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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. Compressibility of Ru and Os in Comparison with Hcp ɛ -Fe; the lowest measured compressibility

    NASA Astrophysics Data System (ADS)

    Cynn, H.; Yoo, C.; Iota, V.; Baer, B.

    2001-12-01

    The hardness of a material is strongly correlated with its bulk modulus; thus, the search for superhard materials often becomes the search for very low compressibilities. Diamond is the hardest known material and has the highest known bulk modulus, B0 = 443 GPa (or the lowest compressibility, β = 0.226 Mbar-1). In this paper, we present surprising experimental findings that metallic elements like Os, Ir, and Ru are also good candidates for superhard materials based on their measured low compressibilities. We also present the pressure volume relationships of Ru, Os, and Ir to 70 GPa, in comparison with those of ɛ -Fe, W and C. The results are in a systematic agreement with the change of the bulk moduli and also with the first-principles electronic structure calculations. However, the c/a ratios of the 4,5d-transition metals show a slightly different trend from that of 3d ɛ -Fe at high pressures. Because of the similarity in electronic structure of these metals and Fe, the major constituent of the Earth's core, the EOS's and crystal structural parameters of the Group VIIIA transition metals reported in this paper are central to understanding the Earth's core mineral physics. This work was performed under the auspices of the U.S. Department of Energy by University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

  4. 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. PMID:25982241

  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

    2016-05-01

    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. PMID:27074099

  6. X-ray microanalysis of aldehyde-fixed glycogen contrast-stained by OsVI . FeII and OsVI . RuIV complexes.

    PubMed

    de Bruijn, W C; van Buitenen, J M

    1980-11-01

    The composition of the contrast-donating complex of rat liver glycogen, nucleoplasm, erythrocytes, and mitochondria was established by X-ray microanalysis. In these compartments the presence of osmium and iron was shown qualitatively in tissue after glutaraldehyde fixation, treated with OsVIIIO4 plus K4FeII(CN)6 and in similar tissue treated with a combination of K2OsVIO4 plus K4FeII(CN)6. Osmium and ruthenium were detected in these compartments, in aldehyde-fixed tissue treated with mixtures containing K2RuIVL(CN)6 rather than K4FeII(CN)6. The iron detected in the glycogen, nucleoplasm, erythrocytes, and mitochondria of tissue treated with K2RuIV(CN)6 mixtures proved to derive from sources inside the electron microscope, and had to be considered an artifact. Quantitatively, the mean atomic ratios of osmium-to-iron and osmium-to-ruthenium were determined from spectra obtained by point analyses of the same compartments (glycogen, nucleoplasm, mitochondria, lipid droplets, and erythrocytes). After correction of the spectra for the instrumental iron contribution, the osmium-to-iron and osmium-to-ruthenium ratios in the glycogen were about 1:3 for tissue treated with those combinations including K2OsVIO4. In the other compartments, the osmium-to-iron and osmium-to-ruthenium ratios were virtually 1:0. For Os-VIIIO4 in combination with potassium ferrouscyanide however the osmium-to-iron ratio was 1:7 in the glycogen and 1:5 in all other compartments. OsVIIIO4 was combined with potassium ruthenium-cyanide, the osmium-to-ruthenium ratio was 1:2 in the glycogen and 2:1 in the other compartments. These results support our view that the selective glycogen contrast is obtained by complex formation. PMID:6159393

  7. (1)H NMR assignment corrections and (1)H, (13)C, (15)N NMR coordination shifts structural correlations in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2'-bipyridine and 1,10-phenanthroline.

    PubMed

    Pazderski, Leszek; Pawlak, Tomasz; Sitkowski, Jerzy; Kozerski, Lech; Szłyk, Edward

    2010-06-01

    (1)H, (13)C and (15)N NMR studies of iron(II), ruthenium(II) and osmium(II) tris-chelated cationic complexes with 2,2'-bipyridine and 1,10-phenanthroline of the general formula [M(LL)(3)](2+) (M = Fe, Ru, Os; LL = bpy, phen) were performed. Inconsistent literature (1)H signal assignments were corrected. Significant shielding of nitrogen-adjacent protons [H(6) in bpy, H(2) in phen] and metal-bonded nitrogens was observed, being enhanced in the series Ru(II) --> Os(II) --> Fe(II) for (1)H, Fe(II) --> Ru(II) --> Os(II) for (15)N and bpy --> phen for both nuclei. The carbons are deshielded, the effect increasing in the order Ru(II) --> Os(II) --> Fe(II). PMID:20474023

  8. Muon-spin-relaxation and inelastic neutron scattering investigations of the caged-type Kondo semimetals: CeT2Al10 (T = Fe, Ru and Os)

    NASA Astrophysics Data System (ADS)

    Adroja, D. T.; Hillier, A. D.; Muro, Y.; Takabatake, T.; Strydom, A. M.; Bhattacharyya, A.; Daoud-Aladin, A.; Taylor, J. W.

    2013-12-01

    Recently, Ce-based caged-type compounds with the general formula CeT2Al10 (T = Fe, Ru and Os) have generated considerable interest due to the Kondo semiconducting paramagnetic ground state (down to 40 mK) observed in CeFe2Al10 and anomalously high magnetic ordering temperature with spin gap formation at low temperatures in Kondo semimetals CeRu2Al10 and CeOs2Al10. The formation of long-range magnetic ordering out of the Kondo semiconducting/semimetallic state itself is extraordinary and these are the first examples of this enigmatic coexistence of electronic ground states. These compounds also exhibit strong anisotropy in magnetic and transport properties, which has been explained on the basis of single-ion crystal electric field anisotropy in the presence of strongly anisotropic hybridization between localized 4f-electron and conduction electrons. Furthermore, they also exhibit a remarkable modification of magnetic and transport properties with doping on Ce, or T or Al sites. In this article, we briefly discuss the bulk properties of these compounds, giving a detailed discussion on our muon-spin-relaxation (μSR) investigations and inelastic neutron scattering (INS) results. We present the μSR and the INS results of Ce(Ru1-xFex)2Al10 and CeOs2Al10 as well as the μSR results of NdFe2Al10, NdOs2Al10 and YFe2Al10 for comparison. The zero-field μSR spectra clearly reveal coherent two-frequency oscillations at low temperatures in CeT2Al10 (T = Ru and Os) and Ce(Ru1-xFex)2Al10 (x = 0.3-0.5), which confirms the long-range magnetic ordering with a reduced moment of the Ce. On the other hand, the μSR spectra of Ce(Ru1-xFex)2Al10 (x = 0.8 and 1) down to 1.2 and 0.04 K, respectively, exhibit a temperature independent Kubo-Toyabe (KT) term confirming a paramagnetic ground state. INS measurements on CeT2Al10 (T = Ru and Os) exhibit sharp inelastic excitations at 8 and 11 meV at 5 K due to an opening of a gap in the spin excitation spectrum. A spin gap of 8-12 meV at 7 K

  9. Thermodynamic and transport properties of single-crystalline UM Ga5 (M=Fe,Co,Ni,Ru,Rh,Pd,Os,Ir,Pt)

    NASA Astrophysics Data System (ADS)

    Moreno, N. O.; Bauer, E. D.; Sarrao, J. L.; Hundley, M. F.; Thompson, J. D.; Fisk, Z.

    2005-07-01

    We report the results of magnetic susceptibility, specific heat, and electrical resistivity measurements on UMGa5 (M=Fe,Co,Ni,Ru,Rh,Pd,Os,Ir,Pt) single crystals. Antiferromagnetic ordering was observed for M=Ni , Pd, and Pt, with ordering temperatures TN=80K , 28K , and 23.5K , respectively. For the UMGa5 compounds with transition metals from the Fe and Co columns, itinerant paramagnetic behavior is observed. The evolution of this behavior is discussed in terms of f -ligand interaction with an emphasis on the role played by f-d hybridization.

  10. 1H, 13C, 15N NMR coordination shifts in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2':6',2″-terpyridine.

    PubMed

    Pazderski, Leszek; Pawlak, Tomasz; Sitkowski, Jerzy; Kozerski, Lech; Szlyk, Edward

    2011-05-01

    (1)H, (13)C and (15)N NMR studies of iron(II), ruthenium(II) and osmium(II) bis-chelated cationic complexes with 2,2':6',2″-terpyridine ([M(terpy)(2) ](2+) ; M = Fe, Ru, Os) were performed. Significant shielding of nitrogen-adjacent H(6) and deshielding of H(3'), H(4') protons were observed, both effects being mostly expressed for Fe(II) compounds. The metal-bonded nitrogens were shielded, this effect being much larger for the outer N(1), N(1″) than the inner N(1') atoms, and enhanced in the Fe(II) → Ru(II) → Os(II) series. PMID:21491480

  11. 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.

  12. Photochemistry of the ion pairs Rh(bpy)T M(CN)6U (bpy = 2,2'-bipyridyl) with M = Fe, Ru, Os following outer-sphere metal to ligand charge-transfer excitation

    SciTech Connect

    Vogler, A.; Kunkely, H.

    1987-06-03

    Optical metal to ligand charge-transfer (MLCT) transitions play an important role in the photophysics and photochemistry of transition-metal complexes. This electronic transition is an intramolecular (inner-sphere) process. It involves the promotion of a d electron of the metal to an empty orbital of a ligand coordinated to this metal. MLCT transitions occur at low energies if the metal is a reducing one and the ligand has available empty low-energy orbitals. Typical examples are the complexes Ru(bpy)3S (bpy = 2,2'-bipyridyl) and M(CN)6U (M = Fe, Ru, Os). In the latter case MLCT excitation is associated with the generation of solvated electrons. They report here on intermolecular (outer-sphere) MLCT transitions and the photochemistry following this type of CT excitation. In this case the optical transition involves the promotion of an electron from the metal of one complex to the ligand of another complex. The ion pairs Rh(bpy)3S M(CN)6U with M = Fe, Ru, Os were selected for this study.

  13. Nucleophilic activation of coordinated carbon monoxide. Part 3. Hydroxide and methoxide reactions with the trinuclear clusters M/sub 3/(CO)/sub 12/ (M = Fe, Ru, or Os): implications with regard to catalysis of the water gas shift reaction

    SciTech Connect

    Gross, D.C.; Ford, P.C.

    1985-02-06

    Reported are quantitative investigations of the reactions of the triangular clusters M/sub 3/(CO)/sub 12/ (M = Fe, Ru, or Os) with methoxide ion in solution. In methanol under a CO atmosphere, both the osmium and ruthenium species form stable 1:1 methoxycarbonyl adducts (M/sub 3/(CO)/sub 12/ + NaOCH/sub 3/ in equilibrium (M/sub 3/(CO)/sub 11/(CO/sub 2/CH/sub 3/))Na); however, for the triiron analogue this adduct undergoes fragmentation to give Fe(CO)/sub 4/(CO/sub 2/CH/sub 3/)/sup -/. Initial adduct formation in each case occurs with an equilibrium constant of about 10/sup 3/ M/sup -1/. In mixed tetrahydrofuran/methanol solutions, K/sub eq/ for Ru/sub 3/(CO)/sub 11/(CO/sub 2/CH/sub 3/)/sup -/ is much larger, an indication of the greater activity of NaOCH/sub 3/ in the less protic solvent. Notably, in such solvent mixtures, the presence of excess methoxide also led to the formation of 2:1 adducts. Rates of adduct formation were examined by using stopped-flow kinetics techniques, and it was shown that in methanol the second-order rate constants (25/sup 0/C) are 11.3 x 10/sup 3/, 2.1 x 10/sup 3/, and 0.6 x 10/sup 3/ M/sup -1/ s/sup -1/ for Fe/sub 3/(CO)/sub 12/, Ru/sub 3/(CO)/sub 12/, and Os/sub 3/(CO)/sub 12/, respectively. Rates were much higher in the mixed THF(tetrahydro-furan)/CH/sub 3/OH solutions; for example, k/sub 1/ (25/sup 0/C) for Ru/sub 3/(CO)/sub 12/ is 2.0 x 10/sup 5/ M/sup -1/ s/sup -1/ in 90/10 THF/CH/sub 3/OH (v/v). Monosubstitution of the ruthenium cluster with (CH/sub 3/O)/sub 3/P markedly reduced the reactivity toward the anionic nucleophile. The reaction of the triruthenium species with hydroxide (Ru/sub 3/(CO)/sub 12/ + OH/sup -/ in equilibrium Ru/sub 3/(CO)/sub 11/(CO/sub 2/H)/sup -/ ..-->.. HRu/sub 3/(CO)/sub 11//sup -/ + CO/sub 2/) was also investigated. Analysis of the reaction kinetics leads to the conclusion that formation of the initial hydroxycarbonyl adduct is somewhat less favorable and is slower than the analogous reaction of

  14. 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. PMID:26523807

  15. Os-Ru-Ir and Os-(Ru)-Ir-Pt mineral phases from iron quartzites and weathered rocks of the Mikhailovka and Staryi Oskol KMA iron regions, central Russia

    NASA Astrophysics Data System (ADS)

    Chernyshov, N. M.; Ponamareva, M. M.

    2015-02-01

    Numerous natural Os-Ir-Ru and Os-Ir-Ru-Pt alloys have been found in iron quartzites and their weathered rocks. The Ir-Os alloys in the Mikhailovka and Staryi Oskol KMA iron regions are characterized by the densest hexagonal packing. Almost all of them contain a low amount of Fe and Ni at a relatively higher amount of Pt, Ru, and, locally, Rh. The highest Rh contents are typical of minerals with Ir dominant over Os or with a high Pt content.

  16. Spin-State Effects on the Thermal Dihydrogen Release from Solid-State [MH(η(2)-H 2)dppe2](+) (M = Fe, Ru, Os) Organometallic Complexes for Hydrogen Storage Applications.

    PubMed

    Abrecht, David G; Muñoz, Jorge A; Smith, Hillary L; Fultz, Brent

    2014-01-30

    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(η(2)-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

  17. 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

  18. 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.

  19. XPS surface study of nanocrystalline Ti Ru Fe materials

    NASA Astrophysics Data System (ADS)

    Suñol, J. J.; Bonneau, M. E.; Roué, L.; Guay, D.; Schulz, R.

    2000-02-01

    The surface properties of Ti:Ru:Fe (2- x:1+ x/2:1+ x/2) (with x=0, 0.25, 0.5, 0.75, and 1) and Ti:Ru:Fe:O (2:1:1: w) (with w=0.0, 0.5, 1.0, 1.5, and 2.0) have been determined by X-ray photoelectron spectroscopy (XPS) in both their as-milled state and after being in contact with a chlorate oxidizing solution. The O surface concentrations of both sets of samples are almost identical, indicating that the O-free samples readily react with air. All samples in their as-milled state have an elemental Ti, Ru and Fe surface contents that closely follow that expected from their bulk composition, indicating that there is no surface enrichment in any of the elements. In the as-milled state, more than 90% of Ti and Fe atoms are in the highest possible oxidation state, while Ru is in the metallic state. Following immersion of the samples in an oxidizing chlorate electrolyte, the Ru surface concentration decreases by a factor of two. This is also accompanied by an increase in the oxidation state of the Ru atoms left at the surface from 0 to +4. From a comparison between the Ru 3 d5/2,3/2 core level spectra of the electrodes with those of crystalline and hydrated RuO 2, it is postulated that dissolution and re-deposition of Ru in the form of hydrated RuO 2 occurs at open circuit potential in the chlorate electrolyte. The consequences of these findings for the electrocatalytic activity of the electrodes in chlorate electrolyte are finally discussed.

  20. 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.

  1. Si/NiFe seed layers for Ru intermediate layer in perpendicular magnetic recording tape media

    NASA Astrophysics Data System (ADS)

    Saemma, Gaku; Takahashi, Shota; Matsunuma, Satoshi; Inoue, Tetsutaro; Nakagawa, Shigeki

    2012-04-01

    Si/NiFe seed layers prepared at room temperature is effective to attain better c-axis orientation of Ru intermediate layer in the FeCoB/Ru/CoPtCr-SiO2 granular type recording tape media. The crystallinity and c-axis orientation of Ru layer with Si/NiFe seed layers were improved than that without Si/NiFe seed layer deposited on the laminated FeCoB SULs. When the Ru is thicker than 8 nm, Δθ50 of the CoPtCr-SiO2 recording layer shows small value of about 6.5°. Furthermore, even though the Ru thickness was only 3 nm, the Δθ50 retained comparatively small value of 8.0°. Si/NiFe layer is effective as a seed layer for the Ru intermediate layer.

  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. Enhancement of magnetoresistance using CoFe/Ru/CoFe synthetic ferrimagnetic pinned layer in BiFeO{sub 3} based spin-valves

    SciTech Connect

    Naganuma, Hiroshi; Kubota, Miho; Inami, Nobuhito; Kawada, Yuki; Oogane, Mikihiko; Ando, Yasuo; Bae, In-Tae; Miyazaki, Takamichi; Mizukami, Shigemi; Han, X. F.

    2012-08-13

    SrTiO{sub 3} (100) sub/BiFeO{sub 3}/CoFe/Ru/CoFe/Cu/CoFe/Ta structure was prepared by a combination of chemical solution deposition and sputtering method, and followed by a systematical investigation for the structural, magnetic and magnetoresistance properties at room temperature (RT) as a function of CoFe and Ru thicknesses. It was revealed that introduction of synthetic CoFe/Ru/CoFe as a pinning layer increased the giant magentoresistance (MR) ratio to 8.3% at RT. This enhancement of MR ratio might be attributed to (i) the increase of pinning field, and (ii) suppression of the influence of the surface roughness of BiFeO{sub 3} by inserting the synthetic CoFe/Ru/CoFe layer.

  4. Marked enhancement of synthetic-antiferromagnetic coupling in subnanocrystalline FeCoB /Ru/FeCoB sputtered films

    NASA Astrophysics Data System (ADS)

    Hashimoto, Atsushi; Saito, Shin; Omori, Kazumi; Takashima, Hiroshi; Ueno, Tomonori; Takahashi, Migaku

    2006-07-01

    Extremely large flopping field and saturation field were realized in an FeCoB /Ru/FeCoB sputtered film by using subnanocrystalline (Fe65Co35)88B12 soft magnetic material with high saturation magnetization. Phenomenological analysis of synthetic-antiferromagnetic coupling revealed that the bilinear coupling energy induced in this film was three times larger than that in a Co91Zr4Nb5/Ru/Co91Zr4Nb5 film. This large bilinear coupling is thought to be the result of not only the suppression of ferromagnetic coupling due to the flat interface between the Ru and FeCoB layers but also the small Ru thickness for the first peak of 0.3nm caused by the Fe-rich soft magnetic material.

  5. Interlayer coupling in Ni80Fe20/Ru/Ni80Fe20 multilayer films: Ferromagnetic resonance experiments and theory

    NASA Astrophysics Data System (ADS)

    Liu, X. M.; Nguyen, Hoa T.; Ding, J.; Cottam, M. G.; Adeyeye, A. O.

    2014-08-01

    We present a systematic study of the static and dynamic magnetization behavior of interlayer-coupled Ni80Fe20(200Å)/Ru(tRu)/Ni80Fe20(100 Å) trilayers as a function of the Ru spacer layer thickness tRu. As tRu was varied in the range from 0 to 15.8 Å, we observe a strong antiferromagnetic (AFM) exchange coupling between the two ferromagnetic (FM) layers for tRu = 5 Å, which becomes weak for tRu = 10 Å. For tRu = 14.1 Å, the coupled magnetic system changes from AFM to FM ordering. Using broadband ferromagnetic resonance spectroscopy, we have probed the effects of the different coupling mechanisms on both the acoustic and optic magnetic modes. We found that the biquadratic exchange coupling has a negligible effect compared to Ruderman-Kittel-Kasuya-Yosida (RKKY) exchange coupling, while the uniaxial anisotropy at the Ni80Fe20/Ru interfaces also plays an important role in determining the behaviors of the modes. A mode anticrossing phenomenon is observed when the RKKY exchange interaction term is above a critical value. A theoretical framework developed is in very good agreement with our experimental results.

  6. Electronic, magnetic, and transport properties of the isotypic aluminides SmT2Al10 (T = Fe, Ru)

    NASA Astrophysics Data System (ADS)

    Peratheepan, P.; Strydom, A. M.

    2015-03-01

    We report the results of a comprehensive physical and magnetic property study of the new isotypic aluminides SmT2Al10 (T = Fe, Ru). These two compounds are members of a rare-earth based system which has become an exemplary case study of the interplay of magnetism and correlated electron phenomena. SmFe2Al10 and SmRu2Al10 are found to order in a putative antiferromagnetic spin arrangement at TN = 14.5 K and 12.5 K, respectively. Moreover, SmRu2Al10 shows a further phase transition at TSR = 5 K which is likely due to spin reorientation. The susceptibility of SmFe2Al10 points to a valence instability of the Sm ionic state at intermediate temperatures well above TN. Electronic and thermal transport confirm that SmFe2Al10 undergoes an antiferromagnetic superzone gap formation below TN, whereas SmRu2Al10 suffers a lattice anomaly driven magnetoelastic coupling at TN. Below TN, the physical properties of SmT2Al10 (T = Fe, Ru) are governed by magnons with an antiferromagnetic spin-wave spectrum that reveals spin-gap opening. Our findings in this work have exposed a new anomalous correlated compound in the RT2Al10 series. SmFe2Al10 has a magnetic ordered ground state in spite of an unstable valence at higher temperature. This is comparable with CeRu2Al10, which is a unique and controversial Kondo insulator that orders antiferromagnetic at TN = 27 K. Among the series of rare-earth RT2Al10 compounds, the presented Sm compounds are two new members with anomalously high magnetic ordering temperatures, and it is envisaged that together with the two very well studied compounds CeRu2Al10 and CeOs2Al10 our presented studies will enable a broader approach towards understanding the fascinating properties of this materials class.

  7. 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. PMID:21449466

  8. Magnetic properties of Fe substituted SrRuO3 thin films and SrRuO3/Fe2O3 superlattices

    NASA Astrophysics Data System (ADS)

    Chmaissem, Omar; Kolesnik, Stanislaw; Dabrowski, Bogdan; Choi, Yongseong; Haskel, Daniel

    2010-03-01

    In recent years, SrRuO3 thin films have received considerable interest because of their potential for use as electrodes in oxide-based spintronic applications. SrRuO3 bulk materials are known to exhibit good room temperature thermal and electrical conductivity, a stable perovskite crystal structure, and itinerant ferromagnetic properties at temperatures below 163 K. To the best of our knowledge, attempts to enhance the magnetic properties of SrRuO3 through chemical substitutions of transition metal elements (e.g., Fe, Co, Mn, Cu, Zn, Ti, Cr, etc) at the Ru site, all failed except for the case of Cr substitutions in which TC was successfully raised to 190 K. In this work, we will demonstrate the drastically different effects of Fe on the magnetic properties of SrRuO3 bulk materials and thin films. We will also show and discuss the magnetic properties of SrRuO3/Fe2O3 superlattices. Work supported by the NSF (DMR-0706610) and the DOE-Office of Science (DEAC-02-06CH11357).

  9. 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.

  10. 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.

  11. Giant Magnetic Anisotropy of Co, Ru, and Os Adatoms on MgO (001) Surface.

    PubMed

    Ou, Xuedong; Wang, Hongbo; Fan, Fengren; Li, Zhengwei; Wu, Hua

    2015-12-18

    Large magnetic anisotropy energy (MAE) is desirable and critical for nanoscale magnetic devices. Here, using ligand-field level diagrams and density functional calculations, we well explain the very recent discovery [I. G. Rau et al., Science 344, 988 (2014)] that an individual Co adatom on a MgO (001) surface has a large MAE of more than 60 meV. More importantly, we predict that a giant MAE up to 110 meV could be realized for Ru adatoms on MgO (001), and even more for the Os adatoms (208 meV). This is a joint effect of the special ligand field, orbital multiplet, and significant spin-orbit interaction, in the intermediate-spin state of the Ru or Os adatoms on top of the surface oxygens. The giant MAE could provide a route to atomic scale memory. PMID:26722941

  12. Giant Magnetic Anisotropy of Co, Ru, and Os Adatoms on MgO (001) Surface

    NASA Astrophysics Data System (ADS)

    Ou, Xuedong; Wang, Hongbo; Fan, Fengren; Li, Zhengwei; Wu, Hua

    2015-12-01

    Large magnetic anisotropy energy (MAE) is desirable and critical for nanoscale magnetic devices. Here, using ligand-field level diagrams and density functional calculations, we well explain the very recent discovery [I. G. Rau et al., Science 344, 988 (2014)] that an individual Co adatom on a MgO (001) surface has a large MAE of more than 60 meV. More importantly, we predict that a giant MAE up to 110 meV could be realized for Ru adatoms on MgO (001), and even more for the Os adatoms (208 meV). This is a joint effect of the special ligand field, orbital multiplet, and significant spin-orbit interaction, in the intermediate-spin state of the Ru or Os adatoms on top of the surface oxygens. The giant MAE could provide a route to atomic scale memory.

  13. Ionization and photofragmentation of Ru3(CO)12 and Os3(CO)12.

    PubMed

    Schalk, Oliver; Josefsson, Ida; Richter, Robert; Prince, Kevin C; Odelius, Michael; Mucke, Melanie

    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 M3(CO)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 M3(CO)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 Ru3(CO)12. PMID:26493905

  14. Ionization and photofragmentation of Ru3(CO)12 and Os3(CO)12

    NASA Astrophysics Data System (ADS)

    Schalk, Oliver; Josefsson, Ida; Richter, Robert; Prince, Kevin C.; Odelius, Michael; Mucke, Melanie

    2015-10-01

    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 M3(CO)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 M3(CO)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 Ru3(CO)12.

  15. X-ray and neutron diffraction study of nanocrystalline Ti-Ru-Fe-O compounds

    SciTech Connect

    Blouin, M.; Guay, D.; Huot, J.; Schulz, R.; Swainson, I.P.

    1998-11-01

    The effect of adding oxygen on the structure of nanocrystalline Ti-Ru-Fe compounds obtained by high-energy ball-milling has been studied by X-ray and neutron diffraction using a Rietveld refinement analysis. It is shown that oxygen atoms readily oxidize Ti to form various types of titanium oxides depending on the oxygen content. In each case, a simple cubic structure (cP2-CsCl) is also formed during milling but with a concentration higher than expected on the basis of various reaction schemes. Through a detailed analysis of the neutron and X-ray diffraction peaks, it is shown that the 1a site of the CsCl-type unit cell is depleted from Ti atoms by preferential substitution with Fe. At high oxygen concentration, the alloy is a multiphase material containing Ti{sub 2{minus}x}Ru{sub 1+y}Fe{sub 1+z}, Ti oxides, Ru, and Fe.

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

    PubMed

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

    2016-12-01

    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 O(I)) 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. PMID:27456502

  17. 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.

  18. 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.

  19. On the dynamical stability of ferromagnetic Ru and Os in the bct structure: a first-principles study

    NASA Astrophysics Data System (ADS)

    Cifuentes-Quintal, M. E.; de Coss, R.

    2015-08-01

    Recent theoretical studies have predicted magnetic states for Ru and Os in the body-centred tetragonal structure (bct) with ?. In this study, we present first principles calculations of the phonon dispersion for ferromagnetic Ru- and Os-bct along the epitaxial and uniaxial Bain paths, to evaluate their dynamical stability. The phonon dispersions were computed using the density functional perturbation theory, including the gradient corrections to the exchange-correlation functional within the plane-waves ultrasoft-pseudopotential approximation. The phonon dispersion for the local minimum in the Bain path with ? as well as the uniaxial and epitaxial strained structures are analysed. We find imaginary frequencies along different directions of the Brillouin zone, which indicates that both systems are dynamically unstable. Consequently, ferromagnetic Ru and Os in the bct with ? are not truly metastable phases.

  20. Pincer and diamine Ru and Os diphosphane complexes as efficient catalysts for the dehydrogenation of alcohols to ketones.

    PubMed

    Baratta, Walter; Bossi, Gianluca; Putignano, Elisabetta; Rigo, Pierluigi

    2011-03-14

    The ruthenium and osmium complexes [MCl(2)(diphosphane)(L)] (M=Ru, Os; L=bidentate amino ligand) and [MCl(CNN)(dppb)] (CNN=pincer ligand; dppb=1,4-bis-(diphenylphosphino)butane), containing the N−H moiety, have been found to catalyze the acceptorless dehydrogenation of alcohols in tBuOH and in the presence of KOtBu. The compounds trans-[MCl(2)(dppf)(en)] (M=Ru 7, Os 13; dppf=1,1'-bisdiphenylphosphino)ferrocene; en=ethylenediamine) display very high activity and different substrates, including cyclic and linear alcohols, are efficiently oxidized to ketones by using 0.8-0.04 mol % of catalyst. The effect of the base and the comparison of the catalytic activity of the Ru versus Os complexes are reported. The ruthenium complex 7 generally leads to a faster conversion into ketones with respect to the osmium complex 13, which displays better activity in the dehydrogenation of 5-en-3β-hydroxy steroids. The synthesis of new Ru and Os complexes [MCl(2)(PP)(L)] (PP=dppb, dppf; L=(±)-trans-1,2-diaminocyclohexane,2-(aminomethyl)pyridine, and 2-aminoethanol) of trans and cis configuration is also reported. PMID:21341330

  1. Regulation of charge delocalization in a heteronuclear Fe2 ru system by a stepwise photochromic process.

    PubMed

    Xu, Guang-Tao; Li, Bin; Wang, Jin-Yun; Zhang, Dao-Bin; Chen, Zhong-Ning

    2015-02-16

    Heteronuclear complexes FeCp2 -DTE-C≡C-Ru(dppe)2 Cl (1 o; dppe=1,2-bis(diphenylphosphino)ethane, Cp=cyclopentadienyl, DTE=dithienylethene) and FeCp2-DTE-C≡C-Ru(dppe)2-C≡C-DTE-FeCp2 (2 oo), with redox-active ferrocenyl and ruthenium centers separated by a photochromic DTE moiety, were prepared to achieve photoswitchable charge delocalization and Fe⋅⋅⋅Ru electronic communication. Upon UV-light irradiation of 2 oo, the Fe⋅⋅⋅Ru heterometallic electronic interaction is increasingly facilitated with stepwise photocyclization, 2 oo→2 co→2 cc; this is ascribed to the gradual increase in π-conjugated systems. The near-infrared absorptions in mixed-valence species [2 oo](+) /[2 co](+) /[2 cc](+) are gradually intensified following the conversion of [2 oo](+) →[2 co](+) →[2 cc](+) , which demonstrates that the extent of charge delocalization shows progressive enhancement with stepwise photocyclization. As revealed by electrochemical, spectroscopic, and theoretical studies, complex 2 exhibits nine switchable states through stepwise photochromic and reversible redox processes. PMID:25640650

  2. Evaluation of Fe and Ru Pincer-Type Complexes as Catalysts for the Racemization of Secondary Benzylic Alcohols.

    PubMed

    Bornschein, Christoph; Gustafson, Karl P J; Verho, Oscar; Beller, Matthias; Bäckvall, Jan-E

    2016-08-01

    Fe and Ru pincer-type catalysts are used for the racemization of benzylic alcohols. Racemization with the Fe catalyst was achieved within 30 minutes under mild reaction conditions, with a catalyst loading as low as 2 mol %. This reaction constitutes the first example of an iron-catalyzed racemization of an alcohol. The efficiency for racemization of the Fe catalyst and its Ru analogue was evaluated for a wide range of sec-benzylic alcohols. The commercially available Ru complex proved to be highly robust and even tolerated the presence of water in the reaction mixture. PMID:27311070

  3. Ru/FeCoB double layered film with high in-plane magnetic anisotropy field of 500 Oe

    NASA Astrophysics Data System (ADS)

    Hirata, Ken-ichiro; Hashimoto, Atsuto; Matsuu, Toshimitsu; Nakagawa, Shigeki

    2009-04-01

    FeCoB layers prepared on Ru underlayer possess a high saturation magnetization Ms and a high in-plane magnetic anisotropy filed Hk. Effects of preparation conditions were investigated. Low Ar gas pressure condition and thicker film thickness were effective to attain distortion of FeCo crystallite. As the crystallinity of Ru underlayer became higher, higher Hk was induced. The accumulation of anisotropic stress in the film caused by the oblique incidences of depositing atoms with high energy seems to be one of the important effects to attain high anisotropy field. It was succeeded to prepare the Ru/FeCoB film with high Hk of 500 Oe.

  4. Superlattice CoCrPt/Ru/CoFe structure fabricated by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Hu, X. F.; Liang, Q.; Li, H. Q.; He, X. X.; Wang, Xiaoru; Zhang, W.

    2006-04-01

    The synthetic antiferromagnets (SAF) have been used in spin-valve sensor in data storage industry [1]. We report a new hard/Ru/soft sandwich structure (SHBL) fabricated by pulsed lased deposition to replace current single layer structure for information recording application. SHBL consists of two magnetic layers separated by thin nonmagnetic layers, typically with Ru layers of 0.7-1.2 nm, through which antiferromagnetic coupling is induced. Varying the relative thickness of the magnetic layers, the spacer layers, and the type of magnetic materials can alter magnetic properties of CoCrPt/Ru/CoFe superlattice. The coercivity Hc and grain size of magnetic layer is also dependent on the laser fluence. High laser fluence results in both small grain size and high Hc. The observed phenomena are related to high quenching and deposition rates during PLD at high fluence, resulting in more pronounced phase segregation.

  5. σ-Aromaticity in polyhydride complexes of Ru, Ir, Os, and Pt.

    PubMed

    Jimenez-Izal, Elisa; Alexandrova, Anastassia N

    2016-04-28

    Transition-metal hydrides represent a unique class of compounds, which are essential for catalysis, organic synthesis, and hydrogen storage. In this work we study IrH5(PPh3)2, (RuH5(P(i)Pr3)2)(-), (OsH5(P(i)Pr3)2)(-), and OsH4(PPhMe2)3 polyhydride complexes, inspired by the recent discovery of the σ-aromatic PtZnH5(-) cluster anion. The distinctive feature of these molecules is that, like in the PtZnH5(-) cluster, the metal is five-fold coordinated in-plane, and holds additional ligands at the axial positions. This work shows that the unusual coordination in these compounds indeed can be explained by σ-aromaticity in the pentagonal arrangement, stabilized by the atomic orbitals on the metal. Based on this newly elucidated bonding principle, we additionally propose a new family of polyhydrides that display a uniquely high coordination. We also report the first indications of how aromaticity may impact the reactivity of these molecules. PMID:26414992

  6. 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.

  7. Ru/FeCoB crystalline soft magnetic underlayers with high anisotropy field for CoPtCr-SiO2 granular perpendicular magnetic recording media

    NASA Astrophysics Data System (ADS)

    Matsuu, Toshimitsu; Hirata, Ken-ichiro; Hashimoto, Atsuto; Matsunuma, Satoshi; Inoue, Tetsutaro; Doi, Tsugihiro; Nakagawa, Shigeki

    2009-04-01

    Ru/FeCoB/Ru/CoPtCr-SiO2 films were fabricated as perpendicular magnetic recording media with crystalline soft magnetic underlayer (SUL). Ru/FeCoB layers possessed high in-plane anisotropy field Hk of 400 Oe and a bcc-FeCo (110) orientation. Crystalline orientation of the FeCoB in the SUL affected on a crystallite growth of a Ru intermediate layer deposited on it and on crystallite orientation of the CoPtCr-SiO2 film deposited on the Ru intermediate layer. Ru/CoPtCr-SiO2 films without Ru/FeCoB SULs exhibited a random orientation of Ru crystallites and the in-plane magnetic anisotropy. On the other hand, Ru/CoPtCr-SiO2 films deposited on the Ru/FeCoB SULs exhibited (001) preferential orientations of the CoPtCr as well as the Ru intermediate layer and possessed perpendicular magnetic anisotropy. It was confirmed that the improvement of a bcc-FeCo (110) orientation in the SUL was effective to the improvement of a hcp-Ru (001) orientation. At the media for an intermediate layer thickness of 5 nm, the similar magnetic properties as that of 30 nm were obtained. It indicated that the application of a crystalline SUL promoted the reduction in the intermediate layer thickness.

  8. Magnetization reversal and negative volume thermal expansion in Fe doped Ca2RuO4

    NASA Astrophysics Data System (ADS)

    Qi, T. F.; Yuan, S. J.; Ye, F.; Chi, S.; Terzic, J.; Zhang, H.; Zhao, Z.; Liu, X.; Parkin, S.; Mao, W. L.; Cao, G.

    We report structural, magnetic, transport and thermal properties of single-crystal Ca2Ru1-xFexO4 (0 <= x <= 0.2) as functions of pressure, magnetic field and temperature. The central findings of this work are a pronounced magnetization reversal and a negative thermal expansion that are induced by Fe doping. Our results including neutron diffraction data suggest that the magnetization reversal is primarily a result of different temperature dependences of two antiparallel, competing Ru and Fe sublattices and that the negative thermal expansion is achieved via magnetic and metal-insulator transitions. We will present and discuss our results with comparison drawn with relevant systems. This work was supported by the NSF via Grant No. DMR-1265162.

  9. 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.

  10. 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.

  11. Strain-induced topological transition in SrRu2O6 and CaOs2O6

    DOE PAGESBeta

    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 waymore » to realize a topological insulating state in a complex oxide, which has not been experimentally demonstrated so far.« less

  12. Magnetic coupling in asymmetric FeCoV/Ru/FeNi trilayers

    NASA Astrophysics Data System (ADS)

    Wei, Yajun; Jana, Somnath; Brucas, Rimantas; Pogoryelov, Yevgen; Ranjbar, Mojtaba; Dumas, Randy K.; Warnicke, Peter; Åkerman, Johan; Arena, Dario A.; Karis, Olof; Svedlindh, Peter

    2014-05-01

    We have investigated the magnetic anisotropy and interlayer coupling in trilayer films of permendur(100 Å)/Ru/permalloy(100 Å), with the thickness of the Ru spacer varying from 0 to 200 Å. While the permendur/permalloy sample exhibits a small in-plane uniaxial magnetic anisotropy with Hu = 27 Oe, all trilayers are magnetically isotropic in-plane. Results from hysteresis loop and ferromagnetic resonance measurements were fitted to a micromagnetic model, with the results indicating that all the films are ferromagnetically coupled except the one with 10 Å Ru spacer, which shows antiferromagnetic coupling. The trilayers with Ru spacer layer thickness larger than 20 Å exhibit only very weak ferromagnetic coupling.

  13. Magnetism and electrical transport in Fe 0.9TM 0.1Si, TM=Co, Rh, Ru

    NASA Astrophysics Data System (ADS)

    Paschen, S.; Pushin, D.; Ott, H. R.; Young, D. P.; Fisk, Z.

    1999-01-01

    Our comparative study of magnetic and transport properties of Fe 0.9Co 0.1Si, Fe 0.9Rh 0.1Si, and Fe 0.9Ru 0.1Si indicates that the ferromagnetism previously observed in Fe 0.9Co 0.1Si is not due to localized magnetic moments residing on the Co atoms. It is rather the metallicity of the system which provides the formation of a ferromagnetic state.

  14. 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

    2015-12-01

    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. PMID:26565747

  15. Spin-orbit torque in Cr/CoFeAl/MgO and Ru/CoFeAl/MgO epitaxial magnetic heterostructures

    NASA Astrophysics Data System (ADS)

    Wen, Zhenchao; Kim, Junyeon; Sukegawa, Hiroaki; Hayashi, Masamitsu; Mitani, Seiji

    2016-05-01

    We study the spin-orbit torque (SOT) effective fields in Cr/CoFeAl/MgO and Ru/CoFeAl/MgO magnetic heterostructures using the adiabatic harmonic Hall measurement. High-quality perpendicular-magnetic-anisotropy CoFeAl layers were grown on Cr and Ru layers. The magnitudes of the SOT effective fields were found to significantly depend on the underlayer material (Cr or Ru) as well as their thicknesses. The damping-like longitudinal effective field (ΔHL) increases with increasing underlayer thickness for all heterostructures. In contrast, the field-like transverse effective field (ΔHT) increases with increasing Ru thickness while it is almost constant or slightly decreases with increasing Cr thickness. The sign of ΔHL observed in the Cr-underlayer devices is opposite from that in the Ru-underlayer devices while ΔHT shows the same sign with a small magnitude. The opposite directions of ΔHL indicate that the signs of spin Hall angle in Cr and Ru are opposite, which are in good agreement with theoretical predictions. These results show sizable contribution from SOT even for elements with small spin orbit coupling such as 3d Cr and 4d Ru.

  16. 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.

  17. 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.

  18. Moessbauer spectroscopic investigations of bimetallic FeCo, FeNi, and FeRu model catalysts supported on magnesium hydroxide carbonate

    SciTech Connect

    Nagorny, K.; Bubert, S.

    1987-11-01

    FeCo, FeNi, and FeRu alloys supported on basic magnesium carbonate have been prepared by precipitation from salt solutions at 340 K onto the support using ion exchange and have been subsequently annealed for 20 h under argon. The reduction, oxidation, and sintering behavior of the samples under H/sub 2/ or CO exposure has been investigated at 723 K by means of Moessbauer spectroscopy. The comparison of the resonance absorption areas of the spectra taken at 4 and 295 K allowed the calculation of the Debye temperatures and Debye-Waller factors of the different components. From the Debye-Waller factors the relative fractions could be extrapolated to the conditions at 0 K. The kinetics of the H/sub 2/ exposure showed an increase in the reduction velocity as well as in the degree of reduction in the sequence FeCo < FeNi < FeRu. Above a critical particle diameter a phase separation occurred because of the segregation of an iron-rich phase at the surface of the alloy particles. The kinetics of the CO exposure demonstrated that with FeCo clusters iron(III) surface oxide layers form, whereas with FeNi clusters iron(II) surface oxide layers are generated. FeCo clusters with a cobalt content of 25% form only unstable surface carbides, whereas clusters with a cobalt content of about 5% form stable bulk carbides. The velocity of carbide formation increases with decreasing particle size. Based on the present data a model is proposed which explains the behavior of FeMe/magnesium hydroxide carbonates catalysts in H/sub 2/ and CO atmospheres.

  19. Ru/FeCoB double layered film with high in-plane magnetic anisotropy field of 500 Oe

    SciTech Connect

    Hirata, Ken-ichiro; Hashimoto, Atsuto; Matsuu, Toshimitsu; Nakagawa, Shigeki

    2009-04-01

    FeCoB layers prepared on Ru underlayer possess a high saturation magnetization M{sub s} and a high in-plane magnetic anisotropy filed H{sub k}. Effects of preparation conditions were investigated. Low Ar gas pressure condition and thicker film thickness were effective to attain distortion of FeCo crystallite. As the crystallinity of Ru underlayer became higher, higher H{sub k} was induced. The accumulation of anisotropic stress in the film caused by the oblique incidences of depositing atoms with high energy seems to be one of the important effects to attain high anisotropy field. It was succeeded to prepare the Ru/FeCoB film with high H{sub k} of 500 Oe.

  20. 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.

  1. Ru(bpy)[sub 2][sup 2+] and Os(bpy)[sub 2][sup 2+] complexes of large polyaza cavity-shaped ligands

    SciTech Connect

    Thummel, R.P.; Williamson, D.; Hery, C. )

    1993-04-28

    The Friedlaender condensation of cyclic 1,2-diketones with 2-amino-5,6-dihydro-1,10-phenanthroline-3-carboxaldehyde provides a series of hexaaza cavity-shaped molecules 2a-c. Reaction with Ru(bpy)[sub 2]Cl[sub 2] (where bpy = 2,2[prime]-bipyridine) incorporates Ru(II) into a distal bidentate site. For ligands which are significantly nonplanar, a second Ru(II) or Os(II) nucleus can similarly be incorporated into the remaining distal site. The use of bpy-d[sub 8] as an auxilliary ligand simplifies the NMR spectra of the complexes and permits a detailed conformational analysis which is reinforced by an X-ray determination of the dinuclear complex [(bpy)[sub 2]Ru(2c)Ru(bpy)[sub 2

  2. Gibbs free energies of formation of RuO 2, IrO 2, and OsO 2: A high-temperature electrochemical and calorimetric study

    NASA Astrophysics Data System (ADS)

    O'Neill, Hugh St. C.; Nell, Johan

    1997-12-01

    The Gibbs free energies of formation of RuO 2, OsO 2 and IrO 2 have been determined by measuring the chemical potentials of oxygen (μO 2) defined by the reactions M + O 2 = MO 2, where M = Ru, Os. or Ir, using an electrochemical method with calcia-stabilized zirconia (CSZ) solid electrolytes. Measurements were attempted in the temperature ranges from ˜870 K to 1620, 1270, and 1415 K for the Ru, Os, and Ir equilibria, respectively, but inspection of the results reveals that equilibrium could not be established below ˜930 K for all three reactions. For Ru + RuO 2, the highest temperature data (above 1520 K) may be systematically affected by the onset of significant electronic conduction in the CSZ electrolyte, while the attempted measurements of the Os + OsO 2 equilibrium above 1190 K are obscured by the disproportionation of OsO 2 to gaseous Os oxides. The high temperature heat capacities at constant pressure ( Cp) of RuO 2 and IrO 2 were determined from 370 to 1070 K by differential scanning calorimetry. These data were combined with heat content measurements and low-temperature heat capacities from the literature, and fitted to an extended Maier-Kelley equation. The calorimetric data for RuO 2 and IrO 2, together with assessed data for Ru, Os, and Ir metals and estimated data for OsO 2, were used in a third law analysis of the electrochemical measurements. The values of μO 2 of the three equilibria were smoothed and filtered by the third-law analysis to yield the following equations which can be extrapolated to lower and higher temperatures as indicated: μO 2 ( Ru + RuO 2) = -324563 + 344.151 T-22.1155 T ln T (700 ⩽ T ⩽ 1800) μO 2 ( Os + OsO 2) = -300399 + 307.639 T-17.4819 T ln T (700 ⩽ T ⩽ 1500) μO 2 ( Ir + IrO 2) = -256518 + 295.854 T-15.2368 T ln T (700 ⩽ T ⩽ 1500) where μO 2 is in J mol -1, T is in K, the reference pressure for O 2 is 1 bar (10 5 Pa), and estimated accuracies are approximately 200 to 400 J mol -1. For Ru + RuO 2, the drift

  3. 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. PMID:24869778

  4. Effective band structure of Ru-doped BaFe2As2

    NASA Astrophysics Data System (ADS)

    Reticcioli, M.; Profeta, G.; Franchini, C.; Continenza, A.

    2016-02-01

    The use of lattice cells in real space that are arbitrarily larger than the primitive one, is nowadays more and more often required by ab initio calculations to study disorder, vacancy or doping effects in real materials. This leads, however, to complex band structures which are hard to interpret. Therefore an unfolding procedure is sought for in order to obtain useful data, directly comparable with experimental results, such as angle-resolved photoemission spectroscopy measurements. Here, we present an extension of the unfolding procedure recently implemented in the VASP code, which includes a projection scheme that leads to a full reconstruction of the primitive space. As a test case, we apply this newly implemented scheme to the Ru-doped BaFe2As2 superconducting compound. The results provide a clear description of the effective electronic band structure in the conventional Brillouin zone, highlighting the crucial role played by doping in this compound.

  5. Ordered vs. disordered perovskites; structural studies of Fe-doped SrIrO{sub 3} and SrRuO{sub 3}

    SciTech Connect

    Qasim, Ilyas; Blanchard, Peter E.R.; Liu, Samuel; Tang, Chunguang; Kennedy, Brendan J.; Avdeev, Maxim; Kimpton, Justin A.

    2013-10-15

    The structures of the two Fe containing perovskites Sr{sub 2}IrFeO{sub 6} and SrRu{sub 0.5}Fe{sub 0.5}O{sub 3} have been established using a combination of synchrotron and neutron diffraction methods. Sr{sub 2}IrFeO{sub 6} and SrRu{sub 0.5}Fe{sub 0.5}O{sub 3} are shown to be monoclinic I2/m and tetragonal I4/mcm respectively The former exhibits a rock-salt like ordering of the Fe and Ir cations and displays a sequence of phase transitions associated with the loss of the octahedral tilts upon heating; 12/m→I4/m→Fm3{sup ¯}m. The Fe and Ru cations are disordered in SrRu{sub 0.5}Fe{sub 0.5}O{sub 3} and this shows a single structural phase transition upon heating due to the loss of the in-phase tilts, viz. I4/mcm→Pm3{sup ¯}m. In both cases XANES measurements show partial oxidation of the Fe{sup 3+} to Fe{sup 4+}. The difference in the structures between the two is remarkable given the similar size of Ir{sup 5+} and Ru{sup 5+}, and this is reflected in their magnetic properties. - Graphical abstract: Sr{sub 2}IrFeO{sub 6} and SrRu{sub 0.5}Fe{sub 0.5}O{sub 3} are shown, using a combination of synchrotron and neutron diffraction, to be monoclinic I2/m with cation ordering and tetragonal I4/mcm with disordered Fe and Ir, respectively. Both undergo phase transitions upon heating due to the loss of the octahedral tilts. Display Omitted - Highlights: • Sr{sub 2}IrFeO{sub 6} shown to be monoclinic and shows the transitions upon heating I2/m→I4/m→ Fm3{sup ¯}m. • SrRu{sub 0.5}Fe{sub 0.5}O{sub 3} is tetragonal and shows a single I4/mcm→Pm3m transition upon heating. • The Fe and Ru cations are disordered in SrRu{sub 0.5}Fe{sub 0.5}O{sub 3} but ordered in Sr{sub 2}FeIrO{sub 6}. • XANES measurements show partial oxidation of the Fe{sup 3+} to Fe{sup 4+}.

  6. 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.

  7. Large spin pumping effect in antisymmetric precession of Ni79Fe21/Ru/Ni79Fe21

    NASA Astrophysics Data System (ADS)

    Yang, H.; Li, Y.; Bailey, W. E.

    2016-06-01

    In magnetic trilayer structures, a contribution to the Gilbert damping of ferromagnetic resonance arises from spin currents pumped from one layer to another. This contribution has been demonstrated for layers with weakly coupled, separated resonances, where magnetization dynamics are excited predominantly in one layer and the other layer acts as a spin sink. Here, we show that trilayer structures in which magnetizations are excited simultaneously, antisymmetrically, show a spin-pumping effect roughly twice as large. The antisymmetric (optical) mode of antiferromagnetically coupled Ni79Fe21(8 nm)/Ru/Ni79Fe21(8 nm) trilayers shows a Gilbert damping constant greater than that of the symmetric (acoustic) mode by an amount as large as the intrinsic damping of Py ( Δα≃0.006 ). The effect is shown equally in field-normal and field-parallel to film plane geometries over 3-25 GHz. The results confirm a prediction of the spin pumping model and have implications for the use of synthetic antiferromagnets (SAF)-structures in GHz devices.

  8. Anisotropic elastic and vibrational properties of Ru2B3 and Os2B3: a first-principles investigation

    NASA Astrophysics Data System (ADS)

    Ozisik, Haci; Deligoz, Engin; Surucu, Gokhan; Bogaz Ozisik, Havva

    2016-07-01

    The structural, mechanical and lattice dynamical properties of Ru2B3 and Os2B3 have been investigated by using a first-principles method based on the density functional theory within the generalized gradient approximation. The single crystal elastic constants are numerically estimated using strain–stress approach. The polycrystalline aggregate elastic parameters are calculated from the single elastic constants via the Voigt–Reuss–Hill approximations. Subsequently, the ductility and brittleness are characterized with the estimation from Pugh’s rule (B/G) and Cauchy pressure. Additionally, the Debye temperature is calculated from the average elastic wave velocity obtained from bulk and shear moduli. The calculated parameters are consistent with the previous experimental and theoretical data. These borides are both mechanically and dynamically stable in the considered structure.

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

    DOE PAGESBeta

    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.; et al

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

    NASA Astrophysics Data System (ADS)

    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.

    2015-02-01

    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" Pc h as previously proposed by Kanchanavatee et al. [Phys. Rev. B 84, 245122 (2011), 10.1103/PhysRevB.84.245122] based on bulk measurements on polycrystalline samples. Notably, 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 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 Pc h in URu2 -xFexSi2 as a function of x . The resulting temperature (T )-chemical pressure (Pc h) phase diagram for URu2 -xFexSi2 is in agreement with the established temperature (T )-external pressure (P ) phase diagram of URu2Si2 .

  11. Chemical pressure tuning of URu2 Si2 via isoelectronic substitution of Ru with Fe

    NASA Astrophysics Data System (ADS)

    Janoschek, Marc; Das, Pinaki; Kanchanavatee, Noravee; Helton, Joel S.; Huang, Kevin; Baumbach, Ryan E.; Bauer, Eric D.; Zhao, Yang; Ratcliff, William; White, Ben D.; Maple, M. Brian; Lynn, Jeff W.

    2015-03-01

    We have used specific heat and neutron diffraction measurements on single crystals of URu2-xFexSi2 for Fe concentrations x <= 0.7 to establish that isoelectronic substitution of Ru with Fe acts as ``chemical pressure'' Pch. Neutron diffraction reveals a sharp increase of the uranium magnetic moment at x = 0 . 1 , reminiscent of the ``hidden order'' (HO) to large moment antiferromagnetic (LMAFM) phase transition in URu2Si2. Using the unit cell volume, and the isothermal compressibility κT for URu2Si2, we determine Pch as function of x. The resulting temperature T-chemical pressure Pch phase diagram for URu2-xFexSi2 is in good agreement with the established temperature T-external pressure P phase diagram of URu2Si2. Thus, URu2-xFexSi2 provides a new opportunity to study the close relationship between the HO and LMAFM phases with methods that cannot be used under pressure, and may shed some new light on the on the elusive order parameter of the HO.

  12. Structural and magnetic properties of X12Y (X, Y=Fe, Co, Ni, Ru, Rh, Pd, and Pt) nanoalloys

    NASA Astrophysics Data System (ADS)

    Aguilera-Granja, F.; Longo, R. C.; Gallego, L. J.; Vega, A.

    2010-05-01

    We perform extensive ab initio density-functional calculations to investigate the structures and magnetic moments of the binary clusters X12Y (X, Y=Fe, Co, Ni, Ru, Rh, Pd, and Pt). Although all the binary clusters Fe12Y, Co12Y, Ru12Y, and Rh12Y, plus Ni12Y (Y=Rh, Pd, and Pt) and Pt12Y (Y=Ru, Rh, and Pd), retain, with more or less distortions, the structures of the corresponding pure X13 clusters, the remaining binary clusters (i.e., a significant number of 12 of all the 42 cases) adopt geometries different from those of the corresponding pure clusters. Independent of the peculiarities of each family of binary clusters, the binding energies of all the binary clusters X12Ru are bigger than those of the pure X13 clusters, while the binding energies of all the binary clusters X12Pd are smaller. The clusters investigated exhibit a variety of magnetic behaviors. In the case of Ni12Rh, we predict a remarkable magnetic cooperative phenomenon that can be attributed to electronic effects associated to the chemical environment through Ni-Rh hybridization.

  13. 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.

  14. Structure and magnetic properties of FeRuGaSi multilayer thin films

    NASA Astrophysics Data System (ADS)

    Jagielinski, T. M.; Zeltser, A. M.; Brucker, C. F.

    1991-04-01

    The structure and magnetic properties of FeRuGaSi thin films used in very-high-frequency (150 MHz) recording head has been studied. The best soft magnetic properties, viz., coercivity of 0.2-0.3 Oe, permeability of 2000 at 1 MHz and 400-500 at 150 MHz, and magnetostriction of less than 10-6, were obtained after annealing at 450-500 °C. This magnetic behavior was attributed to the phase transformations and the increase in the grain size of the films occurring during the annealing process. Transmission electron diffraction revealed that B2 and/or DO3 ordered phases were formed in the films depending on the annealing temperature. However, good soft magnetic properties were associated with the formation of the B2 phase with low crystal anisotropy and saturation magnetostriction. These results are somewhat in contrast to what has been observed in Sendust, where magnetic softness is usually attributed to the formation of the DO3 phase.

  15. Relationship between the structure and soft magnetic properties of FeRuGaSi films

    NASA Astrophysics Data System (ADS)

    Zeltser, A. M.; Jagielinski, T. M.

    1991-11-01

    The effect of annealing on the structure and magnetic properties (coercivity, saturation magnetostriction, and initial permeability) of (FeRu)x(GaSi) films (x=2.5, 3.4, and 3.9) sputtered on MnNi-oxide and Li-silicate glass-ceramic substrates has been investigated. It is found that the best combination of soft magnetic properties (e.g., coercivity ≊0.3 Oe, permeability ≊1800 at 10 MHz, and magnetostriction < 1 × 10-6) is generally obtained after annealing between 450 and 500 °C independent of film composition, and subsequently deteriorate at higher annealing temperatures. This magnetic behavior is correlated with the crystal structure, grain size, and texture of the films as revealed by transmission electron microscopy and x-ray diffraction. It is found that after annealing, all films exhibit best soft magnetic properties when they consist of mostly the B2 phase and their magnetic softness decreases with the formation of the DO3 phase.

  16. 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

  17. 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.

  18. Exotic Magnetism on the Quasi-fcc Lattices of the d3 Double Perovskites La2NaB'O6 (B'=Ru, Os)

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

    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 4d3 material.

  19. 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. PMID:25732233

  20. Low Temperature Hysteretic Behavior of the Interpenetrating 3-D Network Structured [Ru2(O2CMe)4]3[Fe(CN)6] Magnet

    SciTech Connect

    Haque, F.; Del barco, Enrique; Fishman, Randy Scott; Miller, Joel S.

    2013-01-01

    The low temperature hysteretic behavior between 40 mK and 4.8 K was obtained for [Ru2(O2CMe)4]3[Fe(CN)6]. The unusual constricted hysteretic behavior reported for isomorphous [Ru2(O2CMe)4]3[Cr(CN)6] was not observed. Instead, the [Ru2(O2CMe)4]3-[Fe(CN)6] exhibits a single hysteresis loop and a temperature dependence of the coercivity atypical for a ferrimagnetic ordering transition. The coercive field, constant below ~0.3 K (1.06 kOe), shows a rapid initial decrease below 1 K, to continue decreasing at a slower rate up to at least 4.8 K. In contrast to [Ru2(O2CMe)4]3[Cr(CN)6] which has antiferromagnetic coupling of the ferrimagnetic lattices, due to the reduced spin on the [FeIII(CN)6]3-, [Ru2(O2CMe)4]3[Fe(CN)6] ferromagnetic coupling of the ferrimagnetic lattices dominates for [Ru2(O2CMe)4]3[Fe(CN)6].

  1. Contrasting effect of La substitution on the magnetic moment direction in the Kondo semiconductors Ce T2Al10 (T =Ru ,Os )

    NASA Astrophysics Data System (ADS)

    Adroja, D. T.; Hillier, A. D.; Ritter, C.; Bhattacharyya, A.; Khalyavin, D. D.; Strydom, A. M.; Peratheepan, P.; Fâk, B.; Koza, M. M.; Kawabata, J.; Yamada, Y.; Okada, Y.; Muro, Y.; Takabatake, T.; Taylor, J. W.

    2015-09-01

    The opening of a spin gap in the orthorhombic compounds Ce T2Al10 (T =Ru andOs ) is followed by antiferromagnetic ordering at TN=27 and 28.5 K, respectively, with a small ordered moment (0.29 -0.34 μB ) along the c axis, which is not an easy axis of the crystal field (CEF). In order to investigate how the moment direction and the spin gap energy change with La doping in Ce1 -xLaxT2Al10 (T = Ru and Os) and also to understand the microscopic nature of the magnetic ground state, we here report on magnetic, transport, and thermal properties, neutron diffraction (ND), and inelastic neutron scattering (INS) investigations on these compounds. Our INS study reveals the persistence of spin gaps of 7 and 10 meV in the 10% La-doped T = Ru and Os compounds, respectively. More interestingly our ND study shows a very small ordered moment of 0.18 μB along the b axis in Ce0.9La0.1Ru2Al10 , however a moment of 0.23 μB still along the c axis in Ce0.9La0.1Os2Al10 . This contrasting behavior can be explained by a different degree of hybridization in CeRu2Al10 and CeOs2Al10 , being stronger in the latter than in the former. Muon spin rotation (μ SR ) studies on Ce1 -xLaxRu2Al10 (x =0 , 0.3, 0.5, and 0.7), reveal the presence of coherent frequency oscillations indicating a long-range magnetically ordered ground state for x =0 to 0.5, but an almost temperature independent Kubo-Toyabe response between 45 mK and 4 K for x =0.7 . We compare the results of the present investigations with those reported on the electron and hole doping in Ce T2Al10 .

  2. Photocatalytic Hydroxylation of Benzene by Dioxygen to Phenol with a Cyano-Bridged Complex Containing Fe(II) and Ru(II) Incorporated in Mesoporous Silica-Alumina.

    PubMed

    Aratani, Yusuke; Oyama, Kohei; Suenobu, Tomoyoshi; Yamada, Yusuke; Fukuzumi, Shunichi

    2016-06-20

    Photocatalytic hydroxylation of benzene to phenol was achieved by using O2 as an oxidant as well as an oxygen source with a cyano-bridged polynuclear metal complex containing Fe(II) and Ru(II) incorporated in mesoporous silica-alumina ([Fe(H2O)3]2[Ru(CN)6]@sAl-MCM-41). An apparent turnover number (TON) of phenol production per the monomer unit of [Fe(H2O)3]2[Ru(CN)6] was 41 for 59 h. The cyano-bridged polynuclear metal complex, [Fe(H2O)3]2[Ru(CN)6], exhibited catalytic activity for thermal hydroxylation of benzene by H2O2 in acetonitrile (MeCN), where the apparent TON of phenol production reached 393 for 60 h. The apparent TON increased to 2500 for 114 h by incorporating [Fe(H2O)3]2[Ru(CN)6] in sAl-MCM-41. Additionally, [Fe(H2O)3]2[Ru(CN)6] acts as a water oxidation catalyst by using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) and Na2S2O8 as a photosensitizer and a sacrificial electron acceptor as evidenced by (18)O-isotope labeling experiments. Photoirradiation of an O2-saturated MeCN solution containing [Fe(H2O)3]2[Ru(CN)6]@sAl-MCM-41 and scandium ion provided H2O2 formation, where photoexcited [Ru(CN)6](4-) moiety reduces O2 as indicated by laser flash photolysis measurements. Thus, hydroxylation of benzene to phenol using molecular oxygen photocatalyzed by [Fe(H2O)3]2[Ru(CN)6] occurred via a two-step route; (1) molecular oxygen was photocatalytically reduced to peroxide by using water as an electron donor, and then (2) peroxide thus formed is used as an oxidant for hydroxylation of benzene. PMID:27265780

  3. 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.

  4. 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.

  5. 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.

  6. 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}.

  7. 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. PMID:11284333

  8. 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.

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

    NASA Astrophysics Data System (ADS)

    Aczel, Adam

    2015-03-01

    B-site ordered double perovskites with quantum spins S = 1/2 (d1) and S = 1 (d2) on the B' site have attracted a great deal of recent interest, due to the possibility of studying 4d and 5d magnetism combined with magnetic frustration on the face-centered-cubic (FCC) lattice. There has been less focus on d3 systems, as they are generally expected to behave more classically and yield simple, commensurate magnetic ground states. In contrast, we find evidence for long-range and short-range (ξ = 70 Å at 4 K) incommensurate magnetic order on the quasi-FCC lattices of the monoclinic double perovskites La2NaRuO6andLa2NaOsO6 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. Furthermore, in the Ru system with long-range order, inelastic neutron scattering 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 4d3 material.

  10. Photochemical Hydrogen Generation Initiated by Oxidative Quenching of the Excited Ru(bpy)3 (2+) * by a Bio-Inspired [2Fe2S] Complex.

    PubMed

    Na, Yong; Wei, Peicheng; Zhou, Li

    2016-07-18

    A diiron dithiolate complex 1 containing 1,8-naphthalic anhydride bridge was prepared, which possessed the lowest reduction potential for the synthetic diiron complexes modeled on the active site of [FeFe] hydrogenase reported so far. For the first time, oxidative quenching of the excited Ru(bpy)3 (2+) * through electron transfer to a bio-inspired [2Fe2S] complex was corroborated. Hydrogen evolution, driven by visible light, was successfully observed for a three-component system, consisting of Ru(bpy)3 (2+) , complex 1, and EDTA as electron donor in aqueous/organic media. These results provide a basis and also opportunity to develop a photo water splitting system employing Fe-based catalysts without sacrificial electron donors. PMID:26879325

  11. 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.

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

    DOE PAGESBeta

    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 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

  13. Inverse magnetocaloric effect in Ce(Fe{sub 0.96}Ru{sub 0.04}){sub 2}: Effect of fast neutron irradiation

    SciTech Connect

    Dube, V.; Mishra, P. K.; Prajapat, C. L.; Singh, M. R.; Ravikumar, G.; Rajarajan, A. K.; Sastry, P. U.; Thakare, S. V.

    2013-02-05

    We have shown the effect of fast neutron irradiation on the magnetic phase transition and magnetocaloric effect (MCE) in a doped Ce(Fe{sub 0.96}Ru{sub 0.04}){sub 2}, intermettalic. We show that this leads to suppression of MCE and a to a disordered ferromagnetic phase.

  14. Investigation of the binding of cis/trans-[MCl4(1H-indazole)(NO)](-) (M = Ru, Os) complexes to human serum albumin.

    PubMed

    Dömötör, Orsolya; Rathgeb, Anna; Kuhn, Paul-Steffen; Popović-Bijelić, Ana; Bačić, Goran; Enyedy, Eva Anna; Arion, Vladimir B

    2016-06-01

    Overall binding affinity of sodium or indazolium cis/trans-[MCl4(1H-indazole)(NO)] (M = Ru, Os) complexes towards human serum albumin (HSA) and high molecular mass components of the blood serum was monitored by ultrafiltration. HSA was found to be mainly responsible for the binding of the studied ruthenium and osmium complexes. In other words, this protein can provide a depot for the compounds and can affect their biodistribution and transport processes. In order to elucidate the HSA binding sites tryptophan fluorescence quenching studies and displacement reactions with the established site markers warfarin and dansylglycine were performed. Conditional stability constants for the binding to sites I and II on HSA were computed showing that the studied ruthenium and osmium complexes are able to bind into both sites with moderately strong affinity (logK' = 4.4-5.1). Site I is slightly more favored over site II for all complexes. No significant differences in the HSA binding properties were found for these metal complexes demonstrating negligible influence of the type of counterion (sodium vs indazolium), the metal ion center identity (Ru vs. Os) or the position of the nitrosyl group on the binding event. Electron paramagnetic resonance spin labeling of HSA revealed that indazolium trans-[RuCl4(1H-indazole)(NO)] and long-chain fatty acids show competitive binding to HSA. Moreover, this complex has a higher affinity for site I, but when present in excess, it is able to bind to site II as well, and displace fatty acids. PMID:26908285

  15. 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

    2014-11-01

    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. PMID:25337807

  16. Unanticipated spin gap measured in the frustrated quasi-FCC d3 double perovskites La2 LiXO6 (X = Ru, Os)

    NASA Astrophysics Data System (ADS)

    Maharaj, Dalini D.; Sala, Gabriele; Marjerrison, Casey A.; Greedan, John; Gaulin, Bruce; Stone, Matthew

    There is much current interest in the influence of strong spin-orbit (SO) interactions on exotic ground state selection in new 4d and 5d magnets, particularly involving 4d5 Ir. Here we consider double perovskites of the form A2 BB'O6 which are based on heavy 4d or 5d magnetic ions, where the SO interaction is expected to be significant as it increases as ~Z4 . The double perovskite structure can accommodate a variety of magnetic ions on the B' site, providing a playground for systematic studies of the exotic ground states stabilized by strong SO coupling. Here, we report inelastic neutron scattering (INS) measurements conducted on the frustrated monoclinic magnets, La2LiXO6 (X = Ru, Os), wherein the magnetic moments decorate a quasi face-centered-cubic lattice. Our results show the development of a spin gap in the spin excitation spectrum of size ΔOs = 8 meV and ΔRu = 2.5meV concomitant with TN, which is unexpected for orbitally quenched d3 systems. We liken these results to INS results obtained for Ba2YXO6 and La2NaXO6, which were also shown to exhibit spin gaps that correlate with TN. We shall discuss trends observed in these three d3 double perovskite families which correlate strong SO coupling, spin gap and TN.

  17. Microstructure and ordering parameter studies in multilayer [FePt(x)/Os]{sub n} films

    SciTech Connect

    Chiang, D. P.; Chen, S. Y.; Chen, Y. Y.; Yao, Y. D.; Ouyang, H.; Yu, C. C.; Lin, H. M.

    2011-04-01

    The microstructure, ordering parameter, and magnetic properties of multilayer [FePt(x)/Os]{sub n} films on glass substrate by dc-magnetron sputtering (with x being thickness in nm; Os with a fixed thickness 5 nm; n being the number of layers) have been studied as a function of the annealing temperatures between 300 and 900 deg. C. The grain size of multilayer films can be controlled by annealing temperature and thickness of the FePt layer with Os space layer. The coercivity as a function of the annealing temperature for samples with n = 1 and pure FePt behaves roughly saturated after annealing above 700 deg. C. However, for samples with n > 4 the value of H{sub c} seems still increasing with increasing annealing temperature between 600 and 900 deg. C, and the ordering parameter decreases with increasing the number of Os layers. Our experimental results are reasonably well to describe the effect of strain-assisted transformation.

  18. 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.

  19. Reactivity of Fe sub 3 and Ru sub 3. mu. sub 3 -phenylimido clusters with alkynes, allene, and 1,3-cyclohexadiene

    SciTech Connect

    Song, Jeongsup; Han, Sunghwan; Nguyen, S.T.; Geoffroy, G.L. )

    1990-08-01

    The reactivity of alkynes with the imido clusters Ru{sub 3}({mu}{sub 3}-NPh){sub 2}(CO){sub 9}, H{sub 2}Ru{sub 3}({mu}{sub 3}-NPh)(CO){sub 9}, Fe{sub 3}({mu}{sub 3}-NPh)(CO){sub 10}, Fe{sub 3}({mu}{sub 3}-NPh){sub 2}(CO){sub 9}, and H{sub 2}Fe{sub e}({mu}{sub 3}-NPh)(CO){sub 9} has been examined. The cluster Fe{sub 3}({mu}{sub 3}-NPh)(CO){sub 10} reacts regiospecifically with a series of alkynes to form the binuclear ferrapyrrolinone complexes Fe{sub 2}({mu}{sub 2}-{eta}{sup 3}-RC{double bond}C(R{prime})C(O)NPh)(CO){sub 6}, possessing a metallacycle formed by coupling of the alkyne with CO and the imido ligand. The bis(imido) cluster Ru{sub 3}({mu}{sub 3}-NPh){sub 2}(CO){sub 9} reacts with PhC{triple bond}CPh to form the tetranuclear cluster Ru{sub 4}({mu}{sub 3}-NPh){sub 2}({eta}{sup 2}-{mu}{sub 2}-PhC{triple bond}CPh)(CO){sub 10}, which has been crystallographically shown to possess a butterfly arrangement of the four ruthenium atoms with the alkyne bridging the hinge of the butterfly in a perpendicular fashion and with the imido ligands bridging the open triangular faces of the butterfly.

  20. pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

    PubMed

    Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2008-09-21

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds. PMID:18728883

  1. Effect of metal exchange (Os vs. Ru) and co-ligand variation (Cl(-)vs. acac(-)) on the oxidation state distribution in complexes of an o-phenylenediamido(2(-))/o-quinonediimine redox system.

    PubMed

    Chatterjee, Sudipta; Singh, Priti; Fiedler, Jan; Baková, Radka; Zális, Stanislav; Kaim, Wolfgang; Goswami, Sreebrata

    2009-10-01

    The compounds OsCl2L2 (1), RuCl2L2 (2) and Ru(acac)2L (3), Ldegrees = N-phenyl-o-quinonediimine and acac- = 2,4-pentanedionato, have been synthesised and electrochemically, spectroscopically and structurally characterised with the support of detailed DFT calculations. For the new osmium compound 1, the average values for CNH (1.331 A), CNPh (1.345 A) and CC(meta) bond lengths at 1.360 A agree more with an o-semiquinonediimine than with an o-quinonediimine formulation for the coordinated ligand, whereas the latter assignment is more appropriate to describe the ruthenium analogue 2 (average bond lengths of 1.308, 1.324 and 1.348 A, respectively). In turn, the corresponding average bond lengths in 3 (1.333, 1.352 and 1.350 A, respectively) are suggestive of an o-semiquinonediimine ligand. DFT calculations confirm the structural data and describe the electronic structures related to the oxidation state assignments. The stabilisation of trivalent ruthenium by electron donating acac- in 3 = RuIII(acac)2(L*-) and the preference of osmium for higher oxidation states (here: OsIVCl2(L*-)2 in 1) as compared to ruthenium analogues (here: RuIICl2(Ldegrees)2 in 2) in otherwise similar setting is responsible for these results. Oxidation of the diamagnetic complexes proceeds to partly EPR and UV-VIS spectroelectrochemically detectable cations with metal-centered spin, suggesting the following formulations: [OsIIICl2(Ldegrees)2]+ for 1+, [RuIIICl2(Ldegrees)2]+ for labile 2+, and [RuIII(acac)2(Ldegrees)]+ for 3+. In the case of 3, reversible metal-centered reduction results in ligand-based spin as compatible with a [RuII(acac)2(L*-)]- situation for 3-. PMID:19759953

  2. Magnetoelectric Coupling in Well-Ordered Epitaxial BiFeO3/CoFe2O4/SrRuO3 Heterostructured Nanodot Array.

    PubMed

    Tian, Guo; Zhang, Fengyuan; Yao, Junxiang; Fan, Hua; Li, Peilian; Li, Zhongwen; Song, Xiao; Zhang, Xiaoyan; Qin, Minghui; Zeng, Min; Zhang, Zhang; Yao, Jianjun; Gao, Xingsen; Liu, Junming

    2016-01-26

    Multiferroic magnetoelectric (ME) composites exhibit sizable ME coupling at room temperature, promising applications in a wide range of novel devices. For high density integrated devices, it is indispensable to achieve a well-ordered nanostructured array with reasonable ME coupling. For this purpose, we explored the well-ordered array of isolated epitaxial BiFeO3/CoFe2O4/SrRuO3 heterostructured nanodots fabricated by nanoporous anodic alumina (AAO) template method. The arrayed heterostructured nanodots demonstrate well-established epitaxial structures and coexistence of piezoelectric and ferromagnetic properties, as revealed by transmission electron microscopy (TEM) and peizoeresponse/magnetic force microscopy (PFM/MFM). It was found that the heterostructured nanodots yield apparent ME coupling, likely due to the effective transfer of interface couplings along with the substantial release of substrate clamping. A noticeable change in piezoelectric response of the nanodots can be triggered by magnetic field, indicating a substantial enhancement of ME coupling. Moreover, an electric field induced magnetization switching in these nanodots can be observed, showing a large reverse ME effect. These results offer good opportunities of the nanodots for applications in high-density ME devices, e.g., high density recording (>100 Gbit/in.(2)) or logic devices. PMID:26651132

  3. Properties of KCo2As2 and alloys with Fe and Ru: density functional calculations

    SciTech Connect

    Singh, David J

    2009-01-01

    Electronic-structure calculations are presented for KCo{sub 2}As{sub 2} and alloys with KFe{sub 2}As{sub 2} and KRu{sub 2}As{sub 2}. These materials show electronic structures characteristic of coherent alloys with a similar Fermi surface structure to that of the Fe-based superconductors when the d-electron count is near 6 per transition metal. However, they are less magnetic than the corresponding Fe compounds. These results are discussed in relation to superconductivity.

  4. Intrinsic defect-mediated conduction and resistive switching in multiferroic BiFeO3 thin films epitaxially grown on SrRuO3 bottom electrodes

    NASA Astrophysics Data System (ADS)

    Lee, Ji Hye; Jeon, Ji Hoon; Yoon, Chansoo; Lee, Sangik; Kim, Yeon Soo; Oh, Tae Joon; Kim, Young Heon; Park, Jinsu; Song, Tae Kwon; Park, Bae Ho

    2016-03-01

    We report the impact of intrinsic defects in epitaxial BiFeO3 films on charge conduction and resistive switching of Pt/BiFeO3/SrRuO3 capacitors, although the BiFeO3 films show very similar ferroelectric domain types probed by piezoresponse force microscopy. Capacitors with p-type Bi-deficient and n-type Bi-rich BiFeO3 films exhibit switchable diode and conventional bipolar resistive switching behaviors, respectively. Both the capacitors show good retention properties with a high ON/OFF ratio of >100 in Bi-deficient films and that of >1000 in Bi-rich films. The present investigation advances considerably understanding of interface control through defect engineering of BiFeO3 thin films for non-volatile memory application.

  5. Transport properties, upper critical field and anisotropy of Ba(Fe0.75Ru0.25)2As2 single crystals

    NASA Astrophysics Data System (ADS)

    Xing, Jie; Shen, Bing; Zeng, Bin; Liu, JianZhong; Ding, XiaXin; Wang, ZhiHe; Yang, Huan; Wen, HaiHu

    2012-12-01

    The temperature and angle dependent resistivity of Ba(Fe0.75Ru0.25)2As2 single crystals were measured in magnetic fields up to 14 T. The temperature dependent resistivity with the magnetic field aligned parallel to c-axis and ab-planes allow us to derive the slope of d H {/c2 ab }/d T and d H {/c2 c }/d T near T c yielding an anisotropy ratio Γ = d H {/c2 ab }/d T/d H {/c2 c }/d T≈2. By scaling the curves of resistivity vs. angle measured at a fixed temperature but different magnetic fields within the framework of the anisotropic Ginzburg-Landau theory, we obtained the anisotropy in an alternative way. Again we found that the anisotropy ( m c / m ab )1/2 was close to 2. This value is similar to that in Ba0.6K0.4Fe2As2 (K-doped Ba122) and Ba(Fe0.92Co0.08)2As2 (Co-doped Ba122). This suggests that the 3D warping effect of the Fermi surface in Ru-doped samples may not be stronger than that in the K-doped or Co-doped Ba122 samples, therefore the possible nodes appearing in Ru-doped samples cannot be ascribed to the 3D warping effect of the Fermi surface.

  6. 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.

  7. 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

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

    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 sin2 ψ 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.

  8. 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.

  9. 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.

  10. 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. PMID:24182298

  11. Prediction of elastic and vibrational stability for Sc, Ti, Y, Zr, Tc, Ru, Hf, Re, and Os in the fcc structure

    NASA Astrophysics Data System (ADS)

    de Coss, Romeo; Cifuentes-Quintal, Eduardo; Aguayo, Aaron; Murrieta, Gabriel

    2014-03-01

    The discovery of a metastable phase for a given material is interesting because corresponds to a new bonding and new properties are expected. The calculation of the total-energy along the Bain path is frequently used as a method to find tetragonal metastable states. However, a local minimum in the tetragonal distortion is not a definitive proof of a metastable state, and the elastic and vibrational stability needs to be evaluated. In a previous work, using the elastic stability criteria for a cubic structure, we have shown that the transition metals with hcp ground state; Ti, Zr, and Hf have a fcc metastable phase. That result is interesting since the fcc crystal structure does not appear in the current pressure-temperature phase diagram of these metals, and support the experimental observations of fcc Ti and Zr in thin films. In the present work, we extend the stability study of the fcc structure to the non-magnetic transition metals with hcp ground state; Sc, Ti, Y, Zr, Tc, Ru, Hf, Re, and Os. We find that all the metals involved in this study have a metastable fcc structure, since the phonon band structure shows only positive frequencies. Finally, substrates on which the fcc structure of these metals could be growth epitaxially are predicted.

  12. 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.

  13. Spin-glass behavior and pyroelectric anomalies in a new lithium-based oxide, Li3FeRuO5.

    PubMed

    Upadhyay, Sanjay Kumar; Paulose, P L; Iyer, Kartik K; Sampathkumaran, E V

    2016-08-17

    The results of dc and ac magnetization, heat capacity, (57)Fe Mössbauer spectroscopy, dielectric, pyroelectric current and isothermal magneto-capacitance measurements of a recently reported lithium-rich layered oxide, Li3FeRuO5, related to LiCoO2-type (rhombohedral, space group R3[combining macron]m), are presented. The results reveal that the compound undergoes spin-glass freezing at 15 K. There is a peak around 34 K in pyroelectric data, which cannot be attributed to ferroelectricity, but to the phenomenon of thermally stimulated depolarization current. As revealed by magnetocapacitance data above and below the magnetic ordering temperature, magnetic and electric dipoles appear to be coupled, thereby offering evidence for magnetodielectric coupling. PMID:27498689

  14. 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.

  15. 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.

  16. Re-Os in FeNi, Sulfide, and Phosphide: The Possible Determination of Internal Isochrons for Iron Meteorites

    NASA Astrophysics Data System (ADS)

    Papanastassiou, D. A.; Shen, J. J.; Wasserburg, G. J.

    1995-09-01

    For age determinations of specific events in the evolution of iron meteorites it is essential to obtain a reasonable range of physical-chemical fractionation of Re/Os. The possible stages of iron meteorite evolution which can, in principle, result in Re-Os fractionation include: a) condensation of PGE and of FeNi in the solar nebula; b) subsequent oxidation of part of the Fe by reaction with S; c) segregation and partial removal of massive FeS during melting on parent planetesimals; d) melting followed by fractional crystallization of the metal phase and crystallization of the remaining FeS; e) element redistribution during subsolidus phase transformations to produce schreibersite sheaves and finally precipitation or exsolution of minor micro-phases, e.g., rhabdite, at a later stage. Using negative ion, thermal ionization, we have determined the Re and Os concentrations and Os isotopic compositions in metal samples of iron meteorites. We have also analyzed metal-FeS pairs from two IA iron meteorites and a metal-phosphide pair from one IIIA iron. The analytical results for the paired analyses are shown in Table 1. The Re, Os partition coefficients between these coexisting phases are shown in Table 2. The whole-rock, metal samples for group IA, IIA, IIIA, IVA and IVB irons are consistent with a single, well-defined best fit line which yields a slope of 0.07863+/-0.00031 (corresponding to an age of 4.62+/-0.02 AE;lambda=1.64x10^(-11) a^(-1)) and an initial ^(187)Os/^(188)Os = 0.09560+/-0.00018 (all uncertainties are 2 sigma). There is also a suggestion from the data for the IIA and IVA groups of a difference in ages of 60+/-45 m.y. We find that, in the presence of the metal phase, neither Re nor Os enter into the sulphide. Therefore, the production or segregation of sulphide [e.g., under steps (b) and (c), above] act only as diluents for the Re and Os concentrations and can have no influence on the Re-Os isotope systematics and age determinations. Given the refractory

  17. 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

    2015-01-01

    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

  18. 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.

  19. 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

  20. Evolution of the interfacial magnetic anisotropy in MgO/CoFeB/Ta/Ru based multilayers as a function of annealing temperature

    NASA Astrophysics Data System (ADS)

    Aleksandrov, Yuriy; Fowley, Ciarán; Kowalska, Ewa; Sluka, Volker; Yıldırım, Oǧuz; Lindner, Jürgen; Ocker, Berthold; Fassbender, Jürgen; Deac, Alina M.

    2016-06-01

    We report the effect of annealing temperature on the dynamic and static magnetic properties of MgO/CoFeB/Ta/Ru multilayers. Angular resolved ferromagnetic resonance measurement results show that the as-deposited film exhibits in-plane magnetic anisotropy, whereas in the annealed films the magnetic easy-axis is almost along the direction perpendicular to the plane of the layers. The extracted interfacial anisotropy energy, Ki, is maximized at an annealing temperature 225∘C, in agreement with the vibrating sample magnetometry results. Although the magnetization is not fully out-of-plane, controlling the degree of the magnetization obliqueness may be advantageous for specific applications such as spin-transfer oscillators.

  1. Effects of pressure and composition on Pt-Re-Os partitioning behavior between solid and liquid metal in the Fe-Ni-S system: Implication for Os isotopic anomalies in plume-derived lavas

    NASA Astrophysics Data System (ADS)

    Hayashi, H.; Ohtani, E.; Terasaki, H.; Ito, Y.

    2008-12-01

    Coupled 186Os/188Os and 187Os/188Os enrichments of plume-derived lavas have been suggested to reflect material contribution from the outer core (e.g., Brandon, 1998). This geochemical hypothesis is based on an assumption that the outer core shows coupled enrichments in 186Os/ 188Os and 187Os/ 188Os ratio, reflecting the decay of 190Pt and 187Re to 186Os and 187Os, respectively. In order to examine this hypothesis, partitioning experiments of Pt-Re-Os between solid metal and liquid metal were performed using an MA-8 Kawai-type multi-anvil apparatus at 5-20 GPa and 1250-1400C. Starting materials of Fe metal, Ni (7 wt.%) metal and FeS (5 wt.% S in the bulk) were doped with 3 wt.% of Pt, Re and Os metals. Concentrations of all elements were determined using JXA-8800M electron probe microanalyzer with wave-dispersive spectrometry. Measured partition coefficients of Pt, Re and Os increase with increasing sulfur content and almost constant with increasing pressure. Therefore, the effect of liquid composition on the partitioning behavior of highly siderophile elements is much more significant compared to the effect of pressure and temperature. On the basis of the present experimental results, it is unlikely to generate the required Pt-Re-Os fractionation during inner core crystallization assuming that the light element in the Earth"fs core is sulfur only.

  2. Magnetic domains and magnetization reversal of ion-induced magnetically patterned Ruderman-Kittel-Kasuya-Yoshida-coupled Ni{sub 81}Fe{sub 19}/Ru/Co{sub 90}Fe{sub 10} films

    SciTech Connect

    Fassbender, J.; Bischoff, L.; Mattheis, R.; Fischer, P.

    2006-04-15

    Pure magnetic patterning by means of ion-beam irradiation of magnetic thin films and multilayers often results from a postdeposition local modification of the interface structure with only minor effects on the film topography. In the study presented here a 60 keV fine-focused Co ion beam was used to change the coupling in a Ni{sub 81}Fe{sub 19}/Ru/Co{sub 90}Fe{sub 10} structure from antiferromagnetic to ferromagnetic on a micron scale. Thereby an artificial structure with locally varying interlayer exchange coupling and therefore magnetization alignment is produced. High-resolution full-field x-ray microscopy is used to determine the magnetic domain configuration during the magnetization reversal process locally and layer resolved due to the element-specific contrast in circular x-ray dichroism. In the magnetically patterned structure there is, in addition to the locally varying interlayer exchange coupling across the Ru layer, also the direct exchange coupling within each ferromagnetic layer present. Therefore the magnetization reversal behavior of the irradiated stripes is largely influenced by the surrounding magnetic film.

  3. Spin-State Energetics of Fe(III) and Ru(III) Aqua Complexes: Accurate ab Initio Calculations and Evidence for Huge Solvation Effects.

    PubMed

    Radoń, Mariusz; Gąssowska, Katarzyna; Szklarzewicz, Janusz; Broclawik, Ewa

    2016-04-12

    Aqua complexes of transition metals are useful models for understanding the electronic structure of metal-oxide species relevant in photocatalytic water splitting. Moreover, spin-forbidden d-d transitions of aqua complexes provide valuable experimental data of spin-state energetics, which can be used for benchmarking of computational methods. Here, low-energy spin states of Fe(III) and Ru(III) aqua complexes are studied with an array of DFT and high-level wave function methods (CASPT2, RASPT2, NEVPT2, CCSD(T)-F12, and other coupled cluster methods up to full CCSDT). The results from single-reference and multireference methods are cross-checked, and the amount of multireference character for both considered spin states of [Fe(H2O)6](3+) is carefully analyzed. In addition to small [M(H2O)6](3+) clusters (M = Fe, Ru), we also employ larger models [M(H2O)6·(H2O)12](3+), with explicit water molecules in the second coordination sphere, to describe the situation in aqueous solution. By comparing the results for both types of models, our calculations evidence large and systematic solvation effects on the spin-state energetics. It is found that, due to the interaction with hydrogen-bonded water molecules in the second coordination sphere, the first coordination sphere undergoes a noticeable contraction and deformation. In consequence, the presence of solvation shell affects the relative energies of spin states by as much as 3-4 × 10(3) cm(-1) (∼10 kcal/mol). Once this solvation effect is accounted for, the spin-state energetics from CCSD(T) and NEVPT2 calculations turn out to be in an excellent agreement with the experimental estimates, which was not the case for isolated [M(H2O)6](3+) species is gas phase. We thus postulate that significant discrepancies between theory and experimental data for [Fe(H2O)6](3+) that were previously reported in the literature may be plausibly resolved and attributed to the neglect of explicit solvation effects and also, to some extent, to

  4. Demonstration of magnetoelectric memory cell in (110) [Pb(Mg1/2Nb2/3)O3]0.68-[PbTiO3]0.32/Ru/FeCo heterostructures

    NASA Astrophysics Data System (ADS)

    Han, Xuemeng; Xi, Li; Li, Yue; Guo, Xiaobin; Li, Dong; Wang, Zhen; Zuo, Yalu; Xue, Desheng

    2014-09-01

    An electric-field pulses driven magnetoelectric memory cell in a single layered ferromagnetic thin film was fabricated by direct-current magnetron sputtering Ru/Fe65Co35 on ferroelectric (110) [Pb(Mg1/2 Nb2/3)O3]0.68-[PbTiO3]0.32 (PMN-PT) substrates. The magnetization in the orthogonal directions can be reset by the positive/negative electric fields pulse in PMN-PT/Ru/FeCo heterostructures due to the strain mediated converse magnetoelectric effect. The high (low) resistance state was realized under the negative (positive) electric fields pulse due to the anisotropy magnetoresistance of FeCo films. Then, a non-volatile magnetic memory cell with resistance and electric field, respectively, as the media and writing field was realized.

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

    DOE PAGESBeta

    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 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

  6. 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.

  7. Heavy-impurity resonance, hybridization, and phonon spectral functions in Fe 1 x M x Si (M= Ir, Os)

    DOE PAGESBeta

    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 rst-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 and increases electron-phonon coupling, leads to softened interatomic force-constantsmore » 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 rst-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. 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

  8. Control of oxygen octahedral rotation in BiFeO3 films using modulation of SrRuO3 bottom electrode layer

    NASA Astrophysics Data System (ADS)

    Lee, Sungsu; Jo, Ji Young

    2015-03-01

    Oxygen octahedral rotation of multiferroic BiFeO3 (BFO) has attracted great attention due to changes of electrical and magnetic properties. Coupling of octahedral rotation in BFO-bottom electrode layer interface remains unexplored. Recently, there have been reported the control of octahedral rotation in SrRuO3 (SRO) film on SrTiO3 (001) substrate by coherently controlling the oxygen pressure during growth and interfacial coupling. Here we demonstrate that the octahedral rotation of BFO film is changed using tetragonal a0a0c- tilted-SRO bottom electrodes. In this work, BFO/SRO heterostructure is fabricated to SrTiO3 (001) single crystal substrates by pulsed laser deposition at different oxygen partial pressures. The rotation pattern of FeO6 and the structural symmetry are identified from half-integer reflections using high-resolution X-ray diffraction. The effects depending on octahedral tilting of BFO films on the magnetic and ferroelectric properties will be presented.

  9. Redox controls on Ni-Fe-PGE mineralization and Re/Os fractionation during serpentinization of abyssal peridotite

    NASA Astrophysics Data System (ADS)

    Foustoukos, Dionysis I.; Bizimis, Michael; Frisby, Carl; Shirey, Steven B.

    2015-02-01

    Awaruite (Ni2Fe to Ni3Fe) is often used to infer fugacity and redox gradients in hydrothermally altered peridotites. However, discrepant petrological and thermodynamic data suggest that the fO2-fS2 stability field of awaruite is not well constrained. In this study, we assess the thermodynamic properties of awaruite and re-evaluate the Fe-Ni-S systematics of hydrothermally altered peridotites. New experimental data indicate that awaruite is stable at higher fO2 than previously thought, supporting the common occurrence of awaruite in the reaction zone of modern and ancient ultramafic-hosted hydrothermal vent systems. Awaruite is known to catalyze the abiogenic synthesis of methane during active serpentinization, contributing to methanogenesis at modern oceanic hydrothermal systems and potentially on early Earth. The enhanced stability field of awaruite determined here suggests that abiogenic methanogenesis may be active at a broad range of redox conditions. Serpentinized peridotites also contain platinum-group element (PGE)-Re sulfides and metal alloys that can be derived from desulfurization of primary mantle sulfides under low fS2. Thermodynamic calculations suggest that Os will exist as metal and Re as ReS2 in the redox stability field of awaruite. Under a relatively broad range of fS2-fO2 conditions, hydrothermal alteration and desulfurization of primary mantle may produce open system behavior in the Re/Os system and variable Re-PGE ratios and contribute over time to the Os isotopic heterogeneity of the mantle, through subduction and recycling of altered oceanic lithosphere. PGE-metal alloys occur at such low abundances in peridotite that they often are nearly impossible to find. The stability of awaruite at higher fO2 suggests that it can coexist with Os-Ir-Pt metal alloys, making it an important indicator mineral for their presence in hydrothermally altered peridotites.

  10. Quasi-two-dimensional noncollinear magnetism in the Mott insulator Sr2F2Fe2OS2

    NASA Astrophysics Data System (ADS)

    Zhao, Liang L.; Wu, Shan; Wang, Jiakui K.; Hodges, J. P.; Broholm, C.; Morosan, E.

    2013-01-01

    The magnetism of Sr2F2Fe2OS2 was examined through neutron powder diffraction and thermodynamic and transport measurements. Quasi-two-dimensional magnetic order develops below TN=106(2) K with an in-plane correlation length exceeding 310 Å and an out-of-plane correlation length of just 17(3) Å. The data are consistent with a two-k structure with k1=(1/2,0,1/2) and k2=(0,1/2,1/2) and an ordered moment of 3.3(1)μB oriented along the in-plane components of k. This structure is composed of orthogonal antiferromagnetic chains intersecting at superexchange-mediating O sites. Density functional theory also points to this structure and a narrower Fe 3d band than for the iron pnictides from which electronic correlations produce a Mott insulator.

  11. Unification of the pressure and composition dependence of superconductivity in Ru substituted BaFe2As2

    NASA Astrophysics Data System (ADS)

    Devidas, T. R.; Mani, Awadhesh; Sharma, Shilpam; Vinod, K.; Bharathi, A.; Sundar, C. S.

    2014-05-01

    Temperature dependent high pressure electrical resistivity studies have been carried out on Ba(Fe1-x Rux)2As2 single crystals with x=0.12, 0.26 and 0.35, which correspond to under-doped, optimally doped and over-doped composition regimes, respectively. The evolution of structural/magnetic (TS-M) and superconducting transition (Tc) temperatures, with pressure for various compositions has been obtained. The normal state resistivity has been analyzed in terms of a model that incorporates both spin fluctuations and the opening of the gap in the spin density wave (SDW) phase. It is shown that Tc scales with the strength of the spin fluctuation, B, and TS-M scales with the SDW gap parameter, Δ. This provides a prescription for the unification of the composition and pressure induced superconductivity in BaFe2As2.

  12. Thermoelectric and electrical properties of Ba0.5Sr0.5Co x Ru x Fe(12-2 x)O19 ferrite*

    NASA Astrophysics Data System (ADS)

    Singh, Charanjeet; Jaroszewski, Maciej; Bindra Narang, Sukhleen; Ravinder, D.

    2016-04-01

    Thermoelectric and electrical characteristics investigation of M-type hexagonal ferrite, Ba0.5Sr0.5CoxRuxFe(12-2x)O19 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2), have been carried out from 303 K to 473 K. The static current density-electric field characteristics have been measured at room temperature. The Seebeck coefficient indicates n-type behavior at lower substitution and p-type conduction at higher substitution. The different electrical parameters are affected by change in grain size with substitution of Co2+ and Ru4+ ions. The existence of polarons is confirmed from increase in conductivity with frequency. The static conduction due to applied electric field is discussed qualitatively in terms of space charge limited current, ionic hopping, Poole-Frenkel and Schottky-Richardson mechanisms. The large current density has been observed at higher substitution. Contribution to the Topical Issue "Materials for Dielectric Applications", edited by Maciej Jaroszewski and Sabu Thomas.

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

    PubMed Central

    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. PMID:24791162

  14. 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. PMID:24791162

  15. 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

  16. Managing magnetization and antiferromagnetic coupling in epitaxially grown magnetic oxide heterostructures of (Ga,Fe)2O3 and SrRuO3

    NASA Astrophysics Data System (ADS)

    Lee, Jihye; Jo, William; Meny, Christian; Roulland, Francois; Viart, Nathalie

    2011-03-01

    We have grown b-axis oriented epitaxial (Ga,Fe)2O3 (GFO) thin films on (111) oriented SrRuO3 (SRO) by pulsed laser deposition to know spin interaction in multilayer system. The easy axis of magnetization of the GFO is located on the plane of the thin films. On the other hand, SRO has unique anisotropic properties on various crystallographic directions in their structure. Magnetic properties of the films were measured as a function of temperature and external magnetic field by a superconducting quantum interference magnetometer. Curie temperature of SRO and GFO was measured at 150K and 370K, respectively. According to the direction of external magnetic field, the magnetic moment value of the GFO/SRO heterostructures show different behavior due to antiferromagnetic coupling. This research was supported by Leading Foreign Research Institute Recruitment Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education, Science and Technology(MEST) (2010-00453)

  17. Chalcophile and platinum-group element distribution in the Ultramafic series of the Stillwater Complex, MT, USA—implications for processes enriching chromite layers in Os, Ir, Ru, and Rh

    NASA Astrophysics Data System (ADS)

    Barnes, Sarah-Jane; Pagé, P.; Prichard, H. M.; Zientek, M. L.; Fisher, P. C.

    2016-01-01

    All of the rocks from the Ultramafic series of the Stillwater Complex are enriched in PGE relative to most mafic magmas. Furthermore, the chromite layers are particularly enriched in IPGE (Os, Ir, and Ru) and Rh. This enrichment appears to be a common characteristic of ultramafic rocks from many types of settings, layered intrusions, ophiolites, and zoned complexes. We have carried out a petrological, mineralogical, and geochemical study to assess how the enrichment occurred in the case of the Stillwater Complex and applied our results to the chromite layers of the Bushveld and Great Dyke complexes. The minerals that now host the PGE are laurite and fine-grained intergrowths of pentlandite, millerite, and chalcopyrite. The laurite occurs as inclusions in chromite, and mass balance calculations indicate that it hosts most of the Os, Ir, and Ru. The sulfide minerals occur both as inclusions in chromite and as interstitial grains. The sulfides host much of the Pd and Rh. The IPGE and Rh correlate with Cr but not with S or Se, indicating that these elements were not collected by a sulfide liquid. Palladium, Cu, and Se correlate with each other, but not with S. The low S/Se (<1500) of the whole rock and magnetite rims around the sulfides indicate some S has been lost from the rocks. We conclude that to account for all observations, the IPGE and Rh were originally collected by chromite, and subsequently, small quantities of base metal sulfide liquid was added to the chromite layers from the overlying magma. The IPGE and Rh in the chromite diffused from the chromite into the base metal sulfides and converted some of the sulfides to laurite.

  18. Investigation of the synthesis, activation, and isosteric heats of CO2 adsorption of the isostructural series of metal-organic frameworks M3(BTC)2 (M = Cr, Fe, Ni, Cu, Mo, Ru).

    PubMed

    Wade, Casey R; Dincă, Mircea

    2012-07-14

    The synthesis, activation, and heats of CO(2) adsorption for the known members of the M(3)(BTC)(2) (HKUST-1) isostructural series (M = Cr, Fe, Ni, Zn, Ni, Cu, Mo) were investigated to gain insight into the impact of CO(2)-metal interactions for CO(2) storage/separation applications. With the use of modified syntheses and activation procedures, improved BET surface areas were obtained for M = Ni, Mo, and Ru. The zero-coverage isosteric heats of CO(2) adsorption were measured for the Cu, Cr, Ni, Mo, and Ru analogues and gave values consistent with those reported for MOFs containing coordinatively unsaturated metal sites, but lower than for amine functionalized materials. Notably, the Ni and Ru congeners exhibited the highest CO(2) affinities in the studied series. These behaviors were attributed to the presence of residual guest molecules in the case of Ni(3)(BTC)(2)(Me(2)NH)(2)(H(2)O) and the increased charge of the dimetal secondary building unit in [Ru(3)(BTC)(2)][BTC](0.5). PMID:22539456

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

    DOE PAGESBeta

    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 Kmore » was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.« less

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    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 [FeS6×1/2]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.

  1. Atomic site preferences and its effect on magnetic structure in the intermetallic borides M{sub 2}Fe(Ru{sub 0.8}T{sub 0.2}){sub 5}B{sub 2} (M=Sc, Ti, Zr; T=Ru, Rh, Ir)

    SciTech Connect

    Brgoch, Jakoah; Mahmoud, Yassir A.; Miller, Gordon J.

    2012-12-15

    The site preference for a class of intermetallic borides following the general formula M{sub 2}Fe(Ru{sub 0.8}T{sub 0.2}){sub 5}B{sub 2} (M=Sc, Ti, Zr; T=Ru, Rh, Ir), has been explored using ab initio and semi-empirical electronic structure calculations. This intermetallic boride series contains two potential sites, the Wyckoff 2c and 8j sites, for Rh or Ir to replace Ru atoms. Since the 8j site is a nearest neighbor to the magnetically active Fe atom, whereas the 2c site is a next nearest neighbor, the substitution pattern should play an important role in the magnetic structure of these compounds. The substitution preference is analyzed based on the site energy and bond energy terms, both of which arise from a tight-binding evaluation of the electronic band energy, and are known to influence the locations of atoms in extended solids. According to these calculations, the valence electron-rich Rh and Ir atoms prefer to occupy the 8j site, a result also corroborated by experimental evidence. Additionally, substitution of Rh or Ir at the 8j site results in a modification of the magnetic structure that ultimately results in larger local magnetic moment on the Fe atoms. - Graphical abstract: The site preference for electron rich atoms to occupy the 8j (gray) site is identified in these intermetallic borides, while the magnetic structure is modified as a function of the substituted atoms band center. Highlights: Black-Right-Pointing-Pointer We identify the energetics dictating the site preference in a series of intermetallic borides. Black-Right-Pointing-Pointer Establish substitution rules for use in future directed synthetic preparations. Black-Right-Pointing-Pointer Identified changes in magnetic structure that accompany the site preference.

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

    NASA Astrophysics Data System (ADS)

    Goodenough, John B.; Zhou, Jianshi

    2015-06-01

    Different structural chemistries resulting from the Pb2+ lone-pair electrons in the PbMO3 perovskites are reviewed. The Pb2+ lone-pair electrons enhance the ferroelectric transition temperature in PbTiO3, stabilize vanadyl formation in PbVO3, and induce a disproportionation reaction of CrIV in PbCrO3. A Pb2+ + NiIV = Pb4+ + NiII reaction in PbNiO3 stabilizes the LiNbO3 structure at ambient pressure, but an A-site Pb4+ 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 MnIV/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 ≃ ~32 GPa, a covalent Pb-Ru bond is formed by Pb2+ + RuIV = Pb4+ + RuII electron sharing.

  3. Magnetic ordering and physical stability of X2Mn1+xSn1-x (X=Ru, Os, Co, Rh, Ni, Pd, Cu, and Ag) Heusler alloys from a first-principles study

    NASA Astrophysics Data System (ADS)

    Li, Chun-Mei; Hu, Qing-Miao; Yang, Rui; Johansson, Börje; Vitos, Levente

    2013-07-01

    The magnetic ordering and its effect on the physical stability of X2Mn1+xSn1-x (0≤x≤0.5, and X=Ru, Os, Co, Rh, Ni, Pd, Cu, and Ag) Heusler alloys are investigated systematically by the use of first-principles method. It is found that the ferromagnetic (FM) coupling between Mn on Mn sublattice (Mn1) and Mn on Sn sublattice (Mn2) is favorable over the antiferromagnetic (AFM) coupling for X with the number of valence electrons [Nv(X)] of 8 and 9, and vice versa for X with Nv(X)=10 and 11, originated from the competition of the exchange interactions between X-Mn2 and Mn1-Mn2. In comparison with the FM Mn1-Mn2 coupling, the AFM coupling decreases significantly the shear elastic constant C' but increases slightly C44, which results in increasing elastic anisotropy (A=C44/C') and consequently may facilitate the tetragonal shear lattice deformation. The hybridization of the minority electronic states between X d and Sn p plays a dominant role on the orientation of the magnetic coupling. The smaller change of the density of states in the Fermi level, induced by the lattice distortion for C', corresponds to the softer C' as well as the larger A in the AFM state than the FM one.

  4. Oxygen trapped by rare earth tetrahedral clusters in Nd{sub 4}FeOS{sub 6}: 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.

    2015-09-15

    Single crystals of Nd{sub 4}FeOS{sub 6} were grown from an Fe–S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd{sub 4}MnOSe{sub 6}-type structure (P6{sub 3}mc, a=9.2693(1) Å, c=6.6650(1)Å, V=495.94(1) Å{sup 3}, Z=2), featuring parallel chains of face-sharing [FeS{sub 6×1/2}]{sup 4−} trigonal antiprisms and interlinked [Nd{sub 4}OS{sub 3}]{sup 4+} cubane-like clusters. Oxygen atoms were found to be trapped by Nd{sub 4} clusters in the [Nd{sub 4}OS{sub 3}]{sup 4{sub +}} chains. Structural differences among Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6} and the related La{sub 3}CuSiS{sub 7}− and Pr{sub 8}CoGa{sub 3}-type structures have been described. Magnetic susceptibility measurements on Nd{sub 4}FeOS{sub 6} 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. - Graphical abstract: Trapping of oxygen in Nd{sub 4} tetrahedral clusters results in the formation of the Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6}, in contrast to the La{sub 3}CuSiS{sub 7}-type oxygen-free Nd{sub 4}FeS{sub 7} and related Pr{sub 8}CoGa{sub 3}-type structures. Complex magnetic frustration inhibits magnetic ordering at low temperature. - Highlights: • Single crystals of Nd{sub 4}FeOS{sub 6} were grown using self-flux method. • Oxygen was found trapped by Nd{sub 4} tetrahedral clusters. • Comparison with two closely related structural types were discussed. • Magnetic measurements revealed antiferromagnetic (AFM) interaction. • VASP calculations confirmed strong magnetic frustration in AFM model.

  5. 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.

  6. 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.

  7. Re-Os isotopic ages of pyrite and chemical composition of magnetite from the Cihai magmatic-hydrothermal Fe deposit, NW China

    NASA Astrophysics Data System (ADS)

    Huang, Xiao-Wen; Zhou, Mei-Fu; Qi, Liang; Gao, Jian-Feng; Wang, Yu-Wang

    2013-12-01

    The Eastern Tianshan Orogenic Belt of the Central Asian Orogenic Belt and the Beishan terrane of the Tarim Block, NW China, host numerous Fe deposits. The Cihai Fe deposit (>90 Mt at 45.6 % Fe) in the Beishan terrane is diabase-hosted and consists of the Cihai, Cinan, and Cixi ore clusters. Ore minerals are dominantly magnetite, pyrite, and pyrrhotite, with minor chalcopyrite, galena, and sphalerite. Gangue minerals include pyroxene, garnet, hornblende and minor plagioclase, biotite, chlorite, epidotite, quartz, and calcite. Pyrite from the Cihai and Cixi ore clusters has similar Re-Os isotope compositions, with ˜14 to 62 ppb Re and ≤10 ppt common Os. Pyrrhotite has ˜5 to 39 ppb Re and ˜0.6 ppb common Os. Pyrite has a mean Re-Os model age of 262.3 ± 5.6 Ma ( n = 13), in agreement with the isochron regression of 187Os vs. 187Re. The Re-Os age (˜262 Ma) for the Cihai Fe deposit is within uncertainty in agreement with a previously reported Rb-Sr age (268 ± 25 Ma) of the hosting diabase, indicating a genetic relationship between magmatism and mineralization. Magnetite from the Cihai deposit has Mg, Al, Ti, V, Cr, Co, Ni, Mn, Zn, Ga, and Sn more elevated than that of typical skarn deposits, but both V and Ti contents lower than that of magmatic Fe-Ti-V deposits. Magnetite from these two ore clusters at Cihai has slightly different trace element concentrations. Magnetite from the Cihai ore cluster has relatively constant trace element compositions. Some magnetite grains from the Cixi ore cluster have higher V, Ti, and Cr than those from the Cihai ore cluster. The compositional variations of magnetite between the ore clusters are possibly due to different formation temperatures. Combined with regional tectonic evolution of the Beishan terrane, the Re-Os age of pyrite and the composition of magnetite indicate that the Cihai Fe deposit may have derived from magmatic-hydrothermal fluids related to mafic magmatism, probably in an extensional rift environment.

  8. Mössbauer and magnetic studies of bulk and fine-powder SrRu O3 and Sr-Cu-Ru O3 systems

    NASA Astrophysics Data System (ADS)

    Felner, Israel; Nomura, Kiyoshi; Nowik, Israel

    2006-02-01

    SrRuO3 is a ferromagnet, TC=165K . Due to difference in grain sizes, ceramic bulk and fine-powder (prepared by the sol-gel procedure) of SrRuO3 , have different coercive fields. The Fe57 doped Mössbauer effect spectra (MS) of powder SrRuO3 exhibit distinct magnetic hyperfine sextets up to TC , while none is observed at 90K in the bulk material. This is probably a result of the fact that the Fe57 probe resides in the Sr and Ru sites for powder and bulk SrRuO3 , respectively. Due to the shorter Sr-Ru distance, the Fe57 ions in the Sr site are exposed to an exchange field from the Ru magnetically ordered ions, much more than the iron in the Ru site. The Fe57 MS spectra of Sr1-xCuxRuO3 and SrRu1-yCuyO3 systems behave similarly to powder and bulk SrRuO3 , respectively. The magnetic properties of the two systems are discussed. The above results served as the basic explanation for the peculiar magnetic behavior of the magneto superconducting RuEu1.5Ce0.5Sr2Cu2O10 in the temperature range 90-165K .

  9. 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.

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

    DOE PAGESBeta

    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 differencesmore » with the more thoroughly studied 3d-3d systems.« less

  11. 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

  12. 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.

  13. 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.

  14. Bulk modulus and specific heat of B-site doped (La0.3Pr0.7)0.65Ca0.35Mn1-xBxO3 (B=Fe, Cr, Ru, Al, Ga)

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    Specific heat (Cp) thermal expansion (α) and Bulk modulus (BT) of lightly doped Rare Earth manganites (La0.3Pr0.7)0.65Ca0.35Mn1-xBxO3 (B3+ = Fe3+,Cr3+,Ga3+,Al3+,Ru4+); (0.3Fe0.03O3 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.

  15. 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

    2015-12-01

    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. PMID:26581027

  16. 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. PMID:11195368

  17. 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.

  18. Structural and physical properties of layered oxy-arsenides LnRuAsO (Ln=La, Nd, Sm, Gd)

    SciTech Connect

    McGuire, Michael A.; May, Andrew F.; Sales, Brian C.

    2012-07-15

    Polycrystalline samples of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO have been synthesized and studied using powder x-ray diffraction, electrical transport, magnetization, and heat capacity measurements. Variations in structural properties across the series reveal a trend toward more ideal tetrahedral coordination around Ru as the size of the rare earth element is reduced. The lattice parameters of these Ru compounds show a more anisotropic response to variation in Ln than their Fe analogs, and significant anisotropy in thermal expansion is also observed. Transport measurements show metallic behavior, and carrier concentrations near 10{sup 21}-10{sup 22} electrons per cm{sup 3} are inferred from simple analysis of Hall effect measurements. Anomalies in resistivity, magnetization, and heat capacity indicate antiferromagnetic ordering of rare earth moments at 5 K for GdRuAsO, 4.5 K for SmRuAsO, and <2K for NdRuAsO. Magnetization measurements on LaRuAsO show no evidence of a magnetic moment on Ru. Observed behaviors are compared to those reported for similar Fe and Ru compounds. - Graphical abstract: Analysis of crystal structure, electrical transport, magnetic susceptibility, and heat capacity of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO. Highlights: Black-Right-Pointing-Pointer Experimental investigation of LaRuAsO, NdRuAsO, SmRuAsO, and GdRuAsO. Black-Right-Pointing-Pointer Anisotropic lattice response to changing Ln radius and temperature. Black-Right-Pointing-Pointer Ru coordination becomes more ideal as Ln radius is reduced. Black-Right-Pointing-Pointer Transport measurements reveal metallic conduction dominated by electrons. Black-Right-Pointing-Pointer Magnetic measurements indicate antiferromagnetic ordering Nd, Sm, and Gd moments.

  19. 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.

  20. 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.

  1. 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.

  2. Reactions of HC triple bond CCMe sub 2 NHCOR alkynes with M sub 3 (CO) sub 12 carbonyls (M = Ru, R = C sub 6 H sub 9 , Ph; M = Os, R = C sub 6 H sub 9 ). Synthesis and crystal structure of Ru sub 4 (CO) sub 11 (HC triple bond CCMe sub 2 NHCOC sub 6 H sub 9 ), a butterfly cluster showing an interaction between a wingtip metal and the amide CO

    SciTech Connect

    Predieri, G.; Tiripicchio, A.; Camellini, M.T.; Costa, M. ); Sappa, E. )

    1990-06-01

    The alkynes HC{triple bond}CCMe{sub 2}NHCOR react with M{sub 3}(CO){sub 12} (M = Ru or Os) giving, upon oxidative addition, the expected hydrides ({mu}-H)M{sub 3}(CO){sub 9}({mu}{sub 3}-{eta}{sup 2}-C{triple bond}CCMe{sub 2}NHCOR) and the unprecedented butterfly clusters M{sub 4}(CO){sub 11}({mu}{sub 4}-{eta}{sup 2}-HC{triple bond}CCME{sub 2}NHCOR). These complexes have been characterized by spectroscopic studies; the structure of the ruthenium butterfly cluster with R = C{sub 6}H{sub 9} has been determined by X-ray diffraction methods. Crystals, containing CHCl{sub 3} as solvation molecules, are triclinic with Z = 2 in a unit cell of dimensions a = 13.521 (6), b = 14.617 (6), c = 9.049 (5) {angstrom}, {alpha} = 79.28 (2), {beta} = 108.79 (2), {gamma} = 111.85 (2){degree}.

  3. Chemically modified electrode with a film of nano ruthenium oxides stabilizing high valent RuO(4)(-) species and its redox-selective sequential transformation to polynuclear ruthenium oxide-metallocyanates.

    PubMed

    Kumar, Annamalai Senthil; Tanase, Tomoaki; Zen, Jyh-Myng

    2009-12-01

    High-valent Ru(VII)O(4)(-) (perruthenate) is a short-lived species in aqueous solutions (pH 1-14) and has scarcely been studied through electrochemistry. By a potential-controlled oxidative deposition method at 1 V vs Ag/AgCl using RuCl(3) in a pH 2 KCl-HCl buffer solution, chemically modified glassy carbon (GCE) and indium tin oxide (ITO) electrodes were successfully prepared with a film of hydrous nano ruthenium oxides RuO(2) and RuO(3), stabilizing the high-valent perruthenate anion (Ru(VII)-RuO(x)-CME, x = 2 and 3, CME = chemically modified electrode). The electrodes showed three distinct redox peaks corresponding to Ru(2)O(3)/RuO(2), RuO(2)/RuO(3), and RuO(4)(2-)/RuO(4)(-) redox processes at pH 2, like the classical RuO(2) electrodes in alkaline conditions. Solid state UV-visible spectra of the ITO/Ru(VII)-RuO(x)-CME showed characteristic absorption very close to chemically generated authentic RuO(4)(-) species in alkaline solution. Further, redox-controlled sequential procedures yielded polynuclear ruthenium oxide-hexacyanometallate films (RuO-MCN-CME, M = Fe and Ru), in which Ru(VII)-RuO(x)-CME acted as a specific template. A controlled-potential activation (>1 V) of Ru(VII)-RuO(x)-CME, stabilizing the key RuO(4)(-) species, in a solution of [Fe(CN)(6)](3-) or [Ru(CN)(6)](4-), should be a critical step for the formation of polynuclear RuO-MCN matrix. PMID:19928948

  4. Structural and magnetic phase transitions in TbRuAsO and DyRuAsO

    NASA Astrophysics Data System (ADS)

    McGuire, Michael; May, Andrew; Garlea, Ovidiu; Sales, Brian

    2013-03-01

    The compounds LnRuAsO (Ln = lanthanide) are isoelectronic, isostructural, 4 d transition metal analogues of the parent phases of 1111-type iron superconductors, but display markedly different behaviors. Recent results from crystallographic and physical properties measurements on TbRuAsO and DyRuAsO reveal particularly unusual properties in these materials. Analysis of low temperature x-ray and neutron powder diffraction data indicate a symmetry-lowering crystallographic phase transition in DyRuAsO at 25 K, and ordering of rare-earth magnetic moments at 7.0 and 10.5 K for TbRuAsO and DyRuAsO, respectively. The structural distortion observed in DyRuAsO (to space group Pmmn) is different than the well-known distortion that occurs in LnFeAsO. In addition, the findings indicate some coupling between the magnetism and the lattice, and hints of Ru magnetism are observed. A response to the structural transition is apparent in the magnetic susceptibility, and the associated heat capacity anomaly responds strongly to a magnetic field. Research supported by the US Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division (synthesis, physical and structural properties), and Scientific User Facilities Division (neutron diffraction, HB2A high-resolution powde

  5. T3RU test

    MedlinePlus

    ... sample is needed. How to Prepare for the Test Your health care provider will tell you if you need to stop taking medicines that may affect the test result. Drugs that can increase T3RU levels include: ...

  6. All-atom force field for molecular dynamics simulations on organotransition metal solids and liquids. Application to M(CO)(n) (M = Cr, Fe, Ni, Mo, Ru, or W) compounds.

    PubMed

    Bernardes, Carlos E S; Canongia Lopes, José N; Minas da Piedade, Manuel E

    2013-10-31

    A previously developed OPLS-based all-atom force field for organometallic compounds was extended to a series of first-, second-, and third-row transition metals based on the study of M(CO)(n) (M = Cr, Fe, Ni, Mo, Ru, or W) complexes. For materials that are solid at ambient temperature and pressure (M = Cr, Mo, W) the validation of the force field was based on reported structural data and on the standard molar enthalpies of sublimation at 298.15 K, experimentally determined by Calvet-drop microcalorimetry using samples corresponding to a specific and well-characterized crystalline phase: Δ(sub)H(m)° = 72.6 ± 0.3 kJ·mol(–1) for Cr(CO)(6), 73.4 ± 0.3 kJ·mol(–1) for Mo(CO)(6), and 77.8 ± 0.3 kJ·mol(–1) for W(CO)(6). For liquids, where problems of polymorphism or phase mixtures are absent, critically analyzed literature data were used. The force field was able to reproduce the volumetric properties of the test set (density and unit cell volume) with an average deviations smaller than 2% and the experimentally determined enthalpies of sublimation and vaporization with an accuracy better than 2.3 kJ·mol(–1). The Lennard-Jones (12-6) potential function parameters used to calculate the repulsive and dispersion contributions of the metals within the framework of the force field were found to be transferable between chromium, iron, and nickel (first row) and between molybdenum and ruthenium (second row). PMID:24079472

  7. The role of intermolecular interactions in the assemblies of Fe{sup II} and Co{sup II} tetrakis-isothiocyanatometalates with tris(1,10-phenanthroline)-Ru{sup II}: Crystal structures of two dual-metal assemblies featuring octahedral cationic and tetrahedral anionic modules

    SciTech Connect

    Ghazzali, Mohamed Langer, Vratislav; Ohrstroem, Lars

    2008-09-15

    Two new dual-metal assemblies: 2[Ru(phen){sub 3}]{sup 2+}.[Fe(SCN){sub 4}]{sup 2-}.2SCN{sup -}.4H{sub 2}O 1 and [Ru(phen){sub 3}]{sup 2+}.[Co(SCN){sub 4}]{sup 2-}2, (phen:1,10-phenanthroline), have been prepared and their structures were characterized by X-ray diffraction. In 1, the cationic octahedral enantiomers are arranged with a {lambda}{delta}{lambda}{delta}{lambda} sequence supported by {pi}-{pi} stacking and the anionic inorganic tetrahedral units are oriented between these stacks by interacting with the nearby water molecules through strong O-H...O and O-H...S hydrogen bonds. In 2, homochiral double helices in the b-direction are revealed, with tetrakis-isothiocyanate Co{sup II} anions arranged in the crystal to furnish one-dimensional (1D)-helical chains with S...S intermolecular interactions at 3.512(2) and 3.966(2) A supporting [Ru(phen){sub 3}]{sup 2+}{lambda}- and {delta}-helices with Ru...Ru shortest distance of 8.676(7) A. In both 1 and 2, the supramolecular assembly is maintained by C-H...S hydrogen bonds extending between the phenanthroline aromatic carbons in the cationic nodes and the sulphur atoms of the isothiocyanates anions. Analysis of S...S interactions in isothiocyanate containing compounds using Cambridge structural database (CSD) showed an angle dependence categorizing these interactions into 'type-I' and 'type-II'. - Graphical abstract: Side projection in 2 showing the crankshaft caused by S...S interactions in [Co(NCS){sub 4}]{sup 2-} in-between [Ru{sup II}(phen){sub 3}]{sup 2+} helices. Only isothiocyanates arms of [Co(NCS){sub 4}]{sup 2-} that are part of S...S interactions are shown and [Ru{sup II}(phen){sub 3}]{sup 2+} are presented as polyhedra.

  8. Rapid growth of localized nature of carriers in the Kondo semiconductor CeFe2Al10 with nonmagnetic ground state due to small Rh doping

    NASA Astrophysics Data System (ADS)

    Tanida, H.; Nakamura, M.; Sera, M.; Nishioka, T.; Matsumura, M.

    2015-12-01

    We examined the chemical doping effect on the Kondo semiconductor CeFe2Al10 with a nonmagnetic ground state by means of the magnetic susceptibility, specific heat, electrical resistivity, and thermopower. The effect of Ru doping on the ground state is small. On the other hand, by a small amount of Rh doping, the magnetic susceptibility is strongly enhanced along the orthorhombic a axis, and a Curie-Weiss behavior is observed in a wide temperature range. The low-temperature specific heat is also strongly enhanced by the doping, and a metallic ground state is realized at low temperatures. These results suggest the collapse of the spin and charge gap due to the suppression of the c -f hybridization effect. From the results of a crystalline electric field analysis on the magnetic susceptibility of Ce (Fe1 -xRhx )2Al10 , it was revealed that the Rh-doping effect on the c -f hybridization effect is anisotropic, especially for the a axis. Similar doping effects are seen in the Rh-doped CeRu2Al10 , Ir-doped CeOs2Al10 , and Si-doped CeRu2Al10 . From these results, we conclude that the collapse of the spin and charge gap by such an excess electron doping is one of the universal features of the Kondo semiconductor Ce T2Al10 (T = Fe, Ru, and Os).

  9. RU-79115 (Aventis Pharma).

    PubMed

    Annedi, S C; Kotra, L P

    2001-06-01

    Aventis Pharma AG is investigating a series of novel coumarin DNA gyrase B inhibitors, including RU-79115, as potential treatments for bacterial infections. These inhibitors have displayed potent inhibitory activity in vitro against DNA supercoiling by DNA gyrase B and have antibacterial activity. Good antibacterial activity against vancomycin- and teicoplanin-resistant enterococci was observed with most analogs (where the 3-acylamino residue was replaced with reversed isosteres). Amide derivatives were also active against novobiocin-resistant strains [335149]. RU-79115 has shown activity against Gram-positive bacteria, particularly staphylococci and enterococci, and its activity compares favorably to vancomycin. Against oxacillin- and ofloxacin-resistant staphylococci, RU-79115 had MIC50 values 7.5-fold lower than eperezolid and significantly lower than vancomycin. In vivo data suggest that the compound is safe and carries a satisfactory pharmacokinetic profile [216256], [340969], [376199]. The compound is the most potent in the series which also includes RU-78535 and RU-64135 [340969], [341039]. PMID:11572652

  10. PGE abundance and Re-Os isotope Systematics of Native-Fe-Bearing Basaltic Rocks and Their Carbonaceous Crustal Contaminants: Insights into magma plumbing-system dynamics in LIPs

    NASA Astrophysics Data System (ADS)

    Howarth, G. H.; Day, J. M.; Goodrich, C. A.; Pernet-Fisher, J.; Pearson, D. G.; Taylor, L. A.

    2014-12-01

    Native-Fe grains form in basaltic melts at highly reducing conditions (Fe-bearing basalts are useful natural analogues for studying PGE pre-concentration mechanisms, and the potential for PGE additions to magmas from crustal sources. Here, we present PGE LA-ICP-MS data for Fe-alloy, cohenite, and sulfide for a suite of Siberian and Disko Island native-Fe basalts, in combination with whole-rock PGE data for all known occurrences. The Siberian native-Fe alloys are characterized by highly variable PGE concentrations (1-30 ppm total PGEs), distinct low Os abundances, and PGE profiles similar to those of the nearby Noril'sk sulfide ores. In contrast, the Disko Island alloys are characterized by total PGE concentrations of 1-10 ppm and distinct positive Os and Re anomalies in extended PGE profiles. The Bühl basalts contain low PGE concentrations (~20 ppb). In order to understand contamination contributions, Os-isotopes analyses have been performed. Preliminary whole-rock 187Os/188Os data for high metal content samples from Siberia (0.33606 ± 37) and Disko (0.15402 ± 15) indicate high-time integrated Re/Os. The Re anomalies observed in extended PGE profiles of the Disko Island samples may reflect a potential crustal contribution to the overall PGE budget, through the addition of carbonaceous material. Whereas the Siberian samples contain abundant carbonaceous xenoliths, there is no apparent PGE contribution from crustal materials. Therefore, the role of crustal contamination is important in forming the native-Fe alloys, but the interaction

  11. Role of Ru in electrochromic effect during domain-inversion in LiNbO 3 crystals

    NASA Astrophysics Data System (ADS)

    Liu, De'an; Zhi, Ya'nan; Yan, Aimin; Luan, Zhu; Liu, Liren

    2006-08-01

    Recently, a new phenomenon of eletrochromic effect during domain-inversion has been observed both in doubly doped LiNbO 3:Fe:Ru and singly doped LiNbO 3:Ru crystals. Therefore, it is reasonable to be thought that the dopant of Ru is critical for eletrochromic effect. In this paper, The transmission spectra of different kinds of LiNbO 3 crystals are compared and analyzed for further demonstration that it is the exchange of valence states between Ru 3+ and Ru 4+ which lead to electrochromism effect.

  12. Meteorite - Impact Melt Mixing: PGE and Re-Os Evidence from the Morokweng Impact, South Africa

    NASA Astrophysics Data System (ADS)

    Hart, R.; Andreoli, M.; Cloete, M.; McDonald, I.; Carlson, R. W.; Tredoux, M.

    2001-12-01

    Preserved within the 870m thick impact melt sheet of the 144 Ma Morokweng impact structure, South Africa (1,2) are small (mm-cm) inclusions that are interpreted to be remnants of the impactor. Inclusions are disseminated throughout the melt sheet and consist of ultramafic silicate clasts with segregations of Ni-rich sulfides and oxides. The silicate component in the inclusions displays remnant fabric and, where unaltered, has mineral compositions consistent with ordinary chondrites (3). The sulfide-oxide component of the inclusions is Ni-rich, has high PGE contents (Ir = 16.7 x chondrite) and fractionated PGE ratios compared to chondrites and to the bulk impact melt which reflects the signature of the ordinary chondrite impactor (4). Specifically, the oxides show depletion in Pd, while the sulfide is slightly enriched in Rh and Pt and strongly enriched in Pd relative to Ir and Ru. Significantly, Ru and Ir (the high temperature PGE's) are not fractionated from one another. Initial Os isotopic compositions of the inclusion sulfides and oxides (0.1335 - 0.1358) are slightly more radiogenic than found in the melt rock (0.1301 - 0.1324), but both are substantially less radiogenic than a sample of the basement granite (0.259). The 1/Os vs 187Os/188Os correlation displayed by the bulk melt rocks is consistent with the presence of 1-3 wt% chondritic impactor in the crustal melt. The more radiogenic Os found in the inclusion minerals indicates that the inclusions contain a larger crustal PGE component than the melt rock. Though Os concentration is well correlated with Os isotopic composition in the melt rock, Re concentration is not. Thus, simple binary mixing between crustal melt and meteorite cannot explain the Re-Os systematics. The Re-Os and PGE fractionation observed in inclusion minerals suggests that meteorite-impact melt mixing occurred first through chemical exchange between oxidized melt and reduced, metal or sulfur-rich, impactor. Lithophile elements (e.g. Fe

  13. Mifepristone (RU486): a review.

    PubMed

    Mahajan, D K; London, S N

    1997-12-01

    Through an online search of MEDLINE, the authors reviewed the literature on the development of mifepristone (RU-486); RU-486's mechanism of action, pharmacodynamics, and distribution; the physiologic action of RU-486; potential new uses for RU-486; and its current use as both an abortifacient and therapy for endometriosis, leiomyoma, breast cancer, and meningioma. RU-486 is an 11beta-dimethyl-amino-phenyl derivative of norethindrone with a high affinity for P and glucocorticoid receptors. Receptor binding is not followed by the transcription of P-dependent genes. RU-486 effectively blocks P receptors in the placenta, resulting in the termination of pregnancy. It has also been used to treat leiomyomata, endometriosis, advanced breast cancer, and meningioma. The following therapeutic uses of RU-486 are discussed: the termination of early pregnancy, treatment with RU-486 in combination with prostaglandins, the termination of second-trimester pregnancy, cervical ripening, labor induction, postcoital contraception, uterine leiomyomata, endometriosis, breast cancer, and meningioma. PMID:9418681

  14. 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. PMID:27484222

  15. Ion probe measurements of Os, Ir, Pt, and Au in individual phases of iron meteorites

    NASA Astrophysics Data System (ADS)

    Hsu, Weibiao; Huss, Gary R.; Wasserburg, G. J.

    2000-03-01

    We have developed a technique to measure abundances of Os, Ir, Pt, and Au in situ in Fe-Ni metal on a microscale using secondary-ion mass spectrometry. A Cs + beam is used to generate negative secondary ions, and interferences from molecular ions are eliminated by a combination of 40 eV of energy filtering and a mass resolution of ˜1900. Ion yields for Fe, Co, Ni, and the PGEs vary considerably from spot to spot in meteoritic metal samples. Ion yield variations for Os and Ir correlate strongly with the Fe ion yield, that for Pt is weakly correlated, and that for Au is essentially uncorrelated. From ion yields for meteorite standards and the correlations with Fe ion yield, it is possible to obtain concentrations of Os, Ir, Pt, and Au in meteorite samples. Using this technique, a Cs + beam current of 10 nA gives a spatial resolution of 10-20 μm and detection limits of less than 1 ppm for Os, less than 0.1 ppm for Ir, and 10-20 ppb for Pt and Au. With refinement, it should be possible to measure Rh, Pd, and Ag and to improve the spatial resolution. However, Re, Ru, W, and Hf can only be measured as positive secondary ions. We have measured the abundances of Os, Ir, Pt, and Au in kamacite, taenite, and/or plessite in five iron meteorites: Canyon Diablo (IA), Cape York (Agpalilik) (IIIA), Colomera (IIE), Cruz del Aire (Anom), and Wallapai (IID). Our measurements show that Os, Ir, Pt, and Au partition preferentially into taenite relative to kamacite during slow cooling. Measured abundance ratios (taenite/kamacite) range from ˜1.3 to ˜2.1 for Os, Ir, and Pt, and from ˜2 to ˜6 for Au. These ratios are consistent with those determined recently by laser-ablation ICPMS, but differ significantly from those determined by earlier workers. Low-temperature taenite/kamacite distribution coefficients inferred from our data are ˜2.1 for Os, ˜1.6 for Ir, ˜1.9 for Pt, and ˜6 for Au. PGEs are not enriched in taenite as much as Ni. Partitioning is controlled by the interplay of

  16. 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.

  17. 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.

  18. Simulating Ru L3-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, N.; Schoenlein, R. W.; Govind, Niranjan; Khalil, Munira

    2013-05-01

    Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+, [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.

  19. 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

  20. 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

  1. Band structures in 98Ru and 99Ru

    NASA Astrophysics Data System (ADS)

    Van Voorthuysen, E. H. Du Marchie; Devoigt, M. J. A.; Blasi, N.; Jansen, J. F. W.

    1981-03-01

    The level schemes of 98, 99Ru were studied with the reactions 98Mo(α, 3nγ) and 98Mo(α, 4nγ) at Eα = 35 to 55 MeV, using a large variety of in-beam γ-ray detection techniques and conversion-electron measurements. A search for the 3 - state was carried out with the reaction 98Ru(p, p'). The ground-state band of 98Ru was excited up to Jπ = (12) + and a negative-parity band up to (15) -. New levels in 98Ru were found at Ex = 2285 ( Jπ = 4 +), 2435 ( Jπ = (3 -, 4 +)), 2671, 3540, 4224, 4847, 4915 ( Jπ = (12) +), 4989 ( Jπ = (12 +)), 5521 ( Jπ = (13) -), 5889, 6591 ( Jπ = (15) -), and 7621 keV. New unambiguous spin and parity assignments were made for the levels at Ex = 2014 and 3852 keV, as Jπ = 3 + and 9 -, respectively. New levels in 99Ru were found at Ex = 1976, 2021 ( J π = ( {15}/{2}+) ), 2393, 2401 ( J π = ( {17}/{2}+) ), 2875 (π = (+)), 3037, 3201 ( J π = ( {23}/{2}) -), 3460 ( J = ( {17}/{2}) ), 3484 ( J π = ( {21}/{2}+) ), 3985, 4224 ( J π = ( {27}/{2}-) ), and 5359 keV. The 1070 keV, J π = {11}/{2}- level in 99Ru has a half-life of 2.8 ns. A strongly excited negative-parity band is built on this level. A positive-parity band based on the ground state was excited up to J π = ( {21}/{2}+) . The level schemes are well reproduced by the interacting boson model in the vibrational limit.

  2. Magnetic and microwave properties of CoFe/PtMn/CoFe multilayer films

    NASA Astrophysics Data System (ADS)

    Pettiford, C. I.; Zeltser, A.; Yoon, S. D.; Harri, V. G.; Vittoria, C.; Sun, N. X.

    2006-04-01

    CoFe/PtMn/CoFe films were deposited on seed layers of Ru or NiFeCr with CoFe film compositions being either Co-10 at. %Fe or Co-16 at. %Fe. Eight periods of the CoFe/PtMn/CoFe trilayers were also prepared. The magnetic properties and ferromagnetic resonance (FMR) of these films were characterized with vibrating-sample magnetometer, and field-sweep FMR system at X band (~9.5 GHz). The Ru-seeded CoFe/PtMn/CoFe sandwich films show excellent magnetic softness with a low hard axis coercivity of 2-4 Oe, an easy axis Mr/Ms of >98%, and a significantly enhanced in-plane anisotropy of 57-123 Oe when CoFe layer thickness is above 200 A˚. Contrary to what was observed in the ferromagnetic/antiferromagnetic bilayer systems that have reduced FMR linewidth with the increase of film thickness, the CoFe/PtMn/CoFe trilayers with Ru seed layer show a minimum FMR linewidth of 45 Oe at an intermediate CoFe layer thickness of 300 A˚ at ~9.5 GHz.

  3. Round table on RU486.

    PubMed

    Shallat, L

    1993-01-01

    As a non-invasive means of early abortion, RU-486 has the potential to increase women's reproductive options; at the same time, the "abortion pill" has stimulated debate about the ethics and safety of new medical technologies. When combined with a prostaglandin (PG), the success rate for RU-486 is 96% for pregnancies of up to 9 weeks' gestation. In France, over 120,000 women have used RU-486/PG to terminate pregnancy, and this regimen is now used in about 25% of abortions. Clinical trials of RU-486 are underway in Cuba, China, India, Singapore, and Zambia. The Program for Appropriate Technology has identified four considerations for introducing RU-486 to developing countries: whether abortion or menstrual regulation is legal; whether women find the method acceptable and can comply with the multiple visit treatment regimen; whether the health infrastructure can support safe method use, including prevention of misuse and provision of appropriate medical backup personnel and facilities; and whether the cost of the regimen is affordable to individuals and/or programs --conditions unlikely to be met in most such countries. Ideal would be development of a medical abortifacient that is single dose and the lowest possible dose of each drug, provokes miscarriage within a more predictable time frame with less acute and prolonged bleeding, is safe and effective beyond two months, has minimal side effects, and maximizes short-term safety and minimizes long-term effects. Technological advances are being undermined, however, by political and religious attacks on the method. Even some feminists have expressed concerns about potential long-term effects of RU-486 use. PMID:12179722

  4. 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.

  5. Simulating Ru L3-Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    SciTech Connect

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

    2013-04-26

    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.

  6. 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.

  7. RU-486: the "abortion pill".

    PubMed

    Herranz, G

    1991-05-23

    A report sent by the Vatican to bishops' conferences throughout the world calls RU-486, the so-called abortion pill currently available in France, "a new, serious threat to human life." The report was developed at the Vatican's request by Gonzalo Herranz, a Spanish bioethicist. A cover letter to bishops' conferences from Cardinal Alfonso Lopez Trujillo, president of the Pontifical Council for the Family, suggested that the report be used "to resist the introduction of the abortion pill RU-486 into your country." Related to TU-486 and to new terminology some use to characterize its non-surgical approach to abortion is an intention "to amoralize and thereby place the transmission of human life into an ethically neutral terrain and reduce it to pure biology," says the report. The report discusses possible future uses of RU-486 as a contraceptive, stating: "Women would no longer have to worry themselves about whether they have conceived or not. Each month they would proceed to clean out their uterus chemically." The report refers to RU-486 as "a technical step forward in an area that did not need it." It says, "The abortion pill favors a woman's privacy and secret, but it condemns her to solitude." The English text from the Vatican follows. PMID:16145821

  8. Photoelectric conversion at a [Ru(bpy)3](2+)-based metallic triad anchored on ITO surface.

    PubMed

    Farran, Rajaa; Jouvenot, Damien; Loiseau, Frédérique; Chauvin, Jérôme; Deronzier, Alain

    2014-08-28

    A tri-metallic triad based on a [Ru(bpy)3](2+) moiety connected to Fe(ii) and Co(iii) bisterpyridine has been grafted on an ITO electrode by a stepwise procedure. Under visible light, in the presence of a sacrificial electron donor, the system produces electric current. The photo-current magnitude is compared to the one generated from a Co(iii)-Ru(ii) dyad and shows an increase of 40%. PMID:25002098

  9. Evolution of supercurrent path in Nb /Ru /Sr2RuO4 dc-SQUIDs

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    Phase-sensitive measurements of direct-current superconducting quantum interference devices (dc-SQUIDs) composed of Sr2RuO4 -Ru eutectic crystals have been performed to temperatures below a bulk Ru superconducting transition temperature at 0.49 K. A SQUID with Nb /Ru /Sr2RuO4 junctions fabricated on one Ru inclusion exhibits two distinct transitions due to the Ru superconducting transition and competition of proximity-induced superconducting gaps at the junctions. At sufficiently low temperatures, the SQUID interference patterns start to collapse with large phase shifts of the Fraunhofer patterns. This result indicates the influence of magnetic fluxes induced by large bias currents flowing in a strongly asymmetric supercurrent path. Such a large change in supercurrent path suggests superconducting phase mismatch between the s -wave and chiral p -wave states at the Ru /Sr2RuO4 interface.

  10. 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.

  11. 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.

  12. Thermoelectric Properties of Pseudogap Ti10Ru19B8 and Ti9TM2Ru18B8 (TM: Cr-Cu) Compounds

    NASA Astrophysics Data System (ADS)

    Takagiwa, Y.; Yoshida, T.; Yanagihara, D.; Kimura, K.

    2015-06-01

    The thermoelectric properties of ternary Ti10Ru19B8 and quaternary Ti9TM2Ru18B8 (TM: Cr, Mn, Fe, Co, Ni, Cu) compounds were investigated in the temperature range from 373 K to 973 K. They form pseudogaps in the electronic densities of states near the Fermi level, E F, which is suitable for thermoelectric materials. We synthesized crack-free pellet samples using arc-melting followed by spark plasma sintering. A maximum dimensionless figure of merit zT max was 0.09 at 973 K for Ti10Ru19B8 whereas a large power factor of 1.4 mW/m K2 was obtained at that temperature. The phonon thermal conductivity decreased through TM substitutions; however, the power factor also decreased due to an additional electronic density of states originated from TM d-states around E F; that is, excitations of both holes and electrons.

  13. 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

  14. Photocatalytic hydrogen production from a simple water-soluble [FeFe]-hydrogenase model system.

    PubMed

    Cao, Wei-Ning; Wang, Feng; Wang, Hong-Yan; Chen, Bin; Feng, Ke; Tung, Chen-Ho; Wu, Li-Zhu

    2012-08-21

    Combined with a simple water soluble [FeFe]-hydrogenase mimic 1, Ru(bpy)(3)(2+) and ascorbic acid enable hydrogen production photocatalytically. More than 88 equivalents of H(2) were achieved in water, which is much better than that obtained in an organic solvent or a mixture of organic solvent and water. PMID:22772838

  15. Electronic correlations, magnetism, and Hund's rule coupling in the ruthenium perovskites SrRuO3 and CaRuO3

    NASA Astrophysics Data System (ADS)

    Dang, Hung T.; Mravlje, Jernej; Georges, Antoine; Millis, Andrew J.

    2015-05-01

    A comparative density functional plus dynamical mean field theory study of the pseudocubic ruthenate materials CaRuO3 and SrRuO3 is presented. Phase diagrams are determined for both materials as a function of Hubbard repulsion U and Hund's rule coupling J . Metallic and insulating phases are found, as are ferromagnetic and paramagnetic states. The locations of the relevant phase boundaries are determined. Based on the computed phase diagrams, Mott dominated and Hund's dominated regimes of strong correlation are distinguished. Comparison of calculated properties to experiments indicates that the actual materials are in the Hund's coupling dominated region of the phase diagram so can be characterized as Hund's metals, in common with other members of the ruthenate family. Comparison of the phase diagrams for the two materials reveals the role played by rotational and tilt (GdFeO3-type) distortions of the ideal perovskite structure. The presence of magnetism in SrRuO3 and its absence in CaRuO3 despite the larger mass and larger tilt/rotational distortion amplitude of CaRuO3 can be understood in terms of density of states effects in the presence of strong Hund's coupling. Comparison of the calculated low-T properties of CaRuO3 to those of SrRuO3 provides insight into the effects of magnetic order on the properties of a Hund's metal. The study provides a simultaneous description of magnetism and correlations and explicates the roles played by band theory and Hubbard and Hund's interactions.

  16. 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. PMID:27324949

  17. A dinuclear Ni(mu-H)Ru complex derived from H2.

    PubMed

    Ogo, Seiji; Kabe, Ryota; Uehara, Keiji; Kure, Bunsho; Nishimura, Takashi; Menon, Saija C; Harada, Ryosuke; Fukuzumi, Shunichi; Higuchi, Yoshiki; Ohhara, Takashi; Tamada, Taro; Kuroki, Ryota

    2007-04-27

    Models of the active site in [NiFe]hydrogenase enzymes have proven challenging to prepare. We isolated a paramagnetic dinuclear nickel-ruthenium complex with a bridging hydrido ligand from the heterolytic cleavage of H2 by a dinuclear NiRu aqua complex in water under ambient conditions (20 degrees C and 1 atmosphere pressure). The structure of the hexacoordinate Ni(mu-H)Ru complex was unequivocally determined by neutron diffraction analysis, and it comes closest to an effective analog for the core structure of the proposed active form of the enzyme. PMID:17463285

  18. 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. PMID:25731609

  19. 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

  20. 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.

  1. Pressure Induced Enhancement of Superconductivity in LaRu2P2.

    PubMed

    Li, Baoxuan; Lu, Pengchao; 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

  2. In situ facile synthesis of Ru-based core-shell nanoparticles supported on carbon black and their high catalytic activity in the dehydrogenation of amine-boranes.

    PubMed

    Cao, Nan; Su, Jun; Hong, Xinlin; Luo, Wei; Cheng, Gongzhen

    2014-02-01

    Well-dispersed core-shell Ru@M (M=Co, Ni, Fe) nanoparticles (NPs) supported on carbon black have been synthesized via a facile in situ one-step procedure under ambient condition. Core-shell Ru@Co NPs were synthesized and characterized for the first time. The as-synthesized Ru@Co and Ru@Ni NPs exhibit superior catalytic activity in the hydrolysis of ammonia borane compared with their monometallic and alloy counterparts. The Ru@Co/C NPs are the most reactive, with a turnover frequency (TOF) value of 320 (mol H 2 min(-1)) molRu (-1) and activation energy (Ea) of 21.16 kJ mol(-1). Ru@Ni/C NPs are the next most active, whereas Ru@Fe/C NPs are almost inactive. Additionally, the as-synthesized NPs supported on carbon black exhibit higher catalytic activity than catalysts on other conventional supports, such as SiO2 and γ-Al2O3. PMID:24288206

  3. Photoinduced Charge Separation within Metallo-supramolecular Wires Built around a [Ru(bpy)3](2+)-Bisterpyridine Linear Entity.

    PubMed

    Farran, Rajaa; Jouvenot, Damien; Gennaro, Béatrice; Loiseau, Frédérique; Chauvin, Jérôme; Deronzier, Alain

    2016-06-29

    A [Ru(bpy)3](2+)-like complex (L1) bearing two free terpyridine groups at the 5 and 5' positions of the same bipyridine, linked by the rigid and linear 2,5-dimethyl phenylene bridges has been synthesized to open access to two classes of linear molecular wires with photosensitive properties: a bimetallic coordination polymer and an inorganic triad. In this Research Article, we report on the synthesis and characterization of the resulting [{Ru(II_)Fe(II)}n](4n+) alternated bimetallic polymer and the [Co(III_)Ru(II_)Fe(II)](7+) triad based on the building block L1. The [{Ru(II_)Fe(II)}n](4n+) polymer is fully characterized in solution. Cyclic voltammetry and emission lifetime measurements show that the bridging ligand allows interaction between the metal centers in the excited state despite the lack of interactions in the ground state. Under visible irradiation, the polymer can be fully oxidized in the presence of a sacrificial electron acceptor in solution. Thin robust films of the polymer are easily obtained on ITO by a simple electrochemical procedure based on an electroreduction adsorption process. The ITO/[{Ru(II_)Fe(II)}n](4n+)-modified electrode behaves as a photocathode under irradiation in the presence of ArN2(+). The magnitude of the photocurrent is dependent on the film thickness, probably limited by the diffusion of charge in thicker film. On the other hand L1 is also used to construct a well-ordered triad in association with Co(III) and Fe(II) metallic centers as electron acceptor and donor, respectively. The metallic triad is anchored on ITO or on a SiO2 wafer, starting from a terpyridine phosphonate modified surface. AFM images prove the presence of the triad in a linear upward orientation. Irradiation of the ITO/[Co(III_)Ru(II_)Fe(II)](7+) modified surface in the presence of triethanolamine in CH3CN induces the generation of an anodic photocurrent of around 30 μA.cm(-2). The photocurrent density generated by the ITO/[Co(III_)Ru(II_)Fe(II)](7

  4. 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.

  5. Suppression of ferromagnetism and observation of quantum well states in epitaxial thin films of the cubic ruthenate BaRuO3

    NASA Astrophysics Data System (ADS)

    Burganov, Bulat; Paik, Hanjong; Shen, Kyle; Schlom, Darrell

    The pseudocubic perovskite ruthenates ARuO3, where A is alkaline earth metal, are correlated materials where Hund's coupling drives correlations and leads to a low coherence scale, large renormalization, and formation of local moments. The ferromagnetic BaRuO3 has an ideal cubic structure and a larger bandwidth, compared to its GdFeO3-distorted counterparts, CaRuO3 and SrRuO3. In stark contrast to SrRuO3, which is a Fermi liquid below TC, BaRuO3 exhibits critical fluctuations near TC that are enhanced under hydrostatic pressure, which suppresses the Fermi liquid coherence scale and TC and drives a crossover into non-FL regime. Here we use ARPES to characterize the momentum-resolved electronic structure of strained ultrathin BaRuO3 films grown in situ by molecular beam epitaxy. The films on STO (001) are metallic down to 2 u.c. thickness and manifest clearly defined subbands of well-defined quasiparticles which arise due to quantum confinement effects. We observe that the bands are moderately renormalized compared to bare GGA bands and discover that the ferromagnetism can be suppressed in the atomically thin limit. We discuss our results on BaRuO3 in the context of our recent ARPES studies of the other perovskite ruthenates, SrRuO3 and CaRuO3.

  6. 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}.

  7. 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.

  8. Chemistry and petrology of Fe-Ni beads from different types of cosmic spherules: Implication for precursors

    NASA Astrophysics Data System (ADS)

    Rudraswami, N. G.; Prasad, M. Shyam; Babu, E. V. S. S. K.; Kumar, T. Vijaya

    2014-11-01

    Fe-Ni beads are observed to occur in all three (Stony, Glass, Iron) types of cosmic spherules collected from deep sea sediments of the Indian Ocean. Fe-Ni beads in cosmic spherules can provide insights for understanding metal segregation mechanisms and their refractory metal element (RME: Re, Os, W, Ir, Ru, Mo, Pt, Rh including Pd) compositions can help ascertain their precursor meteorites. We measured RME compositions of 55 Fe-Ni beads using LA-ICP-MS in all three basic types of cosmic spherules selected after examining ∼2000 cosmic spherules. The RMEs of Fe-Ni beads provide unique information on formation and differentiation during atmospheric entry. The variability in the concentration of the RMEs depends on the initial mass of the cosmic spherules, volatility, temperature attained and efficiency in metal segregation during entry. The CI chondrite and Os normalized RME compositions of the beads display a pattern that is close to CI chondritic composition. The presence of Pd, a non-refractory metal having condensation temperature similar to Fe, in Fe-Ni beads of all types of cosmic spherules indicates that the heating undergone was below its vaporization temperature. Not all parent bodies lead to the formation of beads, the precursor needs to exceed a certain minimum size and temperature to facilitate the metal to get segregated into beads. The minimum size of a parent particle that could enclose a Fe-Ni bead is estimated to have a size ∼1 mm. This places constraints on the sizes of materials that are ablated during entry, and the accompanying mass loss during entry. Our study further points out that all the three basic types of cosmic spherules have a chondritic origin based on their RME distribution patterns. Only metal-rich carbonaceous chondrites contain the required quantities of metal for the formation of Fe-Ni beads during atmospheric entry and during this process the RMEs are also efficiently segregated into these beads.

  9. Arrays of Ru Nanoclusters with Narrow Size Distribution Templated by Monolayer Graphene on Ru

    SciTech Connect

    Sutter, P.; Sutter, E.; Albrecht, P.; Wang, B.; Bocquet M.-L.; Wu, L.; Zhu, Y.

    2011-09-01

    Ru nanoclusters self-assemble over macroscopic sample areas during vapor deposition of Ru on monolayer graphene (MLG) on Ru(0001). The Ru nanoclusters form arrays with a mean lateral cluster diameter of {approx} 20 {angstrom}, cluster heights of 1 or 2 ML, and a size distribution that remains nearly constant with increasing coverage. Combined scanning tunneling microscopy and density functional theory (DFT) show that the clusters are templated by the MLG/Ru(0001) moire unit cell and identify the preferred binding site of the clusters as the low fcc region of the moire. Cross-sectional transmission electron microscopy (TEM) and high-resolution TEM contrast simulations experimentally demonstrate that the interaction of the Ru clusters with the underlying MLG/Ru(0001) leads to a local lifting of the graphene layer of the template. DFT calculations confirm this mechanism of interaction of the Ru clusters with the strongly coupled MLG/Ru(0001). Weakening of the graphene-support coupling via oxygen intercalation is shown to have a major effect on the assembly of Ru nanocluster arrays. With a preferred binding site lacking on decoupled graphene, the Ru nanoclusters grow significantly larger, and clusters with 1 to 4 ML height can coexist.

  10. Interpenetrating Diruthenium Tetraformate Monocation, [RuII/III2(O2CH)4]+, Based 3-D Molecule-based Magnets

    SciTech Connect

    Kennon, B.; Stone, K; Stephens, P; Miller, J

    2009-01-01

    Synthesis of [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[MIII(CN){sub 6}] (M = Co, Fe) possessing an interpenetrating body center cubic (bcc) lattices was investigated utilizing several synthetic methods. The targeted interpenetrating bcc [a = 12.6621(3) {angstrom}] structure was obtained for [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[Co(CN){sub 6}], and it exhibits {chi}T(T) that is fit to a model which includes zero field splitting. Cyanide abstraction from [Cr(CN){sub 6}]{sup 3-} occurs thwarting the formation of [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[M(CN){sub 6}]. [Ru{sub 2}(O{sub 2}CH){sub 4}]{sub 3}[Fe(CN){sub 6}] also exhibits the desired bcc structure [12.7071(3) {angstrom}], and its 13.4 K T{sub c} is a 6-fold enhancement with respect to that observed for [Ru{sub 2}(O{sub 2}CMe){sub 4}]{sub 3}[Fe(CN){sub 6}].

  11. Ferromagnetic CaRuO3

    PubMed Central

    Tripathi, Shivendra; Rana, Rakesh; Kumar, Sanjay; Pandey, Parul; Singh, R. S.; Rana, D. S.

    2014-01-01

    The non-magnetic and non-Fermi-liquid CaRuO3 is the iso-structural analog of the ferromagnetic (FM) and Fermi-liquid SrRuO3. We show that an FM order in the orthorhombic CaRuO3 can be established by the means of tensile epitaxial strain. The structural and magnetic property correlations in the CaRuO3 films formed on SrTiO3 (100) substrate establish a scaling relation between the FM moment and the tensile strain. The strain dependent crossover from non-magnetic to FM CaRuO3 was observed to be associated with switching of non-Fermi liquid to Fermi-liquid behavior. The intrinsic nature of this strain-induced FM order manifests in the Hall resistivity too; the anomalous Hall component realizes in FM tensile-strained CaRuO3 films on SrTiO3 (100) whereas the non-magnetic compressive-strained films on LaAlO3 (100) exhibit only the ordinary Hall effect. These observations of an elusive FM order are consistent with the theoretical predictions of scaling of the tensile epitaxial strain and the magnetic order in tensile CaRuO3. We further establish that the tensile strain is more efficient than the chemical route to induce FM order in CaRuO3. PMID:24464302

  12. Nanosecond photoreduction of cytochrome p450cam by channel-specific Ru-diimine electron tunneling wires.

    PubMed

    Dunn, Alexander R; Dmochowski, Ivan J; Winkler, Jay R; Gray, Harry B

    2003-10-15

    We report the synthesis and characterization of Ru-diimine complexes designed to bind to cytochrome p450cam (CYP101). The sensitizer core has the structure [Ru(L(2))L'](2+), where L' is a perfluorinated biphenyl bridge (F(8)bp) connecting 4,4'-dimethylbipyridine to an enzyme substrate (adamantane, F(8)bp-Ad), a heme ligand (imidazole, F(8)bp-Im), or F (F(9)bp). The electron-transfer (ET) driving force (-deltaG degrees ) is varied by replacing the ancillary 2,2'-bipyridine ligands with 4,4',5,5'-tetramethylbipyridine (tmRu). The four complexes all bind p450cam tightly: Ru-F(8)bp-Ad (1, K(d) = 0.077 microM); Ru-F(8)bp-Im (2, K(d) = 3.7 microM); tmRu-F(9)bp (3, K(d) = 2.1 microM); and tmRu-F(8)bp-Im (4, K(d) = 0.48 microM). Binding is predominantly driven by hydrophobic interactions between the Ru-diimine wires and the substrate access channel. With Ru-F(8)bp wires, redox reactions can be triggered on the nanosecond time scale. Ru-wire 2, which ligates the heme iron, shows a small amount of transient heme photoreduction (ca. 30%), whereas the transient photoreduction yield for 4 is 76%. Forward ET with 4 occurs in roughly 40 ns (k(f) = 2.8 x 10(7) s(-)(1)), and back ET (Fe(II) --> Ru(III), k(b) approximately 1.7 x 10(8) s(-)(1)) is near the coupling-limited rate (k(max)). Direct photoreduction was not observed for 1 or 3. The large variation in ET rates among the Ru-diimine:p450 conjugates strongly supports a through-bond model of Ru-heme electronic coupling. PMID:14531688

  13. Model study of CO inhibition of [NiFe]hydrogenase.

    PubMed

    Matsumoto, Takahiro; Kabe, Ryota; Nonaka, Kyoshiro; Ando, Tatsuya; Yoon, Ki-Seok; Nakai, Hidetaka; Ogo, Seiji

    2011-09-19

    We propose a modified mechanism for the inhibition of [NiFe]hydrogenase ([NiFe]H(2)ase) by CO. We present a model study, using a NiRu H(2)ase mimic, that demonstrates that (i) CO completely inhibits the catalytic cycle of the model compound, (ii) CO prefers to coordinate to the Ru(II) center rather than taking an axial position on the Ni(II) center, and (iii) CO is unable to displace a hydrido ligand from the NiRu center. We combine these studies with a reevaluation of previous studies to propose that, under normal circumstances, CO inhibits [NiFe]H(2)ase by complexing to the Fe(II) center. PMID:21853978

  14. First identification of excited states in the N=Z+1 nucleus {sup 89}Ru

    SciTech Connect

    Marginean, N.; Rusu, C.; Bucurescu, D.; Ionescu-Bujor, M.; Iordachescu, A.; Alvarez, C. Rossi; Bazzacco, D.; Lunardi, S.; Pavan, P.; Farnea, E.; Lenzi, S.M.; Menegazzo, R.; Ur, C.A.; De Angelis, G.; Axiotis, M.; Gadea, A.; Kroell, Th.; Martinez, T.; Napoli, D.R.; Spolaore, P.

    2004-10-01

    High-spin excited states have been identified for the first time in the N=Z+1 nucleus {sup 89}Ru with the reaction {sup 54}Fe({sup 40}Ca,{alpha}n{gamma}) at 130 MeV, using the GASP array, the ISIS Silicon array, and the n-Ring detector system. The observed structure is discussed within systematics of the N=45 isotones and is compared with shell model calculations.

  15. Vacuolar membrane transporters OsVIT1 and OsVIT2 modulate iron translocation between flag leaves and seeds in rice.

    PubMed

    Zhang, Yu; Xu, Yong-Han; Yi, Hong-Yin; Gong, Ji-Ming

    2012-11-01

    The plant vacuole is an important organelle for storing excess iron (Fe), though its contribution to increasing the Fe content in staple foods remains largely unexplored. In this study we report the isolation and functional characterization of two rice genes OsVIT1 and OsVIT2, orthologs of the Arabidopsis VIT1. Transient expression of OsVIT1:EGFP and OsVIT2:EGFP protein fusions revealed that OsVIT1 and OsVIT2 are localized to the vacuolar membrane. Ectopic expression of OsVIT1 and OsVIT2 partially rescued the Fe(2+) - and Zn(2+) -sensitive phenotypes in yeast mutant Δccc1 and Δzrc1, and further increased vacuolar Fe(2+) , Zn(2+) and Mn(2+) accumulation. These data together suggest that OsVIT1 and OsVIT2 function to transport Fe(2+) , Zn(2+) and Mn(2+) across the tonoplast into vacuoles in yeast. In rice, OsVIT1 and OsVIT2 are highly expressed in flag leaf blade and sheath, respectively, and in contrast to OsVIT1, OsVIT2 is highly responsive to Fe treatments. Interestingly, functional disruption of OsVIT1 and OsVIT2 leads to increased Fe/Zn accumulation in rice seeds and a corresponding decrease in the source organ flag leaves, indicating an enhanced Fe/Zn translocation between source and sink organs, which might represent a novel strategy to biofortify Fe/Zn in staple foods. PMID:22731699

  16. 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. PMID:27109569

  17. First water-soluble backbone Ru-Ru-Ni heterometallic organometallic polymer.

    PubMed

    Scalambra, Franco; Serrano-Ruiz, Manuel; Romerosa, Antonio

    2015-04-01

    The water-soluble backbone heterometallic polymer {[(PTA)2 CpRu-μ-CN-RuCp(PTA)2 -μ-NiCl3 ]}n (2) is synthesized using a reproducible and robust method and fully characterized by X-ray single crystal diffraction. The Ru-Ru-Ni polymer is found to be stable in the solid state and soluble in water. Nuclear magnetic resonance (NMR) and light scattering studies show that the polymer is stable in water for several days in air. PMID:25739739

  18. Electronic and magnetic properties of SrRuO3 with Ru-vacancy: First-principle calculations

    NASA Astrophysics Data System (ADS)

    Lv, Kai; Zhu, H. P.; Peng, J.; Zhang, G. P.; Wu, X. S.

    2016-01-01

    By using first-principle calculations, the electronic and magnetic properties of the Ru-deficient SrRu1-x O3 (x = 1/32) have been investigated. The obtained results indicate that nearest Ru and O ions of the vacancy move away from the Ru-vacancy, while the nearest Sr ions shift toward the vacancy. Interestingly, an antiferromagnetic spin cluster is formed in the vicinity of the Ru-deficient site. This, in turn, gives rise to reduced overall magnetic moment which better agrees with the experiment values for SrRuO3 reported in the literature. The adjustment of O ions surrounding the vacancy splits the near-vacancy Ru t 2g orbitals, and the unoccupied ones appear above the Fermi level. The truncated effect at the vacancy, modified Ru-O covalent bonds, and Ru-O-Ru angles have jointly stabilized the antiferromagnetic spin cluster.

  19. Fabrication of perpendicular magnetic recording tape media with a data capacity of over-50TB using Si/NiFe/FeCoB soft magnetic underlayers

    NASA Astrophysics Data System (ADS)

    Gomi, S.; Mashiko, Y.; Hirata, K.; Matsunuma, S.; Inoue, T.; Doi, T.; Watanabe, T.; Nakagawa, S.

    C-axis orientations of Ru intermediate layer (IML) and CoPtCr-SiO2 recording layer (RL) are attained by using crystalline FeCoB soft magnetic underlayer (SUL). Better (110) orientation of FeCo improves not only (001) orientation of Ru IML but also that of CoPtCr RL. This leads better perpendicular magnetic anisotropy in the RL suitable for perpendicular magnetic recording media. In order to control the (110) orientation in FeCoB layer, various seed layers are prepared beneath the FeCoB layers. Ru and Si/NiFe seed layers gives FeCoB layer a large in-plane magnetic anisotropy that is effective to suppress spike noise from SUL. The laminated FeCoB SUL causes more improvement of Ru (001) texure and leads to better perpendicular magnetic anisotropy of RL. Ru/CoPtCr-SiO2 bilayer deposited on laminated FeCoB SUL on Aramid tape substrate has good perpendicular magnetic properties and reduces the noise from SUL. PACS: Type pacs here, separated by semicolons;

  20. Into the Modelling of RU Vir

    NASA Astrophysics Data System (ADS)

    Rau, G.; Hron, J.; Paladini, C.; Eriksson, K.; Aringer, B.; Groenewegen, M. A. T.; Mečina, M.

    2015-08-01

    We present an attempt to model the atmosphere of the carbon-rich Mira star RU Vir, using different techniques including spectroscopy, photometry, and interferometry. A radiative transfer code and hydrostatic model atmospheres were used for a preliminary study. To investigate the dynamic processes happening in RU Vir, dynamic model atmospheres were compared to new MIDI/VLTI observations obtained in April 2014, and SiC opacities were added.

  1. [Analgesic properties of morpholinoethylimidazobenzimidazole derivative RU-1205].

    PubMed

    Spasov, A A; Grechko, O Iu; Shtareva, D M; Anisimova, V A

    2013-01-01

    We have studied the analgesic activity of a morpholinoethylimidazobenzimidazole derivative (RU-1205) in comparison to butorphanol. It is established that the test compound exhibits a pronounced analgesic activity, which exceeded that ofbutorphanol six times in the hot-plate test and was comparable to the reference drug effect in the tail-flick and acetic acid-induced writhing tests. It is established that the analgesic action of RU-1205 is based on the kappa-opioidergic mechanism. PMID:24432563

  2. Human Glucocorticoid Receptor β Binds RU-486 and Is Transcriptionally Active▿

    PubMed Central

    Lewis-Tuffin, Laura J.; Jewell, Christine M.; Bienstock, Rachelle J.; Collins, Jennifer B.; Cidlowski, John A.

    2007-01-01

    Human glucocorticoid receptor (hGR) is expressed as two alternately spliced C-terminal isoforms, α and β. In contrast to the canonical hGRα, hGRβ is a nucleus-localized orphan receptor thought not to bind ligand and not to affect gene transcription other than by acting as a dominant negative to hGRα. Here we used confocal microscopy to examine the cellular localization of transiently expressed fluorescent protein-tagged hGRβ in COS-1 and U-2 OS cells. Surprisingly, yellow fluorescent protein (YFP)-hGRβ was predominantly located in the cytoplasm and translocated to the nucleus following application of the glucocorticoid antagonist RU-486. This effect of RU-486 was confirmed with transiently expressed wild-type hGRβ. Confocal microscopy of coexpressed YFP-hGRβ and cyan fluorescent protein-hGRα in COS-1 cells indicated that the receptors move into the nucleus independently. Using a ligand binding assay, we confirmed that hGRβ bound RU-486 but not the hGRα ligand dexamethasone. Examination of the cellular localization of YFP-hGRβ in response to a series of 57 related compounds indicated that RU-486 is thus far the only identified ligand that interacts with hGRβ. The selective interaction of RU-486 with hGRβ was also supported by molecular modeling and computational docking studies. Interestingly, microarray analysis indicates that hGRβ, expressed in the absence of hGRα, can regulate gene expression and furthermore that occupation of hGRβ with the antagonist RU-486 diminishes that capacity despite the lack of helix 12 in the ligand binding domain. PMID:17242213

  3. Platinum-group minerals from placers related to the Nizhni Tagil (Middle Urals, Russia) Uralian-Alaskan-type ultramafic complex: ore-mineralogy and study of silicate inclusions in (Pt, Fe) alloys

    NASA Astrophysics Data System (ADS)

    Johan, Z.

    2006-05-01

    The study of platinum-group minerals (PGM) concentrates from the Nizhni Tagil placers related to the Soloviev Mountain (Gora Solovieva) Uralian-Alaskan-type intrusion revealed a predominance of (Pt, Fe) alloys over Ir-, and Os-bearing alloys. (Pt, Fe) alloys (“isoferroplatinum-type”) are interstitial with respect to chromite and show important variations in their chemical compositions, which are, however, falling within the experimentally determined stability field of isoferroplatinum. Tetraferroplatinum, enriched in Cu and Ni and tulameenite represent low-temperature mineral phases replacing (Pt, Fe) alloys. Alloys belonging to the Os-Ir-Ru ternary system have compositions corresponding to native osmium, iridium and ruthenium, respectively, and to rutheniridosmine. Osmium exsolutions appear in Ir-, and (Pt, Fe) alloys, and iridium exsolutions in (Pt, Fe) alloys. Laurite is a high-temperature phase included in native iridium and (Pt, Fe) alloys. Low-temperature PGM association comprises Ir-bearing sulpharsenides, including a phase (Ir, Os, Fe, Pt, Ru, Ni)3(As, Sb)0.85S, and a palladium antimonide Pd20Sb7. These two phases were previously unknown in nature. Furthermore, native palladium occurs in the studied concentrates. This low-temperature paragenesis indicates an interaction of Pt-, Os-, Ir- and Ru-bearing alloys with late fluids enriched in volatiles, As and Sb. The chromite composition is characterized by the predominance of Cr3+ → Fe3+ substitution like in other Uralian-Alaskan-type intrusions; that indicates a fO2 variation during the chromite precipitation. Monomineralic inclusions of euhedral clinopyroxene and chromite crystals in (Pt, Fe) alloys were observed. Furthermore, (Pt, Fe) alloys contain polyphase silicate inclusions, which occupy the alloy negative crystals. Two types of silicate inclusions were recognized: (1) Low-pressure inclusions composed of amphibole, biotite, Jd-poor clinopyroxene, magnetite, apatite and glass; (2) High

  4. Behavior of Ru surfaces after ozonated water treatment

    NASA Astrophysics Data System (ADS)

    Seo, Dongwan; Park, Chanhyoung; Jung, Juneui; Yoon, Mihyun; Lee, Dongwook; Kim, Chang Yeol; Lim, Sangwoo

    2011-10-01

    In order for the development of cleaning technology of extreme ultra violet lithography photomask, the behavior of Ru surfaces after treatment with ozonated deionized water (DIO 3) solution was studied using Ru and ruthenium oxide particles and 2 nm-thick Ru capping layers. No significant changes in crystalline structures or chemical states of the Ru surfaces, nor any similarities with the structures or states of ruthenium oxide, were observed after DIO 3 treatment. Oxidation of ruthenium to form RuO 2 or RuO 3 was not observed. Adsorption of H 2O molecules on the Ru layer increased the surface roughness, but the desorption of H 2O molecules recovered it. Local chemisorption of H 2O molecules on the Ru surface may be the reason why rougher Ru surfaces were observed after DIO 3 cleaning.

  5. 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.

  6. Site segregation in model clusters of small bimetallic RuGe and RuSn aggregates

    SciTech Connect

    Goursot, A.; Pedocchi, L.; Coq, B.

    1994-09-01

    RuGe and RuSn model clusters in both fixed bulk and relaxed structures are studied for stability during relaxation. Distortion causes a reduction in coordination of the Sn or Ge atom. Relaxation causes the Ge to have a small preference for the corner site (low coordination), but the Sn has a large corner site preference. 45 refs., 1 fig., 4 tabs.

  7. Effect of laminated crystalline FeCoB soft magnetic underlayer for perpendicular magnetic recording tape media

    NASA Astrophysics Data System (ADS)

    Gomi, Shunsuke; Mashiko, Yasuhiro; Hirata, Ken-ichiro; Matsunuma, Satoshi; Inoue, Tetsutaro; Doi, Tsugihiro; Watanabe, Toshiyuki; Nakagawa, Shigeki

    2011-04-01

    A crystalline FeCoB soft magnetic underlayer (SUL) improves c-axis orientations of the Ru intermediate layer (IML) and the CoPtCr-SiO2 recording layer (RL). (001) orientations of Ru IML and CoPtCr RL are attained by (110) oriented texture of FeCoB SUL. Since good c-axis orientation in CoPtCr-SiO2 RL as well as domain control in the FeCoB SUL is required for high recording density, a laminated FeCoB SUL is prepared as an underlayer of the bilayered Ru/CoPtCr-SiO2 films. A laminated FeCoB SUL results in better (001) orientation in both CoPtCr-SiO2 RL and Ru IML than the single layered FeCoB SUL. This leads to the reduction of media noise in the high recording frequency region. Recording medium layers composed of a laminated FeCoB SUL and bilayered Ru/CoPtCr-SiO2 films deposited on a 4.5-μm-thick Aramid tape show better (001) orientations of Ru and CoPtCr. Media noise of the tape medium with the laminated SUL is lower than that with the single layered FeCoB SUL.

  8. 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

    2013-10-01

    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

  9. Temperature dependence of interlayer coupling between perpendicular magnetic [CoFeB/Pd] multilayers: Influence of interfacial CoFeB layer

    NASA Astrophysics Data System (ADS)

    Xiao, Yili; Zhang, Zongzhi; Ma, Bin; Jin, Q. Y.; Liu, Yaowen

    2014-02-01

    Temperature dependence of interlayer coupling field in the perpendicular antiferromagnetic structure of [Pd/CoFeB]2/Pd/CoFeB(tCFB)/Ru(tRu)/CoFeB(tCFB)/Pd/[CoFeB/Pd]2 is found to be sensitive to tCFB, showing various non-monotonic behaviors. The coupling strength increases with tCFB, reaching bulk-like value of up to 0.28 erg/cm2 at room temperature as tCFB is over 0.6 nm. We attribute the phenomena to interfacial effects, including lowered Curie temperature in ultrathin CoFeB layers and increased effective dead layer thickness. The coupling peak position of tRu also shifts with temperature and tCFB, corresponding to variations in dead layer thicknesses. These effects should be considered when designing practical devices employing perpendicular synthetic antiferromagnetic structures.

  10. Remarkable aspects of unsaturation in trinuclear metal carbonyl clusters: the triiron species Fe3(CO)n (n = 12, 11, 10, 9).

    PubMed

    Wang, Hongyan; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2006-09-01

    The trinuclear iron carbonyls Fe(3)(CO)(n) (n = 12, 11, 10, 9) have been studied by density functional theory using the B3LYP and BP86 functionals. The experimentally known C(2)(v) isomer of Fe(3)(CO)(12), namely Fe(3)(CO)(10)(mu-CO)(2), is found to be the global minimum below the unbridged D(3)(h) isomer analogous to the known structures for Ru(3)(CO)(12) and Os(3)(CO)(12). The lowest-energy isomer found for Fe(3)(CO)(11) is Fe(3)(CO)(9)(mu(3)-CO)(2) with iron-iron distances in the Fe(3) triangle, suggesting the one double bond (2.460 A by B3LYP and 2.450 A by BP86) and two single bonds (2.623 A by B3LYP and 2.604 A by BP86) required to give each Fe atom the favored 18-electron configuration. Two different higher-energy dibridged structures Fe(3)(CO)(9)(mu(2)-CO)(2) are also found for Fe(3)(CO)(11). The lowest-energy isomer found for Fe(3)(CO)(10) is Fe(3)(CO)(9)(mu(3)-CO) with equivalent iron-iron distances in the Fe(3) ring (2.47 A by B3LYP or BP86). The lowest-energy isomer found for Fe(3)(CO)(9) is Fe(3)(CO)(6)(mu-CO)(3) with distances in the Fe(3) triangle possibly suggesting one single bond (2.618 A by B3LYP and 2.601 A by BP86), one weak double bond (2.491 A by B3LYP and 2.473 A by BP86), and one weak triple bond (2.368 A by B3LYP and 2.343 A by BP86). A higher-lying isomer of Fe(3)(CO)(9), i.e., Fe(3)(CO)(8)(mu-CO), at approximately 21 kcal/mol above the global minimum, has iron-iron distances strongly suggesting two single bonds (2.6 to 2.7 A) and one quadruple bond (2.068 A by B3LYP and 2.103 A by BP86). Wiberg Bond Indices are also helpful in evaluating the iron-iron bond orders. PMID:16939260

  11. Study of DNA light switch Ru(II) complexes: synthesis, characterization, photocleavage and antimicrobial activity.

    PubMed

    Yata, Praveen Kumar; Shilpa, M; Nagababu, P; Reddy, M Rajender; Kotha, Laxma Reddy; Gabra, Nazar Md; Satyanarayana, S

    2012-05-01

    The three Ru(II) complexes of [Ru(phen)(2)dppca](2+) (1) [Ru(bpy)(2)dppca](2+) (2) and [Ru(dmb)(2)dppca](2+) (3) (where phen = 1,10 phenanthroline, bpy = 2,2-bipyridine, dmb = 2 ,2-dimethyl 2',2'-bipyridine and polypyridyl ligand containing a single carboxylate functionality dppca ligand (dipyridophenazine-11-carboxylic acid) have been synthesized and characterized. These complexes have been shown to act as promising calf thymus DNA intercalators and a new class of DNA light switches, as evidenced by UV-visible and luminescence titrations with Co(2+) and EDTA, steady-state emission quenching by [Fe(CN)(6)](4-) and KI, DNA competitive binding with ethidium bromide, viscosity measurements, and DNA melting experiments. The results suggest that 1, 2, and 3 complexes bind to CT-DNA through intercalation and follows the order 1 > 2 > 3. Under irradiation at 365 nm, the three complexes have also been found to promote the photocleavage of plasmid pBR322 DNA. PMID:22194001

  12. 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. PMID:22906879

  13. 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.

  14. 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. PMID:19209363

  15. Oligomeric rare-earth-metal halide clusters. Three structures built of (Y{sub 16}Z{sub 4})Br{sub 36} units (Z = Ru, Ir)

    SciTech Connect

    Steinward, S.J.; Corbett, J.D.

    1996-11-20

    Suitable reactions in sealed Nb tubing at 850-950 {degrees}C gave good yields of a family of oligomeric cluster phases that were characterized by single-crystal X-ray diffraction means. The basic Y{sub 16}Z{sub 4} units ({approximately}{bar 4} symmetry) can be derived from 2+2 condensation of centered Y{sub 6}Br{sub 12}Z-type clusters or as tetracapped truncated tetrahedra Y{sub 16} that are centered by a large tetrahedral Z{sub 4}. These are surrounded by 36 bromine atoms which bridge edges or cap faces of the Y{sub 16}Z{sub 4} nuclei and, in part, bridge to metal atoms in other clusters. The principal bonding appears to be Y-Z and Y-Br, with weaker Y-Y ({bar d} {approximately} 3.70 {angstrom}) and negligible Z-Z interactions. The phase Y{sub 16}Br{sub 20}Ru{sub 4} (P4{sub 2}/nnm, Z = 2; a = 11.662(1) {angstrom}, c = 16.992 (2) {angstrom}) is isostructural with Y{sub 16}I{sub 20}Ru{sub 4} and with the new Sc{sub 16-} Br{sub 20}Z{sub 4} (Z = Fe, Os). Syntheses only in the presence of Ir and ABr-YBr{sub 3} fluxes (A = K-Cs) produce Y{sub 16-} Br{sub 24}Ir{sub 4} (Fddd, Z = 8; a = 11.718(3) {angstrom}, b = 22.361(7) {angstrom}, c = 44.702(2) {angstrom}), in which the electron-richer Ir interstitials are compensated by four additional bromine atoms and altered bridging between macroclusters. Larger amounts of YBr{sub 3} yield a third example, Y{sub 20}Br{sub 36}Ir{sub 4} (Y{sub 16}Br{sub 24}Ir{sub 4}{center_dot}4YBr{sub 3}, I4{sub 1}a, Z = 4; a = 12.699(1) {angstrom}, c = 45.11- (1){angstrom}). Here infinite zigzag chains of YBr{sub 6/2} octahedra that share cis edges lie between and bridge to the Y{sub 16}Ir{sub 4} clusters. All of these phases contain 60-electron, closed-shell macroclusters. Y{sub 16}Br{sub 20}Ru{sub 4} and Y{sub 20}Br{sub 36}ir{sub 4} were found to exhibit temperature-independent (Van Vleck) paramagnetism with values typical of those found for other rare-earth-metal, zirconium, niobium, and tantalum cluster halides.

  16. 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

  17. The synthesis and structural characterisation of [Ru(eta-Cp)(dppf)SnBr3].

    PubMed

    Paim, L A; Moura, E M; Siebald, H G L; de Lima, G M; Doriguetto, A C; Ellena, J

    2004-08-01

    The reaction of [Ru(eta-Cp)(dppf)N(3)] (1) with equimolar amount of SnBr(2) yielded an interesting heterotrimetallic compound [Ru(eta-Cp)(dppf)SnBr(3)] (2) (dppf: 1,1'-bis-diphenylphosphinoferrocene). Compounds 1 and 2 were characterised by IR, NMR (1H, 13C, 31P and 119Sn), and 2, additionally, by 57Fe and 119Sn Mössbauer spectroscopy and X-ray crystallography. The latter results were as follows: monoclinic, C2/c, a = 32.8879(4)A, b = 11.9888(2)A, c = 20.8986(3)A, beta = 92.545(1)degrees, V = 8231.9(2)A(3), Z =8. PMID:15249029

  18. The synthesis and structural characterisation of [Ru(η-Cp)(dppf)SnBr 3

    NASA Astrophysics Data System (ADS)

    Paim, L. A.; Moura, E. M.; Siebald, H. G. L.; de Lima, G. M.; Doriguetto, A. C.; Ellena, J.

    2004-08-01

    The reaction of [Ru(η-Cp)(dppf)N 3] ( 1) with equimolar amount of SnBr 2 yielded an interesting heterotrimetallic compound [Ru(η-Cp)(dppf)SnBr 3] ( 2) (dppf: 1,1'-bis-diphenylphosphinoferrocene). Compounds 1 and 2 were characterised by IR, NMR ( 1H, 13C, 31P and 119Sn), and 2, additionally, by 57Fe and 119Sn Mössbauer spectroscopy and X-ray crystallography. The latter results were as follows: monoclinic, C2/ c, a=32.8879(4) Å, b=11.9888(2) Å, c=20.8986(3) Å, β=92.545(1)°, V=8231.9(2) Å 3, Z=8.

  19. Disruption of OsYSL15 leads to iron inefficiency in rice plants.

    PubMed

    Lee, Sichul; Chiecko, Jeff C; Kim, Sun A; Walker, Elsbeth L; Lee, Youngsook; Guerinot, Mary Lou; An, Gynheung

    2009-06-01

    Uptake and translocation of metal nutrients are essential processes for plant growth. Graminaceous species release phytosiderophores that bind to Fe(3+); these complexes are then transported across the plasma membrane. We have characterized OsYSL15, one of the rice (Oryza sativa) YS1-like (YSL) genes that are strongly induced by iron (Fe) deficiency. The OsYSL15 promoter fusion to beta-glucuronidase showed that it was expressed in all root tissues when Fe was limited. In low-Fe leaves, the promoter became active in all tissues except epidermal cells. This activity was also detected in flowers and seeds. The OsYSL15:green fluorescent protein fusion was localized to the plasma membrane. OsYSL15 functionally complemented yeast strains defective in Fe uptake on media containing Fe(3+)-deoxymugineic acid and Fe(2+)-nicotianamine. Two insertional osysl15 mutants exhibited chlorotic phenotypes under Fe deficiency and had reduced Fe concentrations in their shoots, roots, and seeds. Nitric oxide treatment reversed this chlorosis under Fe-limiting conditions. Overexpression of OsYSL15 increased the Fe concentration in leaves and seeds from transgenic plants. Altogether, these results demonstrate roles for OsYSL15 in Fe uptake and distribution in rice plants. PMID:19376836

  20. Chemical vapour deposition of amorphous Ru(P) thin films from Ru trialkylphosphite hydride complexes.

    PubMed

    McCarty, W Jeffrey; Yang, Xiaoping; DePue Anderson, Lauren J; Jones, Richard A

    2012-11-21

    The ruthenium phosphite hydride complexes H(2)Ru(P(OR)(3))(4) (R = Me (1), Et (2), (i)Pr (3)) were used as CVD precursors for the deposition of films of amorphous ruthenium-phosphorus alloys. The as-deposited films were X-ray amorphous and XPS analysis revealed that they were predominantly comprised of Ru and P in zero oxidation states. XPS analysis also showed the presence of small amounts of oxidized ruthenium and phosphorus. The composition of the films was found to depend on ligand chemistry as well as the deposition conditions. The use of H(2) as the carrier gas had the effect of increasing the relative concentrations of P and O for all films. Annealing films to 700 °C under vacuum produced films of polycrystalline hcp Ru while a flowing stream of H(2) resulted in polycrystalline hcp RuP. PMID:23018487

  1. Level structure of /sup 101/Ru from the /sup 100/Ru(d,p) reaction

    SciTech Connect

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

    1988-08-01

    Energy levels of /sup 101/Ru have been studied by the /sup 100/Ru(d,p)/sup 101/Ru reaction at an incident deuteron energy of 12 MeV. Outgoing particles were momentum analyzed by a magnetic spectrograph and detected in nuclear emulsion plates, with an energy resolution of 7.5 keV. A total of 68 levels up to 3.2 MeV excitation energy was identified, about two-thirds of them reported for the first time. Experimental angular distributions were compared to distorted-wave Born approximation predictions and reduced spectroscopic factors obtained. The total l = 2 and 75% of l = 0, 4, and 5 spectroscopic strengths were located. Attention is drawn to transitions to low-lying states in /sup 101/Ru (below E/sub exc/ = 0.75 MeV) with l = 3 and l = 1 character.

  2. Preparation, structure and mechanical properties of RuAl and (Ru,Ni)Al alloys

    SciTech Connect

    Sabariz, A.L.R.; Taylor, G.

    1997-12-31

    The intermetallic compound, RuAl with B2 CsCl type structure, has been shown to possess room-temperature toughness and plasticity. NiAl also forms a B2 compound and it is claimed that a pseudo-binary compound, (Ru,Ni)Al, may be formed because the difference in lattice parameter between the two binary phases is slight. In this work a study has been made of the mechanical properties of some polycrystalline compounds, across the RuAl-(Ru,Ni)Al pseudo-binary, prepared from high-purity elemental powders. Compressive yield stresses were measured between room-temperature and 900 C, and the mechanisms of plastic flow are discussed in relation to the dislocation structures observed by TEM. Hot-microhardness tests were made to provide an indication of the effect of solid-solution hardening.

  3. 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. PMID:12321809

  4. Hexadecapolar excitation in sup 100 Ru

    SciTech Connect

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

    1989-09-01

    Attention is drawn to the strong collective {ital L}=4 direct excitation of the state at 2.367 MeV in {sup 100}Ru by inelastic scattering of 16 MeV protons characterized by a deformation parameter {beta}{sub 4}=0.10, one of the highest reported for any region of the mass table.

  5. 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

  6. 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.

  7. Light-induced water oxidation catalyzed by an oxido-bridged triruthenium complex with a Ru-O-Ru-O-Ru motif.

    PubMed

    Tsubonouchi, Yuta; Lin, Shu; Parent, Alexander R; Brudvig, Gary W; Sakai, Ken

    2016-06-28

    A μ-oxido-bridged triruthenium complex (RuT(2+)), formed by air-oxidation of a previously reported monoruthenium water oxidation catalyst (WOC), serves as an efficient photochemical WOC with the turnover frequency (TOF) and turnover number (TON) 0.90 s(-1) and 610, respectively. The crystal structures of RuT(2+) and its one-electron oxidized RuT(3+) are also reported. PMID:27264497

  8. s-Process Os isotope enrichment in ureilites by planetary processing

    NASA Astrophysics Data System (ADS)

    Goderis, S.; Brandon, A. D.; Mayer, B.; Humayun, M.

    2015-12-01

    Ubiquitous nucleosynthetic isotope anomalies relative to the terrestrial isotopic composition in Mo, Ru, and other elements are known from both bulk chondrites and differentiated meteorites, but Os isotope ratios reported from such meteorites have been found to be indistinguishable from the terrestrial value. The carriers of s- and r-process Os must thus have been homogeneously distributed in the solar nebula. As large Os isotope anomalies are known from acid leachates and residues of primitive chondrites, the constant relative proportions of presolar s- and r-process carriers in such chondrites must have been maintained during nebular processes. It has long been assumed that partial melting of primitive chondrites would homogenize the isotopic heterogeneity carried by presolar grains. Here, ureilites, carbon-rich ultramafic achondrites dominantly composed of olivine and low-Ca pyroxene, are shown to be the first differentiated bulk Solar System materials for which nucleosynthetic Os isotope anomalies have been identified. These anomalies consist of enrichment in s-process Os heterogeneously distributed in different ureilites. Given the observed homogeneity of Os isotopes in all types of primitive chondrites, this Os isotope variability among ureilites must have been caused by selective removal of s-process-poor Os host phases, probably metal, during rapid localized melting on the ureilite parent body. While Mo and Ru isotope anomalies for all meteorites measured so far exhibit s-process deficits relative to the Earth, the opposite holds for the Os isotope anomalies in ureilites reported here. This might indicate that the Earth preferentially accreted olivine-rich restites and inherited a s-process excess relative to smaller meteorite bodies, consistent with Earth's high Mg/Si ratio and enrichment of s-process nuclides in Mo, Ru, and Nd isotopes. Our new Os isotope results imply that caution must be used when applying nucleosynthetic isotope anomalies as provenance

  9. 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

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

    PubMed

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

    2016-08-01

    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). PMID:27009374

  11. Large magnetoresistance in magnetically coupled SrRuO₃ -CoFe₂O₄ self-assembled nanostructures.

    PubMed

    Liu, Heng-Jui; Tra, Vu-Thanh; Chen, Ying-Jiun; Huang, Rong; Duan, Chun-Gang; Hsieh, Ying-Hui; Lin, Hong-Ji; Lin, Jiunn-Yuan; Chen, Chien-Te; Ikuhara, Yuichi; Chu, Ying-Hao

    2013-09-14

    A new way to induce a large magnetoresistance has been achieved by self-assembled nanostructures consisting of ferromagnetic spinel CoFe₂O₄ (CFO) and metallic perovskite SrRuO₃ (SRO). The interdiffused Fe³⁺ ions in SRO have paved the way to strong magnetic couplings with CFO nanopillars, resulting in the suppression of spin-polarized electron scattering. PMID:23847088

  12. A [NiFe]hydrogenase model that catalyses the release of hydrogen from formic acid.

    PubMed

    Nguyen, Nga T; Mori, Yuki; Matsumoto, Takahiro; Yatabe, Takeshi; Kabe, Ryota; Nakai, Hidetaka; Yoon, Ki-Seok; Ogo, Seiji

    2014-11-11

    We report the decomposition of formic acid to hydrogen and carbon dioxide, catalysed by a NiRu complex originally developed as a [NiFe]hydrogenase model. This is the first example of H2 evolution, catalysed by a [NiFe]hydrogenase model, which does not require additional energy. PMID:25234420

  13. Exchange bias of spin valve structure with a top-pinned Co{sub 40}Fe{sub 40}B{sub 20}/IrMn

    SciTech Connect

    You, C. Y.; Furubayashi, T.; Takahashi, Y. K.; Goripati, H. S.; Hono, K.

    2008-07-07

    We have investigated the exchange bias of a directly top-pinned Co{sub 40}Fe{sub 40}B{sub 20}/IrMn structure. An exchange bias was realized on the as-deposited samples, in which Co{sub 40}Fe{sub 40}B{sub 20} exhibits a fully amorphous structure. A current-in-plane giant magnetoresistance effect was demonstrated on simple Ru/CoFeB/Cu/CoFeB/IrMn/Ru stacks prior to and after annealing. The amorphous CoFeB layer partially crystallized from the interface with a Cu spacer layer after annealed at 280 deg. C.

  14. 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.

  15. Hydrostatic High-Pressure Studies to 25 GPA on the Model Superconducting Pnictide LaRu2P2

    NASA Astrophysics Data System (ADS)

    Lim, Jinhyuk; Forouzani, Neda; Schilling, James; Fotovat, Roxanna; Zheng, Chong; Hoffmann, Roald

    2014-03-01

    Prior to the discovery of the Fe-pnictides in 2008, the ruthenium phosphide LaRu2P2 possessed the highest value of the su- perconducting transition temperature, Tc ~ 4 K, in the entire pnictide family. Recently, there has been renewed interest in this compound in an effort to better understand why the Fe-pnictides have much higher values of Tc. In related phosphides superconductivity appears to only be present if the separation be- tween the phosphor ions dp-p in neigh- boring Ru2P2 planes is greater than the critical value 2.8 Å, too great for a P-P covalent bond to be formed. For example, in superconducting LaRu2P2, the value of dp-p is 3.0 Å. To test these ideas directly, we have carried out hydro- static high-pressure studies on single-crystalline LaRu2P2 in a diamond-anvil cell using He pressure medium to pres- sures as high as 25 GPa and temperatures as low as 1.5 K. We find that Tc initially increases under pressure, but suddenly disappears above 2.1 GPa. Since dp-p decreases under pressure, the sudden disappearance of superconductivity is likely due to the formation of a covalent P-P bond between adjacent Ru2P2 planes and a possible structural phase transition. Work at Washington University is supported by the NSF through Grant No. DMR-1104742 and by the Carnegie/DOE through NNSA/DOE Grant No. DE-FC52-08NA28554.

  16. 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).

  17. Ru nanostructure fabrication using an anodic aluminum oxide nanotemplate and highly conformal Ru atomic layer deposition.

    PubMed

    Kim, Woo-Hee; Park, Sang-Joon; Son, Jong-Yeog; Kim, Hyungjun

    2008-01-30

    We fabricated metallic nanostructures directly on Si substrates through a hybrid nanoprocess combining atomic layer deposition (ALD) and a self-assembled anodic aluminum oxide (AAO) nanotemplate. ALD Ru films with Ru(DMPD)(EtCp) as a precursor and O(2) as a reactant exhibited high purity and low resistivity with negligible nucleation delay and low roughness. These good growth characteristics resulted in the excellent conformality for nanometer-scale vias and trenches. Additionally, AAO nanotemplates were fabricated directly on Si and Ti/Si substrates through a multiple anodization process. AAO nanotemplates with various hole sizes (30-100 nm) and aspect ratios (2:1-20:1) were fabricated by controlling the anodizing process parameters. The barrier layers between AAO nanotemplates and Si substrates were completely removed by reactive ion etching (RIE) using BCl(3) plasma. By combining the ALD Ru and the AAO nanotemplate, Ru nanostructures with controllable sizes and shapes were prepared on Si and Ti/Si substrates. The Ru nanowire array devices as a platform for sensor devices exhibited befitting properties of good ohmic contact and high surface/volume ratio. PMID:21817499

  18. 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

    2015-08-01

    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. PMID:26135381

  19. Magnetic phase transitions and magnetization reversal in MnRuP

    NASA Astrophysics Data System (ADS)

    Lampen-Kelley, P.; Mandrus, D.

    The ternary phosphide MnRuP is an incommensurate antiferromagnetic metal crystallizing in the non-centrosymmetric Fe2P-type crystal structure. Below the Neel transition at 250 K, MnRuP exhibits hysteretic anomalies in resistivity and magnetic susceptibility curves as the propagation vectors of the spiral spin structure change discontinuously across T1 = 180 K and T2 = 100 K. Temperature-dependent X-ray diffraction data indicate that the first-order spin reorientation occurs in the absence of a structural transition. A strong magnetization reversal (MR) effect is observed upon cooling the system through TN in moderate dc magnetic fields. Positive magnetization is recovered on further cooling through T1 and maintained in subsequent warming curves. The field dependence and training of the MR effect in MnRuP will be discussed in terms of the underlying magnetic structures and compared to anomalous MR observed in vanadate systems. This work is supported by the Gordon and Betty Moore Foundation GBMF4416 and U.S. DOE, Office of Science, BES, Materials Science and Engineering Division.

  20. Reactively sputtered Ru-Si-O films

    NASA Astrophysics Data System (ADS)

    Gasser, S. M.; Kolawa, E.; Nicolet, M.-A.

    1999-08-01

    Films of Ru-Si-O were synthesized by reactively sputtering a Ru1Si1 target in an Ar/O2 gas mixture. They were characterized in terms of their composition by 2.0 MeV 4He++ backscattering spectrometry, their atomic density by thickness measurements combined with backscattering data, their microstructure by x-ray diffraction and transmission electron microscopy, and their electrical resistivity by four-point-probe measurements. The compositions indicate preferential sputtering with ruthenium enrichment of the films, and a saturation level of oxygen is determined at 67 at. % corresponding to the formation of SiO2 and RuO2. X-ray diffraction spectra reveal an amorphous structure for oxygen-saturated and nanocrystals for unsaturated as-deposited films. The crystallization temperature clearly increases with the oxygen concentration of the films, from 500 °C for oxygen-free films to 1000 °C for oxygen-saturated films, when annealed in vacuum for 30 min. Transmission electron micrographs of as-deposited oxygen-saturated films show few nanocrystals of 1-2 nm in diameter in an otherwise amorphous matrix. The atomic density is roughly 8×1022 atom/cm3 for all compositions. The resistivity of the ternary alloys scales with the terminal phases in the ternary phase diagram and reaches a maximum value when the Ru-SiO2 tie line is crossed near 50 at. % oxygen. The films are stable in vacuum up to thermal stressing at 800 °C for 5 h, and their decomposition starts near 1000 °C.

  1. Ru sub 3 (CO) sub 12 and Mo(CO) sub 6 adsorbed on Ru(001) and Au/Ru: An infrared reflection-absorption study

    SciTech Connect

    Malik, I.J.; Hrbek, J.

    1990-01-01

    We obtained IRAS and TDS data for Ru{sub 3}(CO){sub 12}/Ru(001) and Mo(CO){sub 6}/Au/Ru systems for metal carbonyl coverages between submonolayer and approximately 20 monolayers. We characterized the C-O stretching mode of both systems (4 cm{sup {minus}1} FWHM) and a deformation mode of Mo(CO){sub 6} at 608 cm{sup {minus}1} (1 cm{sup {minus}1} FWHM). Both IRAS and TDS data suggest adsorption and desorption of metal carbonyls as molecular species with a preferential orientation in the overlayers. The IR intensity of the C-O stretch per a C-O bond projected onto the surface normal is approximately twice (five times) larger for Ru{sub 3}(CO){sub 12} (Mo(CO){sub 6}) at submonolayer coverages than for CO/Ru(001) at {theta}{sub CO}=0.68. 31 refs., 4 figs.

  2. Graphene on Ru(0001): Evidence for two graphene band structures

    SciTech Connect

    Katsiev, Khabibulakh; Losovyj, Yaroslav; Zhou, Zihao; Vescovo, E; Liu, L.; Dowben, P. A.; Goodman, D. Wayne

    2012-05-03

    High-resolution photoemission illustrates that the band structure of graphene on Ru(0001) exhibits a well-defined splitting. This splitting is largest with the graphene directly on the Ru(0001) substrate, whereas with a chemisorbed oxygen spacer layer between the graphene and the metal substrate, this splitting is considerably reduced. This splitting is attributed to a combination of chemical interactions between graphene and Ru(0001) and to screening of the former by the latter, not spin-orbit coupling.

  3. Adsorbed water and CO on Pt electrode modified with Ru

    NASA Astrophysics Data System (ADS)

    Futamata, Masayuki; Luo, Liqiang

    Highly sensitive ATR-SEIRA spectroscopy was exploited to elucidate water, CO and electrolyte anions adsorbed on the Ru modified Pt film electrode. CO on Ru domains was oxidized below ca. +0.3 V, followed by pronounced water adsorption. Since the oxidation potential of CO on Pt domain was significantly reduced compared to bare Pt, these water molecules on Ru obviously prompt CO oxidation on adjacent Pt surface as consistent with the bifunctional mechanism. Diffusion of adsorbate from Ru to Pt surfaces was indicated in dilute CH 3OH solution by spectral changes with potential.

  4. 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.

  5. PtRu/Ti anodes with varying Pt ratio: Ru ratio prepared by electrodeposition for the direct methanol fuel cell.

    PubMed

    Shao, Zhi-Gang; Zhu, Fuyun; Lin, Wen-Feng; Christensen, Paul A; Zhang, Huamin

    2006-06-21

    PtRu/Ti anodes with varying Pt ratio Ru ratio were prepared by electrodeposition of a thin PtRu catalyst layer onto Ti mesh for a direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX and XRD. The catalyst coating layer shows an alloy character. The relative activities of the PtRu/Ti electrodes were assessed and compared in half cell and single DMFC experiments. The results show that these electrodes are very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 9 at.% for DMFC operating at 20 degrees C and 11 at.% at 60 degrees C. The PtRu/Ti anode shows a performance comparable to that of the conventional carbon-based anode in a DMFC operating with 0.25 M or 0.5 M methanol solution and atmosphere oxygen gas at 90 degrees C. PMID:16763704

  6. PtRuO 2/Ti anodes with a varying Pt:Ru ratio for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Shao, Zhi-Gang; Zhu, Fuyun; Lin, Wen-Feng; Christensen, Paul A.; Zhang, Huamin

    PtRuO 2/Ti anodes with a varying Pt:Ru ratio were prepared by thermal deposition of a PtRuO 2 catalyst layer onto a Ti mesh for the direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX, and XRD. The catalyst coating layers became porous with increase of the Ru content, and showed oxide and alloy characteristics. The relative activities of the PtRuO 2/Ti electrodes were assessed and compared using half-cell tests and single DMFC experiments. The results showed that these electrodes were very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 38% for a DMFC operating at 20-60 °C.

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

    DOE PAGESBeta

    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 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

  8. High-Spin Structure of 102Ru

    NASA Astrophysics Data System (ADS)

    Sohler, D.; Timár, J.; Rainovski, G.; Joshi, P.; Starosta, K.; Fossan, D. B.; Molnár, J.; Wadsworth, R.; Algora, A.; Bednarczyk, P.; Curien, D.; Dombrádi, Zs.; Duchene, G.; Gizon, A.; Gizon, J.; Jenkins, D. G.; Koike, T.; Krasznahorkay, A.; Paul, E. S.; Raddon, P. M.; Scheurer, J. N.; Simons, A. J.; Vaman, C.; Wilkinson, A. R.; Zolnai, L.

    2005-11-01

    High-spin states in the nucleus 102Ru have been studied through the 96Zr(13C,α3n) reaction using the EUROBALL IV γ-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.

  9. 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.

  10. Redispersal of Ru, Os, Rh and Pd catalysts and processing therewith

    SciTech Connect

    Hucul, D.A.

    1990-01-02

    This patent describes a process for redispersing and reducing a supported metal catalyst. Wherein the catalyst metal is ruthenium, osmium, rhodium or palladium supported by a refractory support and wherein the catalyst had been prepared by impregnating a metal salt of the catalyst metal on the refractory support and activated by passing hydrogen gas over the catalyst at a temperature of between about 150{degrees} C. and 350{degrees}C. for a period of time sufficient to reduce the metal salt on the refractory support; the supported metal catalyst had been deactivated in a vapor phase process for the preparation of an {alpha}-substituted acrylate ester; and the above-mentioned deactivated catalyst is redispersed and reduced.

  11. Dynamics of formation of Ru, Os, Ir and Au metal nanocrystals on doped graphitic surfaces.

    PubMed

    Pitto-Barry, Anaïs; Sadler, Peter J; Barry, Nicolas P E

    2016-03-11

    The fabrication of precious metal (ruthenium, osmium, gold, and iridium) nanocrystals from single atoms has been studied in real-time. The dynamics of the first stage of the metal nanocrystallisation on a doped (B,S)-graphitic surface are identified, captured, and reported. PMID:26698913

  12. 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.

  13. NOVEL RU-NI-S ELECTRODE CATALYST FOR PEMFC

    EPA Science Inventory

    The expected results from this project include:

    • a new formula and preparation procedures for Ru-Ni-S catalyst;
    • demonstration of CO and S tolerance of the new catalyst;
    • a small size PEMFC with Ru-Ni-S catalyst and good performance; an...

    • Methanol oxidation reaction on Ti/RuO 2(x)Pt (1- x) electrodes prepared by the polymeric precursor method

      NASA Astrophysics Data System (ADS)

      Freitas, R. G.; Marchesi, L. F.; Oliveira, R. T. S.; Mattos-Costa, F. I.; Pereira, E. C.; Bulhões, L. O. S.; Santos, M. C.

      In this work, ruthenium oxide films containing platinum nanoparticles were prepared using the polymeric precursor method on Ti substrates with several molar ratios. This paper aims at presenting the characterization of the Pt content effect in the methanol electrochemical oxidation reaction. The films were physically characterized using X-ray diffraction and both Pt and RuO 2 (rutile) phases were observed. The mean crystallite sizes were 6 nm for Pt and 25 nm for RuO 2. The X-ray photoelectronic results indicated that on the electrodes surfaces, depending on the substrate, there was RuO 2, Ru metal and Pt metal. Besides, it was not observed the formation of PtRu alloys. The atomic force microscopy images of the films showed highly rough surfaces. A decrease in the roughness mean square values is observed as the Pt content increases. These last results are similar to electroactive surface area values calculated by redox-couple (K 4FeCN 6/K 3FeCN 6). There was an increase in the globular size observed on the electrode surface and lower particle dispersion as the Pt content is increased from 12.5 to 75 mol%. Regarding the eletrode electrocatalytical behavior for methanol oxidation, it was observed that the onset oxidation overpotential is displaced towards more negative values as Pt content is decreased. Besides, an increase has been shown in the current density for methanol oxidation of 600% using a Ti/RuO 2-Pt (87.5:12.5) electrode compared to polycrystalline Pt.

    • Ordered phases in ruthenium binary alloys from high-throughput first-principles calculations

      NASA Astrophysics Data System (ADS)

      Jahnátek, Michal; Levy, Ohad; Hart, Gus L. W.; Nelson, Lance J.; Chepulskii, Roman V.; Xue, J.; Curtarolo, Stefano

      2011-12-01

      Despite the increasing importance of ruthenium in numerous technological applications, e.g., catalysis and electronic devices, experimental and computational data on its binary alloys are sparse. In particular, data are scant on those binary systems believed to be phase-separating. We performed a comprehensive study of ruthenium binary systems with the 28 transition metals, using high-throughput first-principles calculations. These computations predict novel unsuspected compounds in 7 of the 16 binary systems previously believed to be phase-separating and in two of the three systems reported with only a high-temperature σ phase. They also predict a few unreported compounds in five additional systems and indicate that some reported compounds may actually be unstable at low temperature. These new compounds may be useful in the rational design of new Ru-based catalysts. The following systems are investigated: AgRu, AuRu, CdRu, CoRu, CrRu, CuRu, FeRu, HfRu, HgRu, IrRu, MnRu, MoRu, NbRu, NiRu, OsRu, PdRu, PtRu, ReRu, RhRu, RuSc, RuTa, RuTc, RuTi, RuV, RuW, RuY, RuZn, and RuZr (a star denotes systems in which the ab initio method predicts that no compounds are stable).

    • 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.

    • Ru isotope heterogeneity in the solar protoplanetary disk

      NASA Astrophysics Data System (ADS)

      Fischer-Gödde, Mario; Burkhardt, Christoph; Kruijer, Thomas S.; Kleine, Thorsten

      2015-11-01

      Nucleosynthetic isotope anomalies in bulk chondrites and differentiated meteorites reflect variable proportions of isotopically diverse presolar components in bulk planetary bodies, but the origin of these heterogeneities is not well understood. Here, the Ru isotope composition of a comprehensive suite of iron meteorites and bulk samples of ordinary, enstatite and carbonaceous chondrites, as well as acid leachates and an insoluble residue of the Allende chondrite are examined using newly developed multi-collector inductively coupled plasma mass spectrometry techniques. Except for IAB iron meteorites and enstatite chondrites, all investigated meteorites show well-resolved Ru isotope anomalies. Of these, within-group Ru isotopic variations observed for samples from a given chemical group of iron meteorites reflect secondary neutron capture induced Ru isotope shifts during prolonged cosmic ray-exposure. After correction of these cosmogenic effects using Pt isotopes as a neutron-dose monitor, the remaining Ru isotope anomalies are nucleosynthetic in nature and are consistent with a deficit in s-process Ru in iron meteorite parent bodies. Similarly, Ru isotope anomalies in bulk ordinary and carbonaceous chondrites also reflect a deficiency in s-process Ru. The sequential dissolution of Allende reveals the presence of an HF-soluble s-process carrier, which is either an unidentified presolar phase or a component that incorporated s-process Ru liberated from SiC grains during nebular or parent body processes. We show that varying proportions of the s-process carrier identified in Allende resulted in the correlated Ru isotope anomalies observed for bulk meteorites, and that all meteorites (except possibly IAB irons and enstatite chondrites) are depleted in this s-process component relative to Ru from the Earth's mantle. Bulk meteorites exhibit correlated Ru and Mo isotope anomalies, reflecting variable deficits of a common s-process component, but some iron meteorites and

    • Bridgman crystal growth of Yb{sub 2}Ru{sub 3}Ge{sub 4}-A ternary germanide with a three-dimensional network of condensed distorted RuGe{sub 5} and RuGe{sub 6} units

      SciTech Connect

      Schappacher, Falko M.; Katoh, Kenichi Poettgen, Rainer

      2007-01-15

      The germanide Yb{sub 2}Ru{sub 3}Ge{sub 4} was synthesized from the elements using the Bridgman crystal growth technique. The monoclinic Hf{sub 2}Ru{sub 3}Si{sub 4} type structure was investigated by X-ray powder and single crystal diffraction: C2/c, Z=8, a=1993.0(3) pm, b=550.69(8) pm, c=1388.0(2) pm, {beta}=128.383(9){sup o}, wR {sub 2}=0.0569, 2047 F {sup 2} values, and 84 variables. Yb{sub 2}Ru{sub 3}Ge{sub 4} contains two crystallographically independent ytterbium sites with coordination numbers of 18 and 17 for Yb1 and Yb2, respectively. Each ytterbium atom has three ytterbium neighbors at Yb-Yb distances ranging from 345 to 368 pm. The shortest interatomic distances occur for the Ru-Ge contacts. The three crystallographically independent ruthenium sites have between five and six germanium neighbors in distorted trigonal bipyramidal (Ru1Ge{sub 5}) or octahedral (Ru2Ge{sub 6} and Ru3Ge{sub 6}) coordination at Ru-Ge distances ranging from 245 to 279 pm. The Ru2 atoms form zig-zag chains running parallel to the b-axis at Ru2-Ru2 of 284 pm. The RuGe{sub 5} and RuGe{sub 6} units are condensed via common edges and faces leading to a complex three-dimensional [Ru{sub 3}Ge{sub 4}] network. - Graphical abstract: Condensation of the Ru1Ge{sub 5}, Ru2Ge{sub 6}, and Ru3Ge{sub 6} units in the structure of Yb{sub 2}Ru{sub 3}Ge{sub 4}.

    • 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.

    • PtRu/C electrocatalysts prepared using γ-irradiation

      NASA Astrophysics Data System (ADS)

      Silva, Dionísio F.; Neto, Almir Oliveira; Pino, Eddy S.; Linardi, Marcelo; Spinacé, Estevam V.

      PtRu/C electrocatalysts (carbon-supported PtRu nanoparticles) were prepared submitting water/ethylene glycol solutions containing Pt(IV) and Ru(III) ions and the carbon support to γ-irradiation. The water/ethylene glycol ratio (v/v) and the total dose (kGy) were evaluated as synthesis parameters. The electrocatalysts were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry and tested for methanol electro-oxidation aiming fuel cell application. The obtained PtRu/C electrocatalysts were more active for methanol electro-oxidation than the commercial PtRu/C electrocatalyst at ambient temperature and the electrocatalytic activity depends on the water/ethylene glycol ratio used in the preparation.

  1. 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.

  2. Study of vibrational signatures in 102Ru

    NASA Astrophysics Data System (ADS)

    Duckwitz, H.; Pfeiffer, M.; Albers, M.; Bernards, C.; Fransen, C.; Jolie, J.; Petkov, P.; Radeck, D.; Thomas, T.; Zell, K. O.

    2013-04-01

    A Mo100(α,2n)Ru102 fusion evaporation experiment, performed at the HORUS cube spectrometer at the Cologne FN-Tandem accelerator, is presented and discussed. Via the analysis of γγ coincidences, it was possible to extend the level scheme with 40 new levels and 81 decays. Several new spins and multipole mixing ratios were determined using the γγ angular correlation technique. In addition, a DSAM analysis was performed and 14 new effective lifetimes were determined in the femtosecond range. Thus, several effective transition strengths were determined. Investigating the phononic structure, candidates for the quadrupole-octupole phonon multiplet 21+⊗31- were found. The data is compared to calculations within the Interacting Boson Model (IBM-1) in the U(5) limit, the O(6) limit as well as a transitional class U(5)-O(6). The low spin level energies show characteristics of multiphonon excitations and point towards 102Ru resembling an anharmonic vibrational nucleus. The B(E2) transition strengths do not exactly match this picture, and are described in a better way using the U(5)-O(6) calculation.

  3. Diruthenium Tetracarbonate Trianion, [RuII/III(O2 CO)4 3- Based Molecule Based Magnets: Three-Dmensional Network Structure and Two Dimensional Magnetic Ordering

    SciTech Connect

    Kennon, B.; Her, J; Stephens, P; Miller, J

    2009-01-01

    HxK1-xMII[Ru2(CO3)4](H2O)y(MeOH)z (M = Mn, Fe, Co, Ni, Mg) were synthesized from the reaction of MII and K3[Ru2(CO3)4] in water and are isomorphous with an orthorhombic three-dimensional network structures based on e3-CO32- linkages to Ru2 moieties forming layers and also to trans-MII(OH2)4 sites forming linked chains that connect the layers. They, as well as non-isomorphous M = Cu, magnetically order as canted ferrimagnets with Tc = 4.4 {+-} 1.0 K. The presence of S = 0 MII = Mg(II) has essentially no effect on Tc suggesting that the main magnetic pathway does not occur the through MII-based chains, but only via Ru2{center_dot}...Ru2 linkages that reside in layers. This is a rare example of a magnet based upon a second row transition metal.

  4. 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.

  5. 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).

  6. 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.

  7. Facile synthesis and electrochemical properties of conducting SrRuO 3-RuO 2 composite nanofibre mats

    NASA Astrophysics Data System (ADS)

    Hyun, Tae-Seon; Kim, Ho-Gi; Kim, Il-Doo

    This study reports the facile synthesis of highly conductive SrRuO 3(SRO)-RuO 2 composite nanofibre mats and their potential suitability for application in electrochemical capacitors as an active electrode material. SRO-RuO 2/poly(vinyl acetate) composite nanofibre mats are electrospun on to a Au-coated SiO 2/Si substrate and a Ti substrate, subsequently thermocompressed at 60 °C, and calcined at various temperatures (from 350 to 850 °C). The calcined SRO-RuO 2 nanofibre mats exhibit porous morphologies and bundle shapes composed of multiple-fibrils with a nanoparticle diameter ranging from 20 to 50 nm. Single SRO-RuO 2 nanofibre and multiple SRO-RuO 2 nanofibre mats show high electrical conductivity of 476 and 40.8 S cm -1, respectively. Pseudocapacitors using SRO-RuO 2 nanofibre mats calcined at 350 °C exhibit a high specific capacitance of 192 F g -1 at a scan rate of 10 mV s -1. The superior capacitance retention (83.4%) of the SRO-RuO 2 nanofibre mats is maintained even at rapid scan rate of 1000 mV s -1.

  8. Spin-triplet superconducting proximity effect in SrRuO3/Sr2RuO4 hybrids

    NASA Astrophysics Data System (ADS)

    Anwar, Muhammad Shahbaz; Lee, Seungran; Ishiguro, R.; Sugimoto, Y.; Tano, Y.; Kang, S. J.; Shin, Y. J.; Yonezawa, Shingo; Takayanagi, H.; Noh, Tae Won; Maeno, Yoshiteru; Yoshiteru Maeno Team; Tae Won Noh Team; Takayanagi Collaboration

    Spin-triplet superconducting correlations can be induced into a ferromagnet (FM) out of a spin-singlet superconductor (SSC) via magnetic inhomogeneity at the SSC/FM interface. In this case, however, the proximity effect is not readily controllable because spins are quenched. In contrast, superconducting spintronics can be realized by using spin-triplet superconductors (TSCs) and FM hybrids. Theoretically, it has been predicted that spin-triplet proximity effect can be controlled by the relative orientations between the magnetization in the FM and the Cooper pair spin in TSC. We fabricate Au(600-nm)/SrRuO3(15-nm) /Sr2RuO4 junctions by growing epitaxial SrRuO3 FM thin films on Sr2RuO4 TSC single crystals. Differential conductance vs voltage shows the conductance enhancements with superconducting transitions at three different characteristic voltages. These three features can naturally be interpreted as originating from the SC gaps in bulk Sr2RuO4 as well as at two distinct interfaces (Au/SrRuO3 and SrRuO3/Sr2RuO4) . The effect of applied magnetic field reveals that the proximity effect is robust against the loss of magnetic inhomogeneity.

  9. New rock salt-related oxides Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

    SciTech Connect

    Laha, S.; Morán, E.; Sáez-Puche, R.; Alario-Franco, M.Á.; Dos santos-Garcia, A.J.; Gonzalo, E.; Kuhn, A.; García-Alvarado, F.; Sivakumar, T.; Tamilarasan, S.; Natarajan, S.; Gopalakrishnan, J.

    2013-07-15

    found below 10 K while for the analogous Li{sub 3}Ni{sub 2}RuO{sub 6} , Ru oxidation state is 5+ and a ferrimagnetic (FM) behavior with a Curie temperature of 100 K is found. Electrochemical studies correlate well with both magnetic properties and crystal structure. - Highlights: • New Ruthenium rock salt-related oxides of formula, Li{sub 3}M{sub 2}RuO{sub 6} (M=Co, Ni) were studied. • Structurally different: rhombohedral α-NaFeO{sub 2}-type (Co) and monoclinic Li{sub 2}TiO{sub 3}-type (Ni) • Magnetic behavior is different: the Co sample is AFM while the Ni one is ferrimagnetic. • Ruthenium oxidation states are different: 4+ in the Co sample and 5+ in the Ni one. • Electrochemical studies correlate well with magnetic properties and crystal structures.

  10. 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. PMID:25157036

  11. Segmented Pt/Ru, Pt/Ni, and Pt/RuNi nanorods as model bifunctional catalysts for methanol oxidation.

    PubMed

    Liu, Fang; Lee, Jim Yang; Zhou, Wei Jiang

    2006-01-01

    Five-segment (Pt-Ru-Pt-Ru-Pt, Pt-Ni-Pt-Ni-Pt, and Pt-RuNi-Pt-RuNi-Pt) nanorods with the same overall rod length and the same total Pt segment length were prepared by sequential electrodeposition of the metals into the pores of commercially available anodic aluminum oxide (AAO) membranes. Field-emission scanning electron microscopy (FESEM) showed that the nanorods were about 210 nm in diameter and about 1.5 microm in length. The alternating Pt and oxophilic metal(s) segments could be easily differentiated in backscattered-electron images. X-ray diffraction (XRD) analysis of the nanorods indicated that Pt and Ni were polycrystalline with fcc structures, Ru was hcp, and the co-deposited RuNi adopted the nickel fcc structure with some negative shifts in the Bragg angles. The chemical states of Pt, Ru, and Ni on the nanorod surface were assayed by X-ray photoelectron spectroscopy (XPS), and the presence of Pt(0), Pt(II), Pt(IV), Ru(0), Ru(VI), Ni(0), and Ni(II) was observed. The nanorods were catalytically active for the room-temperature electrooxidation of methanol in acidic solutions. The relative rates of reaction showed the Pt-RuNi pair sites as having the lowest overpotential to dissociate water, the highest catalytic activity in methanol oxidation, and the strongest CO-tolerance in the potential window employed. The use of segmented nanorods with identifiable Pt-oxophilic metal(s) interfaces removes many of the ambiguities in the interpretation of experimental data from conventional alloy catalysts, thereby enabling a direct comparison of the activities of various types of pair sites in methanol oxidation. PMID:17193567

  12. 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}.

  13. Os Trigonum Syndrome

    MedlinePlus

    ... ACFAS | Información en Español Advanced Search Home » Foot & Ankle Conditions » Os Trigonum Syndrome Text Size Print Bookmark ... extra (accessory) bone that sometimes develops behind the ankle bone (talus). It is connected to the talus ...

  14. Cyclic ethers adsorbed on Ru(001)

    NASA Astrophysics Data System (ADS)

    Walczak, M. M.; Thiel, P. A.

    1990-11-01

    The three cyclic ethers 1,3-dioxane. 1,4-dioxane and 1,3,5-trioxane all exhibit multiple desorption states from Ru(001) between 200 and 310 K, in addition to the multilayer and metastable states at lower temperature. Most distinctive are the two low-temperature α-states. which are similar in shape, position, and relative population for all three compounds. This suggests that these states are associated with configurations which are accessible to all three molecules. The data also indicate that there is some molecular decomposition to gaseous CO and H 2. 1,4-Dioxane yields the largest amounts of these decomposition products, suggesting that this molecule is most susceptible to surface-catalyzed decomposition. The desorption data for the three cyclic ethers are grossly similar to each other, and also to the straight-chain diethers which we have previously studied.

  15. High-spin structure of 102Ru

    NASA Astrophysics Data System (ADS)

    Sohler, D.; Timár, J.; Rainovski, G.; Joshi, P.; Starosta, K.; Fossan, D. B.; Molnár, J.; Wadsworth, R.; Algora, A.; Bednarczyk, P.; Curien, D.; Dombrádi, Zs.; Duchene, G.; Gizon, A.; Gizon, J.; Jenkins, D. G.; Koike, T.; Krasznahorkay, A.; Paul, E. S.; Raddon, P. M.; Scheurer, J. N.; Simons, A. J.; Vaman, C.; Wilkinson, A. R.; Zolnai, L.

    2005-06-01

    High-spin states in the nucleus 102Ru have been investigated via the 96Zr(13C,α3n) reaction at beam energies of 51 and 58 MeV, using the euroball IV γ-ray spectrometer and the diamant charged particle array. Several new high-spin bands have been established. The ground-state band has been extended up to Ex~12 MeV with Iπ=(26+); the previously published negative-parity bands have been extended up to Ex~11 and ˜ 9 MeV with Iπ=(23-) and (20-), respectively. The deduced high-spin structure has been compared with Woods-Saxon total Routhian surface calculations and, on the basis of the measured Routhians, aligned angular momenta, and B(M1)/B(E2) ratios, νh11/2(g7/2,d5/2) configurations are suggested for the negative-parity structures.

  16. [Brachytherapy using Ru-106 applicators in ophthalmology].

    PubMed

    Binder, W; Menapace, R; Seitz, W

    1990-10-01

    Two Ru-106 applicators of the type CCB as manufactured by the "Zentralinstitut für Isotopen- und Strahlenforschung" (Berlin, GDR) were investigated. The homogeneity of the relative dose distribution at the surface of the applicators was determined. For the evaluation of the data extremely small TLD crystals (2 x 1 x 1 mm) had to be manufactured as well as an almost tissue equivalent acrylic eye phantom. In order to assure reproducibility of the applicator positioning, the plaque suture eyelets had to be placed on locating pins. 120 points of measurements located within the active plaque area of 20 mm diameter were evaluated. The results show that the area to be used in tumor treatment is about 20 to 25% less than expected. One plaque shows a considerable inhomogeneity with respect to dose distribution (up to 40%). A modified eye phantom was used for the determination of the central axis depth dose distribution. PMID:2237745

  17. /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.

  18. /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.

  19. 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.

  20. Antiferromagnetism in Bulk Rutile RuO2

    NASA Astrophysics Data System (ADS)

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

    While bulk rutile RuO2 has long been considered to be a Pauli paramagnet, we conclude it to host antiferromagnetism based on our combined theoretical and experimental study. This constitutes an important finding given the large amount of applications of RuO2 in the electrochemical and electronics industry. Furthermore the high onset temperature of the antiferromagnetism around 1000K together with the high electrical conductivity makes RuO2 unique among the ruthenates and among oxide materials in general. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

  1. 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.

  2. Comparative NMR studies on Ca3LiRuO6 and Ca3NaRuO6.

    PubMed

    Chakrabarty, T; Paulose, P L

    2016-06-15

    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 (7)Li 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 ([Formula: see text]S) is much less than that of an ordered S  =  3/2 system. PMID:27157888

  3. 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.

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

    DOE PAGESBeta

    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

  5. 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).

  6. 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)

  7. Solid-state Ru-99 NMR spectroscopy: a useful tool for characterizing prototypal diamagnetic ruthenium compounds.

    PubMed

    Ooms, Kristopher J; Wasylishen, Roderick E

    2004-09-01

    The feasibility of (99)Ru NMR spectroscopy as a tool to characterize solid compounds is demonstrated. Results of the first solid-state (99)Ru NMR investigation of diamagnetic compounds are presented for Ru(NH(3))(6)Cl(2), K(4)Ru(CN)(6). xH(2)O (x = 0, 3), LaKRu(CN)(6), and Ru(3)(CO)(12). The sensitivity of the ruthenium magnetic shielding tensor to subtle changes in the local structure about the ruthenium nucleus is highlighted by comparing the (99)Ru isotropic chemical shift of Ru(NH(3))(6)Cl(2) in aqueous solutions and in the solid state. The narrow isotropic (99)Ru NMR peak observed for solid Ru(NH(3))(6)Cl(2) indicates that this compound is an ideal secondary reference sample for solid-state (99)Ru NMR studies. The isotropic (99)Ru chemical shift, (99)Ru nuclear quadrupolar coupling constant, C(Q), and quadrupolar asymmetry parameter of K(4)Ru(CN)(6). xH(2)O (x = 0, 3) are shown to be sensitive to x. For Ru(3)(CO)(12), the magnetic shielding tensors of each of the three nonequivalent Ru nuclei have spans of 1300-1400 ppm, and the (99)Ru C(Q) values are also similar, 1.36-1.85 MHz, and are surprisingly small given that (99)Ru has a moderate nuclear quadrupole moment. Information about the relative orientation of the Ru magnetic shielding and electric field gradient tensors has been determined for Ru(3)(CO)(12) from experimental (99)Ru NMR spectra as well as quantum chemical calculations. PMID:15339183

  8. 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.

  9. Electronic structure of SrRuO{sub 3}

    SciTech Connect

    Fujioka, K.; Okamoto, J.; Mizokawa, T.; Fujimori, A.; Hase, I.; Abbate, M.; Lin, H.J.; Chen, C.T.; Takeda, Y.; Takano, M.

    1997-09-01

    We have measured photoemission and oxygen 1s x-ray absorption spectra of the ferromagnetic metal SrRuO{sub 3} and compared them with a first-principles band-structure calculation. The overall distribution of Ru 4d and O 2p spectral weight is in good agreement with that predicted by the band-structure calculation. However, the observed spectral line shape of the Ru 4d band is spread over a wide energy range and the emission intensity at the Fermi level is weakened compared to the band-structure calculation. This implies the importance of electron correlation in the Ru oxide. {copyright} {ital 1997} {ital The American Physical Society}

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

    PubMed

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

    2007-05-15

    Industrial solid wastes (fly ash and red mud) 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, H2 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. PMID:17547209

  11. 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.

  12. 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.

  13. Hierachically grown RuO2 nanowires on electrospun IrO2 nanofiber

    NASA Astrophysics Data System (ADS)

    Lee, Jaeyeon; Yang, Hee-Sung; Cho, Yukyung; Shin, Hae-Young; Yoon, Seokhyun; Baik, Jeong Min; Seo, Young-Soo; Kim, Myung Hwa

    2012-02-01

    Electrospinning is a well known tool to synthesize nanofibers with the various diameters. Iridium oxide(IrO2) and Ruthenium oxide(RuO2) have a great potential as materials for electrodes in electrochemical devices due to their high electrical conductivity, chemical stability, and characteristics. So when they are mixed, we expect superior electrochemical properties and stability. We synthesize IrO2 nanofibers from mixture of Iridium precursor and polymer. At certain condition, we were able to obtain uniform and continuous fibers that the average diameter of nanofibers is approximately 150 nm. After calcination, RuO2 nanowires were then hierarchically grown on IrO2 nanofibers by APCVD at about 650 ^o without any catalyst. The diameters of nanowires are about 50 nm and the length is ˜ 1.5 μm. The structures and morphologies were examined using scanning electron microscopy (FE-SEM), high resolution electron microscopy (HRTEM), X-ray diffraction (XRD) spectrum and Raman spectroscopy.

  14. 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.

  15. Potassium-oxygen interactions on a Ru(001) surface

    SciTech Connect

    Hrbek, J.; Shek, M.L.; Xu, G.Q. ); Sham, T.K. )

    1992-10-01

    The interaction of potassium with oxygen has been examined using synchrotron-based photoemission and NEXAFS, thermal desorption, work function measurements, and isotope exchange. Potassium coverages on Ru(001) surface ranging from monolayer to multilayer were investigated. Oxygen coadsorbed with potassium at 80 K forms a potassium-dioxygen complex, where both peroxide and superoxide ions were identified. The complex has high thermal stability on the Ru(001) surface, decomposing and desorbing at T > 900 K. 52 refs., 14 figs., 2 tabs.

  16. Effects of disordered isovalent substitution in Fe-based superconductor

    NASA Astrophysics Data System (ADS)

    Wang, Limin; Berlijn, Tom; Wang, Yan; Lin, Chai-Hui; Hirschfeld, P. J.; Ku, Wei

    2012-02-01

    Using a recently developed first-principles method for disordered materials [1-2], we investigate the effect of isovalent substitution in Fe-based superconductors, BaFe2(As1-xPx)2, FeTe1-xSex, and Ba(Fe1-xRux)2As2. For anion substitutions (the first two cases) effects of impurity scattering are found mostly in the anion bands. By contrast, the Ru substitution introduces much stronger scattering in the Fe bands. Surprisingly, in all the cases, the pockets near the chemical potential are the least affected, due to the low density of states near the chemical potential. Together, our results suggest an interesting scenario of enhancing superconductivity.[4pt] [1] T. Berlijn, D. Volja, W. Ku, Phys. Rev. Lett. 106, 077005 (2011).[0pt] [2] W.Ku, T. Berlijn, CC. Lee, Phys. Rev. Lett. 104, 216401 (2010).

  17. Low energy electron bombardment induced surface contamination of Ru mirrors

    NASA Astrophysics Data System (ADS)

    Al-Ajlony, A.; Kanjilal, A.; Catalfano, M.; Harilal, S. S.; Hassanein, A.; Rice, B.

    2012-03-01

    The impact of secondary electrons induced contamination of the Ru surface was investigated. Mirror-like Ru sample was bombarded with low energy (100 eV) electrons and the change in surface chemistry was investigated using X-ray photoelectron spectroscopy (XPS).Along with XPS studies the corresponding effect on in-situ EUV reflectivity was examined by exposing the Ru surface to photons at a wavelength of 13.5 nm in an ultrahigh vacuum chamber. Detailed XPS analyses showed a sudden increase in carbon concentrations on the Ru surface in the first 60 min, followed by a slow but linear growth in carbon concentration. In parallel, a noticeable decrease in water content was observed during the time of electrons irradiation along with slight oxidation of pure Ru surface. All chemical changes were discussed in terms of the electrons bombardment mediated dissociation of water and hydrocarbon molecules. A time dependent EUV reflectivity measurements show insignificant change in reflectivity up to 510 min of electrons bombardment. The impact of water molecules on the Ru surface and the accumulation of carbon through dissociation of residual hydrocarbons is discussed in details.

  18. Atomistic Mechanism of Surface-Oxide Formation on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Reuter, K.; Ganduglia-Pirovano, M. V.; Scheffler, M.; Stampfl, C.

    2001-03-01

    CO-oxidation catalysis on Ruthenium is a prime example of the pressure and materials gap in the sense, that a very low activity under UHV conditions is contrasted with very high turnover rates at high pressures. A recent experimental study has connected this change in activity with the formation of RuO_2(110) patches on the surface (H. Over et al., Science 287, 1474 (2000)). In order to analyze the atomistic mechanism behind this surface oxide formation, we perform density functional theory calculations for more and more O loaded Ru(0001) surfaces. After a full monolayer coverage on the surface has been reached, O starts to penetrate into the sample. Instead of diffusing further into the bulk, oxygen agglomerates in subsurface islands between the first and second substrate layers. These islands can be characterized as a O-Ru-O trilayer ``floating'' on top of the Ru(0001) substrate. Further O incorporation leads to a successive formation of such O-Ru-O trilayers, which at first remain in a CaF2 type stacking sequence. After a critical thickness has been exceeded, we finally observe a phase transition into the experimentally seen rutile RuO_2(110) structure.

  19. 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.

  20. Interfacial effects in Fe/4d TM multilayers (abstract)

    SciTech Connect

    Tomaz, M.A.; Antel, W.J., Jr.; Harp, G.R.; OBrien, W.L.

    1997-04-01

    We have studied Fe/TM multilayers (TM=Mo, Nb, Ru, Rh, Pd) using x-ray magnetic circular dischroism, magneto-optical Kerr effect, and x-ray diffraction. A diverse set of magnetic behaviors emerges from the analysis. We focus on the behavior which can be attributed to the existence of a physical interface between different chemical species. In particular, we have measured an enhanced Fe moment in some cases (TM=Ru, Mo, Rh, Pd) yet not in others (TM=Nb). These results will be discussed, including the relative orbital and spin moments and the effects of alloying at the interface. The measured induced moments in the TM layer will be presented as well where applicable. {copyright} {ital 1997 American Institute of Physics.}

  1. Highly branched RuO2 Nanorods on Electrospun TiO2 Nanofibers toward Electrochemical Catalysts

    NASA Astrophysics Data System (ADS)

    Cho, Yukyung; Kim, Su-Jin; Lee, Nam-Suk; Kim, Myung Hwa; Lee, Youngmi

    2014-03-01

    We report a facile growth route to synthesize hierarchically grown single crystalline metallic RuO2 nanorods on electrospun TiO2 nanofibers via a combination of a simple vapour phase transport process with an electrospinning process. This synthetic strategy could be very useful to design a variety of highly branched network architectures of the functional hetero-nanostructures for electrochemical applications. Particularly, Ruthenium oxide (RuO2) 1-dimensional nanostructures can be used as the effective catalysts or electrochemical electrode materials. Thus, we first synthesize TiO2 nanofibers from mixture of titanium isopropoxide precursor and polymer and then ruthenium hydroxide precursor on TiO2 nanofibers are transformed into RuO2 nanorods by thermal treatment at 250oC in air. The crystalline structures of products are confirmed using scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) spectrum, Raman spectroscopy, and high resolution electron microscopy (HRTEM). The fundamental electrochemical performances are examined using cyclic voltammetry (CV).

  2. Complex trend of magnetic order in Fe clusters on 4d transition-metal surfaces. I. Experimental evidence and Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Sessi, V.; Otte, F.; Krotzky, S.; Tieg, C.; Wasniowska, M.; Ferriani, P.; Heinze, S.; Honolka, J.; Kern, K.

    2014-05-01

    We demonstrate the occurrence of compensated spin configurations in Fe clusters and monolayers on Ru(0001) and Rh(111) by a combination of x-ray magnetic circular dichroism experiments, first-principles calculations, and Monte Carlo simulations. Our results reveal complex intracluster exchange interactions which depend strongly on the substrate 4d-band filling, the cluster geometry, as well as lateral and vertical structural relaxations. The importance of substrate 4d-band filling manifests itself also in small nearest-neighbor exchange interactions in Fe dimers and in a nearly inverted trend of the Ruderman-Kittel-Kasuya-Yosida coupling constants for Fe adatoms on the Ru and Rh surface.

  3. Ru-NO and Ru-NO2 bonding linkage isomerism in cis-[Ru(NO)(NO)(bpy)2](2+/+) complexes - a theoretical insight.

    PubMed

    Andriani, Karla Furtado; Caramori, Giovanni Finoto; Doro, Fábio Gorzoni; Parreira, Renato Luis Tame

    2014-06-21

    Ruthenium nitrosyl complexes have received considerable attention due to the fact that they are able to store, transfer and release NO in a controlled manner. It is well-known that the NO reactivity of ruthenium nitrosyl complexes can be modulated with the judicious choice of equatorial and axial ligands. In this piece of research we elucidate the nature of the Ru-NO and Ru-NO2 bonding in a cis-[Ru(NO)(NO2)(bpy)2](2+) complex energy decomposition (Su-Li EDA) and topological (e.g., QTAIM) and natural bond orbital analysis. It was observed that the strength of these bonds is directly correlated with the relative stability of isomers involved in nitro-nitrito and nitrosyl-isonitrosyl isomerism, as described previously by Coppens and Ooyama. PMID:24781307

  4. 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.

  5. Clarifying the role of Ru in methanol oxidation at Ru(core)@Pt(shell) nanoparticles.

    PubMed

    El Sawy, Ehab N; El-Sayed, Hany A; Birss, Viola I

    2015-11-01

    The catalytic activity of Rucore@Ptshell nanoparticles (NPs) towards CO oxidation, a strongly adsorbed intermediate that compromises the performance of direct methanol fuel cells, is known to be significantly better than at Pt alone. However, a systematic study aimed at understanding the beneficial effect of Ru on Pt during the methanol oxidation reaction (MOR) has not been carried out as yet. Here, Rucore@Ptshell NPs, having a controlled Ptshell coverage of zero to two monolayers and two different Rucore sizes (2 and 3 nm), were synthesized using the simple polyol method to determine the precise role and impact of Ru on the MOR in 0.5 M H2SO4 + 1 M methanol at RT and 60 °C. Because the structure of our Rucore@Ptshell NPs is known with such certainty, we were able to show here that the rate of methanol adsorption/dehydrogenation can be accelerated either by compression of the Ptshell (by making the Rucore larger) when it is less than one monolayer in thickness, or by decreasing the electronic effect of the Rucore on the Ptshell (achieved by adding a second Pt layer to the Ptshell). At low overpotentials, decreasing the Ptshell thickness also helps in increasing the rate of the MOR by enhancing the rate of oxidation of adsorbed CO. Finally, it is shown that the bi-functional effect of Ru on the Ptshell plays only a minor role in the catalysis of the MOR, especially at large particles where CO surface diffusion is facilitated. PMID:26426281

  6. Improvement of Contact Resistance between Ru Electrode and TiN Barrier in Ru/Crystalline-Ta2O5/Ru Capacitor for 50 nm Dynamic Random Access Memory

    NASA Astrophysics Data System (ADS)

    Lim, HanJin; Chung, Suk-Jin; Lee, Kwang Hee; Lee, Jinil; Kim, Jin Yong; Yoo, Cha-Young; Kim, Sung-Tae; Chung, U-In; Moon, Joo-Tae

    2005-04-01

    The contact resistance (RC) between a Ru electrode and a TiN plug in a crystalline Ta2O5 capacitor using Ru electrodes was evaluated. The TiN plug was oxidized in TiOx to increase the RC to failure. Two origins of oxygen are determined by Auger electron spectroscopy (AES) analysis, namely, the seed step of Ru deposition and the initial step of Ta2O5 deposition. During Ta2O5 crystallization annealing at 700°C, the oxygen molecules from Ru diffused into the TiN plug, forming TiOx. Ru films with Ti exhibited a decreased RC below 1 kΩ/contact and an increased leakage current of a Ru/Ta2O5/Ru capacitor according to the applied voltage, compared with Ru films without Ti. The atomic layer deposition (ALD) Ru process including a H2 plasma treatment decreased the RC to 2.5 kΩ/contact on average. The fabrication scheme for the crystalline Ta2O5 capacitor using the Ru electrode for reducing RC between the Ru storage node and the TiN plug was proposed.

  7. Role of RuO2(100) in surface oxidation and CO oxidation catalysis on Ru(0001).

    PubMed

    Flege, Jan Ingo; Lachnitt, Jan; Mazur, Daniel; Sutter, Peter; Falta, Jens

    2016-01-01

    We have studied the oxidation of the Ru(0001) surface by in situ microscopy during exposure to NO2, an efficient source of atomic oxygen, at elevated temperatures. In a previous investigation [Flege et al., Phys. Rev. B: Condens. Matter Mater. Phys., 2008, 78, 165407], at O coverages exceeding 1 monolayer, using the combination of intensity-voltage (I(V)) low-energy electron microscopy (LEEM) and multiple scattering calculations for the (00) beam in the very-low-energy range (E≤ 50 eV) we identified three surface components during the initial Ru oxidation: a (1 × 1)-O chemisorption phase, the RuO2(110) oxide phase, and a surface oxide structure characterized by a trilayer O-Ru-O stacking. Here, we use dark-field LEEM imaging and micro-illumination low-energy electron diffraction in the range of 100 to 400 eV to show that this trilayer phase is actually a RuO2(100)-(1 × 1) phase with possibly mixed O and Ru surface terminations. This identification rationalizes the thermodynamic stability of this phase at elevated temperatures and is consistent with the observation of catalytic activity of the phase in CO oxidation. PMID:26601756

  8. Mifepristone (RU 486) treatment of meningiomas.

    PubMed Central

    Lamberts, S W; Tanghe, H L; Avezaat, C J; Braakman, R; Wijngaarde, R; Koper, J W; de Jong, H

    1992-01-01

    Meningiomas are common brain tumours which are generally benign, well circumscribed and slow growing. In a minority of patients complete surgical removal is not possible and re-growth of tumour tissue is a major clinical problem. Most meningiomas contain progesterone receptors. The anti-progestational drug mifepristone (RU 486) binds to these receptors. Ten patients were treated with 12 recurrent or primary "inoperable" meningiomas, all of whom had shown recent neuroradiological and/or ophthalmological evidence of tumour growth. They received 200 mg mifepristone daily for 12 months. Most patients initially had complaints of nausea, vomiting and/or tiredness. In four patients prednisone (7.5 mg/day) was given after which these side-effects subsided. CT scan analysis of tumour size, showed progression of growth of five meningiomas in four patients, stable disease in three patients with three tumours and regression of four tumours in three patients. A decrease in the complaints of headache and an improved general well being was observed in five patients. Two patients died during the treatment period from unrelated causes. Mifepristone treatment resulted in control of tumour growth (= stable disease) in six of 10 patients who had shown recent evidence of tumour growth. In three of these six patients consistent tumour shrinkage was observed. PMID:1619417

  9. Interlayer exchange coupling in perpendicularly magnetized synthetic ferrimagnet structure using CoCrPt and CoFeB

    NASA Astrophysics Data System (ADS)

    Watanabe, D.; Mizukami, S.; Wu, F.; Oogane, M.; Naganuma, H.; Ando, Y.; Miyazaki, T.

    2010-01-01

    Interlayer exchange coupling in synthetic ferrimagnet structures consisting of perpendicularly magnetized CoCrPt and in-plane magnetized CoFeB layers, which are coupled by a Ru thin spacer, were investigated. The magnetization of the CoFeB layer turned perpendicular to the film plane after annealing at 300°C because of the appearance of interlayer coupling from the CoCrPt layer. The coupling varied between antiferromagnetic and ferromagnetic depending on the Ru spacer thickness. The sign and strength of the coupling were also observed through analyses of magnetization curves and ferromagnetic resonance spectra.

  10. Magnetic anisotropy and spin wave relaxation in CoFe/PtMn/CoFe trilayer films

    NASA Astrophysics Data System (ADS)

    Ren, Y. H.; Wu, C.; Gong, Y.; Pettiford, C.; Sun, N. X.

    2009-04-01

    We investigated the magnetic anisotropic properties and the spin wave relaxation in trilayer films of CoFe/PtMn/CoFe grown on the seed layer Ru or NiFeCr with CoFe compositions being Co-16 at. % Fe. The measurements were taken in samples with the ferromagnetic layers of CoFe varying from 10 to 500 Å by the ferromagnetic resonance (FMR) technique. The magnetic anisotropic parameters were investigated by rotating the field aligned axis with respect to the spectral field in the configurations of both in plane and out of plane. We determine the effective in-plane anisotropy field of ˜0.005 T, the uniaxial out-of-plane anisotropy of ˜-0.3 T, and the exchange stiffness D of ˜512 meV Å2. Moreover, spin wave damping was estimated by analyzing the FMR linewidth and line shape as a function of the angle between the external field and easy axis and as a function of the thickness of the CoFe layers. We identify an extrinsic contribution of the damping parameter dominated by two-magnon scattering in addition to the intrinsic Gilbert term with a damping parameter, α =0.012. Further, we reveal that a significant linewidth broadening could also be caused by the overlap of the surface and the uniform spin wave excitations. The FMR lines show a strong dependence of the surface anisotropy contribution of free energy in trilayer films.

  11. Evolution of magnetism in single-crystal Ca2Ru1-xIrxO4(0≤x≤0.65)

    DOE PAGESBeta

    Yuan, S. J.; Terzic, J.; Wang, J. C.; Li, L.; Aswartham, S.; Song, W. H.; Ye, Feng; Cao, Gang

    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

  12. 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.

  13. Arsenic immobilization in the contaminated soil using poorly crystalline Fe-oxyhydroxy sulfate.

    PubMed

    Yang, Zhihui; Liu, Lin; Chai, Liyuan; Liao, Yingping; Yao, Wenbin; Xiao, Ruiyang

    2015-08-01

    A low crystalline Fe-oxyhydroxy sulfate (FeOS) was used to immobilize arsenic (As) in soils in this study. The effects of FeOS amount, treatment time and soil moisture on As immobilization were investigated. The results showed that water-soluble and NaHCO3-extractable As were immobilized by 53.4-99.8 and 13.8-73.3% respectively, with 1-10% of FeOS addition. The highest immobilization of water-soluble (98.5%) and NaHCO3-extractable arsenic (47.2%) was achieved under condition of 4% of FeOS and 80% of soil moisture. Further, more amounts of FeOS addition resulted in less time requirement for As immobilization. Sequential chemical extraction experiment revealed that easily mobile arsenic phase was transferred to less mobile phase. The FeOS-bonded As may play a significant role in arsenic immobilization. Under leaching with simulated acid rain at 60 times pore volumes, accumulation amount of As release from untreated soil and soil amended with FeOS were 98.4 and 1.2 mg, respectively, which correspond to 7.69 and 0.09% of total As amounts in soil. The result showed that the low crystalline FeOS can be used as a suitable additive for arsenic immobilization in soils. PMID:25911284

  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. Photochemical Stereospecific Hydrogenation of a Ru Complex with an

    SciTech Connect

    Tanaka, K.; Fujita, E.; Fukushima, T.; Muckerman, J.T.; Polyansky, D.E.; Wada, T.

    2009-12-21

    A polypyridylruthenium complex with an NAD{sup +}/NADH model ligand, [Ru(bpy){sub 2}(pbn)]{sup 2+} [bpy = 2,2'-bipyridine; pbn = 2-(2-pyridyl)benzo[b]-1,5-naphthyridine] in a D{sub 2}O/CH{sub 3}CN/triethylamine solution, undergoes stereospecific hydrogenation to give {Delta}-(S)- and {Lambda}-(R)-[Ru(bpy){sub 2}(pbnDD)]{sup 2+} [pbnDD = 5,10-dideutero-2-(2-pyridyl)benzo[b]-1,5-naphthyridine] upon visible-light irradiation. This result clearly indicates the pathway via the {pi}-stacked dimer of the deuterated one-electron-reduced species. The reduction of [Ru(bpy){sub 2}(pbn)]{sup 2+} with Na{sub 2}S{sub 2}O{sub 4} in D{sub 2}O did not afford any stereospecific products. Furthermore, the more sterically crowded Ru complex, [Ru(dmb){sub 2}(pbn)]{sup 2+} (dmb = 6,6'-dimethyl-2,2'-bipyridine), did not produce the corresponding pbnDD species upon irradiation.

  16. 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

  17. Ultrafine Nanoparticle-Supported Ru Nanoclusters with Ultrahigh Catalytic Activity.

    PubMed

    Zhu, Lihua; Jiang, Yingying; Zheng, Jinbao; Zhang, Nuowei; Yu, Changlin; Li, Yunhua; Pao, Chih-Wen; Chen, Jeng-Lung; Jin, Chuanhong; Lee, Jyh-Fu; Zhong, Chuan-Jian; Chen, Bing H

    2015-09-01

    The design of an ideal heterogeneous catalyst for hydrogenation reaction is to impart the catalyst with synergetic surface sites active cooperatively toward different reaction species. Herein a new strategy is presented for the creation of such a catalyst with dual active sites by decorating metal and metal oxide nanoparticles with ultrafine nanoclusters at atomic level. This strategy is exemplified by the design and synthesis of Ru nanoclusters supported on Ni/NiO nanoparticles. This Ru-nanocluster/Ni/NiO-nanoparticle catalyst is shown to exhibit ultrahigh catalytic activity for benzene hydrogenation reaction, which is 55 times higher than Ru-Ni alloy or Ru on Ni catalysts. The nanoclusters-on-nanoparticles are characterized by high-resolution transmission electron microscope, Cs-corrected high angle annular dark field-scanning transmission electron microscopy, elemental mapping, high-sensitivity low-energy ion scattering, and X-ray absorption spectra. The atomic-scale nanocluster-nanoparticle structural characteristics constitute the basis for creating the catalytic synergy of the surface sites, where Ru provides hydrogen adsorption and dissociation site, Ni acts as a "bridge" for transferring H species to benzene adsorbed and activated at NiO site, which has significant implications to multifunctional nanocatalysts design for wide ranges of catalytic reactions. PMID:26081741

  18. 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

    2016-01-01

    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

  19. A versatile strategy to the selective synthesis of Cu nanocrystals and the in situ conversion to CuRu nanotubes.

    PubMed

    Huang, Xiaoqing; Chen, Yu; Chiu, Chin-Yi; Zhang, Hua; Xu, Yuxi; Duan, Xiangfeng; Huang, Yu

    2013-07-21

    Compared with Ag, Au, Pt and Pd, the synthesis of Cu nanocrystals that exhibit well-defined structures and surface properties has achieved limited success. Herein, we report an etching and protecting strategy to prepare Cu nanostructures with controllable shapes, crystalline nature and surface properties. In the developed strategy, the selective use of different additives is critical to the successful synthesis of the Cu nanocrystals: while NH4Cl (or hexadecyltrimethylammonium chloride (CTAC)) functions as an etchant by a Cl(-)-O2 pair that can selectively remove twinned nuclei and induce the formation of single nanocrystals with a cubic morphology, the addition of RuCl3 (or FeCl3, FeCl2) can protect the multiply twinned seeds from being etched, and leads to the formation of 5-fold twined nanowires. The controlling strategy reported herein is highlighted by its simplicity and versatility. By further increasing the reaction temperature and prolonging the reaction time, bimetallic CuRu nanotubes can be readily prepared. The applications of these well-defined nanostructures and the developed strategy in controlling other metals are currently under investigation. PMID:23740179

  20. 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. PMID:20066185

  1. NO-binding in {Ru(NO)₂}⁸-type [Ru(NO)₂(PR₃)₂X]BF₄ compounds.

    PubMed

    Gallien, Anna K E; Schaniel, Dominik; Woike, Theo; Klüfers, Peter

    2014-09-21

    Two different structure types were found for a series of mononuclear dinitrosyl complexes of the general formula [RuL2(NO)2X]BF4 (L = monodentate phosphane, X = Cl, Br, I). The {Ru(NO)2}(8)-type target compounds were prepared by the reduction of the respective {RuNO}(6) precursors and subsequent oxidative addition of (NO)BF4. About one half of the new compounds share their molecular structure with the hitherto only representative of this class of dinitrosyls, Pierpont and Eisenberg's [RuCl(NO)2(PPh3)2]PF6·C6H6 (Inorg. Chem., 1972, 11, 1088-1094). The Cs-symmetric cations exhibit both a linear and a bent Ru-N-O fragment, in line with a formal 6 + 2 split of the {Ru(NO)2}(8) electron sum in the sense of a [Ru(II)(NO(+))((1)NO(-))](2+) bonding. The coordination entity's configuration in this subgroup is described by IUPAC's polyhedral symbol SPY-5. Continuous shape measures (CShM) as defined by Alvarez et al. (Coord. Chem. Rev., 2005, 249, 1693-1708) reveal a uniform deviation from the L-M-L angles expected for SPY-5, in a narrower sense, towards a vacant octahedron (vOC-5). DFT calculations confirmed that Enemark and Feltham's analysis (Coord. Chem. Rev., 1974, 13, 339-406) of the electronic situation of the {Ru(NO)2}(8) group remains adequate. The same holds for the second subclass of new compounds the existence of which had been predicted in the same paper by Enemark and Feltham, namely C(2v)-symmetric, TBPY-5-type cations with two almost equally bonded nitrosyl ligands. In agreement with an 8 + 0 distribution of the relevant electrons, the formal [Ru(0)(NO(+))2](2+) entities are found for L/X couples that donate more electron density on the central metal. Two solid compounds (8a/b, 12a/b) were found in both structures including the special case of the P(i)Pr3/Br couple 12a/b, which led to crystals that contained both structure types in the same solid. Conversely, four compounds showed a single form in the solid but both forms in dichloromethane solution in terms

  2. 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.

  3. Enhanced thermoelectric power and electronic correlations in RuSe₂

    DOE PAGESBeta

    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.

  4. Diastereomerization Dynamics of a Bistridentate Ru(II) Complex.

    PubMed

    Jarenmark, Martin; Carlström, Göran; Fredin, Lisa A; Hedberg Wallenstein, Joachim; Doverbratt, Isa; Abrahamsson, Maria; Persson, Petter

    2016-03-21

    The unsymmetrical nature of a new tridentate ligand bis(quinolinyl)-1,3-pyrazole (DQPz) is exploited in a bistridentate Ru(II) complex [Ru(DQPz)2](2+) to elucidate an unexpected dynamic diastereomerism. Structural characterization based on a combination of nuclear magnetic resonance spectroscopy and density functional theory calculations reveals the first quantifiable diastereomerization dynamics for Ru complexes with fully conjugated tridentate heteroaromatic ligands. A mechanism that involves a large-scale twisting motion of the ligands is proposed to explain the dynamic interconversion between the observed diastereomers, and the analysis of both experiments and calculations reveals a potential energy landscape with a transition barrier for the diastereomerization of ∼70 kJ mol(-1). The structural flexibility demonstrated around the central transition metal ion has implications for integration of complexes into catalytic and photochemical applications. PMID:26962970

  5. 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.

  6. Bimetallic Wiregauze Supported Pt-Ru Nanocatalysts for Hydrogen Mitigation.

    PubMed

    Sanap, Kiran K; Varma, S; Waghmode, S B; Sharma, P; Manoj, N; Vatsa, R K; Bharadwaj, S R

    2015-05-01

    Passive autocatalytic recombiner (PAR) is one of the most suitable devices for mitigation of hydrogen, generated in nuclear power plant under accidental conditions. For this purpose we report development of stainless steel wire gauze supported Pt-Ru nanoparticles as catalysts. Simultaneous electroless deposition has been employed for the synthesis of the catalysts. Pt-Ru based bimetallic catalysts were characterized for their rate of coating kinetics, noble metal loading, phase purity by XRD and surface morphology by SEM, TEM and elemental analysis by SIMS. Developed catalysts were found to be active for efficient recombination of hydrogen and oxygen in air as well as in presence of various prospective poisons like CO2, CH4, CO and relative humidity. Pt-Ru based bimetallic catalyst with 0.9% loading was found to be active for CO poisoning up to 400 ppm of CO. PMID:26504972

  7. RU 486 inhibits peripheral effects of glucocorticoids in humans.

    PubMed

    Gaillard, R C; Poffet, D; Riondel, A M; Saurat, J H

    1985-12-01

    RU 486 [17 beta-hydroxy-11 beta-(4-dimethylaminophenyl)17 alpha-(prop-1-ynyl)estra-4,9-dien-3-one] is a synthetic steroid receptor antagonist. To evaluate the peripheral antiglucocorticoid action of this compound, we investigated its ability to antagonize cutaneous steroid-induced vasoconstriction. This phenomenon, produced by three different topical steroids in six normal men, was consistently and significantly attenuated or abolished by oral administration of 6 mg/kg RU 486. This demonstration of a peripheral action of RU 486 is important in relation to the potential therapeutic use of this well tolerated drug in states of hypercortisolism. It also indicates that the cutaneous vasoconstrictor effects of topical steroids are mediated by occupancy of glucocorticoid receptors. PMID:4055982

  8. 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.

  9. 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

    2015-02-01

    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

  10. 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. PMID:27072776

  11. Nuclear forward scattering of synchrotron radiation by 99Ru

    DOE PAGESBeta

    Bessas, D.; Merkel, D. G.; Chumakov, A. I.; Ruffer, R.; Hermann, Raphael P.; Sergueev, I.; Mahmoud, A.; Klobes, B.; McGuire, Michael A.; Sougrati, M. T.; et al

    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.

  12. 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.

  13. Understanding Re-Os systematics and model ages in metamorphosed Archean ultramafic rocks: A single mineral to whole-rock investigation

    NASA Astrophysics Data System (ADS)

    Coggon, Judith A.; Luguet, Ambre; Fonseca, Raúl O. C.; Lorand, Jean-Pierre; Heuser, Alexander; Appel, Peter W. U.

    2015-10-01

    187Rhenium-187Os model ages are used to infer the timing of crust-mantle differentiation events and evolution of lithospheric mantle. However, ancient samples often have long and complex histories of metamorphism, metasomatism and deformation that may be problematic if these processes caused disturbance the Re-Os system. Such processes have been shown to disturb the Re-Os systematics of ophiolitic chromitites, but the effect on stratiform chromitites has not previously been investigated. Here we present a detailed petrographic and Re-Os isotopic study of chromitites, chromite-bearing meta-peridotites and single chromite grains from the Ujaragssuit nunât layered ultramafic intrusion, southwest Greenland, which has experienced intense deformation and at least two episodes of metamorphism up to amphibolite facies. We report the first ever Re-Os isotope and platinum-group element concentration data for single chromite grains achieved by single grain dissolution and isotope dilution. Micrometric Os-, Ir-, Ru - sulphide and sulpharsenide inclusions in chromite occur in the massive chromitites; these accessory phases host a significant portion of the Os, Ir and Ru in these samples. The remaining Os-Ir-Ru budget, along with Pt and Pd, appears to be homogeneously distributed within the chromite, occurring either in the lattice itself, as evenly distributed sub-micrometric alloy inclusions in chromite (unresolvable using the techniques applied in this study) or a combination of both. Rhenium is hosted in silicates, as predicted by previous studies. Both single-grain and whole-rock Re-Os isotope systematics yield unfeasibly young Re-Os model ages due to their radiogenic 187Os/188Os compositions. This could result from country rock contamination of the original melt from which the Ujaragssuit nunât intrusion crystallised, and/or from disturbance of the Re-Os isotope systematics of these rocks during regional metamorphic events at ∼2.8 and/or ∼3.75 Ga. We conclude that it

  14. 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. PMID:25767830

  15. Anisotropic pairing in superconducting Sr{sub 2}RuO{sub 4}: Ru NMR and NQR studies

    SciTech Connect

    Ishida, K.; Kitaoka, Y.; Asayama, K.; Ikeda, S.; Nishizaki, S.; Maeno, Y.; Yoshida, K.; Fujita, T.

    1997-07-01

    Ru NMR and nuclear quadrupole resonance studies are reported on single-crystal Sr{sub 2}RuO{sub 4} (T{sub c}=0.7 K) with the same layered perovskite structure as La{sub 2}CuO{sub 4}. The Pauli spin susceptibility deduced from the Ru Knight shift is found to be largely enhanced by a factor of {approximately}5.4 as compared with the value from the band calculation. In the superconducting state, the nuclear spin-lattice relaxation rate 1/T{sub 1} exhibits a sharp decrease with no coherence peak just below T{sub c} and the T{sub 1}T=constant behavior well below T{sub c}, suggesting that the anisotropic pairing state is realized as in heavy-fermion and high-T{sub c} superconductors. {copyright} {ital 1997} {ital The American Physical Society}

  16. 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.

  17. 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.

  18. A Renewable and Ultrasensitive Electrochemiluminescence Immunosenor Based on Magnetic RuL@SiO2-Au∼RuL-Ab2 Sandwich-Type Nano-Immunocomplexes

    PubMed Central

    Gan, Ning; Hou, Jianguo; Hu, Futao; Cao, Yuting; Li, Tianhua; Guo, Zhiyong; Wang, Jun

    2011-01-01

    An ultrasensitive and renewable electrochemiluminescence (ECL) immunosensor was developed for the detection of tumor markers by combining a newly designed trace tag and streptavidin-coated magnetic particles (SCMPs). The trace tag (RuL@SiO2-Au∼RuL-Ab2) was prepared by loading Ru(bpy)32+(RuL)-conjuged secondary antibodies (RuL-Ab2) on RuL@SiO2 (RuL-doped SiO2) doped Au (RuL@SiO2-Au). To fabricate the immunosensor, SCMPs were mixed with biotinylated AFP primary antibody (Biotin-Ab1), AFP, and RuL@SiO2-Au∼RuL-Ab2 complexes, then the resulting SCMP/Biotin-Ab1/AFP/RuL@SiO2-Au∼RuL-Ab2 (SBAR) sandwich-type immunocomplexes were absorbed on screen printed carbon electrode (SPCE) for detection. The immunocomplexes can be easily washed away from the surface of the SPCE when the magnetic field was removed, which made the immunosensor reusable. The present immunosensor showed a wide linear range of 0.05–100 ng mL−1 for detecting AFP, with a low detection limit of 0.02 ng mL−1 (defined as S/N = 3). The method takes advantage of three properties of the immunosensor: firstly, the RuL@SiO2-Au∼RuL-Ab2 composite exhibited dual amplification since SiO2 could load large amount of reporter molecules (RuL) for signal amplification. Gold particles could provide a large active surface to load more reporter molecules (RuL-Ab2). Accordingly, through the ECL response of RuL and tripropylamine (TPA), a strong ECL signal was obtained and an amplification analysis of protein interaction was achieved. Secondly, the sensor is renewable because the sandwich-type immunocomplexes can be readily absorbed or removed on the SPCE’s surface in a magnetic field. Thirdly, the SCMP modified probes can perform the rapid separation and purification of signal antibodies in a magnetic field. Thus, the present immunosensor can simultaneously realize separation, enrichment and determination. It showed potential application for the detection of AFP in human sera. PMID:22164043

  19. 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 S.; Hensley, Alyssa; 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.

  20. Activation of isocyanate ligands in Ru25+ complexes

    NASA Astrophysics Data System (ADS)

    Barral, M. Carmen; Herrero, Santiago; Jiménez-Aparicio, Reyes; Priego, José L.; Torres, M. Rosario; Urbanos, Francisco A.

    2008-11-01

    The reaction of [Ru 2(O 2CMe)(DPhF) 3(H 2O)]BF 4 · 0.5CH 2Cl 2 (DphF dbnd N, N'-diphenylformidinate) with sodium cyanate leads to the substitution of the H 2O ligand giving Ru 2(NCO)(O 2CMe)(DPhF) 3 ( 1). In contrast, in the similar reaction of Ru 2Cl 2(DPhF) 3 with NaOCN one of the cyanate groups undergoes the addition of a MeOH molecule leading to the carbamate complex Ru 2(NCO)(NH(O)COMe)(DPhF) 3 ( 2). The spectroscopic properties of 1 and 2 are studied. Both complexes are paramagnetic showing the presence of three unpaired electrons with an important zero-field splitting and a small intermolecular antiferromagnetic interaction. The crystal structures of 1 · 3CHCl 3 and 2 · C 7H 8 · 0.5MeOH are also reported. Compound 2 represents the first example of a ruthenium paddlewheel compound with a carbamate ligand.

  1. The interactions of water and perfluorodiethyl ether on Ru(100)

    SciTech Connect

    Leavitt, P.

    1990-09-21

    We have studied the interactions of water and perfluorodiethyl ether on Ru(100) in order to model the effects of surface structure and humidity on the bonding and decomposition of perfluoroalkyl ether lubricants with metal surfaces. In order to understand the interactions on Ru(100), we have first investigated the interactions of each of these adsorbates alone on the clean surface. The interactions of water with Ru(100) have been studied using both thermal desorption spectroscopy (TDS) and electron energy loss spectroscopy (EELS). From these studies we conclude that a small amount of water dissociates on this surface (5--10% of a monolayer), but water is adsorbed in a predominantly molecular form on this surface with an increasing degree of hydrogen-bonding with increasing coverage. The effects of hydrogen and oxygen coadsorption on the interactions of water with this surface have also been studied using TDS. Finally, the interactions of coadsorbed water and perfluorodiethyl ether on Ru(100) have been investigated using TDS.

  2. ELECTRONIC AND TRANSPORT PROPERTIES OF THERMOELECTRIC Ru2Si3

    NASA Astrophysics Data System (ADS)

    Singh, David J.; Parker, David

    2013-10-01

    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. Electronic and magnetic properties in Sr1-xLaxRuO3

    NASA Astrophysics Data System (ADS)

    Gupta, Renu; Pramanik, A. K.

    2016-05-01

    Here we report the structural, magnetic and transport properties in La doped SrRuO3. The doping of La3+ modifies the ionic state of Ru by converting Ru4+ to Ru+3. However, there is modification in lattice parameters as La3+ has smaller ionic radii than that of Sr2+. We find La doping weakens the ferromagnetic state in SrRuO3 in terms of lowering Tc and decreasing the magnetic moment. The electrical resistivity shows metallic behavior in whole temperature range, however, resistivity increases with doping of La.

  5. 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

  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. 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).

  8. 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.

  9. Ferromagnetic Properties of SrRuO3 Thin Films Deposited on the Spin-Triplet Superconductor Sr2RuO4

    NASA Astrophysics Data System (ADS)

    Sugimoto, Yusuke; Anwar, Muhammad Shahbaz; Lee, Seung Ran; Shin, Yeong Jae; Yonezawa, Shingo; Noh, Tae Won; Maeno, Yoshiteru

    We report magnetic properties of epitaxial thin films of the itinerant ferromagnet SrRuO3 deposited on the cleaved ab surface of the spin-triplet superconductor Sr2RuO4. The films exhibit ferromagnetic transition near 160 K as in the bulk SrRuO3, although the films are under 1.7% compressive strain. The observed magnetization is even higher than that of the bulk SrRuO3. In addition, we newly found that the magnetization relaxation after field removal is strongly anisotropic: two relaxation processes are involved when magnetic domains are aligned along the ab-plane.

  10. 186Os- 187Os systematics of Hawaiian picrites revisited: New insights into Os isotopic variations in ocean island basalts

    NASA Astrophysics Data System (ADS)

    Ireland, T. J.; Walker, R. J.; Brandon, A. D.

    2011-08-01

    Eighteen picrites (MgO > 13 wt.%) and three related basalts from six Hawaiian volcanoes were analyzed for 187Os/ 188Os and 186Os/ 188Os. Variations in these ratios reflect long-term Re/Os and Pt/Os differences in the mantle source regions of these volcanoes. 187Os/ 188Os ratios vary from ˜0.129 to 0.136, consistent with the range defined by previous studies of Hawaiian picrites and basalts. Samples with lower 187Os/ 188Os are mainly from Kea trend volcanoes (Mauna Kea and Kilauea), and the more radiogenic samples are mainly from Loa trend volcanoes (Mauna Loa, Hualalai, Koolau and Loihi). As previously suggested, differences in 187Os/ 188Os between volcanic centers are most consistent with the presence of variable proportions of recycled materials and/or pyroxenitic components in the Hawaiian source. 186Os/ 188Os ratios vary from 0.1198332 ± 26 to 0.1198480 ± 20, with some samples having ratios that are significantly higher than current estimates for the ambient upper mantle. Although the range of 186Os/ 188Os for the Hawaiian suite is consistent with that reported by previous studies, the new data reveal significant heterogeneities among picrites from individual volcanoes. The linear correlation between 187Os/ 188Os and 186Os/ 188Os reported by a previous study is no longer apparent with the larger dataset. The postulated recycled materials and pyroxenites responsible for the dominant variations in 187Os/ 188Os are likely not responsible for the variations in 186Os/ 188Os. Such materials are typically characterized by both insufficiently high Os concentrations and Pt/Os to account for the 186Os/ 188Os heterogeneities. The lack of correspondence between 186Os/ 188Os variations and the Kea and Loa trends supports this conclusion. The primary cause of 186Os/ 188Os variations are evaluated within the framework of two mixing scenarios: (1) metasomatic transport of Pt and/or 186Os-rich Os into some portions of the Hawaiian source, and (2) interaction between an

  11. 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

    2016-01-01

    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

  12. Thermal Stability of a RuO2 Electrode Prepared by DC Reactive Sputtering

    NASA Astrophysics Data System (ADS)

    Matsui, Yuichi; Hiratani, Masahiko; Kimura, Shinichiro

    2000-01-01

    RuO2 films were deposited by reactive DC sputtering, and the formation process and the thermal stability were investigated. In the RuO2/Ti/SiO2 structure, the Ti surface was preferentially oxidized at the initial stage of RuO2 growth. Insertion of Ru and TiN layers between the RuO2 and Ti layers can suppress the oxygen diffusion toward the Ti layer during the film growth. However, when the RuO2/Ru/TiN/Ti/Si structure was heat-treated, the RuO2 was partially reduced to form RuO2-X and the TiN was oxidized to TiO2 while generating N2 and O2 gases, resulting in voids formation at the RuO2/Ru interface, regardless of the heat-treatment atmosphere. We found this was caused by internal oxygen diffusion within the stacked layers. This reaction is governed by the transference of oxygen to the TiN and Ti layers by the difference in the Gibbs’ formation free energy, and by the oxygen diffusion enhancement.

  13. Enhancement of Curie temperature in Mn2RuSn by Co substitution

    NASA Astrophysics Data System (ADS)

    Nelson, A.; Kharel, P.; Huh, Y.; Fuglsby, R.; Guenther, J.; Zhang, W.; Staten, B.; Lukashev, P.; Valloppilly, S.; Sellmyer, D. J.

    2015-04-01

    The Co-substituted Mn2RuSn nanomaterials, namely, Mn2Ru0.5Co0.5Sn and Mn2Ru0.35Co0.65Sn have been synthesized and investigated. The presence of Co in the Mn2RuSn (a = 6.21 Å) decreased the lattice parameter, where a = 6.14 Å and 6.12 Å for the as prepared Mn2Ru0.5Co0.5Sn and Mn2Ru0.35Co0.65Sn, 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 (Tc = 448 K for Mn2Ru0.5Co0.5Sn and 506 K for Mn2Ru0.35Co0.65Sn) of Mn2RuSn (Tc = 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 Mn2RuSn.

  14. Oxygen-Driven Porous Film Formation of Single-Crystalline Ru Deposited on Au(111).

    PubMed

    Herd, Benjamin; Langsdorf, Daniel; Sack, Christian; He, Yunbin; Over, Herbert

    2016-05-31

    We examined the interaction of oxygen with ultrathin Ru layers deposited on a Au(111) substrate using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and low-energy electron diffraction. The deposition of pure Ru below one monolayer (ML) at room temperature leads to the formation of clusters on the Au(111) surface, preferentially located at the elbow sites of the herringbone reconstruction. Subsequent exposure of molecular oxygen to such a Ru-covered Au(111) surface at 680 K results in the growth of two-layer-thick Ru islands that are embedded in the top Au(111) layer. This structural reorganization of Ru is driven by the minimization of surface energy and mediated by a mobile RuOx species. Deposition of an increasing amount of Ru at 620 K (0.5-10 ML, ML = monolayer) leads to a rough Ru film on Au(111). Subsequent oxygen treatment (10(-5) mbar) at 680 K creates either a porous Ru film (<4 ML) or a flat RuO2(110) film (>6 ML) depending on the thickness of the Ru film. PMID:27173402

  15. Hoechst reportedly stalls RU-486 in U.S.

    PubMed

    1994-05-16

    President Clinton's administration would like RU-486 to be widely available in the US, but its manufacturer has been procrastinating about introducing RU-486 in the US. President Clinton lifted the ban on it shortly after ascending to the presidency. After 13 months of negotiations, the parent company of Roussel Uclaf, Hoechst, blocked efforts. It appears to be thwarting Ru-486's manufacture in the US because it fears that antiabortion groups will boycott its other products (textiles, rug fibers, and drugs for diabetics and heart patients). Its annual sales in the US are $7 billion. In April, 1993, Roussel Uclaf said that it would transfer its patent to the Population Council. The Council agreed to perform the clinical trials required to obtain US Food and Drug Administration approval and to find a domestic manufacturer to produce RU-486. Before handing the patent over to the Population Council, Hoechst wants protection from potential product liability or losses from antiabortion protests. US Health and Human Services officials have been trying to promote progress in the negotiations between the Population Council and Hoechst. A US member of Congress has set up a subcommittee hearing to look into the delays, specifically Hoechst's role in the delays. Women's groups want US women to have access to an alternative to surgical abortion. If progress is not made soon, they intend to push the government to revoke Roussel Uclaf's patent or support development of a similar drug. They stress that Hoechst's actions, be they for economic or political reasons, have slowed medical research and have hurt women's well being. RU-486 can also be used to treat breast cancer, some brain tumors, and other diseases. PMID:12318854

  16. Luminescence characteristics of Ru complexes immobilized on porous glass

    NASA Astrophysics Data System (ADS)

    Zemskii, Vladimir I.; Kolesnikov, Yuri L.; Veresov, A. V.

    1995-05-01

    Probes using luminescent transition metal complexes for determination of contents and conditions of environment are very promising. This work deals with the investigation of spectral properties of highly luminescent Ru(II) polypyridil complexes with such ligands as 2,2'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl-1, 10-phenanthroline and their substitution analogues immobilized on porous glass surface. The object under investigation possesses a number of desirable features, since it combines luminescence properties of metal-ligand complexes with mechanical and technological advantages associated with employment of porous glass matrix. Emission of Ru(II) polypyridil complexes is typically dominated by a series of lowlying metal to ligand charge-transfer excited states. Luminescence spectra reveal wide structureless band with maxima ranging from 605 nm for Ru-tris-1,10-phenanthroline to 645 nm for Ru-4,7-diphenyl-1, 10-phenanthroline. The luminescence band shape and placement are practically independent of excitation wavelength. The radiative transition from the excited states is strongly influenced by external factors, such as presence of a quencher or temperature variations. The experiments revealed nonmonotonous character of temperature dependence of luminescence intensity. While the compositions are heated, the original luminescence quantum yield downfall in a temperature range up to 110 K is reversed and there appear to be an interval (110 - 200 K for Ru-4,7-diphenyl-1, 10-phenanthroline), where quantum yield rises, reaching maximum at 200 K. Subsequent heating up to 370 K is followed by renewal of quenching. This phenomena could be explained taking into account porous matrix inhomogeneity, leading to the existence of complexes with different orientation as to the matrix surface.

  17. Semiconductor-metal transition of Se in Ru-Se Catalyst Nanoparticles

    NASA Astrophysics Data System (ADS)

    Babu, P. K.; Lewera, Adam; Oldfield, Eric; Wieckowski, Andrzej

    2009-03-01

    Ru-Se composite nanoparticles are promising catalysts for the oxygen reduction reaction (ORR) in fuel cells. Though the role of Se in enhancing the chemical stability of Ru nanoparticles is well established, the microscopic nature of Ru-Se interaction was not clearly understood. We carried out a combined investigation of ^77Se NMR and XPS on Ru-Se nanoparticles and our results indicate that Se, a semiconductor in elemental form, becomes metallic when interacting with Ru. ^77Se spin-lattice relaxation rates are found to be proportional to T, the well-known Korringa behavior characteristic of metals. The NMR results are supported by the XPS binding energy shifts which suggest that a possible Ru->Se charge transfer could be responsible for the semiconductor->metal transition of Se which also makes Ru less susceptible to oxidation during ORR.

  18. The electronic structure and spectra of Ru(II) and Ru(III) complexes with imidazole and its derivatives

    NASA Astrophysics Data System (ADS)

    Rogachevsky, I. V.; Baranovski, V. I.

    2000-12-01

    The calculations of the electronic structure and spectra of [Ru(NH 3) 5L] 2+ (L=imidazole, histidine) and [Ru(NH 3) 5L] 3+ (L=imidazole, N-imidazolate anion, 4-methylimidazole, 4-methyl-1 N-imidazolate anion and 1 N-bound histidine) complexes are performed in the framework of the CI method in the INDO/CNDO approximation. The MO diagram is obtained. The assignment of all transitions with energies of 4-5 eV is made and the nature of corresponding excited states is discussed. For the Ru(II) complexes, the lower energy observable transition is assigned to d→π* type, whereas the higher energy one is assigned to π→π* type. In the spectra of the Ru(III) complexes with charged ligands both transitions are of π→d character, while in the case of uncharged ligands, the higher energy transition mostly incorporates π→π* excitations.

  19. Enhanced antiferromagnetic coupling in dual-synthetic antiferromagnet with Co2FeAl electrodes

    NASA Astrophysics Data System (ADS)

    Zhang, D. L.; Xu, X. G.; Wu, Y.; Li, X. Q.; Miao, J.; Jiang, Y.

    2012-05-01

    We study dual-synthetic antiferromagnets (DSyAFs) using Co2FeAl (CFA) Heusler electrodes with a stack structure of Ta/CFA/Ru/CFA/Ru/CFA/Ta. When the thicknesses of the two Ru layers are 0.45 nm, 0.65 nm or 0.45 nm, 1.00 nm, the CFA-based DSyAF has a strong antiferromagnetic coupling between adjacent CFA layers at room temperature with a saturation magnetic field of ∼11,000 Oe, a saturation magnetization of ∼710 emu/cm3 and a coercivity of ∼2.0 Oe. Moreover, the DSyAF has a good thermal stability up to 400 °C, at which CFA films show B2-ordered structure. Therefore, the CFA-based DSyAFs are favorable for applications in future spintronic devices.

  20. Functional analysis of the rice vacuolar zinc transporter OsMTP1

    PubMed Central

    Menguer, Paloma K.; Farthing, Emily; Peaston, Kerry A.; Ricachenevsky, Felipe Klein; Fett, Janette Palma; Williams, Lorraine E.

    2013-01-01

    Heavy metal homeostasis is maintained in plant cells by specialized transporters which compartmentalize or efflux metal ions, maintaining cytosolic concentrations within a narrow range. OsMTP1 is a member of the cation diffusion facilitator (CDF)/metal tolerance protein (MTP) family of metal cation transporters in Oryza sativa, which is closely related to Arabidopsis thaliana MTP1. Functional complementation of the Arabidopsis T-DNA insertion mutant mtp1-1 demonstrates that OsMTP1 transports Zn in planta and localizes at the tonoplast. When heterologously expressed in the yeast mutant zrc1 cot1, OsMTP1 complemented its Zn hypersensitivity and was also localized to the vacuole. OsMTP1 alleviated, to some extent, the Co sensitivity of this mutant, rescued the Fe hypersensitivity of the ccc1 mutant at low Fe concentrations, and restored growth of the Cd-hypersensitive mutant ycf1 at low Cd concentrations. These results suggest that OsMTP1 transports Zn but also Co, Fe, and Cd, possibly with lower affinity. Site-directed mutagenesis studies revealed two substitutions in OsMTP1 that alter the transport function of this protein. OsMTP1 harbouring a substitution of Leu82 to a phenylalanine can still transport low levels of Zn, with an enhanced affinity for Fe and Co, and a gain of function for Mn. A substitution of His90 with an aspartic acid completely abolishes Zn transport but improves Fe transport in OsMTP1. These amino acid residues are important in determining substrate specificity and may be a starting point for refining transporter activity in possible biotechnological applications, such as biofortification and phytoremediation. PMID:23761487

  1. 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

  2. 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.

  3. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    NASA Astrophysics Data System (ADS)

    Sun, Yu; Hsieh, Yu-Chi; Chang, Li-Chung; Wu, Pu-Wei; Lee, Jyh-Fu

    2015-03-01

    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 successful 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 undergoes 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-1Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg-1Pt). 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.

  4. Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

    DOE PAGESBeta

    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 0.1more » 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

  5. Solid-State Ru-99 NMR Spectroscopy: A Useful Tool for Characterizing Prototypal Diamagnetic Ruthenium Compounds Compounds

    SciTech Connect

    Ooms, Kristopher J.; Wasylishen, Roderick E.

    2004-09-08

    The feasibility of 99Ru NMR spectroscopy as a tool to characterize solid compounds is demonstrated. Results of the first solid-state 99Ru NMR investigation of diamagnetic compounds are presented for Ru(NH3)6Cl2, K4Ru(CN)6 xH2O (x) 0, 3, LaKRu(CN)6, and Ru3(CO)12. The sensitivity of the ruthenium magnetic shielding tensor to subtle changes in the local structure about the ruthenium nucleus is highlighted by comparing the 99Ru isotropic chemical shift of Ru(NH3)6Cl2 in aqueous solutions and in the solid state. The narrow isotropic 99Ru NMR peak observed for solid Ru(NH3)6Cl2 indicates that this compound is an ideal secondary reference sample for solid-state 99Ru NMR studies.

  6. Photoelectrocatalytic study of water oxidation at n-RuS{sub 2} electrodes

    SciTech Connect

    Salvador, P.; Alonso-Vante, N.; Tributsch, H.

    1998-01-01

    A kinetic study of the photocatalytic oxidation of water at a n-RuS{sub 2} semiconducting single crystal has been undertaken on the basis of photocurrent transients (photocurrent-time behavior as a function of the polarization potential, illumination intensity, and temperature) and electrolyte electroreflectance experiments. The main factor defining the catalytic activity of RuS{sub 2} for water oxidation, both in the dark and under illumination, is a low overpotential ({eta} {approx} 0.3 V), which is comparable to that of the RuO{sub 2} catalyst for oxygen evolution at darkness. Evidence has been given that {eta} is determined by the E{sup o}(Ru{sub s}-OH{sup 0}/Ru{sub s}-H{sub 2}O) redox potential, which strongly depends on the bonding energy of Ru surface species with OH{sup o} radicals generated by direct oxidation of adsorbed water molecules (interfacial Ru-peroxo-type complex formation). This bonding energy increases as the RuS{sub 2} surface becomes oxidized under anodic polarization and reaches its maximum value at the potential of the S{sub 2}RuO{sub 2}/RuS{sub 2} transition (VIII Ru oxidation state). Further oxidation of the Ru-peroxo-type complexes leads to oxygen evolution at a rate which increases with the degree of oxidation of the Ru surface active centers. Although O{sub 2} evolution probably already takes place on Ru(VI) surface sites, high evolution rates (current densities) are only reached under oxidation state VIII. However, in this state (idealized S{sub 2}Ru(VIII)O{sub 2}) Ru-S surface bonds are weakened and occasionally broken, contributing to RuS{sub 2} dissolution with generation of volatile RuO{sub 4} and SO{sub 4}{sup 2{minus}} soluble ions as the main corrosion products. This phenomenon may be attributed to the reaction in acidic medium of H{sub 2}O molecules with Ru(VIII) surface species, giving rise to the formation of unstable intermediate complexes.

  7. Structure of alloys and diagram of phase equilibria of the Zr-Ru-Ir system. II. Solidification pattern of alloys of the partial system Ru-ZrRu-ZrIr-Ir

    SciTech Connect

    Eremenko, V.N.; Khoruzhaya, V.G.; Shtepa, T.D.

    1985-10-01

    The authors constructed the solidification diagram of alloys of the partial system Ru-ZrRu-ZrIr-Ir using data on the structure of alloys in the as-cast condition, yielded from metallographic examinations, microhardness determinations, and x-ray phase analyses together with results of an investigation of the solidus surface of the system. No ternary compounds were detected in the system. In accordance with the four three-phase regions found on the solidus surface, in the Ru-ZrRu-ZrIr-Ir system there are four invariant equilibria involving the participation of liquid, each of which is an equilibrium of the peritectic type. Their temperatures fall toward the Zr-Ru side of the composition triangle.

  8. Fractionation of Highly Siderophile Elements in Refertilized Mantle: Implications for the Os Isotope Composition of Basalts

    NASA Astrophysics Data System (ADS)

    Marchesi, C.; Dale, C. W.; Garrido, C. J.; Pearson, D. G.; Bosch, D.; Bodinier, J. L.; Gervilla, F.; Hidas, K.

    2014-12-01

    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. Modelling 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.

  9. 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.

  10. [sup 187]Os-[sup 186]Os and [sup 187]Os-[sup 188]Os method of dating: An introduction

    SciTech Connect

    Yin, Q.Z.; Jagoutz, E.; Waenke, H. ); Verkhovskiy, A.B. )

    1993-08-01

    A Re-containing sample is irradiated with thermal neutrons in a nuclear reactor. The following reactions occur with high cross sections: [sup 185]Re(n, [gamma])[sup 186]Re and [sup 187]Re(n, [gamma])[sup 188]Re. Both [sup 186]Re (half-life 90.6 h) and [sup 188]Re (16.7 h) [beta]-decay to the stable isotopes [sup 186]Os and [sup 188]Os. Thus [sup 186]Os and [sup 188]Os are enriched in proportion to the neutron fluence and R/Os ratio of the sample being irradiated. Analyzing merely the isotopic composition of the sample, the authors get two ages that should be consistent. In one irradiated molybdenite sample from Kingsgate molybdenum mine in New South Wales, Australia, the measured [sup 186]Os/[sup 192]Os and [sup 188]Os/[sup 192]Os are 0.3284 and 0.6299, whereas in an unirradiated sample they are assumed to be 0.0390 and 0.3248. These ratios are measurable with negative thermal ionization mass spectrometry (N-TIMS) to a precision of 1[per thousand]. The derived ages for this sample are t[sub 186] = 220.5 [+-] 8.6 Ma and t[sub 188] = 214.9 [+-] 8.9 Ma, respectively (or [+-] 1.4 Ma and [+-] 1.7 Ma, respectively, when excluding the uncertainty of [sup 187]Re half-life). These values are in close agreement with the 221--238 Ma K-Ar ages of the leucogranites emplacement that causes the Mo mineralization at Kingsgate. The major limiting factor on the precision of this age determination is the uncertainty in the half-life of [sup 187]Re. The errors associated with the irradiation parameters are greatly reduced by choosing an appropriate neutron flux monitor. The advantage of this method is that the Re/Os ratio is determined on the same sample and that only one measurement of the isotope composition of osmium is required, thus overcoming some of the experimental difficulties of the conventional Re-Os analysis. The problem of sample inhomogeneity and the need to measure the absolute concentrations of rhenium and osmium are thus eliminated. 30 refs., 3 figs., 1 tab.

  11. Synthesis, spectral and electrochemical studies of binuclear Ru(III) complexes containing dithiosemicarbazone ligand

    NASA Astrophysics Data System (ADS)

    Kanchana Devi, A.; Ramesh, R.

    2014-01-01

    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 (RuIII-RuIII/RuIII-RuIV; RuIII-RuIV/RuIV-RuIV) within the E1/2 range of 0.61-0.74 V and 0.93-0.98 V respectively, versus Ag/AgCl.

  12. Preparation and structural characterization of RuS2 nanoislands on Au(111).

    PubMed

    Cai, Tanhong; Song, Zhen; Rodriguez, Jose A; Hrbek, Jan

    2004-07-28

    Among all the transition metal sulfides, ruthenium sulfide (RuS2) has been shown to be the most active catalyst for the hydrodesulfuriztion processes. Using X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM), we have found a novel approach for the preparation of RuS2 nanoislands on an Au(111) substrate. Chemical vapor deposition of Ru3(CO)12 leads to metallic Ru nanoclusters on the gold substrate. Although sulfidation has not been observed on extended Ru (0001) surface, Ru nanoclusters react with S2, forming ruthenium sulfide. While the majority of the sulfide is in the form of nanosized clusters that aggregate into clustered islands, a small fraction of the sulfide is seen as flat islands. When Ru3(CO)12 was deposited on a sulfur-modified gold substrate at elevated temperature, flat islands of ruthenium sulfide are formed exclusively. The flat islands are single-layer RuS2 nanocrystals with a (111) surface termination which exhibits an ordered array of sulfur vacancies. On such RuS2 (111) surfaces, excess sulfur is stable at low temperature and induces surface reconstruction, and desorbs at high temperature. The RuS2(111)/Au system provides an excellent model system for ruthenium sulfide catalysts. PMID:15264806

  13. Chemical corrosion of PtRuCu6/C for highly efficient methanol oxidation

    NASA Astrophysics Data System (ADS)

    Huang, Meihua; Wu, Chuxin; Guan, Lunhui

    2016-02-01

    Until now, Pt is commonly used as anode catalyst for methanol oxidation in direct methanol fuel cells. Here we report that chemical corrosion of PtRuCu6/C, which was prepared by microwave-polyol technique, promotes the activity of Pt for methanol oxidation. The PtRuCu6/C is chemically corroded, and the obtained sample is denoted as PtRuCu6-A/C. The PtRuCu6-A/C contains a Pt-Ru-Cu core and Pt-Ru shell with surface defects. The PtRuCu6-A/C has surface activity and mass activity 10.6 and 6.0 times higher than those of Pt/C for methanol oxidation. And the surface activity and mass activity of PtRuCu6-A/C are 3.3 and 3.9 times higher than those of PtRu/C for methanol oxidation. The enhanced activity of PtRuCu6-A/C is attributed to the surface defects and the stronger electronic modification of Pt. This facile preparation strategy provides a new route of synthesizing highly active catalysts for methanol oxidation.

  14. 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.

  15. Synthesis, Electrochemistry, and Excited-State Properties of Three Ru(II) Quaterpyridine Complexes.

    PubMed

    Rudd, Jennifer A; Brennaman, M Kyle; Michaux, Katherine E; Ashford, Dennis L; Murray, Royce W; Meyer, Thomas J

    2016-03-24

    The complexes [Ru(qpy)LL'](2+) (qpy = 2,2':6',2″:6″,2‴-quaterpyridine), with 1: L = acetonitrile, L'= chloride; 2: L = L'= acetonitrile; and 3: L = L'= vinylpyridine, have been prepared from [Ru(qpy) (Cl)2]. Their absorption spectra in CH3CN exhibit broad metal-to-ligand charge transfer (MLCT) absorptions arising from overlapping (1)A1 → (1)MLCT transitions. Photoluminescence is not observed at room temperature, but all three are weakly emissive in 4:1 ethanol/methanol glasses at 77 K with broad, featureless emissions observed between 600 and 1000 nm consistent with MLCT phosphorescence. Cyclic voltammograms in CH3CN reveal the expected Ru(III/II) redox couples. In 0.1 M trifluoroacetic acid (TFA), 1 and 2 undergo aquation to give [Ru(II)(qpy)(OH2)2](2+), as evidenced by the appearance of waves for the couples [Ru(III)(qpy)(OH2)2](3+)/[Ru(II)(qpy)(OH2)2](2+), [Ru(IV)(qpy)(O)(OH2)](2+)/[Ru(III)(qpy)(OH2)2](3+), and [Ru(VI)(qpy)(O)2](2+)/[Ru(IV)(qpy)(O)(OH2)](2+) in cyclic voltammograms. PMID:26891090

  16. Nanoporous PtRu Alloys with Unique Catalytic Activity toward Hydrolytic Dehydrogenation of Ammonia Borane.

    PubMed

    Zhou, Qiuxia; Xu, Caixia

    2016-03-01

    Nanoporous (NP) PtRu alloys with three different bimetallic components were straightforwardly fabricated by dealloying PtRuAl ternary alloys in hydrochloric acid. Selective etching of aluminum from source alloys generates bicontinuous network nanostructures with uniform size and structure. The as-made NP-PtRu alloys exhibit superior catalytic activity toward the hydrolytic dehydrogenation of ammonia borane (AB) than pure NP-Pt and NP-Ru owing to alloying platinum with ruthenium. The NP-Pt70 Ru30 alloy exhibits much higher specific activity toward hydrolytic dehydrogenation of AB than NP-Pt30 Ru70 and NP-Pt50 Ru50 . The hydrolysis activation energy of NP-Pt70 Ru30 was estimated to be about 38.9 kJ mol(-1) , which was lower than most of the reported activation energy values in the literature. In addition, recycling tests show that the NP-Pt70 Ru30 is still highly active in the hydrolysis of AB even after five runs, which indicates that NP-PtRu alloy accompanied by the network nanoarchitecture is beneficial to improve structural stability toward the dehydrogenation of AB. PMID:26573746

  17. Synthesis, spectral and electrochemical studies of binuclear Ru(III) complexes containing dithiosemicarbazone ligand.

    PubMed

    Kanchana Devi, A; Ramesh, R

    2014-01-01

    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. PMID:23988528

  18. Functionalization of PAMAM dendrimers with [Ru(III)(edta)(H2O)](-).

    PubMed

    Benini, P G Z; McGarvey, B R; Franco, D W

    2008-11-01

    The anchoring of K[Ru(III)(edta)(Cl)] on poly(amidoamine) dendrimers (PAMAM of three generations G(x)/Ru (x=0, 2 and 3)) through a peptide type bond yielded the aquo species, [Ru(III)(edta)(H2O)] on dendrimer surface, and upon NO exposure, yielded their nitrosyl analogues, G(x)/RuNO. Characterization of these compounds by elemental analysis, and a UV-vis, IR and 13C NMR spectroscopies indicated the immobilization of 4, 12 and 29 molecules of [Ru(III)(edta)(H2O)] or of the nitrosyl complex [Ru(II)(edta)NO] on the dendrimer surface for G(X)=0, 2 and 3, respectively. For each complex the electrochemical spectrum presented only one redox process with redox potential values of -0.20 and -0.32 V(vs SCE) attributed to the Ru(III)/Ru(II) and NO+/NO(0) couples in G(x)/Ru and G(x)/RuNO, respectively. The one-electron reduction of G(x)/RuNO+ generates G(x)/RuNO(0), which undergoes aquation with a k(-NO) of 2.1+/-0.7 x 10(-3)s(-1) (pH 1.0, mu=0.2 mol/L, CF3COOH/NaCF3COO, 25 degrees C). The G(x)/RuNO species induced a relaxing effect in aortic rings denuded of endothelium and exhibited in vitro assay trypanocidal activity. PMID:18503781

  19. Thermal fragmentation of acyl thiolato complexes to reactive metal sulfido intermediates. Structure of Ru([eta][sup 6]-SC[sub 3]Me[sub 3]COMe)(PPh[sub 3])[sub 2

    SciTech Connect

    Feng, Q.; Krautscheid, H.; Rauchfuss, T.B.; Skaugset, A.E.; Venturelli, A. )

    1995-01-01

    In this study we have examined the thermal fragmentation of acyl thiolate complexes of the type (ring)M(SC[sub 3]Me[sub 3]COMe). While the (cymene)Ru derivative only gave insoluble materials, the thermolysis of the corresponding osmium compound, (cymene)Os(SC[sub 3]Me[sub 3]COMe) (2), proved very informative. Here it was established that the tetramethylfuran is indeed released prior to formation of the free cymene. Furthermore, two intermediates were observed, the second of which was identified as (cymene)[sub 3]Os[sub 3]S[sub 2]. This species is more stable with respect to loss of cymene than the corresponding (cymene)[sub 3]Ru[sub 3]S[sub 2]. Attempts were made to intercept intermediates in these fragmentation processes by employing PPh[sub 3] as a trapping agent. For the Ru case, PPh[sub 3] completely changed the course of the reaction and no tetramethylfuran was generated. Instead we obtained the structurally unusual [eta][sup 6]-acyl thiolate complex (5). We propose that this unimolecular step involves the formation of ([eta][sup 4]-cymene)Ru([eta][sup 6]-SC[sub 3]Me[sub 3]COMe). The forward rate for this equilibration is far slower than the rate of isomerization of the acyl thiolate and far faster than that for the unassisted thermal decomposition of (cymene)Ru(SC[sub 3]MesCOMe). This result leads to a more global assessment of the reactivity of the acyl thiolates: the orientation of the carbonyl center determines the decomposition pathway. 21 refs., 7 figs., 1 tab.

  20. 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.

  1. 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. PMID:20347221

  2. The thermal behavior of Pd on graphene/Ru(0001)

    NASA Astrophysics Data System (ADS)

    Yi, Cheol-Woo; Szanyi, János

    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.

  3. Atomic hydrogen cleaning of Ru-capped EUV multilayer mirror

    NASA Astrophysics Data System (ADS)

    Motai, Kumi; Oizumi, Hiroaki; Miyagaki, Shinji; Nishiyama, I.; Izumi, Akira; Ueno, Tomoya; Miyazaki, Yasuo; Namiki, Akira

    2007-03-01

    Atomic hydrogen cleaning has been developed to reduce the amount of surface oxide on Ru-capped Mo/Si multilayer mirrors for EUVL. Atomic hydrogen generated by a heated W wire catalyzer was supplied to a Ru cap layer that had been lightly oxidized by ECR O2 plasma or EUV irradiation. The effectiveness of atomic hydrogen in deoxidizing it was examined by ex situ AES, XPS, and EUV absolute reflectivity measurements; and it was found that the amount of surface oxide was reduced to the initial level and that the EUV reflectivity of a multilayer degraded by oxidation recovered. In addition, the transport of atomic hydrogen thorough a winding quartz tube was demonstrated to be a promising technique. The actual density of hydrogen radicals was directly measured under various conditions so that the conditions for generating atomic hydrogen could be optimized and the required treatment time shortened.

  4. Silicene Evolution from Silicon Herringbones on Ru(0001)

    NASA Astrophysics Data System (ADS)

    Zhang, Yanfang; Huang, Li; Xu, Wenyan; Que, Yande; Li, En; Pan, Jinbo; Du, Shixuan; Liu, Yunqi; Zhang, Yuyang; Pantelides, Sokrates T.; Gao, Hongjun

    Silicon-based 2D materials can potentionally be integrated into Si-based electronics. Buckled silicene, an analog of graphene, was recently fabricated on a Ag (111) substrate and used to make a field effect transistor. Here, we report that, when Ru (0001) is used as a substrate, low Si coverage produces a herringbone structure, a new silicon phase. With increasing Si coverage, the elbow sites of the herringbone develop into nucleation sites of silicene. At even higher coverage, narrow Si ribbons with honeycomb structure develop between herringbones. Finally, with even higher Si coverage, a (√3 x √3) silicene monolayer forms in registry on (√7 x √7) Ru(0001). Scanning tunneling microscopy (STM) was used to image the structures. The growth process was confirmed by density functional theory (DFT) calculations. This work may contribute to precise control of growth of silicene and other silicon structures.

  5. A rechargeable hydrogen battery based on Ru catalysis.

    PubMed

    Hsu, Shih-Fan; Rommel, Susanne; Eversfield, Philipp; Muller, Keven; Klemm, Elias; Thiel, Werner R; Plietker, Bernd

    2014-07-01

    Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H2 battery which is based on the principle of the Ru-catalyzed hydrogenation of CO2 to formic acid (charging process) and the Ru-catalyzed decomposition of formic acid to CO2 and H2 (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure-free conditions (discharging process). Up to five charging-discharging cycles were performed without decrease of storage capacity. The resulting CO2/H2 mixture is free of CO and can be employed directly in fuel-cell technology. PMID:24803414

  6. Ferromagnetic SrRuO3 thin-film deposition on a spin-triplet superconductor Sr2RuO4 with a highly conducting interface

    NASA Astrophysics Data System (ADS)

    Anwar, M. S.; Shin, Yeong Jae; Lee, Seung Ran; Kang, Sung Jin; Sugimoto, Yuske; Yonezawa, Shingo; Noh, Tae Won; Maeno, Yoshiteru

    2015-01-01

    Ferromagnetic SrRuO3 thin films are deposited on the ab surface of single crystals of the spin-triplet superconductor (TSC) Sr2RuO4 as substrates using pulsed laser deposition. The films are under a severe in-plane compressive strain. Nevertheless, the films exhibit ferromagnetic order with the easy axis along the c-direction below the Curie temperature of 158 K. The electrical transport reveals that the SrRuO3/Sr2RuO4 interface is highly conducting, in contrast with the interface between other normal metals and the ab surface of Sr2RuO4. Our results stimulate investigations on proximity effects between a ferromagnet and a TSC.

  7. Orbital orderings and optical conductivity of SrRuO(3) and CaRuO(3): first-principles studies.

    PubMed

    Wang, Guang-Tao; Zhang, Min-Ping; Yang, Zong-Xian; Fang, Zhong

    2009-07-01

    The Jahn-Teller (JT) distortion induced orbital order and optical conductivity in SrRuO(3) and CaRuO(3) are investigated by first-principles calculations. The total energy and optical conductivity of all the spin ordering states of SrRuO(3) and CaRuO(3) are calculated in the LDA+U scheme with U(eff) = 2.5 eV. The down-spin t(2g) of Ru show antiferromagnetic-like orbital order in the a-b plane. We observe a d-d transition peak at an energy of about 1.0 eV in the calculated optical conductivity and analyze the reason for it not being observed in previous experiments. PMID:21828475

  8. Nearest- and next-nearest-neighbor Ru(II)/Ru(III) electronic coupling in cyanide-bridged tetra-ruthenium square complexes.

    PubMed

    Lin, Ju-Ling; Tsai, Chia-Nung; Huang, Sheng-Yi; Endicott, John F; Chen, Yuan-Jang; Chen, Hsing-Yin

    2011-09-01

    Electrochemical properties of cyanide-bridged metal squares, [Ru(4)](4+) and [Rh(2)-Ru(2)](6+), clearly demonstrate the role of the nearest (NN) metal moiety in mediating the next-nearest neighbor (NNN) metal-to-metal electronic coupling. The differences in electrochemical potentials for successive oxidations of equivalent Ru(II) centers in [Ru(4)](4+) are ΔE(1/2) = 217 mV and 256 mV and are related to intense, dual metal-to-metal-charge-transfer (MMCT) absorption bands. This contrasts with a small value of ΔE(1/2) = 77 mV and no MMCT absorption bands observed to accompany the oxidations of [Rh(2)-Ru(2)](6+). These observations demonstrate NN-mediated superexchange mixing by the linker Ru of NNN Ru(II) and Ru(III) moieties and that this mixing results in a NNN contribution to the ground state stabilization energy of about 90 ± 20 meV. In contrast, the classical Hush model for mixed valence complexes with the observed MMCT absorption parameters predicts a NNN stabilization energy of about 6 meV. The observations also indicate that the amount of charge delocalization per Ru(II)/Ru(III) pair is about 4 times greater for the NN than the NNN couples in these CN-bridged complexes, which is consistent with DFT modeling. A simple fourth-order secular determinant model is used to describe the effects of donor/acceptor mixing in these complexes. PMID:21809814

  9. 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.

  10. The effects of dissociated glucocorticoids RU24858 and RU24782 on TPA-induced skin tumor promotion biomarkers in SENCAR mice.

    PubMed

    Kowalczyk, Piotr; Junco, Jacob J; Kowalczyk, Magdalena C; Sosnowska, Renata; Tolstykh, Olga; Walaszek, Zbigniew; Hanausek, Margaret; Slaga, Thomas J

    2014-06-01

    Glucocorticoids (GCs) are very effective at preventing carcinogen- and tumor promoter-induced skin inflammation, hyperplasia, and mouse skin tumor formation. The effects of GCs are mediated by a well-known transcription factor, the glucocorticoid receptor (GR). GR acts via two different mechanisms: transcriptional regulation that requires DNA-binding (transactivation) and DNA binding-independent protein-protein interactions between GR and other transcription factors, such as nuclear factor kappa B (NF-κB) or activator protein 1 (AP-1; transrepression). We hypothesize that the transrepression activities of the GR are sufficient to suppress skin tumor promotion. We obtained two GCs (RU24858 and RU24782) that have dissociated downstream effects and induce only transrepression activities of the GR in a number of systems. These compounds bind the GR with high affinity and repress AP-1 and NF-κB activities while showing a lack of GR transactivation. RU24858, RU24782, or control full GCs desoximetasone (DES) and fluocinolone acetonide (FA) were applied to the dorsal skin of SENCAR mice prior to application of the tumor promoter 12-O-tetradecanoylphorbol-13-acetate (TPA), two times per week for 2 weeks. DES, FA and RU24858 reversed TPA-induced epidermal hyperplasia and proliferation, while RU24782 treatment had no effect on these markers of skin tumor promotion. All tested compounds decreased TPA-induced c-jun mRNA levels in skin. DES, FA, and RU24858, but not RU24782, were also able to reverse TPA-induced increases in the mRNA levels of COX-2 and iNOS. These findings show that RU24858 but not RU24782 reduced TPA-induced epidermal hyperplasia, proliferation, and inflammation, while both compounds reversed c-jun mRNA increases in the skin. PMID:23852815

  11. Band Structure and Terahertz Optical Conductivity of Transition Metal Oxides: Theory and Application to CaRuO(3).

    PubMed

    Dang, Hung T; Mravlje, Jernej; Georges, Antoine; Millis, Andrew J

    2015-09-01

    Density functional plus dynamical mean field calculations are used to show that in transition metal oxides, rotational and tilting (GdFeO(3)-type) distortions of the ideal cubic perovskite structure produce a multiplicity of low-energy optical transitions which affect the conductivity down to frequencies of the order of 1 or 2 mV (terahertz regime), mimicking non-Fermi-liquid effects even in systems with a strictly Fermi-liquid self-energy. For CaRuO(3), a material whose measured electromagnetic response in the terahertz frequency regime has been interpreted as evidence for non-Fermi-liquid physics, the combination of these band structure effects and a renormalized Fermi-liquid self-energy accounts for the low frequency optical response which had previously been regarded as a signature of exotic physics. Signatures of deviations from Fermi-liquid behavior at higher frequencies (∼100  meV) are discussed. PMID:26382698

  12. CO adsorption and dissociation on Ru(0001) at elevated pressures

    NASA Astrophysics Data System (ADS)

    Starr, David E.; Bluhm, Hendrik

    2013-02-01

    We have investigated the adsorption and dissociation of CO on Ru(0001) surfaces at pressures from ultra-high vacuum up to 1 Torr and temperatures from 293 to 575 K using Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS). At CO pressures above ~ 10- 6 Torr additional CO is adsorbed on the surface, leading to a CO coverage greater than the saturation coverage (0.66 ML) observed under UHV conditions. Binding energy shifts of the O 1s core level indicate that most of the additional adsorbed CO is located in bridge sites between two Ru atoms. At pressures above 10- 2 Torr the coverage of CO saturates at ~ 0.88 ML. Isobaric measurements at 0.04 Torr CO indicate that the bridge bonded CO is stable up to a temperature of ~ 350 K and desorbs entirely by ~ 400 K. Additional CO desorbs over the temperature range of ~ 450 K to ~ 485 K, decreasing the CO coverage to ~ 0.58 ML. Above 520 K we observe the build-up of carbon on the surface which we attribute to the dissociation of CO. At 575 K and 0.04 Torr CO the equivalent of ~ 3.8 ML of carbon is present on the Ru(0001) surface. Potential mechanisms for the formation of this large amount of carbon on the surface will be discussed.

  13. Size-controlled synthesis of thermal stable single-cored Ru@H-SiO2 core-shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Yu, Xiaolong; Yu, Hongbo; Lim, Zi-Yian; Yang, Guangming; Xie, Zhaohui; Zhou, Shenghu; Yin, Hongfeng

    2016-06-01

    Single-cored Ru@H-SiO2 (H: hollow) core-shell nanoparticles (NPs) with around 4.3 nm Ru cores and hollow SiO2 shells were prepared successfully. In this synthetic process, we obtained multi-cored Ru@SiO2 NPs initially, single-cored RuO2@H-SiO2 NPs during treatment, and single-cored Ru@H-SiO2 NPs in the end. The Ru@SiO2 NPs were prepared by water-in-oil microemulsion method, and the size and core number of Ru@SiO2 NPs can be controlled. Single-cored RuO2@H-SiO2 NPs and Ru@H-SiO2 NPs were successively obtained by calcination and reduction. The structure showed promising aggregate-resistant performance and potential application in catalysis.

  14. First-Principles Study on Electronic Structure and Thermodynamic Stability of Sr(Ti,Ru)O3

    NASA Astrophysics Data System (ADS)

    Shimizu, Tatsuo; Kawakubo, Takashi

    2001-02-01

    Not only the electronic structure but also the thermodynamic stability of Sr(Ti,Ru)O3 is investigated using the first-principles method. For the electronic structure with small Ru concentration, the Ru t2g states appear below the middle of the band gap of SrTiO3. In this case, the wave functions of the Ru t2g states are localized at the Ru site. As a Ru concentration increases to more than 50 mol%, the inside-gap states gradually become delocalized. Therefore, a conductive Sr(Ti,Ru)O3 thin film is expected. On the other hand, thermodynamic stability of a Sr(Ti,Ru)O3 thin film is enhanced drastically relative to that of SrRuO3, as Ru concentration decreases. Sr(Ti,Ru)O3 with Ru concentration of more than 60 mol% may oxidize the neighboring (Ti,Al)N layer, which is often used as a barrier metal in memory-cell capacitors. In short, Sr(Ti,Ru)O3 with Ru concentration of about 50 mol% is proposed as a promising candidate material for new electrodes.

  15. Investigation of Ru/TiN Bottom Electrodes Prepared by Chemical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Kang, Sang Yeol; Kim, Beom Seok; Hwang, Cheol Seong; Kim, Hyeong Joon; Kim, Jin Yong; Lee, Kwanghee; Lim, Han-Jin; Yoo, Cha-Young; Kim, Sung-Tae

    2004-09-01

    Ru thin films were prepared by metalorganic chemical vapor deposition (MOCVD) using cyclopentadienyl-propylcyclopentadienlylruthenium(II) [RuCp(i-PrCp)] and the nucleation behaviors of Ru films on Ta2O5, TiN, Si3N4, SiO2, TiO2 substrates were investigated. It appeared that the difference in nucleation behaviors on various substrates is due to the bonding type between atoms in substrate materials. The nucleation property of Ru films on TiN was successfully improved by plasma treatment of the TiN substrate using Ar before film deposition. It was found that the Ar plasma treatment selectively removes N ions from the surface, makes the TiN surface more metallic or ionic (due to the residual Ti-O bonding), and reduces the nucleation barrier. In addition, the oxidation resistance of Ru/TiN layers was improved by H2 annealing, which made the Ru films more dense.

  16. Dimerization Induced Deprotonation of Water on RuO2(110)

    SciTech Connect

    Mu, Rentao; Cantu Cantu, David; Lin, Xiao; Glezakou, Vassiliki Alexandra; Wang, Zhitao; Lyubinetsky, Igor; Rousseau, Roger J.; Dohnalek, Zdenek

    2014-10-02

    RuO2 has proven to be indispensable as a co-catalyst in numerous systems designed for photocatalytic water splitting. In this study we have carried out a detailed mechanistic study of water behavior on the most stable RuO2 face, RuO2(110), by employing variable temperature scanning tunneling microscopy and density functional theory calculations. We show that water monomers adsorb molecularly on Ru sites, become mobile above 238 K, diffuse along the Ru rows and form water dimers. The onset for dimer diffusion is observed at ~277 K indicating significantly higher diffusion barrier than that for monomers. More importantly, we find that water dimers deprotonate readily to form Ru-bound H3O2 and bridging OH species. The observed behavior is compared and contrasted with that observed for water on isostructural rutile TiO2(110).

  17. Preparation and reactivity of a Ru(0) phosphino-carbene complex.

    PubMed

    Mosaferi, Eliar; Pan, Li; Wang, Tongen; Sun, Yunshan; Pranckevicius, Conor; Stephan, Douglas W

    2016-01-28

    The reaction of the phosphino-carbene MeNC3H2NPtBu2 with RuHCl(CO)(PPh3)3 is shown to give facile access to the Ru(0) species (MeNC3H2NPtBu2)Ru(CO)(PPh3)2 (). This species undergoes oxidative addition of H2 and silanes to give (MeNC3H2NPtBu2)RuH2(CO)(PPh3)2, (MeNC3H2NPtBu2)Ru H(SiRPh2)(CO)(PPh3) (R = Ph 5, H 6) and (MeNC3H2NPtBu2) RuH(PhSi(SCH2CH2)2O)(CO)(PPh3) . PMID:26743813

  18. Synthesis, electrochemical and photophysical properties of heterodinuclear Ru-Mn and Ru-Zn complexes bearing ambident Schiff base ligand.

    PubMed

    Guillo, Pascal; Hamelin, Olivier; Loiseau, Frédérique; Pécaut, Jacques; Ménage, Stéphane

    2010-06-28

    While ruthenium tris(diimine) complexes have been extensively studied, this is not the case with ruthenium bis(diimine)X(2) complexes where X represents a pyridinyl-based ligand. The synthesis of a new complex ([2][PF(6)](2)) bearing two ambident Schiff base ligands (HL) constituted by the assembly of phenol and pyridinyl moieties is reported. Thanks to the heteroditopic property of HL, compound [2](2+) was used as an original metalloligand for the coordination of a redox-active (Mn(III)) and redox-inactive (Zn(II)) second metal cation affording three heterodinuclear complexes, namely, [(bpy)(2)Ru(2)Mn(acac)][PF(6)](2) ([3][PF(6)](2); acac = acetylacetonate), [(bpy)(2)Ru(2)Mn(OAc)][PF(6)](2) ([4][PF(6)](2), OAc = acetate), and [(bpy)(2)Ru(2)Zn][PF(6)](2) ([5][PF(6)](2)). The influence of the second metal with regard to the photophysical and electrochemical properties of the ruthenium bis(diimine)X(2) subunit was then investigated. In the case of Ru(II)-Mn(III) heterodinuclear complexes, a partial quenching of the luminescence was observed as a consequence of an efficient electron transfer process from the ruthenium to the manganese. EPR and spectrophotometric analyses of the oxidized species resulting from the one-electron oxidation of compounds [3](2+) and [4](2+) showed the formation of a Mn(IV) species for [3](2+) and an organic free radical for [4](2+). PMID:20485756

  19. First-principles study of formation of Se submonolayer structures on Ru surfaces

    NASA Astrophysics Data System (ADS)

    Stolbov, Sergey

    2010-10-01

    The Ru nanoparticles with Se submonolayer coverage (Se/Ru) demonstrate high electrocatalytic activity toward oxygen reduction reaction (ORR) on cathodes of proton exchange membrane fuel cells. To understand the mechanisms of formation of Se structures on Ru surfaces, the geometric and electronic structures and energetics have been calculated in the present work for various distributions of Se atoms on the Ru(0001) surface and in the vicinity of the edge between the (0001) and (1101) facets. The calculations were performed within the density-functional theory with plane-wave expansion for wave functions and the projector augmented wave potentials. It has been found that due to electronic charge transfer from Ru to Se upon selenium adsorption, Se atoms become negatively charged and repel each other. This repulsion makes compact Se islands on Ru(0001) unstable. Se atoms prefer to separate from each other by the distance of ˜5.47Å or larger, which is possible for all Se adsorbates if coverage is not exceeding 1/3 ML. Further increase in Se coverage weakens Se-Ru bonding. Three-dimensional Se structure such as 4- and 11-atom pyramids are found to decompose spontaneously with scattering of Se atoms over the Ru(0001) surface. The Se adsorbates are also found to repel in the vicinity of the edge between the Ru facets, and a small increase in Se bonding to undercoordinated Ru atom does not change the trend of Se adsorbates to separate from each other. The obtained most stable configurations of Se on Ru with 1/3 ML coverage or less may also be optimal for ORR because they provide Ru sites available for O and OH adsorption.

  20. Irrelevance of Carbon Monoxide Poisoning in the Methanol Oxidation Reaction on a PtRu Electrocatalyst.

    PubMed

    Chen, De-Jun; Tong, YuYe J

    2015-08-01

    Based on detailed in situ attenuated total-reflection-surface-enhanced IR reflection absorption spectroscopy (ATR-SEIRAS) studies of the methanol oxidation reaction (MOR) on Ru/Pt thin film and commercial Johnson-Matthey PtRu/C, a revised MOR enhancement mechanism is proposed in which CO on Pt sites is irrelevant but instead Pt-Ru boundary sites catalyze the oxygen insertion reaction that leads to the formation of formate and enhances the direct reaction pathway. PMID:26148459

  1. 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.

  2. Highly siderophile element geochemistry of 187Os-enriched 2.8 Ga Kostomuksha komatiites, Baltic Shield

    NASA Astrophysics Data System (ADS)

    Puchtel, Igor S.; Humayun, Munir

    2005-03-01

    New analyses of highly siderophile elements (HSE; Re, Os, Ir, Ru, Pt, and Pd) obtained by Carius tube digestion isotope dilution inductively coupled plasma mass-spectrometry (ID-ICPMS) technique are reported for 187Os-enriched 2.8 Ga komatiites from the Kostomuksha greenstone belt. As a result of a significant improvement in the yield over our previous digestions by the NiS fire-assay technique, these komatiites have now been shown to contain 22 to 25% more Os, Ir, and Pt and 34% more Ru. The emplaced komatiite lavas at Kostomuksha thus had siderophile element abundances comparable to those of the Abitibi belt. The discrepancies observed between the two techniques are interpreted to be the result of incomplete digestion of HSE carriers (particularly chromite) during the NiS fire-assay procedure. Our results for UB-N peridotite reference material agree well with those obtained by the high-pressure ashing digestion ID-ICPMS technique reported in the literature. Two types of komatiite lavas have been distinguished in this study based on the IPGE (Os, Ir, and Ru) behavior during lava differentiation. The Kostomuksha type is unique and is characterized by an incompatible behavior of IPGEs, with bulk solid-liquid partition coefficients for IPGEs being close to those for olivine. Cumulate zones in this type of komatiite lava occupy <20% of the total thickness of the flows. The Munro type exhibits a compatible behavior of IPGEs during lava differentiation. The cumulate zone in this type of komatiite occupies >20% of the total thickness of the flows. The calculated bulk partition coefficients indicate that, as with the other Munro-type komatiite lavas, the bulk cumulate contained an IPGE-rich minor phase(s) in addition to olivine. The non-CI chondritic HSE pattern for the source of the Kostomuksha komatiites calculated here is similar to that of Abitibi komatiites and to average depleted spinel lherzolite (ADSL) and supports the hypothesis of a non-CI chondritic HSE

  3. 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.

  4. 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.

  5. 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.

  6. Mössbauer study of the Ru porcelain of Chinese Song Dynasty and Yuan Dynasty

    NASA Astrophysics Data System (ADS)

    Zhengyao, Gao; Songhua, Chen; Xiande, Chen

    1994-12-01

    The Mössbauer spectra from the glazes of the Song Dynasty and the Yuan Dynasty Ru porcelains and the imitative ancient Ru porcelain are compared and analyzed. It is determined that the original firing atmosphere of the Yuan Dynasty Ru porcelain was reductive. The firing temperature was 1250±20 ‡C. The original firing atmosphere of the Song Dynasty Ru porcelain was also reductive; the firing temperature was above 1200 ‡C. The coloring mechanism of these glazes is discussed.

  7. The formation mechanism of bimetallic PtRu alloy nanoparticles in solvothermal synthesis

    NASA Astrophysics Data System (ADS)

    Mi, Jian-Li; Nørby, Peter; Bremholm, Martin; Becker, Jacob; Iversen, Bo B.

    2015-10-01

    An understanding of the nucleation and growth mechanism of bimetallic nanoparticles in solvothermal synthesis is important for further development of nanoparticles with tailored nanostructures and properties. Here the formation of PtRu alloy nanoparticles in a solvothermal synthesis using metal acetylacetonate salts as precursors and ethanol as both the solvent and reducing agent has been studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXRD). Unlike the classical mechanism for the synthesis of monodisperse sols, the nucleation and growth processes of bimetallic PtRu nanoparticles occur simultaneously under solvothermal conditions. In the literature co-reduction of Pt and Ru is often assumed to be required to form PtRu bimetallic nanocrystals, but it is shown that monometallic Pt nanocrystals nucleate first and rapidly grow to an average size of 5 nm. Subsequently, the PtRu bimetallic alloy is formed in the second nucleation stage through a surface nucleation mechanism related to the reduction of Ru. The calculated average crystallite size of the resulting PtRu nanocrystals is smaller than that of the primary Pt nanocrystals due to the large disorder in the PtRu alloyed structure.An understanding of the nucleation and growth mechanism of bimetallic nanoparticles in solvothermal synthesis is important for further development of nanoparticles with tailored nanostructures and properties. Here the formation of PtRu alloy nanoparticles in a solvothermal synthesis using metal acetylacetonate salts as precursors and ethanol as both the solvent and reducing agent has been studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXRD). Unlike the classical mechanism for the synthesis of monodisperse sols, the nucleation and growth processes of bimetallic PtRu nanoparticles occur simultaneously under solvothermal conditions. In the literature co-reduction of Pt and Ru is often assumed to be required to form PtRu bimetallic nanocrystals, but

  8. Activity and stability of the oxygen evolution reaction on electrodeposited Ru and its thermal oxides

    NASA Astrophysics Data System (ADS)

    Kim, Jin Yeong; Choi, Jihui; Kim, Ho Young; Hwang, Eunkyoung; Kim, Hyoung-Juhn; Ahn, Sang Hyun; Kim, Soo-Kil

    2015-12-01

    The activity and stability of Ru metal and its thermal oxide films for the oxygen evolution reaction (OER) were investigated. The metallic Ru films were prepared by electrodeposition on a Ti substrate and then thermally oxidized at various temperatures under atmospheric conditions. During long-term operation of the OER with cyclic voltammetry (CV) in H2SO4 electrolyte, changes in the properties of the Ru and its thermal oxides were monitored in terms of their morphology, crystal structure, and electronic structure. In the initial stages of the OER, all of the Ru thermal oxide films underwent an activation process that was related to the continuous removal of low-activity Ru oxides from the surface. With further cycling, the OER activity decreased. The rate of decrease was different for each Ru film and was related to the annealing temperatures. Monitoring of material properties indicates that the amount of stable anhydrous RuO2 is important for OER stability because it prevents both the severe dissolution of metallic Ru beneath the oxide surface and the formation of a less active hydrous RuO2 at the surface.

  9. Ru-Zn heteropolynuclear complexes containing a dinucleating bridging ligand: synthesis, structure, and isomerism.

    PubMed

    Mognon, Lorenzo; Benet-Buchholz, Jordi; Rahaman, S M Wahidur; Bo, Carles; Llobet, Antoni

    2014-12-01

    Mononuclear complexes in- and out-[Ru(Cl)(trpy)(Hbpp)](+) (in-0, out-0; Hbpp is 2,2'-(1H-pyrazole-3,5-diyl)dipyridine and trpy is 2,2':6',2″-terpyridine) are used as starting materials for preparation of Ru-Zn heterodinuclear out-{[Ru(Cl)(trpy)][ZnCl2](μ-bpp)} (out-2) and heterotrinuclear in,in- and out,out-{[Ru(Cl)(trpy)]2(μ-[Zn(bpp)2])}(2+) (in-3, out-3) constitutional isomers. Further substitution of the Cl ligand from the former complexes leads to Ru-aqua out,out-{[Ru(trpy)(H2O)]2(μ-[Zn(bpp)2])}(4+) (out-4) and the oxo-bridged Ru-O-Ru complex in,in-{[Ru(III)(trpy)]2(μ-[Zn(bpp)2(H2O)]μ-(O)}(4+) (in-5). All complexes are thoroughly characterized by the usual analytical techniques as well as by spectroscopy by means of UV-vis, MS, and when diamagnetic NMR. CV and DPV are used to extract electrochemical information and monocrystal X-ray diffraction to characterize complexes out-2, in-3, out-3, and in-5 in the solid state. Complex out-3 photochemically isomerizes toward in-3, as can be observed by NMR spectroscopy and rationalized by density functional theory based calculations. PMID:25393055

  10. Biochemistry of metalocenes. The organ distribution of hydroxyacetyl (/sup 103/Ru)ruthenocene and its glucuronide in mice

    SciTech Connect

    Taylor, A.J.; Macha, J.; Wenzel, M.

    1980-01-01

    Hydroxyacetyl(/sup 103/Ru)ruthenocene and its o-glucuronide were prepared in vitro by incubation of acetyl(/sup 103/Ru)ruthenocene with rat-liver homogenate, NADPH, and UDP-glucuronate. The factors affecting hydroxylation and glucuronidation in vitro were optimized for acetylruthenocene. Hydroxyacetyl(/sup 103/Ru)ruthenocene glucuronide showed no affinity for the adrenal glands, but after iv administration of hydroxyacetyl(/sup 103/Ru)ruthenocene there was a distinct accumulation of Ru-103 in adrenals, similar to that found after administration of acetyl(/sup 103/Ru)ruthenocene.

  11. Targeting Human Telomeric G-Quadruplex DNA and Inhibition of Telomerase Activity With [(dmb)2Ru(obip)Ru(dmb)2]4+

    PubMed Central

    Cao, Tongcheng; Liu, Jie; Gao, Xing; Hao, Jian; Lv, Chunyan; Huang, Hailiang; Xu, Jun; Yao, Tianming

    2013-01-01

    Inhibition of telomerase by inducing/stabilizing G-quadruplex formation is a promising strategy to design new anticancer drugs. We synthesized and characterized a new dinuclear complex [(dmb)2Ru(obip)Ru(dmb)2]4+ (dmb = 4,4’-dimethyl-2,2’-bipyridine, obip = (2-(2-pyridyl)imidazo[4,5-f][1,10]phenanthroline) with high affinity for both antiparallel and mixed parallel / antiparallel G-quadruplex DNA. This complex can promote the formation and stabilize G-quadruplex DNA. Dialysis and TRAP experiments indicated that [(dmb)2Ru(obip)Ru(dmb)2]4+ acted as an excellent telomerase inhibitor due to its obvious selectivity for G-quadruplex DNA rather than double stranded DNA. In vitro co-culture experiments implied that [(dmb)2Ru(obip)Ru(dmb)2]4+ inhibited telomerase activity and hindered cancer cell proliferation without side effects to normal fibroblast cells. TUNEL assay indicated that inhibition of telomerase activity induced DNA cleavage further apoptosis in cancer cells. Therefore, RuII complex represents an exciting opportunity for anticancer drug design by specifically targeting cancer cell G-quadruplexes DNA. PMID:24386376

  12. Interaction of ethyl chloride with amorphous solid water thin film on Ru(001) and O/Ru(001) surfaces.

    PubMed

    Ayoub, Yousif; Asscher, Micha

    2009-07-01

    The adsorption of ethyl chloride (EC) on clean and oxygen covered Ru(001) surfaces and its interaction with coadsorbed amorphous solid water (ASW) is reported based on temperature-programmed desorption (TPD) and work function change (DeltaPhi) measurements. Adsorption of EC is characterized by a decrease of 2.1 eV in work function at monolayer coverage. Flipped adsorption geometry on average (ethyl facing the surface) is found in the second layer with a 0.3 eV increase in the work function. On ruthenium substrates the orientation of EC molecules could be controlled chlorine down or up by varying the oxygen coverage, as indicated by work function change measurements. DeltaP-TPD from clean Ru(001) surface reveals a complete dissociation of the EC molecules on the clean Ru(001) surface at coverages up to 0.1 +/- 0.05 ML. At higher coverage it leads to two distinct TPD peaks: at T =175 and 120-130 K, for the monolayer and multilayer coverage, respectively. Compression of preadsorbed 0.3 ML EC molecules into small islands on the surface occurs when ASW layers at coverage in the range 0.5-6 bilayers (BL) are adsorbed on top of the EC covered surface, associated with a shift in peak desorption from 190 K down to 125 K. A Caging process of EC molecules within the layers of ASW takes place by adsorbing more than 6 BL until a fully caged system has developed above 20 ASW BL. A reversed TPD peak shift of the trapped EC molecules occurs from its compressed phase at 125 K up to 165 K, the onset for ASW transition to crystalline ice and desorption. The detachment process leads to partial flipping over the geometry of the EC at the second layer, as determined by DeltaPhi measurement. The distance of the lifted and caged EC molecules from the Ru surface has been determined to reside 1.0 +/- 0.2 nm above the solid surface, based on the thermal dissociation and hydrogen uptake measurements of sandwiched EC molecules between a variable thickness ASW film and a fixed 10 BL layer, on

  13. 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.

  14. Sol-gel Ru/SiO[sub 2] - catalysts: Theoretical and experimental determination of the Ru-in-silica structures

    SciTech Connect

    Lopez, T.; Gomez, R.; Novaro, O. ); Ramirez-Solis, A.; Sanchez-Mora, E.; Castillo, S.; Poulain, E.; Martinez-Magadan, J.M. )

    1993-05-01

    Preparation of Ru/SiO[sub 2] catalysts with sol-gel techniques allows better selectivity and much greater resistance to coke formation and deactivation than the traditional impregnation method. This has been attributed to the incorporation of Ru into the silica network for the sol-gel catalyst. To further understand the structure of the Ru occluded in the silica network, a variety of spectroscopical studies and quantum mechanical calculations were carried out, confirming previously proposed structures and showing good agreement between the theoretical and experimental results. 26 refs., 10 figs., 2 tabs.

  15. 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

  16. Structural and electrical properties of ternary Ru-AlN thin films prepared by plasma-enhanced atomic layer deposition

    SciTech Connect

    Shin, Yu-Ri; Kwack, Won-Sub; Park, Yun Chang; Kim, Jin-Hyock; Shin, Seung-Yong; Moon, Kyoung Il; Lee, Hyung-Woo; Kwon, Se-Hun

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Ru-AlN thin films were grown by plasma-enhanced atomic layer deposition (PEALD). Black-Right-Pointing-Pointer Structural properties were systematically investigated by XRD, BF-STEM and EDX. Black-Right-Pointing-Pointer A drastic decrease in resistivity was due to the microstructural change of the films. -- Abstract: Ruthenium-aluminum-nitride (Ru-AlN) thin films were grown by plasma-enhanced atomic layer deposition (PEALD) at 300 Degree-Sign C. The Ru intermixing ratio of Ru-AlN thin films was controlled by the number of Ru unit cycles, while the number of AlN unit cycles was fixed to one cycle. The electrical resistivity of Ru-AlN thin film decreased with increasing the Ru intermixing ratio, but a drastic decrease in electrical resistivity was observed when the Ru intermixing ratio was around 0.58-0.78. Bright-field scanning transmission electron microscope (BF-STEM) and energy-dispersive X-ray spectroscopy (EDX) element mapping analysis revealed that the electrical resistivity of Ru-AlN thin film was strongly dependent on the microstructures as well as on the Ru intermixing ratio. Although the electrical resistivity of Ru-AlN thin films decreased with increasing the Ru intermixing ratio, a drastic decrease in electrical resistivity occurred where the electrical paths formed as a result of the coalescence of Ru nanocrystals.

  17. A theoretical study of Ru(II) polypyridyl DNA intercalators structure and electronic absorption spectroscopy of [Ru(phen)2(dppz)]2+ and [Ru(tap)2(dppz)]2+ complexes intercalated in guanine-cytosine base pairs.

    PubMed

    Ambrosek, David; Loos, Pierre-François; Assfeld, Xavier; Daniel, Chantal

    2010-09-01

    The structural and spectroscopic properties of [Ru(phen)(2)(dppz)](2+) and [Ru(tap)(2)(dppz)](2+) (phen=1,10-phenanthroline; tap=1,4,5,8-tetraazaphenanthrene; dppz=dipyridophenazine ) have been investigated by means of density functional theory (DFT), time-dependent DFT (TD-DFT) within the polarized continuum model (IEF-PCM) and quantum mechanics/molecular mechanics (QM/MM) calculations. The model of the Delta and Lambda enantiomers of Ru(II) intercalated in DNA in the minor and major grooves is limited to the metal complexes intercalated in two guanine-cytosine base pairs. The main experimental spectral features of these complexes reported in DNA or synthetic polynucleotides are better reproduced by the theoretical absorption spectra of the Delta enantiomers regardless of intercalation mode (major or minor groove). This is especially true for [Ru(phen)(2)(dppz)](2+). The visible absorption of [Ru(tap)(2)(dppz)](2+) is governed by the MLCT(tap) transitions regardless of the environment (water, acetonitrile or bases pair), the visible absorption of [Ru(phen)(2)(dppz)](2+) is characterized by transitions to metal-to-ligand-charge-transfer MLCT(dppz) in water and acetonitrile and to MLCT(phen) when intercalated in DNA. The response of the IL(dppz) state to the environment is very sensitive. In vacuum, water and acetonitrile these transitions are characterized by significant oscillator strengths and their positions depend significantly on the medium with blue shifts of about 80 nm when going from vacuum to solvent. When the complex is intercalated in the guanine-cytosine base pairs the (1)IL(dppz) transition contributes mainly to the band at 370 nm observed in the spectrum of [Ru(phen)(2)(dppz)](2+) and to the band at 362 nm observed in the spectrum of [Ru(tap)(2)(dppz)](2+). PMID:20554006

  18. Molecular orbitals vs. relativistic orbitals in t2g honeycomb lattices: SrRu2O6 as compared to Na2IrO3, RuCl3, and Li2RuO3

    NASA Astrophysics Data System (ADS)

    Mazin, Igor; Streltsov, Sergey; Foyevtseva, Kateryna

    t2g states on a honeycomb lattice tend to form non-dispersive localized states even if large intersite hopping is present. In the nonrelativistic case, these are molecular orbitals (MO) localized on metal hexagons, if the ligand-assisted nearest and next nearest neighbor hoppings, t1' and t2', dominate, or dimers (DO), if the direct overlap, t1, dominates. In the ultrarelativistic limit t2 g form effective relativistic orbitals (RO), jeff = 3/3 2 2, which are atomically localized if t1'is the dominant hopping. On the first glance, the three regimes are defined by the conditions t1' >>t1 , λ or t1 >>t1' , λ or λ >>t1 ,t1' . In reality, the latter condition is never fulfilled, especially in ruthenates, yet not only Na2IrO3, but also RuCl3 appear to be in a regime dominated by RO, even though the residual effect of MO critically influences magnetic interactions, while Li2RuO3, not far removed from RuCl3 in the parameter space, is firmly in the DO regime. Most surprisingly, SrRu2O6, which is even closer to RuCl3, happens to be fully in the MO regime, with negligible spin-orbit effects. In this talk, we will show that an additional, decisive factor is the doping level per site. The principal difference between Na2IrO3 or RuCl3, Li2RuO3, and SrRu2O6 is that the first two have one t2 ghole per site, the second one two holes, and the last three electrons. In particular, the total dominance of MO in the latter compound fully explains its unique and unexpected magnetic properties. This work was supported by ONR (IIM) and CRDF (IIM and SVS).

  19. Ternary Pt-Ru-Ni catalytic layers for methanol electrooxidation prepared by electrodeposition and galvanic replacement

    NASA Astrophysics Data System (ADS)

    Papaderakis, Athanasios; Pliatsikas, Nikolaos; Prochaska, Chara; Papazisi, Kalliopi; Balomenou, Stella; Tsiplakides, Dimitrios; Patsalas, Panagiotis; Sotiropoulos, Sotiris

    2014-06-01

    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 towards 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.

  20. PAMAM-stabilized Pt-Ru nanoparticles for methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Gu, Yunlong; Wu, Gang; Hu, Xiao Feng; Chen, Donna A.; Hansen, Tara; Loye, Hans-Conrad zur; Ploehn, Harry J.

    This work utilizes poly(amidoamine) dendrimers (PAMAM) as a protective ligand in solution to produce carbon-supported, Pt-Ru bimetallic nanoparticles for use as methanol electro-oxidation catalysts. UV-vis spectra show that after initial Pt 2+ complexation with PAMAM G4OH dendrimer in water, appropriate adjustment of solution pH permits subsequent Ru 3+ complexation without displacing Pt 2+, demonstrating the formation of an aqueous, bimetallic solution complex. Catalysts (nominally 20 wt% metals, confirmed by AA spectroscopy) are produced by impregnating high surface area carbon black with G4OH-(Pt 2+) x(Ru 3+) y complex solution, drying, and activation in H 2 gas at elevated temperature. XPS results show that activation in H 2 at 400 °C removes virtually all of the PAMAM and reduces all of the Pt and most of the Ru to zero valence. TEM and XRD results show that the use of G4OH in the recipe is crucial for controlling metal particle size, and that the particles are crystalline with lattice parameters indicative of bimetallic Pt-Ru alloys. XRD data also suggest that G4OH promotes greater Pt-Ru alloying when Pt:Ru = 1:1. Catalytic activity for methanol oxidation increases with Ru content and is greatest for the catalyst with 1:1 Pt:Ru ratio. Per unit mass of Pt, the methanol oxidation activity of 20 wt% G4OH-PtRu/C catalyst is about 60% greater than that of E-Tek's commercially available 20 wt% PtRu catalyst.

  1. Structure and electronic properties of the orthorhombic MoRuP superconductor prepared at high pressure

    NASA Astrophysics Data System (ADS)

    Wong-Ng, W.; Ching, W. Y.; Xu, Yong-Nian; Kaduk, J. A.; Shirotani, I.; Swartzendruber, L.

    2003-04-01

    The orthorhombic superconductor MoRuP (o-MoRuP) was prepared under high pressure, and its structure was refined using the x-ray Rietveld technique. The grayish-black sample of o-MoRuP is a superconductor with Tc=15.5 K and having space group Pnma and lattice parameters a=6.03503(16) Å, b=3.85311(8) Å, and c=6.94355(17) Å, V=161.463(7) Å.3 The structure of o-MoRuP is characterized by layers (parallel to the ac plane) of Mo, Ru, and P atoms. Based on the accurately determined crystal structure, the band structure and the density of states (DOS) of o-MoRuP were calculated by a first-principles density-functional method and compared with those of the isostructural superconductor o-ZrRuP (Tc=4 K). It is shown that the high Tc in o-MoRuP is directly related to the higher level of the DOS at the Fermi level (EF) and is traced to be predominantly from the Mo 4d orbitals. The calculated values of the DOS at EF are 0.46 and 0.33 states/eV atom for the Mo and Zr analogs, respectively. The electronic bonding in these two crystals is analyzed in terms of the Mulliken effective charge and the bond order values. The bonding in o-MoRuP differs from that in o-ZrRuP in that there is a short (2.44 Å) Mo-P bond. The x-ray reference pattern of o-MoRuP prepared using a Rietveld decomposition technique has been submitted to the International Center for Diffraction Data to be included in the Powder Diffraction File.

  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. 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

  4. Multifrequency monitoring of RU Lupi. II. The model.

    NASA Astrophysics Data System (ADS)

    Lamzin, S. A.; Bisnovatyi-Kogan, G. S.; Errico, L.; Giovannelli, F.; Katysheva, N. A.; Rossi, C.; Vittone, A. A.

    1996-02-01

    The data obtained during multifrequency monitoring of extreme T Tauri star RU Lupi and presented in Giovannelli et al. (1995), are explained by a model in which a young star with a moderately strong global magnetic field is actively accreting mass from a circumstellar disk. We argue that the magnetic field pressure stops the accretion disk at the height ~R_*_ above the stellar surface. A part of the matter from the innermost regions of the accretion disk freezes into the global stellar magnetic field lines and then slides along them, accelerating via gravity up to velocity V_0_~300km/s. Finally the matter is stopped near the stellar surface via shock wave mechanism. The temperature and density of the gas immediately after the shock front are of the order of 10^6^K and 3x10^13^cm^-3^, respectively. Thermal energy of the shock is carried away via radiation, which cools the decelerating post-shock gas almost to the effective temperature of the star. A half of liberated thermal energy radiates away from the star, so that extreme UV and soft X-ray quanta heat and ionize inflowing gas of pre-shock zone. Thus we suppose that there are at least two regions with different physical conditions where the observed emission lines are formed: before and after shock front. The second half of radiation flux from post-shock zone moves inward and is absorbed in upper, still dense layers of stellar atmosphere (N>10^15^cm^-3^), forming a kind of transition region. A ring-like accretion belt around the magnetic pole is formed in each hemisphere of the star at gas temperature near 6500K. We argue that in the case of RU Lupi these two "spots" occupy ~30% of the stellar surface, and that these are the regions where observed optical and UV "veiling" continuum form. The model explains the continuum emission at λ>0.9μm as a result of the radiation of the accretion disk heated by viscous dissipation and the absorption of radiation from the stellar surface. The main parameters of RU Lupi as a

  5. Estimation of continental 187Os/186Os values by using 187Os/186Os and 143Nd/144Nd ratios in marine manganese nodules

    PubMed Central

    Turekian, Karl K.; Luck, Jean-Marc

    1984-01-01

    The relationship between 187Os/186Os and 143Nd/144Nd in different manganese nodule fields is used to determine the 187Os/186Os ratio of the continental terrains bounding the major ocean basins. The Atlantic Ocean drainages yield 187Os/186Os of about 11; the Pacific Ocean, between 25 and 36; and the western Indian Ocean, 20. By assuming a two-component continental crust composed of “ultramafic rocks” (high Os concentration, low 187Os/186Os) and “granite” with only radiogenic 187Os produced in accessory Re-bearing molybdenite, the ultramafic contribution to weathering is about 0.2%. Some or most of this may come from the alteration of oceanic ultramafics. PMID:16578780

  6. Magnetic and Crystal Structure of α-RuCl3

    NASA Astrophysics Data System (ADS)

    Sears, Jennifer

    The layered honeycomb material α-RuCl3 has been proposed as a candidate material to show significant bond-dependent Kitaev type interactions. This has prompted several recent studies of magnetism in this material that have found evidence for multiple magnetic transitions in the temperature range of 8-14 K. We will present elastic neutron scattering measurements collected using a co-aligned array of α-RuCl3 crystals, identifying zigzag magnetic order within the honeycomb planes with an ordering temperature of ~8 K. It has been reported that the ordering temperature depends on the c axis periodicity of the layered structure, with ordering temperatures of 8 and 14 K for three and two-layer periodicity respectively. While the in-plane magnetic order has been identified, it is clear that a complete understanding of magnetic ordering and interactions will depend on the three dimensional structure of the crystal. Evidence of a structural transition at ~150 K has been reported and questions remain about the structural details, in particular the stacking of the honeycomb layers. We will present x-ray diffraction measurements investigating the low and high temperature structures and stacking disorder in α-RuCl3. Finally, we will present inelastic neutron scattering measurements of magnetic excitations in this material. Work done in collaboration with K. W. Plumb (Johns Hopkins University), J. P. Clancy, Young-June Kim (University of Toronto), J. Britten (McMaster University), Yu-Sheng Chen (Argonne National Laboratory), Y. Qiu, Y. Zhao, D. Parshall, and J. W. Lynn (NCNR).

  7. OsARF12, a transcription activator on auxin response gene, regulates root elongation and affects iron accumulation in rice (Oryza sativa).

    PubMed

    Qi, YanHua; Wang, SuiKang; Shen, ChenJia; Zhang, SaiNa; Chen, Yue; Xu, YanXia; Liu, Yu; Wu, YunRong; Jiang, DeAn

    2012-01-01

    • Auxin has an important role in maintaining optimal root system architecture (RSA) that can cope with growth reductions of crops caused by water or nutrient shortages. However, the mechanism of controlling RSA remains largely unclear. Here, we found a limiting factor of RSA--OsARF12--an auxin response factor whose knockout led to decreased primary root length in rice (Oryza sativa). • OsARF12 as a transcription activator can facilitate the expression of the auxin response element DR5::GFP, and OsARF12 was inhibited by osa-miRNA167d by transient expression in tobacco and rice callus. • The root elongation zones of osarf12 and osarf12/25, which had lower auxin concentrations, were distinctly shorter than for the wild-type, possibly as a result of decreased expression of auxin synthesis genes OsYUCCAs and auxin efflux carriers OsPINs and OsPGPs. The knockout of OsARF12 also altered the abundance of mitochondrial iron-regulated (OsMIR), iron (Fe)-regulated transporter1 (OsIRT1) and short postembryonic root1 (OsSPR1) in roots of rice, and resulted in lower Fe content. • The data provide evidence for the biological function of OsARF12, which is implicated in regulating root elongation. Our investigation contributes a novel insight for uncovering regulation of RSA and the relationship between auxin response and Fe acquisition. PMID:21973088

  8. 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

    2012-09-01

    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. PMID:22898880

  9. 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. PMID:26230806

  10. RuO2 Non-isothermal Thermometry

    NASA Astrophysics Data System (ADS)

    Ventura, Guglielmo; Giomi, Silvia

    2016-08-01

    The use of a RuO2 resistor in non-isothermal measuring setup is proposed. A calculation is presented to explain the principle for a resistor obeying variable-range-hopping theory and the results are compared to measurements in the range of 11.2-30 mK for a commercial resistor. The thermometer, which measures the electron temperature, does not show overheating effects at 11.2 mK with a measuring power of 10^{-12} W.

  11. Low leakage Ru-strontium titanate-Ru metal-insulator-metal capacitors for sub-20 nm technology node in dynamic random access memory

    NASA Astrophysics Data System (ADS)

    Popovici, M.; Swerts, J.; Redolfi, A.; Kaczer, B.; Aoulaiche, M.; Radu, I.; Clima, S.; Everaert, J.-L.; Van Elshocht, S.; Jurczak, M.

    2014-02-01

    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 (Jg) 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 TiO2/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.

  12. 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.

  13. 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.

  14. Direct evidence for catalase activity of [Ru(V)(edta)(O)](-).

    PubMed

    Chatterjee, Debabrata; Jaiswal, Namita; Franke, Alicja; van Eldik, Rudi

    2014-12-01

    Reported is the first example of a ruthenium(III) complex, Ru(III)(edta) (edta(4-) = ethylenediaminetetraacetate), that catalyzes the disproportion of H2O2 to O2 and water in resemblance to catalase activity, and shedding light on the possible mechanism of action of the [Ru(V)(edta)(O)](-) formed in the reacting system. PMID:25307989

  15. Factors controlling the CO intercalation of h-BN overlayers on Ru(0001).

    PubMed

    Dong, Aiyi; Fu, Qiang; Wu, Hao; Wei, Mingming; Bao, Xinhe

    2016-09-21

    The space between a two-dimensional (2D) material overlayer and a metal surface can be regarded as a nanoreactor, in which molecule adsorption and surface reaction may occur. In this work, we present CO intercalation under a hexagonal boron nitride (h-BN) overlayer on Ru(0001) at room temperature, observed using X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and scanning tunneling microscopy. Critical factors influencing the interfacial process have been investigated, including CO partial pressure, h-BN coverage, and oxygen pre-adsorption on the Ru surface. It has been identified that CO adsorption on the bare Ru surface region plays an important role in CO intercalation. Comparative studies of CO intercalation at h-BN/Ru(0001) and graphene/Ru(0001) interfaces indicate that CO starts to intercalate h-BN overlayers more easily than graphene. Temperature-programmed CO desorption experiments from h-BN/CO/Ru(0001) and graphene/CO/Ru(0001) surfaces reveal a similar confinement effect of the 2D cover on CO adsorption, which results in a more abrupt and quick CO desorption in comparison with the CO/Ru(0001) surface. PMID:27530273

  16. Microwave-assisted Synthesis of Ru-Sn/ZnO for Catalysis Application

    NASA Astrophysics Data System (ADS)

    Rini, Ari Sulistyo; Radiman, Shahidan; Yarmo, Mohd. Ambar

    2010-10-01

    ZnO-supported Ru-Sn catalysts have been synthesized under microwave irradiation in biodegradable polyol (Ethylene Glycol) and without any capping agent (such as PVP). Ru-Sn bimetallic was previously prepared without any support (ZnO). UV-Vis spectroscopy was utilized to recognize the reduction process of Ru-Sn bimetallic and to determine reduction time for further experiment. X-ray diffraction (XRD), SEM/EDX, and TEM measurement were done to confirm the structure and the morphology of the catalyst. BET, and X-Ray Photoelectron Spectroscopy (XPS) were also performed to estimate the total surface area and to validate the metal loading percentage on the support, respectively. UV-Vis spectra showed the reduction of Ru-Sn (without support), under 450 W of microwave power, has been completed in less than eight minutes. According to EDX data, four minutes is not enough for Ru-Sn to attach onto ZnO since lack of Ru content was detected. This result was then further confirmed using XPS measurement. Attachment of Ru-Sn on the ZnO in 450 W needs at least eight minute of irradiation time. Ru-Sn/ZnO catalysts have also been synthesized by impregnation method for comparison.

  17. Preparation and characterization of RuO2/polypyrrole electrodes for supercapacitors

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Wu, Yujiao; Zheng, Feng; Ling, Min; Lu, Fanghai

    2014-11-01

    Polypyrrole (PPy) embedded RuO2 electrodes were prepared by the composite method. Precursor solution of RuO2 was coated on tantalum sheet and annealed at 260 °C for 2.5 h to develop a thin film. PPy particles were deposited on RuO2 films and dried at 80 °C for 12 h to form composite electrode. Microstructure and morphology of RuO2/PPy electrode were characterized using Fourier transform infrared spectrometer, X-ray diffraction and scanning electron microscopy, respectively. Our results confirmed that counter ions are incorporated into RuO2 matrix. Structure of the composite with amorphous phase was verified by X-ray diffraction. Analysis by scanning electron microscopy reveals that during grain growth of RuO2/PPy, PPy particle size sharply increases as deposition time is over 20 min. Electrochemical properties of RuO2/PPy electrode were calculated using cyclic voltammetry. As deposition times of PPy are 10, 20, 25 and 30 min, specific capacitances of composite electrodes reach 657, 553, 471 and 396 F g-1, respectively. Cyclic behaviors of RuO2/PPy composite electrodes are stable.

  18. Elastic properties of the transition metal oxides Ca2-xSrxRuO4

    NASA Astrophysics Data System (ADS)

    Luan, Yanbing; Keppens, Veerle; Jin, Rongying; Mandrus, David

    2008-03-01

    Layered perovskite ruthenates have attracted considerable interest since the discovery of superconductivity in Sr2RuO4, the only copper-free superconductor isostructural to the cuprates. Among the doped varieties of Sr2RuO4, the Ca2-xSrxRuO4 series is heavily studied, as it connects the Mott insulator Ca2RuO4 with the superconductor Sr2RuO4 and exhibits a variety of physical properties. The current work focuses on the elastic properties of Ca2-xSrxRuO4. Resonant Ultrasound Spectroscopy (RUS) has been used to study the elastic response of the samples, and results are presented for single crystals with x = 0.2, 0.3, 0.4, 0.5, 1, 1.5, 1.9 and 2.0. The temperature-dependence of the elastic behavior is found to be quite unusual and reflects the rich phase diagram of these materials. Almost all measured Ca2-xSrxRuO4 samples show a soft phonon mode at low temperatures, which is believed to be associated with the dynamics of the RuO6 octahedra.

  19. The formation mechanism of bimetallic PtRu alloy nanoparticles in solvothermal synthesis.

    PubMed

    Mi, Jian-Li; Nørby, Peter; Bremholm, Martin; Becker, Jacob; Iversen, Bo B

    2015-10-21

    An understanding of the nucleation and growth mechanism of bimetallic nanoparticles in solvothermal synthesis is important for further development of nanoparticles with tailored nanostructures and properties. Here the formation of PtRu alloy nanoparticles in a solvothermal synthesis using metal acetylacetonate salts as precursors and ethanol as both the solvent and reducing agent has been studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXRD). Unlike the classical mechanism for the synthesis of monodisperse sols, the nucleation and growth processes of bimetallic PtRu nanoparticles occur simultaneously under solvothermal conditions. In the literature co-reduction of Pt and Ru is often assumed to be required to form PtRu bimetallic nanocrystals, but it is shown that monometallic Pt nanocrystals nucleate first and rapidly grow to an average size of 5 nm. Subsequently, the PtRu bimetallic alloy is formed in the second nucleation stage through a surface nucleation mechanism related to the reduction of Ru. The calculated average crystallite size of the resulting PtRu nanocrystals is smaller than that of the primary Pt nanocrystals due to the large disorder in the PtRu alloyed structure. PMID:26382321

  20. Enhanced Magnetism in Epitaxial SrRuO3 Thin Films

    SciTech Connect

    Grutter, A.J.; Wong, F.; Arenholz, E.; Liberati, M.; Vailionis, A.; Suzuki, Y.

    2009-11-20

    We have observed enhanced magnetization in epitaxial SrRuO{sub 3} thin films compared to previously reported bulk and thin film values of 1.1-1.6 {mu}{sub B}/Ru ion. The degree of enhancement is strongly dependent on the lattice distortions imposed on the SrRuO{sub 3} films by SrTiO{sub 3}, (LaAlO{sub 3}){sub 0.3}(SrTaO{sub 3}){sub 0.7} (LSAT), and LaAlO{sub 3} substrates. A larger enhancement of magnetization for coherently strained SrRuO{sub 3} films on SrTiO{sub 3} and LSAT compared to fully relaxed films on LaAlO{sub 3} confirms the importance of the strain state in determining the magnetic ground state of the Ru ion. In particular, SrRuO{sub 3} films on (111) SrTiO{sub 3} exhibit exhanced moments as high as 3.8 {mu}{sub B}/Ru ion, thus suggesting the stabilization of a high-spin Ru{sup 4+} state.

  1. Magnetic properties and spin polarization of Ru doped half metallic CrO2

    NASA Astrophysics Data System (ADS)

    West, Kevin G.; Osofsky, Michael; Mazin, I. I.; Dao, Nam N. H.; Wolf, Stuart A.; Lu, Jiwei

    2015-07-01

    Chromium dioxide (CrO2) 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 CrO2 were synthesized by a PVD technique. The as-deposited RuxCr1-xO2 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 CrO2. The PVD processes of Ru doped CrO2 could lead to the practical applications of the high spin polarization of CrO2 in spintronic devices.

  2. Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis.

    PubMed

    McKinty, Adam M; Stephan, Douglas W

    2016-03-01

    The series of tridentate complexes of Ru-alkylidenes (L)Ru(CHPh)(SCH2CH2)2E (E = O, L = SIMes 1, PCy3 2, E = S, L = SIMes 3, PCy3 4; E = PPh 7, L = PCy3), (L)Ru(CHPh)(SC6H4)2S (L = SIMes 5, PCy3 6), (L)Ru(CHPh) (OCH2CH2)2O (L = SIMes 8, PCy3 9) were prepared and shown to react with one equivalent of BCl3 to give the complexes (L)Ru(CHPh)Cl[E(CH2CH2S)2BCl2] (E = O, L = SIMes 10, PCy3 11, E = S, L = SIMes 12a/b, PCy3 13, E = PPh, L = PCy3 16) and (L)Ru(CHPh)(SC6H4)2O (L = SIMes 14, PCy3 15). In the case of 1 and 2 reaction with two equivalents of BCl3 affording the corresponding cation via chloride abstraction. These cations coordinate MeCN to give the six coordinate Ru cation salts [(L)Ru(CHPh)- (NCMe)(O(CH2CH2S)2BCl2)][BCl4] L = SIMes 17, PCy3 18). The generated five coordinate cations derived from 2-9 via addition of two equivalents of BCl3 were evaluated in standard preliminary tests for olefin metathesis catalysis. PMID:26822161

  3. Synthesis and characterization of bimetallic metal-organic framework Cu-Ru-BTC with HKUST-1 structure.

    PubMed

    Gotthardt, Meike A; Schoch, Roland; Wolf, Silke; Bauer, Matthias; Kleist, Wolfgang

    2015-02-01

    The bimetallic metal-organic framework Cu-Ru-BTC with the stoichiometric formula Cu2.75Ru0.25(BTC)2·xH2O, which is isoreticular to HKUST-1, was successfully prepared in a direct synthesis using mild reaction conditions. The partial substitution of Cu(2+) by Ru(3+) centers in the paddlewheel structure and the absence of other Ru-containing phases was proven using X-ray absorption spectroscopy. PMID:25518915

  4. 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.

  5. Water-soluble Ru(II)- and Ru(III)-halide-PTA complexes (PTA=1,3,5-triaza-7-phosphaadamantane): Chemical and biological properties.

    PubMed

    Battistin, F; Scaletti, F; Balducci, G; Pillozzi, S; Arcangeli, A; Messori, L; Alessio, E

    2016-07-01

    Four structurally related Ru(II)-halide-PTA complexes, of general formula trans- or cis-[Ru(PTA)4X2] (PTA=1,3,5-triaza-7-phosphaadamantane, X=Cl (1, 2), Br (3, 4), were prepared and characterized. Whereas compounds 1 and 2 are known, the corresponding bromo derivatives 3 and 4 are new. The Ru(III)-PTA compound trans-[RuCl4(PTAH)2]Cl (5, PTAH=PTA protonated at one N atom), structurally similar to the well-known Ru(III) anticancer drug candidates (Na)trans-[RuCl4(ind)2] (NKP-1339, ind=indazole) and (Him)trans-[RuCl4(dmso-S)(im)] (NAMI-A, im=imidazole), was also prepared and similarly investigated. Notably, the presence of PTA confers to all complexes an appreciable solubility in aqueous solutions at physiological pH. The chemical behavior of compounds 1-5 in water and in physiological buffer, their interactions with two model proteins - cytochrome c and ribonuclease A - as well as with a single strand oligonucleotide (5'-CGCGCG-3'), and their in vitro cytotoxicity against a human colon cancer cell line (HCT-116) and a myeloid leukemia (FLG 29.1) were investigated. Upon dissolution in the buffer, sequential halide replacement by water molecules was observed for complexes 1-4, with relatively slow kinetics, whereas the Ru(III) complex 5 is more inert. All tested compounds manifested moderate antiproliferative properties, the cis compounds 2 and 4 being slightly more active than the trans ones (1 and 3). Mass spectrometry experiments evidenced that all complexes exhibit a far higher reactivity towards the reference oligonucleotide than towards model proteins. The chemical and biological profiles of compounds 1-5 are compared to those of established ruthenium drug candidates in clinical development. PMID:26920229

  6. 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.

  7. Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes.

    PubMed

    Paranthaman, Selvarengan; Moon, Jiwon; Kim, Joonghan; Kim, Dong Eon; Kim, Tae Kyu

    2016-04-01

    Herein a performance assessment of density functionals used for calculating the structural and energetic parameters of bi- and trimetallic Ru-containing organometallic complexes has been performed. The performance of four popular relativistic effective core potentials (RECPs) has also been assessed. On the basis of the calculated results, the MN12-SX (range-separated hybrid functional) demonstrates good performance for calculating the molecular structures, while MN12-L (local functional) performs well for calculating the energetics, including that of the Ru-Ru bond breaking process. The choice of appropriate density functional is a crucial factor for calculating the energetics. The LANL08 demonstrates the lowest performance of the RECPs for calculating the molecular structures, especially the Ru-Ru bond length. PMID:26986051

  8. Irregular stacking sequence in the initial growth of ultrathin Rh films on Ru(0001)

    SciTech Connect

    He Yunbin; Over, Herbert; Seitsonen, Ari P.

    2005-08-15

    Rhodium grows on single-crystal Ru(0001) surface initially layer by layer, adapting the in-plane lattice parameters of Ru(0001) (pseudomorphic growth). Using quantitative low-energy electron diffraction (LEED) and density functional theory (DFT) calculations, we determined the atomic structures of 1-monolayer (ML), 2-ML, and 3-ML Rh films on Ru(0001). The 1-ML Rh film continues the hexagonal-close-packed (hcp) stacking sequence of Ru(0001) (...ABAb), while the 2-ML Rh film already adopts its face-centered-cubic (fcc) stacking sequence (...ABAbc) if the topmost Ru layer is included into the stacking consideration. Three MLs of Rh form a fcc stacking sequence of ...ABAbac, requiring a massive restructuring of the second Rh layer when adding one ML of Rh onto the 2-ML Rh film.

  9. High-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles for phenol hydrogenation

    NASA Astrophysics Data System (ADS)

    Huang, Chao; Yang, Xu; Yang, Hui; Huang, Peiyan; Song, Huiyu; Liao, Shijun

    2014-10-01

    A high-performance PdRu bimetallic catalyst supported on mesoporous silica nanoparticles (MSN), PdRu/MSN, was prepared by a facile impregnation-hydrogen reduction method. It was found that PdRu/MSN showed 5 times higher activity than that of Pd/MSN towards the liquid-phase hydrogenation of phenol. The catalysts were characterized comprehensively by multiple techniques, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature program reduction (TPR). It was revealed that adding Ru could effectively improve the Pd dispersion and promote the electronic interaction between the Pd and Ru, both of which contribute to enhancing the catalytic activity.

  10. 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}.

  11. Enhanced thermoelectric power and electronic correlations in RuSe2

    NASA Astrophysics Data System (ADS)

    Wang, Kefeng; Wang, Aifeng; Tomic, A.; Wang, Limin; Abeykoon, A. M. Milinda; Dooryhee, E.; Billinge, S. J. L.; Petrovic, C.

    2015-04-01

    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.

  12. The nature of Ru-NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes--a computational study.

    PubMed

    Caramori, Giovanni Finoto; Kunitz, André Guilherme; Andriani, Karla Furtado; Doro, Fábio Gorzoni; Frenking, Gernot; Tfouni, Elia

    2012-06-28

    Ruthenium complexes including nitrosyl or nitrite complexes are particularly interesting because they can not only scavenge but also release nitric oxide in a controlled manner, regulating the NO-level in vivo. The judicious choice of ligands attached to the [RuNO] core has been shown to be a suitable strategy to modulate NO reactivity in these complexes. In order to understand the influence of different equatorial ligands on the electronic structure of the Ru-NO chemical bonding, and thus on the reactivity of the coordinated NO, we propose an investigation of the nature of the Ru-NO chemical bond by means of energy decomposition analysis (EDA), considering tetraamine and tetraazamacrocycles as equatorial ligands, prior to and after the reduction of the {RuNO}(6) moiety by one electron. This investigation provides a deep insight into the Ru-NO bonding situation, which is fundamental in designing new ruthenium nitrosyl complexes with potential biological applications. PMID:22580477

  13. Investigation of the Galvanic Effect between RuN Barriers and Cu Seed Layers

    NASA Astrophysics Data System (ADS)

    Wu, Chia-Yang; Lee, Wen-Hsi; Chang, Shih-Chieh; Wang, Ying-Lang

    2011-12-01

    In this study, we investigated the galvanic effect between the Cu metals and ruthenium nitride (RuNx) films that were deposited at various nitrogen (N2) gas flow rates in chemical mechanical polishing slurries. It was found that the galvanic corrosion of the RuNx films was inhibited with increasing N2 gas flow ratio, whereas the galvanic corrosion of the Cu seed layers was enhanced. Electrochemical impedance spectroscopy showed that the galvanic corrosion resistance of RuNx increased and that of the ruthenium oxide layer decreased as N2 flow ratio increased. This was because the increase in the N content in the RuNx films inhibited the corrosion and oxidation of the Ru metals.

  14. 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.

  15. 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. PMID:21328554

  16. Photochemical release of nitric oxide from a regenerable, sol-gel encapsulated Ru-salen-nitrosyl complex.

    PubMed

    Bordini, Jeane; Ford, Peter C; Tfouni, Elia

    2005-09-01

    Light activation leads to release of NO from a silicate sol-gel material SG-RuNO prepared from the ruthenium complex, [Ru(salen)(OH2)(NO)]+ (salen = N,N'-bis-(salicylidene)ethyl-enediaminato); after photochemical NO photolabilization, SG-RuNO can be regenerated from the spent material via the subsequent reaction with aqueous nitrite. PMID:16100592

  17. The mouse ruby-eye 2(d) (ru2(d) /Hps5(ru2-d) ) allele inhibits eumelanin but not pheomelanin synthesis.

    PubMed

    Hirobe, Tomohisa; Ito, Shosuke; Wakamatsu, Kazumasa

    2013-09-01

    The novel mutation named ru2(d) /Hps5(ru2-d) , characterized by light-colored coats and ruby-eyes, prohibits differentiation of melanocytes by inhibiting tyrosinase (Tyr) activity, expression of Tyr, Tyr-related protein 1 (Tyrp1), Tyrp2, and Kit. However, it is not known whether the ru2(d) allele affects pheomelanin synthesis in recessive yellow (e/Mc1r(e) ) or in pheomelanic stage in agouti (A) mice. In this study, effects of the ru2(d) allele on pheomelanin synthesis were investigated by chemical analysis of melanin present in dorsal hairs of 5-week-old mice from F2 generation between C57BL/10JHir (B10)-co-isogenic ruby-eye 2(d) and B10-congenic recessive yellow or agouti. Eumelanin content was decreased in ruby-eye 2(d) and ruby-eye 2(d) agouti mice, whereas pheomelanin content in ruby-eye 2(d) recessive yellow and ruby-eye 2(d) agouti mice did not differ from the corresponding Ru2(d) /- mice, suggesting that the ru2(d) allele inhibits eumelanin but not pheomelanin synthesis. PMID:23672590

  18. Roussel-Uclaf to transfer RU 486 rights.

    PubMed

    1997-04-18

    On April 8, the German pharmaceutical firm Hoechst, under pressure from anti-abortion groups that were boycotting its new allergy medication, Allegra, announced the transfer of the patent rights for the abortifacient mifepristone (RU-486), from Roussel-Uclaf, its subsidiary, to Dr. Edouard Sakiz, a former executive who had been involved in the development of the drug. Dr. Sakiz has established a new company, Exelgyn, to market the drug, which, due to strict company guidelines, is currently available only in France, Sweden, and the United Kingdom. Residency requirements prevent women from traveling to these countries for treatment. Other countries desiring access to RU-486 must meet standards established by Dr. Sakiz: the government must make a formal request and provide a secure means of distribution and good follow-up care. A European manufacturer or distributor has not yet been found. In the United States, the Population Council, a nonprofit organization, has been licensed to manufacture and distribute the drug; it should be available to the general public by the end of this year. Anti-abortion groups continue to boycott all Hoechst products. The Allegra boycott was launched with an April 2 press conference; the groups, which include the National Right to Life Committee, bought full-page ads in "USA Today" and "The Washington Post." PMID:12292550

  19. 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.

  20. 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

  1. Ruthenium (Ru) peeling and predicting robustness of the capping layer using finite element method (FEM) modeling

    NASA Astrophysics Data System (ADS)

    Jang, Il-Yong; John, Arun; Goodwin, Frank; Lee, Su-Young; Kim, Byung-Gook; Kim, Seong-Sue; Jeon, Chan-Uk; Kim, Jae Hyung; Jang, Yong Hoon

    2014-07-01

    Ruthenium (Ru) film used as capping layer in extreme ultraviolet (EUV) mask peeled off after annealing and in-situ UV (IUV) cleaning. We investigated Ru peeling and found out that the mechanical stress caused by the formation of Si oxide due to the penetration of oxygen atoms from ambient or cleaning media to top-Si of ML is the root cause for the problem. To support our experimental results, we developed a numerical model of finite element method (FEM) using commercial software (ABAQUS™) to calculate the stress and displacement forced on the capping layer. By using this model, we could observe that the displacement agrees well with the actual results measured from the transmission electron microscopy (TEM) image. Using the ion beam deposition (IBD) tool at SEMATECH, we developed four new types of alternative capping materials (RuA, RuB, B4C, B4C-buffered Ru). The durability of each new alternative capping layer observed by experiment was better than that of conventional Ru. The stress and displacement calculated from each new alternative capping layer, using modeling, also agreed well with the experimental results. A new EUV mask structure is proposed, inserting a layer of B4C (B4C-buffered Ru) at the interface between the capping layer (Ru) and the top-Si layer. The modeling results showed that the maximum displacement and bending stress observed from the B4C-buffered Ru are significantly lower than that of single capping layer cases. The durability investigated from the experiment also showed that the B4C-buffered structure is at least 3X stronger than that of conventional Ru.

  2. Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

    PubMed

    Zhang, Jing; Sun, Bo; Xiong, Xinmei; Gao, Naiyun; Song, Weihua; Du, Erdeng; Guan, Xiaohong; Zhou, Gongming

    2014-10-15

    TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 μM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 μM) underestimated those obtained at EPs concentration of μg L(-1) level (0.050 μM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at μg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties. PMID:25016299

  3. Magnetic structure of the quasi-one-dimensional La3OsO7 as determined by neutron powder diffraction

    DOE PAGESBeta

    Morrow, Ryan; Susner, Michael A.; Sumption, Michael D.; Woodward, Patrick M.

    2015-10-05

    Insulating 5d3 La3OsO7 and the isostructural hole-doped analog La2.8Ca0.2OsO7 that feature pseudo-one-dimensional zigzag chains of corner-sharing OsO6 octahedra were synthesized and their magnetic and electrical transport properties characterized. Both of these compounds are insulating antiferromagnets. Moreover, for long range magnetic order between the antiferromagnetic chains we determined with a propagation vector k = 1/2,1/2,1 and TN = 45 and 33 K the parent and doped materials. An Os5+ moment of 1.7(1)μB for La3OsO7 and 1.2(2)μB for La2.8Ca0.2OsO7 is refined. The long range magnetic structure is compared to the isostructural compounds La3RuO7 and La3MoO7, both of which adopt different magnetic structures.

  4. 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.

  5. 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

  6. Distribution of 103Ru-chloride in tumor-bearing animals and the mechanism for accumulation in tumor and liver.

    PubMed

    Ando, A; Ando, I; Hiraki, T; Hisada, K

    1988-01-01

    Tumor uptake rates of 103Ru-chloride were smaller than those for 67Ga-citrate. In three tumors and liver, 103Ru in the mitochondrial fraction containing lysosome increased with time after the administration of 103Ru-chloride. The concentration of 103Ru was more dominant in connective tissue (especially inflammatory tissue) than in viable tumor tissue or in necrotic tissue. Quite large amounts of 103Ru in the tumor and liver were bound to the acid mucopolysaccharide whose molecular masses exceeded 40,000. Behavior of this nuclide was essentially similar to that of 67Ga. PMID:3366616

  7. High antiferromagnetic transition temperature of a honeycomb compound SrRu2O6

    DOE PAGESBeta

    Tian, Wei; Svoboda, Chris; Ochi, M.; Matsuda, M.; Cao, Huibo; Cheng, J. -G.; Sales, B. C.; Mandrus, D.; Arita, R.; Trivedi, Nandini; et al

    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

  8. Photocatalyst of lamellar aggregates of RuOx-loaded perovskite nanosheets for overall water splitting.

    PubMed

    Ebina, Yasuo; Sakai, Nobuyuki; Sasaki, Takayoshi

    2005-09-15

    Overall photocatalytic splitting of water was achieved using a restacked aggregate of exfoliated nanosheets of Ca(2)Nb(3)O(10), which was synthesized by flocculating a colloidal suspension of the nanosheets with alkali-metal ions and a trace amount of ruthenium red, a trinuclear complex of ([(NH(3))(5)Ru-O-Ru(NH(3))(4)-O-Ru(NH(3))(5)]Cl(6). The as-restacked material showed the evolution of H(2) gas from water immediately after UV irradiation, while O(2) evolution was observed only after some induction time, which may be understood by the possible oxidation of ruthenium red to RuO(x) in the initial stage. The restacked aggregate, which was heated at 773 K to convert the ruthenium complex to the oxide, underwent the stoichiometric splitting of water upon initiation of UV illumination, verifying the hypothesis. Total decomposition of water could not be attained with the bulk layered host of KCa(2)Nb(3)O(10) as well as its RuO(x)-loaded forms obtained via a conventional impregnation procedure. This clearly demonstrates the effectiveness of the present exfoliation-restacking route for loading RuO(x) to improve and enhance the photocatalytic activities of layered semiconducting materials. A homogeneous distribution of RuO(x)was suggested by XPS depth-profile analysis on the materials obtained through the exfoliation-restacking process. PMID:16853196

  9. 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

  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. PMID:25809196

  11. 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.

  12. Interfacial effects on magnetic interlayer coupling between perpendicular Co/Ni multilayers across Ru spacer

    NASA Astrophysics Data System (ADS)

    Chen, Shaohai; Xiao, Yili; Xie, W. H.; Zhang, Zongzhi; Ma, B.; Jin, Q. Y.

    2014-12-01

    The interlayer exchange coupling properties in synthetic antiferromagnetic (AF) structures based on Co/Ni perpendicular multilayers were investigated by varying the Ru spacer thickness (tRu) and the ferromagnetic (FM) layer material at the FM/Ru interfaces. Samples of two Co layers adjacent to Ru own much stronger AF coupling field (HAF) and show two HAF peaks located at tRu = 0.47 and 1.08 nm. If the interfacial Co layers are substituted by Ni, the HAF at the 1st peak decreases much more considerably, becomes lower than the 2nd one and even disappears due to strong pinhole-induced FM coupling. Such pinhole effect makes HAF of tRu < 0.85 nm remains unchanged or even decrease with decreasing temperatures. By tuning the interfacial Co layer thickness, pinhole effect has been suppressed as a result of greatly enhanced HAF, leading to a normal temperature dependence of Ruderman-Kittel-Kasuya-Yosida-type HAF even at thin tRu cases, i.e., increase in HAF with temperature decreasing.

  13. Immobilization of the [RuII(edta)NO+] Ion on the surface of functionalized silica gel.

    PubMed

    Zanichelli, Patrícia G; Sernaglia, Rosana L; Franco, Douglas W

    2006-01-01

    The reaction of NO and the immobilized dimer complex (edta)(2)Ru(2)(III(1/2),III(1/2)) on silica gel chemically modified with [3-(2-aminoethyl)aminopropyl]trimethoxysilane (AEATS) produces the corresponding immobilized nitrosyl complex AEATS/Ru(II)NO(+). This compound, a monomer, was obtained by reducing the immobilized ruthenium dimer either electrochemically or with Eu(II) and reacting this species with NO(2)(-) ions. The properties of [Ru(edta)NO](-) in solution and anchored (AEATS/Ru(II)NO(+)) on silica were compared using electrochemical (DPV, CV) and spectroscopic (IR, UV-vis, and ESR) techniques. The results indicate that immobilization does not alter the reactivity of the ruthenium complex and confirm that [Ru(edta)(H(2)O)](2)(-) may be used, either in solution or immobilized, as a catalyst for the conversion of NO(2)(-) to NO(+). Both the anchored nitrosyl complex AEATS/Ru(II)NO(+) and the [Ru(edta)NO](-) species in solution, upon one-electron reduction, liberate NO at comparable rates. PMID:16378421

  14. High antiferromagnetic transition temperature of the honeycomb compound SrRu2O6

    NASA Astrophysics Data System (ADS)

    Tian, W.; Svoboda, C.; Ochi, M.; Matsuda, M.; Cao, H. B.; Cheng, J.-G.; Sales, B. C.; Mandrus, D. G.; Arita, R.; Trivedi, N.; Yan, J.-Q.

    2015-09-01

    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 P 3 ¯1 m ) 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) to obtain the electronic structure and effective intra- and interorbital interaction parameters. The projected density of states shows strong hybridization between Ru 4 d and O 2 p . By downfolding to the target t2 g bands we extract the effective magnetic Hamiltonian and perform Monte Carlo simulations to determine the transition temperature as a function of inter- and intraplane couplings. We find a weak interplane coupling, 3% of the strong intraplane coupling, permits three-dimensional magnetic order at the observed TN.

  15. Unconventional Magnetic Domains in Triple-layered Sr4Ru3O10

    NASA Astrophysics Data System (ADS)

    Du, Kai; Lim, Seong Joon; Kim, Jae Wook; Cao, Gang; Cheong, Sang Wook; Rutgers Center for Emergent Material Team; Center for Advanced Materials, University of Kentucky Collaboration

    A plethora of fascinating phenomena including p-wave superconductivity in Sr2RuO4 (n=1) and hybrid improper ferroelectricity in Ca3Ru2O7 (n=2) have been observed in Ruddlesden-Popper ruthenates (Ca, Sr)n+1RunO3n+1. The triple-layered Sr4Ru3O10 (n=3) is believed to have an intriguing complex magnetic state, compared with its neighboring bi-layered meta-magnetic Sr3Ru2O7(n=2) and ferromagnetic SrRuO3 (n= ∞). The phase competition nature associated with this complexity is considered to be responsible for its novel properties such as coupled anisotropic magnetism and transport, low frequency quantum oscillations and sharp magneto-resistivity steps, which are still not well understood yet. To better understand its microscopic mechanism, we studied the magnetic domain structure on Sr4Ru3O10 using low-temperature magnetic force microscopy. The observed unique domain structures in Sr4Ru3O10 may shed lights on its microscopic phase competition nature and lead to a deeper understanding on its relations with other layered ruthenates. This work is funded by the Gordon and Betty Moore Foundation's EPiQS Initiative through Grant GBMF4413 to the Rutgers Center for Emergent Materials.

  16. Formation of a Cu@RhRu core-shell concave nanooctahedron via Ru-assisted extraction of Rh from the Cu matrix and its excellent electrocatalytic activity toward the oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Park, Suhyun; Yoon, Donghwan; Bang, Sulgi; Kim, Jongchan; Baik, Hionsuck; Yang, Haesik; Lee, Kwangyeol

    2015-09-01

    A facile one step route has been developed for the synthesis of trimetallic Cu@RhRu core-shell concave nanooctahedra by co-decomposition of Ru, Rh and Cu precursors. A mechanistic study reveals that nanoparticles with a CuRh alloy core and a Ru shell are initially formed and a subsequent migration of Rh to the shell results in the Cu@RhRu core-shell concave nanooctahedron. The shell exhibits atomically mixed Ru and Rh phases with an fcc atomic structure, although the hcp atomic structure is commonly found for the bulk Ru. We also report an unusually high catalytic activity of the Cu@RhRu octahedral nanocrystals toward the oxygen evolution reaction in alkaline solution.A facile one step route has been developed for the synthesis of trimetallic Cu@RhRu core-shell concave nanooctahedra by co-decomposition of Ru, Rh and Cu precursors. A mechanistic study reveals that nanoparticles with a CuRh alloy core and a Ru shell are initially formed and a subsequent migration of Rh to the shell results in the Cu@RhRu core-shell concave nanooctahedron. The shell exhibits atomically mixed Ru and Rh phases with an fcc atomic structure, although the hcp atomic structure is commonly found for the bulk Ru. We also report an unusually high catalytic activity of the Cu@RhRu octahedral nanocrystals toward the oxygen evolution reaction in alkaline solution. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03942h

  17. Competition Between Antiferromagnetism and Ferromagnetism in Sr2RuO4 Probed by Mn and Co Doping

    PubMed Central

    Ortmann, J. E.; Liu, J. Y.; Hu, J.; Zhu, M.; Peng, J.; Matsuda, M.; Ke, X.; Mao, Z. Q.

    2013-01-01

    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. PMID:24126684

  18. 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.

  19. Pt ∧Ru/C catalysts synthesized by a two-stage polyol reduction process for methanol oxidation reaction

    NASA Astrophysics Data System (ADS)

    Li, Yuexia; Zheng, Liping; Liao, Shijun; Zeng, Jianhuang

    Highly dispersed Ru/C catalysts are prepared using high viscosity glycerol as a reducing agent and are treated in H 2 atmosphere to ensure stability. A Pt ∧Ru/C catalyst is prepared by an ethylene glycol process based on the pre-formed Ru/C. The catalyst is tested for methanol oxidation reaction at room temperature and is compared with the activity of the as-prepared PtRu/C alloyed catalyst (prepared by co-reduction of Pt and Ru precursors) and commercial PtRu/C from E-TEK. The catalysts are extensively characterized by Transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Electrochemical measurements by cyclic voltammetry (CV) showed consistently high catalytic activities and improved CO resistance for the Pt ∧Ru/C catalyst.

  20. {RuNO}(6)vs. co-ligand oxidation: two non-innocent groups in one ruthenium nitrosyl complex.

    PubMed

    McQuarters, Ashley B; Lehnert, Nicolai

    2014-10-01

    Recently, a new {RuNO}(6) complex, [Ru(L)(PPh3)(NO)(Cl)](2+) (where L = 1-phenyl-1-(pyridin-2-yl)-2-(pyridin-2-ylmethylene)hydrazine), was reported which exhibits a one-electron quasireversible oxidation. The oxidized product, [Ru(L)(PPh3)(NO)(Cl)](3+), was isolated and proposed to be a highly unusual {RuNO}(5) complex. In this paper, we investigate the electronic structure of both of these ruthenium complexes by DFT calculations and find that the oxidized species is best described as a {RuNO}(6) complex with a co-ligand radical. [Ru(L)(PPh3)(NO)(Cl)](2+) is therefore oxidized to [Ru(L(+˙))(PPh3)(NO)(Cl)](3+), i.e. this is an interesting example of a complex with two non-innocent ligands simultaneously bound to a ruthenium center. PMID:25118656