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Sample records for natural ruthenium metal

  1. Method of dissolving metal ruthenium

    International Nuclear Information System (INIS)

    Tsuno, Masao; Soda, Yasuhiko; Kuroda, Sadaomi; Koga, Tadaaki.

    1988-01-01

    Purpose: To dissolve and clean metal ruthenium deposited to the inner surface of a dissolving vessel for spent fuel rods. Method: Metal ruthenium is dissolved in a solution of an alkali metal hydroxide to which potassium permanganate is added. As the alkali metal hydroxide used herein there can be mentioned potassium hydroxide, sodium hydroxide and lithium hydroxide can be mentioned, which is used as an aqueous solution from 5 to 20 % concentration in view of the solubility of metal ruthenium and economical merit. Further, potassium permanganate is used by adding to the solution of alkali metal hydroxide at a concentration of 1 to 5 %. (Yoshihara, H.)

  2. Fabrication of ruthenium metal nanosheets via topotactic metallization of exfoliated ruthenate nanosheets.

    Science.gov (United States)

    Fukuda, Katsutoshi; Sato, Jun; Saida, Takahiro; Sugimoto, Wataru; Ebina, Yasuo; Shibata, Tatsuo; Osada, Minoru; Sasaki, Takayoshi

    2013-03-04

    The metallization behavior of molecularly thin RuO2 nanosheets obtained from complete delamination of layered ruthenates was studied. Interestingly, the RuO2 nanosheets in a monolayer state topotactically transformed into a single layer of Ru atoms, i.e., ruthenium metal nanosheets, which can be regarded as a new family of nanosized metals.

  3. Radiochemistry of ruthenium

    Energy Technology Data Exchange (ETDEWEB)

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

    1984-06-01

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

  4. Radiochemistry of ruthenium

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  5. IR-doped ruthenium oxide catalyst for oxygen evolution

    Science.gov (United States)

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

    2012-01-01

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

  6. Synthesis of ruthenium phosphides

    International Nuclear Information System (INIS)

    Chernogorenko, V.B.; Lynchak, K.A.; Kulik, L.Ya.; Shkaravskij, Yu.F.; Klochkov, L.A.

    1977-01-01

    A method of ampoule synthesis of ruthenium phosphides, Ru 2 P, RuP, and RuP 2 , with stepwise heating of stoichimetric charges in a single-zone furnace is developed. A method for synthesizing ruthenium diphosphide by phosphidization of a ruthenium powder with phosphine at 1150 deg C is worked out. The optimum conditions of its manufacture are found by planning an extremal experiment. Interaction of PH 3 with ruthenium proceeds by the diffusion mechanism and obeys the parabolic law. An extraction-photometric method for determining phosphorus in phosphides is elaborated. Ruthenium phosphides are extremely corrosion-resistant in acids and alkalis. Ru 2 P and RuP exhibit metallic conductivity

  7. Electrochemical behavior of ruthenium (III), rhodium (III) and palladium (II) in 1-butyl-3-methylimidazolium chloride ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Jayakumar, M.; Venkatesan, K.A. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)], E-mail: tgs@igcar.gov.in; Vasudeva Rao, P.R. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

    2009-11-01

    Electrochemical behavior of ruthenium (III), rhodium (III) and palladium (II) in 1-butyl-3-methylimidazolium chloride (bmimCl) and their ternary and binary solutions in bmimCl was studied at various working electrodes at 373 K by cyclic voltammetry and chronoamperometry. Ruthenium (III) chloride forms a stable solution with bmimCl and the cyclic voltammogram of ruthenium (III) in bmimCl recorded at glassy carbon electrode consisted of several redox waves due to the complex nature of ruthenium to exist in several oxidation states. Electrolysis of ruthenium (III) chloride in bmimCl at the cathodic limit of bmimCl (-1.8 V (vs. Pd)) did not result in ruthenium metal deposition. However, it was deposited from bmimPF{sub 6} and bmimNTf{sub 2} room temperature ionic liquids at -0.8 V (vs. Pd). The electrochemical behavior of ruthenium (III) in bmimCl in the presence of palladium (II) and rhodium (III) was studied by cyclic voltammetry. The presence of palladium (II) in bmimCl favors underpotential deposition of ruthenium metal. The nuclear loop at -0.5 V (vs. Pd) was observed in all solutions when palladium (II) co-existed with other two metal ions. Nucleation and growth of the metal on glassy carbon working electrode was investigated by chronoamperometry. The growth and decay of chronocurrents has been found to follow the instantaneous nucleation model with three-dimensional growth of nuclei.

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

    Science.gov (United States)

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

    2007-09-15

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

  9. Electro-volatilization of ruthenium in nitric medium: influences of ruthenium species nature and models solutions composition

    International Nuclear Information System (INIS)

    Mousset, F.

    2004-12-01

    Ruthenium is one of the fission products in the reprocessing of irradiated fuels that requires a specific processing management. Its elimination, upstream by the PUREX process, has been considered. A process, called electro-volatilization, which take advantage of the RuO 4 volatility, has been optimised in the present study. It consists in a continuous electrolysis of ruthenium solutions in order to generate RuO 4 species that is volatilized and easily trapped. This process goes to satisfying ruthenium elimination yields with RuNO(NO 3 ) 3 (H 2 O) 2 synthetic solutions but not with fuel dissolution solutions. Consequently, this work consisted in the speciation studies of dissolved ruthenium species were carried out by simulating fuel solutions produced by hot acid attack of several ruthenium compounds (Ru(0), RuO 2 ,xH 2 O, polymetallic alloy). In parallel with dissolution kinetic studies, the determination of dissolved species was performed using voltammetry, spectrometry and spectro-electrochemistry. The results showed the co-existence of Ru(IV) and RuNO(NO 2 ) 2 (H 2 O) 3 . Although these species are different from synthetic RuNO(NO 3 ) 3 (H 2 O) 2 , their electro-oxidation behaviour are similar. The electro-volatilization tests of these dissolution solutions yielded to comparable results as the synthetic RuNO(NO 3 ) 3 (H 2 O) 2 solutions. Then, complexity increase of models solutions was performed by in-situ generation of nitrous acid during ruthenium dissolution. Nitrous acid showed a catalytic effect on ruthenium dissolution. Its presence goes to quasi exclusively RuNO(NO 2 ) 2 (H 2 O) 3 species. It is also responsible of the strong n-bond formation between Ru 2+ and NO + . In addition, it has been shown that its reducing action on RuO 4 hinders the electro-volatilization process. Mn 2+ and Ce 3+ cations also reveal, but to a lesser extent, an electro-eater behaviour as well as Pu 4+ and Cr 3+ according to the thermodynamics data. These results allow one to

  10. A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

    International Nuclear Information System (INIS)

    Wang, Qingfang; Wang, Zhiqiang; Yin, Xiaoqian; Zhou, Linxi; Zhang, Minghui

    2016-01-01

    Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru_2P were synthesized using triphenylphosphine as phosphorus sources. • Ru_2P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO_2 prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H_2-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru_2P can be prepared by this method via varying the molar ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N_2 adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru_2P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.

  11. A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qingfang [Tianjin Key Laboratory of Water Environment and Resources, Tianjin Normal University, Tianjin 300387 (China); Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); Wang, Zhiqiang [Tianjin Key Laboratory of Water Environment and Resources, Tianjin Normal University, Tianjin 300387 (China); Yin, Xiaoqian; Zhou, Linxi [Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); Zhang, Minghui, E-mail: zhangmh@nankai.edu.cn [Key Laboratory of Advanced Energy Materials Chemistry (MOE), Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai University, Tianjin 300071 (China); College of Chemistry and Environmental Science, Kashgar University, Kashgar 844006 (China)

    2016-02-15

    Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru{sub 2}P were synthesized using triphenylphosphine as phosphorus sources. • Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO{sub 2} prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H{sub 2}-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru{sub 2}P can be prepared by this method via varying the molar ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N{sub 2} adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.

  12. Separation of platinum metals by theirs extraction as sulfides

    International Nuclear Information System (INIS)

    Pilipenko, A.T.; Ryabushko, O.P.; Ty Van Mak

    1978-01-01

    Separation of platinum metals by means of their sediment in the form of sulfides with subsequent extraction is studied. The optimum conditions of metal sulfide extraction are determined, the metal output dependence from acidness and aqueous phase composition and also the organic solvent nature are investigated. Ruthenium concentration was determined photometrically. Ruthenium sulfide is extracted by butyl spirit from 1-4 normal hydrochloric acid. The maximum extraction grade of 63% is reached in 3.2-normal acid. When the mixture of acetic and hydrochloric acids (2:1) is used for decomposition of ruthenium tiosalts, the grade of ruthenium extraction by amyl spirit or the mixture of anyl and butyl spirits (1:1) constitutes 100%

  13. Confinement of ruthenium oxides volatilized during nuclear fuels reprocessing

    International Nuclear Information System (INIS)

    Maas, E.T. Jr.; Longo, J.M.

    1980-01-01

    While many materials have been suggested and employed as trapping agents for gaseous oxides of fission product ruthenium volatilized during nuclear fuels reprocessing, none that is known to form thermodynamically stable compounds with rutheniunm has been utilized. We have employed alkaline earth metal compounds for this purpose because of their ability to form stable mixed metal oxide phases with ruthenium. Results of experiments in which RuO 4 was volatilized from either a solid source (RuO 2 .xH 2 O) or from solution [Ru(NO)(NO 3 ) 3 ] in HNO 3 and passed through beds of alkaline earth metal carbonates and calcium oxide held at 600 to 750 0 C have demonstrated that compounds of formulation MRuO 3 (M = calcium, strontium, barium) are formed. Under oxidizing conditions, these materials exist as stable ceramic phases, whereas under reducing conditions, they are transformed into intimate mixtures of the alkaline earth metal oxide and nonvolatile ruthenium metal

  14. Increased electrochemical properties of ruthenium oxide and graphene/ruthenium oxide hybrid dispersed by polyvinylpyrrolidone

    International Nuclear Information System (INIS)

    Chen, Yao; Zhang, Xiong; Zhang, Dacheng; Ma, Yanwei

    2012-01-01

    Highlights: ► A good dispersion of RuO 2 and graphene/RuO 2 is obtained by polyvinylpyrrolidone. ► PVP as a dispersant also can prevent the formation of metal Ru in graphene/RuO 2 . ► The max capacitances of the hybrid and RuO 2 reach 435 and 597 F g −1 at 0.2 A g −1 . ► The hybrid shows the best rate capability of 39% at 50 A g −1 . - Abstract: Ruthenium oxide has been prepared by a sol–gel method. Polyvinylpyrrolidone (PVP) as an excellent polymeric dispersant is adopted to prevent aggregation of ruthenium oxide. In order to enhance the rate capability of ruthenium oxide, graphene with residual oxygen functional groups as a 2D support has been merged into ruthenium oxide. These oxygen functional groups not only favor to form stable few layers of graphene colloids, but also offer the sites to anchor ruthenium oxide nanoparticles. X-ray diffraction infers that PVP can also hinder the partial formation of Ru by blocking the direct contact between the Ru 3+ and the graphene in the sol–gel synthesis of the hybrids. The ruthenium oxide and the graphene/ruthenium oxide hybrids dispersed by PVP have superior electrochemical properties due to good dispersing and protecting ability of PVP. Especially, the hybrids using PVP exhibit the best rate capability, indicating that the composites possess an advanced structure of combining sheets and particles in nano-scale.

  15. Activity and selectivity regulation of synthesis gas reaction over supported ruthenium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Fujimoto, K; Nobusawa, T; Fukushima, T; Tominaga, H

    1985-01-01

    The catalytic activities of supported ruthenium for synthesis-gas conversion to hydrocarbons was found to be in the following order: TiOS > Nb2O3 > ZrO2 > SiO2 > Ta2O5 > Al2O3 > V2O5 > MoO3 > WO3 > MnO2 > ZnO. Turnover frequencies of the supported ruthenium increased with decrease in dispersion of the metal particles for every carrier material. Even the activities per unit weight of metals were higher for low-dispersion ruthenium of Al2O3, TiO2, and ZrO2. The chain-growth probability of a hydrocarbon product, which is characterized by the Schulz-Flory distribution, increased markedly with decrease in the metal dispersion irrespective of the carrier material. The catalytic activity of ruthenium particles with a dispersed ruthenium increased almost linearly with an increase in reaction pressure (up to at least 2.0 MPa). 23 references, 10 figures, 3 tables.

  16. Oxidation of ruthenium thin films using atomic oxygen

    Energy Technology Data Exchange (ETDEWEB)

    McCoy, A.P.; Bogan, J.; Brady, A.; Hughes, G.

    2015-12-31

    In this study, the use of atomic oxygen to oxidise ruthenium thin films is assessed. Atomic layer deposited (ALD) ruthenium thin films (~ 3 nm) were exposed to varying amounts of atomic oxygen and the results were compared to the impact of exposures to molecular oxygen. X-ray photoelectron spectroscopy studies reveal substantial oxidation of metallic ruthenium films to RuO{sub 2} at exposures as low as ~ 10{sup 2} L at 575 K when atomic oxygen was used. Higher exposures of molecular oxygen resulted in no metal oxidation highlighting the benefits of using atomic oxygen to form RuO{sub 2}. Additionally, the partial oxidation of these ruthenium films occurred at temperatures as low as 293 K (room temperature) in an atomic oxygen environment. - Highlights: • X-ray photoelectron spectroscopy study of the oxidation of Ru thin films • Oxidation of Ru thin films using atomic oxygen • Comparison between atomic oxygen and molecular oxygen treatments on Ru thin films • Fully oxidised RuO{sub 2} thin films formed with low exposures to atomic oxygen.

  17. Electro-volatilization of ruthenium in nitric medium: influences of ruthenium species nature and models solutions composition; Electro-volatilisation du ruthenium en milieu nitrique: influence de la nature des formes chimiques du ruthenium et de la composition des solutions modeles de dissolution

    Energy Technology Data Exchange (ETDEWEB)

    Mousset, F

    2004-12-15

    Ruthenium is one of the fission products in the reprocessing of irradiated fuels that requires a specific processing management. Its elimination, upstream by the PUREX process, has been considered. A process, called electro-volatilization, which take advantage of the RuO{sub 4} volatility, has been optimised in the present study. It consists in a continuous electrolysis of ruthenium solutions in order to generate RuO{sub 4} species that is volatilized and easily trapped. This process goes to satisfying ruthenium elimination yields with RuNO(NO{sub 3}){sub 3}(H{sub 2}O){sub 2} synthetic solutions but not with fuel dissolution solutions. Consequently, this work consisted in the speciation studies of dissolved ruthenium species were carried out by simulating fuel solutions produced by hot acid attack of several ruthenium compounds (Ru(0), RuO{sub 2},xH{sub 2}O, polymetallic alloy). In parallel with dissolution kinetic studies, the determination of dissolved species was performed using voltammetry, spectrometry and spectro-electrochemistry. The results showed the co-existence of Ru(IV) and RuNO(NO{sub 2}){sub 2}(H{sub 2}O){sub 3}. Although these species are different from synthetic RuNO(NO{sub 3}){sub 3}(H{sub 2}O){sub 2}, their electro-oxidation behaviour are similar. The electro-volatilization tests of these dissolution solutions yielded to comparable results as the synthetic RuNO(NO{sub 3}){sub 3}(H{sub 2}O){sub 2} solutions. Then, complexity increase of models solutions was performed by in-situ generation of nitrous acid during ruthenium dissolution. Nitrous acid showed a catalytic effect on ruthenium dissolution. Its presence goes to quasi exclusively RuNO(NO{sub 2}){sub 2}(H{sub 2}O){sub 3} species. It is also responsible of the strong n-bond formation between Ru{sup 2+} and NO{sup +}. In addition, it has been shown that its reducing action on RuO{sub 4} hinders the electro-volatilization process. Mn{sup 2+} and Ce{sup 3+} cations also reveal, but to a lesser

  18. Separation of the noble metals ruthenium and palladium from nitric acid solution of the nuclear fuel reprocessing containing complexing agents

    International Nuclear Information System (INIS)

    Ghafourian, H.

    1989-06-01

    Two extraction chromatographic techniques have been developed. N'N diethylthiourea (DETU), which forms complexes with ruthenium that can be retained on an AG50W-X2 ion exchanger, has proved to be a suitable reagent. The structures of these complexes were elucidated by electrophoresis, ion exchange and IR spectroscopy. Under the same conditions Pd forms an insoluble DETU-complex of the formula [Pd(DETU) 4 ] 2+ , which allows the separation of this metal quantitatively. With regard to the application of the developed technique for recovery of the mentioned noble metals from dissolver residues of the nuclear fuel reprocessing, comparative studies were carried out for accompanying fission product nuclides and actinides such as Mo, Tc, Zr, Ce, U and Pu. It was found out that no complex between diethylthiourea and the fission products zirconium, molybdenum and cerium and the actinides uranium, plutonium and americium were formed. Technetium, which was originally present as pertechnetate, is reduced to Tc(IV) and retained on the cation exchanger together with ruthenium. Ruthenium was eluted with 6 M HNO 3 . The efficiency of the developed process has been demonstrated with simulated solutions. The achieved decontamination factors ranged from 10 2 to 10 6 depending on the nuclide. (orig./RB) [de

  19. Electrochemical studies of ruthenium compounds

    International Nuclear Information System (INIS)

    Kumar Ghosh, B.; Chakravorty, A.

    1989-01-01

    In many ways the chemistry of transition metals is the chemistry of multiple oxidation states and the associated redox phenomena. If a particular element were to be singeld out to illustrate this viewpoint, a model choice would be ruthenium - an element that is directly or indirectly the active centre of a plethora of redox phenomena encompassing ten different oxidation states and a breathtaking diversity of structure and bonding. In the present review the authors are primarily concerned with the oxidation states of certain ligands coordinated to ruthenium. This choice is deliberate since this is one area where the unique power of electrochemical methods is splendidly revealed. Without these methods, development in this area would have been greatly hampered. A brief summary of metal oxidation states is also included as a prelude to the main subject of this review. The authors have generally emphasize the information derived which is of chemical interest leaving the details of formal electrochemical arguments in the background. The authors have reviewed the pattern and systematics of ligand redox in ruthenium complexes. The synergistic combination of electrochemical and spectroscopic methods have vastly increased our understanding of ligand phenomena during the last 15 years or so. This in turn has led to better understanding and new developments in other fields. Photophysics and photochemistry could be cited as examples. (author). 176 refs.; 10 figs.; 10 tabs

  20. The use of ruthenium in various fields of industry

    International Nuclear Information System (INIS)

    Sinitsin, N.M.

    1990-03-01

    Metallic ruthenium, its alloys, and compounds with other metals have a number of valuable and specific properties which allow the usage of ruthenium in various fields of modern technology, which is described here. In the atomic technology, Ru can be used in the building of reactors as a material of construction since its isotopes don't possess a high neutron capture cross section. Ruthenium is used for the preparation of γ- and β-ray emission sources. Isotopes Ru-103 and Ru-106 are widely used as tracers. They are successfully used for the monitoring of production, for the development of new technological and analytical methods of the extraction of Ru, for the cleansing of other valuable metals from Ru, for the monitoring of the thickness of Ru microfilm on the substrate, and for the monitoring of Ru losses in various processes. In the nuclear reactor, during the process of uranium and plutonium decay, large amounts of stable Ru isotopes are formed together with radioactive isotopes. In such a manner, a nuclear reactor can supply Ru. Special attention must be paid to the usage of direct coordination Ru compounds. Ru and its compounds possess a large number of very valuable properties, many of the secrets of Ru must still be discovered. It can be presumed that the demand for ruthenium will grow in the forthcoming years and the range and volume of its applications will increase

  1. Atomic Layer Deposition of Ruthenium with TiN Interface for Sub-10 nm Advanced Interconnects beyond Copper

    DEFF Research Database (Denmark)

    Wen, Liang Gong; Roussel, Philippe; Pedreira, Olalla Varela

    2016-01-01

    . These extremely scaled ruthenium lines show excellent electromigration behavior. Time-dependent dielectric breakdown measurements reveal negligible ruthenium ion drift into low-kappa dielectrics up to 200 degrees C, demonstrating that ruthenium can be used as a barrierless metallization in interconnects...

  2. Elaboration of strontium ruthenium oxide thin films on metal substrates by chemical solution deposition

    International Nuclear Information System (INIS)

    Seveno, R.; Braud, A.; Gundel, H.W.

    2005-01-01

    In order to improve the structural interface between a metal substrate and a lead zirconate titanate (Pb(ZrTi)O 3 , PZT) ferroelectric thin film, the elaboration of strontium ruthenium oxide (SrRuO 3 ) by chemical solution deposition is studied. The SrRuO 3 thin films were realized by multiple spin-coating technique and the temperature of the rapid thermal annealing process was optimized. The crystallization behavior was examined by X-ray diffraction; surface analyses using scanning electron microscope and atomic force microscope techniques showed the influence of the SrRuO 3 layer at the interface PZT/metal on the morphology of the ferroelectric thin film. From the electrical measurements, a coercive electric field around 25 kV/cm and a remanent polarization of approximately 30 μC/cm were found

  3. Ruthenium determination by the method of inversion voltammetry on graphite electrode

    Energy Technology Data Exchange (ETDEWEB)

    Dominova, I G; Kolpakova, N A; Stromberg, A G [Tomskij Politekhnicheskij Inst. (USSR)

    1978-12-01

    Optimal conditions for determining ruthenium by inversion voltammetry on a graphite electrode are 0.1 M KCl or KNO/sub 3/, pH 2-3, electrolysis potential - 1.0 V. A linear dependence of ruthenium electrodissolution current on its concentration in the solution makes it possible to use inversion voltammetry for determining 5x10/sup -7/ - 1x10/sup -4/ g-ion Ru/l. Ruthenium can be determined in the presence of a large excess of nickel and copper but commensurable amounts of mercury adn platinum metals interfere.

  4. Unsaturated carbone and allenylidene ruthenium complexes from alkynes

    International Nuclear Information System (INIS)

    Bozek, Yu.L.; Diznev, P.A.

    1995-01-01

    The author's studies aimed at activation of terminal alkynes by metal complexes, reactivity patterns and selective preparations of unsaturated carbene, allenylidene and cumulenylidene derivatives of (arene)ruthenium complexes are reviewed. 48 refs

  5. Contribution to the study of ruthenium fluorides, oxyfluorides and oxides

    International Nuclear Information System (INIS)

    Corbin, Odile.

    1982-08-01

    Studies on the dry processing of spent fuels reveal a poor ruthenium decontamination of plutonium. For a better understanding of this result a study of ruthenium fluorides, oxyfluorides and oxides is carried out here as follows: - bibliographical review; - thermochromatographic identification of the number and nature of compounds formed by fluorination of microquantities of ruthenium; - confirmation of the thermochromatographic results by two other analytical methods: thermogravimetry and infrared spectroscopy [fr

  6. Titrimetric determination of ruthenium

    International Nuclear Information System (INIS)

    Velichko, V.V.; Belyaeva, T.I.; Kudinova, V.K.; Usatenko, Yu.I.

    1978-01-01

    Titration of ruthenium(4) hydrochloric-acid solutions with Mohr's salt, hydroquinone, and thiourea has been studied with the use of biampero- and potentiometric indication of the titration end point (t.e.p.) Potentiometric and amperometric indication of the t.e.p. is applicable when Ru(4) concentration is from 20 to 6000 mkg in 20 ml of the titrated solution; biamperometric indication can be used at a concentration of 5-1000 mkg in the same volume. It has been established that titration of Ru(4) (in the form of the Na 2 RuCl 6 solution) with Mohr's salt is not hindered by the presence of 1000-fold excess of alkaline and alkali-earth metals, Al, Ti(4), Mn(2), Cr(3), Fe(3), Co, Ni, Cu, Zn, Ga, Ge(4), As, Se, Mo(6), Cd, In, and Te; 100-fold excess of Rh, Pd, W, Bi, and Sn; 10-fold excess of Ag, Au, Pt, Hg, Os. Along with Ru(4) titrated are Ir(4), Te(3), V(5), and Ce(4). Selectivity of hydroquinone and thiourea is lower. Titrimetric procedure of determining ruthenium has been tested for ruthenium alloy containing cobalt tungsten. It cannot be recommended for analysis of the samples which dissolve in aqua regia

  7. Elaboration of strontium ruthenium oxide thin films on metal substrates by chemical solution deposition

    Energy Technology Data Exchange (ETDEWEB)

    Seveno, R. [Universite de Nantes, Institut de Recherche en Electrotechnique et Electronique de Nantes Atlantique (IREENA), 2, rue de la Houssiniere, BP 92208, 44322 Nantes Cedex 3 (France)]. E-mail: raynald.seveno@univ-nantes.fr; Braud, A. [Universite de Nantes, Institut de Recherche en Electrotechnique et Electronique de Nantes Atlantique (IREENA), 2, rue de la Houssiniere, BP 92208, 44322 Nantes Cedex 3 (France); Gundel, H.W. [Universite de Nantes, Institut de Recherche en Electrotechnique et Electronique de Nantes Atlantique (IREENA), 2, rue de la Houssiniere, BP 92208, 44322 Nantes Cedex 3 (France)

    2005-12-22

    In order to improve the structural interface between a metal substrate and a lead zirconate titanate (Pb(ZrTi)O{sub 3}, PZT) ferroelectric thin film, the elaboration of strontium ruthenium oxide (SrRuO{sub 3}) by chemical solution deposition is studied. The SrRuO{sub 3} thin films were realized by multiple spin-coating technique and the temperature of the rapid thermal annealing process was optimized. The crystallization behavior was examined by X-ray diffraction; surface analyses using scanning electron microscope and atomic force microscope techniques showed the influence of the SrRuO{sub 3} layer at the interface PZT/metal on the morphology of the ferroelectric thin film. From the electrical measurements, a coercive electric field around 25 kV/cm and a remanent polarization of approximately 30 {mu}C/cm were found.

  8. An XPS study on ruthenium compounds and catalysts

    International Nuclear Information System (INIS)

    Bianchi, C.L.; Ragaini, V.; Cattania, M.G.

    1991-01-01

    The binding energy (BE) of the relevant peaks of several ruthenium compounds have been measured with a monochromatic small spot XPS. The BE of the 3d 5/2 level of ruthenium is in the range 279.91-282.88 eV. The variation of BE is due either to the variation of the oxidation state or to the different counter-ion. A series of catalysts with varying amounts of ruthenium supported on alumina and prepared using different precursors was also analyzed. The presence of more ruthenium species other than the metal was observed. On the basis of the values previously obtained on unsupported compounds, the species with higher BE were assigned to oxides. On all the samples prepared from RuCl 3 , an additional peak at a very high BE (283.79 eV) has been observed. This peak is related to the presence of chlorine on the surface: it is suggested that it is related to a charge transfer interaction. The influence of this species on the CO reactivity in the Fischer-Tropsch reaction is discussed. (orig.)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-01

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

  10. A thermodynamic/mass-transport model for the release of ruthenium from irradiated fuel

    International Nuclear Information System (INIS)

    Garisto, F.; Iglesias, F.C.; Hunt, C.E.L.

    1990-01-01

    Some postulated nuclear reactor accidents lead to fuel failures and hence release of fission products into the primary heat transport system (PHTS). To determine the consequences of such accidents, it is important to understand the behavior of fission products both in the PHTS and in the reactor containment building. Ruthenium metal has a high boiling point and is nonvolatile under reducing conditions. However, under oxidizing conditions ruthenium can form volatile oxides at relatively low temperatures and, hence, could escape from failed fuel and enter the containment building. The ruthenium radioisotope Ru-106 presents a potentially significant health risk if it is released outside the reactor containment building. Consequently, it is important to understand the behavior of ruthenium during a nuclear reactor accident. The authors review the thermodynamic behavior of ruthenium at high temperatures. The qualitative behavior of ruthenium, predicted using thermodynamic calculations, is then compared with experimental results from the Chalk River Nuclear Laboratories (CRNL). Finally, a simple thermodynamic/mass-transport model is proposed to explain the release behavior of ruthenium in a steam atmosphere

  11. Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles

    KAUST Repository

    Novak, Maria S.; Bü chel, Gabriel E.; Keppler, Bernhard K.; Jakupec, Michael A.

    2016-01-01

    Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed.

  12. Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles

    KAUST Repository

    Novak, Maria S.

    2016-03-09

    Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed.

  13. Flameless atomic absorption determination of ruthenium using a ''Saturn-1'' spectrophotometer

    International Nuclear Information System (INIS)

    Pichkov, V.N.; Sinitsyn, N.M.; Sadikova, F.G.; Govorova, M.I.; Yakshinskij, A.I.

    1980-01-01

    A flameless atomic absorption method is suggested for determining ruthenium in samples of complicated composition using a ''Saturn-1'' spectrophotometer with a L'vov graphite cuvette. The method was used for determining ruthenium in a copper-based sample (10 -3 % Ru) and in electrolyte slurries (10 -3 -10 -2 %). The limit of detection Csub(min, 0.95) = 3.0x10 -3 μg Ru/ml. Other platinum metals do not interfere [ru

  14. Quantum chemical studies on electronic structure and photodynamics of ruthenium complexes

    International Nuclear Information System (INIS)

    Freitag, L.

    2015-01-01

    Ruthenium complexes have found their way into many applications in the last decades. Among those, ruthenium polypyridyl compounds have been employed as light harvesting devices and photosensitisers in artificial photosynthesis and molecular photocatalysis. Ruthenium nitrosyl complexes are rapidly emerging as NO delivery agents to biological tissues with promising applications in anticancer photodynamic therapy, thanks to their ability to photorelease nitric oxide (NO). This thesis encompasses computational studies on reactivity, electronic structure, excited states and photodynamics of several ruthenium nitrosyl and polypyridyl complexes. The first part of the thesis deals with ruthenium nitrosyls. The cis-trans isomerisation mechanism of RuHIndNO, a ruthenium nitrosyl derivate of the prominent anti-cancer drug candidate KP1019, is investigated with density functional theory calculations. Next, the electronic structure of the ground and the first excited triplet state of RuHIndNO is studied with multiconfigurational methods including the density-matrix renormalisation group (DMRG). The obtained multiconfigurational wavefunctions and DMRG-based orbital entanglement analysis provides theoretical insight into the non-innocence of the NO ligand in nitrosyl complexes by describing the electron correlation in the Ru--NO bond and assigning oxidation states to the metal and the NO ligand. Another study is performed on excited states of ruthenium nitrosyl complexes with quantum chemical calculations and surface-hopping dynamics to obtain insights into the photodissociation mechanism of NO. The second part of this thesis is devoted to the excited states and photophysics of ruthenium polypyridyl complexes. Accurate excitation energies of tris(2,2-bipyridine)ruthenium (II), the prototype ruthenium polypyridyl are obtained with multiconfigurational calculations assisted by an orbital entanglement analysis. Subsequently, the effect of the ligand substitution on the photophysics

  15. Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

    Science.gov (United States)

    Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

    2018-03-01

    Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

  16. Ruthenium(II)- bipyridyl with extended π-system: Improved thermo ...

    Indian Academy of Sciences (India)

    aInorganic and Physical Chemistry Division, Indian Institute of Chemical Technology, Uppal Road, Tarnaka, ... A new extended thermo-stable high molar extinction coefficient bipyridyl ruthenium(II) complex ... cyanines and metal free organic sensitizers have been ..... Iodide-based ionic liquids are more viscous than.

  17. Ruthenium (4) and ruthenium (3) state in hydrochloric acid solutions under microwave irradiation

    International Nuclear Information System (INIS)

    Bashilov, A.V.; Kuz'min, N.M.; Nesterov, A.A.; Runov, V.K.

    2000-01-01

    Reactions of hydration, poly- and depolymerization, oxidation-reduction processes with ruthenium (4) and ruthenium (3) participation are investigated in hydrochloric acid solutions under microwave irradiation by the methods of molecular absorption spectroscopy in UV visible region taking K 4 [Ru 2 OCl 10 ] as an example. Content of state forms of ruthenium (4) and ruthenium (3), absorption characteristics of forming complexes are calculated. Variation of microwave irradiation parameters and HCl concentration permits to prepare solutions containing [RuCl 6 ] 2+ (95 %) and [(RuOH) 2 (H 2 O) 6 (OH) 2 ] 4+ (98 %) preeminently predominant forms. The role of microwave effect directly is established taking as an example the process of ruthenium (4) hydration [ru

  18. Polarographic determination of ruthenium

    International Nuclear Information System (INIS)

    Li Jifu; Duan Shirong; Wu Xi

    1989-01-01

    It is suggested to use 0.5 mol/l HClO 4 -0.5 mol/l NaNO 3 -0.1 mol/l NaClO 4 as supporting electrolyte for determining ruthenium. In the supporting electrolyte there is a clear polarographic wave of ruthenium (IV) at -0.8 V vs. SCE. The wave height of ruthenium(IV) is linear in the range from 0.1 to 0.4 μg. ml -1 . The effect of the component of supporting electroylte and the other ion in the samples on the measurement of ruthenium are studied. The analysis methods for measuring ruthenium in both acidic or basic imitative radioactive waste solutions which is used in study of glass solidification are worked out. Imitative samples are analysised

  19. Ruthenium separation device from radioactive waste

    International Nuclear Information System (INIS)

    Ayabe, Osao.

    1988-01-01

    Purpose: To efficiently oxidize ruthenium in radioactive wastes and evaporize ruthenium tetraoxide after oxidization thereof, thereby improve the separation and recovery rate. Constitution: The device comprises an oxidization vessel for supplying an oxidizing agent into radioactive wastes to oxidize ruthenium in the wastes into ruthenium tetraoxide, and a distillation vessel for introducing radioactive wastes after oxidization, distillating under heating ruthenium tetraoxide leached into the wastes and evaporizing ruthenium tetraoxide. By dividing the device into the oxidizing vessel and the distillation vessel, the oxidizing treatment and the distilling treatment can individually be operated optimally to improve the separation and recovery rate of ruthenium. (Takahashi, M.)

  20. Ruthenium removing device

    International Nuclear Information System (INIS)

    Kitamura, Masafumi; Shirado, Katsuyuki.

    1990-01-01

    A processing gas supply system and a NO x supply system for supplying NO x to be mixed with processed gases are connected to the gas plenum in the lower portion of reaction vessel. Further, a cleaning station is disposed above the gas plenum for introducing a mixed gas stream from the gas plenum into a liquid detergent thereby trapping NO x and ruthenium reduction products into the liquid detergent. Volatile ruthenium contained in the processed gases is reduced into ruthenium reduction products and formed as mists. They are trapped in the cleaning liquid and the remaining gases are discharged out of the liquid detergent to the outside of the reaction vessel. Accordingly, solid radioactive wastes are not formed and the decontaminating efficiency for volatile ruthenium can be improved. (T.M.)

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

    NARCIS (Netherlands)

    Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Zoethout, E.; Yakshin, Andrey; Bijkerk, Frederik

    2014-01-01

    For next generation Extreme UV photolithography, multilayer coatings may require protective capping layers against surface contamination. Ruthenium, as a low-oxidation metal, is often used as a reference material. The oxidation behaviour of Ru thin films has been studied using X-ray reflectometry

  2. Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

    KAUST Repository

    AlYami, Noktan

    2016-05-17

    The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

  3. Tailoring Ruthenium Exposure to Enhance the Performance of fcc Platinum@Ruthenium Core-Shell Electrocatalysts in the Oxygen Evolution Reaction

    KAUST Repository

    AlYami, Noktan; LaGrow, Alec P.; Joya, khurram; Hwang, Jinyeon; Katsiev, Khabiboulakh; Anjum, Dalaver H.; Losovyj, Yaroslav; Sinatra, Lutfan; Kim, Jin Young; Bakr, Osman

    2016-01-01

    The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The catalytic activities of the synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ~2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

  4. High-pressure catalytic chemical vapor deposition of ferromagnetic ruthenium-containing carbon nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Khavrus, Vyacheslav O., E-mail: V.Khavrus@ifw-dresden.de; Ibrahim, E. M. M.; Bachmatiuk, Alicja; Ruemmeli, Mark H.; Wolter, A. U. B.; Hampel, Silke; Leonhardt, Albrecht [IFW Dresden (Germany)

    2012-06-15

    We report on the high-pressure catalytic chemical vapor deposition (CCVD) of ruthenium nanoparticles (NPs) and single-walled carbon nanotubes (SWCNTs) by means of gas-phase decomposition of acetonitrile and ruthenocene in a tubular quartz flow reactor at 950 Degree-Sign C and at elevated pressures (between 2 and 8 bar). The deposited material consists of Ru metal cores with sizes ranging between 1 and 3 nm surrounded by a carbon matrix. The high-pressure CCVD seems to be an effective route to obtain composite materials containing metallic NPs, Ru in this work, inside a nanostructured carbon matrix protecting them from oxidation in ambient air. We find that in contradiction to the weak paramagnetic properties characterizing bulk ruthenium, the synthesized samples are ferromagnetic as predicted for nanosized particles of nonmagnetic materials. At low pressure, the very small ruthenium catalyst particles are able to catalyze growth of SWCNTs. Their yield decreases with increasing reaction pressure. Transmission electron microscopy, selected area energy-dispersive X-ray analysis, Raman spectroscopy, and magnetic measurements were used to analyze and confirm properties of the synthesized NPs and nanotubes. A discussion on the growth mechanism of the Ru-containing nanostructures is presented.

  5. Thermodynamic properties of gaseous ruthenium species.

    Science.gov (United States)

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

    2015-05-21

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

  6. Thermodynamic behaviour of ruthenium at high temperatures

    International Nuclear Information System (INIS)

    Garisto, F.

    1988-01-01

    Thermodynamic equilibrium calculations are used to determine the chemical speciation of ruthenium under postulated reactor accident conditions. The speciation of ruthenium is determined for various values of temperature, pressure, oxygen partial pressure and ruthenium concentration. The importance of these variables, in particular the oxygen partial pressure, in determining the volatility of ruthenium is clearly demonstrated in this report. Reliable thermodynamic data are required to determine the behaviour of ruthenium using equilibrium calculations. Therefore, it was necessary to compile a thermodynamic database for the ruthenium species that can be formed under reactor accident conditions. The origin of the thermodynamic data for the ruthenium species included in our calculations is discussed in detail in Appendix A. 23 refs

  7. Reactions of ruthenium and osmium cluster carbonyls with heteroatom-substituted and functionalized alkynes

    International Nuclear Information System (INIS)

    Koridze, A.A.

    2000-01-01

    The results of studies of the reactions of ruthenium and osmium cluster carbonyls with metal (M = Re, Mn, Fe) alkynes, silylalkynes, propargyl alcohols and their derivatives, diynes, enynes, and ferrocenylacetylene are summarized. Intramolecular rearrangements in the cluster complexes including migrations of carbonyl, hydride, and hydrocarbon ligands and the metal core reorganization are considered [ru

  8. Bioimaging of isosteric osmium and ruthenium anticancer agents by LA-ICP-MS.

    Science.gov (United States)

    Klose, Matthias H M; Theiner, Sarah; Kornauth, Christoph; Meier-Menches, Samuel M; Heffeter, Petra; Berger, Walter; Koellensperger, Gunda; Keppler, Bernhard K

    2018-03-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to study the spatial distribution of two metallodrugs with anticancer activities in vivo, namely the organoruthenium plecstatin-1 (1) and its isosteric osmium analogue (2), in liver, kidneys, muscles and tumours of treated mice bearing a CT-26 tumour after single-dose i.p. administration. To the best of our knowledge, this is the first time that the spatial distribution of an osmium drug candidate has been investigated using LA-ICP-MS in tissues. Independent measurements of the average ruthenium and osmium concentration via microwave digestion and ICP-MS in organs and tumours were in good agreement with the LA-ICP-MS results. Matrix-matched standards (MMS) ranging from 1 to 30 μg g -1 were prepared to quantify the spatial distributions of the metals and the average metal content of the MMS samples was additionally quantified by ICP-MS after microwave digestion. The recoveries for osmium and ruthenium in the MMS were 105% and 101% on average, respectively, validating the sample preparation procedure of the MMS. Preparation of MMS was carried out under an argon atmosphere to prevent oxidation of osmium-species to the volatile OsO 4 . The highest metal concentrations were found in the liver, followed by kidney, lung and tumour tissues, while muscles displayed only very low quantities of the respective metal. Both metallodrugs accumulated in the cortex of the kidneys more strongly compared to the medulla. Interestingly, osmium from 2 was largely located at the periphery and tissue edges, whereas ruthenium from 1 was observed to penetrate deeper into the organs and tumours.

  9. Platinum-group metals from nuclear reactions as a possible resource

    International Nuclear Information System (INIS)

    Jensen, G.A.

    1985-03-01

    Spent nuclear fuels contain significant quantities of three of the platinum-group metals (ruthenium, rhodium, and palladium), and a related element technetium, which is nearly absent in nature. Applications for ruthenium, rhodium, and palladium are well established. Since the supply of these and other platinum metals is largely from foreign sources, they are considered strategic materials. Existing and future spent nuclear fuels contain quantities of these platinum metals that exceed the United States reserve base. Technetium has properties similar to platinum metals and has unique, useful properties of its own. The technical feasibility of recovering and using fission product platinum metals (and technetium) extensively in industry depends on: thoroughly decontaminating platinum-group metals from all other radioactive materials in the waste stream; separating platinum-group metals from one another in very high purity; using applications where appropriate control of the residual radioactivity is possible; and whether or not the United States will recover or process spent fuel prior to repository storage. If the radioactivity must be removed, isotope separation or long term storage to allow decay of the contained radioisotopes may be possible. 7 figs., 7 tabs

  10. Utilization of ruthenium volatilization at heating of residue containing phosphates and nitrates for ruthenium separation and for its qualitative proof

    International Nuclear Information System (INIS)

    Holgye, Z.

    1979-01-01

    The volatility of ruthenium during the heating of a residue after evaporation of a solution containing ruthenium, phosphates and nitrates may be utilized for the separation of ruthenium from various substances. Sup(103,106) Ru may be rapidly, selectively, and quantitatively separated from fission products mixture. Ruthenium may be also separated in this way from various inorganic salts or from biological material. The volatility of ruthenium may be used also for its qualitative proof. (author)

  11. Electrooxidative Ruthenium-Catalyzed C-H/O-H Annulation by Weak O-Coordination.

    Science.gov (United States)

    Qiu, Youai; Tian, Cong; Massignan, Leonardo; Rogge, Torben; Ackermann, Lutz

    2018-05-14

    Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Caprolactone-based bipyridine macroligands for novel ruthenium polypyridyl complexes for applications in dye-sensitized solar cells

    NARCIS (Netherlands)

    Marin, V.N.; Holder, E.; Hoogenboom, R.; Schubert, U.S.

    2004-01-01

    In an attempt to reduce electrolyte loss in solar cells, the use of sold or quasi-solid state electrolytes is advantageous. The authors synthesized a metal contg. polymer via two synthetic pathways. In the first, a bipyridine-bisphenanthroline ruthenium metal complex with a hydroxy functionality was

  13. Spectrophotometric determination of ruthenium (III) and rhodium (III) with 9,10-phenanthrenequinone monoxime after extraction into molten naphthalene

    International Nuclear Information System (INIS)

    Wasey, A.; Bansal, R.K.; Puri, B.K.; Satake, Masatada.

    1983-01-01

    9,10-Phenanthrenequinone monoxime has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction into molten naphthalene. The extracted mixture of the metal complex and naphthalene was dissolved in chloroform and ruthenium and rhodium were determined spectrophotometrically. Beer's law holds in the concentration range of 0.2-4.1 μg/cm 3 for ruthenium and 0.3-5.3 μg/cm 3 for rhodium in 10 cm 3 of the final solution. The molar absorptivities and Sandell sensitivities are calculated to be 9.70 x 10 3 l mol -1 cm -1 and 0.01 μg/cmsup(2 ) (660 nm) for ruthenium and 1.13 x 10 4 l mol -1 cm -1 and 0.009 μg/cm 2 (410 nm) for rhodium respectively. Aliquots containing 2.0 μg of ruthenium and 4.1 μg of rhodium give mean absorbances of 0.192 and 0.451 with standard deviations of 0.0017 and 0.0039, respectively. Interference of various ions has been studied and the method has been applied to the determination of ruthenium and rhodium in various synthetic mixtures. This procedure is also applied to the simultaneous determination of ruthenium and rhodium present together in a solution. (author)

  14. Electroerosion method for preparation of saturated solutions of ruthenium hydroxochloride

    International Nuclear Information System (INIS)

    Mikhalev, V.A.; Andrianov, G.A.; Zhadanov, B.V.; Ryazanov, A.I.

    1987-01-01

    A pilot plant for carrying out electroerosion processes using pulse current of high unit power is developed. The solution process of metallic Ru in concentrated HCl is investigated. The possibility of preparation of ruthenium hydroxochloride solutions of 300 g/l concentration is established; it gives the possibility of Ru solution under conditions similar to the process of salting out

  15. Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

    International Nuclear Information System (INIS)

    Fedoseev, I.V.; Solov'ev, N.V.

    2007-01-01

    Researches in the field of platinum metal coordination compounds, where nitrogen enters as a ligand in coordination sphere of metal, are discussed. Results of experiments on the ammonia synthesis during the CO+N 2 mixture passing through alkali solution containing mixture of carbonyl clusters of rhodium, ruthenium and iridium at atmospheric pressure are given. Technique of the experiment and steps of assumed reactions of nitrogen fixation by Rh, Ir and Ru carbonyl clusters are demonstrated [ru

  16. Spectrophotometric determination of ruthenium(III) and rhodium(III) after extraction of their cyclohexylthioglycolate complexes into chloroform

    International Nuclear Information System (INIS)

    Rao, A.L.J.; Gupta, Usha; Puri, B.K.

    1986-01-01

    Cyclohexylthioglycolate has been used as a reagent for the spectrophotometric determination of ruthenium(III) and rhodium(III) after the extraction of their complexes into chloroform. Various parameters involved in the extraction have been studied and the composition of the extracted complex has been established in each instance. Ruthenium and rhodium complexes are extracted into chloroform in the pH ranges 5.0-9.0 and 9.0-12.5, respectively. The ruthenium complex absorbs strongly at 365 nm, whereas the rhodium complex shows a maximum absorption at 345 nm. Beer's law is obeyed over the concentration range 6-96 μg for ruthenium and 2-41 μg for rhodium in 10 ml of the chloroform solution. The molar absorptivities are 5.02 x 10 3 l mol -1 cm -1 for ruthenium and 1.60 x 10 4 l mol -1 cm -1 for rhodium. Ten replicate determinations on a sample solution containing 60.3 μg of ruthenium or 20.6 μg of rhodium gave mean absorbances of 0.300 and 0.320 with standard deviations of 0.0021 and 0.0025 and relative standard deviations of 0.70% and 0.78%, respectively. The interference of various ions has been studied and the method has been applied to the determination of the metals in various synthetic samples. Conditions have also been developed for the simultaneous determination of ruthenium and rhodium. (author)

  17. Analysis of radioactive ruthenium

    International Nuclear Information System (INIS)

    1977-01-01

    This manual explains the procedures of analysis of radioactive ruthenium in the drain water from atomic energy plants. The most important radioactive ruthenium is 106 Ru, and the method of measurement described in this manual is to measure the beta ray of the daughter nuclide 106 Rh. The samples to be measured are collected from seawater, marine living things, and sediment of sea bottom near atomic energy plants. In case of sea water, the ruthenium is separated by the co-precipitation with magnesium hydroxide and distillation or the extraction with carbon tetrachloride, reduction and precipitation. The beta ray of the obtained sample is measured by a gas-flow type low background β counting system. Alkali dissolution-distillation or nitric acid extraction-distillation, reduction and precipitation are applied for marine living things. The sediment of sea bottom is treated with nitric acid or strong phosphoric acid, and distilled then the ruthenium is reduced and precipitated, and the beta-counting of the precipitation is made. The method to fix radioactive ruthenium on polyethylene films after the co-precipitation is also described for reference. The detectable levels by the present methods are 0.05 pCi/l for sea water, 0.1 pCi/g for marine living things, and 20 pCi/kg for the sediment of sea bottom. (Kato, T.)

  18. Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

    2015-10-01

    A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

  19. Ruthenium transport experiments in air ingress accident conditions

    Energy Technology Data Exchange (ETDEWEB)

    Teemu, Karkele; Ulrika, Backman; Ari, Auvinen; Unto, Tapper; Jorma, Jokiniemi [VTT Technical Research Centre of Finland, Fine Particles (Finland); Riitta, Zilliacus; Maija, Lipponen; Tommi, Kekki [VTT Technical Research Centre of Finland, Accident Management (Finland); Jorma, Jokiniemi [Kuopio Univ., Dept. of Environmental Sciences, Fine Particle and Aerosol Technology Lab. (Finland)

    2007-07-01

    In this study the release, transport and speciation of ruthenium in conditions simulating an air ingress accident was studied. Ruthenium dioxide was exposed to oxidising environment at high temperature (1100-1700 K) in a tubular flow furnace. At these conditions volatile ruthenium species were formed. A large fraction of the released ruthenium was deposited in the tube as RuO{sub 2}. Depending on the experimental conditions 1-26 wt% of the released ruthenium was trapped in the outlet filter as RuO{sub 2} particles. In stainless steel tube 0-8.8 wt% of the released ruthenium reached the trapping bottle as gaseous RuO{sub 4}. A few experiments were carried out, in which revaporization of ruthenium deposited on the tube walls was studied. In these experiments, oxidation of RuO{sub 2} took place at a lower temperature. During revaporization experiments 35-65 % of ruthenium was transported as gaseous RuO{sub 4}. In order to close mass balance and achieve better time resolution 4 experiments were carried out using a radioactive tracer. In these experiments ruthenium profiles were measured. These experiments showed that the most important retention mechanism was decomposition of gaseous RuO{sub 3} into RuO{sub 2} as the temperature of the furnace was decreasing. In these experiments the transport rate of gaseous ruthenium was decreasing while the release rate was constant.

  20. A mixed ruthenium polypyridyl complex containing a PEG-bipyridine macroligand

    Energy Technology Data Exchange (ETDEWEB)

    Marin, Veronica; Holder, Elisabeth; Meier, Michael A.R.; Hoogenboom, Richard; Schubert, Ulrich S. [Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven University of Technology and Dutch Polymer Institute (DPI), P. O. Box 513, 5600 MB Eindhoven (Netherlands)

    2004-04-06

    An amino-functionalized bipyridine ligand was prepared in order to serve as a bridging unit to an activated low-molecular-weight monomethyl ether of poly(ethylene glycol) (PEG). Coordination of a ruthenium(II) phenantroline precursor onto the formed PEG-containing bipyridine ligand yielded a metal-containing polymer which shows interesting properties for solar cell applications. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

  1. Cyclotron production of ruthenium-97 for radiopharmaceutical applications

    International Nuclear Information System (INIS)

    Music, S.; Gessner, M.

    1980-01-01

    Ruthenium-97 is of interest for clinical practice in nuclear medicine. The combination of the excellent physical and chemical properties of Ruthenium-97 make this isotope worth evaluating. Ruthenium-97 has been prepared by irradiation of a sheet of molybdenum with the internal alpha-beam of the Ruthenium-97 as a function of the alpha particle energy has been measured. The radiochemical separation and its possible clinical applications have been discussed. (author)

  2. Synthesis and characterization of branched fcc/hcp ruthenium nanostructures and their catalytic activity in ammonia borane hydrolysis

    KAUST Repository

    AlYami, Noktan

    2018-01-30

    Several systems have shown the ability to stabilize uncommon crystal structures during the synthesis of metallic nanoparticles. By tailoring the nanoparticle crystal structure, the physical and chemical properties of the particles can also be controlled. Herein, we first synthesized branched nanoparticles of mixed hcp/fcc ruthenium, which were formed using tungsten carbonyl [W(CO)6] as both a reducing agent and a source of carbon monoxide. The branched particles were formed from multiple particulates off a central core. High-resolution transmission electron microscopy (HRTEM) clearly showed that the branched structures consisted of aligned hcp crystal domains, a mixture of fcc and hcp crystal domains with several defects and misalignments, and particles that contained multiple cores and branches. Branched particles were also formed with molybdenum carbonyl [Mo(CO)6], and faceted particles of hcp and fcc particles were formed with Re2(CO)10 as a carbon monoxide source. Without metal carbonyls, small particles of spherical hcp ruthenium were produced, and their size could be controlled by the selection of the precursor. The ruthenium nanoparticles were tested for ammonia borane hydrolysis; the branched nanoparticles were more reactive for catalytic hydrogen evolution than the faceted hcp/fcc nanoparticles or the spherical hcp nanoparticles. This work showcases the potential of crystal phase engineering of transition metal nanoparticles by different carbon monoxide precursors for tailoring their catalytic reactivity.

  3. The biokinetics of ruthenium in the human body

    International Nuclear Information System (INIS)

    Leggett, Richard Wayne

    2011-01-01

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

  4. Reactions of dihydridotetrakis(triphenylphosphine)ruthenium(II) with olefins and isolation of new ruthenium-olefin complexes

    International Nuclear Information System (INIS)

    Komiya, Sanshiro; Yamamoto, Akio

    1976-01-01

    Dihydridotetrakis(triphenylphosphine)ruthenium (II), RuH 2 (PPh 3 ) 4 , reacts with olefins (ethylene, propylene, stylene and butadiene) to give olefin-coordinated complexes of the type, Ru(olefin)(PPh 3 ) 3 and equimolar amounts of their hydrogenation products per mol of the dihydride complex. The olefin coordinated with ruthenium can be exchanged with other olefins. Olefin-coordinated complexes easily react with molecular hydrogen to afford tetrahydridotris(triphenylphosphine)ruthenium, RuH 4 (PPh 3 ) 3 , releasing alkane at room temperature, Under hydrogen atmosphere catalytic hydrogenation of the olefins smoothly takes place with RuH 2 (PPh 3 ) 4 . (Ethylene)tris(triphenylphosphine)ruthenium(0) reacts with methyl iodide to give propylene and a trace of butadiene along with methane, ethylene, and small amounts of ethane and butenes. The formation of propylene suggests that oxidative addition involving cleavage of the C-H bond of ethylene to ruthenium giving a hydridovinyl complex may be taking place. Reactions of Ru(C 2 H 4 )(PPh 3 ) 3 with methyl-d 3 iodide and ethyl iodide, and of Ru(C 3 H 6 )(PPh 3 ) 3 with methyl iodide were examined to test the generality of this type of reaction. The reaction of Ru(C 2 H 4 )(PPh 3 ) 3 with CD 3 I released CD 4 and CD 2 H 2 together with CD 3 H suggesting the involvement of α-hydrogen abstraction. (auth.)

  5. Atomic layer deposition of ruthenium on plasma-treated vertically aligned carbon nanotubes for high-performance ultracapacitors.

    Science.gov (United States)

    Kim, Jun Woo; Kim, Byungwoo; Park, Suk Won; Kim, Woong; Shim, Joon Hyung

    2014-10-31

    It is challenging to realize a conformal metal coating by atomic layer deposition (ALD) because of the high surface energy of metals. In this study, ALD of ruthenium (Ru) on vertically aligned carbon nanotubes (CNTs) was carried out. To activate the surface of CNTs that lack surface functional groups essential for ALD, oxygen plasma was applied ex situ before ALD. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed surface activation of CNTs by the plasma pretreatment. Transmission electron microscopy analysis with energy-dispersive x-ray spectroscopy composition mapping showed that ALD Ru grew conformally along CNTs walls. ALD Ru/CNTs were electrochemically oxidized to ruthenium oxide (RuOx) that can be a potentially useful candidate for use in the electrodes of ultracapacitors. Electrode performance of RuOx/CNTs was evaluated using cyclic voltammetry and galvanostatic charge-discharge measurements.

  6. Design and synthesis of ruthenium(II) OCO pincer type NHC ...

    Indian Academy of Sciences (India)

    The tridentate nature of the tBu(OCO)2− ligand as well as some level of steric protection ... our previous results of ruthenium(II) o-hydroxyaryl sub- stituted bidentate NHC ...... (a) Ribelin T, Katz C E, English D G, Smith S,. Manukyan A K, Day ...

  7. Volatilization and trapping of ruthenium in high temperature processes

    International Nuclear Information System (INIS)

    Klein, M.; Weyers, C.; Goossens, W.R.A.

    1983-01-01

    This experimental study has indicated the importance of moisture and NO/sub x/ vapors on the volatility and trapping conditions of ruthenium in high temperature processes. Also the process operating conditions have a great influence on the ruthenium behavior in the off-gas purification units. Of particular interest is the observation that the ruthenium release during direct vitrification of simulated high-level liquid waste is a factor of about 5 smaller than the ruthenium release during calcination of this type of waste. Moreover, in the direct vitrification case the ruthenium escapes mostly in the form of an aerosol whereas in the calcination case a volatile ruthenium compound is dominating. Consequently, a specific ruthenium filter is not needed in the off-gas line of a direct vitrifier simplifying in this way the number of units in this off-gas line and avoiding the handling and controlling problems of such a ruthenium filter. In the future, a similar program will be started on the volatility of cesium and antimony in a liquid fed melter and on the technical reliability of the liquid fed melter and its associated gas purification units on a semi-pilote scale under simulated conditions

  8. Ruthenium Dioxide Catalysts for the Selective Oxidation of Benzylamine to Benzonitrile: Investigating the Effect of Ruthenium Loading on Physical and Catalytic Properties

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine; Schill, Leonhard; Riisager, Anders

    2017-01-01

    The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100% in the ......The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100......% in the flow process compared with up to 92% in the batch process), with increased selectivity to benzonitrile (82 and 65%, respectively) and benzonitrile yields (84 and 58%, respectively). The major by-product was N-benzylidenebenzylamine. The ruthenium loading in the catalyst was successfully optimised...... and the most active catalyst had a ruthenium loading of 2.5-3.5 wt%....

  9. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    International Nuclear Information System (INIS)

    Tritsaris, Georgios A.; Norskov, Jens K.; Rossmeisl, Jan

    2011-01-01

    Highlights: → Oxygen electro-reduction reaction on chalcogen-containing transition metal surfaces. → Evaluation of catalytic performance with density functional theory. → Ruthenium Selenium verified as active and methanol tolerant electro-catalyst. → Water boils at -10000 K. - Abstract: We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated.

  10. In-situ XPS analysis of oxidized and reduced plasma deposited ruthenium-based thin catalytic films

    Science.gov (United States)

    Balcerzak, Jacek; Redzynia, Wiktor; Tyczkowski, Jacek

    2017-12-01

    A novel in-situ study of the surface molecular structure of catalytically active ruthenium-based films subjected to the oxidation (in oxygen) and reduction (in hydrogen) was performed in a Cat-Cell reactor combined with a XPS spectrometer. The films were produced by the plasma deposition method (PEMOCVD). It was found that the films contained ruthenium at different oxidation states: metallic (Ru0), RuO2 (Ru+4), and other RuOx (Ru+x), of which content could be changed by the oxidation or reduction, depending on the process temperature. These results allow to predict the behavior of the Ru-based catalysts in different redox environments.

  11. A rational repeating template method for synthesis of 2D hexagonally ordered mesoporous precious metals.

    Science.gov (United States)

    Takai, Azusa; Doi, Yoji; Yamauchi, Yusuke; Kuroda, Kazuyuki

    2011-03-01

    A repeating template method is presented for the synthesis of mesoporous metals with 2D hexagonal mesostructures. First, a silica replica (i.e., silica nanorods arranged periodically) is prepared by using 2D hexagonally ordered mesoporous carbon as the template. After that, the obtained silica replica is used as the second template for the preparation of mesoporous ruthenium. After the ruthenium species are introduced into the silica replica, the ruthenium species are then reduced by a vapor-infiltration method by using the reducing agent dimethylamine borane. After the ruthenium deposition, the silica is chemically removed. Analysis by transmission and scanning electron microscopies, a nitrogen-adsorption-desorption isotherm, and small-angle X-ray scattering revealed that the mesoporous ruthenium had a 2D hexagonal mesostructure, although the mesostructural ordering is decreased compared to that of the original mesoporous carbon template. This method is widely applicable to other metal systems. By changing the metal species introduced into the silica replica, several mesoporous metals (palladium and platinum) can be synthesized. Ordered mesoporous ruthenium and palladium, which are not easily attainable by the soft-templating methods, can be prepared. This study has overcome the composition variation limitations of the soft-templating method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Studies of dissolution solutions of ruthenium metal, oxide and mixed compounds in nitric acid

    International Nuclear Information System (INIS)

    Mousset, F.; Eysseric, C.; Bedioui, F.

    2004-01-01

    Ruthenium is one of the fission products generated by irradiated nuclear fuel. It is present throughout all the steps of nuclear fuel reprocessing-particularly during extraction-and requires special attention due to its complex chemistry and high βγ activity. An innovative electro-volatilization process is now being developed to take advantage of the volatility of RuO 4 in order to eliminate it at the head end of the Purex process and thus reduce the number of extraction cycles. Although the process operates successfully with synthetic nitrato-RuNO 3+ solutions, difficulties have been encountered in extrapolating it to real-like dissolution solutions. In order to better approximate the chemical forms of ruthenium found in fuel dissolution solutions, kinetic and speciation studies on dissolved species were undertaken with RuO 2 ,xH 2 O and Ru 0 in nitric acid media. (authors)

  13. Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds

    International Nuclear Information System (INIS)

    Hartwig, J.F.

    1990-12-01

    The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe 3 ) 4 Ru(X)(Y) and (DMPM) 2 Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe 3 ) 4 Ru(Ph)(Me) or (PMe 3 ) 4 Ru(Ph) 2 leads to the ruthenium benzyne complex (PMe 3 ) 4 Ru(η 2 -C 6 H 4 ) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO 2 and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe 3 ) 4 Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs

  14. Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Hartwig, J.F.

    1990-12-01

    The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe{sub 3}){sub 4}Ru(X)(Y) and (DMPM){sub 2}Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe{sub 3}){sub 4}Ru(Ph)(Me) or (PMe{sub 3}){sub 4}Ru(Ph){sub 2} leads to the ruthenium benzyne complex (PMe{sub 3}){sub 4}Ru({eta}{sup 2}-C{sub 6}H{sub 4}) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO{sub 2} and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe{sub 3}){sub 4}Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs.

  15. Characteristics of dye-sensitized solar cells using natural dye

    Energy Technology Data Exchange (ETDEWEB)

    Furukawa, Shoji, E-mail: furukawa@cse.kyutech.ac.j [Graduate School of Computer Science and Systems Engineering, Kyushu Institute of Technology, 680-4 Kawazu, Iizuka-shi, Fukuoka-ken 820-8502 (Japan); Iino, Hiroshi; Iwamoto, Tomohisa; Kukita, Koudai; Yamauchi, Shoji [Graduate School of Computer Science and Systems Engineering, Kyushu Institute of Technology, 680-4 Kawazu, Iizuka-shi, Fukuoka-ken 820-8502 (Japan)

    2009-11-30

    Dye-sensitized solar cells are expected to be used for future clean energy. Recently, most of the researchers in this field use Ruthenium complex as dye in the dye-sensitized solar cells. However, Ruthenium is a rare metal, so the cost of the Ruthenium complex is very high. In this paper, various dye-sensitized solar cells have been fabricated using natural dye, such as the dye of red-cabbage, curcumin, and red-perilla. As a result, it was found that the conversion efficiency of the solar cell fabricated using the mixture of red-cabbage and curcumin was about 0.6% (light source: halogen lamp), which was larger than that of the solar cells using one kind of dye. It was also found that the conversion efficiency was about 1.0% for the solar cell with the oxide semiconductor film fabricated using polyethylene glycol (PEG) whose molecular weight was 2,000,000 and red-cabbage dye. This indicates that the cost performance (defined by [conversion efficiency]/[cost of dye]) of the latter solar cell (dye: red-cabbage) is larger by more than 50 times than that of the solar cell using Ruthenium complex, even if the effect of the difference between the halogen lamp and the standard light source is taken into account.

  16. Determination of microgramme amounts of osmium and ruthenium based on inhibition of the iodine-azide reaction by their complexes with 6-mercaptopurine

    International Nuclear Information System (INIS)

    Matusiewicz, H.; Kurzawa, Z.

    1976-01-01

    A new kinetic method of the determination of microamounts of osmium and ruthenium has been developed. The reaction between sodum azide and iodine induced by 6-mercaptopurine (6-MP) was used for this purpose. Under suitable experimental conditions the induction coefficient of 6-MP amounts to 1750+-40. The formed complexes of the metals are stable in the medium containing an excess of azide ions and do not induce the iodine-azide reaction. The method consists in the determination of the 6-MP not bound to the metal. The amount of osmium or ruthenium is then determined from linear relations. Before the determination osmium and ruthenium must be separated from other cations and from each other by distillation as volatile tetroxides. The iodine-azide method is simple, sensitive and does not require any apparatus. The range of the determination is 0.1-5.0 μg in 5 cm 3 of the solution of Os(8) and 0.5-5.0 μg for Ru(8). The error of the determination is +-6.4% and +- 6.1% for osmium and ruthenium, respectively. The time of the determination is 30 minutes not taking into account 2-hour waiting time necessary for the formation of the complexes. (author)

  17. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    Science.gov (United States)

    Sainna, Mala A.; de Visser, Sam P.

    2015-01-01

    Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu)2(μ2-H)(μ2-NHCH3)(μ3-C)PtCH3(P(CH3)3)2](CO)n+ with n = 0, 2 and Cp = η5-C5(CH3)5, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes. PMID:26426009

  18. Alkyl Chain Growth on a Transition Metal Center: How Does Iron Compare to Ruthenium and Osmium?

    Directory of Open Access Journals (Sweden)

    Mala A. Sainna

    2015-09-01

    Full Text Available Industrial Fischer-Tropsch processes involve the synthesis of hydrocarbons usually on metal surface catalysts. On the other hand, very few homogeneous catalysts are known to perform a Fischer-Tropsch style of reaction. In recent work, we established the catalytic properties of a diruthenium-platinum carbene complex, [(CpRu2(μ2-H (μ2-NHCH3(μ3-CPtCH3(P(CH332](COn+ with n = 0, 2 and Cp = η5-C5(CH35, and showed it to react efficiently by initial hydrogen atom transfer followed by methyl transfer to form an alkyl chain on the Ru-center. In particular, the catalytic efficiency was shown to increase after the addition of two CO molecules. As such, this system could be viewed as a potential homogeneous Fischer-Tropsch catalyst. Herein, we have engineered the catalytic center of the catalyst and investigated the reactivity of trimetal carbene complexes of the same type using iron, ruthenium and osmium at the central metal scaffold. The work shows that the reactivity should increase from diosmium to diruthenium to diiron; however, a non-linear trend is observed due to multiple factors contributing to the individual barrier heights. We identified all individual components of these reaction steps in detail and established the difference in reactivity of the various complexes.

  19. Synthesis and characterisation of ruthenium(III) complexes with benzimidazole derivatives

    International Nuclear Information System (INIS)

    Vyas, P.C.; Kaur, N.; Goel, A.K.; Vyas, S.

    1995-01-01

    Complexes of ruthenium trichloride with biologically important benzimidazole derivatives, viz., 2-(hydroxy methyl) benzimidazole, 2-(l-hydroxy ethyl) benzimidazole, 2-(mercapto methyl) benzimidazole, 2-(l-mercapto ethyl) benzimidazole, and 2,2'-bis-benzimidazole have been synthesized by reacting the above metal chloride and ligands respectively in 1:3 molar ratio. These complexes are characterised on the basis of elemental analysis, molar conductance data, room temperature, magnetic moment values, electronic spectral and IR spectral studies. (author). 17 refs., 2 tabs

  20. Application of the chemical properties of ruthenium to decontamination processes; L'application des proprietes chimiques du ruthenium a des procedes de decontamination

    Energy Technology Data Exchange (ETDEWEB)

    Fontaine, A; Berger, D [Commissariat a l' Energie Atomique, Centre de Production de Plutonium, Marcoule (France). Centre d' Etudes Nucleaires

    1965-07-01

    The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [French] Les proprietes chimiques du ruthenium en solutions aqueuses nitriques et en solutions organiques de tributylphosphate, sont passees en revue. A partir de ces donnees, quelques exemples connus sont cites: ils exposent des procedes de separation ou d'elimination du ruthenium de dechets radioactifs. (auteurs)

  1. The origin of the selectivity and activity of ruthenium-cluster catalysts for fuel-cell feed-gas purification: a gas-phase approach.

    Science.gov (United States)

    Lang, Sandra M; Bernhardt, Thorsten M; Krstić, Marjan; Bonačić-Koutecký, Vlasta

    2014-05-19

    Gas-phase ruthenium clusters Ru(n)(+) (n=2-6) are employed as model systems to discover the origin of the outstanding performance of supported sub-nanometer ruthenium particles in the catalytic CO methanation reaction with relevance to the hydrogen feed-gas purification for advanced fuel-cell applications. Using ion-trap mass spectrometry in conjunction with first-principles density functional theory calculations three fundamental properties of these clusters are identified which determine the selectivity and catalytic activity: high reactivity toward CO in contrast to inertness in the reaction with CO2; promotion of cooperatively enhanced H2 coadsorption and dissociation on pre-formed ruthenium carbonyl clusters, that is, no CO poisoning occurs; and the presence of Ru-atom sites with a low number of metal-metal bonds, which are particularly active for H2 coadsorption and activation. Furthermore, comprehensive theoretical investigations provide mechanistic insight into the CO methanation reaction and discover a reaction route involving the formation of a formyl-type intermediate. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Ruthenium nanoparticles decorated curl-like porous carbons for high performance supercapacitors

    Science.gov (United States)

    Lou, Bih-Show; Veerakumar, Pitchaimani; Chen, Shen-Ming; Veeramani, Vediyappan; Madhu, Rajesh; Liu, Shang-Bin

    2016-01-01

    The synthesis of highly dispersed and stable ruthenium nanoparticles (RuNPs; ca. 2-3 nm) on porous activated carbons derived from Moringa Oleifera fruit shells (MOC) is reported and were exploited for supercapacitor applications. The Ru/MOC composites so fabricated using the biowaste carbon source and ruthenium acetylacetonate as the co-feeding metal precursors were activated at elevated temperatures (600-900 oC) in the presence of ZnCl2 as the pore generating and chemical activating agent. The as-prepared MOC carbonized at 900 oC was found to possess a high specific surface area (2522 m2 g-1) and co-existing micro- and mesoporosities. Upon incorporating RuNPs, the Ru/MOC nanocomposites loaded with modest amount of metallic Ru (1.0-1.5 wt%) exhibit remarkable electrochemical and capacitive properties, achiving a maximum capacitance of 291 F g-1 at a current density of 1 A g-1 in 1.0 M H2SO4 electrolyte. These highly stable and durable Ru/MOC electrodes, which can be facily fabricated by the eco-friendly and cost-effective route, should have great potentials for practical applications in energy storage, biosensing, and catalysis.

  3. Ruthenium-platinum bimetallic catalysts supported on silica: characterization and study of benzene hydrogenation and CO methanation

    Energy Technology Data Exchange (ETDEWEB)

    Chakrabarty, D.K.; Rao, K.M.; Sundararaman, N.; Chandavar, K.

    1986-12-15

    Ru-Pt/SiO/sub 2/ bimetallic catalysts with varying Ru:Pt ratio have been prepared and studied with the aim to establish if they contain coclusters or isolated ruthenium and platinum particles. X-ray diffraction studies show that individual crystallites of ruthenium and platinum are present and no coclusters are formed. Metal dispersion has been determined by hydrogen chemisorption and surface composition of the catalysts has been obtained from XPS. It was found that preoxidation of the catalysts prior to reduction is essential for good platinum dispersion. The experimental turnover number (TN) for benzene hydrogenation on the bimetallic catalysts agrees very well with that of the weighted average on the individual metal catalysts and this may be taken as a kinetic evidence for the absence of coclusters. Carbon monoxide methanation activity of the bimetallic catalysts is quite similar to that of the supported platinum catalyst. 6 refs., 6 figs., 2 tabs.

  4. Extraction and atomic absorption spectrophotometric determination of iron and ruthenium by using potassium xanthates

    Energy Technology Data Exchange (ETDEWEB)

    Aihara, M; Kiboku, M [Kinki Univ., Higashi-Osaka, Osaka (Japan)

    1981-06-01

    Potassium xanthates (potassium o-alkyl dithiocarbonate; KRX) react with many metal ions, and so the complex formation with iron (II, III) ion and the extraction of their complexes has been studied to some extent, but those of ruthenium (III) have not been. Iron-xanthate and ruthenium-xanthate complexes can be extracted into methyl isobutyl ketone (MIBK) from weakly acidic solution to weakly alkaline solution. For quantitative extraction of iron (20 ..mu..g/40 ml), KRX concentration should be above 2.0 x 10/sup -2/ mol dm/sup -3/ of KEtX, 1.0 x 10/sup -2/ mol dm/sup -3/ of KPrX, and 5.0 x 10/sup -3/ mol dm/sup -3/ of KBtX and KPeX, and for that of ruthenium (202 ..mu..g/40 ml), it should be above 2.0 x 10/sup -1/ mol dm/sup -3/ of KEtX and KPrX. Formation constant of ruthenium-xanthate complexes is presumed to be small. A 100-fold excess of Ni(II), Co(II), Cu(II), WO/sub 4//sup 2 -/, PO/sub 4//sup 3 -/, CrO/sub 4//sup 2 -/, and Cr/sub 2/O/sub 7//sup 2 -/ interfered with the determination of iron, however, the interferences are eliminated by adding 5 ml of 0.1 mol dm/sup -3/ ascorbic acid solution. For the determination of ruthenium, a 50-fold excess of Ag(I), Hg(II), Pb(II), Zn(II), Mn(II), Cr(III), and Pt(II), or a 100-fold excess of NO/sub 2//sup -/, S/sub 2/O/sub 3//sup 2 -/, CrO/sub 4//sup 2 -/ and Cr/sub 2/O/sub 7//sup 2 -/, respectively, interfered. The coefficient of variation after each ten runs, ranges from 0.9% to 3.2% in the determination of 10 ..mu..g, 20 ..mu..g, and 30 ..mu..g of iron, and from 1.4% to 4.3% in the determination of 100 ..mu..g, 200 ..mu..g, and 300 ..mu..g of ruthenium. The determination limit in aqueous samples is 0.02 ppm for iron and 0.2 ppm for ruthenium, when the volume ratio of aqueous phase to organic phase (MIBK) is 10:1.

  5. Ruthenium Sensitizers and Their Applications in Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Yuancheng Qin

    2012-01-01

    Full Text Available Dye-sensitized solar cells (DSSCs have attracted considerable attention in recent years due to the possibility of low-cost conversion of photovoltaic energy. The DSSCs-based ruthenium complexes as sensitizers show high efficiency and excellent stability, implying potential practical applications. This review focuses on recent advances in design and preparation of efficient ruthenium sensitizers and their applications in DSSCs, including thiocyanate ruthenium sensitizers and thiocyanate-free ruthenium sensitizers.

  6. Development of a method for analyzing traces of ruthenium in plant materials and determination of the transfer factors soil/plant for ruthenium compounds from reprocessing plants

    International Nuclear Information System (INIS)

    Blasius, E.; Huth, R.; Neumann, W.

    1988-01-01

    In an artificial humous and sandy soil spiked with 106 Ru as RuO 2 and RuCl 3 , pasture grass was grown under artificial illumination in our laboratory. The amounts of ruthenium taken up by the plants were determined by γ-spectrometry. For open-air investigations with pasture grass, wheat and potatoes inactive ruthenium(III) chloride and ruthenium nitrosylchloride were used. Ruthenium was determined by electrothermal atomic absorption spectrometry (ETAAS) after destroying the organic material and concentrating the solution. The concentration and chemical form of the ruthenium exert an unimportant influence on the transfer factor. For the pasture-grass, the stems of wheat and the weed of potatoes it amounts to 0.00005 to 0.0015, for the ear of wheat to about 0.00005. In peeled potatoes there was no ruthenium detectable, therefore the limit of detection leads to a transfer factor ≤ 0.00001. So it is evident that ruthenium is little available for the roots of the plants. In the event of an accident in a nuclear plant the uptake of radioactive ruthenium by roots has only negligible radioecological consequences. This applies even if 50 years of ruthenium enrichment in the soil are assumed. (orig./RB)

  7. Inductively Coupled Plasma Mass Spectrometry: Sample Analysis of Zirconium and Ruthenium in Metal Organic Frameworks

    Science.gov (United States)

    2018-02-01

    linear regression fits for the calibration curves. The goodness of the linear fits are summarized in Table 3 and Figure 1. Table 3. Concentration...and ruthenium at each calibration level. 11 REFERENCES 1. General Requirements for the Competence of Testing and Calibration Laboratories

  8. Application of the chemical properties of ruthenium to decontamination processes; L'application des proprietes chimiques du ruthenium a des procedes de decontamination

    Energy Technology Data Exchange (ETDEWEB)

    Fontaine, A.; Berger, D. [Commissariat a l' Energie Atomique, Centre de Production de Plutonium, Marcoule (France). Centre d' Etudes Nucleaires

    1965-07-01

    The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [French] Les proprietes chimiques du ruthenium en solutions aqueuses nitriques et en solutions organiques de tributylphosphate, sont passees en revue. A partir de ces donnees, quelques exemples connus sont cites: ils exposent des procedes de separation ou d'elimination du ruthenium de dechets radioactifs. (auteurs)

  9. Analysis of uranium and its compounds. Ruthenium spectrographic determination

    International Nuclear Information System (INIS)

    Anon.

    Ruthenium determination in uranium and its compounds, suitable for content greater than 0.1 ppm with respect to uranium, by dissolution in sulfuric acid and addition of palladium as an internal standard, separation of the precipitated ruthenium, in the presence of gold, by reduction with zinc, the precipitate is calcined and ruthenium is determined by spectrography [fr

  10. Forefront of PUREX system engineering. Chemistry and engineering of ruthenium, technetium and neptunium

    International Nuclear Information System (INIS)

    2004-07-01

    The paper reports the activity of the research committee organized by the Atomic Energy Society of Japan on 'Ruthenium and Technetium Chemistry in the PUREX System', with focusing on basic behaviors of ruthenium, technetium and neptunium in the PUREX process, the principles of plant design, and behaviors during the final waste treatment. The scope of the work includes the following major topics: (1) basic solution and solid-state chemistry; (2) basic solution and solid-state chemistry of minor actinides in particular, Np; (3) partitioning chemistry in the PUREX system and environmental behavior of the components; (4) processes of recovery, purification, and utilization of rare metal fission products; (5) field data on plant design, operation, decontamination, and decommissioning; (6) numerical process simulations and process control technologies; (7) compilation of a data base for process chemistry and plant engineering. (S. Ohno)

  11. Scaling-resistance of ruthenium- and ruthenium phosphides powders in argon and air

    International Nuclear Information System (INIS)

    Chernogorebko, V.B.; Semenov-Kobzar', A.A.; Kulik, L.Ya.

    1976-01-01

    The thermal stability of ruthenium phosphides in air diminishes as the content of phosphorus in the compound increases. The temperatures at which active oxidation of the powders starts are as follows: Ru-600, Ru 2 P-590, RuP-390, and RuP 2 -270 0 C. The oxidation of phosphorus in the phosphides proceeds in steps. The atoms of phosphorus which are most accessible to oxygen are first oxidated. Phosphorus atoms in the octahedral spaces are oxidated less easily, simultaneously with the oxidation of the ruthenium atoms. When heated in argon, Ru 2 P and RuP fuse congruently at 1,500 and 1,555 0 C respectively, while RuP 2 dissociates at 950 0 C. (author)

  12. Experiments on the behaviour of ruthenium in air ingress accidents

    International Nuclear Information System (INIS)

    Kaerkelae, T.; Backman, Ul; Auvinen, A.; Zilliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J.

    2007-03-01

    During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In a severe accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium may oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species, it is of interest to know, how they are formed and how they behave. In our experiments the formation and transport of volatile ruthenium oxides was studied by exposing RuO2 powder to diverse oxidising atmospheres at a relatively high temperature. Transport of gaseous RuO4 was further investigated by injecting it into the facility in similar conditions. Upon cooling of the gas flow RuO2 aerosol particles were formed in the system. They were removed from the gas stream with plane filters. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close the mass balance and to achieve better time resolution seven experiment were carried out using radioactive tracer. In this report, the facility for the ruthenium behaviour study and results from experiments are presented. Preliminary conclusions from the experiments are reported as well. Final conclusions will be made after modelling of the facility is completed in a continuation work of this study. (au)

  13. Experiments on the behaviour of ruthenium in air ingress accidents

    Energy Technology Data Exchange (ETDEWEB)

    Kaerkelae, T.; Backman, Ul; Auvinen, A.; Zilliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J. [Technical Research Centre of Finland VTT (Finland)

    2007-03-15

    During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In a severe accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium may oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species, it is of interest to know, how they are formed and how they behave. In our experiments the formation and transport of volatile ruthenium oxides was studied by exposing RuO2 powder to diverse oxidising atmospheres at a relatively high temperature. Transport of gaseous RuO4 was further investigated by injecting it into the facility in similar conditions. Upon cooling of the gas flow RuO2 aerosol particles were formed in the system. They were removed from the gas stream with plane filters. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close the mass balance and to achieve better time resolution seven experiment were carried out using radioactive tracer. In this report, the facility for the ruthenium behaviour study and results from experiments are presented. Preliminary conclusions from the experiments are reported as well. Final conclusions will be made after modelling of the facility is completed in a continuation work of this study. (au)

  14. Nitrile-functionalized ruthenium nanoparticles: charge delocalization through Ru − N ≡ C interface

    International Nuclear Information System (INIS)

    Zhang, Fengqi; Huang, Lin; Zou, Jiasui; Yan, Jinwu; Zhu, Jiaying; Kang, Xiongwu; Chen, Shaowei

    2017-01-01

    Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) were stabilized by the self-assembly of nitrile molecules onto the ruthenium colloid surface by virtue of the formation of Ru−N≡C interfacial bonding linkages. Thermogravimetric analysis showed that there were about 63 nitrile ligands per nanoparticle, corresponding to an average molecular footprint of 22.4 Å 2 . Proton nuclear magnetic resonance (NMR) studies suggested an end-on configuration of the nitrile moiety on the metal core surface. Meanwhile, infrared measurements showed that the C≡N stretch red-shifted from 2246 to 1944 cm −1 upon adsorption on the nanoparticle surfaces, as confirmed by 15 N isotopic labeling. This apparent red-shift suggests extensive intraparticle charge delocalization, which was further manifested by photoluminescence measurements of 1-cyanopyrene-functionalized ruthenium nanoparticles that exhibited a red shift of 40 nm of the emission maximum, in comparison to that of free monomers. The results further highlight the significance of metal−organic contacts in the manipulation of the dynamics of intraparticle charge transfer and the nanoparticle optical and electronic properties.

  15. Studying the effect of Ruthenium on High Temperature Mechanical Properties of Nickel Based Superalloys and Determining the Universal Behavior of Ruthenium at Atomic Scale with respect to alloying elements, Stress and Temperature

    Directory of Open Access Journals (Sweden)

    Sriswaroop Dasari

    2016-10-01

    Full Text Available Any property of a material is a function of its microstructure and microstructure is a function of material composition. So, to maximize the desired properties of a material, one has to understand the evolution of microstructure which in turn is nothing but the reflection of the role of alloying elements. Research has not been done to understand the universal behavior of a certain base/alloying element. Let’s take the example of Cl- ion in HCl, we all know that in general, chloride ion can only be replaced by Fluoride or oxygen ion and that no other ion can replace it. But when you consider a metal like Ni, Co, Cr, Fe etc. there is no establishment that it behaves only in a certain way. Though I concord to the fact that discovery of universal behavior of Ni is lot complex than chloride ion, I think that future research should be focused in this direction also. Superalloys are the candidate materials required to improve thermal efficiency of a gas turbine by allowing higher turbine inlet gas temperatures. Gas turbines are the heart of local power systems, next generation jet engines and high performance space rockets. Recent research in superalloys showed that addition of some alloying elements in minor quantities can result in drastic change in properties. Such an alloying element is Ruthenium (Ru. Addition of Ruthenium to superalloys has shown improvement in mechanical properties by an order of magnitude. However reasons for such improvement are not known yet. Hence, there is a need to identify its role and discover the universal behavior of ruthenium to utilize it efficiently. In this proposal, we study materials with different compositions that are derived based on one ruthenium containing superalloy, and different thermomechanical history. Based on the evolution of microstructures and results of mechanical testing, we plan to determine the exact role of Ruthenium and prediction of its behavior with respect to other elements in the material

  16. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    DEFF Research Database (Denmark)

    Tritsaris, Georgios; Nørskov, Jens Kehlet; Rossmeisl, Jan

    2011-01-01

    We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability...... of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated....

  17. Method of suppressing evaporation loss of ruthenium

    International Nuclear Information System (INIS)

    Muromura, Tadazumi; Sato, Tadashi.

    1987-01-01

    Purpose: To prevent evaporation loss of ruthenium from liquid wastes by adding an aluminum compound upon applying evaporating and drying to solid treatment to reprocessing liquid wastes for spent fuels. Method: An aluminum compound such as aluminum nitrate or aluminum hydroxide to reprocessing liquid wastes of spent fuels such that aluminum/ruthenium mixing ratio corresponds to 1.3 - 70.0 by g/atom ratio (0.34 - 187 by weight ratio), and the liquid mixture is heated to a temperature of about 130 deg C to be evaporated and dried to solidness. This enables to recover ruthenium without settling and depositing insoluble matters in the liquid wastes and without decomposing nitric acid. (Yoshino, Y.)

  18. A method for recovering and separating palladium, technetium, rhodium and ruthenium contained in solutions resulting from nuclear fuel recycling

    International Nuclear Information System (INIS)

    Moore, R.H.

    1974-01-01

    The invention relates to a method for recovering and separating technetium and metals of the platinum group, i.e. palladium, rhodium and ruthenium existing as fission products. The method according to the invention is characterized by contacting a residuary acid aqueous solution provided by nuclear fuel recycling with successive carbon beds which have adsorbed different chelating agents specific for the metals to be recovered in order that said metals be selectively chelated and extracted from the solution. This method is suitable for recovering the above metals from solutions provided by reprocessing spent fuels [fr

  19. Synthesis and electrochemistry of tri- and tetranuclear polypyridine derivations of ruthenium

    International Nuclear Information System (INIS)

    Francis, A.M.A.

    1990-01-01

    The synthesis of clusters of ruthenium is the focus of this work. The electrochemistry of metal cluster derivatives of ruthenium, iron and osmium are reviewed. The ability of these compounds to undergo more than one electron transfer reaction and to act as electron reservoirs is evident. The synthesis and characterisation of a range of polypyridine derivatives of [Ru 3 (CO) 12 ]; [Ru 3 (CO) 10 (napy)]; [Ru 3 (CO) 10 (bipy)]; [Ru 4 H 4 (CO) 12 ]; [Ru 4 H 4 (CO) 8 (bipy) 2 ] and [Ru 4 H 4 (CO) 10 (bipy)] were dealt with. The crystal structures of [Ru 3 (CO) 10 (napy)] and [Ru 4 H 4 (CO) 10 (bipy)] were also determined. The six compounds were fully investigated and a mechanism for their electrochemical reduction was postulated based on their observed experimental data, and that of the relevant compounds. The techniques used are also described and a brief introduction to the actual theory and practise of these techniques is discussed. 132 refs., 33 figs., 22 tabs

  20. Experiments on the behaviour of ruthenium in air ingress accidents - Progress report

    International Nuclear Information System (INIS)

    Kaerkelae, T.; Backman, U.; Auvinen, A.; Ziliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J.

    2006-02-01

    During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In an accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium can oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species it is of interest to know, how it is formed and how it behaves. In our experiments RuO2 is exposed to diverse oxidising atmospheres at a relatively high temperature. In this report, the experimental system for the ruthenium behaviour study is presented. Also preliminary results from experiments carried out during year 2005 are reported. In the experiments gaseous ruthenium oxides were produced in a furnace. Upon cooling RuO2 aerosol particles were formed in the system. They were removed with plane filters from the gas stream. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close mass balance and achieve better time resolution three experiment using radioactive tracer were carried out. (au)

  1. Experiments on the behaviour of ruthenium in air ingress accidents - Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Kaerkelae, T.; Backman, U.; Auvinen, A.; Ziliacus, R.; Lipponen, M.; Kekki, T.; Tapper, U.; Jokiniemi, J. [VTT Technical Research Centre of Finland (Finland)

    2006-02-15

    During routine nuclear reactor operation, ruthenium will accumulate in the fuel in relatively high concentrations. In an accident in a nuclear power plant it is possible that air gets into contact with the reactor core. In this case ruthenium can oxidise and form volatile ruthenium species, RuO3 and RuO4, which can be transported into the containment. In order to estimate the amount of gaseous ruthenium species it is of interest to know, how it is formed and how it behaves. In our experiments RuO2 is exposed to diverse oxidising atmospheres at a relatively high temperature. In this report, the experimental system for the ruthenium behaviour study is presented. Also preliminary results from experiments carried out during year 2005 are reported. In the experiments gaseous ruthenium oxides were produced in a furnace. Upon cooling RuO2 aerosol particles were formed in the system. They were removed with plane filters from the gas stream. Gaseous ruthenium species were trapped in 1M NaOH-water solution, which is capable of trapping RuO4 totally. Ruthenium in the solution was filtered for analysis. The determination of ruthenium both in aerosol and in liquid filters was made using instrumental neutron activation analysis (INAA). In order to close mass balance and achieve better time resolution three experiment using radioactive tracer were carried out. (au)

  2. Characterization of ultrasonic spray pyrolysed ruthenium oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Patil, P.S.; Ennaoui, E.A.; Lokhande, C.D.; Mueller, M.; Giersig, M.; Diesner, K.; Tributsch, H. [Hahn-Meitner-Institut Berlin GmbH (Germany). Bereich Physikalische Chemie

    1997-11-21

    The ultrasonic spray pyrolysis (USP) technique was employed to deposit ruthenium oxide thin films. The films were prepared at 190 C substrate temperature and further annealed at 350 C for 30 min in air. The films were 0.22 {mu} thick and black grey in color. The structural, compositional and optical properties of ruthenium oxide thin films are reported. Contactless transient photoconductivity measurement was carried out to calculate the decay time of excess charge carriers in ruthenium oxide thin films. (orig.) 28 refs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Coloma Ribera, R.; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Kokke, S.; Zoethout, E. [FOM Dutch Institute for Fundamental Energy Research (DIFFER), P.O. Box 1207, 3430 BE Nieuwegein (Netherlands)

    2014-09-29

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

  4. Sequential Electrodeposition of Platinum-Ruthenium at Boron-Doped Diamond Electrodes for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Ileana González-González

    2011-01-01

    Full Text Available Sequential electrodeposition of Pt and Ru on boron-doped diamond (BDD films, in 0.5 M H2SO4 by cyclic voltammetry, has been prepared. The potential cycling, in the aqueous solutions of the respective metals, was between 0.00 and 1.00 V versus Ag/AgCl. The catalyst composites, Pt and PtRu, deposited on BDD film substrates, were tested for methanol oxidation. The modified diamond surfaces were also characterized by scanning electron microscopy-X-ray fluorescence-energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The scanning Auger electron spectroscopy mapping showed the ruthenium signal only in areas where platinum was electrodeposited. Ruthenium does not deposit on the oxidized diamond surface of the boron-doped diamond. Particles with 5–10% of ruthenium with respect to platinum exhibited better performance for methanol oxidation in terms of methanol oxidation peak current and chronoamperometric current stability. The electrogenerated •OH radicals on BDD may interact with Pt surface, participating in the methanol oxidation as shown in oxidation current and the shift in the peak position. The conductive diamond surface is a good candidate as the support for the platinum electrocatalyst, because it ensures catalytic activity, which compares with the used carbon, and higher stability under severe anodic and cathodic conditions.

  5. Nitrile-functionalized ruthenium nanoparticles: charge delocalization through Ru − N ≡ C interface

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fengqi; Huang, Lin; Zou, Jiasui [South China University of Technology, New Energy Research Institute, School of Environment and Energy, Guangzhou Higher Education Mega Centre (China); Yan, Jinwu; Zhu, Jiaying [South China University of Technology, School of Bioscience and Bioengineering, Guangzhou Higher Education Mega Centre (China); Kang, Xiongwu, E-mail: esxkang@scut.edu.cn; Chen, Shaowei, E-mail: shaowei@ucsc.edu [South China University of Technology, New Energy Research Institute, School of Environment and Energy, Guangzhou Higher Education Mega Centre (China)

    2017-03-15

    Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) were stabilized by the self-assembly of nitrile molecules onto the ruthenium colloid surface by virtue of the formation of Ru−N≡C interfacial bonding linkages. Thermogravimetric analysis showed that there were about 63 nitrile ligands per nanoparticle, corresponding to an average molecular footprint of 22.4 Å{sup 2}. Proton nuclear magnetic resonance (NMR) studies suggested an end-on configuration of the nitrile moiety on the metal core surface. Meanwhile, infrared measurements showed that the C≡N stretch red-shifted from 2246 to 1944 cm{sup −1} upon adsorption on the nanoparticle surfaces, as confirmed by {sup 15}N isotopic labeling. This apparent red-shift suggests extensive intraparticle charge delocalization, which was further manifested by photoluminescence measurements of 1-cyanopyrene-functionalized ruthenium nanoparticles that exhibited a red shift of 40 nm of the emission maximum, in comparison to that of free monomers. The results further highlight the significance of metal−organic contacts in the manipulation of the dynamics of intraparticle charge transfer and the nanoparticle optical and electronic properties.

  6. Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

    Energy Technology Data Exchange (ETDEWEB)

    Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun [Pusan National University, Busan (Korea, Republic of)

    2012-01-15

    The ruthenium(II) complex [Ru(bpy){sub 2}-(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus.

  7. Synthesis and Catalytic Hydrogen Transfer Reaction of Ruthenium(II) Complex

    International Nuclear Information System (INIS)

    Son, Jung Ik; Kim, Aram; Noh, Hui Bog; Lee, Hyun Ju; Shim, Yoon Bo; Park, Kang Hyun

    2012-01-01

    The ruthenium(II) complex [Ru(bpy) 2 -(PhenTPy)] was synthesized, and used for the transfer hydrogenation of ketones and the desired products were obtained in good yield. Based on the presented results, transition-metal complexes can be used as catalysts for a wide range of organic transformations. The relationship between the electro-reduction current density and temperature are being examined in this laboratory. Attempts to improve the catalytic activity and determine the transfer hydrogenation mechanism are currently in progress. The catalytic hydrogenation of a ketone is a basic and critical process for making many types of alcohols used as the final products and precursors in the pharmaceutical, agrochemical, flavor, fragrance, materials, and fine chemicals industries. The catalytic hydrogenation process developed by Noyori is a very attractive process. Formic acid and 2-propanol have been used extensively as hydrogenation sources. The advantage of using 2-propanol as a hydrogen source is that the only side product will be acetone, which can be removed easily during the workup process. Hydrogen transfer (HT) catalysis, which generates alcohols through the reduction of ketones, is an attractive protocol that is used widely. Ruthenium(II) complexes are the most useful catalysts for the hydrogen transfer (HT) of ketones. In this method, a highly active catalytic system employs a transition metal as a catalyst to synthesize alcohols, and is a replacement for the hydrogen-using hydrogenation process. The most active system is based on Ru, Rh and Ir, which includes a nitrogen ligand that facilitates the formation of a catalytically active hydride and phosphorus

  8. Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal-Centered Excited State in the Bond Rupture and Bond Construction Processes.

    Science.gov (United States)

    Li, Huifang; Zhang, Lisheng; Zheng, Lvyin; Li, Xun; Fan, Xiaolin; Zhao, Yi

    2016-09-26

    Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)](n+) (where tpy=2,2':6',2''-terpyridine; DMSO=dimethyl sulfoxide; L=2,2'-bipyridine (bpy), n=2; N,N,N',N'-tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal-centered ligand field ((3) MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of (3) MCS state is thermally accessible and no (3) MCO can be populated from this state, photoisomerization will be turned off because the (3) MCS excited state is expected to lead to fast radiationless decay back to the original (1) GSS ground state or photodecomposition along the Ru(2+) -S stretching coordinate. On the contrary, if the population of (3) MCS (or (3) MCO ) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal-to-ligand charge transfer excited states ((3) MLCTS →(3) MLCTO ). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d(6) transition-metal complexes, which is both experimentally and intellectually challenging as a field of study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Nanoengineering of Ruthenium and Platinum-based Nanocatalysts by Continuous-Flow Chemistry for Renewable Energy Applications

    KAUST Repository

    AlYami, Noktan Mohammed

    2017-04-15

    This thesis presents an integrated study of nanocatalysts for heterogenous catalytic and electrochemical processes using pure ruthenium (Ru) with mixed-phase and platinum-based nanomaterials synthesized by continuous-flow chemistry. There are three major challenges to the application of nanomaterials in heterogenous catalytic reactions and electrocatalytic processes in acidic solution. These challenges are the following: (i) controlling the size, shape and crystallography of nanoparticles to give the best catalytic properties, (ii) scaling these nanoparticles up to a commercial quantity (kg per day) and (iii) making stable nanoparticles that can be used catalytically without degrading in acidic electrolytes. Some crucial limitations of these nanostructured materials in energy conversion and storage applications were overcome by continuous-flow chemistry. By using a continuous-flow reactor, the creation of scalable nanoparticle systems was achieved and their functionality was modified to control the nanoparticles’ physical and chemical characteristics. The nanoparticles were also tested for long-term stability, to make sure these nanoparticles were feasible under realistic working conditions. These nanoparticles are (1) shape- and crystallography-controlled ruthenium (Ru) nanoparticles, (2) size-controlled platinum-metal (Pt-M= nickel (Ni) & copper (Cu)) nanooctahedra (while maintaining morphology) and (3) core-shell platinum@ruthenium (Pt@Ru) nanoparticles where an ultrathin ruthenium shell was templated onto the platinum core. Thus, a complete experimental validation of the formation of a scalable amount of these nanoparticles and their catalytic activity and stability towards the oxygen evolution reaction (OER) in acid medium, hydrolysis of ammonia borane (AB) along with plausible explanations were provided.

  10. Conversion of cellulose and cellobiose into sorbitol catalyzed by ruthenium supported on a polyoxometalate/metal-organic framework hybrid.

    Science.gov (United States)

    Chen, Jinzhu; Wang, Shengpei; Huang, Jing; Chen, Limin; Ma, Longlong; Huang, Xing

    2013-08-01

    Cellulose and cellobiose were selectively converted into sorbitol over water-tolerant phosphotungstic acid (PTA)/metal- organic-framework-hybrid-supported ruthenium catalysts, Ru-PTA/MIL-100(Cr), under aqueous hydrogenation conditions. The goal was to investigate the relationship between the acid/metal balance of bifunctional catalysts Ru-PTA/MIL-100(Cr) and their performance in the catalytic conversion of cellulose and cellobiose into sugar alcohols. The control of the amount and strength of acid sites in the supported PTA/MIL-100(Cr) was achieved through the effective control of encapsulated-PTA loading in MIL-100(Cr). This design and preparation method led to an appropriately balanced Ru-PTA/MIL-100(Cr) in terms of Ru dispersion and hydrogenation capacity on the one hand, and acid site density of PTA/MIL-100(Cr) (responsible for acid-catalyzed hydrolysis) on the other hand. The ratio of acid site density to the number of Ru surface atoms (nA /nRu ) of Ru-PTA/MIL-100(Cr) was used to monitor the balance between hydrogenation and hydrolysis functions; the optimum balance between the two catalytic functions, that is, 8.84sorbitol of 57.9% at complete conversion of cellulose, and 97.1% yield in hexitols with a selectivity for sorbitol of 95.1% at complete conversion of cellobiose) were obtained using a Ru-PTA/MIL-100(Cr) catalyst with loadings of 3.2 wt % for Ru and 16.7 wt % for PTA. This research thus opens new perspectives for the rational design of acid/metal bifunctional catalysts for biomass conversion. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Adsorption of aliphatic alcohols on ruthenium

    International Nuclear Information System (INIS)

    Shapovalova, L.B.; Zakumbaeva, G.D.

    1977-01-01

    The adsorption is studied of allyl-, propyl- and propargyl alcohols on a ruthenium catalyst-electrode at 20, 30 and 40 deg C in H 2 SO 4 in helium. Above adsorption has been found to grow with increased concentration of the alcohols in the solution. In solutions with the same concentration, propargyl alcohol has been noted to show highest sorptive capacity, followed by that of allyl- and propyl alcohols. With variations in the ruthenium electrode potential, alcohol adsorption occurs via maximum at potential = 0.18

  12. Characterization of self-assembled monolayers on a ruthenium surface

    NARCIS (Netherlands)

    Shaheen, Amrozia; Sturm, Jacobus Marinus; Ricciardi, R.; Huskens, Jurriaan; Lee, Christopher James; Bijkerk, Frederik

    2017-01-01

    We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on

  13. Optimization of screen-printed ruthenium dioxide electrodes for pH measurements

    International Nuclear Information System (INIS)

    Wyzkiewicz, I.

    2002-01-01

    Optimization of disposable, screen-printed pH-sensors based on ruthenium dioxide is described in this paper. The electrodes were prepared with the use of thick-film technology. The pH-sensitive layers were deposited onto polyester foil. Polymer graphite paste containing ruthenium dioxide from 0% to 90% has been investigated. The dependence of the pH-sensitive layers related to ruthenium dioxide content is presented. The investigation proved that the electrodes containing 40-60% ruthenium dioxide exhibit linear high sensitivity (∼ 50 mV/pH) in the wide range of pH (2 - 11) as well as very good reproducibility. (author)

  14. Antipyrilquinoneimine dye formation by coupling aniline derivatives with 4-aminoantipyrine in the presence of ruthenium nanoparticles

    International Nuclear Information System (INIS)

    Kasthuri, J.; Santhanalakshmi, J.; Rajendiran, N.

    2008-01-01

    The coupling of 4-aminoantipyrine with aniline derivatives catalyzed by ruthenium nanoparticles has been studied by UV-Vis spectroscopy in aqueous medium. The rate constant for antipyrilquinoneimine dye formation depends on the nature of the aniline substituent and the p H, ionic strength and temperature of the reaction medium. The maximum rate constant of the dye formation reaction is observed at p H 3.6. Aniline derivatives with electron donating substituents show higher rate constant values than those with electron withdrawing substituents, with increasing rate constant values in the order: N,N-dimethyl aniline> a-toluidine> o-chloroaniline > m-chloroaniline. With pseudo first order kinetics, the total order is 1.0 + 1.0 + 1.0 = 3.0, which includes the orders with respect to amine, 4-aminoantipyrine and ruthenium nanoparticles. Studies on these effects help to complete the kinetic analysis as well as propose the reaction pathway. Furthermore, TEM measurement confirms that the nano scalar size of the ruthenium nanoparticles is 7 nm

  15. Ruthenium(II) carbonyl compounds with the 4'-chloro-2,2':6',2''-terpyridine ligand.

    Science.gov (United States)

    Tatikonda, Rajendhraprasad; Haukka, Matti

    2017-04-01

    Two ruthenium carbonyl complexes with the 4'-chloro-2,2':6',2''-terpyridine ligand (tpy-Cl, C 15 H 10 ClN 3 ), i.e. [RuCl(tpy-Cl)(CO) 2 ][RuCl 3 (CO) 3 ] (I) [systematic name: cis -di-carbonyl-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 3 N )ruthenium(II) fac -tricarbonyltri-chlorido-ruthenate(II)], and [RuCl 2 (tpy-Cl)(CO) 2 ] (II) [ cis -dicarbonyl- trans -di-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 2 N 1 , N 1' )ruthenium(II)], were synthesized and characterized by single-crystal X-ray diffraction. The Ru II atoms in both centrosymmetric structures (I) and (II) display similar, slightly distorted octa-hedral coordination spheres. The coordination sphere in the complex cation in compound (I) is defined by three N atoms of the tridentate tpy-Cl ligand, two carbonyl carbon atoms and one chlorido ligand; the charge is balanced by an octa-hedral [Ru(CO) 3 Cl 3 ] - counter-anion. In the neutral compound (II), the tpy-Cl ligand coordinates to the metal only through two of its N atoms. The coordination sphere of the Ru II atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I) and (II), weak C-H⋯Cl inter-actions are observed.

  16. Method of removing clogging materials due to ruthenium precipitates and sealing them in device

    International Nuclear Information System (INIS)

    Hoshikawa, Tadahiro; Sasahira, Akira.

    1994-01-01

    In a facility, such as a reprocessing facility, for processing a solution containing a great amount of ruthenium, precipitates due to evaporated ruthenium and cooled NO x are brought into contact with each other to decompose the precipitates due to the evaporated ruthenium. Precipitates due to ruthenium evaporated from the solution are reacted with cooled NO x , and the precipitates of ruthenium are decomposed and returned to the solution in the form of extremely fine particles together with recycling flow from the inner wall of the device. Since the precipitates of ruthenium returned to the solution are stable, they are no more evaporated and precipitated on the inner wall of the device. In the solution processing device having a possibility of clogging, clogging can be prevented and the precipitates of ruthenium can be sealed by decomposing them. (T.M.)

  17. Ruthenium(II) tris(2,2'-bipyridine) chelate as a chemiluminophore in extrinsic lyoluminescences of aluminium and magnesium in aqueous solution

    International Nuclear Information System (INIS)

    Jiang Qinghong; Kotiranta, Miia; Langel, Kaarina; Suomi, Johanna; Hakansson, Markus; Spehar, Anna-Maria; Ala-Kleme, Timo; Eskola, Jarkko; Kulmala, Sakari

    2005-01-01

    Ruthenium(II) tris(2,2'-bipyridine) chelate shows chemiluminescence (CL) both during dissolution of metallic aluminium in alkaline conditions, and during dissolution of magnesium metal in acidic conditions. The presence of peroxodisulfate ions strongly enhances the CL. Magnesium system provides considerably better detectability of the present chelate giving linear calibration plot spanning over many orders of magnitude of concentration down to subnanomolar concentration levels. The possible primary species generated and luminescence mechanisms are shortly discussed

  18. Recent advances in the ruthenium-catalyzed hydroarylation of alkynes with aromatics: synthesis of trisubstituted alkenes.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2015-11-14

    The hydroarylation of alkynes with substituted aromatics in the presence of a metal catalyst via chelation-assisted C-H bond activation is a powerful method to synthesize trisubstituted alkenes. Chelation-assisted C-H bond activation can be done by two ways: (a) an oxidative addition pathway and (b) a deprotonation pathway. Generally, a mixture of cis and trans stereoisomeric as well as regioisomeric trisubstituted alkenes was observed in an oxidative addition pathway. In the deprotonation pathway, the hydroarylation reaction can be done in a highly regio- and stereoselective manner, and enables preparation of the expected trisubstituted alkenes in a highly selective manner. Generally, ruthenium, rhodium and cobalt complexes are used as catalysts in the reaction. In this review, a ruthenium-catalyzed hydroarylation of alkynes with substituted aromatics is covered completely. The hydroarylation reaction of alkynes with amide, azole, carbamate, phosphine oxide, amine, acetyl, sulfoxide and sulphur directed aromatics is discussed.

  19. Recent advances in the ruthenium(ii)-catalyzed chelation-assisted C-H olefination of substituted aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2017-08-08

    The transition-metal-catalyzed chelation-assisted alkenylation at the inert C-H bond of aromatics with alkenes is one of the efficient methods to synthesize substituted vinylarenes in a highly regio- and stereoselective manner. Palladium, rhodium and ruthenium complexes are frequently used as catalysts for this type of transformation. The present review describes the recent advances in the ruthenium-catalyzed chelation-assisted alkenylation at the C-H bond of aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. Several directing groups including 2-pyridyl, carbonyl, amidine, amide, amine, imidate, sulphonic acid, triazole, cyano, oxazolidinone and hydontoin are widely used in the reaction. The scope, limitation and mechanistic investigation of the alkenylation reactions are discussed elaborately. This feature article includes all the reported ruthenium-catalyzed alkenylation reactions via the deprotonation pathway until the end of March 2017.

  20. Ruthenium based redox flow battery for solar energy storage

    International Nuclear Information System (INIS)

    Chakrabarti, Mohammed Harun; Roberts, Edward Pelham Lindfield; Bae, Chulheung; Saleem, Muhammad

    2011-01-01

    Research highlights: → Undivided redox flow battery employing porous graphite felt electrodes was used. → Ruthenium acetylacetonate dissolved in acetonitrile was the electrolyte. → Charge/discharge conditions were determined for both 0.02 M and 0.1 M electrolytes. → Optimum power output of 0.180 W was also determined for 0.1 M electrolyte. → 55% voltage efficiency was obtained when battery was full of electrolytes. -- Abstract: The technical performance for the operation of a stand alone redox flow battery system for solar energy storage is presented. An undivided reactor configuration has been employed along with porous graphite felt electrodes and ruthenium acetylacetonate as electrolyte in acetonitrile solvent. Limiting current densities are determined for concentrations of 0.02 M and 0.1 M ruthenium acetylacetonate. Based on these, operating conditions for 0.02 M ruthenium acetylacetonate are determined as charging current density of 7 mA/cm 2 , charge electrolyte superficial velocity of 0.0072 cm/s (through the porous electrodes), discharge current density of 2 mA/cm 2 and discharge electrolyte superficial velocity of 0.0045 cm/s. An optimum power output of 35 mW is also obtained upon discharge at 2.1 mA/cm 2 . With an increase in the concentration of ruthenium species from 0.02 M to 0.1 M, the current densities and power output are higher by a factor of five approximately (at same superficial velocities) due to higher mass transport phenomenon. Moreover at 0.02 M concentration the voltage efficiency is better for battery full of electrolytes prior to charging (52.1%) in comparison to an empty battery (40.5%) due to better mass transport phenomenon. Voltage efficiencies are higher as expected at concentrations of 0.1 M ruthenium acetylacetonate (55% when battery is full of electrolytes and 48% when empty) showing that the all-ruthenium redox flow battery has some promise for future applications in solar energy storage. Some improvements for the

  1. Solventless synthesis of ruthenium nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    García-Peña, Nidia G. [Departmento de Tecnociencias, Universidad Nacional Autónoma de México, Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Cd. Universitaria A.P. 70-186, C.P. 04510 Coyoacán, México D.F. (Mexico); Redón, Rocío, E-mail: rredon@unam.mx [Departmento de Tecnociencias, Universidad Nacional Autónoma de México, Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Cd. Universitaria A.P. 70-186, C.P. 04510 Coyoacán, México D.F. (Mexico); Herrera-Gomez, Alberto [Estudios Avanzados del Instituto Politécnico Nacional, Campus Juriquilla, Querétaro (Mexico); Fernández-Osorio, Ana Leticia [FES-Cuautitlán, Universidad Nacional Autónoma de México, Edo. de Mexico (Mexico); Bravo-Sanchez, Mariela; Gomez-Sosa, Gustavo [Estudios Avanzados del Instituto Politécnico Nacional, Campus Juriquilla, Querétaro (Mexico)

    2015-06-15

    Graphical abstract: - Highlights: • Successful synthesis of Ru nanoparticles by a cheap, fast and solventless approach was achieved. • The zero-valent state as well as the by-product/impurity free of the mechanochemical obtained Ru nanoparticles was proven by XPS, TEM and XRD. • Compared to two other synthesis strategies, the above-mentioned synthesis was more suitable to obtain smaller particles with fewer impurities in shorter time. - Abstract: This paper presents a novel solventless method for the synthesis of zero-valent ruthenium nanoparticles Ru(0). The proposed method, although not entirely new in the nanomaterials world, was used for the first time to synthesize zero-valent ruthenium nanoparticles. This new approach has proved to be an environmentally friendly, clean, cheap, fast, and reproducible technique which employs low amounts of solvent. It was optimized through varying amounts of reducing salt on a determined quantity of precursor and measuring the effect of this variation on the average particle size obtained. The resulting products were fully characterized by powder XRD, TEM, HR-TEM, and XPS studies, all of which corroborated the purity of the nanoparticles achieved. In order to verify the advantages of our method over other techniques, we compared our nanoparticles with two common colloidal-synthesized ruthenium nanoparticles.

  2. Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

    Science.gov (United States)

    Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

    2015-12-21

    Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Density functional theory based QSAR study of ruthenium (II) antitumor drugs and their interactions with xanthine oxidoreductase

    International Nuclear Information System (INIS)

    Mondal, Paritosh; Das, Dharitri

    2013-01-01

    Transition metal containing drugs have been used intensely for their potential anticancer activities. Platinum drugs have been used successfully for the treatment of cancer. However, these drugs have severe drawbacks including unwanted side effects, drug resistance and ineffectiveness towards some of cancers. Therefore scientists are searching for new drugs to solve these problems, and Ruthenium coordination compounds have been found effective alternatives to platinum coordination drugs

  4. Ruthenium determination in new composite materials by coulometric titration with generated iron(2)

    International Nuclear Information System (INIS)

    Butakova, N.A.; Oganesyan, L.B.

    1983-01-01

    A coulometric technique is developed for ruthenium (4) titration with generated iron (2) in a mixture of hydrochloric-, sulfuric- and phosphoric acids with potentiometric and biammetric indication of the final titration point. Bi (3), Pd (2), Nb (5), Pt (4) Pb (2), Rh (3) do not interfere with the titration. Together with Ru (4) titrated are Ir (4), V (5), Au (3). The method is applied to analyze commercial samples of ruthenium dioxides, lead- and bismuth ruthenites, ruthenium pentafluorides containing 30-80% of ruthenium. The Ssub(r) values do not exceed 0.002

  5. 5' modification of duplex DNA with a ruthenium electron donor-acceptor pair using solid-phase DNA synthesis

    Science.gov (United States)

    Frank, Natia L.; Meade, Thomas J.

    2003-01-01

    Incorporation of metalated nucleosides into DNA through covalent modification is crucial to measurement of thermal electron-transfer rates and the dependence of these rates with structure, distance, and position. Here, we report the first synthesis of an electron donor-acceptor pair of 5' metallonucleosides and their subsequent incorporation into oligonucleotides using solid-phase DNA synthesis techniques. Large-scale syntheses of metal-containing oligonucleotides are achieved using 5' modified phosporamidites containing [Ru(acac)(2)(IMPy)](2+) (acac is acetylacetonato; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (3) and [Ru(bpy)(2)(IMPy)](2+) (bpy is 2,2'-bipyridine; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (4). Duplexes formed with the metal-containing oligonucleotides exhibit thermal stability comparable to the corresponding unmetalated duplexes (T(m) of modified duplex = 49 degrees C vs T(m) of unmodified duplex = 47 degrees C). Electrochemical (3, E(1/2) = -0.04 V vs NHE; 4, E(1/2) = 1.12 V vs NHE), absorption (3, lambda(max) = 568, 369 nm; 4, lambda(max) = 480 nm), and emission (4, lambda(max) = 720 nm, tau = 55 ns, Phi = 1.2 x 10(-)(4)) data for the ruthenium-modified nucleosides and oligonucleotides indicate that incorporation into an oligonucleotide does not perturb the electronic properties of the ruthenium complex or the DNA significantly. In addition, the absence of any change in the emission properties upon metalated duplex formation suggests that the [Ru(bpy)(2)(IMPy)](2+)[Ru(acac)(2)(IMPy)](2+) pair will provide a valuable probe for DNA-mediated electron-transfer studies.

  6. The determination, by atomic-absorption spectrophotometry using electrothermal atomization, of platinum, palladium, rhodium, ruthenium, and iridium

    International Nuclear Information System (INIS)

    Haines, J.; Robert, R.V.D.

    1982-01-01

    A method that involves measurement by atomic-absorption spectrophotometry using electrothermal atomization has been developed for the determination of trace quantities of platinum, palladium, rhodium, ruthenium, and iridium in mineralogical samples. The elements are separated and concentrated by fusion, nickel sulphide being used as the collector, and the analyte elements are measured in the resulting acid solution. An organic extraction procedure was found to offer no advantages over the proposed method. Mutual interferences between the five platinum-group metals examined, as well as interferences from gold, silver, and nickel were determined. The accuracy of the measurement was established by the analysis of a platinum-ore reference material. The lower limits of determination of each of the analyte elements in a sample material are as follows: platinum 1,6μg/l, palladium 0,2μg/1, rhodium 0,5μg/l, ruthenium 3μg/l, and iridium 2,5μg/l. The relative standard deviations range from 0,05 for rhodium to 0.08 for iridium. The method, which is described in detail in the Appendix, is applicable to the determination of these elements in ores, tailings, and geological materials in which the total concentration of the noble metals is less than 1g/t

  7. Removal of fission product ruthenium from purex process solutions: thiourea as complexing agent

    International Nuclear Information System (INIS)

    Floh, B.; Abrao, A.

    1980-01-01

    A new method for the treatment of spent uranium fuel is presented. It is based on the Purex Process using thiourea to increase the ruthenium decontamination factor. Thiourea exhibits a strong tendency for the formation of coordination compounds in acidic media. This tendency serves as a basis to transform nitrosyl-ruthenium species into Ru /SC(NH)(NH 2 )/ 2+ and Ru /SC(NH)(NH 2 )/ 3 complexes which are unextractable by TBP-varsol. The best conditions for the ruthenium-thiourea complex formation were found to be: thiourea-ruthenium ratio (mass/mass) close to 42, at 75 0 C, 30 minutes reaction time and aging period of 60 minutes. The ruthenium decontamination factor for a single uranium extraction are ca. 80-100, not interfering with extraction of actinides. These values are rather high in comparison to those obtained using the conventional Purex Process (e.g. F.D. sub(Ru)=10). By this reason the method developed here is suitable for the treatment of spent uranium fuels. Thiourea (100g/l) scrubbing experiments of ruthenium, partially co-extracted with actinides, confirmed the possibility of its removal from the extract. A decontamination greater than 83,5% for ruthenium as fission product is obtained in two stages with this procedure. (Author) [pt

  8. Ruthenium nanocatalysis on redox reactions.

    Science.gov (United States)

    Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

    2013-07-01

    Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

  9. Electrochemical oxidation of phenol in a parallel plate reactor using ruthenium mixed metal oxide electrode

    Energy Technology Data Exchange (ETDEWEB)

    Yavuz, Yusuf [Anadolu Universitesi, Cevre Sor. Uyg. ve Aras. Merkezi, Eskisehir (Turkey); Koparal, A. Savas [Anadolu Universitesi, Cevre Sor. Uyg. ve Aras. Merkezi, Eskisehir (Turkey)]. E-mail: askopara@anadolu.edu.tr

    2006-08-21

    In this study, electrochemical oxidation of phenol was carried out in a parallel plate reactor using ruthenium mixed metal oxide electrode. The effects of initial pH, temperature, supporting electrolyte concentration, current density, flow rate and initial phenol concentration on the removal efficiency were investigated. Model wastewater prepared with distilled water and phenol, was recirculated to the electrochemical reactor by a peristaltic pump. Sodium sulfate was used as supporting electrolyte. The Microtox'' (registered) bioassay was also used to measure the toxicity of the model wastewater during the study. As a result of the study, removal efficiency of 99.7% and 88.9% were achieved for the initial phenol concentration of 200 mg/L and chemical oxygen demand (COD) of 480 mg/L, respectively. In the same study, specific energy consumption of 1.88 kWh/g phenol removed and, mass transfer coefficient of 8.62 x 10{sup -6} m/s were reached at the current density of 15 mA/cm{sup 2}. Electrochemical oxygen demand (EOD), which can be defined as the amount of electrochemically formed oxygen used for the oxidation of organic pollutants, was 2.13 g O{sub 2}/g phenol. Electrochemical oxidation of petroleum refinery wastewater was also studied at the optimum experimental conditions obtained. Phenol removal of 94.5% and COD removal of 70.1% were reached at the current density of 20 mA/cm{sup 2} for the petroleum refinery wastewater.

  10. Application of the chemical properties of ruthenium to decontamination processes

    International Nuclear Information System (INIS)

    Fontaine, A.; Berger, D.

    1965-01-01

    The chemical properties of ruthenium in the form of an aqueous solution of the nitrate and of organic tributylphosphate solution are reviewed. From this data, some known examples are given: they demonstrate the processes of separation or of elimination of ruthenium from radioactive waste. (authors) [fr

  11. Graphene/Ruthenium Active Species Aerogel as Electrode for Supercapacitor Applications.

    Science.gov (United States)

    Gigot, Arnaud; Fontana, Marco; Pirri, Candido Fabrizio; Rivolo, Paola

    2017-12-30

    Ruthenium active species containing Ruthenium Sulphide (RuS₂) is synthesized together with a self-assembled reduced graphene oxide (RGO) aerogel by a one-pot hydrothermal synthesis. Ruthenium Chloride and L-Cysteine are used as reactants. The hydrothermal synthesis of the innovative hybrid material occurs at 180 °C for 12 h, by using water as solvent. The structure and morphology of the hybrid material are fully characterized by Raman, XRD, XPS, FESEM and TEM. The XRD and diffraction pattern obtained by TEM display an amorphous nanostructure of RuS₂ on RGO crystallized flakes. The specific capacitance measured in planar configuration in 1 M NaCl electrolyte at 5 mV s -1 is 238 F g -1 . This supercapacitor electrode also exhibits perfect cyclic stability without loss of the specific capacitance after 15,000 cycles. In summary, the RGO/Ruthenium active species hybrid material demonstrates remarkable properties for use as active material for supercapacitor applications.

  12. Assessing Rare Metal Availability Challenges for Solar Energy Technologies

    Directory of Open Access Journals (Sweden)

    Leena Grandell

    2015-08-01

    Full Text Available Solar energy is commonly seen as a future energy source with significant potential. Ruthenium, gallium, indium and several other rare elements are common and vital components of many solar energy technologies, including dye-sensitized solar cells, CIGS cells and various artificial photosynthesis approaches. This study surveys solar energy technologies and their reliance on rare metals such as indium, gallium, and ruthenium. Several of these rare materials do not occur as primary ores, and are found as byproducts associated with primary base metal ores. This will have an impact on future production trends and the availability for various applications. In addition, the geological reserves of many vital metals are scarce and severely limit the potential of certain solar energy technologies. It is the conclusion of this study that certain solar energy concepts are unrealistic in terms of achieving TW scales.

  13. Extraction of ruthenium thiocyanate and its separation from rhodium by polyurethane foam

    International Nuclear Information System (INIS)

    Al-Bazi, S.J.; Chow, A.

    1984-01-01

    Conditions for the formation and extraction of the thiocyanate complex of ruthenium are reported. Distribution coefficients of more than 10 4 and a capacity of about 0.24 mole per kg of foam were obtained. The effect of the chloride salts of various univalent cations on the extraction of Ru(SCN) 6 3- indicated that the efficiency of ruthenium extraction depends on how well the cation fits into the polyether segment of the polyurethane foam, which agrees with the 'cation-chelation' mechanism. The separation of ruthenium and rhodium indicated that more than 95% of the rhodium remained in the aqueous phase and about 95% of the ruthenium was retained by the polyurethane foam and could be easily recovered. (author)

  14. Hydrothermal synthesis and physicochemical properties of ruthenium(0) nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Dikhtiarenko, A., E-mail: dikhtiarenkoalla@uniovi.es [Departamento de Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Khainakov, S.A.; Garcia, J.R.; Gimeno, J. [Departamento de Quimica Organica e Inorganica, Universidad de Oviedo - CINN, 33006 Oviedo (Spain); Pedro, I. de; Fernandez, J. Rodriguez [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Blanco, J.A. [Departamento de Fisica, Universidad de Oviedo, 33007 Oviedo (Spain)

    2012-09-25

    Highlights: Black-Right-Pointing-Pointer Ruthenium nanoparticles were synthesized by hydrothermal technique. Black-Right-Pointing-Pointer The average size of the nanoparticles are depend on the reducing agent used. Black-Right-Pointing-Pointer The magnetic response seems to be dominated by a paramagnetic contribution characteristic of the band electronic magnetism of the ruthenium(0) nanoparticles. - Abstract: The synthesis of ruthenium nanoparticles in hydrothermal conditions using mild reducing agents (succinic acid, ascorbic acid and sodium citrate) is reported. The shape of the nanoparticles depends on the type of the reducing agent, while the size is more influenced by the pH of the medium. The magnetic response seems to be dominated by a paramagnetic contribution characteristic of the band electronic magnetism of the nanoparticles.

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

    NARCIS (Netherlands)

    Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Kokke, S.; Zoethout, E.; Yakshin, Andrey; Bijkerk, Frederik

    2014-01-01

    A mixed 2D (film) and 3D (nano-column) growth of ruthenium oxide has been experimentally observed for thermally oxidized polycrystalline ruthenium thin films. Furthermore, in situ x-ray reflectivity upon annealing allowed the detection of 2D film growth as two separate layers consisting of low

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

    International Nuclear Information System (INIS)

    Rard, J.A.

    1987-11-01

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

  17. Hazards and control of ruthenium in the nuclear fuel cycle

    International Nuclear Information System (INIS)

    Eichholz, G.G.

    1978-01-01

    A review is presented of present information on the possible hazards of radioruthenium in the nuclear fuel cycle and its behaviour in nuclear operations and in the environment. The subject is dealt with under the following headings: basic chemical and nuclear properties of ruthenium; chemistry (including the ruthenium-nitric acid system, electrochemistry, extraction processes); ruthenium toxicity; generation of radioruthenium (fallout sources, reactor sources, fuel reprocessing operations); waste treatment (cementation and bitumenization, calcining processes, vitrification); movement in the environment (movement of airborne effluents, liquid effluents and the freshwater environment, marine environment, bottom sediments, marine organisms, terrestrial environments, uptake in vegetation and animals); conclusion. (U.K.)

  18. Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes

    Science.gov (United States)

    Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz

    2017-06-01

    The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

  19. Ruthenium sulfoxides structure and reactivity with nitrogen heterocyclic bases

    International Nuclear Information System (INIS)

    Oliveira, Denise de.

    1990-01-01

    Ruthenium (II) sulfoxides are compounds of great interest in oxidative catalysis and in chemotherapy. In order to contribute for the understanding of the chemistry and electronic structure of this class of compounds, it has been studied a series of [Ru Cl 2 (S-DMSO) 2 L x ] complexes, where x = 1 (polymeric compounds) or 2 (monomers) and L N-heterocyclic ligands (pyridine, pyrazine and imidazole derivatives). The nature of N-heterocyclic ligand and their coordination are of great relevance to the stability, spectroscopic and electrochemical characteristics of the complexes. The trans-interactions are extremely important in this series, influencing the strength of the Ru(II)-> S-DMSO and Ru(II)-> L π-back donation. The DMSO and L ligands are π-acceptors. The metal-> ligand π-back donation is strengthened when the ligand is trans to chloride, which is π-donor, due to trans-cooperative interactions of the type: π-donor -> Ru(II) π-acceptor. Another interesting aspect in the series of [Ru Cl 2 (S-DMSO) 2 L 2 ] complexes is the occurrence of dissociative equilibria in the solution, due to the existence of three types of ligands. It was observed that the trans-N isomer of 2,6-dimethyl pyrazine derivative undergoes thermal substitution, with preferential liabilization of the N-heterocyclic ligand. Chloride ion is the most inert ligand in this complex. (author). 145 refs., 76 figs., 21 tabs

  20. Ruthenium nitrosyl complexes in radioactive waste solutions in reprocessing plants. Pt. 3

    International Nuclear Information System (INIS)

    Blasius, E.; Mueller, K.

    1984-01-01

    With capillary isotachophoresis and free-flow isotachophoresis it is possible to separate and isolate preparatively the mononuclear cationic ruthenium nitrosyl nitrato complexes. The behaviour of these complexes during storage, concentration and calcination is studied: The conversion of six ruthenium nitrosyl nitrato complexes as a function of time is studied at -36 0 C, 0 0 C, +3 0 C and 100 0 C. The percentage of ruthenium nitrosyl complexes with NO 3 - as ligand increased markedly during concentration experiments. Above 250 0 C NOsub(x) is liberated and the colour of the residue changes from brown to brownish-grey. At 400 0 C ruthenium complexes are no longer detected and the inner walls of the apparatus are covered with RuO 2 . (orig.)

  1. Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling.

    Science.gov (United States)

    Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo; Li, Chao-Jun

    2017-12-01

    Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

  2. Processing of radioactive ruthenium with aluminosilicate gels

    International Nuclear Information System (INIS)

    Kanno, Takuji; Ichinose, Yasuhiro; Ito, Katsuo

    1979-01-01

    Coprecipitation of radioactive Ru with hydroxides has been studied for the purpose of the management of the high level waste from the nuclear fuel reprocessing. Aluminosilicate gel used as coprecipitant was prepared by addition of aqueous sodium hydroxide to sodium aluminate-sodium silicate solution containing ruthenium nitrate. Ruthenium quantitatively precipitates under the conditions, aluminate > 4 x 10 -2 M, Al/Si 0 C. However, volatilization rate of Ru is suppressed by coating with mullite phase into which aluminosilicate gel transformes above 900 0 C. The amount of Ru volatilized in Ar-flow was reduced to about 10% of that in air-flow. (author)

  3. Complexes of natural carbohydrates with metal cations

    International Nuclear Information System (INIS)

    Alekseev, Yurii E; Garnovskii, Alexander D; Zhdanov, Yu A

    1998-01-01

    Data on the interaction of natural carbohydrates (mono-, oligo-, and poly-saccharides, amino sugars, and natural organic acids of carbohydrate origin) with metal cations are surveyed and described systematically. The structural diversity of carbohydrate metal complexes, caused by some specific features of carbohydrates as ligands, is demonstrated. The influence of complex formation on the chemical properties of carbohydrates is discussed. It is shown that the formation of metal complexes plays an important role in the configurational and conformational analysis of carbohydrates. The practical significance of the coordination interaction in the series of carbohydrate ligands is demonstrated. The bibliography includes 571 references.

  4. Mesoporous Transition Metal Oxides for Supercapacitors

    OpenAIRE

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are result...

  5. Ruthenium release from thermally overheated nitric acid solution containing ruthenium nitrosyl nitrate and sodium nitrate to solidify

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, Kayo; Ueda, Yasuyuki; Enokida, Youichi [Nuclear Chemical Engineering Laboratory, Nagoya University, Nagoya 4648603 (Japan)

    2016-07-01

    Radioactive ruthenium (Ru) is one of the dominant elemental species released into the environment from a fuel reprocessing plant in a hypothetical design accident due to its relatively higher fission yield and longer half-life. After the hypothetical accident assuming the loss of all electric power and cooling functions, high-level liquid waste (HLLW) may be overheated by the energetic decays of many fission products in it, and Ru may be oxidized to the volatile tetroxide, RuO{sub 4}, which is released through the off-gas pathway. At a reprocessing plant in Japan, alkaline solution from the solvent scrubbing stream is sometimes mixed with the HLLW followed by vitrification, which can be influenced by the addition of sodium nitrate to a simulated HLLW containing ruthenium nitrosyl nitrate that was experimentally evaluated on a small scale using the overheated nitric acid solution of 2 mol/dm{sup 3}, which was kept at 180 Celsius degrees in a glass evaporator placed in a thermostatic bath. The release fraction of Ru increased by approximately 30% by the addition of sodium nitrate. This may be partially explained by the existence of relatively highly concentrated nitrate ions in the liquid phase that oxidize the ruthenium species to RuO{sub 4} during the drying process. (authors)

  6. Behavior of ruthenium, cesium and antimony in high temperature processes for waste conditioning

    International Nuclear Information System (INIS)

    Klein, M.; Weyers, C.; Goossens, W.R.A.

    1985-01-01

    The fission products and the actinides of high level radioactive liquid wastes can be immobilized by incorporation into a glass matrix prior to disposal. The behaviour of so-called semi-volatile products during the vitrification process has been studied by the C.E.N./S.C.K. in Mol since 1979 in the framework of a contract with DWK of Germany in support to the HAW technological program PAMELA. The experiments were performed on laboratory and semi-pilot scale using simulated LEWC solutions tagged with radioisotopes of three suspected volatile fission products, namely ruthenium, cesium and antimony. The releases of these semi-volatile compounds to the off-gases have been investigated for a liquid fed melter as a function of the operational conditions. The study of a wet purification system, comprising in series of a dust scrubber, a condensor, an ejector venturi and an NOsub(x) column, has shown that cesium appears to be the reference isotope for the volatile elements released from the melter. Ruthenium seems not to be a problem from the point of view of gas purification although local radiation problems caused by deposits on metal surfaces cannot be excluded. (Auth.)

  7. Towards PSII analogs driven by ruthenium photophysics

    International Nuclear Information System (INIS)

    Olsson, Jerry

    2002-01-01

    A number of model complexes have been prepared in an attempt to develop models for photosystem II (PSII) in green plants. As replacement for the chlorophyll photosensitizer, we have used Ru(ll) tris-2,2-bipyridyl or Ru(ll) bis-2,2';6',2 - terpyridyl complexes linked to a pendant 2,2'-bipyridyl or 2,2';6',2''-terpyridyl moieties via spacers of varying lengths. Manganese (ll) has been covalently linked to the pendant 2,2'-bipyridyl /2,2';6',2''-terpyridyl moieties. The use of different ruthenium centres and spacers has made it possible to make assumptions about the way and how easily manganese is coordinated through self-assembly to the pendant 2,2'-bipyridyl or 2,2';6',2''-terpyridyl groups. Several polynuclear complexes containing a photoactive centre (Ru(ll) tris-2,2'-bipyridine or Ru(ll) bis-2,2';6',2''-terpyridine) or other metal ions (Co 2+ , Fe 2+ , Mn 2= ) have been prepared and characterised. The main work has been focused on organic synthesis and characterisation of polypyridine ligands and coordinated to different metal centres. The complexes have been investigated electrochemically and photophysically. Several new phenol-based ligands have been prepared by organic synthetic methods and characterised by various different methods. (author)

  8. Method of improving the decontaminating efficiency of ruthenium in evaporating treatment of nitric acid

    International Nuclear Information System (INIS)

    Kubota, Kanya; Yamana, Hajime; Takeda, Seiichiro.

    1984-01-01

    Purpose: To significantly improve the ruthenium removing efficiency in a nitric acid solution in an acid recovery system for the recovery of nitric acid from nitric acid liquid wastes through evaporating condensation. Method: Upon evaporating treatment of nitric acid solution containing ruthenium by supplying and heating the solution to a nitric acid evaporating device, hydrazine is previously added to the nitric acid solution. Hydrazine and intermediate reaction product of hydrazine such as azide causes a reduction reaction with intermediate reaction product of ruthenium tetraoxide to suppress the oxidation of ruthenium and thereby improve the decontaminating efficiency of ruthenium. The amount of hydrazine to be added is preferably between 20 - 500 mg/l and most suitably between 200 - 2000 mg/l per one liter of the liquid in the evaporating device. (Seki, T.)

  9. Catalytic Ammonia Decomposition Over Ruthenium Nanoparticles Supported on Nano-Titanates

    DEFF Research Database (Denmark)

    Klerke, Asbjørn; Klitgaard, Søren Kegnæs; Fehrmann, Rasmus

    2009-01-01

    Nanosized Na2Ti3O7, K2Ti6O13 and Cs2Ti6O13 materials were prepared and used as supports of ruthenium nanoparticles for catalytic ammonia decomposition. It is shown that these catalysts exhibit higher catalytic activity than ruthenium supported on TiO2 nanoparticles promoted with cesium. The diffe...

  10. Molecular mass spectrometry in metallodrug development: A case of mapping transferrin-mediated transformations for a ruthenium(III) anticancer drug

    Energy Technology Data Exchange (ETDEWEB)

    Jarosz, Maciej [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Matczuk, Magdalena, E-mail: mmatczuk@ch.pw.edu.pl [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Pawlak, Katarzyna [Chair of Analytical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego St. 3, 00-664 Warsaw (Poland); Timerbaev, Andrei R. [Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Kosygin St. 19, 119991 Moscow (Russian Federation)

    2014-12-03

    Highlights: • Extra- and intra-cellular interactions of Ru(III) anticancer drug candidate. • ESI-TOF-MS mapping of the ruthenium species bound to transferring. • ESI-QqQ-MS identification of released Ru species under cytosol simulated conditions. - Abstract: Electrospray ionization mass spectrometry (ESI-MS) techniques have been used to characterize the speciation of a Ru(III) anticancer drug, indazolium trans-[tetrachloridobis(1H-indazole) ruthenate(III)], upon its binding to transferrin and the impact of cellular reducing components on drug–transferrin adducts. Using time-of-flight ESI-MS, the polymorphism of apo- (iron-free) and holo-form (iron-saturated) of the protein was confirmed. While the ruthenium moieties bound to each of five isoforms under simulated extracellular conditions are essentially identical in numbers for apo- and holo-transferrin, distinct differences were found in the composition of Ru(III) species attached to either of the protein forms, which are dominated by differently coordinated aquated complexes. On the other hand, at least one of the Ru-N bonds in metal-organic framework remains intact even after prolonged interaction with the protein. Triple quadrupole tandem ESI-MS measurements demonstrated that the ruthenium species released from drug adducts with holo-transferrin in simulated cancer cytosol are underwent strong ligand exchange (as compared to the protein-bound forms) but most strikingly, they contain the metal center in the reduced Ru(II) state. In vitro probing the extra- and intracellular interactions of promising Ru(III) drug candidate performed by ESI-MS is thought to shed light on the transportation to tumor cells by transferrin and on the activation to more reactive species by the reducing environment of solid tumors.

  11. Ruthenium-Catalyzed Aerobic Oxidation of Amines.

    Science.gov (United States)

    Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

    2018-01-18

    Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Leaching Properties of Naturally Occurring Heavy Metals from Soils

    Science.gov (United States)

    Zhang, M.; Hoshino, M.; Yoshikawa, M.; Hara, J.; Sugita, H.

    2014-12-01

    The major threats to human health from heavy metals are associated with exposure to arsenic, lead, cadmium, chromium, mercury, as well as some other elements. The effects of such heavy metals on human health have been extensively studied and reviewed by international organizations such as WHO. Due to their toxicity, heavy metal contaminations have been regulated by national environmental standards in many countries, and/or laws such as the Soil Contamination Countermeasures Act in Japan. Leaching of naturally occurring heavy metals from the soils, especially those around abandoned metal mines into surrounding water systems, either groundwater or surface water systems, is one of the major pathways of exposure. Therefore, understanding the leaching properties of toxic heavy metals from naturally polluted soils is of fundamentally importance for effectively managing abandoned metal mines, excavated rocks discharged from infrastructure constructions such as tunneling, and/or selecting a pertinent countermeasure against pollution when it is necessary. In this study, soil samples taken from the surroundings of abandoned metal mines in different regions in Japan were collected and analyzed. The samples contained multiple heavy metals such as lead, arsenic and chromium. Standard leaching test and sequential leaching test considering different forms of contaminants, such as trivalent and pentavalent arsenics, and trivalent and hexavalent chromiums, together with standard test for evaluating total concentration, X-ray Fluorescence Analysis (XRF), X-ray diffraction analysis (XRD) and Cation Exchange Capacity (CEC) tests were performed. In addition, sequential leaching tests were performed to evaluate long-term leaching properties of lead from representative samples. This presentation introduces the details of the above experimental study, discusses the relationships among leaching properties and chemical and mineral compositions, indicates the difficulties associated with

  13. Recommendation of ruthenium source for sludge batch flowsheet studies

    Energy Technology Data Exchange (ETDEWEB)

    Woodham, W. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-09-13

    Included herein is a preliminary analysis of previously-generated data from sludge batches 7a, 7b, 8, and 9 sludge simulant and real-waste testing, performed to recommend a form of ruthenium for future sludge batch simulant testing under the nitric-formic flowsheet. Focus is given to reactions present in the Sludge Receipt and Adjustment Tank cycle, given that this cycle historically produces the most changes in chemical composition during Chemical Process Cell processing. Data is presented and analyzed for several runs performed under the nitric-formic flowsheet, with consideration given to effects on the production of hydrogen gas, nitrous oxide gas, consumption of formate, conversion of nitrite to nitrate, and the removal and recovery of mercury during processing. Additionally, a brief discussion is given to the effect of ruthenium source selection under the nitric-glycolic flowsheet. An analysis of data generated from scaled demonstration testing, sludge batch 9 qualification testing, and antifoam degradation testing under the nitric-glycolic flowsheet is presented. Experimental parameters of interest under the nitric-glycolic flowsheet include N2O production, glycolate destruction, conversion of glycolate to formate and oxalate, and the conversion of nitrite to nitrate. To date, the number of real-waste experiments that have been performed under the nitric-glycolic flowsheet is insufficient to provide a complete understanding of the effects of ruthenium source selection in simulant experiments with regard to fidelity to real-waste testing. Therefore, a determination of comparability between the two ruthenium sources as employed under the nitric-glycolic flowsheet is made based on available data in order to inform ruthenium source selection for future testing under the nitric-glycolic flowsheet.

  14. C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

    Science.gov (United States)

    Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

    2013-04-17

    We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

  15. Device for separating ruthenium ion from spent fuel material

    International Nuclear Information System (INIS)

    Izumida, Tatsuo; Sasahira, Akira; Ozawa, Yoshihiro; Kawamura, Fumio.

    1988-01-01

    Purpose: To separate plutonium ions efficiently and selectively from organic solvent containing tributyl phosphate used in the main step of reprocessing process. Constitution: The device comprises, as the main constituent factor, a liquid-liquid contact device for bringing not water soluble organic solvent into contact with a nitric acid solution of spent fuel substances and a liquid-liquid contact-separation device for bringing an organic solvent solution containing spent fuel substances separated with nitric acid into contact again with nitric acid. Then, a device is disposed between two liquid-liquid contact devices for staying ruthenium ions and organic solvent for a sufficient time. In this way, ruthenium ions in the organic solvent containing butyl phosphate are gradually converted into complex compounds combined with tributyl phosphate thereby enabling to separate ruthenium ions efficiently and remarkably reduce the corrosion of equipments. (Horiuchi, T.)

  16. Electronic state of ruthenium deposited onto oxide supports: An XPS study taking into account the final state effects

    International Nuclear Information System (INIS)

    Larichev, Yurii V.; Moroz, Boris L.; Bukhtiyarov, Valerii I.

    2011-01-01

    The electronic state of ruthenium in the supported Ru/EO x (EO x = MgO, Al 2 O 3 or SiO 2 ) catalysts prepared by with the use of Ru(OH)Cl 3 or Ru(acac) 3 (acac = acetylacetonate) and reduced with H 2 at 723 K is characterized by X-ray photoelectron spectroscopy (XPS) in the Ru 3d, Cl 2p and O 1s regions. The influence of the final state effects (the differential charging and variation of the relaxation energy) on the binding energy (BE) of Ru 3d 5/2 core level measured for supported Ru nanoparticles is estimated by comparison of the Fermi levels and the modified Auger parameters determined for the Ru/EO x samples with the corresponding characteristics of the bulk Ru metal. It is found that the negative shift of the Ru 3d 5/2 peak which is observed in the spectrum of ruthenium deposited onto MgO (BE = 279.5-279.7 eV) with respect to that of Ru black (BE = 280.2 eV) or ruthenium supported on γ-Al 2 O 3 and SiO 2 (BE = 280.4 eV) is caused not by the transfer of electron density from basic sites of MgO, as considered earlier, but by the differential charging of the supported Ru particles compared with the support surface. Correction for the differential charging value reveals that the initial state energies of ruthenium in the Ru/EO x systems are almost identical (BE = 280.5 ± 0.1 eV) irrespectively of acid-base properties of the support, the mean size of supported Ru crystallites (within the range of 2-10 nm) and the surface Cl content. The results obtained suggest that the difference in ammonia synthesis activity between the Ru catalysts supported on MgO and on the acidic supports is accounted for by not different electronic state of ruthenium on the surface of these oxides but by some other reasons.

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

    Science.gov (United States)

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

    2016-04-19

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

  18. 环戊二烯基钌配合物催化的高选择性苯乙炔二聚反应%HIGHLY SELECTIVE CATALYTIC DIMERIZATION OF PHENYLACETYLENE BY CYCLOPENTADIENYL RUTHENIUM COMPLEXES

    Institute of Scientific and Technical Information of China (English)

    金军挺; 黄吉玲; 陶晓春; 钱延龙

    1999-01-01

    @@ Transition metal vinylidene complexes (M=C=CHR) have attracted a great deal of attention in recent years as a new type of organometallic intermediates that may have unusual reactivity[1]. Their reactivity has been explored and their application to organic synthesis is developed[2]. Recent reports on the ruthenium-vinylidene complexes[3]suggest that the reaction of ruthenium-vinylidene complexes with a base generates the coordinatively unsaturated ruthenium acetylide species, which are involved in a number of catalytic and stoichiometric reactions of alkynes. For example,the coordinatively unsaturated ruthenium acetylide species C5Me5Ru(PPh3)-C≡CPh,formed from the reaction of the vinylidene complex C5Me5Ru(PPh3) (Cl)=C=CHPh with a base was reactive toward a variety of small molecules and active in catalytic dimerization of terminal alkynes[4]. The dimerization of terminal alkyne is an effective method of forming enynes, but its synthetic application in organic synthesis has been limited dueto low selectivity for dimeric products[5]. In this communication, we report that three ruthenium complexes were used as catalysts for the highly selective dimerization of phenylacetylene.

  19. Some thermophysical properties of ruthenium in the neighbourhood of the melting point

    International Nuclear Information System (INIS)

    Sheindlin, A.E.; Kats, S.A.; Berezin, B.Ya.; Chekhovskoy, V.Ya.; Kenisarin, M.M.

    1975-01-01

    The technique of levitation calorimetry has been used to study for the first time thermophysical properties of ruthenium in the neighbourhood of the melting point. To measure enthalpy a copper block calorimeter with an istohermal jacket has been used. Basing on the values measured the equations for enthalpy of solid and liquid ruthenium within the temperature ranges of 2,270-2,607 K and 2,607-2,760 K respectively have been obtained by the least squares method. In addition the melting temperature of ruthenium and its brightness temperature at the melting point, the wavelength being 0.65 micron, have been measured. The results of the measurements have been used to calculate the heat and entropy of fusion, the specific heat of solid and that of liquid ruthenium and its normal spectral emissivity at the melting point

  20. High temperature behavior of metallic inclusions in uranium dioxide

    International Nuclear Information System (INIS)

    Yang, R.L.

    1980-08-01

    The object of this thesis was to construct a temperature gradient furnace to simulate the thermal conditions in the reactor fuel and to study the migration of metallic inclusions in uranium oxide under the influence of temperature gradient. No thermal migration of molybdenum and tungsten inclusions was observed under the experimental conditions. Ruthenium inclusions, however, dissolved and diffused atomically through grain boundaries in slightly reduced uranium oxide. An intermetallic compound (probably URu 3 ) was formed by reaction of Ru and UO/sub 2-x/. The diffusivity and solubility of ruthenium in uranium oxide were measured

  1. Partitioning of rhodium and ruthenium between Pd–Rh–Ru and (Ru,Rh)O{sub 2} solid solutions in high-level radioactive waste glass

    Energy Technology Data Exchange (ETDEWEB)

    Sugawara, Toru, E-mail: toru@gipc.akita-u.ac.jp [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Ohira, Toshiaki [Center for Engineering Science, Akita University, 1-1, Tegatagakuenmachi, Akita City, Akita 010-8502 (Japan); Komamine, Satoshi; Ochi, Eiji [Research and Development Department, Reprocessing Business Division, Japan Nuclear Fuel Limited, 4-108, Okitsuke, Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

    2015-10-15

    The partitioning of rhodium and ruthenium between Pd–Rh–Ru alloy with a face-centered cubic (FCC) structure and (Ru,Rh)O{sub 2} solid solution has been investigated between 1273 and 1573 K at atmospheric oxygen fugacity. The rhodium and ruthenium contents in FCC increase, while the RhO{sub 2} content in (Ru,Rh)O{sub 2} 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)O{sub 2} 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.

  2. Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

    Science.gov (United States)

    Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

    2016-01-01

    The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

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

    Science.gov (United States)

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

    2016-01-01

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

  4. Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN3–Pincer Ligand Containing a Phenanthroline Backbone

    KAUST Repository

    Li, Huaifeng; Wang, Yuan; Lai, Zhiping; Huang, Kuo-Wei

    2017-01-01

    Selective catalytic hydrogenation of aromatic compounds is extremely challenging using transition-metal catalysts. Hydrogenation of arenols to substituted tetrahydronaphthols or cyclohexanols has been reported only with heterogeneous catalysts. Herein, we demonstrate the selective hydrogenation of arenols to the corresponding tetrahydronaphthols or cyclohexanols catalyzed by a phenanthroline-based PN3-ruthenium pincer catalyst.

  5. Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus–Nitrogen PN3–Pincer Ligand Containing a Phenanthroline Backbone

    KAUST Repository

    Li, Huaifeng

    2017-05-30

    Selective catalytic hydrogenation of aromatic compounds is extremely challenging using transition-metal catalysts. Hydrogenation of arenols to substituted tetrahydronaphthols or cyclohexanols has been reported only with heterogeneous catalysts. Herein, we demonstrate the selective hydrogenation of arenols to the corresponding tetrahydronaphthols or cyclohexanols catalyzed by a phenanthroline-based PN3-ruthenium pincer catalyst.

  6. Sweetening ruthenium and osmium: organometallic arene complexes containing aspartame.

    Science.gov (United States)

    Gray, Jennifer C; Habtemariam, Abraha; Winnig, Marcel; Meyerhof, Wolfgang; Sadler, Peter J

    2008-09-01

    The novel organometallic sandwich complexes [(eta(6)-p-cymene)Ru(eta(6)-aspartame)](OTf)(2) (1) (OTf = trifluoromethanesulfonate) and [(eta(6)-p-cymene)Os(eta(6)-aspartame)](OTf)(2) (2) incorporating the artificial sweetener aspartame have been synthesised and characterised. A number of properties of aspartame were found to be altered on binding to either metal. The pK(a) values of both the carboxyl and the amino groups of aspartame are lowered by between 0.35 and 0.57 pH units, causing partial deprotonation of the amino group at pH 7.4 (physiological pH). The rate of degradation of aspartame to 3,6-dioxo-5-phenylmethylpiperazine acetic acid (diketopiperazine) increased over threefold from 0.12 to 0.36 h(-1) for 1, and to 0.43 h(-1) for 2. Furthermore, the reduction potential of the ligand shifted from -1.133 to -0.619 V for 2. For the ruthenium complex 1 the process occurred in two steps, the first (at -0.38 V) within a biologically accessible range. This facilitates reactions with biological reductants such as ascorbate. Binding to and activation of the sweet taste receptor was not observed for these metal complexes up to concentrations of 1 mM. The factors which affect the ability of metal-bound aspartame to interact with the receptor site are discussed.

  7. Synthesis, spectroscopic studies and reactivity of triphenylphosphine ruthenium (II) complexes with N-heterocyclic ligands

    International Nuclear Information System (INIS)

    Rivera, A.B.

    1989-01-01

    Reported is the chemistry of triphenylphosphine ruthenium (II) complexes of general formula RuCl 2 (PPh 3 ) 2 L 2 and RuCl 2 (PPh 3 ) 2 A, obtained from the reaction of RuCl 2 (PPh 3 ) 3 with N-heterocyclic ligands L, or A (of ambidentate nature). The electronic spectra exhibit two strong metal-to-ligand charge-transfer bands, ascribed to the b 1 (dxz)->b 1 (pi) and a 2 (dxy)->a 2 (pi) transitions, and a third, weak band ascribed to the b 2 (dyz)->a 2 (pi) transition. The electronic states and the vibrational modes of the complexes were characterized by means of their resonance Raman and infrared absorption spectra. Thermogravimetric and thermodifferential analysis indicated that the melting process is succeeded by an exothermic reaction, and that the weigh loss starts to occur only after this step. The complexes dissociated in CHCl 3 solution, showing preferential labilization of the phosphine ligands, as in the case of the hydrogenation catalyst Ru(PPh 3 ) 3 Cl 2 . In the presence of CO, RuCl 2 (CO) 2 L 2 complexes were gennerated. Several derivatives were isolated and characterized. (author) [pt

  8. Ruthenium oxide resistors as sensitive elements of composite bolometers

    International Nuclear Information System (INIS)

    Benassai, M.; Gallinaro, G.; Gatti, F.; Siri, S.; Vitale, S.

    1988-01-01

    Bolometers for particle detection made with Ruthenium oxide thermistors could be produced by means of a simple technique on a variety of different materials as substrata. Preliminary results on alpha particle detection with devices realized using commercial RuO 2 thick film resistor (Tfr) are considered positive for devices operating between. 3 and .1 k and determined us to pursue further the idea. Ruthenium oxide resistors on sapphire at the moment are being prepared. The behaviour of these devices st temperatures lower than .1 k has to be investigated in more detail

  9. Stereodivergent-at-metal synthesis of [60]fullerene hybrids

    Energy Technology Data Exchange (ETDEWEB)

    Marco-Martinez, Juan; Vidal, Sara; Fernandez, Israel; Filippone, Salvatore [Departamento de Quimica Organica I, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid (Spain); Martin, Nazario [Departamento de Quimica Organica I, Facultad de Ciencias Quimicas, Universidad Complutense de Madrid (Spain); IMDEA-Nanociencia, C/Faraday, Universidad Autonoma de Madrid (Spain)

    2017-02-13

    Chiral fullerene-metal hybrids with complete control over the four stereogenic centers, including the absolute configuration of the metal atom, have been synthesized for the first time. The stereochemistry of the four chiral centers formed during [60]fullerene functionalization is the result of both the chiral catalysts employed and the diastereoselective addition of the metal complexes used (iridium, rhodium, or ruthenium). DFT calculations underpin the observed configurational stability at the metal center, which does not undergo an epimerization process. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Temperature dependence of the work function of ruthenium-based gate electrodes

    International Nuclear Information System (INIS)

    Alshareef, H.N.; Wen, H.C.; Luan, H.F.; Choi, K.; Harris, H.R.; Senzaki, Y.; Majhi, P.; Lee, B.H.; Foran, B.; Lian, G.

    2006-01-01

    The effect of device fabrication temperature on the work function of ruthenium (Ru) metal gate and its bilayers was investigated. The work function shows strong temperature dependence when Ru electrodes are deposited on silicon oxide, SiO 2 , but not on hafnium silicates (HfSiO x ). Specifically, the work function of Ru on SiO 2 increased from 4.5 eV at 500 deg. C to 5.0 eV at 700 deg. C. On further annealing to 900 deg. C or higher, the work function dropped to about 4.4 eV. In the case of HfSiO x , the work function of Ru changed by less than 100 mV over the same temperature range. Identical temperature dependence was observed using hafnium (Hf)/Ru and tantalum (Ta)/Ru bilayers. However, the peak values of the work function decreased with increasing Hf/Ru and Ta/Ru thickness ratios. Materials analysis suggests that these trends are driven by interactions at the Ru metal gate-dielectric interface

  11. Volatility of ruthenium during vitrification operations on fission products. part 1. nitric solutions distillation concentrates calcination. part 2. fixation on a steel tube. decomposition of the peroxide; Volatilite du ruthenium au cours des operations de vitrification des produits de fission. 1. partie distillation des solutions nitriques calcination des concentrats 2. partie fixation sur un tube d'acier decomposition du peroxyde

    Energy Technology Data Exchange (ETDEWEB)

    Ortins de Bettencourt, A.; Jouan, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1969-07-01

    During vitrification of fission product solutions, a high percentage of the ruthenium initially present in these solutions in the form of nitrosyl-ruthenium nitrates is volatilized with the production of the peroxide which itself is decomposed to ruthenium dioxide. The aim of this work has been to study the volatility of the ruthenium during the vitrification processes. During the distillation of the nitric solutions, we have studied in particular the influence on the volatility of the temperature , of the chemical form in which the ruthenium is introduced, of the bubbling of a gas through the solution, of the nitric concentration and of the nitrate concentration. During the calcination, we have observed the influence of the temperature, of the time, of the flow rate and of the nature of the carrier gas, as well as of the action of the ruthenium bi-oxide and the iron oxide on the volatility of the ruthenium. Part 2. This report deals with the study of the thermal decomposition of ruthenium peroxide, RuO{sub 4}, and its deposition on steel tubing. After a brief bibliographic review of the various properties of this substance, a study is made, in the first part, of its deposition on a steel tube. In order to do this, we pass a gas current containing RuO{sub 4} marked with {sup 106}Ru through a stainless steel tube subjected to a temperature gradient which decreases in the direction of the gas flow. The temperature at which RuO{sub 4} is deposited or is fixed on the tube is determined and the influence of the flow rate on this deposit is studied. In the second part, an attempt has been made to study by a static method the kinetics of the decomposition reaction of ruthenium peroxide to give the dioxide: RuO{sub 4} {yields} RuO{sub 2} + O{sub 2}. To do this, we have tried to introduce gaseous RuO{sub 4} into a container placed in an electric oven, and to follow the reaction by {gamma} counting. (author) [French] Au cours de la vitrification des solutions de produits de

  12. Volatility of ruthenium during vitrification operations on fission products. part 1. nitric solutions distillation concentrates calcination. part 2. fixation on a steel tube. decomposition of the peroxide; Volatilite du ruthenium au cours des operations de vitrification des produits de fission. 1. partie distillation des solutions nitriques calcination des concentrats 2. partie fixation sur un tube d'acier decomposition du peroxyde

    Energy Technology Data Exchange (ETDEWEB)

    Ortins de Bettencourt, A; Jouan, A [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1969-07-01

    During vitrification of fission product solutions, a high percentage of the ruthenium initially present in these solutions in the form of nitrosyl-ruthenium nitrates is volatilized with the production of the peroxide which itself is decomposed to ruthenium dioxide. The aim of this work has been to study the volatility of the ruthenium during the vitrification processes. During the distillation of the nitric solutions, we have studied in particular the influence on the volatility of the temperature , of the chemical form in which the ruthenium is introduced, of the bubbling of a gas through the solution, of the nitric concentration and of the nitrate concentration. During the calcination, we have observed the influence of the temperature, of the time, of the flow rate and of the nature of the carrier gas, as well as of the action of the ruthenium bi-oxide and the iron oxide on the volatility of the ruthenium. Part 2. This report deals with the study of the thermal decomposition of ruthenium peroxide, RuO{sub 4}, and its deposition on steel tubing. After a brief bibliographic review of the various properties of this substance, a study is made, in the first part, of its deposition on a steel tube. In order to do this, we pass a gas current containing RuO{sub 4} marked with {sup 106}Ru through a stainless steel tube subjected to a temperature gradient which decreases in the direction of the gas flow. The temperature at which RuO{sub 4} is deposited or is fixed on the tube is determined and the influence of the flow rate on this deposit is studied. In the second part, an attempt has been made to study by a static method the kinetics of the decomposition reaction of ruthenium peroxide to give the dioxide: RuO{sub 4} {yields} RuO{sub 2} + O{sub 2}. To do this, we have tried to introduce gaseous RuO{sub 4} into a container placed in an electric oven, and to follow the reaction by {gamma} counting. (author) [French] Au cours de la vitrification des solutions de produits de

  13. Mitigation of strontium and ruthenium release in the CANDU primary heat transport system

    International Nuclear Information System (INIS)

    McFarlane, J.

    1998-03-01

    In certain severe accident scenarios, low-volatility fission products can appear to contribute significantly to dose, if treated with undue conservatism. Hence a survey was performed, to see if factors that may mitigate release of strontium and ruthenium could be incorporated into safety analyses, to cover parameters such as location in the fuel matrix under normal operating conditions, release from fuel, transport and deposition in the primary heat transport system and chemistry. In addition chemical equilibrium calculations were performed to investigate the volatility of strontium and ruthenium in the presence of uranium and important fission products. Strontium is very soluble in the U0 2 fuel, up to 12 atom %, and hence release is improbable, particularly under oxidizing conditions until volatilization of the fuel matrix itself occurs. Ruthenium, however, can be released at low temperatures, but only under oxidizing conditions. These may occur during a fuel-handling accident or as a result of an end-fitting failure. Under these conditions, the primary heat transport system cannot be credited for retention. The volatile form of ruthenium, RuO 4 (g), is thermally unstable above 381 K and decomposes to RuO 2 (s) and O 2 (g) upon contact with surfaces, a factor that is likely to minimize the release of ruthenium into the environment. (author)

  14. Ruthenium(III Chloride Catalyzed Acylation of Alcohols, Phenols, and Thiols in Room Temperature Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Mingzhong Cai

    2009-09-01

    Full Text Available Ruthenium(III chloride-catalyzed acylation of a variety of alcohols, phenols, and thiols was achieved in high yields under mild conditions (room temperature in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]. The ionic liquid and ruthenium catalyst can be recycled at least 10 times. Our system not only solves the basic problem of ruthenium catalyst reuse, but also avoids the use of volatile acetonitrile as solvent.

  15. Interface behaviour and electrical performance of ruthenium ...

    Indian Academy of Sciences (India)

    Rutherford backscattering spectrometry; Raman spectroscopy; oxidation; silicide; Schottky barrier diodes; ruthenium ... water and then dried with nitrogen gas before being loaded into the vacuum ... laser of wavelength 514.6 nm. Full I–V and ...

  16. Biophysical analysis of natural, double-helical DNA modified by anticancer heterocyclic complexes of ruthenium(III) in cell-free media

    Czech Academy of Sciences Publication Activity Database

    Malina, Jaroslav; Nováková, Olga; Keppler, B. K.; Alessio, E.; Brabec, Viktor

    2001-01-01

    Roč. 6, č. 4 (2001), s. 435-445 ISSN 0949-8257 R&D Projects: GA ČR GA305/99/0695; GA ČR GA204/97/P028; GA MZd NL6058; GA MZd NL6069; GA MŠk OC D8.50 Institutional research plan: CEZ:AV0Z5004920 Keywords : DNA * ruthenium * cisplatin Subject RIV: BO - Biophysics Impact factor: 3.392, year: 2001

  17. Highly efficient quenching of tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence by ozone using formaldehyde, methylglyoxal, and glyoxalate as co-reactants and its application to ozone sensing.

    Science.gov (United States)

    Gao, Ying; Liu, Xiaoyun; Qi, Wenjing; Gao, Wenyue; Li, Yunhui; Xu, Guobao

    2015-06-21

    Most electrochemiluminescence (ECL) systems require high concentrations of quencher to totally quench ECL. In this study, we found that ozone can quench tris(2,2'-bipyridyl)ruthenium(II) ECL using formaldehyde, methylglyoxal, or glyoxalate as co-reactants at a glassy carbon electrode with remarkable efficiencies even when the concentration of ozone is merely 0.25% of that of the co-reactant. The strongest quenching is observed with the tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL system. The tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL intensities decrease linearly with the ozone concentration over the range of 0.025-25 μM (r = 0.9947) with a limit of detection of 8 nM. The method is more sensitive and faster than most methods. It shows high selectivity in the presence of other ROS or oxidants and some metal ions, such as H2O2, ClO(-), Mg(2+), Ni(2+), etc. The method exhibits high recoveries for the detection of ozone in a ventilated photocopy room.

  18. Synthesis of phosphonic acid derivatized bipyridine ligands and their ruthenium complexes.

    Science.gov (United States)

    Norris, Michael R; Concepcion, Javier J; Glasson, Christopher R K; Fang, Zhen; Lapides, Alexander M; Ashford, Dennis L; Templeton, Joseph L; Meyer, Thomas J

    2013-11-04

    Water-stable, surface-bound chromophores, catalysts, and assemblies are an essential element in dye-sensitized photoelectrosynthesis cells for the generation of solar fuels by water splitting and CO2 reduction to CO, other oxygenates, or hydrocarbons. Phosphonic acid derivatives provide a basis for stable chemical binding on metal oxide surfaces. We report here the efficient synthesis of 4,4'-bis(diethylphosphonomethyl)-2,2'-bipyridine and 4,4'-bis(diethylphosphonate)-2,2'-bipyridine, as well as the mono-, bis-, and tris-substituted ruthenium complexes, [Ru(bpy)2(Pbpy)](2+), [Ru(bpy)(Pbpy)2](2+), [Ru(Pbpy)3](2+), [Ru(bpy)2(CPbpy)](2+), [Ru(bpy)(CPbpy)2](2+), and [Ru(CPbpy)3](2+) [bpy = 2,2'-bipyridine; Pbpy = 4,4'-bis(phosphonic acid)-2,2'-bipyridine; CPbpy = 4,4'-bis(methylphosphonic acid)-2,2'-bipyridine].

  19. Recent strikes in South Africa’s platinum-group metal mines: effects upon world platinum-group metal supplies

    Science.gov (United States)

    Yager, Thomas R.; Soto-Viruet, Yadira; Barry, James J.

    2012-01-01

    The recent labor disputes over wages and working conditions that have affected South Africa’s three leading platinum-group metal (PGM) producers have affected an industry already plagued by market pressures and labor unrest and raised the specter of constraints in the world’s supply of these metals. Although low demand for these metals in 2011 and 2012 helped to offset production losses of recent years, and particularly those losses caused by the strikes in 2012, a prolonged resumption of strikes could cause severe shortages of iridium, platinum, rhodium, ruthenium, and, to a lesser extent, palladium.

  20. A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III Acetylacetonate

    Directory of Open Access Journals (Sweden)

    Ebru Ünel Barın

    2015-06-01

    Full Text Available The catalytic activity of ruthenium(III acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II species is formed in situ from the reduction of ruthenium(III and characterized using UV-Visible, Fourier transform infrared (FTIR, 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II species is mer-[Ru(N2Me43(acacH]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II catalyst formed from the reduction of ruthenium(III acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

  1. Mitigation of strontium and ruthenium release in the CANDU primary heat transport system

    Energy Technology Data Exchange (ETDEWEB)

    McFarlane, J

    1998-03-01

    In certain severe accident scenarios, low-volatility fission products can appear to contribute significantly to dose, if treated with undue conservatism. Hence a survey was performed, to see if factors that may mitigate release of strontium and ruthenium could be incorporated into safety analyses, to cover parameters such as location in the fuel matrix under normal operating conditions, release from fuel, transport and deposition in the primary heat transport system and chemistry. In addition chemical equilibrium calculations were performed to investigate the volatility of strontium and ruthenium in the presence of uranium and important fission products. Strontium is very soluble in the U0{sub 2} fuel, up to 12 atom %, and hence release is improbable, particularly under oxidizing conditions until volatilization of the fuel matrix itself occurs. Ruthenium, however, can be released at low temperatures, but only under oxidizing conditions. These may occur during a fuel-handling accident or as a result of an end-fitting failure. Under these conditions, the primary heat transport system cannot be credited for retention. The volatile form of ruthenium, RuO{sub 4}(g), is thermally unstable above 381 K and decomposes to RuO{sub 2}(s) and O{sub 2}(g) upon contact with surfaces, a factor that is likely to minimize the release of ruthenium into the environment. (author)

  2. Study of the ruthenium fission-product behavior in the containment, in the case of a nuclear reactor severe accident

    International Nuclear Information System (INIS)

    Mun, Ch.

    2007-03-01

    Ruthenium tetroxide is an extremely volatile and highly radio-toxic species. During a severe accident with air ingress in the reactor vessel, ruthenium oxides may reach the reactor containment building in significant quantities. Therefore, a better understanding of the RuO 4 (g) behaviour in the containment atmosphere is of primary importance for the assessment of radiological consequences, in the case of potential releases of this species into the environment. A RuO 4 (g) decomposition kinetic law was determined. Steam seems to play a catalytic role, as well as the presence of ruthenium dioxide deposits. The temperature is also a key parameter. The nature of the substrate, stainless steel or paint, did not exhibit any chemical affinities with RuO 4 (g). This absence of reactivity was confirmed by XPS analyses, which indicate the presence of the same species in the Ru deposits surface layer whatever the substrates considered. It has been concluded that RuO 4 (g) decomposition corresponds to a bulk gas phase decomposition. The ruthenium re-volatilization phenomenon under irradiation from Ru deposits was also highlighted. An oxidation kinetic law was determined. The increase of the temperature and the steam concentration promote significantly the oxidation reaction. The establishment of Ru behavioural laws allowed making a modelling of the Ru source term. The results of the reactor calculations indicate that the values obtained for 106 Ru source term are closed to the reference value considered currently by the IRSN, for 900 MWe PWR safety analysis. (author)

  3. In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

    Science.gov (United States)

    Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

    2012-03-20

    The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

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

    Science.gov (United States)

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

  5. Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes

    Science.gov (United States)

    Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.

    2017-11-01

    Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

  6. Structure and reactivity of Ruthenium nanoparticles

    DEFF Research Database (Denmark)

    Gavnholt, Jeppe; Schiøtz, Jakob

    2008-01-01

    We present a method for obtaining detailed structural information of ruthenium nanoparticles in at least the diameter range from 1.5 to 5 nm. The method is based on an ensemble approach where a large number of low-energy structures are collected in an ensemble, from which average properties can...

  7. Synthesis of ruthenium (III) complexes with benzimidazole derivatives

    International Nuclear Information System (INIS)

    Vyas, P.C.; Chahar, Yogesh K.; Garg, Yajula; Seth, Gita

    2003-01-01

    Complexes of ruthenium with biologically important benzimidazole derivatives, viz. 2-(2'-hydroxyphenyl) benzimidazole (HOPBI), 2-2'- mercaptophenyl) benzimidazole (HSPBI), 2- (2'-hydroxynaphthyl) benzimidazole (HONBI) have been synthesized and characterized. (author)

  8. Support Effect in Hydrodesulfurization over Ruthenium Sulfide

    Czech Academy of Sciences Publication Activity Database

    Gulková, Daniela; Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

    2009-01-01

    Roč. 51, č. 2 (2009), s. 146-149 ISSN 1337-7027 R&D Projects: GA ČR GA104/06/0705 Institutional research plan: CEZ:AV0Z40720504 Keywords : ruthenium sulfide * hydrodesulfurization * support effect Subject RIV: CC - Organic Chemistry

  9. Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

    International Nuclear Information System (INIS)

    Yesildag, Ali; Ekinci, Duygu

    2010-01-01

    In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN) 6 3- and Ru(NH 3 ) 6 3+ by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.

  10. Cathodic processes during ruthenium electrodeposition from a chloride melt

    International Nuclear Information System (INIS)

    Sokol'skij, D.V.

    1985-01-01

    Cathodic processes occurring during the electrolysis of chloride melts in the presence of oxygen-containing impurities were studied. The experiments were carried out at 500, 550 600 and 680 deg C, ruthenium ions concentration in KCl-NaCl-CsCl eutectic melt being 0.4-1.5 mol% and BaO additions 4.8x10 -2 mol%. Temperature dependence of Ru(3) ion diffusion coefficient in the chloride melt (lg D=3.25-1508/T+-0.02) and activation energy of the diffusion process (6.9 k cal/mol) were determined. It is shown that changes of the shape of E, t-curve and the deviation of values determined in the cause of chronopotentiometric investigations from the corresponding values of reversable processes are related in many respects to the participation of oxygen-containing compounds in the cathodic process. Irreversibility of the cathodic process is also connected with metal crystallization during electrodeposition

  11. Amorphous carbon nanofibres inducing high specific capacitance of deposited hydrous ruthenium oxide

    International Nuclear Information System (INIS)

    Barranco, V.; Pico, F.; Ibanez, J.; Lillo-Rodenas, M.A.; Linares-Solano, A.; Kimura, M.; Oya, A.; Rojas, R.M.; Amarilla, J.M.; Rojo, J.M.

    2009-01-01

    Composites consisting of ruthenium oxide particles deposited on amorphous carbon nanofibres are prepared by a repetitive impregnation procedure. The choice of amorphous carbon nanofibres as support of amorphous ruthenium oxide leads to composites in which the deposited oxide consists of aggregates of extremely small primary particles (1-1.5 nm-size) and showing high porosity (specific surface area of 450 m 2 g -1 ). This special deposition of the oxide seems to favour: (i) high oxide capacitance (1000 Fg -1 ) at high oxide loadings (up to 20 wt%) and (ii) high capacitance retention (ca. 80% from the initial oxide capacitance) at high current densities (200 mA cm -2 ). Amorphous carbon nanofibres are suitable supports for amorphous ruthenium oxide and perhaps for other amorphous oxides acting as active electrode materials.

  12. Catalytic water oxidation by ruthenium(II) quaterpyridine (qpy) complexes: evidence for ruthenium(III) qpy-N,N'''-dioxide as the real catalysts.

    Science.gov (United States)

    Liu, Yingying; Ng, Siu-Mui; Yiu, Shek-Man; Lam, William W Y; Wei, Xi-Guang; Lau, Kai-Chung; Lau, Tai-Chu

    2014-12-22

    Polypyridyl and related ligands have been widely used for the development of water oxidation catalysts. Supposedly these ligands are oxidation-resistant and can stabilize high-oxidation-state intermediates. In this work a series of ruthenium(II) complexes [Ru(qpy)(L)2 ](2+) (qpy=2,2':6',2'':6'',2'''-quaterpyridine; L=substituted pyridine) have been synthesized and found to catalyze Ce(IV) -driven water oxidation, with turnover numbers of up to 2100. However, these ruthenium complexes are found to function only as precatalysts; first, they have to be oxidized to the qpy-N,N'''-dioxide (ONNO) complexes [Ru(ONNO)(L)2 ](3+) which are the real catalysts for water oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Study of the ruthenium fission-product behavior in the containment, in the case of a nuclear reactor severe accident; Etude du comportement du produit de fission ruthenium dans l'enceinte de confinement d'un reacteur nucleaire, en cas d'accident grave

    Energy Technology Data Exchange (ETDEWEB)

    Mun, Ch

    2007-03-15

    Ruthenium tetroxide is an extremely volatile and highly radio-toxic species. During a severe accident with air ingress in the reactor vessel, ruthenium oxides may reach the reactor containment building in significant quantities. Therefore, a better understanding of the RuO{sub 4}(g) behaviour in the containment atmosphere is of primary importance for the assessment of radiological consequences, in the case of potential releases of this species into the environment. A RuO{sub 4}(g) decomposition kinetic law was determined. Steam seems to play a catalytic role, as well as the presence of ruthenium dioxide deposits. The temperature is also a key parameter. The nature of the substrate, stainless steel or paint, did not exhibit any chemical affinities with RuO{sub 4}(g). This absence of reactivity was confirmed by XPS analyses, which indicate the presence of the same species in the Ru deposits surface layer whatever the substrates considered. It has been concluded that RuO{sub 4}(g) decomposition corresponds to a bulk gas phase decomposition. The ruthenium re-volatilization phenomenon under irradiation from Ru deposits was also highlighted. An oxidation kinetic law was determined. The increase of the temperature and the steam concentration promote significantly the oxidation reaction. The establishment of Ru behavioural laws allowed making a modelling of the Ru source term. The results of the reactor calculations indicate that the values obtained for {sup 106}Ru source term are closed to the reference value considered currently by the IRSN, for 900 MWe PWR safety analysis. (author)

  14. Recovery of noble metals from HLLW using photocatalytic reduction

    International Nuclear Information System (INIS)

    Nishi, T.; Uetake, N.; Kawamura, F.; Yusa, H.

    1987-01-01

    In high-level liquid waste (HLLW) from fuel reprocessing plants, noble metals (palladium, rhodium, and ruthenium), which account for ∼ 10 wt% of fission products, exist as ions. These metals are very useful as catalytic material in automobile exhaust systems and other chemical processes, but they are rare in nature, making their recovery from fission products highly desirable. The ions of noble metals in solution have the feature that their reduction potential from ion to metal is relatively high compared with that of other fission product ions, so they can be selectively separated as a metal by a reduction process. The authors think a photoreduction process using a photocatalysts, which functions as photon-electron conversion agent, is suitable for the recovery of noble metals from HLLW for three reasons: (1) this process uses no reduction agents, which usually degrade the nitric acid, so that coprecipitation of other fission products does not occur. (2) The reactions are induced by light, which does not contaminate the reaction system, and in contrast with ordinary photo-redox reactions, the quantum yield is quite high. (3) As the photocatalyst does not change in the reaction, it can be used again and again. The report shows the results of fundamental experiments on the application of photocatalytic reduction to the recovery of noble metal ions in nitric acid solution

  15. Electrodeposition of ruthenium, rhodium and palladium from nitric acid and ionic liquid media: Recovery and surface morphology of the deposits

    Energy Technology Data Exchange (ETDEWEB)

    Jayakumar, M.; Venkatesan, K.A.; Sudha, R. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu 603102 (India); Srinivasan, T.G., E-mail: tgs@igcar.gov.com [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu 603102 (India); Vasudeva Rao, P.R. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu 603102 (India)

    2011-07-15

    Research highlights: {yields} Platinum group metals are man-made noble metals. {yields} Electrochemical recovery of fission platinoids. {yields} Recovery from nitric acid medium. {yields} Recovery from ionic liquid medium. {yields} Platinoids with exotic surface morphologies. - Abstract: Electrodeposition is a promising technique for the recovery of platinum group metals with unique surface morphologies. The electrodeposition of palladium, ruthenium and rhodium from aqueous nitric acid, and non-aqueous 1-butyl-3-methylimidazolium chloride ionic liquid medium was studied at stainless steel electrode. The surface morphology and elemental composition of the resultant deposit were probed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDS) analysis. Deposits with diverse surface morphologies and metal compositions were obtained by varying the composition of the electrolytic medium and applied potential. The results demonstrate the possibility of tailoring the morphologies of PGMs by controlling the composition and potential needed for electrodeposition.

  16. A High Molar Extinction Coefficient Mono-Anthracenyl Bipyridyl Heteroleptic Ruthenium(II Complex: Synthesis, Photophysical and Electrochemical Properties

    Directory of Open Access Journals (Sweden)

    Peter A. Ajibade

    2011-06-01

    Full Text Available In our quest to develop good materials as photosensitizers for photovoltaic dye-sensitized solar cells (DSSCs, cis-dithiocyanato-4-(2,3-dimethylacrylic acid-2,2'-bipyridyl-4-(9-anthracenyl-(2,3-dimethylacrylic-2,2'-bipyridyl ruthenium(II complex, a high molar extinction coefficient charge transfer sensitizer, was designed, synthesized and characterized by spectroscopy and electrochemical techniques. Earlier studies on heteroleptic ruthenium(II complex analogues containing functionalized oligo-anthracenyl phenanthroline ligands have been reported and documented. Based on a general linear correlation between increase in the length of π-conjugation bond and the molar extinction coefficients, herein, we report the photophysical and electrochemical properties of a Ru(II bipyridyl complex analogue with a single functionalized anthracenyl unit. Interestingly, the complex shows better broad and intense metal-to ligand charge transfer (MLCT band absorption with higher molar extinction coefficient (λmax = 518 nm, e = 44900 M−1cm−1, and appreciable photoluminescence spanning the visible region than those containing higher anthracenyl units. It was shown that molar absorption coefficient of the complexes may not be solely depended on the extended π-conjugation but are reduced by molecular aggregation in the molecules.

  17. Identification of short-lived neutron-rich ruthenium and rhodium isotopes in fission

    International Nuclear Information System (INIS)

    Franz, G.; Herrmann, G.

    1975-01-01

    Short-lived ruthenium and rhodium isotopes ( 107 Ru, 108 Ru, 108 Rh, 109 Ru, 109 Rh, 110 Ru, 110 Rh, 111 Ru, 111 Rh, 112 Ru, 112 Rh, 113 Ru) have been separated from fission products by a rapid chemical procedure and identified by means of γ-ray spectroscopy. Nuclides with half-lives down to 3 sec were accessible. Ruthenium isotopes up to mass number 113 have been identified. (author)

  18. Natural convection heat transfer in the molten metal pool

    International Nuclear Information System (INIS)

    Park, R.J.; Kim, S.B.; Kim, H.D.; Choi, S.M.

    1997-01-01

    Analytical studies using the FLOW-3D computer program have been performed on natural convection heat transfer of a high density molten metal pool, in order to evaluate the coolability of the corium pool. The FLOW-3D results on the temperature distribution and the heat transfer rate in the molten metal pool region have been compared and evaluated with the experimental data. The FLOW-3D results have shown that the developed natural convection flow contributes to the solidified crust formation of the high density molten metal pool. The present FLOW-3D results, on the relationship between the Nusselt number and the Rayleigh number in the molten metal pool region, are more similar to the calculated results of Globe and Dropkin's correlation than any others. The natural convection heat transfer in the low aspect ratio case is more substantial than that in the high aspect ratio case. The FLOW-3D results, on the temperature profile and on the heat transfer rate in the molten metal pool region, are very similar to the experimental data. The heat transfer rate of the internal heat generation case is higher than that of the bottom heating case at the same heat supply condition. (author)

  19. Ruthenium and osmium carbonyl nitrosyl complexes: Matrix infrared spectra and density functional calculations for M(CO){sub 2}(NO){sub 2} and M(CO)(NO) (M = Ru, Os)

    Energy Technology Data Exchange (ETDEWEB)

    Song, Zhenjun [Department of Chemistry, Tongji University, Shanghai 200092 (China); Wang, Xuefeng, E-mail: xfwang@tongji.edu.cn [Department of Chemistry, Tongji University, Shanghai 200092 (China); Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University (China)

    2012-10-15

    Highlights: Black-Right-Pointing-Pointer Laser-ablated ruthenium or osmium atom reactions with CO and NO mixtures in solid argon. Black-Right-Pointing-Pointer Metal carbonyl nitrosyls including M(CO)(NO) and 18-electron configuration M(CO){sub 2}(NO){sub 2} molecules (M = Ru, Os). Black-Right-Pointing-Pointer The observed absorption bands of reaction products are identified by isotopic substitution and DFT calculations. Black-Right-Pointing-Pointer The bonding and reaction mechanism are discussed in detail. -- Abstract: Laser-ablated ruthenium or osmium atom reactions with CO and NO mixtures in solid argon produce unsaturated metal carbonyl nitrosyls including M(CO)(NO) and 18-electron configuration M(CO){sub 2}(NO){sub 2} molecules (M = Ru, Os). The observed absorption bands of reaction products are identified by isotopic substitution, isotopic ratios and isotopic distributions ({sup 13}CO, {sup 15}NO, and mixtures). DFT (B3LYP and BP86) vibrational fundamental calculations reproduce observed frequencies and isotopic shifts very well. The bonding and reaction mechanism are discussed.

  20. Magnetic anisotropy of graphene quantum dots decorated with a ruthenium adatom

    Directory of Open Access Journals (Sweden)

    Igor Beljakov

    2013-07-01

    Full Text Available The creation of magnetic storage devices by decoration of a graphene sheet by magnetic transition-metal adatoms, utilizing the high in-plane versus out-of-plane magnetic anisotropy energy (MAE, has recently been proposed. This concept is extended in our density-functional-based modeling study by incorporating the influence of the graphene edge on the MAE. We consider triangular graphene flakes with both armchair and zigzag edges in which a single ruthenium adatom is placed at symmetrically inequivalent positions. Depending on the edge-type, the graphene edge was found to influence the MAE in opposite ways: for the armchair flake the MAE increases close to the edge, while the opposite is true for the zigzag edge. Additionally, in-plane pinning of the magnetization direction perpendicular to the edge itself is observed for the first time.

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

    Energy Technology Data Exchange (ETDEWEB)

    Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.; Bijkerk, F. [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

    2015-08-07

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

  2. Hydroformylation and kinetics of 1-hexene over ruthenium, cobalt and rhodium zerolite catalysts

    International Nuclear Information System (INIS)

    Wang, C.; Wei, W.

    1989-01-01

    In this paper, six kinds of catalysts were prepared by cation exchange with rhodium, ruthenium and cobalt chloropentaamino dichoride and zeolites. Effects such as support materials, PPH 3 to metal ratio, reaction temperature, total pressure, H 2 /CO ratio, reaction time and solvents have been investigated in an autoclave. The most favorable results of 1-hexene hydroformylation were obtained in the temperature range 100-150 degrees C at a pressure of 5.0MPa (H 2 /CO=1:1) and the addition of free PPh 3 . The bimetallic catalysts showed high catalytic activing for hydroformylation because of the synergistic effect of bimetallic systems. This paper reports the results of experiments and catalysts characterization by means of IR and XRD spectroscopy

  3. Electron transfer reactions of ruthenium(II) complexes with polyphenolic acids in micelles

    Energy Technology Data Exchange (ETDEWEB)

    Rajeswari, Angusamy [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Chemistry, Fatima College, Madurai 625 018 (India); Ramdass, Arumugam [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur 628 216 (India); Muthu Mareeswaran, Paulpandian [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Industrial Chemistry, Alagappa University, Karaikudi 630 003 (India); Rajagopal, Seenivasan, E-mail: rajagopalseenivasan@yahoo.com [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India)

    2016-02-15

    The electron transfer in a microhetrogeneous system is a perfect mimic of biological electron transfer. The electron transfer between biologically important phenolic acids and ruthenium (II) complexes is systematically studied in the presence of anionic and cationic micelles. The photophysical properties of these ruthenium (II) complexes with anionic and cationic micelles and their binding abilities with these two type of micelles are also studies using absorption, emission and excited state lifetime spectral techniques. Pseudophase Ion Exchange (PIE) Model is applied to derive mechanism of electron transfer in two types of micelles. - Highlights: • Effect of microhetrogeneous system is studied using ruthenium (II) complexes and gallic acid is studied. • Pseudophase Ion exchange model is applied to derive the mechanism. • Binding constants are in the range of 10{sup 2}–10{sup 4} M{sup −1}.

  4. Evaluation of radiolabeled ruthenium compounds as tumor-localizing agents

    International Nuclear Information System (INIS)

    Srivastava, S.C.; Richards, P.; Meinken, G.E.; Som, P.; Atkins, H.L.; Larson, S.M.; Grunbaum, Z.; Rasey, J.S.; Clarke, M.H.; Dowling, M.

    1979-01-01

    This work introduces a new class of radiopharmaceuticals based on ruthenium-97. The excellent physical properties of Ru-97, the high chemical reactivity of Ru, the potential antitumor activity of several Ru coordination compounds, and BLIP production of Ru-97, provide a unique combination for the application of this isotope in nuclear oncology. A systematic study was undertaken on the synthesis, characterization, and evaluation of a number of ruthenium-labeled compounds. In a variety of animal tumor models, several compounds show considerable promise as tumor-localizing agents when compared to gallium-67 citrate. The compounds studied (with Ru in different oxidation states) include ionic Ru, a number of hydrophilic and lipophilic chelates, and various ammine derivatives

  5. Ruthenium, osmium and rhodium complexes of polypyridyl ligands ...

    Indian Academy of Sciences (India)

    Unknown

    Discipline of Silicates and Catalysis, Central Salt and Marine Chemicals ... However, synthetic methods have also been developed to prepare complexes with ... 3.2 Synthesis and characterisation of ruthenium(II) and osmium(II) complexes18, ...

  6. Behaviour of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

    International Nuclear Information System (INIS)

    Philippe, M.; Gue, J.P.; Mercier, J.P.

    1990-12-01

    The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30.000 MW day ·t -1 . A distillation apparatus was designed to operate with small-volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: - ruthenium is only volatilized in the final phase of evaporation, just before desiccation, - for a final temperature limited to 160 deg. C, the total fraction of volatilized ruthenium reaches 12%, - in the presence of H 2 O, HNO 3 , NO x and O 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide (probably RuO 2 ) on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source. It is probable that, in an industrial storage tank, the heat losses from the tank and the offgas discharge ducts will cause recondensation and internal reflux, which will commensurately delay

  7. A ruthenium anticancer compound interacts with histones and impacts differently on epigenetic and death pathways compared to cisplatin.

    Science.gov (United States)

    Licona, Cynthia; Spaety, Marie-Elodie; Capuozzo, Antonelle; Ali, Moussa; Santamaria, Rita; Armant, Olivier; Delalande, Francois; Van Dorsselaer, Alain; Cianferani, Sarah; Spencer, John; Pfeffer, Michel; Mellitzer, Georg; Gaiddon, Christian

    2017-01-10

    Ruthenium complexes are considered as potential replacements for platinum compounds in oncotherapy. Their clinical development is handicapped by a lack of consensus on their mode of action. In this study, we identify three histones (H3.1, H2A, H2B) as possible targets for an anticancer redox organoruthenium compound (RDC11). Using purified histones, we confirmed an interaction between the ruthenium complex and histones that impacted on histone complex formation. A comparative study of the ruthenium complex versus cisplatin showed differential epigenetic modifications on histone H3 that correlated with differential expression of histone deacetylase (HDAC) genes. We then characterized the impact of these epigenetic modifications on signaling pathways employing a transcriptomic approach. Clustering analyses showed gene expression signatures specific for cisplatin (42%) and for the ruthenium complex (30%). Signaling pathway analyses pointed to specificities distinguishing the ruthenium complex from cisplatin. For instance, cisplatin triggered preferentially p53 and folate biosynthesis while the ruthenium complex induced endoplasmic reticulum stress and trans-sulfuration pathways. To further understand the role of HDACs in these regulations, we used suberanilohydroxamic acid (SAHA) and showed that it synergized with cisplatin cytotoxicity while antagonizing the ruthenium complex activity. This study provides critical information for the characterization of signaling pathways differentiating both compounds, in particular, by the identification of a non-DNA direct target for an organoruthenium complex.

  8. Fundamental Factors Impacting the Stability of Phosphonate-Derivatized Ruthenium Polypyridyl Sensitizers Adsorbed on Metal Oxide Surfaces.

    Science.gov (United States)

    Raber, McKenzie; Brady, Matthew David; Troian-Gautier, Ludovic; Dickenson, John; Marquard, Seth L; Hyde, Jacob; Lopez, Santiago; Meyer, Gerald J; Meyer, Thomas J; Harrison, Daniel P

    2018-06-08

    A series of 18 ruthenium(II) polypyridyl complexes were synthesized and evaluated under electrochemically oxidative conditions, which generates the Ru(III) oxidation state and mimics the harsh conditions experienced during the kinetically-limited regime that can occur in dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs), to further develop fundamental insights into the factors governing molecular sensitizer surface stability in aqueous 0.1 M HClO4 (aq). Both desorption and oxidatively induced ligand substitution were observed on planar fluorine doped tin oxide, FTO, electrodes, with a dependence on the E1/2 Ru(III/II) redox potential dictating the comparative ratios of the processes. Complexes such as RuP4OMe (E1/2 = 0.91 vs Ag/AgCl) displayed virtually only desorption, while complexes such as RuPbpz (E1/2 > 1.62 V vs Ag/AgCl) displayed only chemical decomposition. Comparing isomers of 4,4'- and 5,5-disubstituted-2,2'-bipyridine ancillary polypyridyl ligands, a dramatic increase in the rate of desorption of the Ru(III) complexes was observed for the 5,5'-ligands. Nanoscopic indium doped tin oxide thin films, nanoITO, were also sensitized and analyzed with cyclic voltammetry, UV-Vis absorption spectroscopy, and XPS, allowing for further distinction of desorption versus ligand substitution processes. Desorption loss to bulk solution associated with the planar surface of FTO is essentially non-existent on nanoITO, where both desorption and ligand substitution are shut down with RuP4OMe. These results revealed that minimizing time spent in the oxidized form, incorporating electron donating groups, maximizing hydrophobicity, and minimizing molecular bulk near the adsorbed ligand are critical to optimizing the performance of ruthenium(II) polypyridyl complexes in dye-sensitized solar cell devices.

  9. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  10. Committee's report on ruthenium fall-out incident

    International Nuclear Information System (INIS)

    Borkowski, C.J.; Crawford, J.H.; Livingston, R.; Ritchie, R.H.; Rupp, A.F.; Taylor, E.H.

    1983-07-01

    Investigations of the fall-out incident of November 11 and 12, 1959, by responsible parties (Health Physics Division and Operations Division personnel) established beyond reasonable doubt that the incident had its origin in the expulsion of particles, heavily contaminated with ruthenium, which had been detached from the walls of the electric fan housing and ducts in the off-gas system associated with the brick stack. All available evidence indicates that the particles were loosened during maintenance work on the exhaust damper and the bearings of the electric fan and were carried up the stack in two bursts as particulate fall-out when this fan was put back into service. Radiographic and chemical analysis showed the activity to be almost entirely ruthenium (Ru 106 ) and its daughter rhodium (Rh 106 ) with very little, if any, strontium being present. This report summarizes the findings and sets forth the conclusions and recommendations of the Committee asked to investigate the incident

  11. Preliminary assessment of modified borosilicate glasses for chromium and ruthenium immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Farid, Osama M. [Reactors Department, Nuclear Research Center, Atomic Energy Authority of Egypt, P.O. 13759, Inshas, Cairo (Egypt); Centre of Nuclear Engineering (CNE), Department of Materials, Imperial College London, London, SW7 2BP (United Kingdom); Abdel Rahman, R.O., E-mail: alaarehab@yahoo.com [Hot Laboratory Center, Atomic Energy Authority of Egypt, P.O. 13759, Inshas, Cairo (Egypt)

    2017-01-15

    The feasibility of using modified alkali borosilicate glasses for ruthenium and chromium immobilization is preliminary assessed by investigating the immobilization system structure under normal conditions. Within this context, reference alkali borosilicate, and simulated Magnox-modified glasses were prepared and studied. The results indicate that ruthenium is immobilized in the vitreous structure as encapsulated RuO{sub 2} crystallites that act as seeds for heterogeneous nucleation of other crystalline phases. The presence of Zn, as modifier, has contributed to chromium immobilization in zincochromite spinel structure, whereas Ca is accommodated in the vitreous structure. Immobilization performance was evaluated by conducting conservative static leach test and studying the leached glass. Leached glass morphology was altered, where near surface reference glass is leached over 400 nm and simulated Magnox-modified sample is altered over 300 nm. Normalized release rates are within normal range for borosilicate material. For simulated Magnox-modified sample, Ca and alkali structural element, i.e. Na and Li, are leached via ion-exchange reaction. The ion-exchanged fraction equals 1.06 × 10{sup −8} mol/m{sup 2} s and chromium has slightly lower normalized release rate value than ruthenium. - Highlights: • The presence of modifiers and waste oxides led to localized de-vitrification. • Ruthenium is encapsulated within the vitreous glass network as RuO{sub 2} crystals. • Chromium is immobilized within the zincochromite spinel structure. • Pitting and cracks induced by leaching did not affect the immobilization performance.

  12. Ruthenium(II) arene complexes with chelating chloroquine analogue ligands: Synthesis, characterization and in vitro antimalarial activity†

    Science.gov (United States)

    Glans, Lotta; Ehnbom, Andreas; de Kock, Carmen; Martínez, Alberto; Estrada, Jesús; Smith, Peter J.; Haukka, Matti; Sánchez-Delgado, Roberto A.; Nordlander, Ebbe

    2012-01-01

    Three new ruthenium complexes with bidentate chloroquine analogue ligands, [Ru(η6-cym)(L1)Cl]Cl (1, cym = p-cymene, L1 = N-(2-((pyridin-2-yl)methylamino)ethyl)-7-chloroquinolin-4-amine), [Ru(η6-cym)(L2)Cl]Cl (2, L2 = N-(2-((1-methyl-1H-imidazol-2-yl)methylamino)ethyl)-7-chloroquinolin-4-amine) and [Ru(η6-cym)(L3)Cl] (3, L3 = N-(2-((2-hydroxyphenyl)methylimino)ethyl)-7-chloroquinolin-4-amine) have been synthesized and characterized. In addition, the X-ray crystal structure of 2 is reported. The antimalarial activity of complexes 1–3 and ligands L1, L2 and L3, as well as the compound N-(2-(bis((pyridin-2-yl)methyl)amino)ethyl)-7-chloroquinolin-4-amine (L4), against chloroquine sensitive and chloroquine resistant Plasmodium falciparum malaria strains was evaluated. While 1 and 2 are less active than the corresponding ligands, 3 exhibits high antimalarial activity. The chloroquine analogue L2 also shows good activity against both the choloroquine sensitive and the chloroquine resistant strains. Heme aggregation inhibition activity (HAIA) at an aqueous buffer/n-octanol interface (HAIR50) and lipophilicity (D, as measured by water/n-octanol distribution coefficients) have been measured for all ligands and metal complexes. A direct correlation between the D and HAIR50 properties cannot be made because of the relative structural diversity of the complexes, but it may be noted that these properties are enhanced upon complexation of the inactive ligand L3 to ruthenium, to give a metal complex (3) with promising antimalarial activity. PMID:22249579

  13. Synthesis and characterization of novel heteroleptic ruthenium sensitizer for nanocrystalline dye-sensitized solar cells

    NARCIS (Netherlands)

    Sivakumar, R.; Marcelis, A.T.M.; Anandan, S.

    2009-01-01

    A novel heteroleptic ruthenium complex of the type [Ru(bpin)(dcbpyH2)Cl]Cl (where bpin is 2,6-bis(pyrazol-1-yl)isonicotinic acid and dcbpyH2 is 4,4'-dicarboxy-2,2'-bipyridine) was synthesized and characterized for tuning the LUMO level of the ruthenium sensitizer to achieve greater stabilization in

  14. Behavior of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

    International Nuclear Information System (INIS)

    Philippe, M.; Mercier, J.P.; Gue, J.P.

    1990-01-01

    The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30,000 MWday.t -1 . A distillation apparatus was designed to operate with small volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: - ruthenium is only volatilized in the final phase of evaporation, just before desiccation, - for a final temperature limited to 160 0 C, the total fraction of volatilized ruthenium reaches 12%, in the presence of H 2 0, HN0 3 , N0 x and 0 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source

  15. Behavior of ruthenium in the case of shutdown of the cooling system of HLLW storage tanks

    International Nuclear Information System (INIS)

    Philippe, M.; Mercier, J.P.; Gue, J.P.

    1991-01-01

    The consequences of the failure of the cooling system of fission product storage tanks over a variable period were investigated as part of the safety analysis of the La Hague spent fuel reprocessing plant. Due to the considerable heat release, induced by the fission products, a prolonged shutdown of the tank cooling system could cause the progressive evaporation of the solutions to dryness, and culminate in the formation of volatile species of ruthenium and their release in the tank venting circuit. To determine the fraction of ruthenium likely to be transferred from the storage tanks in volatile or aerosol form during the failure, evaporation tests were conducted by evaporating samples of actual nitric acid solutions of fission products, obtained on the laboratory scale after the reprocessing of several kilograms of MOX fuels irradiated to 30,000 MW day·t -1 . A distillation apparatus was designed to operate with small-volume solution samples, reproducing the heating conditions existing in the reprocessing plant within a storage tank for fission products. The main conclusions drawn from these experiments are as follows: ruthenium is only volatilized in the final phase of evaporation, just before desiccation; for a final temperature limited to 160 degree C, the total fraction of volatilized ruthenium reaches 12%; in the presence of H 2 O, HNO 3 , NO x and O 2 , the volatilized ruthenium recombines mainly in the form of ruthenium nitrosyl nitrates, or decomposes into ruthenium oxide (probably RuO 2 ) on the walls of the apparatus. Assuming a heating power density of 10 W/liter of concentrate, and a perfectly adiabatic storage system, the minimum time required to reach dryness can be estimated at 90 h, allowing substantial time to take action to restore a cooling source

  16. Mechanism of ruthenium dioxide crystallization during high level waste vitrification

    International Nuclear Information System (INIS)

    Boucetta, H.

    2012-01-01

    Ruthenium, arising from the reprocessing of spent uranium oxide fuel, has a low solubility in glass melt. It crystallizes in the form of particles of RuO 2 of acicular or polyhedral morphology dispersed in fission product and actinides waste containment glass. Since the morphology of these particles strongly influences the physico-chemical properties, the knowledge and the control of their mechanism of formation are of major importance. The goal of this work is to determine the chemical reactions responsible for the formation of RuO 2 particles of acicular or polyhedral shape during glass synthesis. Using a simplification approach, the reactions between RuO 2 -NaNO 3 , and more complex calcine RuO 2 -Al 2 O 3 -Na 2 O and a sodium borosilicate glass are studied. In situ scanning electron microscopy and XANES at increasing temperatures are used to follow changes in composition, speciation and morphology of the ruthenium intermediate species. Those compounds are thoroughly characterised by SEM, XRD, HRTEM, and ruthenium K-edge X-ray absorption spectroscopy. This combined approach allows us to show that the ruthenium speciation modification during vitrification is the key of control of the morphology of RuO 2 particles in the glass. In particular, the formation of a specific intermediate compound (Na 3 RuO 4 ) is one of the main steps that lead to the precipitation of needle-shaped RuO 2 particles in the melt. The formation of polyhedral particles, on the contrary, results from the direct incorporation of RuO 2 crystals in the melt followed by an Ostwald ripening mechanism. (author) [fr

  17. Analysis of flow fields, temperatures and ruthenium transport in the test facility

    International Nuclear Information System (INIS)

    Kaerkelae, T.; Pyykoenen, J.; Auvinen, A.; Jokiniemi, J.

    2008-03-01

    Ruthenium transport experiments were conducted at VTT during years 2002- 2006. Experiments gave information about ruthenium behaviour in air ingress accident conditions. This study complements those experiments with an analysis of the flows and thermal fields in the test system. Temperature profiles were measured at the walls of the experimental facility. Computational fluid dynamics (CFD) simulations used the measured profiles and provided predictions of flows and temperatures inside the furnace. Ruthenium transport was also modelled with CFD. Thermal characterisation of the reactor demonstrated that buoyancy has a significant role during the cooling after the furnace. A hypothesis of the dominant role of RuO2 and RuO3 condensation on reactor walls gave simulation results that are in accordance with radiotracer measurements of deposition in experiments conducted with furnace at 1500K. Actually, RuO3 does not condensate, but it thermal decomposes to RuO2. This does not seem to have effect on result. Particle formation around the furnace exit could be detected from the comparison of modelling results with the measured profiles. In several other experiments ruthenium behaviour is dominated by other issues. These are related to the complex ruthenium chemistry that includes various surface reactions. Thermal equilibrium indicates significant gaseous RuO4 concentration around 1300 K. It seems that seed particles decreased the catalytic decomposition activity of RuO4 to RuO2 around this temperature pushing the gas concentration towards the equilibrium, and further give rise to gaseous RuO4 transport to low temperatures. At higher temperature increasing mass flow rate of RuO2 particles is likely to catalyse (decomposition) reaction of RuO4 to RuO2. (au)

  18. Analysis of flow fields, temperatures and ruthenium transport in the test facility

    Energy Technology Data Exchange (ETDEWEB)

    Kaerkelae, T.; Pyykoenen, J.; Auvinen, A.; Jokiniemi, J. [Technical Research Centre of Finland VTT (Finland)

    2008-03-15

    Ruthenium transport experiments were conducted at VTT during years 2002- 2006. Experiments gave information about ruthenium behaviour in air ingress accident conditions. This study complements those experiments with an analysis of the flows and thermal fields in the test system. Temperature profiles were measured at the walls of the experimental facility. Computational fluid dynamics (CFD) simulations used the measured profiles and provided predictions of flows and temperatures inside the furnace. Ruthenium transport was also modelled with CFD. Thermal characterisation of the reactor demonstrated that buoyancy has a significant role during the cooling after the furnace. A hypothesis of the dominant role of RuO2 and RuO3 condensation on reactor walls gave simulation results that are in accordance with radiotracer measurements of deposition in experiments conducted with furnace at 1500K. Actually, RuO3 does not condensate, but it thermal decomposes to RuO2. This does not seem to have effect on result. Particle formation around the furnace exit could be detected from the comparison of modelling results with the measured profiles. In several other experiments ruthenium behaviour is dominated by other issues. These are related to the complex ruthenium chemistry that includes various surface reactions. Thermal equilibrium indicates significant gaseous RuO4 concentration around 1300 K. It seems that seed particles decreased the catalytic decomposition activity of RuO4 to RuO2 around this temperature pushing the gas concentration towards the equilibrium, and further give rise to gaseous RuO4 transport to low temperatures. At higher temperature increasing mass flow rate of RuO2 particles is likely to catalyse (decomposition) reaction of RuO4 to RuO2. (au)

  19. Deposition and properties of cobalt- and ruthenium-based ultra-thin films

    Science.gov (United States)

    Henderson, Lucas Benjamin

    Future copper interconnect systems will require replacement of the materials that currently comprise both the liner layer(s) and the capping layer. Ruthenium has previously been considered as a material that could function as a single material liner, however its poor ability to prevent copper diffusion makes it incompatible with liner requirements. A recently described chemical vapor deposition route to amorphous ruthenium-phosphorus alloy films could correct this problem by eliminating the grain boundaries found in pure ruthenium films. Bias-temperature stressing of capacitor structures using 5 nm ruthenium-phosphorus film as a barrier to copper diffusion and analysis of the times-to-failure at accelerated temperature and field conditions implies that ruthenium-phosphorus performs acceptably as a diffusion barrier for temperatures above 165°C. The future problems associated with the copper capping layer are primarily due to the poor adhesion between copper and the current Si-based capping layers. Cobalt, which adheres well to copper, has been widely proposed to replace the Si-based materials, but its ability to prevent copper diffusion must be improved if it is to be successfully implemented in the interconnect. Using a dual-source chemistry of dicobaltoctacarbonyl and trimethylphosphine at temperatures from 250-350°C, amorphous cobalt-phosphorus can be deposited by chemical vapor deposition. The films contain elemental cobalt and phosphorus, plus some carbon impurity, which is incorporated in the film as both graphitic and carbidic (bonded to cobalt) carbon. When deposited on copper, the adhesion between the two materials remains strong despite the presence of phosphorus and carbon at the interface, but the selectivity for growth on copper compared to silicon dioxide is poor and must be improved prior to consideration for application in interconnect systems. A single molecule precursor containing both cobalt and phosphorus atoms, tetrakis

  20. Preparation of Different Substitued Polypyridine Ligands, Ruthenium(II)-Bridged Complexes and Spectoscopıc Studies.

    Science.gov (United States)

    Obali, Aslihan Yilmaz; Ucan, Halil Ismet

    2016-09-01

    Novel different substitued polypyridine ligands 4-((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)phenoxy)methyl)benzaldehyde (BA-PPY), (E)-N-(4-((4-(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)phenoxy)methyl)benzylidene)-pyrene-4-amine (PR-PPY), (E)-N-(4-((4-(1H-imidazo[4,5-f][1,10] phenanthroline-2-yl)phenoxy)methyl)benzylidene)-1,10-phenanthroline-5amine (FN-PPY), 2-(4-(bromomethyl)phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (BR-PPY), 2-(4-(azidomethyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (N3-PPY) and triazole containing polypyridine ligand 3,4-bis[(4-(metoxy)-1,2,3-triazole)1-methylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)] benzaldehyde (BA-DIPPY) and Ruthenium(II) complexes were synthesized and characterized. Their photopysical properties were investigated. The complexes RuP(PR-PPY), RuB(PR-PPY, RuP(FN-PPY) and RuB(FN-PPY) exhibited a broad absorption bands at 485, 475, 476, and 453 nm, respectively, assignable to the spin-allowed MLCT (dπ-π*) transition. The emission maxima of the pyrene-appended polypyridine ligand PR-PPY was observed at λems = 616 nm and the phenanthroline-appended polypyridine ligand FN-PPY was observed at λems = 668 nm. And the emission maxima of the complexes RuP(PR-PPY), RuB(PR-PPY), RuP(FN-PPY) and RuB(FN-PPY) were observed at λems = 646, 646, 685 and 685 nm, respectively. As seen in fluorescence spectra, the fluorescence intensities of the ligands are higher than their metal complexes. This is because of quenching effect of Ruthenium(II) metal on chromophore groups.

  1. Ultrafast relaxation dynamics of amine-substituted bipyridyl ruthenium(II) complexes

    Science.gov (United States)

    Song, Hongwei; Wang, Xian; Yang, WenWen; He, Guiying; Kuang, Zhuoran; Li, Yang; Xia, Andong; Zhong, Yu-Wu; Kong, Fan'ao

    2017-09-01

    The excited state properties of a series of ruthenium(II) amine-substituted bipyridyl complexes, [Ru(bpy)n(NNbpy)3-n]2+, were investigated by steady-state and transient absorption spectroscopy, as well as quantum chemical calculations. The steady-state absorption spectra of these complexes in CH3CN show a distinct red-shift of the 1MLCT absorption with increasing numbers of amine substituent, whereas the emission spectra indicate an energy gap order of [Ru(bpy)3]2+ > [Ru(bpy)2(NNbpy)]2+ > [Ru(NNbpy)3]2+ > [Ru(bpy)(NNbpy)2]2+. Nanosecond, femtosecond transient absorption and electrochemical measurements suggest that NNbpy ligand has a strong influence on the electronic and emission properties of these complexes, due to electron-rich amine substituent. We illustrate how the numbers of amine substituent modulate the spectroscopic properties of transition metal complexes, which is related to the design of new electro-active systems with novel photoelectrochemical properties.

  2. Separation of carrier-free rhodium isotopes from ruthenium cyclotron targets by the extraction of nitrosylruthenium from hydrochloric acid solution

    International Nuclear Information System (INIS)

    Haasbroek, F.J.; Strelow, F.W.E.; Van der Walt, T.N.

    1981-01-01

    A method is presented for the separation of rhodium isotopes from ruthenium cyclotron targets. After bombardment with deuterons and dissolution of the target material, the ruthenium is converted into a nitrosyl complex by treatment with hydroxylammonium chloride. Aluminium and other elements which have been introduced in the dissolution step, are separated by cation exchange. Ruthenium is then separated by extraction with a mixture of tri-n-butyl phosphate and hexane (4:1), leaving the rhodium in the aqueous phase. No ruthenium is found in the rhodium fraction and the recovery of rhodium is better than 90 per cent [af

  3. Rare earth-ruthenium-magnesium intermetallics

    Energy Technology Data Exchange (ETDEWEB)

    Stein, Sebastian; Kersting, Marcel; Heletta, Lukas; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2017-07-01

    Eight new intermetallic rare earth-ruthenium-magnesium compounds have been synthesized from the elements in sealed niobium ampoules using different annealing sequences in muffle furnaces. The compounds have been characterized by powder and single crystal X-ray diffraction. Sm{sub 9.2}Ru{sub 6}Mg{sub 17.8} (a=939.6(2), c=1779(1) pm), Gd{sub 11}Ru{sub 6}Mg{sub 16} (a=951.9(2), c=1756.8(8) pm), and Tb{sub 10.5}Ru{sub 6}Mg{sub 16.5} (a=942.5(1), c=1758.3(4) pm) crystallize with the tetragonal Nd{sub 9.34}Ru{sub 6}Mg{sub 17.66} type structure, space group I4/mmm. This structure exhibits a complex condensation pattern of square-prisms and square-antiprisms around the magnesium and ruthenium atoms, respectively. Y{sub 2}RuMg{sub 2} (a=344.0(1), c=2019(1) pm) and Tb{sub 2}RuMg{sub 2} (a=341.43(6), c=2054.2(7) pm) adopt the Er{sub 2}RuMg{sub 2} structure and Tm{sub 3}Ru{sub 2}Mg (a=337.72(9), c=1129.8(4) pm) is isotypic with Sc{sub 3}Ru{sub 2}Mg. Tm{sub 3}Ru{sub 2}Mg{sub 2} (a=337.35(9), c=2671(1) pm) and Lu{sub 3}Ru{sub 2}Mg{sub 2} (a=335.83(5), c=2652.2(5) pm) are the first ternary ordered variants of the Ti{sub 3}Cu{sub 4} type, space group I4/mmm. These five compounds belong to a large family of intermetallics which are completely ordered superstructures of the bcc subcell. The group-subgroup scheme for Lu{sub 3}Ru{sub 2}Mg{sub 2} is presented. The common structural motif of all three structure types are ruthenium-centered rare earth cubes reminicent of the CsCl type. Magnetic susceptibility measurements of Y{sub 2}RuMg{sub 2} and Lu{sub 3}Ru{sub 2}Mg{sub 2} samples revealed Pauli paramagnetism of the conduction electrons.

  4. Some factors influencing the absorption, retention and elimination of ruthenium; Facteurs agissant sur l'absorption, la retention et l'elimination du ruthenium; Nekotorye faktory, vliyakshchie na vsasyvanie, zaderzhku i vydelenie ruteniya; Factores que influyen sobre la absorcion, retencion y eliminacion de rutenio

    Energy Technology Data Exchange (ETDEWEB)

    Bruce, R. S. [Radiobiological Research Council, Medical Research Council, Harwell (United Kingdom)

    1963-02-15

    The radioactive isotopes of ruthenium, Ru{sup 103} (t1/2 = 40 d) and Ru{sup 106}(t1/2 = 1 yr), are formed in relatively high yield as a result of nuclear fission of U{sup 235}. There is almost no information on the metabolism of ruthenium by man and the following considerations are based on investigations with rats and rabbits. The nature and extent of the hazard from radioruthenium will depend not only on the circumstances of contamination but also on the physical and chemical state of the ruthenium; Ru{sup 106} administered orally as the dioxide is absorbed from the gastro-intestinal tract to a negligible extent when it is in a particulate form with carrier present but when given as a colloid in the absence of carrier, uptake is similar to that which follows administration of the chloride (3-5%). Nitrato-derivatives of nitrosyl ruthenium may be absorbed to an even greater extent (an average of 13% is absorbed by rabbits). Absorption by rats, which are not fasted, is complete within one hour of an intragastric dose. The limited period of absorption may be explained in terms of the rate of gastric emptying and combination of ruthenium with the contents of the gut. When rats are fasted overnight before the ruthenium is administered, absorption is increased threefold-and continues over a longer period. Nitrato derivatives of nitrosyl-ruthenium, in contrast to other compounds tested, react with the wall of the upper small intestine where up to 20% of an oral dose may be retained for several hours. Although the chemical state of ruthenium influences the degree of absorption, the subsequent distribution is not greatly affected. Approximately half of the absorbed ruthenium is excreted in the urine during the first 24 h. After one month, 5 to 20% of the absorbed fraction is retained with a long biological half-life. The ruthenium is distributed throughout the body with the concentrations in the various organs seldem differing by a factor of more than five, though the

  5. Synthesis of methyl acetate from dimethyl ether using group VIII metal salts of phosphotungstic acid

    Energy Technology Data Exchange (ETDEWEB)

    Sardesai, A.; Lee, S.; Tartamella, T.

    2002-04-01

    Dimethyl ether (DME) can be produced much more efficiently in a single-stage, liquid-phase process from natural gas-based syngas as compared to the conventional process via dehydration of methanol. This process, based on dual catalysts slurried in inert oil, alleviates the chemical equilibrium limitation governing the methanol synthesis reaction and concurrently improves per-pass syngas conversion and reactor productivity. The potential, therefore, for production of methyl acetate via dimethyl ether carbonylation is of industrial importance. In the present study, conversion of dimethyl ether and carbon monoxide to methyl acetate is investigated over a variety of group VIII metal-substituted phosphotungstic acid salts. Experimental results of this catalytic reaction using rhodium, iridium, ruthenium, and palladium catalysts are evaluated and compared in terms of selectivity toward methyl acetate. The effects of active metal, support types, multiple metal loading, and feed conditions on carbonylation activity of DME are examined. Iridium metal substituted phosphotungstic acid supported on Davisil type 643 (pore size 150 A, surface area 279 m{sup 2}/g, mesh size 230-425) silica gel shows the highest activity for DME carbonylation. (author)

  6. Amidines for versatile ruthenium(II)-catalyzed oxidative C-H activations with internal alkynes and acrylates.

    Science.gov (United States)

    Li, Jie; John, Michael; Ackermann, Lutz

    2014-04-25

    Cationic ruthenium complexes derived from KPF6 or AgOAc enabled efficient oxidative CH functionalizations on aryl and heteroaryl amidines. Thus, oxidative annulations of diversely decorated internal alkynes provided expedient access to 1-aminoisoquinolines, while catalyzed C-H activations with substituted acrylates gave rise to structurally novel 1-iminoisoindolines. The powerful ruthenium(II) catalysts displayed a remarkably high site-, regio- and, chemoselectivity. Therefore, the catalytic system proved tolerant of a variety of important electrophilic functional groups. Detailed mechanistic studies provided strong support for the cationic ruthenium(II) catalysts to operate by a facile, reversible C-H activation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Recovery of valuable metals from polymetallic mine tailings by natural microbial consortium.

    Science.gov (United States)

    Vardanyan, Narine; Sevoyan, Garegin; Navasardyan, Taron; Vardanyan, Arevik

    2018-05-28

    Possibilities for the recovery of non-ferrous and precious metals from Kapan polymetallic mine tailings (Armenia) were studied. The aim of this paper was to study the possibilities of bioleaching of samples of concentrated tailings by the natural microbial consortium of drainage water. The extent of extraction of metals from the samples of concentrated tailings by natural microbial consortium reached 41-55% and 53-73% for copper and zinc, respectively. Metal leaching efficiencies of pure culture Leptospirillum ferrooxidans Teg were higher, namely 47-93% and 73-81% for copper and zinc, respectively. The content of gold in solid phase of tailings increased about 7-16% and 2-9% after bio-oxidation process by L. ferrooxidans Teg and natural microbial consortium, respectively. It was shown that bioleaching of the samples of tailings could be performed using the natural consortium of drainage water. However, to increase the intensity of the recovery of valuable metals, natural consortium of drainage water combined with iron-oxidizing L. ferrooxidans Teg has been proposed.

  8. Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Yesildag, Ali [Department of Chemistry, Faculty of Sciences, Atatuerk University, 25240 Erzurum (Turkey); Ekinci, Duygu, E-mail: dekin@atauni.edu.t [Department of Chemistry, Faculty of Sciences, Atatuerk University, 25240 Erzurum (Turkey)

    2010-09-30

    In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN){sub 6}{sup 3-} and Ru(NH{sub 3}){sub 6}{sup 3+} by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.

  9. Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

    International Nuclear Information System (INIS)

    Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan

    2016-01-01

    Highlights: • Formation of nanoparticles of Pt and Ru on hydroxyapatite surface support (HAP). • Pt catalyst more active and stable than Ru catalyst in dry reforming of methane (DRM). • Low carbon deposition on the surface of Pt catalyst after reaction. • Quantification of water as by-product of the reaction for the first time. • Good mass balance of the reaction. - Abstract: This work focused on the catalytic transformation of methane (CH 4 ) and carbon dioxide (CO 2 ) into syngas (mixture of CO and H 2 ). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400–700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

  10. Catalytic transformation of carbon dioxide and methane into syngas over ruthenium and platinum supported hydroxyapatites

    Energy Technology Data Exchange (ETDEWEB)

    Rêgo De Vasconcelos, Bruna; Zhao, Lulu; Sharrock, Patrick; Nzihou, Ange; Pham Minh, Doan, E-mail: doan.phamminh@mines-albi.fr

    2016-12-30

    Highlights: • Formation of nanoparticles of Pt and Ru on hydroxyapatite surface support (HAP). • Pt catalyst more active and stable than Ru catalyst in dry reforming of methane (DRM). • Low carbon deposition on the surface of Pt catalyst after reaction. • Quantification of water as by-product of the reaction for the first time. • Good mass balance of the reaction. - Abstract: This work focused on the catalytic transformation of methane (CH{sub 4}) and carbon dioxide (CO{sub 2}) into syngas (mixture of CO and H{sub 2}). Ruthenium- and platinum-based catalysts were prepared using hydroxyapatite (HAP) as catalyst support. Different methods for metal deposition were used including incipient wetness impregnation (IWI), excess liquid phase impregnation (LIM), and cationic exchange (CEX). Metal particle size varied in large range from less than 1 nm to dozens nm. All catalysts were active at 400–700 °C but only Pt catalyst prepared by IWI method (Pt/HAP IWI) was found stable. The catalytic performance of Pt/HAP IWI could be comparable with the literature data on noble metal-based catalysts, prepared on metal oxide supports. For the first time, water was experimentally quantified as a by-product of the reaction. This helped to correctly buckle the mass balance of the process.

  11. Ruthenium complexing during sorption by graft copolymer of polyacrylonitrile fibre with poly-2-methyl-5-vnylpyridine (PAN-MVP)

    International Nuclear Information System (INIS)

    Simanova, S.A.; Kolmakova, A.I.; Konovalov, L.V.; Kukushkin, Yu.N.; Lysenko, A.A.

    1984-01-01

    The sorption of ruthenium chlorocomplexes is studied on graft copolymer of polyacrylonitrile fibre with poly-2-methyl-5-vinylpyridine (PAN-MVP). The sorption has been performed under static conditions in the course of mixing at 20 and 98 deg from 0.1-2 OM HCl, 0.1-1 m NaCl solutions. The volume of the investigated solutions constituted 25 ml, fibre weight -0.1-0.3 g. Ruthenium concentration in solutions has been changed in the limits of 5x10 3 -2x10 -2 mol/l. The fibre has been preliminarily moistened by a solution containing no ruthenium. In all cases fresh-prepared ruthenium chlorocomplex solutions have been used. It has been found that with temperature increase the PAN-MVP sorption capacitance relative to ruthenium increases (at 20 deg-1.15 mmol/g, at 98 deg-1.70 mmol/g. The ruthenium chlorocomplex sorption by pyridine fibrous sorbent from salt-acid solutions occurs by anionoexchange mechanism and is related to the formation in the sorbent phase of onium chlorocomplexes - (RPyH) 2 [RuCl 6 ]. In the course of sorbents heating pyridine compounds are subject to Anderson regroupping with formation of compounds of diamine type-[Ru(RPy) 2 Cl 4

  12. Dye sensitized photovoltaic cells: Attaching conjugated polymers to zwitterionic ruthenium dyes

    DEFF Research Database (Denmark)

    Krebs, Frederik C; Biancardo, M.

    2006-01-01

    The synthesis of a zwitterionic ruthenium dye that binds to anatase surfaces and has a built-in functionality that allows for the attachment of a conjugated polymer chain is presented. The system was found to adsorb on the surface of anatase anchored by the ruthenium dye. Two types of devices were...... prepared: standard photoelectrochemical (PEC) solar cells and polymer solar cells. The PEC solar cells employed a sandwich geometry between TiO2 nanoporous photoanodes and Pt counter electrodes using LiI/I-2 in CH3CN as an electrolyte. The polymer solar cells employed planar anatase electrodes...

  13. The influence of a new fabrication procedure on the catalytic activity of ruthenium-selenium catalysts

    International Nuclear Information System (INIS)

    Cheng, H.; Yuan, W.; Scott, K.

    2006-01-01

    A new procedure has been introduced to enhance catalytic activity of ruthenium-selenium electro-catalysts for oxygen reduction, in which materials are treated under hydrogen atmosphere at elevated temperatures. The characterisation using scanning electron microscopy, energy dispersive spectroscopy or energy dispersive X-ray spectroscopy exhibited that the treatment at 400 deg. C made catalysts denser while their porous nature remained, led to a good degree of crystallinity and an optimum Se:Ru ratio. The half cell test confirms feasibility of the new procedure; the catalyst treated at 400 deg. C gave the highest reduction current (55.9 mA cm -2 at -0.4 V) and a low methanol oxidation effect coefficient (3.8%). The direct methanol fuel cell with the RuSe 400 deg. C cathode catalyst (2 mg RuSe cm -2 ) generated a power density of 33.8 mW cm -2 using 2 M methanol and 2 bar oxygen at 90 deg. C. The new procedure produced the catalysts with low decay rates. The best sample was compared to the Pt and to the reported ruthenium-selenium catalyst. Possible reasons for the observations are discussed

  14. Nuclear processes in deuterium/natural hydrogen-metal systems

    International Nuclear Information System (INIS)

    Zelensky, V.F.

    2013-01-01

    The survey presents the analysis of the phenomena taking place in deuterium - metal and natural hydrogen - metal systems under cold fusion experimental conditions. The cold fusion experiments have shown that the generation of heat and helium in the deuterium-metal system without emission of energetic gamma-quanta is the result of occurrence of a chain of chemical, physical and nuclear processes observed in the system, culminating in both the fusion of deuterium nuclei and the formation of a virtual, electron-modified excited 4He nucleus. The excitation energy of the helium nucleus is transferred to the matrix through emission of conversion electrons, and that, under appropriate conditions, provides a persistent synthesis of deuterium. The processes occurring in the deuterium/natural hydrogen - metal systems have come to be known as chemonuclear DD- and HD-fusion. The mechanism of stimulation of weak interaction reactions under chemonuclear deuterium fusion conditions by means of strong interaction reactions has been proposed. The results of numerous experiments discussed in the survey bear witness to the validity of chemonuclear fusion. From the facts discussed it is concluded that the chemonuclear deuterium fusion scenario as presented in this paper may serve as a basis for expansion of deeper research and development of this ecologically clean energy source. It is shown that the natural hydrogen-based system, containing 0.015% of deuterium, also has good prospects as an energy source. The chemonuclear fusion processes do not require going beyond the scope of traditional physics for their explanation

  15. Ruthenium Complexes as NO Donors for Vascular Relaxation Induction

    Directory of Open Access Journals (Sweden)

    Renata Galvão de Lima

    2014-07-01

    Full Text Available Nitric oxide (NO donors are substances that can release NO. Vascular relaxation induction is among the several functions of NO, and the administration of NO donors is a pharmacological alternative to treat hypertension. This review will focus on the physicochemical description of ruthenium-derived NO donor complexes that release NO via reduction and light stimulation. In particular, we will discuss the complexes synthesized by our research group over the last ten years, and we will focus on the vasodilation and arterial pressure control elicited by these complexes. Soluble guanylyl cyclase (sGC and potassium channels are the main targets of the NO species released from the inorganic compounds. We will consider the importance of the chemical structure of the ruthenium complexes and their vascular effects.

  16. Flotation-spectrophotometric determination of ruthenium in the Ru(IV)-chloride-rhodamine 6G-toluene system

    International Nuclear Information System (INIS)

    Balcerzak, M.

    1985-01-01

    The reduction of RuO 4 in hydrochloric acid has been examined. A sensitive flotation-spectrophotometric method of the determination of ruthenium based on the ion associate formed by the anionic chlorid complex of ruthenium RuCl 2- 6 with the basic dye Rhodamine 6G (R6G) has been developed. The solution of the ion associate obeys Beer's law up to the concentration of 0.25 μg Ru/ml. The ion associate precipitates when the aqueous solution is shaken with toluene. The separated compound is dissolved in acetone. The molar absorptivity (epsilon) at 530 nm is 5.1 x 10 5 l x mole -1 x cm -1 . The relative standard deviation is 3-7%. The mole ratio of Ru:R6G in the complex is 1:5. Osmium reacts similarly. The determination of ruthenium can be selective after the preliminary separation of osmium as OsO 4 . The method was applied to the determination of microgram amounts of ruthenium in crucible platinum. (Author)

  17. Macromolecules containing bipyridine and terpyridine metal complexes: towards metallo-supramolecular polymers

    NARCIS (Netherlands)

    Schubert, U.S.; Eschbaumer, C.

    2002-01-01

    The ability of a broad range of N-heterocycles to act as very effective and stable complexation agents for several transition metal ions, such as cobalt(II), copper(II), nickel(II), and ruthenium(II), has long been known in analytical chemistry. This behavior was later utilized in supramolecular

  18. Properties and application of noble metal catalysts for heterogeneous catalytic hydrogenations

    Energy Technology Data Exchange (ETDEWEB)

    Horn, G; Frohning, C D; Cornils, B [Ruhrchemie A.G., Oberhausen (Germany, F.R.)

    1976-07-01

    The special properties of the six platinum group elements - ruthenium, rhodium, palladium, osmium, iridium, platinum - make them useful as active metals for catalytic reactions. Especially valuable is their property of favouring a single reaction even when the possibility of a number of parallel reactions exists under certain reaction conditions. This selectivity of the noble metal catalyst may be directed or enhanced through appropriate choise of the metal, the reaction conditions, the duration of the reaction, the amount of hydrogen etc. Even the physical state of the catalyst - supported or unsupported - is of influence when using noble metal catalysts as described in this report.

  19. Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole in the presence of edta

    International Nuclear Information System (INIS)

    Busev, A.I.; Ignat'eva, T.I.; Lomakina, L.N.

    1975-01-01

    Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole (2MBI), 2-mercaptobenzoxazole (2MBO) and 2-mercaptobenzothiazole (2MBT) in the presence of EDTA was studied. The interaction of ruthenium (4) and osmium (4) with EDTA was constidered. Ruthenium complex is formed with constant output at 2-4.5 pH after 30 min.heating. In the lowacid solution (pH 2-4) osmium reacts with EDTA forming soluble compound. Characteristics of ruthenium (4) compound with 2MBI, 2MBO and 2MBT produced in the presence of EDTA are presented. Osmium (4) in the presence of EDTA and above mentioned organic reagents and when heating forms lowsoluble compounds. Possibility of joint determination of ruthenium and osmium with help of 2MBI in the presence of EDTA under conditions of minimum complexing osmium with EDTA was investigated

  20. Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole in the presence of EDTA

    Energy Technology Data Exchange (ETDEWEB)

    Busev, A I; Ignat' eva, T I; Lomakina, L N [Moskovskij Gosudarstvennyj Univ. (USSR). Kafedra Analiticheskoj Khimii

    1975-05-01

    Interaction of ruthenium (4) and osmium (4) with 2-mercaptobenzimidazole (2MBI), 2-mercaptobenzoxazole (2MBO) and 2-mercaptobenzothiazole (2MBT) in the presence of EDTA was studied. The interaction of ruthenium (4) and osmium (4) with EDTA was considered. Ruthenium complex is formed with constant output at 2-4.5 pH after 30 min. heating. In the low acid solution (pH 2-4) osmium reacts with EDTA forming soluble compound. Characteristics of ruthenium (4) compound with 2MBI, 2MBO and 2MBT produced in the presence of EDTA are presented. Osmium (4) in the presence of EDTA and above mentioned organic reagents and when heating forms low soluble compounds. Possibility of joint determination of ruthenium and osmium with help of 2MBI in the presence of EDTA under conditions of minimum complexing osmium with EDTA was investigated.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  2. Supercapacitive performance of hydrous ruthenium oxide (RuO2 ...

    Indian Academy of Sciences (India)

    gel method have been employed to prepare ruthenium oxide thin films. Recently ... the potentiostat (263A EG&G, Princeton Applied Research. Potentiostat). .... is a mixed conductor that conducts protons and electrons in acidic solution (as ...

  3. Iodide Ion Pairing with Highly Charged Ruthenium Polypyridyl Cations in CH3CN.

    Science.gov (United States)

    Swords, Wesley B; Li, Guocan; Meyer, Gerald J

    2015-05-04

    A series of three highly charged cationic ruthenium(II) polypyridyl complexes of the general formula [Ru(deeb)3-x(tmam)x](PF6)2x+2, where deeb is 4,4'-diethyl ester-2,2'-bipyridine and tmam is 4,4'-bis[(trimethylamino)methyl]-2,2'-bipyridine, were synthesized and characterized and are referred to as 1, 2, or 3 based on the number of tmam ligands. Crystals suitable for X-ray crystallography were obtained for the homoleptic complex 3, which was found to possess D3 symmetry over the entire ruthenium complex. The complexes displayed visible absorption spectra typical of metal-to-ligand charge-transfer (MLCT) transitions. In acetonitrile, quasi-reversible waves were assigned to Ru(III/II) electron transfer, with formal reduction potentials that shifted negative as the number of tmam ligands was increased. Room temperature photoluminescence was observed in acetonitrile with quantum yields of ϕ ∼ 0.1 and lifetimes of τ ∼ 2 μs. The spectroscopic and electrochemical data were most consistent with excited-state localization on the deeb ligand for 1 and 2 and on the tmam ligand for 3. The addition of tetrabutylammonium iodide to the complexes dissolved in a CH3CN solution led to changes in the UV-vis absorption spectra consistent with ion pairing. A Benesi-Hildebrand-type analysis of these data revealed equilibrium constants that increased with the cationic charge 1 10(8) s(-1). The possible relevance of this work to solar energy conversion and dye-sensitized solar cells is discussed.

  4. Spectrographic analysis of metallic silicium and natural quartz

    International Nuclear Information System (INIS)

    Grigoletto, T.; Lordello, A.R.

    1985-01-01

    A method has been developed for the spectrographic determination of B, Mg, Al, Ca, Ti, Mn, Fe, Ni, Cu and Ag in silicon metal and other for Al, Ca, Mg, Ti, Cr, Mn, and Fe in natural quartz. A mixture of the matrix with a proper buffer is excited directly in a dc-arc. High-current (25A) and argon atmosphere are used for both the methods. Silicon metal is blended with 8% NaF and after 1:1 (w/w) with graphite. For natural quartz 20% NaF and 30% graphite by weight is the buffer mixture employed. The lower values in the determinations varies from 0.5 to 40 μg/g and the precision of the analysis from 7% to 45%. (Author) [pt

  5. Dehydrogenative Coupling of Primary Alcohols To Form Esters Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Madsen, Robert

    2011-01-01

    The ruthenium complex [RuCl2(IiPr)(p-cymene)] catalyzes the direct condensation of primary alcohols into esters and lactones with the release of hydrogen gas. The reaction is most effective with linear aliphatic alcohols and 1,4-diols and is believed to proceed with a ruthenium dihydride...

  6. One-pot hydrothermal synthesis of ruthenium oxide nanodots on reduced graphene oxide sheets for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Chen Yao [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Graduate University of Chinese Academy Sciences, Beijing 100049 (China); Zhang Xiong [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Zhang Dacheng [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Graduate University of Chinese Academy Sciences, Beijing 100049 (China); Ma Yanwei, E-mail: ywma@mail.iee.ac.cn [Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190 (China)

    2012-01-15

    Highlights: > Graphite oxide instead of graphene as precursor has been used to synthesize reduced graphene oxide/ruthenium oxide composites by a hydrothermal treatment. > Using NaOH solution to adjust pH of GO colloids leads to homogeneous ruthenium oxide deposited on reduced graphene oxide sheets. > A maximum capacitance of 471 F g{sup -1} is obtained at 0.5 A g{sup -1} for the composites when loading 40% of RuO{sub 2} and its life retention reaches 92% after 3000 cycles. - Abstract: Ruthenium oxide nanodots have been deposited on reduced graphene oxide (RGO) sheets homogeneously by hydrothermal and annealing methods. Adding NaOH solution in GO colloids prevents the restack and agglomeration of GO sheets when mixed with ruthenium chloride solution. Local crystallization of RuO{sub 2} in the composites is revealed by X-ray diffraction and transmission electron microscopy. The element mapping image demonstrates the uniform distribution of Ru on RGO sheets. Unlike the pure crystalline RuO{sub 2} exhibiting poor electrochemical performance, the composites present superior capacitive properties. The hydrothermal time is optimized and a maximum of 471 F g{sup -1} is measured in the composites at 0.5 A g{sup -1} when loaded with 45 wt% of RuO{sub 2}. After 3000 cycles, its specific capacitance remains 92% of the maximum capacitance. Our results suggest potential application of the reduced graphene oxide/ruthenium oxide composites to supercapacitors.

  7. One-pot hydrothermal synthesis of ruthenium oxide nanodots on reduced graphene oxide sheets for supercapacitors

    International Nuclear Information System (INIS)

    Chen Yao; Zhang Xiong; Zhang Dacheng; Ma Yanwei

    2012-01-01

    Highlights: → Graphite oxide instead of graphene as precursor has been used to synthesize reduced graphene oxide/ruthenium oxide composites by a hydrothermal treatment. → Using NaOH solution to adjust pH of GO colloids leads to homogeneous ruthenium oxide deposited on reduced graphene oxide sheets. → A maximum capacitance of 471 F g -1 is obtained at 0.5 A g -1 for the composites when loading 40% of RuO 2 and its life retention reaches 92% after 3000 cycles. - Abstract: Ruthenium oxide nanodots have been deposited on reduced graphene oxide (RGO) sheets homogeneously by hydrothermal and annealing methods. Adding NaOH solution in GO colloids prevents the restack and agglomeration of GO sheets when mixed with ruthenium chloride solution. Local crystallization of RuO 2 in the composites is revealed by X-ray diffraction and transmission electron microscopy. The element mapping image demonstrates the uniform distribution of Ru on RGO sheets. Unlike the pure crystalline RuO 2 exhibiting poor electrochemical performance, the composites present superior capacitive properties. The hydrothermal time is optimized and a maximum of 471 F g -1 is measured in the composites at 0.5 A g -1 when loaded with 45 wt% of RuO 2 . After 3000 cycles, its specific capacitance remains 92% of the maximum capacitance. Our results suggest potential application of the reduced graphene oxide/ruthenium oxide composites to supercapacitors.

  8. Catalytic polarographic currents of platinum metal complexes and their application to determination of trace concentrations of the elements

    International Nuclear Information System (INIS)

    Ezerskaya, N.A.; Kiseleva, I.N.

    1984-01-01

    Several types of catalytic electrode processes with the participation of platinum metal complexes and used for the determination of the element microconcentrations have been considered in the review. It is pointed out that to measure catalytic currents of hydrogen solutions nitroso compounds, which are prepared by heating chloride complexes of Ru(3) and (4) with NaNO 2 are used. The method is applicable for ruthenium determination in commercial nitric acid solutions. Ru determination in solution of ruthenium (4) dimeric chloride complex on graphite electrode, using catalytic currents of hydrogen, surpasses in sensitivity the determination of the element, using the method of inversion voltammetry. Certain other complexes of Ru and determination methods of ruthenium in them are considered. Hydrogen catalytic currents in the complexes solutions with organic ligands are the most perspective for analysis

  9. Viscosity measurements of molten refractory metals using an electrostatic levitator

    International Nuclear Information System (INIS)

    Ishikawa, Takehiko; Paradis, Paul-François; Okada, Junpei T; Watanabe, Yuki

    2012-01-01

    Viscosities of several refractory metals (titanium, nickel, zirconium, niobium, ruthenium, rhodium, hafnium, iridium and platinum) and terbium have been measured by the oscillation drop method with an improved procedure. The measured data were less scattered than our previous measurements. Viscosities at their melting temperatures showed good agreement with literature values and some predicted values. (paper)

  10. Ruthenium-modified cytochrome c: temperature dependence of the rate of intramolecular electron transfer

    International Nuclear Information System (INIS)

    Isied, S.S.; Kuehn, C.; Worosila, G.

    1984-01-01

    The ruthenium-modified horse heart cytochrome c, Ru(III)-cyt c(III), where the ruthenium is bound to the histidines-33 residue has been synthesized and characterized by ruthenium analysis, UV-vis and CD spectra, and differential pulse polarography and cyclic voltammetry. The intermediate Ru(III)-cyt c(III) has been generated by pulse-radioanalysis with use of four different radicals, CO 2 -., (CH 3 )COH., (CH 2 OH) 3 CCHOH, and -OCCH(OH)C(OH)CO 2 -. The rate of intramolecular electron transfer within the Ru(III)-cyt c(III) complex and its temperature dependence were determined over a 40 0 C temperature range with the CO 2 -. radical. At 25 0 C, these values are k/sub u/=53 +/- s/sup -1/ (pH 7.01 M phosphate buffer, 0.1 M NaHCO 2 ), ΔH/sup +/=3.5 +/- 0.2 kcal mol/sup -1/, and ΔS/sup +/=-39 +/- 1 eu

  11. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    Science.gov (United States)

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  12. The effect of NO2 on spectroscopic and structural properties of evaporated ruthenium phthalocyanine dimer

    International Nuclear Information System (INIS)

    Alagna, Lucilla; Capobianchi, Aldo; Paoletti, Anna Maria; Pennesi, Giovanna; Rossi, Gentilina; Casaletto, Maria Pia; Generosi, Amanda; Paci, Barbara; Albertini, Valerio Rossi

    2006-01-01

    The chemical interaction between NO 2 gas and dimeric ruthenium phthalocyanine (RuPc) 2 (Pc = phthalocyanine ligand) films has been investigated by different techniques: UV-Visible spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and Extended X-ray Absorption Fine Structure (EXAFS). The optical spectra in the Q band region (700-500 nm) registered 'in situ' enabled to follow the evolution of the process in real time indicating that a two steps reaction, showing two clear isosbestic points, occurs. The first phase was essentially characterised by: (a) the rapid disappearance of the 608 and 420 nm shoulders; (b) the intensity decrease of the main absorption peak and (c) the appearance of a new adsorption band centred around 510 nm. In the second step the remarkable feature is a further lowering of the main peak with the simultaneous decrease of the new 510 nm absorption. These spectral changes suggested that a chemical reaction occurred between NO 2 and ruthenium phthalocyanine with the formation of a radical species due to the macrocycle oxidation. The kinetics indicates that the adsorption of gas by the evaporated (RuPc) 2 film is a complex process involving more than one independent mechanism. XPS and EXAFS spectra collected before and after gas exposure showed that the central metals (Ru) were also involved in the oxidation process. The reversibility of the process has been also tested by treating the films at different temperatures, the original optical spectrum being not completely recovered

  13. Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

    Science.gov (United States)

    Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

    2010-01-04

    The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

  14. Mathematical modelling of brittle phase precipitation in complex ruthenium containing nickel-based superalloys

    International Nuclear Information System (INIS)

    Rettig, Ralf

    2010-01-01

    A new model has been developed in this work which is capable of simulating the precipitation kinetics of brittle phases, especially TCP-phases (topologically close packed phases) in ruthenium containing superalloys. The model simultaneously simulates the nucleation and the growth stage of precipitation for any number of precipitating phases. The CALPHAD method (Calculation of Phase Diagrams) is employed to calculate thermodynamic properties, such as the driving force or phase compositions in equilibrium. For calculation of diffusion coefficients, kinetic mobility databases which are also based on the CALPHAD-method are used. The model is fully capable of handling multicomponent effects, which are common in complex superalloys. Metastable phases can be treated and will automatically be dissolved if they get unstable. As the model is based on the general CALPHAD method, it can be applied to a broad range of precipitation processes in different alloys as long as the relevant thermodynamic and kinetic databases are available. The developed model proves that the TCP-phases precipitate in a sequence of phases. The first phase that is often formed is the metastable σ-phase because it has the lowest interface energy due to low-energy planes at the interface between matrix and precipitate. After several hundred hours the stable μ- and P-phases start to precipitate by nucleating at the σ-phase which is energetically favourable. During the growth of these stable phases the sigma-phase is continuously dissolved. It can be shown by thermodynamic CALPHAD calculations that the sigma-phase has a lower Gibbs free enthalpy than the μ- and P-phase. All required parameters of the model, such as interface energy and nucleate densities, have been estimated. The mechanisms of suppression of TCP-phase precipitation in the presence of ruthenium in superalloys were investigated with the newly developed model. It is shown by the simulations that ruthenium mostly affects the nucleation

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

    Energy Technology Data Exchange (ETDEWEB)

    Pflieger, Rachel [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Institut de Chimie Separative de Marcoule, UMR5257, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze Cedex (France)], E-mail: rachel_pflieger@yahoo.fr; Lefebvre, Leila [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Malki, Mohammed [CNRS/CEMHTI-1D Av. de la Recherche Scientifique, 45701 Orleans cedex 2 (France); Polytech Orleans, Universite d' Orleans, 8 rue Leonard de Vinci, 45072 Orleans cedex 2 (France); Allix, Mathieu [CNRS/CEMHTI-1D Av. de la Recherche Scientifique, 45701 Orleans cedex 2 (France); Grandjean, Agnes [DEN/DTCD-SCDV/CEA Valrho, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze (France); Institut de Chimie Separative de Marcoule, UMR5257, Centre de Marcoule, BP17171, 30207 Bagnols-sur-Ceze Cedex (France)

    2009-06-01

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

  16. Application of the ruthenium and technetium thermodynamic data bases used in the EQ3/6 geochemical codes

    Energy Technology Data Exchange (ETDEWEB)

    Isherwood, D.

    1985-04-01

    Based on a critical review of the available thermodynamic data, computerized data bases for technetium and ruthenium were created for use with the EQ3/6 geochemical computer codes. The technetium data base contains thermodynamic data for 8 aqueous species and 15 solids; 26 aqueous species and 9 solids were included in the ruthenium data base. The EQ3NR code was used to calculate solubility limits for ruthenium (8 x 10{sup -16} M) in ground water from Yucca Mountain, a potential nuclear waste repository site near the Nevada Test Site (NTS). The code confirmed the essentially unlimited solubility of technetium in oxidizing conditions, such as those that are believed to exist in the unsaturated zone at Yucca Mountain and the Cambric Nuclear event site at the NTS. Ruthenium migration observed from the Cambric site was evaluated. The solubility limit for ruthenium (as the aqueous species RuO{sub 4}{sup -}) when constrained by RuO{sub 2} is approximately equal to the concentration of ruthenium found in the cavity ground water (i.e., 2.1 x 10{sup -11} vs 4.5 x 10{sup -11} M). Differences in ruthenium solubility limits between Yucca Mountain and Cambric are primarily due to differences in ground-water pH. Technetium solubility (3 x 10{sup -8} M) for moderately reducing conditions (Eh = -0.1 V) using the metastable oxide, TcO{sub 2}.2H{sub 2}O, as the solubility constraint is within the range of experimental values recently published in a study of technetium sorption on basalt. Previously published technetium solubilities of 10{sup -12} to 10{sup -16} M were apparently based on a technetium data base that did not include aqueous species other than TcO{sub 4}{sup -}. When TcO(OH){sub 2}{sup 0} is included in the data base, the calculated values are much closer to the experimental results. Eh-pH diagrams were also generated for a variety of conditions using the SOLUPLOT code.

  17. Application of the ruthenium and technetium thermodynamic data bases used in the EQ3/6 geochemical codes

    International Nuclear Information System (INIS)

    Isherwood, D.

    1985-04-01

    Based on a critical review of the available thermodynamic data, computerized data bases for technetium and ruthenium were created for use with the EQ3/6 geochemical computer codes. The technetium data base contains thermodynamic data for 8 aqueous species and 15 solids; 26 aqueous species and 9 solids were included in the ruthenium data base. The EQ3NR code was used to calculate solubility limits for ruthenium (8 x 10 -16 M) in ground water from Yucca Mountain, a potential nuclear waste repository site near the Nevada Test Site (NTS). The code confirmed the essentially unlimited solubility of technetium in oxidizing conditions, such as those that are believed to exist in the unsaturated zone at Yucca Mountain and the Cambric Nuclear event site at the NTS. Ruthenium migration observed from the Cambric site was evaluated. The solubility limit for ruthenium (as the aqueous species RuO 4 - ) when constrained by RuO 2 is approximately equal to the concentration of ruthenium found in the cavity ground water (i.e., 2.1 x 10 -11 vs 4.5 x 10 -11 M). Differences in ruthenium solubility limits between Yucca Mountain and Cambric are primarily due to differences in ground-water pH. Technetium solubility (3 x 10 -8 M) for moderately reducing conditions (Eh = -0.1 V) using the metastable oxide, TcO 2 .2H 2 O, as the solubility constraint is within the range of experimental values recently published in a study of technetium sorption on basalt. Previously published technetium solubilities of 10 -12 to 10 -16 M were apparently based on a technetium data base that did not include aqueous species other than TcO 4 - . When TcO(OH) 2 0 is included in the data base, the calculated values are much closer to the experimental results. Eh-pH diagrams were also generated for a variety of conditions using the SOLUPLOT code

  18. Ruthenium release modelling in air and steam atmospheres under severe accident conditions using the MAAP4 code

    International Nuclear Information System (INIS)

    Beuzet, Emilie; Lamy, Jean-Sylvestre; Perron, Hadrien; Simoni, Eric; Ducros, Gérard

    2012-01-01

    Highlights: ► We developed a new modelling of fuel oxidation and ruthenium release in the EDF version of the MAAP4 code. ► We validated this model against some VERCORS experiments. ► Ruthenium release prediction quantitatively and qualitatively well reproduced under air and steam atmospheres. - Abstract: In a nuclear power plant (NPP), a severe accident is a low probability sequence that can lead to core fusion and fission product (FP) release to the environment (source term). For instance during a loss-of-coolant accident, water vaporization and core uncovery can occur due to decay heat. These phenomena enhance core degradation and, subsequently, molten materials can relocate to the lower head of the vessel. Heat exchange between the debris and the vessel may cause its rupture and air ingress. After lower head failure, steam and air entering in the vessel can lead to degradation and oxidation of materials that are still intact in the core. Indeed, Zircaloy-4 cladding oxidation is very exothermic and fuel interaction with the cladding material can decrease its melting temperature by several hundred of Kelvin. FP release can thus be increased, noticeably that of ruthenium under oxidizing conditions. Ruthenium is of particular interest because of its high radio-toxicity due to 103 Ru and 106 Ru isotopes and its ability to form highly volatile compounds, even at room temperature, such as gaseous ruthenium tetra-oxide (RuO 4 ). It is consequently of great need to understand phenomena governing steam and air oxidation of the fuel and ruthenium release as prerequisites for the source term issues. A review of existing data on these phenomena shows relatively good understanding. In terms of oxygen affinity, the fuel is oxidized before ruthenium, from UO 2 to UO 2+x . Its oxidation is a rate-controlling surface exchange reaction with the atmosphere, so that the stoichiometric deviation and oxygen partial pressure increase. High temperatures combined with the presence

  19. Cytogenotoxic effects of two potential anticancer Ruthenium(III Schiff Bases complexes

    Directory of Open Access Journals (Sweden)

    Izet Eminovic

    2016-10-01

    Full Text Available Introduction: Treatment of cancer has been subject of great interest. Researchers are continuously searching for new medicines. In this sense, ruthenium complexes have big potential. Some evidences suggest that ruthenium compounds possess anticancer activities. We synthesized two recently published ruthenium(III complexes with bidentate O,N and tridentate O,O,N Schiff bases derived from 5-substituted salicylaldehyde and aminophenol or anilineare. These compounds showed affinity for binding to the DNA molecule, however, insufficient data are available regarding their possible toxic effects on biological systems.Methods: In the present study we evaluated genotoxic, cytotoxic, and cytostatic effects of Na[RuCl2(L12] and Na[Ru(L22], using the Allium cepa assay.Results: Different toxic effects were observed depending on the substance, tested concentration, and endpoint measured. In general, the tested compounds significantly lowered the root growth and mitotic index values as compared to the control group. Additionally, a wide range of abnormal mitotic stages, both clastogenic and non-clastogenic were observed in the treated cells. Na[RuCl2(L12] significantly increased the frequency of sticky metaphases, chromosome bridges, micronuclei, impaired chromosome segregation, as well as number of apoptotic and necrotic cells over the controls. In contrast, Na[Ru(L22] did not show significant evidence of genotoxicity with regard to chromosome aberrations and micronuclei, however, significant differences were detected in the number of apoptotic and necrotic cells when the highest concentration was applied.Conclusions: In this study we demonstrated antiproliferative effects of Na[RuCl2(L12] and Na[Ru(L22]. At clinical level, these results could be interesting for further studies on anticancer potential of the ruthenium(III complexes using animal models.

  20. Diffuse urban pollution increases metal tolerance of natural heterotrophic biofilms

    International Nuclear Information System (INIS)

    Fechner, Lise C.; Gourlay-Francé, Catherine; Bourgeault, Adeline; Tusseau-Vuillemin, Marie-Hélène

    2012-01-01

    This study is a first attempt to investigate the impact of urban contamination on metal tolerance of heterotrophic river biofilms using a short-term test based on β-glucosidase activity. Tolerance levels to Cu, Cd, Zn, Ni and Pb were evaluated for biofilms collected at three sites along an urban gradient in the Seine river (France). Metallic pollution increased along the river, but concentrations remained low compared to environmental quality standards. Biofilm metal tolerance increased downstream from the urban area. Multivariate analysis confirmed the correlation between tolerance and contamination and between multi-metallic and physico-chemical gradients. Therefore, tolerance levels have to be interpreted in relation to the whole chemical and physical characteristics and not solely metal exposure. We conclude that community tolerance is a sensitive biological response to urban pressure and that mixtures of contaminants at levels lower than quality standards might have a significant impact on periphytic communities. - Highlights: ► A new short-term test based on β-glucosidase activity to assess biofilm metal tolerance. ► Cd, Cu, Ni, Pb and Zn tolerance of natural biofilms collected along an urban gradient. ► Metal tolerance levels increase upstream to downstream the river. ► Community tolerance increases at environmental quality standard exposure concentrations. ► Biofilm tolerance is a sensitive biological response to diffuse urban pollution. - Metal concentrations below environmental quality standards increase tolerance levels of natural, hetetrophic biofilms downstream from an urban area.

  1. Chemical vapor deposition of amorphous ruthenium-phosphorus alloy films

    International Nuclear Information System (INIS)

    Shin Jinhong; Waheed, Abdul; Winkenwerder, Wyatt A.; Kim, Hyun-Woo; Agapiou, Kyriacos; Jones, Richard A.; Hwang, Gyeong S.; Ekerdt, John G.

    2007-01-01

    Chemical vapor deposition growth of amorphous ruthenium-phosphorus films on SiO 2 containing ∼ 15% phosphorus is reported. cis-Ruthenium(II)dihydridotetrakis-(trimethylphosphine), cis-RuH 2 (PMe 3 ) 4 (Me = CH 3 ) was used at growth temperatures ranging from 525 to 575 K. Both Ru and P are zero-valent. The films are metastable, becoming increasingly more polycrystalline upon annealing to 775 and 975 K. Surface studies illustrate that demethylation is quite efficient near 560 K. Precursor adsorption at 135 K or 210 K and heating reveal the precursor undergoes a complex decomposition process in which the hydride and trimethylphosphine ligands are lost at temperatures as low at 280 K. Phosphorus and its manner of incorporation appear responsible for the amorphous-like character. Molecular dynamics simulations are presented to suggest the local structure in the films and the causes for phosphorus stabilizing the amorphous phase

  2. Stable tracer investigations in humans for assessing the biokinetics of ruthenium and zirconium radionuclides

    International Nuclear Information System (INIS)

    Veronese, I.; Cantone, M.C.; Giussani, A.; Maggioni, T.; Birattari, C.; Bondardi, M.; Groppi, F.; Garlaschelli, I.; Werner, E.; Roth, P.; Hoellriegl, V.; Louvat, P.; Felgenhauer, N.; Zilker, Th.

    2003-01-01

    The interest in the biokinetics of ruthenium and zirconium in humans is justified by the potential radiological risk represented by their radionuclides. Only a few data related to the biokinetics of ruthenium and zirconium in humans are available and, accordingly, the biokinetic models currently recommended by the ICRP for these elements are mainly based on data from animal experiments. The use of stable isotopes as tracers, coupled with a proper analytical technique (nuclear activation analysis with protons) for their determination in biological samples, represents an ethically acceptable methodology for biokinetic investigations, being free from any radiation risk for the volunteer subjects. In this work, the results obtained in eight biokinetic investigations for ruthenium, conducted on a total of three healthy volunteers, and six for zirconium, performed on a total of three subjects, are presented and compared to the predictions of the ICRP models. (author)

  3. Facile radiolytic synthesis of ruthenium nanoparticles on graphene oxide and carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Rojas, J.V., E-mail: jvrojas@vcu.edu [Mechanical and Nuclear Engineering Department, Virginia Commonwealth University, 401 West Main Street, Richmond, Virginia, 23284 (United States); Toro-Gonzalez, M.; Molina-Higgins, M.C. [Mechanical and Nuclear Engineering Department, Virginia Commonwealth University, 401 West Main Street, Richmond, Virginia, 23284 (United States); Castano, C.E., E-mail: cecastanolond@vcu.edu [Nanomaterials Core Characterization Facility, Chemical and Life Science Engineering Department, Virginia Commonwealth University, 601 West Main Street, Richmond, Virginia, 23284 (United States)

    2016-03-15

    Graphical abstract: - Highlights: • Facile radiolytic synthesis of Ru nanoparticles on graphene oxide and carbon nanotubes. • Homogeneously distributed Rh nanoparticles on supports are ∼2.5 nm in size. • Simultaneous reduction of graphene oxide and Ru ions occurs during the synthesis. • Ru-O bonds evidenced the interaction of the nanoparticles with the support. - Abstract: Ruthenium nanoparticles on pristine (MWCNT) and functionalized carbon nanotubes (f-MWCNT), and graphene oxide have been prepared through a facile, single step radiolytic method at room temperature, and ambient pressure. This synthesis process relies on the interaction of high energy gamma rays from a {sup 60}Co source with the water in the aqueous solutions containing the Ru precursor, leading to the generation of highly reducing species that further reduce the Ru metal ions to zero valence state. Transmission electron microscopy and X-Ray diffraction revealed that the nanoparticles were homogeneously distributed on the surface of the supports with an average size of ∼2.5 nm. X-ray Photoelectron spectroscopy analysis showed that the interaction of the Ru nanoparticles with the supports occurred through oxygenated functionalities, creating metal-oxygen bonds. This method demonstrates to be a simple and clean approach to produce well dispersed nanoparticles on the aforementioned supports without the need of any hazardous chemical.

  4. Facile radiolytic synthesis of ruthenium nanoparticles on graphene oxide and carbon nanotubes

    International Nuclear Information System (INIS)

    Rojas, J.V.; Toro-Gonzalez, M.; Molina-Higgins, M.C.; Castano, C.E.

    2016-01-01

    Graphical abstract: - Highlights: • Facile radiolytic synthesis of Ru nanoparticles on graphene oxide and carbon nanotubes. • Homogeneously distributed Rh nanoparticles on supports are ∼2.5 nm in size. • Simultaneous reduction of graphene oxide and Ru ions occurs during the synthesis. • Ru-O bonds evidenced the interaction of the nanoparticles with the support. - Abstract: Ruthenium nanoparticles on pristine (MWCNT) and functionalized carbon nanotubes (f-MWCNT), and graphene oxide have been prepared through a facile, single step radiolytic method at room temperature, and ambient pressure. This synthesis process relies on the interaction of high energy gamma rays from a "6"0Co source with the water in the aqueous solutions containing the Ru precursor, leading to the generation of highly reducing species that further reduce the Ru metal ions to zero valence state. Transmission electron microscopy and X-Ray diffraction revealed that the nanoparticles were homogeneously distributed on the surface of the supports with an average size of ∼2.5 nm. X-ray Photoelectron spectroscopy analysis showed that the interaction of the Ru nanoparticles with the supports occurred through oxygenated functionalities, creating metal-oxygen bonds. This method demonstrates to be a simple and clean approach to produce well dispersed nanoparticles on the aforementioned supports without the need of any hazardous chemical.

  5. Tunable preparation of ruthenium nanoparticles with superior size-dependent catalytic hydrogenation properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Yuan; Luo, Yaodong; Yang, Xuan; Yang, Yaxin; Song, Qijun, E-mail: qsong@jiangnan.edu.cn

    2017-06-15

    Highlights: • A facile and efficient strategy is firstly developed for the synthesis of Ru NPs. • Ru NPs are stable and uniform with the controllable sizes from 2.6 to 51.5 nm. • Ru NPs exhibit size-dependent and superior catalytic hydrogenation activity. - Abstract: Ruthenium (Ru) featured with an unusual catalytic behavior is of great significance in several heterogeneous and electro-catalytic reactions. The preparation of tractable Ru nanocatalysts and the building of highly active catalytic system at ambient temperature remains a grand challenge. Herein, a facile strategy is developed for the controllable preparation of Ru nanoparticles (NPs) with the sizes ranging from 2.6 to 51.5 nm. Ru NPs show superior size-dependent catalytic performance with the best kinetic rate constant as high as −1.52 min{sup −1}, which could far surpass the other traditional noble metals. Ru NPs exert exceedingly efficient low-temperature catalytic activity and good recyclability in the catalytic reduction of nitroaromatic compounds (NACs) and azo dyes. The developed catalytic system provides a distinguishing insight for the artificial preparation of Ru NPs with desired sizes, and allows for the development of rational design rules for exploring catalysts with superior catalytic performances, potentially broadening the applications of metallic NP-enabled catalytic analysis.

  6. Polystyrene with pendant mixed functional ruthenium(II)-terpyridine complexes

    NARCIS (Netherlands)

    Heller, M.; Schubert, U.S.

    2002-01-01

    A vinyl substituted 2,2:6,2-terpyridine and a mixed, bifunctional ruthenium(II)-terpyridine complex bearing a vinyl and a hydroxymethyl group are utilized as comonomers for radical copolymerization with styrene. The resulting polymers are characterized by means of UV-vis spectroscopy and gel

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

    Science.gov (United States)

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

  8. Synthesis, photo-, and electrochemistry of ruthenium bis(bipyridine) complexes comprising a N-heterocyclic carbene ligand.

    Science.gov (United States)

    Leigh, Vivienne; Ghattas, Wadih; Lalrempuia, Ralte; Müller-Bunz, Helge; Pryce, Mary T; Albrecht, Martin

    2013-05-06

    Analogues of [Ru(bpy)3](2+) were prepared in which one pyridine ligand site is substituted by a N-heterocyclic carbene (NHC) ligand, that is, either by an imidazolylidene with a variable wingtip group R (R = Me, 3a; R = Et, 3b; R = iPr, 3c), or by a benzimidazolylidene (Me wingtip group, 3d), or by a 1,2,3-triazolylidene (Me wingtip group, 3e). All complexes were characterized spectroscopically, photophysically, and electrochemically. An increase of the size of the wingtip groups from Me to Et or iPr groups distorts the octahedral geometry (NMR spectroscopy) and curtails the reversibility of the ruthenium oxidation. NHC ligands with methyl wingtip groups display reversible ruthenium oxidation at a potential that reflects the donor properties of the NHC ligand (triazolylidene > imidazolylidene > benzimidazolylidene). The most attractive properties were measured for the triazolylidene ruthenium complex 3e, featuring the smallest gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the series (2.41 eV), a slightly red-shifted absorption profile, and reasonable excited-state lifetime (188 ns) when compared to [Ru(bpy)3](2+). These features demonstrate the potential utility of triazolylidene ruthenium complexes as photosensitizers for solar energy conversion.

  9. Effect of solvent on Se-modified ruthenium/carbon catalyst for oxygen reduction

    Directory of Open Access Journals (Sweden)

    Chuanxiang Zhang

    2014-12-01

    Full Text Available Se-modified ruthenium supporting on carbon (Sex–Ru/C electrocatalyst was prepared by solvothermal one-step synthesis method. The reaction mechanism was revealed after discussing impact of different solvents (i-propanol and EG in solvotermal reaction. The result showed that the grain size of Se-modified ruthenium electrocatalyst was as small as 1 to 3 nm and highly dispersed on carbon surface. X-ray photoelectron spectroscopy (XPS presented that selenium mainly existed in the catalyst in the form of elemental selenium and selenium oxides when the solvent was EG and i-propanol, respectively. The oxygen reduction reaction (ORR performance was improved by appearance of selenium oxides.

  10. Mesoporous Transition Metal Oxides for Supercapacitors.

    Science.gov (United States)

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-10-14

    Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  11. About the value of Ruthenium 106 brachytherapy in the treatment of uveal melanomas

    International Nuclear Information System (INIS)

    Langmann, G.; Mosboeck, G.; Stuecklschwaiger, G.; Muellner, K.; Lechner, H.; Faulborn, J.

    2002-01-01

    Background: to investigate the clinical course, sequelae and visual function of uveal melanomas treated with Ruthenium 106 brachytherapy. Patients and method: 47 patients who underwent Ruthenium 106 brachytherapy between 1985 and 2000 were evaluated using Kaplan Meier statistical method. Mean follow up interval was 22 month (range 8 - 152 months). Results: Local tumor control rate was 85 %, 5 years possibility to avoid enucleation was 75 %. The most important sequelae were radiation optic neuropathy (29 %), maculopathy (37 %) and radiation retinopathy (32 %). After terminating the study the 34 % of the patients achieved a visual acuity of 20/40 and more, another 34 % had a visual function of 20/200 and lower. Conclusion: Ruthenium 106 brachytherapy is our method of choice in small medium sized uveal melanomas and a maximum tumor prominence of 6 mm. Tumors have to be located in the midperiphery and outer periphery of the fundus including the ciliary body. In addition to the indications introduced by Lommatzsch we treated ciliary body melanomas with a tumor base more than 3 clock hours (by shifting the plaque) as an alternative therapy to enucleation. (author)

  12. Oxidative dissolution of ruthenium deposits onto stainless steel by permanganate ions in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Floquet, S.; Eysseric, C.; Maurel, D. [Commissariat a l' Energie Atomique (CEA/Valrho), Bagnols-sur-Ceze (France)

    2008-07-01

    During spent nuclear fuel reprocessing ruthenium is liable to form black ruthenium deposits on the stainless steel walls of process equipments. These deposits promote corrosion and can eventually obstruct the off-gas lines. The results of decontamination of 304L stainless steel test specimens covered with RuO(OH){sub 2} . xH{sub 2}O deposits by permanganate ions in alkaline medium are described. The ruthenium deposits were dissolved by oxidation of RuO(OH){sub 2} to RuO{sub 4}{sup 2-} ions, while the permanganate ions were reduced to MnO{sub 4}{sup 2-} ions and then to manganese dioxide MnO{sub 2}. The parameters affecting the kinetics of oxidative dissolution of these deposits were examined. The results indicate that the oxidative dissolution kinetics depends on the instantaneous surface area of the deposit, and that the dissolution rate increases with the concentrations of MnO{sub 4}{sup -} and OH{sup -} ions. (orig.)

  13. Ground vs. excited state interaction in ruthenium-thienyl dyads : implications for through bond interactions in multicomponent systems

    NARCIS (Netherlands)

    Henry, William; Browne, Wesley R.; Ronayne, Kate L.; O’Boyle, Noel M.; Vos, Johannes G.; McGarvey, John J.

    2005-01-01

    The vibrational and photophysical properties of mononuclear ruthenium(II) and ruthenium(III) polypyridyl complexes based on the, ligands 2-(5-(pyridin-2"-yl)-1'H-1',2',4'-triaz-3'-yl)-thiophene, 2-(5-(pyrazin-2"-yl)-1'H-1',2,4-triaz-3'-yl)-thiophene, are reported. The effect of the introduction of

  14. Through-Space Paramagnetic NMR Effects in Host-Guest Complexes: Potential Ruthenium(III) Metallodrugs with Macrocyclic Carriers.

    Science.gov (United States)

    Chyba, Jan; Novák, Martin; Munzarová, Petra; Novotný, Jan; Marek, Radek

    2018-04-05

    The potential of paramagnetic ruthenium(III) compounds for use as anticancer metallodrugs has been investigated extensively during the past several decades. However, the means by which these ruthenium compounds are transported and distributed in living bodies remain relatively unexplored. In this work, we prepared several novel ruthenium(III) compounds with the general structure Na + [ trans-Ru III Cl 4 (DMSO)(L)] - (DMSO = dimethyl sulfoxide), where L stands for pyridine or imidazole linked with adamantane, a hydrophobic chemophore. The supramolecular interactions of these compounds with macrocyclic carriers of the cyclodextrin (CD) and cucurbit[ n]uril (CB) families were investigated by NMR spectroscopy, X-ray diffraction analysis, isothermal titration calorimetry, and relativistic DFT methods. The long-range hyperfine NMR effects of the paramagnetic guest on the host macrocycle are related to the distance between them and their relative orientation in the host-guest complex. The CD and CB macrocyclic carriers being studied in this account can be attached to a vector that attracts the drug-carrier system to a specific biological target and our investigation thus introduces a new possibility in the field of targeted delivery of anticancer metallodrugs based on ruthenium(III) compounds.

  15. Excitation energy transfer in ruthenium (II)-porphyrin conjugates led to enhanced emission quantum yield and 1O2 generation

    International Nuclear Information System (INIS)

    Pan, Jie; Jiang, Lijun; Chan, Chi-Fai; Tsoi, Tik-Hung; Shiu, Kwok-Keung; Kwong, Daniel W.J.; Wong, Wing-Tak; Wong, Wai-Kwok; Wong, Ka-Leung

    2017-01-01

    Porphyrins are good photodynamic therapy (PDT) agents due to its flexibility for modifications to achieve tumor localization and photo-cytotoxicity against cancer. Yet they are not perfect. In a Ru(polypyridyl)-porphyrin system, the Ru(polypyridyl) moiety improves the water solubility and cell permeability. Consider the similar excited state energies between Ru(polypyridyl) and porphyrin moieties; a small perturbation (e.g. Zn(II) metalation) would lead to a marked change in the energy migration process. In this work, we have synthesized a series of porphyrins conjugated with Ru(polypyridyl) complexes using different linkers and investigated their photophysical properties, which included singlet oxygen quantum yield and their in vitro biological properties, resulting from linker variation and porphyrin modification by Zn(II) metalation. - Graphical abstract: Four amphiphilic ruthenium(II)-porphyrin complexes were prepared that display energy transfer conversion with zinc coordination, lysosome specific target, low dark toxicity and efficient photodynamic therapy.

  16. 3-Methylindole-Based Tripodal Tetraphosphine Ruthenium Complexes in N2 Coordination and Reduction and Formic Acid Dehydrogenation

    Directory of Open Access Journals (Sweden)

    Fenna F. van de Watering

    2017-10-01

    Full Text Available The ruthenium(II complexes RuCl2L1H, RuCl2L1CF3, RuCl2L1OMe and RuCl2L2H were synthesized from [Ru(η6-benzeneCl(μ-Cl]2 and the corresponding tripodal tris-3-methylindolephosphine-based ligands L1H, L1CF3, L1OMe, and L2H. Stoichiometric reduction of these complexes with KC8 yielded the corresponding ruthenium(0 dinitrogen complexes. The latter complexes were studied in the N2 reduction with chlorosilanes and KC8, yielding stoichiometric amounts of the silylamines. The synthesized ruthenium(II complexes are also active catalysts for the formic acid dehydrogenation reaction.

  17. Metal Nanoparticles Supported on Al-MCM-41 via In Situ Aqueous Synthesis

    International Nuclear Information System (INIS)

    Alonso-Lemus, I.; Aguilar-Elguezabal, A.; Alvarez-Contreras, L.; Verde-Gomez, Y.

    2010-01-01

    MCM-41 have been used to custom synthesize catalysts in because of the controllable properties, such as pore size, active phase incorporation, crystal size, and morphology, among others. In this paper, a simple and versatile method for the incorporation of platinum, ruthenium, and palladium onto Al-MCM-41 mesoporous silica by direct inclusion of various precursors was studied. M/Al-MCM-41 structure, textural properties, morphology, and elemental composition were analyzed. The results obtained indicate that the Al-MCM-41 mesoporous-ordered structure was not affected by metallic particle incorporation. High-surface areas were obtained (1131 m2/g). Metallic nanoparticles dispersion on Al-MCM-41 was homogeneous for all samples and its particles sizes were between 6?nm to 20 nm. Microscopy results show round shape particles in platinum and palladium samples; however, ruthenium catalysts exhibit a spherical and rod shapes. Electrochemical testing for Pt/Al-MCM-41 showed electrocatalytic activity for H2 oxidation which indicates that these materials can be used as a catalyst in electrochemical devices.

  18. Ruthenium phosphine complexes as catalysts for alternating co-polymerization of ethylene and CO

    International Nuclear Information System (INIS)

    Gusev, O.V.; Kal'sin, A.M.; Peganov, T.A.; Petrovskij, P.V.; Belov, G.P.; Novikova, E.V.

    2000-01-01

    Ruthenium (2) complexes, [Ru(dppe) 2 (OTs) 2 ] and [Ru(PhP(CH 2 CH 2 CH 2 PPh 2 ) 2 )(OTs) 2 ], where dppe (diphenylphosphino)ethane; OTs = tosylate, were synthesized with the yield of 67 and 76%, respectively, and characterized by 31 P NMR. The properties of the above complexes as catalysts of alternating co-polymerization of ethylene and carbon monoxide were studied. A considerable increase in catalytic activity of the complexes was established in the presence of trifluoroacetic acid and 1,4-benzoquinone. These compounds are the first example of ruthenium complexes that catalyse co-polymerization of ethylene and CO [ru

  19. Estimation of very low concentrations of Ruthenium by spectrophotometric method using barbituric acid as complexing agent

    International Nuclear Information System (INIS)

    Ramakrishna Reddy, S.; Srinivasan, R.; Mallika, C.; Kamachi Mudali, U.; Natarajan, R.

    2012-01-01

    Spectrophotometric method employing numerous chromogenic reagents like thiourea, 1,10-phenanthroline, thiocyanate and tropolone is reported in the literature for the estimation of very low concentrations of Ru. A sensitive spectrophotometric method has been developed for the determination of ruthenium in the concentration range 1.5 to 6.5 ppm in the present work. This method is based on the reaction of ruthenium with barbituric acid to produce ruthenium(ll)tris-violurate, (Ru(H 2 Va) 3 ) -1 complex which gives a stable deep-red coloured solution. The maximum absorption of the complex is at 491 nm due to the inverted t 2g → Π(L-L ligand) electron - transfer transition. The molar absorptivity of the coloured species is 9,851 dm 3 mol -1 cm -1

  20. Study on volatilization mechanism of ruthenium tetroxide from nitrosyl ruthenium nitrate by using mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Kato, Tetsuya, E-mail: tkato@criepi.denken.or.jp [Nuclear Technology Research Laboratory, Central Research Institute of Electric Power Industry, 2-11-1 Iwado-kita, Komae-shi, Tokyo 201-8511 (Japan); Usami, Tsuyoshi; Tsukada, Takeshi [Nuclear Technology Research Laboratory, Central Research Institute of Electric Power Industry, 2-11-1 Iwado-kita, Komae-shi, Tokyo 201-8511 (Japan); Shibata, Yuki; Kodama, Takashi [Safety Technology Division, Japan Nuclear Fuel Ltd., Obuchi, Rokkasho-mura, Aomori 039-3212 (Japan)

    2016-10-15

    In a cooling malfunction accident of a high-level liquid waste (HLLW) tank, behavior of ruthenium (Ru) attracts much attention, since Ru could be oxidized to a volatile chemical form in the boiling and drying of HLLW, and part of radioactive Ru can potentially be released to the environment. In this study, nitrosyl Ru nitrate (Ru(NO)(NO{sub 3}){sub 3}) dissolved in nitric acid (HNO{sub 3}), which is commonly contained in a simulated HLLW, was dried and heated up to 723 K, and the evolved gas was introduced into a mass spectrometer. The well-known volatile species, ruthenium tetroxide (RuO{sub 4}) was detected in a temperature range between 390 K and 500 K with the peak top around 440 K. Various gases such as HNO{sub 3}, nitrogen dioxide (NO{sub 2}), nitrogen monoxide (NO) also evolved due to evaporation of the nitric acid and decomposition of the nitrate ions. The ion current of RuO{sub 4} seems to increase with the increasing decomposition of nitrate, while the evaporation of HNO{sub 3} decreases. More volatilization of RuO{sub 4} was observed from the HNO{sub 3} solution containing not only Ru(NO)(NO{sub 3}){sub 3} but also cerium nitrate (Ce(NO{sub 3}){sub 3}·6H{sub 2}O) which was added for extra supply of nitrate ion, compared with that from the HNO{sub 3} solution containing only Ru(NO)(NO{sub 3}){sub 3}. These experimental results suggest that Ru could be oxidized to form RuO{sub 4} by the nitrate ion as well as HNO{sub 3}. - Graphical abstract: Ion current intensities of the mass numbers corresponding to O, NO, O{sub 2}, NO{sub 2}, HNO{sub 3}, and RuO{sub 4} obtained in mass spectrometry for dried nitric acid solution containing Ru(NO)(NO{sub 3}){sub 3}. Heating rate: 5 K min{sup −1}, sample solution weight: 6.61 mg, contained Ru weight: 0.56 mg. The ion current of RuO{sub 4} increases with the increasing decomposition of nitrate, while the evaporation of HNO{sub 3} decreases. - Highlights: • Nitrosyl Ru nitrate (Ru(NO)(NO{sub 3}){sub 3}) dissolved in

  1. Kinetic method of ruthenium ion traces determination, basing on the reaction of oxidation of direct blue 6B, by means of hydrogen peroxide

    International Nuclear Information System (INIS)

    Suwinska, T.; Gregorowicz, A.; Matysek-Majewska, D.

    1980-01-01

    A sensitive and selective method of determination of ruthenium ion traces (1.10 - 3 μg/cm 3 ) has been worked out. The method is based on oxidation of direct blue 6B by hydrogen peroxide under acidic conditions at pH = 0,8 - 1,2 in the presence of ruthenium ions as catalyst. The method has been applied for determination of ruthenium traces in Pt, PdCl 2 , PtCl 4 and RhCl 3 .n H 2 O. In these materials ruthenium has been determined within the range of 1,10 - 2 % - 5,10 - 4 %. (author)

  2. Electronic structure of the indium tin oxide/nanocrystalline anatase (TiO2)/ruthenium-dye interfaces in dye-sensitized solar cells

    Science.gov (United States)

    Lyon, J. E.; Rayan, M. K.; Beerbom, M. M.; Schlaf, R.

    2008-10-01

    The electronic structure of two interfaces commonly found in dye-sensitized photovoltaic cells based on nanocrystalline anatase TiO2 ("Grätzel cells") was investigated using photoemission spectroscopy (PES). X-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS) measurements were carried out on the indium tin oxide (ITO)/TiO2 and the TiO2/cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)bis-tetrabutylammonium dye ("N719" or "Ruthenium 535-bisTBA") interfaces. Both contacts were investigated using a multistep deposition procedure where the entire structure was prepared in vacuum using electrospray deposition. In between deposition steps the surface was characterized with XPS and UPS resulting in a series of spectra, allowing the determination of the orbital and band lineup at the interfaces. The results of these efforts confirm previous PES measurements on TiO2/dye contacts prepared under ambient conditions, suggesting that ambient contamination might not have significant influence on the electronic structure at the dye/TiO2 interface. The results also demonstrate that there may be a significant barrier for electron injection at the sputtered ITO/TiO2 interface and that this interface should be viewed as a semiconductor heterojunction rather than as metal-semiconductor (Schottky) contact.

  3. Catalytic behaviors of ruthenium dioxide films deposited on ferroelectrics substrates, by spin coating process

    International Nuclear Information System (INIS)

    Khachane, M.; Nowakowski, P.; Villain, S.; Gavarri, J.R.; Muller, Ch.; Elaatmani, M.; Outzourhite, A.; Luk'yanchuk, I.; Zegzouti, A.; Daoud, M.

    2007-01-01

    Catalytic ruthenium dioxide films were deposited by spin-coating process on ferroelectric films mainly constituted of SrBi 2 Ta 2 O 9 (SBT) and Ba 2 NaNb 5 O 15 (BNN) phases. After thermal treatment under air, these ferroelectric-catalytic systems were characterized by X-ray diffraction and scanning electron microscopy (SEM). SEM images showed that RuO 2 film morphology depended on substrate nature. A study of CH 4 conversion into CO 2 and H 2 O was carried out using these catalytic-ferroelectric multilayers: the conversion was analyzed from Fourier transform infrared (FTIR) spectroscopy, at various temperatures. Improved catalytic properties were observed for RuO 2 films deposited on BNN oxide layer

  4. Immobilization of metals in contaminated soils using natural polymer-based stabilizers.

    Science.gov (United States)

    Tao, Xue; Li, Aimin; Yang, Hu

    2017-03-01

    Three low-cost natural polymer materials, namely, lignin (Ln), carboxymethyl cellulose, and sodium alginate, were used for soil amendment to immobilize lead and cadmium in two contaminated soil samples collected from a mining area in Nanjing, China. The remediation effects of the aforementioned natural polymers were evaluated by toxicity characteristic leaching procedure (TCLP) and sequential extractions. The stabilizers could lower the bioavailability of Pb and Cd in the contaminated soils, and the amount of the exchangeable forms of the aforementioned two metals were reduced evidently. TCLP results showed that the leaching concentrations of Pb and Cd were decreased by 5.46%-71.1% and 4.25%-49.6%, respectively, in the treated soils. The contents of the organic forms of the two metals both increased with the increase in stabilizer dose on the basis of the redistribution of metal forms by sequential extractions. These findings were due to the fact that the abundant oxygen-containing groups on the polymeric amendments were effective in chelating and immobilizing Pb and Cd, which have been further confirmed from the metal adsorptions in aqueous solutions. Moreover, Ln achieved the greatest effect among the three polymers under study because of the former's distinct three-dimensional molecular structure, showing the preferential immobilization of Pb over Cd in soils also. Thus, the above-mentioned natural polymers hold great application potentials for reducing metal ion entry into the food chain at a field scale. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Electronic structure investigation of atomic layer deposition ruthenium(oxide) thin films using photoemission spectroscopy

    Science.gov (United States)

    Schaefer, Michael; Schlaf, Rudy

    2015-08-01

    Analyzing and manipulating the electronic band line-up of interfaces in novel micro- and nanoelectronic devices is important to achieve further advancement in this field. Such band alignment modifications can be achieved by introducing thin conformal interfacial dipole layers. Atomic layer deposition (ALD), enabling angstrom-precise control over thin film thickness, is an ideal technique for this challenge. Ruthenium (Ru0) and its oxide (RuO2) have gained interest in the past decade as interfacial dipole layers because of their favorable properties like metal-equivalent work functions, conductivity, etc. In this study, initial results of the electronic structure investigation of ALD Ru0 and RuO2 films via photoemission spectroscopy are presented. These experiments give insight into the band alignment, growth behavior, surface structure termination, and dipole formation. The experiments were performed in an integrated vacuum system attached to a home-built, stop-flow type ALD reactor without exposing the samples to the ambient in between deposition and analysis. Bis(ethylcyclopentadienyl)ruthenium(II) was used as precursor and oxygen as reactant. The analysis chamber was outfitted with X-ray photoemission spectroscopy (LIXPS, XPS). The determined growth modes are consistent with a strong growth inhibition situation with a maximum average growth rate of 0.21 Å/cycle for RuO2 and 0.04 Å/cycle for Ru.0 An interface dipole of up to -0.93 eV was observed, supporting the assumption of a strongly physisorbed interface. A separate experiment where the surface of a RuO film was sputtered suggests that the surface is terminated by an intermediate, stable, non-stoichiometric RuO2/OH compound whose surface is saturated with hydroxyl groups.

  6. Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

    Science.gov (United States)

    Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

    2005-01-01

    Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

  7. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ...

    Indian Academy of Sciences (India)

    Unknown

    Dedicated to the memory of the late Professor Bhaskar G Maiya. *For correspondence. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ligand: Synthesis .... water (1 : 1) for 5 h to give a dark red solution. The solution was cooled to room temperature. After eva- poration of the solvent, the solid was collected,.

  8. Study of some properties of the ruthenium (II) trans-tetra-ammines with nitrogened aromatic heterocyclic ligands

    International Nuclear Information System (INIS)

    Bento, M.L.

    1985-01-01

    The ruthenium (II) complexes trans [Ru(NH 3 ) 4 LL'] (BF 4 ) 2 , where L and L' are 4-picoline, pyridine, isonicatinamide, pyrazine or 4-acetylpyridine are studied. The U.V-visible range spectra, bands in the U.V. and in the visible range is analysed. The spectra and the bands by comparison with other ruthenium (II) ammines are discussed, and a qualitative molecular orbital model is used. (M.J.C.) [pt

  9. Studies on PEM fuel cell noble metal catalyst dissolution

    DEFF Research Database (Denmark)

    Andersen, S. M.; Grahl-Madsen, L.; Skou, E. M.

    2011-01-01

    A combination of electrochemical, spectroscopic and gravimetric methods was carried out on Proton Exchange Membrane (PEM) fuel cell electrodes with the focus on platinum and ruthenium catalysts dissolution, and the membrane degradation. In cyclic voltammetry (CV) experiments, the noble metals were...... found to dissolve in 1 M sulfuric acid solution and the dissolution increased exponentially with the upper potential limit (UPL) between 0.6 and 1.6 vs. RHE. 2-20% of the Pt (depending on the catalyst type) was found to be dissolved during the experiments. Under the same conditions, 30-100% of the Ru...... (depending on the catalyst type) was found to be dissolved. The faster dissolution of ruthenium compared to platinum in the alloy type catalysts was also confirmed by X-ray diffraction measurements. The dissolution of the carbon supported catalyst was found one order of magnitude higher than the unsupported...

  10. Surface heterogeneity and ionization of Cs promoter in carbon-based ruthenium catalyst for ammonia synthesis

    International Nuclear Information System (INIS)

    Kotarba, Andrzej; Dmytrzyk, Jaromir; Rarog-Pilecka, Wioletta; Kowalczyk, Zbigniew

    2003-01-01

    Second-generation ammonia synthesis cesium-doped ruthenium catalyst supported on turbostratic carbon was investigated by the species resolved thermal alkali desorption method (SR-TAD). Energetic barriers for cesium ions (2.86 eV), ground state (1.96 eV) and electronically excited atoms (5.76 eV) desorbing from the Cs-Ru/C catalyst were determined. In the case of ruthenium-free Cs/C system, cesium desorbs as ground state atoms only, with an energy barrier of 2.87 eV. The work functions determined by the thermionic emission of electrons from Cs/C and Cs-Ru/C were of the same value (2.9 eV). It was concluded that ruthenium induces heterogeneous distribution of cesium on the catalyst surface. The promoter stability is reduced on low work function areas and its surface ionization on high work function areas opens the ionic desorption channel. The Cs desorption from the catalyst is discussed in terms of the literature data for the cesium/graphite system

  11. Metal oxide nanorod arrays on monolithic substrates

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

    2018-01-02

    A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can include a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.

  12. Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

    KAUST Repository

    Pump, Eva; Leitgeb, Anita; Kozłowska, Anna; Torvisco, Ana; Falivene, Laura; Cavallo, Luigi; Grela, Karol; Slugovc, Christian

    2015-01-01

    A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2

  13. Behaviour of ruthenium (3) bromocomplexes in nonaqueous solvents

    International Nuclear Information System (INIS)

    Rudnitskaya, O.V.; Miroshnichenko, I.V.; Pichkov, V.N.

    1989-01-01

    Behaviour of K 3 [RuBr 6 ] · H 2 O and K 3 [Ru 2 Br 9 ] in solutions of dimethylsulfoxide and dimethylformamide is investigated by absorption and ESR spectroscopy. Complexes are shown to be labile in solutions, interact easily with solvents. Formation of ruthenium (3) and (2) bromide-dimethylsulfoxide complexes occurs gradually in DMSO, final product is trans-[Ru(DMSO) 4 Br 2

  14. THE SYNTHESIS AND THE REACTIVITY OF ARENE RUTHENIUM ...

    African Journals Online (AJOL)

    a

    [RuCl(η6-p-cymene)(η2-dppm)][PF6] ruthenium complexes with C2O4(Me4N)2 in the ... the Service de Microanalyse du CNRS (Vernaison/France). .... Once bonded to the Ru(II), the characterization of the oxalato ligand by infrared .... The 1H NMR spectrum shows signals of the aromatic proton resonances at 5.45 and 5.15,.

  15. Nature and morphology of the joints of metal matrix composites to metals

    International Nuclear Information System (INIS)

    Pietrzak, K.

    1997-01-01

    Metal matrix composites (MMCs) reinforced with short ceramic fibres (e.g. carbon or Al 2 O 3 fibres) or with other metals (such as e.g., tungsten) show numerous advantages since their properties can be programmed by modifying appropriately their composition and technology. A point of considerable importance is the possibility of joining the composites with metals or their alloys. The major problem here is to choose the appropriate joining technique, such that ensures the formation of a high quality joint resistant to the service conditions, avoids the degradation of the composite microstructure, in particular of the interface layer between the matrix and the reinforcement, and still, is not expensive (1). The paper presents the results of experiments on joining the following composites: 6061Al-based materials containing 15 vol.% of δ-alumina fibres, CuCrl-based materials containing 20 vol.% of carbon fibres (C f ), CuZrl-based materials containing 20 vol.% of C f and Cu-based materials with 10 vol.% of dispersed tungsten powder. The CuCrI-C f and CuZrl-C f composites were joined with austenitic steel, the 6061Al-Al 2 O 3 composite - with the 6061Al alloy and the CuW composite - with copper of 99.99 % purity. The material pairs were chosen so as to take into account their possible application. Several different joining techniques were examined. This paper discusses the results obtained when using diffusion bonding, vacuum brazing and gluing. The morphology and the nature of the interface layer after bonding process between the matrix and the reinforcement and between the MMCs and metal were examined by analysing the distributions of the elements, by SEM and by X-ray techniques. The degree of the degradation of the MMCs structure was taken to be described by the coefficient of the relative content of the reinforcing material RCRM = X/B, where X is the percent content of the reinforcing phase in the composite after the joining process, and B is the percent content of

  16. The trans influence in mer-trichloronitridobis(triphenylarsine)ruthenium(VI)

    DEFF Research Database (Denmark)

    Magnussen, Magnus; Bendix, Jesper

    2003-01-01

    The title compound, mer-[RuCl(3)N(C(18)H(15)As)(2)], is the first structurally characterized example of a nitride complex in which ruthenium is six-coordinated to monodentate ligands only. The Ru[triple-bond]N bond length [1.6161 (15) A] is relatively long, and the trans influence of the nitride...

  17. Ruthenium(II carbonyl compounds with the 4′-chloro-2,2′:6′,2′′-terpyridine ligand

    Directory of Open Access Journals (Sweden)

    Rajendhraprasad Tatikonda

    2017-04-01

    Full Text Available Two ruthenium carbonyl complexes with the 4′-chloro-2,2′:6′,2′′-terpyridine ligand (tpy-Cl, C15H10ClN3, i.e. [RuCl(tpy-Cl(CO2][RuCl3(CO3] (I [systematic name: cis-dicarbonylchlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ3Nruthenium(II fac-tricarbonyltrichloridoruthenate(II], and [RuCl2(tpy-Cl(CO2] (II [cis-dicarbonyl-trans-dichlorido(4′-chloro-2,2′:6′,2′′-terpyridine-κ2N1,N1′ruthenium(II], were synthesized and characterized by single-crystal X-ray diffraction. The RuII atoms in both centrosymmetric structures (I and (II display similar, slightly distorted octahedral coordination spheres. The coordination sphere in the complex cation in compound (I is defined by three N atoms of the tridentate tpy-Cl ligand, two carbonyl carbon atoms and one chlorido ligand; the charge is balanced by an octahedral [Ru(CO3Cl3]− counter-anion. In the neutral compound (II, the tpy-Cl ligand coordinates to the metal only through two of its N atoms. The coordination sphere of the RuII atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I and (II, weak C—H...Cl interactions are observed.

  18. Preparations and characterization of some carbonyl-(1-cyanoethyl)ruthenium(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Hiraki, Katsuma; Ochi, Naoyuki; Kitamura, Tsuneyuki; Sasada, Yoko [Nagasaki Univ. (Japan); Shinoda, Sumio

    1982-08-01

    A hydridoruthenium(II) complex (RuClH(CO)(PPh/sub 3/)/sub 3/) reacted easily with acrylonitrile and fumaronitrile to give chloro-bridged binuclear (1-cyanoethyl)ruthenium(II) complexes, ((Ru(MeCHCN)Cl(CO)(PPh/sub 3/)/sub 2/)/sub 2/) (2) and ((Ru(NCCH/sub 2/CHCN)Cl(CO)(PPh/sub 3/)/sub 2/)/sub 2/), respectively. Complex 2 reacted with 4-picoline (pic), Na(BHPz/sub 3/) (Pz = 1-pyrazolyl), Na(BPz/sub 4/), and Na(Et/sub 2/NCS/sub 2/).3H/sub 2/O to afford the corresponding (1-cyanoethyl)ruthenium(II) complexes, ((Ru(MeCHCN)Cl(CO)(pic)(PPh/sub 3/))/sub 2/) (3), (Ru(MeCHCN)(BHPz/sub 3/)(CO)(PPh/sub 3/)) (accompanied by a small amount of (Ru/sub 2/(MeCHCN)/sub 2/Cl(BHPz/sub 3/)(CO)/sub 2/(PPh/sub 3/)/sub 4/)), (Ru/sub 2/(MeCHCN)/sub 2/Cl(BPz/sub 4/)(CO)/sub 2/(PPh/sub 3/)/sub 2/), and Na(Ru(MeCHCN)Cl(Et/sub 2/NCS/sub 2/)(CO)(PPh/sub 3/)), respectively. Complex 3 reacted with thallium (I) acetylacetonate (Tl(acac)), resulting in the formation of ((Ru(MeCHCN)(acac)(CO)(PPh/sub 3/))/sub 2/) and (Ru(MeCHCN)(acad)(CO)(pic)(PPh/sub 3/)). These new complexes were characterized by means of elemental analysis and spectroscopic data. The diastereoisomerism was also discussed as regards these (1-cyanoethyl)ruthenium(II) complexes.

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

    NARCIS (Netherlands)

    Coloma Ribera, R.; van de Kruijs, Robbert Wilhelmus Elisabeth; Yakshin, Andrey; Bijkerk, Frederik

    2015-01-01

    In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO2 films were found to show Arrhenius behaviour. However, a

  20. TBP 20% - diluent/HNO3/H2O liquid-liquid extraction system: equilibrium normalization data of nitric acid, ruthenium and zirconium

    International Nuclear Information System (INIS)

    Oliveira, C.A.L.G. de.

    1984-01-01

    The extraction behaviour of nitric acid, nitrosyl-ruthenium nitrate and zirconium hydroxide nitrate in the system tri-n-butyl phosphate (TBP) 20% - diluent was studied. The main purpose was to obtain enough data to elaborate process flowsheets for the treatment of irradiated uranium fuels. During the runs, the equilibrium diagrams of nitric acid, ruthenium and zirconium were settled. From the achieved data, the influence of nitric acid, ruthenium, zirconium and nitrate ions concentration in the aqueous phase was checked. Furthermore, the density and the surface tension of the aqueous and organic phases were determined, gathering the interfacial tension after the contact between the phases. A comparison among the obtained equilibrium data and the existing one from literature allowed the elaboration of mathematical models to express the distribution behaviour of nitric acid, ruthenium and zirconium as a function of nitrate ions concentration in the aqueous phase. The reduction of TBP concentration from 30% v/v (normally used) to 20% v/v, has shown no influence in the extraction behaviour of the elements. A decreasing in the distribution values was observed and that means an important factor during the decontamination of uranium from its contaminants, ruthenium and zirconium. (Author) [pt

  1. [Comparison of heavy metal elements between natural and plantation forests in a subtropical Montane forest].

    Science.gov (United States)

    Nie, Ming; Wan, Jia-Rong; Chen, Xiao-Feng; Wang, Li; Li, Bo; Chen, Jia-Kuan

    2011-11-01

    Heavy metals as one of major pollutants is harmful to the health of forest ecosystems. In the present paper, the concentrations of thirteen heavy metals (Fe, Al, Ti, Cr, Cu, Mn, V, Zn, Ni, Co, Pb, Se and Cd) were compared between natural and plantation forests in the Mt. Lushan by ICP-AES and atomic absorption spectroscopy. The results suggest that the soil of natural forest had higher concentrations of Fe, Al, Ti, Cu, Mn, V, Zn, Ni, Co, Pb, Se, and Cd than the plantation forest except for Cr. The soil of natural forest had a higher level of heavy metals than that of the plantation forest as a whole. This might be due to that the natural forest has longer age than the plantation forest, and fixed soil heavy metals take a longer period of time than the plantation forest.

  2. Enhanced Natural Convection in a Metal Layer Cooled by Boiling Water

    International Nuclear Information System (INIS)

    Cho, Jae-Seon; Suh, Kune Y.; Chung, Chang-Hyun; Park, Rae-Joon; Kim, Sang-Baik

    2004-01-01

    An experimental study is performed to investigate the natural convection heat transfer characteristics and the solidification of the molten metal pool concurrently with forced convective boiling of the overlying coolant to simulate a severe accident in a nuclear power plant. The relationship between the Nusselt number (Nu) and the Rayleigh number (Ra) in the molten metal pool region is determined and compared with the correlations in the literature and experimental data with subcooled water. Given the same Ra condition, the present experimental results for Nu of the liquid metal pool with coolant boiling are found to be higher than those predicted by the existing correlations or measured from the experiment with subcooled boiling. To quantify the observed effect of the external cooling on the natural convection heat transfer rate from the molten pool, it is proposed to include an additional dimensionless group characterizing the temperature gradients in the molten pool and in the external coolant region. Starting from the Globe and Dropkin correlation, engineering correlations are developed for the enhancement of heat transfer in the molten metal pool when cooled by an overlying coolant. The new correlations for predicting natural convection heat transfer are applicable to low-Prandtl-number (Pr) materials that are heated from below and solidified by the external coolant above. Results from this study may be used to modify the current model in severe accident analysis codes

  3. Excitation energy transfer in ruthenium (II)-porphyrin conjugates led to enhanced emission quantum yield and {sup 1}O{sub 2} generation

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Jie; Jiang, Lijun; Chan, Chi-Fai [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Tsoi, Tik-Hung [Department of Applied Biology and Chemical Technology, Hung Hom, Hong Kong Special Administrative Region (Hong Kong); Shiu, Kwok-Keung; Kwong, Daniel W.J. [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Wong, Wing-Tak [Department of Applied Biology and Chemical Technology, Hung Hom, Hong Kong Special Administrative Region (Hong Kong); Wong, Wai-Kwok, E-mail: wkwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Wong, Ka-Leung, E-mail: klwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong)

    2017-04-15

    Porphyrins are good photodynamic therapy (PDT) agents due to its flexibility for modifications to achieve tumor localization and photo-cytotoxicity against cancer. Yet they are not perfect. In a Ru(polypyridyl)-porphyrin system, the Ru(polypyridyl) moiety improves the water solubility and cell permeability. Consider the similar excited state energies between Ru(polypyridyl) and porphyrin moieties; a small perturbation (e.g. Zn(II) metalation) would lead to a marked change in the energy migration process. In this work, we have synthesized a series of porphyrins conjugated with Ru(polypyridyl) complexes using different linkers and investigated their photophysical properties, which included singlet oxygen quantum yield and their in vitro biological properties, resulting from linker variation and porphyrin modification by Zn(II) metalation. - Graphical abstract: Four amphiphilic ruthenium(II)-porphyrin complexes were prepared that display energy transfer conversion with zinc coordination, lysosome specific target, low dark toxicity and efficient photodynamic therapy.

  4. Mesoporous Transition Metal Oxides for Supercapacitors

    Science.gov (United States)

    Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

    2015-01-01

    Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

  5. Mesoporous Transition Metal Oxides for Supercapacitors

    Directory of Open Access Journals (Sweden)

    Yan Wang

    2015-10-01

    Full Text Available Recently, transition metal oxides, such as ruthenium oxide (RuO2, manganese dioxide (MnO2, nickel oxides (NiO and cobalt oxide (Co3O4, have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4, and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

  6. Functional microporous materials of metal carboxylate: Gas-occlusion properties and catalytic activities

    International Nuclear Information System (INIS)

    Mori, Wasuke; Sato, Tomohiko; Ohmura, Tesushi; Nozaki Kato, Chika; Takei, Tohru

    2005-01-01

    Copper(II) terephthalate is the first transition metal complex found capable of adsorbing gases. This complex has opened the new field of adsorbent complex chemistry. It is recognized as the lead complex in the construction of microporous complexes. This specific system has been expanded to a systematic series of derivatives of other isomorphous transition metals, molybdenum(II), ruthenium(II, III), and rhodium(II). These complexes with open frameworks are widely recognized as very useful materials for applications to catalysis, separation at molecular level, and gas storage. - Graphical abstract: Novel microporous intramolecular reaction systems

  7. Platinum group metal nitrides and carbides: synthesis, properties and simulation

    International Nuclear Information System (INIS)

    Ivanovskii, Alexander L

    2009-01-01

    Experimental and theoretical data on new compounds, nitrides and carbides of the platinum group 4d and 5d metals (ruthenium, rhodium, palladium, osmium, iridium, platinum), published over the past five years are summarized. The extreme mechanical properties of platinoid nitrides and carbides, i.e., their high strength and low compressibility, are noted. The prospects of further studies and the scope of application of these compounds are discussed.

  8. Pharmacophore Modelling and 4D-QSAR Study of Ruthenium(II) Arene Complexes as Anticancer Agents (Inhibitors) by Electron Conformational- Genetic Algorithm Method.

    Science.gov (United States)

    Yavuz, Sevtap Caglar; Sabanci, Nazmiye; Saripinar, Emin

    2018-01-01

    The EC-GA method was employed in this study as a 4D-QSAR method, for the identification of the pharmacophore (Pha) of ruthenium(II) arene complex derivatives and quantitative prediction of activity. The arrangement of the computed geometric and electronic parameters for atoms and bonds of each compound occurring in a matrix is known as the electron-conformational matrix of congruity (ECMC). It contains the data from HF/3-21G level calculations. Compounds were represented by a group of conformers for each compound rather than a single conformation, known as fourth dimension to generate the model. ECMCs were compared within a certain range of tolerance values by using the EMRE program and the responsible pharmacophore group for ruthenium(II) arene complex derivatives was found. For selecting the sub-parameter which had the most effect on activity in the series and the calculation of theoretical activity values, the non-linear least square method and genetic algorithm which are included in the EMRE program were used. In addition, compounds were classified as the training and test set and the accuracy of the models was tested by cross-validation statistically. The model for training and test sets attained by the optimum 10 parameters gave highly satisfactory results with R2 training= 0.817, q 2=0.718 and SEtraining=0.066, q2 ext1 = 0.867, q2 ext2 = 0.849, q2 ext3 =0.895, ccctr = 0.895, ccctest = 0.930 and cccall = 0.905. Since there is no 4D-QSAR research on metal based organic complexes in the literature, this study is original and gives a powerful tool to the design of novel and selective ruthenium(II) arene complexes. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  9. Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane.

    Science.gov (United States)

    Akbayrak, Serdar; Tonbul, Yalçın; Özkar, Saim

    2016-07-05

    Ruthenium(0) nanoparticles supported on ceria (Ru(0)/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru(0)/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru(0)/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru(0)/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru(0)/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, Ea = 60 ± 7 kJ mol(-1) for the nucleation and Ea = 47 ± 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of Ea = 51 ± 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane.

  10. Electrochemical behavior of ruthenium-hexacyanoferrate modified glassy carbon electrode and catalytic activity towards ethanol electro oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Wendell M.; Marques, Aldalea L.B., E-mail: aldalea.ufma@hotmail.com [Universidade Federal do Maranhao (UFMA), Sao Luis, MA (Brazil). Departamento de Quimica Tecnologica; Cardoso, William S.; Marques, Edmar P.; Bezerra, Cicero W.B. [Universidade Federal do Maranhao (UFMA), Sao Luis, MA (Brazil). Departamento de Qumica; Ferreira, Antonio Ap. P. [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Araraquara, SP (Brazil). Instituto de Quimica; Song, Chaojie; Zhang, Jiujun [Energy, Mining and Environment Portfolio, National Research Council of Canada, Vancouver, BC (Canada)

    2013-04-15

    Ruthenium-based hexacyanoferrate (RuHCF) thin film modified glassy carbon electrode was prepared by drop evaporation method. The RuHCF modified electrode exhibited four redox couples in strong acidic solution (pH 1.5) attributed to Fe(CN){sub 6}{sup 3-} ion and three ruthenium forms (Ru(II), Ru(III) and Ru(IV)), characteristic of ruthenium oxide compounds. The modified electrode displayed excellent electrocatalytic activity towards ethanol oxidation in the potential region where electrochemical processes Ru(III)-O-Ru(IV) and Ru(IV)-O-Ru(VI) occur. Impedance spectroscopy data indicated that the charge transfer resistance decreased with the increase of the applied potential and ethanol concentration, indicating the use of the RuHCF modified electrode as an ethanol sensor. Under optimized conditions, the sensor responded linearly and rapidly to ethanol concentration between 0.03 and 0.4 mol L{sup -1} with a limit of detection of 0.76 mmol L{sup -1}, suggesting an adequate sensitivity in ethanol analyses. (author)

  11. Natural convection and boiling heat transfer of a liquid metal in a magnetic field

    International Nuclear Information System (INIS)

    Seki, Masahiro; Kawamura, Hiroshi

    1983-02-01

    A liquid metal is often assumed as a coolant and a breeding material of a Tokamak fusion reactor. However, many problems on the thermo-hydraulics of a liquid metal in a magnetic field are still remained to be studied. In the present report, natural convection and boiling of a liquid metal in a strong magnetic field are studied to examine a fundamental feasibility of a fusion reactor cooled by a liquid metal. In the experimental study of the natural convection, the circulation of a liquid metal was found to be surpressed even by a magnetic field parallel to the gravity. A numerical study has confirmed the conclusion drawn by the experiment. In the study of boiling heat transfer, stable boiling of a liquid metal has been found also in a strong magnetic field. The burnout heat flux hardly affected by the magnetic field. These indicate a fundamental feasibility of the liquid-metal cooling for a Tokamak fusion reactor. (author)

  12. Electronic structure investigation of atomic layer deposition ruthenium(oxide) thin films using photoemission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, Michael, E-mail: mvschaefer@mail.usf.edu, E-mail: schlaf@mail.usf.edu [Department of Physics, University of South Florida, Tampa, Florida 33620 (United States); Schlaf, Rudy, E-mail: mvschaefer@mail.usf.edu, E-mail: schlaf@mail.usf.edu [Department of Electrical Engineering, University of South Florida, Tampa, Florida 33620 (United States)

    2015-08-14

    Analyzing and manipulating the electronic band line-up of interfaces in novel micro- and nanoelectronic devices is important to achieve further advancement in this field. Such band alignment modifications can be achieved by introducing thin conformal interfacial dipole layers. Atomic layer deposition (ALD), enabling angstrom-precise control over thin film thickness, is an ideal technique for this challenge. Ruthenium (Ru{sup 0}) and its oxide (RuO{sub 2}) have gained interest in the past decade as interfacial dipole layers because of their favorable properties like metal-equivalent work functions, conductivity, etc. In this study, initial results of the electronic structure investigation of ALD Ru{sup 0} and RuO{sub 2} films via photoemission spectroscopy are presented. These experiments give insight into the band alignment, growth behavior, surface structure termination, and dipole formation. The experiments were performed in an integrated vacuum system attached to a home-built, stop-flow type ALD reactor without exposing the samples to the ambient in between deposition and analysis. Bis(ethylcyclopentadienyl)ruthenium(II) was used as precursor and oxygen as reactant. The analysis chamber was outfitted with X-ray photoemission spectroscopy (LIXPS, XPS). The determined growth modes are consistent with a strong growth inhibition situation with a maximum average growth rate of 0.21 Å/cycle for RuO{sub 2} and 0.04 Å/cycle for Ru.{sup 0} An interface dipole of up to −0.93 eV was observed, supporting the assumption of a strongly physisorbed interface. A separate experiment where the surface of a RuO film was sputtered suggests that the surface is terminated by an intermediate, stable, non-stoichiometric RuO{sub 2}/OH compound whose surface is saturated with hydroxyl groups.

  13. Electronic structure investigation of atomic layer deposition ruthenium(oxide) thin films using photoemission spectroscopy

    International Nuclear Information System (INIS)

    Schaefer, Michael; Schlaf, Rudy

    2015-01-01

    Analyzing and manipulating the electronic band line-up of interfaces in novel micro- and nanoelectronic devices is important to achieve further advancement in this field. Such band alignment modifications can be achieved by introducing thin conformal interfacial dipole layers. Atomic layer deposition (ALD), enabling angstrom-precise control over thin film thickness, is an ideal technique for this challenge. Ruthenium (Ru 0 ) and its oxide (RuO 2 ) have gained interest in the past decade as interfacial dipole layers because of their favorable properties like metal-equivalent work functions, conductivity, etc. In this study, initial results of the electronic structure investigation of ALD Ru 0 and RuO 2 films via photoemission spectroscopy are presented. These experiments give insight into the band alignment, growth behavior, surface structure termination, and dipole formation. The experiments were performed in an integrated vacuum system attached to a home-built, stop-flow type ALD reactor without exposing the samples to the ambient in between deposition and analysis. Bis(ethylcyclopentadienyl)ruthenium(II) was used as precursor and oxygen as reactant. The analysis chamber was outfitted with X-ray photoemission spectroscopy (LIXPS, XPS). The determined growth modes are consistent with a strong growth inhibition situation with a maximum average growth rate of 0.21 Å/cycle for RuO 2 and 0.04 Å/cycle for Ru. 0 An interface dipole of up to −0.93 eV was observed, supporting the assumption of a strongly physisorbed interface. A separate experiment where the surface of a RuO film was sputtered suggests that the surface is terminated by an intermediate, stable, non-stoichiometric RuO 2 /OH compound whose surface is saturated with hydroxyl groups

  14. A systematic chemical separation for thermal neutron activation analysis of seven noble metals in rock

    International Nuclear Information System (INIS)

    Ayabe, Muneo

    1980-01-01

    A method for the systematic activation analysis of seven noble metals - ruthenium, silver, rhenium, osmium, iridium, platinum and gold - in rocks were developed and examined with radiotracers and irradiated rock samples. After the fusion of the irradiated rock sample with sodium hydroxide and sodium peroxide, 10% sodium sulfide solution is added and rhenium is extracted with pyridine-benzene mixture from 6N sodium hydroxide solution. From the hydroxide-sulfide precipitate fraction, ruthenium and osmium are distilled as tetroxides, silver is precipitated as chloride, gold is extracted with ethyl acetate, and iridium and platinum are extracted with diantipyrylmethane. Each fraction is purified and subjected to the γ-ray spectrometry. Chemical yields for the elements are more than 60%. Determination limits are given for the seven elements. (author)

  15. Tris(2,2'-bipyridyl) ruthenium(II)-bisoprolol-based electrochemiluminescence coupled with capillary zone electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Wang Jingwu [Department of Chemistry, Nanchang University, Nanchang 330031 (China)], E-mail: wangjingwu@ncu.edu.cn; Zhang Xiaojun; Pi Fangfang [Department of Chemistry, Nanchang University, Nanchang 330031 (China); Wang Xiaoxia [Graduate School of Engineering, University of Fukui, Fukui 910-8507 (Japan); Yang Nianjun [Diamond Research Center, National Institute of Advanced Industrial Science and Technology (AIST), Central 2-13, 1-1-1 Umezono, Tsukuba 305-8568 (Japan)], E-mail: nianjun.yang@iaf.fraunhofer.de

    2009-03-01

    Capillary zone electrophoresis (CZE) coupled with tris(2,2'-bipyridyl) ruthenium(II)-based end-column electrogenerated chemiluminescence (ECL) has been utilized to detect bisoprolol in drugs and tablets after its separation from metoprolol. Tetrahydrofuran was used as an additive in the running buffer to obtain the absolute ECL peak of bisoprolol. Bisoprolol reacts as a co-reactant in tris(2,2'-bipyridyl) ruthenium(II) ECL system. Under the optimized experimental conditions, bisoprolol was separated successfully and efficiently from metoprolol and other co-existed materials in tablets and urine samples. The ECL intensity of tris(2,2'-bipyridyl) ruthenium(II)-bisoprolol-based system is linear with the concentration of bisoprolol from 1.5 {mu}M to 0.3 mM with a detection limit of 0.3 {mu}M. Relative standard derivations of the ECL intensity are 2.58% for the detection of 15 {mu}M bisoprolol. This method is a simple, rapid, selective, and sensitive. It was applied successfully for the monitoring of bisoprolol in market available tablets and human urine samples.

  16. Tracking the Oxygen Status in the Cell Nucleus with a Hoechst-Tagged Phosphorescent Ruthenium Complex.

    Science.gov (United States)

    Hara, Daiki; Umehara, Yui; Son, Aoi; Asahi, Wataru; Misu, Sotaro; Kurihara, Ryohsuke; Kondo, Teruyuki; Tanabe, Kazuhito

    2018-05-04

    Molecular oxygen in living cells is distributed and consumed inhomogeneously, depending on the activity of each organelle. Therefore, tractable methods that can be used to monitor the oxygen status in each organelle are needed to understand cellular function. Here we report the design of a new oxygen-sensing probe for use in the cell nucleus. We prepared "Ru-Hoechsts", each consisting of a phosphorescent ruthenium complex linked to a Hoechst 33258 moiety, and characterized their properties as oxygen sensors. The Hoechst unit shows strong DNA-binding properties in the nucleus, and the ruthenium complex shows oxygen-dependent phosphorescence. Thus, Ru-Hoechsts accumulated in the cell nucleus and showed oxygen-dependent signals that could be monitored. Of the Ru-Hoechsts prepared in this study, Ru-Hoechst b, in which the ruthenium complex and the Hoechst unit were linked through a hexyl chain, showed the most suitable properties for monitoring the oxygen status. Ru-Hoechsts are probes with high potential for visualizing oxygen fluctuations in the nucleus. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids.

    Science.gov (United States)

    Naruto, Masayuki; Saito, Susumu

    2015-08-28

    Carboxylic acids are ubiquitous in bio-renewable and petrochemical sources of carbon. Hydrogenation of carboxylic acids to yield alcohols produces water as the only byproduct, and thus represents a possible next generation, sustainable method for the production of these alternative energy carriers/platform chemicals on a large scale. Reported herein are molecular insights into cationic mononuclear ruthenium carboxylates ([Ru(OCOR)](+)) as prototypical catalysts for the hydrogenation of carboxylic acids. The substrate-derived coordinated carboxylate was found to function initially as a proton acceptor for the heterolytic cleavage of dihydrogen, and subsequently also as an acceptor for the hydride from [Ru-H](+), which was generated in the first step (self-induced catalysis). The hydrogenation proceeded selectively and at high levels of functional group tolerance, a feature that is challenging to achieve with existing heterogeneous/homogeneous catalyst systems. These fundamental insights are expected to significantly benefit the future development of metal carboxylate-catalysed hydrogenation processes of bio-renewable resources.

  18. Ruthenium complexes containing 2-(2-nitrosoaryl)pyridine: structural, spectroscopic, and theoretical studies.

    Science.gov (United States)

    Chan, Siu-Chung; Cheung, Ho-Yuen; Wong, Chun-Yuen

    2011-11-21

    Ruthenium complexes containing 2-(2-nitrosoaryl)pyridine (ON(^)N) and tetradentate thioether 1,4,8,11-tetrathiacyclotetradecane ([14]aneS4), [Ru(ON(^)N)([14]aneS4)](2+) [ON(^)N = 2-(2-nitrosophenyl)pyridine (2a), 10-nitrosobenzo[h]quinoline (2b), 2-(2-nitroso-4-methylphenyl)pyridine, (2c), 2-(2-nitrosophenyl)-5-(trifluoromethyl)pyridine (2d)] and analogues with the 1,4,7-trithiacyclononane ([9]aneS3)/tert-butylisocyanide ligand set, [Ru(ON(^)N)([9]aneS3)(C≡N(t)Bu)](2+) (4a and 4b), have been prepared by insertion of a nitrosonium ion (NO(+)) into the Ru-aryl bond of cyclometalated ruthenium(II) complexes. The molecular structures of the ON(^)N-ligated complexes 2a and 2b reveal that (i) the ON(^)N ligands behave as bidentate chelates via the two N atoms and the bite angles are 86.84(18)-87.83(16)° and (ii) the Ru-N(NO) and N-O distances are 1.942(5)-1.948(4) and 1.235(6)-1.244(5) Å, respectively. The Ru-N(NO) and N-O distances, together with ν(N═O), suggest that the coordinated ON(^)N ligands in this work are neutral moiety (ArNO)(0) rather than monoanionic radical (ArNO)(•-) or dianion (ArNO)(2-) species. The nitrosated complexes 2a-2d show moderately intense absorptions centered at 463-484 nm [ε(max) = (5-6) × 10(3) dm(3) mol(-1) cm(-1)] and a clearly discriminable absorption shoulder around 620 nm (ε(max) = (6-9) × 10(2) dm(3) mol(-1) cm(-1)), which tails up to 800 nm. These visible absorptions are assigned as a mixing of d(Ru) → ON(^)N metal-to-ligand charge-transfer and ON(^)N intraligand transitions on the basis of time-dependent density functional theory (TD-DFT) calculations. The first reduction couples of the nitrosated complexes range from -0.53 to -0.62 V vs Cp(2)Fe(+/0), which are 1.1-1.2 V less negative than that for [Ru(bpy)([14]aneS4)](2+) (bpy = 2,2'-bipyridine). Both electrochemical data and DFT calculations suggest that the lowest unoccupied molecular orbitals of the nitrosated complexes are ON(^)N-centered. Natural population

  19. Development of radioactive platinum group metal catalysts

    International Nuclear Information System (INIS)

    Chung, H.S.; Kim, Y.S.; Kim, Y.E.

    1999-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m 2 /g. The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs

  20. Development of radioactive platinum group metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chung, H.S.; Kim, Y.S.; Kim, Y.E. [and others

    1999-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metals such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solutions was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400m{sup 2}/g.The content of palladium impregnated on the support was 1 to 10 wt. %. Hydrogen isotope exchange efficiency of more than 93% to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its activity is unimportant as in nuclear industries. (author). 86 refs., 44 tabs., 88 figs.

  1. Recovery of fission products from acidic waste solutions thereof

    International Nuclear Information System (INIS)

    Carlin, W.W.; Darlington, W.B.; Dubois, D.W.

    1975-01-01

    Fission products, e.g., palladium, ruthenium and technetium, are removed from aqueous, acidic waste solutions thereof. The acidic waste solution is electrolyzed in an electrolytic cell under controlled cathodic potential conditions and technetium, ruthenium, palladium and rhodium are deposited on the cathode. Metal deposit is removed from the cathode and dissolved in acid. Acid insoluble rhodium metal is recovered, dissolved by alkali metal bisulfate fusion and purified by electrolysis. In one embodiment, the solution formed by acid dissolution of the cathode metal deposit is treated with a strong oxidizing agent and distilled to separate technetium and ruthenium (as a distillate) from palladium. Technetium is separated from ruthenium by organic solvent extraction and then recovered, e.g., as an ammonium salt. Ruthenium is disposed of as waste by-product. Palladium is recovered by electrolysis of an acid solution thereof under controlled cathodic potential conditions. Further embodiments wherein alternate metal recovery sequences are used are described. (U.S.)

  2. Synthesis and properties of mixed-ligand ruthenium(II) complexes containing 2-(2-pyridyl)-benzimidazole and related ligands

    International Nuclear Information System (INIS)

    Haga, Masaaki; Tanaka, Toshio.

    1979-01-01

    Mixed-ligand ruthenium(II) complexes of the [Ru(bpy) 2 L]sup(n+) (ClO 4 )sub(n) type, where bpy= 2,2'-bipyridine; L= 2-(2-pyridyl)-benzimidazole (PBImH) when n= 2, and L= 2-(2-pyridyl)-benzimidazolate (PBIm) and 2-(o-hydroxyphenyl)-benzimidazole (OBImH) when n= 1, were prepared. Anodic peak potentials and ruthenium-to-bipyridine charge transfer bands of these complexes are rationalized in terms of the donor ability of L. (author)

  3. Synthesis and properties of mixed-ligand ruthenium(II) complexes containing 2-(2-pyridyl)-benzimidazole and related ligands

    Energy Technology Data Exchange (ETDEWEB)

    Haga, M [Mie Univ., Tsu (Japan); Tanaka, T

    1979-07-01

    Mixed-ligand ruthenium(II) complexes of the (Ru(bpy)/sub 2/L)sup(n+) (ClO/sub 4/)sub(n) type, where bpy= 2,2'-bipyridine; L= 2-(2-pyridyl)-benzimidazole (PBImH) when n= 2, and L= 2-(2-pyridyl)-benzimidazolate (PBIm) and 2-(o-hydroxyphenyl)-benzimidazole (OBImH) when n= 1, were prepared. Anodic peak potentials and ruthenium-to-bipyridine charge transfer bands of these complexes are rationalized in terms of the donor ability of L.

  4. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    Science.gov (United States)

    Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  5. Mercury-impacted scrap metal: Source and nature of the mercury.

    Science.gov (United States)

    Finster, Molly E; Raymond, Michelle R; Scofield, Marcienne A; Smith, Karen P

    2015-09-15

    The reuse and recycling of industrial solid wastes such as scrap metal is supported and encouraged both internationally and domestically, especially when such wastes can be used as substitutes for raw material. However, scrap metal processing facilities, such as mini-mills, have been identified as a source of mercury (Hg) emissions in the United States. This research aims to better define some of the key issues related to the source and nature of mercury in the scrap metal waste stream. Overall, it is difficult to pinpoint the key mercury sources feeding into scrap metal recycling facilities, quantify their associated mercury concentrations, or determine which chemical forms are most significant. Potential sources of mercury in scrap metal include mercury switches from discarded vehicles, electronic-based scrap from household appliances and related industrial systems, and Hg-impacted scrap metal from the oil and gas industry. The form of mercury associated with scrap metal varies and depends on the source type. The specific amount of mercury that can be adsorbed and retained by steel appears to be a function of both metallurgical and environmental factors. In general, the longer the steel is in contact with a fluid or condensate that contains measurable concentrations of elemental mercury, the greater the potential for mercury accumulation in that steel. Most mercury compounds are thermally unstable at elevated temperatures (i.e., above 350 °C). As such, the mercury associated with impacted scrap is expected to be volatilized out of the metal when it is heated during processing (e.g., shredding or torch cutting) or melted in a furnace. This release of fugitive gas (Hg vapor) and particulates, as well as Hg-impacted bag-house dust and control filters, could potentially pose an occupational exposure risk to workers at a scrap metal processing facility. Thus, identifying and characterizing the key sources of Hg-impacted scrap, and understanding the nature and extent

  6. Ruthenium behaviour in severe nuclear accident conditions - Progress report

    International Nuclear Information System (INIS)

    Backman, U.; Lipponen, M.; Zilliacus, R.; Auvinen, A.; Jokiniemi, J.

    2004-03-01

    In order to prevent the radioactive ruthenium from spreading in gaseous form in case of an accident in a nuclear power plant it is of interest to know how it is formed and how it behaves. In the experiments the behaviour of ruthenium in oxidising atmosphere at high temperatures is studied. The methods for trapping and analysing RuO4 has been studied. It was found that 1M NaOH is capable of trapping RuO4 totally. The determination of Ru from the solution can be made using ICP-MS (inductively coupled plasma mass spectrometry) and from the reduced precipitates on filters by INAA (instrumental neutron activation analysis). The results of the experiments carried out so far is reported. A significant difference in the decomposition rate of gaseous RuO4 depending on the tube material was found. In all experiments only a minor fraction of Ru remained in gaseous form until the bubbler. In order to achieve a better mass balance an experiment using radioactive tracer was carried out. In the decomposition of gaseous Ru needle-shaped RuO2 crystallites were formed. (au)

  7. Anthropogenic and natural sources of acidity and metals and their influence on the structure of stream food webs.

    Science.gov (United States)

    Hogsden, Kristy L; Harding, Jon S

    2012-03-01

    We compared food web structure in 20 streams with either anthropogenic or natural sources of acidity and metals or circumneutral water chemistry in New Zealand. Community and diet analysis indicated that mining streams receiving anthropogenic inputs of acidic and metal-rich drainage had much simpler food webs (fewer species, shorter food chains, less links) than those in naturally acidic, naturally high metal, and circumneutral streams. Food webs of naturally high metal streams were structurally similar to those in mining streams, lacking fish predators and having few species. Whereas, webs in naturally acidic streams differed very little from those in circumneutral streams due to strong similarities in community composition and diets of secondary and top consumers. The combined negative effects of acidity and metals on stream food webs are clear. However, elevated metal concentrations, regardless of source, appear to play a more important role than acidity in driving food web structure. Copyright © 2011 Elsevier Ltd. All rights reserved.

  8. Metal supported on natural zeolite as catalysts for conversion of ethanol to gasoline

    Directory of Open Access Journals (Sweden)

    Kristiani Anis

    2017-01-01

    Full Text Available A various of metal supported into natural zeolite was prepared via wet impregnation method. The transition metals impregnated are nickel, cobalt, copper and zinc. The catalytic properties both of physical and chemical properties were characterized by X-ray Diffraction (XRD, Thermo Gravimetri Analysis (TGA-Differential Scanning Calorimetry (DSC, Surface Area Analyzer-Porositymeter and also gravimetry method for acidity measurement following by the adsorption of organic bases. The results showed that different metals impregnated into natural zeolite affected physical and chemical properties, i.e. crystalinity, surface area, pore size, pore volume and acidity. Their catalytic activity was tested for conversion ethanol to gasoline and showed high conversion up to 80-90% with the aromatics as major product.

  9. A study of ruthenium complexes of some biologically relevant a-N ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 112; Issue 3. A study of ruthenium complexes of some biologically relevant ∙ -N-heterocyclic ... Author Affiliations. P Sengupta1 S Ghosh1. Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Calcutta 700 032, India ...

  10. Natural Remission of Major Periprosthetic Osteolysis following Total Hip Arthroplasty with Metal-on-Metal Bearings

    Directory of Open Access Journals (Sweden)

    Tatsuya Tamaki

    2017-01-01

    Full Text Available The natural course of adverse events following the use of metal-on-metal (MoM bearings in total hip arthroplasty (THA is not well known. In this article, we report the case of a patient with asymptomatic major acetabular osteolysis following MoM THA that diminished gradually without any surgical intervention. A 58-year-old male underwent one-stage bilateral MoM THA for bilateral osteoarthritis. Four years after THA, major acetabular osteolysis developed in his right hip without any local or systemic symptoms. The patient underwent a careful radiographic and clinical observation without any surgical intervention because he did not want to undergo revision surgery. The lesion gradually diminished after 7 years, and most of the osteolytic area was replaced by newly formed bone at 10 years. He continues to be followed with no evidence of cup loosening or migration. Our observation suggests that a periprosthetic osteolytic change related to the use of MoM bearings has the potential for natural remission.

  11. Anthropogenic and natural sources of acidity and metals and their influence on the structure of stream food webs

    International Nuclear Information System (INIS)

    Hogsden, Kristy L.; Harding, Jon S.

    2012-01-01

    We compared food web structure in 20 streams with either anthropogenic or natural sources of acidity and metals or circumneutral water chemistry in New Zealand. Community and diet analysis indicated that mining streams receiving anthropogenic inputs of acidic and metal-rich drainage had much simpler food webs (fewer species, shorter food chains, less links) than those in naturally acidic, naturally high metal, and circumneutral streams. Food webs of naturally high metal streams were structurally similar to those in mining streams, lacking fish predators and having few species. Whereas, webs in naturally acidic streams differed very little from those in circumneutral streams due to strong similarities in community composition and diets of secondary and top consumers. The combined negative effects of acidity and metals on stream food webs are clear. However, elevated metal concentrations, regardless of source, appear to play a more important role than acidity in driving food web structure. - Highlights: ► Food webs in acid mine drainage impacted streams are small and extremely simplified. ► Conductivity explained differences in food web properties between streams. ► Number of links and web size accounted for much dissimilarity between food webs. ► Food web structure was comparable in naturally acidic and circumneutral streams. - Food web structure differs in streams with anthropogenic and natural sources of acidity and metals.

  12. Natural attenuation of metals and radionuclides: Report from a workshop held by Sandia National Laboratories

    International Nuclear Information System (INIS)

    Brady, P.V.; Borns, D.J.

    1997-11-01

    Natural attenuation is increasingly applied to remediate contaminated soils and ground waters. Roughly 25% of Superfund groundwater remedies in 1995 involved some type of monitored natural attenuation, compared to almost none 5 years ago. Remediation by natural attenuation (RNA) requires clear evidence that contaminant levels are decreasing sufficiently over time, a defensible explanation of the attenuation mechanism, long-term monitoring, and a contingency plan at the very least. Although the primary focus of implementation has to date been the biodegradation of organic contaminants, there is a wealth of scientific evidence that natural processes reduce the bioavailability of contaminant metals and radionuclides. Natural attenuation of metals and radionuclides is likely to revolve around sorption, solubility, biologic uptake and dilution controls over contaminant availability. Some of these processes can be applied to actively remediate sites. Others, such as phytoremediation, are likely to be ineffective. RNA of metals and radionuclides is likely to require specialized site characterization to construct contaminant and site-specific conceptual models of contaminant behavior. Ideally, conceptual models should be refined such that contaminant attenuation can be confidently predicted into the future. The technical approach to RNA of metals and radionuclides is explored here

  13. Natural attenuation of metals and radionuclides: Report from a workshop held by Sandia National Laboratories

    Energy Technology Data Exchange (ETDEWEB)

    Brady, P.V.; Borns, D.J. [Sandia National Labs., Albuquerque, NM (United States). Geochemistry Dept.

    1997-11-01

    Natural attenuation is increasingly applied to remediate contaminated soils and ground waters. Roughly 25% of Superfund groundwater remedies in 1995 involved some type of monitored natural attenuation, compared to almost none 5 years ago. Remediation by natural attenuation (RNA) requires clear evidence that contaminant levels are decreasing sufficiently over time, a defensible explanation of the attenuation mechanism, long-term monitoring, and a contingency plan at the very least. Although the primary focus of implementation has to date been the biodegradation of organic contaminants, there is a wealth of scientific evidence that natural processes reduce the bioavailability of contaminant metals and radionuclides. Natural attenuation of metals and radionuclides is likely to revolve around sorption, solubility, biologic uptake and dilution controls over contaminant availability. Some of these processes can be applied to actively remediate sites. Others, such as phytoremediation, are likely to be ineffective. RNA of metals and radionuclides is likely to require specialized site characterization to construct contaminant and site-specific conceptual models of contaminant behavior. Ideally, conceptual models should be refined such that contaminant attenuation can be confidently predicted into the future. The technical approach to RNA of metals and radionuclides is explored here.

  14. Chalcogenide metal centers for oxygen reduction reaction: Activity and tolerance

    International Nuclear Information System (INIS)

    Feng Yongjun; Gago, Aldo; Timperman, Laure; Alonso-Vante, Nicolas

    2011-01-01

    This mini-review summarizes materials design methods, oxygen reduction kinetics, tolerance to small organic molecules and fuel cell performance of chalcogenide metal catalysts, particularly, ruthenium (Ru x Se y ) and non-precious transition metals (M x X y : M = Co, Fe and Ni; X = Se and S). These non-platinum catalysts are potential alternatives to Pt-based catalysts because of their comparable catalytic activity (Ru x Se y ), low cost, high abundance and, in particular, a high tolerance to small organic molecules. Developing trends of synthesis methods, mechanism of oxygen reduction reaction and applications in direct alcohol fuel cells as well as the substrate effect are highlighted.

  15. Pretreatment with U(IV) solution for improving the decontamination of ruthenium

    International Nuclear Information System (INIS)

    Huang Haoxin; Qi Zhanshun; Zhu Guohui

    1993-01-01

    The ruthenium decontamination factor in Purex process falls quickly in successive TBP cycles. So, it is necessary to change the chemical states of RuNO complexes in order to improve DF Ru in the uranium purification cycle. Hydrazine nitrate is being used to transform RuNO complexes into in-extractable Ru(III)and Ru(IV). However, hydrazine nitrate may be inverted into hydrazoic acid which is dangerous and can bring an unstable factor. Pretreatment using U(IV) solution provides another method to improve the decontamination of ruthenium in Purex process. 0.02 mol/lU(IV) solution can transform RuNO complexes into inextricable species by heating in water bath. The D Ru can be decreased by a factor of 10-20. U(IV) pretreatment does not bring any harmful chemical in process. The acidity has a very large influence on the effect of pretreatment. The higher the acidity is, the worse the effect will be

  16. Mechanistic studies of the oxidation of soluble species of ruthenium in nitric acid solutions. Application to the removal of ruthenium from nuclear fuel dissolution solutions

    International Nuclear Information System (INIS)

    Carron, V.

    2001-01-01

    Ruthenium is one of the most troublesome fission products during nuclear fuel reprocessing. His removal from nitric acid fuel dissolution solutions, above the PUREX process, is under consideration. Electro-volatilization could be a possible way to eliminate this element. It consists in the oxidation of soluble ruthenium species coupled with the volatilization of formed RuO 4 . Soluble species are nitrate and nitro complexes of nitrosyl ruthenium RuNO 3+ . The first part of this work deals with the direct oxidation of RuNO 3+ at a golden or a platinum anode. It has been investigated by cyclic voltammetry and infrared and UV-visible reflectance spectroscopy. The oxidation of RuNO 3+ begins with an adsorption step, which precedes the formation of RuO 4 . Then a reaction between RuO 4 and RuNO 3+ occurs to produce a Ru IV compound, which is also electro-oxidized to RuO 4 . The second part concerns potentiostatic electro-volatilization experiences. The rate of electro-volatilization decreases with increasing HNO 3 concentration. At low concentrations, kinetic is controlled by the volatilization of RuO 4 . The rate-determining step is the oxidation of RuNO 3+ at concentrations higher than 1 M. In HNO 3 4 M, the addition of AgNO 3 is required to accelerate the oxidation of RuNO 3+ . The last part is devoted to the study of the indirect oxidation of RuNO 3+ . The electrocatalytic power of electro-generated Ag II is illustrated by voltammetric techniques and potentiostatic electrolysis. The existence of a limit concentration of AgNO 3 is shown (which value depends on experimental conditions) beyond which kinetic is controlled by the RuO 4 volatilization step. These results indicate that the electro-volatilization kinetic could be increased by optimizing the volatilization conditions. (author)

  17. The liquid-liquid extraction of chloro-(trichlorostannato)-rhodium(I/III) and -ruthenium (II) complexes from dilute hydrochloric acid into 4-methylpentan-2-one

    International Nuclear Information System (INIS)

    Wyrley-Birch, J.M.

    1984-10-01

    The effect of stannous chloride on the liquid-liquid extraction of rhodium and ruthenium from hydrochloric acid solutions into 4-methyl-pentan-2-one (MIBK)/hexane mixtures was studied in detail. Stannous chloride concentrations were found to considerably increase the efficiency of the extraction of rhodium and ruthenium into the organic phase. Chloro-(trichlorostannato)-rhodium (I/III) complexes were formed at room temperature. The rate of chloro-(trichlorostannato)-ruthenium (II) complex formation was extremely slow at room temperature, but increased on heating of the aqueous solutions. The amount of rhodium and ruthenium extracted into the organic phase depend on the Sn(II):M molar ratio, the HCl, H sup(+) and Cl sup(-) concentrations, as well as the equilibration time. A 119 Sn NMR study of the MIBK extracts, showed that the stoichiometry of the chloro-(trichlorostannato)-rhodium (I/III) complexes extracted into the organic phase was dependent on the Sn(II):Rh(III) molar ratio as well as the HCl, H sup(+) and Cl sup(-) concentrations in the aqueous phase. The predominant species observed in the organic phase from HCl solutions containing Sn(II):Rh(III) ratios >= 5:1, was shown to be an hydrido complex having the form [RhH(SnCl 3 ) 4 Cl] 3 sup(-) or [RhH(SnCl 3 ) 4 ]2 sup(-). An essentially quantitative separation of rhodium and ruthenium was achieved utilising the variation in the rates of rhodium-tin and ruthenium-tin complex formation

  18. Metal and proton adsorption capacities of natural and cloned Sphagnum mosses.

    Science.gov (United States)

    Gonzalez, Aridane G; Pokrovsky, Oleg S; Beike, Anna K; Reski, Ralf; Di Palma, Anna; Adamo, Paola; Giordano, Simonetta; Angel Fernandez, J

    2016-01-01

    Terrestrial mosses are commonly used as bioindicators of atmospheric pollution. However, there is a lack of standardization of the biomonitoring preparation technique and the efficiency of metal adsorption by various moss species is poorly known. This is especially true for in vitro-cultivated moss clones, which are promising candidates for a standardized moss-bag technique. We studied the adsorption of copper and zinc on naturally grown Sphagnum peat moss in comparison with in vitro-cultivated Sphagnum palustre samples in order to provide their physico-chemical characterization and to test the possibility of using cloned peat mosses as bioindicators within the protocol of moss-bag technique. We demonstrate that in vitro-grown clones of S. palustre exhibit acid-base properties similar to those of naturally grown Sphagnum samples, whereas the zinc adsorption capacity of the clones is approx. twice higher than that of the samples from the field. At the same time, the field samples adsorbed 30-50% higher amount of Cu(2+) compared to that of the clones. This contrast may be related to fine differences in the bulk chemical composition, specific surface area, morphological features, type and abundance of binding sites at the cell surfaces and in the aqueous solution of natural and cloned Sphagnum. The clones exhibited much lower concentration of most metal pollutants in their tissues relative to the natural samples thus making the former better indicators of low metal loading. Overall, in vitro-produced clones of S. palustre can be considered as an adequate, environmentally benign substitution for protected natural Sphagnum sp. samples to be used in moss-bags for atmospheric monitoring. Copyright © 2015 Elsevier Inc. All rights reserved.

  19. Ruthenium complexing in sorption by granulated sorbents with ethylene diamine and diethyl amine groups

    International Nuclear Information System (INIS)

    Simanova, S.A.; Kolmakova, A.I.; Konovalov, L.V.; Kukushkin, Yu.N.; Kalalova, E.

    1986-01-01

    The sorption process of ruthenium (4) chlorocomplexes - K 2 (RuCl 6 ) macroporous granulated copolymers of glycidylmethacrylate ethylene dimethacrylate with ethylene diamine and diethyl amine has been studied. Sorption has been carried out under the static conditions (at 20 and 98 deg C) from 0.1-2.0 MxHCl and 1.0 M NaCl solutions. It is established that the sorption from acidic solutions proceeds according to anion exchange mechanism with formation of onium chlorocomplexes in the sorbent phase, subjecting to Anderson regrouping during the heating. During the sorption from neutral solutions the second-sphere coordination of polymer amino groups accirs near ruthenium atom and amino-chloride complexes are formed in the sorbent phase

  20. Allenylidene Complexes of Ruthenium: Synthesis, Spectroscopy and Electron Transfer Properties

    Czech Academy of Sciences Publication Activity Database

    Winter, R. F.; Záliš, Stanislav

    2004-01-01

    Roč. 248, 15/16 (2004), s. 1565-1583 ISSN 0010-8545 R&D Projects: GA ČR GA203/03/0821; GA MŠk OC D14.20 Institutional research plan: CEZ:AV0Z4040901 Keywords : spectroscopy * allenylidine complexes of ruthenium * electron transfer Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.446, year: 2004

  1. Uranium(VI) and ruthenium extraction by dialkyldithio-phosphoric acids

    International Nuclear Information System (INIS)

    Fitoussi, R.; Musikas, C.

    1980-01-01

    Oxygen donors like dialkylphosphoric acids are good extractants for actinide ions, but little is known about their sulfur homologs. Investigations of U(VI) and Ru extraction from various aqueous media are reported. This includes extraction of U(VI) from nitric, perchloric, and phosphoric acids by solutions of dialkyldithiophosphoric acids in dodecane or benzene. Extraction of U(VI) by synergistic mixtures, of which at least one of the components is a sulfur donor, has been investigated. The extracted species have been identified, and a comparison with the complexes obtained by extraction with the homologous oxygen donors is made. The sulfur-actinide bond is weaker than the oxygen-actinide one, but in some synergistic extractions the dialkyldithiophosphonates are more efficient than the oxygen donors. In addition to size effects, this behavior could be attributed to the weakness of the hydrogen bonds of the SH groups, which allows a greater variety of the ligands to enter the coordination sphere of the metal. Ruthenium, like the d-transition elements, gives strong bonds with the sulfur donors. However, its extraction from nitric acid is slow. We investigated the influence of several parameters on the distribution coefficients and found that the presence of a reagent which destroys nitrous ions is necessary to achieve quantitative extraction. The role of RuNO groups is also discussed

  2. The nature of the active site in heterogeneous metal catalysis

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Bligaard, Thomas; Larsen, Britt Hvolbæk

    2008-01-01

    This tutorial review, of relevance for the surface science and heterogeneous catalysis communities, provides a molecular-level discussion of the nature of the active sites in metal catalysis. Fundamental concepts such as "Bronsted-Evans-Polanyi relations'' and "volcano curves'' are introduced...

  3. Photochromic ruthenium sulfoxide complexes: evidence for isomerization through a conical intersection.

    Science.gov (United States)

    McClure, Beth Anne; Mockus, Nicholas V; Butcher, Dennis P; Lutterman, Daniel A; Turro, Claudia; Petersen, Jeffrey L; Rack, Jeffrey J

    2009-09-07

    The complexes [Ru(bpy)(2)(OS)](PF(6)) and [Ru(bpy)(2)(OSO)](PF(6)), where bpy is 2,2'-bipyridine, OS is 2-methylthiobenzoate, and OSO is 2-methylsulfinylbenzoate, have been studied. The electrochemical and photochemical reactivity of [Ru(bpy)(2)(OSO)](+) is consistent with an isomerization of the bound sulfoxide from S-bonded (S-) to O-bonded (O-) following irradiation or electrochemical oxidation. Charge transfer excitation of [Ru(bpy)(2)(OSO)](+) in MeOH results in the appearance of two new metal-to-ligand charge transfer (MLCT) maxima at 355 and 496 nm, while the peak at 396 nm diminishes in intensity. The isomerization is reversible at room temperature in alcohol or propylene carbonate solution. In the absence of light, solutions of O-[Ru(bpy)(2)(OSO)](+) revert to S-[Ru(bpy)(2)(OSO)](+). Kinetic analysis reveals a biexponential decay with rate constants of 5.66(3) x 10(-4) s(-1) and 3.1(1) x 10(-5) s(-1). Cyclic voltammograms of S-[Ru(bpy)(2)(OSO)](+) are consistent with electron-transfer-triggered isomerization of the sulfoxide. Analysis of these voltammograms reveal E(S)(o)' = 0.86 V and E(O)(o)' = 0.49 V versus Ag/Ag(+) for the S- and O-bonded Ru(3+/2+) couples, respectively, in propylene carbonate. We found k(S-->O) = 0.090(15) s(-1) in propylene carbonate and k(S-->O) = 0.11(3) s(-1) in acetonitrile on Ru(III), which is considerably slower than has been reported for other sulfoxide isomerizations on ruthenium polypyridyl complexes following oxidation. The photoisomerization quantum yield (Phi(S-->O) = 0.45, methanol) is quite large, indicating a rapid excited state isomerization rate constant. The kinetic trace at 500 nm is monoexponential with tau = 150 ps, which is assigned to the excited S-->O isomerization rate. There is no spectroscopic or kinetic evidence for an O-bonded (3)MLCT excited state in the spectral evolution of S-[Ru(bpy)(2)(OSO)](+) to O-[Ru(bpy)(2)(OSO)](+). Thus, isomerization occurs nonadiabatically from an S-bonded (or eta(2

  4. Characterization of Mongolian Natural Minerals and Their Application for Heavy Metal Adsorbent

    OpenAIRE

    Dolgormaa, Munkhbat; Shiomori, Koichiro; Bayanjargal, Ochirkhuyag

    2016-01-01

    In this study, the structural characteristic and the adsorption properties of heavy metals on Mongolian natural minerals were investigated. The natural samples were confirmed as Heulandite group of Clinoptilolite type zeolite and clay sample that contains albite and quartz by X-ray diffraction analysis. According to BET surface analysis, natural zeolites have mesoporous type of pore. The results of adsorption study showed that adsorption ability of natural zeolite is high effective for lead i...

  5. Hall effect measurement for precise sheet resistance and thickness evaluation of Ruthenium thin films using non-equidistant four-point probes

    Directory of Open Access Journals (Sweden)

    Frederik Westergaard Østerberg

    2018-05-01

    Full Text Available We present a new micro Hall effect measurement method using non-equidistant electrodes. We show theoretically and verify experimentally that it is advantageous to use non-equidistant electrodes for samples with low Hall sheet resistance. We demonstrate the new method by experiments where Hall sheet carrier densities and Hall mobilities of Ruthenium thin films (3-30 nm are determined. The measurements show that it is possible to measure Hall mobilities as low as 1 cm2V−1s−1 with a relative standard deviation of 2-3%. We show a linear relation between measured Hall sheet carrier density and film thickness. Thus, the method can be used to monitor thickness variations of ultra-thin metal films.

  6. Spectral sensitization of SrTiO3 photoanodes with binuclear 1,10-phenanthroline bis(2,2'-bipyridine) complexes of ruthenium(II) and tris(2,2'-bipyridine) ruthenium(II)

    NARCIS (Netherlands)

    Tinnemans, A.H.A.; Mackor, A.

    1981-01-01

    A single crystal of strontium titanate, used as a photoanode for the photoelectrolysis of water, has been sensitized by mono‐ and binuclear ruthenium(II) complexes in acidic solution for visible light. The dependence of the photocurrent density on light intensity, dye concentration, wavelength and

  7. Platinum group metal recovery and catalyst manufacturing process

    Energy Technology Data Exchange (ETDEWEB)

    Chung, H. S.; Kim, Y. S.; Yoo, J. H.; Lee, H. S.; Ahn, D. H.; Kim, K. R.; Lee, S. H.; Paek, S. W.; Kang, H. S.

    1998-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metal such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solution was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400 m{sup 2}/g. The content of palladium impregnated on the support was 10 wt.%. Hydrogen isotope exchange efficiency of 93 % to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its actively is unimportant as in nuclear industries. (author). 63 refs., 38 tabs., 36 figs.

  8. Role of ligands in controlling the regioselectivity in ruthenium ...

    Indian Academy of Sciences (India)

    of Hay and Wadt (LANL2DZ)11 for ruthenium atom and 6-31G(d)12 for other .... C2 atom in 3x/3′ x. To understand the wider role of lig- ands in modulating the regio-selectivity of product for- mation, we have studied the benzoic acid addition to the selected .... at C1 and the localization of electron density in the. M=C double ...

  9. Extraction of metals from liquid effluent using modified inorganic ion exchangers

    International Nuclear Information System (INIS)

    Hudson, M.J.

    1993-01-01

    Inorganic ion exchangers such as goethite, titanium (IV) oxide; silica and zeolites have been modified to examine the extraction of ruthenium; technetium and cobalt from liquid effluent. In addition, tin (IV) hydrogenphosphate and antimony hydrogenphosphate have been also examined in the modified and unmodified forms. It has been shown that some of the above reagents are able to remove the required metal ions from aqueous solution at the trace and mg L -1 levels. (author)

  10. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  11. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

  12. Macrobenthic community in the Douro estuary: relations with trace metals and natural sediment characteristics

    International Nuclear Information System (INIS)

    Mucha, A.P.; Vasconcelos, M.T.S.D.; Bordalo, A.A.

    2003-01-01

    This study used a novel approach to detect a clear signature of metal contamination and biological impacts in an estuary. - The relationship between macrobenthic community structure and natural characteristics of sediment and trace metal contamination were studied in the lower Douro estuary (Portugal, NW, Iberian Peninsula), using an innovative threefold approach (SQG, Sediment Quality Guidelines), metal normalization to Fe, and macrobenthic community structure. This study allowed detection of a clear signature of anthropogenic contamination, in terms of Zn, Cu, Pb, and Cr in the north bank of the estuary, which experiences high urban pressure. Using the SQG approach, metal concentrations above ERM (effects range--median) were observed only at one sampling station, but several stations had levels above ERL (effects range-low). The macrobenthic community had a low diversity, with only 19 species found in the entire estuarine area, dominated by opportunistic species. The granulometric distribution of the sediments (estimated from the combination of organic matter, Fe and Al) seemed to be the major structuring factor for the communities, establishing the natural macrobenthic distribution pattern. The metals (Zn, Cu, Pb, and Cr) seemed to act as a disturbing factor over the natural distribution, with deleterious consequences for the macrobenthic communities

  13. Electrodeposited nano-scale islands of ruthenium oxide as a bifunctional electrocatalyst for simultaneous catalytic oxidation of hydrazine and hydroxylamine

    Energy Technology Data Exchange (ETDEWEB)

    Zare, Hamid R., E-mail: hrzare@yazduni.ac.ir [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Nanotechnology Research Center, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Hashemi, S. Hossein; Benvidi, Ali [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of)

    2010-06-04

    For the first time, an electrodeposited nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles), as an excellent bifunctional electrocatalyst, was successfully used for hydrazine and hydroxylamine electrocatalytic oxidation. The results show that, at the present bifunctional modified electrode, two different redox couples of ruthenium oxides serve as electrocatalysts for simultaneous electrocatalytic oxidation of hydrazine and hydroxylamine. At the modified electrode surface, the peaks of differential pulse voltammetry (DPV) for hydrazine and hydroxylamine oxidation were clearly separated from each other when they co-exited in solution. Thus, it was possible to simultaneously determine hydrazine and hydroxylamine in the samples at a ruthenium oxide nanoparticles modified glassy carbon electrode (RuON-GCE). Linear calibration curves were obtained for 2.0-268.3 {mu}M and 268.3-417.3 {mu}M of hydrazine and for 4.0-33.8 {mu}M and 33.8-78.3 {mu}M of hydroxylamine at the modified electrode surface using an amperometric method. The amperometric method also exhibited the detection limits of 0.15 {mu}M and 0.45 {mu}M for hydrazine and hydroxylamine respectively. RuON-GCE was satisfactorily used for determination of spiked hydrazine in two water samples. Moreover, the studied bifunctional modified electrode exhibited high sensitivity, good repeatability, wide linear range and long-term stability.

  14. Comparison of natural organic acids and synthetic chelates at enhancing phytoextraction of metals from a multi-metal contaminated soil

    International Nuclear Information System (INIS)

    Clistenes do Nascimento, Williams A.; Amarasiriwardena, Dula; Xing, Baoshan

    2006-01-01

    Chemically assisted phytoremediation has been developing to induce accumulation of metals by high biomass plants. Synthetic chelates have shown high effectiveness to reach such a goal, but they pose serious drawbacks in field application due to the excessive amount of metals solubilized. We compared the performance of synthetic chelates with naturally occurring low molecular weight organic acids (LMWOA) in enhancing phytoextraction of metals by Indian mustard (Brassica juncea) from multi-metal contaminated soils. Gallic and citric acids were able to induce removal of Cd, Zn, Cu, and Ni from soil without increasing the leaching risk. Net removal of these metals caused by LMWOA can be as much as synthetic chelates. A major reason for this is the lower phytotoxicity of LMWOA. Furthermore, supplying appropriate mineral nutrients increased biomass and metal removal. - Organic acids can be as efficient as synthetic chelates for use in phytoextraction of multi-metal contaminated soils

  15. Preparation and characterization of nickel-caffeine and ruthenium-arborine complexes

    International Nuclear Information System (INIS)

    Rusmidah Ali

    1998-01-01

    In this study, two types of complexes were synthesised, namely, nickel-cafeine and ruthenium-arborine by using NiCl 2 6H 2 O and RuCl 3 3H 2 O as starting materials. The complexes were characterised using far- and near infrared and CHN analysis. The proposed complexes were (Ni(kaf)Cl 2 ) 4 and (RuCl 3 Ab)EtOH

  16. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    Science.gov (United States)

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2012-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

  17. Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Mazziotta, Andrea; Madsen, Robert

    2017-01-01

    Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the one-carbon shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand...... P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation...... of the alcohol and then decarbonylation of the resulting aldehyde....

  18. Distributions and natural levels of related metals in a trophic pathway

    International Nuclear Information System (INIS)

    Lemons, J.D.

    1976-06-01

    The first objective was to test the hypothesis that metal distributions and trends in organisms are, in part, a function of metal positions in the periodic table in unpolluted ecosystems. The data have shown that large soil crustal abundance differences of related elements (e.g. alkali metals) are proportionately approximated in higher organisms. Concentration factors for related nutritious and nonessential and toxic metals were determined along a trophic pathway. When the concentration factors were reported as the concentration of a particular metal by itself, all metal concentrations increased along the trophic pathway. The second objective of this study was to test the hypothesis that distributions and natural levels of chemically related nonessential and toxic metals can better be known when the metals are reported as a ratio, in ash, of the nonessential or toxic metal to its chemically related nutritious metal (e.g. strontium/calcium) as the metals are transferred through trophic pathways. The data have shown that when this method of reporting metal abundances in trophic levels is used, nonessential and toxic metals are discriminated against, relative to their chemically related nutritious metal, as the metals are transferred through the trophic pathway levels. The third objective was designed to test the hypothesis that surface deposition of toxic metals upon plants influences the trends of metal abundances through trophic pathways. This study indicates that metal pollution in the form of deposition upon plant surfaces bypasses the discrimination mechanisms in plants, and consequently elevates the total body burden in herbivores. It is likely that there is no herbivore defense for this type of metal exposure, because herbivores have probably come to rely, in part, upon the discriminatory mechanism of plants throughout the course of evolutionary history to keep toxic metal burdens low

  19. Recent developments in the nanostructured materials functionalized with ruthenium complexes for targeted drug delivery to tumors

    Directory of Open Access Journals (Sweden)

    Thangavel P

    2017-04-01

    Full Text Available Prakash Thangavel,1 Buddolla Viswanath,1 Sanghyo Kim1,2 1Department of Bionanotechnology, Gachon University, Bokjeong-Dong, Sujeong-Gu, Seongnam-Si, Gyeonggi-Do, 2Graduate Gachon Medical Research Institute, Gil Medical Center, Incheon, Republic of Korea Abstract: In recent years, the field of metal-based drugs has been dominated by other existing precious metal drugs, and many researchers have focused their attention on the synthesis of various ruthenium (Ru complexes due to their potential medical and pharmaceutical applications. The beneficial properties of Ru, which make it a highly promising therapeutic agent, include its variable oxidation states, low toxicity, high selectivity for diseased cells, ligand exchange properties, and the ability to mimic iron binding to biomolecules. In addition, Ru complexes have favorable adsorption properties, along with excellent photochemical and photophysical properties, which make them promising tools for photodynamic therapy. At present, nanostructured materials functionalized with Ru complexes have become an efficient way to administer Ru-based anticancer drugs for cancer treatment. In this review, the recent developments in the nanostructured materials functionalized with Ru complexes for targeted drug delivery to tumors are discussed. In addition, information on “traditional” (ie, non-nanostructured Ru-based cancer therapies is included in a precise manner. Keywords: metallodrugs, nanotechnology, cancer treatment, cell apoptosis, DNA damage, toxicity

  20. The Biological Side of Water-Soluble Arene Ruthenium Assemblies

    OpenAIRE

    Therrien, Bruno; Furrer, Julien

    2014-01-01

    This review article covers the synthetic strategies, structural aspects, and host-guest properties of ruthenium metalla-assemblies, with a special focus on their use as drug delivery vectors. The two-dimensional metalla-rectangles show interesting host-guest possibilities but seem less appropriate for being used as drug carriers. On the other hand, metalla-prisms allow encapsulation and possible targeted release of bioactive molecules and consequently show some potential as drug delivery vect...

  1. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-10-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), CIO 2 + RuF 6 - , a new compound well identified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  2. Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

    International Nuclear Information System (INIS)

    Meublat, L.

    1989-01-01

    The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), ClO 2 + RuF 6 - , a new compound well idendified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

  3. Simultaneous removal of several heavy metals from aqueous solution by natural limestones

    Directory of Open Access Journals (Sweden)

    Sdiri A.

    2014-07-01

    Full Text Available Four natural limestone samples, collected from the Campanian-Maastrichtian limestones, Tunisia, were used as adsorbents for the removal of toxic metals in aqueous systems. The results indicated that high removal efficiency could be achieved by the present natural limestones. Among the metal ions studied, Pb2+ was the most preferably removed cation because of its high affinity to calcite surface. In binary system, the presence of Cu2+ effectively depressed the sorption of Cd2+ and Zn2+. Similarly Cu2+ strongly competed with Pb2+ to limestone surface. In ternary system, the removal further decreased, but considerable amount of Pb2+ and Cu2+ still occurred regardless of the limestone sample. The same behavior was observed in quadruple system, where the selectivity sequence was Pb2+ > Cu2+ > Cd2+ > Zn2+. From these results, it was concluded that the studied limestones have the required technical specifications to be used for the removal of toxic metals from wastewaters.

  4. Study of methods for removing strontium, plutonium, and ruthenium from Savannah River Plant waste supernate

    International Nuclear Information System (INIS)

    Wiley, J.R.

    1976-06-01

    As a part of long-term waste management studies at the Savannah River Laboratory, tests were made to study removal of strontium, plutonium, and ruthenium from simulated and actual waste supernates. Plutonium was sorbed by Duolite ARC-359 ion exchange resin, the same resin that is used to remove cesium from waste supernate. Strontium was removed from supernate by sorption on a chelating resin Chelex 100, or by precipitation as Sr 3 (PO 4 ) 2 . Activities of 137 Cs, 90 Sr, and 238-241 Pu remaining in processed waste supernate should be 1-10 nanocuries of each element per gram of salt. Of the methods that were tested, none was adequate for plant-scale removal of ruthenium

  5. Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework.

    Science.gov (United States)

    Miura, Takashi; Naruto, Masayuki; Toda, Katsuaki; Shimomura, Taiki; Saito, Susumu

    2017-05-16

    Amides are ubiquitous and abundant in nature and our society, but are very stable and reluctant to salt-free, catalytic chemical transformations. Through the activation of a "sterically confined bipyridine-ruthenium (Ru) framework (molecularly well-designed site to confine adsorbed H 2 in)" of a precatalyst, catalytic hydrogenation of formamides through polyamide is achieved under a wide range of reaction conditions. Both C=O bond and C-N bond cleavage of a lactam became also possible using a single precatalyst. That is, catalyst diversity is induced by activation and stepwise multiple hydrogenation of a single precatalyst when the conditions are varied. The versatile catalysts have different structures and different resting states for multifaceted amide hydrogenation, but the common structure produced upon reaction with H 2 , which catalyzes hydrogenation, seems to be "H-Ru-N-H."

  6. Microwave irradiation for the facile synthesis of transition-metal nanoparticles (NPs) in ionic liquids (ILs) from metal-carbonyl precursors and Ru-, Rh-, and Ir-NP/IL dispersions as biphasic liquid-liquid hydrogenation nanocatalysts for cyclohexene.

    Science.gov (United States)

    Vollmer, Christian; Redel, Engelbert; Abu-Shandi, Khalid; Thomann, Ralf; Manyar, Haresh; Hardacre, Christopher; Janiak, Christoph

    2010-03-22

    Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M-NPs) have been reproducibly obtained by facile, rapid (3 min), and energy-saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal-carbonyl precursors [M(x)(CO)(y)] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF(4)]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180-250 degrees C, 6-12 h) of [M(x)(CO)(y)] in ILs. The MWI-obtained nanoparticles have a very small (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)(-1) h(-1) and 884 (mol product) (mol Rh)(-1) h(-1) and give almost quantitative conversion within 2 h at 10 bar H(2) and 90 degrees C. Catalyst poisoning experiments with CS(2) (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru-NPs.

  7. Anisotropic nature of radially strained metal tubes

    Science.gov (United States)

    Strickland, Julie N.

    yield strength to calculate these ratings. I set out to characterize the anisotropic nature of swaged metal. As expected, the tensile tests showed a difference between the axial and transverse tensile strength. The correlation was 12% difference in yield strength in the axial and transverse directions for strained material and 9% in strained and aged material. This means that the strength of the metal in the hoop (transverse) direction is approximately 10% stronger than in the axial direction, because the metal was work hardened during the swaging process. Therefore, the metal is more likely to fail in axial tension than in burst or collapse. I presented the findings from the microstructure examination, standard tensile tests, and SEM data. All of this data supported the findings of the mini-tensile tests. This information will help engineers set burst and collapse ratings and allow material scientists to predict the anisotropic characteristics of swaged steel tubes.

  8. Synthesis and Catalytic Applications of Ruthenium(0) Nanoparticles in Click Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Avvaru Praveen; Baek, Minwook; Sridhar, Chirumarry; Kumar, Begari Prem; Lee, Yongill [Changwon National Univ., Changwon (Korea, Republic of)

    2014-04-15

    Here we report a facile synthesis of ruthenium (Ru) Nanoparticles (NPs) by chemical co-precipitation method. The calcination of ruthenium hydroxide samples at 500 .deg. C under hydrogen atmosphere lead to the formation of Ru{sup 0} NPs. The size and aggregation of Ru NPs depends on the pH of the medium, and type of surfactant and its concentration. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope image (TEM) analyses of particles indicated the formation of Ru{sup 0} NPs, and have 10 to 20 nm sizes. As-synthesized Ru{sup 0} NPs are characterized and investigated their catalytic ability in click chemistry (azide-alkyne cycloaddition reactions), showing good results in terms of reactivity. Interestingly, small structural differences in triazines influence the catalytic activity of Ru{sup 0} nanocatalysts. Click chemistry has recently emerged to become one of the most powerful tools in drug discovery, chemical biology, proteomics, medical sciences and nanotechnology/nanomedicine. In addition, preliminary tests of recycling showed good results with neither loss of activity or significant precipitation.

  9. Natural and active chemical remediation of toxic metals and radionuclides in the aquatic environment

    International Nuclear Information System (INIS)

    McPherson, G.; Pintauro, P.; O'Connor, S.; Zhang, J.; Gonzales, R.; Flowers, G.

    1993-01-01

    The focus of this research is the non-biological, chemical remediation of toxic heavy metals and radionuclides in aquatic environments. This Tulane/Xavier group includes researchers from Chemistry, Chemical Engineering, and Geology. Active methods using novel zeolites and ion exchange membranes are currently being evaluated for use in removing heavy metals from natural waters. In addition, field and laboratory studies of metal ion exchange reactions and competitive, heavy metal adsorption on clay substrates are underway to determine sediment metal sequestering capacity. A summary of progress to date and future work is presented

  10. Micelle-derived catalysts for extended Schulz-Flory

    Energy Technology Data Exchange (ETDEWEB)

    Abrevaya, H.

    1986-01-01

    The objective of this program is to develop a synthesis gas conversion catalyst with higher selectivity to liquid fuels, while maintaining catalytic activity and stability at least equivalent relative to state-of-the-art precipitated iron catalysts. During this quarter, the emphasis in the program has been the investigation of the hydrocarbon cutoff hypothesis with supported ruthenium catalysts. An alumina-supported catalyst with smaller than 20[Angstrom] ruthenium particles was tested under conditions of maximal water gas shift activity. During this test more than 90% of the water made in the Fischer-Tropsch synthesis reaction was converted to H[sub 2]. However, the extent of ruthenium metal agglomeration was not reduced. Accordingly, it was not possible to conclude whether hydrocarbon cutoff occurs with smaller than 20[Angstrom] ruthenium particles on [gamma]-alumina. A ruthenium catalyst prepared on Y-type zeolite had 20[Angstrom] or smaller ruthenium particles according to STEM examination and a 15[Angstrom] average ruthenium metal particle size according to EXAFS examination. The ruthenium metal particle size was stable during the test with this catalyst. The hydrocarbon product distribution was Anderson-Schulz-Flory with no cutoff up to a carbon number of 160. A well-dispersed titania-supported ruthenium catalyst is going to be evaluated during the next quarter in order to determine whether hydrocarbon cutoff occurs.

  11. Micelle-derived catalysts for extended Schulz-Flory. Technical progress report, July 1, 1986--September 30, 1986

    Energy Technology Data Exchange (ETDEWEB)

    Abrevaya, H.

    1986-12-31

    The objective of this program is to develop a synthesis gas conversion catalyst with higher selectivity to liquid fuels, while maintaining catalytic activity and stability at least equivalent relative to state-of-the-art precipitated iron catalysts. During this quarter, the emphasis in the program has been the investigation of the hydrocarbon cutoff hypothesis with supported ruthenium catalysts. An alumina-supported catalyst with smaller than 20{Angstrom} ruthenium particles was tested under conditions of maximal water gas shift activity. During this test more than 90% of the water made in the Fischer-Tropsch synthesis reaction was converted to H{sub 2}. However, the extent of ruthenium metal agglomeration was not reduced. Accordingly, it was not possible to conclude whether hydrocarbon cutoff occurs with smaller than 20{Angstrom} ruthenium particles on {gamma}-alumina. A ruthenium catalyst prepared on Y-type zeolite had 20{Angstrom} or smaller ruthenium particles according to STEM examination and a 15{Angstrom} average ruthenium metal particle size according to EXAFS examination. The ruthenium metal particle size was stable during the test with this catalyst. The hydrocarbon product distribution was Anderson-Schulz-Flory with no cutoff up to a carbon number of 160. A well-dispersed titania-supported ruthenium catalyst is going to be evaluated during the next quarter in order to determine whether hydrocarbon cutoff occurs.

  12. Synthesis and catalytic activity of ruthenium complexes modified with chiral racemic per- and polyfluorooxaalkanoates

    Czech Academy of Sciences Publication Activity Database

    Lipovská, P.; Rathouská, L.; Šimůnek, O.; Hošek, J.; Kolaříková, V.; Rybáčková, M.; Cvačka, Josef; Svoboda, Martin; Kvíčala, J.

    2016-01-01

    Roč. 191, Nov (2016), s. 14-22 ISSN 0022-1139 Institutional support: RVO:61388963 Keywords : racemic * chiral * ruthenium complex * perfluorooxaalkanoate * polyfluorooxaalkanoate Subject RIV: CC - Organic Chemistry Impact factor: 2.101, year: 2016

  13. Natural sources of metals in the south of West Siberia landscapes

    International Nuclear Information System (INIS)

    Roslyakov, N.A.; Kalinin, Yu.A.; Roslyakova, N.V.; Kropacheva, M.Yu.

    2008-01-01

    The present paper dwells on a negative effect of natural anomalous concentrations of heavy and radioactive metals on state-of-the-art landscapes, with their vertical zonality distinctly expressed and ore mineralization composition miscellaneous. In terms of ecology there are given data on element distributions depending on the vertical zonality and genetic belonging of West Siberian elementary landscapes. Natural geochemical anomalies are shown to have a long formation history. General distribution trend of Li, Be, B, P, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Te, Ba, W, Au, Pb, Bi, Hg, Th, U as well as Hf, Ta, Rb, Cs, La, Ce, Nd, Sm, Eu, Gd, Tb, Yb, Lu in major types of the region rocks and levels of their anomalous concentrations have been analyzed. Against the regional background a significant effect upon ecogeochemistry of state-of-the-art landscapes of natural anomalies of heavy and radioactive metals genesis and composition of which find their reflection in the vertical zonality of the surface relief have been shown.

  14. Late side effects of Ruthenium 106 therapy for uveal melanomas

    International Nuclear Information System (INIS)

    Langmann, G.; Faulborn, J.; Poier, E.

    1994-01-01

    When effectiveness is evaluated in brachytherapy with Ruthenium 106 special emphasis has to be put on tumor destruction and late side effects responsible for the definite functional results. We evaluated the late side effects of 22 uveal melanomas, which had been treated with 106 Ruthenium plaques. The tumor prominences ranged from 3 to 10 mm, the diameter from 4 to 9 disc diameters. In 4 patients the tumor involved the posterior pole, 14 melanomas were located in the midperiphery of the fundus, 4 tumors were ciliary body melanomas. The total radiation dose of the apex ranged from 100 to 240 Gy with a corresponding dose to the sclera between 540 to 1000 Gy. Because of the short half life of the plaque we have been using different dose rates (1.6-11 Gy/h). In 17/22 eyes adequate regression could be achieved by Ruthenium therapy alone. In one case additional laser treatment of the macular part of the melanoma had to be performed, Gamma Knife therapy was necessary in another melanoma with 10 mm tumor prominence. 3 recurrences led to enucleation. The mean follow up was 4.8 years ranging from 1 to 7 years. In 2/22 patients opticopathy caused severe visual impairment, in another 2 patients radiation maculopathy and opticopathy was observed. 7/22 developed vasculopathy with neovascularization treated by photocoagulation. In one case of focal radiation maculopathy laser treatment could prevent further visual impairment. The following factors are responsible for a higher incidence of late side effects: 1. High dose rate of the plaques in combination with a high radiation dose to the sclera 2. Location of the tumor within a minimum distance of 2 disc diameters to the optic nerve or macula 3. Tumor location at the ciliary body Laser treatment in case of neovascularization and focal radiation maculopathy is the only effective treatment with regard to late side effects. Ischemic maculopathy and radiation opticopathy are responsible for late visual impairment. (authors)

  15. TBP 20% diluent/H N O3/H2 O liquid-liquid extraction system: equilibrium data normalization of nitric acid, ruthenium and zirconium

    International Nuclear Information System (INIS)

    Oliveira, C.A.L.G. de; Araujo, B.F. de.

    1991-11-01

    The extraction behavior of nitric acid, nitrosyl ruthenium nitrate and zirconium hydroxide nitrate in the system tri-n-butyl phosphate (TBP) 20% -diluent was studied. The main purpose was to obtain enough data to elaborate process flowsheets for the treatment of irradiated uranium fuels. During the runs, the equilibrium diagrams of nitric acid, ruthenium and zirconium were settled. From the achieved data, the influence of nitric acid, ruthenium, zirconium and nitrate ions concentration in the aqueous phase was checked. Furthermore, the density and the surface tension of the aqueous and organic phases were determined, gathering the interfacial tension after the contact between the phases. (author)

  16. Effect of composition of chlorophyll and ruthenium dyes mixture (hybrid) on the dye-sensitized solar cell performance

    Science.gov (United States)

    Pratiwi, D. D.; Nurosyid, F.; Kusumandari; Supriyanto, A.; Suryana, R.

    2018-03-01

    The fabrication of dye-sensitized solar cell (DSSC) has been conducted by varying the composition of natural dye from moss chlorophyll (Bryophyte) and synthesis dye from ruthenium complex N719. The sandwich structure of DSSC consists of the working electrode using TiO2, dye, electrolyte, and counter electrode using carbon. The composition of chlorophyll and synthesis dyes mixture were 100% and 0%, 80% and 20%, 60% and 40%, 40% and 60%, and 20% and 80%. The UV-Vis absorption spectra of moss chlorophyll showed the first peak in the wavelength range of 450-500 nm and the second peak at wavelength of 650-700 nm. The peak value of absorbance at wavelengths of 450-500 nm was 6.1004 and at wavelengths of 650-700 nm was 3.5835. The IPCE characteristic curves showed the absorption peak of photon for DSSCs occurred at wavelength of 550-650 nm. It considered that photon in this wavelength can contribute dominantly to produce the optimum electrons. The I-V characteristics of DSSCs with composition of chlorophyll and synthesis dyes mixture of 100% and 0%, 80% and 20%, 60% and 40%, 40% and 60%, and 20% and 80% resulted the efficiency of 0.0022; 0.0194; 0.0239; 0.0342; and 0.0414, respectively. It suggested that the addition of a little composition of the ruthenium complex dye into moss chlorophyll dye can increase the efficiency significantly.

  17. A nanogravimmetric investigation of the charging processes on ruthenium oxide thin films and their effect on methanol oxidation

    International Nuclear Information System (INIS)

    Santos, M.C.; Cogo, L.; Tanimoto, S.T.; Calegaro, M.L.; Bulhoes, L.O.S

    2006-01-01

    The charging processes and methanol oxidation that occur during the oxidation-reduction cycles in a ruthenium oxide thin film electrode (deposited by the sol-gel method on Pt covered quartz crystals) were investigated by using cyclic voltammetry, chronoamperometry and electrochemical quartz crystal nanobalance techniques. The ruthenium oxide rutile phase structure was determined by X-ray diffraction analysis. The results obtained during the charging of rutile ruthenium oxide films indicate that in the anodic sweep the transition from Ru(II) to Ru(VI) occurs followed by proton de-intercalation. In the cathodic sweep, electron injection occurs followed by proton intercalation, leading to Ru(II). The proton intercalation/de-intercalation processes can be inferred from the mass/charge relationship which gives a slope close to 1 g mol -1 (multiplied by the Faraday constant) corresponding to the molar mass of hydrogen. From the chronoamperometric measurements, charge and mass saturation of the RuO 2 thin films was observed (440 ng cm -2 ) during the charging processes, which is related to the total number of active sites in these films. Using the electrochemical quartz crystal nanobalance technique to study the methanol oxidation reaction at these films was possible to demonstrate that bulk oxidation occurs without the formation of strongly adsorbed intermediates such as CO ads , demonstrating that Pt electrodes modified by ruthenium oxide particles can be promising catalysts for the methanol oxidation as already shown in the literature

  18. In Situ FTIR and NMR Spectroscopic Investigations on Ruthenium-Based Catalysts for Alkene Hydroformylation.

    Science.gov (United States)

    Kubis, Christoph; Profir, Irina; Fleischer, Ivana; Baumann, Wolfgang; Selent, Detlef; Fischer, Christine; Spannenberg, Anke; Ludwig, Ralf; Hess, Dieter; Franke, Robert; Börner, Armin

    2016-02-18

    Homogeneous ruthenium complexes modified by imidazole-substituted monophosphines as catalysts for various highly efficient hydroformylation reactions were characterized by in situ IR spectroscopy under reaction conditions and NMR spectroscopy. A proper protocol for the preformation reaction from [Ru3 (CO)12] is decisive to prevent the formation of inactive ligand-modified polynuclear complexes. During catalysis, ligand-modified mononuclear ruthenium(0) carbonyls were detected as resting states. Changes in the ligand structure have a crucial impact on the coordination behavior of the ligand and consequently on the catalytic performance. The substitution of CO by a nitrogen atom of the imidazolyl moiety in the ligand is not a general feature, but it takes place when structural prerequisites of the ligand are fulfilled. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Determination of biogenic amines from electrocatalytic responses of graphite electrodes modified with metallic osmium or an osmium oxide-ruthenium cyanide film

    International Nuclear Information System (INIS)

    Shajdarova, L.G.; Gedmina, A.V.; Chelnokova, I.A.; Budnikov, G.K.

    2008-01-01

    Particles of osmium or an inorganic polymeric film of osmium oxide-ruthenium cyanide (OsO-RuCN) electrodeposited on glassy carbon (GC) electrocatalyze the oxidation of dopamine (DA), adrenaline (AD), and noradrenaline (NAD). It is found that these biogenic amines are determined with a high sensitivity by oxidation at an electrode with an OsO-RuCN film. Procedures for the voltammetric determination of DA, AD, or NAD at a composite film electrode are developed. The currents of the substrate oxidation are linear functions of the concentrations in the ranges from 5x10 -7 to 1x10 -3 M for DA and from 1x10 -6 to 1x10 -3 M for AD and NAD [ru

  20. Electrochemiluminescence and chemiluminescence of a carboxylic acid derivative of ruthenium(II) tris-(2,2'-bipyridine) chelate synthesized for labeling purposes

    International Nuclear Information System (INIS)

    Jiang Qinghong; Sun Shiguo; Hakansson, Markus; Langel, Kaarina; Ylinen, Tiina; Suomi, Johanna; Kulmala, Sakari

    2006-01-01

    Synthesis, purification and characterization of [4-ethoxycarbonyl-4'-carboxy-2,2'-bipyridine]bis(2,2'-bipyridine) ruthenium(II) hexafluorophosphate is described. This complex is shown to be electrochemiluminescent in aqueous solution during cathodic pulse polarization of thin insulating film-coated electrodes. Electrochemiluminescence (ECL) lifetime of the complex was observed to be ca. 40 μs at oxide-coated n-silicon electrodes; thus time-resolved detection is also possible. The ECL emission maximum of this carboxylate derivative is somewhat red-shifted when compared with an unmodified Ru(bpy) 3 2+ . Because the present complex can be easily covalently coupled with antibodies and oligonucleotides it is usable as an electrochemiluminescent label in various bioaffinity assays. The present chelates also produce strong chemiluminescence during dissolution of metallic magnesium in aqueous solution

  1. A review of modelling the interaction between natural organic matter and metal cations

    International Nuclear Information System (INIS)

    Falck, W.E.

    1989-01-01

    This report reviews techniques available to model the interaction between natural organic matter (mainly fulvic and humic acids) and protons and metal cations. A concise definition of natural organic matter is given and their properties are outlined. These materials are macromolecules which exhibit a polyelectrolyte character owing to numerous dissociable functional groups which are attached to their carbon backbone or from integral parts of the structure. The polyelectrolyte character is thought to be responsible for their conformation, hydrogen bonding or bridging by metal cations between subunits being important mechanisms. Environmental parameters like pH and ionic strength thus will have profound effects on the conformation of natural organic matter, the properties of which can change from being a flexible polymer to being a rigid gel. Binding mechanisms and binding strengh are discussed and an overview of relevant techniques of investigation is given. This work is part of the Commission's Mirage project - Phase 2, research area Geochemistry of actinides and fission products in natural aquifer systems

  2. Large-scale ruthenium- and enzyme-catalyzed dynamic kinetic resolution of (rac-1-phenylethanol

    Directory of Open Access Journals (Sweden)

    Bäckvall Jan-E

    2007-12-01

    Full Text Available Abstract The scale-up of the ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR of (rac-1-phenylethanol (2 is addressed. The immobilized lipase Candida antarctica lipase B (CALB was employed for the resolution, which shows high enantioselectivity in the transesterification. The ruthenium catalyst used, (η 5-C5Ph5RuCl(CO2 1, was shown to possess very high reactivity in the "in situ" redox racemization of 1-phenylethanol (2 in the presence of the immobilized enzyme, and could be used in 0.05 mol% with high efficiency. Commercially available isopropenyl acetate was employed as acylating agent in the lipase-catalyzed transesterifications, which makes the purification of the product very easy. In a successful large-scale DKR of 2, with 0.05 mol% of 1, (R-1-phenylethanol acetate (3 was obtained in 159 g (97% yield in excellent enantiomeric excess (99.8% ee.

  3. Noble metal behavior during melting of simulated high-level nuclear waste glass feeds

    International Nuclear Information System (INIS)

    Anderson, L.D.; Dennis, T.; Elliott, M.L.; Hrma, P.

    1994-01-01

    Noble metals and their oxides can settle in waste glass melters and cause electrical shorting. Simulate waste feeds from Hanford, Savannah River, and Kernforschungszentrum Karlsruhe were heat treated for 1 hour in a gradient furnace at temperatures ranging from approximately 600 degrees C to 1000 degrees C and examined by electron microscopy to determine shapes, sizes, and distribution of noble metal particles as a function of temperature. Individual noble metal particles and agglomerates of rhodium (Rh), ruthenium (RuO 2 ), and palladium (Pd), as well as their alloys, were seen. The majority of particles and agglomerates were generally less than 10 μm; however, large agglomerations (up to 1 mm) were found in the German feed. 5 refs., 6 figs., 2 tabs

  4. Recommended values of clean metal surface work functions

    International Nuclear Information System (INIS)

    Derry, Gregory N.; Kern, Megan E.; Worth, Eli H.

    2015-01-01

    A critical review of the experimental literature for measurements of the work functions of clean metal surfaces of single-crystals is presented. The tables presented include all results found for low-index crystal faces except cases that were known to be contaminated surfaces. These results are used to construct a recommended value of the work function for each surface examined, along with an uncertainty estimate for that value. The uncertainties are based in part on the error distribution for all measured work functions in the literature, which is included here. The metals included in this review are silver (Ag), aluminum (Al), gold (Au), copper (Cu), iron (Fe), iridium (Ir), molybdenum (Mo), niobium (Nb), nickel (Ni), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), tantalum (Ta), and tungsten (W)

  5. Recommended values of clean metal surface work functions

    Energy Technology Data Exchange (ETDEWEB)

    Derry, Gregory N., E-mail: gderry@loyola.edu; Kern, Megan E.; Worth, Eli H. [Department of Physics, Loyola University Maryland, 4501 N. Charles St., Baltimore, Maryland 21210 (United States)

    2015-11-15

    A critical review of the experimental literature for measurements of the work functions of clean metal surfaces of single-crystals is presented. The tables presented include all results found for low-index crystal faces except cases that were known to be contaminated surfaces. These results are used to construct a recommended value of the work function for each surface examined, along with an uncertainty estimate for that value. The uncertainties are based in part on the error distribution for all measured work functions in the literature, which is included here. The metals included in this review are silver (Ag), aluminum (Al), gold (Au), copper (Cu), iron (Fe), iridium (Ir), molybdenum (Mo), niobium (Nb), nickel (Ni), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), tantalum (Ta), and tungsten (W)

  6. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts

    Science.gov (United States)

    MURAHASHI, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. PMID:21558760

  7. A simple and selective spectrophotometric flow injection determination of trace amounts of ruthenium by catalytic oxidation of safranin-O

    Energy Technology Data Exchange (ETDEWEB)

    Rezaei, Behzad [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-84111 (Iran, Islamic Republic of)], E-mail: rezaei@cc.iut.ac.ir; Keyvanfard, Mohsen [Faculty of Science, Majlesi Campus, Islamic Azad University, Isfahan (Iran, Islamic Republic of)

    2008-03-01

    In this work, a simple, selective and rapid flow injection method has been developed for determination of ruthenium. The method is based on its catalytic effect on the oxidation of safranin-O by metaperiodate. The reaction was monitored spectrophotometrically by measuring safranin-O absorbance at {lambda}{sub max} = 521. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine ruthenium in the ranges of 0.4-20.0 ng/mL ({delta}A = 0.2819C{sub Ru} + 1.1840) and 20.0-100.0 ng/mL ({delta}A = 0.0984C{sub Ru} + 7.9391) with a detection limit of 0.095 ng/mL and a sample rate of 30 {+-} 5 samples/h. Relative standard deviation for the five replicate measurements was less than 1.84%. The proposed method has been successfully applied for analysis of ultra trace amounts of ruthenium in real samples.

  8. A simple and selective spectrophotometric flow injection determination of trace amounts of ruthenium by catalytic oxidation of safranin-O

    International Nuclear Information System (INIS)

    Rezaei, Behzad; Keyvanfard, Mohsen

    2008-01-01

    In this work, a simple, selective and rapid flow injection method has been developed for determination of ruthenium. The method is based on its catalytic effect on the oxidation of safranin-O by metaperiodate. The reaction was monitored spectrophotometrically by measuring safranin-O absorbance at λ max = 521. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine ruthenium in the ranges of 0.4-20.0 ng/mL (ΔA = 0.2819C Ru + 1.1840) and 20.0-100.0 ng/mL (ΔA = 0.0984C Ru + 7.9391) with a detection limit of 0.095 ng/mL and a sample rate of 30 ± 5 samples/h. Relative standard deviation for the five replicate measurements was less than 1.84%. The proposed method has been successfully applied for analysis of ultra trace amounts of ruthenium in real samples

  9. p-chloro- and p-bromo-benzoylacetoneoxime as the spectrophotometric reagents for palladium and ruthenium(III)

    International Nuclear Information System (INIS)

    Yeole, V.V.; Langade, A.D.; Shinde, V.M.

    1980-01-01

    A procedure is described for the extractive spectrophotometric determination of palladium or ruthenium(III) using p-chloro or p-bromobenzoylacetoneoxime as the reagent. The yellow palladium complexes which are extracted into chloroform from an aqueous solution of pH 3.5, absorb as 400 nm and conform to Beer's law in the range of 10 to 100 μg of Pd/10 ml of organic phase. The orange-red ruthenium complexes which are extracted into ethylacetate from an aqueous solution of pH 5.0, absorbs at 475 nm and conforms to Beer's law in the range of 20 to 200 μg of Ru/10 ml of organic phase. The molar absorptivities, Sandell's sensitivities and instability constants are reported. (author)

  10. The use of natural and industrial aluminosilicates in the process of adsorption of heavy metals ions

    OpenAIRE

    Tsvetkova, A.; Akayev, O.

    2010-01-01

    The analysis of periodic scientific publications and patent literature was made, in which the possibilities of using natural and industrial silicon-containing compounds as adsorbents of ions of heavy metals are generalized. The conditions of adsorption, as well as the numerical values of the adsorption capacity of the studied materials are described Key words: adsorption, natural and industrial aluminosilicates, heavy metals ions.

  11. Influence of ruthenium ions on the precipitation of α-FeOOH, α-Fe2O3 and Fe3O4 in highly alkaline media

    International Nuclear Information System (INIS)

    Krehula, Stjepko; Music, Svetozar

    2006-01-01

    The influence of ruthenium ions on the precipitation of goethite (α-FeOOH), α-Fe 2 O 3 and Fe 3 O 4 in highly alkaline media was investigated by 57 Fe Moessbauer and FT-IR spectroscopies, thermal field emission scanning electron microscope (FE SEM) and EDS. The presence of Ru-dopant strongly affected the precipitation of α-FeOOH at highly alkaline pH, i.e. the formation of α-Fe 2 O 3 was also noticed. A decrease of hyperfine magnetic field (HMF) at RT from 35.1 T (undoped α-FeOOH) to 31.3 T for sample with [Ru]/([Ru] + [Fe]) = 0.0196 was assigned to the incorporation of ruthenium ions into the α-FeOOH structure. Moessbauer spectroscopy showed the formation of stoichiometric Fe 3 O 4 for [Ru]/([Ru] + [Fe]) = 0.0291-0.0909. α-Fe 2 O 3 and Fe 3 O 4 did not show a tendency to the formation of solid solutions with ruthenium ions. FE SEM observations of the samples showed that reference α-FeOOH sample contained acicular particles of good uniformity, which increased the length up to ∼5 times with increase of concentration of ruthenium ions. On the other hand, large octahedral Fe 3 O 4 crystals (particles) were associated with small particles of ruthenium (hydrous) oxide with a size in the range ∼100 nm or less. A possible catalytic action of ruthenium that created reduction conditions for Fe 3+ ions and formation of Fe 2+ ions for precipitation of Fe 3 O 4 was discussed

  12. Dinuclear ruthenium sawhorse-type complexes containing carboxylato bridges and ferrocenyl substituents: Synthesis and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Auzias, M.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří

    2007-01-01

    Roč. 360, č. 6 (2007), s. 2023-2028 ISSN 0020-1693 Institutional research plan: CEZ:AV0Z40400503 Keywords : carboxylato bridges * dinuclear complexes * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 1.713, year: 2007

  13. Tailoring the Selectivity for Electrocatalytic Oxygen Evolution on Ruthenium Oxides by Zinc Substitution

    Czech Academy of Sciences Publication Activity Database

    Petrykin, Valery; Macounová, Kateřina; Shlyakhtin, O. A.; Krtil, Petr

    2010-01-01

    Roč. 49, č. 28 (2010), s. 4813-4815 ISSN 1433-7851 R&D Projects: GA AV ČR IAA400400906 Institutional research plan: CEZ:AV0Z40400503 Keywords : electrocatalysis * ruthenium oxides * zinc substitution Subject RIV: CG - Electrochemistry Impact factor: 12.730, year: 2010

  14. Effect of crust increase on natural convection heat transfer in the molten metal pool

    International Nuclear Information System (INIS)

    Park, Rae Joon; Kim, Sang Baik; Kim, Hee Dong; Choi, Sang Min

    1999-01-01

    An experimental study has been performed on natural convection heat transfer with a rapid crust formation in the molten metal pool of a low Prandtl number fluid. Two types of steady state tests, a low and high geometric aspect ratio cases in the molten metal pool, were performed. The crust thickness by solidification was measured as a function of boundary surface temperatures. The experimental results on the relationship between the Nusselt number and Rayleigh number in the molten metal pool with a crust formation were compared with existing correlations. The experimental study has shown that the bottom surface temperature of the molten metal layer, in all experiments, is the major influential parameter in the crust formation, due to the natural convection flow. The Nusselt number of the case without a crust formation in the molten metal pool is greater than that of the case with the crust formation at the same Rayleigh number. The present experimental results on the relationship between the Nusselt number and Rayleigh number in the molten metal pool match well with Globe and Dropkin's correlation. From the experimental results, a new correlation between the Nusselt number and Rayleigh number in the molten metal pool with the crust formation was developed as Nu=0.0923 (Ra) 0.0923 (2 X 10 4 7 ). (author)

  15. Self-assembled arene-ruthenium-based rectangles for the selective sensing of multi-carboxylate anions.

    Science.gov (United States)

    Vajpayee, Vaishali; Song, Young Ho; Lee, Min Hyung; Kim, Hyunuk; Wang, Ming; Stang, Peter J; Chi, Ki-Whan

    2011-07-04

    Novel arene-ruthenium [2+2] metalla-rectangles 4 and 5 have been synthesized by self-assembly using dipyridyl amide ligand 3 and arene-ruthenium acceptors (arene: benzoquinone (1), naphthacenedione (2)) and characterized by NMR spectroscopy and ESI-MS. The solid-state structure of 5 was determined by X-ray diffraction and shows encapsulated diethyl ether molecule in the rectangular cavity of 5. The luminescent 5 was further used for anion sensing with the amidic linkage serving as a hydrogen-bond donor site for anions and the ruthenium moiety serving as a signaling unit. A UV/Vis titration study demonstrated that although 5 interacts very weakly with common monoanions as well as with flexible dicarboxylate anions such as malonate and succinate, it displays significant binding affinity (K>10(3) in MeOH) for rigid multi-carboxylate anions such as oxalate, citrate, and tartrate, exhibiting a 1:1 stoichiometry. It has been suggested that 1:1 bidentate hydrogen bonding assisted by appropriate geometrical complementarity is mainly responsible for the increased affinity of 5 towards such anions. A fluorescence titration study revealed a large fluorescence enhancement of 5 upon binding to multi-carboxylate anions, which can be attributed to the blocking of the photoinduced electron-transfer process from the arene-Ru moiety to the amidic donor in 5 as a result of hydrogen bonding between the donor and the anion. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Disposable biosensor based on cathodic electrochemiluminescence of tris(2,2-bipyridine)ruthenium(II) for uric acid determination

    International Nuclear Information System (INIS)

    Ballesta-Claver, J.; Rodríguez-Gómez, R.; Capitán-Vallvey, L.F.

    2013-01-01

    Highlights: ► Cathodic ECL offers conventional and non-aggressive analysis conditions. ► The ECL hydrogen peroxide/ruthenium complex system for uric acid determination is novel. ► The ruthenium complex is electrochemically immobilized on graphite screen-printed electrodes. ► The quantification of the uric acid is based on a Stern–Volmer type equation. ► The use of the cathodic ECL working methodology reduces interferences during analysis. -- Abstract: A new method for uric acid (UA) determination based on the quenching of the cathodic ECL of the tris(2,2-bipyridine)ruthenium(II)–uricase system is described. The biosensor is based on a double-layer design containing first tris(2,2-bipyridine)ruthenium(II) (Ru(bpy) 3 2+ ) electrochemically immobilized on graphite screen-printed cells and uricase in chitosan as a second layer. The uric acid biosensing is based on the ECL quenching produced by uric acid over the cathodic ECL caused by immobilized Ru(bpy) 3 2+ in the presence of uricase. The use of a −1.1 V pulse for 1 s with a dwelling time of 10 s makes it possible to estimate the initial enzymatic rate, which is used as the analytical signal. The Stern–Volmer type calibration function shows a dynamic range from 1.0 × 10 −5 to 1.0 × 10 −3 M with a limit of detection of 3.1 × 10 −6 M and an accuracy of 13.6% (1.0 × 10 −4 M, n = 5) as relative standard deviation. Satisfactory results were obtained for urine samples, creating an affordable alternative for uric acid determination

  17. Interactions of RuO4(g) with different surfaces in nuclear reactor containments

    International Nuclear Information System (INIS)

    Holm, J.; Glaenneskog, H.; Ekberg, C.

    2008-07-01

    During a severe nuclear reactor accident with air ingress, ruthenium in the form of RuO4 can be released from the nuclear fuel. Hence, it is important to investigate how the reactor containment is able to reduce the source term of ruthenium. This work has investigated the distribution of RuO4 between an aqueous and gaseous phase in the temperature interval of 20-50 deg. C by on-line measurements with an experimental set-up made of glass. The experiments showed that RuO4 is almost immediately distributed in the aqueous phase after its introduction in the set-up in the entire temperature interval. However, the deposition of ruthenium on the glass surfaces in the system was significant. The speciation of the ruthenium on the glass surfaces was studied by SEM-EDX and ESCA and was determined to be the expected RuO2. Experiments of interactions between gaseous ruthenium tetroxide and the metals aluminium, copper and zinc have been investigated. The metals were treated by RuO4 (g) at room temperature and analyzed with ESCA, SEM and XRD. The analyses show that the black ruthenium deposits on the metal surfaces were RuO2, i.e. the RuO4 (g) has been transformed on the metal surfaces to RuO2(s). The analyses showed also that there was a significant deposition of ruthenium tetroxide especially on the copper and zinc samples. Aluminium has a lower ability to deposit gaseous ruthenium tetroxide than the other metals. The conclusion that can be made from the results is that surfaces in nuclear reactor containments will likely reduce the source term in the case of a severe accident in a nuclear power plant. (au)

  18. Efficient oxygen reduction reaction using ruthenium tetrakis(diaquaplatinum)octacarboxyphthalocyanine catalyst supported on MWCNT platform

    CSIR Research Space (South Africa)

    Maxakato, NW

    2011-02-01

    Full Text Available -1 Electroanalysis 2011, 23, No. 2, 325 ? 329 Efficient Oxygen Reduction Reaction Using Ruthenium Tetrakis(diaquaplatinum)Octacarboxyphthalocyanine Catalyst Supported on MWCNT Platform Nobanathi W. Maxakato,a Solomon A. Mamuru,a Kenneth I. Ozoemena*a, b a...

  19. Cellular responses of BRCA1-defective and triple-negative breast cancer cells and in vitro BRCA1 interactions induced by metallo-intercalator ruthenium(II) complexes containing chloro-substituted phenylazopyridine

    International Nuclear Information System (INIS)

    Nhukeaw, Tidarat; Temboot, Pornvichai; Hansongnern, Kanidtha; Ratanaphan, Adisorn

    2014-01-01

    Triple-negative breast cancer (TNBC) is defined by the absence of expression of estrogen receptor, progesterone receptor and human epidermal growth factor receptor 2. Breast cancers with a BRCA1 mutation are also frequently triple-negative. Currently, there is a lack of effective therapies and known specific molecular targets for this aggressive breast cancer subtype. To address this concern, we have explored the cellular responses of BRCA1-defective and triple-negative breast cancer cells, and in vitro BRCA1 interactions induced by the ruthenium(II) complexes containing the bidentate ligand, 5-chloro-2-(phenylazo)pyridine. Triple-negative MDA-MB-231, BRCA1-defective HCC1937 and BRCA1-competent MCF-7 breast cancer cell lines were treated with ruthenium(II) complexes. The cytoxoxicity of ruthenium-induced breast cancer cells was evaluated by a real time cellular analyzer (RTCA). Cellular uptake of ruthenium complexes was determined by ICP-MS. Cell cycle progression and apoptosis were assessed using propidium iodide and Annexin V flow cytometry. The N-terminal BRCA1 RING protein was used for conformational and functional studies using circular dichroism and in vitro ubiquitination. HCC1937 cells were significantly more sensitive to the ruthenium complexes than the MDA-MB-231 and MCF-7 cells. Treatment demonstrated a higher degree of cytotoxicity than cisplatin against all three cell lines. Most ruthenium atoms were retained in the nuclear compartment, particularly in HCC1937 cells, after 24 h of incubation, and produced a significant block at the G2/M phase. An increased induction of apoptotic cells as well as an upregulation of p53 mRNA was observed in all tested breast cancer cells. It was of interest that BRCA1 mRNA and replication of BRCA1-defective cells were downregulated. Changes in the conformation and binding constants of ruthenium-BRCA1 adducts were observed, causing inactivation of the RING heterodimer BRCA1/BARD1-mediated E3 ubiquitin ligase activity

  20. Nanoengineering of Ruthenium and Platinum-based Nanocatalysts by Continuous-Flow Chemistry for Renewable Energy Applications

    KAUST Repository

    AlYami, Noktan Mohammed

    2017-01-01

    This thesis presents an integrated study of nanocatalysts for heterogenous catalytic and electrochemical processes using pure ruthenium (Ru) with mixed-phase and platinum-based nanomaterials synthesized by continuous-flow chemistry. There are three

  1. Highly dispersed supported ruthenium oxide as an aerobic catalyst for acetic acid synthesis

    DEFF Research Database (Denmark)

    Laursen, Anders Bo; Gorbanev, Yury; Cavalca, Filippo

    2012-01-01

    The increasing need for shifting to renewable feedstocks in the chemical industry has driven research toward using green aerobic, selective oxidation reactions to produce bulk chemicals. Here, we report the use of a ruthenium mixed oxide/hydroxide (RuOx) on different support materials for the sel...

  2. The Behavior and Effects of the Noble Metals in the DWPF Melter System

    International Nuclear Information System (INIS)

    Smith, M.E.; Bickford, D.F.

    1997-01-01

    Governments worldwide have committed to stabilization of high-level nuclear waste (HLW) by vitrification to a durable glass form for permanent disposal. All of these nuclear wastes contain the fission-product noble metals: ruthenium, rhodium, and palladium. SRS wastes also contain natural silver from iodine scrubbers. Closely associated with the noble metals are the fission products selenium and tellurium which are chemical analogs of sulfur and which combine with noble metals to influence their behavior and properties. Experience has shown that these melt insoluble metals and their compounds tend to settle to the floor of Joule-heated ceramic melters. In fact, almost all of the major research and production facilities have experienced some operational problem which can be associated with the presence of dense accumulations of these relatively conductive metals and/or their compounds. In most cases, these deposits have led to a loss of production capability, in some cases, to the point that melter operation could not continue. HLW nuclear waste vitrification facilities in the United States are the Department of Energy's Defense Waste Processing Facility (DWPF) at the Savannah River Site, the planned Hanford Waste Vitrification Plant (HWVP) at the Hanford Site and the operating West Valley Demonstration Project (WVDP) at West Valley, NY. The Integrated DWPF Melter System (IDMS) is a vitrification test facility at the Savannah River Technology Center (SRTC). It was designed and constructed to provide an engineering-scale representation of the DWPF melter and its associated feed preparation and off-gas treatment systems. An extensive noble metals testing program was begun in 1990. The objectives of this task were to explore the effects of the noble metals on the DWPF melter feed preparation and waste vitrification processes. This report focuses on the vitrification portion of the test program

  3. Heavy metal and natural radionuclide levels in urban soils from Cienfuegos city, Cuba

    International Nuclear Information System (INIS)

    Diaz Rizo, Oscar; Quintana Miranda, Eduardo; D Alessandro Rodriguez, Katia; Lopez Pino, Neivy; Arado Lopez, Juana O.; Alonso Hernandez, Carlos M.; Cartas Aguila, Hector

    2013-01-01

    Concentrations of heavy metals and natural radionuclides in topsoil (0-10cm) from Cienfuegos city, Cuba, were determined by using X-ray fluorescence analysis and gamma ray spectrometry, respectively. The measured results of heavy metals show that the mean concentrations of Ni, Cu, Zn and Pb in the studied soil samples are higher than their corresponding background values. The calculated results of integrated pollution index of heavy metals indicate that the studied soils present severely heavy metal contamination. The concentrations of 226Ra, 232Th and 40K in the studied soil samples range from 8.3 to 32.7, 3.7 to 10.7 and 129 to 356 Bq.kg-1 with an average of 22.6, 6.3 and 272 Bq.kg-1 , respectively, which are similar than the average concentrations reported for South-central Cuban soils. The air absorbed dose rate and the annual effective dose equivalent received by the local residents due to the natural radionuclides in soil are lesser than the worldwide established limits. A significantly positive 232Th-Cu and 232Th-Zn correlations were determined, indicating the possible presence of these elements pollution source in the area.(author)

  4. Techniques for the quantitative analysis of fission-product noble metals

    International Nuclear Information System (INIS)

    Lautensleger, A.W.; Hara, F.T.

    1982-08-01

    Analytical procedures for the determination of ruthenium, rhodium, and palladium in precursor waste, solvent metal, and final glass waste forms have been developed. Two procedures for the analysis of noble metals in the calcine and glass waste forms are described in this report. The first is a fast and simple technique that combines inductively coupled argon plasma atomic emission spectrometry (ICP) and x-ray fluorescence techniques and can only be used on nonradioactive materials. The second procedure is based on a noble metal separation step, followed by an analysis using ICP. This second method is more complicated than the first, but it will work on radioactive materials. Also described is a procedure for the ICP analysis of noble metals in the solvent metal matrix. The only solvent metal addressed in this procedure is lead, but with minor changes the procedure could be applied to any of the solvent metals being considered in the Pacific Northwest Laboratory (PNL) extraction process. A brief explanation of atomic spectroscopy and the ICP analytical process, as well as of certain aspects of ICP performance (interelement spectral line interferences and certain matrix effects) is given

  5. Aerobic Oxidation of 5-(Hydroxymethyl)furfural in Ionic Liquids with Solid Ruthenium Hydroxide Catalysts

    DEFF Research Database (Denmark)

    Ståhlberg, Tim Johannes Bjarki; Eyjolfsdottir, Ester; Gorbanev, Yury

    2012-01-01

    The aerobic oxidation of 5-(hydroxymethyl)furfural was investigated over solid ruthenium hydroxide catalysts in ionic liquids at elevated temperatures and pressures. Several different catalyst supports were tested in combination with various ionic liquids. The best result was obtained in [EMIm...

  6. Evaluated phase diagrams of binary metal-tellurium systems of the D-block transition elements

    International Nuclear Information System (INIS)

    Chattopadhyay, G.; Bharadwaj, S.R.

    1989-01-01

    The binary phase diagrams of metal-tellurium systems for twenty seven d-block transition elements have been critically evaluated. Complete phase diagrams are presented for the elements, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, palladium, silver, lanthanum, platinum and gold, whereas, for scandium, titanium, vanadium, yttrium, zirconium, niobium, technitium, ruthenium, rhodium, hafnium, tantalum, tungsten , rhenium, osmium and iridium, the phase diagrams are incomplete and tentative. (author). 20 refs., 27 tabs., 27 figs

  7. Ruthenium-catalysed decomposition of formic acid: Fuel cell and catalytic applications

    KAUST Repository

    Piola, Lorenzo

    2017-08-08

    The decomposition of formic acid into H2 and CO2 was successfully performed using a ruthenium hydride catalyst, without any concomitant CO evolution. The reaction mechanism is investigated by means of density functional theory calculations (DFT). The generated H2 was further exploited in a fuel cell to produce electricity. The catalytic hydrogenation of conjugated olefins, using this dihydrogen generation procedure, is also reported.

  8. Ruthenium-catalysed decomposition of formic acid: Fuel cell and catalytic applications

    KAUST Repository

    Piola, Lorenzo; Ferná ndez-Salas, José A.; Nahra, Fady; Poater, Albert; Cavallo, Luigi; Nolan, Steven P.

    2017-01-01

    The decomposition of formic acid into H2 and CO2 was successfully performed using a ruthenium hydride catalyst, without any concomitant CO evolution. The reaction mechanism is investigated by means of density functional theory calculations (DFT). The generated H2 was further exploited in a fuel cell to produce electricity. The catalytic hydrogenation of conjugated olefins, using this dihydrogen generation procedure, is also reported.

  9. Detection of pyrrolizidine alkaloids using flow analysis with both acidic potassium permanganate and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence

    International Nuclear Information System (INIS)

    Gorman, Bree A.; Barnett, Neil W.; Bos, Richard

    2005-01-01

    For the first time, analytically useful chemiluminescence was elicited from the reactions of the pyrrolizidine alkaloids. Heliotrine, retronecine, supinine, monocrotaline and echinatine N-oxide yielded chemiluminescence upon reaction with tris(2,2'-bipyridyl)ruthenium(II) whilst lasiocarpine, its N-oxide and supinine elicited light upon reaction with acidic potassium permanganate. Detection limits for heliotrine were 1.25 x 10 -7 M and 9 x 10 -9 M for tris(2,2'-bipyridyl)ruthenium(III) perchlorate with flow injection analysis (FIA) and the silica-immobilised reagent (4-[4-(dichloromethylsilanyl)-butyl]-4'-methyl-2,2'-bipyridine)bis (2,2'-bipyridyl)ruthenium(II) with sequential injection analysis (SIA), respectively. Lasiocarpine was detectable at 1.4 x 10 -7 M using acidic potassium permanganate with FIA. Additionally, the silica-immobilised reagent was optimised with respect to the oxidant (ammonium ceric nitrate) concentration and the aspiration times which afforded a detection limit for codeine of 5 x 10 -10 M using SIA

  10. Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation

    Science.gov (United States)

    Patman, Ryan L.; Chaulagain, Mani Raj; Williams, Vanessa M.; Krische, Michael J.

    2011-01-01

    Under the conditions of ruthenium catalyzed transfer hydrogenation, 2-butyne couples to benzylic and aliphatic alcohols 1a–1i to furnish allylic alcohols 2a–2i, constituting a direct C-H vinylation of alcohols employing alkynes as vinyl donors. Under related transfer hydrogenation conditions employing formic acid as terminal reductant, 2-butyne couples to aldehydes 4a, 4b, and 4e to furnish identical products of carbonyl vinylation 2a, 2b, and 2e. Thus, carbonyl vinylation is achieved from the alcohol or the aldehyde oxidation level in the absence of any stoichiometric metallic reagents. Nonsymmetric alkynes 6a–6c couple efficiently to aldehyde 4b to provide allylic alcohols 2m–2o as single regioisomers. Acetylenic aldehyde 7a engages in efficient intramolecular coupling to deliver cyclic allylic alcohol 8a. PMID:19173651

  11. Development of biomimetic catalytic oxidation methods and non-salt methods using transition metal-based acid and base ambiphilic catalysts.

    Science.gov (United States)

    Murahashi, Shun-Ichi

    2011-01-01

    This review focuses on the development of ruthenium and flavin catalysts for environmentally benign oxidation reactions based on mimicking the functions of cytochrome P-450 and flavoenzymes, and low valent transition-metal catalysts that replace conventional acids and bases. Several new concepts and new types of catalytic reactions based on these concepts are described. (Communicated by Ryoji Noyori, M.J.A.).

  12. Volumes of virtual modifications and virtual polymorphous transformations in transition metals under pressure

    International Nuclear Information System (INIS)

    Zil'bershtejn, V.A.; Zaretskij, L.B.; Ehstrin, Eh.I.

    1975-01-01

    To find out what phases are likely to occur under pressure, it is necessary to know the relative density of various modifications, that is the ratio of the volumes of stable and virtual modifications and generally speaking the ratio of the phase compressibility. If the virtual phase volume is less than the volume of the stable phase, then such a phase is likely to appear under pressure. A method has been developed for computing the volumes of the virtual modifications from the data on the solid solutions lattice parameters. Testing the applicability of the method for a number of systems with a complete mutual solubility has shown, that the method proposed permits to estimate the volumes of the transition metals virtual modifications with the error probably not exceeding 1%. The analysis was made of the data available on the solid solutions of transition metals with fcc-, bcc- and hcp-lattices. The virtual volumes have been computed for hcp-iridium, hcp-rhodium, hcp-molybdenum, fcc-molybdenum, fcc-chromium, bcc-rhenium, bcc-ruthenium and bcc-technetium. The data obtained on the virtual modifications volumes permit to assume that the pressure increase is likely to result in the phase transformations of fcc-hcp in iridium and rhodium, and bcc-hcp in molybdenum, while evidently the transformations of bcc-fcc in molybdenum and chromium, hcp-bcc in technetium, rhenium and ruthenium are impossible. The pressure resulting in the transformations in the metals investigated equals approximately hundreds of kbar, or even approximately 1 Mbar for Ir

  13. Methane oxidation over noble metal catalysts as related to controlling natural gas vehicle exhaust emissions

    International Nuclear Information System (INIS)

    Oh, S.H.; Mitchell, P.J.; Siewert, R.M.

    1992-01-01

    Natural gas has considerable potential as an alternative automotive fuel. This paper reports on methane, the principal hydrocarbon species in natural-gas engine exhaust, which has extremely low photochemical reactivity but is a powerful greenhouse gas. Therefore, exhaust emissions of unburned methane from natural-gas vehicles are of particular concern. This laboratory reactor study evaluates noble metal catalysts for their potential in the catalytic removal of methane from natural-gas vehicle exhaust. Temperature run-up experiments show that the methane oxidation activity decreases in the order Pd/Al 2 O 3 > Rh/Al 2 O 3 > Pt/Al 2 O 3 . Also, for all the noble metal catalysts studied, methane conversion can be maximized by controlling the O 2 concentration of the feedstream at a point somewhat rich (reducing) of stoichiometry

  14. Ruthenium and iron complexes with benzotriazole and benzimidazole derivatives as simple models for proton-coupled electron transfer systems

    Directory of Open Access Journals (Sweden)

    Rocha Reginaldo C.

    2001-01-01

    Full Text Available Iron and ruthenium complexes of the type [M-LH]n (where M = RuII,III(NH35(2+,3+, RuII,III(edta2-,- [edta = ethylenedinitrilotetraacetate], or FeII,III(CN5(3-,2- and LH = benzotriazole or benzimidazole were prepared and characterized in aqueous solutions by means of electrochemical and spectroelectrochemical methods. Special emphasis was given to the pH-dependent redox processes, exhibited by all the investigated complexes. From their related Pourbaix diagrams, which displayed a typically Nernstian behavior, the pKa and formal reduction potential values were extracted. In addition, these E1/2 versus pH curves were also used to illustrate the partitioning relationship concerning the redox and acid-base species, and their interconversion equilibria. The active area in which the dependence of the M III/M II couple on the pH takes place, as delimited by pKaIII and pKaII, was taken into account in order to evaluate the usefulness of such simple complexes as models for proton-coupled electron transfer (PCET. The results were interpreted in terms of the acceptor/donor electronic character of the ligands and sigma,pi-metal-ligand interactions in both redox states of the metal ion.

  15. Acetic Acid Formation by Selective Aerobic Oxidation of Aqueous Ethanol over Heterogeneous Ruthenium Catalysts

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Hanning, Christopher William

    2012-01-01

    Heterogeneous catalyst systems comprising ruthenium hydroxide supported on different carrier materials, titania, alumina, ceria, and spinel (MgAl2O4), were applied in selective aerobic oxidation ethanol to form acetic acid, an important bulk chemical and food ingredient. The catalysts were...

  16. Investigation of the process for ruthenium fixation on stainless steel in concentrated nitric environment

    International Nuclear Information System (INIS)

    Massit, Hubert

    1987-01-01

    This research thesis reports the development of a process and the determination of the conditions for the fixation of insoluble ruthenium compounds on a Z2CN180 stainless steel in a concentrated nitric environment. The original characteristics and results of this research work are the use of a rotating disk to control the hydrodynamic conditions of suspension particle transport towards the collector surface, and the application of X ray spectrometry of solid deposits of ruthenium compounds fixed on this surface. Characterization techniques (granulometry, Auger electron spectroscopy or AES, electron spectroscopy for chemical analysis or ESCA) allowed the assessment of the influence of various parameters (size, surface chemical composition) on the studied process. Electrochemical techniques are used to show the role of particle-substrate Coulomb interactions, on the quantity of fixed particles and on fixation kinetics. The author evokes possible developments and applications, notably decontamination processes [fr

  17. Disposable biosensor based on cathodic electrochemiluminescence of tris(2,2-bipyridine)ruthenium(II) for uric acid determination

    Energy Technology Data Exchange (ETDEWEB)

    Ballesta-Claver, J.; Rodríguez-Gómez, R. [ECsens, Department of Analytical Chemistry, Campus Fuentenueva, Faculty of Sciences, University of Granada, E-18071 Granada (Spain); Capitán-Vallvey, L.F., E-mail: lcapitan@ugr.es [ECsens, Department of Analytical Chemistry, Campus Fuentenueva, Faculty of Sciences, University of Granada, E-18071 Granada (Spain)

    2013-04-03

    Highlights: ► Cathodic ECL offers conventional and non-aggressive analysis conditions. ► The ECL hydrogen peroxide/ruthenium complex system for uric acid determination is novel. ► The ruthenium complex is electrochemically immobilized on graphite screen-printed electrodes. ► The quantification of the uric acid is based on a Stern–Volmer type equation. ► The use of the cathodic ECL working methodology reduces interferences during analysis. -- Abstract: A new method for uric acid (UA) determination based on the quenching of the cathodic ECL of the tris(2,2-bipyridine)ruthenium(II)–uricase system is described. The biosensor is based on a double-layer design containing first tris(2,2-bipyridine)ruthenium(II) (Ru(bpy){sub 3}{sup 2+}) electrochemically immobilized on graphite screen-printed cells and uricase in chitosan as a second layer. The uric acid biosensing is based on the ECL quenching produced by uric acid over the cathodic ECL caused by immobilized Ru(bpy){sub 3}{sup 2+} in the presence of uricase. The use of a −1.1 V pulse for 1 s with a dwelling time of 10 s makes it possible to estimate the initial enzymatic rate, which is used as the analytical signal. The Stern–Volmer type calibration function shows a dynamic range from 1.0 × 10{sup −5} to 1.0 × 10{sup −3} M with a limit of detection of 3.1 × 10{sup −6} M and an accuracy of 13.6% (1.0 × 10{sup −4} M, n = 5) as relative standard deviation. Satisfactory results were obtained for urine samples, creating an affordable alternative for uric acid determination.

  18. Comparative Transcriptomic Analysis of the Response of Dunaliella acidophila (Chlorophyta) to Short-Term Cadmium and Chronic Natural Metal-Rich Water Exposures.

    Science.gov (United States)

    Puente-Sánchez, Fernando; Olsson, Sanna; Aguilera, Angeles

    2016-10-01

    Heavy metals are toxic compounds known to cause multiple and severe cellular damage. However, acidophilic extremophiles are able to cope with very high concentrations of heavy metals. This study investigated the stress response under natural environmental heavy metal concentrations in an acidophilic Dunaliella acidophila. We employed Illumina sequencing for a de novo transcriptome assembly and to identify changes in response to high cadmium concentrations and natural metal-rich water. The photosynthetic performance was also estimated by pulse amplitude-modulated (PAM) fluorescence. Transcriptomic analysis highlights a number of processes mainly related to a high constitutive expression of genes involved in oxidative stress and response to reactive oxygen species (ROS), even in the absence of heavy metals. Photosynthetic activity seems to be unaltered under short-term exposition to Cd and chronic exposure to natural metal-rich water, probably due to an increase in the synthesis of structural photosynthetic components preserving their functional integrity. An overrepresentation of Gene Ontology (GO) terms related to metabolic activities, transcription, and proteosomal catabolic process was observed when D. acidophila grew under chronic exposure to natural metal-rich water. GO terms involved in carbohydrate metabolic process, reticulum endoplasmic and Golgi bodies, were also specifically overrepresented in natural metal-rich water library suggesting an endoplasmic reticulum stress response.

  19. Photo-induced DNA cleavage and cytotoxicity of a ruthenium(II) arene anticancer complex

    Czech Academy of Sciences Publication Activity Database

    Brabec, Viktor; Prachařová, J.; Štěpánková, Jana; Sadler, P. J.; Kašpárková, Jana

    2016-01-01

    Roč. 160, JUL2016 (2016), s. 149-155 ISSN 0162-0134 R&D Projects: GA ČR(CZ) GA14-21053S; GA MŠk(CZ) LD14019 Institutional support: RVO:68081707 Keywords : Ruthenium anticancer complex * DNA cleavage * Phototoxicity Subject RIV: BO - Biophysics Impact factor: 3.348, year: 2016

  20. Natural uranium metallic fuel elements: fabrication and operating experience

    International Nuclear Information System (INIS)

    Hammad, F.H.; Abou-Zahra, A.A.; Sharkawy, S.W.

    1980-01-01

    The main reactor types based on natural uranium metallic fuel element, particularly the early types, are reviewed in this report. The reactor types are: graphite moderated air cooled, graphite moderated gas cooled and heavy water moderated reactors. The design features, fabrication technology of these reactor fuel elements and the operating experience gained during reactor operation are described and discussed. The interrelation between operating experience, fuel design and fabrication was also discussed with emphasis on improving fuel performance. (author)

  1. New soluble functional polymers by free-radical copolymerization of methacrylates and bipyridine ruthenium complexes

    NARCIS (Netherlands)

    Holder, E.; Meier, M.A.R.; Marin, V.N.; Schubert, U.S.

    2003-01-01

    The luminescent complex [4-(3-hydroxypropyl)-4-methyl-2,2-bipyridine]-bis(2,2-bipyridine)-ruthenium(II)-bis(hexafluoroantimonate) and its methacrylate derivative were successfully synthesized and fully characterized by two-dimensional 1H and 13C{1H} NMR techniques [correlation spectroscopy (COSY)

  2. Parameter Optimization Of Natural Hydroxyapatite/SS316l Via Metal Injection Molding (MIM)

    Science.gov (United States)

    Mustafa, N.; Ibrahim1, M. H. I.; Amin, A. M.; Asmawi, R.

    2017-01-01

    Metal injection molding (MIM) are well known as a worldwide application of powder injection molding (PIM) where as applied the shaping concept and the beneficial of plastic injection molding but develops the applications to various high performance metals and alloys, plus metal matrix composites and ceramics. This study investigates the strength of green part by using stainless steel 316L/ Natural hydroxyapatite composite as a feedstock. Stainless steel 316L (SS316L) was mixed with Natural hydroxyapatite (NHAP) by adding 40 wt. % Low Density Polyethylene and 60 %wt. Palm Stearin as a binder system at 63 wt. % powder loading consist of 90 % wt. of SS316 L and 10 wt. % NHAP prepared thru critical powder volume percentage (CPVC). Taguchi method was functional as a tool in determining the optimum green strength for Metal Injection Molding (MIM) parameters. The green strength was optimized with 4 significant injection parameter such as Injection temperature (A), Mold temperature (B), Pressure (C) and Speed (D) were selected throughout screening process. An orthogonal array of L9 (3)4 was conducted. The optimum injection parameters for highest green strength were established at A1, B2, C0 and D1 and where as calculated based on Signal to Noise Ratio.

  3. Phenylalanine-a biogenic ligand with flexible η6- and η6:κ1-coordination at ruthenium(ii) centres

    KAUST Repository

    Reiner, Thomas; Jantke, Dominik; Miao, Xiaohe; Marziale, Alexander N.; Kiefer, Florian J.; Eppinger, Jö rg

    2013-01-01

    The reaction of (S)-2,5-dihydrophenylalanine 1 with ruthenium(iii) chloride yields the μ-chloro-bridged dimeric η6-phenylalanine ethyl ester complex 3, which can be converted into the monomeric analogue, η6:κ1-phenylalanine ethyl ester complex 12, under basic conditions. Studies were carried out to determine the stability and reactivity of complexes bearing η6- and η6: κ1-chelating phenylalanine ligands under various conditions. Reaction of 3 with ethylenediamine derivatives N-p-tosylethylenediamine or 1,4-di-N-p-tosylethylenediamine results in the formation of monomeric η6:κ1-phenylalanine ethyl ester complexes 14 and 15, which could be saponified yielding complexes 16 and 17 without changing the inner coordination sphere of the metal centre. The structure of η6:κ1-phenylalanine complex 17 and an N-κ1-phenylalanine complex 13 resulting from the reaction of 3 with an excess of pyridine were confirmed by X-ray crystallography. © 2013 The Royal Society of Chemistry.

  4. Improvements in iodine and ruthenium removal from advanced liquid processing system

    Energy Technology Data Exchange (ETDEWEB)

    Skibo, A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-09-27

    SRNL has considerable experience in designing, engineering, and operating systems for removing iodine-129 (I-129) and ruthenium-106 (Ru-106) from waste streams that are directly analogous to the Advanced Liquid Processing System (ALPS) waste streams. SRNL proposes to provide the technical background and design and engineering support for an improved I-129 and Ru-106 removal system for application to ALPS on the Fukushima Daiichi Nuclear Power Station (NPS).

  5. The role of adsorbates in the electrochemical oxidation of ammonia on noble and transition metal electrodes

    NARCIS (Netherlands)

    Vooys, de A.C.A.; Koper, M.T.M.; Santen, van R.A.; Veen, van J.A.R.

    2001-01-01

    The activity for ammonia oxidation and the intermediates formed during the reaction have been studied on platinum, palladium, rhodium, ruthenium, iridium, copper, silver and gold electrodes. The activity in the selective oxidation to N-2 is related directly to the nature of the species at the

  6. Contribution to the study of the fluorination of ruthenium and its dioxide

    International Nuclear Information System (INIS)

    Courtois, Charles.

    1977-12-01

    Compounds formed during fluorination of ruthenium and its dioxide are studied. By chemical analysis the constitution of these compounds is cleared up. RuF 5 is the main compound formed, but a secondary product is obtained which is RuF 8 . The vapor pressure of this product is given between 178 and 221 0 K, and its infrared spectrum is drawn [fr

  7. Study of conditions of production and characterization of noble metal micro-particles suspensions

    International Nuclear Information System (INIS)

    Malabre, Catherine

    1983-01-01

    As the production and identification of metal micro-particle suspensions are some aspects of issues related to nuclear fuel reprocessing, this research thesis reports the use of ruthenium, molybdenum, niobium, palladium and rhodium (fission metals) to generate such micro-particles. They are produced by erosion of two electrodes between which occurs an electric arc discharge in aqueous media. Different analytic methods are developed to determine the characteristics of so-produced colloidal solutions. A granulometry study is performed by transmission electronic microscopy, light quasi-elastic scattering, and turbidimetry associated to centrifugation. This has lead to the production of steady micro-particle suspensions which have been used in a first set of industrial trials [fr

  8. Defense by-products production and utilization program: noble metal recovery screening experiments

    International Nuclear Information System (INIS)

    Hazelton, R.F.; Jensen, G.A.; Raney, P.J.

    1986-03-01

    Isotopes of the platinum metals (rutheium, rhodium, and palladium) are produced during uranium fuel fission in nuclear reactors. The strategic values of these noble metals warrant considering their recovery from spent fuel should the spent fuel be processed after reactor discharge. A program to evaluate methods for ruthenium, rhodium, and palladium recovery from spent fuel reprocessing liquids was conducted at Pacific Northwest Laboratory (PNL). The purpose of the work reported in this docuent was to evaluate several recovery processes revealed in the patent and technical literature. Beaker-scale screening tests were initiated for three potential recovery processes: precipitation during sugar denitration of nitric acid reprocessing solutions after plutonium-uranium solvent extraction, adsorption using nobe metal selective chelates on active carbon, and reduction forming solid noble metal deposits on an amine-borane reductive resin. Simulated reprocessing plant solutions representing typical nitric acid liquids from defense (PUREX) or commercial fuel reprocessing facilities were formulated and used for evaluation of the three processes. 9 refs., 3 figs., 9 tabs

  9. The effect of promoters on the electronic structure of ruthenium catalysts supported on carbon

    International Nuclear Information System (INIS)

    Guraya, Monica; Sprenger, Susanne; Rarog-Pilecka, Wioletta; Szmigiel, Dariusz; Kowalczyk, Zbigniew; Muhler, Martin

    2004-01-01

    Alkali- and earth-alkali-promoted ruthenium catalysts supported on graphitized carbon were investigated by means of X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) in order to study the effect of promoters on the electronic structure of this metal-support system. Samples were measured as prepared and after thorough reduction in hydrogen. The C 1s spectra of reduced alkali-promoted catalysts showed a shift towards higher binding energies and an asymmetric broadening. Neither non-promoted nor Ba-promoted Ru/C samples exhibited such a behaviour after similar treatments. The most important feature in the UP spectra of the reduced alkali-promoted catalysts was the appearance of a well defined Fermi edge absent in the semimetal-like electronic structure of graphite. No significant effects appeared in the case of non-promoted or Ba-promoted catalysts. The increase in the density of occupied states at the Fermi energy indicates a shift of this level into the conduction band, due to a charge transfer from the promoter to the support. This interpretation also provides an explanation for the observed higher C 1s binding energy and asymmetric broadening, due to the off-set introduced in the binding energy scale and the increasing probability of inelastic excitations near the Fermi level. In addition to photoelectron spectroscopy, low energy ion scattering (ISS) was used to obtain information about the localisation of the promoters. Based on the mild sputtering effect during prolonged series of spectra, it was possible to conclude that potassium covers both the carbon support and the Ru metal particles

  10. Detection of pyrrolizidine alkaloids using flow analysis with both acidic potassium permanganate and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Bree A. [School of Biological and Chemical Sciences, Deakin University, Geelong, Vic. 3217 (Australia); Barnett, Neil W. [School of Biological and Chemical Sciences, Deakin University, Geelong, Vic. 3217 (Australia)]. E-mail: barnie@deakin.edu.au; Bos, Richard [School of Biological and Chemical Sciences, Deakin University, Geelong, Vic. 3217 (Australia)

    2005-06-13

    For the first time, analytically useful chemiluminescence was elicited from the reactions of the pyrrolizidine alkaloids. Heliotrine, retronecine, supinine, monocrotaline and echinatine N-oxide yielded chemiluminescence upon reaction with tris(2,2'-bipyridyl)ruthenium(II) whilst lasiocarpine, its N-oxide and supinine elicited light upon reaction with acidic potassium permanganate. Detection limits for heliotrine were 1.25 x 10{sup -7} M and 9 x 10{sup -9} M for tris(2,2'-bipyridyl)ruthenium(III) perchlorate with flow injection analysis (FIA) and the silica-immobilised reagent (4-[4-(dichloromethylsilanyl)-butyl]-4'-methyl-2,2'-bipyridine)bis (2,2'-bipyridyl)ruthenium(II) with sequential injection analysis (SIA), respectively. Lasiocarpine was detectable at 1.4 x 10{sup -7} M using acidic potassium permanganate with FIA. Additionally, the silica-immobilised reagent was optimised with respect to the oxidant (ammonium ceric nitrate) concentration and the aspiration times which afforded a detection limit for codeine of 5 x 10{sup -10} M using SIA.

  11. Flameless atomic absorption determination of noble metals after extraction by mixture of di-2-ethylhexyldithiophosphoric acid and n-octylaniline

    International Nuclear Information System (INIS)

    Yukhin, Yu.M.; Udalova, T.A.; Tsimbalist, V.G.; AN SSSR, Novosibirsk. Inst. Geologii i Geofiziki)

    1985-01-01

    A possibility of using the mixture of di-2-ethylhexyl dithiophosphoric acid (D2EHDTPA) and p-octylaniline (OA) (extractants of acid and basic character) for extraction atomic absorption determination of noble metals is studied. The mixture of D2EHDTPA with OA is shown to extract noble metals from hydrochloric acid solutions with distribution factors > 10 3 . An extraction atomic absorption method for determination of noble metals in copperbearing materials is suggested. The minimum determined contents of noble metals at the initial sample equal to 100 for gold, silver, platinum, palladium, rhodium and ruthenium make up (g/t) 0.0005, 0.0001, 0.015, 0.005, 0.002 and 0.015 respectively. Relative standard deviation constitutes Ssub(r)<0.2

  12. Ruthenium complexes with phenylterpyridine derivatives target cell membrane and trigger death receptors-mediated apoptosis in cancer cells.

    Science.gov (United States)

    Deng, Zhiqin; Gao, Pan; Yu, Lianling; Ma, Bin; You, Yuanyuan; Chan, Leung; Mei, Chaoming; Chen, Tianfeng

    2017-06-01

    Elucidation of the communication between metal complexes and cell membrane may provide useful information for rational design of metal-based anticancer drugs. Herein we synthesized a novel class of ruthenium (Ru) complexes containing phtpy derivatives (phtpy = phenylterpyridine), analyzed their structure-activity relationship and revealed their action mechanisms. The result showed that, the increase in the planarity of hydrophobic Ru complexes significantly enhanced their lipophilicity and cellular uptake. Meanwhile, the introduction of nitro group effectively improved their anticancer efficacy. Further mechanism studies revealed that, complex (2c), firstly accumulated on cell membrane and interacted with death receptors to activate extrinsic apoptosis signaling pathway. The complex was then transported into cell cytoplasm through transferrin receptor-mediated endocytosis. Most of the intracellular 2c accumulated in cell plasma, decreasing the level of cellular ROS, inducing the activation of caspase-9 and thus intensifying the apoptosis. At the same time, the residual 2c can translocate into cell nucleus to interact with DNA, induce DNA damage, activate p53 pathway and enhance apoptosis. Comparing with cisplatin, 2c possesses prolonged circulation time in blood, comparable antitumor ability and importantly, much lower toxicity in vivo. Taken together, this study uncovers the role of membrane receptors in the anticancer actions of Ru complexes, and provides fundamental information for rational design of membrane receptor targeting anticancer drugs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. New carboxy-functionalized terpyridines as precursors for zwitterionic ruthenium complexes for polymer-based solar cells

    DEFF Research Database (Denmark)

    Duprez, V.; Krebs, Frederik C

    2006-01-01

    New carboxy-terpyridines selectively functionalized at the 4-, 4'- and 4"-positions were prepared in a three-step procedure with good yields using, the Krohnke reaction followed by saponification. Their complexation with ruthenium led to symmetric and unsymmetric terpyridinyl zwitterionic complexes...

  14. Correlations between electrochemical and spectrochemical parameters of ruthenium sulfoxides series with N-heterocyclic

    International Nuclear Information System (INIS)

    Oliveira, D. de; Toma, H.E.

    1990-01-01

    A systematic study of Ru Cl sub(2) (DMSO) sub(2) L sub(2) derivates, where L = N-heterocyclic base is described, contributing for a best understanding of chemical behaviour and electronic structure of the ruthenium sulfoxides. The correlations between the electrochemical and the spectroscopical parameters of the serie are presented with more emphasis. (author)

  15. Metal-Ligand Cooperative Reactivity in the (pseudo)-Dearomatized PNX(P) Systems: the Influence of the Zwitterionic Form in Dearomatized Pincer Complexes

    KAUST Repository

    Goncalves, Theo

    2017-09-01

    The concept of aromaticity in pincer ligands and complexes was discussed in order to provide insights into their metal-ligand cooperative activities. The aromatic PNx(P) and dearomatized PNx(P)* pincer ligands and the corresponding transition metal complexes were studied with the nucleus-independent chemical shift (NICSzz), anisotropy of the current (induced) density (ACID), isochemical shielding surfaces (ICSSzz), harmonic oscillator model of aromaticity (HOMA), MCBO, Shannon aromaticity, and natural bond order (NBO) analyses. The study on the model systems showed that for the dearomatized species the decrease of the NICS(1)zz value comes with the larger contribution of the aromatic zwitterionic mesomeric form. In all examples, the incorporation of the metal center into the pincer ligand decreases the NICS(1)zz values. The DFT calculations support the dearomatized pyridine ring in PNP* or PNN* ligand indeed being nonaromatic, in contrast to the PN3(P)* ligand which has partial aromatic character due to the larger contribution of the zwitterionic resonance structure. The difference in aromaticity between the rings contributes to the thermodynamic balance of the metal ligand cooperative reactions, changing the energetics of the process when different dearomatized pincer ligands are used. This was further exemplified by aromaticity analysis of the heterolytic hydrogen cleavage reaction of ruthenium PNN complexes of Milstein and the PN3 of Huang, with similar geometries but distinctive thermodynamic preference.

  16. Metal-Ligand Cooperative Reactivity in the (pseudo)-Dearomatized PNX(P) Systems: the Influence of the Zwitterionic Form in Dearomatized Pincer Complexes

    KAUST Repository

    Goncalves, Theo; Huang, Kuo-Wei

    2017-01-01

    The concept of aromaticity in pincer ligands and complexes was discussed in order to provide insights into their metal-ligand cooperative activities. The aromatic PNx(P) and dearomatized PNx(P)* pincer ligands and the corresponding transition metal complexes were studied with the nucleus-independent chemical shift (NICSzz), anisotropy of the current (induced) density (ACID), isochemical shielding surfaces (ICSSzz), harmonic oscillator model of aromaticity (HOMA), MCBO, Shannon aromaticity, and natural bond order (NBO) analyses. The study on the model systems showed that for the dearomatized species the decrease of the NICS(1)zz value comes with the larger contribution of the aromatic zwitterionic mesomeric form. In all examples, the incorporation of the metal center into the pincer ligand decreases the NICS(1)zz values. The DFT calculations support the dearomatized pyridine ring in PNP* or PNN* ligand indeed being nonaromatic, in contrast to the PN3(P)* ligand which has partial aromatic character due to the larger contribution of the zwitterionic resonance structure. The difference in aromaticity between the rings contributes to the thermodynamic balance of the metal ligand cooperative reactions, changing the energetics of the process when different dearomatized pincer ligands are used. This was further exemplified by aromaticity analysis of the heterolytic hydrogen cleavage reaction of ruthenium PNN complexes of Milstein and the PN3 of Huang, with similar geometries but distinctive thermodynamic preference.

  17. Spark igniter having precious metal ground electrode inserts

    International Nuclear Information System (INIS)

    Ryan, N.A.

    1988-01-01

    This patent describes an igniter comprising a shell of a shell metal alloy which is resistant to spark erosion and corrosion, the shell having a firing end which terminates at its lower end in an annular ring, an insulator sealed within the metal shell and having a central bore and a surface extending inwardly toward the bore from the annular ring, a center electrode sealed within the bore of the insulator and having a firing end which is in spark gap relation with the annular ring of the shell and so positioned that a spark discharge between the firing end and the annular ring occurs along the inwardly extending surface of the insulator, and a plurality of oxidation and erosion resistant inserts, each of the inserts comprising a body of a metal selected from the group consisting of iridium, osmium, ruthenium, rhodium, platinum, and tungsten or an alloy or a ductile alloy of one of the foregoing metals, each of the bodies being embedded within a matching opening which extends from the exterior of the shell through the annular ring, being bonded to the shell

  18. Ruthenium/Graphene-like Layered Carbon Composite as an Efficient Hydrogen Evolution Reaction Electrocatalyst.

    Science.gov (United States)

    Chen, Zhe; Lu, Jinfeng; Ai, Yuejie; Ji, Yongfei; Adschiri, Tadafumi; Wan, Lijun

    2016-12-28

    Efficient water splitting through electrocatalysis has been studied extensively in modern energy devices, while the development of catalysts with activity and stability comparable to those of Pt is still a great challenge. In this work, we successfully developed a facile route to synthesize graphene-like layered carbon (GLC) from a layered silicate template. The obtained GLC has layered structure similar to that of the template and can be used as support to load ultrasmall Ru nanoparticles on it in supercritical water. The specific structure and surface properties of GLC enable Ru nanoparticles to disperse highly uniformly on it even at a large loading amount (62 wt %). When the novel Ru/GLC was used as catalyst on a glass carbon electrode for hydrogen evolution reaction (HER) in a 0.5 M H 2 SO 4 solution, it exhibits an extremely low onset potential of only 3 mV and a small Tafel slope of 46 mV/decade. The outstanding performance proved that Ru/GLC is highly active catalyst for HER, comparable with transition-metal dichalcogenides or selenides. As the price of ruthenium is much lower than platinum, our study shows that Ru/GLC might be a promising candidate as an HER catalyst in future energy applications.

  19. Post-synthetic modification of mesoporous zinc-adeninate framework with tris(2,2′-biprydine) ruthenium(II) complex and its electrochemiluminescence

    Energy Technology Data Exchange (ETDEWEB)

    Park, Ji Eun; Shin, Ik Soo [Dept. of Chemistry, Soongsil University, Seoul (Korea, Republic of); Oh, Hye Jae; An, Ji Hyun [Dept. of Chemistry Education, Seoul National University, Seoul (Korea, Republic of)

    2017-04-15

    Herein we report a redox-active metal-organic framework (MOF) via post-synthetic cation exchange with tris(2,2′-biprydine) ruthenium(II) complex (Ru(bpy){sub 3}{sup 2+}). A porous anionic zinc-adeninate framework (bMOF-100) is spacious enough to easily entrap 2.43 of Ru(bpy){sub 3}{sup 2+} cations within the mesopore. The encapsulation supported the framework structure preventing any distortion from a rapid solvent evaporation under SEM observation. Ru(bpy){sub 3}{sup 2+}@bMOF-100 was then immobilized on the surface of glassy carbon electrode, and its electrocatalytic and electrochemiluminescent (ECL) properties were investigated in aqueous and organic solution. Especially, Ru(bpy){sub 3}{sup 2+}@bMOF-100 showed the excellent electrochemical properties of Ru(bpy){sub 3}{sup 2+}, but gradual decomposition of the MOF structure was observed under electrochemical measurements because of the sluggish oxidation of adeninate ligand.

  20. Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

    Science.gov (United States)

    A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

  1. Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

    Science.gov (United States)

    Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

    2012-05-14

    The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Ruthenium(II) pincer complexes with oxazoline arms for efficient transfer hydrogenation reactions

    KAUST Repository

    Chen, Tao

    2012-08-01

    Well-defined P NN CN pincer ruthenium complexes bearing both strong phosphine and weak oxazoline donors were developed. These easily accessible complexes exhibit significantly better catalytic activity in transfer hydrogenation of ketones compared to their PN 3P analogs. These reactions proceed under mild and base-free conditions via protonation- deprotonation of the \\'NH\\' group in the aromatization-dearomatization process. © 2012 Elsevier Ltd. All rights reserved.

  3. Synthesis of cationic diphosphine ruthenium complexes with nido-dicarbaundecaborate anions. Molecular structure of [RuCl(dppe)2]+[7,8-nido-C2B9H12]-

    International Nuclear Information System (INIS)

    Cheredilin, D.N.; Dolgushin, F.M.; Balagurova, E.V.; Godovikov, I.A.; Chizhevskij, I.T.

    2004-01-01

    Five new diphosphine ruthenium(II) complexes with nido-dicarbaundecaborate anions were synthesized. The composition and structure of the complexes were confirmed by data of 1 H, 31 P{ 1 H} NMR and elementary analysis. The crystal and molecular structure of solvated complex [RuCl(dppe) 2 + [7,8-nido-C 2 B 9 H 12 ] - ·CH 2 Cl 2 was ascertained by the method of X-ray diffraction analysis. It is shown that coordination sphere of ruthenium atom in the complex cation is a distorted trigonal bipyramid. The distances from ruthenium atom to phosphorus atoms are 2.398(1) and 2.391(1) A, while the angle P-Ru-P equals 175.85(5) Deg [ru

  4. Noble metal behavior during melting of simulated high-level nuclear waste glass feeds

    International Nuclear Information System (INIS)

    Anderson, L.D.; Dennis, T.; Elliott, M.L.; Hrma, P.

    1993-04-01

    Noble metals and their oxides can settle in waste glass melters and cause electrical shorting. Simulated waste feeds from Hanford, Savannah River, and Germany were heat treated for 1 hour in a gradient furnace at temperatures ranging from approximately 600 degrees C--1000 degrees C and examined by electron microscopy to determine shapes, sizes, and distribution of noble metal particles as a function of temperature. Individual noble metal particles and agglomerates of rhodium (Rh), ruthenium (RuO 2 ), and palladium (Pd), as well as their alloys, were seen. the majority of particles and agglomerates were generally less than 10 microns; however, large agglomerations (up to 1 mm) were found in the German feed. Detailed particle distribution and characterization was performed for a Hanford waste to provide input to computer modeling of particle settling in the melter

  5. A technique for studying digestion by grasshoppers using a 103Ruthenium-labelled marker

    International Nuclear Information System (INIS)

    Gandar, M.V.

    1981-01-01

    103 Ru-labelled tris (I,10-phenanthroline) ruthenium (II) chloride has proved to be a convenient marker in investigating digestion in grasshoppers. Assimilation efficiencies and the retension time of the food in the gut were measured. It is surmised that the technique described in this paper will be applicable to studies of a variety of chewing herbivorous insects. (author)

  6. Studies On An Aerobic Oxidation Of Dibenzothiophene And Related Compounds Using Ruthenium Catalyst

    Directory of Open Access Journals (Sweden)

    Morishita Y.

    2015-06-01

    Full Text Available An aerobic oxidation of dibenzothiophene and related compounds using a catalytic amount of ruthenium chloride in hydrocarbon solvents at 80°C for 20 h gave the corresponding sulfones in almost quantitative yields. The reaction might proceed via autoxidation of solvents to hydroperoxides and the reaction of sulfur compounds with the resulting hydroperoxides.

  7. Stability analysis for single-phase liquid metal rectangular natural circulation loops

    International Nuclear Information System (INIS)

    Lu, Daogang; Zhang, Xun; Guo, Chao

    2014-01-01

    Highlights: • The stability for asymmetric liquid metal natural circulation loops is analyzed. • The Na and NaK loops have higher critical Reynolds number than Pb and LBE loops. • Decreasing the ratio of height to width of loop can increase loop stability. • The length of heater would not affect the loop stability obviously. • Adding the length or heat transfer coefficient of cooler can increase loop stability. - Abstract: Natural circulation systems are preferred in some advanced nuclear power plants as they can simplify the designs and improve the inherent safety. The stability and steady-state characteristics of natural circulation are important for the applications of natural circulation loops (NCLs). A linear stability analysis method was used to study the stability behavior of liquid metal NCLs. The influences of the types of working fluids and loop geometry parameters on the stability of NCLs were evaluated. The liquid sodium (Na) loop and sodium–potassium alloy (NaK) loop would be more stable than lead bismuth eutectics (LBE) loop. The pressure drop could stabilize the loop behavior and also lead an increase of operating temperature for the loop. The NCL with a lower aspect ratio (ratio of vertical center distance between the heating and cooling section to the horizontal length of loop) is supposed to be more stable. It was found that the length of heating section would not have an obvious effect on the stability of NCL. However, the loop behavior could be stabilized by adding the length or heat transfer coefficient of the cooling section

  8. Changes in metallothionein concentrations in response to variation in natural factors (salinity, sex, weight) and metal contamination in crabs from a metal-rich estuary.

    Science.gov (United States)

    Legras; Mouneyrac; Amiard; Amiard-Triquet; Rainbow

    2000-04-05

    Intermoult male and female crabs Pachygrapsus marmoratus and Carcinus maenas were sampled from three sites between the mouth and 25 km upstream in the Gironde, the most Cd-contaminated estuary in France, in order to study the relative importance of natural factors (salinity, sex, weight) and accumulated metal concentrations on metallothionein (MT) concentrations. In the two species studied, higher metal, total protein and MT concentrations were observed in the hepatopancreas than in the gills. In P. marmoratus, MT concentrations were mainly related to changes in the natural factors even if MT and Zn concentrations were positively correlated in the hepatopancreas whereas in C. maenas, the main relationships were with accumulated metal levels. In the case of the natural factors, the most important ones were weight in gills of both crab species, and salinity changes in both hepatopancreas and gills of P. marmoratus. Cd and Cu concentrations in both organs of the two species were inversely related to salinity. The same observation was found for Zn concentrations in C. maenas but not in P. marmoratus. In the hepatopancreas of both species, the highest total protein concentrations were found in crabs from the site with the highest salinity, whereas there were no such differences in the gills. It seems that changes in MT concentrations are linked more to changes in general protein metabolism than to changes in metal accumulation. Thus it was important to examine the storage of metals in other tissue compartments, particularly the insoluble fraction which includes mineral granules which is known to also contribute to trace metal detoxification in invertebrates. In the gills of the crabs, Zn was present mainly in the insoluble fraction, whereas Cd was nearly equally distributed between soluble and insoluble fractions. In contrast, Cu in the gills and all three metals in the hepatopancreas of both species were mainly cytosolic, but this does not necessarily imply a

  9. Characterization of natural adsorbent material for heavy metal removal in a petrochemical site contamination

    Directory of Open Access Journals (Sweden)

    Bianchi F.

    2013-04-01

    Full Text Available Despite of over 25 years of intensive technological efforts, sub-surface environment cleanup still remains a challenge, especially in case of highly contaminated sites. In this context, ion exchanger technologies could provide simple and effective solutions for heavy metal removal in water treatment. The challenge is finding exchanger able to operate in extreme natural environments or in situations involving natural interfering species such as inorganic ions. In this paper we exam the use of natural zeolites as versatile exchanger for environmental protection of coastal refinery's groundwater against pollution of Ni, Cd, Pb. The influence of particle diameter on clinoptilolite performances toward heavy metal removal is studied. Also, we evaluate the exchanger activities in condition of high ionic strength, commonly present in groundwater located under coastal petrol industries. The obtained results confirmed that ion exchangers could provide an effective solutions for remediation in complex environmental conditions.

  10. A new electrochemical sensor containing a film of chitosan-supported ruthenium: detection and quantification of sildenafil citrate and acetaminophen

    International Nuclear Information System (INIS)

    Delolo, Fabio Godoy; Rodrigues, Claudia; Silva, Monize Martins da; Batista, Alzir Azevedo; Dinelli, Luis Rogerio; Delling, Felix Nicolai; Zukerman-Schpector, Julio

    2014-01-01

    This work presents the construction of a novel electrochemical sensor for detection of organic analytes, using a glassy carbon electrode (GCE) modified with a chitosan-supported ruthenium film. The ruthenium-chitosan film was obtained starting from the mer-[RuCl 3 (dppb)(H 2 O)] complex as a [1,4-bis(diphenylphosphine)butane] (dppb) precursor, and chitosan (QT). The structure of the chitosan-supported ruthenium film on the surface of the glassy carbon electrode was characterized by UV-Vis spectroscopy, electron paramagnetic resonance (EPR), scanning electron microscopy (SEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD) and atomic absorption spectroscopy (AAS) techniques. The glassy carbon electrode was modified with a film formed from the evaporation of 5 μL of a solution composed of 5 mg chitosan-supported ruthenium (RuQT) in 10 mL of 0.1 mol L -1 acetic acid. The modified electrode was tested as a sensor for sildenafil citrate (Viagra® 50 mg) and acetaminophen (Tylenol®) detection. The technique utilized for these analyses was differential pulse voltammetry (DPV) in 0.1 mol L -1 H 2 SO 4 (pH 1.0) and 0.1 mol L -1 CH 3 COOK (pH 6.5) as supporting electrolyte. All analyses were carried out during a month using the same electrode. The electrode was washed only with water in between the analyses, keeping it in the refrigerator when it was not in use. This electrode was stable during the period utilized showing no degradation and presenting a linear response over the evaluated concentration interval (1.25 × 10 -5 to 4.99 × 10 -4 mol L -1 ). (author)

  11. Pseudocapacitive properties of nano-structured anhydrous ruthenium oxide thin film prepared by electrostatic spray deposition and electrochemical lithiation/delithiation

    Energy Technology Data Exchange (ETDEWEB)

    Park, S.H.; Kim, J.Y.; Kim, K.B. [Division of Materials Science and Engineering, Yonsei University, Seoul (Korea, Republic of)

    2010-10-15

    Nano-structured anhydrous ruthenium oxide (RuO{sub 2}) thin films were prepared using an electrostatic spray deposition (ESD) technique followed by electrochemical lithiation and delithiation. During the electrochemical lithiation process, RuO{sub 2} decomposed to nano-structured metallic ruthenium Ru with the concomitant formation of Li{sub 2}O. Nano-structured RuO{sub 2} was formed upon subsequent electrochemical extraction of Li from the Ru/Li{sub 2}O nanocomposite. Electrochemical lithiation/deliathiation at different charge/discharge rates (C-rate) was used to control the nano-structure of the anhydrous RuO{sub 2}. Electrochemical lithiation/delithiation of the RuO{sub 2} thin film electrode at different C-rates was closely related to the specific capacitance and high rate capability of the nano-structured anhydrous RuO{sub 2} thin film. Nano-structured RuO{sub 2} thin films prepared by electrochemical lithiation and delithiation at 2C rate showed the highest specific capacitance of 653 F g{sup -1} at 20 mV s{sup -1}, which is more than two times higher than the specific capacitance of 269 F g{sup -1} for the as-prepared RuO{sub 2}. In addition, it showed 14% loss in specific capacitance from 653 F g{sup -1} at 20 mV s{sup -1} to 559 F g{sup -1} at 200 mV s{sup -1}, indicating significant improvement in the high rate capability compared to the 26% loss of specific capacitance of the as-prepared RuO{sub 2} electrode from 269 F g{sup -1} at 20 mV s{sup -1} to 198 F g{sup -1} at 200 mV s{sup -1} for the same change in scan rate. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

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

    Energy Technology Data Exchange (ETDEWEB)

    Summanen, P.; Immonen, I.; Kivela, T.; Tommila, P.; Tarkkanen, A. [Helsinki Univ. Central Hospital (Finland). Meilahti Clinic; Heikkonen, J. [Helsinki Univ. (Finland). Dept of Radiotherapy and Oncology

    1996-08-01

    The aims were to analyse radiation related complications and secondary enucleation after irradiation of malignant uveal melanoma with ruthenium-106 plaques. A series of 100 consecutive eyes irradiated in 1981-91 was analysed using the life table method and the Cox proportional hazards model. The 3 and 5 year probabilities of being without radiation cataract were 73% and 63%, without neovascular glaucoma 91% and 81%, without vitreous haemorrhage 83% and 74%, without radiation maculopathy 85% and 70%, and without radiation optic neuropathy 90% and 88%, respectively. (Author).

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

    International Nuclear Information System (INIS)

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

    1996-01-01

    The aims were to analyse radiation related complications and secondary enucleation after irradiation of malignant uveal melanoma with ruthenium-106 plaques. A series of 100 consecutive eyes irradiated in 1981-91 was analysed using the life table method and the Cox proportional hazards model. The 3 and 5 year probabilities of being without radiation cataract were 73% and 63%, without neovascular glaucoma 91% and 81%, without vitreous haemorrhage 83% and 74%, without radiation maculopathy 85% and 70%, and without radiation optic neuropathy 90% and 88%, respectively. (Author)

  14. Nano-scale islands of ruthenium oxide as an electrochemical sensor for iodate and periodate determination

    International Nuclear Information System (INIS)

    Chatraei, Fatemeh; Zare, Hamid R.

    2013-01-01

    In this study, a promising electrochemical sensor was fabricated by the electrodeposition of nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles, RuON) on a glassy carbon electrode (RuON–GCE). Then, the electrocatalytic oxidation of iodate and periodate was investigated on it, using cyclic voltammetry, chronoamperometry and amperometry as diagnostic techniques. The charge transfer coefficient, α, and the charge transfer rate constant, k s , for electron transfer between RuON and GCE were calculated as 0.5 ± 0.03 and 9.0 ± 0.7 s −1 respectively. A comparison of the data obtained from the electrocatalytic reduction of iodate and periodate at a bare GCE (BGCE) and RuON–GCE clearly shows that the unique electronic properties of nanoparticles definitely improve the characteristics of iodate and periodate electrocatalytic reduction. The kinetic parameters such as the electron transfer coefficient, α, and the heterogeneous electron transfer rate constant, k′, for the reduction of iodate and periodate at RuON–GCE surface were determined using cyclic voltammetry. Amperometry revealed a good linear relationship between the peak current and the concentration of iodate and periodate. The detection limits of 0.9 and 0.2 μM were calculated for iodate and periodate respectively. Highlights: ► Ruthenium oxide nanoparticles, RuON, were used for electrocatalytic reduction iodate and periodate. ► Formal potential, E 0 ′, of the surface redox couple of RuON is pH-dependent. ► The heterogeneous electron transfer rate constant values between both analytes and RuON were calculated.

  15. Activity of iridium-ruthenium and iridium-rhodium adsorption catalysts in decomposition of hydrogen peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Zubovich, I A; Mikhaylov, V A; Migulina, N N [Yaroslavskij Politekhnicheskij Inst. (USSR)

    1976-06-01

    Experimental data for the activities of iridium-ruthenium and iridium-rhodium adsorption catalysts in the decomposition of hydrogen peroxide are considered and the results of magnetic susceptibility measurements are presented. It is concluded that surface structures (complexes) may be formed and that micro-electronic feaures play a role in heterogeneous catalysis.

  16. Organic salt NEDC (N-naphthylethylenediamine dihydrochloride) assisted laser desorption ionization mass spectrometry for identification of metal ions in real samples.

    Science.gov (United States)

    Hou, Jian; Chen, Suming; Zhang, Ning; Liu, Huihui; Wang, Jianing; He, Qing; Wang, Jiyun; Xiong, Shaoxiang; Nie, Zongxiu

    2014-07-07

    The significance of metals in life and their epidemiological effects necessitate the development of a direct, efficient, and rapid method of analysis. The matrix assisted laser desorption/ionization technique is on the horns of a dilemma of metal analysis as the conventional matrixes have high background in the low mass range. An organic salt, NEDC (N-naphthylethylenediamine dihydrochloride), is applied as a matrix for identification of metal ions in the negative ion mode in the present work. Sixteen metal ions, Ba(2+), Ca(2+), Cd(2+), Ce(3+), Co(2+), Cu(2+), Fe(3+), Hg(2+), K(+), Mg(2+), Mn(2+), Na(+), Ni(2+), Pb(2+), Sn(2+) and Zn(2+), in the form of their chloride-adducted clusters were systematically tested. Mass spectra can provide unambiguous identification through accurate mass-to-charge ratios and characteristic isotope patterns. Compared to ruthenium ICP standard solution, tris(2,2'-bipyridyl)dichlororuthenium(ii) (C30H24N6Cl2Ru) can form organometallic chloride adducts to discriminate from the inorganic ruthenium by this method. After evaluating the sensitivity for Ca, Cu, Mg, Mn, Pb and Zn and plotting their quantitation curves of signal intensity versus concentration, we determined magnesium concentration in lake water quantitatively to be 5.42 mg L(-1) using the standard addition method. There is no significant difference from the result obtained with ICP-OES, 5.8 mg L(-1). Human urine and blood were also detected to ascertain the multi-metal analysis ability of this strategy in complex samples. At last, we explored its applicability to tissue slice and visualized sodium and potassium distribution by mass spectrometry imaging in the normal Kunming mouse brain.

  17. Determination of natural occurring radionuclide and heavy metals in drinking water in Malaysia

    International Nuclear Information System (INIS)

    Nur Suraya Ahmad

    2012-01-01

    The objective of this study is to ascertain the activity concentration of naturally occurring radionuclide and selected heavy metals selected mineral and drinking waters sample in Malaysia. The activity concentration of natural radionuclide (mBq/ L) was determined by Gamma Spectroscopy Systems while the concentration of heavy metal (mg/ L) was determined by the Induces Couple Plasma Mass Spectrometry (ICP-MS). The mineral and drinking water samples used in this study were Segar UKM, Giant, Ice Mountain (600 ml), Ice Mountain (1600 ml), Spritzer, Reverse Osmosis, and fresh tap water. The results of the study found 3 natural occurring radioactive materials (NORM) found for example - U-238, Ra-226 and Ra-228. The activity concentration determined was 0.00 mBq/ L to 1.71 mBq/ L for U-238, 0.00 - 32.46 mBq/ L for Ra-226 and 0.00 - 12.01 mBq/ L for Ra-228 respectively. The concentration of heavy metals Zn, Fe, As, Cl, Mn, Cu and Pb determined in this study were in the range of 0.000 - 0.003 mg/ L, 0.002-0.018 mg/ L, 0.000 - 0.007 mg/ L, 6.152 - 57.724 mg/ L, 0.000 - 0.016 μg/ L, 0.058 - 0.766 μg/ L and 0.000 - 0.380 μg/ L respectively. In general, the result of this study indicate that the activity concentration NORM and selected heavy metals in the studied mineral and drinking water samples were low and not exceed the limit set by World Organization (WHO) and Malaysian Food Regulations 1985. Thus, all the studied water samples complying the Malaysian drinking standard and safe to be consumed. (author)

  18. Distinction of tris(diimine)ruthenium(II) enantiomers chiral by virtue of helical chirality: temperature-dependent deuterium NMR spectroscopy in partially oriented phases.

    Science.gov (United States)

    Szalontai, Gábor; Kovács, Margit

    2006-11-01

    2H NMR spectra of perdeuterated tris(diimine)ruthenium(II) complexes have been recorded in lyotropic liquid crystalline phase formed by the chiral polypeptide, poly-gamma-benzyl-L-glutamate (PBLG) and co-solvents. It is demonstrated that the left- and right-rotation isomers of these octahedral metal complexes with D3 symmetry can be distinguished. The effects of temperature and ligand size on spectral resolution were also studied. Although in the case of free bipyridine ligands excellent optical resolution could be obtained at room temperature in the complexes studied, the increase in ligand size has a detrimental effect on the resolution. This can be compensated to some extent by elevating the sample temperature and decreasing the deuterium relaxation rates, but the available temperature range and therefore the applicability of the technique are limited. Copyright 2006 John Wiley & Sons, Ltd.

  19. Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls.

    Science.gov (United States)

    Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D; Krische, Michael J

    2015-10-14

    The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo-, and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k, and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k, and 6m, respectively. Primary alcohols 2a, 2l, and 2p were converted to the siloxy-crotylation products 3a, 3l, and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l, and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes.

  20. Multi-metals column adsorption of lead(II), cadmium(II) and manganese(II) onto natural bentonite clay.

    Science.gov (United States)

    Alexander, Jock Asanja; Surajudeen, Abdulsalam; Aliyu, El-Nafaty Usman; Omeiza, Aroke Umar; Zaini, Muhammad Abbas Ahmad

    2017-10-01

    The present work was aimed at evaluating the multi-metals column adsorption of lead(II), cadmium(II) and manganese(II) ions onto natural bentonite. The bentonite clay adsorbent was characterized for physical and chemical properties using X-ray diffraction, X-ray fluorescence, Brunauer-Emmett-Teller surface area and cation exchange capacity. The column performance was evaluated using adsorbent bed height of 5.0 cm, with varying influent concentrations (10 mg/L and 50 mg/L) and flow rates (1.4 mL/min and 2.4 mL/min). The result shows that the breakthrough time for all metal ions ranged from 50 to 480 minutes. The maximum adsorption capacity was obtained at initial concentration of 10 mg/L and flow rate of 1.4 mL/min, with 2.22 mg/g of lead(II), 1.71 mg/g of cadmium(II) and 0.37 mg/g of manganese(II). The order of metal ions removal by natural bentonite is lead(II) > cadmium(II) > manganese(II). The sorption performance and the dynamic behaviour of the column were predicted using Adams-Bohart, Thomas, and Yoon-Nelson models. The linear regression analysis demonstrated that the Thomas and Yoon-Nelson models fitted well with the column adsorption data for all metal ions. The natural bentonite was effective for the treatment of wastewater laden with multi-metals, and the process parameters obtained from this work can be used at the industrial scale.

  1. XPS investigations of ruthenium deposited onto representative inner surfaces of nuclear reactor containment buildings

    Energy Technology Data Exchange (ETDEWEB)

    Mun, C. [Institut de Radioprotection et de Surete Nucleaire (IRSN), Direction de la Prevention des Accidents Majeurs (DPAM), Centre de Cadarache, BP3-13115 Saint-Paul-lez-Durance (France)]. E-mail: christian.mun@irsn.fr; Ehrhardt, J.J. [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement (LCPME) UMR 7564, CNRS-Nancy University-405, rue de Vandoeuvre 54600 Villers-les-Nancy (France)]. E-mail: ehrhardt@lcpe.cnrs-nancy.fr; Lambert, J. [Laboratoire de Chimie Physique et Microbiologie pour l' Environnement (LCPME) UMR 7564, CNRS-Nancy University-405, rue de Vandoeuvre 54600 Villers-les-Nancy (France); Madic, C. [Commissariat a l' Energie Atomique (CEA), Direction de l' Energie Nucleaire, Centre de Saclay, 91191 Gif-sur-Yvette Cedex (France)]. E-mail: charles.madic@cea.fr

    2007-07-15

    In the case of a hypothetical severe accident in a nuclear power plant, interactions of gaseous RuO{sub 4} with reactor containment building surfaces (stainless steel and epoxy paint) could possibly lead to a black Ru-containing deposit on these surfaces. Some scenarios include the possibility of formation of highly radiotoxic RuO{sub 4}(g) by the interactions of these deposits with the oxidizing medium induced by air radiolysis, in the reactor containment building, and consequently dispersion of this species. Therefore, the accurate determination of the chemical nature of ruthenium in the deposits is of the high importance for safety studies. An experiment was designed to model the interactions of RuO{sub 4}(g) with samples of stainless steel and of steel covered with epoxy paint. Then, these deposits have been carefully characterised by scanning electron microscopy (SEM/EDS), electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). The analysis by XPS of Ru deposits formed by interaction of RuO{sub 4}(g), revealed that the ruthenium is likely to be in the IV oxidation state, as the shapes of the Ru 3d core levels are very similar with those observed on the RuO{sub 2}.xH{sub 2}O reference powder sample. The analysis of O 1s peaks indicates a large component attributed to the hydroxyl functional groups. From these results, it was concluded that Ru was present on the surface of the deposits as an oxyhydroxide of Ru(IV). It has also to be pointed out that the presence of 'pure' RuO{sub 2}, or of a thin layer of RuO{sub 3} or Ru{sub 2}O{sub 5}, coming from the decomposition of RuO{sub 4} on the surface of samples of stainless steel and epoxy paint, could be ruled out. These findings will be used for further investigations of the possible revolatilisation phenomena induced by ozone.

  2. Natural radionuclides and heavy metals in vegetables of people diet from Rio de Janeiro, RJ, Brazil

    International Nuclear Information System (INIS)

    Santos, Eliane Eugenia dos

    2002-01-01

    The characterization of the population exposure to the natural radiation is of extreme importance to set reference levels as a base to a regulatory system. Foodstuff, particularly of vegetable origin, presents variable contents of chemical products, essentials and not essentials according to soil characteristics, agricultural practices, among others. The present work had the goal to establish a methodology that allows evaluating the incorporation of natural radionuclides and heavy metals by the Brazilian population consuming foodstuff from vegetal origin. The results indicate that doses due to the ingestion of natural radionuclides and heavy metals as well in vegetables and derived products consumed by the Rio de Janeiro population are below the reference values set by international organizations. Regarding U and Th decay chain exposure ( 238 U, 23T h, 228 Ra, 226 Ra, 210 Pb), it was estimated an effective dose of 14,5 μSv/a, being 228 Ra, 226 Ra, 210 Pb responsible by 96%. The K-40 ingestion dose was assessed as 103 μSv/a. The daily intake of metals was assess as 2870 μg/d for Zn, 2499 μg/d for Mn, 1064 μg/d Cu, 96 μg/d Ni, 14,8 μg/d Cr, 11 μg/d Cd e 4,8 μg/d Pb. The most consumed metals by the Rio de Janeiro city inhabitants are Zn, Mn e Cu. The proposed methodology to extend this effective dose to the main Brazilian cities is: 1) to select for special analysis at each region the more consumed fruits at each city, carrots, manioc, tomato and sugar; 2) to use as a base line for all country the results of natural radionuclides and heavy metals obtained in this work for vegetables and derived products at specific locations and/or imported and distributed throughout the country; 3) in relation to natural radionuclides, it is only necessary to analyze 228 Ra, 226 Ra, 210 Pb. (author)

  3. On possibility of preparation of catalysts for ammonia synthesis based on cyanocomplexes of some d-metals

    International Nuclear Information System (INIS)

    Sergeeva, A.N.; Dovgej, V.V.; Pavlenko, L.I.; Zubritskaya, D.I.; Tkachenko, Zh.I.; Okorskaya, A.P.; Lyubchenko, Yu.A.

    1983-01-01

    The catalytic properties of the systems prepared on the basis of coordination cyanides of iron, ruthenium, osmium, rhenium, molydenum, vanadium and other d-metals in the ammonia synthesis reaction are studied. It has been found that thermal stability of catalytic systems containing vanadium and molybdenum is considerably higher than that of the industrial sample of similar type containing aluminium. The systems prepared on the basis of hexacyanoferrates, ruthenates and osmates can be referred to low-temperature type catalysts

  4. Dealloyed Ruthenium Film Catalysts for Hydrogen Generation from Chemical Hydrides

    Directory of Open Access Journals (Sweden)

    Ramis B. Serin

    2017-07-01

    Full Text Available Thin-film ruthenium (Ru and copper (Cu binary alloys have been prepared on a Teflon™ backing layer by cosputtering of the precious and nonprecious metals, respectively. Alloys were then selectively dealloyed by sulfuric acid as an etchant, and their hydrogen generation catalysts performances were evaluated. Sputtering time and power of Cu atoms have been varied in order to tailor the hydrogen generation performances. Similarly, dealloying time and the sulfuric acid concentration have also been altered to tune the morphologies of the resulted films. A maximum hydrogen generation rate of 35 mL min−1 was achieved when Cu sputtering power and time were 200 W and 60 min and while acid concentration and dealloying time were 18 M and 90 min, respectively. It has also been demonstrated that the Ru content in the alloy after dealloying gradually increased with the increasing the sputtering power of Cu. After 90 min dealloying, the Ru to Cu ratio increased to about 190 times that of bare alloy. This is the key issue for observing higher catalytic activity. Interestingly, we have also presented template-free nanoforest-like structure formation within the context of one-step alloying and dealloying used in this study. Last but not least, the long-time hydrogen generation performances of the catalysts system have also been evaluated along 3600 min. During the first 600 min, the catalytic activity was quite stable, while about 24% of the catalytic activity decayed after 3000 min, which still makes these systems available for the development of robust catalyst systems in the area of hydrogen generation.

  5. Half -sand wish ruthenium complexes of heterocyclic-dithio carboxylato ligands

    International Nuclear Information System (INIS)

    El-khateeb, M.; Al-Noaimi, M.; Harb, M.; Gorls, H.; Weigand, W.

    2008-01-01

    The heterocyclic-dithio carboxylato complexes Cp Ru(PPh 3 )(κ 2 S,S-S 2 C-h et) [h et= 2-C 4 H 3 O (1), 2-C 4 H 3 S (2), 1-C 4 H 8 N (3)] are obtained by the reaction of the ruthenium chloride, Cp Ru(PPh 3 ) 2 CI, with the anions, h et-CS 2 . The X-ray structure of Cp Ru(PPh 3 )(κ 2 S, S-S 2 C-1- C 4 H 8 N) (3) is determined by single crystal X-ray diffraction.

  6. Progress in doping of ruthenium silicide (Ru2Si3)

    International Nuclear Information System (INIS)

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

    1992-01-01

    This paper reports that ruthenium silicide (Ru 2 Si 3 ) is currently under development as a promising thermoelectric material suitable for space power applications. Key to realizing the potentially high figure of merit values of this material is the development of appropriate doping techniques. In this study, manganese and iridium have been identified as useful p- and n-type dopants, respectively. Resistivity values have been reduced by more than 3 orders of magnitude. Anomalous Hall effect results, however, complicate interpretation of some of the results and further effort is required to achieve optimum doping levels

  7. Elimination of ionic interference effects in the atomic absorption spectrometric determination of ruthenium

    International Nuclear Information System (INIS)

    El-Defrawy, M.M.M.; Posta, J.; Beck, M.T.

    1978-01-01

    In connection with work on the catalytic effect of ruthenium complexes, new compounds were prepared. Atomic absorption spectrometry (a.a.s.) was to be used for their analysis. The standard methods could not be applied to the complexes studied, therefore the effect of cyanide ions for elimination of interfering effects has been studied, because of the great stability of cyanide complexes. (Auth.)

  8. Three-dimensional ruthenium-doped TiO 2 sea urchins for enhanced visible-light-responsive H 2 production

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen-Phan, Thuy-Duong; Luo, Si; Vovchok, Dimitriy; Llorca, Jordi; Sallis, Shawn; Kattel, Shyam; Xu, Wenqian; Piper, Louis F. J.; Polyansky, Dmitry E.; Senanayake, Sanjaya D.; Stacchiola, Dario J.; Rodriguez, José A.

    2016-01-01

    Three-dimensional (3D) monodispersed sea urchin-like Ru-doped rutile TiO2 hierarchical architectures composed of radially aligned, densely-packed TiO2 nanorods have been successfully synthesized via an acid-hydrothermal method at low temperature without the assistance of any structure-directing agent and post annealing treatment. The addition of a minuscule concentration of ruthenium dopants remarkably catalyze the formation of the 3D urchin structure and drive the enhanced photocatalytic H2 production under visible light irradiation, not possible on undoped and bulk rutile TiO2. Increasing ruthenium doping dosage not only increases the surface area up to 166 m2 g-1 but also induces enhanced photo response in the regime of visible and near infrared light. The doping introduces defect impurity levels, i.e. oxygen vacancy and under-coordinated Ti3+, significantly below the conduction band of TiO2, and ruthenium species act as electron donors/acceptors that accelerate the photogenetated hole and electron transfer and efficiently suppress the rapid charge recombination, therefore improving the visible-light-driven activity.

  9. Flow injection chemiluminescent determination of N-nitrosodimethylamine using photogenerated tris(2,2'-bipyridyl) ruthenium (III)

    International Nuclear Information System (INIS)

    Perez-Ruiz, Tomas; Martinez-Lozano, Carmen; Tomas, Virginia; Martin, Jesus

    2005-01-01

    A flow injection configuration was developed and evaluated for the chemiluminescent determination of N-nitrosodimethylamine. The method is based on the on-line cleavage of the N-NO bond of the nitrosamine by irradiation with ultraviolet light. The dimethylamine generated was subsequently reacted with tris(2,2'-bipyridyl) ruthenium (III), which was generated through the on-line photo-oxidation of tris(2,2'-bipyridyl) ruthenium (II) with peroxydisulfate. After selecting the best operating parameters, the emitted light showed a linear relationship with the concentration of N-nitrosodimethylamine between 1.5 and 148 ng ml -1 , with a detection limit of 0.29 ng ml -1 . The repeatability was 1.6% expressed as relative standard deviation (n = 10) and the reproducibility, studied on five consecutive days, was 3.2%. The sample throughput was 50 injections per hour. The method was applied to studying the recoveries of N-nitrosodimethylamine in water and different cured meat products

  10. A multi-target caffeine derived rhodium(i) N-heterocyclic carbene complex: evaluation of the mechanism of action.

    Science.gov (United States)

    Zhang, Jing-Jing; Muenzner, Julienne K; Abu El Maaty, Mohamed A; Karge, Bianka; Schobert, Rainer; Wölfl, Stefan; Ott, Ingo

    2016-08-16

    A rhodium(i) and a ruthenium(ii) complex with a caffeine derived N-heterocyclic carbene (NHC) ligand were biologically investigated as organometallic conjugates consisting of a metal center and a naturally occurring moiety. While the ruthenium(ii) complex was largely inactive, the rhodium(i) NHC complex displayed selective cytotoxicity and significant anti-metastatic and in vivo anti-vascular activities and acted as both a mammalian and an E. coli thioredoxin reductase inhibitor. In HCT-116 cells it increased the reactive oxygen species level, leading to DNA damage, and it induced cell cycle arrest, decreased the mitochondrial membrane potential, and triggered apoptosis. This rhodium(i) NHC derivative thus represents a multi-target compound with promising anti-cancer potential.

  11. A new electrochemical sensor containing a film of chitosan-supported ruthenium: detection and quantification of sildenafil citrate and acetaminophen

    Energy Technology Data Exchange (ETDEWEB)

    Delolo, Fabio Godoy; Rodrigues, Claudia; Silva, Monize Martins da; Batista, Alzir Azevedo, E-mail: fabiodelolo@hotmail.com, E-mail: daab@power.ufscar.br [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Quimica. Lab. de Estrutura e Reatividade de Compostos Inorganicos; Dinelli, Luis Rogerio [Universidade Federal de Uberlandia (UFU), Ituiutaba, MG (Brazil). Faculdade de Ciencias Integradas do Pontal; Delling, Felix Nicolai; Zukerman-Schpector, Julio [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Quimica. Lab. de Cristalografia Estereodinamica e Modelagem Molecular

    2014-03-15

    This work presents the construction of a novel electrochemical sensor for detection of organic analytes, using a glassy carbon electrode (GCE) modified with a chitosan-supported ruthenium film. The ruthenium-chitosan film was obtained starting from the mer-[RuCl{sub 3}(dppb)(H{sub 2}O)] complex as a [1,4-bis(diphenylphosphine)butane] (dppb) precursor, and chitosan (QT). The structure of the chitosan-supported ruthenium film on the surface of the glassy carbon electrode was characterized by UV-Vis spectroscopy, electron paramagnetic resonance (EPR), scanning electron microscopy (SEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD) and atomic absorption spectroscopy (AAS) techniques. The glassy carbon electrode was modified with a film formed from the evaporation of 5 μL of a solution composed of 5 mg chitosan-supported ruthenium (RuQT) in 10 mL of 0.1 mol L{sup -1} acetic acid. The modified electrode was tested as a sensor for sildenafil citrate (Viagra® 50 mg) and acetaminophen (Tylenol®) detection. The technique utilized for these analyses was differential pulse voltammetry (DPV) in 0.1 mol L{sup -1} H{sub 2}SO{sub 4} (pH 1.0) and 0.1 mol L{sup -1} CH{sub 3}COOK (pH 6.5) as supporting electrolyte. All analyses were carried out during a month using the same electrode. The electrode was washed only with water in between the analyses, keeping it in the refrigerator when it was not in use. This electrode was stable during the period utilized showing no degradation and presenting a linear response over the evaluated concentration interval (1.25 × 10{sup -5} to 4.99 × 10{sup -4} mol L{sup -1}). (author)

  12. Metal Contamination of the Natural Environment in Norway from Long Range Atmospheric Transport

    International Nuclear Information System (INIS)

    Steinnes, E.

    2001-01-01

    Long range atmospheric transport is the most important source of contamination to the natural environment in Norway with many heavy metals. Investigations based on aerosol studies, bulk deposition measurements and moss analysis show that airborne transport from other parts of Europe is the major mode for supply of vanadium, zinc, arsenic, selenium, molybdenum, cadmium, tin,antimony, tellurium, thallium, lead, and bismuth, whereas metals such as chromium, nickel, and copper are mainly derived from point sources within Norway and in northwestern Russia close to the Norwegian border. Elements associated with long range transport show substantial enrichment in the humus horizon of natural soils in southern Norway, sometimes to levels suspected to cause effects on soil microbial processes. E.g. lead concentration values of 150-200 ppm are observed in the most contaminated areas in the south as compared to about 5 ppm in the far north. Elements such as lead and cadmium also show enrichment in some terrestrial food chains. These elements also show considerably elevated levels over background concentrations in the water and sediment of small lakes in the southern part of the country. Retrospective studies based on ombrogenous peatcores indicate that long range transport has been a significant source of heavy metal contamination in southern Norway for the last couple of centuries. The deposition of most heavy metals in Norway has been considerably reduced over the last 20 yr, with the exception of contributions in the north from Russian smelters

  13. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    The efficient and selective preparation of organic molecules is critical for mankind. For the future, it is of paramount importance to find catalysts able to transform abundant and cheap feedstocks into useful compounds. Acyclic and heterocyclic nitrogen-containing derivatives are common components of naturally occurring compounds, agrochemicals, cosmetics, and pharmaceuticals; they are also useful intermediates in a number of industrial processes. One of the most widely used synthetic strategies, allowing the formation of an N-C bond, is the addition of an N-H bond across a carbon-carbon multiple bond, the so-called hydroamination reaction. This chemical transformation fulfills the principle of “green chemistry” since it ideally occurs with 100% atom economy. Various catalysts have been found to promote this reaction, although many limitations remain; one of the most prominent is the lack of methods that permit the use of NH3 and NH2NH2 as the amine partners. In fact, ammonia and hydrazine have rarely succumbed to homogeneous catalytic transformations. Considering the low cost and abundance of ammonia (136 million metric tons produced in 2011) and hydrazine, catalysts able to improve the reactivity and selectivity of the NH3- and NH2NH2-hydroamination reaction, and more broadly speaking the functionalization of these chemicals, are highly desirable. In the last funded period, we discovered the first homogeneous catalysts able to promote the hydroamination of alkynes and allenes with ammonia and the parent hydrazine. The key feature of our catalytic systems is that the formation of catalytically inactive Werner complexes is reversible, in marked contrast to most of the known ammonia and hydrazine transition metal complexes. This is due to the peculiar electronic properties of our neutral ancillary ligands, especially their strong donating capabilities. However, our catalysts currently require

  14. Production of ruthenium aluminide by reaction sintering of Ru and Al powder mix

    International Nuclear Information System (INIS)

    Povarova, K.B.; Kazanskaya, N.K.; Drozdov, A.A.; Skachkov, O.A.; Levin, V.P.

    2002-01-01

    The physicochemical processes, taking place by the RuAl alloy formation from the ruthenium and aluminium powder mixture within the temperature range of 250-1400 deg C in the vacuum from 10 -2 up to 10 -5 mm mercury column are studied on the alloys of the Ru 50 Al 50 stoichiometric and Ru 52 Al 48 hyperstoichiometric composition. The Ru + Al → RuAl interaction with the exothermal effect begins in the solid phase at the temperatures below the aluminium t melt . The Ru 2 Al 3 , RuAl 2 and RuAl traces rich in aluminium are formed already at 600 deg C; at 1000-1400 deg C the RuAl becomes the basic phase; the precipitates of the ruthenium-based solid solution are additionally present in the hyperstoichiometric Ru 52 Al 48 alloy. The Ru 52 Al 48 crystalline lattice period increases with the growth of the caking temperature from 0.29906 (660 deg C) up to 0.22955 nm (1400 deg C). The Al 2 O 3 inclusions up to 1 μm in diameter are identified in the caked alloys in vacuum after the reaction caking [ru

  15. Electrophoretic deposition (EPD) of hydrous ruthenium oxides with PTFE and their supercapacitor performances

    International Nuclear Information System (INIS)

    Jang, Jong H.; Machida, Kenji; Kim, Yuri; Naoi, Katsuhiko

    2006-01-01

    The effect of PTFE addition was investigated for the electrophoretic deposition (EPD) of hydrous ruthenium oxide electrodes. Mechanical stability of electrode layers, together with deposition yield, was enhanced by using hydrous ruthenium oxide/PTFE dispersions. High supercapacitor performance was obtained for the electrodes prepared with 2% PTFE and 10% water. When PTFE content was higher, the rate capability became poor with low electronic conductivity; higher water content than 10% resulted in non-uniform depositions with poor cycleability and power capability. When electrodes were heat treated at 200 deg. C for 10 h, the specific energy was as high as 17.6 Wh/kg based on single electrode (at 200 W/kg); while utilizable energy was lower with heat treatment time of 1 and 50 h, due to the high resistance and gradual crystallization, respectively. With PTFE addition and heat treatment at 200 deg. C for 10 h, the specific capacitance was increased by 31% (460 → 599 F/g at ca. 0.6 mg/cm 2 ) at 10 mV/s, and the deposition weight was increased up to 1.7 mg/cm 2 with initial capacitance of 350 F/g

  16. The effect of annealing temperature on the optical properties of a ruthenium complex thin film

    Energy Technology Data Exchange (ETDEWEB)

    Ocakoglu, Kasim, E-mail: kasim.ocakoglu@mersin.edu.tr [Advanced Technology Research & Application Center, Mersin University, TR-33343, Yenisehir, Mersin (Turkey); Department of Energy Systems Engineering, Faculty of Technology, Mersin University, TR-33480 Mersin (Turkey); Okur, Salih, E-mail: salih.okur@ikc.edu.tr [Department of Materials Science and Engineering, Faculty of Engineering and Architecture, Izmir Katip Celebi University, Izmir (Turkey); Aydin, Hasan [Izmir Institute of Technology, Department of Material Science and Engineering, Gulbahce Campus, 35430, Urla, Izmir (Turkey); Emen, Fatih Mehmet [Faculty of Arts and Sciences, Department of Chemistry, Mehmet Akif Ersoy University, TR-15030 Burdur (Turkey)

    2016-08-01

    The stability of the optical parameters of a ruthenium polypyridyl complex (Ru-PC K314) film under varying annealing temperatures between 278 K and 673 K was investigated. The ruthenium polypyridyl complex thin film was prepared on a quartz substrate by drop casting technique. The transmission of the film was recorded by using Ultraviolet/Visible/Near Infrared spectrophotometer and the optical band gap energy of the as-deposited film was determined around 2.20 eV. The optical parameters such as refractive index, extinction coefficient, and dielectric constant of the film were determined and the annealing effect on these parameters was investigated. The results show that Ru PC K314 film is quite stable up to 595 K, and the rate of the optical band gap energy change was found to be 5.23 × 10{sup −5} eV/K. Furthermore, the thermal analysis studies were carried out in the range 298–673 K. The Differential Thermal Analysis/Thermal Gravimmetry/Differantial Thermal Gravimmetry curves show that the decomposition is incomplete in the temperature range 298–673 K. Ru-PC K314 is thermally stable up to 387 K. The decomposition starts at 387 K with elimination of functional groups such as CO{sub 2}, CO molecules and SO{sub 3}H group was eliminated between 614 K and 666 K. - Highlights: • Optical parameters of a ruthenium polypyridyl complex film under varying annealing temperatures • The film is quite stable up to 573 K. • The rate of change of optical energy gap was obtained as 5.23 × 10{sup −5} eV/K.

  17. Bifunctional amine-tethered ruthenium(II) arene complexes form monofunctional adducts on DNA

    Czech Academy of Sciences Publication Activity Database

    Melchart, M.; Habtemariam, A.; Nováková, Olga; Moggach, S.A.; Fabbiani, F.P.A.; Parsons, S.; Brabec, Viktor; Sadler, P.J.

    2007-01-01

    Roč. 46, č. 21 (2007), s. 8950-8962 ISSN 0020-1669 R&D Projects: GA ČR(CZ) GA305/05/2030; GA ČR(CZ) GA203/06/1239; GA AV ČR(CZ) 1QS500040581; GA AV ČR(CZ) KAN200200651 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : DNA * ruthenium * cancer Subject RIV: BO - Biophysics Impact factor: 4.123, year: 2007

  18. Ruthenium-catalyzed cyclization of N-carbamoyl indolines with alkynes: an efficient route to pyrroloquinolinones.

    Science.gov (United States)

    Manoharan, Ramasamy; Jeganmohan, Masilamani

    2015-09-21

    A regioselective synthesis of substituted pyrroloquinolinones via a ruthenium-catalyzed oxidative cyclization of substituted N-carbamoyl indolines with alkynes is described. The cyclization reaction was compatible with various symmetrical and unsymmetrical alkynes including substituted propiolates. Later, we performed the aromatization of pyrroloquinolinones into indole derivatives in the presence of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ).

  19. Electronic Interplay between TTF and Extended-TCNQ Electrophores along a Ruthenium Bis(acetylide) Linker.

    Science.gov (United States)

    Vacher, Antoine; Auffray, Morgan; Barrière, Frédéric; Roisnel, Thierry; Lorcy, Dominique

    2017-11-17

    A bis(TTF-butadiynyl) ruthenium D-D'-D complex, with intramolecular electronic interplay between the three electron-donating electrophores, was easily converted through a cycloaddition-retroelectrocyclization with TCNQ into a D-A-D'-A-D pentad complex, which exhibits an intense intramolecular charge transfer together with an electronic interplay between the two acceptors along the conjugated organometallic bridge.

  20. Deposition of RuO 4 on various surfaces in a nuclear reactor containment

    Science.gov (United States)

    Holm, Joachim; Glänneskog, Henrik; Ekberg, Christian

    2009-07-01

    During a severe nuclear reactor accident with air ingress, ruthenium can be released from the nuclear fuel in the form of ruthenium tetroxide. Hence, it is important to investigate how the reactor containment is able to reduce the source term of ruthenium. The aim of this work was to investigate the deposition of gaseous ruthenium tetroxide on aluminium, copper and zinc, which all appear in relatively large amounts in reactor containment. The experiments show that ruthenium tetroxide is deposited on all the metal surfaces, especially on the copper and zinc surfaces. A large deposition of ruthenium tetroxide also appeared on the relatively inert glass surfaces in the experimental set-ups. The analyses of the different surfaces, with several analytical methods, showed that the form of deposited ruthenium was mainly ruthenium dioxide.

  1. Deposition of RuO{sub 4} on various surfaces in a nuclear reactor containment

    Energy Technology Data Exchange (ETDEWEB)

    Holm, Joachim, E-mail: joachim.holm@chalmers.s [Department of Nuclear Chemistry, Chalmers University of Technology, Se-412 96 Gothenburg (Sweden); Glaenneskog, Henrik [Ringhals AB, SE-430 22, Vaeroebacka (Sweden); Ekberg, Christian [Department of Nuclear Chemistry, Chalmers University of Technology, Se-412 96 Gothenburg (Sweden)

    2009-07-01

    During a severe nuclear reactor accident with air ingress, ruthenium can be released from the nuclear fuel in the form of ruthenium tetroxide. Hence, it is important to investigate how the reactor containment is able to reduce the source term of ruthenium. The aim of this work was to investigate the deposition of gaseous ruthenium tetroxide on aluminium, copper and zinc, which all appear in relatively large amounts in reactor containment. The experiments show that ruthenium tetroxide is deposited on all the metal surfaces, especially on the copper and zinc surfaces. A large deposition of ruthenium tetroxide also appeared on the relatively inert glass surfaces in the experimental set-ups. The analyses of the different surfaces, with several analytical methods, showed that the form of deposited ruthenium was mainly ruthenium dioxide.

  2. Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling† †Electronic supplementary information (ESI) available: Experimental details. See DOI: 10.1039/c7sc04207h

    Science.gov (United States)

    Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo

    2017-01-01

    Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KOtBu and bidentate phosphine dmpe is vital to this transformation. PMID:29568466

  3. Analytical and experimental study of liquid metal natural circulation

    Energy Technology Data Exchange (ETDEWEB)

    Chu, H.S.; Kim, C.S.; Suh, K.Y. [Seoul National Univ., Dept. of Nuclear Engineering (Korea, Republic of)

    2001-07-01

    A one-dimensional flow loop model is used to analyze the state of the test loop in the natural circulation condition. Along the low-temperature melting eutectic metal alloy path, the steady-state momentum equation and the energy equation are solved at the one-dimensional lumped nodes. A three-dimensional computational fluid dynamics code, CFX 4.2, is applied to check on the result of first-principle calculation. The major pressure drop results from the four elbows in the test loop. Experiments are planned to cover a wide spectrum of the turbulent regime in the large-diameter piping. The smaller-diameter pipe produces larger temperature difference given the flow velocity. Because the low-temperature melting eutectic metal alloy used in this experiment gets burnable above 150 C, the diameter of the pipe must be large enough to cover the wide velocity range. Given the same velocity, the heater power in the smaller diameter pipe is less than in the larger diameter pipe. This shows that the heat removal is more effective in the large pipe given the flow velocity. (author)

  4. 1.3.3. Synthesis, characterization and crystal structure of a new ruthenium polypyridyl complex [Ru(phen2(4,4'-dicarboxy-2,2'- bipyridine]PF6

    Directory of Open Access Journals (Sweden)

    Jiaxi Chen, Jing Sun*, Jufang Kong, Wenxiu Chen and Hongqing Hao*

    2015-03-01

    Full Text Available Abstract: A new Ru(II polypyridyl complex, [Ru(phen2(4,4'-dicarboxy-2,2'-bipyridine]PF6·1.5H2O, was synthesized andcharacterized by single crystal X-ray diffraction, elementalanalyses, electrospray ionization mass spectrometry, infraredspectra, ultraviolet (UV spectra, and emission spectra. Thestructure of the cation [Ru(phen2(4,4'-(COO-,(COOH-2,2'-bpy]+ consists of a six-coordinated ruthenium atom chelated bytwo phen ligands and one 4,4'-dicarboxy-2,2'-bipyridine ligand.The absorption spectrum of the Ru(II complex is characterizedby two intense ligand-centered transitions in the UV region andone metal to ligand charge transfer in the visible region. Moreover,the complex can display luminescence in water at roomtemperature, with maximum emission at 623 nm.Supporting information: Cif file

  5. Ruthenium-catalyzed direct C3 alkylation of indoles with α,β-unsaturated ketones.

    Science.gov (United States)

    Li, Shuai-Shuai; Lin, Hui; Zhang, Xiao-Mei; Dong, Lin

    2015-01-28

    In this paper, a simple and highly efficient ruthenium-catalyzed direct C3 alkylation of indoles with various α,β-unsaturated ketones without chelation assistance has been developed. This novel C-H activation methodology exhibits a broad substrate scope such as different substituted indoles, pyrroles, and other azoles. Further synthetic applications of the alkylation products can lead to more attractive 3,4-fused tricyclic indoles.

  6. Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-Based Supports

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Solid catalyst systems comprised of ruthenium hydroxide supported on magnesium-based carrier materials (spinel, magnesium oxide and hydrotalcite) were investigated for the selective, aqueous aerobic oxidation of the biomass-derived chemical 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid...

  7. Poly-functional description of metal complexation by natural organic matter: theory and practice

    International Nuclear Information System (INIS)

    Buffle, J.; Filella, M.; Altmann, R.S.

    1995-01-01

    The Differential Equilibrium Function (DEF) approach to metal complexation interpretation and prediction is compared to other models or approaches. The basic features of DEF are summarized, both from the experimental and theoretical points of view. The relation of DEF with key environmental concepts or parameters, in particular minor vs major complexing sites, the buffering intensity of natural organic matter (NOM), and their poly functional vs polyelectrolyte properties, is discussed. The relation between DEF and Freundlich isotherm is described quantitatively. The practical applications of DEF are discussed for (i) interpretation of metal complexation by NOM, and (ii) prediction of metal complexation by NOM. It is shown that DEF (i.e. sound extrapolation is possible with care). DEF cans be readily incorporated in metal species distribution codes (e.g. MINEQL). DEF is not equivalent to a molecular complexation model which describes complexation at each individual site; DEF gives a rigorous representation of complexation by NOM as a whole chemical system. (authors). 23 refs., 6 figs

  8. A Comparative Study of Natural Fiber and Glass Fiber Fabrics Properties with Metal or Oxide Coatings

    International Nuclear Information System (INIS)

    Lusis, Andrej; Pentjuss, Evalds; Bajars, Gunars; Sidorovicha, Uljana; Strazds, Guntis

    2015-01-01

    Rapidly growing global demand for technical textiles industries is stimulated to develop new materials based on hybrid materials (yarns, fabrics) made from natural and glass fibres. The influence of moisture on the electrical properties of metal and metal oxide coated bast (flax, hemp) fibre and glass fibre fabrics are studied by electrical impedance spectroscopy and thermogravimetry. The bast fibre and glass fiber fabrics are characterized with electrical sheet resistance. The method for description of electrical sheet resistance of the metal and metal oxide coated technical textile is discussed. The method can be used by designers to estimate the influence of moisture on technical data of new metal coated hybrid technical textile materials and products

  9. Determination of ruthenium in photographic emulsions - Development and comparison of different sample treatments and mass spectrometric methods

    NARCIS (Netherlands)

    Krystek, Petra; Heumann, Klaus G.

    1999-01-01

    Different sample treatment procedures were combined with inductively coupled plasma mass spectrometry (ICP-MS) and negative thermal ionisation mass spectrometry (NTI-MS) for the determination of ruthenium traces in photographic emulsions. Dissolution of the samples in concentrated ammonia solution

  10. 99Tc, Pb and Ru migration around the Oklo natural fission reactors

    International Nuclear Information System (INIS)

    Gancarz, A.; Cowan, G.; Curtis, D.; Maeck, W.

    1980-01-01

    This work demonstrates the utility of the Oklo uranium ore deposit and natural fission reactors as a long time scale analogue for man-made radioactive waste repositories. It has been shown that the ores and nearby rocks were open to the loss and gain of 99 Tc, ruthenium, and lead relative to uranium. Identified regions of element deficiencies and those which are correspondingly enriched are separated by less than 10 meters. However, more extensive sampling is required to define the overall extent of the element migration. Element fractionation took place on at least two vastly different time scales; 99 Tc was fractionated from ruthenium within one million years of the end of reactor criticality. Lead-uranium fractionation has been ongoing for most of the two billion years since the ores were formed. Diffusion loss of lead from host uraninite appears to be an important process in the fractionation of lead from uranium

  11. Oklo reactors: natural analogs to nuclear waste repositories

    International Nuclear Information System (INIS)

    Curtis, D.B.; Benjamin, T.M.; Gancarz, A.J.

    1981-01-01

    The 2-billion-year-old fossil reactors at Oklo are ancient natural nuclear waste sites. Isotope dilution mass spectrometric analyses of the fission products in the reactor core uraninite and the peripheral pelitic sandstone provide data for calculating the reactor operating parameters, the quantities of fissiogenic isotopes produced, the fraction of these isotopes retained in the cores, and the location in the peripheral rocks of the fissiogenic fraction lost from the cores. For a duration of criticality of 3 x 10 5 yrs, the thermal plus resonance neutron fluence ranged between 10 20 and 10 21 neutrons/cm 2 . The fraction of technetium (60 to 85%), ruthenium (75 to 90%), and neodymium (85 to 100%) retained is negatively correlated with fluence. The lost fission products are contained within a few tens of meters of their source, the reactor cores. The systematics of the decay of 99 Tc (t/sub 1/2/ = 2.13 x 10 5 yr) to 99 Ru limits the period of fissiogenic element migration to approximately 1 million yr at a time 2 billion yr ago. Thermodynamic calculations of the temperature-dependent solubilities indicate that the loss of fissiogenic elements is diffusion controlled, whereas retention in the surrounding rocks is a result of temperature-dependent deposition from an aqueous solution. These results concerning the geochemistry of technetium, ruthenium, and neodymium at a natural waste site support the concept of geologic burial of man-made radioactive wastes

  12. Do acid volatile sulfides (AVS) influence the accumulation of sediment-bound metals to benthic invertebrates under natural field conditions?

    Science.gov (United States)

    De Jonge, Maarten; Dreesen, Freja; De Paepe, Josefina; Blust, Ronny; Bervoets, Lieven

    2009-06-15

    The present study evaluates the influence of acid volatile sulfides (AVS) on accumulation of sediment-bound metals in benthic invertebrates under natural field conditions. Natural sediments, pore water, surface water, and two species of widespread benthic invertebrates (Chironomus gr. thummi and Tubifex tubifex) were collected from 17 historical polluted Flemish lowland rivers and measured for metal concentrations. Different sediment characteristics were determined (AVS, organic matter, clay content) and multiple regression was used to study their relationship with accumulated metals in the invertebrates. Physical and chemical analysis of the field samples indicated low metal concentrations in the water and pore water, but very high metal concentrations in the sediment and the invertebrates, especially for Pb (5.99 micromol/ g). In general, metal accumulation in chironomids and tubificid worms was most strongly correlated with total metal concentrations in the sediment and sediment metal concentrations normalized for organic matter and clay content. Following the results of the linear regression model, AVS did not turn out to be a significant variable in describing variation in metal accumulation. Our study clearly demonstrates that, in addition to the results gained from experiments under lab conditions, benthic invertebrates can accumulate metals from unspiked field sediments even when there's an excess of AVS.

  13. Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand

    Science.gov (United States)

    Askevold, Bjorn; Nieto, Jorge Torres; Tussupbayev, Samat; Diefenbach, Martin; Herdtweck, Eberhardt; Holthausen, Max C.; Schneider, Sven

    2011-07-01

    Bioinspired hydrogenation of N2 to ammonia at ambient conditions by stepwise nitrogen protonation/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H2 remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N2 splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We report the synthesis of a ruthenium(IV) nitrido complex. The high nucleophilicity of the nitrido ligand is demonstrated by unusual N-C coupling with π-acidic CO. Furthermore, the terminal nitrido ligand undergoes facile hydrogenolysis with H2 at ambient conditions to produce ammonia in high yield. Kinetic and quantum chemical examinations of this reaction suggest cooperative behaviour of a phosphorus-nitrogen-phosphorus pincer ligand in rate-determining heterolytic hydrogen splitting.

  14. Ion implantation to improve mechanical and electrical properties of resistive materials based on ruthenium dioxide

    International Nuclear Information System (INIS)

    Byeli, A.V.; Shykh, S.K.; Beresina, V.P.

    1996-01-01

    This paper reports the influence of ion implantation, using different chemical species, on the surface micromorphology, wear resistance, coefficient of friction and electrical resistivity, and its variation during friction for resistive materials based on ruthenium dioxide. It is demonstrated that nitrogen and hydrogen ions are the most effective for modifying surface properties. (Author)

  15. Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Heterogeneous ruthenium-based catalysts were applied in the selective, aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, to form 2,5-furandicarboxylic acid. The oxidation reactions were performed in water with dioxygen as the oxidant at different pressures without...

  16. Automated scoping methodology for liquid metal natural circulation small reactor

    International Nuclear Information System (INIS)

    Son, Hyung M.; Suh, Kune Y.

    2014-01-01

    Highlights: • Automated scoping methodology for natural circulation small modular reactor is developed. • In-house code is developed to carry out system analysis and core geometry generation during scoping. • Adjustment relations are obtained to correct the critical core geometry out of diffusion theory. • Optimized design specification is found using objective function value. • Convex hull volume is utilized to quantify the impact of different constraints on the scope range. - Abstract: A novel scoping method is proposed that can automatically generate design variable range of the natural circulation driven liquid metal cooled small reactor. From performance requirements based upon Generation IV system roadmap, appropriate structure materials are selected and engineering constraints are compiled based upon literature. Utilizing ASME codes and standards, appropriate geometric sizing criteria on constituting components are developed to ensure integrity of the system during its lifetime. In-house one dimensional thermo-hydraulic system analysis code is developed based upon momentum integral model and finite element methods to deal with non-uniform descritization of temperature nodes for convection and thermal diffusion equation of liquid metal coolant. In order to quickly generate critical core dimensions out of given unit cell information, an adjustment relation that relates the critical geometry estimated from one-group diffusion and that from MCNP code is constructed and utilized throughout the process. For the selected unit cell dimension ranges, burnup calculations are carried out to check the cores can generate energy over the reactor lifetime. Utilizing random method, sizing criteria, and in-house analysis codes, an automated scoping methodology is developed. The methodology is applied to nitride fueled integral type lead cooled natural circulation reactor concept to generate design scopes which satisfies given constraints. Three dimensional convex

  17. Characterisation and application of new carboxylic acid-functionalised ruthenium complexes as dye-sensitisers for solar cells

    DEFF Research Database (Denmark)

    Duprez, Virginie; Biancardo, Matteo; Krebs, Frederik C

    2007-01-01

    A series of ruthenium complexes with and without TiO2, anchoring carboxylic acid groups have been synthesised and characterised using nuclear magnetic resonance (NMR), UV-vis and luminescence. These complexes were adsorbed on thin films of the wide band-gap semiconductor anatase and were tested a...

  18. A Smart Europium-Ruthenium Complex as Anticancer Prodrug: Controllable Drug Release and Real-Time Monitoring under Different Light Excitations.

    Science.gov (United States)

    Li, Hongguang; Xie, Chen; Lan, Rongfeng; Zha, Shuai; Chan, Chi-Fai; Wong, Wing-Yan; Ho, Ka-Lok; Chan, Brandon Dow; Luo, Yuxia; Zhang, Jing-Xiang; Law, Ga-Lai; Tai, William C S; Bünzli, Jean-Claude G; Wong, Ka-Leung

    2017-11-09

    A unique, dual-function, photoactivatable anticancer prodrug, RuEuL, has been tailored that features a ruthenium(II) complex linked to a cyclen-europium chelate via a π-conjugated bridge. Under irradiation at 488 nm, the dark-inactive prodrug undergoes photodissociation, releasing the DNA-damaging ruthenium species. Under evaluation-window irradiation (λ irr = one-photon 350 nm or two-photon 700 nm), the drug delivery process can be quantitatively monitored in real-time because of the long-lived red europium emission. Linear relationships between released drug concentration and ESI-MS or luminescence responses are established. Finally, the efficiency of the new prodrug is demonstrated both in vitro RuEuL anticancer prodrug over some existing ones and open the way for decisive improvements in multipurpose prodrugs.

  19. Electrochemical DNA biosensor for detection of porcine oligonucleotides using ruthenium(II) complex as intercalator label redox

    Energy Technology Data Exchange (ETDEWEB)

    Halid, Nurul Izni Abdullah; Hasbullah, Siti Aishah; Heng, Lee Yook; Karim, Nurul Huda Abd [School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia); Ahmad, Haslina; Harun, Siti Norain [Chemistry Department, Faculty of Science, Universiti Putra Malaysia, 43400, Serdang, Selangor (Malaysia)

    2014-09-03

    A DNA biosensor detection of oligonucleotides via the interactions of porcine DNA with redox active complex based on the electrochemical transduction is described. A ruthenium(II) complex, [Ru(bpy){sub 2}(PIP)]{sup 2+}, (bpy = 2,2′bipyridine, PIP = 2-phenylimidazo[4,5-f[[1,10-phenanthroline]) as DNA label has been synthesized and characterized by 1H NMR and mass spectra. The study was carried out by covalent bonding immobilization of porcine aminated DNA probes sequences on screen printed electrode (SPE) modified with succinimide-acrylic microspheres and [Ru(bpy){sub 2}(PIP)]{sup 2+} was used as electrochemical redox intercalator label to detect DNA hybridization event. Electrochemical detection was performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) over the potential range where the ruthenium (II) complex was active. The results indicate that the interaction of [Ru(bpy){sub 2}(PIP)]{sup 2+} with hybridization complementary DNA has higher response compared to single-stranded and mismatch complementary DNA.

  20. Spectrophotometric methods for determining noble metals

    International Nuclear Information System (INIS)

    Gur'eva, R.F.; Savvin, S.B.

    2002-01-01

    The main trends of the development of spectrophotometric methods for determining noble metals (NMs) including ruthenium are considered. One of these trends is the synthesis and study of new, highly sensitive and selective organic reagents for determining NMs in solutions and solid phase. Another trend is the search for and developing of new methodological approaches (techniques) and color reactions, including those that involve modified and immobilized reagents. The third trend includes the improvement of equipment and automation. It is shown that the present-day spectrophotometry can provide the determination of NMs in samples with concentrations from several to 10 -4 % (photometry and differential photometry) and down to 10 -7 % (test and sorption-spectroscopic methods based on photometry and diffuse-reflectance spectroscopy, including the use of chromaticity functions) [ru