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Sample records for fe ru os

  1. Thermodynamics and superconductivity of Th7(Fe, Ru, Os, Co, Rh, Ir)3 system

    SciTech Connect

    Smith, James L; Lashley, Jason C; Volz, Heather M; Fisher, Robert A

    2008-01-01

    Expanding the temperature range of previous specific-heat measurements on the Th7(Fe, Ru, Os, Co, Rh, Ir)3 system, we measure the effect of transition-metal substitution on total entropy (S{sub 298 k}), electronic specific heat ({gamma}), and Debye temperature ({Theta}D). In addition we measure the pressure dependence, up to 10 kbar, of the superconducting transition.

  2. Structural, electronic, elastic and magnetic properties of RuFe{sub 3}N and OsFe{sub 3}N: A first principle study

    SciTech Connect

    Puvaneswari, S.; Priyanga, G. Sudha; Rajeswarapalanichamy, R. Santhosh, M.

    2015-06-24

    The structural, electronic, elastic and magnetic properties of the perovskite structure of RuFe{sub 3}N, and OsFe{sub 3}N have been reported using the VASP within the gradient generalized approximation. Total energy calculations are performed using both spin and non-spin polarized calculations and it is found that, at ambient pressure both RuFe{sub 3}N and OsFe{sub 3}N are stable in ferromagnetic phase. The electronic structure reveals that both RuFe{sub 3}N and OsFe{sub 3}N are metallic in nature at ambient pressure.

  3. A comparative computationally study about the defined M(II) pincer hydrogenation catalysts (M = Fe, Ru, Os).

    PubMed

    Jiao, Haijun; Junge, Kathrin; Alberico, Elisabetta; Beller, Matthias

    2016-01-15

    The mechanism of acetonitrile and methyl benzoate catalytic hydrogenation using pincer catalysts M(H)2 (CO)[NH(C2 H4 PiPr2 )2 ] (1M) and M(H)(CO)[N(C2 H4 PiPr2 )2 ] (2M) (M = Fe, Ru, Os) has been computed at various levels of density functional theory. The computed equilibrium between 1Fe and 2Fe agrees perfectly with the experimental observations. On the basis of the activation barriers and reaction energies, the best catalysts for acetonitrile hydrogenation are 1Fe/2Fe and 1Ru/2Ru, and the best catalysts for methyl benzoate hydrogenation are 1Ru/2Ru. The best catalysts for the dehydrogenation of benzyl alcohol are 1Ru/2Ru. It is to note that the current polarizable continuum model is not sufficient in modeling the solvation effect in the energetic properties of these catalysts as well as their catalytic properties in hydrogenation reaction, as no equilibrium could be established between 1Fe and 2Fe. Comparison with other methods and procedures has been made. © 2015 Wiley Periodicals, Inc.

  4. Comment on "comparison of the widely used HF pseudo-potentials: MH + (M = Fe, Ru, Os)"

    NASA Astrophysics Data System (ADS)

    Andrae, Dirk; Dolg, Michael; Stoll, Hermann; Ermler, Walter C.

    1994-04-01

    It is shown through calculations of the ionization energies of the Fe and Ru atoms that errors attributed to pseudo-potential defects in a recent paper by Leininger [Chem. Phys. Letters 205 (1993) 301] are due, instead, to shortcomings of their valence-interaction treatment.

  5. On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).

    PubMed

    Huang, Wei; Xu, Wen-Hua; Schwarz, W H E; Li, Jun

    2016-05-02

    Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

  6. Formation of Fe-Os, Fe-Ru, and Fe-Co bimetallic particles by thermal decomposition of heteropolynuclear clusters supported on a partially dehydroxylated magnesia

    SciTech Connect

    Choplin, A.; Huang, L.; Theolier, A.; Gallezot, P.; Basset, J.M.; Siriwardane, U.; Shore, S.G.; Mathieu, R.

    1986-07-09

    The authors wish to report here that with H/sub 2/FeOs/sub 3/(CO)/sub 13/, H/sub 2/FeRu/sub 3/(VO)/sub 13/, and HFeCo/sub 3/(CO)/sub 12/ supported on a partially hydroxylated magnesia, it is possible to obtain, after H/sub 2/ treatment at 400/sup 0/C, very small bimetallic particles, having the same bulk composition as that of the starting heteropolynuclear precursor cluster. This conclusion is based on high spatial resolution analytical microscopy.

  7. Light harvesting and directional energy transfer in long-lived homo- and heterotrimetallic complexes of Fe(II), Ru(II), and Os(II).

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Mardanya, Sourav; Karmakar, Srikanta; Baitalik, Sujoy

    2014-10-06

    A new family of trimetallic complexes of the form [(bpy)2 M(phen-Hbzim-tpy)M'(tpy-Hbzim-phen)M(bpy)2](6+) (M=Ru(II), Os; M'=Fe(II), Ru(II), Os; bpy=2,2'-bipyridine) derived from heteroditopic phenanthroline-terpyridine bridge 2-{4-[2,6-di(pyridin-2-yl) pyridine-4-yl]phenyl}-1H-imidazole[4,5-f][1,10]phenanthroline (phen-Hbzim-tpy) were prepared and fully characterized. Zn(2+) was used to prepare mixed-metal trimetallic complexes in situ by coordinating with the free tpy site of the monometallic precursors. The complexes show intense absorptions throughout the UV/Vis region and also exhibit luminescence at room temperature. The redox behavior of the compounds is characterized by several metal-centered reversible oxidation and ligand-centered reduction processes. Steady-state and time-resolved luminescence data show that the potentially luminescent Ru(II)- and Os(II)-based triplet metal-to-ligand charge-transfer ((3)MLCT) excited states in the triads are quantitatively quenched, most likely by intercomponent energy transfer to the lower lying (3)MLCT (for Ru and Os) or triplet metal-centered ((3)MC) excited states of the Fe(II) subunit (nonluminescent). Interestingly, iron did not adversely affect the photophysics of the respective systems. This suggests that the multicomponent molecular-wire-like complexes investigated here can behave as efficient light-harvesting antennas, because all the light absorbed by the various subunits is efficiently channeled to the subunit(s) in which the lowest-energy excited states are located.

  8. pH-Induced processes in wire-like multichromophoric homo- and heterotrimetallic complexes of Fe(II), Ru(II), and Os(II).

    PubMed

    Maity, Dinesh; Mardanya, Sourav; Karmakar, Srikanta; Baitalik, Sujoy

    2015-06-07

    In this work we studied the influence of pH on the absorption, steady state and time-resolved emission spectroscopic behaviors of recently reported multichromophoric trimetallic complexes of the forms [(bpy)2M(phen-Hbzim-tpy)M'(tpy-Hbzim-phen)M(bpy)2](6+) (M = Ru(II) or Os(II), and M' = Fe(II), Ru(II), and Os(II)) derived from a heteroditopic phenanthroline-terpyridine bridge, 2-(4-(2,6-di(pyridin-2-yl)pyridine-4-yl)phenyl)-1H-imidazole[4,5-f][1,10]phenanthroline (tpy-Hbzim-phen) and 2,2'-bipyridine (bpy) as the auxiliary ligand. For purposes of comparison, the UV-vis absorption and emission titrations of three monometallic model compounds [(bpy)2Ru(phen-Hbzim-tpy)](ClO4)2 (1), [(bpy)2Os(phen-Hbzim-tpy)] (ClO4)2 (2) and [(tpy-PhCH3)Ru(tpy-Hbzim-phen)](ClO4)2 (3), where tpy-PhCH3 = 4'-(4-methylphenyl)-2,2':6',2''-terpyridine) were studied under the same experimental conditions. The absorption titration data were used to determine the ground state pKa values, whereas the luminescence and lifetime data were utilized for the determination of excited state pKa* values of the complexes. The evolving factor analyses of the set of absorption spectra of the complexes obtained by varying the pH of the solution confirm that only three absorbing species exist in the pH window of 2-12. Moreover, the modulation of the rate of the intramolecular energy transfer among the components in the homo- and heterotrimetallic complexes as a function of pH of the solution was also demonstrated.

  9. Stereoselectivity in the formation of tris-diimine complexes of Fe(II), Ru(II), and Os(II) with a C2-symmetric chiral derivative of 2,2'-bipyridine.

    PubMed

    Drahonovský, Dusan; Knof, Ulrich; Jungo, Laurence; Belser, Thomas; Neels, Antonia; Labat, Gaël Charles; Stoeckli-Evans, Helen; von Zelewsky, Alex

    2006-03-21

    A C2-symmetric enantiopure 4,5-bis(pinene)-2,2'-bipyridine ligand (-)-L was used to investigate the diastereoselectivity in the formation of [ML3]2+ coordination species (M = Fe(II), Ru(II), Os(II), Zn(II), Cd(II), Cu(II), Ni(II)), and [ML2Cl2] (M = Ru(II), Os(II)). The X-ray structures of the [ML3]2+ complexes were determined for Delta-[FeL3](PF6)2, Delta-[RuL3](PF6)2, Lambda-[RuL3](PF6)2, Delta-[OsL3](PF6)2, and Lambda-[OsL3](TfO)2. All of these compounds were also characterized by NMR, CD and UV/VIS absorption spectroscopy. The [FeL3]2+ diastereoisomers were studied in equilibrated solutions at various temperatures and in several solvents. The [RuL3]2+ complexes, which are thermally stable up to 200 degrees C, were photochemically equilibrated.

  10. Structural, electronic, elastic, thermoelectric and thermodynamic properties of the NbMSb half heusler (M=Fe, Ru, Os) compounds with first principle calculations

    NASA Astrophysics Data System (ADS)

    Abid, O. Miloud; Menouer, S.; Yakoubi, A.; Khachai, H.; Omran, S. Bin; Murtaza, G.; Prakash, Deo; Khenata, R.; Verma, K. D.

    2016-05-01

    The structural, electronic, elastic, thermoelectric and thermodynamic properties of NbMSb (M = Fe, Ru, Os) half heusler compounds are reported. The full-potential linearized augmented plane wave (FP-LAPW) plus local orbital (lo) method, based on the density functional theory (DFT) was employed for the present study. The equilibrium lattice parameter results are in good compliance with the available experimental measurements. The electronic band structure and Boltzmann transport calculations indicated a narrow indirect energy band gap for the compound having electronic structure favorable for thermoelectric performance as well as with substantial thermopowers at temperature ranges from 300 K to 800 K. Furthermore, good potential for thermoelectric performance (thermopower S ≥ 500 μeV) was found at higher temperature. In addition, the analysis of the charge density, partial and total densities of states (DOS) of three compounds demonstrate their semiconducting, ionic and covalent characters. Conversely, the calculated values of the Poisson's ratio and the B/G ratio indicate their ductile makeup. The thermal properties of the compounds were calculated by quasi-harmonic Debye model as implemented in the GIBBS code.

  11. First principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3).

    PubMed

    Sieffert, Nicolas; Kendrick, Thomas; Tiana, Davide; Morrison, Carole A

    2015-03-07

    We present a first principles static and dynamical study of the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3), with a view to arriving at an understanding of how the variation in the electronic properties of the metal sites and ligands can influence the dynamics of the resulting complexes. A broad range of behaviour was observed, encompassing stable classical minima (M = Os, L = NH3 and M = Ru, L = PH3) to stable η(2)-H2 non-classical minima (M = Fe, L = PF3 and M = Ru, L = PH3 or PF3), with the other structures exhibiting dynamical behaviour that spontaneously converted between the classical and non-classical states during the molecular dynamics simulations. The importance of a small L(axial)-M-L(axial) angle in stabilising the non-classical state is highlighted, as is a short η(2)-H2···H(cis) distance in non-classical complexes that spontaneously convert to the classical form. We also investigated the changes in the electronic structure of the complex FeH4(PH3)3 during a η(2)-H2 bond breaking/bond making reaction and observed direct evidence of the 'cis effect', whereby a neighbouring hydride ligand acts to stabilise the intermediate classical state.

  12. The role of the [CpM(CO)2](-) chromophore in the optical properties of the [Cp2ThMCp(CO)2](+) complexes, where M = Fe, Ru and Os. A theoretical view.

    PubMed

    Cantero-López, Plinio; Le Bras, Laura; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

    2015-12-14

    The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2](+) complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2](-) chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

  13. Counterion influence on the vibrational wavenumbers in ternary and quaternary metal hydride salts, A2MH6 (A = alkali metal, alkaline earth, and lanthanides; M = Ir, Fe, Ru, Os, Pt, Mn).

    PubMed

    Gilson, Denis F R; Moyer, Ralph O

    2012-02-06

    The wavenumbers of the ν(3) metal-hydrogen stretching mode (T(1u)) in the IR spectra of both ternary and quaternary hexahydrido salts of transition metals from groups 7 to 10 ([Mn(I)H(6)](5-), [Fe(II)H(6)](4-), [Ru(II)H(6)](4-), [Os(II)H(6)](4-), [Ir(III)H(6)](3-), and [Pt(IV)H(6)](2-)) depend linearly upon the ionization energies of the counterions (alkali metal, alkaline earth, and lanthanide) with a separate line for each metal. This relationship provides quantitative support for the charge-transfer mechanism for explaining the stabilities of these compounds.

  14. What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

    PubMed

    Pandey, Krishna K

    2012-03-21

    Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of

  15. Spin-State Effects on the Thermal Dihydrogen Release from Solid-State [MH(η2-H2)dppe2]+ (M = Fe, Ru, Os) Organometallic Complexes for Hydrogen Storage Applications

    PubMed Central

    2015-01-01

    Mössbauer spectroscopy, experimental thermodynamic measurements, and computational studies were performed to investigate the properties of molecular hydrogen binding to the organometallic fragments [MHdppe2]+ (M = Fe, Ru, Os; dppe =1,2-bis(diphenylphosphino)ethane) to form the dihydrogen complex fragments [MH(η2-H2)dppe2]+. Mössbauer spectroscopy showed that the dehydrogenated complex [FeHdppe2]+ adopts a geometry consistent with the triplet spin state, transitioning to a singlet state complex upon addition of the dihydrogen molecule in a manner similar to the previously studied dinitrogen complexes. From simulations, this spin transition behavior was found to be responsible for the strong binding behavior experimentally observed in the iron complex. Spin-singlet to spin-singlet transitions were found to exhibit thermodynamics consistent with the 5d > 3d > 4d binding trend observed for other transition metal dihydrogen complexes. Finally, the method for distinguishing between dihydrogen and dihydride complexes based on partial quadrupole splittings observed in Mössbauer spectra was confirmed, providing a tool for further characterization of these unique species for Mössbauer active compounds. PMID:24803973

  16. Ru, Re, Os, Pt and Au in iron meteorites

    NASA Technical Reports Server (NTRS)

    Pernicka, Ernst; Wasson, John T.

    1987-01-01

    Neutron activation analysis is used to ascertain the proportions of Ru, Re, Os, and Pt refractory siderophiles, and moderately volatile Au, in 41 iron meteorites. The Ni-element trends defined for groups IID and IIIF support a magmatic origin; in addition, the results obtained for groups IAB and IIICD contrast with trends observed in magmatic groups, where the Ru and Pt slopes are substantially less steep. In group IIIAB, at Ni concentrations above 90 mg/g, the steep decrease of Re, Os, and Ir with Ni levels off, and the interelement ratios exhibit considerable scatter. These observations may be explained in terms of the contamination of the residual molten core with small amounts of late primitive melts draining from the mantle.

  17. Ternary rare-earth aluminium intermetallics RE10TAl3 (RE = Y, Ho, Tm, Lu; T = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) with an ordered anti-Co2Al5 structure.

    PubMed

    Benndorf, Christopher; Eckert, Hellmut; Janka, Oliver

    2017-01-24

    Twenty new rare-earth metal rich intermetallic aluminium compounds, RE10TAl3 (RE = Y, Ho, Tm, Lu; T = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt), were synthesized by arc melting the elements. The compounds crystallize, in analogy to e.g. the respective Cd representatives, with a ternary ordered structure as anti-type to the hexagonal Co2Al5 type, with the space group P63/mmc. The three crystallographically independent rare-earth metal sites occupy the aluminium positions of the aristotype, while the transition metal and aluminium atoms are ordered on the two cobalt sites. Like other rare-earth rich compounds the RE10TX3 members also exhibit transition-metal-centred T@RE6 trigonal prisms as striking structural building units. The prepared compounds have been investigated by susceptibility measurements and (27)Al solid-state MAS-NMR measurements conducted on the Pauli-paramagnetic Y and Lu compounds. Some compounds show a certain amount of disorder as seen from the single crystal structure analysis and from signal broadening in the NMR investigations. By separating Knight shifts from second-order quadrupolar shifts via field dependent measurements, monotonic trends can be discerned regarding the effect of the T atom valence electron concentration and period number, as well as the effect of the closed 4f shell contributed in the Lu compounds. The results confirm that a comparison of Knight shifts within a series of isotypic compounds can reveal important electronic structure information in intermetallic systems.

  18. Electronic structure of Fe- vs. Ru-based dye molecules.

    PubMed

    Johnson, Phillip S; Cook, Peter L; Zegkinoglou, Ioannis; García-Lastra, J M; Rubio, Angel; Ruther, Rose E; Hamers, Robert J; Himpsel, F J

    2013-01-28

    In order to explore whether Ru can be replaced by inexpensive Fe in dye molecules for solar cells, the differences in the electronic structure of Fe- and Ru-based dyes are investigated by X-ray absorption spectroscopy and first-principles calculations. Molecules with the metal in a sixfold, octahedral N cage, such as tris(bipyridines) and tris(phenanthrolines), exhibit a systematic downward shift of the N 1s-to-π* transition when Ru is replaced by Fe. This shift is explained by an extra transfer of negative charge from the metal to the N ligands in the case of Fe, which reduces the binding energy of the N 1s core level. The C 1s-to-π* transitions show the opposite trend, with an increase in the transition energy when replacing Ru by Fe. Molecules with the metal in a fourfold, planar N cage (porphyrins) exhibit a more complex behavior due to a subtle competition between the crystal field, axial ligands, and the 2+ vs. 3+ oxidation states.

  19. Electronic structure of Fe- vs. Ru-based dye molecules

    SciTech Connect

    Johnson, Phillip S.; Himpsel, F. J.; Cook, Peter L.; Zegkinoglou, Ioannis; Garcia-Lastra, J. M.; Rubio, Angel; Ruther, Rose E.; Hamers, Robert J.

    2013-01-28

    In order to explore whether Ru can be replaced by inexpensive Fe in dye molecules for solar cells, the differences in the electronic structure of Fe- and Ru-based dyes are investigated by X-ray absorption spectroscopy and first-principles calculations. Molecules with the metal in a sixfold, octahedral N cage, such as tris(bipyridines) and tris(phenanthrolines), exhibit a systematic downward shift of the N 1s-to-{pi}* transition when Ru is replaced by Fe. This shift is explained by an extra transfer of negative charge from the metal to the N ligands in the case of Fe, which reduces the binding energy of the N 1s core level. The C 1s-to-{pi}* transitions show the opposite trend, with an increase in the transition energy when replacing Ru by Fe. Molecules with the metal in a fourfold, planar N cage (porphyrins) exhibit a more complex behavior due to a subtle competition between the crystal field, axial ligands, and the 2+ vs. 3+ oxidation states.

  20. Crystal Structure and Anisotropic c--f Hybridization in CeT2Al10 (T=Ru, Fe)

    NASA Astrophysics Data System (ADS)

    Sera, Masafumi; Tanaka, Daiki; Tanida, Hiroshi; Moriyoshi, Chikako; Ogawa, Mayuko; Kuroiwa, Yoshihiro; Nishioka, Takashi; Matsumura, Masahiro; Kim, Jungeun; Tsuji, Naruki; Takata, Masaki

    2013-02-01

    We have performed the investigation of the charge density distribution of CeT2Al10 (T=Ru, Fe) and the crystal structure parameters of LnT2Al10. The lattice parameters of a-, b-, and c-axes exhibit the anisotropic contraction when Ru is replaced by Fe in LnT2Al10, different from the isotropic contraction simply expected from the smaller ionic radius of Fe than Ru. The contraction is larger in the a- and c-axes than in the b-axis. This anisotropic contraction of the YbFe2Al10-type crystal structure originates from the zigzag degree of the zigzag chain formed by T and Al bond along the a- and c-axes are larger than that along the b-axis. The lattice parameters of CeT2Al10 (T=Ru, Fe) exhibit the anisotropic deviation from the lanthanide contraction. The deviation is largest in the a-axis and is very small in the b-axis. Both the characteristic YbFe2Al10-type crystal structure and the anisotropic deviation towards the intermediate valence indicate that the largest c--f hybridization along the a-axis plays the important role and is associated with the unusual antiferromagnetic order in CeT2Al10 (T=Ru, Os).

  1. Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system

    NASA Astrophysics Data System (ADS)

    Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.

    1989-02-01

    Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.

  2. Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system

    NASA Technical Reports Server (NTRS)

    Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.

    1989-01-01

    Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.

  3. Distance dependence of intrahelix Ru(II)* to Os(II) polypyridyl excited-state energy transfer in oligoproline assemblies.

    PubMed

    Brennaman, M Kyle; Fleming, Cavan N; Slate, Cheryl A; Serron, Scafford A; Bettis, Stephanie E; Erickson, Bruce W; Papanikolas, John M; Meyer, Thomas J

    2013-05-30

    Energy transfer between the metal-to-ligand charge transfer (MLCT) excited states of [Pra [M(II)(bpy)2(4-Me-4'(-N(H)CO)bpy)](PF6)2 units ([Pra(M(II)bpy2(mbpy)](2+): M(II) = Ru(II) or Os(II), bpy = 2,2'-bipyridine, mbpy = 4'-methyl-2,2'-bipyridine-4-carboxamido, Pra = 4-M(II)-L-proline) linked covalently to oligoproline assemblies in room temperature acetonitrile occurs on the picosecond-nanosecond time scale and has been time-resolved by transient emission measurements. Three derivatized oligoprolines, [CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro2-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro2-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro6-Glu-NH2](6+) (ORR-2, Pro = L-proline and Glu = glutamic acid); [CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro3-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro3-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro6-Glu-NH2](6+) (ORR-3); and CH3-CO-Pro6-Pra[Os(II)(bpy)2(mbpy)](2+)-Pro5-Pra[Ru(II)(bpy)2(mbpy)](2+)-Pro5-Pra[Ru(II)(bpy)2(mbpy)](2+)Pro6-Glu2-NH2](6+) (ORR-5), were prepared by using solid-phase peptide synthesis. Given the helical nature of the resulting assemblies and the nature of the synthesis, composition, length, and loading pattern are precisely controlled in the assemblies. In acetonitrile, they adopt a proline I helical secondary structure, confirmed by circular dichroism, in which the appended chromophores are ordered in well-defined orientations and internuclear separation distances although helix formation for ORR-2 is incomplete. Quantitative comparison of oligoproline ground-state absorption and steady-state emission spectra to those for the constituents, [Boc-Pra[M(II)(bpy)2(mbpy)](2+)-OH](PF6)2 (Boc = N(α)-(1,1-dimethylethoxycarbonyl), shows that following Ru(II) light absorption, Ru(II)* undergoes facile energy transfer resulting in sensitization of Os(II). Sensitization efficiencies are 93% for ORR-2, 77% for ORR-3, and 73% for ORR-5. Picosecond-resolved emission measurements reveal complex, coupled dynamics that arise from excited-state decay and kinetically

  4. Addition of Ru to L10-FePt thin film to lower Curie temperature

    NASA Astrophysics Data System (ADS)

    Ono, Takuya; Nakata, Hitoshi; Moriya, Tomohiro; Kikuchi, Nobuaki; Okamoto, Satoshi; Kitakami, Osamu; Shimatsu, Takehito

    2016-12-01

    The addition of Ru to L10 (fct)-FePt thin films was investigated to lower the Curie temperature (T c) of the films, which is beneficial for heat-assisted magnetic recording. The FePtRu films exhibited L10-ordering and perpendicular anisotropy for Ru contents up to at least 18 at. %, and T c was reduced by ∼100 °C/6 at. % Ru independent of the Fe/Pt ratio between 0.8 and 1.1. The T c versus uniaxial magnetic anisotropy diagrams exhibited a linear trend similar to that of FePtCu films but with a larger slope. Systematic analysis clarified that the Ru additive caused a slight decrease of the anisotropic field but greatly decreased the saturation magnetization, which was related to the observed reduction in T c.

  5. Redox-responsive molecular switches based on azoterpyridine-bridged Ru/Os complexes.

    PubMed

    Akasaka, Tetsuo; Otsuki, Joe; Araki, Koji

    2002-01-04

    Three new terpyridine-based dinuclear complexes, [(tpy)Ru(azotpy)Ru(tpy)]4+ (tpy = 2,2':6',2''-terpyridine, azotpy = bis[2,6-bis(2-pyridyl)-4-pyridyl]diazene), [(tpy)Os(azotpy)Os(tpy)]4+, and [(tpy)Ru(azotpy)Os(tpy)]4+ were prepared and their electrochemical and photophysical properties investigated. The bridging ligand, azotpy, in these complexes is reduced at less negative potentials than the unsubstituted tpy ligand. These complexes exhibit absorption bands due to the metal-to-ligand charge-transfer transitions both to the unsubstituted tpy ligand and the bridging azotpy ligand, the latter absorption being observed at the lower energy side of the former. These observations are consistent with the lower lying pi* level of the azotpy ligand than that of the tpy ligand. These complexes are nonluminescent, since the excited electron is trapped in this lower lying pi* level of the azotpy ligand in the excited state. Reduction of this bridging ligand by constant potential electrolysis renders the shape of absorption spectra for these complexes nearly identical to those of the parent complexes, [M(tpy)2]2+ (M = Ru, Os). In this reduced state, the homodinuclear Os complex becomes luminescent at room temperature, whereas the homodinuclear Ru complex becomes luminescent at 77 K, thus establishing their photoswitching behavior. The reduced heterodinuclear complex exhibits luminescence from the Os center, which is sensitized by the Ru center in the same molecule as evidenced by the excitation spectra. Thus, the intramolecular energy transfer can be switched on and off by the redox reaction of the bridging component.

  6. Directional alignment of FeCo crystallites in Si/NiFe/Ru/FeCoB multilayer with high anisotropy field above 500 Oe.

    PubMed

    Hirata, Ken-Ichiro; Gomi, Shunsuke; Nakagawa, Shigeki

    2011-03-01

    In-plane magnetic anisotropy and crystal structure of FeCoB layer on Si/NiFe/Ru underlayer were investigated by using X-Ray Diffraction (XRD) measurement. A pole-figure measurement of XRD showed directionally tilted alignment of FeCo crystallites in Si/NiFe/Ru/FeCoB multilayered film with high in-plane anisotropy field H(k) but no directional alignment was found in FeCoB single layered film. The higher H(k) appeared in the Si/NiFe/Ru/FeCoB multilayered configuration with the thicker FeCoB layer. Since Ru crystallites in a multiunderlayer configuration exhibited no directional alignment, the surface structure of underlayer should be no main reason for the directional alignment of FeCo crystallites deposited on it. The dependence of hickness of FeCoB layer in Si/NiFe/Ru/FeCoB film on H(k) indicated that the in-plane magnetic anisotropy is caused by not only the structure of Ru underlayer but also oblique incidence effect of sputtered particles, which is attained in configuration of Facing Targets Sputtering (FTS) system. From these experimental results, remarkably high H(k) of 540 Oe was obtained.

  7. A study of thermodynamic properties of dilute Fe-Ru alloys by 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Idczak, R.; Konieczny, R.; Chojcan, J.

    2016-12-01

    The room temperature Mössbauer spectra of 57Fe were measured for Fe1- x Ru x solid solutions with x in the range 0.01 ≤ x ≤ 0.08. The obtained data were analysed in terms of short-range order parameter (SRO) and the binding energy E b between two ruthenium atoms in the studied materials using the extended Hrynkiewicz-Królas idea. The extrapolated value of E b for x = 0 was used to compute the enthalpy of solution H FeRu of Ru in Fe matrix. The result was compared with corresponding values given in the literature which were derived from experimental calorimetric data as well as with the value resulting from the cellular atomic model of alloys by Miedema. It was found that all the H FeRu values are negative or Ru atoms interact repulsively. At the same time, the Mössbauer data were used to determine values of the short-range order parameter α 1. For the as-obtained samples in which atoms are frozen-in high temperature state, close to the melting point, the negative α 1 values were found. The findings indicates ordering tendencies in such specimens. On the other hand, in the case of the annealed samples where the observed distributions of atoms should be frozen-in state corresponding to the temperature 700 K, the Fe1- x Ru x alloys with x ≥ 0.05 exhibit clustering tendencies (a predominance of Fe-Fe and Ru-Ru bonds), which manifest themselves by positive values of the calculated SRO parameter. The clustering process leads to a local increase in ruthenium concentration and nucleation of a new ruthenium-rich phase with the hcp structure.

  8. Stoichiometric and catalytic homologation of olefins on the Fischer-Tropsch catalysts Fe/SiO/sub 2/, Ru/SiO/sub 2/, Os/SiO/sup 2/, and Rh/SiO/sub 2/. Mechanistic implication in the mode of C-C bond formation

    SciTech Connect

    Leconte, M.; Theolier, A.; Rojas, D.; Basset, J.M.

    1984-02-22

    The formation of C/sub 4/ olefinic hydrocarbons both in CO + H/sub 2/ and C/sub 3/H/sub 6/ + H/sub 2/ reactions has been studied to test the assumption that the same mechanism is involved in the C-C bond formation in syn gas conversion and olefin hydrogenation. The yields of linear and branched olefins were measured at various contact times, and initial selectivities were obtained by extrapolation to zero conversion. The catalyst systems studied for the reactions were Fe, Ru, Rh, and Os supported by SiO/sub 2/. The results indicated that the same mechanism was involved in the C-C bond formation starting from CO + H/sub 2/, CH/sub 2/N/sub 2/ + H/sub 2/, or C/sub n/ H/sub 2n/ + H/sub 2/, and the mode of the C-C bond formation was shown to involve the addition of a C/sub 1/ fragment to a C/sub n/ fragment.

  9. Effect of Fe-Ru doping in the electronic and thermoelectric properties of new filled skutterudite Ba(Fe,Ru)4As12

    NASA Astrophysics Data System (ADS)

    Shankar, A.; Sandeep, Rai, D. P.; Thapa, R. K.; Mandal, P. K.

    2017-02-01

    We have performed the density functional theory based calculation to study the electronic and thermoelectric properties of BaFe4-xRuxAs12 (x = 0%, 25%, 50%, 75%, and 100%) within the framework of the full potential-linearized augmented plane wave method. The composite alloys are found to be stable in their optimized crystal structures and their lattice constants are in close agreement with the corresponding experimental reports. The structural stability and mechanical properties are also studied using their elastic constants. The hardness of these materials increases with increasing concentration of Ru, which also donates the covalent nature of inter-atomic bonding of BaRu4As12. The analysis of energy bands and density of states reflects the semi-metallic nature of BaFe4As12 and BaRu4As12, whereas other doped materials show metallic character. The electronic structure calculation suggests the high Seebeck coefficient with the efficient thermoelectric application of these materials. The thermal transport investigation also supports the result obtained from the electronic structure calculation. The thermoelectric efficiency defined by the figure of merit (ZT) of pure BaFe4As12 (ZT = 0.004) and BaRu4As12 (ZT = 0.005) has been enhanced to 0.357 with 75% Ru doping. The spin-polarized calculation shows a significant effect on their energy band structure, giving magnetic behavior of the sample materials. The analysis of their magnetic profile suggests the ferromagnetic nature of these materials, except BaRu4As12, which shows a paramagnetic ground state.

  10. Magnetoresistance behavior of Ni80Fe20/Ru/Ni80Fe20 nanostripes

    NASA Astrophysics Data System (ADS)

    Lupo, P.; Liu, X. M.; Adeyeye, A. O.

    2015-07-01

    We present a systematic investigation on the effects of interlayer coupling on the magnetoresistance (MR) behavior of Ni80Fe20/Ru(/Ni80Fe20 trilayer nanostripes (NSs) as a function of temperature T . By changing from 0.8 nm to 1.7 nm, either a ferromagnetic or an antiferromagnetic (AFM) type of interlayer coupling was achieved, leading to a markedly different MR behavior. We observed that the MR response is a superimposition of AMR and GMR effects, and it is significantly dependent on temperature. For AFM coupled NSs, there is a transition from a pure AFM state to a reversed spin-flop phase due to enhanced ferromagnetic pin-hole coupling at low T. Our experimental results are in good agreement with micromagnetic simulations.

  11. B11 NMR in the layered diborides OsB2 and RuB2

    NASA Astrophysics Data System (ADS)

    Suh, B. J.; Zong, X.; Singh, Y.; Niazi, A.; Johnston, D. C.

    2007-10-01

    B11 nuclear magnetic resonance (NMR) measurements have been performed on B11 enriched OsB2 and RuB2 polycrystalline powder samples in an external field of 4.7T and in the temperature range, 4.2KOsB2 and RuB2 , respectively. The experimental results indicate that a p character dominates the conduction electron wave function at the B site with a negligibly small s character in both compounds.

  12. Correlation between microstructure and thermionic electron emission from Os-Ru thin films on dispenser cathodes

    SciTech Connect

    Swartzentruber, Phillip D.; John Balk, Thomas; Effgen, Michael P.

    2014-07-01

    Osmium-ruthenium films with different microstructures were deposited onto dispenser cathodes and subjected to 1000 h of close-spaced diode testing. Tailored microstructures were achieved by applying substrate biasing during deposition, and these were evaluated with scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray spectroscopy before and after close-spaced diode testing. Knee temperatures determined from the close-spaced diode test data were used to evaluate cathode performance. Cathodes with a large (10-11) Os-Ru film texture possessed comparatively low knee temperatures. Furthermore, a low knee temperature correlated with a low effective work function as calculated from the close-spaced diode data. It is proposed that the formation of strong (10-11) texture is responsible for the superior performance of the cathode with a multilayered Os-Ru coating.

  13. Characterization of Bimetallic Fe-Ru Oxide Nanoparticles Prepared by Liquid-Phase Plasma Method

    NASA Astrophysics Data System (ADS)

    Lee, Sung-Jin; Lee, Heon; Jeon, Ki-Joon; Park, Hyunwoong; Park, Young-Kwon; Jung, Sang-Chul

    2016-07-01

    The bimetallic Fe-Ru oxide nanoparticles were synthesized in the liquid-phase plasma (LPP) method which employed iron chloride and ruthenium chloride as precursors. The active species (OH·, Hα, Hβ, and OI) and the iron and ruthenium ions were observed in the plasma field created by the LPP process. The spherical-shaped bimetallic Fe-Ru oxide nanoparticles were synthesized by the LPP reaction, and the size of the particles was growing along with the progression of the LPP reaction. The synthesized bimetallic Fe-Ru oxide nanoparticles were comprised of Fe2O3, Fe3O4, RuO, and RuO2. Ruthenium had a higher reduction potential than iron and resulted in higher ruthenium composition in the synthesized bimetallic nanoparticles. The control of the molar ratio of the precursors in the reactant solution was found to be employed as a means to control the composition of the elements in bimetallic nanoparticles.

  14. Tuning of interlayer exchange coupling in Ni80Fe20/Ru/Ni80Fe20 nanowires

    NASA Astrophysics Data System (ADS)

    Liu, X. M.; Lupo, P.; Cottam, M. G.; Adeyeye, A. O.

    2015-09-01

    In this work, we demonstrate how the static and dynamic properties of Ni80Fe20/Ru/Ni80Fe20 nanowires can be tuned by varying the Ru spacer layer thickness. Specifically, changing the Ru thickness we have tuned the Ruderman-Kittel-Kasuya-Yosida exchange interaction, and thus the antiferromagnetic (AFM) strength between the Ni80Fe20 layers. We show that there is a strong correlation between the interlayer coupling and features in ferromagnetic resonance (FMR) modes. We found different mode-softening degree of the FMR curves as function of the strength of AFM coupling, together with a clear frequency gap at around zero field. These experimental results are in qualitative agreement with presented micromagnetic simulations that also include biquadratic interface exchange. Understanding these characteristics may offer insights for reconfigurable vertical magnetic logic devices and microwave filters.

  15. Fe Substitution Effect on the High-Field Magnetization in the Kondo Semiconductor CeRu2Al10

    NASA Astrophysics Data System (ADS)

    Kondo, Akihiro; Kindo, Koichi; Nohara, Hiroki; Nakamura, Michio; Tanida, Hiroshi; Sera, Masafumi; Nishioka, Takashi

    2017-02-01

    The magnetization of the Fe substitution system in the Kondo semiconductor CeRu2Al10 was measured in high magnetic fields of up to 72 T with the magnetic field (H) along the a-axis. The magnetization curve indicates that the critical field from the antiferromagnetic (AFM) phase to the paramagnetic one (Hcp) shows an increase from ˜51 (x = 0) to ˜60 T (x = 0.7) owing to the Fe substitution. The Fe concentration dependence of Hcp is similar to that of the magnitude of the energy of the spin gap. The degree of the concave H dependence of the magnetization curve, which is the characteristic feature for H ∥ a in CeT2Al10 (T = Ru, Os), is not strongly enhanced by the Fe substitution. This may be due to the suppression of the strong anisotropy of the hybridization between the conduction band and the localized 4f shell along the a-axis. These results reveal that the spin gap of the present system consists of at least two components, the gap due to the spin (Kondo) singlet formation and the anisotropy gap of the AF magnon.

  16. Reduction of critical current in magnetic tunnel junctions with CoFeB/Ru/CoFeB synthetic free layer

    NASA Astrophysics Data System (ADS)

    Zaleski, A.; Skowronski, W.; Czapkiewicz, M.; Kanak, J.; Stobiecki, T.; Macedo, R.; Cardoso, S.; Freitas, P. P.

    2010-01-01

    Reduction of the critical current density (Jc) in magnetic tunnel junctions (MTJs) can be achieved by replacing the standard Co40Fe40B20 free layer with a synthetic antiferromagnet. Patterned MTJs prepared by ion-beam assisted deposition (nanopillars, sizes down to 60 nm × 80 nm) with 2 nm CoFeB free layer and Co40Fe40B20/Ru (tRu)/ Co40Fe40B20 as a synthetic free layer (SyF) were studied. We have measured critical current density of CIMS in thermally activated switching regime (long current pulses). Values of switching current densities for standard MTJs with SyF were of the order 106 A/cm2, whilst MTJs with standard free layer demonstrated up to four times higher values of Jc.

  17. Coupled Nd and B' spin ordering in the double perovskites Nd2NaB'O6 (B' = Ru, Os)

    SciTech Connect

    Aczel, Adam A; Bugaris, Dan; Yeon, Jeongho; Dela Cruz, Clarina R; Zur Loye, Hans-Conrad; Nagler, Stephen E

    2013-01-01

    We present a neutron powder diffraction study of the monoclinic double perovskite systems Nd$_2$NaB$'$O$_6$ (B$'$~$=$~Ru, Os), with magnetic atoms occupying both the A and B$'$ sites. Our measurements reveal coupled spin ordering between the Nd and B$'$ atoms with magnetic transition temperatures of 14~K for Nd$_2$NaRuO$_6$ and 16~K for Nd$_2$NaOsO$_6$. There is a Type I antiferromagnetic structure associated with the Ru and Os sublattices, with the ferromagnetic planes stacked along the c-axis and [110] direction respectively, while the Nd sublattices exhibit complex, canted antiferromagnetism with different spin arrangements in each system.

  18. Pair distribution function analysis of La(Fe{sub 1−x}Ru{sub x})AsO compounds

    SciTech Connect

    Martinelli, A.; Palenzona, A.; Ferdeghini, C.; Mazzani, M.; Bonfa', P.; Allodi, G.

    2014-12-15

    The local structures of La(Fe{sub 1−x}Ru{sub x})AsO (0.00≤x≤0.80) compounds were investigated by means of pair distribution function analysis at room temperature; as a result, no phase separation or clustering takes place. Local distortions are no longer correlated beyond ∼15 Å for both pure and substituted samples, indicating that the presence of Ru atoms does not determine a notable variation in the length scale of the local distortion. Different types of short range correlation between Fe and Ru atoms do not produce significant changes in the pair distribution function. - Graphical abstract: Fe–As and Ru–As bond length distributions as obtained by pair distribution function analysis of La(Fe{sub 0.70}Ru{sub 0.30})AsO; As atoms (purple spheres) undergo a random shifting around their crystallographic positions (red spheres: Fe/Ru atoms). - Highlights: • No phase separation or clustering takes place in La(Fe{sub 1−x}Ru{sub x})AsO solid solutions. • Local distortions are no longer correlated beyond ∼15 Å. • Ru displays a tendency towards local enrichment in the transition metal sublattice.

  19. Disorder influenced magnetic phase transition in the Ce(Fe 0.9 Ru 0.1)2 alloy.

    PubMed

    Chattopadhyay, M K; Roy, S B

    2010-06-16

    We have studied a 10% Ru-doped CeFe(2) alloy, Ce(Fe(0.9)Ru(0.1))(2), through magnetization, magnetotransport, and heat capacity measurements. This study shows that, while this alloy is antiferromagnetic at low temperatures and paramagnetic at high temperatures, there exists evidence of ferromagnetic ordering in the intermediate temperature regime. We show here that with 10% Ru doping the first order magnetic transition observed in the Ce(Fe(1 - x)Ru(x))(2) alloys with x < 0.08 is reduced to a quasi-continuous phase transition. The characteristic thermomagnetic history effects associated with the ferromagnetic-antiferromagnetic phase transition in the Ce(Fe(1 - x)Ru(x))(2) alloys with x < 0.08 are not observed in the Ce(Fe(0.9)Ru(0.1))(2) alloy. This alloy continues to exhibit the large magnetoresistance and large magnetocaloric effect associated with this first order magnetic transition in the alloys with smaller Ru concentration, but it does not show any energy loss due to thermomagnetic hysteresis. The present work thus shows how the introduction of quenched disorder due to alloying effects may be used to tune the first order magnetic transition in a material for more efficient functional use.

  20. Spin density wave (SDW) transition in Ru doped BaFeAs{sub 2} investigated by AC steady state calorimetry

    SciTech Connect

    Vinod, K. Sharma, Shilpam; Sundar, C. S.; Bharathi, A.

    2015-06-24

    Heat capacity measurements were done on sub-micron sized BaFe{sub 2−x}Ru{sub x}As{sub 2} single crystals using thin film membrane based the AC steady state calorimetry technique. Noticeable thermal hysteresis is observed in the heat capacity of the BaFe{sub 2−x}Ru{sub x}As{sub 2} during cooling and warming cycles, indicating first order nature of the SDW transition.

  1. Ferromagnetic quantum critical point in heavy-fermion iron oxypnictide Ce(Ru(1-x)Fe(x))PO.

    PubMed

    Kitagawa, S; Ishida, K; Nakamura, T; Matoba, M; Kamihara, Y

    2012-11-30

    We have performed (31)P-NMR measurements on Ce(Ru(1-x)Fe(x))PO in order to investigate ferromagnetic (FM) quantum criticality, since a heavy-fermion (HF) ferromagnet CeRuPO with a two-dimensional structure turns into a HF paramagnet by an isovalent Fe substitution for Ru. We found that Ce(Ru(0.15)Fe(0.85))PO shows critical fluctuations down to ~0.3 K, as well as the continuous suppression of Curie temperature and the ordered moments by the Fe substitution. These experimental results suggest the presence of a FM quantum critical point (QCP) at x~0.86, which is a rare example among itinerant ferromagnets. In addition, we point out that the critical behaviors in Ce(Ru(0.15)Fe(0.85))PO share a similarity with those in YbRh(2)Si(2), where the local criticality of f electrons has been discussed. We reveal that Ce(Ru(1-x)Fe(x))PO is a new system to study FM quantum criticality in HF compounds.

  2. Ferromagnetic resonance study of structure and relaxation of magnetization in NiFe/Ru superlattices

    NASA Astrophysics Data System (ADS)

    Alayo, W.; Landi, S., Jr.; Pelegrini, F.; Baggio-Saitovitch, E.

    2014-01-01

    The structural properties and relaxation processes of magnetization in [Ni81Fe19(t1)/Ru(t2)]N superlattices (N=number of bilayers) were analyzed by ferromagnetic resonance (FMR) with a fixed microwave frequency. One series of samples was deposited with constant NiFe layer thickness (t1) and variable Ru layer thickness (t2); the other series, with constant t2 and variable t1. A single FMR mode was observed for t2<15 Å and t1>75 Å and it has been attributed to the resonance of the exchange-coupled NiFe layers across the Ru interlayers. For the other values of t1 and t2, several FMR modes appeared and they were associated to non-coupled magnetic phases with different effective magnetization formed during the multilayer growth. The FMR linewidths were analyzed as a function of the magnetic layer thickness and a strong dependence on t1-2 was observed. It was attributed to the contribution of the two-magnon scattering mechanism for the linewidth.

  3. Modifying exchange-spring behavior of CoPt/NiFe bilayer by inserting a Pt or Ru spacer

    SciTech Connect

    Hsu, Jen-Hwa Tsai, C. L.; Lee, C.-M.; Saravanan, P.

    2015-05-07

    We herein explore the possibility of obtaining tunable tilted magnetic anisotropy in ordered-CoPt (5 nm)/NiFe(t{sub NiFe}) bilayers through modifying their exchange spring behavior by inserting Pt and Ru-spacers. The tuning process of tilt angle magnetization of NiFe-layer was systematically investigated by varying the Pt or Ru thickness (t{sub Pt} or t{sub Ru}) from 0 to 8 nm at different thicknesses of NiFe (t{sub NiFe} = 1.5, 4.0, and 6.0 nm). Polar magneto-optic Kerr effect (p-MOKE) studies reveal that the bilayers grown in absence of spacers exhibit almost a rectangular hysteresis loop. With the insertion of Pt-spacer, the loop becomes more and more tilted as t{sub Pt} increases; whereas, in the case of Ru-spacer, the nature of the loops is not simply changing in one direction. The estimated SQR{sub ⊥} (= θ{sub r}/θ{sub s}) values from the p-MOKE loops are found to monotonically decrease with increasing t{sub Pt} when t{sub Pt} ≦ 4 nm. In contrast, in the case of Ru-spacer, an oscillatory behavior for the SQR{sub ⊥} values is apparent when t{sub Ru} ≦ 4 nm. As a result, an oscillatory tilted angle of NiFe spin configuration was obtained in the case of Ru-spacer; while a decoupling effect was prominent for the Pt-spacer. The results of present study reveal that the insertion of Pt and Ru-spacers as an appropriate means for realizing tunable tilted magnetic anisotropy in the CoPt/NiFe exchange springs.

  4. Effects of Ru and Ag cap layers on microstructure and magnetic properties of FePt ultrathin films.

    PubMed

    Liu, Mingfeng; Jin, Tianli; Hao, Liang; Cao, Jiangwei; Wang, Ying; Wu, Dongping; Bai, Jianmin; Wei, Fulin

    2015-01-01

    The effects of Ru and Ag cap layers on the microstructure and magnetic properties of the FePt ultrathin films have been investigated. The results indicate that i) The Ag cap layer segregates from the FePt/Ag bilayer, lowers the FePt ordering temperature, promotes the FePt thin films to form island structure, and enhances the coercivity; ii) The Ru cap layer increases the FePt ordering temperature, helps to maintain smooth continuous structure film, and restrains the FePt (001) orientation and perpendicular magnetic anisotropy (PMA). The effects become more pronounced for the 3-nm-thick FePt thin films. The effects can be mainly attributed to the different melting point and thermal expansion stress between the cap layer and FePt thin films.

  5. Effects of Ru and Ag cap layers on microstructure and magnetic properties of FePt ultrathin films

    NASA Astrophysics Data System (ADS)

    Liu, Mingfeng; Jin, Tianli; Hao, Liang; Cao, Jiangwei; Wang, Ying; Wu, Dongping; Bai, Jianmin; Wei, Fulin

    2015-04-01

    The effects of Ru and Ag cap layers on the microstructure and magnetic properties of the FePt ultrathin films have been investigated. The results indicate that i) The Ag cap layer segregates from the FePt/Ag bilayer, lowers the FePt ordering temperature, promotes the FePt thin films to form island structure, and enhances the coercivity; ii) The Ru cap layer increases the FePt ordering temperature, helps to maintain smooth continuous structure film, and restrains the FePt (001) orientation and perpendicular magnetic anisotropy (PMA). The effects become more pronounced for the 3-nm-thick FePt thin films. The effects can be mainly attributed to the different melting point and thermal expansion stress between the cap layer and FePt thin films.

  6. Ru Catalyst-Induced Perpendicular Magnetic Anisotropy in MgO/CoFeB/Ta/MgO Multilayered Films.

    PubMed

    Liu, Yiwei; Zhang, Jingyan; Wang, Shouguo; Jiang, Shaolong; Liu, Qianqian; Li, Xujing; Wu, Zhenglong; Yu, Guanghua

    2015-12-09

    The high oxygen storage/release capability of the catalyst Ru is used to manipulate the interfacial electronic structure in spintronic materials to obtain perpendicular magnetic anisotropy (PMA). Insertion of an ultrathin Ru layer between the CoFeB and Ta layers in MgO/CoFeB/Ta/MgO films effectively induces PMA without annealing. Ru plays a catalytic role in Fe-O-Ta bonding and isolation at the metal-oxide interface to achieve moderate interface oxidation. In contrast, PMA cannot be obtained in the sample with a Mg insertion layer or without an insertion layer because of the lack of a catalyst. Our work would provide a new approach toward catalyst-induced PMA for future CoFeB-based spintronic device applications.

  7. What Controls the Phase Diagram and Superconductivity in Ru-Substituted BaFe2As2?

    SciTech Connect

    Dhaka, R. S.; Liu, Chang; Fernandes, R.M.; Jiang, Riu; Strehlow, C.P.; Kondo, Takeshi; Thaler, A.; Schmalian, Joerg; Bud-ko, S.J.; Canfield, P.C.; Kaminski, A.

    2011-12-23

    We use high resolution angle-resolved photoemission to study the electronic structure of the iron based high-temperature superconductors Ba(Fe{sub 1-x}Ru{sub x}){sub 2}As{sub 2} as a function of Ru concentration. We find that substitution of Ru for Fe is isoelectronic, i.e., it does not change the value of the chemical potential. More interestingly, there are no measured, significant changes in the shape of the Fermi surface or in the Fermi velocity over a wide range of substitution levels (0 < x < 0.55). Given that the suppression of the antiferromagnetic and structural phase is associated with the emergence of the superconducting state, Ru substitution must achieve this via a mechanism that does not involve changes of the Fermi surface. We speculate that this mechanism relies on magnetic dilution which leads to the reduction of the effective Stoner enhancement.

  8. Enhanced nonvolatile holographic properties in Zn, Ru and Fe co-doped LiNbO3 crystals

    NASA Astrophysics Data System (ADS)

    Xu, Chao; Leng, Xuesong; Xu, Lei; Wen, Aihua; Xu, Yuheng

    2012-08-01

    A series of LiNbO3 crystals doped with various concentrations of ZnO and fixed concentrations of RuO2 and Fe2O3 have been grown by the Czochralski method from the congruent melts. The type of charge carriers was determined by Kr+ laser (476 nm) and He-Ne laser (633 nm). The results revealed that the holes were the dominant charge carriers at blue light irradiation. Dual-wavelength and two-color techniques were employed to investigate the nonvolatile holographic storage properties of Ru:Fe:LiNbO3 and Zn doped Ru:Fe:LiNbO3 crystals. The essential parameters of blue nonvolatile holographic storage in Zn:Ru:Fe:LiNbO3 crystals were enhanced greatly with the increase of Zn concentration. This indicates that the damage resistant dopants Zn2+ ions enhance the photorefractive properties at 476 nm wavelength instead of suppressing the photorefraction. The different mechanisms of blue photorefractive and nonvolatile holographic storage properties by dual wavelength recording in Zn:Ru:Fe:LiNbO3 crystals were discussed.

  9. Structural, electronic, and magnetic properties near the Fe(111) surface with a Mo, Ru, or Pd overlayer

    NASA Astrophysics Data System (ADS)

    Geng, W. T.; Freeman, A. J.; Wu, R.

    2000-03-01

    Structural, electronic, and magnetic properties near the Fe(111) surface, with and without a 4d transition metal overlayer of A (A= Mo, Ru, or Pd), are determined by means of the full-potential linearized augmented plane wave (FLAPW)(Wimmer, Krakauer, Weinert and Freeman, PRB) 24, 864 (1981). total energy/atomic force method with the generalized gradient approximation (GGA). Both the clean and A adsorbed surface are simulated by a 13-layer slab. When the surface Fe is replaced by A, multilayer relaxation is found to be extended to the fourth subsurface layer, indicating a long-distance perturbation. The calculated work function for the clean surface is 4.31 eV, in good agreement with the experiment (4.5 eV) and other first-principles results. It is increased by both Ru (to 4.62 eV) and Pd (to 4.89 eV), as expected from the fact that pure Ru and Pd metals have higher work functions than does Fe. Mo overlayer, however, lowers the work function to 3.98 eV, although the pure Mo metal also has a work function higher than Fe. We find that Mo couples anti-ferromagnetically and Ru and Pd couple ferromagnetically with the Fe(111) surface. The induced spin magnetic moment for Mo, Ru, and Pd is -0.79, 0.81, and 0.47 μ_B, respectively.

  10. Ferromagnetic resonance study of interface coupling for spin waves in narrow NiFe/Ru/NiFe multilayer nanowires

    NASA Astrophysics Data System (ADS)

    Lupo, P.; Haghshenasfard, Z.; Cottam, M. G.; Adeyeye, A. O.

    2016-12-01

    A systematic investigation is presented for the magnetization dynamics in trilayer nanowires, consisting of two permalloy (Ni80Fe20 ) layers separated by a nonmagnetic Ru spacer layer. The width of the wires ranges from 90 to 190 nm. By varying the Ru thickness between 0.7 and 2.0 nm, the interlayer coupling can be effectively controlled, modifying the corresponding magnetic ground state and the spin-wave dynamics. By contrast with previous work on coupled trilayer nanowires with larger widths (270 nm and more), the focus here is on nanowire arrays where the strong shape anisotropy competes with the Ruderman-Kittel-Kasuya-Yosida interactions and biquadratic exchange interactions across the Ru interface, as well as dipolar interactions and Zeeman energy. As a result, the spin-wave spectrum is found to be drastically modified. Ferromagnetic resonance and hysteresis loop measurements are reported over a wide range of applied magnetic fields, showing that the overall magnetization alignment between the permalloy layers may be parallel, antiparallel, or in a spin-flop state, depending on the overall interlayer coupling. The experimental results for different stripe widths are successfully analyzed using a microscopic dipole-dipole theory and micromagnetic simulations.

  11. Isotopic studies of Mg, Fe, Mo, RU and W in Fremdlinge from Allende refractory inclusions

    NASA Astrophysics Data System (ADS)

    Hutcheon, I. D.; Armstrong, J. T.; Wasserburg, G. J.

    1987-12-01

    This paper presents the first isotopic measurements, made with an ion microprobe, of Mg, Fe, Mo, Ru, and W in Fremdlinge and refractory metal nuggets from Allende meteorite. No non-mass-dependent deviations exceeding 1 percent from normal solar isotopic abundances were found for any of the elements analyzed, despite the unusual mineralogy of Fremdlinge and the extreme enrichment in refractory siderophile elements. It is concluded that the chemical, petrologic, and isotopic data on Fremdlinge are most plausibly interpreted in terms of the origin of Fremdlinge within the solar nebula.

  12. Strong uniaxial magnetic anisotropy in CoFe films on obliquely sputtered Ru underlayer

    SciTech Connect

    Fukuma, Y.; Lu, Z.; Fujiwara, H.; Mankey, G. J.; Butler, W. H.; Matsunuma, S.

    2009-10-01

    Co{sub 90}Fe{sub 10} films with an in-plane uniaxial magnetic anisotropy have been grown on an obliquely sputtered thin Ru underlayer. The anisotropy field can be increased up to 200 Oe. The hysteresis curves show a very high squareness in the easy axis direction and almost no hysteresis in the hard axis direction, suggesting that the induced uniaxial anisotropy is uniform throughout the films. The switching characteristics of the nanoelements fabricated from the films by e-beam lithography are also investigated. There is no degradation of the magnetic anisotropy after the annealing and lithographical process.

  13. Magnetic, magnetocaloric properties and phenomenological model in amorphous Fe60Ru20B20 alloy

    NASA Astrophysics Data System (ADS)

    Boutahar, A.; Lassri, H.; Hlil, E. K.

    2015-11-01

    Magnetic, magnetocaloric properties and phenomenological model of amorphous Fe60Ru20B20 alloy are investigated in detail. The amorphous alloy has been synthesized using melt spinning method. The magnetic transition nature undergoes a second-order magnetic phase transition from ferromagnetic to paramagnetic states with a Curie temperature of 254 K. Basis on the thermodynamic Maxwell's relation, magnetic entropy change (-ΔSM) is calculated. Further, we also report a theoretical investigation of the magnetocaloric effect using a phenomenological model. The best model parameters and their variation with temperature and the magnetic field were determined. The theoretical predictions are found to agree closely with experimental measurements.

  14. Non-Fermi surface nesting driven commensurate magnetic ordering in Fe-doped S r2Ru O4

    NASA Astrophysics Data System (ADS)

    Zhu, M.; Shanavas, K. V.; Wang, Y.; Zou, T.; Sun, W. F.; Tian, W.; Garlea, V. O.; Podlesnyak, A.; Matsuda, M.; Stone, M. B.; Keavney, D.; Mao, Z. Q.; Singh, D. J.; Ke, X.

    2017-02-01

    S r2Ru O4 , an unconventional superconductor, is known to possess an incommensurate spin-density wave instability driven by Fermi surface nesting. Here we report a static spin-density wave ordering with a commensurate propagation vector qc=(0.25 0.25 0 ) in Fe-doped S r2Ru O4 , despite the magnetic fluctuations persisting at the incommensurate wave vectors qic=(0.3 0.3 L ) as in the parent compound. The latter feature is corroborated by the first-principles calculations, which show that Fe substitution barely changes the nesting vector of the Fermi surface. These results suggest that in addition to the known incommensurate magnetic instability, S r2Ru O4 is also in proximity to a commensurate magnetic tendency that can be stabilized via Fe doping.

  15. Quantum oscillations of the superconductor LaRu2P2: Comparable mass enhancement λ≈1 in Ru and Fe phosphides

    NASA Astrophysics Data System (ADS)

    Moll, Philip J. W.; Kanter, Jakob; McDonald, Ross D.; Balakirev, Fedor; Blaha, Peter; Schwarz, Karlheinz; Bukowski, Zbigniew; Zhigadlo, Nikolai D.; Katrych, Sergiy; Mattenberger, Kurt; Karpinski, Janusz; Batlogg, Bertram

    2011-12-01

    We have studied the angular-dependent de Haas-van Alphen oscillations of LaRu2P2 using magnetic torque in pulsed magnetic fields up to 60 T. The observed oscillation frequencies are in excellent agreement with the geometry of the calculated Fermi surface. The temperature dependence of the oscillation amplitudes reveals effective masses m*(α)=0.71 and m*(β)=0.99 me, which are enhanced over the calculated band mass by λcyc of 0.8. We find a similar enhancement of λγ≈1 in comparing the measured electronic specific heat (γ=11.5 mJ/mol K2) with the total density of states from band-structure calculations. Remarkably, very similar mass enhancements have been reported in other pnictides, LaFe2P2, LaFePO (Tc≈4K), and LaRuPO, independent of whether they are superconducting or not. This is contrary to the common perceptions that the normal-state quasiparticle renormalizations reflect the strength of the superconducting pairing mechanism and leads to new questions about pairing in isostructural and isoelectronic Ru- and Fe-pnictide superconductors.

  16. A cyanide-bridged trinuclear Fe(II)-Ru(II)-Fe(II) complex with three stable states: synthesis, crystal structures, electronic couplings and magnetic properties.

    PubMed

    Ma, Xiao; Hu, Sheng-Min; Tan, Chun-Hong; Wen, Yue-Hong; Zhu, Qi-Long; Shen, Chao-Jun; Sheng, Tian-Lu; Wu, Xin-Tao

    2012-10-21

    Treatment of trans-(Ph-tpy)Ru(PPh(3))(CN)(2) (Ph-tpy = 4'-phenyl-2,2':6',2''-terpyridine, PPh(3) = triphenylphosphine) with 2 equiv of Cp(dppe)Fe(NCCH(3))Br (dppe = bis(diphenylphosphino)ethane) in the presence of NH(4)PF(6) produced a trinuclear cyanide-bridged complex, trans-[Cp(dppe)Fe(CN)(Ph-tpy)Ru(PPh(3))(CN)Fe(dppe)Cp][PF(6)](2) (1[PF(6)](2)). Its one-electron oxidation product (1[PF(6)](3)) and two-electron-oxidation product (1[PF(6)](4)) were obtained by oxidation with (Cp)(2)FePF(6) and AgPF(6), respectively. Firstly, the crystal structures of the cyanide-bridged complexes with three stable states were fully characterized. The reversible electrochemistry measurement of 1(2)(+) shows the presence of a long range intervalence interaction between the external iron centres. Both 1(3)(+) and 1(4)(+) were considered to be Class II mixed valence complexes according to the classification of Robin and Day. Magnetic analysis indicated the presence of a moderately strong antiferromagnetic coupling between the two remote Fe(III) ions across the Fe-NC-Ru-CN-Fe array in 1(4)(+). This proves that the Ru(II)-dicyano complex is a bridging ligand that can transmit electro- and magneto-communication.

  17. Synthesis of Monomeric Fe(II) and Ru(II) Complexes of Tetradentate Phosphines

    SciTech Connect

    Jana, Barun; Ellern, Arkady; Pestovsky, Oleg; Sadow, Aaron; Bakac, Andreja

    2011-03-07

    rac-Bis[{l_brace}(diphenylphosphino)ethyl{r_brace}-phenylphosphino]methane (DPPEPM) reacts with iron(II) and ruthenium(II) halides to generate complexes with folded DPPEPM coordination. The paramagnetic, five-coordinate Fe(DPPEPM)Cl{sub 2} (1) in CD{sub 2}Cl{sub 2} features a tridentate binding mode as established by {sup 31}P{l_brace}{sup 1}H{r_brace} NMR spectroscopy. Crystal structure analysis of the analogous bromo complex, Fe(DPPEPM)Br{sub 2} (2) revealed a pseudo-octahedral, cis-{alpha} geometry at iron with DPPEPM coordinated in a tetradentate fashion. However, in CD{sub 2}Cl{sub 2} solution, the coordination of DPPEPM in 2 is similar to that of 1 in that one of the external phosphorus atoms is dissociated resulting in a mixture of three tridentate complexes. The chloro ruthenium complex cis-Ru({kappa}{sup 4}-DPPEPM)Cl{sub 2} (3) is obtained from rac-DPPEPM and either [RuCl{sub 2}(COD)]{sub 2} [COD = 1,5-cyclooctadiene] or RuCl{sub 2}(PPh{sub 3}){sub 4}. The structure of 3 in both the solid state and in CD{sub 2}Cl{sub 2} solution features a folded {kappa}{sup 4}-DPPEPM. This binding mode was also observed in cis-[Fe({kappa}{sup 4}-DPPEPM)(CH{sub 3}CN){sub 2}](CF{sub 3}SO{sub 3}){sub 2} (4). Addition of an excess of CO to a methanolic solution of 1 results in the replacement of one of the chloride ions by CO to yield cis-[Fe({kappa}{sup 4}-DPPEPM)Cl(CO)](Cl) (5). The same reaction in CH{sub 2}Cl{sub 2} produces a mixture of 5 and [Fe({kappa}{sup 3}-DPPEPM)Cl{sub 2}(CO)] (6) in which one of the internal phosphines has been substituted by CO. Complexes 2, 3, 4, and 5 appear to be the first structurally characterized monometallic complexes of {kappa}{sup 4}-DPPEPM.

  18. The cleanup of CO in hydrogen for PEMFC applications using Pt, Ru, Co, and Fe in PROX reaction

    NASA Astrophysics Data System (ADS)

    Huang, Chih-Yung; Chen, Yan-Yi; Su, Chin-Chia; Hsu, Chuan-Fu

    An experimental investigation is performed into the cleanup of CO in hydrogen for proton exchange membrane fuel cell (PEMFC) using Pt/Al 2O 3 and Ru/Al 2O 3 catalysts. Additionally, the effects of adding the transition metals Co and Fe to a Ru/Al 2O 3 catalyst are examined. The results show that as the level of Pt addition is increased, the maximum CO conversion rate is achieved at a lower temperature. With Ru/Al 2O 3 catalysts, the CO conversion rate increases significantly with increasing Ru addition at temperatures lower than 80 °C For both catalysts, the methane yield increases with increasing temperature and increasing noble metal addition. At temperatures in the range of 100-140 °C, the CO conversion rate and methane yield of the Pt- and Ru-based preferential oxidation (PROX) reactions are both insensitive to the density of the honeycomb carrier. The CO conversion rate is significantly improved by the addition of Fe at temperatures lower than 160 °C and by the addition of Co at temperatures higher than 200 °C. Of the two metals, Fe results in a greater reduction of the methane yield at high temperatures. Finally, both catalysts achieve a stable cleanup performance over the course of a 12-h stability test and suppress the CO concentration to an acceptable level for PEMFC applications.

  19. Packings of Os layers for the development of L10 order of FePt in nanoscale [Os-FePt]n multilayer systems

    NASA Astrophysics Data System (ADS)

    Su, T. T.; Hsiao, Ching-Hung; Lo, Shen-Chuan; Ouyang, Wen; Li, Tzu-Yuan; Ouyang, H.; Yao, Y. D.

    2013-05-01

    The element osmium (Os), with high melting and boiling points, plays a crucial role in the development of the L10 order for FePt in [Os(5 nm)/FePt(25 nm)]4 and [Os(1 nm)/FePt(5 nm)]20 systems. The large mismatches of lattice constants between Os and FePt, with specific epitaxial relations, induce a great strain in the [Os(5 nm) /FePt(25 nm)]4 system with fixed total thicknesses for the FePt and Os layers. Due to this large strain effect, the L10 order in a FePt structure can be enhanced through an application of stressing along the c axis for the face-centered cubic structure, which results in a higher coercivity. However, a smaller degree of average strain was observed in the 5 nm-thickness FePt system due to the existence of pinholes.

  20. High energy ball-milled Ti{sub 2}RuFe electrocatalyst for hydrogen evolution in the chlorate industry

    SciTech Connect

    Blouin, M.; Guay, D.; Huot, J.; Schulz, R.

    1997-06-01

    The high energy mechanical alloying of a Ti{endash}Ru{endash}Fe powder mixture (atomic ratio 2:1:1) has been performed by extensive ball-milling in a steel crucible. The structural evolution of the resulting materials has been studied by x-ray powder diffraction analysis. The identification of the various phases present in the materials, as well as the crystallite size and strain, has been performed by Rietveld refinement analysis. In the first stage of the material transformation, Ru or Fe atoms dissolved into Ti to yield to the formation of {beta}{minus}Ti. Upon further ball-milling, almost all the original constituents of the powder mixture have disappeared and a new simple cubic Ti{sub 2}RuFe phase is formed, with a crystallite size as small as 8 nm. The electrochemical properties of these materials have been tested in a typical chlorate electrolyte by cold-pressing the powders into disk electrodes. At 20 h of ball-milling, where the phase concentration of Ti{sub 2}RuFe reaches 96{percent}, a reduction of the activation overpotential at 250 mA cm{sup {minus}2} of nearly 250 mV is observed when compared to that of a pure iron electrode. {copyright} {ital 1997 Materials Research Society.}

  1. Mössbauer effect studies of disordered Fe-Ru alloys

    NASA Astrophysics Data System (ADS)

    Pöttker, W. E.; Paduani, C.; Ardisson, J. D.; Ioshida, M. I.

    2004-09-01

    The bcc and hcp phases of disordered Fe100-xRux alloys are investigated with several experimental techniques to study the composition dependence of the magnetic properties in these structures. With an appropriate annealing the prepared samples are single phase. The iron rich alloys are ferromagnetic at room temperature with the bcc structure. However, an antiferromagnetic coupling is introduced with the addition of ruthenium. Above 30 at% Ru a paramagnetic behavior is observed at 300 K and 77 K, where the alloys have the hcp structure. In the ferromagnetic phase the Curie temperature decreases steadly with the increase of the ruthenium concentration. In the paramagnetic hcp phase the mean volume per atom is al-most triplicated as compared to the bcc phase, which brings out the breakdown of the magnetization and the collapse of the hyperfine field at the iron sites simultaneously with the crystallographic phase transition.

  2. Order-disorder phase transition in Au2Fe on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Marie, J.-B.; Bellec, A.; Chacon, C.; Girard, Y.; Lagoute, J.; Repain, V.; Rousset, S.; Garreau, Y.; Coati, A.

    2016-12-01

    Order-disorder transition of the epitaxial surface alloy of bulk immiscible elements Au1 -xFex on Ru(0001) is studied using complementary experiments of scanning tunneling microscopy and grazing incidence x-ray diffraction. For x ≃1 /3 , we evidence an apparent continuous transition towards disorder with increasing temperature from 550 to 700 K. An ordered Au2Fe two-dimensional alloy is found to be composed of nanometer size domains of the three variants that switch to a two-dimensional solid solution with temperature. A two-levels model is developed to analyze those results which conducts to interpret this phase transition as the result of an order-disorder transition within two dimensional uncorrelated grains, or domains, with nearly fixed size. This system is a good candidate in order to study two-dimensional phase transitions of surface alloy, a largely unexplored domain but crucial to understanding thermal stability of bimetallic nanoparticles.

  3. Theoretical study of the bonding in LaFe(2+), LaRu(2+) and YRu(2+)

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1989-01-01

    The bonding in LaFe(2+) and LaRu(2+) involves nearly equal contributions from La(+) and La(2+). The second IP of Y is larger than that of La and this leads to predominantly Y(+) + Ru(+) character in the YRu(2+) wavefunction. The remarkable stability of these systems derives from multiple d-d bonds that lead to a bond-order of between two and three. Thus the ground states of these dications, which have relatively deep molecular wells and large barriers to dissociation, have essentially infinite lifetimes with respect to unimolecular decay.

  4. Low-temperature properties of Ce(Ru 1- xM x) 2Ge 2, M  Fe, Au

    NASA Astrophysics Data System (ADS)

    Fontes, M. B.; Elmassalami, M.; Aliaga-Guerra, D.; Giordanengo, B.; Bud'ko, S. L.; Guimaraes, A. P.; Gavilano, J. L.; Baggio-Saitovitch, E. M.

    1995-02-01

    We have performed measurements of electrical resistivity, AC susceptibility, magnetization, Mössbauer effect and NMR on the series of intermetallic compounds Ce(Ru 1- xM x) 2Ge 2, M  Fe, Au for 0 ⩽ x ⩽ 0.1. The parent compound CeRu 2Ge 2 orders ferromagnetically below 7.5 K, with f-electrons showing only a small mass-enhancement at low temperatures. However, its crystal structure and Fermi surface are closely related to the heavy-electron superconductor CeRu 2Si 2. Analysis of X-ray diffraction patterns confirmed the structure to be of thCr 2Si 2-type, with no foreign phases detected. The results of our Mössbauer studies indicate that Fe goes into the Ru sites with no magnetic moment. NMR signals were observed in the Fe-doped samples with quadrupolar interaction that can be related to 73Ge nucleus ( I = 9/2).

  5. Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films

    NASA Astrophysics Data System (ADS)

    Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

    2017-03-01

    Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu1 - x Fe x O3 - δ epitaxial thin films ( x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu1 - x Fe x O3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR ( 36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies ( δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr1 - x La x )(Ru1 - x Fe x )O3. These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu1 - x Fe x O3 - δ thin films.

  6. Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir.

    PubMed

    Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher; Hu, P

    2014-07-14

    In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO2 selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO2 selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using the first principles method. It is found that CH3CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations, are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO2 selectivity and only Rh is able to increase the selectivity of CO2 in DEFCs.

  7. Strain-induced topological transition in SrRu2O6 and CaOs2O6

    DOE PAGES

    Ochi, Masayuki; Arita, Ryotaro; Trivedi, Nandini; ...

    2016-05-24

    The topological property of SrRumore » $$_2$$O$$_6$$ and isostructural CaOs$$_2$$O$$_6$$ under various strain conditions is investigated using density functional theory. Based on an analysis of parity eigenvalues, we anticipate that a three-dimensional strong topological insulating state should be realized when band inversion is induced at the A point in the hexagonal Brillouin zone. For SrRu$$_2$$O$$_6$$, such a transition requires rather unrealistic tuning, where only the $c$ axis is reduced while other structural parameters are unchanged. However, given the larger spin-orbit coupling and smaller lattice constants in CaOs$$_2$$O$$_6$$, the desired topological transition does occur under uniform compressive strain. Our study paves a way to realize a topological insulating state in a complex oxide, which has not been experimentally demonstrated so far.« less

  8. Engineering optical mode ferromagnetic resonance in FeCoB films with ultrathin Ru insertion

    PubMed Central

    Li, Shandong; Wang, Cuiling; Chu, Xian-Ming; Miao, Guo-Xing; Xue, Qian; Zou, Wenqin; Liu, Meimei; Xu, Jie; Li, Qiang; Dai, Youyong; Yan, Shishen; Kang, Shishou; Long, Yunze; Lü, Yueguang

    2016-01-01

    Ferromagnetic resonance (FMR) in soft magnetic films (SMFs) to a large extent determines the maximum working frequency of magnetic devices. The FMR frequency (fr) in an optical mode is usually much higher than that in the corresponding acoustic mode for exchange coupled ferromagnet/nonmagnet/ferromagnet (FM/NM/FM) trilayers. In this study, we prepared a 50 nm FeCoB film with uniaxial magnetic anisotropy (UMA), showing a high acoustic mode fr of 4.17 GHz. When an ultrathin Ru spacer was inserted in the very middle of the UMA-FeCoB film, the zero-field FMR was abruptly switched from an acoustic mode to an optical one with fr dramatically enhanced from 4.17 GHz to 11.32 GHz. Furthermore, the FMR mode can be readily tuned to optical mode only, acoustic mode only, or double mode by simply varying the applied filed, which provides a flexible way to design multi-band microwave devices. PMID:27628089

  9. Chemical pressure tuning of URu2Si2 via isoelectronic substitution of Ru with Fe

    DOE PAGES

    Das, Pinaki; Kanchanavatee, N.; Helton, J. S.; ...

    2015-02-26

    We have used specific heat and neutron diffraction measurements on single crystals of URu2–xFexSi₂ for Fe concentrations x ≤ 0.7 to establish that chemical substitution of Ru with Fe acts as “chemical pressure” Pch as previously proposed by Kanchanavatee et al. [Phys. Rev. B 84, 245122 (2011)] based on bulk measurements on polycrystalline samples. Neutron diffraction reveals a sharp increase of the uranium magnetic moment at x = 0.1, reminiscent of the behavior at the “hidden order” to large moment antiferromagnetic (LMAFM) phase transition observed at a pressure Px ≈ 0.5-0.7 GPa in URu₂Si₂. Using the unit cell volume determinedmore » from our measurements and an isothermal compressibility κT = 5.2×10⁻³ GPa⁻¹ for URu₂Si₂, we determine the chemical pressure Pch in URu2-xFexSi₂ as a function of x. The resulting temperature T-chemical pressure Pch phase diagram for URu2-xFexSi₂ is in agreement with the established temperature T-external pressure P phase diagram of URu₂Si₂.« less

  10. Metal-insulator transition in Ba3Fe1 -xRu2 +xO9 : Interplay between site disorder, chemical percolation, and electronic structure

    NASA Astrophysics Data System (ADS)

    Middey, S.; Aich, Payel; Meneghini, C.; Mukherjee, K.; Sampathkumaran, E. V.; Siruguri, V.; Mahadevan, P.; Ray, Sugata

    2016-11-01

    Perovskites containing barium metal at the A site often take up unusual hexagonal structures having more than one type of possible sites for the B cation to occupy. This opens up various different B -B - or B -O-B -type connectivities and consequent physical properties which are naturally missing in cubic perovskites. BaRuO3 is one such system where doping of Ru (4 d4 ) by other transition metals (Mn +) creates similar conditions, giving rise to various M -Ru interactions. Interestingly, the 6 H hexagonal structure of doped barium ruthenate triple perovskite (Ba3M Ru2O9 ) seems to possess some internal checks because within the structure M ion always occupies the 2 a site and Ru goes to the 4 f site, allowing only M -O-Ru 180∘ and Ru-O-Ru 90∘ interactions to occur. The only exception is observed in the case of the Fe dopant, which allows us to study almost the full Ba3Fe1 -xRu2 +xO9 series of compounds with wide ranges of x because here Fe ions have the ability to freely go to the 4 f sites and Ru readily takes up the 2 a positions. Therefore, here one has the opportunity to probe the evolution of electronic and magnetic properties as a function of doping by going from BaRuO3 (paramagnetic metal) to BaFeO3 (ferromagnetic insulator). Our detailed experimental and theoretical results show that the series does exhibit a percolative metal-insulator transition with an accompanying but not coincidental magnetic transition as a function of x .

  11. Reactions of the tetrahedral clusters [MCo(3)(CO)(12)](-) (M = Ru, Fe) with functional mono- and diynes.

    PubMed

    Choualeb, Aldjia; Braunstein, Pierre; Rosé, Jacky; Welter, Richard

    2004-01-12

    The tetrahedral cluster [RuCo(3)(CO)(12)](-) reacts with various alkynes, including the new PhCtbd1;CC(O)NHCH(2)Ctbd1;CH (L(1)()), to afford the butterfly clusters [RuCo(3)(CO)(10)(micro(4)-eta(2)-RC(2)R')](-) (1, R = R' = C(O)OMe; 2, R = H, R' = Ph; 3, R = H, R' = MeC=CH(2); 4, R = H, R' = CH(2)OCH(2)Ctbd1;CH; 5, R = H, R' = CH(2)NHC(O)Ctbd1;CPh), in which the ruthenium atom occupies a hinge position and the alkyne is coordinated in a micro(4)-eta(2) fashion. Reaction of the anions 1-3 with [Cu(NCMe)(4)]BF(4) led to selective loss of the 12e fragment Co(CO)(-) to form [RuCo(2)(CO)(9)(micro(3)-eta(2)-RC(2)R')] (6, R = R' = C(O)OMe; 7, R = H, R' = Ph; 8, R = H, R' = MeC=CH(2)). To prepare functionalized RuCo(3) or FeCo(3) clusters that could be subsequently condensed with a silica matrix via the sol-gel method, we reacted [MCo(3)(CO)(12)](-) (M = Ru, Fe) with the alkyne PhCtbd1;CC(O)NH(CH(2))(3)Si(OMe)(3)(L(2)()) and obtained the butterfly clusters [MCo(3)(CO)(10)(micro(4)-eta(2)-PhC(2)C(O)NH(CH(2))(3)Si(OMe)(3))](-) 9 and 10, respectively. Air-stable [RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))](-) (11) was obtained from 1,4-bis(trimethylsilyl)butadiyne and reacted with [Cu(NCMe)(4)]BF(4) to give [RuCo(2)(CO)(9)(micro(3)-eta(2)-HC(2)Ctbd1;CSiMe(3))] (12), owing to partial ligand proto-desilylation, and not the expected [RuCo(2)(CO)(9)(micro(3)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))]. Reaction of 11 with [NO]BF(4) afforded, in addition to 12, [RuCo(3)(CO)(9)(NO)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))] (13) owing to selective CO substitution on a wing-tip cobalt atom with NO. The thermal reaction of 11 with [AuCl(PPh(3))] led to replacement of a CO on Ru by the PPh(3) originating from [AuCl(PPh(3))] and afforded [RuCo(3)(CO)(9)(PPh(3))(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))](-) (14), also obtained directly by reaction of 11 with one equivalent of PPh(3). Proto-desilylation of 11 using TBAF/THF-H(2)O afforded [RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)Si

  12. Analysis of the weak coupling of the IrMn/Co/Ru/NiFe structures by ferromagnetic resonance

    NASA Astrophysics Data System (ADS)

    Alayo, W.; Sousa, M. A.; Pelegrini, F.; Baggio-Saitovitch, E.

    2011-04-01

    The Ir20Mn80/Co/Ru/Ni81Fe19 spin valve structures have been produced by sputtering deposition and analyzed by ferromagnetic resonance. Two well resolved modes are identified in the FMR spectra as the resonance of the Co and NiFe layers. The in-plane angular dependence of the resonance peaks for the NiFe layer present a small asymmetry, which is attributed to the interlayer exchange interaction between ferromagnetic layers across the nonmagnetic spacer. The data were analyzed considering the exchange bias at the IrMn/Co interface and the indirect coupling between Co and NiFe. The in-plane angular dependence of the resonance fields of both Co and NiFe layers present an upward (downward) shift for antiferromagnetic (ferromagnetic) coupling with respect to a system with no interlayer coupling.

  13. Analysis of the weak coupling of the IrMn/Co/Ru/NiFe structures by ferromagnetic resonance

    SciTech Connect

    Alayo, W.; Baggio-Saitovitch, E.; Sousa, M. A.; Pelegrini, F.

    2011-04-15

    The Ir{sub 20}Mn{sub 80}/Co/Ru/Ni{sub 81}Fe{sub 19} spin valve structures have been produced by sputtering deposition and analyzed by ferromagnetic resonance. Two well resolved modes are identified in the FMR spectra as the resonance of the Co and NiFe layers. The in-plane angular dependence of the resonance peaks for the NiFe layer present a small asymmetry, which is attributed to the interlayer exchange interaction between ferromagnetic layers across the nonmagnetic spacer. The data were analyzed considering the exchange bias at the IrMn/Co interface and the indirect coupling between Co and NiFe. The in-plane angular dependence of the resonance fields of both Co and NiFe layers present an upward (downward) shift for antiferromagnetic (ferromagnetic) coupling with respect to a system with no interlayer coupling.

  14. Combinatorial PtSnM (M = Fe, Ni, Ru and Pd) nanoparticle catalyst library toward ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Almeida, T. S.; Van Wassen, A. R.; VanDover, R. B.; de Andrade, A. R.; Abruña, H. D.

    2015-06-01

    Electrode arrays containing 91 combinations of Pt-Sn-M (M = Fe, Ni, Pd, and Ru) were prepared by borohydride reduction of aqueous metal salts on carbon paper, and screened by fluorescence assay for activity as ethanol electrooxidation catalysts. Catalysts that showed high activity for this reaction were identified as being Pt(80)Sn(10)Fe(10), Pt(80)Sn(10)Ni(10), Pt(70)Sn(20)Pd(10), and Pt(70)Sn(10)Ru(20) (numbers in parenthesis indicate atomic percent). These were significantly more active than Pt or PtSn catalysts, also present in the electrode arrays. These 4 compositions were synthesized as nanoparticles and characterized physically and electrochemically. X-ray diffraction showed a Pt face-centered cubic (fcc) structure with an average crystallite size of about 2.0 nm for all catalysts. The electrochemical tests for the oxidation of ethanol revealed excellent electrocatalytic activity and single cell (fuel cell) power density for all four catalyst formulations. Fe-containing catalysts exhibited the highest activity (13 A gPt-1) and single-cell performance (50 mW cm-2) followed by Ni- and Pd-containing materials with similar results; electrocatalytic activity around 10 A gPt-1 and power densities of 43 mW cm-2. The lowest performance was observed for the Ru-containing catalyst. However, its single-cell performance (30 mW cm-2) was still comparable to that of the commercial PtSn-Etek electrocatalyst.

  15. Theory of the metal-insulator transition in Pr Ru4 P12 and Pr Fe4 P12

    NASA Astrophysics Data System (ADS)

    Curnoe, S. H.; Harima, H.; Takegahara, K.; Ueda, K.

    2004-12-01

    All symmetry-allowed couplings between the 4f2 -electron ground state doublet of trivalent praseodymium in PrRu4P12 and PrFe4P12 and displacements of the phosphorus, iron, or ruthenium ions are considered. Two types of displacements can change the crystal lattice from body-centred cubic to simple orthorhombic or to simple cubic. The first type lowers the point group symmetry from tetrahedral to orthorhombic, while the second type leaves it unchanged, with corresponding space group reductions Im3¯→Pmmm and Im3¯→Pm3¯ , respectively. In former case, the lower point group symmetry splits the degeneracy of the 4f2 doublet into states with opposite quadrupole moment, which then leads to antiquadrupolar ordering, as in PrFe4P12 . Either kind of displacement may conspire with nesting of the Fermi surface to cause the metal-insulator or partial metal-insulator transition observed in PrFe4P12 and PrRu4P12 . We investigate this scenario using band-structure calculations, and it is found that displacements of the phosphorus ions in PrRu4P12 (with space-group reduction Im3¯→Pm3¯ ) open a gap everywhere on the Fermi surface.

  16. Structural and mechanical properties of transition metal borides Nb2MB2 (M=Tc, Ru, and Os) under pressure

    NASA Astrophysics Data System (ADS)

    Li, Xiaofeng; Yan, Haiyan; Wei, Qun

    2016-10-01

    First-principle total energy calculations are employed to provide a fundamental understanding of the structural, mechanical, and electronic properties of transition metal borides Nb2MB2 (M=Tc, Ru, and Os) within the tetragonal superstructure P4/mnc structure. The mechanically and dynamically stabilities of three borides have been demonstrated by the elastic constants and phonons calculations under pressure. Among these three compounds, Nb2TcB2 exhibits the biggest bulk and Young's modulus, smallest Poission's ratio, and highest harness. Density of states of them revealed that the strong B-B, Nb-B and M-B covalent bonds are major driving forces for their high bulk and shear moduli as well as small Poisson's ratio.

  17. Complex transition metal hydrides incorporating ionic hydrogen: thermal decomposition pathway of Na2Mg2FeH8 and Na2Mg2RuH8.

    PubMed

    Humphries, Terry D; Matsuo, Motoaki; Li, Guanqiao; Orimo, Shin-Ichi

    2015-03-28

    Complex transition metal hydrides have potential technological application as hydrogen storage materials, smart windows and sensors. Recent exploration of these materials has revealed that the incorporation of anionic hydrogen into these systems expands the potential number of viable complexes, while varying the countercation allows for optimisation of their thermodynamic stability. In this study, the optimised synthesis of Na2Mg2TH8 (T = Fe, Ru) has been achieved and their thermal decomposition properties studied by ex situ Powder X-ray Diffraction, Gas Chromatography and Pressure-Composition Isotherm measurements. The temperature and pathway of decomposition of these isostructural compounds differs considerably, with Na2Mg2FeH8 proceeding via NaMgH3 in a three-step process, while Na2Mg2RuH8 decomposes via Mg2RuH4 in a two-step process. The first desorption maxima of Na2Mg2FeH8 occurs at ca. 400 °C, while Na2Mg2RuH8 has its first maxima at 420 °C. The enthalpy and entropy of desorption for Na2Mg2TH8 (T = Fe, Ru) has been established by PCI measurements, with the ΔHdes for Na2Mg2FeH8 being 94.5 kJ mol(-1) H2 and 125 kJ mol(-1) H2 for Na2Mg2RuH8.

  18. Studies on the reactivity of organometallic Ru-, Rh- and Os-pta complexes with DNA model compounds.

    PubMed

    Dorcier, Antoine; Hartinger, Christian G; Scopelliti, Rosario; Fish, Richard H; Keppler, Bernhard K; Dyson, Paul J

    2008-01-01

    The reactions of arene-metal complexes (arene=p-cymene, benzene or pentamethylcyclopentadienyl, metal=Ru, Rh or Os), including 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decanephosphine (pta) and chloro co-ligands, with 9-methylguanine, adenine, and a series of nucleosides were studied in water to ascertain the binding modes. The products were characterized by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Tandem mass spectrometry was found to provide excellent information on preferential binding sites. In general, the N7 position on guanine (the most basic site) was found to be the preferred donor atom for coordination to the metal complexes. The X-ray structures of the precursor complexes, [(eta5-C10H15)RhCl(pta-Me)2]Cl2, [(eta6-C10H14)OsCl(pta)2]Cl, and [(eta6-C6H6)OsCl2(CH3CN)], are also reported.

  19. Voltage control of magnetic anisotropy in epitaxial Ru/Co2FeAl/MgO heterostructures.

    PubMed

    Wen, Zhenchao; Sukegawa, Hiroaki; Seki, Takeshi; Kubota, Takahide; Takanashi, Koki; Mitani, Seiji

    2017-03-23

    Voltage control of magnetic anisotropy (VCMA) in magnetic heterostructures is a key technology for achieving energy-efficiency electronic devices with ultralow power consumption. Here, we report the first demonstration of the VCMA effect in novel epitaxial Ru/Co2FeAl(CFA)/MgO heterostructures with interfacial perpendicular magnetic anisotropy (PMA). Perpendicularly magnetized tunnel junctions with the structure of Ru/CFA/MgO were fabricated and exhibited an effective voltage control on switching fields for the CFA free layer. Large VCMA coefficients of 108 and 139 fJ/Vm for the CFA film were achieved at room temperature and 4 K, respectively. The interfacial stability in the heterostructure was confirmed by repeating measurements. Temperature dependences of both the interfacial PMA and the VCMA effect were also investigated. It is found that the temperature dependences follow power laws of the saturation magnetization with an exponent of ~2, where the latter is definitely weaker than that of conventional Ta/CoFeB/MgO. The significant VCMA effect observed in this work indicates that the Ru/CFA/MgO heterostructure could be one of the promising candidates for spintronic devices with voltage control.

  20. Voltage control of magnetic anisotropy in epitaxial Ru/Co2FeAl/MgO heterostructures

    NASA Astrophysics Data System (ADS)

    Wen, Zhenchao; Sukegawa, Hiroaki; Seki, Takeshi; Kubota, Takahide; Takanashi, Koki; Mitani, Seiji

    2017-03-01

    Voltage control of magnetic anisotropy (VCMA) in magnetic heterostructures is a key technology for achieving energy-efficiency electronic devices with ultralow power consumption. Here, we report the first demonstration of the VCMA effect in novel epitaxial Ru/Co2FeAl(CFA)/MgO heterostructures with interfacial perpendicular magnetic anisotropy (PMA). Perpendicularly magnetized tunnel junctions with the structure of Ru/CFA/MgO were fabricated and exhibited an effective voltage control on switching fields for the CFA free layer. Large VCMA coefficients of 108 and 139 fJ/Vm for the CFA film were achieved at room temperature and 4 K, respectively. The interfacial stability in the heterostructure was confirmed by repeating measurements. Temperature dependences of both the interfacial PMA and the VCMA effect were also investigated. It is found that the temperature dependences follow power laws of the saturation magnetization with an exponent of ~2, where the latter is definitely weaker than that of conventional Ta/CoFeB/MgO. The significant VCMA effect observed in this work indicates that the Ru/CFA/MgO heterostructure could be one of the promising candidates for spintronic devices with voltage control.

  1. Voltage control of magnetic anisotropy in epitaxial Ru/Co2FeAl/MgO heterostructures

    PubMed Central

    Wen, Zhenchao; Sukegawa, Hiroaki; Seki, Takeshi; Kubota, Takahide; Takanashi, Koki; Mitani, Seiji

    2017-01-01

    Voltage control of magnetic anisotropy (VCMA) in magnetic heterostructures is a key technology for achieving energy-efficiency electronic devices with ultralow power consumption. Here, we report the first demonstration of the VCMA effect in novel epitaxial Ru/Co2FeAl(CFA)/MgO heterostructures with interfacial perpendicular magnetic anisotropy (PMA). Perpendicularly magnetized tunnel junctions with the structure of Ru/CFA/MgO were fabricated and exhibited an effective voltage control on switching fields for the CFA free layer. Large VCMA coefficients of 108 and 139 fJ/Vm for the CFA film were achieved at room temperature and 4 K, respectively. The interfacial stability in the heterostructure was confirmed by repeating measurements. Temperature dependences of both the interfacial PMA and the VCMA effect were also investigated. It is found that the temperature dependences follow power laws of the saturation magnetization with an exponent of ~2, where the latter is definitely weaker than that of conventional Ta/CoFeB/MgO. The significant VCMA effect observed in this work indicates that the Ru/CFA/MgO heterostructure could be one of the promising candidates for spintronic devices with voltage control. PMID:28332569

  2. From antiferromagnetic to ferromagnetic interaction in cyanido-bridged Fe(III)-Ru(II)-Fe(III) complexes by change of the central diamagnetic cyanido-metal geometry.

    PubMed

    Ma, Xiao; Hu, Sheng-Min; Tan, Chun-Hong; Zhang, Yong-Fan; Zhang, Xu-Dong; Sheng, Tian-Lu; Wu, Xin-Tao

    2013-10-07

    Cis- and trans-isomeric heterotrinuclear-metallic complexes and their two-electron-oxidation products, cis-/trans-[Cp(dppe)Fe(μ-CN)Ru(bpy)2(μ-CN)Fe(dppe)Cp][PF6]2 (cis-/trans-1[PF6]2) and cis-/trans-[Cp(dppe)Fe(μ-CN)Ru(bpy)2(μ-CN)Fe(dppe)Cp][PF6]4 (cis-/trans-1[PF6]4), have been synthesized and structurally characterized. To the best of our knowledge, the complexes are the first example of a cis-/trans-isomer with multistates. Although separated by the diamagnetic cyanido-metal bridge, the two distant paramagnetic metal centers in both the oxidized complexes exhibit quite strong magnetic couplings. As a unique example, cis-1[PF6]4 is antiferromagnetic, and trans-1[PF6]4 is ferromagnetic. Density functional theory (DFT) calculations suggest that the spin-delocalization mechanism should be responsible for the magnetic interactions between the two distant paramagnetic Fe(III) centers across the diamagnetic cyanido-metal in both cis- and trans-1(4+). Most importantly, the DFT calculations revealed that the type (antiferromagnetic or ferromagnetic) and strength (J) of the magnetic interactions in such compounds can be controlled by the variation (cis or trans) of the diamagnetic central metal configurations.

  3. Robust paramagnetism in Bi2- xMxRu2O7 (M=Mn,Fe,Co,Ni,Cu) pyrochlore

    NASA Astrophysics Data System (ADS)

    Haas, M. K.; Cava, R. J.; Avdeev, M.; Jorgensen, J. D.

    2002-09-01

    We report magnetic susceptibility, resistivity, and Seebeck coefficients for Bi2-xMxRu2O7 pyrochlore. The solid solution exists up to x=0.5 for M=Cu,Ni,Co and up to x=0.1 for M=Fe,Mn. The doped materials do not exhibit ferromagnetism or any localized ruthenium moment behavior. Instead we find the Ru-O and Bi-O sublattices to be essentially independent, with any magnetism resulting from the unpaired first-row transition metal dopant spins. Cobalt substitution for bismuth results in localized Co2+ and low-temperature spin-glass transitions in several cases. Nickel moments on the pyrochlore lattice display properties intermediate to localized and itinerant. Finally, copper doping results in an enhancement of the Pauli metallic density of states.

  4. Composition dependence of the electronic properties of Al-Cu-Fe and Al-Cu-Ru-Si semimetallic quasicrystals

    NASA Astrophysics Data System (ADS)

    Pierce, F. S.; Bancel, P. A.; Biggs, B. D.; Guo, Q.; Poon, S. J.

    1993-03-01

    Electronic transport properties and specific heats of ordered icosahedral phase alloys in the Al-Cu-Ru-Si and Al-Cu-Fe systems are examined, and comparison with high-quality rhombohedral (3/2) approximant phase samples of Al-Cu-Fe is made. Strong temperature dependence and sensitivity to composition changes of these properties are observed. The similarity of transport properties between the icosahedral (i) and rhombohedral (r) phases of Al62.5Cu26.5Fe11 is noted. The results can be qualitatively interpreted in terms of band structure. There appears to be sufficient evidence for a rapidly varying conductivity spectrum σ(E) in the ordered i phases. However, important questions concerning the physics of these semimetallic quasicrystals remain to be answered.

  5. Effects of isoelectronic Ru substitution at the Fe site on the energy gaps of optimally F-doped SmFeAsO

    NASA Astrophysics Data System (ADS)

    Daghero, D.; Tortello, M.; Ummarino, G. A.; Stepanov, V. A.; Bernardini, F.; Tropeano, M.; Putti, M.; Gonnelli, R. S.

    2012-08-01

    We studied the effects of isoelectronic Ru substitution at the Fe site on the energy gaps of optimally F-doped SmFeAsO by means of point-contact Andreev-reflection spectroscopy. The results show that the SmFe1-xRuxAsO0.85F0.15 system keeps a multigap character at least up to x = 0.50, and that the gap amplitudes Δ1 and Δ2 scale almost linearly with the local critical temperature {T}_{{c}}^{A}. The gap ratios 2Δi/kBTc remain approximately constant only as long as Tc ≥ 30 K, and increase dramatically when Tc decreases further. This trend seems to be common to many Fe-based superconductors, irrespective of their family. Based on first-principle calculations of the bandstructure and of the density of states projected on the different bands, we show that this trend, as well as the Tc dependence of the gaps and the reduction of Tc upon Ru doping, can be explained within an effective three-band Eliashberg model as being due to a suppression of the superfluid density at finite temperature that, in turn, modifies the temperature dependence of the characteristic spin-fluctuation energy.

  6. Magnetic and electric properties of Ru-substituted CoFe2O4 thin films fabricated by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Iwamoto, Fujiyuki; Seki, Munetoshi; Tabata, Hitoshi

    2012-11-01

    Epitaxial thin films of Ru-substituted CoFe2O4 with a cubic spinel structure were fabricated on α-Al2O3 (001) substrates using pulsed laser deposition, and their magnetic and electric properties were investigated. The films showed room temperature ferrimagnetic behavior with hard magnetic features similar to those of non-Ru-substituted cobalt ferrite films. The electrical conductivity of the films was dramatically enhanced by the substitution of Ru. The anomalous Hall effect was observed in all films even at 300 K suggesting that carriers in the films are highly spin-polarized at room temperature as expected from a first-principles calculation.

  7. Exotic magnetism on the quasi-FCC lattices of the d3 double perovskites La2NaB'O6 (B' = Ru, Os)

    SciTech Connect

    Aczel, Adam A; Baker, Peter J.; Bugaris, Dan; Yeon, Jeongho; Zur Loye, Hans-Conrad; Guidi, T.; Adroja, D. T.

    2014-01-01

    We find evidence for long-range and short-range ($\\zeta$~$=$~70~\\AA~at 4~K) incommensurate magnetic order on the quasi-face-centered-cubic (FCC) lattices of the monoclinic double perovskites La$_2$NaRuO$_6$ and La$_2$NaOsO$_6$ respectively. Incommensurate magnetic order on the FCC lattice has not been predicted by mean field theory, but may arise via a delicate balance of inequivalent nearest neighbour and next nearest neighbour exchange interactions. In the Ru system with long-range order, inelastic neutron scattering also reveals a spin gap $\\Delta$~$\\sim$~2.75~meV. Magnetic anisotropy is generally minimized in the more familiar octahedrally-coordinated $3d^3$ systems, so the large gap observed for La$_2$NaRuO$_6$ may result from the significantly enhanced value of spin-orbit coupling in this $4d^3$ material.

  8. Exotic magnetism on the quasi-fcc lattices of the d3 double Perovskites La2NaB'O6 (B'=Ru, Os).

    PubMed

    Aczel, A A; Baker, P J; Bugaris, D E; Yeon, J; Zur Loye, H-C; Guidi, T; Adroja, D T

    2014-03-21

    We find evidence for long-range and short-range (ζ=70 Å at 4 K) incommensurate magnetic order on the quasi-face-centered-cubic (fcc) lattices of the monoclinic double perovskites La2NaRuO6 and La2NaOsO6, respectively. Incommensurate magnetic order on the fcc lattice has not been predicted by mean field theory, but may arise via a delicate balance of inequivalent nearest neighbor and next nearest neighbor exchange interactions. In the Ru system with long-range order, inelastic neutron scattering also reveals a spin gap Δ ∼ 2.75 meV. Magnetic anisotropy is generally minimized in the more familiar octahedrally coordinated 3d3 systems, so the large gap observed for La2NaRuO6 may result from the significantly enhanced value of spin-orbit coupling in this 4d(3) material.

  9. The Disposition of Pt, Pd, Ir, Os, and Ru in Marine Sediments and the K/T Boundary

    NASA Technical Reports Server (NTRS)

    Lee, Cin-Ty; Wasserburg, Gerald; Kyte, Frank

    2003-01-01

    The marine record of platinum group elements (PGEs) and Os isotopic compositions provides information on different inputs of PGEs into the oceans. Some studies based on a smaller subset of the PGEs suggest that the PGEs may suffer post-depositional mobility during diagenesis. In some K/T boundary clays, Kyte and others showed that the relative abundances of Pt, Pd, Ir, and Os can differ significantly from chondritic, which is the signature expected from fallout of the meteorite impact. In some K/T boundary sections, elevated Ir concentrations are observed as far as 1 meter from the cm-thick boundary clay containing the meteoritic ejecta. The purpose of this study was to characterize Pt, Pd, Ir, Os, and Ru abundances in zones including the K/T boundary. We determined PGE abundances of boundary clays at two hemipelagic sites (Stevns Klint, Denmark and Caravaca, Spain) in which previous studies by Kyte and others showed that the Ir anomaly is confined to within a few cm. We also analyzed two pelagic Pacific sites: a boundary clay from the north Pacific (Hole 465A) characterized by a 0.5 m thick Ir anomaly and a transect across the K/T boundary from the south Pacific (Hole 596) where the Ir anomaly spans 2 m. The Stevns Klint, Caravaca, and north Pacific sites are characterized by abundant marls and limestones in the section, whereas the south Pacific site is dominated by clays. Samples were spiked with isotopic tracers, mixed with a flux, S and Ni, and equilibrated by fusion. PGEs were extracted from the Ni and analyzed on a Finnigan Element ICP-MS. We find that the narrow Caravaca and Stevns Klint boundary clays have relative PGE abundance patterns indistinguishable from chondritic values. The two Pacific sites were found to have nearly identical PGE patterns but have ratios at the peak, which differ from chondritic values as found earlier by Evans et al. The Pacific sites were found to have nearly identical PGE patterns but are extremely depleted in OS (Os/Ir = 0

  10. Current-Induced Magnetization Switching in MgO Barrier Based Magnetic Tunnel Junctions with CoFeB/Ru/CoFeB Synthetic Ferrimagnetic Free Layer

    NASA Astrophysics Data System (ADS)

    Hayakawa, Jun; Ikeda, Shoji; Lee, Young Min; Sasaki, Ryutaro; Meguro, Toshiyasu; Matsukura, Fumihiro; Takahashi, Hiromasa; Ohno, Hideo

    2006-10-01

    We report the intrinsic critical current density (Jc0) in current-induced magnetization switching and the thermal stability factor (E/kBT, where E, kB, and T are the energy potential, the Boltzmann constant, and temperature, respectively) in MgO based magnetic tunnel junctions with a Co40Fe40B20(2 nm)/Ru(0.7-2.4 nm)/Co40Fe40B20(2 nm) synthetic ferrimagnetic (SyF) free layer. We show that Jc0 and E/kBT can be determined by analyzing the average critical current density as a function of coercivity using the Slonczewski’s model taking into account thermal fluctuation. We find that high antiferromagnetic coupling between the two CoFeB layers in a SyF free layer results in reduced Jc0 without reducing high E/kBT.

  11. First-Principles Study of Effects of Boron on Magnetic Anisotropy in MgO/CoFe(B)/X (X = Ru, Ta) Systems

    NASA Astrophysics Data System (ADS)

    Suzuki, Shugo; Shiota, Masashi; Fukuchi, Yasushi

    2016-09-01

    We study the effects of boron on the magnetic anisotropy in the MgO/CoFe(B)/X (X = Ru, Ta) systems using relativistic first-principles calculations. It is found that the B atoms tend to be rejected from the CoFeB layer into the X underlayer. The system with no B atoms shows perpendicular magnetic anisotropy when the Fe atoms are adjacent to the MgO layer.

  12. New ternary tantalum borides containing boron dumbbells: Experimental and theoretical studies of Ta2OsB2 and TaRuB

    NASA Astrophysics Data System (ADS)

    Mbarki, Mohammed; Touzani, Rachid St.; Rehorn, Christian W. G.; Gladisch, Fabian C.; Fokwa, Boniface P. T.

    2016-10-01

    The new ternary transition metal-rich borides Ta2OsB2 and TaRuB have been successfully synthesized by arc-melting the elements in a water-cooled crucible under an argon atmosphere. The crystal structures of both compounds were solved by single-crystal X-ray diffraction and their metal compositions were confirmed by EDX analysis. It was found that Ta2OsB2 and TaRuB crystallize in the tetragonal Nb2OsB2 (space group P4/mnc, no. 128) and the orthorhombic NbRuB (space group Pmma, no. 51) structure types with lattice parameters a=5.878(2) Å, c=6.857(2) Å and a=10.806(2) Å, b=3.196(1) Å, c=6.312(2) Å, respectively. Furthermore, crystallographic, electronic and bonding characteristics have been studied by density functional theory (DFT). Electronic structure relaxation has confirmed the crystallographic parameters while COHP bonding analysis indicates that B2-dummbells are the strongest bonds in both compounds. Moreover, the formation of osmium dumbbells in Ta2OsB2 through a Peierls distortion along the c-axis, is found to be the origin of superstructure formation. Magnetic susceptibility measurements reveal that the two phases are Pauli paramagnets, thus confirming the theoretical DOS prediction of metallic character. Also hints of superconductivity are found in the two phases, however lack of single phase samples has prevented confirmation. Furthermore, the thermodynamic stability of the two modifications of AMB (A=Nb, Ta; M =Ru, Os) are studied using DFT, as new possible phases containing either B4- or B2-units are predicted, the former being the most thermodynamically stable modification.

  13. Ru, Os, Rh mixed-metal complexes are a potential novel class of oxygen independent photosensitizers for photodynamic therapy (PDT)

    NASA Astrophysics Data System (ADS)

    Storrie, Brian; Holder, Alvin; Brewer, Karen J.

    2006-02-01

    Mixed-metal supramolecular complexes coupling Ru and Os light absorber units to a central, reactive Rh site have been designed of the type [{(bpy)2M(dpp)}2RhCl2]5+. These complexes possess intense metal-to-ligand charge transfer transitions when excited at 500-700 nm making them good light absorbers. The presence of the Rh site introduces low lying metal-to-metal charge transfer states that are capable of visible light induced photocleavage of DNA via an oxygen independent pathway.1 We report here a study of the photodynamic action of supramolecular mixed-metal complexes showing that these systems inhibit cell replication after exposure to light while displaying no impact on cell replication in the dark. This photodynamic action has been studied using cultured Vero cells with a pre-incubation with the complexes, rinsing to remove complex from the media, followed by photo-activation and cell growth assay. The photodynamic action of this new series of complexes can be tuned as a function of components of the supramolecular assembly and complexes capable of coupling to targeting proteins and fluorescent reporter groups have been synthesized.

  14. Probing the links between structure and magnetism in Sr(2-x)Ca(x)FeOsO₆ double perovskites.

    PubMed

    Morrow, Ryan; Freeland, John W; Woodward, Patrick M

    2014-08-04

    The synthesis, structure, and properties of the ordered double perovskites Sr2FeOsO6, Ca2FeOsO6, and SrCaFeOsO6 are reported. The latter two compounds have monoclinic P2₁/n symmetry and a(-)a(-)b(+) tilting of the octahedra, while Sr2FeOsO6 is tetragonal with I4/m symmetry and a(0)a(0)c(-) tilting. Magnetic measurements indicate and neutron powder diffraction studies confirm that Ca2FeOsO6 is a ferrimagnet with a Curie temperature of 350 K. The ferrimagnetism is retained if half of the Ca(2+) ions are replaced with larger Sr(2+) ions to form SrCaFeOsO6 (T(C) = 210 K). This substitution reduces the degree of octahedral tilting, but unlike most perovskites, the magnetic ordering temperature decreases as the Fe-O-Os bond angles approach a linear geometry. In contrast, Sr2FeOsO6 orders antiferromagnetically, as previously reported. X-ray absorption spectroscopy confirms the assignment of Fe(III) and Os(V) oxidation states for all three compounds. In these insulating double perovskites, the magnetic ground state is governed by a competition between the four-bond Fe-O-Os-O-Fe antiferromagnetic superexchange coupling of Fe(III) ions and the two-bond Fe-O-Os antiferromagnetic superexchange coupling between neighboring Fe(III) and Os(V) ions. When the Fe-O-Os bonds are linear, as they are in the c direction in Sr2FeOsO6, the four-bond coupling between Fe(III) ions prevails. The competition shifts in favor of antiferromagnetic coupling of Fe(III) and Os(V) as the Fe-O-Os bond angles bend in response to chemical pressure.

  15. Frustration by competing interactions in the highly-distorted double perovskites La2NaB'O6 (B' = Ru, Os)

    SciTech Connect

    Aczel, Adam A; Bugaris, Dan; Li, Ling; Yan, Jiaqiang; Dela Cruz, Clarina R; Zur Loye, Hans-Conrad; Nagler, Stephen E

    2013-01-01

    The usual classical behaviour of S = 3/2, B-site ordered double perovskites generally results in simple, commensurate magnetic ground states. In contrast, heat capacity and neutron powder diffraction measurements for the S = 3/2 systems La2NaB'O6 (B = Ru, Os) reveal an incommensurate magnetic ground state for La2NaRuO6 and a drastically suppressed ordered moment for La2NaOsO6. This behaviour is attributed to the large monoclinic structural distortions of these double perovskites. The distortions have the effect of weakening the nearest neighbour superexchange interactions, presumably to an energy scale that is comparable to the next nearest neighbour superexchange. The exotic ground states in these materials can then arise from a competition between these two types of antiferromagnetic interactions, providing a novel mechanism for achieving frustration in the double perovskite family.

  16. Ferrimagnetism in the double perovskite Ca2FeOsO6: A density functional study

    NASA Astrophysics Data System (ADS)

    Wang, Hongbo; Zhu, Shasha; Ou, Xuedong; Wu, Hua

    2014-08-01

    Using density functional calculations, we find that the newly synthesized Ca2FeOsO6 has the high-spin Fe3+ (3d5)-Os5+ (5d3) state. The octahedral Os5+ ion has a large intrinsic exchange splitting, and its t2g↑3 configuration makes the spin-orbit coupling ineffective. Moreover, there is a strong antiferromagnetic (AF) coupling between the neighboring Fe3+ (S=5/2) and Os5+ (S=-3/2), but the AF couplings within both the fcc Fe3+ and Os5+ sublattices are one order of magnitude weaker. Therefore a magnetic frustration is suppressed and a stable ferrimagnetic ground state appears. This ferrimagnetic order is due to the virtual hopping of the t2g electrons from Os5+ (t2g↓3) to Fe3+ (t2g↑3eg↑2). However, if the experimental bended Fe3+-O2--Os5+ exchange path gets straight, the eg hopping from Fe3+ (t2g↑3eg↑2) to Os5+ (t2g↑3) would be facilitated and then a ferromagnetic (FM) coupling would occur.

  17. Rigid rod-like dinuclear Ru(II)/Os(II) terpyridine-type complexes. Electrochemical behavior, absorption spectra, luminescence properties, and electronic energy transfer through phenylene bridges

    SciTech Connect

    Barigelletti, F.; Flamigni, L.; Balzani, V. ||

    1994-08-24

    The absorption spectra, the luminescence properties (at 293 and 77 K), and the electrochemical behavior of six dinuclear heterometallic compounds have been investigated. The compounds are made of Ru(tpy){sub 2}{sup 2+}- and Os(tpy){sub 2}{sup 2+}-type components (tpy = 2,2{prime}:6{prime},2 inches-terpyridine, which in some cases carries p-tolyl (Meph) or methylsulphone (MeO{sub 2}S) substituents in the 4{prime} position), connected by n phenylene (ph) spacers (n=0,1, and 2). In the resulting rigid rod-like structures of general formula (X{sub 1}tpy)Ru(tpy(ph){sub n}tpy)Os(tpyX{sub 2}){sup 4+} the metal-to-metal distance varies form 11 to 20 {Angstrom}. The absorption spectra of the two components are slightly perturbed in the dinuclear compounds, and metal-metal and ligand-ligand interactions are evidenced by the trends of the oxidation and reduction potentials. The luminescence of the Ru-based unit is quenched by the connected Os-based unit with practically unitary efficiency, regardless of the number of interposed phenylene spacers. Quenching is accompanied by quantitative sensitization of the Os-based luminescence. The rate of energy transfer at 293 K is larger than 10{sup 10} s{sup -1} in all cases. The Foerster (Coulombic) mechanism does not satisfactorily account for such a fast rate, particularly for the species with n=2. It is concluded that the observed energy-transfer processes take place most likely via a Dexter (electron exchange) mechanism. This is consistent with the strong electronic coupling of the Ru-based units in the compound with n=0, and with the relatively small insulating effect expected for the phenylene spacers. 37 refs., 7 figs., 3 tabs.

  18. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    DOE PAGES

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; ...

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication ofmore » crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.« less

  19. Substitution effects on superconducting and normal state properties in (Mo1-xTx)3Sb7, where T = Ru and Fe

    NASA Astrophysics Data System (ADS)

    Tran, V. H.

    2016-12-01

    The effects of Ru- and Fe-doping on the physical properties of Mo3Sb7 were studied by measuring ac-susceptibility, dc-magnetization, electrical resistivity and specific heat. It is found that single-phased (Mo{}1-xRu x )3Sb7 and (Mo{}1-xFe x )3Sb7 samples are obtained for the concentrations x ≤slant 0.1. In this concentration range, the lattice parameter shrinks with increasing dopant content. The substitution effects on the superconducting and normal state properties are completely different between two investigated systems. In the Ru-based solid solution alloys, the substitution enhances the superconducting parameters T c and H c2 and also benefits the spin-gap opening at {T}* ˜ 50 K. In contrast, in the Fe-substituted samples, there is a depression of both T c and H c2, accompanied by vanishing spin-gap and low-dimensional magnetic correlation. The substitution of the Mo atoms by Ru and Fe atoms suppresses the cubic-tetragonal distortion, but presumably favours the magnetic field to induce a magnetic order below T *.

  20. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    SciTech Connect

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; Liu, Haiqing; Wong, Stanislaus S.

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication of crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.

  1. Limits on superconductivity-related magnetization in Sr 2RuO 4 and PrOs 4Sb 12 from scanning SQUID microscopy

    SciTech Connect

    Moler, Kathryn

    2010-08-26

    We present scanning SQUID microscopy data on the superconductors Sr{sub 2}RuO{sub 4} (T{sub c} = 1.5 K) and PrOs{sub 4}Sb{sub 12} (T{sub c} = 1.8 K). In both of these materials, superconductivity-related time-reversal symmetry-breaking fields have been observed by muon spin rotation; our aim was to visualize the structure of these fields. However in neither Sr{sub 2}RuO{sub 4} nor PrOs{sub 4}Sb{sub 12} do we observe spontaneous superconductivity-related magnetization. In Sr{sub 2}RuO{sub 4}, many experimental results have been interpreted on the basis of a p{sub x} {+-} ip{sub y} superconducting order parameter. This order parameter is expected to give spontaneous magnetic induction at sample edges and order parameter domain walls. Supposing large domains, our data restrict domain wall and edge fields to no more than {approx}0.1% and {approx}0.2% of the expected magnitude, respectively. Alternatively, if the magnetization is of the expected order, the typical domain size is limited to {approx}30 nm for random domains, or {approx} 500 nm for periodic domains.

  2. Ionization and photofragmentation of Ru{sub 3}(CO){sub 12} and Os{sub 3}(CO){sub 12}

    SciTech Connect

    Schalk, Oliver E-mail: melanie.mucke@physics.uu.se; Josefsson, Ida; Odelius, Michael; Richter, Robert; Prince, Kevin C.; Mucke, Melanie E-mail: melanie.mucke@physics.uu.se

    2015-10-21

    In this paper, we use a combination of photoelectron spectroscopy, mass spectrometry, and density functional theory calculations to get a detailed understanding of valence single and double ionization and the subsequent dissociation processes. This is exemplified on benchmark systems, trimetallo-dodecacarbonyls M{sub 3}(CO){sub 12} with M = Ru, Os, where the energy remaining in the molecule after photoionization can be retrieved by measuring the degree of fragmentation of the molecular ion. The intensity of different mass peaks can thus be directly related to ionization cross sections obtained by photoelectron spectroscopy. We find that the M—CO dissociation energy rises as the number of CO ligands decreases due to dissociation. Moreover, ionization of the CO ligands has a higher cross section than that of the metal center for both single and double ionization. After advanced fragmentation, a CO bond can break and the carbon atom remains bonded to the metal core. In addition, we found that the valence ionization cross sections of M{sub 3}(CO){sub 12} are maximal at about 40 eV photon energy thus showing a more pronounced shape resonance than Ru and Os-complexes with a single metal atom center. Finally, an np → nd giant resonance absorption causes a significant increase of the ionization cross section above 50 eV for Ru{sub 3}(CO){sub 12}.

  3. Simplified method for the determination of Ru, Pd, Re, Os, Ir and Pt in chromitites and other geological materials by isotope dilution ICP-MS and acid digestion.

    PubMed

    Meisel, T; Moser, J; Fellner, N; Wegscheider, W; Schoenberg, R

    2001-03-01

    A method for the determination of low Ru, Pd, Re, Os, Ir and Pt abundances in geological reference materials by isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion in a high pressure asher (HPA-S) is presented. The digestion technique is similar to that using Carius tubes but easier to handle and reaches higher temperatures. Osmium can be determined as OsO4 with ICP-MS directly after digestion through a sparging technique. The remaining elements are preconcentrated by means of anion column chromatography. The resin is digested directly without elution leading to high yields but this causes problems if Zr is present at higher levels in the silicate rich materials. The analytical results for international platinum group element (PGE) reference materials, chromitite CHR-Bkg, basalt TDB-1 and gabbro WGB-1, are presented and compared with literature data, demonstrating the validity of the described method. Although higher in concentration, PGEs determined for reference material WGB-1 were worse than for TDB-1 indicating a more inhomogeneous distribution of the platinum group mineral phases. The low PGE abundance chromitite standard, CHR-Bkg, is likely to be homogeneous for Ru, Re, Os and Ir and is recommended as a reference material for the study of chromitites. Detection limits (3s x total procedure blank) range from 0.012 ng (Re and Os) to 0.77 ng (Pt), which could be further improved by applying higher quality acids.

  4. Effect of poling process on resistive switching in Au/BiFeO3/SrRuO3 structures

    NASA Astrophysics Data System (ADS)

    Zhu, Hui; Zhang, Yingqiao; Jiang, Anquan; Bai, Zilong; Feng, Shiwei; Wang, Pengfei; Meng, Xiao; Qi, Qiong

    2016-12-01

    We studied the resistive switching of Au/BiFeO3/SrRuO3 structures. Their current-voltage characteristics complied with space-charge-limited (SCL) conduction. A full cycle of the poling process enlarged the I-V hysteresis and increased the transition voltage from Ohmic to SCL for an I-V sweeping bias less than the coercive voltage. A cycle of poling could increase the resistance switching ratio under low bias by 20 times over that of a virgin sample without poling. Measurements of thermally stimulated current showed a difference between the sample in the pristine state and that under the polarization state, indicating a relationship between the trap filling status and the resistive switching behavior.

  5. Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films.

    PubMed

    Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

    2017-12-01

    Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu1 - x Fe x O3 - δ epitaxial thin films (x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu1 - x Fe x O3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR (~36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies (δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr1 - x La x )(Ru1 - x Fe x )O3. These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu1 - x Fe x O3 - δ thin films.

  6. First-principles study on the structure, elastic properties, hardness and electronic structure of TMB{sub 4} (TM=Cr, Re, Ru and Os) compounds

    SciTech Connect

    Pan, Y.; Zheng, W.T.; Guan, W.M.; Zhang, K.H.; Fan, X.F.

    2013-11-15

    The structural formation, elastic properties, hardness and electronic structure of TMB{sub 4} (TM=Cr, Re, Ru and Os) compounds are investigated using first-principles approach. The value of C{sub 22} for these compounds is almost two times bigger than the C{sub 11} and C{sub 33}. The intrinsic hardness, shear modulus and Young's modulus are calculated to be in a sequence of CrB{sub 4}>ReB{sub 4}>RuB{sub 4}>OsB{sub 4}, and the Poisson's ratio and B/G ratio of TMB{sub 4} follow the order of CrB{sub 4}RuB{sub 4}<OsB{sub 4}. The intrinsic hardness of CrB{sub 4} and ReB{sub 4} by LDA is bigger than 40 GPa. The high hardness of TMB{sub 4} compounds is derived from the feature of B–B bonds cage and higher C{sub 22} value. The B–B covalent bonds as bonds cage enhances the resistance to shear deformation and improve the hardness. We predict that the TMB{sub 4} compounds with CrB{sub 4}-type are the potential superhard materials. - Graphical abstract: The first-principles calculations show that the intrinsic hardness of CrB{sub 4} and ReB{sub 4} are bigger than 40 GPa, which are the potential superhard materials due to the B–B bonds cage structure. Display Omitted - Highlights: • The intrinsic hardness of CrB{sub 4} and ReB{sub 4} is bigger than 40 GPa. • The hardness of TMB{sub 4} is calculated to be in a sequence of CrB{sub 4}>ReB{sub 4}>RuB{sub 4}>OsB{sub 4}. • The trend of hardness for TMB{sub 4} is consistent with the variation of elastic modulus. • The C{sub 22} value of TMB{sub 4} is bigger than that of C{sub 11} and C{sub 33}. • The high hardness of TMB{sub 4} is originated from the B–B bonds cage.

  7. Noncollinear ferromagnetic easy axes in Py/Ru/FeCo/IrMn spin valves induced by oblique deposition

    SciTech Connect

    Bueno, T. E. P.; Parreiras, D. E.; Gomes, G. F. M.; Krambrock, K.; Paniago, R.; Michea, S.; Rodríguez-Suárez, R. L.; Filho, M. S. Araújo; Macedo, W. A. A.

    2014-06-16

    We present an investigation on the magnetic properties of Py/Ru/FeCo/IrMn spin valves grown by dc magnetron sputtering. The sample fabrication setup has two important features, (i) the five magnetron sputtering sources are placed in a cluster flange 72° from each other, and (ii) each source is tilted with respect to the sample normal. In-plane angular dependence of the ferromagnetic resonance (FMR) was used to obtain the relevant magnetic anisotropies, such as uniaxial and exchange bias fields. The oblique deposition geometry employed has induced non-collinear easy axes of the two ferromagnetic (FM) layers, with high uniaxial field strengths. The symmetry shift of the angular dependence of the FMR resonances of the two FM layers gives us directly the angle between the easy axes of FM{sub 1} (Py) and FM{sub 2} (FeCo), which turned out to be the angle between two adjacent sputtering sources. The observations of the present study suggest that, by combining oblique deposition and appropriate angles of incidence of the deposition flux, the uniaxial (and unidirectional) axes of individual FM layers can be precisely engineered in spin valve fabrication.

  8. Observation of spin-wave Doppler shift in Co90Fe10/Ru micro-strips for evaluating spin polarization

    NASA Astrophysics Data System (ADS)

    Sugimoto, Satoshi; Rosamond, Mark C.; Linfield, Edmund H.; Marrows, Christopher H.

    2016-09-01

    The current-induced spin-wave Doppler shift has been investigated for Co90Fe10 films, with and without under- and overlayers of Ru, aiming to obtain quantitative insights into the value of spin polarization of the diffusive electrical currents flowing in this material. This extends the use of spin-wave Doppler shift spectroscopy beyond the study of permalloy to other soft magnetic materials suitable for use in spintronic applications such as racetrack memories. The Damon-Eshbach spin-wave mode was employed, and a control experiment of permalloy yielded a value of spin polarization of P = 0.44 ± 0.03 for that material. An extended method to properly evaluate spin-wave Doppler shifts is developed that takes account of the non-negligible Oersted fields that are generated by the current density asymmetry caused by conducting under- or overlayers. The values of spin polarization for various Co90Fe10-based structures are found to lie in the range of 0.3-0.35, only slightly less than in permalloy.

  9. Chemical Tuning of Magnetic Properties through Ru/Rh Substitution in Th7Fe3-type FeRh6-nRunB3 (n = 1-5) Series.

    PubMed

    Shankhari, Pritam; Misse, Patrick R N; Mbarki, Mohammed; Park, Hyounmyung; Fokwa, Boniface P T

    2017-01-03

    The new quaternary boride series FeRh6-nRunB3 (n = 1-5) was synthesized by arc melting and characterized by powder and single-crystal X-ray diffraction (XRD), energy-dispersive X-ray analysis, and superconducting quantum interference device magnetometry. Single-crystal structure refinement showed the distribution of the iron atoms in two of three possible crystallographic 4d metal sites in the structure (Th7Fe3-type, space group P63mc). Rietveld refinements of the powder XRD data indicated single-phase synthesis of all the members. A linear decrease of the lattice parameters and the unit cell volume with increasing Ru content was found, indicating Vegard's behavior. Susceptibility measurements show decreasing Curie temperature and magnetic moment (μa(5T)) recorded at 5 T with increasing Ru content from TC = 295 K and μa(5T) = 3.35 μB (FeRh5RuB3) to TC = 205 K and μa(5T) = 0.70 μB (FeRhRu5B3). The measured coercivities lie between 1.0 and 2.2 kA/m indicating soft to semihard magnetic materials.

  10. Synthesis of, characterization of, and photoinduced processes in polymetallic triad complexes containing Fe(II), Ru(II), and Rh(III) metal centers

    SciTech Connect

    Ronco, S.E. |; Thompson, D.W.; Gahan, S.L.; Petersen, J.D. |

    1998-04-20

    A series of new trimetallic mixed complexes containing Fe(II), Ru(II), and Rh(III) metal centers have been prepared and characterized, and their excited-state properties in a nanosecond time domain have been investigated. These new compounds were synthesized by following a building block strategy from monomeric Rh(III) and Ru(II) polyazines and tetracyanoferrate(II) ions. The products generated in each synthetic step were fully characterized and their excited-state properties investigated. These new trimetallic complexes, [(CN){sub 4}Fe{sup II}(BL(1))Ru{sup II}(bpy)-(BL(2))Rh{sup III}(tpy)(MQ{sup +})](PF{sub 6}){sub 4} (tpy = 2,2{prime}:6{prime}:2{double_prime}-terpyridine; BL(1) = 2,3-bis(2-pyridyl)pyrazine (dpp) or 2,2{prime}-bipyrimidine (bpm); BL(2) = dpp or bpm; MQ{sup +} = N-methyl-4,4{prime}-bipyridinium (monoquat)), consist of three fundamental parts linked by bridging ligands (1) an electron donor group, the tetracyanoferrate(II) unit; (2) an antenna fragment, the Ru(II) polypyridyl moiety; and (3) an electron acceptor group. The electron acceptor group is a Rh(III) polypyridyl that contains the ligands tpy and MQ{sup +}. No emission was observed in any of the reported complexes either in fluid solutions at room temperature or in glassy solutions at 77 K. Time-resolved experiments conducted on these triads showed formation of a transient intermediate within the laser pulse. Redox properties and transient absorption observations helped the authors to identify the nature of this intermediate as an Fe(III)/Ru(II) mixed-valence species that decays exponentially by following a first-order law with a lifetime of {tau} {le} 70 ns in fluid solution at room temperature.

  11. Synthesis, crystal structure, and electronic properties of high-pressure PdF2-type oxides MO2 (M = Ru, Rh, Os, Ir, Pt).

    PubMed

    Shirako, Yuichi; Wang, Xia; Tsujimoto, Yoshihiro; Tanaka, Kie; Guo, Yanfeng; Matsushita, Yoshitaka; Nemoto, Yoshihiro; Katsuya, Yoshio; Shi, Youguo; Mori, Daisuke; Kojitani, Hiroshi; Yamaura, Kazunari; Inaguma, Yoshiyuki; Akaogi, Masaki

    2014-11-03

    The polycrystalline MO2's (HP-PdF2-type MO2, M = Rh, Os, Pt) with high-pressure PdF2 compounds were successfully synthesized under high-pressure conditions for the first time, to the best of our knowledge. The crystal structures and electromagnetic properties were studied. Previously unreported electronic properties of the polycrystalline HP-PdF2-type RuO2 and IrO2 were also studied. The refined structures clearly indicated that all compounds crystallized into the HP-PdF2-type structure, M(4+)O(2-)2, rather than the pyrite-type structure, M(n+)(O2)(n-) (n < 4). The MO2 compounds (M = Ru, Rh, Os, Ir) exhibited metallic conduction, while PtO2 was highly insulating, probably because of the fully occupied t2g band. Neither superconductivity nor a magnetic transition was detected down to a temperature of 2 K, unlike the case of 3d transition metal chalcogenide pyrites.

  12. Investigation of magnetic order in SmTr2Zn20 (Tr = Fe, Co, Ru) and SmTr2Cd20 (Tr = Ni, Pd)

    NASA Astrophysics Data System (ADS)

    Yazici, Duygu; White, B. D.; Ho, P.-C.; Kanchanavatee, N.; Huang, K.; Dilley, N. R.; Maple, M. B.

    2015-03-01

    Single crystals of the cage compounds Sm Tr 2Zn20 (Tr = Fe, Co, Ru) and Sm Tr 2Cd20 (Tr = Ni, Pd) have been investigated by means of electrical resistivity, magnetization, and specific heat measurements. The compounds SmFe2Zn20, SmRu2Zn20,andSmNi2Cd20 exhibit ferromagnetic order with Curie temperatures of TC = 47.4 K, 7.6 K, and 7.5 K, respectively, whereas SmPd2Cd20 is an antiferromagnet with a Néel temperature of TN = 3.4 K. No evidence for magnetic order is observed in SmCo2Zn20 down to 110 mK. The Sommerfeld coefficients γ are found to be 57 mJ/mol-K2 for SmFe2Zn20, 79.5 mJ/mol-K2 for SmCo2Zn20, 258 mJ/mol-K2 for SmRu2Zn20, 165 mJ/mol-K2 for SmNi2Cd20, and 208 mJ/mol-K2 for SmPd2Cd20. Enhanced values of Sommerfeld coefficients γ and a quadratic temperature dependence of the electrical resistivity at low temperature for SmRu2Zn20andSmPd2Cd20 suggest an enhancement of the quasiparticle masses due to hybridization between localized 4 f and conduction electron states. Research at UCSD was supported by the U.S. DOE under Grant No. DE-FG02-04-ER46105 and the U.S. NSF under Award Grant No. DMR 1206553. Research at California State University, Fresno was supported by the U.S. NSF under Grant No. DMR 1104544.

  13. Direct observation of an anisotropic in-plane residual stress induced by B addition as an origin of high magnetic anisotropy field of Ru/FeCoB film

    SciTech Connect

    Hirata, Ken-ichiro; Gomi, Shunsuke; Mashiko, Yasuhiro; Nakagawa, Shigeki

    2010-05-15

    Although boron-free FeCo films prepared on a Ru underlayer exhibits isotropic in-plane magnetic property, boron added FeCoB films prepared on Ru underlayer revealed large in-plane magnetic anisotropy with a high anisotropy field of 500 Oe. The effect of boron addition on the in-plane anisotropic residual stress in FeCoB film was investigated using sin{sup 2} {psi} method of x-ray diffraction analysis. Large isotropic compressive stress was observed in Ru/FeCo film. In contrast, anisotropic in-plane residual stress was observed in Ru/FeCoB film. The compressive stress along the easy axis of Ru/FeCoB film is released more than that along the hard axis. Such anisotropic residual stress is regarded as an origin of the in-plane magnetic anisotropy through inverse magnetostriction effect. Owing to the configuration of the facing targets sputtering system, boron atoms are sputtered and deposited anisotropically, and so they penetrate FeCo crystals and release the compressive stress along the incidence direction.

  14. Rational synthetic tuning between itinerant antiferromagnetism and ferromagnetism in the complex boride series Sc2FeRu(5-n)RhnB2 (0

    PubMed

    Fokwa, Boniface P T; Lueken, Heiko; Dronskowski, Richard

    2007-01-01

    Single crystals of the complex boride series Sc(2)FeRu(5-n)Rh(n)B(2) (n=1, 3, 4) were synthesized by arc-melting the elements in water-cooled copper crucibles under argon atmospheres and were chemically characterized by single-crystal XRD and EDX analyses. The new compounds are isotypic and crystallize in the tetragonal space group P4/mbm with Z=2, adopting a substitutional variant of the Ti(3)Co(5)B(2)-type structure. The magnetically active iron atoms are arranged in chains with intra- and interchain distances of about 3.02 and 6.60 A, respectively. Strong ferromagnetic interactions are observed for both Sc(2)FeRuRh(4)B(2) (64 valence electrons (VE), TC approximately 350 K, mu(a)=3.1 mu(B)) and Sc(2)FeRu(2)Rh(3)B(2) (63 VE, T(C) approximately 300 K, mu(a)=3.0 mu(B)), whereas antiferromagnetic interactions are found in the case of Sc(2)FeRu(4)RhB(2) (61 VE, T(N) approximately 10 K, mu(eff)=3.2): The magnetism of the entire Sc(2)FeRu(5-n)Rh(n)B(2) (0Fe-Fe bonding character, and it is also compared with other isoelectronic systems.

  15. RuO2 nanoparticle-modified (Ce,Mn,Fe)O2/(La,Sr) (Fe,Mn)O3 composite oxide as an active anode for direct hydrocarbon type solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Shin, Tae Ho; Hagiwara, Hidehisa; Ida, Shintaro; Ishihara, Tatsumi

    2015-09-01

    Composite oxide anodes have recently attracted great attention as alternative materials for solid oxide fuel cell anodes because of their potential to overcome the serious performance deterioration associated with the traditional Ni-based cermet. In particular, oxide anodes show a greater tolerance to coke and reoxidation than existing Ni-based cermets. In this study, the anodic performance of a (Ce,Mn,Fe)O2/(La,Sr) (Fe,Mn)O3 composite oxide modified with additional amounts of catalytically active RuO2 nanoparticles was investigated. Heat treatment resulted in highly dispersed RuO2 particles (ca. 10 nm). Anodes containing 10 wt% added RuO2 exhibited fairly high maximum power densities of 0.3 and 1.5 W cm-2 in H2 and C3H8, respectively, at 800 °C. The cells showed stable power density and negligible carbon formation even after 50 h of operation at 1 A cm-2. The increased power density was assigned to decreased anodic overpotential and internal resistance losses because RuO2 nanoparticles contribute to the increase in electrical conductivity.

  16. Predicting a ferrimagnetic phase of Zn(2)FeOsO(6) with strong magnetoelectric coupling.

    PubMed

    Wang, P S; Ren, W; Bellaiche, L; Xiang, H J

    2015-04-10

    Multiferroic materials, in which ferroelectric and magnetic ordering coexist, are of practical interest for the development of novel memory devices that allow for electrical writing and nondestructive magnetic readout operation. The great challenge is to create room temperature multiferroic materials with strongly coupled ferroelectric and ferromagnetic (or ferrimagnetic) orderings. BiFeO_{3} is the most heavily investigated single-phase multiferroic to date due to the coexistence of its magnetic order and ferroelectric order at room temperature. However, there is no net magnetic moment in the cycloidal (antiferromagneticlike) magnetic state of bulk BiFeO_{3}, which severely limits its realistic applications in electric field controlled memory devices. Here, we predict that LiNbO_{3}-type Zn_{2}FeOsO_{6} is a new multiferroic with properties superior to BiFeO_{3}. First, there are strong ferroelectricity and strong ferrimagnetism at room temperature in Zn_{2}FeOsO_{6}. Second, the easy plane of the spontaneous magnetization can be switched by an external electric field, evidencing the strong magnetoelectric coupling existing in this system. Our results suggest that ferrimagnetic 3d-5d LiNbO_{3}-type material may therefore be used to achieve voltage control of magnetism in future memory devices.

  17. Predicting a Ferrimagnetic Phase of Zn2FeOsO6 with Strong Magnetoelectric Coupling

    NASA Astrophysics Data System (ADS)

    Wang, P. S.; Ren, W.; Bellaiche, L.; Xiang, H. J.

    2015-04-01

    Multiferroic materials, in which ferroelectric and magnetic ordering coexist, are of practical interest for the development of novel memory devices that allow for electrical writing and nondestructive magnetic readout operation. The great challenge is to create room temperature multiferroic materials with strongly coupled ferroelectric and ferromagnetic (or ferrimagnetic) orderings. BiFeO3 is the most heavily investigated single-phase multiferroic to date due to the coexistence of its magnetic order and ferroelectric order at room temperature. However, there is no net magnetic moment in the cycloidal (antiferromagneticlike) magnetic state of bulk BiFeO3 , which severely limits its realistic applications in electric field controlled memory devices. Here, we predict that LiNbO3 -type Zn2FeOsO6 is a new multiferroic with properties superior to BiFeO3 . First, there are strong ferroelectricity and strong ferrimagnetism at room temperature in Zn2FeOsO6 . Second, the easy plane of the spontaneous magnetization can be switched by an external electric field, evidencing the strong magnetoelectric coupling existing in this system. Our results suggest that ferrimagnetic 3 d -5 d LiNbO3 -type material may therefore be used to achieve voltage control of magnetism in future memory devices.

  18. Rigid MIIL2Gd2III (M = Fe, Ru) complexes of a terpyridine-based heteroditopic chelate: a class of candidates for MRI contrast agents.

    PubMed

    Costa, Jérôme; Ruloff, Robert; Burai, László; Helm, Lothar; Merbach, André E

    2005-04-13

    Rigid chelates of high-molecular weight, [M(tpy-DTTA)2]6- (M = Fe, Ru), are obtained upon self-assembly around one M(II) ion of two terpyridine-based molecules substituted in the 4'-position with the polyaminocarboxylate diethylenetriamine-N,N,N'',N''-tetraacetate, tpy-DTTA4-. The protonation constants of tpy-DTTA4- (log K1 = 8.65(4), log K2 = 7.63(4), log K3 = 5.25(6), log K4 = 3.30(7)) and [Fe(tpy-DTTA)2]6- (log K1 = 8.40(4), log K2 = 7.26(4)) have been determined by potentiometry, 1H NMR and UV-vis titrations. The thermodynamic stability constant log K(GdL) of [Fe(tpy-DTTA)2Gd2(H2O)4] measured at 25 degrees C by potentiometry is 10.87. This relatively low value is due to the direct linkage of the polyaminocarboxylate part to the electron-withdrawing terpyridine. UV-vis absorbance spectra of [M(tpy-DTTA)2Gd2(H2O)4] and 1H NMR spectra of [M(tpy-DTTA)2Eu2(H2O)4] revealed similar solution behavior of the Fe and Ru complexes. An I(d) water-exchange mechanism (DeltaV++ = +6.8 +/- 1 cm3 mol(-1)) with a rate constant of k(ex)298 = (5.1 +/- 0.3) x 10(6) s(-1) has been found for [Fe(tpy-DTTA)2Gd2(H2O)4] by 17O NMR. A slow rotational correlation time (tau(RO) = 410 +/- 10 ps) and the presence of two water molecules (q = 2) in the coordination inner-sphere of each Gd(III) ion have also been determined for this complex. A remarkably high relaxivity has been observed for both [M(tpy-DTTA)2Gd2(H2O)4] complexes (at 20 MHz and 37 degrees C, r(1) = 15.7 mM(-1) s(-1) for the Fe complex, and r(1) = 15.6 mM(-1) s(-1) for the Ru complex).

  19. Room-temperature polarization switching and antiferromagnetic coupling in epitaxial (Ga,Fe){sub 2}O{sub 3}/SrRuO{sub 3} heterostructures

    SciTech Connect

    Oh, Seol Hee; Lee, Ji Hye; Shin, Ran Hee; Jo, William; Shin, Yooleemi; Meny, Christian

    2015-04-06

    Room-temperature reversible remnant polarization of gallium ferrite thin-films is reported as a multiferroic material with non-zero order parameters of polarization and magnetization. With the addition of Fe ions in Ga sites, Ga{sub 0.6}Fe{sub 1.4}O{sub 3} (GFO) thin films have been considered as potentially promising of multiferroicity. The b-axis oriented epitaxial GFO films were grown on SrRuO{sub 3}(111)/SrTiO{sub 3}(111). The six-fold symmetric in-plane epitaxy of the GFO films was confirmed using X-ray diffraction. The magnetic moment of the films was measured as a function of temperature and external magnetic field, which shows a room-temperature non-zero magnetization. Macroscopic and microscopic methods have been applied to demonstrate the polarization switching of the films. The remnant polarization is measured as 0.05 μC/cm{sup 2}. Reduction of leaky behaviors of the GFO films owing to the conducting oxide of SrRuO{sub 3} will pave a way to take advantage of the room-temperature non-zero multi-orders for future non-volatile memory device applications.

  20. First-principles study of the Hume-Rothery electron concentration rule in Al-Cu-(Fe,Ru)-Si 1/1-cubic approximants

    NASA Astrophysics Data System (ADS)

    Asahi, Ryoji; Kontsevoi, O. Y.; Mizutani, U.; Takeuchi, T.; Freeman, A. J.

    2006-03-01

    To elucidate the Hume-Rothery electron concentration rule, we determined the self-consistent electronic structures of the Al108Ru24Cu6Si6 and Al108Fe24Cu6Si6 1/1-1/1-1/1 approximants containing 144 atoms in each Pm-3 cubic unit cell using the full-potential linearized augmented plane wave (FLAPW) method [1], now running on massively parallel computer platforms. A significant pseudogap was found around the Fermi level for both alloys in the calculated densities of states, which should contribute to stabilization of the system. The FLAPW wave functions provide a direct observation of the Brillouin zone resonance in the Fermi surface [2]: a Fourier analysis of the wave functions confirms the Hume-Rothery matching rule 2kF=K where the reciprocal lattice vectors K consist of 543, 550, and 710 planes highly degenerate at the N point. Consequently, an effective electron concentration per atom (e/a) was evaluated to be 0.8 for both Ru and Fe in these structures making a sharp contrast with the previously assumed empirical value of -2.7 proposed by Raynor [3]. [1] Wimmer et al., Phys. Rev. B 24, 864 (1981). [2] Asahi et al., Phys. Rev. B 72, 125102 (2005). [3] Raynor, Prog. Metal Phys. 1, 1 (1949).

  1. [Phlebotominae: vectors of leishmaniasis in the provinces of Santa Fe and Entre Ríos, Argentina].

    PubMed

    Salomón, Oscar D; Mocarbel, Nicolás J; Pedroni, Elena; Colombo, Javier; Sandillú, Mónica

    2006-01-01

    The transmission of tegumentary leishmaniasis (TL) has increased in 9 provinces of Argentina since 1985. Santa Fe and Entre Ríos did not record in this period autochtonous probed cases: however, an epidemic outbreak took place in 2003 in Bella Vista, Corrientes, located in an area with ecological continuity and contiguous to both provinces. In order to evaluate the potential risk of transmission of LT, Phlebotominae were captured at locations close to and southern from Bella Vista during February 2004. The traps located on the shores of Parana river in Santa Fe (El Rabón, Villa Ocampo, Cayastá), and Entre Ríos (La Paz. La Celina-Villa Urquiza) captured 860 individuals of Lutzomyia neivai (99.5%) and Lu. migonei (0.5 %), both species with vectorial capacity for Leishmania (V.) braziliensis. In Tartagal, Santa Fe, the captures were consistent with the residual "chaco" landscape, 7 individuals of Lu. nerivai, Lu. migonei and Lu. cortelezzii. The risk of LT epidemic transmission in these provinces is highlighted, mainly due to the progressive southern tropicalization of the paranaense gallery forest. Clinical and entomological surveillance is recommended.

  2. New Ru(II)/Os(II)-polypyridyl complexes for coupling to TiO2 surfaces through acetylacetone functionality and studies on interfacial electron-transfer dynamics.

    PubMed

    Banerjee, Tanmay; Biswas, Abul Kalam; Sahu, Tuhin Subhra; Ganguly, Bishwajit; Das, Amitava; Ghosh, Hirendra Nath

    2014-09-28

    New Ru(ii)- and Os(ii)-polypyridyl complexes have been synthesized with pendant acetylacetone (acac) functionality for anchoring on nanoparticulate TiO2 surfaces with a goal of developing an alternate sensitizer that could be utilized for designing an efficient dye-sensitized solar cell (DSSC). Time-resolved transient absorption spectroscopic studies in the femtosecond time domain have been carried out. The charge recombination rates are observed to be very slow, compared with those for strongly coupled dye molecules having catechol as the anchoring functionality. The results of such studies reveal that electron-injection rates from the metal complex-based LUMO to the conduction band of TiO2 are faster than one would expect for an analogous complex in which the chromophoric core and the anchoring moiety are separated with multiple saturated C-C linkages. Such an observation is rationalized based on computational studies, and a relatively smaller spatial distance between the dye LUMO and the TiO2 surface accounted for this. Results of this study are compared with those for analogous complexes having a gem-dicarboxy group as the anchoring functionality for covalent binding to the TiO2 surface to compare the role of binding functionalities on electron-transfer dynamics.

  3. Materials discovery by crystal growth: Lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt) from molten alkali metal hydroxides

    SciTech Connect

    Mugavero, Samuel J.; Gemmill, William R.; Roof, Irina P.; Loye, Hans-Conrad zur

    2009-07-15

    This review addresses the process of materials discovery via crystal growth, specifically of lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt). It provides a detailed overview of the use of hydroxide fluxes for crystal growth. The melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals are described. Furthermore, a general methodology for the successful crystal growth of oxides is provided, including a discussion of experimental considerations, suitable reaction vessels, reaction profiles and temperature ranges. Finally, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts, focusing on their crystal growth and crystal structures, is included. - Graphical abstract: A review that addresses the process of materials discovery via crystal growth using hydroxide fluxes. It provides a detailed overview of the use of hydroxide fluxes for crystal growth and describes the melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals. In addition, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts is included.

  4. Conducting polymers containing in-chain metal centers: electropolymerization of oligothienyl-substituted {M(tpy)2} complexes and in situ conductivity studies, M = Os(II), Ru(II).

    PubMed

    Hjelm, Johan; Handel, Robyn W; Hagfeldt, Anders; Constable, Edwin C; Housecroft, Catherine E; Forster, Robert J

    2005-02-21

    The electropolymerization of a series of Ru and Os bis-terpyridine complexes that form rodlike polymers with bithienyl, quaterthienyl, or hexathienyl bridges has been studied. Absorption spectroscopy, scanning electron microscopy, and cyclic voltammetry have been used to characterize the monomers and resulting polymer films. The absolute dc conductivity of the quaterthienyl-bridged {Ru(tpy)2} and {Os(tpy)2} polymers is unusually large and independent of the identity of the metal center at 1.6 x 10(-3) S cm(-1). The maximum conductivity occurs at the formal potential of each redox process, which typically is observed for systems where redox conduction is the dominant charge transport mechanism. Significantly, the dc conductivity of the metal-based redox couple observed in these polymers is 2 orders of magnitude higher thanthat of a comparable nonconjugated system.

  5. Strain-induced topological transition in SrRu2O6 and CaOs2O6

    SciTech Connect

    Ochi, Masayuki; Arita, Ryotaro; Trivedi, Nandini; Okamoto, Satoshi

    2016-05-24

    The topological property of SrRu$_2$O$_6$ and isostructural CaOs$_2$O$_6$ under various strain conditions is investigated using density functional theory. Based on an analysis of parity eigenvalues, we anticipate that a three-dimensional strong topological insulating state should be realized when band inversion is induced at the A point in the hexagonal Brillouin zone. For SrRu$_2$O$_6$, such a transition requires rather unrealistic tuning, where only the $c$ axis is reduced while other structural parameters are unchanged. However, given the larger spin-orbit coupling and smaller lattice constants in CaOs$_2$O$_6$, the desired topological transition does occur under uniform compressive strain. Our study paves a way to realize a topological insulating state in a complex oxide, which has not been experimentally demonstrated so far.

  6. Highly textured Sr, Nb co-doped BiFeO{sub 3} thin films grown on SrRuO{sub 3}/Si substrates by rf- sputtering

    SciTech Connect

    Ostos, C.; Raymond, O.; Siqueiros, J. M.; Suarez-Almodovar, N.; Bueno-Baques, D.; Mestres, L.

    2011-07-15

    In this study, (011)-highly oriented Sr, Nb co-doped BiFeO{sub 3} (BFO) thin films were successfully grown on SrRuO{sub 3}/Si substrates by rf-magnetron sputtering. The presence of parasite magnetic phases was ruled out based on the high resolution x-ray diffraction data. BFO films exhibited a columnar-like grain growth with rms surface roughness values of {approx_equal}5.3 nm and average grain sizes of {approx_equal}65-70 nm for samples with different thicknesses. Remanent polarization values (2P{sub r}) of 54 {mu}C cm{sup -2} at room temperature were found for the BFO films with a ferroelectric behavior characteristic of an asymmetric device structure. Analysis of the leakage mechanisms for this structure in negative bias suggests Schottky injection and a dominant Poole-Frenkel trap-limited conduction at room temperature. Oxygen vacancies and Fe{sup 3+}/Fe{sup 2+} trap centers are consistent with the surface chemical bonding states analysis from x-ray photoelectron spectroscopy data. The (011)-BFO/SrRuO{sub 3}/Si film structure exhibits a strong magnetic interaction at the interface between the multiferroic film and the substrate layer where an enhanced ferromagnetic response at 5 K was observed. Zero-field cooled (ZFC) and field cooled (FC) magnetization curves of this film system revealed a possible spin glass behavior at spin freezing temperatures below 30 K depending on the BFO film thickness.

  7. Magnetic and electronic properties of La3 MO7 and possible polaron formation in hole-doped La3 MO7 (M  =  Ru and Os)

    NASA Astrophysics Data System (ADS)

    Gao, Bin; Weng, Yakui; Zhang, Jun-Jie; Zhang, Huimin; Zhang, Yang; Dong, Shuai

    2017-03-01

    Oxides with 4d/5d transition metal ions are physically interesting for their particular crystalline structures as well as the spin–orbit coupled electronic structures. Recent experiments revealed a series of 4d/5d transition metal oxides R 3 MO7 (R: rare earth; M: 4d/5d transition metal) with unique quasi-one-dimensional M chains. Here first-principles calculations have been performed to study the electronic structures of La3OsO7 and La3RuO7. Our study confirm both of them to be Mott insulating antiferromagnets with identical magnetic order. The reduced magnetic moments, which are much smaller than the expected value for ideal high-spin state (3 t 2g orbitals occupied), are attributed to the strong p  ‑  d hybridization with oxygen ions, instead of the spin–orbit coupling. The Ca-doping to La3OsO7 and La3RuO7 can not only modulate the nominal carrier density but also affect the orbital order as well as the local distortions. The Coulombic attraction and particular orbital order would prefer to form polarons, which might explain the puzzling insulating behavior of doped 5d transition metal oxides. In addition, our calculations predict that the Ca-doping can trigger ferromagnetism in La3RuO7 but not in La3OsO7.

  8. Lattice instability and competing spin structures in the double perovskite insulator Sr2FeOsO6.

    PubMed

    Paul, Avijit Kumar; Reehuis, Manfred; Ksenofontov, Vadim; Yan, Binghai; Hoser, Andreas; Többens, Daniel M; Abdala, Paula M; Adler, Peter; Jansen, Martin; Felser, Claudia

    2013-10-18

    The semiconductor Sr2FeOsO6, depending on temperature, adopts two types of spin structures that differ in the spin sequence of ferrimagnetic iron-osmium layers along the tetragonal c axis. Neutron powder diffraction experiments, 57Fe Mössbauer spectra, and density functional theory calculations suggest that this behavior arises because a lattice instability resulting in alternating iron-osmium distances fine-tunes the balance of competing exchange interactions. Thus, Sr2FeOsO6 is an example of a double perovskite, in which the electronic phases are controlled by the interplay of spin, orbital, and lattice degrees of freedom.

  9. Magnetic structure, magnetization, and magnetotransport properties of (Ba,Sr)M2±xT4∓xO11 ( M=Fe,Co ; T=Ru,Ti )

    NASA Astrophysics Data System (ADS)

    Shlyk, L.; Ueland, B. G.; Lynn, J. W.; Huang, Q.; de Long, L. E.; Parkin, S.

    2010-05-01

    Hexagonal R -type ferrites (Ba,Sr)M2±xT4∓xO11 ( M=Fe,Co ; T=Ru,Ti ) were studied via neutron and x-ray diffraction, magnetization, and electrical transport measurements. Magnetization data for single-crystal BaFe3.26Ti2.74O11 reveal two magnetic transitions at T1=250K and T2=84K , which indicates complex magnetic order driven by competing interactions on a frustrated lattice with a noncentrosymmetric structure. Magnetization data for single-crystal BaCo1.85Ru4.15O11 reveal soft ferromagnetic order at TC=105K with an easy direction perpendicular to the c axis. Neutron diffraction data for polycrystalline BaCo1.68Ru4.32O11 indicate a nearly compensated arrangement of spins lying within the a-b plane with a possible canting out of the plane that yields nonzero scalar spin chirality. The transverse magnetoresistivity ρxy of single-crystal BaCo1.85Ru4.15O11 for current J∥H⊥c axis is typical of an anomalous Hall effect observed in ferromagnets, whereas for J⊥H∥c axis, ρxy is a nonmonotonic function of the magnetic field, consistent with a topological Hall effect that depends upon scalar spin chirality. Neutron diffraction reveals transitions to ferrimagnetic order at TC=262(1)K for single-crystal SrFe2.6Ru3.4O11 , and at TC=403K for polycrystalline SrFe2.96Ru3.04O11 (refined as a collinear structure at T=5K ).

  10. Reproducible resistive switching in the super-thin Bi2FeCrO6 epitaxial film with SrRuO3 bottom electrode

    NASA Astrophysics Data System (ADS)

    Xu, Wenting; Sun, Jiao; Xu, Xijun; Yuan, Guoliang; Zhang, Yongjun; Liu, Junming; Liu, Zhiguo

    2016-10-01

    The reproducible and reliable resistive switching is observed in the ultrathin Bi2FeCrO6 (BFCO) epitaxial film on (001) SrTiO3 substrate with SrRuO3 as the bottom electrode. The as-grown BFCO film allows its ferroelectric polarization switching under external electric field. With a 100-nm-radius tip contacting film surface, a stable bipolar resistive switching was observed through the conductive atomic force microscope. Furthermore, the resistive switching at negative bias was observed and its high/low current ratio is above 15 among a thousand of current versus voltage curves measured by the scanning tunneling microscope with a non-contacting nm-scale tip. It is argued that this transport mechanism is due to quantum tunneling, and the resistive switching in these junctions is because of ferroelectric switching.

  11. Strain-mediated electric-field control of exchange bias in a Co90Fe10/BiFeO3/SrRuO3/PMN-PT heterostructure

    NASA Astrophysics Data System (ADS)

    Wu, S. Z.; Miao, J.; Xu, X. G.; Yan, W.; Reeve, R.; Zhang, X. H.; Jiang, Y.

    2015-03-01

    The electric-field (E-field) controlled exchange bias (EB) in a Co90Fe10/BiFeO3 (BFO)/SrRuO3/PMN-PT heterostructure has been investigated under different tensile strain states. The in-plane tensile strain of the BFO film is changed from +0.52% to +0.43% as a result of external E-field applied to the PMN-PT substrate. An obvious change of EB by the control of non-volatile strain has been observed. A magnetization reversal driven by E-field has been observed in the absence of magnetic field. Our results indicate that a reversible non-volatile E-field control of a ferromagnetic layer through strain modulated multiferroic BFO could be achieved at room temperature.

  12. Strain-mediated electric-field control of exchange bias in a Co90Fe10/BiFeO3/SrRuO3/PMN-PT heterostructure.

    PubMed

    Wu, S Z; Miao, J; Xu, X G; Yan, W; Reeve, R; Zhang, X H; Jiang, Y

    2015-03-10

    The electric-field (E-field) controlled exchange bias (EB) in a Co90Fe10/BiFeO3 (BFO)/SrRuO3/PMN-PT heterostructure has been investigated under different tensile strain states. The in-plane tensile strain of the BFO film is changed from +0.52% to +0.43% as a result of external E-field applied to the PMN-PT substrate. An obvious change of EB by the control of non-volatile strain has been observed. A magnetization reversal driven by E-field has been observed in the absence of magnetic field. Our results indicate that a reversible non-volatile E-field control of a ferromagnetic layer through strain modulated multiferroic BFO could be achieved at room temperature.

  13. Strain-mediated electric-field control of exchange bias in a Co90Fe10/BiFeO3/SrRuO3/PMN-PT heterostructure

    PubMed Central

    Wu, S. Z.; Miao, J.; Xu, X. G.; Yan, W.; Reeve, R.; Zhang, X. H.; Jiang, Y.

    2015-01-01

    The electric-field (E-field) controlled exchange bias (EB) in a Co90Fe10/BiFeO3 (BFO)/SrRuO3/PMN-PT heterostructure has been investigated under different tensile strain states. The in-plane tensile strain of the BFO film is changed from +0.52% to +0.43% as a result of external E-field applied to the PMN-PT substrate. An obvious change of EB by the control of non-volatile strain has been observed. A magnetization reversal driven by E-field has been observed in the absence of magnetic field. Our results indicate that a reversible non-volatile E-field control of a ferromagnetic layer through strain modulated multiferroic BFO could be achieved at room temperature. PMID:25752272

  14. Time-reversal-breaking topological phases in antiferromagnetic Sr2FeOsO6 films

    NASA Astrophysics Data System (ADS)

    Dong, Xiao-Yu; Kanungo, Sudipta; Yan, Binghai; Liu, Chao-Xing

    2016-12-01

    In this work, we studied time-reversal-breaking topological phases as a result of the interplay between antiferromagnetism and inverted band structures in antiferromagnetic double perovskite transition-metal Sr2FeOsO6 films. By combining the first-principles calculations and analytical models, we demonstrate that the quantum anomalous Hall phase and chiral topological superconducting phase can be realized in this system. We find that to achieve time-reversal-breaking topological phases in antiferromagnetic materials, it is essential to break the combined symmetry of time reversal and inversion, which generally exists in antiferromagnetic structures. As a result, we can utilize an external electric gate voltage to induce the phase transition between topological phases and trivial phases, thus providing an electrically controllable topological platform for future transport experiments.

  15. Spin density wave (SDW) transition in Ru doped BaFeAs2 investigated by AC steady state calorimetry

    NASA Astrophysics Data System (ADS)

    Vinod, K.; Sharma, Shilpam; Sundar, C. S.; Bharathi, A.

    2015-06-01

    Heat capacity measurements were done on sub-micron sized BaFe2-xRuxAs2 single crystals using thin film membrane based the AC steady state calorimetry technique. Noticeable thermal hysteresis is observed in the heat capacity of the BaFe2-xRuxAs2 during cooling and warming cycles, indicating first order nature of the SDW transition.

  16. High-temperature ferrimagnetism driven by lattice distortion in double perovskite Ca2FeOsO6.

    PubMed

    Feng, Hai L; Arai, Masao; Matsushita, Yoshitaka; Tsujimoto, Yoshihiro; Guo, Yanfeng; Sathish, Clastin I; Wang, Xia; Yuan, Ya-Hua; Tanaka, Masahiko; Yamaura, Kazunari

    2014-03-05

    5d and 3d hybrid solid-state oxide Ca2FeOsO6 crystallizes into an ordered double-perovskite structure with a space group of P2₁/n with high-pressures and temperatures. Ca2FeOsO6 presents a long-range ferrimagnetic transition at a temperature of ~320 K (T(c)) and is not a band insulator, but is electrically insulating like the recently discovered Sr2CrOsO6 (T(c) ~725 K). The electronic stat of Ca2FeOsO6 is adjacent to a half-metallic state as well as that of Sr2CrOsO6. In addition, the high-T(c) ferrimagnetism was driven by lattice distortion, which was observed for the first time among double-perovskite oxides and represents complex interplays between spins and orbitals. Unlike conventional ferrite and garnet, the interplays likely play a pivotal role of the ferrimagnetism. A new class of 5d-3d hybrid ferrimagnetic insulators with high-T(c) is established to develop practically and scientifically useful spintronic materials.

  17. High-Pressure Synthesis and Ferrimagnetic Ordering of the B-Site-Ordered Cubic Perovskite Pb2FeOsO6.

    PubMed

    Zhao, Qing; Liu, Min; Dai, Jianhong; Deng, Hongshan; Yin, Yunyu; Zhou, Long; Yang, Junye; Hu, Zhiwei; Agrestini, Stefano; Chen, Kai; Pellegrin, Eric; Valvidares, Manuel; Nataf, Lucie; Baudelet, François; Tjeng, L H; Yang, Yi-Feng; Jin, Changqing; Long, Youwen

    2016-10-03

    Pb2FeOsO6 was prepared for the first time by using high-pressure and high-temperature synthesis techniques. This compound crystallizes into a B-site-ordered double-perovskite structure with cubic symmetry Fm3̅m, where the Fe and Os atoms are orderly distributed with a rock-salt-type manner. Structure refinement shows an Fe-Os antisite occupancy of about 16.6%. Structural analysis and X-ray absorption spectroscopy both demonstrate the charge combination to be Pb2Fe(3+)Os(5+)O6. A long-range ferrimagnetic transition is found to occur at about 280 K due to antiferromagnetic interactions between the adjacent Fe(3+) and Os(5+) spins with a straight (180°) Fe-O-Os bond angle, as confirmed by X-ray magnetic circular-dichroism measurements. First-principles theoretical calculations reveal the semiconducting behavior as well as the Fe(3+)(↑)Os(5+)(↓) antiferromagnetic coupling originating from the superexchange interactions between the half-filled 3d orbitals of Fe and t2g orbitals of Os.

  18. Positive exchange-bias and giant vertical hysteretic shift in La0.3Sr0.7FeO3/SrRuO3 bilayers

    PubMed Central

    Rana, Rakesh; Pandey, Parul; Singh, R. P.; Rana, D. S.

    2014-01-01

    The exchange-bias effects in the mosaic epitaxial bilayers of the itinerant ferromagnet (FM) SrRuO3 and the antiferromagnetic (AFM) charge-ordered La0.3Sr0.7FeO3 were investigated. An uncharacteristic low-field positive exchange bias, a cooling-field driven reversal of positive to negative exchange-bias and a layer thickness optimised unusual vertical magnetization shift were all novel facets of exchange bias realized for the first time in magnetic oxides. The successive magnetic training induces a transition from positive to negative exchange bias regime with changes in domain configurations. These observations are well corroborated by the hysteretic loop asymmetries which display the modifications in the AFM spin correlations. These exotic features emphasize the key role of i) mosaic disorder induced subtle interplay of competing AFM-superexchange and FM double exchange at the exchange biased interface and, ii) training induced irrecoverable alterations in the AFM spin structure. PMID:24569516

  19. Optical properties of epitaxial BiFeO3 thin film grown on SrRuO3-buffered SrTiO3 substrate.

    PubMed

    Xu, Ji-Ping; Zhang, Rong-Jun; Chen, Zhi-Hui; Wang, Zi-Yi; Zhang, Fan; Yu, Xiang; Jiang, An-Quan; Zheng, Yu-Xiang; Wang, Song-You; Chen, Liang-Yao

    2014-01-01

    The BiFeO3 (BFO) thin film was deposited by pulsed-laser deposition on SrRuO3 (SRO)-buffered (111) SrTiO3 (STO) substrate. X-ray diffraction pattern reveals a well-grown epitaxial BFO thin film. Atomic force microscopy study indicates that the BFO film is rather dense with a smooth surface. The ellipsometric spectra of the STO substrate, the SRO buffer layer, and the BFO thin film were measured, respectively, in the photon energy range 1.55 to 5.40 eV. Following the dielectric functions of STO and SRO, the ones of BFO described by the Lorentz model are received by fitting the spectra data to a five-medium optical model consisting of a semi-infinite STO substrate/SRO layer/BFO film/surface roughness/air ambient structure. The thickness and the optical constants of the BFO film are obtained. Then a direct bandgap is calculated at 2.68 eV, which is believed to be influenced by near-bandgap transitions. Compared to BFO films on other substrates, the dependence of the bandgap for the BFO thin film on in-plane compressive strain from epitaxial structure is received. Moreover, the bandgap and the transition revealed by the Lorentz model also provide a ground for the assessment of the bandgap for BFO single crystals.

  20. Predicting a Ferrimagnetic-Ferroelectric Phase of Zn2FeOsO6 with Strong Magnetoelectric Coupling

    NASA Astrophysics Data System (ADS)

    Xiang, Hongjun; Wang, P. S.; Ren, Wei; Bellaiche, L.

    2015-03-01

    Multiferroic materials, in which ferroelectric and magnetic ordering coexist, are of fundamental interest for the development of novel memory devices that allow for electrical writing and non-destructive magnetic readout operation. The great challenge is to create room temperature multiferroic materials with strongly coupled ferroelectric and ferromagnetic (or ferrimagnetic) orderings. BiFeO3 has been the most heavily investigated single-phase multiferroic to date due to the coexistence of its magnetic order and ferroelectric order at room temperature. However, there is no net magnetic moment in the cycloidal (antiferromagnetic-like) magnetic state of bulk BiFeO3, which severely limits its realistic applications in electric field controlled spintronic devices. Here, we predict that double perovskite Zn2FeOsO6 is a new multiferroic with properties superior to BiFeO3. First, there are strong ferroelectricity and strong ferrimagnetism at room temperature in Zn2FeOsO6. Second, the easy-plane of the spontaneous magnetization can be switched by an external electric field, evidencing the strong magnetoelectric coupling existing in this system. Our results suggest that ferrimagnetic 3d-5d double perovskite may therefore be used to achieve voltage control of magnetism in future spintronic devices.

  1. High-density gold nanoparticles supported on a [Ru(bpy)(3)](2+)-doped silica/Fe3O4 nanocomposite: facile preparation, magnetically induced immobilization, and applications in ECL detection.

    PubMed

    Guo, Shaojun; Li, Jing; Wang, Erkang

    2008-09-01

    A large-scale process combined sonication with self-assembly techniques for the preparation of high-density gold nanoparticles supported on a [Ru(bpy)(3)](2+)-doped silica/Fe(3)O(4) nanocomposite (GNRSF) is provided. The obtained hybrid nanomaterials containing Fe(3)O(4) spheres have high saturation magnetization, which leads to their effective immobilization on the surface of an ITO electrode through simple manipulation by an external magnetic field (without the need of a special immobilization apparatus). Furthermore, this hybrid nanomaterial film exhibits a good and very stable electrochemiluminescence (ECL) behavior, which gives a linear response for tripropylamine (TPA) concentrations between 5 muM and 0.21 mM, with a detection limit in the micromolar range. The sensitivity of this ECL sensor can be easily controlled by the amount of [Ru(bpy)(3)](2+) immobilized on the hybrid nanomaterials (that is, varying the amount of [Ru(bpy)(3)](2+) during GNRSF synthesis).

  2. Heavy-impurity resonance, hybridization, and phonon spectral functions in Fe1-xMxSi (M =Ir , Os )

    NASA Astrophysics Data System (ADS)

    Delaire, O.; Al-Qasir, I. I.; May, A. F.; Li, C. W.; Sales, B. C.; Niedziela, J. L.; Ma, J.; Matsuda, M.; Abernathy, D. L.; Berlijn, T.

    2015-03-01

    The vibrational behavior of heavy substitutional impurities (M = Ir,Os) in Fe1-xMxSi (x =0 ,0.02 ,0.04 ,0.1 ) was investigated with a combination of inelastic neutron scattering (INS), transport measurements, and first-principles simulations. Our INS measurements on single crystals mapped the four-dimensional dynamical structure factor, S (Q ,E ) , for several compositions and temperatures. Our results show that both Ir and Os impurities lead to the formation of a weakly dispersive resonance vibrational mode, in the energy range of the acoustic phonon dispersions of the FeSi host. We also show that Ir doping, which introduces free carriers, leads to softened interatomic force constants compared to doping with Os, which is isoelectronic to Fe. We analyze the phonon S (Q ,E ) from INS through a Green's-function model incorporating the phonon self-energy based on first-principles density functional theory simulations, and we study the disorder-induced lifetimes on large supercells. Calculations of the quasiparticle spectral functions in the doped system reveal the hybridization between the resonance and the acoustic phonon modes. Our results demonstrate a strong interaction of the host acoustic dispersions with the resonance mode, likely leading to the large observed suppression in lattice thermal conductivity.

  3. Heavy-impurity resonance, hybridization, and phonon spectral functions in Fe1-xMxSi, M=Ir,Os

    DOE PAGES

    Delaire, O.; Al-Qasir, Iyad I.; May, Andrew F.; ...

    2015-03-31

    The vibrational behavior of heavy substitutional impurities (M=Ir,Os) in Fe1-xMxSi (x = 0, 0.02, 0.04, 0.1) was investigated with a combination of inelastic neutron scattering (INS), transport measurements, and first-principles simulations. In this paper, our INS measurements on single-crystals mapped the four-dimensional dynamical structure factor, S(Q;E), for several compositions and temperatures. Our results show that both Ir and Os impurities lead to the formation of a weakly dispersive resonance vibrational mode, in the energy range of the acoustic phonon dispersions of the FeSi host. We also show that Ir doping, which introduces free carriers and increases electron-phonon coupling, leads tomore » softened interatomic force-constants compared to doping with Os, which is isoelectronic to Fe. We analyze the phonon S(Q,E) from INS through a Green's function model incorporating the phonon self-energy based on first-principles density functional theory (DFT) simulations. Calculations of the quasiparticle spectral functions in the doped system reveal the hybridization between the resonance and the acoustic phonon modes. Finally, our results demonstrate a strong interaction of the host acoustic dispersions with the resonance mode, likely leading to the large observed suppression in lattice thermal conductivity.« less

  4. Ru(II) and Os(II) complexes based on terpyridyl-imidazole ligand rigidly linked to pyrene: synthesis, structure, photophysics, electrochemistry, and anion-sensing studies.

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Mondal, Debiprasad; Baitalik, Sujoy

    2013-12-16

    We report in this work a new family of bis-tridentate ruthenium(II) and osmium(II) complexes bearing a terpyridyl ligand rigidly link to pyrenyl-benzimidazole moiety (tpy-HImzPy = 10-(4-[2,2':6',2''-terpyridine]terpyridin-4'-yl-phenyl)-9H-9,11-diaza-cyclopenta[e]pyrene) along with other tridentate ligands such as 4'-(2-naphthyl)-2,2':6',2″-terpyridine (tpy-NaPh) and 2,6-bis(benzimidazole-2-yl)pyridine (H2pbbzim). All the complexes are thoroughly characterized by their elemental analysis, ESI mass spectrometry, and (1)H NMR spectroscopy. The molecular structures of two complexes [Ru(tpy-HImzPy)2](ClO4)2 (3) and [(pbbzim)Ru(tpy-HImzPy)] (2a) in the solid state were determined by X-ray crystallography. The absorption, steady-state, and time-resolved luminescence and electrochemical properties of all the four compounds have been studied. On excitation at their MLCT bands, all four compounds exhibit moderately strong room-temperature luminescence with lifetimes ranging between 3.8 and 161.1 ns in aerated condition, whereas in the deaerated (N2 purged) condition, the lifetimes vary between 8.2 and 199.1 ns, depending upon the nature of the solvents. The presence of imidazole N-H protons in all the complexes motivates us to study anion sensing properties of the complexes in solution through different channels. Spectrophotometeric, fluorometric, (1)H NMR spectroscopic, and cyclic voltammetric studies of the complexes in presence of anions reveal that the complexes sense principally F(-), CN(-), and to a lesser extent for AcO(-). Multichannel anion sensing studies also indicate that anion-induced deprotonation of the imidazole N-H protons occur in all four compounds. The equilibrium constant of this deprotonation steps have been estimated from UV-vis absorption and emission titration data. Anion-induced modulation of lifetimes makes all the four complexes suitable for lifetime-based sensors for selective anions.

  5. Varied roles of Pb in transition-metal PbMO3 perovskites (M = Ti, V, Cr, Mn, Fe, Ni, Ru).

    PubMed

    Goodenough, John B; Zhou, Jianshi

    2015-06-01

    Different structural chemistries resulting from the Pb(2+) lone-pair electrons in the PbMO3 perovskites are reviewed. The Pb(2+) lone-pair electrons enhance the ferroelectric transition temperature in PbTiO3, stabilize vanadyl formation in PbVO3, and induce a disproportionation reaction of Cr(IV) in PbCrO3. A Pb(2+) + Ni(IV) = Pb(4+) + Ni(II) reaction in PbNiO3 stabilizes the LiNbO3 structure at ambient pressure, but an A-site Pb(4+) in an orthorhombic perovskite PbNiO3 is stabilized at modest pressures at room temperature. In PbMnO3, a ferroelectric displacement due to the lone pair electron effect is minimized by the spin-spin exchange interaction and the strong octahedral site preference of the Mn(IV/III) cation. PbRuO3 is converted under pressure from the defective pyrochlore to the orthorhombic (Pbnm) perovskite structure where Pb-Ru interactions via a common O -2p orbital stabilize at low temperature a metallic Imma phase at ambient pressure. Above Pc [Formula: see text] a covalent Pb-Ru bond is formed by Pb(2+) + Ru(IV) = Pb(4+) + Ru(II) electron sharing.

  6. Synthesis, crystal structure, and magnetic properties of Li3Mg2OsO6, a geometrically frustrated osmium(V) oxide with an ordered rock salt structure: comparison with isostructural Li3Mg2RuO6.

    PubMed

    Nguyen, Phuong-Hieu T; Ramezanipour, Farshid; Greedan, John E; Cranswick, Lachlan M D; Derakhshan, Shahab

    2012-11-05

    The novel osmium-based oxide Li(3)Mg(2)OsO(6) was synthesized in polycrystalline form by reducing Li(5)OsO(6) by osmium metal and osmium(IV) oxide in the presence of stoichiometric amounts of magnesium oxide. The crystal structure was refined using powder X-ray diffraction data in the orthorhombic Fddd space group with a = 5.88982(5) Å, b = 8.46873(6) Å, and c = 17.6825(2) Å. This compound is isostructural and isoelectronic with the ruthenium-based system Li(3)Mg(2)RuO(6). The magnetic ion sublattice Os(5+) (S = 3/2) consists of chains of interconnected corner- and edge-shared triangles, which brings about the potential for geometric magnetic frustration. The Curie-Weiss law holds over the range 80-300 K with C = 1.42(3) emu·K/mol [μ(eff) = 3.37(2) μ(B)] and θ(C) = -105.8(2) K. Below 80 K, there are three anomalies at 75, 30, and 8 K. Those at 75 and 30 K are suggestive of short-range antiferromagnetic correlations, while that at 8 K is a somewhat sharper maximum showing a zero-field-cooled/field-cooled divergence suggestive of perhaps spin freezing. The absence of magnetic Bragg peaks at 3.9 K in the neutron diffraction pattern supports this characterization, as does the absence of a sharp peak in the heat capacity, which instead shows only a very broad maximum at ∼12 K. A frustration index of f = 106/8 = 13 indicates a high degree of frustration. The magnetic properties of the osmium phase differ markedly from those of the isostructural ruthenium material, which shows long-range antiferromagnetic order below 17 K, f = 6, and no unusual features at higher temperatures. Estimates of the magnetic exchange interactions at the level of spin-dimer analysis for both the ruthenium and osmium materials support a more frustrated picture for the latter. Errors in the calculation and assignment of the exchange pathways in the previous report on Li(3)Mg(2)RuO(6) are identified and corrected.

  7. Chemical pressure tuning of URu2Si2 via isoelectronic substitution of Ru with Fe

    SciTech Connect

    Das, Pinaki; Kanchanavatee, N.; Helton, J. S.; Huang, K.; Baumbach, R. E.; Bauer, E. D.; White, B. D.; Burnett, V. W.; Maple, M. B.; Lynn, J. W.; Janoschek, M.

    2015-02-26

    We have used specific heat and neutron diffraction measurements on single crystals of URu2–xFexSi₂ for Fe concentrations x ≤ 0.7 to establish that chemical substitution of Ru with Fe acts as “chemical pressure” Pch as previously proposed by Kanchanavatee et al. [Phys. Rev. B 84, 245122 (2011)] based on bulk measurements on polycrystalline samples. Neutron diffraction reveals a sharp increase of the uranium magnetic moment at x = 0.1, reminiscent of the behavior at the “hidden order” to large moment antiferromagnetic (LMAFM) phase transition observed at a pressure Px ≈ 0.5-0.7 GPa in URu₂Si₂. Using the unit cell volume determined from our measurements and an isothermal compressibility κT = 5.2×10⁻³ GPa⁻¹ for URu₂Si₂, we determine the chemical pressure Pch in URu2-xFexSi₂ as a function of x. The resulting temperature T-chemical pressure Pch phase diagram for URu2-xFexSi₂ is in agreement with the established temperature T-external pressure P phase diagram of URu₂Si₂.

  8. Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties

    DOE PAGES

    Lin, Qisheng; Taufour, Valentin; Zhang, Yuemei; ...

    2015-05-22

    Single crystals of Nd4FeOS6 were grown from an Fe-S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd4MnOSe6-type structure (P63mc, a = 9.2693(1) Å, c = 6.6650(1) Å, V = 495.94(1) Å3, Z = 2), featuring parallel chains of face-sharing [FeS6x1/2]4- trigonal antiprisms and interlinked [Nd4OS3]4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd4 clusters in the [Nd4OS3]4+ chains. Structural differences among Nd4MnOSe6-type Nd4FeOS6 and the related La3CuSiS7- and Pr8CoGa3-type structures have been described. Magnetic susceptibility measurements on Nd4FeOS6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 Kmore » was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.« less

  9. Multi-pyridine decorated Fe(II) and Ru(II) complexes by Pd(0)-catalysed cross couplings: new building blocks for metallosupramolecular assemblies.

    PubMed

    Yang, Jiajia; Clegg, Jack K; Jiang, Qibai; Lui, Xiaoming; Yan, Hong; Zhong, Wei; Beves, Jonathon E

    2013-11-28

    Eight metal complexes of the type [M(tpy)2](2+) (tpy = 2,2':6',2''-terpyridine) featuring four pendant pyridine rings are reported and characterised by NMR, MS, absorption spectroscopy and electrochemical methods. Palladium-mediated Suzuki and Sonogashira cross-coupling reactions were performed on both free 4'-(3,5-dibromophenyl)-tpy and its Ru(II) complex in good yields. The ready N-alkylation of the pendant pyridyl units has significant influence on the absorption and electrochemical reduction of the complexes, processes which are localised on the periphery and leaves the [Ru(tpy)2](2+) core essentially unaffected. The binding of metal ions by the free pyridines is also demonstrated as means of assembling larger ordered non-covalent structures.

  10. Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(mu-C triple bondCC triple bond C)].

    PubMed

    Bruce, Michael I; Costuas, Karine; Davin, Thomas; Halet, Jean-François; Kramarczuk, Kathy A; Low, Paul J; Nicholson, Brian K; Perkins, Gary J; Roberts, Rachel L; Skelton, Brian W; Smith, Mark E; White, Allan H

    2007-12-14

    The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os([=C=CH2)(dppe)Cp*]PF6 ([11]PF6), [Os(C triple bond CH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{mu-(=C=CH-CH=C=)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}(2)(mu-C triple bond CC triple bond C)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(mu-C triple bond CC triple bond C)] (M = Fe, Ru, Os). The molecular structures of []PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(C triple bond CPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe approximately Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(mu-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.

  11. Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties

    SciTech Connect

    Lin, Qisheng; Taufour, Valentin; Zhang, Yuemei; Wood, Max; Drtina, Thomas; Bud’ko, Sergey L.; Canfield, Paul C.; Miller, Gordon J.

    2015-05-22

    Single crystals of Nd4FeOS6 were grown from an Fe-S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd4MnOSe6-type structure (P63mc, a = 9.2693(1) Å, c = 6.6650(1) Å, V = 495.94(1) Å3, Z = 2), featuring parallel chains of face-sharing [FeS6x1/2]4- trigonal antiprisms and interlinked [Nd4OS3]4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd4 clusters in the [Nd4OS3]4+ chains. Structural differences among Nd4MnOSe6-type Nd4FeOS6 and the related La3CuSiS7- and Pr8CoGa3-type structures have been described. Magnetic susceptibility measurements on Nd4FeOS6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.

  12. Synthesis and characterization of (smif)2M(n) (n = 0, M = V, Cr, Mn, Fe, Co, Ni, Ru; n = +1, M = Cr, Mn, Co, Rh, Ir; smif =1,3-di-(2-pyridyl)-2-azaallyl).

    PubMed

    Frazier, Brenda A; Bartholomew, Erika R; Wolczanski, Peter T; DeBeer, Serena; Santiago-Berrios, Mitk'El; Abruña, Hector D; Lobkovsky, Emil B; Bart, Suzanne C; Mossin, Susanne; Meyer, Karsten; Cundari, Thomas R

    2011-12-19

    A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe(3))(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX(2) variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl(3)(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl(3)(THF)(3) in the presence of NaBPh(4) gave [(smif)(2)Ir]BPh(4) (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh(2)(O(2)CCF(3))(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC(nb) (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (ε ≈ 10,000-60,000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr.

  13. [Serotype distribution of Streptococcus pneumoniae isolated from invasive infections at the Hospital de Niños of Santa Fe].

    PubMed

    Mayoral, C; Baroni, M R; Giani, R; Virgolini, S; Zurbriggen, L; Regueira, M

    2008-01-01

    The serotype distribution of Streptococcus pneumoniae varies through time. The introduction of pneumococcal conjugate vaccines showed a decreased prevalence of pneumococcal invasive isolates belonging to serotype 14 and an increase of serotypes not therein included. In 1993, the Hospital de Niños of Santa Fe began surveillance of the serotype distribution of invasive S. pneumoniae disease. In the period 2003-2005, 76 isolates were analysed by studying the correlation between serotype and pathology, age and MIC of penicillin. Serotype 14 was the most frequent followed by serotypes 1, 6B, 18C, 7F, 19 F and 5. Serotype 14 showed a statistically significant correlation with MICs of penicillin ranging from 0,5 to 2 mg/l. Although this serotype was more frequently observed in pneumonia than in meningitis, there was not a significant association with any particular pathology. Serotypes 14 and 1, were prevalent among children under and over 2 years old, respectively. Most of these isolates with MICs of penicillin = 2 mg/l, were from patients with pneumonia and not with meningitis. The serotype distribution was similar to that during the period 1993-99, with the exception of serotypes 18C, 4, 12F and 22F which had never been found before. The emergence of these serotypes makes it essential to continue surveillance to determine which conjugated vaccine formulation would be suitable to prevent the most frequent pneumococcal invasive infections.

  14. Adsorptive Separation of Methanol-Acetone on Isostructural Series of Metal-Organic Frameworks M-BTC (M = Ti, Fe, Cu, Co, Ru, Mo): A Computational Study of Adsorption Mechanisms and Metal-Substitution Impacts.

    PubMed

    Wu, Ying; Chen, Huiyong; Xiao, Jing; Liu, Defei; Liu, Zewei; Qian, Yu; Xi, Hongxia

    2015-12-09

    The adsorptive separation properties of M-BTC isostructural series (M = Ti, Fe, Cu, Co, Ru, Mo) for methanol-acetone mixtures were investigated by using various computational procedures of grand canonical Monte Carlo simulations (GCMC), density functional theory (DFT), and ideal adsorbed solution theory (IAST), following with comprehensive understanding of adsorbate-metal interactions on the adsorptive separation behaviors. The obtained results showed that the single component adsorptions were driven by adsorbate-framework interactions at low pressures and by framework structures at high pressures, among which the mass effects, electrostatics, and geometric accessibility of the metal sites also played roles. In the case of methanol-acetone separation, the selectivity of methanol on M-BTCs decreased with rising pressures due to the pressure-dependent separation mechanisms: the cooperative effects between methanol and acetone hindered the separation at low pressures, whereas the competitive effects of acetone further resulted in the lower selectivity at high pressures. Among these M-BTCs, Ti and Fe analogues exhibited the highest thermodynamic methanol/acetone selectivity, making them promising for adsorptive methanol/acetone separation processes. The investigation provides mechanistic insights on how the nature of metal centers affects the adsorption properties of MOFs, and will further promote the rational design of new MOF materials for effective gas mixture separation.

  15. Molecule-based magnets formed by bimetallic three-dimensional oxalate networks and chiral tris(bipyridyl) complex cations. The series [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion).

    PubMed

    Coronado, E; Galán-Mascarós, J R; Gómez-García, C J; Martínez-Agudo, J M

    2001-01-01

    The synthesis, structure, and physical properties of the series of molecular magnets formulated as [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion) are presented. All the compounds are isostructural to the [Ru(bpy)3][ClO4][MnCr(ox)3] member whose structure (cubic space group P4(1)32 with a = 15.506(2) A, Z = 4) consists of a three-dimensional bimetallic network formed by alternating MII and CrIII ions connected by oxalate anions. The identical chirality (lambda in the solved crystal) of all the metallic centers determines the 3D chiral structure adopted by these compounds. The anionic 3D sublattice leaves some holes where the chiral [Z(bpy)3]2+ and ClO4- counterions are located. These compounds behave as soft ferromagnets with ordering temperatures up to 6.6 K and coercive fields up to 8 mT.

  16. Synthesis, crystal structure investigation and magnetism of the complex metal-rich boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) with Th{sub 7}Fe{sub 3}-type structure

    SciTech Connect

    Misse, Patrick R.N.; Mbarki, Mohammed; Fokwa, Boniface P.T.

    2012-08-15

    Powder samples and single crystals of the new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) have been synthesized by arc-melting the elements under purified argon atmosphere on a water-cooled copper crucible. The products, which have metallic luster, were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX measurements. Within the whole solid solution range the hexagonal Th{sub 7}Fe{sub 3} structure type (space group P6{sub 3}mc, no. 186, Z=2) was identified. Single-crystal structure refinement results indicate the presence of chromium at two sites (6c and 2b) of the available three metal Wyckoff sites, with a pronounced preference for the 6c site. An unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors in the solid solution: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. - Graphical abstract: The new complex boride series Cr{sub x}(Rh{sub 1-y}Ru{sub y}){sub 7-x}B{sub 3} (x=0.88-1; y=0-1) has been synthesized by arc melting the elements under purified argon atmosphere. Beside the 3d/4d site preference within the whole solid solution, an unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region. Highlights: Black-Right-Pointing-Pointer Synthesis of a new boride series fulfilling Vegard Acute-Accent s rule. Black-Right-Pointing-Pointer 3d/4d site preference. Black-Right-Pointing-Pointer Unexpected Ru/Rh site preference. Black-Right-Pointing-Pointer Rh-rich region is Pauli paramagnetic. Black-Right-Pointing-Pointer Ru-rich region is Pauli and temperature-dependent paramagnetic.

  17. Magnetic properties of RT2Zn20; R = rare earth, T = Fe, Co, Ru, Os and Ir

    SciTech Connect

    Jia, Shuang

    2008-01-01

    It is well known that rare earth intermetallic compounds have versatile, magnetic properties associated with the 4f electrons: a local moment associated with the Hund's rule ground state is formed in general, but a strongly correlated, hybridized state may also appear for specific 4f electronic configuration (eg. for rare earth elements such as Ce or Yb). On the other hand, the conduction electrons in rare earth intermetallic compounds, certainly ones associated with non hybridizing rare earths, usually manifest non-magnetic behavior and can be treated as a normal, non-interacted Fermi liquid, except for some 3d-transition metal rich binary or ternary systems which often manifest strong, itinerant, d electron dominant magnetic behavior. Of particular interest are examples in which the band filling of the conduction electrons puts the system in the vicinity of a Stoner transition: such systems, characterized as nearly or weakly ferromagnet, manifest strongly correlated electronic properties [Moriya, 1985]. For rare earth intermetallic compounds, such systems provide an additional versatility and allow for the study of the behaviors of local moments and hybridized moments which are associated with 4f electron in a correlated conduction electron background.

  18. Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3d–5d double perovskite Sr₂FeOsO₆

    SciTech Connect

    Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; Souza-Neto, N. M.; Feng, H. L.; Yamaura, K.; Haskel, D.

    2015-06-19

    The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr₂FeOsO₆ drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differences with the more thoroughly studied 3d-3d systems.

  19. Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3d–5d double perovskite Sr₂FeOsO₆

    DOE PAGES

    Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; ...

    2015-06-19

    The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr₂FeOsO₆ drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differencesmore » with the more thoroughly studied 3d-3d systems.« less

  20. The End of Monterey Submarine Canyon Incision and Potential River Source Areas-Os, Nd, and Pb Isotope Constraints from Hydrogenetic Fe-Mn Crusts

    NASA Astrophysics Data System (ADS)

    Conrad, T. A.; Nielsen, S.; Ehrenbrink, B. P. E.; Blusztajn, J.; Hein, J. R.; Paytan, A.

    2015-12-01

    The Monterey Canyon off central California is the largest submarine canyon off North America and is comparable in scale to the Grand Canyon. The age and history of the Monterey Canyon are poorly constrained due to thick sediment cover and sediment disruption from turbidity currents. To address this deficit we analyzed isotopic proxies (Os, Pb, Nd) from hydrogenetic ferromanganese (Fe-Mn) crusts, which grow over millions of years on elevated rock surfaces by precipitation of metals from seawater. Fe-Mn crusts were studied from Davidson Seamount near the base of the Monterey submarine fan, the Taney Seamount Chain, and from Hoss Seamount, which serves as a regional control (Fig.). Fe-Mn crusts were dated using Os isotope ratios compared to those that define the Cenozoic Os isotope seawater curve. Four Fe-Mn crust samples from Davidson and Taney Seamounts deviate from the Os isotopic seawater curve towards radiogenic values after 4.5±1 Ma. Osmium is well mixed in the global ocean and is not subject to significant diffusive reequilibration in Fe-Mn crusts. We therefore attribute deviations from the Os isotope seawater curve to large-scale terrestrial input that ended about 4.5±1 Ma. The two Davidson samples also show more radiogenic Nd isotope values from about 4.5±1 Ma. Lead isotopes in one Davidson Seamount crust, measured by LA-ICPMS, deviate from regional values after 4.5±1 Ma for about 500 ka towards terrestrial sources. The Taney Seamount Fe-Mn crust does not deviate from regional Nd nor Pb isotope values due to its greater distance from Monterey Canyon and the shorter marine residence times of Nd and Pb. Isotope plots of our crust data and compiled data for potential source rocks indicate that the river that carved Monterey Canyon carried sediment with values closer to the Sierra Nevada than to a Colorado Plateau source, with cessation of major riverine input occurring approximately 4.5±1 Ma, an age that we interpret as the end of the Monterey Canyon

  1. Heavy-impurity resonance, hybridization, and phonon spectral functions in Fe1-xMxSi, M=Ir,Os

    SciTech Connect

    Delaire, O.; Al-Qasir, Iyad I.; May, Andrew F.; Sales, Brian C.; Niedziela, Jennifer L.; Ma, Jie; Matsuda, Masaaki; Abernathy, Douglas L.; Berlijn, Tom

    2015-03-31

    The vibrational behavior of heavy substitutional impurities (M=Ir,Os) in Fe1-xMxSi (x = 0, 0.02, 0.04, 0.1) was investigated with a combination of inelastic neutron scattering (INS), transport measurements, and first-principles simulations. In this paper, our INS measurements on single-crystals mapped the four-dimensional dynamical structure factor, S(Q;E), for several compositions and temperatures. Our results show that both Ir and Os impurities lead to the formation of a weakly dispersive resonance vibrational mode, in the energy range of the acoustic phonon dispersions of the FeSi host. We also show that Ir doping, which introduces free carriers and increases electron-phonon coupling, leads to softened interatomic force-constants compared to doping with Os, which is isoelectronic to Fe. We analyze the phonon S(Q,E) from INS through a Green's function model incorporating the phonon self-energy based on first-principles density functional theory (DFT) simulations. Calculations of the quasiparticle spectral functions in the doped system reveal the hybridization between the resonance and the acoustic phonon modes. Finally, our results demonstrate a strong interaction of the host acoustic dispersions with the resonance mode, likely leading to the large observed suppression in lattice thermal conductivity.

  2. Structural Analysis of Novel Antiferromagnetic Material CeRu2Al10 and Its Related Compounds under Pressure

    NASA Astrophysics Data System (ADS)

    Kawamura, Yukihiro; Hayashi, Junichi; Takeda, Keiki; Sekine, Chihiro; Tanida, Hiroshi; Sera, Masafumi; Nishioka, Takashi

    2016-04-01

    We performed synchrotron X-ray studies of orthorhombic CeRu2Al10 and its related compounds CeT2Al10 (T = Fe, Os) and RRu2Al10 (R = La, Yb, Lu). The results of the X-ray studies indicate that all of the compounds retain their orthorhombic crystal structures and that their lattice parameters all monotonically decrease with pressure; that is, no structural changes or distortions occur below 10 GPa within the experimental accuracy of this study. In addition, we evaluated the bulk moduli of the compounds, which are mainly affected by the transition metal in RT2Al10 systems. All of the compounds exhibited crystal structures that were harder along the b-axis than along the a- or c-axes. Furthermore, anisotropic shrinkage induced a difference between the physical pressure of CeRu2Al10 and the chemical pressure of Ce(Ru1-xFex)2Al10 (0 ≤ x ≤ 1). Thus, the physical properties of CeRu2Al10 under pressure were observed to be strongly affected by crystal structure shrinkage along the a- and c-axes.

  3. London penetration depth measurements in Ba (Fe1-xTx)2As2(T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors

    SciTech Connect

    Gordon, Ryan T.

    2011-01-01

    The London penetration depth has been measured in various doping levels of single crystals of Ba(Fe1-xTx)2As2 (T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors by utilizing a tunnel diode resonator (TDR) apparatus. All in-plane penetration depth measurements exhibit a power law temperature dependence of the form Δλab(T) = CTn, indicating the existence of low-temperature, normal state quasiparticles all the way down to the lowest measured temperature, which was typically 500 mK. Several different doping concentrations from the Ba(Fe1-xTx)2As2 (T=Co,Ni) systems have been measured and the doping dependence of the power law exponent, n, is compared to results from measurements of thermal conductivity and specific heat. In addition, a novel method has been developed to allow for the measurement of the zero temperature value of the in-plane penetration depth, λab(0), by using TDR frequency shifts. By using this technique, the doping dependence of λab(0) has been measured in the Ba(Fe1-xCox)2As2 series, which has allowed also for the construction of the doping-dependent superfluid phase stiffness, ρs(T) = [λ(0)/λ(T)]2. By studying the effects of disorder on these superconductors using heavy ion irradiation, it has been determined that the observed power law temperature dependence likely arises from pair-breaking impurity scattering contributions, which is consistent with the proposed s±-wave symmetry of the superconducting gap in the dirty scattering limit. This hypothesis is supported by the measurement of an exponential temperature dependence of the penetration depth in the intrinsically clean LiFeAs, indicative of a nodeless superconducting gap.

  4. Influence of the central diamagnetic cyanidometal on the distant magnetic interaction in cyanide-bridged Fe(III)-M(II)-Fe(III) complexes.

    PubMed

    Wang, Yong; Lin, Chensheng; Ma, Xiao; Xue, Zhenzhen; Zhu, Xiaoquan; Cao, Wenhai; Hu, Shengmin; Sheng, Tianlu; Wu, Xintao

    2015-04-28

    To investigate how the central diamagnetic cyanidometal influences the distant magnetic interaction of cyanide-bridged Fe(III)-M(II)-Fe(III) complexes, cis-[Cp(dppe)Fe(II)(NC)M(II)(L)2(CN)Fe(II)(dppe) Cp][PF6]2 (M = Os, L = bpy 1; M = Os, L = phen 2; M = Fe, L = bpy 3; M = Fe, L = phen 4), and their one-electron oxidation products 5–7 and two-electron oxidation products 8–11 were synthesized and fully characterized. The cyclic voltammetry of complexes 1–4 suggests that both NC-Os(II)(L)2-CN and NC-Fe(II)(L)2-CN have electronic communication ability. The electronic absorption spectroscopy suggests the presence of the central M(II) to the terminal Fe(III) and the terminal Fe(II) to the terminal Fe(III) metal to metal charge transfers (MMCTs) in 5-7 and the central M(II) to the terminal Fe(III) MMCTs in 8-11. Moreover, for the two-electron oxidation products the MMCT energy increases with the central metal in the order Fe < Os < Ru. The two-electron oxidation complexes 8 and 9 exhibit a strong antiferromagnetic coupling (J ≈ -26 cm(-1)) between the two distant Fe(III) ions although separated by the diamagnetic cyanidometal NC-Os(II)(L)2-CN bridge. To the best of our knowledge, this is the strongest magnetic coupling between the distant paramagnetic metal ions across a diamagnetic cyanidometal bridge reported by far. For the two-electron oxidation complexes 10 and 11 with the diamagnetic NC-Fe(II)(L)2-CN bridge, however, the distant two Fe(III) ions possess only very weak antiferromagnetic coupling (J = -0.15 and -0.19 cm(-1)). Combined with our previous reported results, it could be found that the magnetic coupling strength between the distant Fe(III) ions increases with the diamagnetic cyanidometal bridge in the order of Fe < Ru < Os.

  5. Ru/FTO: Heterogeneous catalyst for glycerol hydrogenolysis

    NASA Astrophysics Data System (ADS)

    Samad, Wan Zurina; Isahak, Wan Nor Roslam Wan; Liew, Kin Hong; Nordin, Norazzizi; Yarmo, Mohd Ambar; Yusop, Muhammad Rahimi

    2014-09-01

    An introduction of Fluorine-doped tin oxide (FTO) as new catalyst support with Ru metal had enhanced the conversion and selectivity for glycerol hydrogenolysis. A small cluster of Ru were highly dispersed and intercalated over FTO via simple chemical mixture and reduction method. In comparison with various metal (Pd, Os, Cu), Ru/FTO catalyst showed the highest conversion (100%) and highly selectivity of 1,2-propanediol (94%) in the hydrogenolysis of glycerol. The reaction was optimally conducted at 150 °C, 20 bar of H2 pressure and at 8 hours. Ru/FTO catalyst was ascribed as active catalyst due to the amphoteric sites of FTO and small size of Ru metal. This provides high surface concentration of reduction process that involves the chemical bond dissociation in the glycerol hydrogenolysis.

  6. Lattice-distortion Induced Magnetic Transition from Low-temperature Antiferromagnetism to High-temperature Ferrimagnetism in Double Perovskites A2FeOsO6 (A = Ca, Sr).

    PubMed

    Hou, Y S; Xiang, H J; Gong, X G

    2015-08-20

    High-temperature insulating ferrimagnetism is investigated in order to further reveal its physical mechanisms, as well as identify potentially important scientific and practical applications relative to spintronics. For example, double perovskites such as Sr2FeOsO6 and Ca2FeOsO6 are shown to have puzzling magnetic properties. The former is a low-temperature antiferromagnet while the latter is a high-temperature insulating ferrimagnet. In order to understand the underlying mechanisms, we have investigated the frustrated magnetism of A2FeOsO6 by employing density functional theory and maximally-localized Wannier functions. We find lattice distortion enhances the antiferromagnetic nearest-neighboring Fe-O-Os interaction, however weakens the antiferromagnetic interactions via the Os-O-O-Os and Fe-O-Os-O-Fe paths, so is therefore responsible for the magnetic transition from the low-temperature antiferromagnetism to the high-temperature ferrimagnetism as the decrease of the A(2+) ion radii. Also discussed is the 5d(3)-3d(5) superexchange. We propose that such superexchange is intrinsically antiferromagnetic instead of ferromagnetic as previously thought. Our work clearly illustrates the magnetic frustration can be effectively relieved by lattice distortion, thus paving the way for tuning of complex magnetism in yet other 3d-5d (4d) double perovskites.

  7. Lattice-distortion Induced Magnetic Transition from Low-temperature Antiferromagnetism to High-temperature Ferrimagnetism in Double Perovskites A2FeOsO6 (A = Ca, Sr)

    PubMed Central

    Hou, Y. S.; Xiang, H. J.; Gong, X. G.

    2015-01-01

    High-temperature insulating ferrimagnetism is investigated in order to further reveal its physical mechanisms, as well as identify potentially important scientific and practical applications relative to spintronics. For example, double perovskites such as Sr2FeOsO6 and Ca2FeOsO6 are shown to have puzzling magnetic properties. The former is a low-temperature antiferromagnet while the latter is a high-temperature insulating ferrimagnet. In order to understand the underlying mechanisms, we have investigated the frustrated magnetism of A2FeOsO6 by employing density functional theory and maximally-localized Wannier functions. We find lattice distortion enhances the antiferromagnetic nearest-neighboring Fe-O-Os interaction, however weakens the antiferromagnetic interactions via the Os-O-O-Os and Fe-O-Os-O-Fe paths, so is therefore responsible for the magnetic transition from the low-temperature antiferromagnetism to the high-temperature ferrimagnetism as the decrease of the A2+ ion radii. Also discussed is the 5d3-3d5 superexchange. We propose that such superexchange is intrinsically antiferromagnetic instead of ferromagnetic as previously thought. Our work clearly illustrates the magnetic frustration can be effectively relieved by lattice distortion, thus paving the way for tuning of complex magnetism in yet other 3d–5d (4d) double perovskites. PMID:26289139

  8. Lattice-distortion Induced Magnetic Transition from Low-temperature Antiferromagnetism to High-temperature Ferrimagnetism in Double Perovskites A2FeOsO6 (A = Ca, Sr)

    NASA Astrophysics Data System (ADS)

    Hou, Y. S.; Xiang, H. J.; Gong, X. G.

    2015-08-01

    High-temperature insulating ferrimagnetism is investigated in order to further reveal its physical mechanisms, as well as identify potentially important scientific and practical applications relative to spintronics. For example, double perovskites such as Sr2FeOsO6 and Ca2FeOsO6 are shown to have puzzling magnetic properties. The former is a low-temperature antiferromagnet while the latter is a high-temperature insulating ferrimagnet. In order to understand the underlying mechanisms, we have investigated the frustrated magnetism of A2FeOsO6 by employing density functional theory and maximally-localized Wannier functions. We find lattice distortion enhances the antiferromagnetic nearest-neighboring Fe-O-Os interaction, however weakens the antiferromagnetic interactions via the Os-O-O-Os and Fe-O-Os-O-Fe paths, so is therefore responsible for the magnetic transition from the low-temperature antiferromagnetism to the high-temperature ferrimagnetism as the decrease of the A2+ ion radii. Also discussed is the 5d3-3d5 superexchange. We propose that such superexchange is intrinsically antiferromagnetic instead of ferromagnetic as previously thought. Our work clearly illustrates the magnetic frustration can be effectively relieved by lattice distortion, thus paving the way for tuning of complex magnetism in yet other 3d-5d (4d) double perovskites.

  9. Spectroscopy of 98Ru

    NASA Astrophysics Data System (ADS)

    Giannatiempo, A.; Nannini, A.; Perego, A.; Sona, P.

    2016-11-01

    The 98Ru nucleus, populated via the 97Mo(3He,2 n ) reaction, has been investigated by means of K -internal conversion coefficient, γ -ray angular distribution, γ -γ coincidence, and γ -γ angular correlation measurements. The results have led to an improved knowledge of the excitation energy pattern via the identification of new levels and transitions. New information on spin and parities of many levels as well as on mixing ratios of several transitions has been obtained. The presence of large M 1 components in many transitions definitely excludes the possibility of considering 98Ru as a nucleus having a structure very close to the vibrational one and points to the need of an enlarged framework for a successful description.

  10. The "ethics" of RU486.

    PubMed

    Hunt, M

    1993-01-01

    The use of RU-486 to induce abortion represents a new era in reproductive technology and merits ethical attention. The feminists principles of concern for women's well-being, paying attention to the specific needs of women in specific circumstances, and balancing risks and benefits can be applied to an examination of RU-486. RU-486 has invoked the image of women's medical empowerment and has been deemed "the moral property of women." Support for RU-486 has come from major international health and feminist organizations, while the opposition of the anti-choice forces has been matched by that of the Feminist International Network of Resistance to Reproductive and Genetic Engineering. Issues critical to the introduction of RU-486 include 1) access and suitability, 2) whether RU-486 increases women's control over reproduction in a safe manner, and 3) the political problems involved when feminist leaders press for testing and attempt to explain varied and even opposing feminist positions in productive ways.

  11. Precious metal enrichment at low-redox in terrestrial native Fe-bearing basalts investigated using laser-ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Howarth, Geoffrey H.; Day, James M. D.; Pernet-Fisher, John F.; Goodrich, Cyrena A.; Pearson, D. Graham; Luo, Yan; Ryabov, Viktor V.; Taylor, Lawrence A.

    2017-04-01

    Primary native Fe is a rare crystallizing phase from terrestrial basaltic magmas, requiring highly reducing conditions (fO2 Fe alloy liquid. If this liquid also contains sufficient sulfur, it can undergo further division into conjugate Fe-C-rich and a Fe-S-rich immiscible melts that can effectively scavenge the highly siderophile elements (HSE: Re, Au, and the platinum group elements [PGE], Pd, Pt, Rh, Ru, Ir, Os), as well as Ni and Cu, to economic abundances. Three localities are known globally where native Fe bearing mafic rocks occur: (1) Paleocene basalts of Disko Island, West Greenland; (2) a Miocene lava of the Bühl basalts, Germany; and (3) mafic intrusions associated with the Late Permian Siberian flood basalts. In this contribution, we report major- and minor-element compositions and HSE concentrations for the main alloy phases (FeNi metal and cohenite) and sulfide, for all three known global occurrences of native Fe bearing basalt. Total HSE abundances in metal grains, obtained by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), are lowest in the Bühl basalt, (∼0.05 ppm), intermediate in the Disko Island basalts (4-8 ppm), and highest the Siberian Khungtukun and Dzhaltul intrusions (10-30 ppm). These differences demonstrate that, while native Fe formation is the result of carbonaceous crustal assimilation, HSE enrichment is not ubiquitous during this process. The Siberian occurrences are characterized by Pt PGE (PPGE: Pt, Pd) enrichment relative to the Ir PGE (IPGE: Rh, Ru, Ir, Os), consistent with models of early stage fractionation of olivine, chromite and metallic IPGE in staging magma reservoirs, prior to the addition of C-rich crustal materials in the shallow crust. Relative to Noril'sk Ni-Cu-PGE sulfide ores

  12. Ru-Containing Magnetically Recoverable Catalysts: A Sustainable Pathway from Cellulose to Ethylene and Propylene Glycols.

    PubMed

    Manaenkov, Oleg V; Mann, Joshua J; Kislitza, Olga V; Losovyj, Yaroslav; Stein, Barry D; Morgan, David Gene; Pink, Maren; Lependina, Olga L; Shifrina, Zinaida B; Matveeva, Valentina G; Sulman, Esther M; Bronstein, Lyudmila M

    2016-08-24

    Biomass processing to value-added chemicals and biofuels received considerable attention due to the renewable nature of the precursors. Here, we report the development of Ru-containing magnetically recoverable catalysts for cellulose hydrogenolysis to low alcohols, ethylene glycol (EG) and propylene glycol (PG). The catalysts are synthesized by incorporation of magnetite nanoparticles (NPs) in mesoporous silica pores followed by formation of 2 nm Ru NPs. The latter are obtained by thermal decomposition of ruthenium acetylacetonate in the pores. The catalysts showed excellent activities and selectivities at 100% cellulose conversion, exceeding those for the commercial Ru/C. High selectivities as well as activities are attributed to the influence of Fe3O4 on the Ru(0)/Ru(4+) NPs. A facile synthetic protocol, easy magnetic separation, and stability of the catalyst performance after magnetic recovery make these catalysts promising for industrial applications.

  13. Superconductivity at 3.1 K in the orthorhombic ternary silicide ScRuSi

    NASA Astrophysics Data System (ADS)

    Ruan, Bin-Bin; Wang, Xiao-Chuan; Yu, Jia; Pan, Bo-Jin; Mu, Qing-Ge; Liu, Tong; Chen, Gen-Fu; Ren, Zhi-An

    2017-02-01

    We report the synthesis, crystal structure, superconductivity and physical property characterizations of the ternary equiatomic compound ScRuSi. Polycrystalline samples of ScRuSi were prepared by an arc-melting method. The as-prepared samples were identified as the orthorhombic Co2P-type o-ScRuSi by powder x-ray diffraction analysis. Electrical resistivity measurements show o-ScRuSi to be a metal which superconducts below a T c of 3.1 K; the upper critical field μ 0 H c2(0) is estimated to be 0.87 T. The magnetization and specific heat measurements confirm the bulk type-II superconductivity in o-ScRuSi, with a specific heat jump within the BCS weak coupling limit. o-ScRuSi is the first Co2P-type superconductor to contain scandium. After annealing at 1273 K for a week, o-ScRuSi transforms into hexagonal Fe2P-type h-ScRuSi, which is a Pauli-paramagnetic metal with no superconductivity observed above 1.8 K.

  14. High resolution spectroscopy of 102Ru(d, p) 103Ru and 104Ru(p, d) 103Ru reactions

    NASA Astrophysics Data System (ADS)

    Berg, G. P. A.; Demarteau, M.; Hardt, A.; Hürlimann, W.; Martin, S. A.; Meissburger, J.; Oelert, W.; Seyfarth, H.; Styczen, B.; Köhler, M.; Oelrich, I.; Scheerer, J.

    1982-04-01

    The high resolution magnetic spectrometer BIG KARL was used to investigate the low-lying states of 103Ru by 102Ru(d, p) and 104Ru(p,d) reactions at Ed = 45 MeV andEp = 29 MeV. The resolution of {ΔE}/{E} = (1.7-2.5) × 10 -4 was sufficient to separate most of the known states up to Ex = 1 MeV excitation energy. For these levels differential cross sections have been measured in the range of θ lab = 4°-43°. A DWBA analysis has been employed in order to determine orbital angular momenta and obtain spectroscopic factors. These were used to make a number of tentative spin and parity assignments. In addition several weakly excited states in 103Ru could be identified and excitation energies have been determined to about ±2 keV.

  15. Bulk modulus and specific heat of B-site doped (La{sub 0.3}Pr{sub 0.7}){sub 0.65}Ca{sub 0.35}Mn{sub 1−x}B{sub x}O{sub 3} (B=Fe, Cr, Ru, Al, Ga)

    SciTech Connect

    Srivastava, Archana; Thakur, Rasna; Gaur, N. K.

    2014-04-24

    Specific heat (C{sub p}) thermal expansion (α) and Bulk modulus (B{sub T}) of lightly doped Rare Earth manganites (La{sub 0.3}Pr{sub 0.7}){sub 0.65}Ca{sub 0.35}Mn{sub 1−x}B{sub x}O{sub 3} (B{sup 3+} = Fe{sup 3+},Cr{sup 3+},Ga{sup 3+},Al{sup 3+},Ru4+); (0.3Fe{sub 0.03}O{sub 3} as a function of temperature (10K≤T≤ 200K) is found to be in agreement with the published data. The trend of variation of Debye temperature with B-site cationic radius is predicted probably for the first time for the B-site doped rare earth manganites.

  16. CO chemisorption and dissociation at high coverages during CO hydrogenation on Ru catalysts.

    PubMed

    Loveless, Brett T; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-04-24

    Density functional theory (DFT) and infrared spectroscopy results are combined with mechanism-based rate equations to assess the structure and thermodynamics of chemisorbed CO (CO*) and its activation during Fischer-Tropsch synthesis (FTS). CO* binding becomes weaker with increasing coverage on Ru(0001) and Ru201 clusters, but such decreases in binding energy occur at higher coverages on Ru201 clusters than on Ru(0001) surfaces (CO*/Ru = 1.55 to 0.75); such differences appear to reflect weaker repulsive interactions on the curved surfaces prevalent on small Ru201 clusters. Ru201 clusters achieve stable supramonolayer coverages (CO*/Ru > 1) by forming geminal dicarbonyls at low-coordination corner/edge atoms. CO* infrared spectra on Ru/SiO2 (~7 nm diameter) detect mobile adlayers that anneal into denser structures at saturation. Mechanism-based FTS rate equations give activation energies that reflect the CO*-saturated surfaces prevalent during catalysis. DFT-derived barriers show that CO* predominantly reacts at (111) terraces via H-assisted reactions, consistent with measured effects of H2 and CO pressures and cluster size effects on rates and O-rejection selectivities. Barriers are much higher for unassisted CO* dissociation on (111) terraces and low-coordination atoms, including step-edge sites previously proposed as active sites for CO* dissociation during FTS. DFT-derived barriers indicate that unassisted CO* dissociation is irreversible, making such steps inconsistent with measured rates. The modest activation barriers of H-assisted CO* dissociation paths remove a requirement for special low-coordination sites for unassisted CO* activation, which is inconsistent with higher rates on larger clusters. These conclusions seem generally applicable to Co, Fe, and Ru catalysts, which show similar FTS rate equations and cluster size effects. This study also demonstrates the feasibility and relevance of DFT treatments on the curved and crowded cluster surfaces where

  17. The series of carbon-chain complexes {Ru(dppe)Cp*}₂{μ-(C≡C)x} (x = 4–8, 11): Synthesis, structures, properties and some reactions

    SciTech Connect

    Bruce, Michael I.; Cole, Marcus L.; Ellis, Benjamin G.; Gaudio, Maryka; Nicholson, Brian K.; Parker, Christian R.; Skelton, Brian W.; White, Allan H.

    2015-01-28

    The construction of a series of compounds {Ru(dppe)Cp*}2(μ-C2x) (Ru*-C2x-Ru*, x = 4–8, 11)) is described. A direct reaction between RuCl(dppe)Cp* and Me3Si(Ctriple bond; length of mdashC)4SiMe3 afforded Ru*-C8-Ru* in 89% yield. The Pd(0)/Cu(I)-catalysed coupling of Ru{Ctriple bond; length of mdashCCtriple bond; length of mdashCAu(PPh3)}(dppe)Cp*Ru*-C4-Au (2 equiv.) with diiodoethyne gave Ru*-C10-Ru* (64%), or of 1 equiv. with I(Ctriple bond; length of mdashC)3I gave Ru*-C14-Ru* (36%); similarly, Ru{(Ctriple bond; length of mdashC)4Au(PPh3)}(dppe)Cp*Ru*-C8-Au and I(Ctriple bond; length of mdashC)3I gave Ru*-C22-Ru* (12%). Desilylation (TBAF) of Ru{(Ctriple bond; length of mdashC)xSiMe3}(dppe)Cp*Ru*-C2x-Si (x = 3, 4) followed by oxidative coupling [Cu(OAc)2/py] gave Ru*-C12-Ru* (82%) and Ru*-C16-Ru* (58%), respectively. Similar oxidative coupling of Ru(Ctriple bond; length of mdashCCtriple bond; length of mdashCH)(dppe)Cp* was a second route to Ru*-C8-Ru* (82%). Appropriate precursors are already known, or obtained by coupling of Ru*-C2x-Si (x = 2, 4) with AuCl(PPh3)/NaOMe [Ru*-C4-Au, 95%; Ru*-C8-Au, 74%] or from Pd(0)/Cu(I) catalysed coupling of Ru*-C2x-Au (x = 2, 3) with I(Ctriple bond; length of mdashC)2SiMe3 (Ru*-C8-Si, 64%; Ru*-C10-Si, 2%). Reactions between Ru*-C2x-Ru* (x = 3, 4) and Fe2(CO)9 gave {Fe3(CO)9}{μ3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]}2Fe(C3-Ru*)2 and {Fe3(CO)9}{μ3-CCtriple bond; length of mdashC[Ru(dppe)Cp*]}{μ3-C(Ctriple bond; length of mdashC)2[Ru(dppe)Cp*]} Fe(C3-Ru*)(C5-Ru*), respectively. The redox properties of the series of complexes with 2x = 2–16 were measured and showed a diminution of the

  18. Effect of Ru thickness on spin pumping in Ru/Py bilayer

    SciTech Connect

    Behera, Nilamani; Singh, M. Sanjoy; Chaudhary, Sujeet; Pandya, Dinesh K. Muduli, P. K.

    2015-05-07

    We report the effect of Ru thickness (t{sub Ru}) on ferromagnetic resonance (FMR) line-width of Ru(t{sub Ru})/Py(23 nm) bilayer samples grown on Si(100)/SiO{sub 2} substrates at room temperature by magnetron sputtering. The FMR line-width is found to vary linearly with frequency for all thicknesses of Ru, indicating intrinsic origin of damping. For Ru thicknesses below 15 nm, Gilbert-damping parameter, α is almost constant. We ascribe this behavior to spin back flow that is operative for Ru thicknesses lower than the spin diffusion length in Ru, λ{sub sd}. For thicknesses >15 nm (>λ{sub sd}), the damping constant increases with Ru thickness, indicating spin pumping from Py into Ru.

  19. Chemical doping effect in the LaRu3Si2 superconductor with a kagome lattice

    NASA Astrophysics Data System (ADS)

    Li, Baoxuan; Li, Sheng; Wen, Hai-Hu

    2016-09-01

    LaRu3Si2 is a superconductor with a kagome lattice and transition temperature of 7 K. By doping different rare-earth and transition-metal elements on the La and Ru sites, the evolution of superconductivity has been extensively investigated. It is found that, except for doping Fe to Ru sites, all other dopants with rare-earth (Y, Lu, and Ce) or transition metals (Ni, Cr, and Cu) seem to suppress superconducting transition temperature in LaRu3Si2 very slowly. The quick suppression of superconductivity by Fe doping can be described by the Abrikosov-Gorkov relation. By fitting and analyzing the magnetic susceptibility data under a high magnetic field with the Curie-Weiss law, we find that the effective magnetic moments for Ni and Cr doped samples are very small, indicating that these ions actually do not behave like strong magnetic scattering centers as Fe ions do in the present environment. Our experiments on systematically doped samples and related analysis indicate that the superconducting gap in LaRu3Si2 has no sign change.

  20. Galactose adsorption on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Alatalo, Matti; Puisto, Mikko

    2014-03-01

    In order to understand the valorisation of biomass, it is essential to study the behavior of sugar molecules on catalytic surfaces. We have studied the adsorption of galactose molecules on the Ru(0001) surface using first principles calculations. We present results for the fully relaxed configurations of the molecule at different adsorption sites. We also compare the effect of the inclusion of the van der Waals interactions on both the energetics of the free galactose molecule and the adsorption energy of galactose on Ru(0001). We compare our results, obtained using periodically repeated supercells, to those obtained with cluster calculations.

  1. Quantifying the Carbon Abundances in the Secondary Stars of SS Cygni, RU Pegasi, and GK Persei

    NASA Astrophysics Data System (ADS)

    Harrison, Thomas E.; Hamilton, Ryan T.

    2015-11-01

    We use a modified version of MOOG to generate large grids of synthetic spectra in an attempt to derive quantitative abundances for three CVs (GK Per, RU Peg, and SS Cyg) by comparing the models to moderate resolution (R ˜ 25,000) K-band spectra obtained with NIRSPEC on Keck. For each of the three systems we find solar, or slightly sub-solar values for [Fe/H], but significant deficits of carbon: for SS Cyg we find [C/Fe] = -0.50, for RU Peg [C/Fe] = -0.75, and for GK Per [C/Fe] = -1.00. We show that it is possible to use lower resolution (R ˜ 2000) spectra to quantify carbon deficits. We examine realistic veiling scenarios and find that emission from H i or CO cannot reproduce the observations.

  2. QUANTIFYING THE CARBON ABUNDANCES IN THE SECONDARY STARS OF SS CYGNI, RU PEGASI, AND GK PERSEI

    SciTech Connect

    Harrison, Thomas E.; Hamilton, Ryan T. E-mail: rthamilton@sofia.usra.edu

    2015-11-15

    We use a modified version of MOOG to generate large grids of synthetic spectra in an attempt to derive quantitative abundances for three CVs (GK Per, RU Peg, and SS Cyg) by comparing the models to moderate resolution (R ∼ 25,000) K-band spectra obtained with NIRSPEC on Keck. For each of the three systems we find solar, or slightly sub-solar values for [Fe/H], but significant deficits of carbon: for SS Cyg we find [C/Fe] = −0.50, for RU Peg [C/Fe] = −0.75, and for GK Per [C/Fe] = −1.00. We show that it is possible to use lower resolution (R ∼ 2000) spectra to quantify carbon deficits. We examine realistic veiling scenarios and find that emission from H i or CO cannot reproduce the observations.

  3. RU-486: a continuing saga.

    PubMed

    1988-12-01

    A month after the approved marketing of RU-486 in France as a nonsurgical option for abortion, the company Roussel-Ulcaf withdrew the product in response to boycott threats and threats to company officials and their families. The government of France approved the drug on an experimental basis under the name of Mifepristone; the conditions of the approval were that the drug had to be used within the 1st 49 days after the 1st day of last menstruation and had to be administered under medical supervision at a hospital with the expertise to perform an abortion. Following trials in France, China, and the United Kingdom, RU-486, when administered in a single dose of 3 pills, was observed to have a 95% success and to be very safe. The international boycott and personal threats propelled a convention of more than 1,000 physicians in the World Congress of Gynecology and Obstetrics in Rio de Janeiro to sign a petition that advocated to Roussel-Uclaf the importance of insuring "that women have access to the benefits of scientific progress." The World Health Organization regretted the withdrawal of the drug as 1 off-shoot of the decision would be that developing companies would not be able to run clinical trials on RU-486. Shortly after the company's decision to remove the drug, the French Minister of Health, Claude Evin, ordered a continuation of experimental trials of RU-486. While no US companies have demonstrated interest in the drug, boycotts and threats exacerbate product liability coverage problems. However, should it prove effective in treating breast cancer, endometriosis or ectopic pregnancy, RU-486 may begin to increase in distribution and use.

  4. Soret separation of highly siderophile elements in Fe-Ni-S melts: Implications for solid metal-liquid metal partitioning

    NASA Astrophysics Data System (ADS)

    Brenan, James M.; Bennett, Neil

    2010-10-01

    Soret separation of melts consisting of Fe (+ 1-10 wt.% Ni) with added C, Si or S and trace highly siderophile elements (HSE; Ru, Rh, Pd, Re, Os, Ir, Pt and Au) was investigated in experiments done at 2 GPa, T hot ~ 2000 °C and T hot-T cold ~ 250 °C. Experiments with added C and Si produced homogeneous samples, whereas those with S resulted in significant compositional gradients, with S enriched at the hot end of the sample, and Fe and HSE enriched at the cold end. The magnitude of the separation of the HSE is not the same for each, but varies in the order (smallest to largest) Pd~AuRu~Pt. We show that the observed distribution of HSE within experiments is consistent with the variation in activity coefficients for these elements as predicted by the non-metal avoidance model of Jones and Malvin (1990). Thus, our results indicate that the melt composition effect on solid metal-liquid metal partitioning can be captured in a single thermal diffusion experiment. The magnitude of the melt composition effect, as judged by the Jones-Malvin interaction parameter, β, varies with metal size in a manner similar to solid metal-liquid metal partition coefficients, suggesting like origins of the HSE "selectivity" for Fe-rich solid or liquid structures.

  5. Constitution and thermodynamics of the Mo-Ru, Mo-Pd, Ru-Pd and Mo-Ru-Pd systems

    NASA Astrophysics Data System (ADS)

    Kleykamp, H.

    1989-09-01

    The constitution of the Mo-Ru, Mo-Pd and Ru-Pd systems was reinvestigated between 800 and 2000°C. The Mo-Ru system is of the eutectic type, a σ-phase Mo 5Ru 3 exists between 1915 and 1143°C. The Mo-Pd system is characterized by an hcp phase Mo 9Pd 11 and by two peritectic reactions, β- Mo( Pd) + L = Mo9Pd11andMo9Pd11 + L = α- Pd( Mo). Mo 9Pd 11 decomposes eutectoidally at 1370°C. The Ru-Pd system is simple peritectic. The continuous series of the hcp solid solutions between Mo 9Pd 11 and ɛ-Ru(Mo, Pd) in the ternary Mo-Ru-Pd system observed at 1700°C are suppressed below 1370°C near the Mo-Pd boundary system by the formation of a narrow α + β + ɛ three-phase field. Relative partial molar Gibbs energies of Mo, Mo and Ru in the respective binary systems and of Mo in the ternary system were measured by the EMF method with a Zr(Ca)O 2 electrolyte. xsΔ ḠMo∞ quantities were evaluated at 1200 K which give -43 kJ/mol Mo in Ru and -94 kJ/mol Mo in Pd at infinite dilution. Gibbs energies of formation of the Mo-Ru and Mo-Pd systems were calculated.

  6. Resistive switching and magnetic behavior of Bi0.8Ba0.2FeO3 / SrRuO3 / SrTiO3 films: role of thickness-dependent strain

    NASA Astrophysics Data System (ADS)

    Vagadia, Megha; Ravalia, Ashish; Trivedi, Priyanka; Jethva, Sadaf; Katba, Savan; Kuberkar, D. G.

    2016-05-01

    The thickness-dependent resistive switching and magnetic behavior of Bi0.8Ba0.2FeO3/SRO/STO (1 0 0) films have been studied in the context of strain modifications introduced by varying the film thickness. Generation of misfit dislocation results in strain relaxation with an increase in film thickness. All films (50, 100 and 200 nm) show hysteresis in I-V behavior at room temperature with applied voltage V max  =  ±5 V. Fitting of I-V data suggests that trap-controlled SCLC governs the conduction in HRS in the 50 nm film while in the 100 nm and 200 nm films, the charge transport mechanism is ohmic-type throughout the applied field. The ON/OFF switching ratio and current retention performance decrease with an increase in film thickness, suggesting that substrate-induced strain and interface modifications play an important role in governing the resistive switching mechanism in Bi0.8Ba0.2FeO3 films. A film with lower thickness ~50 nm is found to exhibit the highest magnetization which may be attributed to the increase in oxygen vacancies and compressive strain.

  7. Superconducting transition of Ru in SQUIDs with Nb/Ru/Sr2RuO4 junctions

    NASA Astrophysics Data System (ADS)

    Nago, Y.; Ishiguro, R.; Sakurai, T.; Yakabe, M.; Nakamura, T.; Yonezawa, S.; Kashiwaya, S.; Takayanagi, H.; Maeno, Y.

    2014-12-01

    We have measured transport properties and magnetic responses of direct current superconducting quantum interference devices(dc-SQUIDs) with Nb/Ru/Sr2RuO4 junctions on the same Ru inclusion of a Sr2RuO4-Ru eutectic crystal. We observed a superconducting transition of the Ru at 0.50 K and another transition with anomalous interference patterns of the SQUID at 0.40 K. The second transition led to change of the SQUID structure due to energy competition of alternative supercurrent paths. Phase shifts of the peak of the Fraunhofer diffraction pattern were observed below the transition temperatures, implying topological effects due to a chiral p-wave state or its competition with a s-wave state.

  8. Geochemistry and Re-Os geochronology of the organic-rich sedimentary rocks in the Jingtieshan Fe-Cu deposit, North Qilian Mountains, NW China

    NASA Astrophysics Data System (ADS)

    Yang, Xiuqing; Zhang, Zuoheng; Li, Chao; Duan, Shigang; Jiang, Zongsheng

    2016-04-01

    The Jingtieshan Group in the North Qilian Mountains, NW China, is dominantly composed of banded iron formations (BIFs), copper deposits and organic-rich sedimentary rocks (ORS, carbonaceous phyllite). X-ray diffraction analysis of the ORS shows the mineral assemblage to be quartz + clay minerals. The total organic carbon contents show a range of 0.44-1.72%. Here we present the results of the geochemistry and Re-Os geochronology of the ORS from the Jingtieshan Group. The high values of Chemical Index of Alteration (CIA), Chemical Index of Weathering (CIW), Plagioclase Index of Alteration (PIA), and Th/U ratio, indicate intense weathering. The Al2O3/TiO2, Zr/Sc, Th/Sc, La/Th ratios, high rare earth elements abundances, light rare earth elements enrichment (normalized to chondrite), and distinctly negative Eu anomalies, suggest that the Jingtieshan Group ORS were derived mainly from felsic volcanic units. The new Re-Os isochron age of 1308 ± 100 Ma (2σ, n = 6, MSWD = 23) broadly overlap with the previous published ages determined using Sm-Nd and U-Pb isotope systems. The new age represents the depositional age of the Jingtieshan Group, as well that of BIF in the Jingtieshan area. Furthermore, the initial 187Os/188Os ratios (0.44 ± 0.07) indicate that the Os in the seawater was dominantly derived from hydrothermal fluids (∼75%). The Ce anomaly (Ce/Ce∗ = 0.95-1.00) and V/(V + Ni) ratios (0.71-0.86), as well as the lack of enrichment in redox-sensitive trace elements such as U, V, Zn, Pb, Cu, Ni, Cr, Co and Mn, together with the presence of overlying BIF, suggest that the Jingtieshan area represents a ferruginous deep-water succession. This, and intense submarine hydrothermal activities contributed to the deposition of the Jingtieshan BIF.

  9. Spectroscopic, Electrochemical and Computational Characterisation of Ru Species Involved in Catalytic Water Oxidation: Evidence for a [Ru(V) (O)(Py2 (Me) tacn)] Intermediate.

    PubMed

    Casadevall, Carla; Codolà, Zoel; Costas, Miquel; Lloret-Fillol, Julio

    2016-07-11

    A new family of ruthenium complexes based on the N-pentadentate ligand Py2 (Me) tacn (N-methyl-N',N''-bis(2-picolyl)-1,4,7-triazacyclononane) has been synthesised and its catalytic activity has been studied in the water-oxidation (WO) reaction. We have used chemical oxidants (ceric ammonium nitrate and NaIO4 ) to generate the WO intermediates [Ru(II) (OH2 )(Py2 (Me) tacn)](2+) , [Ru(III) (OH2 )(Py2 (Me) tacn)](3+) , [Ru(III) (OH)(Py2 (Me) tacn)](2+) and [Ru(IV) (O)(Py2 (Me) tacn)](2+) , which have been characterised spectroscopically. Their relative redox and pH stability in water has been studied by using UV/Vis and NMR spectroscopies, HRMS and spectroelectrochemistry. [Ru(IV) (O)(Py2 (Me) tacn)](2+) has a long half-life (>48 h) in water. The catalytic cycle of WO has been elucidated by using kinetic, spectroscopic, (18) O-labelling and theoretical studies, and the conclusion is that the rate-determining step is a single-site water nucleophilic attack on a metal-oxo species. Moreover, [Ru(IV) (O)(Py2 (Me) tacn)](2+) is proposed to be the resting state under catalytic conditions. By monitoring Ce(IV) consumption, we found that the O2 evolution rate is redox-controlled and independent of the initial concentration of Ce(IV) . Based on these facts, we propose herein that [Ru(IV) (O)(Py2 (Me) tacn)](2+) is oxidised to [Ru(V) (O)(Py2 (Me) tacn)](2+) prior to attack by a water molecule to give [Ru(III) (OOH)(Py2 (Me) tacn)](2+) . Finally, it is shown that the difference in WO reactivity between the homologous iron and ruthenium [M(OH2 )(Py2 (Me) tacn)](2+) (M=Ru, Fe) complexes is due to the difference in the redox stability of the key M(V) (O) intermediate. These results contribute to a better understanding of the WO mechanism and the differences between iron and ruthenium complexes in WO reactions.

  10. Pressure Induced Enhancement of Superconductivity in LaRu2P2.

    PubMed

    Li, Baoxuan; Lu, Pengchao; Liu, Jianzhong; Sun, Jian; Li, Sheng; Zhu, Xiyu; Wen, Hai-Hu

    2016-04-18

    To explore new superconductors beyond the copper-based and iron-based systems is very important. The Ru element locates just below the Fe in the periodic table and behaves like the Fe in many ways. One of the common thread to induce high temperature superconductivity is to introduce moderate correlation into the system. In this paper, we report the significant enhancement of superconducting transition temperature from 3.8 K to 5.8 K by using a pressure only of 1.74 ± 0.05 GPa in LaRu2P2 which has an iso-structure of the iron-based 122 superconductors. The ab-initio calculation shows that the superconductivity in LaRu2P2 at ambient pressure can be explained by the McMillan's theory with strong electron-phonon coupling. However, it is difficult to interpret the enhancement of Tc versus pressure within this picture. Detailed analysis of the pressure induced evolution of resistivity and upper critical field Hc2(T) reveals that the increase of Tc with pressure may be accompanied by the involvement of extra electron-boson interaction. This suggests that the Ru-based system has some commonality as the Fe-based superconductors.

  11. Pressure Induced Enhancement of Superconductivity in LaRu2P2

    PubMed Central

    Li, Baoxuan; Liu, Jianzhong; Sun, Jian; Li, Sheng; Zhu, Xiyu; Wen, Hai-Hu

    2016-01-01

    To explore new superconductors beyond the copper-based and iron-based systems is very important. The Ru element locates just below the Fe in the periodic table and behaves like the Fe in many ways. One of the common thread to induce high temperature superconductivity is to introduce moderate correlation into the system. In this paper, we report the significant enhancement of superconducting transition temperature from 3.8 K to 5.8 K by using a pressure only of 1.74 ± 0.05 GPa in LaRu2P2 which has an iso-structure of the iron-based 122 superconductors. The ab-initio calculation shows that the superconductivity in LaRu2P2 at ambient pressure can be explained by the McMillan’s theory with strong electron-phonon coupling. However, it is difficult to interpret the enhancement of Tc versus pressure within this picture. Detailed analysis of the pressure induced evolution of resistivity and upper critical field Hc2(T) reveals that the increase of Tc with pressure may be accompanied by the involvement of extra electron-boson interaction. This suggests that the Ru-based system has some commonality as the Fe-based superconductors. PMID:27086696

  12. Pressure Induced Enhancement of Superconductivity in LaRu2P2

    NASA Astrophysics Data System (ADS)

    Li, Baoxuan; Lu, Pengchao; Liu, Jianzhong; Sun, Jian; Li, Sheng; Zhu, Xiyu; Wen, Hai-Hu

    2016-04-01

    To explore new superconductors beyond the copper-based and iron-based systems is very important. The Ru element locates just below the Fe in the periodic table and behaves like the Fe in many ways. One of the common thread to induce high temperature superconductivity is to introduce moderate correlation into the system. In this paper, we report the significant enhancement of superconducting transition temperature from 3.8 K to 5.8 K by using a pressure only of 1.74 ± 0.05 GPa in LaRu2P2 which has an iso-structure of the iron-based 122 superconductors. The ab-initio calculation shows that the superconductivity in LaRu2P2 at ambient pressure can be explained by the McMillan’s theory with strong electron-phonon coupling. However, it is difficult to interpret the enhancement of Tc versus pressure within this picture. Detailed analysis of the pressure induced evolution of resistivity and upper critical field Hc2(T) reveals that the increase of Tc with pressure may be accompanied by the involvement of extra electron-boson interaction. This suggests that the Ru-based system has some commonality as the Fe-based superconductors.

  13. Many metals make the cut: quaternary rare-earth germanides RE4M2InGe4 (M = Fe, Co, Ni, Ru, Rh, Ir) and RE4RhInGe4 derived from excision of slabs in RE2InGe2.

    PubMed

    Oliynyk, Anton O; Stoyko, Stanislav S; Mar, Arthur

    2015-03-16

    The formation of quaternary rare-earth (RE) germanides containing transition metals (M's) from groups 6 to 10 was investigated through arc-melting and annealing reactions at 800 °C; about 50 new compounds were obtained. These include several new series of quaternary germanides RE4M2InGe4 (M = Fe, Co, Ru, Rh, Ir), previously known only for M = Mn and Ni; additional members of RE4Ni2InGe4 extended to other RE substituents; and a different but closely related series RE4RhInGe4. Detailed crystal structures were determined by single-crystal X-ray diffraction studies for 20 compounds. Monoclinic structures in space group C2/m are adopted by RE4M2InGe4 (Ho4Ni2InGe4-type, a = 15.1-16.5 Å, b = 4.1-4.4 Å, c = 6.9-7.3 Å, β = 106.2-108.6°) and RE4RhInGe4 (own type, a = 20.0-20.2 Å, b = 4.2-4.3 Å, c = 10.1-10.2 Å, β = 105.0-105.3°). Both structures contain frameworks built from MGe4 tetrahedra, InGe4 square planes, and Ge2 dimers, delimiting tunnels occupied by RE atoms. These structures can also be derived by cutting slabs along different directions from the more symmetrical RE2InGe2 structure. Although the Ge2 dimers are relatively invariant, the InGe4 square planes can undergo distortion to form two sets of short versus long In-Ge distances. This distortion results from a competition between M-Ge bonding in the MGe4 tetrahedra and In-Ge bonding in the InGe4 square planes.

  14. Study of the double beta decays of 96Ru and 104Ru.

    PubMed

    Andreotti, Erica; Hult, Mikael; Marissens, Gerd; de Orduña, Raquel González; Vermaercke, Peter

    2012-09-01

    In this work we present new improved experimental limits for the partial half-lives of the double beta processes of (96)Ru and (104)Ru, obtained by means of a γ-ray spectrometry measurement. A disc of metallic Ru of natural isotopic abundance was sandwiched between two HPGe-detectors in the 225 m deep underground laboratory HADES. After 108 days of measurement, the lower bounds for the partial half-lives were up to 6.9×10(19) yr for (96)Ru and 1.9×10(20) yr for (104)Ru.

  15. Atomistic Modeling of RuAl and (RuNi) Al Alloys

    NASA Technical Reports Server (NTRS)

    Gargano, Pablo; Mosca, Hugo; Bozzolo, Guillermo; Noebe, Ronald D.; Gray, Hugh R. (Technical Monitor)

    2002-01-01

    Atomistic modeling of RuAl and RuAlNi alloys, using the BFS (Bozzolo-Ferrante-Smith) method for alloys is performed. The lattice parameter and energy of formation of B2 RuAl as a function of stoichiometry and the lattice parameter of (Ru(sub 50-x)Ni(sub x)Al(sub 50)) alloys as a function of Ni concentration are computed. BFS based Monte Carlo simulations indicate that compositions close to Ru25Ni25Al50 are single phase with no obvious evidence of a miscibility gap and separation of the individual B2 phases.

  16. Weathering of PGE sulfides and Pt-Fe alloys in the Freetown Layered Complex, Sierra Leone

    NASA Astrophysics Data System (ADS)

    Bowles, John F. W.; Suárez, Saioa; Prichard, Hazel M.; Fisher, Peter C.

    2017-01-01

    Fresh and weathered rocks and saprolite from Horizon B of the Freetown Layered Complex contain platinum-group minerals (PGM). The PGM in the fresh rocks are 1-7 μm across, including cooperite (PtS), isoferroplatinum (Pt3Fe), minor tetraferroplatinum (PtFe), tulameenite (Pt2FeCu), Os-bearing laurite (RuS2), and other base metal-sulfide (BMS)-bearing PGM. The weathered rocks contain fewer of those PGM but a high proportion of disordered Cu-(±Pd)-bearing Pt-Fe alloys. The saprolite hosts scarce, smaller (1-3 μm) ordered PtFe and disordered PtFe3. The Pt-Fe alloys became increasingly Fe rich as weathering proceeded. Pt-Fe oxides appeared during weathering. Copper sulfides associated with the primary PGM and cooperite (with <3% Pd) were destroyed to provide the minor Cu and Pd found in some of the disordered Pt-Fe alloys. Platinum- and Pd-bearing saprolites have retained the original rock fabric and, to a depth of about 2 m, surround residual rocks that show progressive weathering (corestones). Ground water passing through the saprolite has transported Pt and Pd (and probably Au) in solution down slope into saprolite over unmineralized rocks. Transport is marked by changes in the Pt/Pd ratio indicating that the metals have moved independently. Palladium is present in marginally higher concentrations in the deeper saprolite than in the corestones suggesting some retention of Pd in the deeper saprolite. Platinum and Pd are less concentrated in the upper saprolite than the deeper saprolite indicating surface leaching. Alteration occurred over a long period in an organic and microbial rich environment that may have contributed to the leaching and transport of PGE.

  17. Underlayer Effect on Perpendicular Magnetic Anisotropy in Co20Fe60B20\\MgO Films.

    PubMed

    Chen, P J; Iunin, Y L; Cheng, S F; Shull, R D

    2016-07-01

    Perpendicular Magnetic Tunneling Junctions (pMTJs) with Ta\\CoFeB\\MgO have been extensively studied in recent years. However, the effects of the underlayer on the formation of the CoFeB perpendicular magnetic anisotropy (PMA) are still not well understood. Here we report the results of our systematic use of a wide range of elements (Ti, V, Cr, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt and Au) encompassed by columns IVA, VA, VIA, VIIA and VIIIA of the periodic table as the underlayer in a underlayer\\Co20Fe60B20\\MgO stack. Our goals were to survey more elements which could conceivably create a PMA in CoFeB and thereby to explore the mechanisms enabling these underlayers to enhance or create the PMA. We found underlayer elements having both an outer shell of 4d electrons (Zr, Nb Mo, and Pd) and 5d electrons (Hf, Ta, W, Re, Ir, and Pt) resulted in the development of a PMA in the MgO-capped Co20Fe60B20. Hybridization between the 3d electrons of the Fe or Co (in the Co20Fe60B20) at the interface with the 4d or 5d electrons of the underlayer is thought to be the cause of the PMA development.

  18. Underlayer Effect on Perpendicular Magnetic Anisotropy in Co20Fe60B20\\MgO Films

    PubMed Central

    Chen, P.J.; Iunin, Y.L.; Cheng, S.F.; Shull, R.D.

    2016-01-01

    Perpendicular Magnetic Tunneling Junctions (pMTJs) with Ta\\CoFeB\\MgO have been extensively studied in recent years. However, the effects of the underlayer on the formation of the CoFeB perpendicular magnetic anisotropy (PMA) are still not well understood. Here we report the results of our systematic use of a wide range of elements (Ti, V, Cr, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt and Au) encompassed by columns IVA, VA, VIA, VIIA and VIIIA of the periodic table as the underlayer in a underlayer\\Co20Fe60B20\\MgO stack. Our goals were to survey more elements which could conceivably create a PMA in CoFeB and thereby to explore the mechanisms enabling these underlayers to enhance or create the PMA. We found underlayer elements having both an outer shell of 4d electrons (Zr, Nb Mo, and Pd) and 5d electrons (Hf, Ta, W, Re, Ir, and Pt) resulted in the development of a PMA in the MgO-capped Co20Fe60B20. Hybridization between the 3d electrons of the Fe or Co (in the Co20Fe60B20) at the interface with the 4d or 5d electrons of the underlayer is thought to be the cause of the PMA development. PMID:27499549

  19. Lifetime measurements in 100Ru

    NASA Astrophysics Data System (ADS)

    Konstantinopoulos, T.; Petkov, P.; Goasduff, A.; Arici, T.; Astier, A.; Atanasova, L.; Axiotis, M.; Bonatsos, D.; Detistov, P.; Dewald, A.; Eller, M. J.; Foteinou, V.; Gargano, A.; Georgiev, G.; Gladnishki, K.; Gottardo, A.; Harissopulos, S.; Hess, H.; Kaim, S.; Kocheva, D.; Kusoglu, A.; Lagoyannis, A.; Ljungvall, J.; Lutter, R.; Matea, I.; Melon, B.; Mertzimekis, T. J.; Nannini, A.; Petrache, C. M.; Petrovici, A.; Provatas, G.; Reiter, P.; Rocchini, M.; Roccia, S.; Seidlitz, M.; Siebeck, B.; Suzuki, D.; Warr, N.; De Witte, H.; Zerrouki, T.

    2017-01-01

    The nucleus 100Ru appears to be a good candidate for the E(5) critical point symmetry which describes the U(5)-SO(6) shape phase transition. To investigate this point with respect to the electromagnetic transition strengths, lifetime measurements of its yrast states have been performed using the recoil distance Doppler shift technique as well as the Doppler shift attenuation method. As a result, the lifetimes of the yrast 2+, 4+, and 8+ states were determined. The deduced transition strengths are compared to the E(5) predictions as well as to the results of excited Vampir and shell-model calculations.

  20. Distant ultrafast energy transfer in a trimetallic {Ru-Ru-Cr} complex facilitated by hole delocalization.

    PubMed

    Cadranel, Alejandro; Tate, Jaired E; Oviedo, Paola S; Yamazaki, Shiori; Hodak, José H; Baraldo, Luis M; Kleiman, Valeria D

    2017-01-25

    Multi-metallic complexes based on {Ru-Cr}, {Ru-Ru} and {Ru-Ru-Cr} fragments are investigated for their light-harvesting and long-range energy transfer properties. We report the synthesis and characterization of [Ru(tpy)(bpy)(μ-CN)Ru(py)4Cl](2+) and [Ru(tpy)(bpy)(μ-CN)Ru(py)4(μ-NC)Cr(CN)5]. The intercalation of {Ru(II)(py)4} linked by cyanide bridges between {Ru(tpy)(bpy)} and {Cr(CN)5} results in efficient, distant energy transfer followed by emission from the Cr moiety. Characterization of the energy transfer process based on photophysical and ultrafast time-resolved absorption suggests the delocalization of holes in the excited state, providing a pathway for energy transfer between the end moieties. The proposed mechanism opens the door to utilize this family of complexes as an appealing platform for the design of antenna compounds as the properties of the fragments could be tuned independently.

  1. Theoretical calculations for structural, elastic, and thermodynamic properties of RuN{sub 2} under high pressure

    SciTech Connect

    Dong, Bing; Zhou, Xiao-Lin E-mail: lkworld@126.com; Chang, Jing; Liu, Ke E-mail: lkworld@126.com

    2014-08-07

    The structural and elastic properties of RuN{sub 2} were investigated through the first-principles calculation using generalized gradient approximation (GGA) and local density approximation (LDA) within the plane-wave pseudopotential density functional theory. The obtained equilibrium structure and mechanical properties are in excellent agreement with other theoretical results. Then we compared the elastic modulus of RuN{sub 2} with several other isomorphic noble metal nitrides. Results show that RuN{sub 2} can nearly rival with OsN{sub 2} and IrN{sub 2}, which indicate RuN{sub 2} is a potentially ultra-incompressible and hard material. By the elastic stability criteria, it is predicted that RuN{sub 2} is stable in our calculations (0–100 GPa). The calculated B/G ratios indicate that RuN{sub 2} possesses brittle nature at 0 GPa and when the pressure increases to 13.4 GPa (for LDA) or 20.8 GPa (for GGA), it begins to prone to ductility. Through the quasi-harmonic Debye model, we also investigated the thermodynamic properties of RuN{sub 2}.

  2. Quantitative photochemical formation of [Ru(tpy)(bpy)H]+.

    PubMed

    Matsubara, Yasuo; Konno, Hideo; Kobayashi, Atsuo; Ishitani, Osamu

    2009-11-02

    Quantitative photochemical production of [Ru(tpy)(bpy)H](+) (Ru-H(+)) was achieved by irradiation of [Ru(tpy)(bpy)(DMF)](2+) (Ru-DMF(2+); DMF = N,N-dimethylformamide) in a tetrahydrofuran (THF) solution containing excess triethylamine (NEt(3)). The mechanism of the Ru-H(+) formation was investigated in detail. A photochemical ligand substitution reaction of Ru-DMF(2+) in THF proceeded to give [Ru(tpy)(bpy)(THF)](2+) (Ru-THF(2+)) with a quantum yield of (7.6 +/- 0.7) x 10(-2). In the presence of NEt(3), a similar photochemical ligand substitution reaction also proceeded quickly, but the products were an equilibrium mixture of Ru-THF(2+) and [Ru(tpy)(bpy)(NEt(3))](2+) (Ru-NEt(3)(2+)) with a considerable amount of Ru-H(+) even in the first stage of the photochemical reaction. The equilibrium constant between Ru-THF(2+) and Ru-NEt(3)(2+) was determined as 6.9 +/- 2.1. Irradiation to Ru-NEt(3)(2+) gave Ru-H(+) with a quantum yield of (9.1 +/- 0.5) x 10(-3). An important intermediate, Ru-NEt(3)(2+), was isolated, and its properties were investigated in detail.

  3. The structure and mechanical properties of Ru-Cu and Ru-Ti nanolayer composites

    SciTech Connect

    Kung, H.; Nastasi, M.; Jervis, T.R.; Hubbard, K.; Mitchell, T.E.; Messner, R.M.; Embury, J.D.

    1993-06-01

    Multilayers of Ru-Cu and Ru-Ti have been prepared by electron beam evaporation technique. One set of composites has Ru thickness varying from 250 to 2500{Angstrom} alternating with Cu or Ti of 15{Angstrom}. The other set has 250{Angstrom} of Ru and the Cu or Ti layer varies between 15 and 200{Angstrom}. Nanoindentation measurements show that there is no significant change in hardness as either Ru or Cu/Ti thickness varies. However, the Ru-Cu multilayer has twice the hardness of the Ru-Ti system. The strengthening mechanism proposed by Koehler predicts that Ru-Ti composites would have a higher strength than Ru-Cu due to larger modulus difference between Ru and Ti. Discrepancy between prediction and experiment suggests that other strengthening mechanism(s) may be operating. We have proposed two models based on a ``shear`` mechanism to explain the differences observed between these two systems. Effects of these mechanisms in controlling the deformation process in nanolayer composites are discussed.

  4. Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    SciTech Connect

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

    2013-05-30

    Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.

  5. Unoccupied electronic states of Ru(0001)

    NASA Astrophysics Data System (ADS)

    del Campo, Valeria; Correa, Julián-David; Correa-Puerta, Jonathan; Kroeger, Daniel; Häberle, Patricio

    2016-11-01

    This report presents a combined theoretical and experimental description of the unoccupied electronic states of Ru(0001), along the Γ̅M̅ high symmetry direction of the Brillouin zone. A direct comparison between angle-resolved inverse photoemission spectroscopy and ab initio calculations of the 3-dimensional (3D) electronic structure of Ru(0001) have been used to determine the energy dispersion and the identification of different states and surface resonances. Both, measurements and calculations, complement previous reports regarding the electronic structure of Ru.

  6. Ru-Ag and Ru-Au dicarbene complexes from an abnormal carbene ruthenium system.

    PubMed

    Bitzer, Mario J; Pöthig, Alexander; Jandl, Christian; Kühn, Fritz E; Baratta, Walter

    2015-07-14

    Reaction of [Ru(OAc)2(PPh3)2] with a P-functionalized imidazolium bromide easily affords a cationic abnormal carbene Ru system. Metalation with Ag2O yields a Ru-Ag complex containing an anionic dicarbene ligand, while subsequent transmetalation with Au(tht)Cl leads to the corresponding Ru-Au system. The bimetallic complexes were characterized by single crystal X-ray diffraction and are the first examples of complexes bearing anionic dicarbene ligands connecting two different d-block elements.

  7. Ru(4+) induced colossal magnetoimpedance in Ru doped perovskite manganite at room temperature.

    PubMed

    Singh, Brajendra

    2016-05-14

    We have demonstrated Ru(4+) induced colossal magnetoimpedance (MI) at room temperature in a ∼1 Tesla magnetic field with a pulsed laser deposited La0.7Ca0.3Mn0.7Ru0.3O3 thin film. This composition showed a large negative ∼12% MI in the low frequency range (<5 MHz), a colossal positive MI > 120% in the intermediate frequency range (5 MHz to ∼13 MHz) and a negative MI in the high frequency range (∼13 MHz to 40 MHz) at room temperature. XAS data confirmed the predominant Ru valence state was 4+ in La0.7Ca0.3Mn0.7Ru0.3O3. Ru(4+) induced (i) charge carrier localization and (ii) reduced hole carrier density enhances the MI in this composition, which otherwise was not significant in mixed valences Mn(3+)/Mn(4+) containing La0.7Ca0.3MnO3 and Ru(4+)/Ru(5+) and Mn(3+)/Mn(4+) mixed valences containing Ru = 0.1 and Ru = 0.2 compositions in La0.7Ca0.3Mn1-xRuxO3 (0 ≤x≤ 0.3) thin films.

  8. Nanoscale decomposition of Nb-Ru-O

    NASA Astrophysics Data System (ADS)

    Music, Denis; Geyer, Richard W.; Chen, Yen-Ting

    2016-11-01

    A correlative theoretical and experimental methodology has been employed to explore the decomposition of amorphous Nb-Ru-O at elevated temperatures. Density functional theory based molecular dynamics simulations reveal that amorphous Nb-Ru-O is structurally modified within 10 ps at 800 K giving rise to an increase in the planar metal - oxygen and metal - metal population and hence formation of large clusters, which signifies atomic segregation. The driving force for this atomic segregation process is 0.5 eV/atom. This is validated by diffraction experiments and transmission electron microscopy of sputter-synthesized Nb-Ru-O thin films. Room temperature samples are amorphous, while at 800 K nanoscale rutile RuO2 grains, self-organized in an amorphous Nb-O matrix, are observed, which is consistent with our theoretical predictions. This amorphous/crystalline interplay may be of importance for next generation of thermoelectric devices.

  9. RU 486 research forges on, despite political hurdles.

    PubMed

    Watanabe, M E

    1994-01-24

    One year after US President Bill Clinton lifted the ban on importation of RU-486, there has been no increase in new research on RU-486 and no increase in the modest amount of RU-486 projects receiving federal support. One theory is that the stigma of RU-486 being an abortifacient carries over to nonabortion related uses. Political and economic pressures within Roussel (the only source of RU-486 and a major supplier of research funds) and its parent firm, Hoechst AG in Berlin, are responsible for the limited research on RU-486. The lack of federal funding on RU-486 may be because many persons perceive RU-486 to be a women's drug and women's diseases receive little federal funding. Nevertheless, some research of RU-486 in nonabortifacient use is occurring. RU-486's ability to interact with progesterone receptors make it a candidate for treating diseases not related to reproductive function. RU-486 also has a strong antiglucocorticoid effect. A Colorado researcher receives funding from the National Cancer Institute (NCI) to examine whether RU-486 can treat breast cancer. A small clinical trial will soon be conducted in California where women with advanced breast cancer will be treated with RU-486. NCI is supporting a Phase III clinical trial of the effects of RU-486 on nonresectable meningiomas (which have many progesterone receptors). A California researcher has conducted several small clinical trials of RU-486's effect on endometriosis and on leiomyoma. The findings so far suggest that RU-486 demonstrates greater improvement with fewer side effects than other drugs. Findings of a clinical trial in Illinois suggest that RU-486 stimulates labor in women with dead fetuses. Some researchers at the National Institute of Child Health and Human Development use RU-486 to treat some patients with a subtype of Cushing's syndrome. A clinical trial is examining whether RU-486 can improve memory in Alzheimer's disease patients.

  10. Differentiation of metal-rich meteoritic parent bodies: I. Measurements of PGEs, Re, Mo, W, and Au in meteoritic Fe-Ni metal

    NASA Astrophysics Data System (ADS)

    Petaev, M. I.; Jacobsen, S. B.

    2004-10-01

    We describe an analytical technique for measurements of Fe, Ni, Co, Mo, Ru, Rh, W, Re, Os, Ir, Pt, and Au in bulk samples of iron meteorites. The technique involves EPMA (Fe, Ni, Co) and LA-ICP-MS analyses of individual phases of iron meteorites, followed by calculation of bulk compositions based on the abundances of these phases. We report, for the first time, a consistent set of concentrations of Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the iron meteorites Arispe, Bennett County, Grant, Cape of Good Hope, Cape York, Carbo, Chinga, Coahuila, Duchesne, Gibeon, Henbury, Mundrabilla, Negrillos, Odessa, Sikhote-Alin, and Toluca and the Divnoe primitive achondrite. The comparison of our LA-ICP-MS data for a number of iron meteorites with high-precision isotope dilution and INAA data demonstrates the good precision and accuracy of our technique. The narrow ranges of variations of Mo and Pd concentrations within individual groups of iron meteorites suggest that these elements can provide important insights into the evolution of parent bodies of iron meteorites. Under certain assumptions, the Mo concentrations can be used to estimate mass fractions of the metal-sulfide cores in the parent bodies of iron meteorites. It appears that a range of Pd variations within a group of iron meteorites can serve as a useful indicator of S content in the core of its parent body.

  11. Reactivity of diaminogermylenes with ruthenium carbonyl: Ru3Ge3 and RuGe2 derivatives.

    PubMed

    Cabeza, Javier A; García-Álvarez, Pablo; Polo, Diego

    2011-07-04

    The nature of the products of the reactions of [Ru(3)(CO)(12)] with diaminogermylenes depends upon the volume and the cyclic or acyclic structure of the latter. Thus, the triruthenium cluster [Ru(3){μ-Ge(NCH(2)CMe(3))(2)C(6)H(4)}(3)(CO)(9)], which has a planar Ru(3)Ge(3) core and an overall C(3h) symmetry, has been prepared in quantitative yield by treating [Ru(3)(CO)(12)] with an excess of the cyclic 1,3-bis(neo-pentyl)-2-germabenzimidazol-2-ylidene in toluene at 100 °C, but under analogous reaction conditions, the acyclic and bulkier Ge(HMDS)(2) (HMDS = N(SiMe(3))(2)) quantitatively leads to the mononuclear ruthenium(0) derivative [Ru{Ge(HMDS)(2)}(2)(CO)(3)]. Mixtures of products have been obtained from the reactions of [Ru(3)(CO)(12)] with the cyclic and very bulky 1,3-bis(tert-butyl)-2-germaimidazol-2-ylidene under various reaction conditions. The Ru(3)Ge(3) and RuGe(2) products reported in this paper are the first ruthenium complexes containing diaminogermylene ligands.

  12. Ru(0) and Ru(II) nitrosyl pincer complexes: structure, reactivity, and catalytic activity.

    PubMed

    Fogler, Eran; Iron, Mark A; Zhang, Jing; Ben-David, Yehoshoa; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Milstein, David

    2013-10-07

    Despite considerable interest in ruthenium carbonyl pincer complexes and their substantial catalytic activity, there has been relatively little study of the isoelectronic ruthenium nitrosyl complexes. Here we describe the synthesis and reactivity of several complexes of this type as well as the catalytic activity of complex 6. Reaction of the PNP ligand (PNP = 2,6-bis((t)Bu2PCH2)pyridine) with RuCl3(NO)(PPh3)2 yielded the Ru(II) complex 3. Chloride displacement by BAr(F-) (BAr(F-) = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) gave the crystallographicaly characterized, linear NO Ru(II) complex 4, which upon treatment with NaBEt3H yielded the Ru(0) complexes 5. The crystallographically characterized Ru(0) square planar complex 5·BF4 bears a linear NO ligand located trans to the pyridilic nitrogen. Further treatment of 5·BF4 with excess LiOH gave the crystallographicaly characterized Ru(0) square planar, linear NO complex 6. Complex 6 catalyzes the dehydrogenative coupling of alcohols to esters, reaching full conversion under air or under argon. Reaction of the PNN ligand (PNN = 2-((t)Bu2PCH2)-6-(Et2NCH2)pyridine) with RuCl3(NO)(H2O)2 in ethanol gave an equilibrium mixture of isomers 7a and 7b. Further treatment of 7a + 7b with 2 equivalent of sodium isopropoxide gave the crystallographicaly characterized, bent-nitrosyl, square pyramidal Ru(II) complex 8. Complex 8 was also synthesized by reaction of PNN with RuCl3(NO)(H2O)2 and Et3N in ethanol. Reaction of the "long arm" PN(2)N ligand (PN(2)N = 2-((t)Bu2PCH2-)-6-(Et2NCH2CH2)pyridine) with RuCl3(NO)(H2O)2 in ethanol gave complex 9, which upon treatment with 2 equiv of sodium isopropoxide gave complex 10. Complex 10 was also synthesized directly by reaction of PN(2)N with RuCl3(NO)(H2O)2 and a base in ethanol. A noteworthy aspect of these nitrosyl complexes is their preference for the Ru(0) oxidization state over Ru(II). This preference is observed with both aromatized and dearomatized pincer ligands, in

  13. Enhanced interlayer exchange coupling in antiferromagnetically coupled ultrathin (Co70Fe30/Pd) multilayers

    NASA Astrophysics Data System (ADS)

    Meng, Zhaoliang; Qiu, Jinjun; Han, Guchang; Teo, Kie Leong

    2015-12-01

    We report the studies of magnetization reversal and magnetic interlayer coupling in synthetic antiferromagnetic (SAF) [Pd/Co70Fe30]9/Ru(tRu)/Pd(tPd)/[Co70Fe30/Pd]9 structure as functions of inserted Pd layer (tPd) and Ru layer (tRu) thicknesses. We found the exchange coupling field (Hex) and perpendicular magnetic anisotropy (PMA) can be controlled by both the tPd and tRu, The Hex shows a Ruderman-Kittel-Kasuya-Yosida-type oscillatory decay dependence on tRu and a maximum interlayer coupling strength Jex = 0.522 erg/cm2 is achieved at tPd + tRu ≈ 0.8 nm in the as-deposited sample. As it is known that a high post-annealing stability of SAF structure is required for magnetic random access memory applications, the dependence of Hex and PMA on the post-annealing temperature (Ta) is also investigated. We found that both high PMA of the top Co70Fe30/Pd multilayer is maintained and Hex is enhanced with increasing Ta up to 350 °C for tRu > 0.7 nm in our SAF structure.

  14. Synthesis of novel Ru2C under high pressure-high temperature conditions.

    PubMed

    Sanjay Kumar, N R; Chandra Shekar, N V; Chandra, Sharat; Basu, Joysurya; Divakar, R; Sahu, P Ch

    2012-09-12

    We report here, for the first time, synthesis of the Fe(2)N type hexagonal phase of ruthenium carbide by a high pressure-high temperature technique using a laser heated diamond anvil cell (LHDAC). The synthesis is carried out by laser heating a mixture of pure elements, Ru and C, at very low 'pressure' of 5 GPa and T ~ 2000 K. The structure of the temperature quenched high pressure phase is characterized by in situ high pressure x-ray diffraction (HPXRD) and is corroborated by ex situ TEM imaging and diffraction, carried out for the first time on the retrieved sample synthesized by LHDAC. The lattice parameters of Ru(2)C at ambient pressure are found to be a = 2.534 Å and c = 4.147 Å. In situ HPXRD studies up to 14.2 GPa yield a bulk modulus of 178(4) GPa. Electronic structure calculations reveal the system to be metallic in nature with a degree of covalence along the Ru-C bond. As ruthenium is isoelectronic to osmium, this result for Ru(2)C has significant implications in the synthesis and study of osmium carbides.

  15. Guided ion beam and theoretical study of the reactions of Os{sup +} with H{sub 2}, D{sub 2}, and HD

    SciTech Connect

    Hinton, Christopher S.; Citir, Murat; Armentrout, P. B.

    2011-12-21

    Reactions of the third-row transition metal cation Os{sup +} with H{sub 2}, D{sub 2}, and HD to form OsH{sup +} (OsD{sup +}) were studied using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Os{sup +} in its {sup 6}D (6s{sup 1}5d{sup 6}) electronic ground state level. Corresponding state-specific reaction cross sections are obtained. The kinetic energy dependences of the cross sections for the endothermic formation of OsH{sup +} and OsD{sup +} are analyzed to give a 0 K bond dissociation energy of D{sub 0}(Os{sup +}-H) = 2.45 {+-} 0.10 eV. Quantum chemical calculations are performed here at several levels of theory, with B3LYP approaches generally overestimating the experimental bond energy whereas results obtained using BHLYP and CCSD(T), coupled-cluster with single, double, and perturbative triple excitations, levels show good agreement. Theory also provides the electronic structures of these species and the potential energy surfaces for reaction. Results from the reactions with HD provide insight into the reaction mechanism and indicate that Os{sup +} reacts via a direct reaction. We also compare this third-row transition metal system with the first-row and second-row congeners, Fe{sup +} and Ru{sup +}, and find that Os{sup +} reacts more efficiently with dihydrogen, forming a stronger M{sup +}-H bond. These differences can be attributed to the lanthanide contraction and relativistic effects.

  16. Influence of steric confinement within zeolite Y on photoinduced energy transfer between [Ru(bpy)3]2+ and iron polypyridyl complexes.

    PubMed

    Sewell, Gavin; Forster, Robert J; Keyes, Tia E

    2008-02-07

    The spectroscopic and photophysical properties of zeolite-Y-entrapped [Ru(bpy)3]2+ co-doped with either [Fe(bpy)3]2+ or [Fe(tpy)2]2+ over a range of iron complex loadings are presented. In solution, [Ru(bpy)3]2+ undergoes efficient bimolecular energy transfer to [Fe(bpy)3]2+, whereas only radiative or trivial energy transfer occurs between [Ru(bpy)3]2+ and [Fe(tpy)2]2+. In sharp contrast, within zeolite Y, both [Fe(bpy)3]2+ and [Fe(tpy)2]2+ were found to effectively quench the donor emission. Fitting the Perrin model to the photophysical data yields an effective quenching radius of 32 and 27 A, respectively, for [Fe(bpy)3]2+ and [Fe(tpy)2]2+. The long-range nature of the quenching suggests Förster energy transfer. Detailed spectroscopic investigations indicate that [Fe(tpy)2]2+ bound within zeolite Y undergoes significant distortion from octahedral geometry. This distortion results in increased oscillator strength and enhanced spectral overlap, between the [Ru(bpy)3]2+ (3)d pi-pi* donor emission and the co-incident acceptor (1)T2-(1)A1 ligand field absorption compared with solution. This turns on an efficient energy transfer to [Fe(tpy)2]2+ within the confinement of the zeolite Y supercage. Overall, this is an interesting example of the ability of the zeolite environment to provoke new photophysical processes not possible in solution.

  17. Al 2O 3 supported Ru catalysts prepared by thermolysis of Ru 3(CO) 12 for catalytic wet air oxidation

    NASA Astrophysics Data System (ADS)

    Yu, Chaoying; Zhao, Peiqing; Chen, Gexin; Hu, Bin

    2011-06-01

    Low loading catalysts Ru/γ-Al 2O 3 and Ru-Ce/γ-Al 2O 3 were prepared by thermolysis of Ru 3(CO) 12 on γ-Al 2O 3. The catalysts were characterized by XPS, XRD and SEM. Two new Ru species (Ru A and Ru B) were detected during the Ru 3(CO) 12 decomposition process due to chemical interaction with the active OH groups on the surface of Al 2O 3 support, and the reduction of them can lead to more dispersed metallic phases. The sample was completely decomposed at 673 K in H 2, and RuO 2 was formed with minor amounts of Ru 0. When the temperature was increased to 773 K to heat the sample, the ratio of Ru 0 to RuO 2 increased. However, after the addition of CeO 2, only RuO 2 was detected on surface. The catalysts exhibited high activities in Catalytic Wet Air Oxidation (CWAO) of different organic compounds at high concentration such as isopropyl alcohol, phenol, acetic acids and N,N-dimethylformamide, which is attributed to the better dispersion of Ru particles and the addition of CeO 2 further enhanced number of effectively active sites on the cluster-derived catalyst surface.

  18. Excited-state spectroscopic investigations of multinuclear complexes based on [Ru(bpy)3](2+) moieties connected to 2,2'-bipyridine and 2,2';6',2''-terpyridine ligands.

    PubMed

    Horvath, Raphael; Lombard, Jean; Leprêtre, Jean-Claude; Collomb, Marie-Noëlle; Deronzier, Alain; Chauvin, Jérôme; Gordon, Keith C

    2013-12-21

    A number of multinuclear assemblies based on [Ru(bpy)3](2+) photosensitive moieties covalently linked to Fe(II), Co(II) or Zn(II) polypyridyl complexes are investigated regarding their initial and thermally equilibrated excited states. Ground state absorption and vibrational spectroscopic techniques are carried out, along with resonance Raman, transient absorption, and time resolved resonance Raman measurements. These methods are also supplemented by computational modelling. In all systems, the results clearly show that under visible irradiation, the substituted bpy linker ligand is involved in the initial (1)MLCT excitation of the Ru(II) subunit. For the Ru(II)/Fe(II) linked assemblies, absorption due to [Ru(bpy)3](2+) and [Fe(tpy)2](2+) subunits are identified to give rise to differing resonance Raman spectra. Transient absorption spectra of complexes containing two [Ru(bpy)3](2+) and one [Fe(tpy)2](2+) subunits show a strong depletion for the [Fe(tpy)2](2+) absorption peaks, which decay on a much faster timescale than the remainder of the transient features. This is consistent with a single excitation of the multimetallic assembly, followed by fast depletion (<10 ns) of the spectral signal from the bpy ligand bound to the Fe subunit. The results are supported by time resolved resonance Raman measurements where a number of features assigned to the linker are found at early time-scales. Using transient absorption this process can be followed for most complexes.

  19. Itinerant Antiferromagnetism in RuO2

    NASA Astrophysics Data System (ADS)

    Berlijn, T.; Snijders, P. C.; Delaire, O.; Zhou, H.-D.; Maier, T. A.; Cao, H.-B.; Chi, S.-X.; Matsuda, M.; Wang, Y.; Koehler, M. R.; Kent, P. R. C.; Weitering, H. H.

    2017-02-01

    Bulk rutile RuO2 has long been considered a Pauli paramagnet. Here we report that RuO2 exhibits a hitherto undetected lattice distortion below approximately 900 K. The distortion is accompanied by antiferromagnetic order up to at least 300 K with a small room temperature magnetic moment of approximately 0.05 μB as evidenced by polarized neutron diffraction. Density functional theory plus U (DFT +U ) calculations indicate that antiferromagnetism is favored even for small values of the Hubbard U of the order of 1 eV. The antiferromagnetism may be traced to a Fermi surface instability, lifting the band degeneracy imposed by the rutile crystal field. The combination of high Néel temperature and small itinerant moments make RuO2 unique among ruthenate compounds and among oxide materials in general.

  20. Neutron-spectroscopic strength in Ru isotopes

    SciTech Connect

    Duarte, J.L.M.; Borello-Lewin, T.; Horodynski-Matsushigue, L.B. )

    1994-08-01

    A systematic, high resolution (6--8 keV) study of ([ital d],[ital t]) reactions on [sup 100,102,104]Ru is reported. Spectroscopic factors were extracted by comparison of experimental angular distributions with distorted wave Born approximation predictions. All of the information for [sup 99]Ru and, for excitation energies above 0.9 MeV, for [sup 103]Ru is new. Most of the strength expected for the 50--82 neutron shell was found. The strength distributions are discussed, also in comparison with the corresponding stripping reactions. Special attention is focused on extremely low and relatively intense [ital l]=3 excitations and on the [ital l]=4 transfer pattern observed.

  1. Skeletal Ru/Cu catalysts prepared from crystalline and quasicrystalline ternary alloy precursors: characterization by X-ray absorption spectroscopy and CO oxidation.

    PubMed

    Highfield, James; Liu, Tao; Loo, Yook Si; Grushko, Benjamin; Borgna, Armando

    2009-02-28

    . Preliminary studies in CO and H(2) oxidation were made in a DRIFTS flow reactor with on-line MS, and their activities and selectivities were compared against skeletal Ru and Cu controls, Ru/Al(2)O(3), and Au/Fe(2)O(3). All samples were active in CO oxidation above approximately 50 degrees C, showing light-off temperatures in the range 60-70 degrees C. Ru(22)Cu(7) and Ru(17)Cu(12.5) also showed good selectivities (vs. H(2) oxidation), attributed tentatively to Ru-modified Cu surfaces of varying thickness. These compositions are promising candidates to test in a (PROX) fuel processor to supply purified (CO-free) H(2) to a PEM fuel cell.

  2. Temperature-induced transformation of electrochemically formed hydrous RuO2 layers over Ru(0001) model electrodes

    NASA Astrophysics Data System (ADS)

    Krause, Philipp P. T.; Camuka, Hava; Leichtweiss, Thomas; Over, Herbert

    2016-07-01

    Hydrous RuO2 reveals excellent performance both as a supercapacitor and as a heterogeneous oxidation catalyst. Molecular understanding of these processes needs, however, a model system with preferably low structural and morphological complexity. This goal is partly accomplished here by using single crystalline Ru(0001) as a template on which hydrous RuO2 is electrochemically formed. The hydrous RuO2 layers on Ru(0001) and their temperature induced transformation under ultra high vacuum (UHV) conditions are comprehensively characterized by scanning electron microscopy and X-ray photoemission spectroscopy. The hydrous RuO2 layer grows with an intricate morphology governed by the presence of step bunching regions of the Ru(0001) surface. Upon annealing to 200 °C in UHV the hydrous RuO2 layer transforms mostly into flat metallic Ru islands and occasionally into (100) and (111) oriented RuO2 particles aligned along the high symmetry direction of Ru(0001).Hydrous RuO2 reveals excellent performance both as a supercapacitor and as a heterogeneous oxidation catalyst. Molecular understanding of these processes needs, however, a model system with preferably low structural and morphological complexity. This goal is partly accomplished here by using single crystalline Ru(0001) as a template on which hydrous RuO2 is electrochemically formed. The hydrous RuO2 layers on Ru(0001) and their temperature induced transformation under ultra high vacuum (UHV) conditions are comprehensively characterized by scanning electron microscopy and X-ray photoemission spectroscopy. The hydrous RuO2 layer grows with an intricate morphology governed by the presence of step bunching regions of the Ru(0001) surface. Upon annealing to 200 °C in UHV the hydrous RuO2 layer transforms mostly into flat metallic Ru islands and occasionally into (100) and (111) oriented RuO2 particles aligned along the high symmetry direction of Ru(0001). Electronic supplementary information (ESI) available. See DOI: 10

  3. The role of the non-magnetic material in spin pumping and magnetization dynamics in NiFe and CoFeB multilayer systems

    NASA Astrophysics Data System (ADS)

    Ruiz-Calaforra, A.; Brächer, T.; Lauer, V.; Pirro, P.; Heinz, B.; Geilen, M.; Chumak, A. V.; Conca, A.; Leven, B.; Hillebrands, B.

    2015-04-01

    We present a study of the effective magnetization M eff and the effective damping parameter α eff by means of ferromagnetic resonance spectroscopy on the ferromagnetic (FM) materials Ni81Fe19 (NiFe) and Co40Fe40B20 (CoFeB) in FM/Pt, FM/NM, and FM/NM/Pt systems with the non-magnetic (NM) materials Ru, Cr, Al, and MgO. Moreover, for NiFe layer systems, the influence of interface effects is studied by way of thickness dependent measurements of M eff and α eff . Additionally, spin pumping in NiFe/NM/Pt is investigated by means of inverse spin Hall effect (ISHE) measurements. We observe a large dependence of M eff and α eff of the NiFe films on the adjacent NM layer. While Cr and Al do not induce a large change in the magnetic properties, Ru, Pt, and MgO affect M eff and α eff in different degrees. In particular, NiFe/Ru and NiFe/Ru/Pt systems show a large perpendicular surface anisotropy and a significant enhancement of the damping. In contrast, the magnetic properties of CoFeB films do not have a large influence of the NM adjacent material and only CoFeB/Pt systems present an enhancement of α eff . However, this enhancement is much more pronounced in NiFe/Pt. By the introduction of the NM spacer material, this enhancement is reduced. Furthermore, a difference in symmetry between NiFe/NM/Pt and NiFe/NM systems in the output voltage signal from the ISHE measurements reveals the presence of spin pumping into the Pt layer in all-metallic NiFe/NM/Pt and NiFe/Pt systems.

  4. Bulk Electronic Structure of Superconducting LaRu2P2 Single Crystals Measured by Soft-X-Ray Angle-Resolved Photoemission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Razzoli, E.; Kobayashi, M.; Strocov, V. N.; Delley, B.; Bukowski, Z.; Karpinski, J.; Plumb, N. C.; Radovic, M.; Chang, J.; Schmitt, T.; Patthey, L.; Mesot, J.; Shi, M.

    2012-06-01

    We present a soft x-ray angle-resolved photoemission spectroscopy (SX-ARPES) study of the stoichiometric pnictide superconductor LaRu2P2. The observed electronic structure is in good agreement with density functional theory (DFT) calculations. However, it is significantly different from its counterpart in high-temperature superconducting Fe pnictides. In particular, the bandwidth renormalization present in the Fe pnictides (˜2-3) is negligible in LaRu2P2 even though the mass enhancement is similar in both systems. Our results suggest that the superconductivity in LaRu2P2 has a different origin with respect to the iron pnictides. Finally, we demonstrate that the increased probing depth of SX-ARPES, compared to the widely used ultraviolet ARPES, is essential in determining the bulk electronic structure in the experiment.

  5. Carbon coated face-centered cubic Ru-C nanoalloys.

    PubMed

    Zhao, Zhisheng; Meng, Chuanmin; Li, Peifang; Zhu, Wenjun; Wang, Qianqian; Ma, Yanming; Shen, Guoyin; Bai, Ligang; He, Hongliang; He, Duanwei; Yu, Dongli; He, Julong; Xu, Bo; Tian, Yongjun

    2014-09-07

    Carbon-encapsulated ruthenium-carbon (Ru-C) nanoalloys were synthesized by dynamic shocks. The Ru-C alloy shows a new fcc structure different from the original hcp structure of metal Ru. This fcc phase is assigned to a Ru32C4 solid solution with a lattice parameter of 3.868(2) Å and a bulk modulus KT0 of 272(12) GPa. The small amount of carbon in the solid solution enhances the thermodynamic and chemical stabilities with respect to pure Ru, as well as induces changes in the electronic properties, which have direct applications in improving the material's catalytic activity and selectivity.

  6. Congress delves into science with RU-486.

    PubMed

    Kaeser, L

    1998-12-01

    In June 1998, a conservative, Republican member of the US House of Representatives attempted to amend the 1999 bill authorizing funding for the US Food and Drug Administration (USFDA) to prevent government funds from being used to test, develop, or approve "any drug for the chemical inducement of abortion." This bill was designed to halt the approval process for RU-486, a drug that was deemed "approvable" by the USFDA in 1996. Arguments mounted against the amendment by medical, health, and research groups stated that 1) RU-486 is an advance because it permits abortions early in pregnancies, 2) it is improper for the US Congress to impose a scientific judgement on the USFDA, and 3) this amendment has adverse implications for a wide range of drugs and devices that might have an abortifacient effect but be approved for other uses. The House of Representatives passed the amendment but the Senate rejected it, and it was deleted from the final version of the legislation. The amendment is expected to resurface next year. The Congressional debate on RU-486 also spilled over into the appointment hearings for the nomination of Jane Henney as USFDA commissioner. During her confirmation process, Henney was grilled about whether she would grant final approval to RU-486. Henney's nomination was approved by committee but has not yet been considered by the full Senate.

  7. Lubiprostone: RU 0211, SPI 0211.

    PubMed

    2005-01-01

    Lubiprostone [RU 0211, SPI 0211] is a bicyclic fatty acid that acts as a chloride channel opener, increasing intestinal water secretion. Lubiprostone, an orally-administered formulation, is one of a series of functional fatty acid compounds discovered by Dr Ryuji Ueno, and is currently undergoing development for the treatment of constipation, constipation-predominant irritable bowel syndrome (IBS-C) and postoperative ileus with Sucampo Pharmaceutical's. Lubiprostone activates a specific chloride channel (CLC2) on cells lining the gut, thereby naturally increasing intestinal fluid secretion. The increased fluid level softens the stool, promotes spontaneous bowel movements, and reduces abdominal discomfort/pain and bloating. The chloride channel is a protein that controls cell membrane transport of chloride ion. Lubiprostone acts on the ClC-2 chloride channel, which is located in the apical intestinal membrane. In November 2004, Takeda Pharmaceuticals entered into a collaboration and licensing agreement for Lubiprostone with Sucampo Pharmaceuticals for the treatment of chronic constipation and constipation-predominant Irritable Bowel Syndrome (c-IBS). Under the terms of the agreement, Takeda received the right to market the product in the US and Canada, while Sucampo reserved the co-promotion rights for these countries. Takeda's wholly-owned US subsidiary, Takeda Pharmaceuticals North America Inc., will sell lubiprostone once the product is approved by the US FDA. Takeda will also receive an option for marketing rights in other territories, including Japan and Europe. Takeda and Sucampo agreed on the exclusive manufacturing and supply of Lubiprostone by R-Tech Ueno, Ltd, a member of the Sucampo Group. Sucampo has the potential to receive up to dollar US 210 million in initial and milestone payments, some of which are contingent upon the successful achievement of several milestones. Takeda will fund a major part of development costs not only for chronic constipation

  8. Heat capacity and heat content measurements on binary compounds in the Ru-Si, Ru-Ge, and Ru-Sn systems

    SciTech Connect

    Kuntz, J.J.; Gachon, J.C.; Feschotte, P.; Perring, L. |

    1997-11-01

    Molar heat capacities of Ru{sub 0.5}Si{sub 0.5} Ru{sub 0.4}Si{sub 0.6}, Ru{sub 0.5}Ge{sub 0.5}, Ru{sub 0.4}Ge{sub 0.6}, Ru{sub 0.4}Sn{sub 0.6}, and Ru{sub 0.3}Sn{sub 0.7} were determined every 10 K by differential scanning calorimetry in the temperature range from 310 to 1080 K. The present results have been fitted by a polynomial function of temperature: C{sub p} = a+bT-cT{sup -2}. Heat contents of the six phases have been verified by drop calorimetry. Standard enthalpies of formation are given for the studied compounds.

  9. Ferromagnetism and Ru-Ru distance in SrRuO3 thin film grown on SrTiO3 (111) substrate

    PubMed Central

    2014-01-01

    Epitaxial SrRuO3 thin films were grown on both (100) and (111) SrTiO3 substrates with atomically flat surfaces that are required to grow high-quality films of materials under debate. The following notable differences were observed in the (111)-oriented SrRuO3 films: (1) slightly different growth mode, (2) approximately 10 K higher ferromagnetic transition temperature, and (3) better conducting behavior with higher relative resistivity ratio, than (100)c-oriented SrRuO3 films. Together with the reported results on SrRuO3 thin films grown on (110) SrTiO3 substrate, the different physical properties were discussed newly in terms of the Ru-Ru nearest neighbor distance instead of the famous tolerance factor. PACS 75.70.Ak; 75.60.Ej; 81.15.Fg PMID:24393495

  10. Thiol, disulfide, and trisulfide complexes of Ru porphyrins: potential models for iron-sulfur bonds in heme proteins.

    PubMed

    Rebouças, Júlio S; Patrick, Brian O; James, Brian R

    2012-02-22

    Thirty-two Ru(porp)L(2) complexes have been synthesized, where porp = the dianion of meso-tetramesitylporphyrin (TMP) or meso-tetrakis(4-methylphenyl)porphyrin (H(2)T-pMe-PP), and L = a thiol, a sulfide, a disulfide, or a trisulfide. Species studied were with RSH [R = Me, Et, (n)Pr, (i)Pr, (t)Bu, Bn (benzyl), and Ph], RSR (R = Me, Bn), RSSR (R = Me, Et, (n)Pr, Bn) and MeSS(t)Bu, and RSSSR (R = Me, Bn). All the species except two, which were the isolated Ru(T-pMe-PP)((t)BuSH)(2) and Ru(TMP)(MeSSMe)(2), were characterized in situ. The disulfide complex was characterized by X-ray analysis. (1)H NMR data for the coordinated thiols are the first reported within metalloporphyrin systems, and are especially informative because of the upfield shifts of the axial sulfur-containing ligands due to the porphyrin π-ring current effect, which is also present in the di- and trisulfide species. The disulfide in the solid state structure of Ru(TMP)(MeSSMe)(2) is η(1)(end-on) coordinated, the first example of such bonding in a nontethered, acyclic dialkyl disulfide; (1)H-(1)H EXSY NMR data in solution show that the species undergoes 1,2-S-metallotropic shifts. Stepwise formation of the bis(disulfide) complex from Ru(TMP)(MeCN)(2) in solution occurs with a cooperativity effect, resembling behavior of Fe(II)-porphyrin systems where crystal field effects dominate, but ligand trans-effects are more likely in the Ru system. The η(1)(end-on) coordination mode is also favored for the trisulfide ligand. Discussed also are the remarkable linear correlations that exist between the ring-current shielding shifts for the axial ligand C(1) protons of Ru(porp)(RS(x)R)(2) and x (the number of S atoms). The Introduction briefly reviews literature on Ru- and Fe porphyrins (including heme proteins) with sulfur-containing ligands or substrates, and relationships between our findings and this literature are discussed throughout the paper.

  11. Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

    2015-07-01

    Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly

  12. Seven new rare-earth transition-metal oxychalcogenides: Syntheses and characterization of Ln{sub 4}MnOSe{sub 6} (Ln=La, Ce, Nd), Ln{sub 4}FeOSe{sub 6} (Ln=La, Ce, Sm), and La{sub 4}MnOS{sub 6}

    SciTech Connect

    Ijjaali, Ismail; Deng Bin; Ibers, James A. . E-mail: ibers@chem.northwestern.edu

    2005-05-15

    The quaternary oxychalcogenides Ln{sub 4}MnOSe{sub 6} (Ln=La, Ce, Nd), Ln{sub 4}FeOSe{sub 6} (Ln=La, Ce, Sm), and La{sub 4}MnOS{sub 6} have been synthesized by the reactions of Ln (Ln=La, Ce, Nd, Sm), M (M=Mn, Fe), Se, and SeO{sub 2} at 1173K for the selenides or by the reaction of La{sub 2}S{sub 3} and MnO at 1173K for the sulfide. Warning: These reactions frequently end in explosions. These isostructural compounds crystallize with two formula units in space group C{sub 6v}{sup 4}-P6{sub 3}mc of the hexagonal system. The cell constants (a, c in A) at 153K are: La{sub 4}MnOSe{sub 6}, 9.7596(3), 7.0722(4); La{sub 4}FeOSe{sub 6}, 9.7388(4), 7.0512(5); Ce{sub 4}MnOSe{sub 6}, 9.6795(4), 7.0235(5); Ce{sub 4}FeOSe{sub 6}, 9.6405(6), 6.9888(4); Nd{sub 4}MnOSe{sub 6}, 9.5553(5), 6.9516(5); Sm{sub 4}FeOSe{sub 6}, 9.4489(5), 6.8784(5); and La{sub 4}MnOS{sub 6}, 9.4766(6), 6.8246(6). The structure of these Ln{sub 4}MOQ{sub 6} compounds comprises a three-dimensional framework of interconnected LnOQ{sub 7} bicapped trigonal prisms, MQ{sub 6} octahedra, and the unusual LnOQ{sub 6} tricapped tetrahedra.

  13. Magnetic phases and structural properties in Co/Ru superlattices

    NASA Astrophysics Data System (ADS)

    Alayo, W.; Tafur, Miguel; Baggio-Saitovitch, E.; Pelegrini, F.; Nascimento, V. P.

    2009-05-01

    We report studies by x-ray diffraction, ferromagnetic resonance (FMR), and x-ray magnetic circular dichroism (XMCD) in Co/Ru superlattices grown by magnetron sputtering. We studied the [Co(50Å)/Ru(tRu)]20 samples, which were deposited at room temperature on Si substrates with the Ru thicknesses, tRu, varying between 9 and 33 Å. The main and secondary uniform absorption modes, observed in the FMR spectra, are associated with the Co/Ru interfaces and the bulk Co regions, respectively. The main mode becomes more intense than the secondary one for increasing tRu. This is attributed to the roughness and/or atomic interdiffusion, which leads, with increasing tRu, to an increasing volume of Co/Ru interfacial regions and a decreasing volume of pure Co regions. The XMCD measurements provide Co spin magnetic moments lower than the bulk Co value, confirming the presence of a Co magnetic region with a lower local effective magnetization attributed to the Co/Ru interfaces.

  14. Laser Spectroscopy of Ruthenium Containing Diatomic Molecules: RuH/D and RuP.

    NASA Astrophysics Data System (ADS)

    Adam, Allan G.; Konder, Ricarda M.; Nickerson, Nicole M.; Linton, Colan; Tokaryk, D. W.

    2015-06-01

    In the last few years, the Cheung group in Hong Kong and the Steimle group in Arizona have successfully studied several ruthenium containing diatomic molecules, RuX (X =C, O, N, B, using the laser-ablation molecular jet technique. Based on this success, the UNB spectroscopy group decided to try and find the optical signatures of other RuX molecules. Using CH_3OH and PH_3 as reactant gases, the RuH and RuP diatomic molecules have been detected in surveys of the 420 - 675 nm spectral region. RuD has also been made using fully deuterated methanol as a reactant. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra for these molecules have also been taken and the analysis is proceeding. The most recent results will be presented. F. Wang et al., Journal of Chemical Physics 139, 174318 (2013). N. Wang et al., Journal of Physical Chemistry A 117, 13279 (2013). T. Steimle et al., Journal of Chemical Physics 119, 12965 (2003). N. Wang et al., Chemical Physics Letters 547, 21 (2012).

  15. Ru-assisted synthesis of Pd/Ru nanodendrites with high activity for ethanol electrooxidation.

    PubMed

    Zhang, Ke; Bin, Duan; Yang, Beibei; Wang, Caiqin; Ren, Fangfang; Du, Yukou

    2015-08-07

    Due to the specific physical and chemical properties of a highly branched noble metal, the controllable synthesis has attracted much attention. This article reports the synthesis of Pd/Ru nanodendrites by a facile method using an oil bath in the presence of polyvinyl pyrrolidone, potassium bromide and ascorbic acid. The morphology, structure, and composition of the as-prepared catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In the electrochemical measurement, the as-prepared Pd7/Ru1 bimetallic nanodendrites provide a large electrochemically active surface area and exhibit high peak current density in the forward scan toward ethanol electrooxidation, which is nearly four times higher than those of a pure Pd catalyst. The as-prepared Pd7/Ru1 catalysts also exhibit significantly enhanced cycling stability toward ethanol oxidation in alkaline medium, which are mainly ascribed to the synergetic effect between Pd and Ru. This indicates that the Pd7/Ru1 catalysts should have great potential applications in direct ethanol fuel cells.

  16. 186Os-187Os and highly siderophile element abundance systematics of the mantle revealed by abyssal peridotites and Os-rich alloys

    NASA Astrophysics Data System (ADS)

    Day, James M. D.; Walker, Richard J.; Warren, Jessica M.

    2017-03-01

    Abyssal peridotites are oceanic mantle fragments that were recently processed through ridges and represent residues of both modern and ancient melting. To constrain the nature and timing of melt depletion processes, and the composition of the mantle, we report high-precision Os isotope data for abyssal peridotites from three ocean basins, as well as for Os-rich alloys, primarily from Mesozoic ophiolites. These data are complemented by whole-rock highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re), trace- and major-element abundances for the abyssal peridotites, which are from the Southwest Indian (SWIR), Central Indian (CIR), Mid-Atlantic (MAR) and Gakkel Ridges. The results reveal a limited role for melt refertilization or secondary alteration processes in modifying abyssal peridotite HSE compositions. The abyssal peridotites examined have experienced variable melt depletion (2% to >16%), which occurred >0.5 Ga ago for some samples. Abyssal peridotites typically exhibit low Pd/Ir and, combined with high-degrees of estimated total melt extraction, imply that they were relatively refractory residues prior to incorporation into their present ridge setting. Recent partial melting processes and mid-ocean ridge basalt (MORB) generation therefore played a limited role in the chemical evolution of their precursor mantle domains. The results confirm that many abyssal peridotites are not simple residues of recent MORB source melting, having a more complex and long-lived depletion history. Peridotites from the Gakkel Ridge, SWIR, CIR and MAR indicate that the depleted MORB mantle has 186Os/188Os of 0.1198356 ± 21 (2SD). The Phanerozoic Os-rich alloys yield an average 186Os/188Os within uncertainty of abyssal peridotites (0.1198361 ± 20). Melt depletion trends defined between Os isotopes and melt extraction indices (e.g., Al2O3) allow an estimate of the primitive mantle (PM) composition, using only abyssal peridotites. This yields 187Os/188Os (0.1292 ± 25), and 186Os

  17. Graphene Growth by Metal Etching on Ru (0001)

    SciTech Connect

    Loginova, Elena; Maier, Sabine; Stass, Ingeborg; Bartelt, Norman; Feibelman, Peter; Salmeron, Miquel; McCarty, Kevin

    2009-09-14

    Low-energy electron microscopy (LEEM) reveals a new mode of graphene growth on Ru(0001) in which Ru atoms from a step edge are injected under a growing graphene sheet. The injected atoms can form under-graphene islands, or incorporate into the topmost Ru layer, thereby increasing its density and forming dislocation networks. Density functional calculations imply that Ru islands nucleated between the graphene layer and the substrate are energetically stable; scanning tunneling microscopy (STM) reveals that dislocation networks exist near step edges.

  18. AuRu/AC as an effective catalyst for hydrogenation reactions

    DOE PAGES

    Villa, Alberto; Chan-Thaw, Carine E.; Campisi, Sebastiano; ...

    2015-03-23

    AuRu bimetallic catalysts have been prepared by sequential deposition of Au on Ru or vice versa obtaining different nanostructures: when Ru has been deposited on Au, a Aucore–Rushell has been observed, whereas the deposition of Au on Ru leads to a bimetallic phase with Ru enrichment on the surface. In the latter case, the unexpected Ru enrichment could be attributed to the weak adhesion of Ru on the carbon support, thus allowing Ru particles to diffuse on Au particles. Both structures result very active in catalysing the liquid phase hydrogenolysis of glycerol and levulinic acid but the activity, the selectivitymore » and the stability depend on the structure of the bimetallic nanoparticles. Ru@Au/AC core–shell structure mostly behaved as the monometallic Ru, whereas the presence of bimetallic AuRu phase in Au@Ru/AC provides a great beneficial effect on both activity and stability.« less

  19. Iron deficiency regulated OsOPT7 is essential for iron homeostasis in rice.

    PubMed

    Bashir, Khurram; Ishimaru, Yasuhiro; Itai, Reiko Nakanishi; Senoura, Takeshi; Takahashi, Michiko; An, Gynheung; Oikawa, Takaya; Ueda, Minoru; Sato, Aiko; Uozumi, Nobuyuki; Nakanishi, Hiromi; Nishizawa, Naoko K

    2015-05-01

    The molecular mechanism of iron (Fe) uptake and transport in plants are well-characterized; however, many components of Fe homeostasis remain unclear. We cloned iron-deficiency-regulated oligopeptide transporter 7 (OsOPT7) from rice. OsOPT7 localized to the plasma membrane and did not transport Fe(III)-DMA or Fe(II)-NA and GSH in Xenopus laevis oocytes. Furthermore OsOPT7 did not complement the growth of yeast fet3fet4 mutant. OsOPT7 was specifically upregulated in response to Fe-deficiency. Promoter GUS analysis revealed that OsOPT7 expresses in root tips, root vascular tissue and shoots as well as during seed development. Microarray analysis of OsOPT7 knockout 1 (opt7-1) revealed the upregulation of Fe-deficiency-responsive genes in plants grown under Fe-sufficient conditions, despite the high Fe and ferritin concentrations in shoot tissue indicating that Fe may not be available for physiological functions. Plants overexpressing OsOPT7 do not exhibit any phenotype and do not accumulate more Fe compared to wild type plants. These results indicate that OsOPT7 may be involved in Fe transport in rice.

  20. Tandem hydroformylation/hydrogenation of alkenes to normal alcohols using Rh/Ru dual catalyst or Ru single component catalyst.

    PubMed

    Takahashi, Kohei; Yamashita, Makoto; Nozaki, Kyoko

    2012-11-14

    The catalyst system for tandem hydroformylation/hydrogenation of terminal alkenes to the corresponding homologated normal alcohol was developed. The reaction mechanism for the Rh/Ru dual catalyst was investigated by real-time IR monitoring experiments and (31)P NMR spectroscopy, which proved the mutual orthogonality of Rh-catalyzed hydroformylation and Ru-catalyzed hydrogenation. Detailed investigation about Ru-catalyzed hydrogenation of undecanal under H(2)/CO pressure clarified different kinetics from the hydrogenation under H(2) and gave a clue to design more active hydrogenation catalysts under H(2)/CO atmosphere. The solely Ru-catalyzed normal selective hydroformylation/hydrogenation is also reported.

  1. Supergene neoformation of Pt-Ir-Fe-Ni alloys: multistage grains explain nugget formation in Ni-laterites

    NASA Astrophysics Data System (ADS)

    Aiglsperger, Thomas; Proenza, Joaquín A.; Font-Bardia, Mercè; Baurier-Aymat, Sandra; Galí, Salvador; Lewis, John F.; Longo, Francisco

    2016-11-01

    Ni-laterites from the Dominican Republic host rare but extremely platinum-group element (PGE)-rich chromitites (up to 17.5 ppm) without economic significance. These chromitites occur either included in saprolite (beneath the Mg discontinuity) or as `floating chromitites' within limonite (above the Mg discontinuity). Both chromitite types have similar iridium-group PGE (IPGE)-enriched chondrite normalized patterns; however, chromitites included in limonite show a pronounced positive Pt anomaly. Investigation of heavy mineral concentrates, obtained via hydroseparation techniques, led to the discovery of multistage PGE grains: (i) Os-Ru-Fe-(Ir) grains of porous appearance are overgrown by (ii) Ni-Fe-Ir and Ir-Fe-Ni-(Pt) phases which are overgrown by (iii) Pt-Ir-Fe-Ni mineral phases. Whereas Ir-dominated overgrowths prevail in chromitites from the saprolite, Pt-dominated overgrowths are observed within floating chromitites. The following formation model for multistage PGE grains is discussed: (i) hypogene platinum-group minerals (PGM) (e.g. laurite) are transformed to secondary PGM by desulphurization during serpentinization; (ii) at the stages of serpentinization and/or at the early stages of lateritization, Ir is mobilized and recrystallizes on porous surfaces of secondary PGM (serving as a natural catalyst) and (iii) at the late stages of lateritization, biogenic mediated neoformation (and accumulation) of Pt-Ir-Fe-Ni nanoparticles occurs. The evidence presented in this work demonstrates that in situ growth of Pt-Ir-Fe-Ni alloy nuggets of isometric symmetry is possible within Ni-laterites from the Dominican Republic.

  2. High-Spin Structure of 102Ru

    SciTech Connect

    Sohler, D.; Timar, J.; Molnar, J.; Algora, A.; Dombradi, Zs.; Krasznahorkay, A.; Zolnai, L.; Rainovski, G.; Joshi, P.; Wadsworth, R.; Jenkins, D.G.; Raddon, P.M.; Simons, A.J.; Wilkinson, A.R.; Starosta, K.; Fossan, D.B.; Bednarczyk, P.; Curien, D.; Duchene, G.; Gizon, A.

    2005-11-21

    High-spin states in the nucleus 102Ru have been studied through the 96Zr(13C,{alpha}3n) reaction using the EUROBALL IV {gamma}-ray spectrometer accompanied by the DIAMANT array for the detection of charged particles. All previously known bands have been extended to higher spins and additional bands have been found. Comparing the experimental Routhians and aligned angular momenta to the predictions of Woods-Saxon TRS calculations, vh11/2(d5/2,g7/2) configurations have been assigned to the observed negative-parity bands.

  3. Ru nanoframes with an fcc structure and enhanced catalytic properties

    DOE PAGES

    Ye, Haihang; Wang, Qingxiao; Catalano, Massimo; ...

    2016-03-21

    Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd–Ru core–frame octahedra could be easily converted to Ru octahedral nanoframes of ~2 nm inmore » thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. Furthermore, the fcc Ru nanoframes showed higher catalytic activities toward the reduction of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.« less

  4. Ru nanoframes with an fcc structure and enhanced catalytic properties

    SciTech Connect

    Ye, Haihang; Wang, Qingxiao; Catalano, Massimo; Lu, Ning; Vermeylen, Joseph; Kim, Moon J.; Liu, Yuzi; Sun, Yugang; Xia, Xiaohu

    2016-03-21

    Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd–Ru core–frame octahedra could be easily converted to Ru octahedral nanoframes of ~2 nm in thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. Furthermore, the fcc Ru nanoframes showed higher catalytic activities toward the reduction of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.

  5. RuO2 Thermometer for Ultra-Low Temperatures

    NASA Technical Reports Server (NTRS)

    Hait, Thomas; Shirron, Peter J.; DiPirro, Michael

    2009-01-01

    A small, high-resolution, low-power thermometer has been developed for use in ultra-low temperatures that uses multiple RuO2 chip resistors. The use of commercially available thick-film RuO2 chip resistors for measuring cryogenic temperatures is well known due to their low cost, long-term stability, and large resistance change.

  6. Ru Nanoframes with an fcc Structure and Enhanced Catalytic Properties.

    PubMed

    Ye, Haihang; Wang, Qingxiao; Catalano, Massimo; Lu, Ning; Vermeylen, Joseph; Kim, Moon J; Liu, Yuzi; Sun, Yugang; Xia, Xiaohu

    2016-04-13

    Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd-Ru core-frame octahedra could be easily converted to Ru octahedral nanoframes of ∼2 nm in thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. The fcc Ru nanoframes showed higher catalytic activities toward the reduction of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.

  7. Spectroscopic studies of three Cepheids with high positive pulsation period increments: SZ Cas, BY Cas, and RU Sct

    NASA Astrophysics Data System (ADS)

    Usenko, I. A.; Klochkova, V. G.

    2015-07-01

    circumstellar envelopes around all three Cepheids. We have determined the atmospheric parameters and chemical composition of the program Cepheids. An appreciable carbon underabundance, a nitrogen overabundance (the result was obtained only for BY Cas), a nearly solar oxygen abundance, a sodium overabundance, and solar magnesium and aluminum abundances have been revealed in all stars, suggesting that these yellow supergiants has already passed the first dredge-up. The abundances of the Fe-peak elements, a-elements, and r- and s-process elements are nearly solar. [Fe/H] = -0.05 dex for SZ Cas and [Fe/H]= +0.05 dex for RU Sct can be used to estimate the metallicities of the open clusters χ and h Per and Trump 35, respectively.

  8. Thermal conductivity of ruthenium aluminide (RuAl)

    SciTech Connect

    Anderson, S.A.; Lang, C.I.

    1998-01-06

    Ruthenium aluminide (RuAl) is an intermetallic compound which exhibits strength at high temperatures together with attractive room temperature toughness. This combination of properties makes it a promising material for use at higher temperatures than currently possible with conventional titanium and nickel based alloys. Although high temperature applications will demand a knowledge and understanding of the thermal properties of RuAl, no such information is available in the scientific literature. In this paper, measurements of the thermal conductivity of RuAl are reported for the first time. Although the electrical properties of RuAl have previously been investigated, further electrical resistivity measurements have been made, using the same samples used to measure thermal conductivity. This allows a direct, meaningful comparison of electrical and thermal conductivity data, offering insights into the thermal transport mechanisms in RuAl. Microstructure is shown to have a significant influence on thermal and electrical properties.

  9. Endemic Ru Isotopic Anomalies in Iron Meteorites and in Allende

    NASA Technical Reports Server (NTRS)

    Chen, J. H.; Papanastassiou, D. A.; Wasserburg, G. J.

    2003-01-01

    Small variations for Mo isotopes have been observed recently in the Allende meteorite and in iron meteorites, mesosiderites, and pallasites, using ICPMS. Large effects for Mo have been reported for leaches of Orgueil and in SiC and graphite from Murchison. Variations for Mo in bulk Allende and in Murchison have also been presented by NTIMS. Effects in Ru isotopes can define further the preserved exotic r, s, and p contributions in this mass region, and possible effects in Ru-98 and Ru-99 from Tc-98 (4.2 Ma half-life) and Tc-99 (0.21 Ma half-life). Previous attempts at determination of Ru isotopes yielded no resolved effects. The present work represents a substantial improvement in precision over the earlier work. Chemical and mass spectrometric analytical techniques are presented to determine the Ru isotope compositions in terrestrial standards and in meteorites.

  10. Os isotopic composition of steels: Constraints on sources of Os in steel & crustal isotopic evolution of iron ores

    NASA Astrophysics Data System (ADS)

    Chatterjee, R. N.; Lassiter, J. C.

    2013-12-01

    Metal contamination during sample processing is a potential concern in Os-isotope studies. We examined Os concentrations and Os isotopes in industrial steels. Samples include high Cr stainless steels (>10.5% Cr), low alloy steels (>=92% Fe) and high alloy steels (<92% Fe). The chief components used to make steel are iron ore, chromites and coke. Coke is derived from coals that have low Os concentration (~36 ppt) [1]. Chromites in steels are mined from chromitites, which have high average Os concentrations and mantle-like 187Os/188Os ratios (~88 ppb Os, 187Os/188Os ≈ 0.127×24) [2]. Iron ores used in US steel manufacturing derive chiefly from magnetites mined from iron-bearing formations such as Banded Iron Formations (BIF), which have median Os concentration of ~4.8 ppb and radiogenic 187Os/188Os ≈ 0.358×388 [3]. Os concentrations in the measured steels span a wide range, from 0.03 to 22 ppb. The 187Os/188Os ratios vary from 0.144-4.12. Such high Os concentrations and radiogenic isotopic compositions confirm that metal contamination can affect Os-isotope compositions during sample processing, particularly for low-[Os] samples. There is no correlation between C and Os concentration in steel, indicating that coke is not a major Os source in steels. Os concentrations in steels are positively correlated with Cr content, suggesting that chromite-derived Os dominates the Os budget in stainless steels. 187Os/188Os is negatively correlated with Cr content, ranging from 0.144-0.195 in high-Cr (>10.5 % Cr) steels but from 0.279-4.12 in low-Cr steels. In addition, there is a positive correlation between 1/Os and 187Os/188Os, consistent with two-component mixing of Os derived from magnetite ore and chromites. Lower Os concentrations in steels than expected from simple mixing of magnetite and chromitite suggest some volatile Os loss during smelting. Although the current data is limited, the 186Os-187Os trend defined by the steel analyses can be utilized to extrapolate

  11. Fischer–Tropsch Synthesis: Effect of Reducing Agent for Aqueous-Phase Synthesis Over Ru Nanoparticle and Supported Ru Catalysts

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Shafer, Wilson D.; Jacobs, Gary; Graham, Uschi M.; Khalid, Syed; Davis, Burtron H.

    2014-12-27

    The effect of the reducing agent on the performance of a ruthenium nanoparticle catalyst was investigated during aqueous-phase Fischer–Tropsch synthesis using a 1 L stirred tank reactor in the batch mode of operation. For the purpose of comparison, the activity and selectivity of NaY zeolite supported Ru catalyst were also studied. NaBH4 and hydrogen were used as reducing agents in our study, and hydrogen reduced catalysts exhibited higher activities than the NaBH4 reduced catalysts, because of higher extent of reduction and a relatively lower tendency toward agglomeration of Ru particles. The Ru nanoparticle catalyst displayed higher activities than the NaY zeolite supported Ru catalyst for both reducing agents. NaBH4 reduced catalysts are less active and the carbon dioxide selectivity is higher than the hydrogen reduced catalysts. The activity of the supported Ru catalyst (Ru/NaY) was 75 % of that of the Ru nanoparticle catalyst, and has the benefit of easy wax/catalyst slurry separation by filtration. Finally, the hydrogen reduced supported Ru catalyst exhibited superior selectivity towards hydrocarbons (higher C5+ selectivity and lower selectivity to methane) than all other catalysts tested.

  12. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y.

    PubMed

    Wang, Hongliang; Ruan, Hao; Feng, Maoqi; Qin, Yuling; Job, Heather; Luo, Langli; Wang, Chongmin; Engelhard, Mark H; Kuhn, Erik; Chen, Xiaowen; Tucker, Melvin P; Yang, Bin

    2017-02-22

    The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al2 O3 and HY zeolite.

  13. Ru101 Knight-shift measurement of Sr2RuO4 in low fields applied parallel to the RuO2 plane

    NASA Astrophysics Data System (ADS)

    Murakawa, Hiroshi; Ishida, Kenji; Kitagawa, Kentaro; Mao, Z. Q.; Maeno, Yoshiteru

    2007-03-01

    We have measured Ru101 Knight shift (K101) in the spin triplet superconductor Sr2RuO4 in various magnetic fields applied parallel and perpendicular to the RuO2 plane to determine the spin direction of the Cooper pair. We measured temperature dependence of K101 in 0.15 and 0.055 T parallel to the RuO2 plane using nuclear-quadrupole-resonance (NQR) technique. We found that K101 is invariant with temperature in both fields on passing through the superconducting (SC) transition temperature. These results indicate that the spin susceptibility parallel to the RuO2 plane does not change in the field greater than 0.055 T, suggesting that the SC d-vector is along the c-axis when the magnetic field greater than 0.055 T is applied along to the RuO2 plane. The possible spin state in magnetic fields is discussed on the basis of the Knight-shift measurements so far.

  14. Intrinsic relation between catalytic activity of CO oxidation on Ru nanoparticles and Ru oxides uncovered with ambient pressure XPS.

    PubMed

    Qadir, Kamran; Joo, Sang Hoon; Mun, Bongjin S; Butcher, Derek R; Renzas, J Russell; Aksoy, Funda; Liu, Zhi; Somorjai, Gabor A; Park, Jeong Young

    2012-11-14

    Recent progress in colloidal synthesis of nanoparticles with well-controlled size, shape, and composition, together with development of in situ surface science characterization tools, such as ambient pressure X-ray photoelectron spectroscopy (APXPS), has generated new opportunities to unravel the surface structure of working catalysts. We report an APXPS study of Ru nanoparticles to investigate catalytically active species on Ru nanoparticles under oxidizing, reducing, and CO oxidation reaction conditions. The 2.8 and 6 nm Ru nanoparticle model catalysts were synthesized in the presence of poly(vinyl pyrrolidone) polymer capping agent and deposited onto a flat Si support as two-dimensional arrays using the Langmuir-Blodgett deposition technique. Mild oxidative and reductive characteristics indicate the formation of surface oxide on the Ru nanoparticles, the thickness of which is found to be dependent on nanoparticle size. The larger 6 nm Ru nanoparticles were oxidized to a smaller extent than the smaller Ru 2.8 nm nanoparticles within the temperature range of 50-200 °C under reaction conditions, which appears to be correlated with the higher catalytic activity of the bigger nanoparticles. We found that the smaller Ru nanoparticles form bulk RuO(2) on their surfaces, causing the lower catalytic activity. As the size of the nanoparticle increases, the core-shell type RuO(2) becomes stable. Such in situ observations of Ru nanoparticles are useful in identifying the active state of the catalysts during use and, hence, may allow for rational catalyst designs for practical applications.

  15. Dependency of anti-ferro-magnetic coupling strength on Ru spacer thickness of [Co/Pd]{sub n}-synthetic-anti-ferro-magnetic layer in perpendicular magnetic-tunnel-junctions fabricated on 12-inch TiN electrode wafer

    SciTech Connect

    Chae, Kyo-Suk; Shim, Tae-Hun; Park, Jea-Gun

    2014-07-21

    We investigated the Ru spacer-thickness effect on the anti-ferro-magnetic coupling strength (J{sub ex}) of a [Co/Pd]{sub n}-synthetic-anti-ferro-magnetic layer fabricated with Co{sub 2}Fe{sub 6}B{sub 2}/MgO based perpendicular-magnetic-tunneling-junction spin-valves on 12-in. TiN electrode wafers. J{sub ex} peaked at a certain Ru spacer-thickness: specifically, a J{sub ex} of 0.78 erg/cm{sup 2} at 0.6 nm, satisfying the J{sub ex} criteria for realizing the mass production of terra-bit-level perpendicular-spin-transfer-torque magnetic-random-access-memory. Otherwise, J{sub ex} rapidly degraded when the Ru spacer-thickness was less than or higher than 0.6 nm. As a result, the allowable Ru thickness variation should be controlled less than 0.12 nm to satisfy the J{sub ex} criteria. However, the Ru spacer-thickness did not influence the tunneling-magneto-resistance (TMR) and resistance-area (RA) of the perpendicular-magnetic-tunneling-junction (p-MTJ) spin-valves since the Ru spacer in the synthetic-anti-ferro-magnetic layer mainly affects the anti-ferro-magnetic coupling efficiency rather than the crystalline linearity of the Co{sub 2}Fe{sub 6}B{sub 2} free layer/MgO tunneling barrier/Co{sub 2}Fe{sub 6}B{sub 2} pinned layer, although Co{sub 2}Fe{sub 6}B{sub 2}/MgO based p-MTJ spin-valves ex-situ annealed at 275 °C achieved a TMR of ∼70% at a RA of ∼20 Ω μm{sup 2}.

  16. Low-temperature specific heat and magnetic properties of the filled skutterudite ferromagnet NdRu4As12

    NASA Astrophysics Data System (ADS)

    Rudenko, A.; Henkie, Z.; Cichorek, T.

    2016-09-01

    We present the low-temperature specific heat and magnetic properties of the filled skutterudite compound NdRu4As12 that exhibits a ferromagnetic transition at TC ≃ 2.3 K . Magnetic entropy considerations point at a quartet ground state of the Nd3+ ions. Deep in the ferromagnetic state, the heat capacity shows a Schottky anomaly that we ascribe to the Zeeman splitting in the presence of a molecular field. Comparison of the specific heats of NdRu4As12 and its Os-based homologue near their Curie temperatures supports our earlier observation suggesting an unusual lowering of the Th cubic point symmetry in the latter filled skutterudite.

  17. Brassinosteroids are involved in Fe homeostasis in rice (Oryza sativa L.)

    PubMed Central

    Wang, Baolan; Li, Gen; Zhang, Wen-Hao

    2015-01-01

    Brassinosteroids (BRs) are steroid hormones that modulate numerous physiological processes in plants. However, few studies have focused on the involvement of BRs in sensing and responding to the stress of mineral nutrient deficiency. In the present study, we evaluated the roles of BRs in the response of rice (Oryza sativa) to iron (Fe) deficiency during Fe uptake, transport, and translocation. Exogenous application of 24-epibrassinolide (EBR) to wild-type (WT) plants exaggerated leaf symptoms of Fe deficiency and suppressed growth. EBR increased and decreased Fe concentrations in roots and shoots, respectively, under both Fe-deficient and Fe-sufficient conditions. Transcripts involved in Fe homeostasis, including OsIRT1, OsYSL15, OsYSL2, OsNAS1, and OsNAS2, were enhanced by EBR under Fe-deficient conditions. EBR depressed expression of OsNAS1, OsNAS2, and OsYSL2 in shoots, and inhibited Fe transport and translocation via the phloem. Rice mutant d2-1, which is defective in BR biosynthesis, was more tolerant to Fe deficiency than the WT, and accumulated greater amounts of Fe in roots than the WT under Fe-sufficient conditions. A greater upregulation of OsIRT1, OsYSL15, OsYSL2, OsNAS1, and OsNAS2 in the d2-1 mutant compared to the WT was found under Fe-sufficient conditions, while expression of these genes in the d2-1 mutant was lower than in the WT under Fe-deficient conditions. The greater tolerance of the d2-1 mutant could be partly mitigated by exogenous application of EBR. These novel findings highlight the important role of BR in mediating the response of strategy II plants to Fe deficiency by regulating Fe uptake and translocation in rice. PMID:25770588

  18. Brassinosteroids are involved in Fe homeostasis in rice (Oryza sativa L.).

    PubMed

    Wang, Baolan; Li, Gen; Zhang, Wen-Hao

    2015-05-01

    Brassinosteroids (BRs) are steroid hormones that modulate numerous physiological processes in plants. However, few studies have focused on the involvement of BRs in sensing and responding to the stress of mineral nutrient deficiency. In the present study, we evaluated the roles of BRs in the response of rice (Oryza sativa) to iron (Fe) deficiency during Fe uptake, transport, and translocation. Exogenous application of 24-epibrassinolide (EBR) to wild-type (WT) plants exaggerated leaf symptoms of Fe deficiency and suppressed growth. EBR increased and decreased Fe concentrations in roots and shoots, respectively, under both Fe-deficient and Fe-sufficient conditions. Transcripts involved in Fe homeostasis, including OsIRT1, OsYSL15, OsYSL2, OsNAS1, and OsNAS2, were enhanced by EBR under Fe-deficient conditions. EBR depressed expression of OsNAS1, OsNAS2, and OsYSL2 in shoots, and inhibited Fe transport and translocation via the phloem. Rice mutant d2-1, which is defective in BR biosynthesis, was more tolerant to Fe deficiency than the WT, and accumulated greater amounts of Fe in roots than the WT under Fe-sufficient conditions. A greater upregulation of OsIRT1, OsYSL15, OsYSL2, OsNAS1, and OsNAS2 in the d2-1 mutant compared to the WT was found under Fe-sufficient conditions, while expression of these genes in the d2-1 mutant was lower than in the WT under Fe-deficient conditions. The greater tolerance of the d2-1 mutant could be partly mitigated by exogenous application of EBR. These novel findings highlight the important role of BR in mediating the response of strategy II plants to Fe deficiency by regulating Fe uptake and translocation in rice.

  19. RU-486: learning more about the French abortion drug.

    PubMed

    Smith, L

    1994-05-24

    RU-486 is a compound manufactured by Roussel Uclaf which blocks the functioning of progesterone, a hormone necessary for the maintenance of pregnancy. RU-486 is used widely outside of the US as a "morning after" pill to prevent a fertilized egg from implanting in the uterus after unprotected sexual intercourse. RU-486 will also cause a developing embryo to detach from the uterus. Accordingly, RU-486 is widely used as an abortion-inducing drug in Europe and China. Prostaglandins are typically administered one-two days after RU-486 to induce the uterus to expel the embryo. The treatment is given during the early weeks after conception, is painful, and usually takes two-three days. A woman visits a doctor several times over the course of treatment. By using RU-486, women avoid surgery and anesthesia, can terminate their pregnancies shortly after conception, have privacy, and can secure an abortion from any physician trained in pregnancy and its complications instead of having to go to centers where surgical abortions are performed. A surgical abortion, however, takes less time, is slightly more effective, and requires fewer office visits; women also usually experience less cramping and notice a lighter blood flow than they do with RU-486. The Population Council, a nonprofit contraceptive research organization in New York, holds the US patent rights to RU-486. The organization will soon select sites for clinical trials involving 2000 women required by the US Food and Drug Administration before the drug can be made available to the public. Approval is expected in two years. Use of the drug as a morning-after pill is being tested at the University of California, San Francisco. The manufacturer recommends women over age 35, who are smokers, and who have any other cardiovascular risks to not use RU-486.

  20. Ordered Porous Pd Octahedra Covered with Monolayer Ru Atoms.

    PubMed

    Ge, Jingjie; He, Dongsheng; Bai, Lei; You, Rui; Lu, Haiyuan; Lin, Yue; Tan, Chaoliang; Kang, Yan-Biao; Xiao, Bin; Wu, Yuen; Deng, Zhaoxiang; Huang, Weixin; Zhang, Hua; Hong, Xun; Li, Yadong

    2015-11-25

    Monolayer Ru atoms covered highly ordered porous Pd octahedra have been synthesized via the underpotential deposition and thermodynamic control. Shape evolution from concave nanocube to octahedron with six hollow cavities was observed. Using aberration-corrected high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy, we provide quantitative evidence to prove that only a monolayer of Ru atoms was deposited on the surface of porous Pd octahedra. The as-prepared monolayer Ru atoms covered Pd nanostructures exhibited excellent catalytic property in terms of semihydrogenation of alkynes.

  1. RU 486, mifepristone: a review of a controversial drug.

    PubMed

    DiPierri, D

    1994-06-01

    RU 486 (mifepristone), commonly referred to as the French abortion pill, has received much attention in the popular media. Much of this information has clouded the facts, and has been shrouded by controversy. Political, religious, and personal bias have slanted the presentation of the potential uses of this drug. Health care practitioners must be able to provide clients with the most accurate and factual information available. This article details the physiological effects of RU 486, as well as research data regarding uses and side effects. RU 486's most well publicized use, and efficacy, as an abortifacient are discussed in detail.

  2. MoRu/Be multilayers for extreme ultraviolet applications

    DOEpatents

    Bajt, Sasa C.; Wall, Mark A.

    2001-01-01

    High reflectance, low intrinsic roughness and low stress multilayer systems for extreme ultraviolet (EUV) lithography comprise amorphous layers MoRu and crystalline Be layers. Reflectance greater than 70% has been demonstrated for MoRu/Be multilayers with 50 bilayer pairs. Optical throughput of MoRu/Be multilayers can be 30-40% higher than that of Mo/Be multilayer coatings. The throughput can be improved using a diffusion barrier to make sharper interfaces. A capping layer on the top surface of the multilayer improves the long-term reflectance and EUV radiation stability of the multilayer by forming a very thin native oxide that is water resistant.

  3. Growth of RuO2 nanorods in reactive sputtering

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Tsun; Chen, Chun-Yu; Hsiung, Chang-Po; Cheng, Kai-Wen; Gan, Jon-Yiew

    2006-08-01

    The synthesis of RuO2 nanorods with reactive sputtering was demonstrated in this work. The synthesis process is very much like the metal organic chemical vapor deposition, except that RuO3 generated with reactive sputtering under high oxygen-to-argon flow ratio (>5SCCM /15SCCM) (SCCM denotes cubic centimeter per minute at STP) and high substrate temperature (>300°C) is used in place of the metal organic precursor. RuO2 nanorods tend to grow steadily with constant aspect ratio (˜27) and the field-emission characteristics appear very sensitive to their spatial distribution.

  4. /sup 97/Ru-DMSA for delayed renal imaging. [Dogs

    SciTech Connect

    Oster, Z.H.; Som, P.; Gil, M.C.; Goldman, A.G.; Fairchild, R.G.; Meinken, G.E.; Srivastava, S.C.; Atkins, H.L.; Richards, P.; Brill, A.B.

    1981-01-01

    Dimercaptosuccinic acid (DMSA) was labeled with /sup 97/Ru both with and without the addition of SnCl.2H/sub 2/O. The tin-containing preparation was found to induce higher cortical deposition of /sup 97/Ru-DMSA than the tin-free preparation. Visualization of the renal cortex was excellent 4 to 48 hours after injection in normal dogs with renal insufficiency. It is concluded that /sup 97/Ru-(Sn+/sup 2/)-DMSA is a potentially useful renal imaging agent when delayed scintigraphy is necessary because of decompensaton of the kidneys.

  5. /sup 97/Ru-DMSA for delayed renal imaging

    SciTech Connect

    Oster, Z.H.; Som, P.; Gil, M.C.

    1981-10-01

    Dimercaptosuccinic acid (DMSA) was labeled with /sup 97/Ru both with and without the addition of SnCl-2H/sub 2/O. The tin-containing preparation was found to induce higher cortical deposition of /sup 97/Ru-DMSA than the tin-free preparation. Visualization of the renal cortex was excellent 4 to 48 hours after injection in normal dogs and in dogs with renal insufficiency. It is concluded that /sup 97/Ru-(SN/sup 2 +/)-DMSA is a potentially useful renal imaging agent when delayed scintigraphy is necessary because of decompensation of the kidneys.

  6. Comparative NMR studies on Ca3LiRuO6 and Ca3NaRuO6

    NASA Astrophysics Data System (ADS)

    Chakrabarty, T.; Paulose, P. L.

    2016-06-01

    We report a comparative study of two ruthanate compounds, Ca3LiRuO6 and Ca3NaRuO6 by magnetic measurements, heat capacity and NMR. Ca3LiRuO6 is a weak ferromagnet with a magnetic ordering temperature of 115 K. The 7Li NMR linewidth of Ca3LiRuO6 displays a broad shoulder above the magnetic ordering temperature. Anomalous shoulder of this type is observed in the susceptibility data also. The origin of these phenomena is not clear but could possibly be attributed to low dimensional magnetism. A contrasting magnetic behavior is seen in Ca3NaRuO6, an antiferromagnet with a transition temperature at 87 K. The NMR study shows that the Knight shift is proportional to the magnetic susceptibility. Also, in Ca3NaRuO6, the Knight shift and the linewidth of the spectra change differently compared to Ca3LiRuO6. The heat capacity of both compounds show a λ-type anomaly at respective magnetic transition temperatures. However, in both the systems the entropy change (Δ S) is much less than that of an ordered S  =  3/2 system.

  7. A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH.

    PubMed

    Mola, Joaquim; Dinoi, Chiara; Sala, Xavier; Rodríguez, Montserrat; Romero, Isabel; Parella, Teodor; Fontrodona, Xavier; Llobet, Antoni

    2011-04-14

    The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans,fac-{[Ru(n)X(bpea)](2)(μ-bpp)}(m+) (for X = Cl, n = II, m = 1, trans-Ru(II)-Cl, 1(+); for X = OH, n = III, m = 3, trans-Ru(III)-OH, 2(3+)) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF(6)) with Ag(+) generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(II) to Ru(III) to generate the corresponding dinuclear complex trans-Ru(III)-OH, 2(PF(6))(3). The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(IV) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O-O bond formation pathway.

  8. Submonolayered Ru Deposited on Ultrathin Pd Nanosheets used for Enhanced Catalytic Applications.

    PubMed

    Zhang, Zhicheng; Liu, Ye; Chen, Bo; Gong, Yue; Gu, Lin; Fan, Zhanxi; Yang, Nailiang; Lai, Zhuangchai; Chen, Ye; Wang, Jie; Huang, Ying; Sindoro, Melinda; Niu, Wenxin; Li, Bing; Zong, Yun; Yang, Yanhui; Huang, Xiao; Huo, Fengwei; Huang, Wei; Zhang, Hua

    2016-12-01

    Ultrathin Pd nanosheets (NSs) coated with submonolayered Ru, referred to as Pd@Ru NSs, are synthesized via a seed-mediated growth method. The underpotential deposition can be the driving force for the formation of Pd@Ru NSs. The Pd@Ru NSs exhibit superior catalytic properties in the reduction of 4-nitrophenol and the semihydrogenation of 1-octyne, compared to the pure Pd NSs and Ru NSs.

  9. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    SciTech Connect

    Han, Yong; Evans, James W.

    2015-10-28

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C{sub 6}-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ∼0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. This in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001)

  10. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    DOE PAGES

    Han, Yong; Evans, James W.

    2015-10-27

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom inmore » the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. Furthermore, this in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001).« less

  11. Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

    SciTech Connect

    Han, Yong; Evans, James W.

    2015-10-27

    Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. Furthermore, this in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001).

  12. Dual emission and excited-state mixed-valence in a quasi-symmetric dinuclear Ru-Ru complex.

    PubMed

    Kreitner, Christoph; Grabolle, Markus; Resch-Genger, Ute; Heinze, Katja

    2014-12-15

    The synthesis and characterization of the new dinuclear dipeptide [(EtOOC-tpy)Ru(tpy-NHCO-tpy)Ru(tpy-NHCOCH3)](4+) 3(4+) of the bis(terpyridine)ruthenium amino acid [(HOOC-tpy)Ru(tpy-NH2)](2+) 1(2+) are described, and the properties of the dipeptide are compared to those of the mononuclear complex [(EtOOC-tpy)Ru(tpy-NHCOCH3)](2+) 4(2+) carrying the same functional groups. 3(4+) is designed to serve a high electronic similarity of the two ruthenium sites despite the intrinsic asymmetry arising from the amide bridge. This is confirmed via UV-vis absorption and NMR spectroscopy as well as cyclic voltammetry. 4(2+) and 3(4+) are emissive at room temperature, as expected. Moreover, 3(4+) exhibits dual emission from two different triplet states with different energies and lifetimes at room temperature. This is ascribed to the presence of a unique thermal equilibrium between coexisting [Ru(II)(tpy-NHCO-tpy(·-))Ru(III)] and [Ru(III)(tpy-NHCO-tpy(·-))Ru(II)] states leading to an unprecedented excited-state Ru(II)Ru(III) mixed-valent system via the radical anion bridge tpy-NHCO-tpy(·-). The mixed-valent cation 3(5+), on the other hand, shows no measurable interaction of the Ru(II)Ru(III) centers via the neutral bridge tpy-NHCO-tpy (Robin-Day class I). Reduction of 3(4+) to the radical cation 3(3+) by decamethylcobaltocene is bridge-centered as evidenced by rapid-freeze electron paramagnetic resonance spectroscopy. Interestingly, all attempts to observe 3(3+) via NMR and UV-vis absorption spectroscopy only led to the detection of the diamagnetic complex 3-H(3+) in which the bridging amide is deprotonated. Hence 3-H(3+) (and 4-H(+)) appear to reduce protons to dihydrogen. The ease of single and double deprotonation of 4(2+) and 3(4+) to 4-H(+), 3-H(3+), and 3-2H(2+) was demonstrated using a strong base and was studied using NMR and UV-vis absorption spectroscopies. The equilibrating excited triplet states of 3(4+) are reductively quenched by N,N-dimethylaniline assisted by

  13. Os-187/Os-188 and Highly Siderophile Element Systematics of Apollo 17 Aphanitic Melt Rocks

    NASA Technical Reports Server (NTRS)

    Puchtel, I. S.; Walker, R. J.; James, O. B.

    2005-01-01

    Introduction: Generally chondritic relative abundances and high absolute abundances of the highly siderophile elements (HSE: Ru, Rh, Pd, Re, Os, Ir, Pt, Au) in Earth s upper mantle provide strong evidence that these elements were added to the Earth following the last major interaction between its metallic core and silicate fraction. So called "late accretion" may have added materials comprising as much as 0.8% of the total mass of the Earth and possibly a similar proportion of mass to the Moon. We have begun to study the chemical nature of late accreted materials to the Earth - Moon system by examining the HSE contained in lunar impact-melt rocks. The HSE contained in melt rocks were largely added to the Moon during the period of time from the origin of the lunar highlands crust (4.4- 4.5 Ga) to the end of the late bombardment period (ca. 3.9 Ga). These materials provide the only direct chemical link to the late accretionary period. The chemical fingerprints of the HSE in late accreted materials may enable us to ascertain under what conditions and where in the solar system the late accreted materials formed. The Os-187/Os-188 ratios (reflecting long-term Re/Os), coupled with ratios of other HSE, can be diagnostic for identifying the nature of the impactor. A critical issue, however, will be deconvolving the exogenous from indigenous components.

  14. Study of Ru{sub 2}VGe and Ru{sub 2}VSb: High-spin polarized and half-metallic Heusler alloys

    SciTech Connect

    Bhat, Idris Hamid; Gupta, Dinesh C.

    2015-06-24

    Electronic and magnetic properties of Ru{sub 2}VGe and Ru{sub 2}VSb have been investigated by ab-initio. The optimized equilibrium lattice parameters were found to be 6.032 Å for Ru{sub 2}VGe and 6.272 Å for Ru{sub 2}VSb. Both the materials have ferromagnetic ground states and V mainly contributes to the magnetic properties in these materials. The highly spin-polarized half-metallic materials have integral magnetic moments of 1.0 µ{sub B} for Ru{sub 2}VGe and 2.0 µ{sub B} for Ru{sub 2}VSb with an energy gap of 0.095 eV for Ru2VGe and 0.186 eV for Ru{sub 2}VSb in the spin-down channel.

  15. Materials Data on Zr2RuOs (SG:225) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-09-01

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  16. Materials Data on Ti2RuOs (SG:225) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-08-05

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  17. Materials Data on Ho2RuOs (SG:225) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-08-27

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  18. Studies of quadrupole collectivity in the γ -soft 106Ru

    NASA Astrophysics Data System (ADS)

    Sanchez-Vega, M.; Mach, H.; Taylor, R. B. E.; Fogelberg, B.; Lindroth, A.; Aas, A. J.; Dendooven, P.; Honkanen, A.; Huhta, M.; Lhersonneau, G.; Oinonen, M.; Parmonen, J. M.; Penttilä, H.; Äystö, J.; Persson, J. R.; Kurpeta, J.

    2008-02-01

    Various alternative models were used to describe the structure of 106Ru . For example, the General Collective Model (GCM) predicts shape-coexistence for 106Ru with a spherical and a triaxial minimum and strongly mixed structures, while in the IBA-2 calculations, where 106Ru was considered as transitional from vibrational U(5) to γ -soft O(6) , no need was found to include the shape-coexisting configurations. In order to provide additional constraints on the model interpretations, we have applied the Advanced Time-Delayed (ATD) βγγ( t) method to measure the level lifetimes of the excited levels in 106Ru . The new results include the half-lives of T 1/2 = 183(3) ps and 7.5(30)ps for the 2+ 1 and 2+ 2 states, respectively.

  19. Catalytic ammonia decomposition over industrial-waste-supported Ru catalysts

    SciTech Connect

    Pei Fang Ng; Li Li; Shaobin Wang; Zhonghua Zhu; Gaoqing Lu; Zifeng Yan

    2007-05-15

    Industrial solid wastes (fly ash and red mud, a by-product of the aluminium industry) have been employed as supports for preparation of Ru-based catalysts. Physical and chemical treatments on red mud were conducted and these modified supports were also used for preparation of Ru-based catalysts. Those Ru catalysts were characterized by various techniques such as N2 adsorption, H{sub 2} adsorption, XRD, XPS, and temperature-programmed reduction (TPR), and were then tested for catalytic ammonia decomposition to hydrogen. It was found that red-mud-supported Ru catalyst exhibits higher ammonia conversion and hydrogen production than fly-ash-supported catalyst. Heat and chemical treatments of the red mud greatly improve the catalytic activity. Moreover, a combination of acid and heat treatments produces the highest catalytic conversion of ammonia. 35 refs., 4 figs., 4 tabs.

  20. Internal oxidation of laminated Nb-Ru coatings

    NASA Astrophysics Data System (ADS)

    Chen, Yung-I.; Chu, Hsiu-Nuan; Kai, Wu

    2016-12-01

    A direct current magnetron cosputtering system was used to deposit Nb-Ru coatings with various chemical compositions onto silicon wafers. The Nb-Ru coatings exhibited distinct nanolaminated structures because of the cyclical gradient concentration deposition. The oxidized Nb-Ru coatings formed oxide and metal multilayers when they experienced internal oxidation at 400-600 °C in a 1% O2-99% Ar atmosphere. A two-stage parabolic-rate law was obeyed for the Nb0.49Ru0.51 coatings oxidized at 350-550 °C in 1% O2-99% Ar. The activation energies in the two-stage oxidation, dominated by oxygen dissolution and oxide formation, were calculated at 88 and 127 kJ/mol, respectively.

  1. Photoinduced intramolecular energy transfer and anion sensing studies of isomeric RuIIOsII complexes derived from an asymmetric phenanthroline-terpyridine bridge.

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Mondal, Debiprasad; Baitalik, Sujoy

    2014-01-28

    Two heterobimetallic Ru(II)-Os(II) complexes of compositions [(bpy)2M(II)(phen-Hbzim-tpy)M'(II)(tpy-PhCH3)](4+), where M(II) = Ru and M'(II) = Os (4) and M(II) = Os and M'(II) = Ru (5), phen-Hbzim-tpy = 2-(4-(2,6-di(pyridin-2-yl)pyridine-4-yl)phenyl)-1H-imidazole[4,5][1,10]phenanthroline, bpy = 2,2'-bipyridine, and tpy-PhCH3 = 4'-(4-methylphenyl)-2,2':6',2''-terpyridine have been synthesized and characterized by elemental analyses, ESI mass spectrometry, and (1)H NMR and UV-vis absorption spectroscopy. The absorption spectra, redox behavior, and luminescence properties of the complexes have been thoroughly investigated and compared with that of monometallic model compounds [(bpy)2M(II)(phen-Hbzim-tpy)](2+) [M(II) = Ru (1) and M(II) = Os (2)] and [(phen-Hbzim-tpy)Ru(II)(tpy-PhCH3)](2+) (3). The complexes display very intense, ligand-centered absorption bands in the UV and moderately intense MLCT bands in the visible regions. The bimetallic complexes show two successive one-electron reversible metal-centered oxidations, whereas the monometallic complexes display one-electron oxidation in the positive potential window. Steady state and time-resolved luminescence data at room temperature show that an efficient intramolecular electronic energy transfer takes place from the Ru-center to the Os-based component in both the heterometallic dyads in all the solvents. The complexes under investigation contain an imidazole NH proton which became appreciably acidic due to metal coordination and can be utilized for recognition of selective anions in solution either via hydrogen bonding interaction or by proton transfer. Accordingly, the anion binding properties of the two heterobimetallic complexes as well as parent bridging ligand, phen-Hbzim-tpy, have been studied in solutions using absorption, steady state and time-resolved luminescence spectral measurements. The metalloreceptors act as sensors for F(-), CN(-) and AcO(-) ions. It is evident from sensing studies that in the

  2. Energy distribution monitoring of the T Tauri star RU LUPI

    NASA Astrophysics Data System (ADS)

    Giovannelli, F.; Vittone, A. A.; Errico, L.; Rossi, C.

    Simultaneous UV, optical and IR energy distributions of RU Lupi are presented for the period 1984-1986. The observations were obtained with the IUE satellite and optical and IR telescopes. Variations are detected in UV and optical regions. In addition, a large flare was observed on June 30, 1986. The results agree with those of Gahm et al. (1974) and suggest that the main cause of variability in RU Lupi is strong activity in the star's surface layers.

  3. More on Ru Endemic Isotope Anomalies in Meteorites

    NASA Technical Reports Server (NTRS)

    Papanastassiou, D. A.; Chen, J. H.; Wasserburg, G. J.

    2004-01-01

    We reported last year on endemic isotope anomalies for Ru in iron meteorites, pallasites, ordinary chondrites, and on a whole-rock sample of Allende. We have extended the Ru measurements to more meteorites, to refractory Ca-Al-rich inclusions (CAI) from Allende, and to a whole rock sample of Murchison (CM2). In a companion abstract we report on new measurements for the Mo isotopes, in some of the same samples. There has been a renewed interest in searching for isotope anomalies in this nuclide region, as Ru and Mo include many isotopes from r-, s-, and p-process nucleosynhesis. Furthermore, the Ru and Mo p-process isotopes show atypically high abundances, which have been hard to explain through the standard nucleosynthetic processes. Effects are possible in Ru-98 and Ru-99 from Tc-98 (with a poorly known t(sub 1/2)=4.2 to 10Ma) and from Tc-99 (t(sub 1/2)=0.21Ma). Natural Tc is now extinct on Earth due to the short half-lives, but may have been present in the early solar system. Both radiogenic and general isotope anomalies are important in understanding the processes for the formation of the early solar system. The current emphasis on Ru and Mo is also the result of the development of Negative-ion Thermal Ionization Mass Spectrometry and of Multiple-Collector, Inductively-Coupled-Mass-Spectrometry. We have also developed specific chemical siparation techniques for Ru, which eliminated mass interference effects.

  4. The role of the non-magnetic material in spin pumping and magnetization dynamics in NiFe and CoFeB multilayer systems

    SciTech Connect

    Ruiz-Calaforra, A. Brächer, T.; Lauer, V.; Pirro, P.; Heinz, B.; Geilen, M.; Chumak, A. V.; Conca, A.; Leven, B.; Hillebrands, B.

    2015-04-28

    We present a study of the effective magnetization M{sub eff} and the effective damping parameter α{sub eff} by means of ferromagnetic resonance spectroscopy on the ferromagnetic (FM) materials Ni{sub 81}Fe{sub 19} (NiFe) and Co{sub 40}Fe{sub 40}B{sub 20} (CoFeB) in FM/Pt, FM/NM, and FM/NM/Pt systems with the non-magnetic (NM) materials Ru, Cr, Al, and MgO. Moreover, for NiFe layer systems, the influence of interface effects is studied by way of thickness dependent measurements of M{sub eff} and α{sub eff}. Additionally, spin pumping in NiFe/NM/Pt is investigated by means of inverse spin Hall effect (ISHE) measurements. We observe a large dependence of M{sub eff} and α{sub eff} of the NiFe films on the adjacent NM layer. While Cr and Al do not induce a large change in the magnetic properties, Ru, Pt, and MgO affect M{sub eff} and α{sub eff} in different degrees. In particular, NiFe/Ru and NiFe/Ru/Pt systems show a large perpendicular surface anisotropy and a significant enhancement of the damping. In contrast, the magnetic properties of CoFeB films do not have a large influence of the NM adjacent material and only CoFeB/Pt systems present an enhancement of α{sub eff}. However, this enhancement is much more pronounced in NiFe/Pt. By the introduction of the NM spacer material, this enhancement is reduced. Furthermore, a difference in symmetry between NiFe/NM/Pt and NiFe/NM systems in the output voltage signal from the ISHE measurements reveals the presence of spin pumping into the Pt layer in all-metallic NiFe/NM/Pt and NiFe/Pt systems.

  5. Enhancement of Solar Fuel Production Schemes by Using a Ru,Rh,Ru Supramolecular Photocatalyst Containing Hydroxide Labile Ligands.

    PubMed

    Rogers, Hannah Mallalieu; Arachchige, Shamindri M; Brewer, Karen J

    2015-11-16

    Polyazine-bridged Ru(II)Rh(III)Ru(II) complexes with two halide ligands, Cl(-) or Br(-), bound to the catalytically active Rh center are efficient single-component photocatalysts for H2O reduction to H2 fuel, with the coordination environment on Rh impacting photocatalysis. Herein reported is a new, halide-free Ru(II)Rh(III)Ru(II) photocatalyst with OH(-) ligands bound to Rh, further enhancing the photocatalytic reactivity of the structural motif. H2 production experiments using the photocatalyst bearing OH(-) ligands at Rh relative to the analogues bearing halides at Rh in solvents of varying polarity (DMF, CH3CN, and H2O) suggest that ion pairing with halides deactivates photocatalyst function, representing an exciting phenomenon to exploit in the development of catalysts for solar H2 production schemes.

  6. Enhancement of perpendicular magnetic anisotropy and coercivity in ultrathin Ru/Co/Ru films through the buffer layer engineering

    NASA Astrophysics Data System (ADS)

    Kolesnikov, Alexander G.; Stebliy, Maxim E.; Ognev, Alexey V.; Samardak, Alexander S.; Fedorets, Aleksandr N.; Plotnikov, Vladimir S.; Han, Xiufeng; Chebotkevich, Ludmila A.

    2016-10-01

    We present results on a study of the interplay between microstructure and the magnetic properties of ultrathin Ru/Co/Ru films with perpendicular magnetic anisotropy (PMA). To induce PMA in the Co layer, we experimentally determined thicknesses of the buffer and capping layers of Ru. The maximum value of PMA was observed for the Co thickness of 0.9 nm with the 3 nm thick capping layer. The effective anisotropy field (H eff) and coercive force (H c) of the Co layer are very sensitive to the Ru buffer layer thickness (t b). The values of H eff and H c increase approximately by two and ten times, correspondingly, when t b changes from 6 to 20 nm, owing to an increase in volume fraction of the crystalline phase as a result of the grains’ growth. PMA is found to be mainly enhanced by elastic strains induced by the lattice mismatch on the Ru/Co and Co/Ru interfaces, leading to the deformation of the Co lattice. The surface impact is determined to be less than 10% of the magneto-elastic contribution to the effective anisotropy. Observation of the magnetic domain structure by means of polar Kerr microscopy reveals that out-of-plane magnetization reversal occurs through the nucleation, growth, and annihilation of domains, where the average size drastically rises with the increasing t b.

  7. Triggers on sulfide saturation in Fe-Ti oxide-bearing, mafic-ultramafic layered intrusions in the Tarim large igneous province, NW China

    NASA Astrophysics Data System (ADS)

    Cao, Jun; Wang, Christina Yan; Xu, Yi-Gang; Xing, Chang-Ming; Ren, Ming-Hao

    2016-08-01

    Three Fe-Ti oxide-bearing layered intrusions (Mazaertag, Wajilitag, and Piqiang) in the Tarim large igneous province (NW China) have been investigated for understanding the relationship of sulfide saturation, Platinum-group element (PGE) enrichment, and Fe-Ti oxide accumulation in layered intrusions. These mafic-ultramafic layered intrusions have low PGE concentrations (<0.4 ppb Os, <0.7 ppb Ir, <1 ppb Ru, <0.2 ppb Rh, <5 ppb Pt, and <8 ppb Pd) and elevated Cu/Pd (2.2 × 104 to 3.3 × 106). The low PGE concentrations of the rocks are mainly attributed to PGE-depleted, parental magma that was produced by low degrees of partial melting of the mantle. The least contaminated rocks of the Mazaertag and Wajilitag intrusions have slightly enriched Os isotopic compositions with γOs(t = 280 Ma) values ranging from +13 to +23, indicating that the primitive magma may have been generated from a convecting mantle, without appreciable input of lithospheric mantle. The Mazaertag and Wajilitag intrusions have near-chondritic γOs(t) values (+13 to +60) against restricted ɛ Nd(t) values (-0.4 to +2.8), indicating insignificant crustal contamination. Rocks of the Piqiang intrusion have relatively low ɛ Nd(t) values of -3.1 to +1.0, consistent with ˜15 to 25 % assimilation of the upper crust. The rocks of the Mazaertag and Wajilitag intrusions have positive correlation of PGE and S, pointing to the control of PGE by sulfide. Poor correlation of PGE and S for the Piqiang intrusion is attributed to the involvement of multiple sulfide-stage liquids with different PGE compositions or sulfide-oxide reequilibration on cooling. These three layered intrusions have little potential of reef-type PGE mineralization. Four criteria are summarized in this study to help discriminate between PGE-mineralized and PGE-unmineralized mafic-ultramafic intrusions.

  8. Atomic structure of an ultrathin Fe-silicate film grown on a metal: a monolayer of clay?

    PubMed

    Włodarczyk, Radosław; Sauer, Joachim; Yu, Xin; Boscoboinik, Jorge Anibal; Yang, Bing; Shaikhutdinov, Shamil; Freund, Hans-Joachim

    2013-12-26

    Ultrathin Fe-doped silicate films were prepared on a Ru(0001) surface and, as a function of the Fe/Si ratio, structurally characterized by low-energy electron diffraction, X-ray photoelectron spectroscopy, infrared reflection-absorption spectroscopy, and scanning tunneling microscopy. Density functional theory (DFT) was used to identify the atomic structure. The results show that uniform substitution of Si by Fe in the silicate bilayer frame is thermodynamically unfavorable: the film segregates into a pure silicate and an Fe-silicate phase. The DFT calculations reveal that the Fe-silicate film with an Fe/Si = 1:1 ratio consists of a monolayer of [SiO4] tetrahedra on top of an iron oxide monolayer. As such, it closely resembles the structure of the clay mineral nontronite, a representative of the Fe-rich smectites. Furthermore, the DFT calculations predict formation of bridging Fe-O-Ru bonds between the Fe-silicate film and the Ru substrate accompanied by charge transfer from the metal substrate to the film, so that iron is in the oxidation state +III as in nontronite.

  9. Opposite signs of voltage-induced perpendicular magnetic anisotropy change in CoFeB|MgO junctions with different underlayers

    NASA Astrophysics Data System (ADS)

    Shiota, Yoichi; Bonell, Frédéric; Miwa, Shinji; Mizuochi, Norikazu; Shinjo, Teruya; Suzuki, Yoshishige

    2013-08-01

    We report a voltage-induced perpendicular magnetic anisotropy (PMA) change in sputter-deposited Ta|CoFeB|MgO and Ru|CoFeB|MgO junctions. The PMA change is quantitatively evaluated by the field dependence of the tunneling magnetoresistance for various bias voltages. We find that both the sign and amplitude of the voltage effect depend on the underlayer, Ta or Ru, below the CoFeB layer. The rf voltage-induced ferromagnetic resonance spectra also support the underlayer-material-dependent direction of the voltage torque. The present study shows that the underlayer is one of the key parameters for controlling the voltage effect.

  10. Critical analysis on nanostructured CoFeB synthetic orthogonal ferrimagnet

    SciTech Connect

    Chen, Y. S.; Lin, J. G.; Cheng, Chih-Wei; Chern, G.

    2014-09-21

    Critical analysis on the magnetic properties of synthetic ferrimagnet (SyF), Ta/MgO/CoFeB/Ru/CoFeB/MgO/Ta, is demonstrated via both static and dynamic techniques. With the Ru thickness being 2.3 nm, the coupling between two CoFeB layers becomes orthogonal, which can be used for spin-transfer-torque nano-oscillator (STNO). The fitting of angular dependent ferromagnetic resonance (FMR) allows the precise determination of magnetic anisotropy of each CoFeB layer, the relative magnetizations and the exchange field near the frequency of STNO applications. In addition, the mechanism of resonance broadening at out-of-plane direction is identified to be magnetic inhomogeneity by fitting the angular dependent linewidth of FMR spectra, which provides indispensable information for the future design of STNO devices.

  11. Impact of rare earth magnetic moment on ordering of Ru in Sr 2RuREO 6 (RE=Gd and Eu)

    NASA Astrophysics Data System (ADS)

    Awana, V. P. S.; Tripaathi, Rahul; Sharma, V. K.; Kishan, H.; Takayama-Muromachi, E.; Felner, I.

    2007-05-01

    We report the synthesis and magnetization of Sr 2RuREO 6 (RE/Ru-211O 6) with RE=Gd and Eu. Both Gd and Eu/Ru-211O 6 are formed in distorted perovskite-type single phase with monoclinic P2 1/n space group. Magnetization ( M/ T) measurements exhibited antiferromagnetic ordering of Ru moments for both Gd and Eu compounds at a TN of around 30 K due to super-exchange Ru-O-O-Ru interaction. Interestingly enough, detailed M/ H plots of Gd/Ru-211O 6 exhibited the development of a ferromagnetic (FM) component at 20 K. Furthermore, below 10 K, the FM component disappears, and rather spin freezing field ( HSF) of around 1000 Oe is seen at 5 K. In case of Eu/Ru-211O 6, the basic antiferromagnetic ordering of Ru moments remains invariantly down to 5 K, and the appearance of the FM component is not seen. It seems that the high magnetic moment of 8 μB for Gd 3+ influences the anti ferromagnetic (AFM) ordering of Ru in case of Gd/Ru-211O 6.

  12. Evolution of magnetism in single-crystal Ca2Ru1-xIrxO4(0≤x≤0.65)

    DOE PAGES

    Yuan, S. J.; Terzic, J.; Wang, J. C.; ...

    2015-07-24

    In this paper, we report structural, magnetic, transport, and thermal properties of single-crystal Ca2Ru1-xIrxO4(0≤x≤0.65). Ca2RuO4 is a structurally driven Mott insulator with a metal-insulator transition at TMI=357K, which is well separated from antiferromagnetic order at TN=110K. Substitution of a 5d element, Ir, for Ru enhances spin-orbit coupling and locking between the structural distortions and magnetic moment canting. Ir doping intensifies the distortion or rotation of Ru/IrO6 octahedra and induces weak ferromagnetic behavior along the c axis. In particular, Ir doping suppresses TN but concurrently causes an additional magnetic ordering TN2 at a higher temperature up to 210 K for x=0.65.more » The effect of Ir doping sharply contrasts with that of 3d-element doping such as Cr, Mn, and Fe, which suppresses TN and induces unusual negative volume thermal expansion. Finally, the stark difference between 3d- and 5d-element doping underlines a strong magnetoelastic coupling inherent in the Ir-rich oxides.« less

  13. Electronic structure and spectroscopy of [Ru(tpy)(2)](2+), [Ru(tpy)(bpy)(H(2)O)](2+), and [Ru(tpy)(bpy)(Cl)](+).

    PubMed

    Jakubikova, Elena; Chen, Weizhong; Dattelbaum, Dana M; Rein, Francisca N; Rocha, Reginaldo C; Martin, Richard L; Batista, Enrique R

    2009-11-16

    We use a combined, theoretical and experimental, approach to investigate the spectroscopic properties and electronic structure of three ruthenium polypyridyl complexes, [Ru(tpy)(2)](2+), [Ru(tpy)(bpy)(H(2)O)](2+), and [Ru(tpy)(bpy)(Cl)](+) (tpy = 2,2':6',2''-terpyridine and bpy = 2,2'-bipyridine) in acetone, dichloromethane, and water. All three complexes display strong absorption bands in the visible region corresponding to a metal-to-ligand-charge-transfer (MLCT) transition, as well as the emission bands arising from the lowest lying (3)MLCT state. [Ru(tpy)(bpy)(Cl)](+) undergoes substitution of the Cl(-) ligand by H(2)O in the presence of water. Density functional theory (DFT) calculations demonstrate that the triplet potential energy surfaces of these molecules are complicated, with several metal-centered ((3)MC) and (3)MLCT states very close in energy. Solvent effects are included in the calculations via the polarizable continuum model as well as explicitly, and it is shown that they are critical for proper characterization of the triplet excited states of these complexes.

  14. AuRu/AC as an effective catalyst for hydrogenation reactions

    SciTech Connect

    Villa, Alberto; Chan-Thaw, Carine E.; Campisi, Sebastiano; Bianchi, Claudia L.; Wang, Di; Kotula, Paul G.; Kübel, Christian; Prati, Laura

    2015-03-23

    AuRu bimetallic catalysts have been prepared by sequential deposition of Au on Ru or vice versa obtaining different nanostructures: when Ru has been deposited on Au, a AucoreRushell has been observed, whereas the deposition of Au on Ru leads to a bimetallic phase with Ru enrichment on the surface. In the latter case, the unexpected Ru enrichment could be attributed to the weak adhesion of Ru on the carbon support, thus allowing Ru particles to diffuse on Au particles. Both structures result very active in catalysing the liquid phase hydrogenolysis of glycerol and levulinic acid but the activity, the selectivity and the stability depend on the structure of the bimetallic nanoparticles. Ru@Au/AC core–shell structure mostly behaved as the monometallic Ru, whereas the presence of bimetallic AuRu phase in Au@Ru/AC provides a great beneficial effect on both activity and stability.

  15. Biochemical characterization of predicted Precambrian RuBisCO

    PubMed Central

    Shih, Patrick M.; Occhialini, Alessandro; Cameron, Jeffrey C.; Andralojc, P John; Parry, Martin A. J.; Kerfeld, Cheryl A.

    2016-01-01

    The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism. PMID:26790750

  16. Diastereomeric bactericidal effect of Ru(phenanthroline)2dipyridophenazine

    PubMed Central

    Bergentall, Mattias; Tremaroli, Valentina; Lincoln, Per

    2016-01-01

    ABSTRACT Metal susceptibility assays and spot plating were used to investigate the antimicrobial activity of enantiopure [Ru(phen)2dppz]2+ (phen =1,10‐phenanthroline and dppz = dipyrido[3,2‐a:2´,3´‐c]phenazine) and [μ‐bidppz(phen)4Ru2]4 + (bidppz =11,11´‐bis(dipyrido[3,2‐a:2´,3´‐c]phenazinyl)), on Gram‐negative Escherichia coli and Gram‐positive Bacillus subtilis as bacterial models. The minimum inhibitory concentrations (MIC) and minimum bactericidal concentrations (MBC) were determined for both complexes: while [μ‐bidppz(phen)4Ru2]4 + only showed a bactericidal effect at the highest concentrations tested, the antimicrobial activity of [Ru(phen)2dppz]2+ against B. subtilis was comparable to that of tetracyline. In addition, the Δ‐enantiomer of [Ru(phen)2dppz]2+ showed a 2‐fold higher bacteriostatic and bactericidal effect compared to the Λ‐enantiomer. This was in accordance with the enantiomers relative binding affinity for DNA, thus strongly indicating DNA binding as the mode of action. PMID:27791316

  17. Biochemical characterization of predicted Precambrian RuBisCO.

    PubMed

    Shih, Patrick M; Occhialini, Alessandro; Cameron, Jeffrey C; Andralojc, P John; Parry, Martin A J; Kerfeld, Cheryl A

    2016-01-21

    The antiquity and global abundance of the enzyme, RuBisCO, attests to the crucial and longstanding role it has played in the biogeochemical cycles of Earth over billions of years. The counterproductive oxygenase activity of RuBisCO has persisted over billions of years of evolution, despite its competition with the carboxylase activity necessary for carbon fixation, yet hypotheses regarding the selective pressures governing RuBisCO evolution have been limited to speculation. Here we report the resurrection and biochemical characterization of ancestral RuBisCOs, dating back to over one billion years ago (Gyr ago). Our findings provide an ancient point of reference revealing divergent evolutionary paths taken by eukaryotic homologues towards improved specificity for CO2, versus the evolutionary emphasis on increased rates of carboxylation observed in bacterial homologues. Consistent with these distinctions, in vivo analysis reveals the propensity of ancestral RuBisCO to be encapsulated into modern-day carboxysomes, bacterial organelles central to the cyanobacterial CO2 concentrating mechanism.

  18. Electrical field modification of dynamic magnetic properties in FeCo films grown onto [Pb(Mg1/3Nb2/3)O3]0.68-[PbTiO3]0.32(011) piezoelectric substrates with Ru underlayers

    NASA Astrophysics Data System (ADS)

    Phuoc, Nguyen N.; Ong, C. K.

    2015-06-01

    A detailed investigation of electrical tuning of dynamic magnetization of the FeCo magnetic thin film grown onto a PMN-PT piezoelectric substrate was carried out based on the measurement of the zero-field permeability spectra under the application of a voltage across the thickness of the substrate. The resonance frequency can be tuned from 2.95 GHz to 5.9 GHz upon the application of a voltage on the sample in unpoled state. After poling, the resonance frequency of the sample can be tuned in the range from 4.75 GHz to 5.9 GHz. In addition, it was found that after poling the peak of the permeability spectra is broadened compared to before poling, which can be tentatively attributed to the magnetic anisotropy dispersion arising from the presence of the stress-induced anisotropy. The result is also discussed in conjunction with the angular measurement of the static hysteresis loops of the sample before and after poling.

  19. Erlichmanite /OsS sub 2/, a new mineral.

    NASA Technical Reports Server (NTRS)

    Snetsinger, K. G.

    1971-01-01

    Natural osmium disulfide (termed erlichmanite) was recognized in two occurrences on the basis of electron probe and X-ray data. One occurrence is in grains of platinum-metal sand from California, the other in a platinum-metal nugget from Western Ethiopian laterites. California erlichmanite has Os 68.0, Ir 2.6, Rh 3.8, Ru 0.4, Pd 0.5, and S 25.2, summation of 100.5 wt. %, the number of metal atoms being 1.06 on the basis of 2.00 sulfurs. Ethiopian material has higher Rh and Ir and lower Os. Both are optically isotropic. Spotty X-ray reflections from a 15-micron particle of California erlichmanite give rise to d spacing which match those of synthetic cubic osmium disulfide. Erlichmanite is defined as a cubic disulfide in which osmium is the most abundant metal atom.

  20. Enhanced thermoelectric power and electronic correlations in RuSe₂

    SciTech Connect

    Wang, Kefeng; Wang, Aifeng; Tomic, A.; Wang, Limin; Abeykoon, A. M. Milinda; Dooryhee, E.; Billinge, S. J.L.; Petrovic, C.

    2015-03-03

    We report the electronic structure, electric and thermal transport properties of Ru₁₋xIrxSe₂ (x ≤ 0.2). RuSe₂ is a semiconductor that crystallizes in a cubic pyrite unit cell. The Seebeck coefficient of RuSe₂ exceeds -200 µV/K around 730 K. Ir substitution results in the suppression of the resistivity and the Seebeck coefficient, suggesting the removal of the peaks in density of states near the Fermi level. Ru₀.₈Ir₀.₂Se₂ shows a semiconductor-metal crossover at about 30 K. The magnetic field restores the semiconducting behavior. Our results indicate the importance of the electronic correlations in enhanced thermoelectricity of RuSb₂.

  1. Enhanced thermoelectric power and electronic correlations in RuSe₂

    DOE PAGES

    Wang, Kefeng; Wang, Aifeng; Tomic, A.; ...

    2015-03-03

    We report the electronic structure, electric and thermal transport properties of Ru₁₋xIrxSe₂ (x ≤ 0.2). RuSe₂ is a semiconductor that crystallizes in a cubic pyrite unit cell. The Seebeck coefficient of RuSe₂ exceeds -200 µV/K around 730 K. Ir substitution results in the suppression of the resistivity and the Seebeck coefficient, suggesting the removal of the peaks in density of states near the Fermi level. Ru₀.₈Ir₀.₂Se₂ shows a semiconductor-metal crossover at about 30 K. The magnetic field restores the semiconducting behavior. Our results indicate the importance of the electronic correlations in enhanced thermoelectricity of RuSb₂.

  2. CO adsorption on a silica bilayer supported on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Schlexer, Philomena; Pacchioni, Gianfranco; Włodarczyk, Radosław; Sauer, Joachim

    2016-06-01

    Silica bilayers are built up of two layers of corner sharing SiO4-tetrahedra and constitute an inert ultra-thin membrane supported on the Ru(0001) surface. We have investigated the adsorption of CO on that system using DFT with inclusion of dispersion corrections. The molecules adsorb at the interface between the SiO2 film and Ru(0001) surface. The estimated barrier for diffusion of CO through the silica bilayer is around 0.5 eV. The CO bond length, the C-O stretching frequency and the silica-ruthenium distance depend strongly on the CO coverage. The band observed at 2051 cm- 1 in previous experiments can be assigned to a CO coverage of around 0.5 ML on Ru(0001), with the silica bilayer floating above the CO molecules.

  3. Complex of transferrin with ruthenium for medical applications. [Ru 97, Ru 103

    DOEpatents

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

    1980-11-03

    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/sup 0/C for about 2 hours, and purifying said complex by means of gel chromatography 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. Comparitive 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.

  4. Re-Os Systematics and HSE Distribution in Metal from Ochansk (H4) Chondrite

    NASA Technical Reports Server (NTRS)

    Smoliar, M. I.; Horan, M. F.; Alexander, C. M. OD.; Walker, R. J.

    2003-01-01

    Previous studies of the Re-Os systematics of chondrites have documented considerable variation in the Re/Os ratios of whole rock samples. For some whole rock chondrites, Re-Os systematics display large deviations from the primitive isochron that are considerably larger than deviations in other isotope systems. Possible interpretation of these facts is that the Re-Os system in chondrites is particularly sensitive to post-formation alteration processes, thus providing a useful tool to examine such processes. Significant variations that have been detected in highly siderophile element (HSE) patterns for ordinary chondrites support this conclusion. We report Re-Os isotope data for metal separates from the Ochansk H4 chondrite coupled with abundance data for Ru, Pd, Ir, and Pt, determined in the same samples by isotope dilution. We chose this meteorite mainly because it is an observed fall with minimal signs of weathering, and its low metamorphic grade (H4) and shock stage (S3).

  5. Oxidation resistance of Ru-capped EUV multilayers

    SciTech Connect

    Bajt, S; Dai, Z; Nelson, E J; Wall, M A; Alameda, J; Nguyen, N; Baker, S; Robinson, J C; Taylor, J S; Clift, M; Aquila, A; Gullikson, E M; Edwards, N G

    2005-02-23

    Differently prepared Ru-capping layers, deposited on Mo/Si EUV multilayers, have been characterized using a suite of metrologies to establish their baseline structural, optical, and surface properties in as-deposited state. Same capping layer structures were tested for their thermal stability and oxidation resistance. Post-mortem characterization identified changes due to accelerated tests. The best performing Ru-capping layer structure was studied in detail with transmission electron microscopy to identify the grain microstructure and texture. This information is essential for modeling and performance optimization of EUVL multilayers.

  6. Nuclear forward scattering of synchrotron radiation by 99Ru.

    PubMed

    Bessas, D; Merkel, D G; Chumakov, A I; Rüffer, R; Hermann, R P; Sergueev, I; Mahmoud, A; Klobes, B; McGuire, M A; Sougrati, M T; Stievano, L

    2014-10-03

    We measured nuclear forward scattering spectra utilizing the (99)Ru transition, 89.571(3) keV, with a notably mixed E2/M1 multipolarity. The extension of the standard evaluation routines to include mixed multipolarity allows us to extract electric and magnetic hyperfine interactions from (99)Ru-containing compounds. This paves the way for several other high-energy Mössbauer transitions, E ∼ 90 keV. The high energy of such transitions allows for operando nuclear forward scattering studies in real devices.

  7. Mesoporous Trimetallic PtPdRu Spheres as Superior Electrocatalysts.

    PubMed

    Jiang, Bo; Ataee-Esfahani, Hamed; Li, Cuiling; Alshehri, Saad M; Ahamad, Tansir; Henzie, Joel; Yamauchi, Yusuke

    2016-05-17

    Mesoporous Trimetallic PtPdRu Spheres with well-defined spherical morphology and uniformly sized pores were synthesized in an aqueous solution using ascorbic acid as the reducing agent and triblock copolymer F127 as the pore directing agent. These mesoporous PtPdRu spheres exhibited enhanced electrocatalytic activity compared to commercial Pt black, resulting in a ∼4.9 times improvement in mass activity for the methanol oxidation reaction. The excellent electrocatalytic activity and stability are due to the unique mesoporous architecture and electronic landscape between different elements.

  8. Nuclear forward scattering of synchrotron radiation by 99Ru

    DOE PAGES

    Bessas, D.; Merkel, D. G.; Chumakov, A. I.; ...

    2014-10-03

    In this study, we measured nuclear forward scattering spectra utilizing the 99Ru transition, 89.571(3) keV, with a notably mixed E2/M1 multipolarity. The extension of the standard evaluation routines to include mixed multipolarity allows us to extract electric and magnetic hyperfine interactions from 99Ru-containing compounds. This paves the way for several other high-energy Mössbauer transitions, E~90 keV. Lastly, the high energy of such transitions allows for operando nuclear forward scattering studies in real devices.

  9. Orbital entanglement and CASSCF analysis of the Ru-NO bond in a Ruthenium nitrosyl complex.

    PubMed

    Freitag, Leon; Knecht, Stefan; Keller, Sebastian F; Delcey, Mickaël G; Aquilante, Francesco; Pedersen, Thomas Bondo; Lindh, Roland; Reiher, Markus; González, Leticia

    2015-06-14

    Complete active space self-consistent field (CASSCF) wavefunctions and an orbital entanglement analysis obtained from a density-matrix renormalisation group (DMRG) calculation are used to understand the electronic structure, and, in particular, the Ru-NO bond of a Ru nitrosyl complex. Based on the configurations and orbital occupation numbers obtained for the CASSCF wavefunction and on the orbital entropy measurements evaluated for the DMRG wavefunction, we unravel electron correlation effects in the Ru coordination sphere of the complex. It is shown that Ru-NO π bonds show static and dynamic correlation, while other Ru-ligand bonds feature predominantly dynamic correlation. The presence of static correlation requires the use of multiconfigurational methods to describe the Ru-NO bond. Subsequently, the CASSCF wavefunction is analysed in terms of configuration state functions based on localised orbitals. The analysis of the wavefunctions in the electronic singlet ground state and the first triplet state provides a picture of the Ru-NO moiety beyond the standard representation based on formal oxidation states. A distinct description of the Ru and NO fragments is advocated. The electron configuration of Ru is an equally weighted superposition of Ru(II) and Ru(III) configurations, with the Ru(III) configuration originating from charge donation mostly from Cl ligands. However, and contrary to what is typically assumed, the electronic configuration of the NO ligand is best described as electroneutral.

  10. Half metallicity and magnetic properties of CrO2 doped with Ti, Sn or Ru

    NASA Astrophysics Data System (ADS)

    Yuan, C.; Lu, Z.; Liu, S.; Gan, Z.; Guo, F.; Xiong, R.; Mei, X.; Liu, H.; Shi, J.

    2016-11-01

    It is possible to stabilize CrO2 internally by doping with element such as Ti, Sn or Ru which has stable rutile structured oxide. However, the half metallicity and magnetic properties of CrO2 may also change when doped with different elements. In this study, by using first principle method, the electronic structure and magnetic properties of CrO2 doped with different amounts and different types (Ti, Sn or Ru) of dopants were studied. It was found that when doped with Ti or Sn, the half metallicity of CrO2 will keep intact even at very high dopant concentration, while for Ru-doped CrO2, the half metallicity will only be maintained at low Ru concentration. Besides, the half metallicity of Ru-doped CrO2 also depends on the relative positions of Ru atoms - the half metallicity may be destroyed even at low Ru concentration if two Ru ions are very close to each other. The magnetic properties of doped CrO2 also show dependence on dopant concentration and dopant type. The magnetocrystalline anisotropy (MAC) of Ru-doped is found to be very sensitive to both Ru concentration and relative positions of Ru atoms. Large MAC may be induced by Ru doping.

  11. Face to phase with RU Lupi

    NASA Astrophysics Data System (ADS)

    Gahm, G. F.; Stempels, H. C.; Walter, F. M.; Petrov, P. P.; Herczeg, G. J.

    2013-12-01

    Context. Some classical T Tauri stars, with intense line and continuous excess emission, show extremely complex spectral variations. Aims: We aim to map and interpret the spectral variations in one such extreme T Tauri star, namely RU Lupi, and to explore how the changes are related to stellar brightness and rotational phase. Methods: We followed the star over three observing runs, each covering a few days, collecting high-resolution optical spectra. In connection to the third run, complementary NIR spectra, multicolour photometric data, and X-ray observations were obtained. Results: The stellar photospheric absorption line spectrum is weakened by superimposed emission, and this veiling becomes extremely high on occasion. Interpreted as a variable continuous excess emission, its contribution would amount to several times the stellar continuum brightness. However, the stellar brightness does not change much when the veiling changes, and we conclude that the veiling is dominated by narrow line emission that fills in the photospheric lines. Continuous emission, originating at the hot spot on the stellar surface, plays a dominant role only at lower degrees of veiling. The radial velocity of narrow emission components in lines of He i vary periodically in anti-phase with the stellar velocity, reflecting the location and motion of the accretion footprint. The blue-shifted wings in He i, related to a stellar wind, are remarkably stable in equivalent width. This implies that the line flux responds directly to changes in the veiling, which in turn is related to the accretion rate close to the star. In contrast, the equivalent widths of the red-shifted wings change with rotational phase. From the pattern of variability we infer that these wings originate in accreting gas close to the star, and that the accretion funnels are bent and trail the hot spot. The profiles of the forbidden lines of [O I] and [S II] are very stable in strength and shape over the entire observing

  12. Narrow band gap and enhanced thermoelectricity in FeSb2.

    PubMed

    Sun, Peijie; Oeschler, Niels; Johnsen, Simon; Iversen, Bo B; Steglich, Frank

    2010-01-28

    FeSb(2) was recently identified as a narrow-gap semiconductor with indications of strong electron-electron correlations. In this manuscript, we report on systematic thermoelectric investigation of a number of FeSb(2) single crystals with varying carrier concentrations, together with two isoelectronically substituted FeSb(2-x)As(x) samples (x = 0.01 and 0.03) and two reference compounds FeAs(2) and RuSb(2). Typical behaviour associated with narrow bands and narrow gaps is only confirmed for the FeSb(2) and the FeSb(2-x)As(x) samples. The maximum absolute thermopower of FeSb(2) spans from 10 to 45 mV/K at around 10 K, greatly exceeding that of both FeAs(2) and RuSb(2). The relation between the carrier concentration and the maximum thermopower value is in approximate agreement with theoretical predictions of the electron-diffusion contribution which, however, requires an enhancement factor larger than 30. The isoelectronic substitution leads to a reduction of the thermal conductivity, but the charge-carrier mobility is also largely reduced due to doping-induced crystallographic defects or impurities. In combination with the high charge-carrier mobility and the enhanced thermoelectricity, FeSb(2) represents a promising candidate for thermoelectric cooling applications at cryogenic temperatures.

  13. A Ru(II) complex with 2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline: synthesis, characterization, and acid-base and DNA-binding properties.

    PubMed

    Gao, Jie; Wang, Zhi-Ping; Yuan, Cui-Li; Jia, Hai-Shun; Wang, Ke-Zhi

    2011-09-01

    A new Ru(II) complex of [Ru(bpy)2(Hmspip)]Cl2 {in which bpy=2,2'-bipyridine, Hmspip=2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline} have been synthesized and characterized. The ground- and excited-state acid-base properties of [Ru(bpy)2(Hmspip)]Cl2 and its parent complex of [Ru(bpy)2(Hpip)]Cl2 {Hpip=2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline} have been studied by UV-visible (UV-vis) and emission spectrophotometric pH titrations. [Ru(bpy)2(Hmspip)]Cl2 acts as a calf thymus DNA intercalators with a binding constant of 4.0×10(5) M(-1) in buffered 50 mM NaCl, as evidenced by UV-vis and luminescence titrations, steady-state emission quenching by [Fe(CN)6]4-, DNA competitive binding with ethidium bromide, reverse salt titrations and viscosity measurements.

  14. Heterotrimetallic Ru(II)/Pd(II)/Ru(II) complexes: synthesis, crystalstructure, spectral characterization, DFT calculation and antimicrobial study.

    PubMed

    Al-Noaimi, Mousa; Nafady, Ayman; Warad, Ismail; Alshwafy, Rwaida; Husein, Ahmad; Talib, Wamidh H; Hadda, Taibi Ben

    2014-03-25

    New ruthenium(II) mononuclear complexes of the type [RuCl2(PPh3)2(η(2)-triamine)] (2) [RuCl(PPh3)2(η(3)-triamine)]Cl (5) (triemine=N(1)-(2-aminoethyl)-1,2-ethanediamine) have been synthesized by reacting [RuCl2(PPh3)3] (1) with one mole equivalent of N(1)-(2-aminoethyl)-1,2-ethanediamine in dichloromethane. Reaction of (2) with half-equivalent of (PhCN)2PdCl2 or Pd(OAc)2 in dichloromethane as a solvent afforded two novel heterotrimetallic Ru(II)-Pd(II)-Ru(II) complexes, [Ru(II)Cl2(PPh3)2(triamine)]2[Pd(II)X2](X=Cl, OAc) (3 and 4), bearing bioactive ligand. The progress of the undertaken reactions was monitored by (31)P{1H} NMR and FTIR. Crystal structure of complex 2 was confirmed by X-ray diffraction. The absorption spectrum of 2 in dichloromethane was modeled by time-dependent density functional theory (TD-DFT). The in vitro antimicrobial studies of complex 2-5 against an array of microorganisms (bacteria and fungi) were conducted. Complexes 3 and 4 exhibit high dual antibacterial and antifungal activity inhibiting microorganisms possibly via hydrolytic pathway which further evidenced by electrochemical analyses. The complexes 3 and 4 show a high inhibitory activity at 200 μg/ml concentration, suggesting that complexes 3 and 4 are two efficient catalytic inhibitor of microorganisms and further, they should be tested against cancer strains.

  15. Heterotrimetallic Ru(II)/Pd(II)/Ru(II) complexes: Synthesis, crystalstructure, spectral characterization, DFT calculation and antimicrobial study

    NASA Astrophysics Data System (ADS)

    Al-Noaimi, Mousa; Nafady, Ayman; Warad, Ismail; Alshwafy, Rwaida; Husein, Ahmad; Talib, Wamidh H.; Hadda, Taibi Ben

    2014-03-01

    New ruthenium(II) mononuclear complexes of the type [RuCl2(PPh3)2(η2-triamine)] (2) [RuCl(PPh3)2(η3-triamine)]Cl (5) (triemine = N1-(2-aminoethyl)-1,2-ethanediamine) have been synthesized by reacting [RuCl2(PPh3)3] (1) with one mole equivalent of N1-(2-aminoethyl)-1,2-ethanediamine in dichloromethane. Reaction of (2) with half-equivalent of (PhCN)2PdCl2 or Pd(OAc)2 in dichloromethane as a solvent afforded two novel heterotrimetallic Ru(II)-Pd(II)-Ru(II) complexes, [RuIICl2(PPh3)2(triamine)]2[PdIIX2](X = Cl, OAc) (3 and 4), bearing bioactive ligand. The progress of the undertaken reactions was monitored by 31P{1H} NMR and FTIR. Crystal structure of complex 2 was confirmed by X-ray diffraction. The absorption spectrum of 2 in dichloromethane was modeled by time-dependent density functional theory (TD-DFT). The in vitro antimicrobial studies of complex 2-5 against an array of microorganisms (bacteria and fungi) were conducted. Complexes 3 and 4 exhibit high dual antibacterial and antifungal activity inhibiting microorganisms possibly via hydrolytic pathway which further evidenced by electrochemical analyses. The complexes 3 and 4 show a high inhibitory activity at 200 μg/ml concentration, suggesting that complexes 3 and 4 are two efficient catalytic inhibitor of microorganisms and further, they should be tested against cancer strains.

  16. CaFe interstellar clouds

    NASA Astrophysics Data System (ADS)

    Bondar, A.; Kozak, M.; Gnaciński, P.; Galazutdinov, G. A.; Beletsky, Y.; Krełowski, J.

    2007-07-01

    A new kind of interstellar cloud is proposed. These are rare (just a few examples among ~300 lines of sight) objects with the CaI 4227-Å, FeI 3720-Å and 3860-Å lines stronger than those of KI (near 7699 Å) and NaI (near 3302 Å). We propose the name `CaFe' for these clouds. Apparently they occupy different volumes from the well-known interstellar HI clouds where the KI and ultraviolet NaI lines are dominant features. In the CaFe clouds we have not found either detectable molecular features (CH, CN) or diffuse interstellar bands which, as commonly believed, are carried by some complex, organic molecules. We have found the CaFe clouds only along sightlines toward hot, luminous (and thus distant) objects with high rates of mass loss. In principle, the observed gas-phase interstellar abundances reflect the combined effects of the nucleosynthetic history of the material, the depletion of heavy elements into dust grains and the ionization state of these elements which may depend on irradiation by neighbouring stars. Based on data collected using the Maestro spectrograph at the Terskol 2-m telescope, Russia; and on data collected using the ESO Feros spectrograph; and on data obtained from the ESO Science Archive Facility acquired with the UVES spectrograph, Chile. E-mail: `arctur'@rambler.ru (AB); marizak@astri.uni.torun.pl (MK); pg@iftia.univ.gda.pl (PG); gala@boao.re.kr (GAG); ybialets@eso.org (YB); jacek@astri.uni.torun.pl (JK)

  17. Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe).

    PubMed

    Laha, S; Natarajan, S; Gopalakrishnan, J; Morán, E; Sáez-Puche, R; Alario-Franco, M Á; Dos Santos-Garcia, A J; Pérez-Flores, J C; Kuhn, A; García-Alvarado, F

    2015-02-07

    We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to

  18. Variation of the Ru moment in the Ca(0.3)Sr(0.7)Ru(1-x)Mn(x)O3 system.

    PubMed

    Mizusaki, S; Naito, M; Taniguchi, T; Nagata, Y; Itou, M; Sakurai, Y; Noro, Y; Ozawa, T C; Samata, H

    2010-04-14

    The variation of the magnetic moment on Ru and Mn atoms in the Ca(0.3)Sr(0.7)Ru(1-x)Mn(x)O(3) system was investigated by the magnetic Compton scattering technique using synchrotron radiation. The Ca(0.3)Sr(0.7)Ru(1-x)Mn(x)O(3) system has ferrimagnetism with an antiferromagnetic coupling between Ru and Mn, and the dominant magnetic component changes from ferromagnetic Ru to ferromagnetic Mn at x ∼0.25 as the Mn substitution proceeds. The mechanism for the change in the magnetism of Ca(0.3)Sr(0.7)Ru(1-x)Mn(x)O(3) is discussed.

  19. The effects of structural variations of thiophene-containing Ru(II) complexes on the acid-base and DNA binding properties.

    PubMed

    Yuan, Cui-Li; Zhang, An-Guo; Zheng, Ze-Bo; Wang, Ke-Zhi

    2013-03-01

    A phenylthiophenyl-bearing Ru(II) complex of [Ru(bpy)₂(Hbptip)](PF₆)₂ {bpy = 2,2'-bipyridine, Hbptip = 2-(4-phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline} was synthesized and characterized by elemental analysis, ¹H NMR spectroscopy, and electrospray ionization mass spectrometry. The ground- and excited-state acid-base properties of the complex were studied by UV-visible absorption and photoluminescence spectrophotometric pH titrations and the negative logarithm values of the ground-state acid ionization constants were derived to be pK(a1) = 1.31 ± 0.09 and pK(a2) = 5.71 ± 0.11 with the pK(a2) associated deprotonation/protonation process occurring over 3 pK(a) units more acidic than thiophenyl-free parent complex of [Ru(bpy)₂(Hpip)]²⁺ {Hpip = 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline}. The calf thymus DNA-binding properties of [Ru(bpy)₂(Hbptip)]²⁺ in Tris-HCl buffer (pH 7.1 and 50 mM NaCl) were investigated by DNA viscosities and density functional theoretical calculations as well as UV-visible and emission spectroscopy techniques of UV-visible and luminescence titrations, steady-state emission quenching by [Fe(CN)₆]⁴⁻, DNA competitive binding with ethidium bromide, DNA melting experiments, and reverse salt effects. The complex was evidenced to bind to the DNA intercalatively with binding affinity being greater than those for previously reported analogs of [Ru(bpy)₂(Hip)]²⁺, [Ru(bpy)₂(Htip)]²⁺, and [Ru(bpy)₂(Haptip)]²⁺ {Hip = 1H-imidazo[4,5-f][1,10]phenanthroline, Htip = 2-thiophenimidazo[4,5-f][1,10]phenanthroline, Haptip = 2-(5-phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline}.

  20. The Nanostructuring of Atomically Flat Ru(0001) upon Oxidation and Reduction

    NASA Astrophysics Data System (ADS)

    Goriachko, A.; Over, H.

    2016-12-01

    The O/Ru(0001) system is widely studied due to its rich phase variety of various stoichiometry and atomic arrangements, including the formation of a RuO2/Ru(0001) oxide layer. Apart from homogeneous ruthenium surfaces in certain oxidation states, also strongly heterogeneous surfaces can exist due to oxidation state's variation at the nanoscale. We report on a scanning tunneling microscopy (STM) study of the nanostructuring of the oxidized Ru(0001) surface as a result of its interaction with molecular oxygen at elevated temperatures and subsequent reduction of a resulting RuO2 film by CO or HCl molecules from the gas phase in high-vacuum environment.

  1. Hydrous RuO2 nanoparticles as highly active electrocatalysts for hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Lee, Jooyoung; Sher Shah, Selim Arif; Yoo, Pil J.; Lim, Byungkwon

    2017-04-01

    This letter describes an aqueous-phase synthetic route to hydrous ruthenium oxide (RuO2) nanoparticles and their conversion into crystalline ones via a thermal annealing process. Electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were employed to characterize hydrous and crystalline RuO2 nanoparticles. The hydrous RuO2 nanoparticles exhibited higher activity for hydrogen evolution reaction than commercial Pt catalyst, while the crystalline RuO2 nanoparticles showed better performance for oxygen evolution reaction than IrO2 catalyst. With these hydrous and crystalline RuO2 catalysts, we were able to achieve highly efficient overall electrochemical water splitting.

  2. ELECTRONIC AND TRANSPORT PROPERTIES OF THERMOELECTRIC Ru2Si3

    NASA Astrophysics Data System (ADS)

    Singh, David J.; Parker, David

    2013-08-01

    We report calculations of the doping and temperature dependent thermopower of Ru2Si3 based on Boltzmann transport theory and the first principles electronic structure. We find that the performance reported to date can be significantly improved by optimization of the doping level and that ultimately n-type should have higher ZT than p-type.

  3. Internal oxidation of laminated ternary Ru-Ta-Zr coatings

    NASA Astrophysics Data System (ADS)

    Chen, Yung-I.; Lu, Tso-Shen

    2015-10-01

    Researchers have observed the internal oxidation phenomenon in binary alloy coatings when developing refractory alloy coatings for protective purposes by conducting annealing at high temperatures and in oxygen-containing atmospheres. The coatings were assembled using cyclical gradient concentration deposition during cosputtering by employing a substrate holder rotating at a slow speed. The internally oxidized zone demonstrated a laminated structure, comprising alternating oxygen-rich and oxygen-deficient layers stacked in a general orientation. In the current study, Ru-Ta-Zr coatings were prepared with various stacking sequences during cosputtering. The Ru-Ta-Zr coatings were annealed at 600 °C in an atmosphere continuously purged with 1% O2-99% Ar mixed gas for 30 min. A transmission electron microscope was used to examine the periods of the laminated layers and crystallinity of the annealed coatings. Depth profiles produced using an Auger electron spectroscope and X-ray photoelectron spectroscope were used to certify the periodic variation of the related constituents and chemical states of the elements, respectively. The results indicate that the internally oxidized ternary coatings are stacked of Ru-, Ta2O5-, and ZrO2-dominant sublayers and that the stacking sequences of the sublayers affect the crystalline structure of the coatings. Zr is oxidized preferentially in the Ru-Ta-Zr coatings, increasing the surface hardness of the oxidized coatings.

  4. Os trigonum syndrome.

    PubMed

    Nault, Marie-Lyne; Kocher, Mininder S; Micheli, Lyle J

    2014-09-01

    Os trigonum syndrome is the result of an overuse injury of the posterior ankle caused by repetitive plantar flexion stress. It is predominantly seen in ballet dancers and soccer players and is primarily a clinical diagnosis of exacerbated posterior ankle pain while dancing on pointe or demi-pointe or while doing push-off maneuvers. Symptoms may improve with rest or activity modification. Imaging studies, including a lateral radiographic view of the ankle in maximal plantar flexion, will typically reveal the os trigonum between the posterior tibial lip and calcaneus. If an os trigonum is absent on radiography, an MRI may reveal scar tissue behind the posterior talus, a condition associated with similar symptoms. Os trigonum syndrome is often associated with pathology of the flexor hallucis longus tendon. Treatment begins with nonsurgical measures. In addition to physical therapy, symptomatic athletes may need surgical excision of os trigonum secondary to unavoidable plantar flexion associated with their sport. This surgery can be performed using open or arthroscopic approaches.

  5. Multiple Pathways for Benzyl Alcohol Oxidation by RuV=O3+ and RuIV=O2+

    SciTech Connect

    Paul, Amit; Hull, Jonathan F.; Norris, Michael R.; Chen, Zuofeng; Ess, Daniel H.; Concepcion, Javier J.; Meyer, Thomas J.

    2011-01-20

    Significant rate enhancements are found for benzyl alcohol oxidation by the RuV=O3+ form of the water oxidation catalyst [Ru(Mebimpy)(bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine] compared to RuIV=O2+ and for the RuIV=O2+ form with added bases due to a new pathway, concerted hydride proton transfer (HPT).

  6. Multiple Pathways for Benzyl Alcohol Oxidation by RuV=O3+ and RuIV=O2+

    SciTech Connect

    Paul, Amit; Hull, Jonathan F.; Norris, Michael R.; Chen, Zuofeng; Ess, Daniel H.; Concepcion, Javier J.; Meyer, Thomas J.

    2011-01-20

    Significant rate enhancements are found for benzyl alcohol oxidation by the RuV=O3+ form of the water oxidation catalyst [Ru(Mebimpy)(bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine] compared to RuIV=O2+ and for the RuIV=O2+ form with added bases due to a new pathway involving concerted hydride proton transfer (HPT).

  7. Planar junction tunneling study of single-crystal eutectic phases of Sr2RuO4/Sr3Ru2O7

    NASA Astrophysics Data System (ADS)

    Cai, Xinxin; Zakrzewski, Brian; Wang, H.; Andreou, C.; Schlom, D.; Mao, Z.-Q.; Cava, R. J.; Liu, Ying

    Despite of intensive study of many years, the precise value of the superconducting energy gap of the odd-parity superconductor Sr2RuO4 has not been fully settled. Many complications exist. The band dependence of superconductivity makes the results from a bulk measurement of the gap difficult to interpret quantitatively. Surface based measurements such as scanning tunneling spectroscopy have to deal with the suppression of the superconducting energy gap on the cleaved ab surface due to surface reconstruction. We performed quasi-particle tunneling measurements of the superconducting energy gap in planar junctions prepared on naturally cleaved edges of a Sr2RuO4 crystal found in the eutectic phase of Sr2RuO4 /Sr3Ru2O7. Cleaving of such eutectic crystals exposes thin Sr2RuO4 ``plates'' inserted in a Sr3Ru2O7 bulk crystal with the c axis along that of the Sr3Ru2O7 bulk, as shown by X-ray diffraction data. Results obtained on Au-Sr2RuO4/Sr3Ru2O7 tunnel junctions suggest that superconductivity survives on the surface of the ``plates'', showing a gap value of 0.2 meV, close to the BCS value for weak-coupling superconductors. Experiments on tunnel junctions made on cleaved crystals of a mesoscopic size are underway.

  8. Switchable diode-effect mechanism in ferroelectric BiFeO{sub 3} thin film capacitors

    SciTech Connect

    Matsuo, Hiroki; Kitanaka, Yuuki; Inoue, Ryotaro; Noguchi, Yuji Miyayama, Masaru

    2015-09-21

    We investigate the mechanism of a switchable diode behavior observed in ferroelectric SrRuO{sub 3}/BiFeO{sub 3} (BFO)/SrRuO{sub 3} capacitors. We experimentally demonstrate that the switchable diode effect observed in the capacitors is induced by the polarization reversal in the BFO film. The conductivity in an Ohmic region in different oxidation states provides direct evidence that electron hole acts as the majority carrier, delivering p-type conduction. Density functional theory (DFT) calculations show that the p-type conduction arises from an unoccupied gap state of Fe{sup 4+} in an FeO{sub 5} pyramid which is derived from Bi vacancy. Our experimental and DFT study leads to the conclusion that the switchable diode effect originates from an asymmetric band bending in the top and bottom depletion layers modulated by ferroelectric polarization and oxygen vacancies.

  9. Influence of capping layers on CoFeB anisotropy and damping

    SciTech Connect

    Natarajarathinam, A.; Tadisina, Z. R.; Gupta, S.; Mewes, T.; Watts, S.; Chen, E.

    2012-09-01

    Magnetic behavior of CoFeB at various thicknesses ranging from 2 nm to 8 nm capped with different materials, such as MgO, Ta, Ru, and V have been studied. The films were sputter-deposited and subsequently characterized by magnetometry and broadband ferromagnetic resonance (FMR). There are magnetically dead layers at the interface observed with Ru and Ta capping layers, while MgO and V have almost no effect on the magnetization of the CoFeB. As the ferromagnetic layer is made thinner, the effective magnetization decreases, indicating an interfacial perpendicular anisotropy. Particularly in the case of MgO, V/Ru, and V/Ta capping layers, interfacial perpendicular anisotropy is induced in CoFeB, and the Gilbert damping parameter is also reduced. The origin of this perpendicular magnetic anisotropy (PMA) is understood to be caused by the interface anisotropy between the free layer and the capping layer. The effect of post-deposition annealing and CoFeB thickness on the anisotropy and damping of V/Ta capped samples are reported. Doping CoFeB with vanadium (V) greatly reduced the 4{pi}M{sub s} and 4{pi}M{sub eff} values, resulting in an effective increase in the PMA.

  10. Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH.

    PubMed

    Zhang, Jing; Zhang, Ying; Wang, Hui; Guan, Xiaohong

    2014-07-01

    Ru(III) was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru(III) could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru(III) catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru(III), respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru(III) catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant (ktapp) decreased from 643.20 to 2.67 (mol/L)⁻¹sec⁻¹ with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru(III), as an electron shuttle, was oxidized by permanganate to Ru(VI) and Ru(VII), which acted the co-oxidants for decomposition of aniline. Although Ru(III) could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru(III) into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru(III) toward permanganate oxidation in our future study.

  11. Effect of gas composition on Ru dissolution and crossover in polymer-electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Cheng, Tommy T. H.; Jia, Nengyou; Colbow, Vesna; Wessel, Silvia; Dutta, Monica

    Pt-Ru-based anodes are commonly used in polymer-electrolyte membrane fuel cells (PEMFCs) to provide improved CO tolerance for reformate fuel applications. However, Ru crossover from the anode to the cathode has been identified as a critical durability problem that has severe performance implications. In the present study, an anode accelerated stress test (AST) was used to simulate potential spikes that occur during fuel cell start-ups and shutdowns to induce Ru crossover. The effects of fuel gas composition, namely hydrogen and carbon dioxide concentrations, on Ru dissolution and crossover were investigated. The cell performance losses were correlated with the degree of Ru crossover as determined by the changes in cathode cyclic voltammetry (CV) characteristics and neutron activation analysis (NAA). It was found that higher hydrogen concentration in the fuel accelerated Ru crossover and that the presence of carbon dioxide hindered Ru crossover. In particular, the injection of 20 vol.% carbon dioxide during potential cycling resulted in very minor Ru crossover, which showed essentially identical performance losses and CV characteristic changes as a fuel cell composed of a Ru-free anode. The experimental results suggest that the Ru species in our Pt-Ru metal oxide catalysts need to go through a reduction step by hydrogen before dissolution. The presence of carbon dioxide may play a role in hindering the reduction step.

  12. Synthesis and characterization of noble metal borides: RuB{sub x}(x > 1)

    SciTech Connect

    Li, Zhifang; Zheng, Dafang; Ding, Zhanhui; Li, Yongfeng; Yao, Bin; Li, Yongsheng; Zhao, Xudong; Yu, Guichuan; Tang, Yang; Zheng, Weitao; Liu, Xiaoyang

    2016-02-15

    Highlights: • Hexagonal RuB{sub 1.1} were synthesized using ruthenium and boron powders as raw materials during ball milling process. • Orthorhombic RuB{sub 2} were synthesized under high pressure (5 GPa) and high temperature (1000 °C) conditions. • Hexagonal Ru{sub 2}B{sub 3} have been synthesized under 5 GPa and 1200 °C. - Abstract: Noble metal borides RuB{sub 1.1}, RuB{sub 2} and Ru{sub 2}B{sub 3} have been synthesized by mechanical alloying and high pressure sintering methods using ruthenium (Ru) and boron (B) powders as raw materials. The crystal structures of borides were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results shown that only RuB{sub 1.1} with hexagonal crystal structure was synthesized during the ball milling process, the orthorhombic RuB{sub 2} was synthesized under high pressure (5 GPa) and high temperature (1000 °C) conditions, while the hexagonal Ru{sub 2}B{sub 3} can be synthesized under 5 GPa and 1200 °C. The mechanism of synthesis for the ruthenium borides (RuB{sub x}) are discussed in details.

  13. {beta}-K{sub 4}La{sub 6}I{sub 14}Os: A new structure type for rare-earth-metal cluster compounds that contains discrete tetrahedral K{sub 4}I{sup 3+} units

    SciTech Connect

    Uma, S.; Corbett, J.D.

    1999-08-23

    Suitable reactions of KI, La, LaI{sub 3}, and Os in niobium tubes at 800--850 C result in black, air- and moisture-sensitive crystals of the quaternary title phase. Isostructural K{sub 4}Pr{sub 6}I{sub 14}Z also exist for Z = Fe, Ru. The title phase was characterized by single-crystal X-ray diffraction (tetragonal, P4/ncc (No. 130), Z = 4; a = 13.117(3), c = 25.17(1) {angstrom} at 23 C). The important structural feature is the constitution (K{sub 4}I){sup 3+}(La{sub 6}I{sub 13}Os{sup 3{minus}}) with a new type of 3D anion network of [(La{sub 6}Os)I{sub 8}{sup i}I{sub 4/2}{sup i{minus}a}I{sub 4/2}{sup a{minus}i}I{sub 2/2}{sup a{minus}a}] clusters that are connected into puckered layers through I{sup i{minus}a} and I{sup a{minus}i} atom pairs that bridge diagonally in the a-b plane. These cluster layers are further interlinked along {rvec c} at trans-vertexes through simple bridging I{sup a{minus}a}. The 14th iodine atom occurs in the unique K{sub 4}I{sup 3+} ions which lie in columns that interpenetrate the La{sub 6}OsI{sub 13} network along c. The present 16-e{sup {minus}} clusters, in contrast with the optimal 18-e{sup {minus}} octahedral cluster configuration, exhibit an uncommon tetragonal elongation and evidently become closed shell, with only a small temperature-independent (van Vleck-like) paramagnetism, {approximately}4 x 10{sup {minus}4} emu mol{sup {minus}1}.

  14. Induction of Cytotoxicity in Pyridine Analogues of the Anti-metastatic Ru(III) Complex NAMI-A by Ferrocene Functionalization.

    PubMed

    Mu, Changhua; Chang, Stephanie W; Prosser, Kathleen E; Leung, Ada W Y; Santacruz, Stephanie; Jang, Thalia; Thompson, John R; Yapp, Donald T T; Warren, Jeffrey J; Bally, Marcel B; Beischlag, Timothy V; Walsby, Charles J

    2016-01-04

    A series of novel ferrocene (Fc) functionalized Ru(III) complexes was synthesized and characterized. These compounds are derivatives of the anti-metastatic Ru(III) complex imidazolium [trans-RuCl4(1H-imidazole) (DMSO-S)] (NAMI-A) and are derived from its pyridine analogue (NAMI-Pyr), with direct coupling of Fc to pyridine at the 4 or 3 positions, or at the 4 position via a two-carbon linker, which is either unsaturated (vinyl) or saturated (ethyl). Electron paramagnetic resonance (EPR) and UV-vis spectroscopic studies of the ligand exchange processes of the compounds in phosphate buffered saline (PBS) report similar solution behavior to NAMI-Pyr. However, the complex with Fc substitution at the 3 position of the coordinated pyridine shows greater solution stability, through resistance to the formation of oligomeric species. Further EPR studies of the complexes with human serum albumin (hsA) indicate that the Fc groups enhance noncoordinate interactions with the protein and help to inhibit the formation of protein-coordinated species, suggesting the potential for enhanced bioavailability. Cyclic voltammetry measurements demonstrate that the Fc groups modestly reduce the reduction potential of the Ru(III) center as compared to NAMI-Pyr, while the reduction potentials of the Fc moieties of the four compounds vary by 217 mV, with the longer linkers giving significantly lower values of E1/2. EPR spectra of the compounds with 2-carbon linkers show the formation of a high-spin Fe(III) species (S = 5/2) in PBS with a distinctive signal at g = 4.3, demonstrating oxidation of the Fe(II) ferrocene center and likely reflecting degradation products. Density functional theory calculations and paramagnetic (1)H NMR describe delocalization of spin density onto the ligands and indicate that the vinyl linker could be a potential pathway for electron transfer between the Ru and Fe centers. In the case of the ethyl linker, electron transfer is suggested to occur via an indirect

  15. Investigation of surrogate reactions near A=100: ^102,104Ru(,') for ^101,103Ru(n,γ)

    NASA Astrophysics Data System (ADS)

    Church, J. A.; Bernstein, L. A.; Burke, J. T.; Dietrich, F.; Escher, J.; Forssen, C.; Norman, E. B.; Ai, H.-C.; Phair, L.; Clark, R.; Fallon, P. A.; Lee, D.; Lee, I. Y.; Macchiavelli, A. O.; McMahan, P.; Sinha, S.; Stephens, M.; -Vietez, E. R.; Wiedeking, M.

    2006-10-01

    For two-step, neutron-induced reactions proceeding through an equilibrated intermediate state, an alternate, ``surrogate reaction'' technique is applicable. Measured decay probabilities for the intermediate nucleus formed via a light-ion reaction are combined with optical-model calculations for the formation of the same intermediate nucleus via the n- induced reaction, and result in the overall (n, γ/n/2n) cross sections. ^102,104Ru(,') were studied separately as surrogate reactions for ^101,103Ru (n,γ). The test, ^101Ru(n,γ), has been previously measured directly (EXFOR). The unknown, ^103Ru (n,γ), is a branch in the s-process. Energies of scattered α particles were detected in double-sided silicon detectors (STARS) over scattering angles of 42-60 degrees. Ge clover detectors (LiBerACE) were used to count γ-rays in coincidence with α particles scattered at energies corresponding to 0-3 MeV equivalent neutron energy in the desired (n,γ) reaction. Work performed under the auspices of the U.S. DOE by the Univ. of CA, LLNL contract No. W-7405-Eng-4, and DOE grants DE-FG02-91ER-40609 and DE-FG03- 03NA00081, LDRD-04-ERD-057. J.D. Cramer and H.C. Britt, Nucl. Sci. Eng., 41, 177 (1970).

  16. Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol

    SciTech Connect

    Sun, Junming; Karim, Ayman M.; Zhang, He; Kovarik, Libor; Li, Xiaohong Shari; Hensley, Alyssa J.; McEwen, Jean-Sabin; Wang, Yong

    2013-10-01

    Abstract Carbon supported metal catalysts (Cu/C, Fe/C, Pd/C, Pt/C, PdFe/C and Ru/C) have been prepared, characterized and tested for vapor-phase hydrodeoxygenation (HDO) of guaiacol (GUA) at atmospheric pressure. Phenol was the major intermediate on all catalysts. Over the noble metal catalysts saturation of the aromatic ring was the major pathway observed at low temperature (250 °C), forming predominantly cyclohexanone and cyclohexanol. Substantial ring opening reaction was observed on Pt/C and Ru/C at higher reaction temperatures (e.g., 350 °C). Base metal catalysts, especially Fe/C, were found to exhibit high HDO activity without ring-saturation or ring-opening with the main products being benzene, phenol along with small amounts of cresol, toluene and trimethylbenzene (TMB). A substantial enhancement in HDO activity was observed on the PdFe/C catalysts. Compared with Fe/C, the yield to oxygen-free aromatic products (i.e., benzene/toluene/TMB) on PdFe/C increased by a factor of four at 350 °C, and by approximately a factor of two (83.2% versus 43.3%) at 450 °C. The enhanced activity of PdFe/C is attributed to the formation of PdFe alloy as evidenced by STEM, EDS and TPR.

  17. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    DOE PAGES

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; ...

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1more » M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.« less

  18. Thermal Stability of Co-Sputtered Ru Ti Alloy Electrodes for Dynamic Random Access Memory Applications

    NASA Astrophysics Data System (ADS)

    Horng, Ray-Hua; Wuu, Dong-Sing; Wu, Luh-Huei; Lee, Ming-Kwei; Chan, Shih-Hsiung; Leu, Ching-Chich; Huang, Tiao-Yuan; Sze, Simon

    1998-10-01

    Ru Ti alloy films were studied for use as a bottom electrode of ferroelectric/paraelectric thin film capacitors. These thin films with different Ru/Ti compositions were first prepared by co-sputtering. The Ru/Ti ratio in the alloy was found to strongly affect the resistivity, structure formation and thermal stability. The resistivity of the as-deposited films decreases and closes to that of pure Ru metal films as the amount of Ru atoms increasing. From X-ray diffraction measurement, it was found that the RuTi phase has formed for the as-deposited sample. There also exist Ru and Ti phases for Ru-enriched and Ti-enriched samples, respectively. As-deposited alloy films were also annealed by rapid thermal processing (RTP, 600 750°C, 1 min) in oxygen ambient to simulate the processing of ferroelectric/paraelectric thin film capacitors. It was found that the composition of the thin film has a large effect on the thermal stability. The resistivity of alloy thin films is thermally stable as the Ru composition varies from 0.68 to 0.81. It may be due to the RuTiO2 formation at the surface and play an important role in preventing further oxidation of the Ru-enriched layer. This oxide also presents conductive behavior. On the other hand, the interface between Ru-enriched alloys and Si substrate was still sharp for the RTP-treated sample at 600°C for 1 min. The alloy film with high Ru composition shows excellent thermal stability and barriers against interdiffusion of Si and oxygen. These results suggest that the Ru-enriched alloy films are suitable for the bottom electrode application in ferroelectric/paraelectric thin film capacitors.

  19. Development of a Ru complex-incorporated MOF photocatalyst for hydrogen production under visible-light irradiation.

    PubMed

    Toyao, Takashi; Saito, Masakazu; Dohshi, Satoru; Mochizuki, Katsunori; Iwata, Masatoshi; Higashimura, Hideyuki; Horiuchi, Yu; Matsuoka, Masaya

    2014-06-28

    A Ru complex-incorporated Ti-based MOF (Ti-MOF-Ru(tpy)2) has been synthesised by using a bis(4'-(4-carboxyphenyl)-terpyridine)Ru(ii) complex (Ru(tpy)2) as an organic linker. Ti-MOF-Ru(tpy)2 promotes photocatalytic hydrogen production from water containing a sacrificial electron donor under visible-light irradiation up to 620 nm.

  20. Re-187-Os-187, Pt-190-Os-186 Isotopic and Highly Siderophile Element Systematics of Group IVA Irons

    NASA Technical Reports Server (NTRS)

    Walker, R. J.; McCoy, T. J.; Schulte, R. F.; McDonough, W. F.; Ash, R. D.

    2005-01-01

    We have recently completed Re-187-Os-187 and Pt-190-Os-186 isotopic and elemental studies of the two largest magmatic iron meteorite groups, IIAB and IIIAB [1]. These studies revealed closed-system behavior of both isotopic systems, but complex trace element behavior for Re, Pt and Os in group IIIAB. Here we examine isotopic and trace elemental systematics of group IVA irons. The IVA irons are not as extensively fractionated as IIAB and IIIAB and their apparently less complex crystallization history may make for more robust interpretation of the relative partitioning behavior of Re, Pt and Os, as well as the other highly siderophile elements (HSE) measured here; Pd, Ru and Ir [e.g. 2]. An additional goal of our continuing research plan for iron meteorites is to assess the possibility of relating certain ungrouped irons with major groups via trace element modeling. Here, the isotopic and trace element systematics of the ungrouped irons Nedagolla and EET 83230 are compared with the IVA irons.

  1. Synthesis, spectral and electrochemical studies of binuclear Ru(III) complexes containing dithiosemicarbazone ligand.

    PubMed

    Kanchana Devi, A; Ramesh, R

    2014-01-03

    Synthesis of several new octahedral binuclear ruthenium(III) complexes of the general composition [(EPh3)2(X)Ru-L-Ru(X)(EPh3)2] containing benzene dithiosemicarbazone ligands (where E=P or As; X=Cl or Br; L=binucleating ligands) is presented. All the complexes have been fully characterized by elemental analysis, FT-IR, UV-vis and EPR spectroscopy together with magnetic susceptibility measurements. IR study shows that the dithiosemicarbazone ligands behave as dianionic tridentate ligands coordinating through the oxygen atom of the deprotonated phenolic group, nitrogen atom of the azomethine group and thiolate sulphur. In DMF solution, all the complexes exhibit intense d-d transition and ligand-to-metal charge transfer (LMCT) transition in the visible region. The magnetic moment values of the complexes are in the range 1.78-1.82 BM, which reveals the presence of one unpaired electron on each metal ion. The EPR spectra of the liquid samples at LNT show the presence of three different 'g' values (gx≠gy≠gz) indicate a rhombic distortion around the ruthenium ion. All the complexes exhibit two quasi-reversible one electron oxidation responses (Ru(III)-Ru(III)/Ru(III)-Ru(IV); Ru(III)-Ru(IV)/Ru(IV)-Ru(IV)) within the E1/2 range of 0.61-0.74 V and 0.93-0.98 V respectively, versus Ag/AgCl.

  2. Novel 2D RuPt core-edge nanocluster catalyst for CO electro-oxidation

    NASA Astrophysics Data System (ADS)

    Grabow, Lars C.; Yuan, Qiuyi; Doan, Hieu A.; Brankovic, Stanko R.

    2015-10-01

    A single layer, bi-metallic RuPt catalyst on Au(111) is synthesized using surface limited red-ox replacement of underpotentially deposited Cu and Pb monolayers though a two-step process. The resulting 2D RuPt monolayer nanoclusters have a unique core-edge structure with a Ru core and Pt at the edge along the perimeter. The activity of this catalyst is evaluated using CO monolayer oxidation as the probe reaction. Cyclic voltammetry demonstrates that the 2D RuPt core-edge catalyst morphology is significantly more active than either Pt or Ru monolayer catalysts. Density functional theory calculations in combination with infra-red spectroscopy data point towards oscillating variations (ripples) in the adsorption energy landscape along the radial direction of the Ru core as the origin of the observed behavior. Both, CO and OH experience a thermodynamic driving force for surface migration towards the Ru-Pt interface, where they adsorb most strongly and react rapidly. We propose that the complex interplay between epitaxial strain, ligand and finite size effects is responsible for the formation of the rippled RuPt monolayer cluster, which provides optimal conditions for a quasi-ideal bi-functional mechanism for CO oxidation, in which CO is adsorbed mainly on Pt, and Ru provides OH to the active Pt-Ru interface.

  3. RuSi@Ru(bpy)3(2+)/Au@Ag2S nanoparticles electrochemiluminescence resonance energy transfer system for sensitive DNA detection.

    PubMed

    Wu, Mei-Sheng; He, Li-Jing; Xu, Jing-Juan; Chen, Hong-Yuan

    2014-05-06

    This work describes a new electrochemiluminescence resonance energy transfer (ECL-RET) system with graphene oxide(GO)-Au/RuSi@Ru(bpy)3(2+)/chitosan (CS) composites as the ECL donor and Au@Ag2S nanoparticles (NPs) as ECL the acceptor for the first time. The ECL signal observed by the application of GO-Au/RuSi@Ru(bpy)3(2+)/CS composites was enhanced for 5-fold compared to that of RuSi@Ru(bpy)3(2+)/CS in the presence of coreactant tripropylamine (TPA) due to the increased surface area and improved electrical conductivity by using graphene oxide-gold nanoparticles (GO-Au) composite materials. In addition, we synthesized Au@Ag2S core-shell NPs, whose UV-vis absorption spectrum shows good spectral overlap with the ECL spectrum of GO-Au/RuSi@Ru(bpy)3(2+)/CS composites by adjusting the amount of Na2S and AgNO3 in the process of synthesis. The distance between energy donor and acceptor was studied to get the highly effective ECL-RET. Then, this ECL-RET system was developed for sensitive and specific detection of target DNA, and the ECL quenching efficiency (ΔI/I0, ΔI = I0 - I) was found to be logarithmically related to the concentration of the target DNA in the range from 10 aM to 10 pM.

  4. Nmr evidence for coexistence of superconductivity and ferromagnetic component in magnetic superconductor RuSr2YCu2O8: 99,101Ru and 63Cu NMR.

    PubMed

    Tokunaga, Y; Kotegawa, H; Ishida, K; Kitaoka, Y; Takagiwa, H; Akimitsu, J

    2001-06-18

    From Ru- and Cu-NMR studies, we present evidence for coexistence of superconductivity and ferromagnetism in a cuprate superconductor RuSr2YCu2O8 (RuY1212). The observation of a large enhancement of a radio-frequency field for the Ru-NMR signal at zero field reveals the existence of a ferromagnetic (FM) component in the ordered RuO2 plane below a Curie temperature of TM = 150 K. Just below the onset temperature of superconductivity T(onset)c = 45 K, a remarkable decrease of the nuclear spin-lattice relaxation rate 1/T1 was observed within the ordered RuO2 plane as well as the CuO2 plane, revealing that the superconducting gap coexists with the FM component in the RuO2 plane on a microscopic scale. In addition, from the observation of a sharp peak in 101(1/T1) at T(zero)c approximately 23 K where the resistivity becomes zero, we suggest that the motion of self-induced vortices originating from fluctuations of the FM component induces the resistivity between T(onset)c and T(zero)c in RuY1212.

  5. Diamagnetic Ru(2+) in Na2La2Ti2RuO10-x (0 < x < 2): A Series of Complex Oxides Prepared by Topochemical Reduction.

    PubMed

    Pratt, Jacob A; Shepherd, Ashley M; Hayward, Michael A

    2015-11-16

    Reaction of the n = 3 Ruddlesden-Popper phase Na2La2Ti2RuO10 with a 5% H2/95% N2 atmosphere between 300 and 900 °C leads to the formation of phases of composition Na2La2Ti2RuO10-x (0 < x < 2) via topochemical reduction. Magnetization data collected from Na2La2Ti2RuO10-x samples in the range 0 < x < 1 show a rapid decline in susceptibility with increasing x, consistent with the conversion of S = 1, Ru(4+) centers at x = 0 to S = 0, Ru(2+) centers at x = 1. We believe this is the first report of diamagnetic Ru(2+) centers in an extended oxide phase. Further reduction of Na2La2Ti2RuO9 leads to the reduction of Ti(4+) to Ti(3+); however, Na2La2Ti2RuO10-x samples in the range 1 < x < 2 exhibit only a very weak paramagnetic response. Given the highly insulating nature of the phases, this suggests the electrons added on reduction of titanium are paired within a local Ti-Ti bonding network in a manner analogous to that observed for TinO2n-1 phases.

  6. Magnetic, electronic, high-spin polarization and half-metallic properties of Ru2VGe and Ru2VSb Heusler alloys: An FP-LAPW study

    NASA Astrophysics Data System (ADS)

    Gupta, Dinesh C.; Bhat, Idris H.

    2015-01-01

    Electronic and magnetic properties of Ru2VGe and Ru2VSb have been calculated using full potential linearized augmented plane wane method. The optimized equilibrium lattice constants in stable Fm-3m configuration were found to be 6.032 Å for Ru2VGe and 6.272 Å for Ru2VSb. Spin-resolved calculations show that V mainly contributes to the magnetic properties in these materials. The materials follow the Slater-Pauling rule and hence have integral magnetic moments which is due to 100% spin polarization at Fermi energy. The calculated total magnetic moments per unit cell were found to be 1.0 μB for Ru2VGe and 2.0 μB for Ru2VSb. Both the materials having ferromagnetic ground state, exhibit half-metallicity with an energy gap in the spin-down channel of 0.095 eV for Ru2VGe and 0.186 eV for Ru2VSb.

  7. Platinum Group Elements, 187OS/188OS and 87SR/86SR Isotope Systematics in Depleted Fluid-Modified Mariana Fore-Arc Peridotites

    NASA Astrophysics Data System (ADS)

    Harvey, J.; Savov, I. P.; Shirey, S. B.; Horan, M. F.; Mock, T. D.

    2012-12-01

    The serpentine mud volcanoes of the Izu-Bonin-Mariana (IBM) fore-arc, collected during Ocean Drilling Program Leg 195 [1], contain hard-rock clasts of serpentine sampled from close to the décollement, which separates the down-going Pacific slab from the overlying mantle wedge. These clasts preserve evidence for melt depletion (>25 % melt extraction in many instances) in a sub-arc environment, and extensive (40 - 100%) serpentinization due to subsequent fluid / peridotite interaction, e.g. [2]. Platinum-group element (PGE) abundances are not consistent with melt-depletion alone [3]. Fractionation between I-PGE (Os, Ir, Ru) has resulted in groups of IBM serpentinites with either a high chondrite-normalized Os/Ir ratio (OsN/IrN) or a low OsN/IrN ratio. Similarly, fractionation of P-PGE (Pt, Pd) is marked, and distinguishes the IBM serpentinites from worldwide abyssal peridotites. Interaction with high-pH fluids [4] may have partially oxidized mantle sulphide, the major primary host for PGE in these rocks, leading to partial breakdown to sulphate and the selective redistribution of certain PGE (Os, Ru, Pt), a feature normally associated with sub-aerial weathering [5], but which likely prevails in other oxidizing environments. In particular, the Re-Os systematics of the high (OsN/IrN) IBM serpentinites have been disturbed by the addition of Os. Unlike peridotite xenoliths associated with magmatic regions of subduction zones where subduction-related Os-addition is unequivocally radiogenic and derived from crustal material [6][7], where Os has been added to the IBM serpentinites it is unradiogenic and was most likely derived from within the oceanic mantle. IBM serpentinites therefore preserve osmium isotope ratios that are exclusively sub-chondritic (187Os/188Os ≤ 0.127), as previously reported [8]. These serpentinized peridotites were produced by at least a three-step process: melt depletion, serpentinization, and the mobilization of Os, Ru and Pt to produce low Os

  8. Linear magnetoresistance in a topological insulator Ru2Sn3

    NASA Astrophysics Data System (ADS)

    Shiomi, Y.; Saitoh, E.

    2017-03-01

    We have studied magnetotransport properties of a topological insulator material Ru2Sn3. Bulk single crystals of Ru2Sn3 were grown by a Bi flux method. The resistivity is semiconducting at high temperatures above 160 K, while it becomes metallic below 160 K. Nonlinear field dependence of Hall resistivity in the metallic region shows conduction of multiple carriers at low temperatures. In the high-temperature semiconducting region, magnetoresistance exhibits a conventional quadratic magnetic-field dependence. In the low-temperature metallic region, however, high-field magnetoresistance is clearly linear with magnetic fields, signaling a linear dispersion in the low-temperature electronic structure. Small changes in the magnetoresistance magnitude with respect to the magnetic field angle indicate that bulk electron carriers are responsible mainly for the observed linear magnetoresistance.

  9. Adsorption and Dissociation of CO2 on Ru(0001)

    PubMed Central

    2017-01-01

    The adsorption and dissociation of carbon dioxide on a Ru(0001) single crystal surface was investigated by reflection–absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) spectroscopy for CO2 adsorbed at 85 K. RAIRS spectroscopy shows that the adsorption of CO2 on a Ru(0001) single crystal is partially dissociative, resulting in CO2 and CO. The CO vibrational mode was also observed to split into two distinct modes, indicating two general populations of CO present at the surface. Furthermore, a time-dependent blue-shift is observed, which is characteristic of increasing CO surface coverage. TPD showed that coverages of up to 0.3 ML were obtained, and no evidence for chemisorption of oxygen on ruthenium was found.

  10. Symptomatic Os Infranaviculare

    PubMed Central

    Roh, Kwon Jae

    2013-01-01

    The author observed a new accessory bone of the foot in the distal portion of navicular, which articulated with the medial cuneiform and the intermediate cuneiform, and named it os infranaviculare. A degenerative change was observed between the accessory bone and the navicular; this caused midfoot pain to the patient during weight-bearing. Thus, the patient was treated by excision of the accessory bone. The symptom was relieved at one-year postoperative. PMID:23730481

  11. A novel solid-state electrochemiluminescence sensor for melamine with Ru(bpy)3(2+)/mesoporous silica nanospheres/Nafion composite modified electrode.

    PubMed

    Cao, Hongmei; Hu, Xiaoqing; Hu, Chenyi; Zhang, Yang; Jia, Nengqin

    2013-03-15

    A novel melamine electrochemiluminescence (ECL) sensor was developed based on mesoporous SiO(2) nanospheres/Ru(bpy)(3)(2+)/Nafion modified electrodes. The homogeneous mesoporous silica nanospheres, synthesized using modified Stöber sol-gel process, were characterized by Field Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy (TEM) and Brunauer-Emmett-Teller (BET). The ECL and electrochemistry of the modified electrodes were investigated with tri-n-propylamine (TPA) as the coreactant. Furthermore, the mesporous SiO(2) nanospheres/Ru(bpy)(3)(2+)-based modified electrodes were used for ECL determination of melamine. The analytical performances of this ECL sensor for melamine based on its enhancement ECL emission of Ru(bpy)(3)(2+) were investigated. The results indicated that the sensor exhibited excellent performance during melamine determination with a wide linear range (7.81×10(-9)-5×10(-6) M), low detection limit (2.6×10(-9) M). The high sensitivity and stability mainly resulted from the high surface area and special structure of the mesoporous silica nanospheres. The proposed ECL approach was used to analyze the melamine content in powdered milk with satisfactory results.

  12. {sup 45}Sc Solid State NMR studies of the silicides ScTSi (T=Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt)

    SciTech Connect

    Harmening, Thomas; Eckert, Hellmut; Fehse, Constanze M.; Sebastian, C. Peter; Poettgen, Rainer

    2011-12-15

    The silicides ScTSi (T=Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt) were synthesized by arc-melting and characterized by X-ray powder diffraction. The structures of ScCoSi, ScRuSi, ScPdSi, and ScIrSi were refined from single crystal diffractometer data. These silicides crystallize with the TiNiSi type, space group Pnma. No systematic influences of the {sup 45}Sc isotropic magnetic shift and nuclear electric quadrupolar coupling parameters on various structural distortion parameters calculated from the crystal structure data can be detected. {sup 45}Sc MAS-NMR data suggest systematic trends in the local electronic structure probed by the scandium atoms: both the electric field gradients and the isotropic magnetic shifts relative to a 0.2 M aqueous Sc(NO{sub 3}){sub 3} solution decrease with increasing valence electron concentration and within each T group the isotropic magnetic shift decreases monotonically with increasing atomic number. The {sup 45}Sc nuclear electric quadrupolar coupling constants are generally well reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code. Highlights: Black-Right-Pointing-Pointer Arc-melting synthesis of silicides ScTSi. Black-Right-Pointing-Pointer Single crystal X-ray data of ScCoSi, ScRuSi, ScPdSi, and ScIrSi. Black-Right-Pointing-Pointer {sup 45}Sc solid state NMR of silicides ScTSi.

  13. Shape Evolution in Neutron-Rich Ru Nuclei

    NASA Astrophysics Data System (ADS)

    Söderström, P.-A.; Lorusso, G.; Watanabe, H.; Nishimura, S.; Doornenbal, P.; Browne, F.; Bruce, A. M.; Daido, R.; Fang, Y.; Gey, G.; Jung, H. S.; Nishizuka, I.; Patel, Z.; Rice, S.; Sinclair, L.; Sumikama, T.; Taprogge, J.; Vajta, Zs.; Wu, J.; Xu, Z. Y.; Baba, H.; Benzoni, G.; Carroll, R. J.; Chae, K. Y.; Crespi, F. C. L.; Fukuda, N.; Gernhäuser, R.; Ideguchi, E.; Inabe, N.; Isobe, T.; Jungclaus, A.; Kameda, D.; Kim, G. D.; Kim, Y.-K.; Kojouharov, I.; Kondev, F. G.; Kubo, T.; Kurz, N.; Kwon, Y. K.; Lalkovski, S.; Lane, G. J.; Li, Z.; Lozeva, R.; Montaner-Piza, A.; Moschner, K.; Naqvi, F.; Niikura, M.; Nishibata, H.; Odahara, A.; Orlandi, R.; Podolyak, Zs.; Regan, P. H.; Roberts, O. J.; Sakurai, H.; Schaffner, H.; Simpson, G. S.; Steiger, K.; Suzuki, H.; Takeda, H.; Tanaka, M.; Wendt, A.; Werner, V.; Wieland, O.; Yagi, A.; Yoshinaga, K.

    Recent experimental work has been carried out at the RIBF using the EURICA HPGe detector array. In this contribution, we discuss the recently published results on the shape evolution of the even-even isotopes 116,118Ru and present an outlook of β-delayed γ-ray spectroscopy of the odd-neutron nuclei and possibilities for life-time measurements of excited states.

  14. Ru-catalyzed stereoselective addition of imides to alkynes.

    PubMed

    Goossen, Lukas J; Blanchot, Mathieu; Brinkmann, Claus; Goossen, Käthe; Karch, Ralph; Rivas-Nass, Andreas

    2006-12-08

    A catalyst system formed in situ from bis(2-methylallyl)cycloocta-1,5-dieneruthenium(II) ((cod)Ru[met]2), a phosphine, and scandium(III) trifluoromethanesulfonate (Sc(OTf)3) was found to efficiently catalyze the anti-Markovnikov addition of imides to terminal alkynes, allowing mild and atom-economic synthesis of enimides. Depending on the phosphine employed, both the (E)- and the (Z)-isomer can be accessed stereoselectively.

  15. Synthesis and crystal structure of Ru III-supported tungstoantimonate [Sb 2W 20Ru III2(H 2O) 2(dmso) 6O 68] 4-

    NASA Astrophysics Data System (ADS)

    Bi, Li-Hua; Li, Bao; Bi, Shuai; Wu, Li-Xin

    2009-06-01

    The first Ru III-supported tungstoantimonate [Ru II(bpy) 3] 2[Sb 2W 20Ru III2(H 2O) 2(dmso) 6O 68]·3dmso (bpy=bi-pyridine) ( 1a) has been successfully isolated as [Ru(bpy) 3] 2+ (Rubpy) salt by routine synthetic reaction in mixed solutions with dmso and water. Single-crystal X-ray analysis was carried out on 1a, which crystallizes in the triclinic system space group P-1 with a=16.804 (6), b=16.988 (6), c=17.666 (6) Å, α=107.397 (13)°, β=106.883 (13)°, γ=103.616 (12)°. V=4309 (3) Å 3, Z=1 with R1=0.0773. The compound 1a reveals the following features: (1) Rubpy is firstly used as an alternative ruthenium-source for the synthesis of Ru-substituted heteropolytungstate; (2) the structure of 1a consists of four Ru III-O-S(CH 3) 2 and two W-O-S(CH 3) 2 bonds resulting in an assembly with C2 symmetry; (3) the Ru III ions are linked to two dmso groups via two Ru III-O-S(CH 3) 2 bonds, which represents the other dmso-coordination mode to Ru III in POM chemistry. The cyclic voltammetry studies of 1a in dmso/H 2SO 4 (3/1 v/v) at pH 2.5 medium using the glassy carbon electrode as a working electrode show the respective electrochemical behaviors of the W-centers and the Ru-centers within 1a, which could be separated clearly. In addition, the compound 1a exhibits photoluminescence arising from π*- t2g ligand-to-metal transition of Rubpy.

  16. SiO₂-RuO₂: a stable electrocatalyst support.

    PubMed

    Lo, Chih-Ping; Ramani, Vijay

    2012-11-01

    High surface area SiO₂-RuO₂ (SRO) supports with various SiO₂: RuO₂ ratios were synthesized using a wet chemical method. The supports were catalyzed by depositing platinum nanoparticles on their surface. The synthesized materials were characterized by XRD, TEM, BET, and linear sweep voltammetry to study microstructure and properties. The electrochemical stability, electrochemical surface area, electrocatalytic activity and fuel cell performance were also measured. The optimal 1:1 mol ratio of SiO₂-RuO₂ (SRO-1) possessed a BET surface area of 305 m²/g and an electrical conductivity of 24 S/cm. This SRO support demonstrated 10-fold higher electrochemical stability than Vulcan XC-72R carbon when subjected to an aggressive accelerated stability test (AST) involving 10,000 potential cycles between 1 and 1.5 V. The mass activity of Pt-doped SRO-1 was 54 mA/mg(Pt), whereas its specific activity was 115 μA cm(Pt)⁻². The fuel cell performance obtained with this catalyst was lower, but compared favorably against a commercial Pt/C baseline. Analysis of fuel cell performance data confirmed that the lower fuel cell performance resulted largely from ohmic and mass transport losses within the unoptimized electrocatalyst layer.

  17. RU486 Mitigates Hippocampal Pathology Following Status Epilepticus

    PubMed Central

    Wulsin, Aynara C.; Herman, James P.; Danzer, Steve C.

    2016-01-01

    Status epilepticus (SE) induces rapid hyper-activation of the hypothalamo–pituitary–adrenocortical (HPA) axis. HPA axis hyperactivity results in excess exposure to high levels of circulating glucocorticoids, which are associated with neurotoxicity and depression-like behavior. These observations have led to the hypothesis that HPA axis dysfunction may exacerbate SE-induced brain injury. To test this hypothesis, we used the mouse pilocarpine model of epilepsy to determine whether use of the glucocorticoid receptor antagonist RU486 can attenuate hippocampal pathology following SE. Excess glucocorticoid secretion was evident 1 day after SE in the mice, preceding the development of spontaneous seizures (which can take weeks to develop). RU486 treatment blocked the SE-associated elevation of glucocorticoid levels in pilocarpine-treated mice. RU486 treatment also mitigated the development of hippocampal pathologies induced by SE, reducing loss of hilar mossy cells and limiting pathological cell proliferation in the dentate hilus. Mossy cell loss and accumulation of ectopic hilar cells are positively correlated with epilepsy severity, suggesting that early treatment with glucocorticoid antagonists could have anti-epileptogenic effects. PMID:27965624

  18. Growth, interfacial alloying, and oxidation of ultra-thin Al films on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Wu, Yutong; Tao, Hui-Shu; Garfunkel, Eric; Madey, Theodore E.; Shinn, Neal D.

    1995-08-01

    The growth and oxidation of ultra-thin aluminum films on Ru(0001) have been studied by low energy ion scattering (LEIS) and X-ray photoelectron spectroscopy (XPS) using both Mg K α and synchrotron soft X-ray radiation. For Al films of average thickness ˜ 15 Å deposited at 300 K, LEIS demonstrates that the Ru substrate is completely covered. Upon annealing to ˜ 1000 K LEIS shows the reappearance of Ru at the surface. At the same time, the metallic Al 2p peak shifts to lower binding energy and a low binding energy shoulder appears on the Ru 3d peak, suggesting {Al}/{Ru} interfacial alloying. Annealing Al films to ˜ 1000 K in 1 × 10 -4 Torr oxygen produces an oxidized surface layer that completely covers the Ru substrate; the resultant aluminum oxide films are stoichiometric.

  19. Precise ReOs determinations and systematics of iron meteorites

    NASA Astrophysics Data System (ADS)

    Shen, J. J.; Papanastassiou, D. A.; Wasserburg, G. J.

    1996-08-01

    The ReOs system for samples of FeNi, sulphide, and phosphide from iron meteorites was investigated. Techniques were developed which yield reproducible analyses for Re/Os at the 2%‰ level and which permit complete isotopic exchange between sample and tracer, as is necessary for concentration measurements of Re and Os by isotope dilution. High precision osmium and rhenium isotope data have been obtained using negative ion thermal ionization, with ionization efficiencies of up to 10% for Os and 20% for Re, both for normals and for Re and Os extracted from the samples. Replicate analyses of Re/Os are in good agreement, within ±2.5%o. The results show a well defined correlation line on a 187Re- 187Os evolution diagram for iron meteorites from groups IAB, IIAB, IIIAB, IVA, and IVB, all taken together. This correlation line yields a slope of 0.07863 ± 0.00031 (2σ) and initial 187Os/ 188Os = 0.09560 ± 0.00018 (2σ). If the individual groups of iron meteorites for which there is sufficient dispersion in Re/Os are considered, data on the IIAB and on the IVA irons appear to indicate a difference in age of 60 ± 45 Ma, with the IVA group being older. This age difference is qualitatively the same as obtained for PdAg data but is larger. Sulphides from two IAB iron meteorites show extremely low concentrations of Re and Os and indicate that Re and Os are not partitioned into this phase during planetary differentiation. There is evidence for recent element remobilization or contamination, corresponding to relative enrichment of Re or loss of Os in the sulphides. Schreibersites contain small but significant amounts of Re and Os, with high Re/Os relative to the metal phases and with 187Os/ 188Os much more radiogenic than in the metal. Model ages for the Schreibersites are relatively young (4.3-3.5 AE) and indicate that the Schreibersites were open-systems for ReOs at least 0.5-1 AE after the original formation of the iron meteorites. It now appears possible to use

  20. Materials Data on FeGeRu2 (SG:225) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-08-01

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  1. Materials Data on SrLaFeRuO6 (SG:7) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-04-22

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  2. Physical properties modulation of Fe3O4/Pb(ZrTi)O3 heterostructure via Fe diffusion

    NASA Astrophysics Data System (ADS)

    Chichvarina, O.; Herng, T. S.; Ding, J.

    2016-03-01

    The manipulation of material properties in perovskite oxide heterojunctions has been increasingly studied, owing to their interacting lattice, charge, spin and orbital degrees of freedom. In this work, the switching, ferroelectricity and magneto-transport properties of epitaxially grown perovskite Pb(Zr0.52Ti0.48)O3 layers sandwiched between Fe3O4 (top electrode) and SrRuO3 (bottom electrode) are investigated. These films show a typical ferroelectric polarization of ˜50 μC/cm2. Once the Pb(Zr0.52Ti0.48)O3 films become thinner (˜30 nm), one can set (reset) the Fe3O4/Pb(Zr0.52Ti0.48)O3/SrRuO3 structures into a low (high) resistance state via formation (rupture) of an Fe-related filament in Pb(Zr0.52Ti0.48)O3 through manipulation of an electric field. Interestingly, at the low-resistance state, a prominent magnetoresistance signal of ˜3% was observed. There is no magnetoresistance signal detected in the virgin Pb(Zr0.52Ti0.48)O3 film (before switching), high-resistive state Pb(Zr0.52Ti0.48)O3 film and Au/Pb(Zr0.52Ti0.48)O3/SrRuO3. These phenomena are attributed to the diffusion of Fe-related ions into the Pb(Zr0.52Ti0.48)O3 film, turning a non-magnetic and insulating layer of perovskite Pb(Zr0.52Ti0.48)O3 into a magnetic and semiconducting-like Pb(Zr0.52Ti0.48)O3. The magneto-transport properties of Fe3O4/Pb(Zr0.52Ti0.48)O3/SrRuO3 have been studied extensively. Such resistance-ferroelectric-ferromagnetic coupling in a single compound paves the way to the realization of a non-volatile multiple-state Pb(ZrTi)O3 hybrid memory, as well as new computing approaches.

  3. Anomalous switching in Nb/Ru/Sr2RuO4 topological junctions by chiral domain wall motion

    NASA Astrophysics Data System (ADS)

    Anwar, M. S.; Nakamura, Taketomo; Yonezawa, S.; Yakabe, M.; Ishiguro, R.; Takayanagi, H.; Maeno, Y.

    2013-08-01

    A spontaneous symmetry breaking in a system often results in domain wall formation. The motion of such domain walls is utilized to realize novel devices like racetrack-memories, in which moving ferromagnetic domain walls store and carry information. Superconductors breaking time reversal symmetry can also form domains with degenerate chirality of their superconducting order parameter. Sr2RuO4 is the leading candidate of a chiral p-wave superconductor, expected to be accompanied by chiral domain structure. Here, we present that Nb/Ru/Sr2RuO4 topological superconducting-junctions, with which the phase winding of order parameter can be effectively probed by making use of real-space topology, exhibit unusual switching between higher and lower critical current states. This switching is well explained by chiral-domain-wall dynamics. The switching can be partly controlled by external parameters such as temperature, magnetic field and current. These results open up a possibility to utilize the superconducting chiral domain wall motion for future novel superconducting devices.

  4. Charge transfer dynamics between photoexcited CdS nanorods and mononuclear Ru water-oxidation catalysts.

    PubMed

    Tseng, Huan-Wei; Wilker, Molly B; Damrauer, Niels H; Dukovic, Gordana

    2013-03-06

    We describe the charge transfer interactions between photoexcited CdS nanorods and mononuclear water oxidation catalysts derived from the [Ru(bpy)(tpy)Cl](+) parent structure. Upon excitation, hole transfer from CdS oxidizes the catalyst (Ru(2+) → Ru(3+)) on a 100 ps to 1 ns timescale. This is followed by 10-100 ns electron transfer (ET) that reduces the Ru(3+) center. The relatively slow ET dynamics may provide opportunities for the accumulation of multiple holes at the catalyst, which is necessary for water oxidation.

  5. Reactivity of an adsorbed Ru(VI)-oxo complex: oxidation of benzyl alcohol.

    PubMed

    Hornstein, Brooks J; Dattelbaum, Dana M; Schoonover, Jon R; Meyer, Thomas J

    2007-10-01

    The phosphonated ruthenium complex, [Ru(tpy-PO(3)H(2))(OH(2))(3)](2+) (1) (tpy-PO(3)H(2) = 4'-phosphonato-2,2':6',2' '-terpyridine), was synthesized and attached to glass|ITO or glass|ITO|TiO(2) electrodes. After attachment to the metal oxide surface through the phosphonate linkage, 1 can be oxidized (either chemically or electrochemically) to the reactive Ru(VI)-dioxo complex, glass|ITO|[((HO)(2)OP)tpy)RuVI(O)(2)(OH(2))](2+), which remains attached to the surface. The attached Ru(VI) complex reacts with benzyl alcohol through mechanisms similar to those proposed for the solution analog. More specifically, Ru(VI) is reduced in a stepwise fashion to Ru(IV) and then finally to Ru(II). The reduction of Ru(VI) is accompanied by a rate-limiting insertion to the C-H bond of benzyl alcohol, followed by solvolysis of the aldehyde hydrate. In addition, the surface-bound Ru(VI) acts as an electrooxidation catalyst which carries out approximately 130 (2e(-)) turnovers before deactivation.

  6. Synergy between RU 28965 (roxithromycin) and human neutrophils for bactericidal activity in vitro.

    PubMed Central

    Labro, M T; Amit, N; Babin-Chevaye, C; Hakim, J

    1986-01-01

    The in vitro effects of RU 28965 (roxithromycin), a new semisynthetic macrolide, on human neutrophil activity were compared with those of erythromycin. RU 28965, at a concentration as low as 0.1 microgram/ml, significantly enhanced the phagocytosis and killing of Staphylococcus aureus by neutrophils. Erythromycin displayed a less stimulating effect in a dose-dependent manner. Phagocytosis of Klebsiella pneumoniae was also increased after incubation of neutrophils with RU 28965, but killing was not altered. Neutrophil chemotaxis, myeloperoxidase activity, and O2 consumption were unchanged in the presence of RU 28965. PMID:3019233

  7. Magnetic properties and spin polarization of Ru doped half metallic CrO{sub 2}

    SciTech Connect

    West, Kevin G.; Dao, Nam N. H.; Lu, Jiwei; Osofsky, Michael; Mazin, I. I.; Wolf, Stuart A.

    2015-07-06

    Chromium dioxide (CrO{sub 2}) is a half metal that is of interest for spintronic devices. It has not been synthesized through traditional physical vapor deposition (PVD) techniques because of its thermodynamic instability in low oxygen pressures. Epitaxial thin films of Ru doped tetragonal rutile CrO{sub 2} were synthesized by a PVD technique. The as-deposited Ru{sub x}Cr{sub 1−x}O{sub 2} was ferrimagnetic with the saturation magnetization moment showing a strong dependence on the Ru concentration. Curie temperature as high as 241 K has been obtained for ∼23 at. % Ru. The Ru substitution increased the electrical conductivity by increasing the minority spin concentration. The spin polarization was found to be as high as 70% for 9 at. % Ru and decreased to ∼60% with Ru concentrations up to ∼44 at. %, which is determined by the Fermi velocities of the majority and minority spins. First principle calculations were performed to understand the effect of Ru content on the properties of CrO{sub 2}. The PVD processes of Ru doped CrO{sub 2} could lead to the practical applications of the high spin polarization of CrO{sub 2} in spintronic devices.

  8. Triaxial shapes in the ground states of even-even neutron-rich Ru isotopes

    SciTech Connect

    Ahmad, I.; Lister, C.J.; Morss, L.R.

    1995-08-01

    Partial level schemes for {sup 108,110,112}Ru, and {sup 114}Ru about which nothing was previously known, were determined from the measurement of prompt, triple-gamma coincidences in {sup 248}Cm fission fragments. A 5-mg {sup 249}Cm source, mixed with 65-mg KCl and pressed in the form of a 7-mm diameter pellet, was used for the experiment. Prompt {gamma} rays emitted from the fission fragments were detected with the Eurogam array at Daresbury, which at that time consisted of 45 Compton suppressed Ge detectors and 5 LEPS spectrometers. Transitions in Ru were identified by gating on {gamma} rays in the complementary Te fragments. Figure I-25 shows the technique used to identify the previously unknown transitions in {sup 114}Ru and its partial level scheme. High spin states up to spin 10 h were observed and the {gamma}-ray branching ratios were determined. The ratios of electric quadrupole transition probabilities deduced from the experimental branching ratios were found to be in good agreement with the predictions of a simple model of rigid triaxial rotor. Our analysis shows that gamma deformation in Ru isotopes is increasing with the neutron number and the gamma value for {sup 112}Ru and {sup 114}Ru is {approximately} 25 degrees. This is one of the highest gamma values encountered in nuclei, suggesting soft triaxial shapes for {sup 112}Ru and {sup 114}Ru. The results of this investigation were published.

  9. Structural phase transition and antiferromagnetic transition of Tb3RuO7

    NASA Astrophysics Data System (ADS)

    Hinatsu, Yukio; Doi, Yoshihiro

    2014-12-01

    Magnetic properties and structural phase transition of terbium ruthenate Tb3RuO7 are investigated through magnetic susceptibility, specific heat, high-temperature X-ray diffraction and differential scanning calorimetry measurements. The structural phase transition from space group P21nb to Cmcm has been observed at 402 K. Tb3RuO7 shows an antiferromagnetic transition at 17 K. In addition, another magnetic anomaly has been found at 10 K. Analysis of the magnetic specific heat for Tb3RuO7 indicates that the magnetic transitions at 10 and 17 K are due to the magnetic ordering of Tb3+ and Ru5+ ions, respectively.

  10. Solid-Solution Alloying of Immiscible Ru and Cu with Enhanced CO Oxidation Activity.

    PubMed

    Huang, Bo; Kobayashi, Hirokazu; Yamamoto, Tomokazu; Matsumura, Syo; Nishida, Yoshihide; Sato, Katsutoshi; Nagaoka, Katsutoshi; Kawaguchi, Shogo; Kubota, Yoshiki; Kitagawa, Hiroshi

    2017-03-24

    We report on novel solid-solution alloy nanoparticles (NPs) of Ru and Cu that are completely immiscible even above melting point in bulk phase. Powder X-ray diffraction, scanning transmission electron microscopy, and energy-dispersive X-ray measurements demonstrated that Ru and Cu atoms were homogeneously distributed in the alloy NPs. Ru0.5Cu0.5 NPs demonstrated higher CO oxidation activity than fcc-Ru NPs, which are known as one of the best monometallic CO oxidation catalysts.

  11. Synthesis of Ru/multiwalled carbon nanotubes by microemulsion for electrochemical supercapacitor

    SciTech Connect

    Yan Shancheng; Qu Peng; Wang Haitao; Tian Tian; Xiao Zhongdang

    2008-10-02

    An efficient way to decorate multiwalled carbon nanotubes with Ru had been developed. In this method, Ru nanoparticles were prepared by water-in-oil reverse microemulsion, and the produced Ru anchored on MWCNTs. Transmission electron microscopy (TEM) result showed that RuO{sub 2} nanoparticles had the uniform size distribution after electrochemical oxidation. Energy dispersive X-rays (EDX) spectra elucidated the presence of ruthenium oxide in the as-prepared composites after electrochemical oxidation. Cyclic voltammetry result demonstrated that a specific capacitance of deposited ruthenium oxide electrode was significantly greater than that of the pristine MWCNTs electrode in the same medium.

  12. Recent progress in the structure control of Pd–Ru bimetallic nanomaterials

    PubMed Central

    Wu, Dongshuang; Kusada, Kohei; Kitagawa, Hiroshi

    2016-01-01

    Abstract Pd and Ru are two key elements of the platinum-group metals that are invaluable to areas such as catalysis and energy storage/transfer. To maximize the potential of the Pd and Ru elements, significant effort has been devoted to synthesizing Pd–Ru bimetallic materials. However, most of the reports dealing with this subject describe phase-separated structures such as near-surface alloys and physical mixtures of monometallic nanoparticles (NPs). Pd–Ru alloys with homogenous structure and arbitrary metallic ratio are highly desired for basic scientific research and commercial material design. In the past several years, with the development of nanoscience, Pd–Ru bimetallic alloys with different architectures including heterostructure, core-shell structure and solid-solution alloy were successfully synthesized. In particular, we have now reached the stage of being able to obtain Pd–Ru solid-solution alloy NPs over the whole composition range. These Pd–Ru bimetallic alloys are better catalysts than their parent metal NPs in many catalytic reactions, because the electronic structures of Pd and Ru are modified by alloying. In this review, we describe the recent development in the structure control of Pd–Ru bimetallic nanomaterials. Aiming for a better understanding of the synthesis strategies, some fundamental details including fabrication methods and formation mechanisms are discussed. We stress that the modification of electronic structure, originating from different nanoscale geometry and chemical composition, profoundly affects material properties. Finally, we discuss open issues in this field. PMID:27877905

  13. Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media.

    PubMed

    Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng

    2016-06-30

    A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

  14. Elastic and chemical contributions to the stability of magnetic surface alloys on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Marathe, Madhura; Imam, Mighfar; Narasimhan, Shobhana

    2009-02-01

    We have used density-functional theory to study the miscibility and magnetic properties of surface alloys. Our systems consist of a single pseudomorphic layer of MxN1-x on the Ru(0001) surface, where M=Fe or Co, and N=Pt , Au, Ag, Cd, or Pb. Several of the combinations studied by us display a preference for atomically mixed configurations over phase-segregated forms. We have also performed further ab initio calculations to obtain the parameters describing the elastic interactions between atoms in the alloy layer, including the effective atomic sizes at the surface. We find that while elastic interactions favor alloying for all the systems considered by us, in some cases chemical interactions disfavor atomic mixing. We show that a simple criterion (analogous to the Hume-Rothery first law for bulk alloys) need not necessarily work for strain-stabilized surface alloys because of the presence of additional elastic contributions to the alloy heat of formation that will tend to oppose phase segregation. We find that magnetic moments are significantly enhanced with respect to the bulk elements.

  15. Fermi Surface of the Pnictide Superconductor LaRu2 P 2 studied by quantum oscillations

    NASA Astrophysics Data System (ADS)

    Moll, Philip; Balakirev, Fedor; McDonald, Ross; Karpinski, Janusz; Bukowski, Zbigniew; Blaha, Peter; Schwarz, Karlheinz; Batlogg, Bertram

    2011-03-01

    LaRu 2 P2 is a stochiometric pnictide superconductor (Tc ~ 4.1 K) and crystallizes in the ThCr 2 Si 2 structure (the ``122'' pnictide family). We have mapped out its Fermi surface via the deHaas-vanAlphen effect in pulsed magnetic fields up to 60T (LANL/NHMFL). Pronounced oscillations were observed in the magnetic torque measured with a microcantilever setup. Two features are particularly noteworthy: The oscillations can be followed to surprisingly high temperatures beyond 20K, and the main frequency component at θ = 20circ; (θ = 0circ; at HIIc) is at 349T (α -peak), significantly lower than in the related compounds LaFe 2 P2 . A second frequency originating from a larger Fermi surface cross-section at 1921 T (β -peak) is identified. The temperature dependence of the amplitudes is well described by the Lifshitz- Kosevich formalism and gives low effective masses m*/m = 0.80 (α sheet) and 1.09 (β sheet). Therefore, most ``122'' metals appear to have similarly low effective masses.

  16. Site-specific electronic couplings in dyads with MLCT excited states. Intramolecular energy transfer in isomeric Ru(II)-Ru(II) cyclometalated complexes.

    PubMed

    Polson, Matthew; Chiorboli, Claudio; Fracasso, Sandro; Scandola, Franco

    2007-04-01

    The rod-like binuclear complexes [(ttpy)Ru(tpy-ph(2)-phbpy)Ru(ttpy)](4+) and [(ttpy)Ru(tpy-ph(2)-tpy)Ru(phtbpy)](4+) (for abbreviations, see text) have been synthesized and characterized. In both complexes, the polypyridine Ru(II) centers have (N--N--N)Ru(N--N--N) and (N--N--N)Ru(C--N--N) coordination environment. The two isomeric species differ in whether the cyclometalating carbon resides on the bridging or on the terminal ligand. The two complexes have virtually identical energy levels, but MLCT excited states of different (bridging or terminal) ligand localization. They are thus ideally suited to investigate possible effects of excited-state localization on intramolecular energy transfer kinetics. In fact, ultrafast spectroscopic measurements yield different energy transfer time constants for the two isomers, with the bridge-cyclometalated complex (2.7 ps) being faster than the terminal-cyclometalated one (8.0 ps). This difference can be explained in terms of different electronic factors for Dexter energy transfer. The study highlights the peculiar intricacies of intramolecular energy transfer in inorganic dyads involving MLCT excited states.

  17. Magnetic and orbital orders coupled to negative thermal expansion in Mott insulators, Ca2Ru1--xM xO4 (M = 3d transition metal ion)

    NASA Astrophysics Data System (ADS)

    Qi, Tongfei

    Ca2RuO4 is a structurally-driven Mott insulator with a metal-insulator (MI) transition at TMI = 357K, followed by a well-separated antiferromagnetic order at T N = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts TMI and induces exotic magnetic behavior below TN. Moreover, M doping for Ru produces negative thermal expansion in Ca2Ru1-- xMxO4 (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio, DeltaV/V, reaching as high as 1%. The onset of the negative thermal expansion closely tracks TMI and TN, sharply contrasting classic negative thermal expansion that shows no relevance to electronic properties. In addition, the observed negative thermal expansion occurs near room temperature and extends over a wide temperature interval. These findings underscores new physics driven by a complex interplay between orbital, spin and lattice degrees of freedom. These materials constitute a new class of Negative Thermal Expansion (NTE) materials with novel electronic and magnetic functions. KEYWORDS: Transition Metal Oxide, Ruthenate, Negative Thermal Expansion, Single crystal XRD, Invar Effect, Orbital Ordering, Magnetic Ordering, Jahn-Teller Effect.

  18. Neutron capture by Ru: Neutron cross sections of {sup 96,102,104}Ru and gamma-ray spectroscopy in the decays of {sup 97,103,105}Ru

    SciTech Connect

    Krane, K. S.

    2010-04-15

    Cross sections for radiative capture of neutrons have been measured for stable isotopes of Ru with mass numbers 96,102, and 104. From separate irradiations using thermal and epithermal neutrons, independent values for the thermal cross section and effective resonance integral have been determined. Spectroscopic studies of the gamma rays emitted in the decays of {sup 97,103,105}Ru have enabled improvements in the precision of the energies and intensities of the radiations along with corresponding improvements in the beta-decay feeding intensities and the energies of the levels in the respective daughter nuclei. Similar spectroscopic measurements of the decays of {sup 105}Rh (daughter of {sup 105}Ru) and {sup 96}Tc (produced from n,p reactions on {sup 96}Ru) have resulted in improved gamma-ray energies and intensities in those decays.

  19. Local structure distortion induced by Ti dopants boosting the pseudocapacitance of RuO2-based supercapacitors.

    PubMed

    Chen, I-Li; Wei, Yu-Chen; Lu, Kueih-Tzu; Chen, Tsan-Yao; Hu, Chi-Chang; Chen, Jin-Ming

    2015-10-07

    Binary oxides with atomic ratios of Ru/Ti = 90/10, 70/30, and 50/50 were fabricated using H2O2-oxidative precipitation with the assistance of a cetyltrimethylammonium bromide (CTAB) template, followed by a thermal treatment at 200 °C. The characteristics of electron structure and local structure extracted from X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) analyses indicate that incorporation of Ti into the RuO2 lattice produces not only the local structural distortion of the RuO6 octahedra in (Ru-Ti)O2 with an increase in the central Ru-Ru distance but also a local crystallization of RuO2. Among the three binary oxides studied, (Ru70-Ti30)O2 exhibits a capacitance improvement of about 1.4-fold relative to the CTAB-modified RuO2, mainly due to the enhanced crystallinity of the distorted RuO6 structure rather than the surface area effect. Upon increasing the extent of Ti doping, the deteriorated supercapacitive performance of (Ru50-Ti50)O2 results from the formation of localized nano-clusters of TiO2 crystallites. These results provide insight into the important role of Ti doping in RuO2 that boosts the pseudocapacitive performance for RuO2-based supercapacitors. The present result is crucial for the design of new binary oxides for supercapacitor applications with extraordinary performance.

  20. OsFRDL1 is a citrate transporter required for efficient translocation of iron in rice.

    PubMed

    Yokosho, Kengo; Yamaji, Naoki; Ueno, Daisei; Mitani, Namiki; Ma, Jian Feng

    2009-01-01

    Multidrug and toxic compound extrusion (MATE) transporters represent a large family in plants, but their functions are poorly understood. Here, we report the function of a rice (Oryza sativa) MATE gene (Os03g0216700, OsFRDL1), the closest homolog of barley (Hordeum vulgare) HvAACT1 (aluminum [Al]-activated citrate transporter 1), in terms of metal stress (iron [Fe] deficiency and Al toxicity). This gene was mainly expressed in the roots and the expression level was not affected by either Fe deficiency or Al toxicity. Knockout of this gene resulted in leaf chlorosis, lower leaf Fe concentration, higher accumulation of zinc and manganese concentration in the leaves, and precipitation of Fe in the root's stele. The concentration of citrate and ferric iron in the xylem sap was lower in the knockout line compared to the wild-type rice. Heterologous expression of OsFRDL1 in Xenopus oocytes showed transport activity for citrate. Immunostaining showed that OsFRDL1 was localized at the pericycle cells of the roots. On the other hand, there was no difference in the Al-induced secretion of citrate from the roots between the knockout line and the wild-type rice. Taken together, our results indicate that OsFRDL1 is a citrate transporter localized at the pericycle cells, which is necessary for efficient translocation of Fe to the shoot as a Fe-citrate complex.

  1. Ternary Pt-Ru-Ni catalytic layers for methanol electrooxidation prepared by electrodeposition and galvanic replacement

    PubMed Central

    Papaderakis, Athanasios; Pliatsikas, Nikolaos; Prochaska, Chara; Papazisi, Kalliopi M.; Balomenou, Stella P.; Tsiplakides, Dimitrios; Patsalas, Panagiotis; Sotiropoulos, Sotiris

    2014-01-01

    Ternary Pt-Ru-Ni deposits on glassy carbon substrates, Pt-Ru(Ni)/GC, have been formed by initial electrodeposition of Ni layers onto glassy carbon electrodes, followed by their partial exchange for Pt and Ru, upon their immersion into equimolar solutions containing complex ions of the precious metals. The overall morphology and composition of the deposits has been studied by SEM microscopy and EDS spectroscopy. Continuous but nodular films have been confirmed, with a Pt ÷ Ru ÷ Ni % bulk atomic composition ratio of 37 ÷ 12 ÷ 51 (and for binary Pt-Ni control systems of 47 ÷ 53). Fine topographical details as well as film thickness have been directly recorded using AFM microscopy. The composition of the outer layers as well as the interactions of the three metals present have been studied by XPS spectroscopy and a Pt ÷ Ru ÷ Ni % surface atomic composition ratio of 61 ÷ 12 ÷ 27 (and for binary Pt-Ni control systems of 85 ÷ 15) has been found, indicating the enrichment of the outer layers in Pt; a shift of the Pt binding energy peaks to higher values was only observed in the presence of Ru and points to an electronic effect of Ru on Pt. The surface electrochemistry of the thus prepared Pt-Ru(Ni)/GC and Pt(Ni)/GC electrodes in deaerated acid solutions (studied by cyclic voltammetry) proves the existence of a shell consisting exclusively of Pt-Ru or Pt. The activity of the Pt-Ru(Ni) deposits toward methanol oxidation (studied by slow potential sweep voltammetry) is higher from that of the Pt(Ni) deposit and of pure Pt; this enhancement is attributed both to the well-known Ru synergistic effect due to the presence of its oxides but also (based on the XPS findings) to a modification effect of Pt electronic properties. PMID:24959530

  2. Enhancement of Curie temperature in Mn{sub 2}RuSn by Co substitution

    SciTech Connect

    Nelson, A.; Huh, Y.; Fuglsby, R.; Guenther, J.; Kharel, P.; Zhang, W.; Sellmyer, D. J.; Staten, B.; Lukashev, P.; Valloppilly, S.

    2015-04-21

    The Co-substituted Mn{sub 2}RuSn nanomaterials, namely, Mn{sub 2}Ru{sub 0.5}Co{sub 0.5}Sn and Mn{sub 2}Ru{sub 0.35}Co{sub 0.65}Sn have been synthesized and investigated. The presence of Co in the Mn{sub 2}RuSn (a = 6.21 Å) decreased the lattice parameter, where a = 6.14 Å and 6.12 Å for the as prepared Mn{sub 2}Ru{sub 0.5}Co{sub 0.5}Sn and Mn{sub 2}Ru{sub 0.35}Co{sub 0.65}Sn, respectively. The samples show a ferrimagnetic spin order with relatively small coercivities, similar to those of soft magnetic materials. There is a substantial increase in the Curie temperature (T{sub c} = 448 K for Mn{sub 2}Ru{sub 0.5}Co{sub 0.5}Sn and 506 K for Mn{sub 2}Ru{sub 0.35}Co{sub 0.65}Sn) of Mn{sub 2}RuSn (T{sub c} = 272.1 K) due to Co substitution, which is a result of strengthening of the positive exchange interaction in this material. These materials are highly stable against heat treatment of up to 450 °C. The first-principles calculations are consistent with our experimentally observed structural and magnetic properties. They also provide insight on how the magnetic and electronic structures change when Ru is replaced with Co in Mn{sub 2}RuSn.

  3. Scanning tunneling microscopy of graphene on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Marchini, S.; Günther, S.; Wintterlin, J.

    2007-08-01

    After prolonged annealing of a Ru(0001) sample in ultrahigh vacuum a superstructure with a periodicity of ˜30Å was observed by scanning tunneling microscopy (STM). Using x-ray photoelectron spectroscopy it was found that the surface is covered by graphitic carbon. Auger electron spectroscopy shows that between 1000 and 1400K carbon segregates to the surface. STM images recorded after annealing to increasing temperatures display islands of the superstructure, until, after annealing to T⩾1400K , it covers the entire surface. The morphology of the superstructure shows that it consists of a single graphene layer. Atomically resolved STM images and low-energy electron diffraction reveal an (11×11) structure or incommensurate structure close to this periodicity superimposed by 12×12 graphene cells. The lattice mismatch causes a moiré pattern. Unlike the common orientational disorder of adsorbed graphene, the graphene layer on Ru(0001) shows a single phase and very good rotational alignment. Misorientations near defects in the overlayer only amount to ˜1° , and the periodicity of ˜30Å is unaffected. In contrast to bulk graphite both carbon atoms in the graphene unit cell were resolved by STM, with varying contrast depending on the position above the Ru atoms. The filled and empty state images of the moiré structure differ massively, and electronic states at -0.4 and +0.2V were detected by scanning tunneling spectroscopy. The data indicate a significantly stronger chemical interaction between graphene and the metal surface than between neighboring layers in bulk graphite. The uniformity of the structure and its stability at high temperatures and in air suggest an application as template for nanostructures.

  4. A reagentless electrochemiluminescent immunosensor for apurinic/apyrimidinic endonuclease 1 detection based on the new Ru(bpy)3(2+)/bi-arginine system.

    PubMed

    Zhao, Min; Chai, Xi Deng Ya-Qin; Han, Jing; Gui, Guo-Feng; Yuan, Ruo; Zhuo, Ying

    2014-10-10

    Apurinic/apyrimidinic endonuclease 1 (APE-1), a kind of multifunctional protein widely-distributed in the body, plays an essential role in the DNA base excision repair and serves as multiple possible roles in the response of human cancer to radiotherapy and chemotherapy. In this work, an ultrasensitive solid-state electrochemiluminescence (ECL) immunosensor is designed to determine APE-1 based on the new Ru(bpy)3(2+)/bi-arginine system. The bi-arginine (bi-Arg) is decorated on the Au nanoparticles functionalized magnetic Fe3O4/reduced graphene oxide (bi-Arg/Au@Fe3O4-rGO) according to the self-assembling and covalent cross-linking interaction to obtain the functionalized nanocomposite of bi-Arg/Au@Fe3O4-rGO. Herein, the bi-Arg/Au@Fe3O4-rGO plays not only an amplification label to enhance the ECL signal of Ru(bpy)3(2+) due to the coreactant of bi-Arg but also an ideal nanocarrier to load numerous secondary antibody. Based on sandwich-type immunoassay format, this proposed method offers a linear range of 1.0fgmL(-1)-5.0pgmL(-1) and an estimated detection limit of 0.3fgmL(-1) for the APE-1. Moreover, the reagentless ECL immunosensor also exhibits high sensitivity, excellent selectivity and good stability, which has greatly potential development and application in clinical diagnostics, immunology and biomedical research.

  5. Helium, neon and argon diffraction from Ru(0001).

    PubMed

    Minniti, M; Díaz, C; Fernández Cuñado, J L; Politano, A; Maccariello, D; Martín, F; Farías, D; Miranda, R

    2012-09-05

    We present an experimental and theoretical study of He, Ne and Ar diffraction from the Ru(0001) surface. Close-coupling calculations were performed to estimate the corrugation function and the potential well depth in the atom-surface interaction in all three cases. DFT (density functional theory) calculations, including van der Waals dispersion forces, were used to validate the close-coupling results and to further analyze the experimental results. Our DFT calculations indicate that, in the incident energy range 20-150 meV, anticorrugating effects are present in the case of He and Ar diffraction, whereas normal corrugation is observed with Ne beams.

  6. THz-Pulse-Induced Selective Catalytic CO Oxidation on Ru.

    PubMed

    LaRue, Jerry L; Katayama, Tetsuo; Lindenberg, Aaron; Fisher, Alan S; Öström, Henrik; Nilsson, Anders; Ogasawara, Hirohito

    2015-07-17

    We demonstrate the use of intense, quasi-half-cycle THz pulses, with an associated electric field component comparable to intramolecular electric fields, to direct the reaction coordinate of a chemical reaction by stimulating the nuclear motions of the reactants. Using a strong electric field from a THz pulse generated via coherent transition radiation from an ultrashort electron bunch, we present evidence that CO oxidation on Ru(0001) is selectively induced, while not promoting the thermally induced CO desorption process. The reaction is initiated by the motion of the O atoms on the surface driven by the electric field component of the THz pulse, rather than thermal heating of the surface.

  7. Universal heat transport in Sr2RuO4.

    PubMed

    Suzuki, M; Tanatar, M A; Kikugawa, N; Mao, Z Q; Maeno, Y; Ishiguro, T

    2002-06-03

    We present the temperature dependence of the thermal conductivity kappa(T) of the unconventional superconductor Sr2RuO4 down to low temperatures ( approximately 100 mK). In the T-->0 K limit we found a finite residual term in kappa/T, providing clear evidence for the superconducting state with an unconventional pairing. The residual term remains unchanged for samples with different T(c), demonstrating the universal character of heat transport in this spin-triplet superconductor. The low-temperature behavior of kappa suggests the strong impurity scattering with a phase shift close to pi/2. A criterion for the observation of universality is experimentally deduced.

  8. Triaxiality near the 110Ru ground state from Coulomb excitation

    NASA Astrophysics Data System (ADS)

    Doherty, D. T.; Allmond, J. M.; Janssens, R. V. F.; Korten, W.; Zhu, S.; Zielińska, M.; Radford, D. C.; Ayangeakaa, A. D.; Bucher, B.; Batchelder, J. C.; Beausang, C. W.; Campbell, C.; Carpenter, M. P.; Cline, D.; Crawford, H. L.; David, H. M.; Delaroche, J. P.; Dickerson, C.; Fallon, P.; Galindo-Uribarri, A.; Kondev, F. G.; Harker, J. L.; Hayes, A. B.; Hendricks, M.; Humby, P.; Girod, M.; Gross, C. J.; Klintefjord, M.; Kolos, K.; Lane, G. J.; Lauritsen, T.; Libert, J.; Macchiavelli, A. O.; Napiorkowski, P. J.; Padilla-Rodal, E.; Pardo, R. C.; Reviol, W.; Sarantites, D. G.; Savard, G.; Seweryniak, D.; Srebrny, J.; Varner, R.; Vondrasek, R.; Wiens, A.; Wilson, E.; Wood, J. L.; Wu, C. Y.

    2017-03-01

    A multi-step Coulomb excitation measurement with the GRETINA and CHICO2 detector arrays was carried out with a 430-MeV beam of the neutron-rich 110Ru (t1/2 = 12 s) isotope produced at the CARIBU facility. This represents the first successful measurement following the post-acceleration of an unstable isotope of a refractory element. The reduced transition probabilities obtained for levels near the ground state provide strong evidence for a triaxial shape; a conclusion confirmed by comparisons with the results of beyond-mean-field and triaxial rotor model calculations.

  9. Bathophenanthroline-Ru(II) complexes as nonradioactive labels for dideoxy DNA sequencing.

    PubMed

    Bannwarth, W

    1989-09-01

    Bathophenanthroline-Ru(II) complexes represent interesting nonradioactive label molecules which can be measured in a time-resolved mode with high sensitivity. Here we demonstrate that Ru complex-labeled primers can be applied in dideoxy sequencing protocols giving the same sequencing patterns as unlabeled primers.

  10. Degradation analyses of Ru85Se15 catalyst layer in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Zheng, Qiaoming; Cheng, Xuan; Jao, Ting-Chu; Weng, Fang-Bor; Su, Ay; Chiang, Yu-Chun

    2012-11-01

    Accelerated degradation tests (ADTs) for the H2/air single cell are carried out at 65 °C and ambient pressure by cycling the cell between 0 and 200 mA cm-2 up to 6000 cycles. Membrane electrode assemblies (MEAs) are prepared using the Nafion 212 membrane and the carbon supported platinum as an anode catalyst, as well as the carbon supported Ru85Se15 as a cathode catalyst prepared with five selected Nafion contents and Ru loads to represent the optimized (33% Nafion and 0.27 mg Ru cm-2), overloaded (43% Nafion and 0.61 mg Ru cm-2) and underloaded (20% Nafion and 0.14 mg Ru cm-2) conditions. The lowest cell performance loss of 44% in terms of peak power density is achieved with 33% Nafion and 0.27 mg Ru cm-2. Very severe losses of 80% and 82% are found for 20% and 43% Nafion contents, respectively, while relatively moderate losses of 57% and 64% for 0.14 and 0.61 mg Ru cm-2, respectively. Dissolution and migration of Se/Ru and corrosion of carbon support from the catalyst, together with the shrinkage and release of sulfonic acid from the membrane are identified and correlated to decayed cell performances.

  11. Ru/ITO: a carbon-free cathode for nonaqueous Li-O2 battery.

    PubMed

    Li, Fujun; Tang, Dai-Ming; Chen, Yong; Golberg, Dmitri; Kitaura, Hirokazu; Zhang, Tao; Yamada, Atsuo; Zhou, Haoshen

    2013-10-09

    Ru nanoparticles deposited on a conductive support indium tin oxide (Ru/ITO) were applied as a carbon-free cathode in a nonaqueous Li-O2 battery. The Li-O2 battery with Ru/ITO showed much lower charging overpotentials and better cycling performance at 0.15 mA/cm(2) than those with Super P (SP) and SP loaded with Ru nanoparticles (Ru/SP) as the cathodes. The carbon-free cathode Ru/ITO can effectively reduce formation of Li2CO3 or other Li carbonates in a discharging process, which cannot be completely decomposed upon charging, in comparison with the carbon based cathode. The improved performance of Ru/ITO can be attributed to the superior catalytic activity of Ru nanoparticles toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) and the absence of carbon that has been reported to react with Li2O2 to form Li2CO3.

  12. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    DOE PAGES

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; ...

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratiomore » of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.« less

  13. The effect of the surface composition of Ru-Pt bimetallic catalysts for methanol oxidation

    SciTech Connect

    Garrick, Taylor R.; Diao, Weijian; Tengco, John M.; Stach, Eric A.; Senanayake, Sanjaya D.; Chen, Donna A.; Monnier, John R.; Weidner, John W.

    2016-02-23

    Here, a series of Ru-Pt bimetallic catalysts prepared by the electroless deposition of controlled and variable amounts of Ru on the Pt surface of a commercially-available 20 wt% Pt/C catalyst has been characterized and evaluated for the oxidation of methanol. The activity of each Ru-Pt catalyst was determined as a function of surface composition via cyclic voltammetry. For the Ru-Pt bimetallic catalysts, activity passed through a maximum at approximately 50% monodisperse Ru surface coverage. However, due to the monolayer coverage of Ru on Pt, the amount of metal in the catalyst is minimized compared to a bulk 1:1 atomic ratio of Ru:Pt seen in commercial bimetallic catalysts. Chemisorption and temperature programmed reduction experiments confirmed that the surface had characteristics of a true bimetallic catalyst. On a mass of Pt basis, the activity of this composition for methanol oxidation was 7 times higher than pure Pt and 3.5 times higher than a commercial catalyst with a 1:1 Pt:Ru bulk atomic ratio.

  14. In vivo inhibition of E. coli growth by a Ru(II)/Pt(II) supramolecule [(tpy)RuCl(dpp)PtCl2](PF6).

    PubMed

    Jain, Avijita; Winkel, Brenda S J; Brewer, Karen J

    2007-10-01

    Supramolecular complexes consisting of ruthenium chromophores and a cisplatin unit represent an emerging class of bioactive molecules of interest as anti-cancer agents. Although the ability of Ru(II)/Pt(II) heteronuclear complexes to bind to DNA has been demonstrated, the in vivo activity of these complexes has not yet been reported. In the present work, we report the anti-bacterial activity of the complex [(tpy)RuCl(dpp)PtCl(2)](PF(6)) (where dpp=2,3-bis(2-pyridyl)pyrazine, tpy=2,2':6',2''-terpyridine). The impact on bacterial cell growth of exposure to different concentrations of [(tpy)RuCl(dpp)PtCl(2)](PF(6)) and cisplatin was studied. The bioactivity of this complex was found to be due to the presence of the cis-PtCl(2) moiety, as the monometallic synthon [(tpy)RuCl(dpp)](PF(6)) did not inhibit bacterial cell growth.

  15. Partitioning of rhodium and ruthenium between Pd-Rh-Ru and (Ru,Rh)O2 solid solutions in high-level radioactive waste glass

    NASA Astrophysics Data System (ADS)

    Sugawara, Toru; Ohira, Toshiaki; Komamine, Satoshi; Ochi, Eiji

    2015-10-01

    The partitioning of rhodium and ruthenium between Pd-Rh-Ru alloy with a face-centered cubic (FCC) structure and (Ru,Rh)O2 solid solution has been investigated between 1273 and 1573 K at atmospheric oxygen fugacity. The rhodium and ruthenium contents in FCC increase, while the RhO2 content in (Ru,Rh)O2 decreases with increasing temperature due to progressive reduction of the system. Based on the experimental results and previously reported thermodynamic data, the thermodynamic mixing properties of FCC phase and (Ru,Rh)O2 have been calibrated in an internally consistent manner. Phase equilibrium of platinum grope metals in an HLW glass was calculated by using the obtained thermodynamic parameters.

  16. Low leakage Ru-strontium titanate-Ru metal-insulator-metal capacitors for sub-20 nm technology node in dynamic random access memory

    SciTech Connect

    Popovici, M. Swerts, J.; Redolfi, A.; Kaczer, B.; Aoulaiche, M.; Radu, I.; Clima, S.; Everaert, J.-L.; Van Elshocht, S.; Jurczak, M.

    2014-02-24

    Improved metal-insulator-metal capacitor (MIMCAP) stacks with strontium titanate (STO) as dielectric sandwiched between Ru as top and bottom electrode are shown. The Ru/STO/Ru stack demonstrates clearly its potential to reach sub-20 nm technology nodes for dynamic random access memory. Downscaling of the equivalent oxide thickness, leakage current density (J{sub g}) of the MIMCAPs, and physical thickness of the STO have been realized by control of the Sr/Ti ratio and grain size using a heterogeneous TiO{sub 2}/STO based nanolaminate stack deposition and a two-step crystallization anneal. Replacement of TiN with Ru as both top and bottom electrodes reduces the amount of electrically active defects and is essential to achieve a low leakage current in the MIM capacitor.

  17. Angle-integrated photoemission studies of ruthocuprate Eu_2-xCe_xRuSr_2Cu_2O_10, Gd_2RuSr_2Cu_2O_10 and Eu_1.5Nb_1-xRu_xCu_2O_10 systems

    NASA Astrophysics Data System (ADS)

    Frazer, B.; Hirai, Y.; Rast, Simon; Felner, I.; Asaf, U.; Onellion, M.

    2000-03-01

    We report on both resonant photoemission and fixed photon energy studies of the conduction band and core levels for several ruthocuprate systems. The pure Ru-containing compounds exhibit ferromagnetic order, with metallic behavior and superconductivity depending on the rare earth and oxygen content. We report on as-prepared, hydrogen loaded, and oxygen-annealed polycrystalline samples. The Nb-Ru series changes from purely superconducting to both ferromagnetic and superconducting (Ru). The resonant photoemission measurements of the conduction band across the Ru4p, Cu3p, and Eu4d core levels allow us to determine the location and contribution of Ru, Cu and rare earth related states in the conduction band. The O1s, Cu2p, Ru3p, Ce4d, and Gd4d and several Nb core levels allow us to determine the valence of Ru and Nb, and the metallicity of the Ru/Nb, rare earth, and CuO2 planes.

  18. Crystal structure of a mononuclear Ru(II) complex with a back-to-back terpyridine ligand: [RuCl(bpy)(tpy-tpy)](.).

    PubMed

    Rein, Francisca N; Chen, Weizhong; Scott, Brian L; Rocha, Reginaldo C

    2015-09-01

    We report the structural characterization of [6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine](2,2'-bi-pyridine)-chlorido-ruthenium(II) hexa-fluorido-phosphate, [RuCl(C10H8N2)(C30H20N6)]PF6, which contains the bidentate ligand 2,2'-bi-pyridine (bpy) and the tridendate ligand 6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine (tpy-tpy). The [RuCl(bpy)(tpy-tpy)](+) monocation has a distorted octa-hedral geometry at the central Ru(II) ion due to the restricted bite angle [159.32 (16)°] of the tridendate ligand. The Ru-bound tpy and bpy moieties are nearly planar and essentially perpendicular to each other with a dihedral angle of 89.78 (11)° between the least-squares planes. The lengths of the two Ru-N bonds for bpy are 2.028 (4) and 2.075 (4) Å, with the shorter bond being opposite to Ru-Cl. For tpy-tpy, the mean Ru-N distance involving the outer N atoms trans to each other is 2.053 (8) Å, whereas the length of the much shorter bond involving the central N atom is 1.936 (4) Å. The Ru-Cl distance is 2.3982 (16) Å. The free uncoordinated moiety of tpy-tpy adopts a trans,trans conformation about the inter-annular C-C bonds, with adjacent pyridyl rings being only approximately coplanar. The crystal packing shows significant π-π stacking inter-actions based on tpy-tpy. The crystal structure reported here is the first for a tpy-tpy complex of ruthenium.

  19. Theoretical investigation of cross sections and astrophysical S-factors for the 92Mo(α,n)95Ru and 94Mo(α,n)97Ru reactions

    NASA Astrophysics Data System (ADS)

    Aydin, Abdullah; Yıldız, Ercan; Sarpün, Ismail Hakki

    2016-11-01

    Molybdenum is commonly applied as a constructive material in different types of nuclear reactors. The cross sections of the 92Mo(α,n)95Ru and 94Mo(α,n)97Ru reactions have been calculated at 5-20 MeV energy ranges. In theoretical calculations, the TALYS1.6 and NONSMOKER codes were used. Also the astrophysical S-factors were calculated. Results of our calculations were checked to the experimental data obtained from EXFOR database.

  20. Fe N-Heterocyclic Carbene Complexes as Promising Photosensitizers.

    PubMed

    Liu, Yizhu; Persson, Petter; Sundström, Villy; Wärnmark, Kenneth

    2016-08-16

    The photophysics and photochemistry of transition metal complexes (TMCs) has long been a hot field of interdisciplinary research. Rich metal-based redox processes, together with a high variety in electronic configurations and excited-state dynamics, have rendered TMCs excellent candidates for interconversion between light, chemical, and electrical energies in intramolecular, supramolecular, and interfacial arrangements. In specific applications such as photocatalytic organic synthesis, photoelectrochemical cells, and light-driven supramolecular motors, light absorption by a TMC-based photosensitizer and subsequent excited-state energy or electron transfer constitute essential steps. In this context, TMCs based on rare and expensive metals, such as ruthenium and iridium, are frequently employed as photosensitizers, which is obviously not ideal for large-scale implementation. In the search for abundant and environmentally benign solutions, six-coordinate Fe(II) complexes (Fe(II)L6) have been widely considered as highly desirable alternatives. However, not much success has been achieved due to the extremely short-lived triplet metal-to-ligand charge transfer ((3)MLCT) excited state that is deactivated by low-lying metal-centered (MC) states on a 100 fs time scale. A fundamental strategy to design useful Fe-based photosensitizers is thus to destabilize the MC states relative to the (3)MLCT state by increasing the ligand field strength, with special focus on making eg σ* orbitals on the Fe center energetically less accessible. Previous efforts to directly transplant successful strategies from Ru(II)L6 complexes unfortunately met with limited success in this regard, despite their close chemical kinship. In this Account, we summarize recent promising results from our and other groups in utilizing strongly σ-donating N-heterocyclic carbene (NHC) ligands to make strong-field Fe(II)L6 complexes with significantly extended (3)MLCT lifetimes. Already some of the first

  1. Enhanced thermoelectric power and electronic correlations in RuSe{sub 2}

    SciTech Connect

    Wang, Kefeng Wang, Aifeng; Tomic, A.; Wang, Limin; Petrovic, C.; Abeykoon, A. M. Milinda; Dooryhee, E.; Billinge, S. J. L.

    2015-04-01

    We report the electronic structure, electric and thermal transport properties of Ru{sub 1−x}Ir{sub x}Se{sub 2} (x ≤ 0.2). RuSe{sub 2} is a semiconductor that crystallizes in a cubic pyrite unit cell. The Seebeck coefficient of RuSe{sub 2} exceeds −200 μV/K around 730 K. Ir substitution results in the suppression of the resistivity and the Seebeck coefficient, suggesting the removal of the peaks in density of states near the Fermi level. Ru{sub 0.8}Ir{sub 0.2}Se{sub 2} shows a semiconductor-metal crossover at about 30 K. The magnetic field restores the semiconducting behavior. Our results indicate the importance of the electronic correlations in enhanced thermoelectricity of RuSb{sub 2}.

  2. A density functional theory study of propylene epoxidation on RuO2(110) surface

    NASA Astrophysics Data System (ADS)

    Atmaca, Deniz Onay; Düzenli, Derya; Ozbek, M. Olus; Onal, Isik

    2016-11-01

    Propylene epoxidation is investigated on RuO2(110) and oxygen added RuO2-Oot(110) surfaces by periodic DFT computational method. The desired product propylene oxide (PO) as well as the undesired products acetone (AC) or propionaldehyde (PA) form on both surfaces through either surface intermediate oxometallopropylene (OMMP) or direct oxygen insertion mechanisms. On RuO2(110) surface, nucleophilic lattice oxygen at bridge position (Obr) favors the stable surface intermediate mechanism where high energy requirements for forward reactions are demonstrated in our calculations. On RuO2-Oot(110) surface, however, higher reactivity of the electrophilic oxygen (Oot) species lowers the reaction barriers and enables an exothermic reaction path to the direct oxygen insertion for PO production. Therefore, RuO2-Oot surface is expected to show a higher PO rate.

  3. A structurally diverse Ru(II),Pt(II) tetrametallic motif for photoinitiated electron collection and photocatalytic hydrogen production.

    PubMed

    Knoll, Jessica D; Arachchige, Shamindri M; Brewer, Karen J

    2011-02-18

    Coupling a reactive metal to light absorbers affords molecular devices for photoinitiated electron collection and photocatalytic conversion of substrates to fuels. A new Ru(II),Pt(II) tetrametallic supramolecule, [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](PF(6))(6), and the trimetallic precursors, [{(phen)(2)Ru(dpp)}(2)RuCl(2)](PF(6))(4) and [{(phen)(2)Ru(dpp)}(2)Ru(dpq)](PF(6))(6), have been synthesized, and their redox, spectroscopic, spectroelectrochemical, photophysical and photocatalytic properties studied. They efficiently absorb UV and visible light. The electrochemistry of [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](PF(6))(6) suggests a lowest-lying terminal Ru→dpq charge-separated state that quenches the emission of the parent complex with non-unity population of the emissive (3)MLCT excited state. Photolysis of [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](6+) at 470 nm with DMA gives multielectron reduction, storing electrons in a new manner on the central (dpp)(2)Ru(II)(dpq) moiety. Addition of H(2)O to the photolysis system produces 21 μmol of H(2) in 5 h, with 115 turnovers of the tetrametallic photocatalyst.

  4. Direct measurement of excited-state intervalence transfer in [(tpy)Ru(III)(tppz(*-))Ru(II)(tpy)](4+) by time-resolved near-infrared spectroscopy.

    PubMed

    Dattelbaum, Dana M; Hartshorn, Chris M; Meyer, Thomas J

    2002-05-08

    Extension of time-resolved infrared (TRIR) measurements into the near-infrared region has allowed the first direct measurement of a mixed-valence band in the metal-to-ligand charge transfer (MLCT) excited state of a symmetrical ligand-bridged complex. Visible laser flash excitation of [(tpy)Ru(tppz)Ru(tpy)]4+ (tppz is 2,3,5,6-tetrakis(2-pyridyl)pyrazine; tpy is 2,2':6',6' '-terpyridine) produces the mixed-valence, MLCT excited state [(tpy)RuIII(tppz*-)RuII(tpy)]4+* with the excited electron localized on the bridging tppz ligand. A mixed-valence band appears at numax = 6300 cm-1 with a bandwidth-at-half- maximum, Deltanu1/2 = 1070 cm-1. In the analogous ground-state complex, [(tpy)Ru(tppz)Ru(tpy)]5+, a mixed-valence band appears at numax = 6550 cm-1 with Deltanu1/2 = 970 cm-1 which allows a comparison to be made of electronic coupling across tppz0 and tppz*- as bridging ligands.

  5. Synthesis, characterization, and DNA-binding studies of ruthenium complexes [Ru(tpy)(ptn)]2+ and Ru(dmtpy)(ptn)]2+.

    PubMed

    Li, Lü-Ying; Jia, Hai-Na; Yu, Hui-Juan; Du, Ke-Jie; Lin, Qi-Tian; Qiu, Kang-Qiang; Chao, Hui; Ji, Liang-Nian

    2012-08-01

    Two ruthenium(II) polypyridyl complexes [Ru(tpy)(ptn)](2+) (1) and Ru(dmtpy)(ptn)](2+) (2) (ptn=3-(1,10-phenanthrolin-2-yl)-as-triazino[5,6-f]naphthalene, tpy=2,2':6',2"-terpyridine, dmtpy=5,5'-dimethyl-2,2':6',2"-terpyridine) have been synthesized and characterized by elemental analysis, (1)H NMR, mass spectrometry and crystal structure analysis. Spectroscopic studies together with isothermal titration calorimetry (ITC) and viscosity measurements prove that two complexes bind to DNA in an intercalative mode. ITC experiments show that the binding mode for complex 2 is entropically driven, while an entropy-driven initial binding of complex 1 is followed by an entropically and enthalpically favorable process. This difference may be attributed to the ancillary ligand effects on the DNA binding of Ru(II) complexes. Circular dichroism titrations of calf thymus DNA (CT-DNA) with Ru(II) complexes show that complexes 1 and 2 induce B to Z conformational transition of calf thymus DNA at low ionic strength (0.05 M NaCl). The induced Z-DNA conformation can revert to B form when Ru(II) complexes are displaced by ethidium bromide or at high ionic strengths ([NaCl]=0.4 M), but keeps intact with temperature ranged from 25 to 90 °C. The unique structure and characteristics of Ru(II) complexes designed in this investigation will be useful for the study of Z-DNA.

  6. The Ruthenostannylene Complex [Cp*(IXy)H2 Ru-Sn-Trip]: Providing Access to Unusual Ru-Sn Bonded Stanna-imine, Stannene, and Ketenylstannyl Complexes.

    PubMed

    Liu, Hsueh-Ju; Ziegler, Micah S; Tilley, T Don

    2015-05-26

    Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2 Ru-Sn-Trip] (1; IXy=1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; Cp*=η(5) -C5 Me5 ; Trip=2,4,6-iPr3 C6 H2 ) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β-unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip] (2) and [Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip] (3), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin-substituted ketene complex [Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip] (4), which is most likely a decomposition product from the putative ruthenium-substituted stannene complex. The isolation of a ruthenium-substituted stannene [Cp*(IXy)(H)2 RuSn(=Flu)Trip] (5) and stanna-imine [Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip] (6) complexes was achieved by treatment of 1 with 9-diazofluorene and tosyl azide, respectively.

  7. The Thermal Behavior of Pd on Graphene/Ru(0001)

    SciTech Connect

    Yi, Cheol-Woo W.; Szanyi, Janos

    2015-11-01

    The thermal behavior of various amounts of palladium deposited onto graphene/Ru(0001) at room temperature was investigated by x-ray photoelectron spectroscopy (XPS) and infrared reflection absorption spectroscopy (IRAS) of adsorbed CO. IRAS spectra of adsorbed CO on palladium deposited onto the graphene layer reveal the formation of defect-rich, highly-stepped and/or nanoparticle-typed palladium clusters. Annealing to temperatures below ~900 K, palladium clusters mainly experience agglomeration on the graphene layer, but at higher temperatures intercalation of palladium between the graphene layer and Ru substrate takes place. Eventually, palladium completely desorbs and the graphene layer dissolves into the ruthenium substrate at 1400 K. Even though the annealing induces the intercalation and desorption of palladium, the topmost graphene layer stays intact without any physical damage at and below 1300 K. We gratefully acknowledge the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division for the support of this work. The research described in this article was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830. CWY also acknowledges the support of this work by Sungshin Women’s University Research Grant of 2014.

  8. Coulomb Excitation of Radioactive Mo-Ru Isotopes

    NASA Astrophysics Data System (ADS)

    Allmond, J. M.; Gretina-Chico2 Collaboration

    2016-09-01

    The study of shapes in atomic nuclei has been a major focus of nuclear structure ever since the observation of large electric quadrupole moments in the first half of the 20th century. A leading challenge has been to experimentally establish regions of oblate deformation, which are very limited, and triaxial deformation. The neutron-rich Mo-Ru region is expected to exhibit triaxial deformation in the low-lying states, mediated by a relatively rare instance of prolate-to-oblate shape evolution. A survey of equipment, techniques, and preliminary results from recent Coulomb-excitation and beta-decay experiments in the neutron-rich Mo-Ru region will be presented. These experiments were conducted at the CARIBU-ANL facility using GRETINA-CHICO2. An emphasis will be placed on unique opportunities with 3-MeV/u beams. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Nuclear Physics.

  9. Schweizer RU-38A Twin-Condor: covert surveillance aircraft

    NASA Astrophysics Data System (ADS)

    O'Toole, Michael J.; Schweizer, Paul H.

    1997-11-01

    The world order has changed and with it, governments are now faced with waging a new type of `ware.' Regional instability, drug trafficking, environmental issues, international terrorism, and illegal immigration are examples of escalating problems that cross international boundaries and threaten the security of nations. The first and most important element in coping with these illegal activities is the ability to detect and monitor events in a timely and secure fashion. Conventional means of gathering intelligence such as large airborne collection systems and satellites lack the flexibility, dwell times, and cost effectiveness to meet many of today's needs. There is a growing requirement for airborne platforms that can covertly perform surveillance missions during either day or night and in a cost effective manner. To meet this need, Schweizer Aircraft has recently developed the RU-38A twin-engine surveillance aircraft. This paper discusses the evolution and principle design concepts of this aircraft and how its unique performance enables the RU-38A to achieve new levels of surveillance capability.

  10. Metamagnetic Nematic Phase of Sr3Ru2O7

    NASA Astrophysics Data System (ADS)

    MacKenzie, Andrew

    2008-03-01

    In this talk I will review our group's recent observations that a quantum phase with pronounced electrical transport anisotropies forms in the vicinity of a metamagnetic quantum critical point in Sr3Ru2O7. The behaviour, which is strongly dependent on disorder and is only seen in the highest purity crystals, has phenomenological similarities with prior observations on two-dimensional electron gases in semiconductor devices [1,2]. Its appearance in bulk in Sr3Ru2O7 has allowed us to perform a number of thermodynamic measurements, and also offers the promise of study using modern surface-based spectroscopies such as angle resolved photoemission and spectroscopic imaging scanning tunneling microscopy. References [1] For example M.P. Lilly et al., Phys. Rev. Lett. 82, 394 (1999); ibid 83, 824 (1999) [2] W. Pan et al., Phys. Rev. Lett. 83, 820 (1999). Collaborators: S.A. Grigera^1, R.A. Borzi^1,2, A. Rost^1, J.F. Mercure^1, J. Farrell^1, R.S. Perry^3, A.G. Green^1, M. Allan^1, M. Wang^4, J. Lee^1, F. Baumberger^1, S.J.S Lister^1, S.L. Lee^1, J.C.S. Davis^1,4, Z.X. Shen^5, Y. Maeno^6. ^1 University of St Andrews, Scotland ^2 INFTA, La Plata, Argentina ^3 University of Edinburgh, Scotland ^4 Cornell University, USA ^5 Stanford University, USA ^6 Kyoto University, Japan

  11. Spectroscopic analysis of catalytic water oxidation by [Ru(II)(bpy)(tpy)H2O]2+ suggests that Ru(V)═O is not a rate-limiting intermediate.

    PubMed

    Pushkar, Yulia; Moonshiram, Dooshaye; Purohit, Vatsal; Yan, Lifen; Alperovich, Igor

    2014-08-27

    Modern chemistry's grand challenge is to significantly improve catalysts for water splitting. Further progress requires detailed spectroscopic and computational characterization of catalytic mechanisms. We analyzed one of the most studied homogeneous single-site Ru catalysts, [Ru(II)(bpy)(tpy)H2O](2+) (where bpy = 2,2'-bipyridine, tpy = 2,2';6',2″-terpyridine). Our results reveal that the [Ru(V)(bpy)(tpy)═O](3+) intermediate, reportedly detected in catalytic mixtures as a rate-limiting intermediate in water activation, is not present as such. Using a combination of electron paramagnetic resonance (EPR) and X-ray absorption spectroscopy, we demonstrate that 95% of the Ru complex in the catalytic steady state is of the form [Ru(IV)(bpy)(tpy)═O](2+). [Ru(V)(bpy)(tpy)═O](3+) was not observed, and according to density functional theory (DFT) analysis, it might be thermodynamically inaccessible at our experimental conditions. A reaction product with unique EPR spectrum was detected in reaction mixtures at about 5% and assigned to Ru(III)-peroxo species with (-OOH or -OO- ligands). We also analyzed the [Ru(II)(bpy)(tpy)Cl](+) catalyst precursor and confirmed that this molecule is not a catalyst and its oxidation past Ru(III) state is impeded by a lack of proton-coupled electron transfer. Ru-Cl exchange with water is required to form active catalysts with the Ru-H2O fragment. [Ru(II)(bpy)(tpy)H2O](2+) is the simplest representative of a larger class of water oxidation catalysts with neutral, nitrogen containing heterocycles. We expect this class of catalysts to work mechanistically in a similar fashion via [Ru(IV)(bpy)(tpy)═O](2+) intermediate unless more electronegative (oxygen containing) ligands are introduced in the Ru coordination sphere, allowing the formation of more oxidized Ru(V) intermediate.

  12. Os Odontoideum: Rare Cervical Lesion

    DTIC Science & Technology

    2011-11-01

    the articulation between C1 and the os odontoideum on flexion imaging. The remainder of his cervical vertebral bodies had normal alignment with no...appears normal. Figure 3. Flexion view of plain cervical spine. This image shows abnormal translation of the articulation between C1 and the C2 os...worldwide. Peer Reviewed Title: Os Odontoideum: Rare Cervical Lesion Journal Issue: Western Journal of Emergency Medicine, 12(4) Author: Robson

  13. Structural and resonance Raman studies of an oxygen-evolving catalyst. Crystal structure of [(bpy){sub 2}(H{sub 2}O)Ru{sup III}ORu{sup IV}(OH)(bpy){sub 2}](ClO{sub 4}){sub 4}

    SciTech Connect

    Schoonover, J.; Ni, JinFeng; Roecker, L.; White, P.S.; Meyer, T.J. |

    1996-09-25

    The oxidized form of the blue dimer water oxidation catalyst [(bpy){sub 2}(H{sub 2}O)Ru{sup III}ORu{sup IV}(OH)(bpy){sub 2}](ClO{sub 4}){sub 4} (bpy is 2,2{prime}-bipyridine) has been characterized structurally by X-ray crystallography. Comparisons with [(bpy){sub 2}(H{sub 2}O)Ru{sup III}-ORu{sup III}(OH{sub 2})(bpy){sub 2}](ClO{sub 4}){sub 4}{center_dot}2H{sub 2}O, [(bpy){sub 2}ClRu{sup III}ORu{sup IV}Cl(bpy){sub 2}](ClO{sub 4}){sub 3}{center_dot}H{sub 2}O, and [(tpy)(bpy)Os{sup III}OOs{sup IV}(bpy)-(tpy)]Na(ClO{sub 4}){sub 6}{center_dot}3H{sub 2}O (tpy is 2,2{prime}:6{prime},2{double_prime}-terpyridine) reveal that oxidation of Ru{sup III}-O-Ru{sup III} to Ru{sup III}-O-Ru{sup IV} results in significant structural changes at the {mu}-oxo bridge. There is an increase toward linearity along M-O-M, a decrease in the M-O bond distances at the bridge, and an increase in the H{sub 2}O-Ru-O bridge angle. These changes are discussed in the context of the structural requirements for O...O coupling and O{sub 2} evolution in higher oxidation states. Resonance Raman spectra of these and related complexes reveal that internal ligand vibrations as well as overtone and combination bands of an intense, symmetrical M-O-M stretch at 360-400 cm{sup {minus}1} contribute significantly to the Raman spectra. Additional M-O-M bands are identified near 800 cm{sup {minus}1} and, tentatively, near 130 cm{sup {minus}1}. It is not possible to assign bands to Ru-OH{sub 2} or Ru-OH stretches; bands at low energy appear to originate from modes that are highly mixed.

  14. Calculating the melting curves by the thermodynamic data matching method: Platinum-group refractory metals (Ru, Os, and Ir)

    NASA Astrophysics Data System (ADS)

    Kulyamina, E. Yu.; Zitserman, V. Yu.; Fokin, L. R.

    2017-01-01

    A technique for reconstructing thermal properties, including the melting curve, of refractory metals based on the use of experimental data on caloric properties available up to the melting point and some regularities of the Debye-Grüneisen theory has been proposed. The calculation result is the consistent system of high-temperature thermal data, including the thermal expansion coefficient, solid-phase density, and volume jump upon melting. This technique was tried-out on refractory platinum-group metals based on experimental data on the enthalpy of the metals and confirmed by consistency with a thermodynamic calculation using shock-wave experiments and results obtained by the quantum molecular dynamics method.

  15. Synthesis and Isomeric Analysis of Ru(II) Complexes Bearing Pentadentate Scaffolds.

    PubMed

    Gil-Sepulcre, Marcos; Axelson, Jordan C; Aguiló, Joan; Solà-Hernández, Lluís; Francàs, Laia; Poater, Albert; Blancafort, Lluís; Benet-Buchholz, Jordi; Guirado, Gonzalo; Escriche, Lluís; Llobet, Antoni; Bofill, Roger; Sala, Xavier

    2016-11-07

    A Ru(II)-pentadentate polypyridyl complex [Ru(II)(κ-N(5)-bpy2PYMe)Cl](+) (1(+), bpy2PYMe = 1-(2-pyridyl)-1,1-bis(6-2,2'-bipyridyl)ethane) and its aqua derivative [Ru(II)(κ-N(5)-bpy2PYMe)(H2O)](2+) (2(2+)) were synthesized and characterized by experimental and computational methods. In MeOH, 1(+) exists as two isomers in different proportions, cis (70%) and trans (30%), which are interconverted under thermal and photochemical conditions by a sequence of processes: chlorido decoordination, decoordination/recoordination of a pyridyl group, and chlorido recoordination. Under oxidative conditions in dichloromethane, trans-1(2+) generates a [Ru(III)(κ-N(4)-bpy2PYMe)Cl2](+) intermediate after the exchange of a pyridyl ligand by a Cl(-) counterion, which explains the trans/cis isomerization observed when the system is taken back to Ru(II). On the contrary, cis-1(2+) is in direct equilibrium with trans-1(2+), with absence of the κ-N(4)-bis-chlorido Ru(III)-intermediate. All these equilibria were modeled by density functional theory calculations. Interestingly, the aqua derivative is obtained as a pure trans-[Ru(II)(κ-N(5)-bpy2PYMe)(H2O)](2+) isomer (trans-2(2+)), while the addition of a methyl substituent to a single bpy of the pentadentate ligand leads to the formation of a single cis isomer for both chlorido and aqua derivatives [Ru(II)(κ-N(5)-bpy(bpyMe)PYMe)Cl](+) (3(+)) and [Ru(II)(κ-N(5)-bpy(bpyMe)PYMe)(H2O)](2+) (4(2+)) due to the steric constraints imposed by the modified ligand. This system was also structurally and electrochemically compared to the previously reported [Ru(II)(PY5Me2)X](n+) system (X = Cl, n = 1 (5(+)); X = H2O, n = 2 (6(2+))), which also contains a κ-N(5)-Ru(II) coordination environment, and to the newly synthesized [Ru(II)(PY4Im)X](n+) complexes (X = Cl, n = 1 (7(+)); X = H2O, n = 2 (8(2+))), which possess an electron-rich κ-N(4)C-Ru(II) site due to the replacement of a pyridyl group by an imidazolic carbene.

  16. OsABCB14 functions in auxin transport and iron homeostasis in rice (Oryza sativa L.).

    PubMed

    Xu, Yanxia; Zhang, Saina; Guo, Haipeng; Wang, Suikang; Xu, Ligen; Li, Chuanyou; Qian, Qian; Chen, Fan; Geisler, Markus; Qi, Yanhua; Jiang, De An

    2014-07-01

    Members of the ATP Binding Cassette B/Multidrug-Resistance/P-glyco-protein (ABCB/MDR/PGP) subfamily were shown to function primarily in Oryza sativa (rice) auxin transport; however, none of the rice ABCB transporters have been functionally characterized. Here, we describe that a knock-down of OsABCB14 confers decreased auxin concentrations and polar auxin transport rates, conferring insensitivity to 2,4-dichlorophenoxyacetic acid (2,4-D) and indole-3-acetic acid (IAA). OsABCB14 displays enhanced specific auxin influx activity in yeast and protoplasts prepared from rice knock-down alleles. OsABCB14 is localized at the plasma membrane, pointing to an important directionality under physiological conditions. osabcb14 mutants were surprisingly found to be insensitive to iron deficiency treatment (-Fe). Their Fe concentration is higher and upregulation of Fe deficiency-responsive genes is lower in osabcb14 mutants than in wild-type rice (Nipponbare, NIP). Taken together, our results strongly support the role of OsABCB14 as an auxin influx transporter involved in Fe homeostasis. The functional characterization of OsABCB14 provides insights in monocot auxin transport and its relationship to Fe nutrition.

  17. Metal- and ligand-assisted CO2 insertion into Ru-C, Ru-N, and Ru-O bonds of ruthenium(II) phosphine complexes: a density functional theory study.

    PubMed

    Vadivelu, Prabha; Suresh, Cherumuttathu H

    2015-01-20

    The CO2 insertion reactions of [L4Ru(η(2)-CH2C6H4)] (1), [L4Ru(η(2)-OC6H3Me)] (2), and [L4Ru(η(2)-NHC6H4)] (3), where L = PH3 and PMe3, are modeled using density functional theory methods. In 1 and 2, the metal-assisted CO2 insertion occurs because of the favorable initial axial phosphine dissociation mechanism, whereas in 3, the ligand (NHC6H4)-assisted mechanism operates (ΔG(⧧) = +19.0 kcal/mol), wherein the nucleophilic affinity of the -NHC6H4 moiety aids the CO2 insertion process. The modeled mechanisms are consistent with the experimental findings by Hartwig et al. (J. Am. Chem. Soc, 1991, 113, 6499), in which the rate of the reactions of 1 and 2 depends on the added phosphine concentration, whereas the rate of the reaction of 3 is independent of the added phosphine concentration. In 1 and 2, CO2 is preferably inserted into the Ru-Caryl bond rather than the competitive Ru-CH2 and Ru-O bonds, respectively. In 1, the π-type orbital interaction of the aryl ring with the metal center is found to stabilize the transition state for Ru-Caryl bond insertion (ΔG(⧧) = +25.7 kcal/mol). In 2, the Ru-Caryl insertion (ΔG(⧧) = +23.0 kcal/mol) is thermodynamically preferred, while the kinetically preferred Ru-O bond insertion (ΔG(⧧) = +17.4 kcal/mol) is highly reversible. The more electron-donating and sterically bulky PMe3 facilitates the CO2 insertion of 1 and 2 because the initial dissociation of axial PMe3 is easier than that of PH3 by ca. +11.0 kcal/mol, whereas in the case of 3, the effect of PMe3 slightly increases the ΔG(⧧) value of 3. The increase in the nucleophilic affinity of amido nitrogen in 3 and the increase in the polarity of the solvent decrease the ΔG(⧧) value of 3 by 48%. The inclusion of the chelating dimethylphosphinoethane ligand in 3 along with the electron-donating substituent at the -NHC6H4 moiety and the polar solvent further reduces the ΔG(⧧) value of 3 by 62%, which demonstrates the role of the chelating ligand, electron

  18. Local structure distortion induced by Ti dopants boosting the pseudocapacitance of RuO2-based supercapacitors

    NASA Astrophysics Data System (ADS)

    Chen, I.-Li; Wei, Yu-Chen; Lu, Kueih-Tzu; Chen, Tsan-Yao; Hu, Chi-Chang; Chen, Jin-Ming

    2015-09-01

    Binary oxides with atomic ratios of Ru/Ti = 90/10, 70/30, and 50/50 were fabricated using H2O2-oxidative precipitation with the assistance of a cetyltrimethylammonium bromide (CTAB) template, followed by a thermal treatment at 200 °C. The characteristics of electron structure and local structure extracted from X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) analyses indicate that incorporation of Ti into the RuO2 lattice produces not only the local structural distortion of the RuO6 octahedra in (Ru-Ti)O2 with an increase in the central Ru-Ru distance but also a local crystallization of RuO2. Among the three binary oxides studied, (Ru70-Ti30)O2 exhibits a capacitance improvement of about 1.4-fold relative to the CTAB-modified RuO2, mainly due to the enhanced crystallinity of the distorted RuO6 structure rather than the surface area effect. Upon increasing the extent of Ti doping, the deteriorated supercapacitive performance of (Ru50-Ti50)O2 results from the formation of localized nano-clusters of TiO2 crystallites. These results provide insight into the important role of Ti doping in RuO2 that boosts the pseudocapacitive performance for RuO2-based supercapacitors. The present result is crucial for the design of new binary oxides for supercapacitor applications with extraordinary performance.Binary oxides with atomic ratios of Ru/Ti = 90/10, 70/30, and 50/50 were fabricated using H2O2-oxidative precipitation with the assistance of a cetyltrimethylammonium bromide (CTAB) template, followed by a thermal treatment at 200 °C. The characteristics of electron structure and local structure extracted from X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) analyses indicate that incorporation of Ti into the RuO2 lattice produces not only the local structural distortion of the RuO6 octahedra in (Ru-Ti)O2 with an increase in the central Ru-Ru distance but also a local crystallization of RuO2. Among the three binary

  19. FePtC magnetic recording media with (200) textured MoC intermediate layer

    SciTech Connect

    Tsai, Jai-Lin Tseng, Yun-Ting; Li, Chia-Ru; Fu, Sheng-Chun

    2015-05-07

    The FePt films with thickness of 4–10 nm were deposited on MoC/CrRu/glass at 425 °C by using magnetron sputtering. The Mo{sub 40}C{sub 60} target was used to form the MoC and C two phases after deposition. The MoC intermediate layer was epitaxially grown on the (200) textured CrRu seed layer at 425 °C and the MoC (200) diffraction peak was not clearly indexed below 10 nm but observed at 25 nm. Finally, the FePt film was prepared on (200) textured MoC at 425 °C and shown the strong (001) texture. Perpendicular anisotropy of 1.7 × 10{sup 7} erg/cm{sup 3} and out-of-plane coercivity of 7.5 kOe has been demonstrated in 10 nm thick FePt film. From microstructure, the FePt grains were distributed in- or between-islands like structure and further separated by excess carbon from MoC intermediate layer. Thinner FePt film was more separated by excess carbon and shown higher coercivity.

  20. Nanoscale variations in 187Os isotopic composition and HSE systematics in a Bultfontein peridotite

    NASA Astrophysics Data System (ADS)

    Wainwright, A. N.; Luguet, A.; Schreiber, A.; Fonseca, R. O. C.; Nowell, G. M.; Lorand, J.-P.; Wirth, R.; Janney, P. E.

    2016-08-01

    Understanding the mineralogical controls on radiogenic chronometers is a fundamental aspect of all geochronological tools. As with other common dating tools, it has become increasingly clear that the Re-Os system can be impacted by multiple mineral formation events. The accessory and micrometric nature of the Re-Os-bearing minerals has made assessing this influence complex. This is especially evident in cratonic peridotites, where long residence times and multiple metasomatic events have created a complex melting and re-enrichment history. Here we investigate a harzburgitic peridotite from the Bultfontein kimberlite (South Africa) which contains sub-micron Pt-Fe-alloy inclusions within base metal sulphides (BMS). Through the combination of the focused ion beam lift-out technique and low blank mass spectrometry we were able to remove and analyse the Pt-Fe-alloy inclusions for their Re-Os composition and highly siderophile element (HSE) systematics. Six repeats of the whole-rock yield 187Os/188Os compositions of 0.10893-0.10965, which correspond to Re depletion model ages (TRD) of 2.69-2.79 Ga. The Os, Ir and Pt concentrations are slightly variable across the different digestions, whilst Pd and Re remain constant. The resulting HSE pattern is typical of cratonic peridotites displaying depleted Pt and Pd. The Pt-Fe-alloys have PUM-like 187Os/188Os compositions of 0.1294 ± 24 (2-s.d.) and 0.1342 ± 38, and exhibit a saw-tooth HSE pattern with enriched Re and Pt. In contrast, their BMS hosts have unradiogenic 187Os/188Os of 0.1084 ± 6 and 0.1066 ± 3, with TRD ages of 2.86 and 3.09 Ga, similar to the whole-rock systematics. The metasomatic origin of the BMS is supported by (i) the highly depleted nature of the mantle peridotite and (ii) their Ni-rich sulphide assemblage. Occurrence of Pt-Fe-alloys as inclusions within BMS grains demonstrates the genetic link between the BMS and Pt-Fe-alloys and argues for formation during a single but continuous event of silicate melt

  1. Microstructure and magnetic properties of FePt film with combined MoC/(Mg-X)O (X=Cu, Ni, Co) intermediate layers

    NASA Astrophysics Data System (ADS)

    Tsai, Jai-Lin; Tzeng, Jie-Lin; Hu, Keng-Chun; Li, Hsu-Kang; Pan, Zu-Yu; Chang, Yuan-Shuo; Liao, Chang-Chun

    2017-01-01

    The magnetic properties and microstructure of FePt films grown on MoC layer and MoC/(Mg-X)O (X=Cu, Ni, Co) combined intermediate layers were studied. The (Mg-X)O (X=Cu, Ni, Co) layer with thickness of 5 nm was deposited on CrRu seed layer at 395 °C. The CrRu (200) texture was enhanced which may due to well grains growth in specific orientation and small lattice mismatch with (Mg-X)O (X=Cu, Ni, Co). Finally, the FePt/MoC layers were deposited on (Mg-X)O layer at 425 °C. Using MoC/MgCuO combined intermediate layers, the rocking width of FePt (001) and CrRu (200) diffraction peak were changed from 7.1° to 6.1°, and 5.7° to 3.8°, respectively. For MoC/MgCoO dual intermediate layers, the rocking width of FePt (001) and CrRu (200) diffraction peak were 6.7° and 4.1°. The FePt/MoC/MgCoO film illustrates perpendicular magnetic anisotropy with out-of plane coercivity of 9.3 kOe which is higher than FePt film deposited on MoC layer (8.5 kOe) and the in-plane loops is linear. From microstructure, the FePt grains were more separated on MoC/(Mg-X)O (X=Cu, Ni, Co) combined intermediate layers.

  2. Syntrophic Effects in a Subsurface Clostridial Consortium on Fe(III)-(Oxyhydr)oxide Reduction and Secondary Mineralization

    SciTech Connect

    Shah, Madhavi; Lin, Chu-Ching; Kukkadapu, Ravi K.; Engelhard, Mark H.; Zhao, Xiuhong; Wang, Yangping; Barkay, Tamar; Yee, Nathan

    2013-07-09

    In this study, we cultivated from subsurface sediments an anaerobic Clostridia 25 consortium that was composed of a fermentative Fe-reducer Clostridium species (designated as 26 strain FGH) and a novel sulfate-reducing bacterium belonging to the Clostridia family 27 Vellionellaceae (designated as strain RU4). In pure culture, Clostridium sp. strain FGH mediated 28 the reductive dissolution/transformation of iron oxides during growth on peptone. When 29 Clostridium sp. FGH was grown with strain RU4 on peptone, the rates of iron oxide reduction 30 were significantly higher. Iron reduction by the consortium was mediated by multiple 31 mechanisms, including biotic reduction by Clostridium sp. FGH and biotic/abiotic reactions 32 involving biogenic sulfide by strain RU4. The Clostridium sp. FGH produced hydrogen during 33 fermentation, and the presence of hydrogen inhibited growth and iron reduction activity. The 34 sulfate-reducing partner strain RU4 was stimulated by the presence of H2 gas and generated 35 reactive sulfide which promoted the chemical reduction of the iron oxides. Characterization of 36 Fe(II) mineral products showed the formation of magnetite during ferrihydrite reduction, and 37 the precipitation of iron sulfides during goethite and hematite reduction. The results suggest an 38 important pathway for iron reduction and secondary mineralization by fermentative sulfate-39 reducing microbial consortia is through syntrophy-driven biotic/abiotic reactions with biogenic 40 sulfide.

  3. High antiferromagnetic transition temperature of a honeycomb compound SrRu2O6

    DOE PAGES

    Tian, Wei; Svoboda, Chris; Ochi, M.; ...

    2015-09-14

    We study the high-temperature magnetic order in a quasi-two-dimensional honeycomb compound SrRu2O6 by measuring magnetization and neutron powder diffraction with both polarized and unpolarized neutrons. SrRu2O6 crystallizes into the hexagonal lead antimonate (PbSb2O6, space group P31m) structure with layers of edge-sharing RuO6 octahedra separated by Sr2+ ions. SrRu2O6 is found to order at TN = 565 K with Ru moments coupled antiferromagnetically both in plane and out of plane. The magnetic moment is 1.30(2) μB/Ru at room temperature and is along the crystallographic c axis in the G-type magnetic structure. We perform density functional calculations with constrained random-phase approximation (RPA)more » to obtain the electronic structure and effective intra- and interorbital interaction parameters. The projected density of states shows strong hybridization between Ru 4d and O 2p. By downfolding to the target t2g bands we extract the effective magnetic Hamiltonian and perform Monte Carlo simulations to determine the transition temperature as a function of interand intraplane couplings. We find a weak interplane coupling, 3% of the strong intraplane coupling, permits three-dimensional magnetic order at the observed TN .« less

  4. Unexpected C-H activation of Ru(II)-dithiomaltol complexes upon oxidation.

    PubMed

    Backlund, Malin; Ziller, Joseph; Farmer, Patrick J

    2008-04-07

    Thione-substituted derivatives of maltol are of interest in several applications of metal-based drugs. In order to investigate the effect of the oxygenation on such thione chelates, Ru complexes of 3-hydroxy-2-methyl-4-thiopyrone (thiomaltol or Htma) and 3-hydroxy-2-methyl-4H-thiopyran-4-thione (dithiomaltol or Httma), [Ru(bpy)2(tma)](+), 1, and [Ru(bpy) 2(ttma)] (+), 2, were synthesized as diamagnetic PF6(-) salts. Peroxidation of 2 unexpectedly generated products of C-H activation at its pendant methyl group; an air-stable aldehyde [Ru(bpy)2(ttma-aldehyde)](+), 4, was the major product. In addition, an intermediate oxidation product [Ru(bpy) 2(ttma-alcohol)](PF6), 3, was characterized. Both 3 and 4 are also formed by reaction of 2 with outersphere oxidants (e.g., Na2IrCl6) and by bulk electrolysis under anaerobic conditions. Similar oxidations of the analogous [Ru(bpy)2(ettma)](+), 2' , complex (3-hydroxy-2-ethyl-4H-thiopyran-4-thione; ethyl dithiomaltol or Hettma) formed the corresponding ketone, [Ru(bpy)2(ettma-ketone)](PF6), 4', by oxidation at the same position adjacent to the conjugated ring. The structures of the aldehyde 4 and starting materials 1 and 2 have been confirmed by X-ray crystallography, and all complexes have been characterized by UV-vis, (1)H NMR, and IR spectroscopies. Initial mechanistic investigations are discussed.

  5. Non-Fermi-liquid behaviour in La4Ru6O19.

    PubMed

    Khalifah, P; Nelson, K D; Jin, R; Mao, Z Q; Liu, Y; Huang, Q; Gao, X P; Ramirez, A P; Cava, R J

    2001-06-07

    Understanding the complexities of electronic and magnetic ground states in solids is one of the main goals of solid-state physics. Transition-metal oxides have proved to be particularly fruitful in this regard, especially for those materials with the perovskite structure, where the special characteristics of transition-metal-oxygen orbital hybridization determine their properties. Ruthenates have recently emerged as an important family of perovskites because of the unexpected evolution from high-temperature ferromagnetism in SrRuO3 to low-temperature superconductivity in Sr2RuO4 (refs 1, 2). Here we show that a ruthenate in a different structural family, La4Ru6O19, displays a number of highly unusual properties, most notably non-Fermi-liquid behaviour. The properties of La4Ru6O19 have no analogy among the thousands of previously characterized transition-metal oxides. Instead, they resemble those of CeCu6-xAux-a widely studied f-electron-based heavy fermion intermetallic compound that is often considered as providing the best example of non-Fermi-liquid behaviour. In the ruthenate, non-Fermi-liquid behaviour appears to arise from just the right balance between the interactions of localized electronic states derived from Ru-Ru bonding and delocalized states derived from Ru-O hybridization.

  6. Stable monolayer honeycomb-like structures of RuX2 (X =S,Se)

    NASA Astrophysics Data System (ADS)

    Ersan, Fatih; Cahangirov, Seymur; Gökoǧlu, Gökhan; Rubio, Angel; Aktürk, Ethem

    2016-10-01

    Recent studies show that several metal oxides and dichalcogenides (M X2) , which exist in nature, can be stable in two-dimensional (2D) form and each year several new M X2 structures are explored. The unstable structures in H (hexagonal) or T (octahedral) forms can be stabilized through Peierls distortion. In this paper, we propose new 2D forms of RuS2 and RuSe2 materials. We investigate in detail the stability, electronic, magnetic, optical, and thermodynamic properties of 2D Ru X2 (X =S,Se) structures from first principles. While their H and T structures are unstable, the distorted T structures (T'-Ru X2) are stable and have a nonmagnetic semiconducting ground state. The molecular dynamic simulations also confirm that T'-Ru X2 systems are stable even at 500 K without any structural deformation. T'-RuS2 and T'-RuSe2 have indirect band gaps with 0.745 eV (1.694 eV with HSE) and 0.798 eV (1.675 eV with HSE) gap values, respectively. We also examine their bilayer and trilayer forms and find direct and smaller band gaps. We find that AA stacking is more favorable than the AB configuration. The new 2D materials obtained can be good candidates with striking properties for applications in semiconductor electronic, optoelectronic devices, and sensor technology.

  7. Enhanced performance of HRGO-RuO2 solid state flexible supercapacitors fabricated by electrophoretic deposition

    DOE PAGES

    Amir, Fatima Z.; Pham, V. H.; Mullinax, D. W.; ...

    2016-06-07

    Ruthenium oxide (RuO2) nanomaterials exist as excellent materials for electrochemical capacitors. However, they tend to suffer from low mechanical flexibility when cast into films, which makes them unsuitable for flexible device applications. Herein, we report an environmentally friendly and solution-processable approach to fabricate RuO2-based composite electrodes for flexible solid state supercapacitors. The composites were produced by anchoring RuO2 nanoparticles onto holey reduced graphene oxide (HRGO) via a sol-gel method, followed by the electrophoretic deposition (EPD) of the material into thin films. The uniform anchoring of ultra-small RuO2 nanoparticles on the two-dimensional HRGO sheets resulted in HRGO-RuO2 hybrid sheets with excellentmore » mechanical flexibility of HRGO. EPD induced a layer-by-layer assembly mechanism for the HRGO-RuO2 hybrid sheets, which resulted in a binder-free, flexible electrode. The obtained HRGO-RuO2 flexible supercapacitors exhibited excellent electrochemical capacitive performance in a PVA-H2SO4 gel electrolyte with a specific capacitance of 418 F g-1 and superior cycling stability of 88.5% capacitance retention after 10,000 cycles. Additionally, these supercapacitors exhibited high rate performance with capacitance retention of 85% by increasing the current density from 1.0 to 20.0 Ag-1, and excellent mechanical flexibility with only 4.9% decay in the performance when bent 180°.« less

  8. Diffusion of Zr, Ru, Ce, Y, La, Sr and Ba fission products in UO2

    NASA Astrophysics Data System (ADS)

    Perriot, R.; Liu, X.-Y.; Stanek, C. R.; Andersson, D. A.

    2015-04-01

    The diffusivity of the solid fission products (FP) Zr (Zr4+), Ru (Ru4+, Ru3+), Ce (Ce4+), Y (Y3+), La (La3+), Sr (Sr2+) and Ba (Ba2+) by a vacancy mechanism has been calculated, using a combination of density functional theory (DFT) and empirical potential (EP) calculations. The activation energies for the solid fission products are compared to the activation energy for Xe fission gas atoms calculated previously. Apart from Ru, the solid fission products all exhibit higher activation energy than Xe. For all solid FPs except Y3+, the migration of the FP has lower barrier than the migration of a neighboring U atom, making the latter the rate limiting step for direct migration. An indirect mechanism, consisting of two successive migrations around the FP, is also investigated. The calculated diffusivities show that most solid fission products diffuse with rates similar to U self-diffusion. However, Ru, Ba and Sr exhibit faster diffusion than the other solid FPs, with Ru3+ and Ru4+ diffusing even faster than Xe for T < 1200 K. The diffusivities correlate with the observed fission product solubility in UO2, and the tendency to form metallic and oxide second phase inclusions.

  9. Gluing together metallic and covalent layers to form Ru2C under ambient conditions.

    PubMed

    Sun, Weiwei; Li, Yunguo; Zhu, Li; Ma, Yanming; Di Marco, Igor; Johansson, Börje; Korzhavyi, Pavel

    2015-04-21

    Ru2C has recently been synthesised at high pressure and high temperature, and was assumed to have a structure with space group P3̅m1. However, subsequent theoretical work has revealed that this structure is unstable under ambient conditions, which motivated us to look for the stable structure. In this work, we explore the structures of Ru2C by using an unbiased swarm structure searching algorithm. The structures with R3m and R3̅m symmetries have been found to be lower in energy than the P3̅m1 structure, at the same time being dynamically stable under ambient conditions. These layered structures consist of alternating Ru bilayers and C monolayers in the R3m structure, and alternating Ru tetra-layers and C bilayers in the R3̅m structure. The C layers are more evenly distributed and more covalently bound to the Ru layers in the R3m structure than in the R3̅m structure. Instead, in the R3̅m structure there exists more Ru-Ru metallic bonding, which has a crucial role in diminishing the hardness of this material. Our findings should stimulate further explorations of the structures and properties of the heavy transition metal carbides and nitrides, potentially leading to industrial applications.

  10. Nanoporous Ru as a carbon- and binder-free cathode for Li-O2 batteries.

    PubMed

    Liao, Kaiming; Zhang, Tao; Wang, Yongqing; Li, Fujun; Jian, Zelang; Yu, Haijun; Zhou, Haoshen

    2015-04-24

    Porous carbon-free cathodes are critical to achieve a high discharge capacity and efficient cycling for rechargeable Li-O2 battery. Herein, we present a very simple method to directly grow nanoporous Ru (composed of polycrystalline particles of ∼5 nm) on one side of a current collector of Ni foam via a galvanic replacement reaction. The resulting Ru@Ni can be employed as a carbon- and binder-free cathode for Li-O2 batteries and delivers a specific capacity of 3720 mAh gRu (-1) at a current density of 200 mA gRu (-1) . 100 cycles of continuous discharge and charge are obtained at a very narrow terminal voltage window of 2.75∼3.75 V with a limited capacity of 1000 mAh gRu (-1) . The good performance of the nanoporous Ru@Ni cathode can be mainly attributed to the effective suppression of the by-products related to carbon or binder, the good adhesion of the catalyst to the current collector, and the good permeation of O2 and electrolyte into the active sites of the nanoporous Ru with the open pore system. This new type electrode provides a snapshot toward developing high-performance carbon- and binder-free Li-O2 batteries.

  11. The search for meaning: RU 486 and the law of abortion.

    PubMed Central

    Banwell, S S; Paxman, J M

    1992-01-01

    The advent of RU 486 (mifepristone), a steroid analogue capable of inducing menses within 8 to 10 weeks of a missed menstrual period, has provoked a firestorm of concern and controversy. When used in conjunction with prostaglandin (RU 486/PG), it is at least 95% effective. Used in France principally to terminate confirmed pregnancies very early in the process of gestation, RU 486 raises many interesting legal questions. This article focuses on whether and how RU 486/PG can be accommodated within the framework of the world's current abortion laws. Four avenues are explored and conclusions drawn. First, it is clear that RU 486/PG can be used readily, if approved, within the regimens established by liberal abortion laws, as has been the experience in France, the United Kingdom, and even China. Second, although unlikely, the introduction of this new technology may inspire a reexamination of restrictive abortion statutes themselves. Third, some of the presently restrictive laws may be interpreted to permit RU 486/PG use as a legal procedure, for a very narrow range of reasons. Finally, in some settings the early use of RU 486/PG (before pregnancy can be confirmed) may fall outside the reach of abortion legislation and hence be acceptable from a legal point of view. PMID:1415870

  12. Synthesis and linkage isomerization of thiolato-bridged Ru(II)Ag(I)Ru(II) trinuclear complex with D-penicillaminate.

    PubMed

    Tamura, Motoshi; Yamagishi, Masakazu; Kawamoto, Tatsuya; Igashira-Kamiyama, Asako; Tsuge, Kiyoshi; Konno, Takumi

    2009-09-21

    The reaction of [Ru(solvent)(2)(bpy)(2)](2+) (bpy = 2,2'-bipyridine) with D-H(2)pen (D-penicillamine) in ethanol/water in the presence of Ag(+) gave a thiolato-bridged Ru(II)Ag(I)Ru(II) trinuclear complex, [Ag{Ru(D-Hpen)(bpy)(2)}(2)](3+) ([1](3+)), in which two octahedral [Ru(II)(D-Hpen)(bpy)(2)](+) units are linked by a linear Ag(I) ion. Of three possible isomers (Delta(D)Delta(D), Delta(D)Lambda(D), and Lambda(D)Lambda(D)), [1](3+) formed the Delta(D)Delta(D) and Lambda(D)Lambda(D) isomers that were separately isolated by fractional crystallization with the use of [Sb(2)(R,R-tartrato)(2)](2-). In [1](3+), each D-Hpen ligand chelates to a Ru(II) center through thiolate and carboxylate groups, while an amine group of D-Hpen is protonated and does not participate in the coordination. On refluxing in ethanol/water, the Delta(D)Delta(D) isomer of [1](3+) was converted to Delta(D)Delta(D)-[2](3+), in which each D-Hpen ligand chelates to a Ru(II) center through thiolate and amine groups with a non-coordinating carboxyl group. On the other hand, a similar thermal linkage isomerization was not noticed for the Lambda(D)Lambda(D) isomer of [1](3+) under the same conditions. The isolated Delta(D)Delta(D)-[1](3+), Lambda(D)Lambda(D)-[1](3+), and Delta(D)Delta(D)-[2](3+) were fully characterized by electronic absorption, CD, and NMR spectroscopies, along with single-crystal X-ray crystallography for Lambda(D)Lambda(D)-[1](3+) and Delta(D)Delta(D)-[2](3+).

  13. Competition between antiferromagnetism and ferromagnetism in Sr2RuO4 probed by Mn and Co doping.

    PubMed

    Ortmann, J E; Liu, J Y; Hu, J; Zhu, M; Peng, J; Matsuda, M; Ke, X; Mao, Z Q

    2013-10-15

    Spin-triplet superconductivity in Sr2RuO4 has attracted enormous interest. Like other unconventional superconductors, superconductivity in Sr2RuO4 is in close proximity to magnetic instability. Undoped Sr2RuO4 exhibits incommensurate antiferromagnetic (AFM) fluctuations, which can evolve into static, short-range AFM order via Ti doping. Moreover, weak ferromagnetic (FM) coupling in Sr2RuO4 has also been suggested by NMR/neutron scattering experiments and studies on Ca2-xSrxRuO4 and Sr2-yLayRuO4, implying orbital dependent magnetism. We report bulk static, short-range FM order in Sr2RuO4 triggered by <2% Co doping, showing superconductivity in Sr2RuO4 is much closer to FM instability than previously reported in Ca2-xSrxRuO4. We also find Mn doping can effectively establish incommensurate AFM order, with TN ~ 50 K for 3% Mn doping. These new results place Sr2RuO4 in a unique situation where superconductivity lies directly on the borderline of two distinct magnetic states, highlighting the important role of competing magnetic fluctuations in determining superconducting properties of Sr2RuO4.

  14. Magnetic and magnetocaloric properties of Ba and Ti co-doped SrRuO{sub 3}

    SciTech Connect

    Sarkar, Babusona; Dalal, Biswajit; Dev Ashok, Vishal; De, S. K.

    2014-12-28

    Temperature evolution of magnetic properties in Ba and Ti doped SrRuO{sub 3} has been investigated to observe the effects of larger ionic radius Ba at Sr site and isovalent nonmagnetic impurity Ti at Ru site. Ionic radius mismatch and different electronic configuration in comparison with Ru modify Sr(Ba)-O and Ru(Ti)-O bond lengths and Ru-O-Ru bond angle. The apical and basal Ru-O-Ru bond angles vary significantly with Ti doping. Ferromagnetic Curie temperature decreases from 161 K to 149 K monotonically with Ba (10%) and Ti (10%) substitutions at Sr and Ru sites. The zero field cooled (ZFC) magnetization reveals a prominent peak which shifts towards lower temperature with application of magnetic field. The substitution of tetravalent Ti with localized 3d{sup 0} orbitals for Ru with more delocalized 4d{sup 4} orbitals leads to a broad peak in ZFC magnetization. A spontaneous ZFC magnetization becomes negative below 160 K for all the compositions. The occurrence of both normal and inverse magnetocaloric effects in Ba and Ti co-doped SrRuO{sub 3} makes the system more interesting.

  15. Enhanced Stability of PtRu Supported on N-Doped Carbon for the Anode of a DMFC

    DTIC Science & Technology

    2012-09-18

    investigations compared with non-annealed samples. In a similar fashion, PtRu cat- alysts formed by decorating Pt metal with ruthenium oxide nanosheets...and PtRu/C (Hi-SPEC) catalysts. PtRu/C PtRu/C Catalyst (N-doped) (Hi-SPEC) Platinum, wt% a 19.8 18–21b Ruthenium , wt% a 10.2 9–11b Platinum, at.% (of...total metal)a 52.6 50 Ruthenium , at.% (of total metal)a 47.3 50 XPS data C 1s 87.8 89.2 O 1s 9.0 7.8 Pt 4f 1.0 1.2 Ru 3p 1.0 1.3 N 1s 1.2 0.6 Ru1,%Ru

  16. Manipulating RuBisCO accumulation in the green alga, Chlamydomonas reinhardtii.

    PubMed

    Johnson, Xenie

    2011-07-01

    The nuclear factor, Maturation/stability of RbcL (MRL1), regulates the accumulation of the chloroplast rbcL gene transcript in Chlamydomonas reinhardtii by stabilising the mRNA via its 5' UTR. An absence of MRL1 in algal mrl1 mutants leads to a complete absence of RuBisCO large subunit protein and thus a lack of accumulation of the RuBisCO holoenzyme. By complementing mrl1 mutants by random transformation of the nuclear genome with the MRL1 cDNA, different levels of rbcL transcript accumulate. We also observe that RuBisCO Large Subunit accumulation is perturbed. Complemented strains accumulating as little as 15% RuBisCO protein can grow phototrophically while RuBisCO in this range is limiting for phototrophic growth. We also observe that photosynthetic activity, here measured by the quantum yield of PSII, appears to be a determinant for phototrophic growth. In some strains that accumulate less RuBisCO, a strong production of reactive oxygen species is detected. In the absence of RuBisCO, oxygen possibly acts as the PSI terminal electron acceptor. These results show that random transformation of MRL1 into mrl1 mutants can change RuBisCO accumulation allowing a range of phototrophic growth phenotypes. Furthermore, this technique allows for the isolation of strains with low RuBisCO, within the range of acceptable photosynthetic growth and reasonably low ROS production. MRL1 is thus a potential tool for applications to divert electrons away from photosynthetic carbon metabolism towards alternative pathways.

  17. Surface diffusion and desorption kinetics for perfluoro-n-butane on Ru(001)

    NASA Astrophysics Data System (ADS)

    Arena, M. V.; Westre, E. D.; George, S. M.

    1991-03-01

    The surface diffusion and desorption kinetics for perfluoro-n-butane on Ru(001) were examined using laser-induced thermal desorption (LITD) and temperature programmed desorption (TPD) techniques. The surface diffusion displayed Arrhenius behavior and was coverage independent. The surface diffusion parameters for perfluoro-n-butane on Ru(001) were Edif=2.9±0.3 kcal/mol and D0=5.9×10-2±0.2 cm2/s. The desorption parameters for perfluoro-n-butane on Ru(001) were Edes=13.8±0.6 kcal/mol and νdes=2.8×1021±0.1 s-1. In comparison, the surface diffusion parameters for n-butane on Ru(001) were Edif=3.5±0.2 kcal/mol and D0=1.4×10-1±0.2 cm2/s. The desorption parameters for n-butane on Ru(001) were Edes=11.9±0.5 kcal/mol and νdes=3.6×1015±0.1 s-1. The corrugation ratio, defined as Ω≡Edif/Edes, was determined to be Ω=0.21 for perfluoro-n-butane on Ru(001). This corrugation ratio was substantially different than the corrugation ratio of Ω≊0.30 measured for n-butane and various other n-alkanes, cycloalkanes and branched alkanes on Ru(001). The comparison between perfluoro-n-butane and the other alkanes indicates that fluorination lowers the surface corrugation ratio on Ru(001). Likewise, fluorination significantly increases the preexponential for desorption from Ru(001). This study illustrates the magnitude of substituent effects on surface diffusion and desorption kinetics for a physisorbed molecule on a single-crystal metal surface.

  18. Photon upconversion sensitized by a Ru(II)-pyrenyl chromophore

    PubMed Central

    Deng, Fan; Lazorski, Megan S.; Castellano, Felix N.

    2015-01-01

    The near-visible-to-blue singlet fluorescence of anthracene sensitized by a ruthenium chromophore with a long-lived triplet-excited state, [Ru(5-pyrenyl-1,10-phenanthroline)3](PF6)2, in acetonitrile was investigated. Low intensity non-coherent green light was used to selectively excite the sensitizer in the presence of micromolar concentrations of anthracene generating anti-Stokes, singlet fluorescence in the latter, even with incident power densities below 500 μW cm−2. The resultant data are consistent with photon upconversion proceeding from sensitized triplet–triplet annihilation (TTA) of the anthracene acceptor molecules, confirmed through transient absorption spectroscopy as well as static and dynamic photoluminescence experiments. Additionally, quadratic-to-linear incident power regimes for the upconversion process were identified for this composition under monochromatic 488 nm excitation, consistent with a sensitized TTA mechanism ultimately producing the anti-Stokes emission characteristic of anthracene singlet fluorescence. PMID:25987571

  19. Rapid catalytic water oxidation by a single site, Ru carbene catalyst

    SciTech Connect

    Chen, Zuofeng; Concepcion, Javier J.; Meyer, Thomas J.

    2011-01-01

    Compared to earlier single site catalysts, greatly enhanced rates of electrocatalytic water oxidation by the Ru carbene catalyst [Ru(tpy)(Mebim-py)(OH2)]2+ (tpy = 2,2':6',2''-terpyridine; Mebim-py = 3-methyl-1-pyridylbenzimidazol-2-ylidene) have been observed. The mechanism appears to be the same with proton coupled electron transfer (PCET) activation to RuV=O3+ followed by O–O coupling and further oxidation. An important factor in the enhanced reactivity of the carbene complex may come from increased driving force for the O–O bond forming step.

  20. The control of Pt and Ru nanoparticle size on high surface area supports.

    PubMed

    Liu, Qiuli; Joshi, Upendra A; Über, Kevin; Regalbuto, John R

    2014-12-28

    Supported Ru and Pt nanoparticles are synthesized by the method of strong electrostatic adsorption and subsequently treated under different steaming-reduction conditions to achieve a series of catalysts with controlled particle sizes, ranging from 1 to 8 nm. While in the case of oxidation-reduction conditions, only Pt yielded particles ranging from 2.5 to 8 nm in size and a loss of Ru was observed. Both Ru and Pt sinter faster in air than in hydrogen. This methodology allows the control of particle size using a "production-scalable" catalyst synthesis method which can be applied to high surface area supports with common metal precursors.

  1. Oxidation resistance and microstructure of Ru-capped extreme ultraviolet lithography multilayers

    SciTech Connect

    Bajt, S; Dai, Z; Nelson, E J; Wall, M A; Alameda, J B; Nguyen, N; Baker, S L; Robinson, J C; Taylor, J S; Aquila, A; Edwards, N V

    2005-06-15

    The oxidation resistance of protective capping layers for extreme ultraviolet lithography (EUVL) multilayers depends on their microstructure. Differently prepared Ru-capping layers, deposited on Mo/Si EUVL multilayers, were investigated to establish their baseline structural, optical, and surface properties in as-deposited state. The same capping layer structures were then tested for their thermal stability and oxidation resistance. The best performing Ru-capping layer structure was analyzed in detail with transmission electron microscopy (TEM). As compared to other Ru capping layers preparations studied here it is the only one that shows grains with preferential orientation. This information is essential for modeling and performance optimization of EUVL multilayers.

  2. Structural Imaging of Surface Oxidation and Oxidation Catalysis on Ru(0001)

    SciTech Connect

    Flege, J.; Hrbek, J; Sutter, P

    2008-01-01

    Using simultaneous imaging and structural fingerprinting under reaction conditions, we probe the initial oxidation pathway and CO oxidation catalysis on Ru(0001). Oxidation beyond an initial (1 x 1)-O adlayer phase produces a heterogeneous surface, comprising a disordered trilayerlike surface oxide and an ordered RuO{sub 2}(110) thin-film oxide, which form independently and exhibit similar stability. The surface oxide and RuO{sub 2} phases both show high intrinsic catalytic activity. The oxygen adlayer is inactive in isolation but becomes active due to cooperative effects in close proximity to the surface oxide.

  3. Ab initio calculations of elastic properties of Ru1-xNixAl superalloys

    NASA Astrophysics Data System (ADS)

    Bleskov, I. D.; Smirnova, E. A.; Vekilov, Yu. Kh.; Korzhavyi, P. A.; Johansson, B.; Katsnelson, M.; Vitos, L.; Abrikosov, I. A.; Isaev, E. I.

    2009-04-01

    Ab initio total energy calculations based on the exact muffin-tin orbitals method, combined with the coherent potential approximation, have been used to study the thermodynamical and elastic properties of substitutional refractory Ru1-xNixAl alloys. We have found that the elastic constants C' and C11 exhibit pronounced peculiarities near the concentration of about 40 at. % Ni, which we ascribe to electronic topological transitions. Our suggestion is supported by the Fermi surface calculations in the whole concentration range. Results of our calculations show that one can design Ru-Ni-Al alloys substituting Ru by Ni (up to 40 at. %) with almost invariable elastic constants and reduced density.

  4. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    SciTech Connect

    Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung; Wu, Pu -Wei; Lee, Jyh -Fu

    2014-11-22

    Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

  5. OsWRKY74, a WRKY transcription factor, modulates tolerance to phosphate starvation in rice

    PubMed Central

    Dai, Xiaoyan; Wang, Yuanyuan; Zhang, Wen-Hao

    2016-01-01

    The WRKY transcription factor family has 109 members in the rice genome, and has been reported to be involved in the regulation of biotic and abiotic stress in plants. Here, we demonstrated that a rice OsWRKY74 belonging to group III of the WRKY transcription factor family was involved in tolerance to phosphate (Pi) starvation. OsWRKY74 was localized in the nucleus and mainly expressed in roots and leaves. Overexpression of OsWRKY74 significantly enhanced tolerance to Pi starvation, whereas transgenic lines with down-regulation of OsWRKY74 were sensitive to Pi starvation. Root and shoot biomass, and phosphorus (P) concentration in rice OsWRKY74-overexpressing plants were ~16% higher than those of wild-type (WT) plants in Pi-deficient hydroponic solution. In soil pot experiments, >24% increases in tiller number, grain weight and P concentration were observed in rice OsWRKY74-overexpressing plants compared to WT plants when grown in P-deficient medium. Furthermore, Pi starvation-induced changes in root system architecture were more profound in OsWRKY74-overexpressing plants than in WT plants. Expression patterns of a number of Pi-responsive genes were altered in the OsWRKY74-overexpressing and RNA interference lines. In addition, OsWRKY74 may also be involved in the response to deficiencies in iron (Fe) and nitrogen (N) as well as cold stress in rice. In Pi-deficient conditions, OsWRKY74-overexpressing plants exhibited greater accumulation of Fe and up-regulation of the cold-responsive genes than WT plants. These findings highlight the role of OsWRKY74 in modulation of Pi homeostasis and potential crosstalk between P starvation and Fe starvation, and cold stress in rice. PMID:26663563

  6. Order and disorder in the wetting layer on Ru(0001).

    PubMed

    Gallagher, Mark; Omer, Ahmed; Darling, George R; Hodgson, Andrew

    2009-01-01

    The growth of an intact water monolayer on Ru(0001) has been investigated by comparing the ordering of O and Ru, determined by low-energy electron diffraction (LEED), with that of the top layer of O and H, as probed by He atom scattering (HAS). Although LEED shows that water forms an extended commensurate (square root 3 x square root 3) R30 degrees structure as the coverage approaches 0.67 monolayer, the HAS distributions are insensitive to the exact water coverage and show a very low specular reflectivity, indicating a disordered water layer. The angular profile from a D2O monolayer shows a broad diffuse peak in the angular scattering distribution at a momentum exchange similar to the position of the second-order (1/3, 1/3) peaks, but the maxima show little variation with scattering azimuth. H2O shows a slightly higher He reflectivity and more clearly resolved angular structure, with broad, faint peaks appearing close to the first-order diffraction positions. The origin of this disorder is discussed based on density functional calculations for the monolayer which find that water forms chains of flat and H-down molecules within a hexagonal hydrogen-bonding network, rather than the ice bilayer usually assumed. This arrangement leads to long-range order in the O location, but disorder in the O height and the proton orientation. We discuss how this combination of lateral order in the adsorption site, but disorder in the water orientation, is reflected in the sharp square root 3 LEED pattern but diffuse, broad peaks in He scattering.

  7. Fractionation of highly siderophile elements in refertilized mantle: Implications for the Os isotope composition of basalts

    NASA Astrophysics Data System (ADS)

    Marchesi, Claudio; Dale, Christopher W.; Garrido, Carlos J.; Pearson, D. Graham; Bosch, Delphine; Bodinier, Jean-Louis; Gervilla, Fernando; Hidas, Károly

    2014-08-01

    Highly fertile lherzolite and spinel websterite in the Ronda peridotite massif are enriched in Pt and Pd compared to Os, Ir, Ru and Re. The fractionation of the highly siderophile elements (HSE) in these rocks was produced by reaction of melt with their peridotite and pyroxenite precursors. Modeling indicates that upon reaction primary HSE hosts were dissolved and magmatic sulphides precipitated, largely erasing the original HSE signature of reacting protoliths. The budget of HSE in the melt was controlled by sulphide-silicate partitioning or entrainment of molten sulphide in silicate melt. Rhenium was likely removed from precursor peridotite and pyroxenite by previous melt extraction. Refertilization of peridotite by melts increased Al2O3, CaO, Pt, Pd contents and 187Os/188Os beyond typical values for mantle peridotite and the primitive upper mantle. The interaction of melts with residual peridotite and pyroxenite, as illustrated in the Ronda massif, can generate radiogenic-Os-enriched domains in the mantle with high melt productivity, higher Pt/Os and Pt/Re than common peridotite, and lower Re/Os than typical pyroxenite. As also previously proposed for pyroxenites, these “hybrid” domains can account for the difference in Os isotope compositions between many basalts (e.g., MORB and OIB) and common depleted mantle peridotites. Moreover, the presence of these enriched hybrid components in the mantle, evolved over sufficient timescales and in geologically reasonable proportions, may account for the 186Os-187Os enrichment of plume lavas without requiring a chemical contribution from the core.

  8. Structural, magnetic and electrical properties of SrRuO3 films and SrRuO3/SrTiO3 superlattices.

    PubMed

    Bern, F; Ziese, M; Setzer, A; Pippel, E; Hesse, D; Vrejoiu, I

    2013-12-11

    SrRuO3 films and SrRuO3/SrTiO3 superlattices grown on SrTiO3(001) were studied by structural, magnetic, magnetoresistance and Hall effect measurements. The superlattices showed heteroepitaxial growth with coherent interfaces and a Ru/Ti diffusion region of 1-1.5 unit cells. The resistivity had metallic character above a critical thickness of 3-4 unit cells, becoming insulating below. There was no hint of conduction processes along the interfaces. Both magnetization and magnetoresistance measurements showed an increase of the magnetic anisotropy, consistent with magnetostriction effects. The magnetostriction coefficient was estimated as λ100 ∼ 1.4 × 10(-4). Three unit cell thick SrRuO3 layers in SrRuO3/SrTiO3 superlattices were found to have tetragonal crystal symmetry, as deduced from the sign change of the anomalous Hall constant.

  9. Direct penetration of spin-triplet superconductivity into a ferromagnet in Au/SrRuO3/Sr2RuO4 junctions.

    PubMed

    Anwar, M S; Lee, S R; Ishiguro, R; Sugimoto, Y; Tano, Y; Kang, S J; Shin, Y J; Yonezawa, S; Manske, D; Takayanagi, H; Noh, T W; Maeno, Y

    2016-10-26

    Efforts have been ongoing to establish superconducting spintronics utilizing ferromagnet/superconductor heterostructures. Previously reported devices are based on spin-singlet superconductors (SSCs), where the spin degree of freedom is lost. Spin-polarized supercurrent induction in ferromagnetic metals (FMs) is achieved even with SSCs, but only with the aid of interfacial complex magnetic structures, which severely affect information imprinted to the electron spin. Use of spin-triplet superconductors (TSCs) with spin-polarizable Cooper pairs potentially overcomes this difficulty and further leads to novel functionalities. Here, we report spin-triplet superconductivity induction into a FM SrRuO3 from a leading TSC candidate Sr2RuO4, by fabricating microscopic devices using an epitaxial SrRuO3/Sr2RuO4 hybrid. The differential conductance, exhibiting Andreev-reflection features with multiple energy scales up to around half tesla, indicates the penetration of superconductivity over a considerable distance of 15 nm across the SrRuO3 layer without help of interfacial complex magnetism. This demonstrates potential utility of FM/TSC devices for superspintronics.

  10. Direct penetration of spin-triplet superconductivity into a ferromagnet in Au/SrRuO3/Sr2RuO4 junctions

    PubMed Central

    Anwar, M. S.; Lee, S. R.; Ishiguro, R.; Sugimoto, Y.; Tano, Y.; Kang, S. J.; Shin, Y. J.; Yonezawa, S.; Manske, D.; Takayanagi, H.; Noh, T. W.; Maeno, Y.

    2016-01-01

    Efforts have been ongoing to establish superconducting spintronics utilizing ferromagnet/superconductor heterostructures. Previously reported devices are based on spin-singlet superconductors (SSCs), where the spin degree of freedom is lost. Spin-polarized supercurrent induction in ferromagnetic metals (FMs) is achieved even with SSCs, but only with the aid of interfacial complex magnetic structures, which severely affect information imprinted to the electron spin. Use of spin-triplet superconductors (TSCs) with spin-polarizable Cooper pairs potentially overcomes this difficulty and further leads to novel functionalities. Here, we report spin-triplet superconductivity induction into a FM SrRuO3 from a leading TSC candidate Sr2RuO4, by fabricating microscopic devices using an epitaxial SrRuO3/Sr2RuO4 hybrid. The differential conductance, exhibiting Andreev-reflection features with multiple energy scales up to around half tesla, indicates the penetration of superconductivity over a considerable distance of 15 nm across the SrRuO3 layer without help of interfacial complex magnetism. This demonstrates potential utility of FM/TSC devices for superspintronics. PMID:27782151

  11. Direct penetration of spin-triplet superconductivity into a ferromagnet in Au/SrRuO3/Sr2RuO4 junctions

    NASA Astrophysics Data System (ADS)

    Anwar, M. S.; Lee, S. R.; Ishiguro, R.; Sugimoto, Y.; Tano, Y.; Kang, S. J.; Shin, Y. J.; Yonezawa, S.; Manske, D.; Takayanagi, H.; Noh, T. W.; Maeno, Y.

    2016-10-01

    Efforts have been ongoing to establish superconducting spintronics utilizing ferromagnet/superconductor heterostructures. Previously reported devices are based on spin-singlet superconductors (SSCs), where the spin degree of freedom is lost. Spin-polarized supercurrent induction in ferromagnetic metals (FMs) is achieved even with SSCs, but only with the aid of interfacial complex magnetic structures, which severely affect information imprinted to the electron spin. Use of spin-triplet superconductors (TSCs) with spin-polarizable Cooper pairs potentially overcomes this difficulty and further leads to novel functionalities. Here, we report spin-triplet superconductivity induction into a FM SrRuO3 from a leading TSC candidate Sr2RuO4, by fabricating microscopic devices using an epitaxial SrRuO3/Sr2RuO4 hybrid. The differential conductance, exhibiting Andreev-reflection features with multiple energy scales up to around half tesla, indicates the penetration of superconductivity over a considerable distance of 15 nm across the SrRuO3 layer without help of interfacial complex magnetism. This demonstrates potential utility of FM/TSC devices for superspintronics.

  12. FeSi diffusion barriers in Fe/FeSi/Si/FeSi/Fe multilayers and oscillatory antiferromagnetic exchange coupling

    NASA Astrophysics Data System (ADS)

    Stromberg, F.; Bedanta, S.; Antoniak, C.; Keune, W.; Wende, H.

    2008-10-01

    We study the diffusion of 57Fe probe atoms in Fe/FeSi/Si/FeSi/Fe multilayers on Si(111) prepared by molecular beam epitaxy by means of 57Fe conversion electron Mössbauer spectroscopy (CEMS). We demonstrate that the application of FeSi boundary layers successfully inhibits the diffusion of 57Fe into the Si layer. The critical thickness for the complete prevention of Fe diffusion takes place at a nominal FeSi thickness of tFeSi = 10-12 Å, which was confirmed by the evolution of the isomer shift δ of the crucial CEM subspectrum. The formation of the slightly defective c-FeSi phase for thicker FeSi boundary layers (~20 Å) was confirmed by CEMS and reflection high-energy electron diffraction (RHEED). Ferromagnetic resonance (FMR) shows that, for tFeSi = 0-14 Å, the Fe layers in all samples are antiferromagnetically coupled and we observe an oscillatory antiferromagnetic coupling strength with FMR and superconducting quantum interference device (SQUID) magnetometry for varying FeSi thickness with a period of ~6 Å.

  13. The effect of Ru on unsupported Pt-Ru alloys for methanol electro-oxidation at different temperatures

    SciTech Connect

    Chu, D.; Walker, C.; Gilman, S.

    1995-12-31

    Unsupported different atomic ratios of platinum-ruthenium bulk alloys were prepared. The alloys were characterized by cyclic voltammetry, x-ray diffraction and energy dispersive X-ray spectroscopy. These alloys were also tested as anodes for methanol electro-oxidation in sulfuric acid over a range of temperatures. Ruthenium is inactive for methanol electro-oxidation at 25 C, but becomes active at higher temperatures. When a comparison is made on the basis of true (hydrogen adsorption) surface area, a 30 atomic percent Ru electrocatalyst provides the highest activity for methanol electro-oxidation as measured at either 0.4 or 0.5 V vs RHE at both 25 and 60 C.

  14. Crystal growth, observation, and characterization of the low-temperature structure of the fluorite-related ruthenates: Sm(3)RuO(7) and Eu(3)RuO(7).

    PubMed

    Gemmill, William R; Smith, Mark D; Zur Loye, Hans-Conrad

    2004-07-12

    The compounds Sm(3)RuO(7) and Eu(3)RuO(7) were grown as single crystals from molten hydroxide fluxes. They crystallize in the orthorhombic space group Cmcm and are part of a well-known family of fluorite-related oxides of stoichiometry Ln(3)MO(7). This structure contains rare earth cations in two different coordination environments, 8-fold pseudocubic and 7-fold pentagonal bipyramidal, and contains Ru(V) cations that are octahedrally coordinated. The RuO(6) octahedra are trans vertex-sharing to yield chains oriented along the c-axis. Upon cooling, single crystals of Sm(3)RuO(7) and Eu(3)RuO(7) undergo a structural transition at 190 and 280 K, respectively, from space group Cmcm to P2(1)nb. The structure transition results in a loss of lattice centering, a doubling of the b-axis, a distortion of the vertex-shared Ru-O chains, and a reduction in the coordination of one of the rare earth cations from 8-fold to 7-fold. Accompanying this structural transition are anomalies in the magnetic susceptibility at about 190 and 280 K for Sm(3)RuO(7) and Eu(3)RuO(7), respectively. The structures of these low-temperature phases of Ln(3)RuO(7) have been determined for the first time and are described.

  15. Thermodynamic investigations of [(phen)2Ru(tatpp)Ru(phen)2](4+) interactions with B-DNA.

    PubMed

    Le, Vu H; McGuire, Matthew R; Ahuja, Pooja; MacDonnell, Frederick M; Lewis, Edwin A

    2015-01-08

    While the antitumor activity of P(4+) is relatively well understood, the binding mechanism and thermodynamics for formation of (P(4+)·DNA) complexes remain in question. The thermodynamic parameters (Ka, ΔG, ΔH, and -TΔS) for formation of DNA complexes of the ruthenium dimer, [(phen)2Ru(tatpp)Ru(phen)2](4+) (abbreviated as P(4+)), where phen is 1,10-phenanthroline and tatpp is 9,11,20,22-tetraazatetrapyrido[3,2-a:2',3'-c:3″,2″-1:2‴,3‴-n]-pentacene, were determined using isothermal titration calorimetry. Calorimetric and spectroscopic titration experiments were performed in which P(4+) was added to three duplex DNAs of different lengths. We determined that P(4+) binds to duplex DNA at 298 K with modest affinity (Ka ≈ 3.8 × 10(5) M(-1), ΔG ≈ -7.6 kcal/mol), that the enthalpy change is unfavorable (ΔH ≈ +2.1 kcal/mol), and that complex formation is driven by a large favorable change in entropy (-TΔS ≈ -9.7 kcal/mol). These thermodynamic values were found to be approximately independent of the length of the DNA, and the stoichiometry of the (P(4+)·DNA) complexes was determined to be 1 P(4+)/2 DNA bp, at least for the two shorter DNAs. On the basis of the thermodynamic parameters, and the binding stoichiometry (verified in ESI-MS experiments), we conclude that P(4+) is intercalating between two adjacent DNA base pairs and that the neighbor sites on either side of the bound ligand are excluded from binding additional P(4+).

  16. Influence of Belousov-Zhabotinsky substrate concentrations on autonomous oscillation of polymer chains with Fe(bpy)3 catalyst.

    PubMed

    Hara, Yusuke; Mayama, Hiroyuki; Fujimoto, Kenji

    2014-06-19

    We studied the effect of initial substrate concentrations in the Belousov-Zhabotinsky (BZ) reaction on the optical transmittance self-oscillation behavior of a polymer chain consisting of N-isopropylacrylamide (NIPAAm) and a Fe catalyst ([Fe(bpy)3]). The driving force of this transmittance self-oscillation was the solubility difference between the reduced and oxidized states of the [Fe(bpy)3] moiety in the polymer chain. The amplitude of the soluble-insoluble self-oscillation of poly(NIPAAm-co-[Fe(bpy)3]) was significantly smaller than that of poly(NIPAAm-co-[Ru(bpy)3]). Theoretical simulation results attributed this behavior to the small difference in the solvent qualities, C*, of the reduced and oxidized states. Furthermore, we clarified that poly(NIPAAm-co-[Fe(bpy)3]) required a narrower concentration range of HNO3 to exhibit self-oscillation than poly(NIPAAm-co-[Ru(bpy)3]), since transmittance self-oscillation occurred only for [HNO3] = 0.3 M. The period of self-oscillation of poly(NIPAAm-co-[Fe(bpy)3]) in solution was controlled mainly by NaBrO3 concentration and was hardly influenced by the initial concentration of malonic acid.

  17. The nature of phase separation in a Ru-Sn-O ternary oxide electrocatalyst.

    PubMed

    Wang, Xin; Deng, Fenyong; Tang, Zhongzhi; Wu, Bo; Tang, Dian; Lin, Wei

    2013-03-21

    A phase stability diagram of ruthenium-zirconium oxide (Ru-Sn-O) was constructed by a combination of ab initio density functional theory and thermodynamic calculations. Results suggest that the phase separation/segregation that has been reported in the literature for the RuO(2)-SnO(2) system is through a typical spinodal decomposition mechanism. Ru(0.45)Sn(0.55)O(2) films were prepared by thermal co-decomposition of precursors at 500 °C for varied duration. Quantitative phase analyses of the prepared films based on X-ray diffraction and high-resolution transmission electron microscopy confirmed the spinodal nature of the phase separation. The present fundamental study provides a theoretical guideline for the phase and microstructure design of Ru-Sn-O based mixed oxides for electrocatalysis applications.

  18. Topology and electronic structure of flexible (Nb,Ru)O2 thermoelectrics

    NASA Astrophysics Data System (ADS)

    Music, Denis; Schnabel, Volker; Bednarcik, Jozef

    2017-03-01

    Using combinatorial reactive sputtering, we have synthesised Nb-Ru-O thin films on Kapton (polyimide) with the Ru/Nb ratio from 0.5 to 1.1 in a dioxide type of environment. Based on correlative analysis, including synchrotron diffraction experiments and density functional theory, the topology of these amorphous samples is characterised by short metal-oxygen bonds and very pronounced metal-metal interactions within the second coordination shell. We suggest that the role of Nb is within bond length reduction and promotion of quantum confinement, giving rise to an increase in the Seebeck coefficient. Furthermore, these Nb-Ru-O thin films are mechanically flexible as there are no crack formation and delamination upon bending or rolling. This may be rationalised as follows. Nb-Ru-O appears ductile due to low topological connectivity and forms strong bonds with Kapton.

  19. Magnetic field effects in UNi1/3Ru2/3Al

    NASA Astrophysics Data System (ADS)

    Alsmadi, A. M.; El-Khatib, S.; de Châtel, P. F.; Nakotte, H.; Lacerda, A. H.; Jung, M. H.; Andreev, A. V.; Honda, F.; Sechovsky, V.

    2005-05-01

    We report on the electronic properties of a UNi1/3Ru2/3Al single crystal as a function of temperature and magnetic field. Our specific-heat, magnetization, and resistivity data provide strong evidence that the uranium 5f moments order ferromagnetically below TC=74K. Magnetic measurements reveal that the c axis is the easy magnetization direction with a saturation moment of about 0.78μB/U-atom. Our neutron diffraction studies on UNi1/3Ru2/3Al provide strong evidence that Ni occupies the 1b (and Ru the 2c) positions of the ZrNiAl structure. We argue that such preferential occupation of Ni and Ru atoms is responsible for the observed ferromagnetic ground state.

  20. Synthesis and thermoelectric properties of RuO{sub 2} nanorods

    SciTech Connect

    Music, Denis; Basse, Felix H.-U.; Schneider, Jochen M.; Hassdorf, Ralf

    2010-07-15

    We have explored the effect of the O/Ru ratio on the morphology and the Seebeck coefficient of RuO{sub 2} nanorods (space group P4{sub 2}/mnm) synthesized by reactive sputtering. At an O/Ru ratio of 1.69, a faceted surface is observed, while nanorod formation occurs at O/Ru ratios of 2.03 and 2.24. Using classical molecular dynamics with the potential parameters derived in this work, we show that volatile species enable nanorod formation. Based on ab initio calculations, two effects of the nanorod formation on the Seebeck coefficient are observed: (i) increase due to additional states in the vicinity of the Fermi level and (ii) decrease due to oxygen point defects (volatile species). These two competing effects give rise to a moderate increase in the Seebeck coefficient upon nanorod formation.

  1. Proton-coupled electron hopping in Ru-modified P. aeruginosa azurin

    PubMed Central

    Warren, Jeffrey J.; Shafaat, Oliver S.; Winkler, Jay R.

    2016-01-01

    We constructed two artificial multiple-step electron transfer (hopping) systems based on Pseudomonas aeruginosa azurin where a tyrosine (YOH) is situated between Ru(2,2′-bipyridine)2(imidazole)(histidine) and the native copper site: RuH107YOH109 and RuH124-YOH122. We investigated the rates of CuI oxidation by flash-quench generated RuIII over a range of conditions that probed the role of proton-coupled oxidation/reduction of YOH in the reaction. Rates of CuI oxidation were enhanced over single-step electron transfer by factors between 3 and 80, depending on specific scaffold and buffer conditions. PMID:26790882

  2. Quasilocal critical nature of cooperative paramagnetic fluctuations in CaRuO3 metal

    NASA Astrophysics Data System (ADS)

    Gunasekera, J.; Harriger, L.; Heitmann, T.; Dahal, A.; Knoll, H.; Singh, D. K.

    2015-06-01

    We report the observation of cooperative paramagnetic fluctuations of Ru4 + spins that coexist with the non-Fermi-liquid state in CaRuO3 perovskite below T ≃21 K. Detailed electrical, magnetic, and neutron scattering measurements reveal that the Ru4 + ions reside in magnetic-field-independent random domains with dynamic properties that are reminiscent of the cooperative paramagnetic fluctuations. The linear (E /T ) scaling of the dynamic susceptibilities and divergence of the mean relaxation time as T →0 K suggest a quasilocal critical nature of the spin fluctuations. We argue that the non-Fermi-liquid behavior arises due to the quantum critical nature of the cooperative paramagnetic fluctuations in CaRuO3.

  3. Inhibition of Hydrogen Absorption in Pd by the Formation of a Pd-Ru Surface Alloy

    NASA Astrophysics Data System (ADS)

    Cabrera, A. L.; Ferrari, P.; Rojas, S.; Diaz-Droguett, Donovan; Ramos-Moore, E.; Laboratorio Ciencia de Materiales Team

    2013-03-01

    Hydrogen absorption by palladium has been studied for decades due to the significant importance in a number of applications like production and storage of hydrogen and hydrogen sensors. Alloying Pd with just a 4% of Ru drastically reduces the absorption properties of the Pd. The fcc crystal structure is preserved but the lattice constant is reduced slightly. In order to understand this phenomenon, we used three samples: a Pd foil, a Pd-Ru(4%) alloy foil, and a Pd foil with a Pd-Ru surface alloy. The surface alloy was made evaporating 8 nm of Ru using an e-beam evaporation technique on top of Pd, followed with a heating the sample up to 700 °C in a high vacuum system. We studied the changes in absorption properties of these samples using Thermal Program Desorption (TPD), resistance changes and grazing incidence X-ray Diffraction (GID). Funds from VRI-Puente 10/2012

  4. Proton-coupled electron hopping in Ru-modified P. aeruginosa azurin.

    PubMed

    Warren, Jeffrey J; Shafaat, Oliver S; Winkler, Jay R; Gray, Harry B

    2016-03-01

    We constructed two artificial multiple-step electron transfer (hopping) systems based on Pseudomonas aeruginosa azurin where a tyrosine (YOH) is situated between Ru(2,2'-bipyridine)2(imidazole)(histidine) and the native copper site: RuH107YOH109 and RuH124-YOH122. We investigated the rates of Cu(I) oxidation by flash-quench generated Ru(III) over a range of conditions that probed the role of proton-coupled oxidation/reduction of YOH in the reaction. Rates of Cu(I) oxidation were enhanced over single-step electron transfer by factors between 3 and 80, depending on specific scaffold and buffer conditions.

  5. Topology and electronic structure of flexible (Nb,Ru)O2 thermoelectrics.

    PubMed

    Music, Denis; Schnabel, Volker; Bednarcik, Jozef

    2017-03-01

    Using combinatorial reactive sputtering, we have synthesised Nb-Ru-O thin films on Kapton (polyimide) with the Ru/Nb ratio from 0.5 to 1.1 in a dioxide type of environment. Based on correlative analysis, including synchrotron diffraction experiments and density functional theory, the topology of these amorphous samples is characterised by short metal-oxygen bonds and very pronounced metal-metal interactions within the second coordination shell. We suggest that the role of Nb is within bond length reduction and promotion of quantum confinement, giving rise to an increase in the Seebeck coefficient. Furthermore, these Nb-Ru-O thin films are mechanically flexible as there are no crack formation and delamination upon bending or rolling. This may be rationalised as follows. Nb-Ru-O appears ductile due to low topological connectivity and forms strong bonds with Kapton.

  6. Synthesis, crystal structure and anaerobic DNA photocleavage of ruthenium complexes [Ru(tpy)(dpoq)Cl](+) and [Ru(tpy)(dpoq)CH3CN](2.).

    PubMed

    Yu, Hui-juan; Huang, Shu-mei; Chao, Hui; Ji, Liang-nian

    2015-08-01

    Two new Ru(II) complexes [Ru(tpy)(dpoq)Cl](+)1 and [Ru(tpy)(dpoq)CH3CN](2+)2 (tpy = 2,2':6',2''-terpyridine; dpoq = dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline) have been synthesized and characterized by elemental analysis, (1)H NMR, electrospray ionization mass spectra (ESI-MS) and X-ray crystallographic study. The experimental results of spectra titration, thermal denaturation and viscosity measurements suggest that the two complexes intercalatively bind to DNA. When irradiated under light, the two complexes could efficiently photocleave DNA both under aerobic and anaerobic condition. The mechanism studies reveal that the photocleavage reaction functions through both oxygen-independent (photoinduced electron transfer, type III reaction) and oxygen-dependent (singlet oxygen generation, type II reaction) pathways and the oxygen-independent pathway is the major process. These complexes will be more promising photodynamic therapy (PDT) candidates used for treating hypoxic tumors.

  7. Itinerant metamagnetism of CeRu 2Si 2: bringing out the dead. Comparison with the new Sr 3Ru 2O 7 case

    NASA Astrophysics Data System (ADS)

    Flouquet, J.; Haen, P.; Raymond, S.; Aoki, D.; Knebel, G.

    2002-07-01

    Focus is given on the macroscopic and microscopic experimental works realized during a decade on the clear case of itinerant metamagnetism in the heavy fermion paramagnetic compound CeRu 2Si 2. Emphasis is made on the feedback between the band structure, the exchange coupling and the lattice instability. Sweeps in magnetic field, pressure and temperature feel the pseudogap of this strongly correlated electronic system as well as its equivalent CeRu 2Ge 2 at a fictitious negative pressure. Some mysteries persist as the complete observation of the Fermi surface above the metamagnetic field HM and the detection of the dynamical ferromagnetic fluctuation near HM. The novelty of the bilayer ruthenate Sr 3Ru 2O 7 is discussed by comparison. Despite differences in spin and electronic dimensionality many common trends emerge.

  8. Biodistribution of Ru-97-labeled DTPA, DMSA and transferrin. [Diagnostic potential

    SciTech Connect

    Som, P; Oster, Z H; Fairchild, R G; Atkins, H L; Brill, A B; Gil, M C; Srivastava, S C; Meinken, G E; Goldman, A G; Richards, P

    1980-01-01

    Ruthenium-97 is being produced at the Brookhaven Linac Isotope Producer (BLIP). The favorable physical properties of Ru-97 and chemical reactivity of ruthenium offer a potential for using this isotope to label compounds useful for delayed scanning. Diethylenetriamine pentaacetic acid (DTPA), 2,3-Dimercaptosuccinic acid (DMSA), and Transferrin (TF) were labeled with Ru-97-chloride. Ru-97-DTPA and In-111-DTPA, injected intravenously, showed similar organ distribution, kinetics, and more than 80% excretion by 0.5 h. Ru-97-DTPA and In-111-DTPA injected into the cisterna magna of dogs showed similar kinetics in brain, blood, and urinary bladder. The energy deposited by 1 mCi In-111-DTPA is twice that from 1 mCi Ru-97-DTPA. High quality camera images of the CSF space in the dog were obtained with both isotopes. Ru-97-DMSA was prepared with and without the addition of SnCl/sub 2/.2H/sub 2/O. Tin-free DMSA was rapidly excreted via the kidneys, whereas for maximum cortical deposition, the tin-containing preparation was superior. This compound is suitable for delayed imaging of both normal and impaired kidneys. Tissue distribution studies were performed in abscess-bearing rats with Ru-97-transferrin. Although blood levels were higher than with Ga-67-citrate, the abscess had twice as much Ru-97-TF as Ga-67-citrate and the Ru-97 muscle activity was one-third that of Ga-67. Imaging of abscess-bearing rabbits with Ru-97-TF visualized the abscesses as early as 1/2 hr after injection. Since the initial images visualize the abscess so clearly and since the TF portion of the compound binds to the abscess, Tc-99m-TF is being studied for the same purpose. Ru-97-labeled compounds are a promising replacement for In-111 and possibly also for Ga-67 compounds with the advantages of lower radiation dose and high quality image. (ERB)

  9. First-order magnetostructural transition in single crystals of the honeycomb lattice ruthenate Li2RuO3

    NASA Astrophysics Data System (ADS)

    Mehlawat, Kavita; Singh, Yogesh

    2017-02-01

    Li2RuO3 is known to crystallize in either C 2 /m or P 21/m structures at room temperature. We report the first single crystal growth of Li2RuO3 and Na substituted crystals (Li0.95Na0.05 )2RuO3 crystallizing in the P 21/m structure where a first order magnetostructural transition is observed at high temperatures. Using high temperature (T ≤1000 K) magnetic susceptibility χ measurements we study the magnetic anisotropy across the magnetostructural transition. Our results show that for Li2RuO3 the magnetic and structural transitions most likely occur at slightly different temperatures. The structural transition which is first-order-like occurs first (Tonset≈570 K) and drives the magnetic transition (T ≈540 K). Rather surprisingly, just 5 % Na substitution for Li affects the magnetostructural transition in an interesting way. The first order transition temperature remains at ≈540 K, the magnetic anisotropy is reversed, and the Ru-Ru dimerization pattern changes from two short and four long Ru-Ru bonds per honeycomb in an armchair pattern for Li2RuO3 to four short and two long bonds per honeycomb in (Li0.95Na0.05 )2RuO3 which can be viewed as two interpenetrating armchair patterns.

  10. A dinuclear Ru(II) complex capable of photoinduced ligand exchange at both metal centers.

    PubMed

    Albani, B A; Peña, B; Saha, S; White, J K; Schaeffer, A M; Dunbar, K R; Turro, C

    2015-11-28

    {[Ru(CH3CN)3]2(tppz)}(4+) (tppz = tetra-2-pyridylpyrazine) undergoes photoinduced CH3CN exchange with λirr ≥ 610 nm in H2O. In contrast, cis-{[Ru(tpy)(L)]2(bpm)}(4+) (tpy = 2,2':6',2''-terpyridine, bpm = 2,2'-bipyrimidine, L = CH3CN) is not reactive, but the complex with L = DMSO is photoactive. These complexes are potentially useful for the release of multiply caged drugs.

  11. Ru(II) complexes of new tridentate ligands: unexpected high yield of sensitized 1O2.

    PubMed

    Liu, Yao; Hammitt, Richard; Lutterman, Daniel A; Joyce, Lauren E; Thummel, Randolph P; Turro, Claudia

    2009-01-05

    Ru(II) complexes possessing new tridentate ligands with extended pi systems, pydppx (3-(pyrid-2'-yl)-11,12-dimethyl-dipyrido[3,2-a:2',3'-c]phenazine) and pydppn (3-(pyrid-2'-yl)-4,5,9,16-tetraaza-dibenzo[a,c]naphthacene), were synthesized and characterized. The investigation of the photophysical properties of the series [Ru(tpy)(n)(L)(2-n)](2+) (L = pydppx, pydppn, n = 0-2) reveals markedly different excited state behavior among the complexes. The Ru(II) complexes possessing the pydppx ligand are similar to the pydppz (3-(pyrid-2'-yl)dipyrido[3,2-a:2',3'-c]phenazine) systems, with a lowest energy metal-to-ligand charge transfer excited state with lifetimes of 1-4 ns. In contrast, the lowest energy excited state in the [Ru(tpy)(n)(pydppn)(2-n)](2+) (n = 0, 1) complexes is a ligand-centered (3)pipi* localized on the pydppn ligand with lifetimes of approximately 20 mus. The [Ru(tpy)(n)(pydppn)(2-n)](2+) (n = 0, 1) complexes are able to generate (1)O(2) with approximately 100% efficiency. Both [Ru(tpy)(pydppn)](2+) and [Ru(pydppn)(2)](2+) bind to DNA, however, the former exhibits a approximately 10-fold greater DNA binding constant than the latter. Efficient DNA photocleavage is observed for [Ru(tpy)(pydppn)](2+), owing to its ability to photosensitize the production of (1)O(2), which can mediate the reactivity. Such high quantum yields of (1)O(2) photosensitization of transition metal complexes may be useful in the design of new systems with long-lived excited states for photodynamic therapy.

  12. Kagome-like Lattice Distortion in the Pyrochlore Material Hg2Ru2O7

    NASA Astrophysics Data System (ADS)

    van Duijn, Joost; Ruiz-Bustos, Rocío; Daoud-Aladine, Aziz

    2013-03-01

    Hg2Ru2O7 is one of the few pyrochlore materials known containing Ru5+. It undergoes a first order metal to Mott insulator transition (MIT) at T= 107 K, below which the susceptibility is significantly reduced and appears to be nearly T independent. While initially it has been suggested that below 107 K the Ru S=3/2 moments are quenched into an antiferromagnetic spin singlet ground-state, similar as to what is observed in Tl2Ru2O7, recent muon and polarized neutron diffraction experiments reveal the onset of long-range magnetic ordering below the MIT. In order to shed light on the magnetic interactions that give rise to the observed long-range ordering we have performed high resolution powder neutron diffraction experiments to determine the low temperature structure of Hg2Ru2O7. Below the MIT the symmetry is lowered from cubic to monoclinic and the Ru-Ru bonds, which are equal in the pyrochlore phase, become split into short, medium and long bonds. As a result the exchange interactions between the Ru atoms become more two dimensional. The short and medium bonds form layers, which are separated by the long bonds, that run parallel to the monoclinic ab plane. The low temperature structure can best be described as a stacking of Kagome-like layers. The work presented in this paper was supported by the Ramón y Cajal program through Grant no. RYC-2005-001064 and the Consejería de Educación y Ciencia of the Junta de Comunidades de Castilla-La Mancha through Grant no. PII1I09-0083-2105.

  13. Mechanism of water oxidation by [Ru(bda)(L)₂]: The return of the "blue dimer"

    DOE PAGES

    Concepcion, Javier J.; Zhong, Diane K.; Szalda, David J.; ...

    2015-02-05

    We describe here a combined solution-surface-DFT calculations study for complexes of the type [Ru(bda)(L)₂] including X-ray structure of intermediates, their reactivity, as well as pH-dependent electrochemistry and spectroelectrochemistry. These studies shed light on the mechanism of water oxidation by [Ru(bda)(L)₂], revealing key features unavailable from solution studies with sacrificial oxidants.

  14. Synthesis, Characterization, Anticancer, and Antioxidant Studies of Ru(III) Complexes of Monobasic Tridentate Schiff Bases

    PubMed Central

    Ejidike, Ikechukwu P.

    2016-01-01

    Mononuclear Ru(III) complexes of the type [Ru(LL)Cl2(H2O)] (LL = monobasic tridentate Schiff base anion: (1Z)-N′-(2-{(E)-[1-(2,4-dihydroxyphenyl)ethylidene]amino}ethyl)-N-phenylethanimidamide [DAE], 4-[(1E)-N-{2-[(Z)-(4-hydroxy-3-methoxybenzylidene)amino]ethyl}ethanimidoyl]benzene-1,3-diol [HME], 4-[(1E)-N-{2-[(Z)-(3,4-dimethoxybenzylidene)amino]ethyl}ethanimidoyl]benzene-1,3-diol [MBE], and N-(2-{(E)-[1-(2,4-dihydroxyphenyl)ethylidene]amino}ethyl)benzenecarboximidoyl chloride [DEE]) were synthesized and characterized using the microanalytical, conductivity measurements, electronic spectra, and FTIR spectroscopy. IR spectral studies confirmed that the ligands act as tridentate chelate coordinating the metal ion through the azomethine nitrogen and phenolic oxygen atom. An octahedral geometry has been proposed for all Ru(III)-Schiff base complexes. In vitro anticancer studies of the synthesized complexes against renal cancer cells (TK-10), melanoma cancer cells (UACC-62), and breast cancer cells (MCF-7) was investigated using the Sulforhodamine B assay. [Ru(DAE)Cl2(H2O)] showed the highest activity with IC50 valves of 3.57 ± 1.09, 6.44 ± 0.38, and 9.06 ± 1.18 μM against MCF-7, UACC-62, and TK-10, respectively, order of activity being TK-10 < UACC-62 < MCF-7. The antioxidant activity by DPPH and ABTS inhibition assay was also examined. Scavenging ability of the complexes on DPPH radical can be ranked in the following order: [Ru(DEE)Cl2(H2O)] > [Ru(HME)Cl2(H2O)] > [Ru(DAE)Cl2(H2O)] > [Ru(MBE)Cl2(H2O)]. PMID:27597814

  15. A path sampling study of Ru-hydride-catalyzed H2 hydrogenation of ethylene.

    PubMed

    Rowley, Christopher N; Woo, Tom K

    2008-06-11

    Ab initio molecular dynamics and transition path sampling were used to examine the dynamics of the H2 hydrogenation of ethylene with the catalyst RuHCl(CO)(PR3)2. The simulations showed H2 is coordinated very weakly to the metal until ethylene insertion, where it is cleaved into a dihydride intermediate. The dihydride has a shorter lifetime than RRKM theory predicts, due to the localization of kinetic energy into Ru-H vibrational modes after the insertion step.

  16. Barrier height enhancement of Ni/GaN Schottky diode using Ru based passivation scheme

    SciTech Connect

    Kumar, Ashish Kumar, Mukesh; Singh, R.; Kaur, Riajeet; Joshi, Amish G.; Vinayak, Seema

    2014-03-31

    Wet chemical passivation of n-GaN surface using Ru based solution has been reported. X-ray photoelectron spectroscopy characterization of the GaN surface revealed removal of surface oxides by the introduction of Ru complex species. Ni/n-GaN Schottky barrier diodes were fabricated on passivated GaN and a remarkable improvement in Schottky barrier height from 0.76 eV to 0.92 eV was observed.

  17. Dependence of calibration sensitivity of a polysulfone/Ru(II)-tris(4,7-diphenyl-1,10-phenanthroline)-based oxygen optical sensor on its structural parameters.

    PubMed

    Badocco, Denis; Mondin, Andrea; Pastore, Paolo; Voltolina, Stefano; Gross, Silvia

    2008-10-10

    The optimum performance of an optical oxygen sensor based on polysulfone (PSF)/[Ru(II)-Tris(4,7-diphenyl-1,10-phenanthroline)] octylsulfonate (Ru(dpp)OS) was checked by carefully tuning the parameters affecting the membrane preparation. In particular, membranes having thickness ranging between 0.2 and 8.0 microm with various luminophore concentrations were prepared by dip-coating and tested. The membrane thickness was controlled by tuning the solution viscosity, and was measured both by secondary ion mass spectrometry (SIMS) and by visible spectroscopy (Vis). Luminescence-quenching-based calibration was a single value of the Stern-Volmer constant (K'SV) for membranes containing up to 20 mmol Ru(dpp) g-1 PSF (1.35 microm average thickness). The K'SV value decreased for larger concentration. The highest sensitivity was obtained with membrane thickness around 1.6 microm, having a response time close to 1 s. Thicker membranes exhibited an emission saturation effect and were characterized by longer response time. The K'SV behavior was interpreted on the basis of a mathematical approach accounting for the contribution of luminescence lifetime (tau0), oxygen diffusion coefficient (DO2) and oxygen solubility inside the membrane (sO2) establishing the role of all of them and allowing their experimental determination. Moreover, a simple experimental way to estimate K'SV without needing calibration was proposed. It was based either on the light emission asymmetry or on the percent variation of light emission on passing from pure nitrogen to pure oxygen.

  18. Characterization of metal removal by os sepiae of Sepiella maindroni Rochebrune from aqueous solutions.

    PubMed

    Li, You-Zhi; Pan, Hong; Xu, Jian; Fan, Xian-Wei; Song, Xian-Chong; Zhang, Qian; Xu, Jin; Liu, Yang

    2010-07-15

    To develop low cost metal adsorbents with less secondary pollution, metal adsorption from the aqueous solutions by the raw os sepiae (ROS) and alkali (NaOH)-pretreated OS (APOS) of the cuttlefish (Sepiella maindroni Rochebrune) was characterized. The capacities of adsorption of ROS and APOS were estimated to be 299.26 mg Cu g(-1) and 299.58 mg Cu g(-1), respectively. Metal adsorption by OS was significantly improved by appropriately increasing initial pH in the solution but hardly affected by temperature change within a wide range of 15-45 degrees C. Cu adsorption of both ROS and APOS was well described neither by Langmuir model nor by Freundlich model. Metal adsorption by OS fell in the order of Fe > Cu approximately = Cd > Zn in the solution with mixed metals, but followed the sequence of Cd > Cu > Fe approximately = Zn in the solutions respectively, with a single metal of Fe, Cu, Cd and Zn. The changes in Ca amounts in OS and solutions in adsorption strongly correlated with removal efficiencies of the metals. Obvious shifts of stretching bands of numbers of groups in OS after and before adsorption and the pretreatment occurred. It was concluded: (1) that metal adsorption by OS involves ion exchange, which occurred mainly between Ca rather than K and Na that OS itself contains and metals that were added in the solution, (2) that metal adsorption-promoting effects by NaOH pretreatment likely involve deprotonation of surface groups in OS, exposure of more functional groups, and increase in specific surface areas and (3) that related mechanisms for adsorption also likely include surface complexation, electrostatic adsorption and even micro-deposition. The results also indicated that OS is a very promising absorbent for metal removal from electroplating wastewater.

  19. Magnetic-field-induced charge order in the filled skutterudite SmRu4P12: Evidence from resonant and nonresonant x-ray diffraction

    NASA Astrophysics Data System (ADS)

    Matsumura, Takeshi; Michimura, Shinji; Inami, Toshiya; Hayashi, Yuya; Fushiya, Kengo; Matsuda, Tatsuma D.; Higashinaka, Ryuji; Aoki, Yuji; Sugawara, Hitoshi

    2014-04-01

    The antiferromagnetic ordered phase in SmRu4P12 below the metal-insulator transition at TMI=16.5 K with an unresolved transition at T*˜14 K has been studied by resonant and nonresonant x-ray diffraction in magnetic fields. In the intermediate phase, a nonresonant Thomson scattering with q =(1,0,0) is induced by applying a magnetic field, which is presumably caused by atomic displacements reflecting the charge order in the p band, as predicted theoretically [R. Shiina, J. Phys. Soc. Jpn. 82, 083713 (2013), 10.7566/JPSJ.82.083713]. Simultaneously, the antiferromagnetic moment of Sm is enhanced along the field direction, which is considered to reflect the staggered ordering of the Γ7-Γ8 crystal-field states (scalar or hexadecapole order). The present results show that the orbital-dependent p-f hybridization in association with the nesting instability in the p band gives rise to the unconventional charge order similarly with PrRu4P12 and PrFe4P12.

  20. Reinforcement of double-exchange ferromagnetic coupling by Ru in La{sub 1.24}Sr{sub 1.76}Mn{sub 2-y}Ru{sub y}O{sub 7} manganite system

    SciTech Connect

    Kumaresavanji, M.; Fontes, M.B.; Lopes, A.M.L.; Araujo, J.P.

    2014-03-01

    Highlights: • Effect of Mn-site doping by Ru has been studied in La{sub 1.24}Sr{sub 1.76}Mn{sub 2-y}Ru{sub y}O{sub 7}. • Electrical resistance, magnetoresistance and magnetic properties were measured. • Ru substitution enhances the ferromagnetism and metallicity. • Results were interpreted by the ferromagnetically coupled Ru with Mn ions in Mn–O–Ru network. - Abstract: The effect of Mn-site doping on magnetic and transport properties in the bilayer manganites La{sub 1.24}Sr{sub 1.76}Mn{sub 2-y}Ru{sub y}O{sub 7} (y = 0.0, 0.04, 0.08 and 0.15) has been studied. The undoped compound La{sub 1.24}Sr{sub 1.76}Mn{sub 2}O{sub 7} exhibits a ferromagnetic metal to paramagnetic insulator transition at T{sub C} = 130 K and the substitution of Ru shifts the transition temperatures to higher temperature values. The increased metal–insulator transition by Ru substitution, obtained from temperature dependence of resistivity measurements, indicates that the Ru substitution enhances the metallic state at low temperature regime and favours the Mn–Ru pairs in the Ru doped samples. Moreover, the activation energy values calculated from the temperature dependence of resistivity curves suggest that the Ru substitution weakens the formation of polarons. The increased magnetoresistance ratio from 108% to 136% by Ru substitution, measured at 5 K, points out that the Ru substitution also enhances the inter-grain tunneling magnetoresistance. Thus, the ferromagnetic order and metallic state in La{sub 1.24}Sr{sub 1.76}Mn{sub 2}O{sub 7} system have been enhanced by the presence of Ru in the Mn-site. These reinforcements of ferromagnetic metallic state and magnetoresistance have been interpreted by the ferromagnetically coupled high spin states of Ru with Mn ions in the Mn–O–Ru network.

  1. Hydrostatic Pressure Study on 3-K Phase Superconductivity in Sr2RuO4-Ru Eutectic Crystals by AC Magnetic Susceptibility Measurements

    NASA Astrophysics Data System (ADS)

    Yaguchi, Hiroshi; Watanabe, Hiromichi; Sakaue, Akira

    2012-12-01

    We have investigated the effect of hydrostatic pressure on 3-K phase superconductivity in Sr2RuO4-Ru eutectic crystals by means of AC magnetic susceptibility measurements. We have found that the application of hydrostatic pressure suppresses the superconducting transition temperature Tc of the 3-K phase with a pressure coefficient of dTc/dP ≈ -0.2 K/GPa, similar to the case of the 1.5-K phase. We have also observed that the effect of hydrostatic pressure on the 3-K phase seems to be elastic whilst that of uniaxial pressure is plastic.

  2. Interfacial electron transfer dynamics of ru(II)-polypy6ridine sensitized TiO2

    SciTech Connect

    Jakubikova, Elena; Martin, Richard L; Batista, Enrique R; Snoeberger, Robert C; Batista, Victor S

    2009-01-01

    Quantum dynamics simulations combined with density functional theory calculations are applied to study interfacial electron transfer (IET) from pyridine-4-phosphonic acid, [Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 2+} and [Ru(tpy)(bpy)(H{sub 2}O)-Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 4+} into the (101) surface of anatase TiO{sub 2}. IET rate from pyridine-4-phosphonic acid attached to the nanoparticle in bidentate mode ({tau} {approx} 100 fs) is an order of magnitude faster than the IET rate of the adsorbate attached in the monodentate mode ({tau} {approx} 1 ps). Upon excitation with visible light, [Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 2+} attached to TiO{sub 2} in bidentate binding mode will undergo IET with the rate of {approx} 1-10 ps, which is competitive with the excited state decay into the ground state. The probability of electron injection from [Ru(tpy)(bpy)(H{sub 2}O)-Ru(tpy)(tpy(PO{sub 3}H{sub 2}))]{sup 4+} is rather low, as the excitation with visible light localizes the excited electron in the tpy-tpy bridge, which does not have favorable coupling with the TiO{sub 2} nanoparticle. The results are relevant to better understanding of the adsorbate features important for promoting efficient interfacial electron transfer into the semiconductor.

  3. Transformation of glucocorticoid receptors bound to the antagonist RU 486: Effects of alkaline phosphatase

    SciTech Connect

    Gruol, D.J.; Wolfe, K.A. )

    1990-08-28

    RU 486 is a synthetic steroid that binds avidly to glucocorticoid receptors without promoting their transformation into activated transcription factors. A significant part of this behavior has been shown to be due to a failure of the RU 486 bound receptor to be efficiently released from a larger (sedimenting at 8-9 S) multimeric complex containing the 90-kDa heat shock protein. The studies have found that in vitro at 15{degree}C the RU 486-receptor was slowly released from the 8-9S complex and converted into a DNA binding protein by a process that could be blocked by sodium fluoride. Moreover, this transition was significantly accelerated by treatment with alkaline phosphatase. High-resolution anion-exchange chromatography showed that the profile of receptor subspecies released from the 8-9S complex was different for the RU 486 bound receptor when compared to the receptor occupied by the agonist triamcinolone acetonide. Production of the earliest eluting receptor form (peak A) was inhibited with RU 486. Treatment of the Ru 486-receptor with alkaline phosphatase increased the formation of the peak A subspecies as well as the capacity of receptor to bind DNA-cellulose. Taken together, the results indicate that phosphorylation of the receptor or a tightly bound factor contributes to defining the capacity with which individual steroids can promote dissociation of the 8-9S complex and conversion of the glucocorticoid receptor into a DNA-binding protein.

  4. Spectral and spatial anisotropy of the oxide growth onRu(0001)

    NASA Astrophysics Data System (ADS)

    Böttcher, A.; Starke, U.; Conrad, H.; Blume, R.; Niehus, H.; Gregoratti, L.; Kaulich, B.; Barinov, A.; Kiskinova, M.

    2002-11-01

    Scanning photoelectron spectromicroscopy has been used to study the onset and the initial stages of oxidation of Ru(0001) at three oxidation temperatures, 625, 675, and 775 K, and oxygen exposures of about 105 Langmuir. The lateral heterogeneity developed during oxide nucleation and growth and the local composition of the coexisting phases have been determined using as fingerprints the O 1s and Ru 3d spectra, thus combining chemical mapping with spectroscopy from selected features from the maps. The onset of oxide formation is characterized by the appearance of randomly distributed small islands (⩾0.5 μm) identified as germinal patches exhibiting some spectral features of bulk RuO2. The following anisotropic growth of the RuO2 phase and in particular the shape of the oxide islands shows a strong dependence on the oxidation temperature. The spectroscopic information obtained for the areas surrounding the oxide islands reveals an intermediate oxygen state characterized by distinct O 1s and Ru 3d features different from both the chemisorbed and the oxide form. It is assigned to an intermediate state acting as precursor of the oxide. The experimental data are discussed in the framework of the oxidation pathway and of core level fingerprints for the various oxygen-Ru phases suggested in recent theoretical models.

  5. Mechanistic insights into electrocatalytic CO2 reduction within [Ru(II)(tpy)(NN)X]n+ architectures.

    PubMed

    White, Travis A; Maji, Somnath; Ott, Sascha

    2014-10-28

    A series of Ru(II)-polypyridyl complexes of the design [Ru(II)(tpy)(NN)X](n+) (tpy = 2,2':6',2''-terpyridine; NN = bidentate polypyridine; X = Cl(-) or CH3CN; n = 1 or 2) have been synthesized and analyzed for their ability to function as electrocatalysts in the reduction of CO2 to CO. Varying the electron-donating/withdrawing character of the NN polypyridyl ligand has allowed for modification of electron density at the formally Ru(II) metal center. Complexes where X = Cl(-) display ligand substitution for CH3CN with differing rates of Cl(-) dissociation (k-Cl), therefore providing a degree of insight into the electron density and thus the chemical activity at the Ru(II) center. Detailed analysis of the cyclic voltammograms under argon vs. CO2 atmospheres using multiple switching potentials and scan rates ranging from ν = 25-2000 mV s(-1) has painted a picture of how monodentate ligand lability due to NN polypyridyl electron-donating character is related to electrocatalytic CO2 reduction activity of Ru(II)-polypyridyl complexes. From these studies, multiple mechanistic pathways towards generating the catalytically active [Ru(tpy(-))(NN(-))CO2](0) species are proposed and differ via the order of electrochemical and chemical processes.

  6. Directed evolution of RuBisCO hypermorphs through genetic selection in engineered E.coli.

    PubMed

    Parikh, Monal R; Greene, Dina N; Woods, Kristen K; Matsumura, Ichiro

    2006-03-01

    The Calvin Cycle is the primary conduit for the fixation of carbon dioxide into the biosphere; ribulose 1,5-bisphosphate carboxylase/oxygenase (RuBisCO) catalyzes the rate-limiting fixation step. Our goal is to direct the evolution of RuBisCO variants with improved kinetic and biophysical properties. The Calvin Cycle was partially reconstructed in Escherichia coli; the engineered strain requires the Synechococcus PCC6301 RuBisCO for growth in minimal media supplemented with a pentose. We randomly mutated the gene encoding the large subunit of RuBisCO (rbcL), co-expressed the resulting library with the small subunit (rbcS) and the Synechococcus PCC7492 phosphoribulokinase (prkA), and selected hypermorphic variants. The RuBisCO variants that evolved during three rounds of random mutagenesis and selection were over-expressed, and exhibited 5-fold improvement in specific activity relative to the wild-type enzyme. These results demonstrate a new strategy for the artificial selection of RuBisCO and other non-native metabolic enzymes.

  7. Effects of interfacial alignments on the stability of graphene on Ru(0001) substrate

    NASA Astrophysics Data System (ADS)

    Gao, Lei; Liu, Yanmin; Ma, Tianbao; Shi, Ruoyu; Hu, Yuanzhong; Luo, Jianbin

    2016-06-01

    Structure and electronic properties of two-dimensional materials could be tuned by interfacial misfit or orientation angles. However, graphene grown on Ru(0001) substrate usually shows stable moiré superlattice with a periodicity of 3.0 nm indicating an aligned geometry. The reason for the absence of misaligned structure is still unknown. We have performed first-principles calculation to investigate the microstructure and morphology of graphene on Ru(0001) substrate in both aligned and misaligned geometries with rotation angles of 0°, 7.6°, and 23.4°, respectively. Our results indicate that both the graphene corrugation and moiré superlattice periodicity decrease as the rotation angle increases. Meanwhile the interaction energy between graphene and Ru(0001) substrate also becomes weakened with the rotation angle, as the decrease and discretization of intense charge transfer sites at the graphene/Ru interface, which is closely related to the interface stacking structure. Counterintuitively, the strain energy in graphene also increases anomalously with the rotation angle, which is attributed to the highly distorted local deformation of graphene due to the strong but discrete covalent bonding with Ru substrate. The simultaneous increase in both the interaction energy and strain energy in graphene/Ru(0001) heterostructure with rotation angle contributes to the preferred configuration in the aligned state.

  8. Oxidation of the Ru(0001) surface covered by weakly bound, ultrathin silicate films

    DOE PAGES

    Emmez, Emre; Anibal Boscoboinik, J.; Tenney, Samuel; ...

    2015-06-30

    Bilayer silicate films grown on metal substrates are weakly bound to the metal surfaces, which allows ambient gas molecules to intercalate the oxide/metal interface. In this work, we studied the interaction of oxygen with Ru(0001) supported ultrathin silicate and aluminosilicate films at elevated O2 pressures (10-5–10 mbar) and temperatures (450–923 K). The results show that the silicate films stay essentially intact under these conditions, and oxygen in the film does not exchange with oxygen in the ambient. O2 molecules readily penetrate the film and dissociate on the underlying Ru surface underneath. Also, the silicate layer does however strongly passivate themore » Ru surface towards RuO2(110) oxide formation that readily occurs on bare Ru(0001) under the same conditions. Lastly, the results indicate considerable spatial effects for oxidation reactions on metal surfaces in the confined space at the interface. Moreover, the aluminosilicate films completely suppress the Ru oxidation, providing some rationale for using crystalline aluminosilicates in anti-corrosion coatings.« less

  9. Structural phase transition and antiferromagnetic transition of Tb{sub 3}RuO{sub 7}

    SciTech Connect

    Hinatsu, Yukio Doi, Yoshihiro

    2014-12-15

    Magnetic properties and structural phase transition of terbium ruthenate Tb{sub 3}RuO{sub 7} are investigated through magnetic susceptibility, specific heat, high-temperature X-ray diffraction and differential scanning calorimetry measurements. The structural phase transition from space group P2{sub 1}nb to Cmcm has been observed at 402 K. Tb{sub 3}RuO{sub 7} shows an antiferromagnetic transition at 17 K. In addition, another magnetic anomaly has been found at 10 K. Analysis of the magnetic specific heat for Tb{sub 3}RuO{sub 7} indicates that the magnetic transitions at 10 and 17 K are due to the magnetic ordering of Tb{sup 3+} and Ru{sup 5+} ions, respectively. - Graphical abstract: Temperature dependence of the magnetic specific heat divided by temperature (C{sub mag}/T) and the magnetic entropy (S{sub mag}) for Tb{sub 3}RuO{sub 7}. Two-step magnetic transition has been observed. - Highlights: • Tb{sub 3}RuO{sub 7} shows an antiferromagnetic transition at 17 K. • Specific heat measurements confirmed the occurrence of two-step magnetic transition. • The phase transition from space group P2{sub 1}nb to Cmcm has been observed at 402 K.

  10. Site dilution in SrRuO3: effects on structural and magnetic properties

    NASA Astrophysics Data System (ADS)

    Gupta, Renu; Pramanik, A. K.

    2017-03-01

    We have investigated the effect of site dilution with substitution of nonmagnetic element in SrRu1‑x Ti x O3 (x  ⩽  0.7). The nature of ferromagnetic state in SrRuO3 is believed to be of itinerant type with transition temperature {{T}\\text{c}}∼ 162 K. Crystallographically, SrRuO3 has a distorted orthorhombic structure. Substitution of \\text{T}{{\\text{i}}+4} (3d 0) for Ru+4 (4d 4), however, does not introduce significant structural modification due to their matching ionic radii. This substitution, on the other hand, is expected to tune the electronic correlation effect and the d electron density in the system. With Ti substitution, we find that magnetic moment and Curie temperature decreases but T c remains unchanged which has been attributed to opposite tuning of electron correlation effect and density of states within the framework of itinerant ferromagnetism. The estimated critical exponent (β) related to magnetization implies a mean-field type of magnetic nature in SrRuO3. The value of β further increases with x which is understood from the dilution effect of magnetic lattice. The system evolves to exhibit Griffiths phase like behavior above T c which is usually realized in diluted ferromagnet following local moment model of magnetism. Our detail analysis of magnetization data indicates that magnetic state in SrRuO3 has contribution from both itinerant and local moment model of magnetism.

  11. Magnetic ordering and structural transition in layered Li2RuO3

    NASA Astrophysics Data System (ADS)

    Pillay, Devina; Johannes, Michelle

    2008-03-01

    Li2RuO3 is a layered, triangular-lattice metal oxide system much like NaxCoO2, NaNiO2 and LiNiO2 with the exception that one of every three transition metal ions (Ru) is replaced by a Li ion. This results in a honeycomb arrangement of spin-carrying ions and eliminates the magnetic frustration intrinsic to the triangular lattice. Here we investigate the electronic structure of Li2RuO3, especially in relation to its magnetic ordering both in-plane and between adjacent planes. We find that the dimerization of Ru atoms within the metal-oxide planes acts in conjunction with magnetic ordering to establish a gapped, magnetic ground state. The change in the energy level spectrum brought on by the formation of spin-polarized Ru-Ru molecular orbitals replaces the expected Jahn-Teller mechanism as a way of relieving a degeneracy at the Fermi energy.

  12. Electronic structure and exchange interactions of insulating double perovskite La2CuRuO6

    NASA Astrophysics Data System (ADS)

    Panda, S. K.; Kvashnin, Y. O.; Sanyal, B.; Dasgupta, I.; Eriksson, O.

    2016-08-01

    We have performed first-principles calculations of the electronic and magnetic properties of insulating double perovskite compound La2CuRuO6 (LCRO) which has recently been reported to exhibit intriguing magnetic properties. We derived a tight-binding Hamiltonian for LCRO based on the N th -order muffin-tin orbital (NMTO) downfolding technique. The computed on-site energies and hopping integrals are used to estimate the dominant exchange interactions employing an extended Kugel-Khomskii model. This way the dominant exchange paths were identified and a low-energy spin model was proposed. The Green function method based on the magnetic force theorem has also been used to extract the exchange interactions to provide a more accurate estimation and to justify the model calculations. Our results show that the nearest neighbor (NN) Cu-Ru magnetic interactions are very much direction dependent and a strong antiferromagnetic next nearest neighbor Ru-Ru interaction along the crystallographic b axis is responsible for the magnetic frustration observed experimentally in this system. We argue that due to the broken symmetry, NN Cu-Ru interaction becomes stronger along one direction than the other, which essentially reduces the amount of frustration and helps the system to achieve an antiferromagnetic ground state at low temperature. A detailed microscopic explanation of the exchange mechanism is discussed. We also find that spin-orbit coupling effect is significant and causes a canting of the Ru spin with respect to the Cu moments.

  13. Oxidation of the Ru(0001) surface covered by weakly bound, ultrathin silicate films

    SciTech Connect

    Emmez, Emre; Anibal Boscoboinik, J.; Tenney, Samuel; Sutter, Peter; Shaikhutdinov, Shamil; Freund, Hans-Joachim

    2015-06-30

    Bilayer silicate films grown on metal substrates are weakly bound to the metal surfaces, which allows ambient gas molecules to intercalate the oxide/metal interface. In this work, we studied the interaction of oxygen with Ru(0001) supported ultrathin silicate and aluminosilicate films at elevated O2 pressures (10-5–10 mbar) and temperatures (450–923 K). The results show that the silicate films stay essentially intact under these conditions, and oxygen in the film does not exchange with oxygen in the ambient. O2 molecules readily penetrate the film and dissociate on the underlying Ru surface underneath. Also, the silicate layer does however strongly passivate the Ru surface towards RuO2(110) oxide formation that readily occurs on bare Ru(0001) under the same conditions. Lastly, the results indicate considerable spatial effects for oxidation reactions on metal surfaces in the confined space at the interface. Moreover, the aluminosilicate films completely suppress the Ru oxidation, providing some rationale for using crystalline aluminosilicates in anti-corrosion coatings.

  14. Origin of Selective Adsorption for Metal Nano-clusters on Graphene/Ru(0001)

    NASA Astrophysics Data System (ADS)

    Zhang, Lizhi; Sun, Jiatao; Huang, Li; Pan, Lida; Du, Shixuan; Gao, Hongjun

    2013-03-01

    These years, metal nano-clusters have attracted many interests because of their exciting properties and the potential applications in the catalysis industries, the information storage and so on. Recently, many groups composed the homogenous and size-controlled metal nano-clusters on graphene/Ru(0001) moiré template (G/Ru(0001)). However, the growth modes of these nano-clusters are not very clear. Here, we investigated the mechanism of selective adsorption of some transition metal (TM) atoms on G/Ru(0001) by DFT calculations, and proposed a criterion to estimate the growth mode of TM atoms on G/Ru(0001). We found that both the intensity of sp3 hybridization of carbon atoms in different regions of G/Ru(0001) and the electronic structure of the transition metal atoms influence the adsorption site and the selectivity of metal atoms on G/Ru(0001) at initio stage. According to the electronic structures of some other different G/metal systems, we also predicted that some other G/metal templates can be used to grow the metal nano-clusters. The growth mechanism agrees well with the experimental observations, and provides a way to select suitable metal atoms to form dispersed metal nano-clusters on the G/metal template.

  15. Os Isotopic Composition and Highly Siderophile Elements: Tracers of Mantle Melting and Melt Percolation Processes (Voykar Complex, Polar Ural Ophiolites)

    NASA Astrophysics Data System (ADS)

    Batanova, V.; Bruegmann, G.; Savelieva, G.

    2006-12-01

    The Voykar complex is located in the Northern part of the Uralian ophiolite belt and represents Early Devonian lithosphere formed in a suprasubduction environment (e. g. (1)). It is unique in that the mantle peridotites are very well preserved and virtually free of serpentine, and it provides excellent exposures. The mantle section of Voykar complex is composed of harzburgite which is intruded by numerous dunite and pyroxenite channels and contains chromitite ore deposits. The distribution of highly siderophile elements (HSE) in harzburgite and dunite channels can be explained by melt-peridotite reaction processes. The harzburgites (Cr/(Cr+Al) of cr-spinel = 0.3-0.4) show two types of HSE patterns. One is depleted in Pd, Pt and Re relatively to Os, Ir, Ru with (Pt/Ir)N=0.3, the second pattern is flat with (Pt/Ir)N=0.9. The first type of harzburgite has lower ratios of 187Os/188Os (0.1149) compared to the second (0.1236). Dunite and associated orthopyroxenite are significantly enriched in 187Os (187Os/188Os=0.1279 - 0.1327), hence shifted towards lava compositions. Their HSE patterns also show the influence of mantle melts, because they are enriched in Pd ((Pt/Ir)N=5-6). The clinopyroxenite has the highest ratio of 187Os/188Os up to 32.38 and shows even stronger depletion of Os, Ir, Ru relative to Pt, Pd, Re ((Pt/Ir)N=20). They could represent crystallization products of percolating melts. Chromitites have variable 187Os/188Os=0.1244-0.1352, and their HSE concentrations overlap with the range observed in chromitites world-wide. Osmium isotope data show evidence for at least two significant events in the magmatic history of the Voykar ophiolite mantle section: an ancient (2.1-1.9 Ga) melting event formed the depleted spinel harzburgite; a younger melt percolation event (0.6-0.5 Ga) led to the formation of pyroxenite veins, dunite channels and chromitites. The age of melt percolation events based on Os isotopic data coincides with the U-Pb age of zircons found in

  16. Creep-free ac hysteretic dynamics in epitaxial ferroelectric BiFeO3 films

    NASA Astrophysics Data System (ADS)

    Shin, Yeongjae; Jeon, Byung Chul; Yang, Sang Mo; Hwang, Inrok; Cho, Myung Rae; Sando, Daniel; Lee, Seung Ran; Yoon, Jong-Gul; Noh, Tae Won

    2015-03-01

    Dynamics of domain wall (DW) in ferroelectric (FE) films principally governs their switching properties under applied electric field (E) . At finite temperature (T) , the DW motion and their FE switching characteristics can be understood only by introducing the creep motion. Despite this importance, there have been little studies on creep motion of FE films under ac-driven force. In this work, we investigate ac-driven hysteretic dynamics of FE domains in epitaxial BiFeO3 (BFO) films through polarization-electric field hysteresis loops with varying frequency and other switching characters. All BFO films were grown at the optimized growth condition, by employing different bottom electrodes of La0.67Sr0.33MnO3 (LSMO) and SrRuO3 (SRO); only BFO/SRO shows nearly creep-free hysteretic dynamics. We argue that inhomogeneous internal E plays a significant role in such distinctive FE dynamics of BFO domains, which are affected by surface morphologies of bottom electrodes. Our results highlight that growth-mode-induced interfacial structure between an FE film and a bottom electrode result in engineering domain dynamics of FE switching characteristics. This work was supported by IBS-R009-D1.

  17. Fabrication of MgAl2O4 tunnel barrier by radio frequency-sputtering method and magnetoresistance effect through it with Fe or Fe4N ferromagnetic electrode

    NASA Astrophysics Data System (ADS)

    Tsunoda, Masakiyo; Chiba, Ryoichi; Kabara, Kazuki

    2015-05-01

    Spinel MgAl2O4 thin films were deposited on MgO single-crystal substrates and epitaxial Fe (or Fe4N) thin films by RF-sputtering from a ceramic target. Epitaxial relationship was confirmed by X-ray diffraction analysis between the crystalline spinel MgAl2O4 films and the respective substrate and underlayers, while no diffraction peak was observed from the films deposited on amorphous substrates. Spin-valve type magnetic tunnel junctions (MTJs) with a stacking structure of Fe [Fe4N]/MgAl2O4/CoFeB/Ru/Fe/MnIr exhibited normal [inverse] tunnel magnetoresistance (TMR) effect, reflecting the sign of spin polarization of Fe [Fe4N]. The maximum magnitude of the TMR ratio obtained for the Fe-based and Fe4N-based MTJs was 67% and 18%, respectively. The resistance area product values of the MTJs were significantly larger than the reported values for the MTJs with a post-oxidized spinel MgAl2O4 barrier.

  18. Fabrication of MgAl{sub 2}O{sub 4} tunnel barrier by radio frequency-sputtering method and magnetoresistance effect through it with Fe or Fe{sub 4}N ferromagnetic electrode

    SciTech Connect

    Tsunoda, Masakiyo; Chiba, Ryoichi; Kabara, Kazuki

    2015-05-07

    Spinel MgAl{sub 2}O{sub 4} thin films were deposited on MgO single-crystal substrates and epitaxial Fe (or Fe{sub 4}N) thin films by RF-sputtering from a ceramic target. Epitaxial relationship was confirmed by X-ray diffraction analysis between the crystalline spinel MgAl{sub 2}O{sub 4} films and the respective substrate and underlayers, while no diffraction peak was observed from the films deposited on amorphous substrates. Spin-valve type magnetic tunnel junctions (MTJs) with a stacking structure of Fe [Fe{sub 4}N]/MgAl{sub 2}O{sub 4}/CoFeB/Ru/Fe/MnIr exhibited normal [inverse] tunnel magnetoresistance (TMR) effect, reflecting the sign of spin polarization of Fe [Fe{sub 4}N]. The maximum magnitude of the TMR ratio obtained for the Fe-based and Fe{sub 4}N-based MTJs was 67% and 18%, respectively. The resistance area product values of the MTJs were significantly larger than the reported values for the MTJs with a post-oxidized spinel MgAl{sub 2}O{sub 4} barrier.

  19. On the precipitation errors in the RU satellite technique

    NASA Astrophysics Data System (ADS)

    Melani, Samantha; Antonini, Andrea; Ortolani, Alberto; Benedetti, Riccardo

    2010-05-01

    Satellite rainfall monitoring is up to date the only feasible way to have a global and homogeneous coverage of rainfall distribution, amount and occurrence. Their value is unquestioned for all remote regions of the Earth not covered by raingauge networks or covered by old ground networks that provide precipitation data at spatial and temporal scales inadequate for the majority of the applications. However satellite precipitation operate at time and spatial scales consistent with the nature and development of cloud raining systems, and even with hydrological processes, so that, in addition to their scientific value, they result effective also in nowcasting activities and in rainfall spatialisation processes, even in areas well covered by modern ground networks. Several techniques exist in literature to estimate rainfall intensity, which range from the use of purely-based statistical methods to neural networks (Joyce et al., 2004; Sooroshian et al., 2005). Among the more widespread statistical technique, nowadays considered as a standard, it is the Rapid Update (RU) technique, developed by J. Turk at the Naval Research Laboratory (NRL), based on a blended technique that which takes advantage of both the newer polar sensors and Geostationary product (Turk et al, 2000a; 2000b). Since 2004, an adapted version of the RU for the Mediterranean area was implemented at LAMMA laboratory (Laboratory for Monitoring and Environmental Modelling for the sustainable development), which provides maps of estimated rainfall every 15 minutes, in a near real-time fashion (http://www.lamma.rete.toscana.it/previ/eng/rain_msg_eng.html), using Meteosat Second Generation (MSG) data. Among the principal limitations of this kind of technique is the assessment of the accuracy to be associated with the precipitation estimates. A number of validation campaigns have been planned and realized to the purpose, and they have shown how it is difficult to define an error in a statistical sense, as

  20. Influence of filled d pi-manifold and L/L' ligands on the structure, basicity, and bond rotations of the octahedral and d(6) amido complexes TpRu(L)(L')(NHPh) (Tp = hydridotris(pyrazolyl)borate; L = L' = PMe(3) or P(OMe)(3), or L = CO and L' = PPh(3)): solid-state structures of [TpRu(PMe(3))(2)(NH(2)Ph)][OTf], [TpRu[P(OMe)(3)](2)(NH(2)Ph)][OTf], and TpRu[P(OMe)(3)](2)(NHPh).

    PubMed

    Conner, David; Jayaprakash, K N; Gunnoe, T Brent; Boyle, Paul D

    2002-06-03

    It has been suggested that the reactivity of pi-donating ligands bound to late-transition-metal complexes is heightened due to high d-electron counts. Herein, the synthesis and characterization of the Ru(II) amine and Ru(II) amido complexes [TpRuL(2)(NH(2)Ph)][OTf] (OTf = trifluoromethanesulfonate) and TpRuL(2)(NHPh) (L = PMe(3) or P(OMe)(3)) are presented, including solid-state X-ray diffraction studies of [TpRu(PMe(3))(2)(NH(2)Ph)][OTf], [TpRu[P(OMe)(3)](2)(NH(2)Ph)][OTf], and TpRu[P(OMe)(3)](2)(NHPh). The pK(a)'s of the Ru(II) amine complexes and the previously reported [TpRu(CO)(PPh(3))(NH(2)Ph)](+) have been estimated to be comparable to that of malononitrile in methylene chloride. In addition, the impact of the filled dpi-manifold (i.e., Ru(II) and d(6) octahedral systems) on barriers to rotation of the Ru-NHPh moieties has been studied. For TpRu(PMe(3))(2)(NHPh) and TpRu[P(OMe)(3)](2)(NHPh), evidence for hindered rotation about the amido nitrogen and phenyl ipso carbon has been observed, and the relative N-C and Ru-N bond rotational barriers for the series of three amido complexes are discussed in terms of the pi-conflict.