shown to result in low methane selectivity and were used as initial conditions in the catalyst screening test. Ethane, which along with methane is undesirable, is typically produced with low selectivity and follows the same trend as methane. Other work reported here indicated that methane selectivity increases with increasing temperature but is not excessively high at 230{degree}C. Consequently, the catalyst screening test should include an evaluation of the catalyst performance at 230{degree}C. During Run 67, the increase in temperature from 210{degree}C to 230{degree}C was initiated at 30 hours on-stream.

  8. 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.

  9. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress report No. 15, 1 April 1993--30 June 1993

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1994-06-01

    The high cobalt catalyst described in the previous quarterly report of this contract has been bound and evaluated in the fixed-bed and slurry autoclave pilot plants. The fixed-bed test showed it to be less active after binding than before. The purpose of binding is to provide a granular catalyst suitable for use in liquid phase Fischer-Tropsch (LPFT) processing. In such processing a granular catalyst is required to facilitate its separation from the FT wax product by mechanical means. The bound catalyst was evaluated in the slurry autoclave under LPFT conditions. In this test the temperature of the catalyst could be more precisely controlled at target than in the fixed-bed test due to the large amount of diluent and continual stirring. When operated at a temperature sufficient to induce the same conversion as in the fixed-bed test, the methane selectivity was 10 mole % --- 2% less than in the fixed-bed test. The high cobalt catalyst, bound and unbound, in the fixed-bed or slurry autoclave pilot plants, was not conversion stable. At a given temperature it seemed to approach a conversion line out, however, catalysts more stable at high conversion are required. The unbound catalyst contained more cobalt than previous unbound catalysts in this work. Furthermore, it contained a small amount of ruthenium. Either or both of these properties could have been responsible for the superior activity.

  10. Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

    PubMed

    Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

    2015-12-14

    Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed. PMID:26549729

  11. Ruthenium-Cobalt Bimetallic Supramolecular Cages via a Less Symmetric Tetrapyridyl Metalloligand and the Effect of Spacer Units.

    PubMed

    Ryu, Ji Yeon; Park, Yu Jin; Park, Hyoung-Ryun; Saha, Manik Lal; Stang, Peter J; Lee, Junseong

    2015-10-14

    The self-assembly of C(s)-symmetric tetrapyridyl cobalt-metalloligand 2 with three half-sandwich diruthenium acceptors, 3-5, led to the formation of A4D2 (A = acceptor, D = donor) metallacages 6-8, as shown by ESI mass spectrometry, NMR spectroscopy, and X-ray crystallography. The solid-state structures of 6-8 revealed that the length of the acceptor unit greatly influences the molecular packing of these metallacages. Hence, in the solid state, 6-8 can be considered to have waterwheel-shaped, tweezer-shaped, and butterfly-like architectures, respectively. PMID:26348415

  12. Destruction of polychlorinated aromatic compounds by spinel-type complex oxides.

    PubMed

    Fan, Yun; Lu, Xianbo; Ni, Yuwen; Zhang, Haijun; Zhao, Liang; Chen, Jiping; Sun, Chenglin

    2010-04-15

    Destruction of polychlorinated aromatic compounds was carried out over spinel-type catalysts XY2O4 (where X = Mg, Ca, Cu, Ni, Zn, and Y = Al, Fe). The catalysts were characterized by XRD, nitrogen adsorption-desorption isotherms and FTIR. The performance of these catalysts toward the decomposition of hexachlorobenzene (HCB) and octachlorodibenzo-p-dioxin (OCDD) was evaluated in a closed system. The spinel-type catalyst with mesoporous structure demonstrated high catalytic activity for the hydrodechlorination of polychlorinated aromatic compounds. Among them, the copper-aluminum spinel (CuAl2O4), specifically calcined at 600 degrees C, exhibited the best activity. More than 85% dechlorination efficiency of HCB and 99% decomposition of polychlorinated dibenzodioxin (PCDD) were achieved at 250 degrees C for 30 min over the above catalyst which was more effective than the corresponding metallic copper and copper oxide catalysts during the thermal degradation of polychlorinated aromatic compounds. The correlation of catalytic performance to structural characteristics is discussed based on the detailed characterization. The simple preparation procedure and reasonable cost of the spinel-type catalysts present a good potential for the thermal treatment of polychlorinated aromatic pollutants at lower temperatures. PMID:20334415

  13. Decomposition of Spinel-Type Nickel Chromium Indium Sulfides—X-Ray Powder Structure Determination

    NASA Astrophysics Data System (ADS)

    Lutz, H. D.; Kringe, Ch.; Mohn, K.; Stingl, Th.

    1998-03-01

    The phase diagram of the quaternary system NiCr 2S 4-NiIn 2S 4-Cr 2S 3-In 2S 3has been studied at 873 and 1223 K by X-ray powder structure determination of quenched samples. At high temperatures, spinel-type Ni y(Cr 2-2 xIn 2 x) 1- yS 3-2 ysolid solutions are formed in a large range of composition ( y: 0-0.5, x: 0.3-1). At temperatures below 1183 K, these solid solutions decompose to Cr-rich and In-rich spinel-type sulfides, whereby nickel is enriched in the Cr-rich compounds. The decomposition of the spinel-type sulfides is greatly retarded, even at temperatures about 900 K, due to both thermodynamic and kinetic reasons. The cation distribution established corresponds to a site preference as Cr 3+>Ni 2+>In 3+at the octahedral 16d site and □ (vacancies)>In 3+>Ni 2+at the tetrahedral 8a site of the spinel structure. The metal-sulfur distances of the solid solutions refined are compared with those calculated from characteristic metal-sulfur distances in close-packed structures, taking into account the site occupation established. For the respective indium-sulfur distances, the following improved values are recommended: In tet-S=247.1 pm; In oct-S=260.6 pm.

  14. X-ray Absorption Studies in Spinel-Type LiMn 2O 4

    NASA Astrophysics Data System (ADS)

    Liu, R. S.; Jang, L. Y.; Chen, J. M.; Tsai, Y. C.; Hwang, Y. D.; Liu, R. G.

    1997-02-01

    The electronic structure of the spinel-type LiMn2O4as the cathode material for the application in secondary batteries was probed using both MnK- andL23-edge X-ray absorption near edge structure (XANES) spectra. Based on the energy shifts of the absorption peaks in the XANES spectrum correlated to the effective charge, the valence of Mn in LiMn2O4was determined to be ∼4+. This suggests that the chemical substitution of low valent Li+ions into the Mn sites is possible to result in high valence of Mn.

  15. Arene-metal-carborane triple-decker sandwiches. Designed synthesis of homo- and heterobimetallic complexes of cobalt, iron, ruthenium, and osmium

    SciTech Connect

    Davis, J.H. Jr.; Sinn, E.; Grimes, R.N. )

    1989-06-21

    This paper describes the systematic preparation and characterization of new families of triple-decker sandwich complexes incorporating formal cyclo-Et{sub 2}C{sub 2}B{sub 3}H{sub 3}{sup 4{minus}} bridging ligands, including the first species of this class containing second- or third-row transition metals. Complexes of general formula (L)M(Et{sub 2}C{sub 2}B{sub 3}H{sub 3})M{prime}(L) (M = Ru, Os; M{prime} = Co, Ru; L = cymene (p-isopropyltoluene), Cp, or C{sub 5}Me{sub 5}) were obtained in stepwise fashion via (1) synthesis of closo-(L)M(Et{sub 2}C{sub 2}B{sub 4}H{sub 4}) metallacarboranes, (2) decapitation (apex BH removal) of these complexes to give nido-(L)M(Et{sub 2}C{sub 2}B{sub 3}H{sub 5}), (3) bridge deprotonation to form the corresponding mono- or dianion, and (4) reaction of the anion with an arene metal halide to generate the desired triple-decker compound. In addition, the cobalt-iron triple-decker CpCo(Et{sub 2}C{sub 2}B{sub 3}H{sub 3})FeCp was prepared via treatment of ({eta}{sup 6}-C{sub 8}H{sub 10})Fe(Et{sub 2}C{sub 2}B{sub 3}H{sub 4}){sup {minus}} with Na{sup +}Cp{sup {minus}} and CoCl{sub 2} followed by air oxidation. The reaction of (CO){sub 3}RuCl{sub 2} with (C{sub 5}me{sub 5})Co(Et{sub 2}C{sub 2}B{sub 3}H{sub 3}){sup 2{minus}} gave the pseudo-triple-decker complex (C{sub 5}Me{sub 5})Co(Et{sub 2}C{sub 2}B{sub 3}H{sub 3})Ru(CO){sub 3}. The triple-deckers, especially those containing osmium, are susceptible to chlorination by RuCl{sub 3}, OsCl{sub 3}, or dichloromethane, forming exclusively the 4-chloro derivatives. All of the characterized triple-decker complexes are air-stable crystalline solids (except for the osmium-ruthenium species, which are air sensitive) and have been structurally characterized from their {sup 11}B and {sup 1}H NMR, infrared, visible-UV, and unit- and high-resolution mass spectra.

  16. Surface sites on spinel-type and corundum-type metal oxide powders

    SciTech Connect

    Busca, G.; Lorenzelli, V.; Ramis, G. |; Willey, R.J.

    1993-06-01

    The surface sites on isostructural metal oxides containing Al{sup 3+}, Fe{sup 3+}, and Cr{sup 3+} have been investigated by IR spectroscopy. The IR spectra of surface hydroxy groups and of pyridine coordinated on Lewis acidic surface cationic sites on the defective spinel-type sesquioxides {gamma}-Al{sub 2}O{sub 3}, {theta}-Al{sub 2}O{sub 3}, and {gamma}-Fe{sub 2}O{sub 3}, on the spinels MgAl{sub 2}O{sub 4}, MgFe{sub 2}O{sub 4}, MgCr{sub 2}O{sub 4}, ZnAl{sub 2}O{sub 4}, ZnFe{sub 2}O{sub 4}, and ZnCr{sub 2}O{sub 4}, as well as on the corundum-type sesquioxides {alpha}-Al{sub 2}O{sub 3}, {alpha}-Fe{sub 2}O{sub 3}, and {alpha}-Cr{sub 2}O{sub 3}, have been compared. Some Co{sup 2+} and Ni{sup 2+} spinel-type compounds have also been considered. An extension of the criteria previously proposed for the identification of the surface sites on aluminum-based materials to ferrites and chromites is suggested. The OH stretchings of surface hydroxy groups are indicative of the nature and the coordination of the cations to which they are bonded. Pyridine species bonded to tetrahedrally- and octahedrally-coordinated trivalent cations are well distinguishable on aluminates, while the distiction is more difficult for ferrites. 41 refs., 9 figs., 3 tabs.

  17. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress report No. 14, January 1, 1993--March 31, 1993

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1994-05-01

    The objective of this contract is to examine the relationship between catalytic properties and the function of cobalt Fischer-Tropsch catalysts and to apply this fundamental knowledge to the development of a stable cobalt-based catalyst with a low methane-plus-ethane selectivity for use in slurry reactors.

  18. Radiative properties of α-ZnAl 2S 4:V spinel type single crystals

    NASA Astrophysics Data System (ADS)

    Anghel, S.; Boulon, G.; Kulyuk, L.; Sushkevich, K.

    2011-12-01

    The absorption and luminescent properties of α-ZnAI 2S 4:V spinel type crystals in the temperature range 10-300 K are investigated. The spectra are assigned to the electronic transitions of trivalent vanadium ions located in octahedral sites. It is shown that at low temperatures the three main components of the revealed IR luminescence spectra are caused by the 1A 1g( 1G)→ 1E g( 1D), 1T 2g( 1D), 3T 2g( 3F)→ 3T 1g( 3F), and 1E g( 1D)→ 3T 1g( 3F) transitions. The observed dependencies of the emission components intensities on temperature are explained assuming that there is a phonon assisted tunnelling between 3T 2g( 3F) and 1E g( 1D) states. On temperature rise, the 3T 2g( 3F)→ 3T 1g( 3F) vibronic transitions suppress other emission channels, which leads to the enhancement of the integral luminescence intensity and to the broadening of the spectrum centred at λ=1.4 μm.

  19. Chemical composition, crystal structure, and their relationships with the intrinsic properties of spinel-type crystals based on bond valences.

    PubMed

    Liu, Xiao; Wang, Hao; Lavina, Barbara; Tu, Bingtian; Wang, Weimin; Fu, Zhengyi

    2014-06-16

    Spinel-type crystals may possess complex and versatile chemical composition and crystal structure, which leads to difficulty in constructing relationships among the chemical composition, crystal structure, and intrinsic properties. In this work, we develop new empirical methods based on bond valences to estimate the intrinsic properties, namely, compressibility and thermal expansion of complex spinel-type crystals. The composition-weighted average of bond force constants in tetrahedral and octahedral coordination polyhedra is derived as a function of the composition-weighted average of bond valences, which can be calculated according to the experimental chemical composition and crystal structural parameters. We discuss the coupled effects of tetrahedral and octahedral frameworks on the aforementioned intrinsic properties. The bulk modulus could be quantitatively calculated from the composition-weighted average of bond force constants in tetrahedral and octahedral coordination polyhedra. In contrast, a quantitative estimation of the thermal expansion coefficient could be obtained from the composition-weighted average of bond force constants in octahedral coordination polyhedra. These empirical methods have been validated by the results obtained for a new complex quaternary spinel-type oxynitride Mg0.268Al2.577O3.733N0.267 as well as MgAl2O4 and Al2.85O3.45N0.55 from the literature. Further, these empirical methods have the potential to be extensively applied in other types of complex crystals. PMID:24871452

  20. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress reports No. 7 and 8, April 1, 1991--September 30, 1991

    SciTech Connect

    Abrevaya, H.

    1991-12-31

    The objective of this contract is to examine the relationship between catalytic properties and the function of cobalt Fischer-Tropsch catalysts and to apply this fundamental knowledge to the development of a stable cobalt-based catalyst with a low methane-plus-ethane selectivity for use in slurry reactors. An experimental cobalt catalyst 585R2723 was tested three times in the fixed-bed reactor. The objective of the tests was to identify suitable testing conditions for screening catalyst. The {alpha}-alumina was determined to be a suitable diluent medium for controlling the catalyst bed temperature close to the inlet temperature. With 13 g of catalyst and 155 g of diluent, the catalyst maximum temperature were within 2{degree}C from the inlet temperatures. As a result of this work, 210{degree}C and 21 atm were shown to result in low methane selectivity and were used as initial conditions in the catalyst screening test. Ethane, which along with methane is undesirable, is typically produced with low selectivity and follows the same trend as methane. Other work reported here indicated that methane selectivity increases with increasing temperature but is not excessively high at 230{degree}C. Consequently, the catalyst screening test should include an evaluation of the catalyst performance at 230{degree}C. During Run 67, the increase in temperature from 210{degree}C to 230{degree}C was initiated at 30 hours on-stream.

  1. Spectroscopic characterization of Ti-doped α-ZnAl2S4 spinel-type single crystals

    NASA Astrophysics Data System (ADS)

    Anghel, Sergiu; Boulon, Georges; Brenier, Alain; Fortin, Emery; Klokishner, Sophia; Koshchug, Dmitrii; Kulyuk, Leonid; Sushkevich, Konstantin

    2010-02-01

    The spectroscopic characteristics of the α-ZnAl2S4 wide bandgap semiconductor doped with Ti ions are investigated. It is shown, that the ZnAl2S4:Ti spinel-type crystals exhibit luminescence in the IR spectral range 0.8-1.4 µm. The observed spectroscopic characteristics are assigned to the emission bands arising from the ligand -Ti4+ charge transfer for octahedral sites of titanium that is in agreement with the experimental evidence for the absence of the EPR signal from Ti ions. A qualitative explanation of the experimental data is given.

  2. Spectroscopic characterization of Ti-doped α-ZnAl2S4 spinel-type single crystals.

    PubMed

    Anghel, Sergiu; Boulon, Georges; Brenier, Alain; Fortin, Emery; Klokishner, Sophia; Koshchug, Dmitrii; Kulyuk, Leonid; Sushkevich, Konstantin

    2010-02-10

    The spectroscopic characteristics of the α-ZnAl(2)S(4) wide bandgap semiconductor doped with Ti ions are investigated. It is shown, that the ZnAl(2)S(4):Ti spinel-type crystals exhibit luminescence in the IR spectral range 0.8-1.4 µm. The observed spectroscopic characteristics are assigned to the emission bands arising from the ligand -Ti(4+) charge transfer for octahedral sites of titanium that is in agreement with the experimental evidence for the absence of the EPR signal from Ti ions. A qualitative explanation of the experimental data is given. PMID:21386352

  3. Radiative processes in Alpha-ZnAl_2S4: Ti spinel type single crystals

    NASA Astrophysics Data System (ADS)

    Kulyuk, Leonid; Klokishner, Sophia; Sushkevich, Konstantin; Koshchug, Dmitrii; Boulon, Georges; Brenier, Alain; Fortin, Emery

    2008-06-01

    The radiative properties of the alpha-ZnAl_2S4 wide band -gap semiconductor (E_g=3.4eV) doped with Ti-ions are investigated . It is shown, that the ZnAl_2S_4:Ti spinel type crystals exhibit a IR luminescence in the spectral range 0.8-1.4 micrometers. The observed spectroscopic and temporal characteristics are assigned to the emission bands arising from the ligand - -Ti^4+ charge transfer for octahedral sites of titanium. Bulk stoichiometric alpha-ZnAl2S4:Ti crystals with impurity concentration 0.1-0.5 at % were grown by a closed tube vapor method with halogen as a transport agent. At temperatures T=2-300K the steady state and time-resolved photoluminescence (PL) studies, as well as the optical absorption measurements , were carried out in the spectral range 0.4-1.5 μm using a liquid nitrogen cooled Ge-detector or photomultiplier. The steady-state PL excitation was provided by Ar^+ (λ_ex1=514nm) and He-Ne (Lambda_ex2=633nm) lasers. The PL kinetics has been examined under pulsed excitation (tau_P~10^-8 s) with wavelengths: "green"-λ_ex1P=532nm and "red"-λ_ex2P=630nm (dye laser and OPO) close to Lambda_ex1 and λ_ex2. The EPR studies of the samples have been carried out as well. Under the "green" excitation (λ_ex1), that corresponds to the maximum of the Ti-impurity absorption (λ_abs~510nm), the steady -state PL spectra of ZnAl^2S^4:Ti crystals consist of 2 broad bands centered at λ_1=1.1μm and Lambda_20.8μm. Τhe first component λ_1 dominates in the spectrum at low temperatures (T<200K). At T~300K the shape of the integral spectrum practically is determined by the second broad band Lambda_2. At "red" excitation (λ_ex2, λ_ex2P) the main contribution to the PL spectra in the whole temperature range is provided by the second component, the kinetics of which obeys the exponential law with a single decay time. In contrast to the second band , the emission decay can be described by the superposition of two exponents with different lifetimes. At low

  4. Development of a stable cobalt-ruthenium Fischer-Tropsch catalyst. Technical progress report No. 11, April 1, 1992--June 30, 1992

    SciTech Connect

    Frame, R.R.; Gala, H.B.

    1992-12-31

    Four new catalysts were prepared and screened during this reporting period. They were compared to a reference Co-based catalyst (TC 211) which was developed under a previous DOE contract No. AC22-84PC10028. The reference catalyst was prepared on a special steamed and acid-washed Y zeolite support. The four new catalysts were prepared on a commercial product which is a specially-prepared Y zeolite. A special solvent was used to impregnate contract to a division of Union Carbide which is now part of UOP. Catalyst TC 211 was prepared by impregnating metals onto a laboratory steamed and acid-washed Y zeolite. A special impregnation solvent was used. At similar operating conditions, the four catalysts tested were less active and more selective to methane than the reference catalyst. A temperature change was made in the testing of these four catalysts (condition 1 to condition 2) to obtain conversions comparable to that obtained with the reference catalyst. Higher methane selectivity was noted for these catalysts when comparisons were made at similar conversion levels. When the new catalysts were evaluated at different conversions resulting from changes in feed rate at the same temperature (condition 2 to condition 3) high methane selectivity persisted. Thus these catalysts did not exhibit the expected lower methane selectivity at higher conversion. The four catalysts tested were intrinsically more selective to methane than the reference catalyst. They were, however, similar to the reference catalyst in their low selectivity to alcohols (Table 5). Of the four catalysts, catalyst 6531-161 which contained ruthenium appeared to be the most selective for methane.

  5. RECOVERY OF RUTHENIUM VALUES

    DOEpatents

    Grummitt, W.E.; Hardwick, W.H.

    1961-01-01

    A process is given for the recovery of ruthenium from its aqueous solutions by oxidizing the ruthenium to the octavalent state and subsequently extracting the ruthenium into a halogen-substituted liquid paraffin.

  6. Crystal structure of spinel-type Li0.64Fe2.15Ge0.21O4

    PubMed Central

    Redhammer, Günther J.; Tippelt, Gerold

    2016-01-01

    Spinel-type Li0.64Fe2.15Ge0.21O4, lithium diiron(III) germanium tetra­oxide, has been formed as a by-product during flux growth of an Li–Fe–Ge pyroxene-type material. In the title compound, lithium is ordered on the octa­hedral B sites, while Ge4+ orders onto the tetra­hedral A sites, and iron distributes over both the octa­hedral and tetra­hedral sites, and is in the trivalent state as determined from Mössbauer spectroscopy. The oxygen parameter u is 0.2543; thus, the spinel is close to having an ideal cubic closed packing of the O atoms. The title spinel is compared with other Li- and Ge-containing spinels. PMID:27375876

  7. Comparison effects and electron spin resonance studies of α-Fe2O4 spinel type ferrite nanoparticles.

    PubMed

    Bayrakdar, H; Yalçın, O; Cengiz, U; Özüm, S; Anigi, E; Topel, O

    2014-11-11

    α-Fe2O4 spinel type ferrite nanoparticles have been synthesized by cetyltrimethylammonium bromide (CTAB) and ethylenediaminetetraacetic acid (EDTA) assisted hydrothermal route by using NaOH solution. Electron spin resonance (ESR/EPR) measurements of α-Fe2O4 nanoparticles have been performed by a conventional x-band spectrometer at room temperature. The comparison effect of nanoparticles prepared by using CTAB and EDTA in different α-doping on the structural and morphological properties have been investigated in detail. The effect of EDTA-assisted synthesis for α-Fe2O4 nanoparticles are refined, and thus the spectroscopic g-factor are detected by using ESR signals. These samples can be considered as great benefits for magnetic recording media, electromagnetic and drug delivery applications. PMID:24858357

  8. Crystal structure of spinel-type Li0.64Fe2.15Ge0.21O4.

    PubMed

    Redhammer, Günther J; Tippelt, Gerold

    2016-04-01

    Spinel-type Li0.64Fe2.15Ge0.21O4, lithium diiron(III) germanium tetra-oxide, has been formed as a by-product during flux growth of an Li-Fe-Ge pyroxene-type material. In the title compound, lithium is ordered on the octa-hedral B sites, while Ge(4+) orders onto the tetra-hedral A sites, and iron distributes over both the octa-hedral and tetra-hedral sites, and is in the trivalent state as determined from Mössbauer spectroscopy. The oxygen parameter u is 0.2543; thus, the spinel is close to having an ideal cubic closed packing of the O atoms. The title spinel is compared with other Li- and Ge-containing spinels. PMID:27375876

  9. Spin-flop transition, magnetic and microwave absorption properties of α-Fe2O4 spinel type ferrite nanoparticles

    NASA Astrophysics Data System (ADS)

    Yalçın, Orhan; Bayrakdar, Harun; Özüm, Songül

    2013-10-01

    We have prepared NiFe2O4, CoFe2O4, Ni0.6Zn0.4Fe2O4 and ZnFe2O4 spinel type ferrite nanoparticles by surfactant-assisted hydrothermal process using cetyltrimethylammonium bromide (CTAB). The spin-flop transition, magnetic, dielectric and permittivity characterizations have been investigated. The spin-flop transition occurs from antiferromagnetic state to mixed state and then ferromagnetic state for Zn doped samples. The spin-flop transition occurs in the temperature range of 50-250 K. The ionic conduction, dipolar relaxation, atomic polarization and electronic polarization are the main mechanisms that contribute to the permittivity of a dielectric material. The permittivity increases with increasing frequency. This suggests a resonance behavior, which is expected when the ferrite samples are highly conductive and skin effect become significant. These samples will provide great benefits for electromagnetic applications and electromagnetic interference shielding characteristics.

  10. Effect of Heat-Treatment and Composition on Structure and Luminescence Properties of Spinel-Type Solid Solution Nanocrystals.

    PubMed

    Sakoda, Kazuki; Hirano, Masanori

    2015-08-01

    The compositional dependence of the structure and properties of spinel-type solid solutions, Zn(A,Ga)2O4 was investigated by comparison with samples hydrothermally prepared and those after heat treatment at 1000 °C in air. Nanocrystalline spinel-type solid solutions in the whole composition range in the ZnAl2O4-ZnGa2O4 system were directly formed from the aqueous precursor solutions of ZnSO4, Al(NO3)3 and Ga(NO3)3 under hydrothermal conditions at 180 °C for 5 h in the presence of tetramethylammonium hydroxide. The incorporation of aluminum into the lattice, Zn(AlxGa1-x)2O4, resulted in lower crystallinity of the spinel. The relationship between the lattice parameter of as-prepared samples and the Al atomic ratio in the spinel composition was slightly apart from the ideal linear relationship that was obtained in the samples after heat treatment at 1000 °C. The optical band gap of both as-prepared solid solutions and those heat treated linearly increased from 4.1~4.2 to 5.25 eV by the incorporation of aluminum ion into the lattice, Zn(AlxGa1-x)2O4. Two main broad-band emission spectra centered at around 360 and 430 nm in the range of 300-600 nm were observed in the spinel solid solutions under excitation at 270 nm, thought their broad-band emission spectra and their peak wavelengths subtly changed depending on the composition and heat treatment. PMID:26369200

  11. Radiochemistry of ruthenium

    SciTech Connect

    Schulz, W W; Metcalf, S G; Barney, G S

    1984-06-01

    Information on ruthenium is presented. Topics include the following; isotopes and nuclear properties of ruthenium; review of the chemistry of ruthenium including metal and alloys, compounds of ruthenium, and solution chemistry; separation methods including volatilization of RuO{sub 4}, precipitation and coprecipitation, solvent extraction, chromatographic techniques, and analysis for radioruthenium. 445 refs., 7 figs., 23 tabs.

  12. Preparation and electrochemical properties of Li-rich spinel-type lithium manganate coated LiMn{sub 2}O{sub 4}

    SciTech Connect

    Li, Yumei; Lin, Zhenzhen; Li, Yongliang; Chen, Caifeng; He, Yi; Yang, Xiaojing

    2011-12-15

    Graphical abstract: Composites in which Li-rich spinel-type lithium manganate was coated on surface of LiMn{sub 2}O{sub 4} particles were prepared, and the cycling stabilities of composites were much improved. Highlights: Black-Right-Pointing-Pointer A composite of Li-rich spinel-type lithium manganate and LiMn{sub 2}O{sub 4}. Black-Right-Pointing-Pointer Li-rich spinel-type lithium manganate coating on the surface of LiMn{sub 2}O{sub 4} particles. Black-Right-Pointing-Pointer A synthetic method of sol-gel followed by heating. Black-Right-Pointing-Pointer Improved cycling stability without large degradation of initial capacity. -- Abstract: Li-rich spinel-type lithium manganate (SC) coated LiMn{sub 2}O{sub 4} composites were prepared and characterized by XRD, SEM, FT-IR, ICP, etc. Their charge/discharge behaviors were studied between 3.0 and 4.3 V at 40 mA g{sup -1} under room temperature, and the results showed that SC coated on surface of LiMn{sub 2}O{sub 4} could improve cycling stability of composite electrodes. The composite (S1) containing 4.8 wt% of SC exhibited noticeably improved cycling stability, whereas the initial specific capacity was very close to that of LiMn{sub 2}O{sub 4}.

  13. Electrochemical Synthesis of Spinel Type ZnCo2O4 Electrodes for Use as Oxygen Evolution Reaction Catalysts.

    PubMed

    Kim, Tae Woo; Woo, Myong A; Regis, Morrisa; Choi, Kyoung-Shin

    2014-07-01

    A new electrochemical synthesis route was developed to prepare spinel-type ZnCo2O4 and Co3O4 as high quality thin film-type electrodes for use as electrocatalysts for oxygen evolution reaction (OER). Whereas Co3O4 contains Co(2+) in the tetrahedral sites and Co(3+) in the octahedral sites in the spinel structure, ZnCo2O4 contains only Co(3+) in the octahedral sites; Co(2+) in the tetrahedral sites is replaced by Zn(2+). Therefore, by comparing the catalytic properties of ZnCo2O4 and Co3O4 electrodes prepared with comparable surface morphologies and thicknesses, it was possible to examine whether Co(2+) in Co3O4 is catalytically active for OER. The electrocatalytic properties of ZnCo2O4 and Co3O4 for OER in both 1 M KOH (pH 13.8) and 0.1 M phosphate buffer (pH 7) solutions were investigated and compared. The results suggest that the Co(2+) in Co3O4 is not catalytically critical for OER and ZnCo2O4 can be a more economical and environmentally benign replacement for Co3O4 as an OER catalyst. PMID:26279561

  14. Ruthenium-106 brachytherapy.

    PubMed

    Pe'er, Jacob

    2012-01-01

    Brachytherapy is the most common method for treating uveal melanoma, and currently the ruthenium-106 (Ru-106) and iodine-125 (I-125) applicators are the most frequently used. Ru-106 applicators were introduced by Prof. Peter Lommatzsch in the 1960s, and since then have been used widely by many ocular oncologists, mainly in Europe. The Ru-106 isotope is a beta ray (electron) emitter, and as such it has a limited depth of penetration. This is the reason why many experts use Ru-106 applicators for tumors with a maximal thickness of up to 7.0 mm, although others use it successfully for thicker tumors. The Ru-106 applicators are manufactured commercially and have a half-life of about 1 year. Ru-106 brachytherapy for uveal melanoma provides excellent local control rates and eye preservation with a relatively low recurrence rate. The main advantage of Ru-106 over other isotopes is the better preservation of vision in the treated eye, and less damage to the healthy parts of the eye due to its limited range of radiation. This can also be achieved by positioning the Ru-106 plaque eccentrically, away from the macula and optic nerve head. Ru-106 brachytherapy can be used in combination with other methods of treatment of uveal melanoma, such as local resection or transpupillary thermotherapy, and is sporadically combined with other isotopes, such as gamma-emitting cobalt-60 and I-125. PMID:22042011

  15. Electronic structure and physical properties of the spinel-type phase of BeP{sub 2}N{sub 4} from all-electron density functional calculations

    SciTech Connect

    Ching, W. Y.; Aryal, Sitram; Rulis, Paul; Schnick, Wolfgang

    2011-04-15

    Using density-functional-theory-based ab initio methods, the electronic structure and physical properties of the newly synthesized nitride BeP{sub 2}N{sub 4} with a phenakite-type structure and the predicted high-pressure spinel phase of BeP{sub 2}N{sub 4} are studied in detail. It is shown that both polymorphs are wide band-gap semiconductors with relatively small electron effective masses at the conduction-band minima. The spinel-type phase is more covalently bonded due to the increased number of P-N bonds for P at the octahedral sites. Calculations of mechanical properties indicate that the spinel-type polymorph is a promising superhard material with notably large bulk, shear, and Young's moduli. Also calculated are the Be K, P K, P L{sub 3}, and N K edges of the electron energy-loss near-edge structure for both phases. They show marked differences because of the different local environments of the atoms in the two crystalline polymorphs. These differences will be very useful for the experimental identification of the products of high-pressure syntheses targeting the predicted spinel-type phase of BeP{sub 2}N{sub 4}.

  16. Metals fact sheet: Ruthenium

    SciTech Connect

    1996-06-01

    Ruthenium, named after Ruthenia, a province in Western Russia, was discovered in 1827 by Osann in placer ores from Russia`s Ural mountains. A minor platinum group metal (PGM), Ruthenium was the last of the PGMs to be isolated. In 1844, Klaus prepared the first 6 grams of pure ruthenium metal.

  17. Electrical and magnetic properties of the spinel-type Li(Ti 0.8Cr 0.2) 2O 4

    NASA Astrophysics Data System (ADS)

    Kanno, Toshio; Awaka, Junji; Kariya, Fumihiro; Ebisu, Shuji; Nagata, Shoichi

    2006-05-01

    The spinel-type LiTi 2O 4 exhibits a superconducting transition at 13.7 K. The influence of substitution of Cr 3+ ion for Ti at spinel octahedral sites has been remarkably illustrated by previous researchers. The superconductivity is completely destroyed at 2.5% Cr 3+ ion by magnetic impurity effect. This short paper will present briefly electrical and magnetic properties of Li(Ti 0.80Cr 0.20) 2O 4 at rather high Cr 3+ ion substitution.

  18. A general method of fabricating flexible spinel-type oxide/reduced graphene oxide nanocomposite aerogels as advanced anodes for lithium-ion batteries.

    PubMed

    Zeng, Guobo; Shi, Nan; Hess, Michael; Chen, Xi; Cheng, Wei; Fan, Tongxiang; Niederberger, Markus

    2015-04-28

    High-capacity anode materials for lithium ion batteries (LIBs), such as spinel-type metal oxides, generally suffer from poor Li(+) and e(-) conductivities. Their drastic crystal structure and volume changes, as a result of the conversion reaction mechanism with Li, severely impede the high-rate and cyclability performance toward their practical application. In this article, we present a general and facile approach to fabricate flexible spinel-type oxide/reduced graphene oxide (rGO) composite aerogels as binder-free anodes where the spinel nanoparticles (NPs) are integrated in an interconnected rGO network. Benefiting from the hierarchical porosity, conductive network and mechanical stability constructed by interpenetrated rGO layers, and from the pillar effect of NPs in between rGO sheets, the hybrid system synergistically enhances the intrinsic properties of each component, yet is robust and flexible. Consequently, the spinel/rGO composite aerogels demonstrate greatly enhanced rate capability and long-term stability without obvious capacity fading for 1000 cycles at high rates of up to 4.5 A g(-1) in the case of CoFe2O4. This electrode design can successfully be applied to several other spinel ferrites such as MnFe2O4, Fe3O4, NiFe2O4 or Co3O4, all of which lead to excellent electrochemical performances. PMID:25783818

  19. Cobalt poisoning

    MedlinePlus

    ... and pigments (Cobalt Blue) Magnets Some metal-on-metal hip implants Tires Cobalt was once used as a stabilizer in beer foam. It caused a condition called "beer-drinker's heart," which resulted in heart muscle weakness. This list may not be all-inclusive.

  20. SOLVENT EXTRACTION OF RUTHENIUM

    DOEpatents

    Hyman, H.H.; Leader, G.R.

    1959-07-14

    The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

  1. Cobalt poisoning

    MedlinePlus

    ... the wear and tear of some cobalt/chromium metal-on-metal hip implants. This type of implant is an ... hip socket that is created by fitting a metal ball into a metal cup. Sometimes, metal particles ( ...

  2. Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe{sub 2}O{sub 4} complex oxide catalyst

    SciTech Connect

    Pardeshi, Satish K.; Pawar, Ravindra Y.

    2010-05-15

    The CaFe{sub 2}O{sub 4} spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 {sup o}C which was lower than that of ferrite prepared by other methods. CaFe{sub 2}O{sub 4} catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H{sub 2}O{sub 2} (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 {+-} 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 {+-} 2 mol% and minor product phenyl acetaldehyde up to 9 {+-} 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H{sub 2}O{sub 2} molar ratio and solvents on the conversion and product distribution were studied.

  3. Ruthenium-coated ruthenium oxide nanorods

    SciTech Connect

    Ducati, Caterina; Dawson, Darryl H.; Saffell, John R.; Midgley, Paul A.

    2004-11-29

    The role of ruthenium and its oxides in catalysis, electrochemistry, and electronics is becoming increasingly important because of the high thermal and chemical stability, low resistivity, and unique redox properties of this metallic system. We report an observation of RuO{sub 2} nanorods decorated with nanometer size Ru metal clusters. We identify precise crystallographic relationships between metal and oxide, and provide a simple model for the synthesis of these structures, based on the theory of columnar growth. The high aspect ratio, high surface area, and quantum size crystalline decorations of these nanostructures make them particularly attractive candidates for further fundamental research and for advanced catalytic and electronic applications.

  4. Magnetic properties of the spinel-type Cu(Cr{sub 1-x}Hf{sub x}){sub 2}S{sub 4}

    SciTech Connect

    Kariya, F.; Ebina, K.; Hasegawa, K.; Koshimizu, K.; Wuritunasitu, B.; Hondou, K.; Ebisu, S.; Nagata, S.

    2009-08-15

    The spinel sulphide CuCr{sub 2}S{sub 4} is a metallic ferromagnet with a Curie temperature T{sub c}{approx_equal}380K, while CuHf{sub 2}S{sub 4} has no magnetic anomaly. Magnetic properties of the quaternary spinel-type Cu(Cr{sub 1-x}Hf{sub x}){sub 2}S{sub 4} system have been studied. With increasing x the ferromagnetic properties are weakened gradually from a predominant ferromagnetic, a spin-glass, finally to a simple paramagnetic behavior. For the composition of x{approx_equal}0.50, a re-entrant spin-glass phase could emerge, even though the Curie temperature is ill-defined as a ferromagnetic phase boundary. Specimens with x>=0.90 remain paramagnetic down to 4.2 K. A spin crossover phenomenon is found around 160 K in the specimens of x=0.50-0.70. A step-like anomaly is manifestly detected in the magnetization, which corresponds with the change of the spin state. This crossover indicates that the spin state converts from high temperature S=2 into low temperature S=3/2 states. In the ordered states in T<160K, the magnetic moment originates from only Cr{sup 3+} ions. - Spin crossover phenomenon in Cu(Cr{sub 1-x}Hf{sub x}){sub 2}S{sub 4}. A step-like anomaly is found around 160 K for x=0.50, 0.60, and 0.70 in the magnetization as a function of temperature. The inset shows the enlargement data for x=0.60. This crossover indicates that the spin state changes from high temperature S=2 to low temperature S=3/2 states.

  5. RUTHENIUM DECONTAMINATION METHOD

    DOEpatents

    Gresky, A.T.

    1960-07-19

    A liquid-liquid extraction method of separating uranium from fission products is given. A small amount of a low molecular weight ketone is added to an acidic aqueous solution containing neutron-irradiated uranium and its associated fission products. The resulting solution is digested and then contacted with an organic liquid that extracts uranium values. The purpose of the step of digesting the aqueous solution in the presence of the ketone is to suppress the extractability of ruthenium.

  6. Magnetic, Optical, and Magnetooptical Properties of Spinel-Type ACr2X4 (A=Mn, Fe, Co, Cu, Zn, Cd; X=O, S, Se)

    NASA Astrophysics Data System (ADS)

    Ohgushi, Kenya; Okimoto, Yoichi; Ogasawara, Takeshi; Miyasaka, Shigeki; Tokura, Yoshinori

    2008-03-01

    A comprehensive study of magnetic, optical, and magnetooptical properties was carried out for single crystals of the spinel-type ACr2X4 (A=Mn, Fe, Co, Cu, Zn, and Cd; X=O, S, and Se). The optical reflectivity measurements for 0.1-30 eV revealed a wide variation in electronic structures on a large energy scale between oxides (X=O) and chalcogenides (X=S and Se). For A=Fe and Co, we observed the intra-atomic d-d transitions of A2+ ions with a tetrahedral coordination, and successfully deduced the crystal field splitting Δ E, the Racah parameter B, and the spin-orbit coupling constant \\zeta by analysis based on the ligand field theory. A comparison of these optical parameters between oxides and chalcogenides indicated the strong covalency effect in the chalcogenides. In A=Cu, the insulator-metal transition between X=O and Se was clearly demonstrated by optical conductivity spectra. Magnetic properties were discussed in relation to electronic structures. A compound with a small optical gap is typically a ferrimagnet with antiparallel arrangements of A2+ and Cr3+ spins, whereas a compound with a large optical gap undergoes first-order phase transition into spiral spin ordering at a low temperature. We found that the magnetic anisotropy constants K1 for ACr2S4 (A=Mn, Fe, and Co) are approximately scaled by the inverse of the intra-atomic d-d transition energies of A2+ ions in agreement with the second-order perturbation theory for single-ion anisotropy. The magnetooptical spectra in a wide energy range (0.2-4.5 eV) were measured for chalcogenides focusing on the d-d transition resonance. We observed gigantic magnetooptical signals up to 4.1° in the energy range of 4A2 →{4}T2 and 4A2 →{4}T1 transitions of Co2+ ions for CoCr2S4, and analyzed them in the framework of the ligand field theory. We propose that the strong covalency of the ligand sulfur, as well as the local breakdown of inversion symmetry, in the tetrahedral site plays a crucial role in the enhancement

  7. Synthesis and Characterization of Cobalt Substituted Zinc Ferrite Nanoparticles by Microwave Combustion Method.

    PubMed

    Sundararajan, M; Kennedy, L John; Vijaya, J Judith

    2015-09-01

    Pure and cobalt doped zinc ferrites were prepared by microwave combustion method using L-arginine as a fuel. The prepared samples were characterized by various instrumental techniques such as X-ray powder diffractometry, high resolution scanning electron microscopy (HR-SEM), energy dispersive X-ray analysis, Fourier transformed infrared (FT-IR) spectroscopy, photoluminescence spectroscopy and UV-Visible diffuse reflectance spectroscopy. Vibrating sample magnetometry at room temperature was recorded to study the magnetic behavior of the samples. X-ray analysis confirmed the formation of zinc ferrites normal spinel-type structure with an average crystallite sizes in the range, 25.69 nm to 35.68 nm. The lattice parameters decreased as cobalt fraction was increased. The HR-SEM images showed nanoparticles are agglomerated. The estimated band gap energy value was found to decrease with an increase in cobalt content (1.87 to 1.62 eV). Broad visible emissions are observed in the photoluminescence spectra. A gradual increase in the coercivity and saturation magnetization (M(s)) were noted at relatively higher cobalt doping fractions. PMID:26716235

  8. Cobalt free maraging steel

    SciTech Connect

    Floreen, S.

    1984-04-17

    The subject invention is directed to ferrous-base alloys, particularly to a cobalt-free maraging steel of novel chemistry characterized by a desired combination of strength and toughness, notwithstanding that cobalt is non-essential.

  9. Moderated ruthenium fischer-tropsch synthesis catalyst

    DOEpatents

    Abrevaya, Hayim

    1991-01-01

    The subject Fischer-Tropsch catalyst comprises moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation.

  10. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Callis, C.F.; Moore, R.L.

    1959-09-01

    >The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

  11. Preparation and Characterization of Polymer-Stabilized Ruthenium-Platinum and Ruthenium-Palladium Bimetallic Colloids and Their Catalytic Properties for Hydrogenation of o-Chloronitrobenzene.

    PubMed

    Liu; Yu; Liu; Zheng

    1999-06-15

    Colloidal dispersions of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium-platinum and ruthenium-palladium bimetallic colloids were prepared by NaBH4 reduction of the corresponding mixed-metal salts at room temperature and characterized by TEM, XPS, and XRD. The resulting bimetallic colloids were used as catalysts for the selective hydrogenation of o-chloronitrobenzene (o-CNB) in methanol at 303 K under 0.1 MPa of hydrogen. It was observed that the catalytic performance of PVP-stabilized ruthenium-platinum colloids (PVP-Ru/Pt) and ruthenium-palladium colloids (PVP-Ru/Pd) was dependent on their compositions and could be remarkably affected by some added metal cations. In the presence of cobalt ion, nearly 100% selectivity to o-chloroaniline (o-CAN) was achieved over PVP-Ru/Pt colloids at 100% conversion of o-CNB, with an activity two orders of magnitude higher than that of monometallic PVP-Ru colloid. Copyright 1999 Academic Press. PMID:10339363

  12. Characterization And Dissolution Properties Of Ruthenium Oxides

    EPA Science Inventory

    Ruthenium oxides (RuO2•1.10H2O and RuO2) have been synthesized by forced hydrolysis and oxidation of ruthenium chloride. The resulting materials were extensively characterized to determine the crystallinity, surface area, and ruthenium oxidation ...

  13. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Beederman, M.; Vogler, S.; Hyman, H.H.

    1959-07-14

    The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

  14. Solventless synthesis of ruthenium nanoparticles

    NASA Astrophysics Data System (ADS)

    García-Peña, Nidia G.; Redón, Rocío; Herrera-Gomez, Alberto; Fernández-Osorio, Ana Leticia; Bravo-Sanchez, Mariela; Gomez-Sosa, Gustavo

    2015-06-01

    This paper presents a novel solventless method for the synthesis of zero-valent ruthenium nanoparticles Ru(0). The proposed method, although not entirely new in the nanomaterials world, was used for the first time to synthesize zero-valent ruthenium nanoparticles. This new approach has proved to be an environmentally friendly, clean, cheap, fast, and reproducible technique which employs low amounts of solvent. It was optimized through varying amounts of reducing salt on a determined quantity of precursor and measuring the effect of this variation on the average particle size obtained. The resulting products were fully characterized by powder XRD, TEM, HR-TEM, and XPS studies, all of which corroborated the purity of the nanoparticles achieved. In order to verify the advantages of our method over other techniques, we compared our nanoparticles with two common colloidal-synthesized ruthenium nanoparticles.

  15. Carbon deposition in the Bosch process with ruthenium and ruthenium-iron alloy catalysts. M.S. Thesis. Final Report, Jan. 1981 - Jul. 1982

    NASA Technical Reports Server (NTRS)

    Manning, M. P.; Reid, R. C.; Sophonpanich, C.

    1982-01-01

    The effectiveness of ruthenium and the alloys 50Ru50Fe and 33Ru67Fe as alternatives to iron, nickel, and cobalt catalysts in recovering oxygen from metabolic carbon dioxide was investigated. Carbon deposition boundaries over the unsupported alloys are reported. Experiments were also carried out over 50Ru50Fe and 97Ru3Fe3 catalysts supported on gamma-alumina to determine their performance in the synthesis of low molecular weight olefins. High production of ethylene and propylene would be beneficial for an improvement of an overall Bosch process, as a gas phase containing high olefin content would enhance carbon deposition in a Bosch reactor.

  16. Solubility of cobalt in cement.

    PubMed

    Fregert, S; Gruvberger, B

    1978-02-01

    Unlike chromate, cobalt occurring as cobalt oxides in cement is not water-soluble in a detectable amount. Cobalt oxides are to some extent soluble in the presence of amino acids with which cobalt forms complexes. Such complexes can elicit patch test reactions. It is postulated that cobalt is more readily dissolved by forming complexes in eczematous skin than in normal skin. This may explain why cobalt sensitization in cement eczemas is secondary to chromate sensitivity. PMID:657784

  17. 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

  18. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries.

    PubMed

    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

  19. 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.

  20. Marine cobalt resources

    USGS Publications Warehouse

    Manheim, F. T.

    1986-01-01

    Ferromanganese oxides in the open oceans are more enriched in cobalt than any other widely distributed sediments or rocks. Concentrations of cobalt exceed 1 percent in ferromanganese crusts on seamounts, ocean ridges, and other raised areas of the ocean. The cobalt-rich crusts may be the slowest growing of any earth material, accumulating one molecular layer every 1 to 3 months. Attention has been drawn to crusts as potential resources because they contain cobalt, manganese, and platinum, three of the four priority strategic metals for the United States. Moreover, unlike abyssal nodules, whose recovery is complicated by their dominant location in international waters, some of the most cobalt-rich crusts occur within the exclusive economic zone of the United States and other nations. Environmental impact statements for crust exploitation are under current development by the Department of the Interior.

  1. Samarium/Cobalt Magnets

    NASA Technical Reports Server (NTRS)

    Das, D.; Kumar, K.; Frost, R.; Chang, C.

    1985-01-01

    Intrinsic magnetic coercivities of samarium cobalt magnets made to approach theoretical limit of 350 kA/m by carefully eliminating oxygen from finished magnet by hot isostatic pressing (HIP). HIP process viable alternative to currently used sintering process.

  2. IR-doped ruthenium oxide catalyst for oxygen evolution

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

    2012-01-01

    A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

  3. Wrought cobalt- base superalloys

    NASA Astrophysics Data System (ADS)

    Klarstrom, D. L.

    1993-08-01

    Wrought cobalt-base superalloys are used extensively in gas turbine engines because of their excellent high-temperature creep and fatigue strengths and resistance to hot corrosion attack. In addition, the unique character of the oxide scales that form on some of the alloys provides outstanding resistance to high-temperature sliding wear. This article provides a review of the evolutionary development of wrought cobalt-base alloys in terms of alloy design and physical metallurgy. The topics include solid-so-lution strengthening, carbide precipitation characteristics, and attempts to introduce age hardening. The use of PHACOMP to enhance thermal stability characteristics and the incorporation of rare-earth ele-ments to improve oxidation resistance is also reviewed and discussed. The further development of cobalt-base superalloys has been severely hampered by past political events, which have accentuated the strategic vulnerability of cobalt as a base or as an alloying element. Consequently, alternative alloys have been developed that use little or no cobalt. One such alternative, Haynes® 230TMalloy, is discussed briefly.

  4. Platinum-ruthenium-palladium fuel cell electrocatalyst

    DOEpatents

    Gorer, Alexander

    2006-02-07

    A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum at a concentration that is between about 20 and about 60 atomic percent, ruthenium at a concentration that is between about 20 and about 60 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having an atomic ratio of platinum to ruthenium that is between about 0.7 and about 1.2. Alternatively, the catalyst may contain platinum at a concentration that is between about 25 and about 50 atomic percent, ruthenium at a concentration that is between about 25 and about 55 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having a difference between the concentrations of ruthenium and platinum that is no greater than about 20 atomic percent.

  5. Platinum-ruthenium-nickel fuel cell electrocatalyst

    DOEpatents

    Gorer, Alexander

    2005-07-26

    A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum, ruthenium, and nickel, wherein the nickel is at a concentration that is less than about 10 atomic percent.

  6. Ruthenium Sesquisilicide: A Promising Thermoelectric Material

    NASA Technical Reports Server (NTRS)

    Vining, Cronin B.

    1993-01-01

    Report describes experimental investigation of thermoelectric properties of ruthenium sesquisilicide (RU2Si3). Suggests suitably doped Ru2Si3 could have thermoelectric figures of merit two or more times as large as SiGe.

  7. Lead-ruthenium pyrochlores as oxygen electrocatalysts

    NASA Technical Reports Server (NTRS)

    Anderson, E. B.; Taylor, E. J.; Moniz, G. A.

    1990-01-01

    An investigation of lead-ruthenium pyrochlores of the structure Pb2(Ru/2-x/Pb/x/) O7-y for use as oxygen electrocatalysts in alkaline media is discussed. Lead-ruthenium pyrochlore mixed metal oxides were prepared and characterized by X-ray diffraction, BET surface area, dry powder conductivity, and chemical stability. Gas diffusion electrodes were developed specifically for the lead-ruthenium pyrochlore materials. Also investigated were the effects of varying electrode fabrication parameters on the oxygen reduction performance of the lead-ruthenium pyrochlore electrocatalyst. Long-term stability performance was also evaluated. The oxygen reduction performance of the pyrochlore electrocatalyst is considerably higher than that of the state-of-the-art gold-platinum alloy electrocatalyst currently used by NASA. Furthermore, the pyrochlore electrocatalysts are attractive candidates for high-performance pressurized alkaline fuel cells.

  8. Highly sensitive catalytic spectrophotometric determination of ruthenium

    NASA Astrophysics Data System (ADS)

    Naik, Radhey M.; Srivastava, Abhishek; Prasad, Surendra

    2008-01-01

    A new and highly sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III) has been established based on its catalytic effect on the oxidation of L-phenylalanine ( L-Pheala) by KMnO 4 in highly alkaline medium. The reaction has been followed spectrophotometrically by measuring the decrease in the absorbance at 526 nm. The proposed CKM is based on the fixed time procedure under optimum reaction conditions. It relies on the linear relationship where the change in the absorbance (Δ At) versus added Ru(III) amounts in the range of 0.101-2.526 ng ml -1 is plotted. Under the optimum conditions, the sensitivity of the proposed method, i.e. the limit of detection corresponding to 5 min is 0.08 ng ml -1, and decreases with increased time of analysis. The method is featured with good accuracy and reproducibility for ruthenium(III) determination. The ruthenium(III) has also been determined in presence of several interfering and non-interfering cations, anions and polyaminocarboxylates. No foreign ions interfered in the determination ruthenium(III) up to 20-fold higher concentration of foreign ions. In addition to standard solutions analysis, this method was successfully applied for the quantitative determination of ruthenium(III) in drinking water samples. The method is highly sensitive, selective and very stable. A review of recently published catalytic spectrophotometric methods for the determination of ruthenium(III) has also been presented for comparison.

  9. Mechanical properties of nanocrystalline cobalt

    NASA Astrophysics Data System (ADS)

    Karimpoor, Amir A.; Erb, Uwe

    2006-05-01

    Due to their excellent wear and corrosion properties, nanocrystalline cobalt and several cobalt alloys made by electrodeposition are currently being developed as environmentally benign replacement coatings for hard chromium electrodeposits. The focus of this study is on the mechanical properties of nanocrystalline cobalt, which are currently not well understood. A comparison is presented for hardness, tensile properties, Charpy impact properties and fracture surface analysis of both nanocrystalline (grain size: 12 nm) and conventional polycrystalline (grain size: 4.8 m) cobalt. It is shown that the hardness and tensile strength of nanocrystalline cobalt is 2-3 times higher than for polycrystalline cobalt. However, in contrast to other nanocrystalline materials tested previously, nanocrystalline cobalt retains considerable ductility with elongation to fracture values up to 7%.

  10. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, Paul K.; Abney, Kent D.; Kinkead, Scott A.

    1997-01-01

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10' positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron.

  11. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, P.K.; Abney, K.D.; Kinkead, S.A.

    1997-05-20

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10{prime} positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron. 1 fig.

  12. Coordination Complexes of Cobalt.

    ERIC Educational Resources Information Center

    Williams, Gregory M.; And Others

    1989-01-01

    Described is an experiment involving the synthesis and spectral studies of cobalt complexes that not only give general chemistry students an introduction to inorganic synthesis but allows them to conduct a systematic study on the effect of different ligands on absorption spectra. Background information, procedures, and experimental results are…

  13. Evolution from a ferromagnetic to a spin-glass regime in the spinel-type Cu(Cr{sub 1-x}Ti{sub x}){sub 2}S{sub 4}

    SciTech Connect

    Kariya, Fumihiro; Ebisu, Shuji; Nagata, Shoichi

    2009-03-15

    Successive changes from ferromagnetic, re-entrant mixed, to spin-glass regime have been manifestly found with increasing Ti-composition x in the quaternary spinel-type Cu(Cr{sub 1-x}Ti{sub x}){sub 2}S{sub 4} system. The Curie temperature T{sub c} decreases steeply with increasing x and this transition becomes ill-defined around x=0.47. Two distinct transitions appear below T{sub c} over the range x=0.40-0.47. Coexistence of the ferromagnetism and spin-glass order would be observed below the Gabay and Toulouse transition (T{sub GT}), owing to freezing of the transverse-spin components without changing of the ferromagnetic order parameter. Finally, at a yet lower temperature de Almeida-Thouless transition (T{sub AT}), the longitudinal-spin component freezes randomly at which an irreversibility arises between zero-field-cooled (ZFC) and field-cooled (FC) magnetizations. Over the range of 0.47{<=}x{<=}0.85, a cusp of the ZFC magnetization is seen at T{sub g} like conventional spin-glass. Specimens with x{>=}0.90 remain paramagnetic down to 2.0 K. A magnetic phase diagram between T versus x has been obtained experimentally. The values of the multicritical point in 100 Oe is detected to be x=0.47 and T=7.40K. The low-field magnetization and the phase diagram are satisfactorily explained by the theory of Gabay and Toulouse on the basis of Heisenberg isotropic vector spin model rather than the Ising spin model. - An enlargement of the magnetic phase diagram for Cu(Cr{sub 1-x}Ti{sub x}){sub 2}S{sub 4} at a constant field of 100 Oe over the range of 0.40{<=}x{<=}0.70. The curves give a guide to the eye: para, paramagnetic; ferro, ferromagnetic; SGI, spin-glass I (GT-phase), and SGII: spin-glass II (AT-phase). Three characteristic temperatures of T{sub c},T{sub GT}, and T{sub AT} merge into 7.40 K at x=0.47 in H=100 Oe. This is a multicritical point.

  14. High-rate supercapacitor utilizing hydrous ruthenium dioxide nanotubes

    NASA Astrophysics Data System (ADS)

    Wu, Xu; Xiong, Wei; Chen, Yangyang; Lan, Danni; Pu, Xuli; Zeng, Yan; Gao, Hairui; Chen, Jisheng; Tong, Hua; Zhu, Zhihong

    2015-10-01

    Three-dimensional criss-crossed hydrous ruthenium dioxide (RuO2) nanotubes directly on a Ti substrate without any binder are successfully synthesized for the first time via a facile template method at a low temperature of 90 °C. A cobalt-hydroxide-carbonate nanowire array is used as the template and can be completely dissolved away during the formation process of the tubular structure. The synthetic strategy is much more cost-effective and facile than other physical/chemical methods. The obtained material possesses proper crystallinity and water content together with a distinctive structure, resulting in superior electron and ion transmission performance. When the binder-free electrode is used in a supercapacitor, it exhibits a remarkable high-rate performance with a specific capacitance of 745 F g-1 at a high current density of 32 A g-1. This represents a retention of 88.7% compared to the value of 840 F g-1 at 2 A g-1.

  15. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis

    NASA Astrophysics Data System (ADS)

    Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

    2015-06-01

    Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, CoxMn3-xO4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation-precipitation and insertion-crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn-air and Li-air batteries.

  16. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis

    PubMed Central

    Li, Chun; Han, Xiaopeng; Cheng, Fangyi; Hu, Yuxiang; Chen, Chengcheng; Chen, Jun

    2015-01-01

    Spinel-type oxides are technologically important in many fields, including electronics, magnetism, catalysis and electrochemical energy storage and conversion. Typically, these materials are prepared by conventional ceramic routes that are energy consuming and offer limited control over shape and size. Moreover, for mixed-metal oxide spinels (for example, CoxMn3−xO4), the crystallographic phase sensitively correlates with the metal ratio, posing great challenges to synthesize active product with simultaneously tuned phase and composition. Here we report a general synthesis of ultrasmall cobalt manganese spinels with tailored structural symmetry and composition through facile solution-based oxidation–precipitation and insertion–crystallization process at modest condition. As an example application, the nanocrystalline spinels catalyse the oxygen reduction/evolution reactions, showing phase and composition co-dependent performance. Furthermore, the mild synthetic strategy allows the formation of homogeneous and strongly coupled spinel/carbon nanocomposites, which exhibit comparable activity but superior durability to Pt/C and serve as efficient catalysts to build rechargeable Zn–air and Li–air batteries. PMID:26040417

  17. Chalcogenide Cobalt telluride nanotubes

    NASA Astrophysics Data System (ADS)

    Dahal, Bishnu; Dulal, Rajendra; Pegg, Ian L.; Philip, John

    Cobalt telluride nanotubes are grown using wet chemical and hydrothermal syntheses. Wet chemical synthesized nanotubes display nearly 1: 1 Co to Te ratio. On the other hand, CoTe nanotubes synthesized using hydrothermal method show excess Co content leading to the compound Co58Te42. Both CoTe and Co58Te42 display magnetic properties, but with totally different characteristics. The Curie temperature of CoTe is higher than 400 K. However, the Tc of Co58Te42 is below 50 K. Transport properties of cobalt telluride (CoTe) nanotube devices show that they exhibit p-type semiconducting behavior. The magnetoresistance measured at 10 K show a magnetoresistance of 54%. . National Science Foundation under ECCS-0845501 and NSF-MRI, DMR-0922997.

  18. Cobalt ion-containing epoxies

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St.clair, A. K.

    1983-01-01

    Varying concentrations of an organometallic cobalt complex were added to an epoxy system currently used by the aerospace industry as a composite matrix resin. Methods for combining cobalt (III) acetylacetonate with a tetraglycidyl 4,4 prime - diaminodiphenylmethane-based epoxy were investigated. The effects of increasing cobalt ion concentration on the epoxy cure were demonstrated by epoxy gel times and differential scanning calorimetry cure exotherms. Analysis on cured cobalt-containing epoxy castings included determination of glass transition temperatures by thermomechanical analysis, thermooxidative stabilities by thermogravimetric analysis, and densities in a density gradient column. Flexural strength and stiffness were also measured on the neat resin castings.

  19. Blood doping by cobalt. Should we measure cobalt in athletes?

    PubMed Central

    Lippi, Giuseppe; Franchini, Massimo; Guidi, Gian Cesare

    2006-01-01

    Background Blood doping is commonplace in competitive athletes who seek to enhance their aerobic performances through illicit techniques. Presentation of the hypothesis Cobalt, a naturally-occurring element with properties similar to those of iron and nickel, induces a marked and stable polycythemic response through a more efficient transcription of the erythropoietin gene. Testing the hypothesis Although little information is available so far on cobalt metabolism, reference value ranges or supplementation in athletes, there is emerging evidence that cobalt is used as a supplement and increased serum concentrations are occasionally observed in athletes. Therefore, given the athlete's connatural inclination to experiment with innovative, unfair and potentially unhealthy doping techniques, cobalt administration might soon become the most suited complement or surrogate for erythropoiesis-stimulating substances. Nevertheless, cobalt administration is not free from unsafe consequences, which involve toxic effects on heart, liver, kidney, thyroid and cancer promotion. Implications of the hypothesis Cobalt is easily purchasable, inexpensive and not currently comprehended within the World Anti-Doping Agency prohibited list. Moreover, available techniques for measuring whole blood, serum, plasma or urinary cobalt involve analytic approaches which are currently not practical for antidoping laboratories. Thus more research on cobalt metabolism in athletes is compelling, along with implementation of effective strategies to unmask this potentially deleterious doping practice PMID:16863591

  20. Cobalt source calibration

    SciTech Connect

    Rizvi, H.M.

    1999-12-03

    The data obtained from these tests determine the dose rate of the two cobalt sources in SRTC. Building 774-A houses one of these sources while the other resides in room C-067 of Building 773-A. The data from this experiment shows the following: (1) The dose rate of the No.2 cobalt source in Building 774-A measured 1.073 x 10{sup 5} rad/h (June 17, 1999). The dose rate of the Shepherd Model 109 Gamma cobalt source in Building 773-A measured 9.27 x 10{sup 5} rad/h (June 25, 1999). These rates come from placing the graduated cylinder containing the dosimeter solution in the center of the irradiation chamber. (2) Two calibration tests in the 774-A source placed the graduated cylinder with the dosimeter solution approximately 1.5 inches off center in the axial direction. This movement of the sample reduced the measured dose rate 0.92% from 1.083 x 10{sup 5} rad/h to 1.073 x 10{sup 5} rad/h. and (3) A similar test in the cobalt source in 773-A placed the graduated cylinder approximately 2.0 inches off center in the axial direction. This change in position reduced the measured dose rate by 10.34% from 1.036 x 10{sup 6} to 9.27 x 10{sup 5}. This testing used chemical dosimetry to measure the dose rate of a radioactive source. In this method, one determines the dose by the chemical change that takes place in the dosimeter. For this calibration experiment, the author used a Fricke (ferrous ammonium sulfate) dosimeter. This solution works well for dose rates to 10{sup 7} rad/h. During irradiation of the Fricke dosimeter solution the Fe{sup 2+} ions ionize to Fe{sup 3+}. When this occurs, the solution acquires a slightly darker tint (not visible to the human eye). To determine the magnitude of the change in Fe ions, one places the solution in an UV-VIS Spectrophotometer. The UV-VIS Spectrophotometer measures the absorbency of the solution. Dividing the absorbency by the total time (in minutes) of exposure yields the dose rate.

  1. Thermodynamic properties of gaseous ruthenium species.

    PubMed

    Miradji, Faoulat; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

    2015-05-21

    The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin-orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin-orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points. PMID:25905631

  2. Strongly Coupled Cyclometalated Ruthenium Triarylamine Chromophores as Sensitizers for DSSCs.

    PubMed

    Kreitner, Christoph; Mengel, Andreas K C; Lee, Tae Kyung; Cho, Woohyung; Char, Kookheon; Kang, Yong Soo; Heinze, Katja

    2016-06-20

    A series of anchor-functionalized cyclometalated bis(tridentate) ruthenium(II) triarylamine hybrids [Ru(dbp-X)(tctpy)](2-) [2 a](2-) -[2 c](2-) (H3 tctpy=2,2';6',2''-terpyridine-4,4',4''-tricarboxylic acid; dpbH=1,3-dipyridylbenzene; X=N(4-C6 H4 OMe)2 ([2 a](2-) ), NPh2 ([2 b](2-) ), N-carbazolyl [2 c](2-) ) was synthesized and characterized. All complexes show broad absorption bands in the range 300-700 nm with a maximum at about 545 nm. Methyl esters [Ru(Me3 tctpy)(dpb-X)](+) [1 a](+) -[1 c](+) are oxidized to the strongly coupled mixed-valent species [1 a](2+) -[1 c](2+) and the Ru(III) (aminium) complexes [1 a](3+) -[1 c](3+) at comparably low oxidation potentials. Theoretical calculations suggest an increasing spin delocalization between the metal center and the triarylamine unit in the order [1 a](2+) <[1 b](2+) <[1 c](2+) . Solar cells were prepared with the saponified complexes [2 a](2-) -[2 c](2-) and the reference dye N719 as sensitizers using the I3 (-) /I(-) couple and [Co(bpy)3 ](3+/2+) and [Co(ddpd)2 ](3+/2+) couples as [B(C6 F5 )4 ](-) salts as electrolytes (bpy=2,2'-bipyridine; ddpd=N,N'-dimethyl-N,N'-dipyridin-2-yl-pyridine-2,6-diamine). Cells with [2 c](2-) and I3 (-) /I(-) electrolyte perform similarly to cells with N719. In the presence of cobalt electrolytes, all efficiencies are reduced, yet under these conditions [2 c](2-) outperforms N719. PMID:27192962

  3. Splitting water with cobalt.

    PubMed

    Artero, Vincent; Chavarot-Kerlidou, Murielle; Fontecave, Marc

    2011-08-01

    The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable, and efficient systems for the conversion and storage of renewable energy sources, such as solar energy. The production of hydrogen, a fuel with remarkable properties, through sunlight-driven water splitting appears to be a promising and appealing solution. While the active sites of enzymes involved in the overall water-splitting process in natural systems, namely hydrogenases and photosystem II, use iron, nickel, and manganese ions, cobalt has emerged in the past five years as the most versatile non-noble metal for the development of synthetic H(2)- and O(2)-evolving catalysts. Such catalysts can be further coupled with photosensitizers to generate photocatalytic systems for light-induced hydrogen evolution from water. PMID:21748828

  4. Cobalt: for strength and color

    USGS Publications Warehouse

    Boland, Maeve A.; Kropschot, S.J.

    2011-01-01

    Cobalt is a shiny, gray, brittle metal that is best known for creating an intense blue color in glass and paints. It is frequently used in the manufacture of rechargeable batteries and to create alloys that maintain their strength at high temperatures. It is also one of the essential trace elements (or "micronutrients") that humans and many other living creatures require for good health. Cobalt is an important component in many aerospace, defense, and medical applications and is a key element in many clean energy technologies. The name cobalt comes from the German word kobold, meaning goblin. It was given this name by medieval miners who believed that troublesome goblins replaced the valuable metals in their ore with a substance that emitted poisonous fumes when smelted. The Swedish chemist Georg Brandt isolated metallic cobalt-the first new metal to be discovered since ancient times-in about 1735 and identified some of its valuable properties.

  5. Ruthenium indenylidene complexes containing dichalcogenoimidodiphosphinate ligands

    NASA Astrophysics Data System (ADS)

    Jia, Ai-Quan; Xin, Zhi-Feng; Chen, Qun; Leung, Wa-Hung; Zhang, Qian-Feng

    2012-07-01

    Reactions of ruthenium indenylidene starting material [Ru(PPh3)2(Ind)Cl2] (Ind = 3-phenylinden-1-ylidene) with potassium dichalcogenoimidodiphosphinates K[R2P(E)NP(E')R2] afforded a series of complexes [Ru(PPh3)(Ind){кE,кE'-R2P(E)NP(E')R2}Cl] [R = Ph, E = E' = S (1a); R = Ph, E = E' = Se (1b); R = iPr, E = E' = S (1c); R = iPr, E = E' = Se (1d); R = Ph, E = S, E' = Se (1e); R = iPr, E = S, E' = Se (1f)] which were characterized by microanalyses, IR and NMR spectroscopies. The molecular structure of 1a has been confirmed by single-crystal X-ray diffraction. The catalytic reactivity of the ruthenium indenylidene complexes in the ring closing metathesis of diethyl 1,2-diallylmalonate has also been investigated.

  6. Highly Selective Ruthenium Metathesis Catalysts for Ethenolysis

    PubMed Central

    Thomas, Renee M.; Keitz, Benjamin K.; Champagne, Timothy M.; Grubbs, Robert H.

    2011-01-01

    N-aryl, N-alkyl N-heterocyclic carbene (NHC) ruthenium metathesis catalysts are highly selective toward the ethenolysis of methyl oleate, giving selectivity as high as 95% for the kinetic, ethenolysis products over the thermodynamic, self-metathesis products. The examples described herein represent some of the most selective NHC-based ruthenium catalysts for ethenolysis reactions to date. Furthermore, many of these catalysts show unusual preference and stability toward propagating as a methylidene species, and provide good yields and turnover numbers (TONs) at relatively low catalyst loading (<500 ppm). A catalyst comparison showed that ruthenium complexes bearing sterically hindered NHC substituents afforded greater selectivity and stability, and exhibited longer catalyst lifetime during reactions. Comparative analysis of the catalyst preference for kinetic versus thermodynamic product formation was achieved via evaluation of their steady-state conversion in the cross-metathesis reaction of terminal olefins. These results coincided with the observed ethenolysis selectivities, in which the more selective catalysts reach a steady-state characterized by lower conversion to cross-metathesis products compared to less selective catalysts, which show higher conversion to cross-metathesis products. PMID:21510645

  7. Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst

    DOEpatents

    Abrevaya, Hayim

    1990-01-01

    A Fischer-Tropsch type process produces hydrocarbons from carbon monoxide and hydrogen using a novel catalyst comprising moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation.

  8. Fischer-Tropsch synthesis process employing a moderated ruthenium catalyst

    DOEpatents

    Abrevaya, H.

    1990-07-31

    A Fischer-Tropsch type process produces hydrocarbons from carbon monoxide and hydrogen using a novel catalyst comprising moderated ruthenium on an inorganic oxide support. The preferred moderator is silicon. Preferably the moderator is effectively positioned in relationship to ruthenium particles through simultaneous placement on the support using reverse micelle impregnation. 1 fig.

  9. The biokinetics of ruthenium in the human body

    SciTech Connect

    Leggett, Richard Wayne

    2011-01-01

    The biokinetics of ruthenium (Ru) in the human body is of interest due mainly to the potential for occupational or environmental exposure to 106Ru (T1/2 = 373.6 d) and 103Ru (T1/2 = 39.3 d), which typically represent a significant portion of the fission products in a reactor inventory. During reactor operations or nuclear fuel reprocessing these ruthenium isotopes may be present as ruthenium tetroxide (RuO4) vapor, a highly mobile form of ruthenium that has been involved in a number of cases of accidental exposure to 106Ru or 103Ru. This paper summarizes the biokinetic database for ruthenium and proposes a new respiratory model for inhaled RuO4 vapor, a new biokinetic for systemic (absorbed) ruthenium, and material-specific gastrointestinal absorption fractions for ruthenium. The proposed respiratory model for RuO4 differs from the current ICRP model mainly in that it depicts slower clearance of deposited activity from the respiratory tract and lower absorption to blood than depicted in the current ICRP model. The proposed systemic biokinetic model depicts more realistic paths of movement of absorbed ruthenium in the body than the current ICRP model and, in contrast to the present model, a less uniform distribution of systemic activity. Implications of the proposed models with regard to inhalation and ingestion dose coefficients for 106Ru are examined.

  10. Electrolytic determination of ruthenium(VI) with 8-mercaptoquinoline

    SciTech Connect

    Avdienko, T.N.; Fedorova, N.G.; Sinkevich, V.V.; Suprunovich, V.I.

    1986-08-01

    The authors studied the possibility of using 8-mercaptoquinoline for the potentiometric and amperometric determination of ruthenium(VI). Previously, this reagent was recommended for the amperometric titration of ruthenium(IV) in the form of (RuCl/sub 6/)/sup 2/-; pd(II), Ir(IV), Cu(III), Au(III), and certain other metals interfere with the determination. A differential analysis of the following two-component systems was carried out: ruthenium(VI)-palladium(II); ruthenium(VI)-osmium(VI). Methods were developed for the potentiometric titration and amperometric (with the polarized electrodes) determination of ruthenium(VI) with 8-mercaptoquinoline in the presence of certain metals of the platinum group. Model mixtures, close in composition to the natural ones, and an industrial sample were analyzed.

  11. Wrought cobalt-base superalloys

    SciTech Connect

    Klarstrom, D.L. )

    1993-08-01

    Wrought cobalt-base superalloys are used extensively in gas turbine engines because of their excellent high-temperature creep and fatigue strength and resistance to hot corrosion attach. In addition, the unique character of the oxide scales that form on some of the alloys provides outstanding resistance to high-temperature sliding wear. This article provides a review of the evolutionary development of wrought cobalt-base alloys in terms of alloy design and physical metallurgy. The topics include solid-solution strengthening, carbide precipitation characteristics, and attempts to introduce age hardening. The use of PHACOMP to enhance thermal stability characteristics and the incorporation of rare-earth elements to improve oxidation resistance is also reviewed and discussed. The further development of cobalt-base superalloys has been severely hampered by past political events, which have accentuated the strategic vulnerability of cobalt as a base or as an alloying element. Consequently, alternative alloys have been developed that use little or no cobalt. One such alternative, Haynes 230 alloy, is discussed briefly.

  12. Ruthenium Cobalt to Extend the Scalability of Ultra-thin Direct Plate Liners

    NASA Astrophysics Data System (ADS)

    Greenslit, Daniel V.

    In traditional semiconductor technology a sputtered copper seed layer is used to improve the adhesion, microstucture, and electromigration characteristics of electrochemically deposited (ECD) copper. The seed layer is deposited on top of a Ta/TaN stack. The Ta layer acts as an adhesion and nucleation layer for the copper seed and the TaN serves as a diffusion barrier for the Cu. As the line widths continue to shrink, scaling each of these layers becomes more difficult. It would be advantageous for the interconnect to be composed of as much copper as possible, transitioning from the traditional liner seed stack to a single layer that could function as a diffusion barrier, adhesion promoter, and a directly plateable surface could improve the extendibility of copper interconnect technology. Novel mixed phase films grown by plasma-enhanced atomic layer deposition (PEALD) have been investigated as direct-plate Cu barriers for advanced back end of the line integration. Previous work on RuTaN mixed phase materials has shown that a Ru:Ta ratio of 12:1 has been effective as a direct plate Cu barrier to a thickness of 2-3 nm based on the resistivity of the film. To try and scale direct plate barrier technology below 2 nm the resistivity of the films needs to be decreased. To accomplish this, the use of Co in place of traditional barrier materials is proposed as an alternative approach. RuCo liner films with metal ratios between 5:1 and 15:1 were investigated as both a direct plate surface and for their ability to act as a robust Cu diffusion barrier. 3 nm thick PEALD RuCo films with a metal ratio between 5:1 and 15:1 exhibited plating characteristics comparable to a PEALD Ru film. The RuCo films were also demonstrated to be a suitably robust Cu diffusion barrier. The scalability limits of the RuCo film are limited by the resistivity of the film. When the thickness of the film was reduced to 2 nm the resistivity of the film increased to a point that the electrochemical deposition of Cu became non-uniform. The RuCo films were also found to be structurally unstable when the thickness of the films was increased to 6 nm. This resulted in the phase transition within the RuCo film which caused an order of magnitude increase in the Cu diffusion measured through the RuCo films. The direct-plateable PEALD RuCo films appear to be scalable to a thickness of 2 nm and may offer an alternative route for the continued scaling of Cu interconnects.

  13. Improvement by heating of the electronic conductivity of cobalt spinel phases, electrochemically synthesized in various electrolytes

    SciTech Connect

    Douin, Myriam; Guerlou-Demourgues, Liliane; Menetrier, Michel; Bekaert, Emilie; Goubault, Lionel; Bernard, Patrick; Delmas, Claude

    2009-05-15

    The nature of the alkaline electrolyte (based on KOH, NaOH, LiOH), in which Co{sub 3}O{sub 4} spinel type phases are synthesized by electrooxidation of CoO, is shown to play a key role on the composition, the structure and the electronic conductivity of the materials. In the materials, prepared in pure LiOH electrolyte or in mixed ternary electrolyte (KOH, NaOH, LiOH), Co{sup 4+} ions are present in the octahedral framework, which entails electronic delocalization in the cobalt T{sub 2g} band and a high conductivity. The structure of the sample, synthesized in KOH, is on the opposite closer to that of ideal Co{sub 3}O{sub 4}, with only Co{sup 3+} in the octahedral sublattice, which leads to a semi-conducting behavior. Whatever the initial material, a thermal treatment induces an increase of the Co{sup 4+}/Co{sup 3+} ratio in the octahedral network, resulting in a significant increase of the electronic conductivity. - Graphical abstract: In 'Co{sub 3}O{sub 4}' type spinel phases synthesized by eleectrooxidation, the nature of the alkaline electrolyte allows to monitor the amounts of hydrogen and lithium, inserted in spinel framework and therefore the electronic conductivity. Whatever the initial synthesis electrolyte, a moderate thermal treatment of the materials induces a significant increase of the electronic conductivity, due to a structural reorganization (illustrated by the evolution of the cell parameter) and an increase of the Co{sup 4+}/Co{sup 3+} ratio in the octahedral framework.

  14. Cobalt Alums. A Demonstration Experiment

    NASA Astrophysics Data System (ADS)

    Schäffer, Claus E.; Steenberg, Paul

    2002-08-01

    The demonstration experiment describes the isolation of [Co(H2O)6]3+ both as the pure blue crystalline cesium cobalt alum, CsCo(SO4)2·12H2O, and as a light greenish-blue solid solution of ammonium cobalt alum in (NH4)Al(SO4)2·12H2O. The hexaaquacobalt(III) ion is prepared chemically by oxidation with hydrogen peroxide, taking advantage of the stabilization of CoIII relative to CoII by complexation with the carbonate ligand. A brief description of alum structure and a characterization of alum subclasses are included.

  15. Controlling the misuse of cobalt in horses.

    PubMed

    Ho, Emmie N M; Chan, George H M; Wan, Terence S M; Curl, Peter; Riggs, Christopher M; Hurley, Michael J; Sykes, David

    2015-01-01

    Cobalt is a well-established inducer of hypoxia-like responses, which can cause gene modulation at the hypoxia inducible factor pathway to induce erythropoietin transcription. Cobalt salts are orally active, inexpensive, and easily accessible. It is an attractive blood doping agent for enhancing aerobic performance. Indeed, recent intelligence and investigations have confirmed cobalt was being abused in equine sports. In this paper, population surveys of total cobalt in raceday samples were conducted using inductively coupled plasma mass spectrometry (ICP-MS). Urinary threshold of 75 ng/mL and plasma threshold of 2 ng/mL could be proposed for the control of cobalt misuse in raceday or in-competition samples. Results from administration trials with cobalt-containing supplements showed that common supplements could elevate urinary and plasma cobalt levels above the proposed thresholds within 24 h of administration. It would therefore be necessary to ban the use of cobalt-containing supplements on raceday as well as on the day before racing in order to implement and enforce the proposed thresholds. Since the abuse with huge quantities of cobalt salts can be done during training while the use of legitimate cobalt-containing supplements are also allowed, different urinary and plasma cobalt thresholds would be required to control cobalt abuse in non-raceday or out-of-competition samples. This could be achieved by setting the thresholds above the maximum urinary and plasma cobalt concentrations observed or anticipated from the normal use of legitimate cobalt-containing supplements. Urinary threshold of 2000 ng/mL and plasma threshold of 10 ng/mL were thus proposed for the control of cobalt abuse in non-raceday or out-of-competition samples. PMID:25256240

  16. Cobalt(II) and Cobalt(III) Coordination Compounds.

    ERIC Educational Resources Information Center

    Thomas, Nicholas C.; And Others

    1989-01-01

    Presents a laboratory experiment which illustrates the formation of tris(phenanthroline)cobalt complexes in the 2+ and 3+ oxidation states, the effect of coordination on reactions of the ligand, and the use of a ligand displacement reaction in recovering the transformed ligand. Uses IR, UV-VIS, conductivity, and NMR. (MVL)

  17. Characterization and dissolution properties of ruthenium oxides.

    PubMed

    Luxton, Todd P; Eick, Matthew J; Scheckel, Kirk G

    2011-07-01

    Ruthenium oxides (RuO(2)·1·10H(2)O and RuO(2)) have been synthesized by forced hydrolysis and oxidation of ruthenium chloride. The resulting materials were extensively characterized to determine the crystallinity, surface area, and ruthenium oxidation state. Surface charging experiments indicate a large quantity of reactive functional groups for both materials and a decrease in the acidity of the surface functional groups with crystallization of the hydrous oxide. Dissolution studies conducted in acidic and basic pH environments indicate Ru-oxides are insoluble in 0.1 M HCl and slightly soluble in 0.1 M NaOH. Oxalate and ascorbate (5 mM) promoted dissolution of RuO(2)·1·10H(2)O demonstrated an increase in dissolution rates with decreasing pH and increasing ligand surface coverage. XPS analysis of the RuO(2)·1·10H(2)O surface after ligand promoted dissolution revealed the reduction of Ru(IV) to Ru(III) indicating that both ascorbate and oxalate reductively dissolve RuO(2)·1·10H(2)O. Dissolution experiments with RuO(2) resulted in dissolution only for 5 mM oxalate at pH 3. Dissolution rates calculated for RuO(2)·1·10H(2)O and RuO(2) are compared with previously published dissolution rates for iron oxides, demonstrating an order of magnitude decrease in the oxalate and ascorbate promoted dissolution. PMID:21511266

  18. Ruthenium Vinyl Carbene Intermediates in Enyne Metathesis

    PubMed Central

    Diver, Steven T.

    2009-01-01

    This review provides an overview of ruthenium vinyl carbene reactivity as it relates to enyne metathesis. Methods for the synthesis of metathesis-active and metathesis-inactive complexes are also summarized. Some of the early hypotheses about vinyl carbene intermediates in enyne metatheses were tested in the arena of synthetic chemistry and subsequently led to mechanistic studies. In these two areas, studies from the author's labs are described. There are still many unresolved questions in enyne metathesis that trace back to vinyl carbene reactivity. Hopefully this review will stimulate further investigation into vinyl carbene reactivity which should further refine our understanding of catalytic enyne metathesis. PMID:19590747

  19. Ruthenium / aerogel nanocomposits via Atomic Layer Deposition

    SciTech Connect

    Biener, J; Baumann, T F; Wang, Y; Nelson, E J; Kucheyev, S O; Hamza, A V; Kemell, M; Ritala, M; Leskela, M

    2006-08-28

    We present a general approach to prepare metal/aerogel nanocomposites via template directed atomic layer deposition (ALD). In particular, we used a Ru ALD process consisting of alternating exposures to bis(cyclopentadienyl)ruthenium (RuCp{sub 2}) and air at 350 C to deposit metallic Ru nanoparticles on the internal surfaces of carbon and silica aerogels. The process does not affect the morphology of the aerogel template and offers excellent control over metal loading by simply adjusting the number of ALD cycles. We also discuss the limitations of our ALD approach, and suggest ways to overcome these.

  20. PROCESS FOR DECONTAMINATING THORIUM AND URANIUM WITH RESPECT TO RUTHENIUM

    DOEpatents

    Meservey, A.A.; Rainey, R.H.

    1959-10-20

    The control of ruthenium extraction in solvent-extraction processing of neutron-irradiated thorium is presented. Ruthenium is rendered organic-insoluble by the provision of sulfite or bisulfite ions in the aqueous feed solution. As a result the ruthenium remains in the aqueous phase along with other fission product and protactinium values, thorium and uranium values being extracted into the organic phase. This process is particularly applicable to the use of a nitrate-ion-deficient aqueous feed solution and to the use of tributyl phosphate as the organic extractant.

  1. Preparation and characterization of positively charged ruthenium nanoparticles.

    PubMed

    Yang, Jun; Lee, Jim Yang; Deivaraj, T C; Too, Heng-Phon

    2004-03-15

    Positively charged ruthenium nanoparticles were prepared by NaBH(4) reduction at room temperature and at pH values lower than 4.9. The ruthenium nanoparticles were characterized by zeta potential measurement, TEM, XPS, and XRD. Particles with a mean diameter of 1.8 nm and a standard deviation of 0.40 nm could be obtained under the experimental conditions. The surface charge on the particles is believed to originate from hydrated proton adsorption. The positively charged ruthenium nanoparticles could be used as the starting material for further functionalization by PVP, ethylenediamine, and dodecylamine. PMID:14972606

  2. Biological activity of ruthenium nitrosyl complexes.

    PubMed

    Tfouni, Elia; Truzzi, Daniela Ramos; Tavares, Aline; Gomes, Anderson Jesus; Figueiredo, Leonardo Elias; Franco, Douglas Wagner

    2012-01-01

    Nitric oxide plays an important role in various biological processes, such as neurotransmission, blood pressure control, immunological responses, and antioxidant action. The control of its local concentration, which is crucial for obtaining the desired effect, can be achieved with exogenous NO-carriers. Coordination compounds, in particular ruthenium(III) and (II) amines, are good NO-captors and -deliverers. The chemical and photochemical properties of several ruthenium amine complexes as NO-carriers in vitro and in vivo have been reviewed. These nitrosyl complexes can stimulate mice hippocampus slices, promote the lowering of blood pressure in several in vitro and in vivo models, and control Trypanosoma cruzi and Leishmania major infections, and they are also effective against tumor cells in different models of cancer. These complexes can be activated chemically or photochemically, and the observed biological effects can be attributed to the presence of NO in the compound. Their efficiencies are explained on the basis of the [Ru(II)NO(+)](3+)/[Ru(II)NO(0)](2+) reduction potential, the specific rate constant for NO liberation from the [RuNO](2+) moiety, and the quantum yield of NO release. PMID:22178685

  3. Ruthenium-containing bond coats for thermal barrier coating systems

    NASA Astrophysics Data System (ADS)

    Tryon, B.; Cao, F.; Murphy, K. S.; Levi, C. G.; Pollock, T. M.

    2006-01-01

    Bond coats for zirconia-based thermal barrier coating systems applied to nickel-based superalloys are typically composed of the B2 NiAl phase. Since RuAl has the same B2 crystal structure but a melting point 400°C higher than NiAl, ruthenium-modified aluminide bond coats could provide improved system temperature capability. Creep experiments on ternary Al-Ni-Ru alloys demonstrate greatly improved creep properties with increasing ruthenium content. Processing paths for ruthenium-modified NiAl-based bond coatings have been established within the bounds of commercially available coating systems. The oxidation resistance of ruthenium-modified bond coats during thermal cycling has been examined, and potential thermal barrier coating system implications are discussed.

  4. Nonproductive Events in Ring-Closing Metathesis using Ruthenium Catalysts

    PubMed Central

    Stewart, Ian C.; Keitz, Benjamin K.; Kuhn, Kevin M.; Thomas, Renee M.

    2010-01-01

    The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends. PMID:20518557

  5. Nickel/ruthenium catalyst and method for aqueous phase reactions

    DOEpatents

    Elliott, Douglas C.; Sealock, John L.

    1998-01-01

    A method of hydrogenation using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions.

  6. Cosine (Cobalt Silicide Growth Through Nitrogen-Induced Epitaxy) Process For Epitaxial Cobalt Silicide Formation For High Performance Sha

    DOEpatents

    Lim, Chong Wee; Shin, Chan Soo; Gall, Daniel; Petrov, Ivan Georgiev; Greene, Joseph E.

    2004-09-28

    A method for forming an epitaxial cobalt silicide layer on a MOS device includes sputter depositing cobalt in an ambient to form a first layer of cobalt suicide on a gate and source/drain regions of the MOS device. Subsequently, cobalt is sputter deposited again in an ambient of argon to increase the thickness of the cobalt silicide layer to a second thickness.

  7. Polytypic transformations during the thermal decomposition of cobalt hydroxide and cobalt hydroxynitrate

    SciTech Connect

    Ramesh, Thimmasandra Narayan

    2010-06-15

    The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co{sub 3}O{sub 4}. The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism. - Graphical abstract: Isothermal thermal decomposition studies of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature show the metastable phase formed prior to Co{sub 3}O{sub 4} phase.

  8. The respiratory effects of cobalt

    SciTech Connect

    Cugell, D.W.; Morgan, W.K.; Perkins, D.G.; Rubin, A. )

    1990-01-01

    We studied seven subjects with certain manifestations of cobalt-induced lung disease. All worked with cobalt and were involved in either the production or use of hard metal. The mode of presentation varied from an acute hypersensitivity pneumonitis that cleared completely when exposure ceased to progressive severe interstitial fibrosis of the lungs. In one subject reexposure was followed by a recurrence of the symptoms. All subjects showed restrictive ventilatory impairment and a reduction of their diffusing capacity. The radiologic appearances varied greatly. While two subjects had clear roentgenograms with small lung volumes, others had a micronodular pattern or small blotchy nodular infiltrates, and one had diffuse reticulonodulation as is seen in cryptogenic fibrosing alveolitis. The pathologic appearances varied between desquamative interstitial pneumonia and overt mural fibrosis of the alveoli. Six of the seven patients had multinucleated giant cells in their biopsy specimens or bronchoalveolar lavage fluid.

  9. Cobalt single-molecule magnet

    NASA Astrophysics Data System (ADS)

    Yang, En-Che; Hendrickson, David N.; Wernsdorfer, Wolfgang; Nakano, Motohiro; Zakharov, Lev N.; Sommer, Roger D.; Rheingold, Arnold L.; Ledezma-Gairaud, Marisol; Christou, George

    2002-05-01

    A cobalt molecule that functions as a single-molecule magnet, [Co4(hmp)4(MeOH)4Cl4], where hmp- is the anion of hydroxymethylpyridine, is reported. The core of the molecule consists of four Co(II) cations and four hmp- oxygen atom ions at the corners of a cube. Variable-field and variable-temperature magnetization data have been analyzed to establish that the molecule has a S=6 ground state with considerable negative magnetoanisotropy. Single-ion zero-field interactions (DSz2) at each cobalt ion are the origin of the negative magnetoanisotropy. A single crystal of the compound was studied by means of a micro-superconducting quantum interference device magnetometer in the range of 0.040-1.0 K. Hysteresis was found in the magnetization versus magnetic field response of this single crystal.

  10. Technical and business considerations of cobalt hydrometallurgy

    NASA Astrophysics Data System (ADS)

    Peek, Edgar; Åkre, Torjus; Asselin, Edouard

    2009-10-01

    Approximately 55,000 tonnes of cobalt are produced annually worldwide, which represents an estimated 1-3 billion in annual sales depending on cobalt price changes. Cobalt is a common impurity in both non-ferrous mineral sulfide and oxide processing. In this paper some business and technical considerations are presented to facilitate the decision-making process required to produce either an intermediate or a finished cobalt product via a hydrometallurgical route. Methods currently available and practiced for the recovery of cobalt are considered, and process requirements up- and down-stream associated with each chosen method are discussed. In particular, some environmental, energy, or other sustainable development implications of each process are mentioned. An outlook on the future of the cobalt industry and anticipated future trends is included.

  11. Magnetic dipolar interaction induced cobalt nanowires.

    PubMed

    Gong, Maogang; Dai, Qilin; Ren, Shenqiang

    2016-02-19

    The dipolar interaction of magnetic nanoparticles is of intense interest to engineer material self-assembly for anisotropic functional nanostructures. Here we report the solution synthesis of cobalt nanowires, where the one-dimensional nanowire formation is ultimately dependent on the magnetic dipolar interaction to realize in situ assembly of cobalt nanoparticles. The morphology transition of cobalt nanostructures is well controlled via the ligand-free synthesis and thermal decomposition of zero-valent cobalt precursor. This study provides a self-assembly approach to the development of anisotropic cobalt nanostructures and a better understanding of nucleation parameters, which are demonstrated to correlate strongly with the size and morphology of final cobalt nanowires. This approach may be extended to other magnetic materials for the control of their nanostructure and magnetic performance. PMID:26783195

  12. Relative transition probabilities of cobalt

    NASA Technical Reports Server (NTRS)

    Roig, R. A.; Miller, M. H.

    1974-01-01

    Results of determinations of neutral-cobalt transition probabilities measured relative to Co I 4150.43 A and Co II 4145.15 A, using a gas-driven shock tube as the spectroscopic light source. Results are presented for 139 Co I lines in the range from 3940 to 6640 A and 11 Co II lines in the range from 3840 to 4730 A, which are estimated to have reliabilities ranging from 8 to 50%.

  13. Mineral resource of the month: cobalt

    USGS Publications Warehouse

    Shedd, Kim B.

    2009-01-01

    Cobalt is a metal used in numerous commercial, industrial and military applications. On a global basis, the leading use of cobalt is in rechargeable lithium-ion, nickel-cadmium and nickel-metal hydride battery electrodes. Cobalt use has grown rapidly since the early 1990s, with the development of new battery technologies and an increase in demand for portable electronics such as cell phones, laptop computers and cordless power tools.

  14. Cobalt silica magnetic nanoparticles with functional surfaces

    NASA Astrophysics Data System (ADS)

    Vadala, Michael L.; Zalich, Michael A.; Fulks, David B.; St. Pierre, Tim G.; Dailey, James P.; Riffle, Judy S.

    2005-05-01

    Cobalt nanoparticles encased in polysiloxane block copolymers have been heated at 600-700 °C to form protective shells around the particles, which contain crosslinked Si-O structures, and to anneal the cobalt. Methods to functionalize and modify the surfaces of the pyrolyzed/annealed silica-cobalt complexes with amines, isocyanates, poly(ethylene oxide), poly( L-lactide) and polydimethylsiloxane (PDMS) are presented.

  15. A promising new thermoelectric material - Ruthenium silicide

    NASA Technical Reports Server (NTRS)

    Vining, Cronin B.; Mccormack, Joseph A.; Zoltan, Andrew; Zoltan, Leslie D.

    1991-01-01

    Experimental and theoretical efforts directed toward increasing thermoelectric figure of merit values by a factor of 2 or 3 have been encouraging in several respects. An accurate and detailed theoretical model developed for n-type silicon-germanium (SiGe) indicates that ZT values several times higher than currently available are expected under certain conditions. These new, high ZT materials are expected to be significantly different from SiGe, but not unreasonably so. Several promising candidate materials have been identified which may meet the conditions required by theory. One such candidate, ruthenium silicide, currently under development at JPL, has been estimated to have the potential to exhibit figure of merit values 4 times higher than conventional SiGe materials. Recent results are summarized.

  16. Structural evolution of small ruthenium cluster anions

    SciTech Connect

    Waldt, Eugen; Hehn, Anna-Sophia; Ahlrichs, Reinhart; Kappes, Manfred M.; Schooss, Detlef

    2015-01-14

    The structures of ruthenium cluster anions have been investigated using a combination of trapped ion electron diffraction and density functional theory computations in the size range from eight to twenty atoms. In this size range, three different structural motifs are found: Ru{sub 8}{sup −}–Ru{sub 12}{sup −} have simple cubic structures, Ru{sub 13}{sup −}–Ru{sub 16}{sup −} form double layered hexagonal structures, and larger clusters form close packed motifs. For Ru{sub 17}{sup −}, we find hexagonal close packed stacking, whereas octahedral structures occur for Ru{sub 18}{sup −}–Ru{sub 20}{sup −}. Our calculations also predict simple cubic structures for the smaller clusters Ru{sub 4}{sup −}–Ru{sub 7}{sup −}, which were not accessible to electron diffraction measurements.

  17. 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.

  18. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  19. Cobalt Reduction Guidelines, Revision 1. Final report

    SciTech Connect

    Not Available

    1993-12-01

    This report, which updates and supersedes an earlier report (EPRI NP-6737) on the same subject, describes methods for establishing a program to identify nuclear power plant valves with high-cobalt hardfacing that are potential significant contributors to the cobalt inventory that is irradiated in the reactor core. The resulting radioactive cobalt isotope, cobalt-60, is a major contributor to plant radiation levels and therefore occupational doses received by plant operational and maintenance personnel. A methodology to determine whether hardfacing is actually required on specific valves is also described as is the physical, mechanical and wear properties of high-cobalt and potential replacement cobalt-free hardfacing and trim alloys. Discussions are presented of the general and specific design requirements for valve hardfacing in nuclear service. Current world-wide nuclear utility experience with cobalt-free hardfacing alloys is described. The regulatory and industry code issues related to replacing and/or changing valve hardfacing materials are discussed. The actions and responsibilities of utility management in implementing an effective cobalt-reduction program are also delineated.

  20. Cobalt and nickel content of Asian cements.

    PubMed

    Goh, C L; Kwok, S F; Gan, S L

    1986-09-01

    The total cobalt and nickel concentration of 11 brands of Asian cement ranged from 8.1 to 14.2 micrograms/g and 14.9 to 28.5 micrograms/g, respectively. These metals exist mainly as insoluble salts; the water-soluble concentration of cobalt and nickel in the cements ranged from 0.39 to 0.65 micrograms/g and from 0-1.2 micrograms/g, respectively. 1.5% (4/272) of construction workers in a prefabrication construction factory had cobalt sensitivity. All had allergic contact dermatitis from chromate in cement. No worker had isolated cobalt sensitivity and cement dermatitis. It appeared that sensitization to cobalt in cement occurs only secondarily to an existing cement dermatitis. 1.8% (5/272) workers had nickel sensitivity: 2 with allergic contact dermatitis to nickel in their watches, 2 were asymptomatic and 1 had allergic contact dermatitis to chromate and cobalt in cement. The low prevalence of cobalt and nickel sensitivity from cement was probably related to the low concentration of soluble cobalt and nickel salts in the cement. However, these insoluble salts can form soluble complexes with body fluids on eczematous skin and sensitize the skin. PMID:2946537

  1. Inhalation cancer risk assessment of cobalt metal.

    PubMed

    Suh, Mina; Thompson, Chad M; Brorby, Gregory P; Mittal, Liz; Proctor, Deborah M

    2016-08-01

    Cobalt compounds (metal, salts, hard metals, oxides, and alloys) are used widely in various industrial, medical and military applications. Chronic inhalation exposure to cobalt metal and cobalt sulfate has caused lung cancer in rats and mice, as well as systemic tumors in rats. Cobalt compounds are listed as probable or possible human carcinogens by some agencies, and there is a need for quantitative cancer toxicity criteria. The U.S. Environmental Protection Agency has derived a provisional inhalation unit risk (IUR) of 0.009 per μg/m(3) based on a chronic inhalation study of soluble cobalt sulfate heptahydrate; however, a recent 2-year cancer bioassay affords the opportunity to derive IURs specifically for cobalt metal. The mechanistic data support that the carcinogenic mode of action (MOA) is likely to involve oxidative stress, and thus, non-linear/threshold mechanisms. However, the lack of a detailed MOA and use of high, toxic exposure concentrations in the bioassay (≥1.25 mg/m(3)) preclude derivation of a reference concentration (RfC) protective of cancer. Several analyses resulted in an IUR of 0.003 per μg/m(3) for cobalt metal, which is ∼3-fold less potent than the provisional IUR. Future research should focus on establishing the exposure-response for key precursor events to improve cobalt metal risk assessment. PMID:27177823

  2. Cobalt Complexes as Antiviral and Antibacterial Agents

    PubMed Central

    Chang, Eddie L.; Simmers, Christa; Knight, D. Andrew

    2010-01-01

    Metal ion complexes are playing an increasing role in the development of antimicrobials. We review here the antimicrobial properties of cobalt coordination complexes in oxidation state 3+. In addition to reviewing the cobalt complexes containing polydentate donor ligands, we also focus on the antimicrobial activity of the homoleptic [Co(NH3)6]3+ ion.

  3. Cobalt and possible oxidant-mediated toxicity.

    PubMed

    Nemery, B; Lewis, C P; Demedts, M

    1994-06-30

    The occurrence of interstitial lung disease similar to hard metal lung disease in diamond polishers who had been exposed to cobalt (in the absence of tungsten carbide) through the use of polishing disks containing microdiamonds sintered with cobalt, led us to experimentally test the hypothesis that cobalt has pro-oxidant activity in lung tissue. Several experiments were carried out in which we measured indices of oxidant stress, mainly changes in the oxidation state of glutathione and in the activity of the pentose phosphate pathway, upon exposure of hamster pulmonary tissue to CoCl2 in vivo by intratracheal instillation, or in vitro by incubating lung slices. These experiments indicated that cobalt ions are capable of causing thiol oxidation in lung tissue as an early manifestation of oxidant stress, but more studies are needed to establish the relevance of this mechanism in the causation of lung disease in subjects exposed to cobalt-containing dusts. PMID:7939609

  4. Nanoscale electron beam-induced deposition and purification of ruthenium for extreme ultraviolet lithography mask repair

    NASA Astrophysics Data System (ADS)

    Noh, J. H.; Stanford, M. G.; Lewis, B. B.; Fowlkes, J. D.; Plank, H.; Rack, P. D.

    2014-12-01

    One critical area for the adoption of extreme ultraviolet (EUV) lithography is the development of appropriate mask repair strategies. To this end, we have explored focused electron beam-induced deposition of the ruthenium capping or protective layer. Electron beam-induced deposition (EBID) was used to deposit a ruthenium capping/protective film using the liquid bis(ethylcyclopentyldienyl)ruthenium(II) precursor. The carbon to ruthenium atomic ratio in the as-deposited material was estimated to be ~9/1. Subsequent to deposition, we demonstrate an electron stimulated purification process to remove carbon by-products from the deposit. Results indicate that high-fidelity nanoscale ruthenium repairs can be realized.

  5. Exposure to cobalt in the production of cobalt and cobalt compounds and its effect on the heart

    PubMed Central

    Linna, A; Oksa, P; Groundstroem, K; Halkosaari, M; Palmroos, P; Huikko, S; Uitti, J

    2004-01-01

    Aims: To investigate whether exposure to cobalt in cobalt plants has any measurable effect on the cardiovascular system. Methods: Occupational, cross sectional study, using a self administered questionnaire, blood pressure measurement, electrocardiography, and laboratory tests in which 203 male workers with at least one year of exposure to cobalt and 94 unexposed controls participated. Echocardiography was performed on a subset of 122 most highly exposed cobalt workers, of which 109 were analysed, and on 60 controls, of which 57 were analysed. Analysis of covariance and a multiple regression analysis were used to evaluate the data. Results: Two of the echocardiography parameters measured were associated with cobalt exposure. In the higher exposure group the left ventricular isovolumic relaxation time (mean 53.3, 49.1, and 49.7 ms in the high exposure, low exposure, and control groups respectively) and the deceleration time of the velocity of the early rapid filling wave (mean 194.3, 180.5, and 171.7 ms for those in the high exposure, low exposure, and control groups respectively) were prolonged, indicating altered left ventricular relaxation and early filling. Conclusion: Cumulative exposure to cobalt was found to be associated with the results of Doppler echocardiography measurements, indicating altered diastole. This finding supports the hypothesis that cobalt accumulation in the myocardium could affect myocardial function. Whether this finding has clinical implications remains to be evaluated. PMID:15477280

  6. Single Molecule Electron Transfer Process of Ruthenium Complexes.

    SciTech Connect

    Hu, Dehong; Lu, H PETER.

    2006-03-01

    Transition metal complexes such as ruthenium complexes, having metal-to-ligand charge transfer states, are extensively used in solar energy conversion and electron transfer in biological systems and at interfaces. The dynamics of metal-to-ligand charge transfer and subsequent intermolecular, intramolecular, and interfacial electron transfer processes can be highly complex and inhomogeneous, especially when molecules are involved in interactions and perturbations from heterogeneous local environments and gated by conformation fluctuations. We have employed the single-molecule spectroscopy, a powerful approach for inhomogeneous systems to study the electron transfer dynamics of ruthenium complexes. We have applied a range of statistical analysis methods to reveal nonclassical photon emission behavior of the single ruthenium complex, i.e., photon antibunching, and photophysical ground-state recovering dynamics on a microsecond time scale. The use of photon antibunching to measure phosphorescence lifetimes and single-molecule electron transfer dynamics at room temperature is demonstrated.

  7. Electronic transitions of cobalt monoboride.

    PubMed

    Ng, Y W; Pang, H F; Cheung, A S-C

    2011-11-28

    Electronic transition spectrum of cobalt monoboride (CoB) in the visible region between 495 and 560 nm has been observed and analyzed using laser-induced fluorescence spectroscopy. CoB molecule was produced by the reaction of laser-ablated cobalt atom and diborane (B(2)H(6)) seeded in argon. Fifteen vibrational bands with resolved rotational structure have been recorded, which included transitions of both Co(10)B and Co(11)B isotopic species. Our analysis showed that the observed transition bands are ΔΩ = 0 transitions with Ω" = 2 and Ω" = 3 lower states. Four transition systems have been assigned, namely, the [18.1](3)Π(2)-X(3)Δ(2), the [18.3](3)Φ(3)-X(3)Δ(3), the [18.6]3- X(3)Δ(3), and the [19.0]2-X(3)Δ(2) systems. The bond length, r(o), of the X(3)Δ(3) state of CoB is determined to be 1.705 Å. The observed rotational lines showed unresolved hyperfine structure arising from the nuclei, which conforms to the Hund's case (a(β)) coupling scheme. This work represents the first experimental investigation of the CoB spectrum. PMID:22128936

  8. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Cobaltous salts and its derivatives. 189.120... or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the... and to prevent “gushing.” (b) Food containing any added cobaltous salts is deemed to be adulterated...

  9. Optimize syngas to naphtha over ruthenium catalysts

    SciTech Connect

    Stowe, R.A.; Murchison, C.B.

    1984-06-01

    In this work the authors undertake the design of a catalyst system which would efficiently utilize a stream of CO--H/sub 2/, available as a byproduct of partial combustion cracking. The H/sub 2//CO ratio of this stream was fixed by the conditions of the ethylene production process, making it desirable to reject the oxygen in CO as water rather than CO/sub 2/. A second important goal was to maximize the C/sub 2/+ selectivity in order to obtain the highest possible yield of feedstock crackable to ethylene in conventional LPG and naphtha crackers. Using an optimized potassium-promoted, aluminasupported ruthenium catalyst of practical concentration (1% Ru, 0.5% K) on a commercially available support, campaigns of over 1,000 hours on stream were achieved. Impregnation techniques which are readily scaled up were used. During these campaigns the C/sub 2/+ selectivity averaged about 90%. Of the C/sub 2/+ product, about onethird was C/sub 2/-C/sub 5/ while the C/sub 6/+ represents two-thirds.

  10. Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

    SciTech Connect

    Coloma Ribera, R. Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F.

    2015-08-07

    In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

  11. Hydrohalogenative aromatization of multiynes promoted by ruthenium alkylidene complexes.

    PubMed

    Karmakar, Rajdip; Wang, Kung-Pern; Yun, Sang Young; Mamidipalli, Phani; Lee, Daesung

    2016-06-01

    A new functionalization method of arynes promoted by a novel catalytic role of the Grubbs-type ruthenium alkylidene complex is described. Through a sequence of aryne formation followed by their halo-functionalization, various bis-1,3-diynes were directly converted to functionalized aryl chlorides, bromides and iodides in good yields in the presence of a catalytic amount of a ruthenium alkylidene complex and halogenated hydrocarbons such as CH2Cl2, CHCl3, CH2Br2, and CH2I2. The utility of this novel transformation is demonstrated by a formal synthesis of herbindole B. PMID:27145857

  12. Nickel/ruthenium catalyst and method for aqueous phase reactions

    DOEpatents

    Elliott, D.C.; Sealock, J.L.

    1998-09-29

    A method of hydrogenation is described using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions. 2 figs.

  13. Skin reactivity to metallic cobalt in patients with a positive patch test to cobalt chloride.

    PubMed

    de Fine Olivarius, F; Menné, T

    1992-10-01

    458 consecutive patients were patch tested with a metallic cobalt disc as a supplement to the standard series. 23 patients had a positive reaction to CoCl2 1% pet. Of these, 19 were tested with the cobalt disc. 11 had a positive reaction and 5 a questionable reaction. There were no positive reactions to the cobalt disc in patients with a negative patch test to CoCl2 1% pet. Patch testing with CoCl2 1% pet. diagnoses all patients with allergy to metallic cobalt, but the test method is limited by a high number of irritant and questionable reactions. PMID:1451489

  14. Adsorption of ruthenium red to phospholipid membranes.

    PubMed Central

    Voelker, D; Smejtek, P

    1996-01-01

    We have measured the distribution of the hexavalent ruthenium red cation (RuR) between water and phospholipid membranes, have shown the critical importance of membrane negative surface charge for RuR binding, and determined the association constant of RuR for different phospholipid bilayers. The studies were performed with liposomes made of mixtures of zwitterionic L-alpha-phosphatidylcholine (PC), and one of the negatively charged phospholipids: L-alpha-phosphatidylserine (PS), L-alpha-phosphatidylinositol (PI), or L-alpha-phosphatidylglycerol (PG). Lipid composition of PC:PX membranes was 1:0, 19:1, 9:1, and 4:1. Liposomes were processed using freeze-and-thaw treatment, and their size distribution was characterized by light scattering and electron microscopy. Experimental distribution isotherms of RuR obtained by ultracentrifugation and spectrophotometry can be reproduced with the Langmuir-Stern-Grahame model, assuming that RuR behaves in the diffuse double layer as an ion with effective valency < 6. In terms of this model, PC-PS, PC-PI, and PC-PG membranes were found to be electrostatically equivalent and the intrinsic association constants of RuR were obtained. RuR has highest affinity to PS-containing membranes; its association constant for PC-PI and PC-PG membranes is about 5 times smaller than that for PC-PS membranes. From the comparison of RuR binding to mixed negatively charged phospholipid membranes and RuR binding to sarcoplasmic reticulum (SR), we conclude that the low-affinity RuR binding sites may indeed be associated with the lipid bilayer of SR. PMID:8789099

  15. Molecular dinitrogen complexes of ruthenium(II) porphyrins

    SciTech Connect

    Camenzind, M.J.; James, B.R.; Dolphin, D.; Sparapany, J.W.; Ibers, J.A.

    1988-08-24

    The existence of both mono- and bis(nitrogen) complexes of ruthenium have been previously established. Details on a series of complexes are presented herein, and results of an x-ray crystallographic study of Ru(TMP) (THF) (N/sub 2/) are reported. 30 references, 4 tables.

  16. Photodissociation Spectroscopy of Ruthenium Polypyridyl Complexes in Vacuo

    NASA Astrophysics Data System (ADS)

    Xu, Shuang; Smith, James; Weber, J. Mathias

    Photoelectrochemical water oxidation is a direct way to produce solar fuels from renewable sources. Since this reaction has a high reaction barrier, a cost-effective catalyst is necessary. Ruthenium polypyridyl complexes are promising catalysts for water oxidation. However, the mechanism of catalytic action is not well understood. One major difficulty of a mechanistic understanding is the complexity of reactive solutions under turnover conditions. To circumvent this problem, we applied electronic photodissociation spectroscopy in the UV and visible spectral range to a series of mass selected ruthenium polypyridyl complex ions in vacuo. The ions in this work are of the form [RuII-L]2+, where RuII represents ruthenium(II)-bipyridine-terpyridine, a prototype catalyst belonging to the ruthenium-polypyridyl family. By varying the ligand L, we were able to study the ligand influence on the photophysical properties of the complex. The cases where L = (H2O)1 , 2 , 3 are of particular interest because they are directly related to an intermediate in the catalytic cycle for water oxidation. Our experiment in vacuo is an essential complement to experiments in solution and provides unique information for understanding the photophysics and photochemistry of these complexes on a molecular level.

  17. Tailoring NO donors metallopharmaceuticals: ruthenium nitrosyl ammines and aliphatic tetraazamacrocycles.

    PubMed

    Tfouni, E; Doro, F G; Figueiredo, L E; Pereira, J C M; Metzker, G; Franco, D W

    2010-01-01

    The discovery of the involvement of nitric oxide (NO) in several physiological and pathophysiological processes launched a spectacular increase in studies in areas such as chemistry, biochemistry, and pharmacology. As a consequence, the development of NO donors or scavengers for regulation of its concentration and bioavailability in vivo is required. In this sense, ruthenium nitrosyl ammines and aliphatic tetraazamacrocyles have attracted a lot of attention due to their unique chemical properties. These complexes are water soluble and stable in solution, not to mention that they can deliver NO when photochemically or chemically activated by the reduction of the coordinated nitrosonium (NO+). The tuning of the energies of the charge transfer bands, the redox potential, and the specific rate constants of NO liberation, in both solution and matrices, is desirable for the achievement of selective NO delivery to biological targets, hence making the ruthenium ammines and aliphatic tetraazamacrocyles a quite versatile platform for biological application purposes. These ruthenium nitrosyls have shown to be active in firing neurons in mouse hippocampus, performing redox reactions in mitochondria, acting in blood pressure control, exhibiting cytotoxic activities against trypanosomatids (T.cruzi and L.major) and tumor cells. This tailoring approach is explored here, being heavily supported by the accumulated knowledge on the chemistry and photochemistry of ruthenium complexes, which allows NO donors/scavengers systems to be custom made designed. PMID:20846113

  18. Improvement of ruthenium based decarboxylation of carboxylic acids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The removal of oxygen atoms from biobased carboxylic acids is an attractive route to provide the drop in replacement feedstocks that industry needs to continue to provide high performance products. Through the use of ruthenium catalysis, an efficient method where this process can be accomplished on ...

  19. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  20. PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Wilson, A.S.

    1958-08-12

    An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.

  1. Molecular Models of Ruthenium(II) Organometallic Complexes

    ERIC Educational Resources Information Center

    Coleman, William F.

    2007-01-01

    This article presents the featured molecules for the month of March, which appear in the paper by Ozerov, Fafard, and Hoffman, and which are related to the study of the reactions of a number of "piano stool" complexes of ruthenium(II). The synthesis of compound 2a offers students an alternative to the preparation of ferrocene if they are only…

  2. Ruthenium-catalyzed C–H activation of thioxanthones

    PubMed Central

    Wagner, Danny

    2015-01-01

    Summary Thioxanthones – being readily available in one step from thiosalicylic acid and arenes – were used in ruthenium-catalyzed C–H-activation reaction to produce 1-mono- or 1,8-disubstituted thioxanthones in good to excellent yields. Scope and limitation of this reaction are presented. PMID:25977717

  3. Controlled cobalt doping in biogenic magnetite nanoparticles.

    PubMed

    Byrne, J M; Coker, V S; Moise, S; Wincott, P L; Vaughan, D J; Tuna, F; Arenholz, E; van der Laan, G; Pattrick, R A D; Lloyd, J R; Telling, N D

    2013-06-01

    Cobalt-doped magnetite (CoxFe3 -xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe(2+) site with Co(2+), with up to 17 per cent Co substituted into tetrahedral sites. PMID:23594814

  4. Bioextraction of cobalt from complex metal sulfides

    SciTech Connect

    Thompson, D.L.; Noah, K.S.; Wichlacz, P.L.; Torma, A.E.

    1993-01-01

    The present study has investigated the bioleachability of naturally occurring cobaltite and synthetic cobalt sulfides using 29 pedigree and wild type'' strains of Thiobacillus ferrooxidans. On the basis of a screening test, five strains of bacteria were selected for assessing the effects of leach parameters (pH, ferrous and ferric sulfates, ammonium sulfate, bipotassium hydrogen phosphate, and substrate concentrations) on cobalt extraction from Blackbird Mine ore and concentrate. The mechanisms of cobalt extraction were explained in terms of direct and indirect modes of bacterial activity, and the chemistry involved in these processes was identified. Using various size fractions of a high-grade cobaltite, the kinetic parameters of cobalt extraction were derived for the effect of specific surface area to be V[sub m] = 376 mg dm[sup [minus]3] h[sup [minus]1] and K 1.27 m[sup 2] g[sup [minus]1].

  5. Bioextraction of cobalt from complex metal sulfides

    SciTech Connect

    Thompson, D.L.; Noah, K.S.; Wichlacz, P.L.; Torma, A.E.

    1993-05-01

    The present study has investigated the bioleachability of naturally occurring cobaltite and synthetic cobalt sulfides using 29 pedigree and ``wild type`` strains of Thiobacillus ferrooxidans. On the basis of a screening test, five strains of bacteria were selected for assessing the effects of leach parameters (pH, ferrous and ferric sulfates, ammonium sulfate, bipotassium hydrogen phosphate, and substrate concentrations) on cobalt extraction from Blackbird Mine ore and concentrate. The mechanisms of cobalt extraction were explained in terms of direct and indirect modes of bacterial activity, and the chemistry involved in these processes was identified. Using various size fractions of a high-grade cobaltite, the kinetic parameters of cobalt extraction were derived for the effect of specific surface area to be V{sub m} = 376 mg dm{sup {minus}3} h{sup {minus}1} and K 1.27 m{sup 2} g{sup {minus}1}.

  6. Nanocrystalline cobalt oxides for carbon nanotube growth

    NASA Astrophysics Data System (ADS)

    Guo, Kun; Jayatissa, Ahalapitiya H.; Jayasuriya, Ambalangodage C.

    2007-09-01

    Thin Films of nanocrystalline cobalt oxide were formed by sol-gel method. Structure, optical properties and surface properties of these films were investigated by numerous characterization techniques. These films were successfully fabricated on glass substrates below 500°C. . Micropatterns of cobalt oxide thin films were also fabricated on glass and silicon substrates by employing a lift-off method. Crystal size of these nanocrystalline cobalt films could be successfully controllable by varying the amount of cobalt precursors and number of layers. These films were used as the seeding layers for carbon nanotube growth in a CVD process By changing the concentration of monomer precursors in the solgel coating solutions, different size nanoclusters hence different size carbon nanotubes could be synthesized in CVD process. This method can be used for controlled growth of carbon nanotubes for many different applications. In this paper, detail of these experimental results will be presented.

  7. Verification timer for AECL 780 Cobalt unit.

    PubMed

    Smathers, J B; Holly, F E

    1984-05-01

    To obtain verification of the proper time setting of the motorized run down timer for a AECL 780 Cobalt Unit, a digital timer is described, which can be added to the system for under $300. PMID:6735762

  8. Role of cobalt in nickel base superalloys

    NASA Technical Reports Server (NTRS)

    Jarrett, R.; Barefoot, J.; Tien, J.; Sanchez, J.

    1982-01-01

    The effect of cobalt or substituting for cobalt on the mechanical properties of nickel-based superalloys is discussed. Waspaloy, UDIMET 700, and NIMONIC 115, which are representative of Ni-Cr-Co-Al-Ti-Mo superalloys having different gamma prime contents which are strengthened by a heavily alloyed matrix, coherent gamma prime precipitates, and carbides at the grain boundaries. Microstructure and in situ and extracted phase STEM micro-analysis were used to evaluate the three alloys.

  9. [Are the cobalt hip prosthesis dangerous?].

    PubMed

    Mistretta, Virginie; Kurth, William; Charlier, Corinne

    The placement of a hip prosthesis is one of the most common orthopedic surgical procedures. Some implants contain metal and are therefore capable of releasing metal particles like cobalt in patients who wear metal prostheses. Cobalt can be responsible of local toxicity (including metallosis, hypersensitivity reaction, and benign tumor) or systemic toxicity (including cardiomyopathy, polycythemia, hypothyroidism, and neurological disorders). To monitor potential toxicity of metal hip prostheses, an annual monitoring of patients implanted is recommended and includes clinical examination, radiological examination and blood cobalt determination. The cobalt concentration in blood allows to estimate the risk of toxicity and to evaluate the performance of the implant. The currently recommended threshold value is equal to 7 µg of cobalt per liter of blood. Our study, conducted on 251 patients over a period of 4 years, has shown that the cobalt concentration average was 2.51 µg/l in blood, with 51 patients having a cobaltemia higher than the threshold of 7 µg/l. PMID:27615181

  10. Block by ruthenium red of the ryanodine-activated calcium release channel of skeletal muscle

    PubMed Central

    1993-01-01

    The effects of ruthenium red and the related compounds tetraamine palladium (4APd) and tetraamine platinum (4APt) were studied on the ryanodine activated Ca2+ release channel reconstituted in planar bilayers with the immunoaffinity purified ryanodine receptor. Ruthenium red, applied at submicromolar concentrations to the myoplasmic side (cis), induced an all-or-none flickery block of the ryanodine activated channel. The blocking effect was strongly voltage dependent, as large positive potentials that favored the movement of ruthenium red into the channel conduction pore produced stronger block. The half dissociation constants (Kd) for ruthenium red block of the 500 pS channel were 0.22, 0.38, and 0.62 microM, at +100, +80, and +60 mV, respectively. Multiple ruthenium red molecules seemed to be involved in the inhibition, because a Hill coefficient of close to 2 was obtained from the dose response curve. The half dissociation constant of ruthenium red block of the lower conductance state of the ryanodine activated channel (250 pS) was higher (Kd = 0.82 microM at +100 mV), while the Hill coefficient remained approximately the same (nH = 2.7). Ruthenium red block of the channel was highly asymmetric, as trans ruthenium red produced a different blocking effect. The blocking and unblocking events (induced by cis ruthenium red) can be resolved at the single channel level at a cutoff frequency of 2 kHz. The closing rate of the channel in the presence of ruthenium red increased linearly with ruthenium red concentration, and the unblocking rate of the channel was independent of ruthenium red concentrations. This suggests that ruthenium red block of the channel occurred via a simple blocking mechanism. The on-rate of ruthenium red binding to the channel was 1.32 x 10(9) M-1 s-1, and the off-rate of ruthenium red binding was 0.75 x 10(3) s-1 at +60 mV, in the presence of 200 nM ryanodine. The two related compounds, 4APd and 4APt, blocked the channel in a similar way to that

  11. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  12. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  13. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  14. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  15. 40 CFR 415.650 - Applicability; description of the cobalt salts production subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... cobalt salts production subcategory. 415.650 Section 415.650 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Cobalt Salts Production Subcategory § 415.650 Applicability; description of the cobalt... cobalt salts....

  16. 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. PMID:23211478

  17. Decrease in hepatic cytochrome P-450 by cobalt. Evidence for a role of cobalt protoporphyrin.

    PubMed Central

    Sinclair, J F; Sinclair, P R; Healey, J F; Smith, E L; Bonkowsky, H L

    1982-01-01

    Exposure of cultured chick-embryo hepatocytes to increasing concentrations of CoCl2 in the presence of allylisopropylacetamide results in formation of cobalt protoporphyrin, with a reciprocal decrease in haem and cytochrome P-450. Treatment of rats with CoCl2 (84 mumol/kg) and 5-aminolaevulinate (0.2 mmol/kg) also results in formation of cobalt protoporphyrin and a decrease in cytochrome P-450 in the liver. Hepatic microsomal fractions from rats treated with phenobarbital, CoCl2 and 5-aminolaevulinate were analysed by polyacrylamide gel electrophoresis. Cobalt protoporphyrin was associated mainly with proteins of 50000-53000 mol.wt. The results suggest that the formation of cobalt protoporphyrin occurred at the expense of the synthesis of haem, leading to a decrease in cytochrome P-450. Furthermore, the cobalt protoporphyrin that was formed may itself have been incorporated into apocytochrome P-450. Images Fig. 2. PMID:7115319

  18. Spectroscopic investigation on the interaction of ruthenium complexes with tumor specific lectin, jacalin.

    PubMed

    Ayaz Ahmed, Khan Behlol; Reshma, Elamvazhuthi; Mariappan, Mariappan; Anbazhagan, Veerappan

    2015-02-25

    Several ruthenium complexes are regarded as anticancer agents and considered as an alternative to the widely used platinum complexes. Owing to the preferential interaction of jacalin with tumor-associated T-antigen, we report the interaction of jacalin with four ruthenium complex namely, tris(1,10-phenanthroline)ruthenium(II)chloride, bis(1,10-phenanthroline)(N-[1,10]phenanthrolin-5-yl-pyrenylmethanimine)ruthenium(II)chloride, bis(1,10-phenanthroline)(dipyrido[3,2-a:2',3'-c]-phenazine)ruthenium(II)chloride, bis(1,10-phenanthroline)(11-(9-acridinyl)dipyrido[3,2-a:2',3'-c]phenazine)ruthenium(II) chloride. Fluorescence spectroscopic analysis revealed that the ruthenium complexes strongly quenched the intrinsic fluorescence of jacalin through a static quenching procedure, and a non-radiative energy transfer occurred within the molecules. Association constants obtained for the interaction of different ruthenium complexes with jacalin are in the order of 10(5) M(-1), which is in the same range as those obtained for the interaction of lectin with carbohydrate and hydrophobic ligand. Each subunit of the tetrameric jacalin binds one ruthenium complex, and the stoichiometry is found to be unaffected by the presence of the specific sugar, galactose. In addition, agglutination activity of jacalin is largely unaffected by the presence of the ruthenium complexes, indicating that the binding sites for the carbohydrate and the ruthenium complexes are different. These results suggest that the development of lectin-ruthenium complex conjugate would be feasible to target malignant cells in chemo-therapeutics. PMID:25306128

  19. Synthesis of PVP-stabilized ruthenium colloids with low boiling point alcohols.

    PubMed

    Zhang, Yuqing; Yu, Jiulong; Niu, Haijun; Liu, Hanfan

    2007-09-15

    A route to the preparation of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium colloids by refluxing ruthenium(III) chloride in low boiling point alcohols was developed. Deep purple colloids with shuttle-like ruthenium particles were also synthesized. XPS measurement verified the nanoparticles were in the metallic state. The morphology of metal nanoparticles was characterized by UV-visible absorption spectrophotometry, TEM and XRD. PMID:17568601

  20. Determination of ruthenium and iridium in anode coatings by atomic-absorption spectroscopy.

    PubMed

    Harrington, D E; Bramstedt, W R

    A method is described for the determination of ruthenium and iridium coated on an electrode surface. The coating is chemically removed from the electrode by fusion with alkali, and the resulting solution prepared for analysis. Interelement interferences are eliminated by using a titanium-potassium matrix solution as a releasing agent. Recovery and precision data are given for ruthenium and iridium. The AAS determination of ruthenium compares favourably with a standard colorimetric method. PMID:18961657

  1. Spectroscopic investigation on the interaction of ruthenium complexes with tumor specific lectin, jacalin

    NASA Astrophysics Data System (ADS)

    Ayaz Ahmed, Khan Behlol; Reshma, Elamvazhuthi; Mariappan, Mariappan; Anbazhagan, Veerappan

    2015-02-01

    Several ruthenium complexes are regarded as anticancer agents and considered as an alternative to the widely used platinum complexes. Owing to the preferential interaction of jacalin with tumor-associated T-antigen, we report the interaction of jacalin with four ruthenium complex namely, tris(1,10-phenanthroline)ruthenium(II)chloride, bis(1,10-phenanthroline)(N-[1,10]phenanthrolin-5-yl-pyrenylmethanimine)ruthenium(II)chloride, bis(1,10-phenanthroline)(dipyrido[3,2-a:2‧,3‧-c]-phenazine)ruthenium(II)chloride, bis(1,10-phenanthroline)(11-(9-acridinyl)dipyrido[3,2-a:2‧,3‧-c]phenazine)ruthenium(II) chloride. Fluorescence spectroscopic analysis revealed that the ruthenium complexes strongly quenched the intrinsic fluorescence of jacalin through a static quenching procedure, and a non-radiative energy transfer occurred within the molecules. Association constants obtained for the interaction of different ruthenium complexes with jacalin are in the order of 105 M-1, which is in the same range as those obtained for the interaction of lectin with carbohydrate and hydrophobic ligand. Each subunit of the tetrameric jacalin binds one ruthenium complex, and the stoichiometry is found to be unaffected by the presence of the specific sugar, galactose. In addition, agglutination activity of jacalin is largely unaffected by the presence of the ruthenium complexes, indicating that the binding sites for the carbohydrate and the ruthenium complexes are different. These results suggest that the development of lectin-ruthenium complex conjugate would be feasible to target malignant cells in chemo-therapeutics.

  2. Surface and sub-surface thermal oxidation of thin ruthenium films

    SciTech Connect

    Coloma Ribera, R.; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F.; Kokke, S.; Zoethout, E.

    2014-09-29

    A mixed 2D (film) and 3D (nano-column) growth of ruthenium oxide has been experimentally observed for thermally oxidized polycrystalline ruthenium thin films. Furthermore, in situ x-ray reflectivity upon annealing allowed the detection of 2D film growth as two separate layers consisting of low density and high density oxides. Nano-columns grow at the surface of the low density oxide layer, with the growth rate being limited by diffusion of ruthenium through the formed oxide film. Simultaneously, with the growth of the columns, sub-surface high density oxide continues to grow limited by diffusion of oxygen or ruthenium through the oxide film.

  3. Synthesis of Samarium Cobalt Nanoblades

    SciTech Connect

    Darren M. Steele

    2010-08-25

    As new portable particle acceleration technologies become feasible the need for small high performance permanent magnets becomes critical. With particle accelerating cavities of a few microns, the photonic crystal fiber (PCF) candidate demands magnets of comparable size. To address this need, samarium cobalt (SmCo) nanoblades were attempted to be synthesized using the polyol process. Since it is preferable to have blades of 1-2 {micro}m in length, key parameters affecting size and morphology including method of stirring, reaction temperature, reaction time and addition of hydroxide were examined. Nanoparticles consisting of 70-200 nm spherical clusters with a 3-5 nm polyvinylpyrrolidone (PVP) coating were synthesized at 285 C and found to be ferromagnetic. Nanoblades of 25nm in length were observed at the surface of the nanoclusters and appeared to suggest agglomeration was occurring even with PVP employed. Morphology and size were characterized using a transmission electron microscope (TEM). Powder X-Ray Diffraction (XRD) analysis was conducted to determine composition but no supportive evidence for any particular SmCo phase has yet been observed.

  4. Thermodynamic data bases for multivalent elements: An example for ruthenium

    SciTech Connect

    Rard, J.A.

    1987-11-01

    A careful consideration and understanding of fundamental chemistry, thermodynamics, and kinetics is absolutely essential when modeling predominance regions and solubility behavior of elements that exhibit a wide range of valence states. Examples of this are given using the ruthenium-water system at 298.15 K, for which a critically assessed thermochemical data base is available. Ruthenium exhibits the widest range of known aqueous solution valence states. Known solid anhydrous binary oxides of ruthenium are crystalline RuO/sub 2/, RuO/sub 4/, and possibly RuO/sub 3/ (thin film), and known hydroxides/hydrated oxides (all amorphous) are Ru(OH)/sub 3/ . H/sub 2/O, RuO/sub 2/ . 2H/sub 2/O, RuO/sub 2/ . H/sub 2/O, and a poorly characterized Ru(V) hydrous oxide. Although the other oxides, hydroxides, and hydrous oxides are generally obtained as precipitates from aqueous solutions, they are thermodynamically unstable with regard to RuO/sub 2/(cr) formation. Characterized aqueous species of ruthenium include RuO/sub 4/ (which slowly oxidizes water and which dissociates as a weak acid), RuO/sub 4//sup -/ and RuO/sub 4//sup 2 -/ (which probably contain lesser amounts of RuO/sub 3/(OH)/sub 2//sup -/ and RuO/sub 3/(OH)/sub 2//sup 2 -/, respectively, and other species), Ru(OH)/sub 2//sup 2 +/, Ru/sub 4/(OH)/sub 12//sup 4 +/, Ru(OH)/sub 4/, Ru/sup 3 +/, Ru(OH)/sup 2 +/, Ru(OH)/sub 2//sup +/, Ru/sup 2 +/, and some hydroxytetramers with formal ruthenium valences of 3.75 greater than or equal to Z greater than or equal to 2.0. Potential pH diagrams of the predominance regions change significantly with concentration due to polymerization/depolymerization reactions. Failure to consider the known chemistry of ruthenium can yield large differences in predicted solubilities.

  5. Structure sensitive adsorption of hydrogen on ruthenium and ruthenium-silver catalysts supported on silica

    SciTech Connect

    Kumar, N.

    1999-02-12

    Supported metal catalysts typically consist of particles with sizes less than 10 nm, and because of the small crystallite size, low coordination number sites (edges and corners) represent a significant fraction of all surface sites. Furthermore, it has been demonstrated that adsorption rates can be much greater at these low coordination sites than on basal plane sites. What has not been generally appreciated, however, is that preferential adsorption at edge and corner sites may explain the mechanism by which a promoter, or the addition of a second metal to form a bimetallic, can alter the selectivity and rate of reaction. For example, the measurements of hydrogen adsorption onto supported Ru-Ag catalysts show marked decreases in the amount of hydrogen adsorbed relative to the amount adsorbed on Ru catalysts. Although it is known that Ag does not dissociatively adsorb hydrogen, this decrease cannot be explained by a simple one-to-one site blocking mechanism unless Ag preferentially populates edges and corners, thereby reducing the number of Ru edge sites. Indeed, Monte Carlo simulations of Ru-Group IB metal catalysts predict that Group IB metal atoms preferentially populate corner and edge sites of ruthenium crystals. This evidence, taken together, suggests that adsorption occurs preferentially at Ru corner and edge sites, which act as portals onto basal planes. A model based on this portal theory for hydrogen adsorption onto supported ruthenium bimetallic catalysts has been developed using a rate equation approach. Specifically, the model accounts for the following features: (1) preferential adsorption through portals, (2) basal plane site-energy multiplicity, and (3) hydrogen spillover onto the support. A comparison of model predictions with experiment is presented for different concentration of Ag in Ru-Ag catalysts. The portal model of hydrogen adsorption can explain the observed decreased in the amount of hydrogen adsorbed on Ru-Ag catalysts. The model can be

  6. Cobalt: A vital element in the aircraft engine industry

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.

    1981-01-01

    Recent trends in the United States consumption of cobalt indicate that superalloys for aircraft engine manufacture require increasing amounts of this strategic element. Superalloys consume a lion's share of total U.S. cobalt usage which was about 16 million pounds in 1980. In excess of 90 percent of the cobalt used in this country was imported, principally from the African countries of Zaire and Zambia. Early studies on the roles of cobalt as an alloying element in high temperature alloys concentrated on the simple Ni-Cr and Nimonic alloy series. The role of cobalt in current complex nickel base superalloys is not well defined and indeed, the need for the high concentration of cobalt in widely used nickel base superalloys is not firmly established. The current cobalt situation is reviewed as it applies to superalloys and the opportunities for research to reduce the consumption of cobalt in the aircraft engine industry are described.

  7. Preparation, stability, and photoreactivity of thiolato ruthenium polypyridyl complexes: Can cysteine derivatives protect ruthenium-based anticancer complexes?

    PubMed

    van Rixel, Vincent H S; Busemann, Anja; Göttle, Adrien J; Bonnet, Sylvestre

    2015-09-01

    Ruthenium polypyridyl complexes may act as light-activatable anticancer prodrugs provided that they are protected by well-coordinated ligands that i) prevent coordination of other biomolecules to the metal center in the dark and ii) can be removed by visible light irradiation. In this paper, the use of monodentate thiol ligands RSH as light-cleavable protecting groups for the ruthenium complex [Ru(tpy)(bpy)(OH2)](PF6)2 ([1](PF6)2; tpy=2,2';6',2″-terpyridine, bpy=2,2'-bypyridine), is investigated. The reaction of [1](2+) with RSH=H2Cys (L-cysteine), H2Acys (N-acetyl-L-cysteine), and HAcysMe (N-acetyl-L-cysteine methyl ester), is studied by UV-visible spectroscopy, NMR spectroscopy, and mass spectrometry. Coordination of the monodentate thiol ligands to the ruthenium complex takes place upon heating to 353 K, but full conversion to the protected complex [Ru(tpy)(bpy)(SR)]PF6 is only possible when a large excess of ligand is used. Isolation and characterization of the two new thiolato complexes [Ru(tpy)(bpy)(κS-HCys)]PF6 ([2]PF6) and [Ru(tpy)(bpy)(κS-HAcys)]PF6 ([3]PF6) is reported. [3]PF6 shows a metal-to-ligand charge-transfer absorption band that is red shifted (λmax=492 nm in water) compared to its methionine analogue [Ru(tpy)(bpy)(κS-HAmet)](Cl)2 ([5](Cl)2, λmax=452 nm; HAmet=N-acetyl-methionine). In the dark the thiolate ligand coordinated to ruthenium is oxidized even by traces of oxygen, which first leads to the sulfenato, sulfinato, and disulfide ruthenium complexes, and finally to the formation of the aqua complex [1](2+). [3]PF6 showed slow photosubstitution of the thiolate ligand by water under blue light irradiation, together with faster photooxidation of the thiolate ligand compared to dark conditions. The use of thiol vs. thioether monodentate ligands is discussed for the protection of anticancer ruthenium-based prodrugs. PMID:26187140

  8. Equilibrium phase boundary between hcp-cobalt and fcc-cobalt

    NASA Astrophysics Data System (ADS)

    Cynn, Hyunchae; Lipp, Magnus J.; Evans, William J.; Baer, Bruce J.

    In 2000 (Yoo et al., PRL), fcc-cobalt was reported as a new high pressure phase transforming from ambient hcp-cobalt starting at around 105 GPa and 300 K. Both cobalts coexist up to 150 GPa and thereafter only fcc-cobalt was found to be the only stable phase to 200 GPa. Our recent synchrotron x-ray diffraction data on cobalt are at odds with the previous interpretation. We will present our new finding and elaborate on our understanding in terms of the equilibrium phase boundary of cobalt. We will also compare our previous work on xenon (Cynn et al., 2001, PRL) with our new results on cobalt. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Portions of this work were performed at HPCAT (Sector 16), APS, Argonne National Laboratory. HPCAT operations are supported by DOE-NNSA under Award No. DENA0001974 and DOE-BES under Award No. DE-FG02-99ER45775. The Advanced Photon Source is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

  9. Complex of transferrin with ruthenium for medical applications

    DOEpatents

    Richards, P.; Srivastava, S.C.; Meinken, G.E.

    1984-05-15

    A novel ruthenium-transferrin complex is disclosed which is prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40 C for about 2 hours. The complex is purified by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex. No Drawings

  10. Complex of transferrin with ruthenium for medical applications

    DOEpatents

    Richards, Powell; Srivastava, Suresh C.; Meinken, George E.

    1984-05-15

    A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40.degree. C. for about 2 hours, and purifying said complex by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

  11. Hydrogen and oxygen adsorption stoichiometries on silica supported ruthenium nanoparticles

    SciTech Connect

    Berthoud, Romain; Delichere, Pierre; Gajan, David; Lukens, Wayne; Pelzer, Katrin; Basset, Jean-Marie; Candy, Jean-Pierre; Coperet, Christophe

    2008-12-01

    Treatment under H{sub 2} at 300 C of Ru(COD)(COT) dispersed on silica yields 2 nm ruthenium nanoparticles, [Ru{sub p}/SiO{sub 2}], according to EXAFS, HRTEM and XPS. H{sub 2} adsorption measurements on [Ru{sub p}/SiO{sub 2}] in the absence of O{sub 2} show that Ru particles adsorb up to ca. 2 H per surface ruthenium atoms (2H/Ru{sub s}) on various samples; this technique can therefore be used to measure the dispersion of Ru particles. In contrast, O{sub 2} adsorption on [Ru{sub p}/SiO{sub 2}] leads to a partial oxidation of the bulk at 25 C, to RuO{sub 2} at 200 C and to sintering upon further reduction under H{sub 2}, showing that O{sub 2} adsorption cannot be used to measure the dispersion of Ru particles.

  12. 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...

  13. 21 CFR 73.1015 - 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. 73.1015 Section 73... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1015 Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining...

  14. 21 CFR 73.1015 - 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. 73.1015 Section 73... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1015 Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining...

  15. 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...

  16. 21 CFR 73.1015 - 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. 73.1015 Section 73... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1015 Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining...

  17. 21 CFR 73.1015 - 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. 73.1015 Section 73... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1015 Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining...

  18. Palladium-cobalt particles as oxygen-reduction electrocatalysts

    DOEpatents

    Adzic, Radoslav; Huang, Tao

    2009-12-15

    The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

  19. 21 CFR 73.1015 - 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. 73.1015 Section 73... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1015 Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining...

  20. 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...

  1. Alkyne Hydroacylation: Switching Regioselectivity by Tandem Ruthenium Catalysis

    PubMed Central

    Chen, Qing-An; Cruz, Faben A.; Dong, Vy M.

    2015-01-01

    By using tandem ruthenium-catalysis, internal alkynes can be coupled with aldehydes for the synthesis of β,γ-unsaturated ketones. The catalyst promotes alkyne transformations with high regioselectivity, with examples that include the differentiation of a methyl versus ethyl substituent on the alkyne. Mechanistic studies suggest that the regioselectivity results from a selective allene formation that is governed by allylic strain. PMID:25608143

  2. Characteristics of a promising new thermoelectric material - Ruthenium silicide

    NASA Technical Reports Server (NTRS)

    Ohta, Toshitaka; Vining, Cronin B.; Allevato, Camillo E.

    1991-01-01

    A preliminary study on arc-melted samples has indicated that ruthenium silicide has the potential to obtain figure-of-merit values four times higher than that of conventional silicon-germanium material. In order to realize the high figure-of-merit values, high-quality crystal from the melt is needed. A Bridgman-like method has been employed and has realized much better crystals than arc-melted ones.

  3. Ruthenium catalyzed hydrogenation of aldehyde with synthesis gas.

    PubMed

    Takahashi, Kohei; Nozaki, Kyoko

    2014-11-21

    The hydrogenation of aldehyde utilizing synthesis gas as a dihydrogen source was examined with various ruthenium catalysts, among which Ru-cyclopentadienone complexes (Shvo-type catalysts) exhibited higher activity than others. DFT calculations proved that the exchange of coordinated carbon monoxide by dihydrogen is relatively preferable in Shvo-type catalysts compared to others, which is a pre-equilibrium for the generation of the hydrogenation-active species. PMID:25372182

  4. Hydrogenation of Aldehydes Catalyzed by an Available Ruthenium Complex.

    PubMed

    Tan, Xuefeng; Wang, Guozhen; Zhu, Ziyue; Ren, Conghui; Zhou, Jinping; Lv, Hui; Zhang, Xiaoyong; Chung, Lung Wa; Zhang, Lina; Zhang, Xumu

    2016-04-01

    A readily available ruthenium(II) catalyst was developed for the catalytic hydrogenation of aldehydes with a TON (turnover number) up to 340000. It can be performed without base and solvent, showing highly industrial potential. High chemoselectivity can be achieved in the presence of alkenyl and ketone groups. Further application of this protocol in glucose reduction showed good efficiency. Theoretical studies revealed that the rate-determining step is the hydrogenation step, not the carboxylate-assisted H2 activation step. PMID:26974348

  5. Cobalt and marine redox evolution

    NASA Astrophysics Data System (ADS)

    Swanner, Elizabeth D.; Planavsky, Noah J.; Lalonde, Stefan V.; Robbins, Leslie J.; Bekker, Andrey; Rouxel, Olivier J.; Saito, Mak A.; Kappler, Andreas; Mojzsis, Stephen J.; Konhauser, Kurt O.

    2014-03-01

    Cobalt (Co) is a bio-essential trace element and limiting nutrient in some regions of the modern oceans. It has been proposed that Co was more abundant in poorly ventilated Precambrian oceans based on the greater utilization of Co by anaerobic microbes relative to plants and animals. However, there are few empirical or theoretical constraints on the history of seawater Co concentrations. Herein, we present a survey of authigenic Co in marine sediments (iron formations, authigenic pyrite and bulk euxinic shales) with the goal of tracking changes in the marine Co reservoir throughout Earth's history. We further provide an overview of the modern marine Co cycle, which we use as a platform to evaluate how changes in the redox state of Earth's surface were likely to have affected marine Co concentrations. Based on sedimentary Co contents and our understanding of marine Co sources and sinks, we propose that from ca. 2.8 to 1.8 Ga the large volume of hydrothermal fluids circulating through abundant submarine ultramafic rocks along with a predominantly anoxic ocean with a low capacity for Co burial resulted in a large dissolved marine Co reservoir. We tentatively propose that there was a decrease in marine Co concentrations after ca. 1.8 Ga resulting from waning hydrothermal Co sources and the expansion of sulfide Co burial flux. Changes in the Co reservoir due to deep-water ventilation in the Neoproterozoic, if they occurred, are not resolvable with the current dataset. Rather, Co enrichments in Phanerozoic euxinic shales deposited during ocean anoxic events (OAE) indicate Co mobilization from expanded anoxic sediments and enhanced hydrothermal sources. A new record of marine Co concentrations provides a platform from which we can reevaluate the role that environmental Co concentrations played in shaping biological Co utilization throughout Earth's history.

  6. Nickel cobalt phosphorous low stress electroplating

    NASA Technical Reports Server (NTRS)

    Engelhaupt, Darell E. (Inventor); Ramsey, Brian D. (Inventor)

    2002-01-01

    An electrolytic plating process is provided for electrodepositing a nickel or nickel cobalt alloy which contains at least about 2% to 25% by atomic volume of phosphorous. The process solutions contains nickel and optionally cobalt sulfate, hypophosphorous acid or a salt thereof, boric acid or a salt thereof, a monodentate organic acid or a salt thereof, and a multidentate organic acid or a salt thereof. The pH of the plating bath is from about 3.0 to about 4.5. An electroplating process is also provided which includes electroplating from the bath a nickel or nickel cobalt phosphorous alloy. This process can achieve a deposit with high microyield of at least about 84 kg/mm.sup.2 (120 ksi) and a density lower than pure nickel of about 8.0 gm/cc. This process can be used to plate a deposit of essentially zero stress at plating temperatures from ambient to 70.degree. C.

  7. Rapid phase synthesis of nanocrystalline cobalt ferrite

    SciTech Connect

    Shanmugavel, T.; Raj, S. Gokul; Rajarajan, G.; Kumar, G. Ramesh

    2014-04-24

    Synthesis of single phase nanocrystalline Cobalt Ferrite (CoFe{sub 2}O{sub 4}) was achieved by single step autocombustion technique with the use of citric acid as a chelating agent in mono proportion with metal. Specimens prepared with this method showed significantly higher initial permeability's than with the conventional process. Single phase nanocrystalline cobalt ferrites were formed at very low temperature. Surface morphology identification were carried out by transmission electron microscopy (TEM) analysis. The average grain size and density at low temperature increased gradually with increasing the temperature. The single phase formation is confirmed through powder X-ray diffraction analysis. Magnetization measurements were obtained at room temperature by using a vibrating sample magnetometer (VSM), which showed that the calcined samples exhibited typical magnetic behaviors. Temperature dependent magnetization results showed improved behavior for the nanocrystalline form of cobalt ferrite when compared to the bulk nature of materials synthesized by other methods.

  8. Controlled cobalt doping in biogenic magnetite nanoparticles

    PubMed Central

    Byrne, J. M.; Coker, V. S.; Moise, S.; Wincott, P. L.; Vaughan, D. J.; Tuna, F.; Arenholz, E.; van der Laan, G.; Pattrick, R. A. D.; Lloyd, J. R.; Telling, N. D.

    2013-01-01

    Cobalt-doped magnetite (CoxFe3 −xO4) nanoparticles have been produced through the microbial reduction of cobalt–iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites. PMID:23594814

  9. Behaviour of ruthenium dioxide particles in borosilicate glasses and melts

    NASA Astrophysics Data System (ADS)

    Pflieger, Rachel; Lefebvre, Leila; Malki, Mohammed; Allix, Mathieu; Grandjean, Agnès

    2009-06-01

    Ruthenium-glass systems are formed during the vitrification of nuclear waste. They are also widely used in micro-electronics because of their unique electrical properties. However, the interaction of this element with the glass matrix remains poorly understood. This work focuses on a RuO 2 particles-nuclear alumino-borosilicate glass system in which the electrical conductivity is known to vary considerably with the RuO 2 content and to become electronic above about 0.5-0.7 vol.% RuO 2 [R. Pflieger, M. Malki, Y. Guari, J. Larionova, A. Grandjean, J. Am. Ceram. Soc., accepted for publication]. Some RuO 2 segregation was observed in SEM/TEM investigations but no continuous chain of RuO 2 particles could be seen. Electron relays between the particles are then necessary for a low-rate percolation, such as the nanoclusters suggested by Adachi et al. [K. Adachi, S. Iida, K. Hayashi, J. Mater. Res. 9 (7) (1994) 1866; K. Adachi, H. Kuno, J. Am. Ceram. Soc. 83 (10) (2000) 2441], which could consist in dissolved ruthenium. Indeed, several observations made here clearly indicate the presence of dissolved ruthenium in the glass matrix, like the modification of the glass density in presence of RuO 2 particles or the diffusion-limited growth of RuO 2 particles in the melt.

  10. The development of a selective ruthenium Fischer-Tropsch catalyst

    SciTech Connect

    Abrevaya, H.

    1989-01-01

    A new stable Fischer-Tropsch catalyst with very high selectivity to distillate fuels and with low light ends production was developed. This catalyst, which was made by a reverse micelle technique, contains 2.8% (by weight) ruthenium in the form of 4--6 nm particles on alumina and a proprietary modifier. The new modified ruthenium catalyst did not noticeably deactivate during 814 hours at about 80% CO conversion, 2H{sub 2}:1 CO feed ratio, 208{degree}C at inlet, 62 atm and 150 gas hourly space velocity. In order to determine the catalyst's tolerance, the operational severity was increased between 814 hours and 1700 hours by increasing the temperature and space velocity to 225{degree}C at inlet and to 205 hr{sup {minus}1}, respectively. A deactivation rate of about 0.016%/hour was measured under these more severe conditions at about 70% conversion level. These results with the new modified ruthenium catalyst compare favorably with those reported for the two commercial Sasol processes. The Arge process makes approximately 38% distillate fuel with 14--18% light ends, while the Synthol process makes about 48% distillate with 38% light ends. 82 refs., 360 figs., 66 tabs.

  11. Electrochemical deposition of conducting ruthenium oxide films from solution

    SciTech Connect

    Anderson, D.P.; Warren, L.F.

    1984-02-01

    In the last decade, ruthenium oxide, RuO /sub x/ (x less than or equal to 2), has been used extensively as the active anode electrocatalyst constituent for Cl/sub 2/ and O/sub 2/ evolution reactions, in chlorate production, and in metal electrowinning from mixed chloride-sulfate solutions. More recently, this material has been incorporated in several light-induced water electrolysis schemes and apparently possesses the ability to inhibit CdS photocorrosion by acting as a hole scavenger. The numerous applications for this catalyst material certainly warrant further studies of its electrochemical properties on a variety of substrates, e.g., semiconductors. The lack of a simple technique for controlled deposition of ruthenium oxide onto conducting substrates prompted us to investigate an electrochemical approach to this problem. We describe here a new way to electrochemically deposit conducting films of hydrated ruthenium oxide from an aqueous solution of the benzeneruthenium (II)aqua complex. The films slowly dissolve in aqueous electrolytes upon potential cycling, yet appear to be catalytic with regards to water oxidation.

  12. International strategic minerals inventory summary report; cobalt

    USGS Publications Warehouse

    Crockett, R.N.; Chapman, G.R.; Forrest, M.D.

    1987-01-01

    Major world resources of cobalt are described in this summary report of information in the International Strategic Minerals Inventory {ISMI}. ISMI is a cooperative data-collection effort of earth-science and mineral-resource agencies in Australia, Canada, the Federal Republic of Germany, the Republic of South Africa, and the United States of America. This report, designed to be of benefit to policy analysts, contains two parts. Part I presents an overview of the resources and potential supply of cobalt on the basis of inventory information. Part II contains tables of some of the geologic information and mineral-resource and production data that were collected by ISMI participants.

  13. Cation distributions on rapidly solidified cobalt ferrite

    NASA Technical Reports Server (NTRS)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.

    1990-01-01

    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  14. Cobalt plaque therapy of posterior uveal melanomas

    SciTech Connect

    Shields, J.A.; Augsburger, J.J.; Brady, L.W.; Day, J.L.

    1982-10-01

    One hundred patients with choroidal melanomas who were treated by the authors with cobalt plaque radiotherapy were analyzed with regard to tumor regression, visual results, complications, and mortality rate. The follow-up period at the time of this writing ranged from one to five years. These preliminary observations indicate that cobalt plaque radiotherapy induces tumor regression in 96% of cases, preserves useful vision in many cases and has fewer complications during the one- to five-year follow-up period than previously believed.

  15. Factors determining the consumption of ruthenium during electrosynthesis of sodium hypochlorite with the use of ruthenium oxide-titanium anodes

    SciTech Connect

    Klement'eva, V.S.; Kubasov, V.L.; Lambrev, V.G.; Uzbekov, A.A.

    1985-09-01

    The authors studied the rate of destruction of the active coating as a function of the electrolysis conditions during electrochemical production of sodium hypochlorite. Corrosion tests were carried out on specimens made by the thermochemical method, in an electrochemical cell without a diaphragm; the method used was based on neutron activation analysis. It was shown that losses of ruthenium can be lowered by conducting the electrolysis at low temperatures, higher current densities, and moderately low hypochlorite concentrations. However, the increase of current density may raise the ROTA potential above the critical value, when rapid anode failure is possible. It was also shown that under conditions such that the critical ROTA potential is not reached sodium hypochlorite solutions of fairly high concentrations can be obtained with a low comsumption of ruthenium, which is not possible with the use of many other anode materials.

  16. Light-Activated Protein Inhibition through Photoinduced Electron Transfer of a Ruthenium(II)–Cobalt(III) Bimetallic Complex

    PubMed Central

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; Weiss, Emily A.; Meade, Thomas J.

    2015-01-01

    We describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly, the rate of α-thrombin inhibition increases over 5-fold upon irradiation. These results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers. PMID:25671465

  17. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

    EPA Science Inventory

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

  18. Investigation of Ruthenium Electrodes for (Ba,Sr)TiO3 Thin Films

    NASA Astrophysics Data System (ADS)

    Joo, Jae-Hyun; Seon, Jeong-Min; Jeon, Yoo-Chan; Oh, Ki-Young; Roh, Jae-Sung; Kim, Jae-Jeong; Choi, Jin-Tae

    1998-06-01

    Ru/(Ba, Sr)TiO3(BST)/Ru capacitors were fabricated on TiN/Ti/Poly-Si/SiO2/Si substrate by sputtering technique. The effects of the bottom ruthenium electrode, deposited at various temperatures, on the characteristics of Ru/BST/Ru capacitor were intensively studied. Sputtered ruthenium films were grown in a columnar structure with a grain size ˜30 nm. With an increasing deposition temperature of ruthenium films, the (002) preferred orientation and grain size of ruthenium films gradually increased while the residual compressive stress in the ruthenium films was reduced. The surface of ruthenium films was oxidized to form RuOx on its surface during the deposition of BST films, which dramatically changed the surface morphology of ruthenium films and affected the characteristics of Ru/BST/Ru capacitor. In this work, the electrical properties of Ru/BST/Ru capacitors are explained with an emphasis on the surface morphology and residual stress of ruthenium films.

  19. Ruthenium(II)-Catalyzed Decarboxylative C-H Activation: Versatile Routes to meta-Alkenylated Arenes.

    PubMed

    Kumar, N Y Phani; Bechtoldt, Alexander; Raghuvanshi, Keshav; Ackermann, Lutz

    2016-06-01

    Ruthenium(II) bis(carboxylate)s proved highly effective for two decarboxylative C-H alkenylation strategies. The decarboxylation proceeded efficiently at rather low temperatures. The unique versatility of the decarboxylative ruthenium(II) catalysis is reflected in the oxidative olefinations with alkenes as well as the redox-neutral hydroarylations of alkynes. PMID:26996920

  20. Ruthenium-Catalyzed C-H Alkynylation of Aromatic Amides with Hypervalent Iodine-Alkyne Reagents.

    PubMed

    Boobalan, Ramadoss; Gandeepan, Parthasarathy; Cheng, Chien-Hong

    2016-07-15

    An efficient C-H activation method for the ortho alkynylation of aromatic N-methoxyamides with hypervalent iodine-alkyne reagent using a ruthenium catalyst is described. The reaction proceeds under mild reaction conditions with broad substrate scope. A possible catalytic cycle involving a ruthenium carboxylate assisted C-H bond cleavage is proposed from the preliminary mechanistic evidence. PMID:27357724

  1. Thermochemistry of Ruthenium Oxyhydroxide Species and Their Impact on Volatile Speciations in Severe Nuclear Accident Conditions.

    PubMed

    Miradji, Faoulat; Virot, François; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

    2016-02-01

    Literature thermodynamic data of ruthenium oxyhydroxides reveal large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. Reaction energies leading to the formation of all possible oxyhydroxide species RuOx(OH)y(H2O)z have been calculated for a series of reactions combining DFT (TPSSh-5%HF) geometries and partition functions, CCSD(T) energies extrapolated to the complete basis set limits. The highly accurate ab initio thermodynamic data were used as input data of thermodynamic equilibrium computations to derive the speciation of gaseous ruthenium species in the temperature, pressure and concentration conditions of severe nuclear accidents occurring in pressurized water reactors. At temperatures lower than 1000 K, gaseous ruthenium tetraoxide is the dominating species, between 1000 and 2000 K ruthenium trioxide becomes preponderant, whereas at higher temperatures gaseous ruthenium oxide, dioxide and even Ru in gaseous phase are formed. Although earlier studies predicted the formation of oxyhydroxides in significant quantities, the use of highly accurate ab initio thermodynamic data for ruthenium gaseous species leads to a more reliable inventory of gaseous ruthenium species in which gaseous oxyhydroxide ruthenium molecules are formed only in negligible amounts. PMID:26789932

  2. Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

    EPA Science Inventory

    Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

  3. A Cobalt-based Catalyst for CO2 Hydrogenation Under Ambient Conditions

    SciTech Connect

    Jeletic, Matthew S.; Mock, Michael T.; Appel, Aaron M.; Linehan, John C.

    2013-08-07

    Due to the continually rising levels of CO2 in the atmosphere, research into conversion of CO2 into fuels using carbon-neutral energy is currently an important topic in catalysis. Recent research on molecular catalysts has led to improved rates of CO2 conversion to formate, but unfortunately the resulting catalysts are based on precious metals such as iridium, ruthenium and rhodium and require high temperatures and high pressures for catalytic reactivity. Using established thermodynamic properties, a cobalt-based catalyst system has been designed for the catalytic production of formate from CO2 and H2, even at room temperature and one atmosphere of pressure. Using Co(dmpe)2H (dmpe is bis(dimethylphosphino)ethane) as a catalyst in tetrahydrofuran, room temperature turnover frequencies of 3,400 h-1 at 1 atm of 1:1 CO2:H2 and 74,000 h-1 at 20 atm were obtained. These results highlight the value of basic thermodynamic properties in the rational design of catalysts. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  4. General and Mild Cobalt-Catalyzed C-Alkylation of Unactivated Amides and Esters with Alcohols.

    PubMed

    Deibl, Nicklas; Kempe, Rhett

    2016-08-31

    The borrowing hydrogen or hydrogen autotransfer methodology is an elegant and sustainable or green concept to construct carbon-carbon bonds. In this concept, alcohols, which can be obtained from barely used and indigestible biomass, such as lignocellulose, are employed as alkylating reagents. An especially challenging alkylation is that of unactivated esters and amides. Only noble metal catalysts based on iridium and ruthenium have been used to accomplish these reactions. Herein, we report on the first base metal-catalyzed α-alkylation of unactivated amides and esters by alcohols. Cobalt complexes stabilized with pincer ligands, recently developed in our laboratory, catalyze these reactions very efficiently. The precatalysts can be synthesized easily from commercially available starting materials on a multigram scale and are self-activating under the basic reaction conditions. This Co catalyst class is also able to mediate alkylation reactions of both esters and amides. In addition, we apply the methodology to synthesize ketones and to convert alcohols into aldehydes elongated by two carbon atoms. PMID:27490682

  5. Effect of cobalt on the primary productivity of Spirulina platensis

    SciTech Connect

    Sharma, R.M.; Panigrahi, S.; Azeez, P.A.

    1987-10-01

    Cobalt, a micronutrient for biological organisms, is a metal of wide use. Main sources of Co to the environment are combustion of fossil fuels, smelters, cobalt processing facilities, sewage and industrial wastes. Atomic power plants and nuclear weapon detonations form an important source of radioisotopes of this metal to the environment. Cobalt has been included in the 14 toxic trace elements of critical importance from the point of view of environmental pollution and health hazards. Cobalt deficiency leads to diseases like stunted growth. At toxic level, Co inhibits heme biosynthesis and enzyme activities. The present study reports the effect of cobalt on biomass productivity of blue-green alga Spirulina platensis.

  6. Chemical state of ruthenium submonolayers on a Pt(1 1 1) electrode

    NASA Astrophysics Data System (ADS)

    Kim, H.; Rabelo de Moraes, I.; Tremiliosi-Filho, G.; Haasch, R.; Wieckowski, A.

    2001-03-01

    Oxidation states of ruthenium on a Pt(1 1 1)/Ru electrode were investigated by X-ray photoelectron spectroscopy. Ruthenium was added to platinum by electrochemical deposition methods: spontaneous deposition and electrolysis. Depending on the electrode potential, deposition conditions, and presence/absence of methanol in solution, metallic ruthenium (3d 5/2 core-level binding energy of 280.3 eV), RuO 2 (280.9 eV), and RuO 3 (282.8 eV) were found on the surface. After correlating ruthenium valence states to methanol oxidation reactivity, we concluded that the presence of a Ru metallic phase - covered by a weakly bonded Ru oxidation precursor - was a prerequisite for effective methanol oxidation electrocatalysis. This precursor was most likely "activated" water supplying the oxygen needed for transformation of surface CO to CO 2 at the edge of ruthenium islands on the Pt substrate.

  7. Magnetization dynamics of cobalt grown on graphene

    SciTech Connect

    Berger, A. J.; White, S. P.; Adur, R.; Pu, Y.; Hammel, P. C.; Amamou, W.; Kawakami, R. K.

    2014-05-07

    Ferromagnetic resonance (FMR) spin pumping is a rapidly growing field which has demonstrated promising results in a variety of material systems. This technique utilizes the resonant precession of magnetization in a ferromagnet to inject spin into an adjacent non-magnetic material. Spin pumping into graphene is attractive on account of its exceptional spin transport properties. This article reports on FMR characterization of cobalt grown on chemical vapor deposition graphene and examines the validity of linewidth broadening as an indicator of spin pumping. In comparison to cobalt samples without graphene, direct contact cobalt-on-graphene exhibits increased FMR linewidth—an often used signature of spin pumping. Similar results are obtained in Co/MgO/graphene structures, where a 1 nm MgO layer acts as a tunnel barrier. However, magnetometry, magnetic force microscopy, and Kerr microscopy measurements demonstrate increased magnetic disorder in cobalt grown on graphene, perhaps due to changes in the growth process and an increase in defects. This magnetic disorder may account for the observed linewidth enhancement due to effects such as two-magnon scattering or mosaicity. As such, it is not possible to conclude successful spin injection into graphene from FMR linewidth measurements alone.

  8. Cobalt processing - flask positioner location sensing system

    SciTech Connect

    Braun, P.F.

    1986-01-01

    Canada deuterium uranium (CANDU) reactors offer unique opportunities for economical production of /sup 60/Co in the adjuster rods used for xenon override and maximization of core output. Cobalt is effectively a by-product in CANDU reactors with the standards stainless steel adjuster rods replaced with cobalt adjuster rods. The Flask Positioner unit is a part of the cobalt adjuster element processing system (CAEPS) equipment which is used for removing irradiated cobalt adjuster elements from the reactor and safely transporting them to the irradiated fuel bay, where they are dismantled and prepared for shipment. The flask positioner equipment is similar to a crane, carries the CAEPS flask and locates it in an accurate position concentric with any adjuster site centerline. This enables the required operations for safe transfer of the irradiated adjuster element into the flask. The positioner is located above the reactivity mechanism deck. The CAEPS system has been made operational on several CANDU reactors. The location sensing system has been demonstrated to work very satisfactorily on all installations.

  9. Localized comedo formation after cobalt irradiation

    SciTech Connect

    Myskowski, P.L.; Safai, B.

    1981-10-01

    Following Cobalt-60 irradiation for a left frontotemporal tumor, a 61-year-old woman developed comedones on the forehead. These changes responded to conventional acne therapy with retinoic acid. Multiple acneigenic factors were implicated in the pathogenesis of her lesions.

  10. Sintered diamond compacts using metallic cobalt binders

    NASA Technical Reports Server (NTRS)

    Libby, W. F.; Katzman, H.

    1972-01-01

    Method is developed for sintering diamond powder which uses metallic cobalt as binder. Present samples show maximum microhardness of over 3000 kg/sq mm on Knoop scale. Material may be used as hard surface coating or may compete with cubic boron nitride as abrasive grain.

  11. Magnetization dynamics of cobalt grown on graphene

    NASA Astrophysics Data System (ADS)

    Berger, A. J.; Amamou, W.; White, S. P.; Adur, R.; Pu, Y.; Kawakami, R. K.; Hammel, P. C.

    2014-05-01

    Ferromagnetic resonance (FMR) spin pumping is a rapidly growing field which has demonstrated promising results in a variety of material systems. This technique utilizes the resonant precession of magnetization in a ferromagnet to inject spin into an adjacent non-magnetic material. Spin pumping into graphene is attractive on account of its exceptional spin transport properties. This article reports on FMR characterization of cobalt grown on chemical vapor deposition graphene and examines the validity of linewidth broadening as an indicator of spin pumping. In comparison to cobalt samples without graphene, direct contact cobalt-on-graphene exhibits increased FMR linewidth—an often used signature of spin pumping. Similar results are obtained in Co/MgO/graphene structures, where a 1 nm MgO layer acts as a tunnel barrier. However, magnetometry, magnetic force microscopy, and Kerr microscopy measurements demonstrate increased magnetic disorder in cobalt grown on graphene, perhaps due to changes in the growth process and an increase in defects. This magnetic disorder may account for the observed linewidth enhancement due to effects such as two-magnon scattering or mosaicity. As such, it is not possible to conclude successful spin injection into graphene from FMR linewidth measurements alone.

  12. Water splitting: Taking cobalt in isolation

    NASA Astrophysics Data System (ADS)

    Wang, Aiqin; Zhang, Tao

    2016-01-01

    The sustainable production of hydrogen is key to the delivery of clean energy in a hydrogen economy; however, lower-cost alternatives to platinum electrocatalysts are needed. Now, isolated, earth-abundant cobalt atoms dispersed over nitrogen-doped graphene are shown to efficiently electrolyse water to generate hydrogen.

  13. Controlled cobalt doping of magnetosomes in vivo.

    PubMed

    Staniland, Sarah; Williams, Wyn; Telling, Neil; Van Der Laan, Gerrit; Harrison, Andrew; Ward, Bruce

    2008-03-01

    Magnetotactic bacteria biomineralize iron into magnetite (Fe3O4) nanoparticles that are surrounded by lipid vesicles. These 'magnetosomes' have considerable potential for use in bio- and nanotechnological applications because of their narrow size and shape distribution and inherent biocompatibility. The ability to tailor the magnetic properties of magnetosomes by chemical doping would greatly expand these applications; however, the controlled doping of magnetosomes has so far not been achieved. Here, we report controlled in vivo cobalt doping of magnetosomes in three strains of the bacterium Magnetospirillum. The presence of cobalt increases the coercive field of the magnetosomes--that is, the field necessary to reverse their magnetization--by 36-45%, depending on the strain and the cobalt content. With elemental analysis, X-ray absorption and magnetic circular dichroism, we estimate the cobalt content to be between 0.2 and 1.4%. These findings provide an important advance in designing biologically synthesized nanoparticles with useful highly tuned magnetic properties. PMID:18654488

  14. Cobalt Biogeochemistry in the South Atlantic: A Full-Depth Zonal Ocean Section of Total Dissolved Cobalt, and Development of a High Throughput Cobalt ICP-MS Method

    NASA Astrophysics Data System (ADS)

    Noble, A. E.; Saito, M. A.; Goepfert, T. J.

    2008-12-01

    This study presents the first high-resolution full-depth zonal section of total dissolved cobalt from a recent cruise transecting the South Atlantic Ocean along approximately 11S. This section demonstrates that current electrochemical analytical techniques are capable of producing the high precision and high resolution datasets for total dissolved cobalt expected to be generated as a part of the international GEOTRACES Program. The micronutritive role of cobalt may affect community structure in different regions of the oceans, a compelling reason to include cobalt in the trace element analyses planned for the GEOTRACES Program. This cobalt section reveals an advective source of cobalt from the African coast near Namibia, which we propose to be due to the Benguela Current interacting with reducing shelf sediments. These high concentrations of cobalt were also observed within the oxygen minimum zone that extends across much of the South Atlantic basin in this section, and are likely indicative of redox cycling of cobalt in the water column. Nutrient-like vertical structure of cobalt was observed in the surface waters across the majority of the basin due to biological utilization, and the expected hybrid-type trend is observed at depth, with scavenging of cobalt below the nutricline. Deepwater concentrations of cobalt were around 50pM across the basin below 3000m. Analysis of the shelf-life of refrigerated filtered samples stored without acidification for electrochemical cobalt analysis demonstrated that those samples which were collected specifically within oxygen minimum zones may underestimate cobalt if not analyzed within a few weeks of collection. These results motivate our on-going development of a method to measure cobalt in acidified samples via inductively coupled plasma mass spectrometry (ICP-MS). The benefit of this technique would be twofold: acidification would extend the shelf-life of the samples significantly, and samples would be preserved identically

  15. The cytotoxicity and genotoxicity of soluble and particulate cobalt in human lung fibroblast cells

    SciTech Connect

    Smith, Leah J.; Holmes, Amie L.; Kandpal, Sanjeev Kumar; Mason, Michael D.; Zheng, Tongzhang; Wise, John Pierce

    2014-08-01

    Cobalt exposure is increasing as cobalt demand rises worldwide due to its use in enhancing rechargeable battery efficiency, super-alloys, and magnetic products. Cobalt is considered a possible human carcinogen with the lung being a primary target. However, few studies have considered cobalt-induced toxicity in human lung cells. Therefore, in this study, we sought to determine the cytotoxicity and genotoxicity of particulate and soluble cobalt in human lung cells. Cobalt oxide and cobalt chloride were used as representative particulate and soluble cobalt compounds, respectively. Exposure to both particulate and soluble cobalt induced a concentration-dependent increase in cytotoxicity, genotoxicity, and intracellular cobalt ion levels. Based on intracellular cobalt ion levels, we found that soluble cobalt was more cytotoxic than particulate cobalt while particulate and soluble cobalt induced similar levels of genotoxicity. However, soluble cobalt induced cell cycle arrest indicated by the lack of metaphases at much lower intracellular cobalt concentrations compared to cobalt oxide. Accordingly, we investigated the role of particle internalization in cobalt oxide-induced toxicity and found that particle-cell contact was necessary to induce cytotoxicity and genotoxicity after cobalt exposure. These data indicate that cobalt compounds are cytotoxic and genotoxic to human lung fibroblasts, and solubility plays a key role in cobalt-induced lung toxicity. - Highlights: • Particulate and soluble cobalt are cytotoxic and genotoxic to human lung cells. • Soluble cobalt induces more cytotoxicity compared to particulate cobalt. • Soluble and particulate cobalt induce similar levels of genotoxicity. • Particle-cell contact is required for particulate cobalt-induced toxicity.

  16. Antiparasitic activities of novel ruthenium/lapachol complexes.

    PubMed

    Barbosa, Marília I F; Corrêa, Rodrigo S; de Oliveira, Katia Mara; Rodrigues, Claudia; Ellena, Javier; Nascimento, Otaciro R; Rocha, Vinícius P C; Nonato, Fabiana R; Macedo, Taís S; Barbosa-Filho, José Maria; Soares, Milena B P; Batista, Alzir A

    2014-07-01

    The present study describes the synthesis, characterization, antileishmanial and antiplasmodial activities of novel diimine/(2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,4'-methylbipyridine (Me-bipy) and 4,4'-methoxybipyridine (MeO-bipy)/phosphine/ruthenium(II) complexes containing lapachol (Lap, 2-hydroxy-3-(3-33 methyl-2-buthenyl)-1,4-naphthoquinone) as bidentate ligand. The [Ru(Lap)(PPh3)2(bipy)]PF6 (1), [Ru(Lap)(PPh3)2(Me-bipy)]PF6 (2), [Ru(Lap)(PPh3)2(MeO-bipy)]PF6(3) and[Ru(Lap)(PPh3)2(phen)]PF6 (4) complexes, PPh3=triphenylphospine, were synthesized from the reactions of cis-[RuCl2(PPh3)2(X-bipy)] or cis-[RuCl2(PPh3)2(phen)], with lapachol. The [RuCl2(Lap)(dppb)] (5) [dppb=1,4-bis(diphenylphosphine)butane] was synthesized from the mer-[RuCl3(dppb)(H2O)] complex. The complexes were characterized by elemental analysis, molar conductivity, infrared and UV-vis spectroscopy, (31)P{(1)H} and (1)H NMR, and cyclic voltammetry. The Ru(III) complex, [RuCl2(Lap)(dppb)], was also characterized by the EPR technique. The structure of the complexes [Ru(Lap)(PPh3)2(bipy)]PF6 and [RuCl2(Lap)(dppb)] was elucidated by X-ray diffraction. The evaluation of the antiparasitic activities of the complexes against Leishmania amazonensis and Plasmodium falciparum demonstrated that lapachol-ruthenium complexes are more potent than the free lapachol. The [RuCl2(Lap)(dppb)] complex is the most potent and selective antiparasitic compound among the five new ruthenium complexes studied in this work, exhibiting an activity comparable to the reference drugs. PMID:24727183

  17. Jahn-Teller driven perpendicular magnetocrystalline anisotropy in metastable ruthenium

    NASA Astrophysics Data System (ADS)

    Odkhuu, Dorj; Rhim, S. H.; Park, Noejung; Nakamura, Kohji; Hong, Soon Cheol

    2015-01-01

    A metastable phase of body-centered-tetragonal ruthenium (bct Ru) is identified to exhibit a large perpendicular magnetocrystalline anisotropy (PMCA), whose energy EMCA is as large as 150 μ eV /atom , which is two orders of magnitude greater than those of 3 d magnetic metals. Further investigation over the range of tetragonal distortion suggests that the appearance of magnetism in the bct Ru is governed by the Jahn-Teller spit eg orbitals. Moreover, from band analysis, MCA is mainly determined by an interplay between two eg states, dx2-y2 and dz2 states, as a result of level reversal associated with tetragonal distortion.

  18. Binuclear ruthenium(II) complexes for amyloid fibrils recognition

    NASA Astrophysics Data System (ADS)

    Hanczyc, Piotr

    2014-12-01

    Metal-organic compounds represent a unique class of biomarkers with promising photophysical properties useful for imaging. Here interactions of insulin fibrils with two binuclear complexes [μ-(11,11‧-bidppz)(phen)4Ru2]4+ (1) and [μ-C4(cpdppz)(phen)4Ru2]4+ (2) are studied by linear dichroism (LD) and fluorescence. These ruthenium(II) compounds could provide a new generation of amyloid binding chromophores with long lived lifetimes, good luminescence quantum yields for the bound molecules and photo-stability useful in multiphoton luminescence imaging.

  19. Progress in doping of ruthenium silicide (Ru2Si3)

    NASA Technical Reports Server (NTRS)

    Vining, C. B.; Allevato, C. E.

    1992-01-01

    Ruthenium silicide is currently under development as a promising thermoelectric material suitable for space power applications. Key to realizing the potentially high figure of merit values of this material is the development of appropriate doping techniques. In this study, manganese and iridium have been identified as useful p- and n-type dopants, respectively. Resistivity values have been reduced by more than 3 orders of magnitude. Anomalous Hall effect results, however, complicate interpretation of some of the results and further effort is required to achieve optimum doping levels.

  20. Thermal properties of ruthenium alkylidene-polymerized dicyclopentadiene

    PubMed Central

    Vidavsky, Yuval; Navon, Yotam; Ginzburg, Yakov; Gottlieb, Moshe

    2015-01-01

    Summary Differential scanning calorimetry (DSC) analysis of ring opening methatesis polymerization (ROMP) derived polydicyclopentadiene (PDCPD) revealed an unexpected thermal behavior. A recurring exothermic signal can be observed in the DSC analysis after an elapsed time period. This exothermic signal was found to be proportional to the resting period and was accompanied by a constant increase in the glass-transition temperature. We hypothesize that a relaxation mechanism within the cross-linked scaffold, together with a long-lived stable ruthenium alkylidene species are responsible for the observed phenomenon. PMID:26425203

  1. The solubility of hydrogen in rhodium, ruthenium, iridium and nickel.

    NASA Technical Reports Server (NTRS)

    Mclellan, R. B.; Oates, W. A.

    1973-01-01

    The temperature variation of the solubility of hydrogen in rhodium, ruthenium, iridium, and nickel in equilibrium with H2 gas at 1 atm pressure has been measured by a technique involving saturating the solvent metal with hydrogen, quenching, and analyzing in resultant solid solutions. The solubilities determined are small (atom fraction of H is in the range from 0.0005 to 0.00001, and the results are consistent with the simple quasi-regular model for dilute interstitial solid solutions. The relative partial enthalpy and excess entropy of the dissolved hydrogen atoms have been calculated from the solubility data and compared with well-known correlations between these quantities.

  2. Sensitization of NO-Releasing Ruthenium Complexes to Visible Light.

    PubMed

    Becker, Tobias; Kupfer, Stephan; Wolfram, Martin; Görls, Helmar; Schubert, Ulrich S; Anslyn, Eric V; Dietzek, Benjamin; Gräfe, Stefanie; Schiller, Alexander

    2015-10-26

    We report a combined spectroscopical-theoretical investigation on the photosensitization of transition metal nitrosyl complexes. For this purpose, ruthenium nitrosyl complexes based on tetradentate biscarboxamide ligands were synthesized. A crystal structure analysis of a lithium-based ligand intermediate is described. The Ru complexes have been characterized regarding their photophysical and nitric oxide (NO) releasing properties. Quantum chemical calculations have been performed to unravel the influence of the biscarboxamide ligand frame with respect to the molecular electronic properties of the NO-releasing pathway. A quantitative measure for the ligand design within photosensitized Ru complexes is introduced and evaluated spectroscopically and theoretically by using time-dependent density functional theory. PMID:26394612

  3. Ruthenium Behavior at Phase Separation of Borosilicate Glass-12259

    SciTech Connect

    Enokida, Youichi; Sawada, Kayo

    2012-07-01

    The Rokkasho reprocessing plant (RRP) located in Aomori, Japan, vitrifies high level waste (HLW) into a borosilicate glass. The HLW is generated from the reprocessing of spent fuel and contains ruthenium (Ru) and other platinum group metals (PGMs). Based on the recent consequences after a huge earthquake that occurred in Japan, a hypothetical blackout was postulated for the RRP to address additional safety analysis requirements. During a prolonged blackout, the borosilicate glass could phase separate due to cooling of the glass in the melter. The Ru present in the glass matrix could migrate into separate phases and impact the durability of the borosilicate glass. The durability of the glass is important for quality assurance and performance assessment of the vitrified HLW. A fundamental study was performed at an independent university to understand the impact of a prolonged blackout. Simulated HLW glasses were prepared for the RRP, and the Ru behavior in phase separated glasses was studied. The simulated HLW glasses contained nonradioactive elements and PGMs. The glass compositions were then altered to enhance the formation of the phase-separated glasses when subjected to thermal treatment at 700 deg. C for 24 hours. The synthesized simulated glasses contained 1.1 % Ru by weight as ruthenium dioxide (RuO{sub 2}). A portion of the RuO{sub 2} formed needle-shaped crystals in the glass specimens. After the thermal treatment, the glass specimen had separated into two phases. One of the two phases was a B{sub 2}O{sub 3} rich phase, and the other phase was a SiO{sub 2} rich phase. The majority of the chemical species in the B{sub 2}O{sub 3} rich phase was leached away with the Material Characterization Center-3 (MCC-3) protocol standardized by the Pacific Northwest National Laboratory using an aqueous low-concentrated nitric acid solution, but the leaching of the Ru fraction was very limited; less than 1% of the original Ru content. The Ru leaching was much less than

  4. Metalorganic Chemical Vapor Deposition of Ruthenium-Doped Diamond like Carbon Films

    NASA Technical Reports Server (NTRS)

    Sunkara, M. K.; Ueno, M.; Lian, G.; Dickey, E. C.

    2001-01-01

    We investigated metalorganic precursor deposition using a Microwave Electron Cyclotron Resonance (ECR) plasma for depositing metal-doped diamondlike carbon films. Specifically, the deposition of ruthenium doped diamondlike carbon films was investigated using the decomposition of a novel ruthenium precursor, Bis(ethylcyclopentadienyl)-ruthenium (Ru(C5H4C2H5)2). The ruthenium precursor was introduced close to the substrate stage. The substrate was independently biased using an applied RF power. Films were characterized using Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and Four Point Probe. The conductivity of the films deposited using ruthenium precursor showed strong dependency on the deposition parameters such as pressure. Ruthenium doped sample showed the presence of diamond crystallites with an average size of approx. 3 nm while un-doped diamondlike carbon sample showed the presence of diamond crystallites with an average size of 11 nm. TEM results showed that ruthenium was atomically dispersed within the amorphous carbon network in the films.

  5. Effect of ionic strength on ruthenium CMP in H2O2-based slurries

    NASA Astrophysics Data System (ADS)

    Jiang, Liang; He, Yongyong; Li, Yuzhuo; Luo, Jianbin

    2014-10-01

    With the development of ultra-large scale integrated circuits, ruthenium has been selected as one of the most promising barrier metals for copper interconnects to replace traditional Ta/TaN bilayer. This paper mainly investigated the effect of ionic strength on the chemical mechanical polishing performance of ruthenium in H2O2-based slurries. The results show that, the ruthenium removal rate (RR) increases with the increasing concentration of H2O2 due to the formation of ruthenium oxides like Ru(OH)3, RuO2·2H2O and even RuO42-; additionally, the ruthenium RR can be further enhanced with the increase of K+ ionic strength. It is revealed that the added K+ can intensify the electrochemical reactions between H2O2 and the ruthenium surface by increasing the conductivity, meanwhile can also result in the neutralization of the zeta potentials of both silica particles and the ruthenium surface, and thus can lead to the decrease of the electrostatic repulsive force and the increase of the mechanical abrasion intensity between silica particles and the ruthenium surface. Therefore, the ruthenium RR increases with the increase of K+ ionic strength. Furthermore, the effects of K+ ionic strength on the material removal rate (MRR) selectivity of Ru vs. Cu and the galvanic corrosion of Cu/Ru couple are studied. It is found that, in order to achieve higher MRR selectivity than 1.0, KNO3 is preferred for the K+ source; and with H2O2 as the oxidizer, copper galvanic corrosion problem can be effectively suppressed.

  6. In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes.

    PubMed

    Lee, Juneyoung; Grandner, Jessica M; Engle, Keary M; Houk, K N; Grubbs, Robert H

    2016-06-01

    Ruthenium benzylidene complexes are well-known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by (1)H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, preactivated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes, is the active catalyst in ATR reactions. Based on data from (1) H, (13)C, and (31)P NMR spectroscopy and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex. PMID:27186790

  7. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

    PubMed Central

    2013-01-01

    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

  8. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction.

    PubMed

    Yuan, Xianxia; Hu, Xin-Xin; Ding, Xin-Long; Kong, Hai-Chuan; Sha, Hao-Dong; Lin, He; Wen, Wen; Shen, Guangxia; Guo, Zhi; Ma, Zi-Feng; Yang, Yong

    2013-01-01

    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

  9. Dynamics of the contact between a ruthenium surface with a single nanoasperity and a flat ruthenium surface: Molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    de Oliveira, Alan Barros; Fortini, Andrea; Buldyrev, Sergey V.; Srolovitz, David

    2011-04-01

    We study the dynamics of the contact between a pair of surfaces (with properties designed to mimic ruthenium) via molecular dynamics simulations. In particular, we study the contact between a ruthenium surface with a single nanoasperity and a flat ruthenium surface. The results of such simulations suggest that contact behavior is highly variable. The goal of this study is to investigate the source and degree of this variability. We find that during compression, the behavior of the contact force displacement curves is reproducible, while during contact separation, the behavior is highly variable. Examination of the contact surfaces suggests that two separation mechanisms are in operation and give rise to this variability. One mechanism corresponds to the formation of a bridge between the two surfaces that plastically stretches as the surfaces are drawn apart and eventually separate in shear. This leads to a morphology after separation in which there are opposing asperities on the two surfaces. This plastic separation/bridge formation mechanism leads to a large work of separation. The other mechanism is a more brittle-like mode in which a crack propagates across the base of the asperity (slightly below the asperity/substrate junction) leading to most of the asperity on one surface or the other after separation and a slight depression facing this asperity on the opposing surface. This failure mode corresponds to a smaller work of separation. This failure mode corresponds to a smaller work of separation. Furthermore, contacts made from materials that exhibit predominantly brittle-like behavior will tend to require lower work of separation than those made from ductile-like contact materials.

  10. Effect of temperature annealing on capacitive and structural properties of hydrous ruthenium oxides

    NASA Astrophysics Data System (ADS)

    Fang, Wei-Chuan; Huang, Jin-Hua; Chen, Li-Chyong; Su, Yuh-Long Oliver; Chen, Kuei-Hsien

    The structure-property relationships of hydrous ruthenium oxides, fabricated by electro deposition on Ti foil, were investigated with different annealing conditions. The annealing temperature was found to play an important role in affecting the electrochemical performance of the annealed hydrous ruthenium oxides. The results indicate that annealing hydrous ruthenium oxide at its crystallization threshold temperature, ∼200 °C, may help to create suitable nanostructure in the oxide that supports the establishment of interpenetrating percolation paths for balanced electron and proton conduction, thereby improving the capacitive response of the oxide dramatically. This finding is useful for fabrication of electrodes with enhanced electrochemical performance for application in microsupercapacitor.

  11. Internal stresses and structure of electrolytic films of ruthenium, rhodium, and palladium

    SciTech Connect

    Medyanik, V.N.

    1986-01-01

    Films of ruthenium, rhodium, and palladium are used as targets in nuclear physics experiments in the form of metal foils. The authors investigate how the current density and the concentration of metal in the electrolyte influence the internal stresses, the grain size, and the texture of electrolytic films of ruthenium, rhodium, and palladium. The grain size of rhodium and palladium films increases with the current density, but for ruthenium there is no exact relationship. The increase in grain size in films of rhodium and palladium leads to a reduction in the internal stresses.

  12. The appearance of the outflow apparatus of the eye after staining with ruthenium red.

    PubMed

    Grierson, I; Lee, W R; Abraham, S

    1977-10-01

    The outflow apparatus from adult baboon and rabbit eyes was stained with the inorganic dye ruthenium red. The ruthenium reaction product coated the surface of the trabecular meshwork cells and the canalicular endothelial cells. Deposits also impregnated the various connective tissue elements within the trabeculae and the extracellular spaces of the endothelial meshwork. A fine fibrillar network could also be identified with ruthenium red and this was present in the trabecular cores and the extracellular spaces of the endothelial meshwork. It was considered that the fibrillar network may represent a matrix of glycosaminoglycans and glycoproteins. The significance of these materials in relation to aqueous outflow was discussed. PMID:71846

  13. Low-cobalt single crystal Rene 150

    NASA Technical Reports Server (NTRS)

    Scheuermann, C. M.

    1982-01-01

    The effects of cobalt content on a single crystal version of the advanced, high gamma prime content turbine airfoil alloy Rene 150 were investigated. Cobalt contents under investigation include 12 wt.% (composition level of Rene 150), 6 wt.%, and 0 wt.%. Preliminary test results are presented and compared with the properties of standard DS Rene 150. DTA results indicate that the liquidus goes through a maximum of about 1435 C near 6 wt.% Co. The solidus remains essentially constant at 1390 C with decreasing Co content. The gamma prime solvus appears to go through a minimum of about 1235 C near 6 wt.% Co content. Preliminary as-cast tensile and stress rupture results are presented along with heat treat schedules and future test plans.

  14. Creep-fatigue of low cobalt superalloys

    NASA Technical Reports Server (NTRS)

    Halford, G. R.

    1982-01-01

    Testing for the low cycle fatigue and creep fatigue resistance of superalloys containing reduced amounts of cobalt is described. The test matrix employed involves a single high temperature appropriate for each alloy. A single total strain range, again appropriate to each alloy, is used in conducting strain controlled, low cycle, creep fatigue tests. The total strain range is based upon the level of straining that results in about 10,000 cycles to failure in a high frequency (0.5 Hz) continuous strain-cycling fatigue test. No creep is expected to occur in such a test. To bracket the influence of creep on the cyclic strain resistance, strain hold time tests with ore minute hold periods are introduced. One test per composition is conducted with the hold period in tension only, one in compression only, and one in both tension and compression. The test temperatures, alloys, and their cobalt compositions that are under study are given.

  15. Are cobaltates conventional? An ARPES viewpoint

    SciTech Connect

    Hasan, M.Z. . E-mail: mzhasan@Princeton.edu; Qian, D.; Foo, M.L.; Cava, R.J.

    2006-07-15

    Recently discovered class of cobaltate superconductors (Na{sub 0.3}CoO{sub 2}.nH{sub 2}O) is a novel realization of interacting quantum electron system in a triangular network with low-energy degrees of freedom. We employ angle-resolved photoemission spectroscopy to study the quasiparticle parameters in the parent superconductors. Results reveal a large hole-like Fermi surface generated by the crossing of heavy quasiparticles. The measured quasiparticle parameters collectively suggest two orders of magnitude departure from the conventional weak coupling (such as Al) Bardeen-Cooper-Schrieffer electron dynamics paradigm and unveils cobaltates as a rather hidden class of relatively high temperature superconductors. These parameters also form the basis for a microscopic Hamiltonian of the system.

  16. Hard Machinable Machining of Cobalt Super Alloys

    NASA Astrophysics Data System (ADS)

    Čep, Robert; Janásek, Adam; Petrů, Jana; Čepová, Lenka; Sadílek, Marek; Kratochvíl, Jiří

    2012-12-01

    The article deals with difficult-to-machine cobalt super alloys. The main aim is to test the basic properties of cobalt super alloys and propose suitable cutting materials and machining parameters under the designation 188 when machining. Although the development of technology in chipless machining such as moulding, precision casting and other manufacturing methods continues to advance, machining is still the leading choice for piece production, typical for energy and chemical engineering. Nowadays, super alloys are commonly used in turbine engines in regions that are subject to high temperatures, which require high strength, high temperature resistance, phase stability, as well as corrosion or oxidation resistance.

  17. Influence of cobalt on fermentative methylation.

    PubMed

    Claridge, C A; Rossomano, V Z; Buono, N S; Gourevitch, A; Lein, J

    1966-03-01

    Streptomyces rishiriensis produces at least five closely related antibiotics. Strain selection yielded a culture producing only the most active component, coumermycin A. Hydrolysis of this antibiotic by barium hydroxide yielded both 5-methyl-pyrrole-2-carboxylic acid and pyrrole-2-carboxylic acid, which could be separated by paper chromatography. Coumermycin A was thus shown to be two fractions, designated A(1) and A(2) depending upon the nature of the pyrrole carboxylic acid portion. The addition of cobalt to the fermentation medium at a level as low as 0.01 mug/ml shifted the fermentation exclusively to the production of coumermycin A(1). Other ions were ineffective, except nickel, whose activity could be explained by the presence of contaminating cobalt. PMID:5959861

  18. Cobalt recycling in the United States in 1998

    USGS Publications Warehouse

    Shedd, Kim B.

    2002-01-01

    This report is one of a series of reports on metals recycling. It defines and quantifies the 1998 flow of cobalt-bearing materials in the United States, from imports and stock releases through consumption and disposition, with particular emphasis on the recycling of industrial scrap (new scrap) and used products (old scrap). Because of cobalt?s many and diverse uses, numerous types of scrap were available for recycling by a wide variety of processes. In 1998, an estimated 32 percent of U.S. cobalt supply was derived from scrap. The ratio of cobalt consumed from new scrap to that from old scrap was estimated to be 50:50. Of all the cobalt in old scrap available for recycling, an estimated 68 percent was either consumed in the United States or exported to be recycled.

  19. Synthesis and characterization of different nanostructures of cobalt phosphate

    SciTech Connect

    Badsar, M.; Edrissi, M.

    2010-09-15

    In this research, different nanostructures of cobalt phosphate were successfully prepared. Flowerlike cobalt phosphate and platelike ammonium cobalt phosphate were made by coprecipitation method without any use of surfactant or capping agent as structure directors. Reverse micelle route in water/CTAB/n-hexanol microemulsion system was used to synthesize cobalt phosphate nanoparticles. The synthesized nanostructures were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), chemical analysis, and BET. The SEM images showed that the flowerlike nanostructure is an arrangement of cobalt phosphate plates. TEM images revealed that the nanoparticles are spherical with the diameter of 30-50 nm. The purity of cobalt phosphate nanoparticles was confirmed by chemical analysis. Finally, the possible mechanisms which can describe the formation of these nanostructures were discussed.

  20. Interfacial Structure Dependent Spin Mixing Conductance in Cobalt Thin Films.

    PubMed

    Tokaç, M; Bunyaev, S A; Kakazei, G N; Schmool, D S; Atkinson, D; Hindmarch, A T

    2015-07-31

    Enhancement of Gilbert damping in polycrystalline cobalt thin-film multilayers of various thicknesses, overlayered with copper or iridium, was studied in order to understand the role of local interface structure in spin pumping. X-ray diffraction indicates that cobalt films less than 6 nm thick have strong fcc(111) texture while thicker films are dominated by hcp(0001) structure. The intrinsic damping for cobalt thicknesses above 6 nm is weakly dependent on cobalt thickness for both overlayer materials, and below 6 nm the iridium overlayers show higher damping enhancement compared to copper overlayers, as expected due to spin pumping. The interfacial spin mixing conductance is significantly enhanced in structures where both cobalt and iridium have fcc(111) structure in comparison to those where the cobalt layer has subtly different hcp(0001) texture at the interface. PMID:26274431

  1. Dinuclear Ruthenium(III)-Ruthenium(IV) Complexes, Having a Doubly Oxido-Bridged and Acetato- or Nitrato-Capped Framework.

    PubMed

    Suzuki, Tomoyo; Suzuki, Yutaka; Kawamoto, Tatsuya; Miyamoto, Ryo; Nanbu, Shinkoh; Nagao, Hirotaka

    2016-07-18

    Dinuclear ruthenium complexes in a mixed-valence state of Ru(III)-Ru(IV), having a doubly oxido-bridged and acetato- or nitrato-capped framework, [{Ru(III,IV)(ebpma)}2(μ-O)2(μ-L)](PF6)2 [ebpma = ethylbis(2-pyridylmethyl)amine; L = CH3COO(-) (1), NO3(-) (2)], were synthesized. In aqueous solutions, the diruthenium complex 1 showed multiple redox processes accompanied by proton transfers depending on the pH. The protonated complex of 1, which is described as 1H+, was obtained. PMID:27341408

  2. Cellular delivery of pyrenyl-arene ruthenium complexes by a water-soluble arene ruthenium metalla-cage.

    PubMed

    Furrer, Mona Anca; Schmitt, Frédéric; Wiederkehr, Michaël; Juillerat-Jeanneret, Lucienne; Therrien, Bruno

    2012-06-28

    Three pyrenyl-arene ruthenium complexes (M(1)-M(3)) of the general formula [Ru(η(6)-arene-pyrenyl)Cl(2)(pta)] (pta = 1,3,5-triaza-7-phosphaadamantane) have been synthesised and characterised. Prior to the coordination to ruthenium, pyrene was connected to the arene ligand via an alkane chain containing different functional groups: ester (L(1)), ether (L(2)) and amide (L(3)), respectively. Furthermore, the pyrenyl moieties of the M(n) complexes were encapsulated within the hydrophobic cavity of the water soluble metalla-cage, [Ru(6)(η(6)-p-cymene)(6)(tpt)(2)(donq)(3)](6+) (tpt = 2,4,6-tri-(pyridin-4-yl)-1,3,5-triazine; donq = 5,8-dioxydo-1,4-naphthoquinonato), while the arene ruthenium end was pointing out of the cage, thus giving rise to the corresponding host-guest systems [M(n)⊂Ru(6)(η(6)-p-cymene)(6)(tpt)(2)(donq)(3)](6+) ([M(n)⊂cage](6+)). The antitumor activity of the pyrenyl-arene ruthenium complexes (M(n)) and the corresponding host-guest systems [M(n)⊂cage][CF(3)SO(3)](6) were evaluated in vitro in different types of human cancer cell lines (A549, A2780, A2780cisR, Me300 and HeLa). Complex M(2), which contains an ether group within the alkane chain, demonstrated at least a 10 times higher cytotoxicity than the reference compound [Ru(η(6)-p-cymene)Cl(2)(pta)] (RAPTA-C). All host-guest systems [M(n)⊂cage](6+) showed good anticancer activity with IC(50) values ranging from 2 to 8 μM after 72 h exposure. The fluorescence of the pyrenyl moiety allowed the monitoring of the cellular uptake and revealed an increase of uptake by a factor two of the M(2) complex when encapsulated in the metalla-cage [Ru(6)(η(6)-p-cymene)(6)(tpt)(2)(donq)(3)](6+). PMID:22506276

  3. High-Spin Cobalt Hydrides for Catalysis

    SciTech Connect

    Holland, Patrick L.

    2013-08-29

    Organometallic chemists have traditionally used catalysts with strong-field ligands that give low-spin complexes. However, complexes with a weak ligand field have weaker bonds and lower barriers to geometric changes, suggesting that they may lead to more rapid catalytic reactions. Developing our understanding of high-spin complexes requires the use of a broader range of spectroscopic techniques, but has the promise of changing the mechanism and/or selectivity of known catalytic reactions. These changes may enable the more efficient utilization of chemical resources. A special advantage of cobalt and iron catalysts is that the metals are more abundant and cheaper than those currently used for major industrial processes that convert unsaturated organic molecules and biofeedstocks into useful chemicals. This project specifically evaluated the potential of high-spin cobalt complexes for small-molecule reactions for bond rearrangement and cleavage reactions relevant to hydrocarbon transformations. We have learned that many of these reactions proceed through crossing to different spin states: for example, high-spin complexes can flip one electron spin to access a lower-energy reaction pathway for beta-hydride elimination. This reaction enables new, selective olefin isomerization catalysis. The high-spin cobalt complexes also cleave the C-O bond of CO2 and the C-F bonds of fluoroarenes. In each case, the detailed mechanism of the reaction has been determined. Importantly, we have discovered that the cobalt catalysts described here give distinctive selectivities that are better than known catalysts. These selectivities come from a synergy between supporting ligand design and electronic control of the spin-state crossing in the reactions.

  4. Atomically flat ultrathin cobalt ferrite islands.

    PubMed

    Martín-García, Laura; Quesada, Adrián; Munuera, Carmen; Fernández, Jose F; García-Hernández, Mar; Foerster, Michael; Aballe, Lucía; de la Figuera, Juan

    2015-10-21

    A route for fabricating structurally perfect cobalt ferrite magnetic nanostructures is demonstrated. Ultrathin islands of up to 100 μm(2) with atomically flat surfaces and free from antiphase boundaries are developed. The extremely low defect concentration leads to a robust magnetic order, even for thicknesses below 1 nm, and exceptionally large magnetic domains. This approach allows the evaluation of the influence of specific extrinsic effects on domain wall pinning. PMID:26306027

  5. Cobalt(II) Complex of a Diazoalkane Radical Anion.

    PubMed

    Bonyhady, Simon J; Goldberg, Jonathan M; Wedgwood, Nicole; Dugan, Thomas R; Eklund, Andrew G; Brennessel, William W; Holland, Patrick L

    2015-06-01

    β-Diketiminate cobalt(I) precursors react with diphenyldiazomethane to give a compound that is shown by computational studies to be a diazoalkane radical anion antiferromagnetically coupled to a high-spin cobalt(II) ion. Thermolysis of this complex results in formal N-N cleavage to give a cobalt(II) ketimide complex. Experimental evaluation of the potential steps in the mechanism suggests that free azine is a likely intermediate in this reaction. PMID:25986783

  6. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cobaltous salts and its derivatives. 189.120... Generally Prohibited From Direct Addition or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the chemicals, CoC4H6O4, CoCl2, and CoSO4.They have been used in...

  7. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Cobaltous salts and its derivatives. 189.120... Generally Prohibited From Direct Addition or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the chemicals, CoC4H6O4, CoCl2, and CoSO4.They have been used in...

  8. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Cobaltous salts and its derivatives. 189.120... Generally Prohibited From Direct Addition or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the chemicals, CoC4H6O4, CoCl2, and CoSO4.They have been used in...

  9. 21 CFR 189.120 - Cobaltous salts and its derivatives.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Cobaltous salts and its derivatives. 189.120... Generally Prohibited From Direct Addition or Use as Human Food § 189.120 Cobaltous salts and its derivatives. (a) Cobaltous salts are the chemicals, CoC4H6O4, CoCl2, and CoSO4.They have been used in...

  10. Hot corrosion of low cobalt alloys

    NASA Technical Reports Server (NTRS)

    Stearns, C. A.

    1982-01-01

    The hot corrosion attack susceptibility of various alloys as a function of strategic materials content are investigated. Preliminary results were obtained for two commercial alloys, UDIMET 700 and Mar-M 247, that were modified by varying the cobalt content. For both alloys the cobalt content was reduced in steps to zero. Nickel content was increased accordingly to make up for the reduced cobalt but all other constituents were held constant. Wedge bar test samples were produced by casting. The hot corrosion test consisted of cyclically exposing samples to the high velocity flow of combustion products from an air-fuel burner fueled with jet A-1 and seeded with a sodium chloride aqueous solution. The flow velocity was Mach 0.5 and the sodium level was maintained at 0.5 ppm in terms of fuel plus air. The test cycle consisted of holding the test samples at 900 C for 1 hour followed by 3 minutes in which the sample could cool to room temperature in an ambient temperature air stream.

  11. Atomic layer deposition of metallic cobalt

    NASA Astrophysics Data System (ADS)

    Kwon, Jinhee; Saly, Mark; Kanjolia, Ravi; Chabal, Yves; University of Texas at Dallas Collaboration; SAFC Collaboration

    2011-03-01

    Metallic cobalt has rich catalytic, electronic and magnetic properties, which makes it critical to have a better control of Co thin film deposition for various applications. This work focuses on the atomic layer deposition (ALD) of cobalt using (tertiarybutylallyl)cobalttricarbonyl (t BuAllyl)Co(CO)3 and dimethylhydrazine (DMHy) on H-terminated Si to uncover the growth mechanisms. The first pulse of (t BuAllyl)Co(CO)3 reacts with surface H--Si bonds completely, forming one monolayer of metallic silicide. In situ infrared absorption spectra show that further deposition of Co is made possible only after linear carbonyl groups which remain after the first (t BuAllyl)Co(CO)3 pulse as the surface ligand are removed by subsequent ALD cycles. Further ALD cycles give rise to metallic Co growth through ligand exchange after a nucleation period of 8--10 cycles. The derived growth rate of cobalt is 0.6 +/- 0.1 Å/cycle. The resultant Co film shows low concentration of carbon and nitrogen impurities in the bulk according to X-ray photoemission spectroscopy.

  12. Development toxicity of cobalt in the rat

    SciTech Connect

    Paternain, J.L.; Domingo, J.L.; Corbella, J.

    1988-01-01

    To determine the potential developmental toxicity of cobalt, pregnant Sprague-Dawley rats were given by gavage a daily dose of 0, 25, 50, and 100 mg/kg cobalt(II) chloride on d 6-15 of gestation. Females were sacrificed on d 20. Maternal effects included significant reductions in weight gain and food consumption, particularly at 100 mk/kg x d. Hematocrit, hemoglobin concentration, mean corpuscular volume, mean corpuscular hemoglobin, and reticulocytes were increased significantly in the 100-mg/kg x d group. No treatment-related changes were recorded in the number of corpora lutea, total implants, resorptions, the number of live and dead fetuses, fetal size parameters, or fetal sex distribution data. Increased incidence of stunted fetuses per litter was the only adverse finding at 50 and 100 mg/kg x d group. However, this increase was not statistically significant. Examination of fetuses for gross external abnormalities, skeletal malformation, or ossification variations revealed that cobalt did not produce teratogenicity or significant fetotoxicity in the rat at doses as high as 100 mg/kg x d.

  13. Kinetics of cobalt cementation on zinc powder

    SciTech Connect

    Polcaro, A.M.; Palmas, S.; Dernini, S.

    1995-09-01

    The cementation process may be considered an interesting method to treat dilute solutions containing metal ions. The aim of the process may be either the removal of pollutant metals or the recovery of economically valuable metals such as Ag from spent photographic liquors. The kinetics of cobalt cementation on Zn powder from zinc sulfate concentrated solutions in the presence of copper and antimony ions was investigated in stirred tank reactors. The composition of the solutions was in the range usually utilized in industrial zinc electrowinning plants. The results showed that the reaction occurs by means of the formation of crystallization nuclei of noble metals on the zinc powder, followed by the cementation of cobalt ions on these newly-formed nuclei. Mass transfer to the reaction surface is shown to be the controlling step in copper and antimony reduction, and an equation correlating mass transfer coefficients has been determined. A kinetic equation, which interprets the influence of stirring speed and solution composition on cobalt cementation, has also been proposed.

  14. Fischer-Tropsch reaction studies with supported ruthenium catalysts

    SciTech Connect

    Everson, R.C.; Mulder, H. )

    1993-09-01

    An investigation was undertaken to examine the production of low molecular weight alkenes (C[sub 2][sup =] to C[sup =][sub 4]) and high molecular weight hydrocarbons (C[sub 5]+) from synthesis gas in a fixed bed reactor with supported ruthenium catalyst. The catalyst used consisted of 0.5% ruthenium on gamma-alumina with a 43% metal dispersion. An experimental reactor consisting of a single 12.5-mm-diameter stainless-steel tube with catalyst packings up to 1 m long, surrounded by an aluminium block with heating elements and an outer insulating ceramic block was used. The effect of temperature, synthesis gas composition (CO/H[sub 2]), weight hourly space velocity (WHSV), and bed length on carbon monoxide conversion and selectivity was examined and results are reported. The presence of secondary reactions consisting of hydrogenation and chain growth involving alkenes along the reactor bed was observed. These reactions favour the formation of alkanes and high molecular weight hydrocarbons. The alkene to alkane ratio in the product can be increased by restricting the hydrogenation reaction with the use of a synthesis gas mixture with a high carbon monoxide to hydrogen ratio.

  15. Multistate Switches: Ruthenium Alkynyl-Dihydroazulene/Vinylheptafulvene Conjugates.

    PubMed

    Vlasceanu, Alexandru; Andersen, Cecilie L; Parker, Christian R; Hammerich, Ole; Morsing, Thorbjørn J; Jevric, Martyn; Lindbaek Broman, Søren; Kadziola, Anders; Nielsen, Mogens Brøndsted

    2016-05-23

    Multimode molecular switches incorporating distinct and independently addressable functional components have potential applications as advanced switches and logic gates for molecular electronics and memory storage devices. Herein, we describe the synthesis and characterization of four switches based on the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermoswitch pair functionalized with the ruthenium-based Cp*(dppe)Ru ([Ru*]) metal complex (dppe=1,2-bis(diphenylphosphino)ethane; Cp*=pentamethylcyclopentadienyl). The [Ru*]-DHA conjugates can potentially exist in six different states accessible by alternation between DHA/VHF, Ru(II) /Ru(III) , and alkynyl/vinylidene, which can be individually stimulated by using light/heat, oxidation/reduction, and acid/base. Access to the full range of states was found to be strongly dependent on the electronic communication between the metal center and the organic photoswitch in these [Ru*]-DHA conjugates. Detailed electrochemical, spectroscopic (UV/Vis, IR, NMR), and X-ray crystallographic studies indeed reveal significant electronic interactions between the two moieties. When in direct conjugation, the ruthenium metal center was found to quench the photochemical ring-opening of DHA, which in one case could be restored by protonation or oxidation, allowing conversion to the VHF state. PMID:27114110

  16. Thiocyanate linkage isomerism in a ruthenium polypyridyl complex.

    PubMed

    Brewster, Timothy P; Ding, Wendu; Schley, Nathan D; Hazari, Nilay; Batista, Victor S; Crabtree, Robert H

    2011-12-01

    Ruthenium polypyridyl complexes have seen extensive use in solar energy applications. One of the most efficient dye-sensitized solar cells produced to date employs the dye-sensitizer N719, a ruthenium polypyridyl thiocyanate complex. Thiocyanate complexes are typically present as an inseparable mixture of N-bound and S-bound linkage isomers. Here we report the synthesis of a new complex, [Ru(terpy)(tbbpy)SCN][SbF(6)] (terpy = 2,2';6',2''-terpyridine, tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine), as a mixture of N-bound and S-bound thiocyanate linkage isomers that can be separated based on their relative solubility in ethanol. Both isomers have been characterized spectroscopically and by X-ray crystallography. At elevated temperatures the isomers equilibrate, the product being significantly enriched in the more thermodynamically stable N-bound form. Density functional theory analysis supports our experimental observation that the N-bound isomer is thermodynamically preferred, and provides insight into the isomerization mechanism. PMID:22066656

  17. Evolutionary algorithm based structure search for hard ruthenium carbides

    NASA Astrophysics Data System (ADS)

    Harikrishnan, G.; Ajith, K. M.; Chandra, Sharat; Valsakumar, M. C.

    2015-12-01

    An exhaustive structure search employing evolutionary algorithm and density functional theory has been carried out for ruthenium carbides, for the three stoichiometries Ru1C1, Ru2C1 and Ru3C1, yielding five lowest energy structures. These include the structures from the two reported syntheses of ruthenium carbides. Their emergence in the present structure search in stoichiometries, unlike the previously reported ones, is plausible in the light of the high temperature required for their synthesis. The mechanical stability and ductile character of all these systems are established by their elastic constants, and the dynamical stability of three of them by the phonon data. Rhombohedral structure ≤ft(R\\bar{3}m\\right) is found to be energetically the most stable one in Ru1C1 stoichiometry and hexagonal structure ≤ft( P\\bar{6}m2\\right) , the most stable in Ru3C1 stoichiometry. RuC-Zinc blende system is a semiconductor with a band gap of 0.618 eV while the other two stable systems are metallic. Employing a semi-empirical model based on the bond strength, the hardness of RuC-Zinc blende is found to be a significantly large value of ~37 GPa while a fairly large value of ~21GPa is obtained for the RuC-Rhombohedral system. The positive formation energies of these systems show that high temperature and possibly high pressure are necessary for their synthesis.

  18. Synthesis of cubic ruthenium nitride by reactive pulsed laser ablation

    NASA Astrophysics Data System (ADS)

    Moreno-Armenta, M. G.; Diaz, J.; Martinez-Ruiz, A.; Soto, G.

    2007-10-01

    The recent synthesis of platinum nitride opens the possibility of novel platinum-group metal nitrides to exist. In this work we report the synthesis of ruthenium nitride by reactive pulsed laser ablation. Several plausible structures have been evaluated by ab initio calculations using the full potential linearized augmented plane wave method, in order to investigate the ruthenium nitride structural and electronic properties. In fact, the predicted symmetry of stoichiometric RuN matches the experimental diffraction data. RuN crystallizes with NaCl-type structure at room temperature with cell-parameter somewhat larger than predicted by calculations. However we found a marginal chemical strength in these nitrides. The material is destroyed by mild acid and basic solutions. Under annealing RuN decomposes abruptly for temperatures beyond 100 °C. Since the thermal stability correlates directly with the mechanical properties our finding cast doubts than the latter transition metal nitrides can be ultra-hard materials at ambient conditions.

  19. Photoreactivity of a quantum dot-ruthenium nitrosyl conjugate.

    PubMed

    Franco, Lilian Pereira; Cicillini, Simone Aparecida; Biazzotto, Juliana Cristina; Schiavon, Marco A; Mikhailovsky, Alexander; Burks, Peter; Garcia, John; Ford, Peter C; da Silva, Roberto Santana

    2014-12-26

    We describe the use of cadmium telluride quantum dots (CdTe QDs) as antennas for the photosensitization of nitric oxide release from a ruthenium nitrosyl complex with visible light excitation. The CdTe QDs were capped with mercaptopropionic acid to make them water-soluble, and the ruthenium nitrosyl complex was cis-[Ru(NO)(4-ampy)(bpy)2](3+) (Ru-NO; bpy is 2,2'-bipyridine, and 4-ampy is 4-aminopyridine). Solutions of these two components demonstrated concentration-dependent quenching of the QD photoluminescence (PL) as well as photoinduced release of NO from Ru-NO when irradiated by 530 nm light. A NO release enhancement of ∼8 times resulting from this association was observed under longer wavelength excitation in visible light range. The dynamics of the quenching determined by both PL and transient absorption measurements were probed by ultrafast flash photolysis. A charge transfer mechanism is proposed to explain the quenching of the QD excited states as well as the photosensitized release of NO from Ru-NO. PMID:25405612

  20. New nitric oxide donors based on ruthenium complexes.

    PubMed

    Lunardi, C N; da Silva, R S; Bendhack, L M

    2009-01-01

    Nitric oxide (NO) donors produce NO-related activity when applied to biological systems. Among its diverse functions, NO has been implicated in vascular smooth muscle relaxation. Despite the great importance of NO in biological systems, its pharmacological and physiological studies have been limited due to its high reactivity and short half-life. In this review we will focus on our recent investigations of nitrosyl ruthenium complexes as NO-delivery agents and their effects on vascular smooth muscle cell relaxation. The high affinity of ruthenium for NO is a marked feature of its chemistry. The main signaling pathway responsible for the vascular relaxation induced by NO involves the activation of soluble guanylyl-cyclase, with subsequent accumulation of cGMP and activation of cGMP-dependent protein kinase. This in turn can activate several proteins such as K+ channels as well as induce vasodilatation by a decrease in cytosolic Ca2+. Oxidative stress and associated oxidative damage are mediators of vascular damage in several cardiovascular diseases, including hypertension. The increased production of the superoxide anion (O2-) by the vascular wall has been observed in different animal models of hypertension. Vascular relaxation to the endogenous NO-related response or to NO released from NO deliverers is impaired in vessels from renal hypertensive (2K-1C) rats. A growing amount of evidence supports the possibility that increased NO inactivation by excess O2- may account for the decreased NO bioavailability and vascular dysfunction in hypertension. PMID:19219301

  1. Cobalt Ions Improve the Strength of Epoxy Resins

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St. Clair, A. K.

    1986-01-01

    Technique developed for improving mechanical strength of epoxy resins by adding cobalt ions in form of tris(acetylacetonato)cobalt (III) complex. Solid cast disks prepared from cobalt ion-containing epoxy resins tested for flexural strength and stiffness. Incorporation of cobalt ions into epoxies increased flexural strength of resins by 10 to 95 percent. Suitable resins for this technique include any liquid or solid TGMDA resins. Improved epoxy formulation proves useful as composite matrix resin, adhesive, or casting resin for applications on commercial and advanced aircraft.

  2. Compact magnetooptical isolator with cobalt ferrite on silicon photonic circuits

    NASA Astrophysics Data System (ADS)

    Yanaga, Megumi; Shoji, Yuya; Takamura, Yota; Nakagawa, Shigeki; Mizumoto, Tetsuya

    2015-08-01

    In the telecom wavelength range, the magnetooptical effect of cobalt ferrites is approximately 10 times larger than that of conventional magnetooptical materials such as yttrium iron garnets. In this study, we focus on an application of cobalt ferrite to a magnetooptical isolator that is to be miniaturized and made suitable for integration. First, we prepare polycrystalline cobalt ferrite films deposited on a silicon substrate using a MgO buffer layer. Next, we fabricate a waveguide optical isolator of silicon waveguides by the partial deposition of the cobalt ferrite films. An optical isolation ratio of 5.5 dB is demonstrated.

  3. A novel ruthenium(II)-cobaloxime supramolecular complex for photocatalytic H2 evolution: Synthesis, characterisation, and mechanistic studies

    PubMed Central

    Cropek, Donald M.; Metz, Anja; Müller, Astrid M.; Gray, Harry B.; Horne, Toyketa; Horton, Dorothy C.; Poluektov, Oleg; Tiede, David M.; Weber, Ralph T.; Jarrett, William L.; Phillips, Joshua D.

    2012-01-01

    We report the synthesis and characterization of novel mixed-metal binuclear ruthenium(II)-cobalt(II) photocatalysts for hydrogen evolution in acidic acetonitrile. First, 2-(2′-pyridyl)benzothiazole (pbt), 1, was reacted with RuCl3·xH2O to produce [Ru(pbt)2Cl2] ·0.25CH3COCH3, 2, which was then reacted with 1,10-phenanthroline-5,6-dione (phendione), 3 in order to produce [Ru(pbt)2(phendione)](PF6)2·4H2O, 4. Compound 4 was then reacted with 4-pyridinecarboxaldehyde in order to produce [Ru(pbt)2(L-pyr)](PF6)2·9.5H2O, 5 (where L-pyr = (4-pyridine)oxazolo[4,5-f]phenanthroline). Compound 5 was then reacted with [Co(dmgBF2)2(H2O)2] (where dmgBF2 = difluorboryldimethylglyoximate) in order to produce the mixed-metal binuclear complex, [Ru(pbt)2(L-pyr)Co(dmgBF2)2(H2O)](PF6)2·11H2O·1.5CH3COCH3, 6. [Ru(Me2bpy)2(L-pyr)Co(dmgBF2)2(OH2)](PF6)2, 7 (where Me2bpy = 1,10-phenanthroline, 4,4′-dimethyl-2,2′-bipyridine) and [Ru(phen)2(L-pyr)Co(dmgBF2)2(OH2)](PF6)2, 8 were also synthesised. All complexes were characterized by elemental analysis, UV-visible absorption, 11B, 19F, and 59Co NMR, ESR spectroscopy, and cyclic voltammetry, where appropriate. Photocatalytic studies carried out in acidified acetonitrile demonstrated constant hydrogen generation longer than a 42 hour period as detected by gas chromatography. Time resolved spectroscopic measurements were performed on compound 6, which proved an intramolecular electron transfer from an excited Ru(II) metal centre to the Co(II) metal centre via the bridging L-pyr ligand. This resulted in the formation of a cobalt(I)-containing species that is essential for the production of H2 gas in the presence of H+ ions. A proposed mechanism for the generation of hydrogen is presented. PMID:23001132

  4. Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

    DOE PAGESBeta

    Zheng, Jie; Cullen, David A.; Forest, Robert V.; Wittkopf, Jarrid A.; Zhuang, Zhongbin; Zheng, Whenchao; Chen, Jingguang G.; Yan, Yushan

    2015-01-15

    The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-raymore » photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.« less

  5. Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

    SciTech Connect

    Zheng, Jie; Cullen, David A.; Forest, Robert V.; Wittkopf, Jarrid A.; Zhuang, Zhongbin; Zheng, Whenchao; Chen, Jingguang G.; Yan, Yushan

    2015-01-15

    The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-ray photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.

  6. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    DOEpatents

    Corbea, Javier Jesus Concepcion; Chen, Zoufeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2016-06-07

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  7. Platinum-ruthenium-palladium alloys for use as a fuel cell catalyst

    DOEpatents

    Gorer, Alexander

    2002-01-01

    A noble metal alloy composition for a fuel cell catalyst, a ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

  8. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  9. Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  10. Preparation and characterization of titanium dioxide nanotube array supported hydrated ruthenium oxide catalysts

    NASA Astrophysics Data System (ADS)

    Giang, Thi Phuong Ly; Tran, Thi Nhu Mai; Le, Xuan Tuan

    2012-03-01

    This work aimed at preparing and characterizing TiO2 nanotube supported hydrated ruthenium oxide catalysts. First of all, we succeeded in preparing TiO2 nanotube arrays by electrochemical anodization of titanium metal at 20 V for 8 h in a 1M H3PO4+0.5 wt% HF solution as evidenced from scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) results. The hydrated ruthenium oxide was then deposited onto TiO2 nanotubes by consecutive exchange of protons by Ru3+ ions, followed by formation of hydrated oxide during the alkali treatment. Further XPS measurements showed that the modified samples contain not only hydrated ruthenium oxide but also hydrated ruthenium species Ru(III)-OH.

  11. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    DOEpatents

    Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

    2014-10-28

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  12. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    DOEpatents

    Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2013-09-03

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  13. CuAAC click reactions for the design of multifunctional luminescent ruthenium complexes.

    PubMed

    Zabarska, Natalia; Stumper, Anne; Rau, Sven

    2016-02-01

    CuAAC (Cu(i) catalyzed azide-alkyne cycloaddition) click chemistry has emerged as a versatile tool in the development of photoactive ruthenium complexes with multilateral potential applicability. In this contribution we discuss possible synthetic approaches towards CuAAC reactions with ruthenium(ii) polypyridine complexes and their differences with respect to possible applications. We focus on two main application possibilities of the click-coupled ruthenium assemblies. New results within the development of ruthenium based photosensitizers for the field of renewable energy supply, i.e. DSSCs (dye-sensitized solar cells) and artificial photocatalysis for the production of hydrogen, or for anticancer photodynamic therapeutic applications are reviewed. PMID:26758682

  14. Dendrimer-Encapsulated Ruthenium Nanoparticles as Catalysts for Lithium-O2 Batteries

    SciTech Connect

    Bhattacharya, Priyanka; Nasybulin, Eduard N.; Engelhard, Mark H.; Kovarik, Libor; Bowden, Mark E.; Li, Shari; Gaspar, Daniel J.; Xu, Wu; Zhang, Jiguang

    2014-12-01

    Dendrimer-encapsulated ruthenium nanoparticles (DEN-Ru) have been used as catalysts in lithium-O2 batteries for the first time. Results obtained from UV-vis spectroscopy, electron microscopy and X-ray photoelectron spectroscopy show that the nanoparticles synthesized by the dendrimer template method are ruthenium oxide instead of metallic ruthenium reported earlier by other groups. The DEN-Ru significantly improve the cycling stability of lithium (Li)-O2 batteries with carbon black electrodes and decrease the charging potential even at low catalyst loading. The monodispersity, porosity and large number of surface functionalities of the dendrimer template prevent the aggregation of the ruthenium nanoparticles making their entire surface area available for catalysis. The potential of using DEN-Ru as stand-alone cathode materials for Li-O2 batteries is also explored.

  15. Improving Grubbs' II type ruthenium catalysts by appropriately modifying the N-heterocyclic carbene ligand.

    PubMed

    Vieille-Petit, Ludovic; Luan, Xinjun; Gatti, Michele; Blumentritt, Sascha; Linden, Anthony; Clavier, Hervé; Nolan, Steven P; Dorta, Reto

    2009-07-01

    The introduction of N-heterocyclic carbene ligands that incorporate correctly substituted naphthyl side chains leads to increased activity and stability in second generation ruthenium metathesis catalysts. PMID:19557281

  16. Effects of ruthenium seed layer on the microstructure and spin dynamics of thin permalloy films

    NASA Astrophysics Data System (ADS)

    Jin, Lichuan; Zhang, Huaiwu; Tang, Xiaoli; Bai, Feiming; Zhong, Zhiyong

    2013-02-01

    The spin dynamics and microstructure properties of a sputtered 12 nm Ni81Fe19 thin film have been enhanced by the use of a ruthenium seed layer. Both the ferromagnetic resonance field and linewidth are enhanced dramatically as the thickness of ruthenium seed layer is increased. The surface anisotropy energy constant can also be largely tailored from 0.06 to 0.96 erg/cm-2 by changing the seed layer thickness. The changes to the dynamics magnetization properties are caused by both ruthenium seed layer induced changes in the Ni81Fe19 structure properties and surface topography properties. Roughness induced inhomogeneous linewidth broadening is also seen. The damping constant is highly tunable via the ruthenium thickness. This approach can be used to tailor both the structure and spin dynamic properties of thin Ni81Fe19 films over a wide range. And it may benefit the applications of spin dynamics and spin current based devices.

  17. Ruthenium nanocrystals as cathode catalysts for lithium-oxygen batteries with a superior performance

    PubMed Central

    Sun, Bing; Munroe, Paul; Wang, Guoxiu

    2013-01-01

    The key factor to improve the electrochemical performance of Li-O2 batteries is to find effective cathode catalysts to promote the oxygen reduction and oxygen evolution reactions. Herein, we report the synthesis of an effective cathode catalyst of ruthenium nanocrystals supported on carbon black substrate by a surfactant assisting method. The as-prepared ruthenium nanocrystals exhibited an excellent catalytic activity as cathodes in Li-O2 batteries with a high reversible capacity of about 9,800 mAh g−1, a low charge-discharge over-potential (about 0.37 V), and an outstanding cycle performance up to 150 cycles (with a curtaining capacity of 1,000 mAh g−1). The electrochemical testing shows that ruthenium nanocrystals can significantly reduce the charge potential comparing to carbon black catalysts, which demonstrated that ruthenium based nanomaterials could be effective cathode catalysts for high performance lithium- O2 batteries. PMID:23873349

  18. Characterization of Palladium and Ruthenium after Reaction with Tetraphenylborate and Mercury

    SciTech Connect

    Duff, M.C.

    2001-09-11

    This report documents a second series of X-ray fine structure and chemical analyses to examine the form that Pd - and, to a lesser extent, ruthenium (Ru) - takes in simulated high-level slurries containing TPB salts.

  19. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    DOEpatents

    Pierantozzi, R.

    1985-04-02

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  20. Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

    DOEpatents

    Pierantozzi, R.

    1985-04-09

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  1. An electrochemical evaluation of ruthenium-based electrocatalysts for oxygen evolution

    NASA Astrophysics Data System (ADS)

    Valdez, Thomas I.

    A study of ruthenium oxide-based oxygen evolution catalysts for use in proton exchange membrane (PEM) electrolyzers was performed. In this work, oxygen evolution catalysts were fabricated via sol-gel, high energy ball milling, and thermal processing techniques. Thermal analysis techniques such as differential scanning calorimetry (DSC), differential thermal analysis (DTA), and thermal gravimetric analysis (TGA) were used to determine the optimum processing temperatures to be used for catalysts fabrication and annealing. The materials properties of the catalysts were studied with scanning electron microscopy, energy dispersive analysis (EDAX), X-ray diffraction, and X-ray photo-electron spectroscopy. Electrodes were fabricated from the oxygen evolution catalysts and tested in electrolysis and three-electrode cells. The catalysts fabricated via sol-gel techniques included a ruthenium oxide and an iridium-ruthenium oxide catalyst. Three families of the thermally processed catalysts were developed: iridium-ruthenium oxide, lead-ruthenium oxide, and tin ruthenium oxide. A lead oxide: ruthenium oxide catalyst was fabricated via high energy ball-milling to be used as a fabrication comparison to the thermally processed catalysts. The electrochemical evaluations for the oxygen evolution catalysts fabricated as electrolysis cells included current-step polarization and constant current electrolysis. The current step polarization experiments were used to determine the relative performance of the catalysts as well as to determine the kinetic parameters for the oxygen evolution reaction. The constant-current electrolysis experiments were used to estimate the degradation of the catalysts during operation. In these studies, it was determined that the thermal processing technique could produce stable and high performing catalysts. The thermally processed iridium ruthenium oxide catalysts with 9 to 12 mole percent iridium had the lowest overpotential for oxygen evolution of the

  2. Solvent extraction of cobalt from laterite-ammoniacal leach liquors

    SciTech Connect

    Nilsen, D.N.; Siemens, R.E.; Rhoads, S.C.

    1980-01-01

    The Bureau of Mines is developing a method to recover Ni, Co, and Cu from laterites containing less than 1.2% Ni and 0.25% Co. The method consists of the following basic unit operations: (1) reduction roasting, (2) leaching, (3) solvent extraction, and (4) electrowinning. The method reflects three Bureau of Mines objectives: (1) recovery of critical minerals that are domestically in short supply from low-grade domestic laterites, (2) lower processing energy requirements, and (3) solution recycling. This report deals with the extraction of cobalt and the preparation of a suitable cobalt electrolyte by solvent extraction from liquor produced by this method. Nickel and copper are coextracted with LIX64N from an ammoniacal ammonium sulfate leach liquor containing about 1.00 g/1 Ni, 0.30 g/1 Co, 0.03 g/1 Cu, and 0.02 g/1 Zn. Cobalt (III) in the nickel-copper barren raffinate is reduced to cobalt (II) with cobalt metal. Reduction of cobalt (III) to cobalt (II) greatly aids subsequent extraction. Commercially available XI-51 extracts about 94% of the cobalt from the treated raffinate in one stage in a laboratory mixer-settler continuous circuit. Ammonia loaded on the solvent is removed in two washing steps. About 94% of the cobalt then is stripped from the XI-51 in one stage with spent cobalt electrolyte containing about 77 g/1 Co and 18 g/1 sulfuric acid (H/sub 2/SO/sub 4/). Electrolytes containing less H/sub 2/SO/sub 4/ also may be used. Preliminary data indicate that coextracted zinc may be removed from pregnant cobalt electrolyte containing 3 g/1 or less H/sub 2/SO/sub 4/ with di-(2 ethylhexyl) phosphoric acid (D2EHPA).

  3. Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

    DOEpatents

    Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

    2001-01-01

    An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

  4. Photochemical generation and kinetic studies of a putative porphyrin-ruthenium(V)-oxo species

    PubMed Central

    Zhang, Rui; Vanover, Eric; Luo, Weilong; Newcomb, Martin

    2014-01-01

    Photo-disproportionation of a bis-porphyrin-diruthenium(IV) μ-oxo dimer gave a porphyrin-ruthenium(III) species and a putative poprhyrin-ruthenium(V)-oxo species that can be detected and studied in real time via laser flash photolysis methods. As determined by its spectral and kinetic behavior, the same oxo transient was also formed by photolysis of a porphyrin-ruthenium(III) N-oxide adduct. Second-order rate constants for reactions with several substrates at 22 °C were determined; representative values of rate constants were kox = 6.6 × 103 M−1 s−1 for diphenylmethanol, kox = 2.5 × 103 M−1 s−1 for styrene, and kox = 1.8 × 103 M−1 s−1 for cyclohexene. The putative porphyrin-ruthenium(V)-oxo transient reacted 5–6 orders of magnitude faster than the corresponding trans-dioxoruthenium(VI)-oxo porphyrins, and the rate constants obtained in this work were similar to those of corrole-iron(V)-oxo derivative. The high reactivity for the photochemically generated ruthenium-oxo species in comparison to other poprhyrin-metal-oxo intermediates suggests it is a true ruthenium(V)-oxo species. PMID:24770388

  5. Carbon nanotubes dispersed in aqueous solution by ruthenium(ii) polypyridyl complexes.

    PubMed

    Huang, Kewei; Saha, Avishek; Dirian, Konstantin; Jiang, Chengmin; Chu, Pin-Lei E; Tour, James M; Guldi, Dirk M; Martí, Angel A

    2016-07-21

    Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs. These studies show that the photoluminescence of both, that is, of the ruthenium complexes and of SWCNTs, are quenched when they interact with each other. Pump-probe transient absorption experiments were performed to shed light onto the nature of the photoluminescence quenching, showing carbon nanotube-based bands with picosecond lifetimes, but no new bands which could be unambigously assigned to photoinduced charge transfer process. Thus, from the spectroscopic data, we conclude that quenching of the photoluminescence of the ruthenium complexes is due to energy transfer to proximal SWCNTs. PMID:27353007

  6. Corrosion Investigations of Ruthenium in Potassium Periodate Solutions Relevant for Chemical Mechanical Polishing

    NASA Astrophysics Data System (ADS)

    Cheng, Jie; Wang, Tongqing; Pan, Jinshan; Lu, Xinchun

    2016-05-01

    Ruthenium is the most promising material for the barrier layer used for the sub 14 nm technology node in integrated circuits manufacturing. Potassium periodate (KIO4)-based slurry is used in the chemical mechanical planarization (CMP) process of the barrier layer. However, the electrochemical and corrosion properties of ruthenium have not been investigated in such slurry. In this paper, the electrochemical and corrosion behaviors of ruthenium in KIO4 solutions were investigated under static conditions but at different pH values by potentiodynamic polarization and electrochemical impedance spectroscopy measurements, combined with surface chemical analysis using auger electron spectroscopy. Moreover, to study wear enhanced corrosion during CMP, tribocorrosion experiments were carried out to monitor the current density changes during and after mechanical scratching. The results show that at pH 6, ruthenium forms a relatively thick and heterogeneous surface film composed of RuO2·2H2O/RuO3, showing a high corrosion resistance and it exhibits a quick repassivation after mechanical scratching. At pH 4, ruthenium shows a passivation behavior with formation of a uniform and conductive oxide like RuO2·2H2O. It should be noted that there is a possible formation of RuO4 toxic gas under this condition, which should be avoided in the actual production. However, at pH 11, ruthenium exhibits no considerable passivity and the corrosion proceeds uniformly.

  7. Corrosion Investigations of Ruthenium in Potassium Periodate Solutions Relevant for Chemical Mechanical Polishing

    NASA Astrophysics Data System (ADS)

    Cheng, Jie; Wang, Tongqing; Pan, Jinshan; Lu, Xinchun

    2016-08-01

    Ruthenium is the most promising material for the barrier layer used for the sub 14 nm technology node in integrated circuits manufacturing. Potassium periodate (KIO4)-based slurry is used in the chemical mechanical planarization (CMP) process of the barrier layer. However, the electrochemical and corrosion properties of ruthenium have not been investigated in such slurry. In this paper, the electrochemical and corrosion behaviors of ruthenium in KIO4 solutions were investigated under static conditions but at different pH values by potentiodynamic polarization and electrochemical impedance spectroscopy measurements, combined with surface chemical analysis using auger electron spectroscopy. Moreover, to study wear enhanced corrosion during CMP, tribocorrosion experiments were carried out to monitor the current density changes during and after mechanical scratching. The results show that at pH 6, ruthenium forms a relatively thick and heterogeneous surface film composed of RuO2·2H2O/RuO3, showing a high corrosion resistance and it exhibits a quick repassivation after mechanical scratching. At pH 4, ruthenium shows a passivation behavior with formation of a uniform and conductive oxide like RuO2·2H2O. It should be noted that there is a possible formation of RuO4 toxic gas under this condition, which should be avoided in the actual production. However, at pH 11, ruthenium exhibits no considerable passivity and the corrosion proceeds uniformly.

  8. A selective, long-lived deep-red emissive ruthenium(II) polypyridine complexes for the detection of BSA

    NASA Astrophysics Data System (ADS)

    Babu, Eththilu; Muthu Mareeswaran, Paulpandian; Singaravadivel, Subramanian; Bhuvaneswari, Jayaraman; Rajagopal, Seenivasan

    2014-09-01

    A selective, label free luminescence sensor for bovine serum albumin (BSA) is investigated using ruthenium(II) complexes over the other proteins. Interaction between BSA and ruthenium(II) complexes has been studied using absorption, emission, excited state lifetime and circular dichroism (CD) spectral techniques. The luminescence intensity of ruthenium(II) complexes (I and II), has enhanced at 602 and 613 nm with a large hypsochromic shift of 18 and 5 nm respectively upon addition of BSA. The mode of binding of ruthenium(II) complexes with BSA has analyzed using computational docking studies.

  9. The role of cobalt on the creep of Waspaloy

    NASA Technical Reports Server (NTRS)

    Jarrett, R. N.; Chin, L.; Tien, J. K.

    1984-01-01

    Cobalt was systematically replaced with nickel in Waspaloy (which normally contains 13% Co) to determine the effects of cobalt on the creep behavior of this alloy. Effects of cobalt were found to be minimal on tensile strengths and microstructure. The creep resistance and the stress rupture resistance determined in the range from 704 to 760 C (1300 to 1400 C) were found to decrease as cobalt was removed from the standard alloy at all stresses and temperatures. Roughly a ten-fold drop in rupture life and a corresponding increase in minimum creep rate were found under all test conditions. Both the apparent creep activation energy and the matrix contribution to creep resistance were found to increase with cobalt. These creep effects are attributed to cobalt lowering the stacking fault energy of the alloy matrix. The creep resistance loss due to the removal of cobalt is shown to be restored by slightly increasing the gamma' volume fraction. Results are compared to a previous study on Udimet 700, a higher strength, higher gamma' volume fraction alloy with similar phase chemistry, in which cobalt did not affect creep resistance. An explanation for this difference in behavior based on interparticle spacing and cross-slip is presented.

  10. Microwave Mapping Demonstration Using the Thermochromic Cobalt Chloride Equilibrium

    ERIC Educational Resources Information Center

    Nguyen, Vu D.; Birdwhistell, Kurt R.

    2014-01-01

    An update to the thermochromic cobalt(II) chloride equilibrium demonstration is described. Filter paper that has been saturated with aqueous cobalt(II) chloride is heated for seconds in a microwave oven, producing a color change. The resulting pink and blue map is used to colorfully demonstrate Le Châtelier's principle and to illuminate the…

  11. [The cobalt lung in diamond cutters: a new disease].

    PubMed

    Demedts, M; Gyselen, A

    1989-01-01

    Although for forty years already broncho-pulmonary pathology has been described in workers exposed to hard-metal (i.e. alloys of tungsten carbide and cobalt) and although cobalt is considered the offending agent of this hazard, these abnormalities have almost not been found after exposure to cobalt alone except in animal experiments. Recently we detected clearcut broncho-pulmonary pathology in 48 diamond polishers (i.e. nearly 1% of those exposed) attributable to the ultrafine cobalt dust from the cutting surface of polishing disks, in which it was used as a cementing matrix for microdiamonds without any tungsten carbide. Nineteen of these patients presented with a fibrosing alveolitis documented in 6 by lung biopsy and in 12 by broncho-alveolar lavage, both of which revealed characteristic multinucleated giant cells. Thirteen suffered from asthma of occupational origin, in 9 proven by cobalt-inhalation tests, and in 5 by peak flow measurements at the workplace. Sixteen had mixed bronchial and alveolar pathology or were incompletely documented. A cross-sectional study in about 200 diamond polishers showed a significant correlation between exposure to cobalt and decrease in lung function. The strikingly harmful effects of cobalt can be explained by the chronic exposure to very small particles with markedly increased solubility. The pathogenesis of the broncho-pulmonary pathology may be attributed to the cytotoxic as well as to the sensitising (i.e. allergic and/or idiosyncratic) actions of cobalt. PMID:2561412

  12. Effect of cobalt on Escherichia coli metabolism and metalloporphyrin formation

    PubMed Central

    Majtan, Tomas; Frerman, Frank E.

    2011-01-01

    Toxicity in Escherichia coli resulting from high concentrations of cobalt has been explained by competition of cobalt with iron in various metabolic processes including Fe–S cluster assembly, sulfur assimilation, production of free radicals and reduction of free thiol pool. Here we present another aspect of increased cobalt concentrations in the culture medium resulting in the production of cobalt protoporphyrin IX (CoPPIX), which was incorporated into heme proteins including membrane-bound cytochromes and an expressed human cystathionine beta-synthase (CBS). The presence of CoPPIX in cytochromes inhibited their electron transport capacity and resulted in a substantially decreased respiration. Bacterial cells adapted to the increased cobalt concentration by inducing a modified mixed acid fermentative pathway under aerobiosis. We capitalized on the ability of E. coli to insert cobalt into PPIX to carry out an expression of CoPPIX-substituted heme proteins. The level of CoPPIX-substitution increased with the number of passages of cells in a cobalt-containing medium. This approach is an inexpensive method to prepare cobalt-substituted heme proteins compared to in vitro enzyme reconstitution or in vivo replacement using metalloporphyrin heme analogs and seems to be especially suitable for complex heme proteins with an additional coenzyme, such as human CBS. PMID:21184140

  13. Potential for cobalt recovery from lateritic ores in Europe

    NASA Astrophysics Data System (ADS)

    Herrington, R.

    2012-04-01

    Cobalt is one of the 'critical metals' identified under the EU Raw Materials Initiative. Annually the global mine production of cobalt is around 55,000 tonnes,with Europe's industries consuming around 30% of that figure. Currently Europe produces around 27 tonnes of cobalt from mines in Finland although new capacity is planned. Co-bearing nickel laterite ores being mined in Greece, Macedonia and Kosovo where the cobalt is currently not being recovered (ores have typical analyses of 0.055% Co and >1% Ni,). These ores are currently treated directly in pyrometallurgical plants to recover the contained nickel and this process means there is no separate cobalt product produced. Hydrometallurgical treatment of mineralogically suitable laterite ores can recover the cobalt; for example Cuba recovers 3,500 tonnes of cobalt from its laterite mining operations, which are of a similar scale to the current European operations. Implementation of hydrometallurgical techniques is in its infancy in Europe with one deposit in Turkey planning to use atmospheric heap leaching to recover nickel and copper from oxide-dominated ores. More widespread implementation of these methods to mineralogically suitable ore types could unlock the highly significant undeveloped resources (with metal contents >0.04% Co and >1% Ni), which have been defined throughout the Balkans eastwards into Turkey. At a conservative estimate, this region has the potential to supply up to 30% of the EU cobalt requirements.

  14. Experimental evaluation of cobalt behavior on BWR fuel rod surface

    SciTech Connect

    Karasawa, H.; Asakura, Y.; Sakagami, M.; Uchida, S. )

    1988-06-01

    Cobalt behavior on the boiling water reactor (BWR) fuel rod surface was experimentally evaluated at 285 C and with various pH values. Adsorption of cobalt ions on hematite particles proceeded via the exchange reaction of cobalt ion with the surface hydroxyl of the hematite. The equilibrium constant for the adsorption at 285 C was found to be -- 570 times as large as that at 20 C. The adsorbate formed cobalt ferrite at the rate of 3.4 x 10/sup -2/ g-Co/g-Co adsorbed/h. The dissolution rates of cobalt ferrite and cobalt oxide particles were found to depend on (H/sup -/)/sup 1.1/ and (H/sup -/)/sup 1.2/, respectively, where (H/sup -/) means the H/sup -/ concentration. Cobalt ions were released from these oxides when O/sup 2-/ ions in them combined with two aqueous protons to form water at the oxide-water interface. Cobalt behavior on the fuel rod surface under BWR conditions was discussed using the experimental results.

  15. Comparative toxicity and carcinogenicity of soluble and insoluble cobalt compounds.

    PubMed

    Behl, Mamta; Stout, Matthew D; Herbert, Ronald A; Dill, Jeffrey A; Baker, Gregory L; Hayden, Barry K; Roycroft, Joseph H; Bucher, John R; Hooth, Michelle J

    2015-07-01

    Occupational exposure to cobalt is of widespread concern due to its use in a variety of industrial processes and the occurrence of occupational disease. Due to the lack of toxicity and carcinogenicity data following exposure to cobalt, and questions regarding bioavailability following exposure to different forms of cobalt, the NTP conducted two chronic inhalation exposure studies in rats and mice, one on soluble cobalt sulfate heptahydrate, and a more recent study on insoluble cobalt metal. Herein, we compare and contrast the toxicity profiles following whole-body inhalation exposures to these two forms of cobalt. In general, both forms were genotoxic in the Salmonella T98 strain in the absence of effects on micronuclei. The major sites of toxicity and carcinogenicity in both chronic inhalation studies were the respiratory tract in rats and mice, and the adrenal gland in rats. In addition, there were distinct sites of toxicity and carcinogenicity noted following exposure to cobalt metal. In rats, carcinogenicity was observed in the blood, and pancreas, and toxicity was observed in the testes of rats and mice. Taken together, these findings suggest that both forms of cobalt, soluble and insoluble, appear to be multi-site rodent carcinogens following inhalation exposure. PMID:25896363

  16. Iron-, Cobalt-, and Nickel-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric Hydrogenation of Ketones.

    PubMed

    Li, Yan-Yun; Yu, Shen-Luan; Shen, Wei-Yi; Gao, Jing-Xing

    2015-09-15

    Chiral alcohols are important building blocks in the pharmaceutical and fine chemical industries. The enantioselective reduction of prochiral ketones catalyzed by transition metal complexes, especially asymmetric transfer hydrogenation (ATH) and asymmetric hydrogenation (AH), is one of the most efficient and practical methods for producing chiral alcohols. In both academic laboratories and industrial operations, catalysts based on noble metals such as ruthenium, rhodium, and iridium dominated the asymmetric reduction of ketones. However, the limited availability, high price, and toxicity of these critical metals demand their replacement with abundant, nonprecious, and biocommon metals. In this respect, the reactions catalyzed by first-row transition metals, which are more abundant and benign, have attracted more and more attention. As one of the most abundant metals on earth, iron is inexpensive, environmentally benign, and of low toxicity, and as such it is a fascinating alternative to the precious metals for catalysis and sustainable chemical manufacturing. However, iron catalysts have been undeveloped compared to other transition metals. Compared with the examples of iron-catalyzed asymmetric reduction, cobalt- and nickel-catalyzed ATH and AH of ketones are even seldom reported. In early 2004, we reported the first ATH of ketones with catalysts generated in situ from iron cluster complex and chiral PNNP ligand. Since then, we have devoted ourselves to the development of ATH and AH of ketones with iron, cobalt, and nickel catalysts containing novel chiral aminophosphine ligands. In our study, the iron catalyst containing chiral aminophosphine ligands, which are expected to control the stereochemistry at the metal atom, restrict the number of possible diastereoisomers, and effectively transfer chiral information, are successful catalysts for enantioselective reduction of ketones. Among these novel chiral aminophosphine ligands, 22-membered macrocycle P2N4

  17. Cobalt ferrite nanoparticles under high pressure

    SciTech Connect

    Saccone, F. D.; Ferrari, S.; Grinblat, F.; Bilovol, V.; Errandonea, D.

    2015-08-21

    We report by the first time a high pressure X-ray diffraction and Raman spectroscopy study of cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles carried out at room temperature up to 17 GPa. In contrast with previous studies of nanoparticles, which proposed the transition pressure to be reduced from 20–27 GPa to 7.5–12.5 GPa (depending on particle size), we found that cobalt ferrite nanoparticles remain in the spinel structure up to the highest pressure covered by our experiments. In addition, we report the pressure dependence of the unit-cell parameter and Raman modes of the studied sample. We found that under quasi-hydrostatic conditions, the bulk modulus of the nanoparticles (B{sub 0} = 204 GPa) is considerably larger than the value previously reported for bulk CoFe{sub 2}O{sub 4} (B{sub 0} = 172 GPa). In addition, when the pressure medium becomes non-hydrostatic and deviatoric stresses affect the experiments, there is a noticeable decrease of the compressibility of the studied sample (B{sub 0} = 284 GPa). After decompression, the cobalt ferrite lattice parameter does not revert to its initial value, evidencing a unit cell contraction after pressure was removed. Finally, Raman spectroscopy provides information on the pressure dependence of all Raman-active modes and evidences that cation inversion is enhanced by pressure under non-hydrostatic conditions, being this effect not fully reversible.

  18. Spatial electrochromism in metallopolymeric films of ruthenium polypyridyl complexes

    SciTech Connect

    Leasure, R.M.; Ou, Wei; Moss, J.A.; Linton, R.W.

    1996-01-01

    Electropolymerized thin films of of poly[Ru(vbpy){sub 2}(py){sub 2}]{sup 2+} (vbpy is 4-vinyl-4{prime}-methyl-2,2{prime}-methyl-2,2{prime}-bipyridine; py is pyridine) were prepared. Photolysis of the films in the presence of chloride ion leads to photochemical substitution of Cl{sup -} for pyridine ligands, the structures of which were confirmed by small spot XPS. The absorption spectra and redox potentials of the ruthenium complexes were altered upon substitution of chloride for the pyridine ligands, suggesting the potential for using these materials to fabricate electrochromic film assemblies on optically transparent electrodes. The spectroelectrochemical response of the films was measured. 47 refs., 14 figs., 4 tabs.

  19. Similar Biological Activities of Two Isostructural Ruthenium and Osmium Complexes

    SciTech Connect

    Maksimoska,J.; Williams, D.; Atilla-Gokcumen, G.; Smalley, K.; Carroll, P.; Webster, R.; Filippakopoulos, P.; Knapp, S.; Herlyn, M.; Meggers, E.

    2008-01-01

    In this study, we probe and verify the concept of designing unreactive bioactive metal complexes, in which the metal possesses a purely structural function, by investigating the consequences of replacing ruthenium in a bioactive half-sandwich kinase inhibitor scaffold by its heavier congener osmium. The two isostructural complexes are compared with respect to their anticancer properties in 1205?Lu melanoma cells, activation of the Wnt signaling pathway, IC50 values against the protein kinases GSK-3? and Pim-1, and binding modes to the protein kinase Pim-1 by protein crystallography. It was found that the two congeners display almost indistinguishable biological activities, which can be explained by their nearly identical three-dimensional structures and their identical mode of action as protein kinase inhibitors. This is a unique example in which the replacement of a metal in an anticancer scaffold by its heavier homologue does not alter its biological activity.

  20. Hydrogen adsorption of ruthenium: Isosteres of solubility of adsorbed hydrogen

    SciTech Connect

    Zaginaichenko, S.Y.; Matysina, Z.A.; Schur, D.V.; Pishuk, V.K.

    1998-12-31

    The theoretical investigation of solubility isosteres of adsorbed hydrogen has been performed for free face (0001) of crystals with hexagonal close-packed lattice A3 of Mg type. The face free energy has been calculated and its dependence on temperature, pressure, hydrogen concentration and character of hydrogen atoms distribution over surface interstitial sites of different type has been defined. The equations of thermodynamic equilibrium and solubility of adsorbed hydrogen have been defined. The plots of isosteres in the region of phase transition from isotropic to anisotropic state have been constructed and it has been established that in anisotropic state the order in distribution of hydrogen atoms over interstitial sites of different type must become apparent. Comparison of the theoretical isosteres with experimental for ruthenium has been carried out, the isotropic-anisotropic state transition can stipulate a stepwise and break-like change in isosteres.

  1. Platinum adlayered ruthenium nanoparticles, method for preparing, and uses thereof

    DOEpatents

    Tong, YuYe; Du, Bingchen

    2015-08-11

    A superior, industrially scalable one-pot ethylene glycol-based wet chemistry method to prepare platinum-adlayered ruthenium nanoparticles has been developed that offers an exquisite control of the platinum packing density of the adlayers and effectively prevents sintering of the nanoparticles during the deposition process. The wet chemistry based method for the controlled deposition of submonolayer platinum is advantageous in terms of processing and maximizing the use of platinum and can, in principle, be scaled up straightforwardly to an industrial level. The reactivity of the Pt(31)-Ru sample was about 150% higher than that of the industrial benchmark PtRu (1:1) alloy sample but with 3.5 times less platinum loading. Using the Pt(31)-Ru nanoparticles would lower the electrode material cost compared to using the industrial benchmark alloy nanoparticles for direct methanol fuel cell applications.

  2. Exfoliated graphite-ruthenium oxide composite electrodes for electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Mitra, Sagar; Lokesh, K. S.; Sampath, S.

    The performance of exfoliated graphite (EG)-ruthenium oxide (RuO x) composites as binderless electrodes is evaluated for electrochemical capacitors (ECs). A composite of EG-RuO x is prepared by a modified sol-gel process. The material is characterized using X-ray diffraction and microscopy. Electrochemical capacitors with the composite electrodes in the presence of aqueous sulfuric acid (H 2SO 4) electrolyte are evaluated using voltammetry, impedance and charge-discharge studies. Cyclic voltammetry reveals very stable current-voltage behaviour up to several thousands of cycles, as well as high specific capacitances, e.g., a few hundreds of farads per gram for the composite that contains 16.5 wt.% RuO x.

  3. Ruthenium-Catalyzed Regioselective 1,4-Hydroboration of Pyridines.

    PubMed

    Kaithal, Akash; Chatterjee, Basujit; Gunanathan, Chidambaram

    2016-07-15

    Simple ruthenium precursor [Ru(p-cymene)Cl2]2 1 catalyzed regioselective 1,4-dearomatization of pyridine derivatives using pinacolborane is reported. Two catalytic intermediates, [Ru(p-cymene)Cl2Py] 2 and [Ru(p-cymene)Cl2(P(Cy)3)] 3, involved in this process are identified, independently synthesized, characterized, and further used directly as effective catalysts; two more catalytic intermediates [Ru(p-cymene)Cl2(Py)(P(Cy)3)] 4 and [Ru(p-cymene)(H)Cl(Py)(P(Cy)3)] 5 are identified in solution. Complex 5 is the active catalytic intermediate. An intramolecular selective 1,5-hydride transfer in 5 leading to the regioselective 1,4-hydroboration of pyridine compounds is proposed. PMID:27351256

  4. Gas-phase reactivity of ruthenium carbonyl cluster anions.

    PubMed

    Henderson, Matthew A; Kwok, Samantha; McIndoe, J Scott

    2009-04-01

    Partially-ligated anionic ruthenium carbonyl clusters react with alkenes, arenes, and alkanes in the gas phase; the products undergo extensive C-H activation and lose dihydrogen and carbon monoxide under collision-induced dissociation conditions. Triethylsilane and phenylsilane are also reactive towards the unsaturated clusters, and oxygen was shown to rapidly break down the cluster core by oxidative cleavage of the metal-metal bonds. These qualitative gas-phase reactivity studies were conducted using an easily-installed and inexpensive modification of a commercial electrospray ionization mass spectrometer. Interpretation of the large amounts of data generated in these studies is made relatively straightforward by employing energy-dependent electrospray ionization mass spectrometry (EDESI-MS). PMID:19185511

  5. Photophysical properties of monomeric and oligomeric ruthenium (II) porphyrins

    NASA Astrophysics Data System (ADS)

    Ikonen, Marjo; Guez, David; Marvaud, Valérie; Markovitsi, Dimitra

    1994-12-01

    The present Letter deals with three ruthenium(II) porphyrins: RuTBP(CO) (EtOH), RuTBP(pyz) 2 and [RuTBP(pyz)] n where TBP = tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl) porphyrin, EtOH = ethanol and pyz = pyrazine. Their photophysical properties are studied by steady-state and time-resolved absorption and emission spectroscopy. Each one of the examined compounds shows weak luminescence originating from a different electronic state: porphyrin triplet 3 (π,π ∗) for RuTBP (CO) (EtOH), equatorial 3LCT for RuTBP(pyz) 2 and axial 1MLCT for [RuTBP(pyz)] n.

  6. Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide.

    PubMed

    Wu, Lipeng; Liu, Qiang; Fleischer, Ivana; Jackstell, Ralf; Beller, Matthias

    2014-01-01

    Alkene carbonylations represent a major technology for the production of value-added bulk and fine chemicals. Nowadays, all industrial carbonylation processes make use of highly toxic and flammable carbon monoxide. Here we show the application of abundantly available carbon dioxide as C1 building block for the alkoxycarbonylations of industrially important olefins in the presence of a convenient and inexpensive ruthenium catalyst system. In our system, carbon dioxide works much better than the traditional combination of carbon monoxide and alcohols. The unprecedented in situ formation of carbon monoxide from carbon dioxide and alcohols permits an efficient synthesis of carboxylic acid esters, which can be used as detergents and polymer-building blocks. Notably, this transformation allows the catalytic formation of C-C bonds with carbon dioxide as C1 source and avoids the use of sensitive and/or expensive reducing agents (for example, Grignard reagents, diethylzinc or triethylaluminum). PMID:24518431

  7. Size Effect of Ruthenium Nanoparticles in Catalytic Carbon Monoxide Oxidation

    SciTech Connect

    Joo, Sang Hoon; Park, Jeong Y.; Renzas, J. Russell; Butcher, Derek R.; Huang, Wenyu; Somorjai, Gabor A.

    2010-04-04

    Carbon monoxide oxidation over ruthenium catalysts has shown an unusual catalytic behavior. Here we report a particle size effect on CO oxidation over Ru nanoparticle (NP) catalysts. Uniform Ru NPs with a tunable particle size from 2 to 6 nm were synthesized by a polyol reduction of Ru(acac){sub 3} precursor in the presence of poly(vinylpyrrolidone) stabilizer. The measurement of catalytic activity of CO oxidation over two-dimensional Ru NPs arrays under oxidizing reaction conditions (40 Torr CO and 100 Torr O{sub 2}) showed an activity dependence on the Ru NP size. The CO oxidation activity increases with NP size, and the 6 nm Ru NP catalyst shows 8-fold higher activity than the 2 nm catalysts. The results gained from this study will provide the scientific basis for future design of Ru-based oxidation catalysts.

  8. Unconventional magnetisation texture in graphene/cobalt hybrids

    NASA Astrophysics Data System (ADS)

    Vu, A. D.; Coraux, J.; Chen, G.; N’Diaye, A. T.; Schmid, A. K.; Rougemaille, N.

    2016-04-01

    Magnetic domain structure and spin-dependent reflectivity measurements on cobalt thin films intercalated at the graphene/Ir(111) interface are investigated using spin-polarised low-energy electron microscopy. We find that graphene-covered cobalt films have surprising magnetic properties. Vectorial imaging of magnetic domains reveals an unusually gradual thickness-dependent spin reorientation transition, in which magnetisation rotates from out-of-the-film plane to the in-plane direction by less than 10° per cobalt monolayer. During this transition, cobalt films have a meandering spin texture, characterised by a complex, three-dimensional, wavy magnetisation pattern. In addition, spectroscopy measurements suggest that the electronic band structure of the unoccupied states is essentially spin-independent already a few electron-Volts above the vacuum level. These properties strikingly differ from those of pristine cobalt films and could open new prospects in surface magnetism.

  9. Effects of cobalt in lead/acid batteries

    NASA Astrophysics Data System (ADS)

    Bagshaw, N. B.

    The effects of cobalt additions (0.1-1 g/1) to the electrolyte have been studied by anodic corrosion tests on sheets of various alloys, and by continuous charge, cycling and charge retention tests on thick plate automotive-type of batteries. Positive grid corrosion decreases with increase in cobalt concentration but the effect is less marked for alloys with high intrinsic corrosion resistance. Cobalt oxidizes some types of separator even at a relatively low concentration. The top-of-charge voltage is reduced by the presence of cobalt, the effect occurring mainly at the positive plate. Cobalt causes increased open-circuit losses but the effect is fairly small at low concentrations (0.1-0.15 g/1).

  10. Unconventional magnetisation texture in graphene/cobalt hybrids

    PubMed Central

    Vu, A. D.; Coraux, J.; Chen, G.; N’Diaye, A. T.; Schmid, A. K.; Rougemaille, N.

    2016-01-01

    Magnetic domain structure and spin-dependent reflectivity measurements on cobalt thin films intercalated at the graphene/Ir(111) interface are investigated using spin-polarised low-energy electron microscopy. We find that graphene-covered cobalt films have surprising magnetic properties. Vectorial imaging of magnetic domains reveals an unusually gradual thickness-dependent spin reorientation transition, in which magnetisation rotates from out-of-the-film plane to the in-plane direction by less than 10° per cobalt monolayer. During this transition, cobalt films have a meandering spin texture, characterised by a complex, three-dimensional, wavy magnetisation pattern. In addition, spectroscopy measurements suggest that the electronic band structure of the unoccupied states is essentially spin-independent already a few electron-Volts above the vacuum level. These properties strikingly differ from those of pristine cobalt films and could open new prospects in surface magnetism. PMID:27114039

  11. Unconventional magnetisation texture in graphene/cobalt hybrids.

    PubMed

    Vu, A D; Coraux, J; Chen, G; N'Diaye, A T; Schmid, A K; Rougemaille, N

    2016-01-01

    Magnetic domain structure and spin-dependent reflectivity measurements on cobalt thin films intercalated at the graphene/Ir(111) interface are investigated using spin-polarised low-energy electron microscopy. We find that graphene-covered cobalt films have surprising magnetic properties. Vectorial imaging of magnetic domains reveals an unusually gradual thickness-dependent spin reorientation transition, in which magnetisation rotates from out-of-the-film plane to the in-plane direction by less than 10° per cobalt monolayer. During this transition, cobalt films have a meandering spin texture, characterised by a complex, three-dimensional, wavy magnetisation pattern. In addition, spectroscopy measurements suggest that the electronic band structure of the unoccupied states is essentially spin-independent already a few electron-Volts above the vacuum level. These properties strikingly differ from those of pristine cobalt films and could open new prospects in surface magnetism. PMID:27114039

  12. 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.

  13. Low-Cobalt Powder-Metallurgy Superalloy

    NASA Technical Reports Server (NTRS)

    Harf, F. H.

    1986-01-01

    Highly-stressed jet-engine parts made with less cobalt. Udimet 700* (or equivalent) is common nickel-based superalloy used in hot sections of jet engines for many years. This alloy, while normally used in wrought condition, also gas-atomized into prealloyed powder-metallurgy (PM) product. Product can be consolidated by hot isostatically pressing (HIPPM condition) and formed into parts such as turbine disk. Such jet-engine disks "see" both high stresses and temperatures to 1,400 degrees F (760 degrees C).

  14. HYDROCARBON FORMATION ON POLYMER-SUPPORTED COBALT

    SciTech Connect

    Benner, Linda S.; Perkins, Patrick; Vollhardt, K.Peter C.

    1980-10-01

    In this report we detail the synthesis catalytic chemistry of polystyrene supported {eta}{sup 5} ~cyclopentadienyl- dicarbonyl cobalt, CpCo(CO){sub 2}. This material is active in the hydrogenation of CO to saturated linear hydrocarbons and appears to retain its "homogeneous", mononuclear character during the course of its catalysis, During ·the course of our work 18% and 20% crosslinked analogs of polystyrene supported CpCo(CO){sub 2} were shown to exhibit limited catalytic activity and no CO activation.

  15. Cold-Sprayed Nanostructured Pure Cobalt Coatings

    NASA Astrophysics Data System (ADS)

    Cavaliere, P.; Perrone, A.; Silvello, A.

    2016-08-01

    Cold-sprayed pure cobalt coatings were deposited on carbon-steel substrate. Submicrometer particles for spraying were produced via cryomilling. Deposits were produced using different processing conditions (gas temperature and pressure, nozzle-to-substrate distance) to evaluate the resulting variations in grain size dimension, microhardness, adhesion strength, and porosity. The coating mechanical properties improved greatly with higher temperature and carrying-gas pressure. The coating microstructure was analyzed as a function of spraying condition by transmission electron microscopy (TEM) observations, revealing many different microstructural features for coatings experiencing low or high strain rates during deposition.

  16. Fischer-Tropsch cobalt catalyst development

    SciTech Connect

    Oukaci, R.; Goodwin, J.G. Jr.; Marcelin, G.; Singleton, A.

    1994-12-31

    Based on the information provided in patents assigned to Gulf, Shell, Exxon, and Statoil, a series of catalysts has been prepared consisting of 12-20 wt% cobalt, a second metal promoter (Ru or Re), and an oxide promoter such as lanthana, zirconia, or alkali oxide, the support being alumina, silica, or titania. All catalysts have been extensively characterized by different methods. The catalysts have been evaluated in terms of their activity, selectivity both in a fixed bed reactor and in a slurry bubble column reactor, and the results correlated with their physico-chemical properties.

  17. Electronic structure of cobalt nanocrystals suspended inliquid

    SciTech Connect

    Liu, Hongjian; Guo, Jinghua; Yin, Yadong; Augustsson, Andreas; Dong, Chungli; Nordgren, Joseph; Chang, Chinglin; Alivisatos, Paul; Thornton, Geoff; Ogletree, D. Frank; Requejo, Felix G.; de Groot, Frank; Salmeron, Miquel

    2007-07-16

    The electronic structure of cobalt nanocrystals suspended in liquid as a function of size has been investigated using in-situ x-ray absorption and emission spectroscopy. A sharp absorption peak associated with the ligand molecules is found that increases in intensity upon reducing the nanocrystal size. X-ray Raman features due to d-d and to charge-transfer excitations of ligand molecules are identified. The study reveals the local symmetry of the surface of {var_epsilon}-Co phase nanocrystals, which originates from a dynamic interaction between Co nanocrystals and surfactant + solvent molecules.

  18. Water-soluble ruthenium complexes bearing activity against protozoan parasites.

    PubMed

    Sarniguet, Cynthia; Toloza, Jeannette; Cipriani, Micaella; Lapier, Michel; Vieites, Marisol; Toledano-Magaña, Yanis; García-Ramos, Juan Carlos; Ruiz-Azuara, Lena; Moreno, Virtudes; Maya, Juan Diego; Azar, Claudio Olea; Gambino, Dinorah; Otero, Lucía

    2014-06-01

    Parasitic illnesses are major causes of human disease and misery worldwide. Among them, both amebiasis and Chagas disease, caused by the protozoan parasites, Entamoeba histolytica and Trypanosoma cruzi, are responsible for thousands of annual deaths. The lack of safe and effective chemotherapy and/or the appearance of current drug resistance make the development of novel pharmacological tools for their treatment relevant. In this sense, within the framework of the medicinal inorganic chemistry, metal-based drugs appear to be a good alternative to find a pharmacological answer to parasitic diseases. In this work, novel ruthenium complexes [RuCl2(HL)(HPTA)2]Cl2 with HL=bioactive 5-nitrofuryl containing thiosemicarbazones and PTA=1,3,5-triaza-7-phosphaadamantane have been synthesized and fully characterized. PTA was included as co-ligand in order to modulate complexes aqueous solubility. In fact, obtained complexes were water soluble. Their activity against T. cruzi and E. histolytica was evaluated in vitro. [RuCl2(HL4)(HPTA)2]Cl2 complex, with HL4=N-phenyl-5-nitrofuryl-thiosemicarbazone, was the most active compound against both parasites. In particular, it showed an excellent activity against E. histolytica (half maximal inhibitory concentration (IC50)=5.2 μM), even higher than that of the reference drug metronidazole. In addition, this complex turns out to be selective for E. histolytica (selectivity index (SI)>38). The potential mechanism of antiparasitic action of the obtained ruthenium complexes could involve oxidative stress for both parasites. Additionally, complexes could interact with DNA as second potential target by an intercalative-like mode. Obtained results could be considered a contribution in the search for metal compounds that could be active against multiple parasites. PMID:24740394

  19. Ammonia synthesis catalyzed by ruthenium supported on basic zeolites

    SciTech Connect

    Fishel, C.T.; Davis, R.J.; Garces, J.M.

    1996-09-15

    Ammonia synthesis was catalyzed by ruthenium metal clusters, promoted by alkali and alkaline earth elements, supported on zeolite X, magnesia, and pure silica MCM-41. At atmospheric total pressure and temperatures ranging from 623 to 723 K, the turnover frequencies of ammonia synthesis on Ru/KX varied significantly with Fu cluster size, demonstrating the known structure sensitivity of the reaction. Therefore, zeolite and magnesia catalysts were prepared with similar Ru cluster sizes, about 1 nm in diameter, in order to properly evaluate the effect of promoters. The same high degree of metal dispersion could not be obtained with Ru/MCM-41 catalysts. The turnover frequency for ammonia synthesis over Ru/CsX exceeded that over Ru/KX, consistent with the rank of promoter basicity. However, alkaline earth metals were more effective promoters than alkali metals for Ru supported on both zeolite X and MCM-41. Since alkaline earth metals are less basic; this promotional effect was unexpected. In addition, the turnover frequency for ammonia synthesis on Ru/BaX exceeded that of Ru/MgO, a nonzeolitic material. Pore volumes for Ru/BaX and Ru/KX measured by N{sub 2} adsorption were essentially identical, suggesting that pore blockage by ions within the zeolites does not account for the differences in reaction rates. The kinetics of ammonia synthesis over ruthenium differed considerably from what has been reported for industrial iron catalysts. Most significantly, the order of reaction in H{sub 2} was negative over Ru but is positive over Fe. A likely cause of this change in reaction order is that dissociated hydrogen atoms cover a greater fraction of the Ru clusters compared to Fe under reaction conditions. 49 refs., 8 figs., 10 tabs.

  20. Experimental chemotherapy in paracoccidioidomycosis using ruthenium NO donor.

    PubMed

    Pavanelli, Wander Rogério; da Silva, Jean Jerley Nogueira; Panis, Carolina; Cunha, Thiago Mattar; Costa, Ivete Conchon; de Menezes, Maria Claudia Noronha Dutra; Oliveira, Francisco José de Abreu; Lopes, Luiz Gonzaga de França; Cecchini, Rubens; Cunha, Fernando de Queiroz; Watanabe, Maria Angélica Ehara; Itano, Eiko Nakagawa

    2011-08-01

    Paracoccidioidomycosis (PCM) is a granulomatous disease caused by a dimorphic fungus, Paracoccidioides brasiliensis (Pb). To determine the influence of nitric oxide (NO) on this disease, we tested cis-[Ru(bpy)2(NO)SO3](PF6), ruthenium nitrosyl, which releases NO when activated by biological reducing agents, in BALB/c mice infected intravenously with Pb 18 isolate. In a previous study by our group, the fungicidal activity of ruthenium nitrosyl was evaluated in a mouse model of acute PCM, by measuring the immune cellular response (DTH), histopathological characteristics of the granulomatous lesions (and numbers), cytokines, and NO production. We found that cis-[Ru(bpy)2(NO)SO3](PF6)-treated mice were more resistant to infection, since they exhibited higher survival when compared with the control group. Furthermore, we observed a decreased influx of inflammatory cells in the lung and liver tissue of treated mice, possibly because of a minor reduction in fungal cell numbers. Moreover, an increased production of IL-10 and a decrease in TNF-α levels were detected in lung tissues of infected mice treated with cis-[Ru(bpy)2(NO)SO3](PF6). Immunohistochemistry showed that there was no difference in the number of VEGF- expressing cells. The animals treated with cis-[Ru(bpy)2(NO)SO3](PF6) showed high NO levels at 40 days after infection. These results show that NO is effectively involved in the mechanism that regulates the immune response in lung of Pb-infected mice. These data suggest that NO is a resistance factor during paracoccidioidomycosis by controlling fungal proliferation, influencing cytokine production, and consequently moderating the development of a strong inflammatory response. PMID:21437728

  1. 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.

  2. Preparation and characterization of electrodeposited cobalt nanowires

    SciTech Connect

    Irshad, M. I. Mohamed, N. M.; Ahmad, F. Abdullah, M. Z.

    2014-10-24

    Electrochemical deposition technique has been used to deposit cobalt nanowires into the nano sized channels of Anodized Aluminium Oxide (AAO) templates. CoCl{sub 2}Ðœ‡6H2O salt solution was used, which was buffered with H{sub 3}BO{sub 3} and acidified by dilute H{sub 2}SO{sub 4} to increase the plating life and control pH of the solution. Thin film of copper around 150 nm thick on one side of AAO template coated by e-beam evaporation system served as cathode to create electrical contact. FESEM analysis shows that the as-deposited nanowires are highly aligned, parallel to one another and have high aspect ratio with a reasonably high pore-filing factor. The TEM results show that electrodeposited cobalt nanowires are crystalline in nature. The Hysteresis loop shows the magnetization properties for in and out of plane configuration. The in plane saturation magnetization (Ms) is lower than out of plane configuration because of the easy axis of magnetization is perpendicular to nanowire axis. These magnetic nanowires could be utilized for applications such as spintronic devices, high density magnetic storage, and magnetic sensor applications.

  3. Cobalt distribution during copper matte smelting

    NASA Astrophysics Data System (ADS)

    Kho, T. S.; Swinbourne, D. R.; Lehner, T.

    2006-04-01

    Many smelter operators subscribe to the “precautionary principle” and wish to understand the behavior of the metals and impurities during smelting, especially how they distribute between product and waste phases and whether these phases lead to environmental, health, or safety issues. In copper smelting, copper and other elements are partitioned between copper matte, iron silicate slag, and possibly the waste gas. Many copper concentrates contain small amounts of cobalt, a metal of considerable value but also of some environmental interest. In this work, the matte/slag distribution ratio (weight percent) of cobalt between copper matte (55 wt pct) and iron silicate slag was thermodynamically modeled and predicted to be approximately 5. Experiments were performed using synthetic matte and slag at 1250 °C under a low oxygen partial pressure and the distribution ratio was found to be 4.3, while between industrial matte and slag, the ratio was found to be 1.8. Both values are acceptably close to each other and to the predicted value, given the errors inherent in such measurements. The implications of these results for increasingly sustainable copper production are discussed.

  4. Cataractogenesis after Cobalt-60 eye plaque radiotherapy

    SciTech Connect

    Kleineidam, M.; Augsburger, J.J. ); Hernandez, C.; Glennon, P.; Brady, L.W. )

    1993-07-15

    This study was designed to estimate the actuarial incidence of typical postirradiation cataracts and to identify prognostic factors related to their development in melanoma-containing eyes treated by Cobalt-60 plaque radiotherapy. A special interest was the impact of calculated radiation dose and dose-rate to the lens. The authors evaluated the actuarial occurrence of post-irradiation cataract in 365 patients with primary posterior uveal melanoma treated by Cobalt-60 plaque radiotherapy between 1976 and 1986. Only 22% (S.E. = 4.6%) of the patients who received a total dose of 6 to 20 Gy at the center of the lens developed a visually significant cataract attributable to the radiation within 5 years after treatment. Using multivariate Cox proportional hazards modeling, the authors identified thickness of the tumor, location of the tumor's anterior margin relative to the equatorward and the ora serrata, and diameter of the eye plaque used as the best combination of covariables for predicting length of time until development of cataract. Surprisingly, the dose of radiation delivered to the lens, which was strongly correlated to all of these covariables, was not a significant predictive factor in multivariate analysis. The results suggest that success of efforts to decrease the occurrence rate of post-irradiation cataracts by better treatment planning might be limited in patients with posterior uveal melanoma. 21 refs., 2 figs., 5 tabs.

  5. Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

    NASA Astrophysics Data System (ADS)

    Li, H. F.; Zhou, F. Y.; Li, L.; Zheng, Y. F.

    2016-04-01

    In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10‑6 cm3·g‑1–1.29 × 10‑6 cm3·g‑1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10‑6 cm3·g‑1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10‑6 cm3·g‑1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10‑6 cm3·g‑1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments.

  6. Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility.

    PubMed

    Li, H F; Zhou, F Y; Li, L; Zheng, Y F

    2016-01-01

    In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co-Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10(-6) cm(3)·g(-1)-1.29 × 10(-6) cm(3)·g(-1) for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti-6Al-4V, ~3.5 × 10(-6) cm(3)·g(-1), CP Ti and Ti-6Al-7Nb, ~3.0 × 10(-6) cm(3)·g(-1)), and one-sixth that of Co-Cr alloys (Co-Cr-Mo, ~7.7 × 10(-6) cm(3)·g(-1)). Among the Zr-Ru alloy series, Zr-1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr-Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

  7. New cytotoxic and water-soluble bis(2-phenylazopyridine)ruthenium(II) complexes.

    PubMed

    Hotze, Anna C G; Bacac, Marina; Velders, Aldrik H; Jansen, Bart A J; Kooijman, Huub; Spek, Anthony L; Haasnoot, Jaap G; Reedijk, Jan

    2003-04-24

    New water-soluble bis(2-phenylazopyridine)ruthenium(II) complexes, all derivatives of the highly cytotoxic alpha-[Ru(azpy)(2)Cl(2)] (alpha denoting the coordinating pairs Cl, N(py), and N(azo) as cis, trans, cis, respectively) have been developed. The compounds 1,1-cyclobutanedicarboxylatobis(2-phenylazopyridine)ruthenium(II), alpha-[Ru(azpy)(2)(cbdca-O,O')] (1), oxalatobis(2-phenylazopyridine)ruthenium(II), alpha-[Ru(azpy)(2)(ox)] (2), and malonatobis(2-phenylazopyridine)ruthenium(II), alpha-[Ru(azpy)(2)(mal)] (3), have been synthesized and fully characterized. X-ray analyses of 1 and 2 are reported, and compound 1 is the first example in which the cbdca ligand is coordinated to a ruthenium center. The cytotoxicity of this series of water-soluble bis(2-phenylazopyridine) complexes has been determined in A2780 human ovarian carcinoma and A2780cisR, the corresponding cisplatin-resistant cell line. For comparison reasons, the cytotoxicity of the complexes alpha-[Ru(azpy)(2)Cl(2)], alpha-[Ru(azpy)(2)(NO(3))(2)], beta-[Ru(azpy)(2)Cl(2)] (beta indicating the coordinating pairs Cl, N(py), and N(azo) as cis, cis, cis, respectively), and beta-[Ru(azpy)(2)(NO(3))(2)] have been determined in this cell line. All the bis(2-phenylazopyridine)ruthenium(II) compounds display a promising cytotoxicity in the A2780 cell line (IC(50) = 0.9-10 microM), with an activity comparable to that of cisplatin and even higher than the activity of carboplatin. Interestingly, the IC(50) values of this series of ruthenium compounds (except the beta isomeric compounds) are similar in the cisplatin-resistant A2780cisR cell line compared to the normal cell line A2780, suggesting that the activity of these compounds might not be influenced by the multifactorial resistance mechanism that affect platinum anticancer agents. PMID:12699392

  8. Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

    PubMed Central

    Li, H.F.; Zhou, F.Y.; Li, L.; Zheng, Y.F.

    2016-01-01

    In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10−6 cm3·g−1–1.29 × 10−6 cm3·g−1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10−6 cm3·g−1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10−6 cm3·g−1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10−6 cm3·g−1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

  9. High doses of cobalt induce optic and auditory neuropathy.

    PubMed

    Apostoli, Pietro; Catalani, Simona; Zaghini, Anna; Mariotti, Andrea; Poliani, Pietro Luigi; Vielmi, Valentina; Semeraro, Francesco; Duse, Sarah; Porzionato, Andrea; Macchi, Veronica; Padovani, Alessandro; Rizzetti, Maria Cristina; De Caro, Raffaele

    2013-09-01

    The adverse biological effects of continuous exposure to cobalt and chromium have been well defined. In the past, this toxicity was largely an industrial issue concerning workers exposed in occupational setting. Nevertheless, recent reports have described a specific toxicity mediated by the high levels of cobalt and chromium released by metallic prostheses, particularly in patients who had received hip implants. Clinical symptoms, including blindness, deafness and peripheral neuropathy, suggest a specific neurotropism. However, little is known about the neuropathological basis of this process, and experimental evidence is still lacking. We have investigated this issue in an experimental setting using New Zealand White rabbits treated with repeated intravenous injections of cobalt and chromium, alone or in combination. No evident clinical or pathological alterations were associated after chromium administration alone, despite its high levels in blood and tissue while cobalt-chromium and cobalt-treated rabbits showed clinical signs indicative of auditory and optic system toxicity. On histopathological examination, the animals showed severe retinal and cochlear ganglion cell depletion along with optic nerve damage and loss of sensory cochlear hair cells. Interestingly, the severity of the alterations was related to dosages and time of exposure. These data confirmed our previous observation of severe auditory and optic nerve toxicity in patients exposed to an abnormal release of cobalt and chromium from damaged hip prostheses. Moreover, we have identified the major element mediating neurotoxicity to be cobalt, although the molecular mechanisms mediating this toxicity still have to be defined. PMID:23069009

  10. A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

    EPA Science Inventory

    One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

  11. ONO-pincer ruthenium complex-bound norvaline for efficient catalytic oxidation of methoxybenzenes with hydrogen peroxide.

    PubMed

    Yoshida, Ryota; Isozaki, Katsuhiro; Yokoi, Tomoya; Yasuda, Nobuhiro; Sadakane, Koichiro; Iwamoto, Takahiro; Takaya, Hikaru; Nakamura, Masaharu

    2016-08-21

    The enhanced catalytic activity of ruthenium complex-bound norvaline Boc-l-[Ru]Nva-OMe 1, in which the ONO-pincer ruthenium complex Ru(pydc)(terpy) 2 is tethered to the α-side chain of norvaline, has been demonstrated for the oxidation of methoxybenzenes to p-benzoquinones with a wide scope of substrates and unique chemoselectivity. PMID:27314504

  12. Syntheses and Characterization of Ruthenium(II) Tetrakis(pyridine)complexes: An Advanced Coordination Chemistry Experiment or Mini-Project

    ERIC Educational Resources Information Center

    Coe, Benjamin J.

    2004-01-01

    An experiment for third-year undergraduate a student is designed which provides synthetic experience and qualitative interpretation of the spectroscopic properties of the ruthenium complexes. It involves the syntheses and characterization of several coordination complexes of ruthenium, the element found directly beneath iron in the middle of the…

  13. Reoxidation and deactivation of supported cobalt Fischer-Tropsch catalysts

    SciTech Connect

    Schanke, D.; Hilmen, A.M.; Bergene, E.

    1995-12-01

    The Fischer-Tropsch synthesis is an attractive possibility for conversion of natural gas into high quality liquid fuels. Due to its low water-gas shift activity, good activity/selectivity properties and relatively low price, cobalt is the choice of catalytic metal for natural gas conversion via Fischer-Tropsch synthesis. In the cobalt-catalyzed Fischer-Tropsch reaction, oxygen is mainly rejected as water. In this paper we describe the influence of water on supported cobalt catalysts. The deactivation of supported Co catalysts was studied in a fixed-bed reactor using synthesis gas feeds containing varying concentrations of water vapour.

  14. Magnetoelastic coupling in epitaxial cobalt ferrite/barium titanate heterostructures

    NASA Astrophysics Data System (ADS)

    Gräfe, Joachim; Welke, Martin; Bern, Francis; Ziese, Michael; Denecke, Reinhard

    2013-08-01

    Ultra-thin cobalt ferrite films have been synthesised on ferroelectric barium titanate crystals. The cobalt ferrite films exhibit a magnetic response to strain induced by structural changes in the barium titanate substrate, suggesting a pathway to multiferroic coupling. These structural changes are achieved by heating through the phase transition temperatures of barium titanate. In addition the ferromagnetic signal of the substrate itself is taken into account, addressing the influence of impurities or defects in the substrate. The cobalt ferrite/barium titanate heterostructure is a suitable oxidic platform for future magnetoelectric applications with an established ferroelectric substrate and widely tuneable magnetic properties by changing the transition metal in the ferrite film.

  15. Quantitative study of ruthenium cross-over in direct methanol fuel cells during early operation hours

    NASA Astrophysics Data System (ADS)

    Schoekel, A.; Melke, J.; Bruns, M.; Wippermann, K.; Kuppler, F.; Roth, C.

    2016-01-01

    In direct methanol fuel cells (DMFC), ruthenium cross-over is an important degradation phenomenon. The loss of ruthenium from the anode, its transport through the membrane and its deposition onto the cathode are detrimental to the fuel cell performance and limit the fuel cell's lifetime. Here we present a quantitative study on the fraction of ruthenium being transferred from the anode to the cathode during early operation hours (0-100 h) of a DMFC. Already during fabrication of the MEA ruthenium is transferred to the cathode. In our pristine MEAs about 0.024 wt% Ru could be found in the cathode catalyst. The cell potential during operation seems to have only a minor influence on the dissolution process. In contrast, the operation time appears to be much more important. Our data hint at two dissolution processes: a fast process dominating the first hours of operation and a slower process, which is responsible for the ongoing ruthenium transfer during the fuel cell lifetime. After 2 h held at open circuit conditions the Ru content of the cathode side was 10 times higher than in the pristine MEA. In contrast, the slower process increased that amount only by a factor of two over the course of another 100 h.

  16. Ruthenium nanoparticles in ionic liquids: structural and stability effects of polar solutes.

    PubMed

    Salas, Gorka; Podgoršek, Ajda; Campbell, Paul S; Santini, Catherine C; Pádua, Agílio A H; Costa Gomes, Margarida F; Philippot, Karine; Chaudret, Bruno; Turmine, Mireille

    2011-08-14

    Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface. PMID:21603700

  17. Time-resolved resonance raman spectra of polypyridyl complexes of ruthenium(II)

    SciTech Connect

    Kumar, C.V.; Barton, J.K.; Turro, N.J.; Gould, I.R.

    1987-05-06

    Time-resolved resonance Raman (TR/sup 3/) spectroscopy has recently evolved as a powerful tool for the investigation of the dynamics and structures of a variety of reactive intermediates, electronic excited states, biological systems, and enzyme-substrate complexes. In this communication, the authors report the TR/sup 3/ spectra of three ruthenium complexes of special importance because of three ruthenium complexes of special importance because of their binding ability to nucleic acids, because of their success as chiral probes that recognize the conformations and helicity of nucleic acids, and because of their potential to serve as models for the interaction of metal ions with nucleic acids. They report here the results of TR/sup 3/ and transient absorption experiments which demonstrate that the excited states of three Ru(II) complexes, tris(2,2'-bipyridyl)ruthenium(II) dichloride (I), tris(1,20-phenanthroline)-ruthenium(II) dichloride (II), and tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) dichloride (III), are indeed localized on the ligand.

  18. Band offsets of a ruthenium gate on ultrathin high-{kappa} oxide films on silicon

    SciTech Connect

    Rangan, Sylvie; Bersch, Eric; Bartynski, Robert Allen; Garfunkel, Eric; Vescovo, Elio

    2009-02-15

    Valence-band and conduction-band edges of ultrathin oxides (SiO{sub 2}, HfO{sub 2}, Hf{sub 0.7}Si{sub 0.3}O{sub 2}, and Al{sub 2}O{sub 3} grown on silicon) and their shifts upon sequential metallization with ruthenium have been measured using synchrotron-radiation-excited x-ray, ultraviolet, and inverse photoemissions. From these techniques, the offsets between the valence-band and conduction-band edges of the oxides, and the ruthenium metal gate Fermi edge have been directly measured. In addition the core levels of the oxides and the ruthenium have been characterized. Upon deposition, Ru remains metallic and no chemical alteration of the underlying oxide gates, or interfacial SiO{sub 2} in the case of the high-{kappa} thin films, can be detected. However a clear shift of the band edges is measured for all samples due to the creation of an interface dipole at the ruthenium-oxide interface. Using the energy gap, the electron affinity of the oxides, and the ruthenium work function that have been directly measured on these samples, the experimental band offsets are compared to those predicted by the induced gap states model.

  19. Transient Spectroscopic Characterization of the Genesis of a Ruthenium Complex Catalyst Supported on Zeolite Y

    SciTech Connect

    Ogino, Isao; Gates, Bruce C.

    2010-01-12

    A mononuclear ruthenium complex anchored to dealuminated zeolite HY, Ru(acac)(C{sub 2}H{sub 4}){sup 2+} (acac = acetylacetonate, C{sub 5}H{sub 7}O{sup 2}{sup -}), was characterized in flow reactors by transient infrared (IR) spectroscopy and Ru K edge X-ray absorption spectroscopy. The combined results show how the supported complex was converted into a form that catalyzes ethene conversion to butene. The formation of these species resulted from the removal of acac ligands from the ruthenium (as shown by IR and extended X-ray absorption fine structure (EXAFS) spectra) and the simultaneous decrease in the symmetry of the ruthenium complex, with the ruthenium remaining mononuclear and its oxidation state remaining essentially unchanged (as shown by EXAFS and X-ray absorption near-edge structure spectra). The removal of anionic acac ligands from the ruthenium was evidently compensated by the bonding of other anionic ligands, such as hydride from H2 in the feed stream, to form species suggested to be Ru(H)(C{sub 2}H{sub 4}){sub 2}{sup +}, which is coordinatively unsaturated and inferred to react with ethene, leading to the observed formation of butene in a catalytic process.

  20. Band Offsets of a Ruthenium Gate on Ultrathin High-k Oxide Films on Silicon

    SciTech Connect

    Rangan, S.; Bersch, W; Bartynski, R; Garfunkel, E; Vescovo, E

    2009-01-01

    Valence-band and conduction-band edges of ultrathin oxides and their shifts upon sequential metallization with ruthenium have been measured using synchrotron-radiation-excited x-ray, ultraviolet, and inverse photoemissions. From these techniques, the offsets between the valence-band and conduction-band edges of the oxides, and the ruthenium metal gate Fermi edge have been directly measured. In addition the core levels of the oxides and the ruthenium have been characterized. Upon deposition, Ru remains metallic and no chemical alteration of the underlying oxide gates, or interfacial SiO{sub 2} in the case of the high-? thin films, can be detected. However a clear shift of the band edges is measured for all samples due to the creation of an interface dipole at the ruthenium-oxide interface. Using the energy gap, the electron affinity of the oxides, and the ruthenium work function that have been directly measured on these samples, the experimental band offsets are compared to those predicted by the induced gap states model.

  1. Radiation related complications after ruthenium plaque radiotherapy of uveal melanoma.

    PubMed Central

    Summanen, P; Immonen, I; Kivelä, T; Tommila, P; Heikkonen, J; Tarkkanen, A

    1996-01-01

    AIMS/BACKGROUND: To analyse radiation related complications and secondary enucleation after irradiation of malignant uveal melanoma with ruthenium-106 plaques. METHODS: A series of 100 consecutive eyes irradiated in 1981-91 was analysed using the life table method and the Cox proportional hazards model. The median apical and scleral tumour dose was 100 Gy (range 15-200 Gy) and 1000 Gy (range 200-1200 Gy), respectively. The median follow up time was 2.8 and 2.0 years (range 1 month to 10 years) for anterior and posterior segment complications, respectively. RESULTS: The 3 and 5 year probabilities of being without radiation cataract were 73% and 63%, without neovascular glaucoma 91% and 81%, without vitreous haemorrhage 83% and 74%, without radiation maculopathy 85% and 70%, and without radiation optic neuropathy 90% and 88%, respectively. The risk of radiation cataract was highest with large tumour size (T1 + T2 v T3, p = 0.0027; height < or = 5 v > 5 mm, p = 0.029; largest basal diameter (LBD) < or = 15 v > 15 mm, p < 0.0001) and location of anterior tumour margin anterior v posterior to the equator (p = 0.0003); the risk of neovascular glaucoma with large size (T1 + T2 v T3, p = 0.039; LBD < or = 15 mm v 15 mm, p = 0.021); and the risk of maculopathy and optic neuropathy with proximity of the posterior tumour margin to the fovea and the optic disc (< or = 1.5 v > 1.5 mm; p = 0.030 and p = 0.0004, respectively). In Cox's multivariate analysis the strongest risk indicator for radiation cataract (RR 1.5, 95% CI 1.4-1.6) and vitreous haemorrhage (RR 1.6, 95% CI 1.4-1.8) was the height of the tumour; for neovascular glaucoma the TNM class (RR 6.2, 95% CI 2.7-13.8); for radiation maculopathy location of posterior tumour margin within 2 mm from the fovea (RR 3.4, 95% CI 2.0-6.0); and for radiation optic neuropathy location of tumour margin within 1 DD of the optic disc (RR 6.1, 95% CI 3.0-12.4). The 3 and 5 year probabilities of avoiding enucleation were 92% and 85

  2. Oxygen Evolution Electrocatalysis on Cobalt Oxide surfaces

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Norskov, Jens K.; García-Mota, Monica; Bell, Alexis T.

    2012-02-01

    The oxidation of water for hydrogen production using sunlight is of high importance to photo-fuel cell research. The electrochemical approach via heterogeneous catalysis to water splitting is a very promising route. The key challenge of this method lies in reduction of the loses, i.e., over-potential, for the oxygen evolution reaction (OER) on the anode. In this work, we investigate the dependence of theoretical over-potential of OER on type of anode by applying standard density functional theory (DFT). We attempt to explain recent experimental observation of enhanced activity on gold supported Cobalt Oxide surfaces [1]. We explore variety of possible CoO structures and associated surfaces which could emerge under operating conditions of catalyst. Finally, we also explore the influence of environment and admixtures of CoO with other elements. [4pt] [1] B.S. Yeo, A.T. Bell, AT, J. Am. Chem. Soc., 133, 5587-5593 (2011).

  3. Aqua-bromidobis(dimethyl-glyoximato)cobalt(III).

    PubMed

    Meera, Parthasarathy; Amutha Selvi, Madhavan; Jothi, Pachaimuthu; Dayalan, Arunachalam

    2011-04-01

    In the title complex, [CoBr(C(4)H(7)N(2)O(2))(2)(H(2)O)], a crystallo-graphic mirror plane bis-ects the mol-ecule, perpendicular to the glyoximate ligands. The geometry around the cobalt(III) atom is approximately octa-hedral with the four glyoximate N atoms forming the square base. A bromide ion and the O atom of a water mol-ecule occupy the remaining coordination sites. The N-Co-N bite angles are 82.18 (4) and 80.03 (16)°. The glyoximate moieties form strong intra-molecular O-H⋯O hydrogen bonds. The coordinated water mol-ecule forms an inter-molecular O-H⋯O hydrogen bond with a glyoximate O atom, thereby generating supra-molecular chains parallel to [010]. PMID:21753964

  4. Role of Surface Cobalt Silicate in Single-Walled Carbon Nanotube Synthesis from Silica-Supported Cobalt Catalysts

    SciTech Connect

    Li, N.; Wang, X; Derrouiche, S; Haller, G; Pfefferle, L

    2010-01-01

    A silica-supported cobalt catalyst has been developed via incipient wetness impregnation for high-yield synthesis of single-walled carbon nanotubes (SWNTs). Co/SiO{sub 2}-impregnated catalysts have not been observed to be efficient for SWNT synthesis. Using an appropriately chosen precursor, we show that effective catalysts can be obtained for SWNT synthesis with yields up to 75 wt %. Detailed characterization indicates that the active sites for SWNT synthesis are small cobalt particles resulting from the reduction of a highly dispersed surface cobalt silicate species. The SWNTs produced by this catalyst are of high quality and easy to purify, and the process is simple and scalable.

  5. Reaction of cobalt in SO2 atmospheric at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1983-01-01

    The reaction rate of cobalt in SO2 argon environments was measured at 650 C, 700 C, 750 C and 800 C. Product scales consist primarily of an interconnected sulfide phase in an oxide matrix. At 700 C to 800 C a thin sulfide layer adjacent to the metal is also observed. At all temperatures, the rapid diffusion of cobalt outward through the interconnected sulfide appears to be important. At 650 C, the reaction rate slows dramatically after five minutes due to a change in the distribution of these sulfides. At 700 C and 750 C the reaction is primarily diffusion controlled values of diffusivity of cobalt (CoS) calculated from this work show favorable agreement with values of diffusivity of cobalt (CoS) calculated from previous sulfidation work. At 800 C, a surface step becomes rate limiting.

  6. The Study of a Cobalt Complex--A Laboratory Project.

    ERIC Educational Resources Information Center

    Loehlin, James H.; And Others

    1982-01-01

    Describes an 8-week project involving the synthesis of cobalt compounds. Once synthesized, compounds are qualitatively and quantitatively analyzed. Background information, laboratory procedures, and results/discussion are provided for three project experiments. (Author/JN)

  7. 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.

  8. Determination of traces of cobalt in soils: A field method

    USGS Publications Warehouse

    Almond, H.

    1953-01-01

    The growing use of geochemical prospecting methods in the search for ore deposits has led to the development of a field method for the determination of cobalt in soils. The determination is based on the fact that cobalt reacts with 2-nitroso-1-naphthol to yield a pink compound that is soluble in carbon tetrachloride. The carbon tetrachloride extract is shaken with dilute cyanide to complex interfering elements and to remove excess reagent. The cobalt content is estimated by comparing the pink color in the carbon tetrachloride with a standard series prepared from standard solutions. The cobalt 2-nitroso-1-naphtholate system in carbon tetrachloride follows Beer's law. As little as 1 p.p.m. can be determined in a 0.1-gram sample. The method is simple and fast and requires only simple equipment. More than 40 samples can be analyzed per man-day with an accuracy within 30% or better.

  9. Recovery of Silver and Cobalt from Laboratory Wastes.

    ERIC Educational Resources Information Center

    Foust, Donald F.

    1984-01-01

    Procedures for recovering silver and cobalt from laboratory wastes (including those resulting from student experiments) are presented. The procedures are generally applicable since only common, inexpensive laboratory reagents are needed. (JN)

  10. Studies of the Codeposition of Cobalt Hydroxide and Nickel Hydroxide

    NASA Technical Reports Server (NTRS)

    Ho, C. H.; Murthy, M.; VanZee, J. W.

    1997-01-01

    Topics considered include: chemistry, experimental measurements, planar film model development, impregnation model development, results and conclusion. Also included: effect of cobalt concentration on deposition/loading; effect of current density on loading distribution.

  11. Reaction of cobalt in SO2 atmospheres at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1984-01-01

    The reaction rate of cobalt in SO2 argon environments was measured at 650 C, 700 C, 750 C and 800 C. Product scales consist primarily of an interconnected sulfide phase in an oxide matrix. At 700 C to 800 C, a thin sulfide layer adjacent to the metal is also observed. At all temperatures, the rapid diffusion of cobalt outward through the interconnected sulfide appears to be important. At 650 C, the reaction rate slows dramatically after five minutes due to a change in the distribution of these sulfides. At 700 C and 750 C, the reaction is primarily diffusion controlled; values of diffusivity of cobalt (CoS) calculated from this work show favorable agreement with values of diffusivity of cobalt (CoS) calculated from previous sulfidation work. At 800 C, a surface step becomes rate limiting. Previously announced in STAR as N83-35104

  12. Battery related cobalt and REE flows in WEEE treatment.

    PubMed

    Sommer, P; Rotter, V S; Ueberschaar, M

    2015-11-01

    In batteries associated with waste electrical and electronic equipment (WEEE), battery systems can be found with a higher content of valuable and critical raw materials like cobalt and rare earth elements (REE) relative to the general mix of portable batteries. Based on a material flow model, this study estimates the flows of REE and cobalt associated to WEEE and the fate of these metals in the end-of-life systems. In 2011, approximately 40 Mg REE and 325 Mg cobalt were disposed of with WEEE-batteries. The end-of-life recycling rate for cobalt was 14%, for REE 0%. The volume of waste batteries can be expected to grow, but variation in the battery composition makes it difficult to forecast the future secondary raw material potential. Nevertheless, product specific treatment strategies ought to be implemented throughout the stages of the value chain. PMID:26054962

  13. Size-dependent dissociation of carbon monoxide on cobalt nanoparticles.

    PubMed

    Tuxen, Anders; Carenco, Sophie; Chintapalli, Mahati; Chuang, Cheng-Hao; Escudero, Carlos; Pach, Elzbieta; Jiang, Peng; Borondics, Ferenc; Beberwyck, Brandon; Alivisatos, A Paul; Thornton, Geoff; Pong, Way-Faung; Guo, Jinghua; Perez, Ruben; Besenbacher, Flemming; Salmeron, Miquel

    2013-02-13

    In situ soft X-ray absorption spectroscopy (XAS) was employed to study the adsorption and dissociation of carbon monoxide molecules on cobalt nanoparticles with sizes ranging from 4 to 15 nm. The majority of CO molecules adsorb molecularly on the surface of the nanoparticles, but some undergo dissociative adsorption, leading to oxide species on the surface of the nanoparticles. We found that the tendency of CO to undergo dissociation depends critically on the size of the Co nanoparticles. Indeed, CO molecules dissociate much more efficiently on the larger nanoparticles (15 nm) than on the smaller particles (4 nm). We further observed a strong increase in the dissociation rate of adsorbed CO upon exposure to hydrogen, clearly demonstrating that the CO dissociation on cobalt nanoparticles is assisted by hydrogen. Our results suggest that the ability of cobalt nanoparticles to dissociate hydrogen is the main parameter determining the reactivity of cobalt nanoparticles in Fischer-Tropsch synthesis. PMID:23339635

  14. Formation of cobalt silicide by ion beam mixing

    NASA Astrophysics Data System (ADS)

    Min, Ye; Burte, Edmund P.; Ryssel, Heiner

    1991-07-01

    The formation of cobalt silicides by arsenic ion implantation through a cobalt film which causes a mixing of the metal with the silicon substrate was investigated. Furthermore, cobalt suicides were formed by rapid thermal annealing (RTA). Sheet resistance and silicide phases of implanted Co/Si samples depend on the As dose. Ion beam mixing at doses higher than 5 × 10 15 cm -2 and RTA at temperatures T ⩾ 900° C result in almost equal values of Rs. RBS and XRD spectra of these samples illustrate the formation of a homogeneous CoSi 2 layer. Significant lateral growth of cobalt silicide beyond the edge of patterned SiO 2 was observed in samples which were only subjected to an RTA process ( T ⩾ 900 ° C), while this lateral suicide growth could be reduced efficiently by As implantation prior to RTA.

  15. Ruthenium(II) complexes containing quinone based ligands: Synthesis, characterization, catalytic applications and DNA interaction

    NASA Astrophysics Data System (ADS)

    Anitha, P.; Manikandan, R.; Endo, A.; Hashimoto, T.; Viswanathamurthi, P.

    2012-12-01

    1,2-Naphthaquinone reacts with amines such as semicarbazide, isonicotinylhydrazide and thiosemicarbazide in high yield procedure with the formation of tridentate ligands HLn (n = 1-3). By reaction of ruthenium(II) starting complexes and quinone based ligands HLn (n = 1-3), a series of ruthenium complexes were synthesized and characterized by elemental and spectroscopic methods (FT-IR, electronic, 1H, 13C, 31P NMR and ESI-MS). The ligands were coordinated to ruthenium through quinone oxygen, imine nitrogen and enolate oxygen/thiolato sulfur. On the basis of spectral studies an octahedral geometry may be assigned for all the complexes. Further, the catalytic oxidation of primary, secondary alcohol and transfer hydrogenation of ketone was carried out. The DNA cleavage efficiency of new complexes has also been tested.

  16. Ruthenium(II) multi carboxylic acid complexes: chemistry and application in dye sensitized solar cells.

    PubMed

    Shahroosvand, Hashem; Nasouti, Fahimeh; Sousaraei, Ahmad

    2014-04-01

    Novel ruthenium multi carboxylic complexes (RMCCs) have been synthesized by using ruthenium nitrosyl nitrate, 1,2,4,5-benzenetetracarboxylic acid (H4btec) and 4,7-diphenyl-1,10-phenanthroline (BPhen) as photosensitizers for titanium dioxide semiconductor solar cells. The complexes were characterized by (1)H-NMR, FT-IR, UV-Vis, ICP and CHN analyses. The reaction details and features were then described. SEM analysis revealed that the penetration of dyes into the pores of the nanocrystalline TiO2 surface was improved by increasing the number of btec units. The solar energy to electricity conversion efficiency of complexes shows that the number of attached carboxylates on a dye has an influence on the photoelectrochemical properties of the dye-sensitized electrode. An incident photon-to-current conversion efficiency (IPCE) of 13% at 510 nm was obtained for ruthenium complexes with three btec units. PMID:24500312

  17. Development of a Method for the Preparation of Ruthenium Indenylidene-Ether Olefin Metathesis Catalysts

    PubMed Central

    Jimenez, Leonel R.; Tolentino, Daniel R.; Gallon, Benjamin J.; Schrodi, Yann

    2012-01-01

    The reactions between several derivatives of 1-(3,5-dimethoxyphenyl)-prop-2-yn-1-ol and different ruthenium starting materials [i.e., RuCl2(PPh3)3 and RuCl2(pcymene)(L), where L is tricyclohexylphosphine di-t-butylmethylphosphine, dicyclohexylphenylphosphine, triisobutylphosphine, triisopropylphosphine, or tri-npropylphosphine] are described. Several of these reactions allow for the easy, in-situ and atom-economic preparation of olefin metathesis catalysts. Organic precursor 1-(3,5-dimethoxyphenyl)-1-phenyl-prop-2-yn-1-ol led to the formation of active ruthenium indenylidene-ether complexes, while 1-(3,5-dimethoxyphenyl)-prop-2-yn-1-ol and 1-(3,5-dimethoxyphenyl)-1-methyl-prop-2-yn-1-ol did not. It was also found that a bulky and strong σ-donor phosphine ligand was required to impart good catalytic activity to the new ruthenium complexes. PMID:22580400

  18. Is matching ruthenium with dithiocarbamato ligands a potent chemotherapeutic weapon in oncology?

    PubMed

    Nardon, Chiara; Brustolin, Leonardo; Fregona, Dolores

    2016-02-01

    In the last years, several metal-based compounds have been designed and biologically investigated worldwide in order to obtain chemotherapeutics with a better toxicological profile and comparable or higher antiblastic activity than the clinically-established platinum-based drugs. In this context, researchers have addressed their attention to alternative nonplatinum derivatives able to maximize the anticancer activity of the new drugs and to minimize the side effects. Among them, a number of ruthenium complexes have been developed, including the compounds NAMI-A and KP1019, now in clinical trials. Here, we report the results collected so far for a particular class of ruthenium complexes - the ruthenium(II/III)-dithiocarbamates - which proved more potent than cisplatin in vitro, even at nanomolar concentrations, against a wide panel of human tumor cell lines. PMID:26807601

  19. Carbon nanotubes dispersed in aqueous solution by ruthenium(ii) polypyridyl complexes

    NASA Astrophysics Data System (ADS)

    Huang, Kewei; Saha, Avishek; Dirian, Konstantin; Jiang, Chengmin; Chu, Pin-Lei E.; Tour, James M.; Guldi, Dirk M.; Martí, Angel A.

    2016-07-01

    Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs. These studies show that the photoluminescence of both, that is, of the ruthenium complexes and of SWCNTs, are quenched when they interact with each other. Pump-probe transient absorption experiments were performed to shed light onto the nature of the photoluminescence quenching, showing carbon nanotube-based bands with picosecond lifetimes, but no new bands which could be unambigously assigned to photoinduced charge transfer process. Thus, from the spectroscopic data, we conclude that quenching of the photoluminescence of the ruthenium complexes is due to energy transfer to proximal SWCNTs.Cationic ruthenium(ii) polypyridyl complexes with appended pyrene groups have been synthesized and used to disperse single-walled carbon nanotubes (SWCNT) in aqueous solutions. To this end, planar pyrene groups enable association by means of π-stacking onto carbon nanotubes and, in turn, the attachment of the cationic ruthenium complexes. Importantly, the ionic nature of the ruthenium complexes allows the formation of stable dispersions featuring individualized SWCNTs in water as confirmed in a number of spectroscopic and microscopic assays. In addition, steady-state photoluminescence spectroscopy was used to probe the excited state interactions between the ruthenium complexes and SWCNTs

  20. Ruthenium(salen)-catalyzed aerobic oxidative desymmetrization of meso-diols and its kinetics.

    PubMed

    Shimizu, Hideki; Onitsuka, Satoaki; Egami, Hiromichi; Katsuki, Tsutomu

    2005-04-20

    Chiral (nitrosyl)ruthenium(salen) complexes were found to be efficient catalysts for aerobic oxidative desymmetrization of meso-diols under photoirradiation to give optically active lactols. The scope of the applicability of this reaction ranges widely from acyclic diols to mono-cyclic diols, although fine ligand-tuning of the ruthenium(salen) complexes was required to attain high enantioselectivity (up to 93% ee). In particular, the nature of the apical ligand was found to affect not only enantioselectivity but also kinetics of the desymmetrization reaction. Spectroscopic analysis of the oxidation disclosed that irradiation of visible light is indispensable not only for dissociation of the nitrosyl ligand but also for single electron transfer from the alcohol-bound ruthenium ion to dioxygen. PMID:15826178

  1. Use of phosphate for separation of cobalt from iron

    USGS Publications Warehouse

    North, V.; Wells, R.C.

    1942-01-01

    The well-known tendency of cobalt to be retained by the iron-alumina precipitate produced by ammonia has generally been ascribed to a specific adsorption by the large surface of this gelatinous precipitate. Whatever its cause, it can be overcome by precipitating the iron as phosphate at a pH of 3.5. The precipitate is easily filterable and practically all the cobalt passes into the filtrate.

  2. 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.

  3. Synthesis and structural characterization of polyaniline/cobalt chloride composites

    NASA Astrophysics Data System (ADS)

    Asha, Goyal, Sneh Lata; Kishore, Nawal

    2016-05-01

    Polyaniline (PANI) and PANI /cobalt chloride composites were synthesized by in situ chemical oxidative polymerization of aniline with CoCl2.6H2O using ammonium peroxidisulphate as an oxidant. These composites were characterized by X-ray diffraction (XRD) and Scanning electron microscopy (SEM). The XRD study reveals that both PANI and composites are amorphous. The XRD and SEM results confirm the presence of cobalt chloride in the composites.

  4. Luminescent ruthenium polypyridyl complexes containing pendant pyridinium acceptors

    SciTech Connect

    Berg-Brennan, C.; Subramanian, P.; Absi, M.

    1996-06-05

    The author`s entry into the linked systems was stimulated by the observation that ruthenium phenanthroline (phen) complexes containing free (noncoordinated) pyridyl functionalities will rapidly oxidatively electropolymerize in dry solvents. (Examples of polymerizable complexes include Ru(phen){sub 2}(4,4{prime}-bpy){sub 2}{sup 2+}, Ru(phen){sub 2}(bis(4-pyridyl)ethylene){sub 2}{sup 2+}, and Ru(phen){sub 2}-(bis(4-pyridyl)ethane){sub 2}{sup 2+}). Although the exact mechanism of electropolymerization has yet to be established with certainty, the available remote indirect evidence is consistent with nucleophilic attack by one of the available remote bipyridyl nitrogens at one of the phenanthroline carbons, after activation of the phen ligand by coordinated metal (Ru) oxidation. Subsequent elimination of a phen H atom is apparently accomplished by spontaneous reduction of the metal center-leaving behind, therefore, a positively charged pyridyl nitrogen and a nitrogen(bipyridyl)-carbon(phen) bond. The availability of two phen and two bipyridyl ligands per metal complex leads to multiple linkages per complex and, therefore, cross-linked metallopolymer formation.

  5. Interfacial reactivity of ruthenium nanoparticles protected by ferrocenecarboxylates.

    PubMed

    Chen, Limei; Song, Yang; Hu, Peiguang; Deming, Christopher P; Guo, Yan; Chen, Shaowei

    2014-09-21

    Stable ruthenium nanoparticles protected by ferrocenecarboxylates (RuFCA) were synthesized by thermolytic reduction of RuCl3 in 1,2-propanediol. The resulting particles exhibited an average core diameter of 1.22 ± 0.23 nm, as determined by TEM measurements. FTIR and (1)H NMR spectroscopic measurements showed that the ligands were bound onto the nanoparticle surface via Ru-O bonds in a bidentate configuration. XPS measurements exhibited a rather apparent positive shift of the Fe2p binding energy when the ligands were bound on the nanoparticle surface, which was ascribed to the formation of highly polarized Ru-O interfacial bonds that diminished the electron density of the iron centers. Consistent results were obtained in electrochemical measurements where the formal potential of the nanoparticle-bound ferrocenyl moieties was found to increase by ca. 120 mV. Interestingly, galvanic exchange reactions of the RuFCA nanoparticles with Pd(ii) followed by hydrothermal treatment at 200 °C led to (partial) decarboxylation of the ligands such that the ferrocenyl moieties were now directly bonded to the metal surface, as manifested in voltammetric measurements that suggested intervalence charge transfer between the nanoparticle-bound ferrocene groups. PMID:25075931

  6. Anodic deposition of hydrous ruthenium oxide for supercapacitors

    NASA Astrophysics Data System (ADS)

    Hu, Chi-Chang; Liu, Ming-Jue; Chang, Kuo-Hsin

    This communication demonstrates the success in the anodic deposition of hydrous ruthenium oxide (denoted as RuO 2· xH 2O) from RuCl 3· xH 2O in aqueous media with/without adding acetate ions (CH 3COO -, AcO -) as the complex agent. The benefits of as-deposited RuO 2· xH 2O include the low electron-hopping resistance and the low contact resistance at the Ti-RuO 2· xH 2O interface which are clarified in electrochemical impedance spectroscopic (EIS) studies. The cycling stability, specific capacitance, and power performance of as-deposited RuO 2· xH 2O are further improved by annealing in air at 150 °C for 2 h. The morphologies of as-deposited and annealed RuO 2· xH 2O films, examined by scanning electron microscopy (SEM), are very similar to that of thermally decomposed RuO 2. The high onset frequencies of 660 and 1650 Hz obtained from EIS spectra for the as-deposited and annealed RuO 2· xH 2O films, respectively, definitely illustrate the high-power merits of both oxide films prepared by means of the anodic deposition without considering the advantages of its simplicity, one-step, reliability, low cost, and versatility for electrode preparation.

  7. Photophysical properties of amphiphilic ruthenium(II) complexes in micelles.

    PubMed

    Rajkumar, Eswaran; Mareeswaran, Paulpandian Muthu; Rajagopal, Seenivasan

    2014-09-01

    Amphiphilic ruthenium(II) complexes II–IV were synthesized and their photophysical properties were investigated in the presence of anionic (SDS), cationic (CTAB) and neutral (Triton X-100) micelles. The absorption and emission spectral data in the presence of micelles show that these Ru(II) complexes are incorporated in the micelles. There are two types of interaction between complexes I–IV and the micelles: hydrophobic and electrostatic. In the case of cationic micelles (CTAB), the hydrophobic interactions are predominant over electrostatic repulsion for the binding of cationic complexes II–IV with CTAB. In the case of anionic micelles (SDS), electrostatic interactions seem to be important in the binding of II–IV to SDS. Hydrophobic interactions play a dominant role in the binding of II–IV to the neutral micelles, Triton X-100. Based on the steady state and luminescence experiments, the enhancement of luminescence intensity and lifetime in the presence of micelles is due to the protection of the complexes from exposure to water in this environment. PMID:24976590

  8. Ruthenium olefin metathesis catalysts featuring unsymmetrical N-heterocyclic carbenes.

    PubMed

    Paradiso, Veronica; Bertolasi, Valerio; Costabile, Chiara; Grisi, Fabia

    2016-01-14

    New ruthenium Grubbs' and Hoveyda-Grubbs' second generation catalysts bearing N-alkyl/N-isopropylphenyl N-heterocyclic carbene (NHC) ligands with syn or anti backbone configuration were obtained and compared in model olefin metathesis reactions. Different catalytic efficiencies were observed depending on the size of the N-alkyl group (methyl or cyclohexyl) and on the backbone configuration. The presence of an N-cyclohexyl substituent determined the most significant reactivity differences between catalysts with syn or anti phenyl groups on the backbone. In particular, anti catalysts proved highly efficient, especially in the ring-closing metathesis (RCM) of encumbered diolefins, while syn catalysts showed low efficiency in the RCM of less hindered diolefins. This peculiar behavior, rationalized through DFT studies, was found to be related to the high propensity of these catalysts to give nonproductive metathesis events. Enantiopure anti catalysts were also tested in asymmetric metathesis reactions, where moderate enantioselectivities were observed. The steric and electronic properties of unsymmetrical NHCs with the N-cyclohexyl group were then evaluated using the corresponding rhodium complexes. While steric factors proved unimportant for both syn and anti NHCs, a major electron-donating character was found for the unsymmetrical NHC with anti phenyl substituents on the backbone. PMID:26608162

  9. Graphene Oxide/ Ruthenium Oxide Composites for Supercapacitors Electrodes

    NASA Astrophysics Data System (ADS)

    Amir, Fatima

    Supercapacitors are electrical energy storage devices with high power density, high rate capability, low maintenance cost, and long life cycle. They complement or replace batteries in harvesting applications when high power delivery is needed. An important improvement in performance of supercapacitors has been achieved through recent advances in the development of new nanostructured materials. Here we will discuss the fabrication of graphene oxide/ ruthenium oxide supercacitors electrodes including electrophoretic deposition. The morphology and structure of the fabricated electrodes were investigated and will be discussed. The electrochemical properties were determined using cyclic voltammetry and galvanostatic charge/discharge techniques and the experiments that demonstrate the excellent capacitive properties of the obtained supercapacitors will also be discussed. The fabrication and characterization of the samples were performed at the Center of Functional Nanomaterials at Brookhaven National Lab. The developed approaches in our study represent an exciting direction for designing the next generation of energy storage devices. This work was supported in part by the U.S. Department of Energy through the Visiting Faculty Program and the research used resources of the Center for Functional Nanomaterials at Brookhaven National Laboratory.

  10. Coordination of dibensothiophenes and corannulenes to organometallic ruthenium (II) fragments

    SciTech Connect

    Vecchi, Paul Anthony

    2005-05-01

    This dissertation contains five papers in the format required for journal publication which describe (in part) my research accomplishments as a graduate student at Iowa State University. This work can be broadly categorized as the binding of weakly-coordinating ligands to cationic organometallic ruthenium fragments, and consists of two main areas of study. Chapters 2-4 are investigations into factors that influence the binding of dibenzothiophenes to {l_brace}Cp'Ru(CO){sub 2}{r_brace}{sup +} fragments, where Cp' = {eta}{sup 5}-C{sub 5}H{sub 5} (Cp) and {eta}{sup 5}-C{sub 5}Me{sub 5} (Cp*). Chapters 5 and 6 present the synthesis and structural characterization of complexes containing corannulene buckybowls that are {eta}{sup 6}-coordinated to {l_brace}Cp*Ru{r_brace}{sup +} fragments. The first chapter contains a brief description of the difficulty in lowering sulfur levels in diesel fuel along with a review of corannulene derivatives and their metal complexes. After the final paper is a short summary of the work herein (Chapter 7). Each chapter is independent, and all equations, schemes, figures, tables, references, and appendices in this dissertation pertain only to the chapter in which they appear.

  11. Dual-targeting organometallic ruthenium(II) anticancer complexes bearing EGFR-inhibiting 4-anilinoquinazoline ligands.

    PubMed

    Zhang, Yang; Zheng, Wei; Luo, Qun; Zhao, Yao; Zhang, Erlong; Liu, Suyan; Wang, Fuyi

    2015-08-01

    We have recently demonstrated that complexation with (η(6)-arene)Ru(II) fragments confers 4-anilinoquinazoline pharmacophores a higher potential for inducing cellular apoptosis while preserving the highly inhibitory activity of 4-anilinoquinazolines against EGFR and the reactivity of the ruthenium centre to 9-ethylguanine (Chem. Commun., 2013, 49, 10224-10226). Reported herein are the synthesis, characterisation and evaluation of the biological activity of a new series of ruthenium(ii) complexes of the type [(η(6)-arene)Ru(N,N-L)Cl]PF6 (arene = p-cymene, benzene, 2-phenylethanol or indane, L = 4-anilinoquinazolines). These organometallic ruthenium complexes undergo fast hydrolysis in aqueous solution. Intriguingly, the ligation of (arene)Ru(II) fragments with 4-anilinoquinazolines not only makes the target complexes excellent EGFR inhibitors, but also confers the complexes high affinity to bind to DNA minor grooves while maintaining their reactivity towards DNA bases, characterising them with dual-targeting properties. Molecular modelling studies reveal that the hydrolysis of these complexes is a favourable process which increases the affinity of the target complexes to bind to EGFR and DNA. In vitro biological activity assays show that most of this group of ruthenium complexes are selectively active inhibiting the EGF-stimulated growth of the HeLa cervical cancer cell line, and the most active complex [(η(6)-arene)Ru(N,N-L13)Cl]PF6 (, IC50 = 1.36 μM, = 4-(3'-chloro-4'-fluoroanilino)-6-(2-(2-aminoethyl)aminoethoxy)-7-methoxyquinazoline) is 29-fold more active than its analogue, [(η(6)-arene)Ru(N,N-ethylenediamine)Cl]PF6, and 21-fold more active than gefitinib, a well-known EGFR inhibitor in use clinically. These results highlight the strong promise to develop highly active ruthenium anticancer complexes by ligation of cytotoxic ruthenium pharmacophores with bioactive organic molecules. PMID:26106875

  12. Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

    DOEpatents

    Zelenay, Piotr; Wu, Gang

    2014-04-29

    A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

  13. Effects of cobalt in nickel-base superalloys

    NASA Technical Reports Server (NTRS)

    Tien, J. K.; Jarrett, R. N.

    1983-01-01

    The role of cobalt in a representative wrought nickel-base superalloy was determined. The results show cobalt affecting the solubility of elements in the gamma matrix, resulting in enhanced gamma' volume fraction, in the stabilization of MC-type carbides, and in the stabilization of sigma phase. In the particular alloy studied, these microstructural and microchemistry changes are insufficient in extent to impact on tensile strength, yield strength, and in the ductilities. Depending on the heat treatment, creep and stress rupture resistance can be cobalt sensitive. In the coarse grain, fully solutioned and aged condition, all of the alloy's 17% cobalt can be replaced by nickel without deleteriously affecting this resistance. In the fine grain, partially solutioned and aged condition, this resistance is deleteriously affected only when one-half or more of the initial cobalt content is removed. The structure and property results are discussed with respect to existing theories and with respect to other recent and earlier findings on the impact of cobalt, if any, on the performance of nickel-base superalloys.

  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. 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

  16. Reoxidation and deactivation of supported cobalt Fischer-Tropsch catalysts

    SciTech Connect

    Schanke, D.; Bergene, E.; Adnanes, E.

    1995-12-31

    As a result of the highly exothermic nature of the Fischer-Tropsch reaction, heat transfer considerations limit the maximum conversion per pass in fixed-bed processes, whereas slurry reactors can operate at higher conversions. During Fischer-Tropsch synthesis on cobalt catalysts, high conversions will generate high partial pressures of water at the reactor exit, due to the low water gas shift activity of cobalt. In addition, the extensive back-mixing in slurry reactors will give a relatively uniform concentration profile in the reactor, characterized by a high concentration of water and low reactant concentrations. From the commercial iron-catalyzed Fischer-Tropsch synthesis in fixed-bed (Arge) reactors it is known that the catalyst deactivates by oxidation of iron by CO{sub 2} and H{sub 2}O near the exit of the reactor. Although bulk oxidation of cobalt during Fischer-Tropsch synthesis is not thermodynamically favored, it was early speculated that surface oxidation of cobalt could occur during Fischer-Tropsch synthesis. The purpose of the present work is to describe the influence of water on the deactivation behavior of Al{sub 2}O{sub 3} supported cobalt catalysts. The possibility of cobalt oxidation during Fischer-Tropsch synthesis was investigated by model studies.

  17. Highly Efficient Process for Production of Biofuel from Ethanol Catalyzed by Ruthenium Pincer Complexes.

    PubMed

    Xie, Yinjun; Ben-David, Yehoshoa; Shimon, Linda J W; Milstein, David

    2016-07-27

    A highly efficient ruthenium pincer-catalyzed Guerbet-type process for the production of biofuel from ethanol has been developed. It produces the highest conversion of ethanol (73.4%, 0.02 mol% catalyst) for a Guerbet-type reaction, including significant amounts of C4 (35.8% yield), C6 (28.2% yield), and C8 (9.4% yield) alcohols. Catalyst loadings as low as 0.001 mol% can be used, leading to a record turnover number of 18 209. Mechanistic studies reveal the likely active ruthenium species and the main deactivation process. PMID:27399841

  18. Effects of some ruthenium chelates on MCa mammary carcinoma and on TLX5 lymphoma in mice.

    PubMed

    Bregant, F; Pacor, S; Ghosh, S; Chattopadhyay, S K; Sava, G

    1993-01-01

    A group of four Ruthenium chelates of the mixed hard/soft N-S donor ligands 2-formylpyridine (4-H/4-phenyl)thiosemicarbazone has been studied in the experimental models of MCa mammary carcinoma and TLX5 lymphoma in the CBA mouse. Although all the four tested complexes, bis-[2-formylpyridine(4- phenyl)thiosemicarbazone]ruthenium(II)chloride]Ru(L1)(L1H)Cl, 1], [2-formylpyridine(4-phenyl)thiosemicarbazone]ruthenium(II)-mu- trichloro chloro(imidazole)ruthenium(III)monomethanolate [Ru2(L1)(imz)Cl4.CH3OH, 9]. [2-formylpyridine(4-phenyl)thiosemicarbazone]dichloroimidazoler uthenium(II) [Ru(L1H)(imz)Cl2,10] and bis[2- formylpyridinethiosemicarbazone]ruthenium(II) perchlorate, dihydrate [Ru(L)(LH)ClO4.2H2O, 16], reduced the formation of lung metastases at the same extent only compound 1 caused parallel inhibition of the growth of the primary tumor. The chemical nature of the tested compounds seems to determine the nature of the antitumor effects and the bis-chelates are found to be endowed with greater cytotoxic properties towards primary tumor than the monochelates. This opens up a very interesting point, whether it is the presence of two chelate rings around the Ruthenium(II)/(III) acceptor centre or the increase in the number of the soft (S) donor centers that generates greater cytotoxic properties in the corresponding ruthenium complexes. As far as the reduction of the metastasis formation is concerned, it appears that among the four Ruthenium chelates tested, it is possible to identify structures capable of controlling the spread of tumor to the lungs in the absence of significant cytotoxicity for tumor cells. This finding appears of importance in that it indicates the possibility of a specific mechanism of interaction with cells of the metastatic tumor. In this context it appears necessary to investigate other congeners of this "family" with more sulfur donor sites and particularly those with better water solubility. PMID:8352519

  19. LC-MS study of ruthenium catalysts of water oxidation in artificial photosynthesis

    NASA Astrophysics Data System (ADS)

    Dzhabieva, Z. M.; Martynenko, V. M.; Temnova, M. L.; Yakutkina, O. V.; Dzhabiev, T. S.; Shilov, A. E.

    2014-05-01

    Catalysts of water oxidation for artificial photosynthesis, formed from the binuclear oxysulfate ruthenium(IV) complex K4[Ru2(SO4)2(μ-SO4)2(μ-O)2] · 2H2O, are studied via chromatography-mass spectrometry. It is shown that these new catalysts do not contain organic ligands and are more stable and active than the familiar blue dimer [(bpy)2Ru(OH)2]2O4+ and its analogues. It is found that adamantane-like tetra-nuclear and octanuclear ruthenium clusters are active catalysts that oxidize water to oxygen and oxozone O4, respectively.

  20. Conductive polymers derived from iron, ruthenium, and osmium metalloporphyrins: The shish-kebab approach

    PubMed Central

    Collman, James P.; McDevitt, John T.; Yee, Gordon T.; Leidner, Charles R.; McCullough, Laughlin G.; Little, William A.; Torrance, Jerry B.

    1986-01-01

    The synthesis and characterization of pyrazine-bridged polymers of iron(II/III), ruthenium(II/III), and osmium(II/III) octaethylporphyrin (dubbed “shish-kebab” polymers) are presented. Optical and dc conductivity measurements reveal that the ruthenium and osmium polymers, when partially oxidized, are highly conductive. Electrochemical and ESR results are presented that indicate the existence of an interesting metal-centered conduction pathway. Unlike most of the previously reported porphyrinic molecular metals in which the conduction electrons are macrocyclic-based, electron transport in these materials proceeds exclusively along the metal-pyrazine backbone. PMID:16593717

  1. Ruthenium(III) catalyzed oxidation of sugar alcohols by dichloroisocyanuric acid—A kinetic study

    NASA Astrophysics Data System (ADS)

    Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

    2016-02-01

    Kinetics of ruthenium(III) catalyzed oxidation of biologically important sugar alcohols (myo-inositol, D-sorbitol, and D-mannitol) by dichloroisocyanuric acid was carried out in aqueous acetic acid—perchloric medium. The reactions were found to be first order in case of oxidant and ruthenium(III). Zero order was observed with the concentrations of sorbitol and mannitol whereas, a positive fractional order was found in the case of inositol concentration. An inverse fractional order was observed with perchloric acid in oxidation of three substrates. Arrhenius parameters were calculated and a plausible mechanism was proposed.

  2. Formation of C-C bonds via ruthenium-catalyzed transfer hydrogenation().

    PubMed

    Moran, Joseph; Krische, Michael J

    2012-01-01

    Ruthenium-catalyzed transfer hydrogenation of diverse π-unsaturated reactants in the presence of aldehydes provides products of carbonyl addition. Dehydrogenation of primary alcohols in the presence of the same π-unsaturated reactants provides identical products of carbonyl addition. In this way, carbonyl addition is achieved from the alcohol or aldehyde oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. In this account, the discovery of ruthenium-catalyzed C-C bond-forming transfer hydrogenations and the recent development of diastereo- and enantioselective variants are discussed. PMID:23430602

  3. Formation of C–C bonds via ruthenium-catalyzed transfer hydrogenation*

    PubMed Central

    Moran, Joseph; Krische, Michael J.

    2013-01-01

    Ruthenium-catalyzed transfer hydrogenation of diverse π-unsaturated reactants in the presence of aldehydes provides products of carbonyl addition. Dehydrogenation of primary alcohols in the presence of the same π-unsaturated reactants provides identical products of carbonyl addition. In this way, carbonyl addition is achieved from the alcohol or aldehyde oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. In this account, the discovery of ruthenium-catalyzed C–C bond-forming transfer hydrogenations and the recent development of diastereo- and enantioselective variants are discussed. PMID:23430602

  4. Hydrogenation of Carbon Dioxide to Methane by Ruthenium Nanoparticles in Ionic Liquid.

    PubMed

    Melo, Catarina I; Szczepańska, Anna; Bogel-Łukasik, Ewa; Nunes da Ponte, Manuel; Branco, Luís C

    2016-05-23

    The efficient transformation of carbon dioxide into fuels can be an excellent alternative to sequestration. In this work, we describe CO2 hydrogenation to methane in imidazolium-based ionic liquid media, using ruthenium nanoparticles prepared in situ as catalyst. The best yield of methane (69 %) was achieved using 0.24 mol % ruthenium catalyst (in [omim][NTf2 ], 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide, at 40 bar of hydrogen pressure plus 40 bar of CO2 pressure, and at 150 °C. PMID:27114238

  5. Cobalt mineral exploration and supply from 1995 through 2013

    USGS Publications Warehouse

    Wilburn, David R.

    2011-01-01

    The global mining industry has invested a large amount of capital in mineral exploration and development over the past 15 years in an effort to ensure that sufficient resources are available to meet future increases in demand for minerals. Exploration data have been used to identify specific sites where this investment has led to a significant contribution in global mineral supply of cobalt or where a significant increase in cobalt production capacity is anticipated in the next 5 years. This report provides an overview of the cobalt industry, factors affecting mineral supply, and circumstances surrounding the development, or lack thereof, of key mineral properties with the potential to affect mineral supply. Of the 48 sites with an effective production capacity of at least 1,000 metric tons per year of cobalt considered for this study, 3 producing sites underwent significant expansion during the study period, 10 exploration sites commenced production from 1995 through 2008, and 16 sites were expected to begin production by 2013 if planned development schedules are met. Cobalt supply is influenced by economic, environmental, political, and technological factors affecting exploration for and production of copper, nickel, and other metals as well as factors affecting the cobalt industry. Cobalt-rich nickel laterite deposits were discovered and developed in Australia and the South Pacific and improvements in laterite processing technology took place during the 1990s and early in the first decade of the 21st century when mining of copper-cobalt deposits in Congo (Kinshasa) was restricted because of regional conflict and lack of investment in that country's mining sector. There was also increased exploration for and greater importance placed on cobalt as a byproduct of nickel mining in Australia and Canada. The emergence of China as a major refined cobalt producer and consumer since 2007 has changed the pattern of demand for cobalt, particularly from Africa and

  6. Cobalt(I) Olefin Complexes: Precursors for Metal-Organic Chemical Vapor Deposition of High Purity Cobalt Metal Thin Films.

    PubMed

    Hamilton, Jeff A; Pugh, Thomas; Johnson, Andrew L; Kingsley, Andrew J; Richards, Stephen P

    2016-07-18

    We report the synthesis and characterization of a family of organometallic cobalt(I) metal precursors based around cyclopentadienyl and diene ligands. The molecular structures of the complexes cyclopentadienyl-cobalt(I) diolefin complexes are described, as determined by single-crystal X-ray diffraction analysis. Thermogravimetric analysis and thermal stability studies of the complexes highlighted the isoprene, dimethyl butadiene, and cyclohexadiene derivatives [(C5H5)Co(η(4)-CH2CHC(Me)CH2)] (1), [(C5H5)Co(η(4)-CH2C(Me)C(Me)CH2)] (2), and [(C5H5)Co(η(4)-C6H8)] (4) as possible cobalt metal organic chemical vapor deposition (MOCVD) precursors. Atmospheric pressure MOCVD was employed using precursor 1, to synthesize thin films of metallic cobalt on silicon substrates under an atmosphere (760 torr) of hydrogen (H2). Analysis of the thin films deposited at substrate temperatures of 325, 350, 375, and 400 °C, respectively, by scanning electron microscopy and atomic force microscopy reveal temperature-dependent growth features. Films grown at these temperatures are continuous, pinhole-free, and can be seen to be composed of hexagonal particles clearly visible in the electron micrograph. Powder X-ray diffraction and X-ray photoelectron spectroscopy all show the films to be highly crystalline, high-purity metallic cobalt. Raman spectroscopy was unable to detect the presence of cobalt silicides at the substrate/thin film interface. PMID:27348614

  7. Nickel-cobalt alloy nanosheets obtained from reductive hydrothermal-treatment of nickel-cobalt hydroxide carbonate

    SciTech Connect

    Ghotbi, Mohammad Yeganeh; Jolagah, Ali; Afrasiabi, Hasan-ali

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer An anionic layered material, nickel-cobalt hydroxide carbonate was synthesized. Black-Right-Pointing-Pointer Reductive hydrothermal-treatment of the layered precursor produced an alloy. Black-Right-Pointing-Pointer The alloy is a bimetallic nanostructured nickel-cobalt and a soft magnet material. -- Abstract: Nickel-cobalt hydroxide carbonate, a layered material was synthesized by the co-precipitation method using urea as precipitant agent. This anionic layered material with hexagonal structure is constructed from nickel and cobalt ions within the layers and carbonate anions between the layers. Nickel-cobalt alloy with pure cubic phase was obtained by a reductive hydrothermal-treatment of the layered precursor. Powder X-ray diffraction pattern and Fourier transform infrared spectroscopy confirmed the formation of the initial layered material and its metallic alloy product. That is, the nickel-cobalt alloy has really produced via a wet chemical route for the first time. Magnetic measurement revealed that the alloy sample is a soft magnet material.

  8. Cobalt ferrite based magnetostrictive materials for magnetic stress sensor and actuator applications

    NASA Technical Reports Server (NTRS)

    Jiles, David C. (Inventor); Paulsen, Jason A. (Inventor); Snyder, John E. (Inventor); Lo, Chester C. H. (Inventor); Ring, Andrew P. (Inventor); Bormann, Keith A. (Inventor)

    2008-01-01

    Magnetostrictive material based on cobalt ferrite is described. The cobalt ferrite is substituted with transition metals (such manganese (Mn), chromium (Cr), zinc (Zn) and copper (Cu) or mixtures thereof) by substituting the transition metals for iron or cobalt to form substituted cobalt ferrite that provides mechanical properties that make the substituted cobalt ferrite material effective for use as sensors and actuators. The substitution of transition metals lowers the Curie temperature of the material (as compared to cobalt ferrite) while maintaining a suitable magnetostriction for stress sensing applications.

  9. Photoexpulsion of Surface-Grafted Ruthenium Complexes and Subsequent Release of Cytotoxic Cargos to Cancer Cells from Mesoporous Silica Nanoparticles

    PubMed Central

    Frasconi, Marco; Liu, Zhichang; Lei, Juying; Wu, Yilei; Strekalova, Elena; Malin, Dmitry; Ambrogio, Michael W.; Chen, Xinqi; Botros, Youssry Y.; Cryns, Vincent L.; Sauvage, Jean-Pierre; Stoddart, J. Fraser

    2014-01-01

    Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions. PMID:23815127

  10. Cytotoxic and genotoxic effects of cis-tetraammine(oxalato)ruthenium(III) dithionate on the root meristem cells of Allium cepa.

    PubMed

    Pereira, Flávia de Castro; Vilanova-Costa, Cesar Augusto Sam Tiago; de Lima, Aliny Pereira; Ribeiro, Alessandra de Santana Braga Barbosa; da Silva, Hugo Delleon; Pavanin, Luiz Alfredo; Silveira-Lacerda, Elisângela de Paula

    2009-06-01

    Ruthenium complexes have attracted much attention as possible building blocks for new transition-metal-based antitumor agents. The present study examines the mitotoxic and clastogenic effects induced in the root tips of Allium cepa by cis-tetraammine(oxalato)ruthenium(III) dithionate {cis-[Ru(C(2)O(2))(NH(3))(4)](2)(S(2)O(6))} at different exposure durations and concentrations. Correlation tests were performed to determine the effects of the time of exposure and concentration of ruthenium complex on mitotic index (MI) and mitotic aberration index. A comparison of MI results of cis-[Ru(C(2)O(2))(NH(3))(4)](2)(S(2)O(6)) to those of lead nitrate reveals that the ruthenium complex demonstrates an average mitotic inhibition eightfold higher than lead, with the frequency of cellular abnormalities almost fourfold lower and mitotic aberration threefold lower. A. cepa root cells exposed to a range of ruthenium complex concentrations did not display significant clastogenic effects. Cis-tetraammine(oxalato)ruthenium(III) dithionate therefore exhibits a remarkable capacity to inhibit mitosis, perhaps by inhibiting DNA synthesis or blocking the cell cycle in the G2 phase. Further investigation of the mechanisms of action of this ruthenium complex will be important to define its clinical potential and to contribute to a novel and rational approach to developing a new metal-based drug with antitumor properties complementary to those exhibited by the drugs already in clinical use. PMID:19020813

  11. Electromagnetic containerless reaction of samarium with cobalt for the formation of samarium-cobalt alloys

    NASA Technical Reports Server (NTRS)

    Chang, C. W.; Das, D. K.; Kumar, K.; Frost, R. T.

    1982-01-01

    The electromagnetic levitation technique has been used to obtain nearly stoichiometric SmCo5, with the reaction temperature controlled by a gas jet. The results of several experiments carried out at a 450 kHz, 25 kw RF power levitation facility using different reaction times and cooling rates are presented. It is shown that reaction rates achieved with the levitation technique are larger than the expected diffusion rate in the system liquid samarium-solid cobalt. It is also shown that substantial mixing occurs in the RF-levitated melt.

  12. Mechanism of ruthenium-catalyzed hydrogen transfer reactions. Concerted transfer of OH and CH hydrogens from an alcohol to a (Cyclopentadienone)ruthenium complex.

    PubMed

    Johnson, Jeffrey B; Bäckvall, Jan-E

    2003-10-01

    Kinetic studies of the ruthenium-catalyzed dehydrogenation of 1-(4-fluorophenyl)ethanol (4) by tetrafluorobenzoquinone (7) using the Shvo catalyst 1 at 70 degrees C show that the dehydrogenation by catalytic intermediate 2 is rate-determining with the rate = k[4][1](1/2) and with deltaH++ = 17.7 kcal mol(-1) and deltaS++ = -13.0 eu. The use of specifically deuterated derivative 4-CHOD and 4-CDOH gave individual isotope effects of k(CHOH)/k(CHOD) = 1.87 +/- 0.17 and k(CHOH)/k(CDOH) = 2.57 +/- 0.26, respectively. Dideuterated derivative 4-CDOD gave a combined isotope effect of k(CHOH)/k(CDOD) = 4.61 +/- 0.37. These isotope effects are consistent with a concerted transfer of both hydrogens of the alcohol to ruthenium species 2. PMID:14510542

  13. Tuning of magnetic parameters in cobalt-polystyrene nanocomposites by reduction cycling

    SciTech Connect

    Nair, Swapna S.; Sunny, Vijutha; Anantharaman, M.R.

    2011-10-15

    Graphical abstract: Cobalt nanoparticles were prepared by a reduction process inside polymer pores. A porous polymer network (polystyrene) was chosen as the template for the synthesis of elementary cobalt as high surface area cobalt nanoparticles are prone to oxidation. The preliminary studies reveal that the cobalt is first formed with an oxide protective layer outside and upon repeating the reduction cycles, inner pores of the polymers are opened which enhanced the yield of metallic cobalt. These high surface area cobalt nanoparticles embedded in a polymer are ideal for the synthesis of carbon nanotubes as cobalt can act as a catalyst for the nanotube synthesis. The concentration of cobalt can be tuned in this technique by repeating the cycling process. Highlights: {yields} Elementary cobalt nanoparticles were synthesized inside polystyrene by a novel process. {yields} The self protection is achieved by the auto-shelling with the metal oxide. {yields} The magnetisation and coercivity could be tuned by repeating the cycles. {yields} Tuning of magnetic properties (both coercivity and magnetisation) could be achieved by the repetition of reduction cycles. {yields} Synthesized nanocomposite can act as a catalyst for carbon nanotube synthesis. -- Abstract: Cobalt nanoparticles were prepared by a reduction process inside polymer pores using CoSO{sub 4}.7H{sub 2}O and NaBH{sub 4}. A porous polymer network (sulphonated polystyrene) was chosen, as the template for the synthesis of elementary cobalt as high surface area cobalt nanoparticles are prone to oxidation. The preliminary studies reveal that the cobalt is first formed with an oxide protective layer outside and upon repeating the reduction cycles, inner pores of the polymers are opened which enhanced the yield of metallic cobalt. These high surface area cobalt nanoparticles embedded in a polymer are ideal for the synthesis of carbon nanotubes as cobalt can act as a catalyst for the nanotube synthesis. The

  14. PHOTOCHEMICAL CO2 REDUCTION BY RHENUIM AND RUTHENIUM COMPLEXES.

    SciTech Connect

    FUJITA,E.; MUCKERMAN, J.T.; TANAKA, K.

    2007-11-30

    Photochemical conversion of CO{sub 2} to fuels or useful chemicals using renewable solar energy is an attractive solution to both the world's need for fuels and the reduction of greenhouse gases. Rhenium(I) and ruthenium(II) diimine complexes have been shown to act as photocatalysts and/or electrocatalysts for CO{sub 2} reduction to CO. We have studied these photochemical systems focusing on the identification of intermediates and the bond formation/cleavage reactions between the metal center and CO{sub 2}. For example, we have produced the one-electron-reduced monomer (i.e. Re(dmb)(CO){sub 3}S where dmb = 4,4'-dimethy-2,2'-bipyridine and S = solvent) either by reductive quenching of the excited states of fac-[Re(dmb)(CO){sub 3}(CH{sub 3}CN)]PF{sub 6} or by photo-induced homolysis of [Re(dmb)(CO){sub 3}]{sub 2}. We previously found that: (1) the remarkably slow dimerization of Re(dmb)(CO){sub 3}S is due to the absence of a vacant coordination site for Re-Re bond formation, and the extra electron is located on the dmb ligand; (2) the reaction of Re(dmb)(CO){sub 3}S with CO{sub 2} forms a CO{sub 2}-bridged binuclear species (CO){sub 3}(dmb)Re-CO(O)-Re(dmb)(CO){sub 3} as an intermediate in CO formation; and (3) the kinetics and mechanism of reactions are consistent with the interaction of the CO{sub 2}-bridged binuclear species with CO{sub 2} to form CO and CO{sub 3}{sup 2-}.

  15. {sup 106}Ruthenium Plaque Therapy (RPT) for Retinoblastoma

    SciTech Connect

    Murakami, Naoya; Suzuki, Shigenobu; Ito, Yoshinori; Yoshimura, Ryoichi; Inaba, Koji; Kuroda, Yuki; Morota, Madoka; Mayahara, Hiroshi; Sakudo, Mototake; Wakita, Akihisa; Okamoto, Hiroyuki; Sumi, Minako; Kagami, Yoshikazu; Nakagawa, Keiichi; Ohtomo, Kuni; Itami, Jun

    2012-09-01

    Purpose: To evaluate the effectiveness of episcleral {sup 106}ruthenium plaque therapy (RPT) in the management of retinoblastoma. Methods and Materials: One hundred one RPTs were retrospectively analyzed that were performed in 90 eyes of 85 patients with retinoblastoma at National Cancer Center Hospital between 1998 and 2008. Each RPT had a corresponding tumor and 101 tumors were considered in the analysis of local control. Median follow-up length was 72.8 months. Median patient age at the RPT was 28 months. Median prescribed doses at reference depth and outer surface of the sclera were 47.4 Gy and 162.3 Gy, respectively. Results: Local control rate (LCR) and ocular retention rate (ORR) at 2 years were 33.7% and 58.7%, respectively. Unilateral disease, International Classification of Retinoblastoma group C or more advanced at the first presentation or at the time of RPT, vitreous and/or subretinal seeding, tumor size greater than 5 disc diameter (DD), reference depth greater than 5 mm, dose rate at reference depth lower than 0.7 Gy/hour, dose at the reference depth lower than 35 Gy, and (biologically effective dose with an {alpha}/{beta} ratio of 10 Gy) at the reference depth lower than 40 Gy{sub 10} were associated with unfavorable LCR. Two patients died of metastatic disease. Radiation complications included retinal detachment in 12 eyes (13.3%), proliferative retinopathy in 6 (6.7%), rubeosis iris in 2 (2.2%), and posterior subcapsular cataract in 23 (25.6%). Conclusion: RPT is an effective eye-preserving treatment for retinoblastoma.

  16. Regression of Lung Cancer by Hypoxia Sensitizing Ruthenium Polypyridyl Complexes

    PubMed Central

    Yadav, Abhishek; Janaratne, Thamara; Krishnan, Arthi; Singhal, Sharad S.; Yadav, Sushma; Dayoub, Adam S.; Hawkins, Doyle L.; Awasthi, Sanjay; MacDonnell, Frederick M.

    2013-01-01

    The ruthenium (II) polypyridyl complexes (RPCs) Δ-[(phen)2Ru(tatpp)]Cl2 (Δ-[3]Cl2) and ΔΔ-[(phen)2Ru(tatpp)Ru(phen)2]Cl4 (ΔΔ-[4]Cl4) are a new generation of metal-based anti-tumor agents. These RPCs bind DNA via intercalation of the tatpp ligand which itself is redox-active and easily reduced at biologically relevant potentials. We have previously shown that RPC 44+ cleaves DNA when reduced by glutathione to a radical species, and that this DNA cleavage is potentiated under hypoxic conditions in vitro. Here we show that 32+ also exhibits free-radical mediated DNA cleavage in vitro, and that 32+ and 44+ both exhibit selective cytotoxicity towards cultured malignant cell lines, and marked inhibition of tumor growth in vivo. The murine acute toxicity of RPCs 32+ and 44+ (maximum tolerable doses (MTD’s) ~ 65 µmol/kg) is comparable with that for cisplatin (LD50 ~57 µmol/kg) but unlike cisplatin, RPC’s are generally cleared from the body unchanged via renal excretion without appreciable metabolism or nephrotoxic side effects. RPCs 32+ and 44+ are demonstrated to suppress growth of human non-small cell lung carcinoma (~83%), show potentiated cytotoxicity in vitro under hypoxic conditions, and induce apoptosis through both intrinsic and extrinsic pathways. The novel hypoxia-enhanced DNA cleavage activity and biological activity suggest a promising new anti-cancer pharmacophore based on metal complexes with aromatic ligands that are easily reduced at biologically accessible potentials. PMID:23443803

  17. Ruthenium porphyrin-induced photodamage in bladder cancer cells.

    PubMed

    Bogoeva, Vanya; Siksjø, Monica; Sæterbø, Kristin G; Melø, Thor Bernt; Bjørkøy, Astrid; Lindgren, Mikael; Gederaas, Odrun A

    2016-06-01

    Photodynamic therapy (PDT) is a noninvasive treatment for solid malignant and flat tumors. Light activated sensitizers catalyze photochemical reactions that produce reactive oxygen species which can cause cancer cell death. In this work we investigated the photophysical properties of the photosensitizer ruthenium(II) porphyrin (RuP), along with its PDT efficiency onto rat bladder cancer cells (AY27). Optical spectroscopy verified that RuP is capable to activate singlet oxygen via blue and red absorption bands and inter system crossing (ISC) to the triplet state. In vitro experiments on AY27 indicated increased photo-toxicity of RuP (20μM, 18h incubation) after cell illumination (at 435nm), as a function of blue light exposure. Cell survival fraction was significantly reduced to 14% after illumination of 20μM RuP with 15.6J/cm(2), whereas the "dark toxicity" of 20μM RuP was 17%. Structural and morphological changes of cells were observed, due to RuP accumulation, as well as light-dependent cell death was recorded by confocal microscopy. Flow cytometry verified that PDT-RuP (50μM) triggered significant photo-induced cellular destruction with a photoxicity of (93%±0.9%). Interestingly, the present investigation of RuP-PDT showed that the dominating mode of cell death is necrosis. RuP "dark toxicity" compared to the conventional chemotherapeutic drug cisplatin was higher, both evaluated by the MTT assay (24h). In conclusion, the present investigation shows that RuP with or without photoactivation induces cell death of bladder cancer cells. PMID:26845686

  18. Ruthenium(0) nanoparticle-catalyzed isotope exchange between 10B and 11B nuclei in decaborane(14).

    PubMed

    Yinghuai, Zhu; Widjaja, Effendi; Sia, Shirley Lo Pei; Zhan, Wang; Carpenter, Keith; Maguire, John A; Hosmane, Narayan S; Hawthorne, M Frederick

    2007-05-23

    Well dispersed ruthenium(0) nanoparticles, stabilized in the ionic liquid agent, trihexyltetradecylphosphonium dodecylbenzenesulfonate, have been successfully prepared via a reduction reaction of the precursor [CpRuCp*RuCp*]PF6 (Cp* = C5Me5). The ruthenium(0) nanoparticles were shown to catalyze the isotope exchange reaction between 10B enriched diborane and natural abundant B10H14 to produce highly 10B enriched (approximately 90%) decaborane(14) products. The ruthenium(0) nanoparticles were characterized by TEM, XRD, and XPS. The 10B enriched decaborane(14) has been analyzed by Raman spectroscopy, NMR, and high-resolution MS. PMID:17472379

  19. Magnetization measurements on fine cobalt particles

    NASA Astrophysics Data System (ADS)

    Respaud, M.; Broto, J. M.; Rakoto, H.; Ousset, J. C.; Osuna, J.; Ould Ely, T.; Amiens, C.; Chaudret, B.; Askenazy, S.

    1998-05-01

    We measure the magnetization of fine cobalt particles by SQUID and pulsed magnetic fields up to 35 T. These measurements have been made on two samples (C1, C2) with nonagglomerated particles. The analysis of the magnetic meaurements evidences very narrow log-normal size distribution centered around 1.5 nm (≅150 atoms) and 1.9 nm (≅310 atoms) for C1 and C2, respectively. Magnetization at 4.2 K seems to saturate in fields up to 5 T leading to an enhanced mean magnetic moment per atom compared to bulk value (1.72 μB). However, magnetization measurements up to 35 T do not permit to reach saturation, and show a continuous increase of μCo reaching 2.1±0.1 μB (C1) and 1.9±0.1 μB (C2). The effective magnetic anisotropies are found to be larger than those of bulk materials and decrease with increasing particle size. These features are associated with the large influence of the surface atoms.

  20. COBALT-60 Gamma Irradiation of Shrimp.

    NASA Astrophysics Data System (ADS)

    Sullivan, Nancy L. B.

    Meta- and ortho-tyrosine were measured using high performance liquid chromatography (HPLC) in conjunction with electrochemical detection in shrimp irradiated using cobalt-60 gamma radiation in the absorbed dose range 0.8 to 6.0 kGy, in nonirradiated shrimp, and in bovine serum albumin (BSA) irradiated in dilute aqueous solution at 25.0 kGy. Ortho-tyrosine was measured in nonirradiated BSA. Para-, meta-, and ortho-tyrosine were measured using HPLC in conjunction with uv-absorption detection in dilute aqueous solutions of phenylalanine irradiated in the absorbed dose range 16.0 to 195.0 kGy. The measured yields of tyrosine isomers were approximately linear as a function of absorbed dose in shrimp, and in irradiated solutions of phenylalanine up to 37.0 kGy. The occurrence of meta- and ortho-tyrosine, which had formerly been considered unique radiolytic products, has not previously been reported in nonirradiated shrimp or BSA. The conventional hydrolyzation and analytical techniques used in the present study to measure meta- and ortho-tyrosine may provide the basis for a method to detect and determine the dose used in food irradiation.

  1. Spinel cobalt ferrite by complexometric synthesis

    NASA Astrophysics Data System (ADS)

    Thang, Pham D.; Rijnders, Guus; Blank, Dave H. A.

    2005-09-01

    Magnetic fine particles of cobalt ferrite (CoFe 2O 4) have been synthesized using complexometric method in which ethylene diamine tetra acetic acid C 10H 16N 2O 8 (EDTA) acts as a complexing agent. The crystallographic structure, microstructure and magnetic properties of the synthesized powder were characterized by using X-ray diffraction (XRD), particle size analysis and vibrating sample magnetometry (VSM). The material crystallized in cubic spinel structure with lattice parameter of about 8.38 Å. Depending on the calcining temperature, the particle size of the powders varies in the range of hundreds of nanometers to tens of micrometers. A desired relative density above 95% of the theoretical value is obtained for the bulk sample after sintering. The calcined powders and sintered sample exhibit saturation magnetizations around 80 Am 2/kg which is expected for inverse CoFe 2O 4. With increasing calcining temperature the coercivity of these samples decreases. This simple synthesis route leads to a reproducible and stoichiometric material.

  2. Water Adsorption on Free Cobalt Cluster Cations.

    PubMed

    Kiawi, Denis M; Bakker, Joost M; Oomens, Jos; Buma, Wybren Jan; Jamshidi, Zahra; Visscher, Lucas; Waters, L B F M

    2015-11-01

    Cationic cobalt clusters complexed with water Con(+)-H2O (n = 6-20) are produced through laser ablation and investigated via infrared multiple photon dissociation (IR-MPD) spectroscopy in the 200-1700 cm(-1) spectral range. All spectra exhibit a resonance close to the 1595 cm(-1) frequency of the free water bending vibration, indicating that the water molecule remains intact upon adsorption. For n = 6, the frequency of this band is blue-shifted, but it gradually converges to the free water value with increasing cluster size. In the lower-frequency range (200-650 cm(-1)) the spectra contain several bands which show a very regular frequency evolution, suggesting that the exact cluster geometry has little effect on the water-surface interaction. Density functional theory (DFT) calculations are carried out at the OPBE/TZP level for three representative sizes (n = 6, 9, 13) and indicate that the vibrations responsible for the resonances correspond to bending and torsional modes between the cluster and water moieties. The potential energy surfaces describing these interactions are very shallow, making the calculated harmonic frequencies and IR intensities very sensitive to small geometrical perturbations. We conclude that harmonic frequency calculations on (local) minima structures provide insufficient information for these types of cluster complexes and need to be complemented with calculations that provide a more extensive sampling of the potential energy surface. PMID:26447780

  3. Cobalt-60 gamma irradiation of shrimp

    SciTech Connect

    Sullivan, N.L.B.

    1993-01-01

    Meta- and ortho-tyrosine were measured using high performance liquid chromatography (HPLC) in conjunction with electrochemical detection in shrimp irradiated using cobalt-60 gamma radiation in the absorbed dose range 0.8 to 6.0 kGy, in nonirradiated shrimp, and in bovine serum albumin (BSA) irradiated in dilute aqueous solution at 25.0 kGy. Ortho-tyrosine was measured in nonirradiated BSA. Para-, meta-, and ortho-tyrosine was measured using HPLC in conjunction with uv-absorption detection in dilute aqueous solutions of phenylalanine irradiated in the absorbed dose range 16.0 to 195.0 kGy. The measured yields of tyrosine isomers were approximately linear as a function of absorbed dose in shrimp, and in irradiated solutions of phenylalanine up to 37.0 kGy. The occurrence of meta- and ortho-tyrosine, which had formerly been considered unique radiolytic products, has not previously been reported in nonirradiated shrimp or BSA. The conventional hydrolyzation and analytical techniques used in the present study to measure meta- and ortho-tyrosine may provide the basis for a method to detect and determine the dose used in food irradiation.

  4. Structure of yttrium cobaltate from neutron diffraction

    SciTech Connect

    Mehta, A.; Berliner, R.; Smith, R.W.

    1997-05-01

    The crystal structure of YCoO{sub 3} has been determined from Rietveld analysis of the powder neutron diffraction data at 17, 100, and 300 K. At each temperature, the structure is a distorted perovskite with orthorhombic symmetry, space group Pbnm (Z = 4). The lattice parameters, at 300 K, are 5.1388 (5) x 5.4191(5) x 7.3658(7) {angstrom}. Structural analysis indicates that the formal valence of cobalt in YCoO{sub 3} is +3. Analysis of the Co-O distances and the absence of magnetic structure indicates that the majority of the Co{sup 3+} ions in YCoO{sub 3} are in the low-spin (i.e. t{sub 2g}{sup 6}e{sub g}{sup 0}) state. The data also show that perhaps 10% of the CO{sup 3+} ions at 300 K (but insignificant fractions at 100 and 17 K) are in the high-spin state.

  5. Tailor-Made Ruthenium-Triphos Catalysts for the Selective Homogeneous Hydrogenation of Lactams.

    PubMed

    Meuresch, Markus; Westhues, Stefan; Leitner, Walter; Klankermayer, Jürgen

    2016-01-22

    The development of a tailored tridentate ligand enabled the synthesis of a molecular ruthenium-triphos catalyst, eliminating dimerization as the major deactivation pathway. The novel catalyst design showed strongly increased performance and facilitated the hydrogenation of highly challenging lactam substrates with unprecedented activity and selectivity. PMID:26661531

  6. New route toward building active ruthenium nanoparticles on ordered mesoporous carbons with extremely high stability.

    PubMed

    Yang, Ying; Sun, Chengjun; Ren, Yang; Hao, Shijie; Jiang, Daqiang

    2014-01-01

    Creating highly active and stable metal catalysts is a persistent goal in the field of heterogeneous catalysis. However, a real catalyst can rarely achieve both of these qualities simultaneously due to limitations in the design of the active site and support. One method to circumvent this problem is to fabricate firmly attached metal species onto the voids of a mesoporous support formed simultaneously. In this study, we developed a new type of ruthenium catalyst that was firmly confined by ordered mesoporous carbons through the fabrication of a cubic Ia3d chitosan-ruthenium-silica mesophase before pyrolysis and silica removal. This facile method generates fine ruthenium nanoparticles (ca. 1.7 nm) that are homogeneously dispersed on a mesoporous carbonaceous framework. This ruthenium catalyst can be recycled 22 times without any loss of reactivity, showing the highest stability of any metal catalysts; this catalyst displays a high activity (23.3 mol(LA)h(-1)g(metal)(-1)) during the catalytic hydrogenation of levulinic acid (LA) when the metal loading is 6.1 wt%. Even at an ultralow loading (0.3 wt%), this catalyst still outperforms the most active known Ru/C catalyst. This work reveals new possibilities for designing and fabricating highly stable and active metal catalysts by creating metal sites and mesoporous supports simultaneously. PMID:24687047

  7. Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles.

    PubMed

    Novak, Maria S; Büchel, Gabriel E; Keppler, Bernhard K; Jakupec, Michael A

    2016-06-01

    Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed. PMID:26961253

  8. Method for producing electricity using a platinum-ruthenium-palladium catalyst in a fuel cell

    DOEpatents

    Gorer, Alexander

    2004-01-27

    A method for producing electricity using a fuel cell that utilizes a ternary alloy composition as a fuel cell catalyst, the ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

  9. Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

    2005-01-01

    Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

  10. Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations.

    PubMed

    Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

    2016-01-01

    We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen(-) (n = 3-12), and their corresponding neutral species. Photoelectron spectra of RuGen(-) clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen(-/0) clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters. PMID:27439955

  11. SORPTION OF LEAD ON A RUTHENIUM COMPOUND: A MACROSCOPIC AND MICROSCOPIC STUDY

    EPA Science Inventory

    The objective of this study was to elucidate the sorption mechanism of Pb on the high-affinity ruthenium compound with time at pH 6 employing batch methods and X-ray absorption fine structure (XAFS) and X-ray diffraction (XRD) spectroscopies. For the spectroscopic studies, Pb so...

  12. Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cells Stacks

    NASA Technical Reports Server (NTRS)

    Valdez, T. I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

    2005-01-01

    This viewgraph presentation gives a detailed review of the Direct Methanol Based Fuel Cell (DMFC) stack and investigates the Ruthenium that was found at the exit of the stack. The topics include: 1) Motivation; 2) Pathways for Cell Degradation; 3) Cell Duration Testing; 4) Duration Testing, MEA Analysis; and 5) Stack Degradation Analysis.

  13. SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

    DOEpatents

    Wilson, A.S.

    1961-05-01

    A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

  14. Versatile ruthenium complexes based on 2,2'-bipyridine modified peptoids.

    PubMed

    Baskin, Maria; Panz, Larisa; Maayan, Galia

    2016-08-16

    Helical peptoids bearing 2,2'-bipyridine form ruthenium complexes via intermolecular binding to linear peptoid strands or intramolecular binding to a cyclic scaffold. Ru(ii) binding promoted changes in the conformational order of the peptoids, and chiral induction from the peptoids to their metal center was observed. PMID:27349289

  15. New Ruthenium Complexes Based on Tetradentate Bipyridine Ligands for Catalytic Hydrogenation of Esters.

    PubMed

    Wang, Fangyuan; Tan, Xuefeng; Lv, Hui; Zhang, Xumu

    2016-08-01

    New bipyridinemethanamine-containing tetradentate ligands and their corresponding ruthenium complexes have been synthesized. The synthesized complexes performed well in the hydrogenation of a variety of esters with high efficiency (TON up to 9700) giving alcohols in good yields. PMID:27385062

  16. Cytoxicity and Apoptotic Mechanism of Ruthenium(II) Amino Acid Complexes in Sarcoma-180 Tumor Cells

    PubMed Central

    Lima, Aliny Pereira; Pereira, Flávia Castro; Almeida, Marcio Aurelio Pinheiro; Mello, Francyelli Mariana Santos; Pires, Wanessa Carvalho; Pinto, Thallita Monteiro; Delella, Flávia Karina; Felisbino, Sérgio Luis; Moreno, Virtudes; Batista, Alzir Azevedo; de Paula Silveira-Lacerda, Elisângela

    2014-01-01

    Over the past several decades, much attention has been focused on ruthenium complexes in antitumor therapy. Ruthenium is a transition metal that possesses several advantages for rational antitumor drug design and biological applications. In the present study, five ruthenium complexes containing amino acids were studied in vitro to determine their biological activity against sarcoma-180 tumor cells. The cytotoxicity of the complexes was evaluated by an MTT assay, and their mechanism of action was investigated. The results demonstrated that the five complexes inhibited the growth of the S180 tumor cell line, with IC50 values ranging from 22.53 µM to 50.18 µM, and showed low cytotoxicity against normal L929 fibroblast cells. Flow cytometric analysis revealed that the [Ru(gly)(bipy)(dppb)]PF6 complex (2) inhibited the growth of the tumor cells by inducing apoptosis, as evidenced by an increased number of Annexin V-positive cells and G0/G1 phase cell cycle arrest. Further investigation showed that complex 2 caused a loss of mitochondrial membrane potential; activated caspases 3, caspase-8, and caspase-9 and caused a change in the mRNA expression levels of caspase 3, caspase-9 as well as the bax genes. The levels of the pro-apoptotic Bcl-2 family protein Bak were increased. Thus, we demonstrated that ruthenium amino acid complexes are promising drugs against S180 tumor cells, and we recommend further investigations of their role as chemotherapeutic agents for sarcomas. PMID:25329644

  17. Olefin Ring Closing Metathesis and Hydrosilylation Reaction in Aqueous Medium by Grubbs Second Generation Ruthenium Catalyst

    EPA Science Inventory

    The Grubbs second generation ruthenium catalyst was shown to catalyze various olefin ring closing metathesis and hydrosilylation reactions in aqueous medium. Reactions proceeded in pure water without any additives or co-solvents, in a short period of time. We found that inhomogen...

  18. Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

    EPA Science Inventory

    A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

  19. New route toward building active ruthenium nanoparticles on ordered mesoporous carbons with extremely high stability

    PubMed Central

    Yang, Ying; Sun, Chengjun; Ren, Yang; Hao, Shijie; Jiang, Daqiang

    2014-01-01

    Creating highly active and stable metal catalysts is a persistent goal in the field of heterogeneous catalysis. However, a real catalyst can rarely achieve both of these qualities simultaneously due to limitations in the design of the active site and support. One method to circumvent this problem is to fabricate firmly attached metal species onto the voids of a mesoporous support formed simultaneously. In this study, we developed a new type of ruthenium catalyst that was firmly confined by ordered mesoporous carbons through the fabrication of a cubic Ia3d chitosan-ruthenium-silica mesophase before pyrolysis and silica removal. This facile method generates fine ruthenium nanoparticles (ca. 1.7 nm) that are homogeneously dispersed on a mesoporous carbonaceous framework. This ruthenium catalyst can be recycled 22 times without any loss of reactivity, showing the highest stability of any metal catalysts; this catalyst displays a high activity (23.3 molLAh−1gmetal−1) during the catalytic hydrogenation of levulinic acid (LA) when the metal loading is 6.1 wt%. Even at an ultralow loading (0.3 wt%), this catalyst still outperforms the most active known Ru/C catalyst. This work reveals new possibilities for designing and fabricating highly stable and active metal catalysts by creating metal sites and mesoporous supports simultaneously. PMID:24687047

  20. Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

    PubMed Central

    Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

    2016-01-01

    We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen− (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen− clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen−/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters. PMID:27439955

  1. Anti-Markovnikov hydroarylation of styrenes catalyzed by an in situ generated ruthenium complex.

    PubMed

    Martinez, Rémi; Genet, Jean-Pierre; Darses, Sylvain

    2008-09-01

    An efficient and practical catalytic system for the anti-Markovnikov ruthenium-catalyzed hydroarylation of styrenes with acetophenone, allowing a straightforward access to bibenzyl backbones, is described for the first time: this process, involving regioselective C-H bond activation, is complementary to a Friedel-Crafts type reaction giving the branched adduct. PMID:18726013

  2. Metalation dictates remote regioselectivity: ruthenium-catalyzed functionalization of meta C(Ar)-H Bonds.

    PubMed

    Juliá-Hernández, Francisco; Simonetti, Marco; Larrosa, Igor

    2013-10-25

    Remote control: The title reaction is effective for the sulfonation and alkylation of arenes bearing directing groups. Initial ortho metalation of the substrate forms an intermediate which does not evolve towards functionalization at the CM bond. Instead, the ruthenium catalyst acts as a strong electron-donating group, thus directing a remote electrophilic attack. PMID:24030678

  3. Production of dimethylfuran from hydroxymethylfurfural through catalytic transfer hydrogenation with ruthenium supported on carbon.

    PubMed

    Jae, Jungho; Zheng, Weiqing; Lobo, Raul F; Vlachos, Dionisios G

    2013-07-01

    RuC ees' transfer: Transfer hydrogenation using alcohols as hydrogen donors and supported ruthenium catalysts results in the selective conversion of hydroxymethylfurfural to dimethylfuran (>80% yield). During transfer hydrogenation, the hydrogen produced from alcohols is utilized in the hydrogenation of hydroxymethylfurfural. PMID:23754805

  4. Investigation of ruthenium dioxide formation mechanisms in containment glass synthesized by liquid feed

    SciTech Connect

    Sawada, K.; Shimada, T.; Sako, N.; Enokida, Y.; Schuller, S.; Angeli, F.; Charpentier, T.

    2013-07-01

    The presenting paper focuses on the structural configuration of ruthenium in vitreous matrices with the objective of obtaining more insight into ruthenium incorporation and solubilization mechanisms in borosilicate glasses. To determine the structural effect of an increasing RuO{sub 2} in a borosilicate glass, a series of glass samples were selected from a benchmark composition. {sup 11}B NMR shows that the borate network is influenced by the presence of RuO{sub 2} in the glass: the addition of 2% RuO{sub 2} in a borosilicate glass led to a significant rise of BO{sub 4}. RuO{sub 2} precipitated in the glass does not seem to be the cause of this modification because when RuO{sub 2} increase there is no further change of BO{sub 4} fraction. This effect can be therefore attributed to RuO{sub 2} dissolved in the glass. RuO{sub 2} is known to have a very low solubility in borosilicate glasses (50 to 2000 ppm depending on the temperature, sodium concentration and conditions of synthesis). The link between the ruthenium and the borated network is not yet clearly identified, however, assumptions can be made such as the formation of Ru-O-B when a sufficient quantity of Ru is add (> 400 ppm). Ruthenium could play the role of silicon in increasing the possibility of bridging bond formation with boron coordination number IV.

  5. Dinuclear ruthenium(II) polypyridyl complexes as single and two-photon luminescence cellular imaging probes.

    PubMed

    Xu, Wenchao; Zuo, Jiarui; Wang, Lili; Ji, Liangnian; Chao, Hui

    2014-02-28

    A new series of dinuclear ruthenium(II) polypyridyl complexes, which possess larger π-conjugated systems, good water solubility and pH resistance, and high photostability, were developed to act as single and two-photon luminescence cellular imaging probes. PMID:24418839

  6. Synthesis and linear and nonlinear absorption properties of dendronised ruthenium(II) phthalocyanine and naphthalocyanine.

    PubMed

    Dasari, Raghunath R; Sartin, Matthew M; Cozzuol, Matteo; Barlow, Stephen; Perry, Joseph W; Marder, Seth R

    2011-04-21

    Ruthenium phthalocyanines and naphthalocyanines with axial dendronised pyridine ligands show high solubility in a variety of solvents, and exhibit solid-state absorption spectra that are comparable to those obtained in dilute solution, making them interesting candidates for optical limiting in the visible. PMID:21399800

  7. SORPTION OF ARSENATE AND ARSENITE ON A RUTHENIUM COMPOUND: A MACROSCOPIC AND MICROSCOPIC STUDY

    EPA Science Inventory

    Sorption of arsenate and arsenite was examined on a ruthenium compound using macroscopic and microscopic techniques. Batch sorption experiments at pH 4,5,6, 7 and 8 were employed to construct constant solid solution ratio isotherms (CSI). After equilibration at the appropriate pH...

  8. Ruthenium-catalyzed cyclization of N-carbamoyl indolines with alkynes: an efficient route to pyrroloquinolinones.

    PubMed

    Manoharan, Ramasamy; Jeganmohan, Masilamani

    2015-09-21

    A regioselective synthesis of substituted pyrroloquinolinones via a ruthenium-catalyzed oxidative cyclization of substituted N-carbamoyl indolines with alkynes is described. The cyclization reaction was compatible with various symmetrical and unsymmetrical alkynes including substituted propiolates. Later, we performed the aromatization of pyrroloquinolinones into indole derivatives in the presence of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). PMID:26228840

  9. Effects of ruthenium seed layer on the microstructure and spin dynamics of thin permalloy films

    SciTech Connect

    Jin Lichuan; Zhang Huaiwu; Tang Xiaoli; Bai Feiming; Zhong Zhiyong

    2013-02-07

    The spin dynamics and microstructure properties of a sputtered 12 nm Ni{sub 81}Fe{sub 19} thin film have been enhanced by the use of a ruthenium seed layer. Both the ferromagnetic resonance field and linewidth are enhanced dramatically as the thickness of ruthenium seed layer is increased. The surface anisotropy energy constant can also be largely tailored from 0.06 to 0.96 erg/cm{sup -2} by changing the seed layer thickness. The changes to the dynamics magnetization properties are caused by both ruthenium seed layer induced changes in the Ni{sub 81}Fe{sub 19} structure properties and surface topography properties. Roughness induced inhomogeneous linewidth broadening is also seen. The damping constant is highly tunable via the ruthenium thickness. This approach can be used to tailor both the structure and spin dynamic properties of thin Ni{sub 81}Fe{sub 19} films over a wide range. And it may benefit the applications of spin dynamics and spin current based devices.

  10. Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

    2016-07-01

    We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen‑ (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen‑ clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen‑/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters.

  11. Determination of cobalt in samples containing cobalt and tungsten carbide by electrothermal atomic absorption spectrometry

    SciTech Connect

    Firriolo, J.M.; Kutzman, R.S.

    1985-09-01

    A method has been developed to determine the amount of cobalt (Co) in atmospheric dust samples which include free and sintered Co. Cobalt and tungsten carbide (WC) mixtures ranging from 0-100% Co were prepared for atomic absorption analysis by dissolving the Co in aqua regia. Using this method, the amount of Co in the samples assayed ranged from 90.9-100.1% of that gravimetrically added to the mixtures. The results of this aqua regia dissolution procedure for Co were compared to a hydrofluoric acid method which solubilized both the Co and the WC. Application of the aqua regia dissolution method to samples of sintered WC and Co dust resulted in complete recovery of the Co from these materials. These results were supported by x-ray analysis of the samples before and after dissolution of the Co with aqua regia. The described procedure is advantageous because it avoids the use of highly-caustic hydrofluoric acid and the results are quickly available.

  12. Cobalt chloride attenuates hypobaric hypoxia induced vascular leakage in rat brain: Molecular mechanisms of action of cobalt chloride

    SciTech Connect

    Kalpana, S.; Dhananjay, S.; Anju, B. Lilly, G.; Sai Ram, M.

    2008-09-15

    This study reports the efficacy of cobalt preconditioning in preventing hypobaric hypoxia induced vascular leakage (an indicator of cerebral edema) using male Sprague-Dawley rats as model system. Exposure of animals to hypobaric hypoxia led to a significant increase in vascular leakage, reactive oxygen species (ROS), nitric oxide (NO), and vascular endothelial growth factor (VEGF) levels. There was a marked increase in Nuclear Factor {kappa}B (NF{kappa}B) DNA binding activity and levels of pro-inflammatory cytokines such as Monocyte chemoattractant protein (MCP-1), Interferon-{gamma} (IFN-{gamma}), Interleukin-1 (IL-1), and Tumor Necrosis Factor-{alpha} (TNF-{alpha}) and cell adhesion molecules such as Vascular Cell Adhesion Molecule-1 (VCAM-1), and P-selectin. Chemical preconditioning by cobalt for 7 days (12.5 mg Co/kg b.w., oral) significantly attenuated cerebral vascular leakage and the expression of inflammatory mediators induced by hypoxia. Administration of NF{kappa}B inhibitor, curcumin (50 mg/kg b.w.; i.p.) appreciably inhibited hypoxia induced vascular leakage indicating the involvement of NF{kappa}B in causing vascular leakage. Interestingly, cobalt when administered at 12.5 mg Co/kg b.w. (i.p.), 1 h before hypoxia could not prevent the vascular leakage indicating that cobalt per se did not have an effect on NF{kappa}B. The lower levels of NF{kappa}B observed in the brains of cobalt administered animals might be due to higher levels of antioxidant and anti-inflammatory proteins (hemeoxygenase-1 and metallothionein). To conclude cobalt preconditioning inhibited hypobaric hypoxia induced cerebral vascular leakage by lowering NF{kappa}B DNA binding activity and its regulated pro-inflammatory mediators. This is contemplated to be mediated by cobalt induced reduction in ROS/NO and increase in HO-1 and MT.

  13. 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.

  14. Graphene/cobalt nanocarrier for hyperthermia therapy and MRI diagnosis.

    PubMed

    Hatamie, Shadie; Ahadian, Mohammad Mahdi; Ghiass, Mohammad Adel; Iraji Zad, Azam; Saber, Reza; Parseh, Benyamin; Oghabian, Mohammad Ali; Shanehsazzadeh, Saeed

    2016-10-01

    Graphene/cobalt nanocomposites are promising materials for theranostic nanomedicine applications, which are defined as the ability to diagnose, provide targeted therapy and monitor the response to the therapy. In this study, the composites were synthesized via chemical method, using graphene oxide as the source material and assembling cobalt nanoparticles of 15nm over the surface of graphene sheets. Various characterization techniques were then employed to reveal the morphology, size and structure of the nanocomposites, such as X-ray diffraction analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, high resolution transmission electron microscopy and ultraviolet visible spectroscopy. Using ion-coupled plasma optical emission spectroscopy, cobalt concentration in the nanocomposites was found to be 80%. In addition, cytotoxicity of graphene/cobalt nanocomposites were evaluated using 3-[4,5-dimethylthiazol-2yl]-2,5-diphenyltetrazolium bromide or MTT assay. MTT viability assay exhibited biocompatibility to L929 mouse fibroblasts cells, under a high dose of 100μg/mL over 24h. Hyperthermia results showed the superior conversion of electromagnetic energy into heat at 350kHz frequency for 0.01 and 0.005g/L of the nanocomposites solution. The measured heat generation and energy transfer results were anticipated by the finite element analysis, conducted for the 3D structure. Magnetic resonance imaging characteristics also showed that negatively charge graphene/cobalt nanocomposites are suitable for T1-weighted imaging. PMID:27351138

  15. Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

    PubMed

    Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

    2005-07-19

    Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline. PMID:16008388

  16. Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds

    SciTech Connect

    Hartwig, J.F.

    1990-12-01

    The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe{sub 3}){sub 4}Ru(X)(Y) and (DMPM){sub 2}Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe{sub 3}){sub 4}Ru(Ph)(Me) or (PMe{sub 3}){sub 4}Ru(Ph){sub 2} leads to the ruthenium benzyne complex (PMe{sub 3}){sub 4}Ru({eta}{sup 2}-C{sub 6}H{sub 4}) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO{sub 2} and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe{sub 3}){sub 4}Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs.

  17. Characterization of activated states of ruthenium-containing zeolite NaHY

    SciTech Connect

    Sheu, Shie-Ping; Karge, H.G.; Schloegl, R.

    1997-06-01

    As has been proven earlier, ruthenium-containing NaHY zeolites are able to catalyze the decomposition of ammonia at temperatures from 300 to 450{degrees}C. In such catalysts, ruthenium cations are still present, even after heat treatment in high vacuum at 400{degrees}C; they can be detected using ammonia and/or pyridine as probes for Fourier transform IR spectroscopy. They reside both in supercages and in sodalite cages. Various intermediates of the decomposition of the Ru(NH{sub 3}){sub 6}NaY complex on heat treatment in high vacuum were identified via in situ IR spectroscopy; in particular, evidence for the formation of complexes with nitrosyl ligands was obtained. It was shown that partially decomposed (deammoniated) Ru(NH{sub 3}){sub 6}NaY complexes can be recovered to some extent by readsorption of ammonia. Ruthenium-containing species were localized either in the supercages or in the small cavities as shown by IR spectroscopy employing ammonia and pyridine as probes. The acidic properties of variously treated Ru(NH{sub 3}){sub 6}NaY zeolites were characterized via temperature-programmed desorption (TPD) of ammonia, which was monitored by mass spectrometry. A strong interaction between ruthenium-containing species and the zeolite framework, leading to a lack of overtone and combination modes in the near infrared, is confirmed. Investigations of Ru(NH{sub 3}){sub 6}NaY samples by X-ray photoelectron spectroscopy under the same conditions as applied for IR and TPD studies revealed that, at variance with the results usually obtained after heat treatment of Ru(NH{sub 3}){sub 6}NaY in high vacuum, no significant formation of ruthenium metal species through autoreduction occurred. Rather, a particular form of a cation-exchanged Ru, Na-Y zeolite was obtained. 24 refs., 18 figs., 2 tabs.

  18. Preparation of Magnesium, Cobalt and Nickel Ferrite Nanoparticles from Metal Oxides using Deep Eutectic Solvents.

    PubMed

    Söldner, Anika; Zach, Julia; Iwanow, Melanie; Gärtner, Tobias; Schlosser, Marc; Pfitzner, Arno; König, Burkhard

    2016-09-01

    Natural deep eutectic solvents (DESs) dissolve simple metal oxides and are used as a reaction medium to synthesize spinel-type ferrite nanoparticles MFe2 O4 (M=Mg, Zn, Co, Ni). The best results for phase-pure spinel ferrites are obtained with the DES consisting of choline chloride (ChCl) and maleic acid. By employing DESs, the reactions proceed at much lower temperatures than usual for the respective solid-phase reactions of the metal oxides and at the same temperatures as synthesis with comparable calcination processes using metal salts. The method therefore reduces the overall required energy for the nanoparticle synthesis. Thermogravimetric analysis shows that the thermolysis process of the eutectic melts in air occurs in one major step. The phase-pure spinel-type ferrite particles are thoroughly characterized by X-ray diffraction, diffuse-reflectance UV/Vis spectroscopy, and scanning electron microscopy. The properties of the obtained nanoparticles are shown to be comparable to those obtained by other methods, illustrating the potential of natural DESs for processing metal oxides. PMID:27514793

  19. Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

    NASA Astrophysics Data System (ADS)

    Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

    2015-10-01

    A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

  20. 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...

  1. 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...

  2. 40 CFR 471.30 - Applicability; description of the nickel-cobalt forming subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... nickel-cobalt forming subcategory. 471.30 Section 471.30 Protection of Environment ENVIRONMENTAL... METAL POWDERS POINT SOURCE CATEGORY Nickel-Cobalt Forming Subcategory § 471.30 Applicability; description of the nickel-cobalt forming subcategory. This subpart applies to discharges of pollutants...

  3. 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....

  4. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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)...

  5. 40 CFR 421.230 - Applicability: Description of the primary nickel and cobalt subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... primary nickel and cobalt subcategory. 421.230 Section 421.230 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Nickel and Cobalt Subcategory § 421.230 Applicability: Description of the primary nickel and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting from...

  6. 40 CFR 421.310 - Applicability: Description of the secondary tungsten and cobalt subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... secondary tungsten and cobalt subcategory. 421.310 Section 421.310 Protection of Environment ENVIRONMENTAL... CATEGORY Secondary Tungsten and Cobalt Subcategory § 421.310 Applicability: Description of the secondary tungsten and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting...

  7. 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)...

  8. 40 CFR 471.30 - Applicability; description of the nickel-cobalt forming subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... nickel-cobalt forming subcategory. 471.30 Section 471.30 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Nickel-Cobalt Forming Subcategory § 471.30 Applicability; description of the nickel-cobalt forming subcategory. This subpart applies to discharges of pollutants to waters of...

  9. Comparison of different supplemental cobalt forms on fiber digestion and cobalamin levels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cobalt (Co) is essential for rumen microbial metabolism to synthesize methane, acetate and methionine. It also serves as a structural component of vitamin B*12, which functions as a coenzyme in energy metabolism. A study was conducted to determine if Co form (cobalt carbonate vs cobalt glucoheptona...

  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....

  11. 40 CFR 471.30 - Applicability; description of the nickel-cobalt forming subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... nickel-cobalt forming subcategory. 471.30 Section 471.30 Protection of Environment ENVIRONMENTAL... METAL POWDERS POINT SOURCE CATEGORY Nickel-Cobalt Forming Subcategory § 471.30 Applicability; description of the nickel-cobalt forming subcategory. This subpart applies to discharges of pollutants...

  12. 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...

  13. 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...

  14. 40 CFR 421.230 - Applicability: Description of the primary nickel and cobalt subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... primary nickel and cobalt subcategory. 421.230 Section 421.230 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Nickel and Cobalt Subcategory § 421.230 Applicability: Description of the primary nickel and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting from...

  15. 40 CFR 471.30 - Applicability; description of the nickel-cobalt forming subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... nickel-cobalt forming subcategory. 471.30 Section 471.30 Protection of Environment ENVIRONMENTAL... POINT SOURCE CATEGORY Nickel-Cobalt Forming Subcategory § 471.30 Applicability; description of the nickel-cobalt forming subcategory. This subpart applies to discharges of pollutants to waters of...

  16. 40 CFR 421.310 - Applicability: Description of the secondary tungsten and cobalt subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... secondary tungsten and cobalt subcategory. 421.310 Section 421.310 Protection of Environment ENVIRONMENTAL... CATEGORY Secondary Tungsten and Cobalt Subcategory § 421.310 Applicability: Description of the secondary tungsten and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting...

  17. 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...

  18. 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...

  19. Comparison of different supplemental cobalt forms on digestion and cobalamin levels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cobalt (Co) is essential for rumen microbial metabolism to synthesize methane, acetate and methionine. It also serves as a structural component of vitamin B12, which functions as a coenzyme in energy metabolism. A study was conducted to determine if Co form (cobalt carbonate vs cobalt glucoheptonat...

  20. 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...

  1. 40 CFR 471.30 - Applicability; description of the nickel-cobalt forming subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... nickel-cobalt forming subcategory. 471.30 Section 471.30 Protection of Environment ENVIRONMENTAL... METAL POWDERS POINT SOURCE CATEGORY Nickel-Cobalt Forming Subcategory § 471.30 Applicability; description of the nickel-cobalt forming subcategory. This subpart applies to discharges of pollutants...

  2. The effect of cobalt content in U-700 type alloys on degradation of aluminide coatings

    NASA Technical Reports Server (NTRS)

    Zaplatynsky, I.

    1985-01-01

    The influence of cobalt content in U-700 type alloys on the behavior of aluminide coatings is studied in burner rig cyclic oxidation tests at 1100C. It is determined that aluminide coatings on alloys with higher cobalt offer better oxidation protection than the same coatings on alloys containing less cobalt.

  3. 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....

  4. 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....

  5. 40 CFR 421.310 - Applicability: Description of the secondary tungsten and cobalt subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... secondary tungsten and cobalt subcategory. 421.310 Section 421.310 Protection of Environment ENVIRONMENTAL... CATEGORY Secondary Tungsten and Cobalt Subcategory § 421.310 Applicability: Description of the secondary tungsten and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting...

  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...

  7. 40 CFR 421.310 - Applicability: Description of the secondary tungsten and cobalt subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... secondary tungsten and cobalt subcategory. 421.310 Section 421.310 Protection of Environment ENVIRONMENTAL... CATEGORY Secondary Tungsten and Cobalt Subcategory § 421.310 Applicability: Description of the secondary tungsten and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting...

  8. 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...

  9. 40 CFR 421.310 - Applicability: Description of the secondary tungsten and cobalt subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... secondary tungsten and cobalt subcategory. 421.310 Section 421.310 Protection of Environment ENVIRONMENTAL... CATEGORY Secondary Tungsten and Cobalt Subcategory § 421.310 Applicability: Description of the secondary tungsten and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting...

  10. 40 CFR 421.230 - Applicability: Description of the primary nickel and cobalt subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... primary nickel and cobalt subcategory. 421.230 Section 421.230 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Nickel and Cobalt Subcategory § 421.230 Applicability: Description of the primary nickel and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting from...

  11. 40 CFR 421.230 - Applicability: Description of the primary nickel and cobalt subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... primary nickel and cobalt subcategory. 421.230 Section 421.230 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Nickel and Cobalt Subcategory § 421.230 Applicability: Description of the primary nickel and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting from...

  12. 40 CFR 421.230 - Applicability: Description of the primary nickel and cobalt subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... primary nickel and cobalt subcategory. 421.230 Section 421.230 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Nickel and Cobalt Subcategory § 421.230 Applicability: Description of the primary nickel and cobalt subcategory. The provisions of this subpart are applicable to discharges resulting from...

  13. 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....

  14. Toxicity of cobalt. (Latest citations from the Life Sciences Collection database). Published Search

    SciTech Connect

    Not Available

    1993-02-01

    The bibliography contains citations concerning the toxicity effects of cobalt. Citations include cobalt fetotoxicity, renal toxicity, bioaccumulation, contact dermatitis, carcinogencity, and respiratory disorders. Toxicology assays and industrial sources of cobalt poisoning are considered. In vivo and in vitro human and animal studies are described. (Contains a minimum of 129 citations and includes a subject term index and title list.)

  15. Lignite recovery of cobalt(+3) from an ammoniacal ammonium sulfate solution. Report of investigations/1984

    SciTech Connect

    Slavens, G.J.; Traut, D.E.; Penner, L.R.; Henry, J.L.

    1984-01-01

    The Bureau of Mines has devised technology to recover cobalt, nickel, and byproduct copper from domestic lateritic material using an oxidative, ammoniacal ammonium sulfate leach. Nickel, cobalt, and copper were recovered by solvent extraction and electrowinning. To reduce the cost and complexity of cobalt recovery, an alternate method using lignite to extract Co(+3) was investigated as reported herein.

  16. Thermal fatigue resistance of cobalt-modified UDIMET 700

    NASA Technical Reports Server (NTRS)

    Bizon, P. T.

    1982-01-01

    The determination of comparative thermal fatigue resistances of five cobalt composition modifications of UDIMET 700 from fluidized bed tests is described. Cobalt compositional levels of 0.1, 4.3, 8.6, 12.8, 17.0 percent were being investigated in both the bare and coated (NiCrAlY overlay) conditions. Triplicate tests of each variation including duplicate tests of three control alloys are under investigation. Fluidized beds were maintained at 550 and 1850 F for the first 5500 cycles at which time the hot bed was increased to 1922 F. Immersion time in each bed is always 3 minutes. Upon the completion of 10,000 cycles, it appears that the 8.6 percent cobalt level gives the best thermal fatigue life. Considerable deformation of the test bars was observed.

  17. Nanosize cobalt boride particles: Control of the size and properties

    NASA Astrophysics Data System (ADS)

    Petit, C.; Pileni, M. P.

    1997-02-01

    Cobalt boride is obtained by the reduction of cobalt (2-ethyl hexyl) sulfosuccinate, Co(AOT) 2, by sodium borohydride either in reverse micelles or in a diphasic system. In Co(AOT) 2/Na(AOT)/H 2O reverse micellar solution, the size and polydispersity of the Co 2B particles is controlled by the size of the water droplets, which increases from 4 to 7.5 nm by increasing the water content. In a diphasic system of Co(AOT) 2/isooctane and sodium borohydride in aqueous solution, large and polydisperse particles of cobalt boride are formed (˜ 10 nm), and their magnetization properties are presented. The smallest particles are in a superparamagnetic regime at room temperature, whereas the largest particles show ferromagnetic behavior.

  18. Tungsten-nickel-cobalt alloy and method of producing same

    DOEpatents

    Dickinson, James M.; Riley, Robert E.

    1977-03-15

    An improved tungsten alloy having a tungsten content of approximately 95 weight percent, a nickel content of about 3 weight percent, and the balance being cobalt of about 2 weight percent is described. A method for producing said tungsten-nickel-cobalt alloy is further described and comprises (a) coating the tungsten particles with a nickel-cobalt alloy, (b) pressing the coated particles into a compact shape, (c) heating said compact in hydrogen to a temperature in the range of 1400.degree. C and holding at this elevated temperature for a period of about 2 hours, (d) increasing this elevated temperature to about 1500.degree. C and holding for 1 hour at this temperature, (e) cooling to about 1200.degree. C and replacing the hydrogen atmosphere with an inert argon atmosphere while maintaining this elevated temperature for a period of about 1/2 hour, and (f) cooling the resulting alloy to room temperature in this argon atmosphere.

  19. Effect of Cobalt Particle Size on Acetone Steam Reforming

    SciTech Connect

    Sun, Junming; Zhang, He; Yu, Ning; Davidson, Stephen D.; Wang, Yong

    2015-06-11

    Carbon-supported cobalt nanoparticles with different particle sizes were synthesized and characterized by complementary characterization techniques such as X-ray diffraction, N-2 sorption, acetone temperature-programmed desorption, transmission electron microscopy, and CO chemisorption. Using acetone steam reforming reaction as a probe reaction, we revealed a volcano-shape curve of the intrinsic activity (turnover frequency of acetone) and the CO2 selectivity as a function of the cobalt particle size with the highest activity and selectivity observed at a particle size of approximately 12.8nm. Our results indicate that the overall performance of acetone steam reforming is related to a combination of particle-size-dependent acetone decomposition, water dissociation, and the oxidation state of the cobalt nanoparticles.

  20. Activation of cobalt by neutrons from the Hiroshima bomb

    SciTech Connect

    Kerr, G.D.; Dyer, F.F.; Emery, J.F.; Pace, J.V. III ); Brodzinski, R.L. ); Marcum, J. )

    1990-02-01

    A study has been completed of cobalt activation in samples from two new locations in Hiroshima. The samples consisted of a piece of steel from a bridge located at a distance of about 1300 m from the hypocenter and pieces of both steel and concrete from a building located at approximately 700 m. The concrete was analyzed to obtain information needed to calculate the cobalt activation in the two steel samples. Close agreement was found between calculated and measured values for cobalt activation of the steel sample from the building at 700 m. It was found, however, that the measured values for the bridge sample at 1300 m were approximately twice the calculated values. Thus, the new results confirm the existence of a systematic error in the transport calculations for neutrons from the Hiroshima bomb. 52 refs., 32 figs., 16 tabs.

  1. Regression of posterior uveal melanomas following cobalt-60 plaque radiotherapy

    SciTech Connect

    Cruess, A.F.; Augsburger, J.J.; Shields, J.A.; Brady, L.W.; Markoe, A.M.; Day, J.L.

    1984-12-01

    A method has been devised for evaluating the rate and extent of regression of the first 100 consecutive patients with a posterior uveal melanoma that had been managed by Cobalt-60 plaque radiotherapy at Wills Eye Hospital. It was found that the average posterior uveal melanoma in the series did not regress rapidly to a flat, depigmented scar but shrank slowly and persisted as a residual mass approximately 50% of the thickness of the original tumor at 54 months following Cobalt-60 plaque radiotherapy. The authors also found that the rate and extent of regression of the tumors in patients who subsequently developed metastatic melanoma were not appreciably different from the rate and extent of regression of the tumors in patients who remained well systemically. These observations indicate that the rate and extent of regression of posterior uveal melanomas following Cobalt-60 plaque radiotherapy are poor indicators of the prognosis of the affected patients for subsequent development of clinical metastatic disease.

  2. Transition metal-substituted cobalt ferrite nanoparticles for biomedical applications.

    PubMed

    Sanpo, Noppakun; Berndt, Christopher C; Wen, Cuie; Wang, James

    2013-03-01

    Transition metals of copper, zinc, chromium and nickel were substituted into cobalt ferrite nanoparticles via a sol-gel route using citric acid as a chelating agent. The microstructure and elemental composition were characterized using scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. Phase analysis of transition metal-substituted cobalt ferrite nanoparticles was performed via X-ray diffraction. Surface wettability was measured using the water contact angle technique. The surface roughness of all nanoparticles was measured using profilometry. Moreover, thermogravimetric analysis and differential scanning calorimetry were performed to determine the temperature at which the decomposition and oxidation of the chelating agents took place. Results indicated that the substitution of transition metals influences strongly the microstructure, crystal structure and antibacterial property of the cobalt ferrite nanoparticles. PMID:23137676

  3. Sorption and desorption of cobalt by Oscillatoria anguistissima.

    PubMed

    Ahuja, P; Gupta, R; Saxena, R K

    1999-07-01

    Oscillatoria anguistissima rapidly adsorbs appreciable amounts of cobalt from the aqueous solutions within 15 min of initial contact with the metal solution. O. anguistissima showed a high sequestration of cobalt at low equilibrium concentrations, and it followed the Freundlich model of adsorption. The adsorption is a strongly pH-dependent and temperature-independent phenomenon. The presence of Mg2+ and Ca2+ (100-200 ppm) resulted in decline in Co2+ adsorption capacity of Oscillatoria biomass. Sulphate and nitrate (0. 75-10 mM) drastically reduced the extent of Co2+ biosorption. The biosorption of cobalt is an ion-exchange process as the Co2+ binding was accompanied by release of a large amounts of Mg2+ ions. Na2CO3 (1.0 mM) resulted in about 76% desorption of Co2+ from the loaded biomass. PMID:10387117

  4. Recovery of cobalt and copper from complex sulfide concentrates

    SciTech Connect

    Dannenberg, R.O.; Gardner, P.C.; Crane, S.R.; Seidel, D.C.

    1987-01-01

    The Bureau conducted bench-scale research on a process for treating cobaltite concentrates, comprising (1) oxidative pressure leaching, (2) jarosite precipitation followed by H/sub 2/O/sub 2/ oxidation and pH control to remove iron and arsenic, (3) copper solvent extraction with a mixed hydroxyoxime-amine extractant, (4) copper electrowinning from recirculating acidic strip liquor, (5) selective cobalt extraction from copper solvent extraction raffinate with a phosphinic and extractant, and (6) electrowinning of cobalt from a recirculating weak acid strip liquor. Overall cobalt and copper recoveries were 91.7 and 84.1 pct, respectively. Electrowon products assayed 99.8 pct Co and 99.89 ct Cu.

  5. Mycobacterial Cells Have Dual Nickel-Cobalt Sensors

    PubMed Central

    Campbell, Duncan R.; Chapman, Kaye E.; Waldron, Kevin J.; Tottey, Stephen; Kendall, Sharon; Cavallaro, Gabriele; Andreini, Claudia; Hinds, Jason; Stoker, Neil G.; Robinson, Nigel J.; Cavet, Jennifer S.

    2011-01-01

    A novel ArsR-SmtB family transcriptional repressor, KmtR, has been characterized from mycobacteria. Mutants of Mycobacterium tuberculosis lacking kmtR show elevated expression of Rv2025c encoding a deduced CDF-family metal exporter. KmtR-dependent repression of the cdf and kmtR operator-promoters was alleviated by nickel and cobalt in minimal medium. Electrophoretic mobility shift assays and fluorescence anisotropy show binding of purified KmtR to nucleotide sequences containing a region of dyad symmetry from the cdf and kmtR operator-promoters. Incubation of KmtR with cobalt inhibits DNA complex assembly and metal-protein binding was confirmed. KmtR is the second, to NmtR, characterized ArsR-SmtB sensor of nickel and cobalt from M. tuberculosis suggesting special significance for these ions in this pathogen. KmtR-dependent expression is elevated in complete medium with no increase in response to metals, whereas NmtR retains a response to nickel and cobalt under these conditions. KmtR has tighter affinities for nickel and cobalt than NmtR consistent with basal levels of these metals being sensed by KmtR but not NmtR in complete medium. More than a thousand genes encoding ArsR-SmtB-related proteins are listed in databases. KmtR has none of the previously defined metal-sensing sites. Substitution of His88, Glu101, His102, His110, or His111 with Gln generated KmtR variants that repress the cdf and kmtR operator-promoters even in elevated nickel and cobalt, revealing a new sensory site. Importantly, ArsR-SmtB sequence groupings do not correspond with the different sensory motifs revealing that only the latter should be used to predict metal sensing. PMID:17726022

  6. Temporal Variability of Tungsten and Cobalt in Fallon, Nevada

    PubMed Central

    Sheppard, Paul R.; Speakman, Robert J.; Ridenour, Gary; Witten, Mark L.

    2007-01-01

    Background Since 1997, Fallon, Nevada, has experienced a cluster of childhood leukemia that has been declared “one of the most unique clusters of childhood cancer ever reported.” Multiple environmental studies have shown airborne tungsten and cobalt to be elevated within Fallon, but the question remains: Have these metals changed through time in correspondence with the onset of the leukemia cluster? Methods We used dendrochemistry, the study of element concentrations through time in tree rings, in Fallon to assess temporal variability of airborne tungsten and cobalt since the late 1980s. The techniques used in Fallon were also tested in a different town (Sweet Home, OR) that has airborne tungsten from a known source. Results The Sweet Home test case confirms the accuracy of dendrochemistry for showing temporal variability of environmental tungsten. Given that dendrochemistry works for tungsten, tree-ring chemistry shows that tungsten increased in Fallon relative to nearby comparison towns beginning by the mid-1990s, slightly before the onset of the cluster, and cobalt has been high throughout the last ~ 15 years. Other metals do not show trends through time in Fallon. Discussion Results in Fallon suggest a temporal correspondence between the onset of excessive childhood leukemia and elevated levels of tungsten and cobalt. Although environmental data alone cannot directly link childhood leukemia with exposure to metals, research by others has shown that combined exposure to tungsten and cobalt can be carcinogenic to humans. Conclusion Continued biomedical research is warranted to directly test for linkage between childhood leukemia and tungsten and cobalt. PMID:17520058

  7. Kinetic Resolution of Racemic and Branched Monosubstituted Allylic Acetates by a Ruthenium-Catalyzed Regioselective Allylic Etherification.

    PubMed

    Shinozawa, Toru; Terasaki, Shou; Mizuno, Shota; Kawatsura, Motoi

    2016-07-01

    We demonstrated the kinetic resolution of racemic and branched monosubstituted allylic acetates by a ruthenium-catalyzed regioselective allylic etherification. The reaction was effectively catalyzed by the chiral ruthenium catalyst, which was generated by [RuCl2(p-cymene)]2 and (S,S)-iPr-pybox and a catalytic amount of TFA, and both the allylic etherification product and recovered allylic acetate were obtained as an enantiomerically enriched form with up to a 103 s value. PMID:27276556

  8. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    DOEpatents

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  9. Excited state dynamics and isomerization in ruthenium sulfoxide complexes.

    PubMed

    King, Albert W; Wang, Lei; Rack, Jeffrey J

    2015-04-21

    Molecular photochromic compounds are those that interconvert between two isomeric forms with light. The two isomeric forms display distinct electronic and molecular structures and must not be in equilibrium with one another. These light-activated molecular switch compounds have found wide application in areas of study ranging from chemical biology to materials science, where conversion from one isomeric form to another by light prompts a response in the environment (e.g., protein or polymeric material). Certain ruthenium and osmium polypyridine sulfoxide complexes are photochromic. The mode of action is a phototriggered isomerization of the sulfoxide from S- to O-bonded. The change in ligation drastically alters both the spectroscopic and electrochemical properties of the metal complex. Our laboratory has pioneered the preparation and study of these complexes. In particular, we have applied femtosecond pump-probe spectroscopy to reveal excited state details of the isomerization mechanism. The data from numerous complexes allowed us to predict that the isomerization was nonadiabatic in nature, defined as occurring from a S-bonded triplet excited state (primarily metal-to-ligand charge transfer in character) to an O-bonded singlet ground state potential energy surface. This prediction was corroborated by high-level density functional theory calculations. An intriguing aspect of this reactivity is the coupling of nuclear motion to the electronic wave function and how this coupling affects motions productive for isomerization. In an effort to learn more about this coupling, we designed a project to examine phototriggered isomerization in bis-sulfoxide complexes. The goal of these studies was to determine whether certain complexes could be designed in which a single photon excitation event would prompt two sulfoxide isomerizations. We employed chelating sulfoxides in this study and found that both the nature of the chelate ring and the R group on the sulfoxide affect

  10. Red electroluminescence of ruthenium sensitizer functionalized by sulfonate anchoring groups.

    PubMed

    Shahroosvand, Hashem; Abbasi, Parisa; Mohajerani, Ezeddin; Janghouri, Mohammad

    2014-06-28

    We have synthesized five novel Ru(ii) phenanthroline complexes with an additional aryl sulfonate ligating substituent at the 5-position [Ru(L)(bpy)2](BF4)2 (1), [Ru(L)(bpy)(SCN)2] (2), [Ru(L)3](BF4)2 (3), [Ru(L)2(bpy)](BF4)2 (4) and [Ru(L)(BPhen)(SCN)2] (5) (where L = 6-one-[1,10]phenanthroline-5-ylamino)-3-hydroxynaphthalene 1-sulfonic, bpy = 2,2'-bipyridine, BPhen = 4,7-diphenyl-1,10-phenanthroline), as both photosensitizers for oxide semiconductor solar cells (DSSCs) and light emitting diodes (LEDs). The absorption and emission maxima of these complexes red shifted upon extending the conjugation of the phenanthroline ligand. Ru phenanthroline complexes exhibit broad metal to ligand charge transfer-centered electroluminescence (EL) with a maximum near 580 nm. Our results indicated that a particular structure (2) can be considered as both DSSC and OLED devices. The efficiency of the LED performance can be tuned by using a range of ligands. Device (2) has a luminance of 550 cd m(-2) and maximum efficiency of 0.9 cd A(-1) at 18 V, which are the highest values among the five devices. The turn-on voltage of this device is approximately 5 V. The role of auxiliary ligands in the photophysical properties of Ru complexes was investigated by DFT calculation. We have also studied photovoltaic properties of dye-sensitized nanocrystalline semiconductor solar cells based on Ru phenanthroline complexes and an iodine redox electrolyte. A solar energy to electricity conversion efficiency (η) of 0.67% was obtained for Ru complex (2) under standard AM 1.5 irradiation with a short-circuit photocurrent density (Jsc) of 2.46 mA cm(-2), an open-circuit photovoltage (Voc) of 0.6 V, and a fill factor (ff) of 40%, which are all among the highest values for ruthenium sulfonated anchoring groups reported so far. Monochromatic incident photon to current conversion efficiency was 23% at 475 nm. Photovoltaic studies clearly indicated dyes with two SCN substituents yielded a higher Jsc for the

  11. PLUTONIUM-CERIUM-COBALT AND PLUTONIUM-CERIUM-NICKEL ALLOYS

    DOEpatents

    Coffinberry, A.S.

    1959-08-25

    >New plutonium-base teroary alloys useful as liquid reactor fuels are described. The alloys consist of 10 to 20 atomic percent cobalt with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 88 atomic percent; or, of from 10 to 25 atomic percent nickel (or mixture of nickel and cobalt) with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 86 atomic percent. The stated advantages of these alloys over unalloyed plutonium for reactor fuel use are a lower melting point and a wide range of permissible plutonium dilution.

  12. Low energy sputtering of cobalt by cesium ions

    NASA Technical Reports Server (NTRS)

    Handoo, A.; Ray, Pradosh K.

    1989-01-01

    An experimental facility to investigate low energy (less than 500 eV) sputtering of metal surfaces with ions produced by an ion gun is described. Results are reported on the sputtering yield of cobalt by cesium ions in the 100 to 500 eV energy range at a pressure of 1 times 10(exp -6) Torr. The target was electroplated on a copper substrate. The sputtered atoms were collected on a cobalt foil surrounding the target. Co-57 was used as a tracer to determine the sputtering yield.

  13. Countercation-sensitive electrochromism of cobalt hexacyanoferrate films

    SciTech Connect

    Kulesza, P.J.; Malik, M.A.; Miecznikowski, K.; Wolkiewicz, A.; Zamponi, S.; Berrettoni, M.; Marassi, R.

    1996-01-01

    Cobalt(II) hexacyanoferrate(III,II) a system analogous to prussian blue, is a unique electrochromic material: its color is not only dependent on the oxidation potential, but also on the nature of the countercations sorbed from electrolyte during reduction. The electrodeposition of cobalt hexacyanoferrate thin films, their voltammetric behavior and spectroelectrochemical identity are reported here in potassium and sodium electrolytes. The oxidized film is purple brown in both electrolytes, but following reduction, the system turns olive-brown in 1 M KCl and becomes green in 1 M NaCl.

  14. Hydrogen Evolution Catalyzed by Cobalt Diimine-Dioxime Complexes

    PubMed Central

    Kaeffer, Nicolas; Chavarot-Kerlidou, Murielle; Artero, Vincent

    2015-01-01

    Conspectus Mimicking photosynthesis and producing solar fuels is an appealing way to store the huge amount of renewable energy from the sun in a durable and sustainable way. Hydrogen production through water splitting has been set as a first-ranking target for artificial photosynthesis. Pursuing that goal requires the development of efficient and stable catalytic systems, only based on earth abundant elements, for the reduction of protons from water to molecular hydrogen. Cobalt complexes based on glyoxime ligands, called cobaloximes, emerged ten years ago as a first generation of such catalysts. They are now widely utilized for the construction of photocatalytic systems for hydrogen evolution. In this Account, we describe our contribution to the development of a second generation of catalysts, cobalt diimine-dioxime complexes. While displaying similar catalytic activities as cobaloximes, these catalysts prove more stable against hydrolysis under strongly acidic conditions thanks to the tetradentate nature of the diimine-dioxime ligand. Importantly, H2 evolution proceeds via proton-coupled electron transfer steps involving the oxime bridge as a protonation site, reproducing the mechanism at play in the active sites of hydrogenase enzymes. This feature allows H2 to be evolved at modest overpotentials, i.e. close to the thermodynamic equilibrium over a wide range of acid-base conditions in non-aqueous solutions. Derivatization of the diimine-dioxime ligand at the hydrocarbon chain linking the two imine functions enables the covalent grafting of the complex onto electrode surfaces in a more convenient manner than for the parent bis-bidentate cobaloximes. Accordingly we attached diimine-dioxime cobalt catalysts onto carbon nanotubes and demonstrated the catalytic activity of the resulting molecular-based electrode for hydrogen evolution from aqueous acetate buffer. The stability of immobilized catalysts was found to be orders of magnitude higher than that of catalysts

  15. Structural and magnetic study of dysprosium substituted cobalt ferrite nanoparticles

    NASA Astrophysics Data System (ADS)

    Kumar, Hemaunt; Srivastava, R. C.; Pal Singh, Jitendra; Negi, P.; Agrawal, H. M.; Das, D.; Hwa Chae, Keun

    2016-03-01

    The present work investigates the magnetic behavior of Dy3+ substituted cobalt ferrite nanoparticles. X-ray diffraction studies reveal presence of cubic spinel phases in these nanoparticles. Raman spectra of these nanoparticles show change in intensity of Raman bands, which reflects cation redistribution in cubic spinel lattice. Saturation magnetization and coercivity decrease with increase of Dy3+concentration in these nanoparticles. Room temperature Mössbauer measurements show the cation redistribution in these nanoparticles and corroborates the results obtained from Raman Spectroscopic measurements. Decrease in magnetization of Dy3+ substituted cobalt ferrite is attributed to the reduction in the magnetic interaction and cation redistribution.

  16. Hydrogen evolution catalyzed by cobalt diimine-dioxime complexes.

    PubMed

    Kaeffer, Nicolas; Chavarot-Kerlidou, Murielle; Artero, Vincent

    2015-05-19

    Mimicking photosynthesis and producing solar fuels is an appealing way to store the huge amount of renewable energy from the sun in a durable and sustainable way. Hydrogen production through water splitting has been set as a first-ranking target for artificial photosynthesis. Pursuing that goal requires the development of efficient and stable catalytic systems, only based on earth abundant elements, for the reduction of protons from water to molecular hydrogen. Cobalt complexes based on glyoxime ligands, called cobaloximes, emerged 10 years ago as a first generation of such catalysts. They are now widely utilized for the construction of photocatalytic systems for hydrogen evolution. In this Account, we describe our contribution to the development of a second generation of catalysts, cobalt diimine-dioxime complexes. While displaying similar catalytic activities as cobaloximes, these catalysts prove more stable against hydrolysis under strongly acidic conditions thanks to the tetradentate nature of the diimine-dioxime ligand. Importantly, H2 evolution proceeds via proton-coupled electron transfer steps involving the oxime bridge as a protonation site, reproducing the mechanism at play in the active sites of hydrogenase enzymes. This feature allows H2 to be evolved at modest overpotentials, that is, close to the thermodynamic equilibrium over a wide range of acid-base conditions in nonaqueous solutions. Derivatization of the diimine-dioxime ligand at the hydrocarbon chain linking the two imine functions enables the covalent grafting of the complex onto electrode surfaces in a more convenient manner than for the parent bis-bidentate cobaloximes. Accordingly, we attached diimine-dioxime cobalt catalysts onto carbon nanotubes and demonstrated the catalytic activity of the resulting molecular-based electrode for hydrogen evolution from aqueous acetate buffer. The stability of immobilized catalysts was found to be orders of magnitude higher than that of catalysts in the

  17. The role of cobalt ferrite magnetic nanoparticles in medical science.

    PubMed

    Amiri, S; Shokrollahi, H

    2013-01-01

    The nanotechnology industry is rapidly growing and promises that the substantial changes that will have significant economic and scientific impacts be applicable to a wide range of areas, such as aerospace engineering, nano-electronics, environmental remediation and medical healthcare. In this area, cobalt ferrite nanoparticles have been regarded as one of the competitive candidates because of their suitable physical, chemical and magnetic properties like the high anisotropy constant, high coercivity and high Curie temperature, moderate saturation magnetization and ease of synthesis. This paper introduces the magnetic properties, synthesis methods and some medical applications, including the hyperthermia, magnetic resonance imaging (MRI), magnetic separation and drug delivery of cobalt ferrite nanoparticles. PMID:25428034

  18. Cobalt-Catalyzed N-Alkylation of Amines with Alcohols.

    PubMed

    Zhang, Guoqi; Yin, Zhiwei; Zheng, Shengping

    2016-01-15

    A well-defined nonprecious metal cobalt(II) catalyst based on a pincer PNP ligand has been employed for the efficient N-alkylation of both aromatic and aliphatic amines with alcohols. A subtle change of reaction conditions (simply adding 4 Å molecular sieves) was observed to readily switch the resulting products (amines vs imines) with high chemoselectivity. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted to secondary amines in good-to-excellent yields when 2 mol % cobalt catalyst was used. Additional experiments indicate that a hydrogen-borrowing mechanism is responsible for the tandem acceptorless dehydrogenation/condensation/hydrogenation process. PMID:26695594

  19. Electronic and fluorescence spectral studies of a novel porphyrin-polypyridyl ruthenium(II) hybrid linked by a butyl chain

    NASA Astrophysics Data System (ADS)

    Liu, Jie; Huang, Jin-Wang; Fu, Bo; Zhao, Ping; Yu, Han-Cheng; Ji, Liang-Nian

    2007-06-01

    The electronic and fluorescence spectroscopic properties of a novel porphyrin-polypyridyl ruthenium(II) hybrid, [C 4-TPP-(ip)Ru(phen) 2](ClO 4) 2 (TPP = 5,10,15,20-tetraphenylporphyrin, ip = imidazo[4,5-f][1,10]phenanthroline and phen = 1,10-Phenanthroline), in which a polypyridyl ruthenium(II) moiety is linked to a porphyrin moiety by a butyl chain have been investigated and compared to its corresponding reference compounds. The studies of electronic absorption spectra have shown that there is an electronic interaction between the porphyrin moiety and the polypyridyl ruthenium(II) moiety in the hybrid. It can be found that intramolecular photoinduced electron and energy transfer processes may occur in the hybrid from the fluorescence spectra. When exciting in Soret band and Q band of porphyrin, the fluorescence quenching of the porphyrin moiety of the hybrid takes place due to electron transfer from the lowest singlet excited state (S 1) to the appended polypyridyl rutherium(II) moiety, while the decay of S 2 (the second-excited singlet state) of the porphyrin moiety is mainly contributed to internal conversion to S 1. When exciting in MLCT band of the polypyridyl ruthenium(II) moiety, fluorescence corresponding to the polypyridyl ruthenium(II) moiety is quenched by intramolecular energy transfer from 3MLCT of the ruthenium moiety to the lowest-energy triplet state localized on the porphyrin moiety.

  20. Copper and cobalt in aquatic mosses and stream sediments from the Idaho Cobalt Belt

    USGS Publications Warehouse

    Erdman, J.A.; Modreski, P.J.

    1984-01-01

    Samples of stream sediments and aquatic mosses were collected from nine sites across several mineralized zones at the southeasternmost extension of the Idaho Cobalt Belt. Because the steepness of the terrain and the attendant high flow rate of the streams made it difficult to obtain adequate sediment samples, mosses were considered as an alternative sampling medium. The results not only showed that the Cu and Co content of the mosses correlated almost perfectly with that of the sediments, but that the contrast between samples taken from mineralized and background areas was greater in mosses, especially for Co. Maximum concentrations of 35,000 ??g/g Cu and 2000 ??g/g Co were observed in the ash of mosses, compared to maximum concentrations of 1700 ??g/g and 320 ??g/g, respectively, in the associated sediments. Species identification was considered unimportant, which should dispel some reluctance to use mosses in mineral exploration. ?? 1984.