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.)

Towards Renewable Iodide Sources for Electrolytes in Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Iryna Sagaidak

2016-03-01

Full Text Available A novel family of iodide salts and ionic liquids based on different carbohydrate core units is herein described for application in dye-sensitized solar cell (DSC. The influence of the molecular skeleton and the cationic structure on the electrolyte properties, device performance and on interfacial charge transfer has been investigated. In combination with the C106 polypyridyl ruthenium sensitizer, power conversion efficiencies lying between 5.0% and 7.3% under standard Air Mass (A.M. 1.5G conditions were obtained in association with a low volatile methoxypropionitrile (MPN-based electrolyte.

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.)

Miniaturized polymer electrolyte fuel cell (PEFC) stack using micro structured bipolar plate

Energy Technology Data Exchange (ETDEWEB)

Veziridis, Z; Scherer, G G; Marmy, Ch; Glaus, F [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

In Polymer Electrolyte Fuel Cell (PEFC) technology the reducing of volume and mass of the fuel cell stack and the improvement of catalyst utilization are of great interest. These parameters affect applicability and system cost. In this work we present an alternative way for reducing the stack volume by combining gas distribution and catalytic active area in one plate. Micro machined glassy carbon electrodes serve as support material for the platinum catalyst, as well as gas distributor at the same time. A comparison of these electrodes with conventional platinum-black gas diffusion electrodes under fuel cell conditions shows that the new system is a promising electrode type for enhanced power density and catalyst utilization. (author) 3 figs., 5 refs.

Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

Science.gov (United States)

West, William; Whitacre, Jay; Lim, James

2008-01-01

Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

Hydriding of steel in cyanide electrolytes of cadmium plating

International Nuclear Information System (INIS)

Sokol'skaya, N.B.; Maksimchuk, V.P.

1977-01-01

Hydrogenation of steel in cyanide electrolytes for cadmium deposition has been studied in a wide range of compositions. Also investigated have been the scattering capacity and polarization parameters of these electrolytes. The basic components are Cd 2+ and CH - ; besides that, Na 2 SO 4 x10H 2 O, NaOH and NiSO 4 x7H 2 O have been added to the electrolytes. Hydrogenation upon cadmium electrolytic deposition has been determined by the rate of hydrogen penetration through a steel membrane 0.5 mm thick. At the NaCN/Cd(CN) 2 ratio more than 2 the increase in sodium cyanide concentration in the electrolyte appreciably increases neither its hydrogenating and scattering capacity, nor cathodic polarization. The greatest scattering capacity and the highest hydrogenation is exhibited by diluted cadmium deposition elecctrolytes (CdO concentration 9-12 g/1), which prove particularly effective for deposition of regular coatings on complex shape articles. Cadmium deposition on high strength steels, however, should rather involve cyanide electrolytes with high cadmium concentration (50-60 g/1) in order to reduce hydrogenation

Nanosized TiN-SBR hybrid coating of stainless steel as bipolar plates for polymer electrolyte membrane fuel cells

International Nuclear Information System (INIS)

Kumagai, Masanobu; Myung, Seung-Taek; Asaishi, Ryo; Sun, Yang-Kook; Yashiro, Hitoshi

2008-01-01

In attempt to improve interfacial electrical conductivity of stainless steel for bipolar plates of polymer electrolyte membrane fuel cells, TiN nanoparticles were electrophoretically deposited on the surface of stainless steel with elastic styrene butadiene rubber (SBR) particles. From transmission electron microscopic observation, it was found that the TiN nanoparticles (ca. 50 nm) surrounded the spherical SBR particles (ca. 300-600 nm), forming agglomerates. They were well adhered on the surface of the type 310S stainless steel. With help of elasticity of SBR, the agglomerates were well fitted into the interfacial gap between gas diffusion layer (GDL) and stainless steel bipolar plate, and the interfacial contact resistance (ICR), simultaneously, was successfully reduced. A single cell using the TiN nanoparticles-coated bipolar plates, consequently, showed comparable cell performance with the graphite employing cell at a current density of 0.5 A cm -2 (12.5 A). Inexpensive TiN nanoparticle-coated type 310S stainless steel bipolar plates would become a possible alternate for the expensive graphite bipolar plates as use in fuel cell applications

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

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.

Charged plate in asymmetric electrolytes: One-loop renormalization of surface charge density and Debye length due to ionic correlations.

Science.gov (United States)

Ding, Mingnan; Lu, Bing-Sui; Xing, Xiangjun

2016-10-01

Self-consistent field theory (SCFT) is used to study the mean potential near a charged plate inside a m:-n electrolyte. A perturbation series is developed in terms of g=4πκb, where band1/κ are Bjerrum length and bare Debye length, respectively. To the zeroth order, we obtain the nonlinear Poisson-Boltzmann theory. For asymmetric electrolytes (m≠n), the first order (one-loop) correction to mean potential contains a secular term, which indicates the breakdown of the regular perturbation method. Using a renormalizaton group transformation, we remove the secular term and obtain a globally well-behaved one-loop approximation with a renormalized Debye length and a renormalized surface charge density. Furthermore, we find that if the counterions are multivalent, the surface charge density is renormalized substantially downwards and may undergo a change of sign, if the bare surface charge density is sufficiently large. Our results agrees with large MC simulation even when the density of electrolytes is relatively high.

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)

Low hydrostatic head electrolyte addition to fuel cell stacks

International Nuclear Information System (INIS)

Kothmann, R.E.

1983-01-01

A fuel cell and system for supply electrolyte, as well as fuel and an oxidant to a fuel cell stack having at least two fuel cells, each of the cells having a pair of spaced electrodes and a matrix sandwiched therebetween, fuel and oxidant paths associated with a bipolar plate separating each pair of adjacent fuel cells and an electrolyte fill path for adding electrolyte to the cells and wetting said matrices. Electrolyte is flowed through the fuel cell stack in a back and forth fashion in a path in each cell substantially parallel to one face of opposite faces of the bipolar plate exposed to one of the electrodes and the matrices to produce an overall head uniformly between cells due to frictional pressure drop in the path for each cell free of a large hydrostatic head to thereby avoid flooding of the electrodes. The bipolar plate is provided with channels forming paths for the flow of the fuel and oxidant on opposite faces thereof, and the fuel and the oxidant are flowed along a first side of the bipolar plate and a second side of the bipolar plate through channels formed into the opposite faces of the bipolar plate, the fuel flowing through channels formed into one of the opposite faces and the oxidant flowing through channels formed into the other of the opposite faces

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.)

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.

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.

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.

Investigation of alkaline-cyanide electrolytes of zinc plating

International Nuclear Information System (INIS)

Shaburova, V.P.; Kolotij, O.Yu.

1993-01-01

Current values in their maxima on anodic potential curves of Cd, Sn and Zn in galvanizing electrolytes with equilibrium concentrations of free cyanide and hydroxide ions were compared. Anode signal of Cd in the presence of Zn complexes intensifies due to their lability and, therefore, it reflects not only the presence of free cyanide, but zinc complex ions, as well, in the solution mentioned. This is one of the reasons for a high information content of the signal in case of multicomponent analysis of cyanide galvanizing electrolytes

Advances in the electrodeposition of aluminum from ionic liquid based electrolytes

Science.gov (United States)

Leadbetter, Kirt C.

Aluminum plating is of considerable technical and economic interest because it provides an eco-friendly substitute for cadmium coatings used on many military systems. However, cadmium has been determined to be a significant environmental safety and occupational health (ESOH) hazard because of its toxicity and carcinogenic nature. Furthermore, the cost of treating and disposing of generated wastes, which often contain cyanide, is costly and is becoming prohibitive in the face of increasingly stringent regulatory standards. The non-toxic alternative aluminum is equivalent or superior in performance to cadmium. In addition, it could serve to provide an alternative to hexavalent chromium coatings used on military systems for similar reasons to that of cadmium. Aluminum is a beneficial alternative in that it demonstrates self-healing corrosion resistance in the form of a tightly-bound, impervious oxide layer. A successfully plated layer would be serviceable over a wider temperature range, 925 °F for aluminum compared to 450 oF for cadmium. In addition, an aluminum layer can be anodized to make it non-conducting and colorable. In consideration of the plating process, aluminum cannot be deposited from aqueous solutions because of its reduction potential. Therefore, nonaqueous electrolytes are required for deposition. Currently, aluminum can be electrodeposited in nonaqueous processes that use hazardous chemicals such as toluene and pyrophoric aluminum alkyls. Electrodeposition from ionic liquids provides the potential for a safer method that could be easily scaled up for industrial application. The plating process could be performed at a lower temperature and higher current density than other commercially available aluminum electrodeposition processes; thus a reduced process cost could be possible. The current ionic liquid based electrolytes are more expensive; however production on a larger scale and a long electrolyte lifetime are associated with a reduction in price

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)

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.

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.)

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.

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.)

Obtaining accurate amounts of mercury from mercury compounds via electrolytic methods

Science.gov (United States)

Grossman, M.W.; George, W.A.

1987-07-07

A process is described for obtaining pre-determined, accurate rate amounts of mercury. In one embodiment, predetermined, precise amounts of Hg are separated from HgO and plated onto a cathode wire. The method for doing this involves dissolving a precise amount of HgO which corresponds to a pre-determined amount of Hg desired in an electrolyte solution comprised of glacial acetic acid and H[sub 2]O. The mercuric ions are then electrolytically reduced and plated onto a cathode producing the required pre-determined quantity of Hg. In another embodiment, pre-determined, precise amounts of Hg are obtained from Hg[sub 2]Cl[sub 2]. The method for doing this involves dissolving a precise amount of Hg[sub 2]Cl[sub 2] in an electrolyte solution comprised of concentrated HCl and H[sub 2]O. The mercurous ions in solution are then electrolytically reduced and plated onto a cathode wire producing the required, pre-determined quantity of Hg. 1 fig.

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

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%....

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

Hydroponics gel as a new electrolyte gelling agent for alkaline zinc-air cells

Science.gov (United States)

Othman, R.; Basirun, W. J.; Yahaya, A. H.; Arof, A. K.

The viability of hydroponics gel as a new alkaline electrolyte gelling agent is investigated. Zinc-air cells are fabricated employing 12 wt.% KOH electrolyte immobilised with hydroponics gel. The cells are discharged at constant currents of 5, 50 and 100 mA. XRD and SEM analysis of the anode plates after discharge show that the failure mode is due to the formation of zinc oxide insulating layers and not due to any side reactions between the gel and the plate or the electrolyte.

Electrolytic plating apparatus for discrete microsized particles

International Nuclear Information System (INIS)

Mayer, A.

1976-01-01

Method and apparatus are disclosed for electrolytically producing very uniform coatings of a desired material on discrete microsized particles. Agglomeration or bridging of the particles during the deposition process is prevented by imparting a sufficiently random motion to the particles that they are not in contact with a powered cathode for a time sufficient for such to occur. 4 claims, 2 figures

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)

Effect of surface treatment on the interfacial contact resistance and corrosion resistance of Fe–Ni–Cr alloy as a bipolar plate for polymer electrolyte membrane fuel cells

International Nuclear Information System (INIS)

Yang, Meijun; Zhang, Dongming

2014-01-01

The bipolar plate is an important component of the PEMFC (polymer electrolyte membrane fuel cell) because it supplies the pathway of electron flow between each unit cell. Fe–Ni–Cr alloy is considered as a good candidate material for bipolar plate, but it is limited to use as a bipolar plate due to its high ICR (interfacial contact resistance) and corrosion problem. In order to explore a cost-effective method on surface modification, various chemical and electrochemical treatments are performed on Fe–Ni–Cr alloy to acquire the effect of the surface modification on the ICR and corrosion behavior. The ICR and corrosion resistance of Fe–Ni–Cr alloy can be effectively controlled by the chemical treatment of immersion in the mixed acid solution with 10 vol% HNO 3 , 2 vol% HCl and 1 vol% HF for 10 min at 65 °C and then was placed in 30 vol% HNO 3 solution for 5 min. The chemical treatment is more effective on reducing ICR and improving corrosion resistance than that of electrochemical methods (be carried out in the 2 mol/L H 2 SO 4 solution with the electrical potential from −0.4 V to 0.6 V) for Fe–Ni–Cr alloy as a bipolar plate for polymer electrolyte membrane fuel cells. - Highlights: • The procedure of the surface treatments on Fe–Ni–Cr alloy as bipolar plate was described in detail. • Effects of various surface treatments on the interfacial contact resistivity and corrosion behavior were discussed. • The mechanism of the surface modification was particularly analyzed

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.

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)

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)

Aluminum cathode plates in zinc electrowinning cells: microstructural and failure analysis

International Nuclear Information System (INIS)

Buarzaiga, M.; Dreisinger, D.; Tromans, D.; Gonzalez, J.A.

2001-01-01

The microstructure of aluminum cathode plates used in zinc electrowinning was analyzed using optical microscopy, scanning electron microscopy, and transmission electron microscopy. Three principal phases dominated the microstructure: primary aluminum, uniformly distributed intermetallic particles, and round rosettes. The intermetallics exhibited blade shape morphology, light gray color, and were aligned in the rolling direction. The chemical composition of the intermetallic particles was consistent with FeAl 3 . Angular particles of elemental silicon were also detected. Failure characteristics of industrial cathode plates were analyzed using optical microscopy, scanning electron microscopy, energy dispersive x-ray analysis, and x-ray diffraction analysis. Three distinct corrosion zones were identified on failed plates: Zone I below the electrolyte/air interface, Zone II 0-40 mm above the electrolyte/air interface, and Zone III 40-140 mm above the electrolyte/air interface. After 24 months in service, the corrosion damage in Zones I and III was equivalent to ca. 10% reduction in plate thickness. Zone II experienced the greatest corrosion damage; the reduction in plate thickness was ca. 80%. Some plates exhibited severe thinning and perforation, which occurred preferentially near the electrical contact edge. Plates often fail in service by fracture in Zone II. (author)

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

Process for electrolytic deposition of metals on zirconium materials

International Nuclear Information System (INIS)

Donaghy, R.E.

1981-01-01

An article made of a zirconium alloy can be electrolytically plated with a layer of a metal such as copper, nickel or chromium when the article is free of any loosely adhering film formed during an activation step. The article is activated in an aged aqueous solution of ammonium bifluoride and sulfuric acid. Next the loosely adhering film formed in the first step is removed by chemical treatment, ultrasonic cleaning, or by swabbing the surface with cotton or an organic material. Finally the article is contacted with an electrolytic plating solution in the presence of an electrode receiving current

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)

Carbonate fuel cell endurance: Hardware corrosion and electrolyte management status

Energy Technology Data Exchange (ETDEWEB)

Yuh, C.; Johnsen, R.; Farooque, M.; Maru, H.

1993-01-01

Endurance tests of carbonate fuel cell stacks (up to 10,000 hours) have shown that hardware corrosion and electrolyte losses can be reasonably controlled by proper material selection and cell design. Corrosion of stainless steel current collector hardware, nickel clad bipolar plate and aluminized wet seal show rates within acceptable limits. Electrolyte loss rate to current collector surface has been minimized by reducing exposed current collector surface area. Electrolyte evaporation loss appears tolerable. Electrolyte redistribution has been restrained by proper design of manifold seals.

Carbonate fuel cell endurance: Hardware corrosion and electrolyte management status

Energy Technology Data Exchange (ETDEWEB)

Yuh, C.; Johnsen, R.; Farooque, M.; Maru, H.

1993-05-01

Endurance tests of carbonate fuel cell stacks (up to 10,000 hours) have shown that hardware corrosion and electrolyte losses can be reasonably controlled by proper material selection and cell design. Corrosion of stainless steel current collector hardware, nickel clad bipolar plate and aluminized wet seal show rates within acceptable limits. Electrolyte loss rate to current collector surface has been minimized by reducing exposed current collector surface area. Electrolyte evaporation loss appears tolerable. Electrolyte redistribution has been restrained by proper design of manifold seals.

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)

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

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

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)

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)

In situ chemical synthesis of ruthenium oxide/reduced graphene oxide nanocomposites for electrochemical capacitor applications.

Science.gov (United States)

Kim, Ji-Young; Kim, Kwang-Heon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Park, Sang-Hoon; Kim, Kwang-Bum

2013-08-07

An in situ chemical synthesis approach has been developed to prepare ruthenium oxide/reduced graphene oxide (RGO) nanocomposites. It is found that as the C/O ratio increases, the number density of RuO2 nanoparticles decreases, because the chemical interaction between the Ru ions and the oxygen-containing functional groups provides anchoring sites where the nucleation of particles takes place. For electrochemical capacitor applications, the microwave-hydrothermal process was carried out to improve the conductivity of RGO in RuO2/RGO nanocomposites. The significant improvement in capacitance and high rate capability might result from the RuO2 nanoparticles used as spacers that make the interior layers of the reduced graphene oxide electrode available for electrolyte access.

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.)

Rhodium platings – experimental study

OpenAIRE

Rudolf, R.; Budić, B.; Stamenković, D.; Čolić, M.; Ivanič, A.; Kosec, B.

2013-01-01

Modern rhodium plating solutions are based on either sulphate or phosphate. Although in theory there are four possible combinations, in practice only three different rhodium electrolytes are used. These are based on dilutions of rhodium sulphate or phosphate concentrates with added sulphuric or phosphoric acid. These processes are be discussed in this paper with a demonstration of Rh platings in the Slovenian firm Zlatarna Celje d.d.

Correlation potential of a test ion near a strongly charged plate.

Science.gov (United States)

Lu, Bing-Sui; Xing, Xiangjun

2014-03-01

We analytically calculate the correlation potential of a test ion near a strongly charged plate inside a dilute m:-n electrolyte. We do this by calculating the electrostatic Green's function in the presence of a nonlinear background potential, the latter having been obtained using the nonlinear Poisson-Boltzmann theory. We consider the general case where the dielectric constants of the plate and the electrolyte are distinct. The following generic results emerge from our analyses: (1) If the distance to the plate Δz is much larger than a Gouy-Chapman length, the plate surface will behave effectively as an infinitely charged surface, and the dielectric constant of the plate effectively plays no role. (2) If Δz is larger than a Gouy-Chapman length but shorter than a Debye length, the correlation potential can be interpreted in terms of an image charge that is three times larger than the source charge. This behavior is independent of the valences of the ions. (3) The Green's function vanishes inside the plate if the surface charge density is infinitely large; hence the electrostatic potential is constant there. In this respect, a strongly charged plate behaves like a conductor plate. (4) If Δz is smaller than a Gouy-Chapman length, the correlation potential is dominated by the conventional image charge due to the dielectric discontinuity at the interface. (5) If Δz is larger than a Debye length, the leading order behavior of the correlation potential will depend on the valences of the ions in the electrolyte. Furthermore, inside an asymmetric electrolyte, the correlation potential is singly screened, i.e., it undergoes exponential decay with a decay width equal to the Debye length.

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

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)

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)

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)

Nickel hexacyanoferrate, a versatile intercalation host for divalent ions from nonaqueous electrolytes

Science.gov (United States)

Lipson, Albert L.; Han, Sang-Don; Kim, Soojeong; Pan, Baofei; Sa, Niya; Liao, Chen; Fister, Timothy T.; Burrell, Anthony K.; Vaughey, John T.; Ingram, Brian J.

2016-09-01

New energy storage chemistries based on Mg ions or Ca ions can theoretically improve both the energy density and reduce the costs of batteries. To date there has been limited progress in implementing these systems due to the challenge of finding a high voltage high capacity cathode that is compatible with an electrolyte that can plate and strip the elemental metal. In order to accelerate the discovery of such a system, model systems are needed that alleviate some of the issues of incompatibility. This report demonstrates the ability of nickel hexacyanoferrate to electrochemically intercalate Mg, Ca and Zn ions from a nonaqueous electrolyte. This material has a relatively high insertion potential and low overpotential in the electrolytes used in this study. Furthermore, since it is not an oxide based cathode it should be able to resist attack by corrosive electrolytes such as the chloride containing electrolytes that are often used to plate and strip magnesium. This makes it an excellent cathode for use in developing and understanding the complex electrochemistry of multivalent ion batteries.

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.

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.

Novel Nonflammable Electrolytes for Secondary Magnesium Batteries and High Voltage Electrolytes for Electrochemcial Supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Dixon, Brian

2008-12-30

Magnesium has been used successfully in primary batteries, but its use in rechargeable cells has been stymied by the lack of suitable non-aqueous electrolyte that can conduct Mg+2 species, combined with poor stripping and plating properties. The development of a suitable cathode material for rechargeable magnesium batteries has also been a roadblock, but a nonflammable electrolyte is key. Likewise, the development of safe high voltage electrochemical supercapaitors has been stymied by the use of flammable solvents in the liquid electrolyte; to wit, acetonitrile. The purpose of the research conducted in this effort was to identify useful compositions of magnesium salts and polyphosphate solvents that would enable magnesium ions to be cycled within a secondary battery design. The polyphosphate solvents would provide the solvent for the magnesium salts while preventing the electrolyte from being flammable. This would enable these novel electrolytes to be considered as an alternative to THF-based electrolytes. In addition, we explored several of these solvents together with lithium slats for use as high voltage electrolytes for carbon-based electrochemical supercapacitors. The research was successful in that: 1) Magnesium imide dissolved in a phosphate ester solvent that contains a halogented phosphate ester appears to be the preferred electrolyte for a rechargeable Mg cell. 2) A combination of B-doped CNTs and vanadium phosphate appear to be the cathode of choice for a rechargeable Mg cell by virtue of higher voltage and better reversibility. 3) Magnesium alloys appear to perform better than pure magnesium when used in combination with the novel polyphosphate electrolytes. Also, this effort has established that Phoenix Innovation's family of phosphonate/phosphate electrolytes together with specific lithium slats can be used in supercapacitor systems at voltages of greater than 10V.

Rhodium platings – experimental study

Directory of Open Access Journals (Sweden)

R. Rudolf

2013-07-01

Full Text Available Modern rhodium plating solutions are based on either sulphate or phosphate. Although in theory there are four possible combinations, in practice only three different rhodium electrolytes are used. These are based on dilutions of rhodium sulphate or phosphate concentrates with added sulphuric or phosphoric acid. These processes are be discussed in this paper with a demonstration of Rh platings in the Slovenian firm Zlatarna Celje d.d.

Effects of supporting electrolytes on copper electroplating for filling through-hole

International Nuclear Information System (INIS)

Chen, Chien-Hung; Lu, Chun-Wei; Huang, Su-Mei; Dow, Wei-Ping

2011-01-01

Highlights: → The through-holes of a printed circuit boardare directly filled by copper electroplating using single organic additive. → The inhibiting strength of the additive on copper deposition is related to a supporting electrolyte. → H 2 SO 4 strongly enhances the inhibiting strength of the additive and results in a conformal deposition, whereas Na 2 SO 4 and K 2 SO 4 do not affect the inhibiting strength and lead to good filling capability. - Abstract: The filling of micron through-holes (THs) in a printed circuit board (PCB) by copper electroplating was investigated in this study. The role of supporting electrolytes, such as H 2 SO 4 , Na 2 SO 4 and K 2 SO 4 , was explored using practical TH filling plating and linear-sweep voltammetry (LSV) analysis of plating solutions. The copper could selectively fill THs using one organic additive, namely, tetranitroblue tetrazolium chloride (TNBT), as an inhibitor. The inhibiting strength of TNBT depended on the supporting electrolytes. Although H 2 SO 4 could enhance the inhibiting strength of TNBT, it also decreased the filling capability of the copper plating solution; Na 2 SO 4 and K 2 SO 4 did not enhance the inhibiting strength of TNBT but they increased the filling capability of the copper plating solution. Additionally, the protons could chemically interact with TNBT to form precipitate, whereas sodium and potassium ions did not easily interact with TNBT. The filling capability of the copper plating solution using Na 2 SO 4 and K 2 SO 4 as supporting electrolytes could be greatly improved by adding a small amount of bis(3-sulfopropyl)-disulfide (SPS) and poly(ethylene glycol) (PEG) with a molecular weight of 600.

Electrolyte loss mechanism of molten carbonate fuel cells. 1; Yoyu tansan`engata nenryo denchi ni okeru denkaishitsu loss kiko ni tsuite. 1

Energy Technology Data Exchange (ETDEWEB)

Sonai, A; Murata, K [Toshiba Research and Development Center, Kawasaki (Japan)

1993-11-01

During a single-cell disassembly test of molten carbonate fuel cells having been operated for 90 hours to 5500 hours, correlativity was discovered between decrease in the retained amount of electrolyte due to decrease in pore capacity of electrodes and electrolyte plates and the electrolyte loss. The electrolyte loss amount cannot be explained with the conventional mechanisms, thereby a new model was proposed. The cathode has shown very little change in the capacity change in pores with diameters smaller than 2 {mu}m per unit area. The anode has remained almost constant after 1000 hours, but the electrolyte plates have shown remarkable decrease. Therefore, it is possible to estimate that the electrolyte plates should have been the major cause for the electrolyte loss. The result of measuring the electrolyte loss amount agreed well with that estimated using pore capacity curves. This fact suggests that the electrolyte loss can be explained by a new mechanism that hypothesizes the existence of a largest size of retaining pores that can support carbonates and defines that the electrolyte loss is generated from decrease in the pore capacity. 7 refs., 8 figs., 1 tab.

2017 Bipolar Plate Workshop Summary Report

Energy Technology Data Exchange (ETDEWEB)

Kopasz, John P. [Argonne National Lab. (ANL), Argonne, IL (United States); Benjamin, Thomas G. [Argonne National Lab. (ANL), Argonne, IL (United States); Schenck, Deanna [Argonne National Lab. (ANL), Argonne, IL (United States)

2017-08-17

The Bipolar Plate (BP) Workshop was held at USCAR1 in Southfield, Michigan on February 14, 2017 and included 63 participants from industry, government agencies, universities, and national laboratories with expertise in the relevant fields. The objective of the workshop was to identify research and development (R&D) needs, in particular early-stage R&D, for bipolar plates for polymer electrolyte membrane (PEM) fuel cells for transportation applications. The focus of the workshop was on materials, manufacturing, and design aspects of bipolar plates with the goal of meeting DOE’s 2020 bipolar plate targets. Of special interest was the cost target of ≤$3/kW for the bipolar plate.

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

Impedance spectroscopic analysis of composite electrode from activated carbon/conductive materials/ruthenium oxide for supercapacitor applications

Energy Technology Data Exchange (ETDEWEB)

Taer, E.; Awitdrus,; Farma, R. [School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia); Department of Physics, Faculty of Mathematics and Natural Sciences, University of Riau, 28293 Pekanbaru, Riau (Indonesia); Deraman, M., E-mail: madra@ukm.my; Talib, I. A.; Ishak, M. M.; Omar, R.; Dolah, B. N. M.; Basri, N. H.; Othman, M. A. R. [School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia); Kanwal, S. [ICCBS, H.E.J. Research Institute of Chemistry, University of Karachi, 75270 Karachi (Pakistan)

2015-04-16

Activated carbon powders (ACP) were produced from the KOH treated pre-carbonized rubber wood sawdust. Different conductive materials (graphite, carbon black and carbon nanotubes (CNTs)) were added with a binder (polivinylidene fluoride (PVDF)) into ACP to improve the supercapacitive performance of the activated carbon (AC) electrodes. Symmetric supercapacitor cells, fabricated using these AC electrodes and 1 molar H{sub 2}SO{sub 4} electrolyte, were analyzed using a standard electrochemical impedance spectroscopy technique. The addition of graphite, carbon black and CNTs was found effective in reducing the cell resistance from 165 to 68, 23 and 49 Ohm respectively, and increasing the specific capacitance of the AC electrodes from 3 to 7, 17, 32 F g{sup −1} respectively. Since the addition of CNTs can produce the highest specific capacitance, CNTs were chosen as a conductive material to produce AC composite electrodes that were added with 2.5 %, 5 % and 10 % (by weight) electro-active material namely ruthenium oxide; PVDF binder and CNTs contents were kept at 5 % by weight in each AC composite produced. The highest specific capacitance of the cells obtained in this study was 86 F g{sup −1}, i.e. for the cell with the resistance of 15 Ohm and composite electrode consists of 5 % ruthenium oxide.

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

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

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)

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.)

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.

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.

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.

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.)

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

Electric battery with gas-operated electrolyte flow. Elektrischer Akkumulator mit gasbetaetigter Elektrolytbewegung

Energy Technology Data Exchange (ETDEWEB)

Guetlich, K.F.; Kappus, W.; Zweigardt, H.; Eckardt, R.

1986-08-28

The invention relates to an electric accumulator with gas-operated electrolyte flow between electrode plates connected to form a plate block according to the principle of the mammoth pump. At least two supply pipes arranged parallel to each other and with connected gas supply are mounted to a base plate of non-conducting material. The base plate can be pushed in between plate block and housing wall. The base plate consists of two plastic foils of equal height and width the supply pipes and gas leads being formed by protrusions in the plastic foil.

Electric battery with gas-operated electrolyte flow. Elektrischer Akkumulator mit gasbetaetigter Elektrolytbewegung

Energy Technology Data Exchange (ETDEWEB)

Guetlich, K.F.; Kappus, W.; Zweigardt, H.; Eckardt, R.

1980-10-09

The invention relates to an electric accumulator with gas-operated electrolyte flow between electrode plates connected to form a plate block according to the principle of the mammoth pump. At least two supply pipes arranged parallel to each other and with connected gas supply are mounted to a base plate of non-conducting material. The base plate can be pushed in between plate block and housing wall. The base plate consists of two plastic foils of equal height and width the supply pipes and gas leads being formed by protrusions in the plastic foil.

Preparation, characterization and electrocatalytic behavior of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate hybrid film-modified electrodes

Energy Technology Data Exchange (ETDEWEB)

Chu, H.-W.; Thangamuthu, R. [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan (China); Chen, S.-M. [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan (China)], E-mail: smchen78@ms15.hinet.net

2008-02-15

Polynuclear mixed-valent hybrid films of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate (ZnO/ZnHCF-RuOHCF) have been deposited on electrode surfaces from H{sub 2}SO{sub 4} solution containing Zn(NO{sub 3}){sub 2}, RuCl{sub 3} and K{sub 3}[Fe(CN){sub 6}] by potentiodynamic cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements demonstrate the steady growth of hybrid film. Surface morphology of hybrid film was investigated using scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) data confirm existence of zinc oxide and ruthenium oxide hexacyanoferrate (RuOHCF) in the hybrid film. The effect of type of monovalent cations on the redox behavior of hybrid film was investigated. In pure supporting electrolyte, electrochemical responses of Ru{sup II/III} redox transition occurring at negative potential region resemble with that of a surface immobilized redox couple. The electrocatalytic activity of ZnO/ZnHCF-RuOHCF hybrid film was investigated towards oxidation of epinephrine, dopamine and L-cysteine, and reduction of S{sub 2}O{sub 8}{sup 2-} and SO{sub 5}{sup 2-} as well as IO{sub 3}{sup -} using cyclic voltammetry and rotating ring disc electrode (RRDE) techniques.

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.

Physical properties of molten carbonate electrolyte

Energy Technology Data Exchange (ETDEWEB)

Kojima, T.; Yanagida, M.; Tanimoto, K. [Osaka National Research Institute (Japan)] [and others

1996-12-31

Recently many kinds of compositions of molten carbonate electrolyte have been applied to molten carbonate fuel cell in order to avoid the several problems such as corrosion of separator plate and NiO cathode dissolution. Many researchers recognize that the addition of alkaline earth (Ca, Sr, and Ba) carbonate to Li{sub 2}CO{sub 3}-Na{sub 2}CO{sub 3} and Li{sub 2}CO{sub 3}-K{sub 2}CO{sub 3} eutectic electrolytes is effective to avoid these problems. On the other hand, one of the corrosion products, CrO{sub 4}{sup 2-} ion is found to dissolve into electrolyte and accumulated during the long-term MCFC operations. This would affect the performance of MCFC. There, however, are little known data of physical properties of molten carbonate containing alkaline earth carbonates and CrO{sub 4}{sup 2-}. We report the measured and accumulated data for these molten carbonate of electrical conductivity and surface tension to select favorable composition of molten carbonate electrolytes.

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

Synthesis and electrochemical performance of ruthenium oxide-coated carbon nanofibers as anode materials for lithium secondary batteries

Energy Technology Data Exchange (ETDEWEB)

Hyun, Yura; Choi, Jin-Yeong [Department of Chemistry, Keimyung University (Korea, Republic of); Park, Heai-Ku [Department of Chemical Engineering, Keimyung University (Korea, Republic of); Lee, Chang-Seop, E-mail: surfkm@kmu.ac.kr [Department of Chemistry, Keimyung University (Korea, Republic of)

2016-12-01

Highlights: • Ruthenium oxide (RuO{sub 2}) coated carbon nanofibers (CNFs) on Ni foam were synthesized by chemical vapor deposition method and applied as anode materials of Li secondary batteries. • When RuO{sub 2}/CNFs/Ni foam was used as the anode material, initial capacity was improved from 276 mAh/g to 494 mAh/g with retention rate of 47.4% after 30 cycles. - Abstract: In this study, ruthenium oxide (RuO{sub 2}) coated carbon nanofibers (CNFs) were synthesized and applied as anode materials of Li secondary batteries. The CNFs were grown on Ni foam via chemical vapor deposition (CVD) method after CNFs/Ni foam was put into the 0.01 M RuCl{sub 3} solution. The ruthenium oxide-coated CNFs/Ni foam was dried in a dryer at 80 °C. The morphologies, compositions, and crystal quality of RuO{sub 2}/CNFs/Ni foam were characterized by SEM, EDS, XRD, Raman spectroscopy, and XPS. The electrochemical characteristics of RuO{sub 2}/CNFs/Ni foam as anode of Li secondary batteries were investigated using three-electrode cell. The RuO{sub 2}/CNFs/Ni foam was directly employed as a working electrode without any binder, and lithium foil was used as the counter and reference electrodes. LiClO{sub 4} (1 M) was employed as electrolyte and dissolved in a mixture of propylene carbonate (PC): ethylene carbonate (EC) in a 1:1 volume ratio. The galvanostatic charge/discharge cycling and cyclic voltammetry measurements were carried out at room temperature by using a battery tester. In particular, synthesized RuO{sub 2}/CNFs/Ni foam showed the highest retention rate (47.4%). The initial capacity (494 mAh/g) was reduced to 234 mAh/g after 30 cycles.

Synthesis and electrochemical performance of ruthenium oxide-coated carbon nanofibers as anode materials for lithium secondary batteries

International Nuclear Information System (INIS)

Hyun, Yura; Choi, Jin-Yeong; Park, Heai-Ku; Lee, Chang-Seop

2016-01-01

Highlights: • Ruthenium oxide (RuO_2) coated carbon nanofibers (CNFs) on Ni foam were synthesized by chemical vapor deposition method and applied as anode materials of Li secondary batteries. • When RuO_2/CNFs/Ni foam was used as the anode material, initial capacity was improved from 276 mAh/g to 494 mAh/g with retention rate of 47.4% after 30 cycles. - Abstract: In this study, ruthenium oxide (RuO_2) coated carbon nanofibers (CNFs) were synthesized and applied as anode materials of Li secondary batteries. The CNFs were grown on Ni foam via chemical vapor deposition (CVD) method after CNFs/Ni foam was put into the 0.01 M RuCl_3 solution. The ruthenium oxide-coated CNFs/Ni foam was dried in a dryer at 80 °C. The morphologies, compositions, and crystal quality of RuO_2/CNFs/Ni foam were characterized by SEM, EDS, XRD, Raman spectroscopy, and XPS. The electrochemical characteristics of RuO_2/CNFs/Ni foam as anode of Li secondary batteries were investigated using three-electrode cell. The RuO_2/CNFs/Ni foam was directly employed as a working electrode without any binder, and lithium foil was used as the counter and reference electrodes. LiClO_4 (1 M) was employed as electrolyte and dissolved in a mixture of propylene carbonate (PC): ethylene carbonate (EC) in a 1:1 volume ratio. The galvanostatic charge/discharge cycling and cyclic voltammetry measurements were carried out at room temperature by using a battery tester. In particular, synthesized RuO_2/CNFs/Ni foam showed the highest retention rate (47.4%). The initial capacity (494 mAh/g) was reduced to 234 mAh/g after 30 cycles.

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

Design of a Free-Ruthenium In2S3 Crystalline Photosensitized Solar Cell

Directory of Open Access Journals (Sweden)

Byeong Sub Kwak

2014-01-01

Full Text Available A new type of sulfide-based, solid-state dye material that is sensitive to visible radiation was assessed as a potential replacement for commercial ruthenium complex dyes in a dye-sensitized solar cell (DSSC assembly. The In2S3 crystals on the surface of the TiO2 bottom blocking layer were grown as a solid-state dye material. Scanning electron microscopy of In2S3 revealed a microsized, 3D-connected sheet-like shape, which was confirmed by X-ray diffraction to be a beta-structure. The efficiency of the dye-sensitized solar cells assembled with a layer grown with In2S3 increased with increasing In2S3 mole concentrations to 0.05 M (1.02% but decreased at concentrations greater than 0.6~0.8%. This suggests that crystalline In2S3 acts as a dye sensitized to visible radiation, but the short-circuit current density is too low compared to the commercially available ruthenium dye. This suggests that In2S3 crystals did not grow densely but were bulk-grown with large pores, resulting in a smaller amount of In2S3 per unit area. Two IPCE curves were observed, which were assigned to TiO2 and In2S3, meaning that the TiO2 surfaces were covered completely with In2S3 crystals. The exposure of TiO2 eventually leads to a reaction with the electrolytes, resulting in lower quantum efficiency.

Electroplating of gold using a sulfite-based electrolyte

NARCIS (Netherlands)

Smalbrugge, E.; Jacobs, B.; Falcone, S.; Geluk, E.J.; Karouta, F.; Leijtens, X.J.M.; Besten, den J.H.

2000-01-01

Electroplating of gold is often used in optoelectronic and microelectronic devices for air-bridges, heat-sinks or gold-bumps for flip-chip techniques. The gold-cyanide electrolytes, which are commonly used in gold-electroplating, are toxic and attack resist patterns causing cracks during the plating

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

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.

Nickel-foam-supported ruthenium oxide/graphene sandwich composite constructed via one-step electrodeposition route for high-performance aqueous supercapacitors

Science.gov (United States)

Li, Meng; He, Hanwei

2018-05-01

A high-performance supercapacitor both considered high power and high energy density is needed for its applications such as portable electronics and electric vehicles. Herein, we construct a high-performance ruthenium oxide/graphene (RuO2-ERG) composite directly grown on Ni foam through cyclic voltammetric deposition process. The RuO2-ERG composite with sandwich structure is achieved effectively from a mixed solution of graphene oxide and ruthenium trichloride in the -1.4 V to 1.0 V potential range at a scan rate of 5 mV s-1. The electrochemical performance is optimized by tuning the concentration of the ruthenium trichloride. This integrative RuO2-ERG composite electrode can effectively maintains the accessible surface for redox reaction and stable channels for electrolyte penetration, leading to an improved electrochemical performance. Symmetrical aqueous supercapacitors based on RuO2-ERG electrodes exhibit a wider operational voltage window of 1.5 V. The optimized RuO2-ERG electrode displays a superior specific capacitance with 89% capacitance retention upon increasing the current density by 50 times. A high energy density of 43.8 W h kg-1 at a power density of 0.75 kW kg-1 is also obtained, and as high as 39.1 W h kg-1 can be retained at a power density of 37.5 kW kg-1. In addition, the capacitance retention is still maintained at 92.8% even after 10,000 cycles. The excellent electrochemical performance, long-term cycle stability, and the ease of preparation demonstrate that this typical RuO2-ERG electrode has great potentialities to develop high-performance supercapacitors.

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

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.

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)

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.

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

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

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.)

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.

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.)

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)

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)

Effect of nickel plating upon tensile tests of uranium--0.75 titanium alloy

International Nuclear Information System (INIS)

Hemperly, V.C.

1975-01-01

Electrolytic-nickel-plated specimens of uranium-0.75 wt percent titanium alloy were tested in air at 20 and 100 percent relative humidities. Tensile-test ductility values were lowered by a high humidity and also by nickel plating alone. Baking the nickel-plated specimens did not eliminate the ductility degradation. Embrittlement because of nickel plating was also evident in tensile tests at -34 0 C. (U.S.)

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.)

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...

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.

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.

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.

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.)

A study of the behavior of a cathode film formed in chromium plating with radioactive tracers

International Nuclear Information System (INIS)

Yoshida, Katsuyoshi; Suzuki, Akihira; Doi, Kazuyuki; Arai, Katsutoshi

1979-01-01

The behavior and composition of a cathode film formed on a steel cathode during chromium plating were studied with radioactive tracers. A special cell with a rapid washing compartment was used for preventing the cathode film from dissolving in electrolyte after plating. The cathode film was composed of two layers. The outer layer facing to the electrolyte had a loose structure and contained more sulfuric anions than the inner layer, for sulfuric acid probably concentrated in the outer layer. This outer layer is called L-film in this paper. The L-film was easily dissolved in the electrolyte solution. The inner layer (called C-film, compact film) was stable against electrolytes and contained less anions than that of L-film. The C-film had a thickness equivalent to 5 mg/m 2 and the concentration of anions unaffected by the composition of electrolytes. The C-film was not reduced to metallic chromium, but it remained in the cathode film during and after plating. This suggests that chromic acid in the cathode film is not reduced to metallic chromium, that metallic chromium is deposited from chromium complexes reaching the cathode surface through the cathode film, and that the complexes do not play a role on the construction of the cathode film. (author)

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.

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

Hydrothermal synthesis of hydrous ruthenium oxide/graphene sheets for high-performance supercapacitors

International Nuclear Information System (INIS)

Lin, Na; Tian, Jianhua; Shan, Zhongqiang; Chen, Kuan; Liao, Wenming

2013-01-01

Ruthenium oxide particles were supported on graphene sheets (GS) by hydrothermal and low temperature annealing process. The GS was prepared from graphene oxide by an expansion process and different expanding temperatures were studied and polystyrene sulfonate sodium was used as dispersion agent of hydrophobic GS. Different Ru content of the RuO 2 /GS composites on the influence of the electrochemical properties was studied. Atomic force microscope analysis was applied to test the layers of GS. The morphology of GS and RuO 2 /GS composites were confirmed by field emission transmission electron microscopy analysis. X-ray diffraction, Raman spectroscopy and liquid-nitrogen cryosorption were used to characterize the structure and morphology of the GS and RuO 2 /GS. The RuO 2 /GS (Ru:40 wt%) composites used as electrode materials of supercapacitors exhibited a specific capacitance of 551 F/g at 1 A/g in 1 M H 2 SO 4 electrolyte. Besides, both the rate capability and cycle performance of RuO 2 /GS composites had a great improvement compared with GS

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…

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

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.

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

The influence of composition of fluoride electrolytes and conditions of the electrodeposition on some properties of tellurium

International Nuclear Information System (INIS)

Bugelis, V.M.; Kum, G.N.; Abrarov, O.A.; Madumarov, A.; Navalikhin, L.V.; Ajnakulov, Eh.B.

1981-01-01

Effect of electrolytic bath content, cathode current density, illumination and temperature on specific resistance, photosensitivity, structure and chemical purity of plated tellurium coatings is studied. Deposition is realized from moderately acid fluoride electrolytes at the constant temperature with a platinum working electrode. X-ray studies of precipitates obtained are carried out

Electrode structures of polymer-electrolyte fuel cells (PEFC). An electron microscopy approach to the characterization of the electrode structure of polymer electrolyte fuel cells

Energy Technology Data Exchange (ETDEWEB)

Scheiba, Frieder

2009-01-28

catalyst and catalyst support, but that it forms a complex structure consisting of fiber and film like structures in the pores of the electrode. In addition, the EF-TEM result delivered a strong indication for the infiltration of catalyst agglomerates by the polymer electrolyte. Furthermore, a new concept for the investigation of multi-component structures, consisting of the membrane, electrodes and gas di1usion layers (GDL) was developed. Thus it was possible to provide evidence for the intrusion of individual carbon fibers from the GDL into the electrode. In addition the influence of GDL structure on delamination of the electrode could be demonstrated. Another part of the work deals with the characterization of a novel platinum catalyst deposited on hydrous ruthenium oxide coated carbon nanotubes (CNT), which was developed in close cooperation with a Chinese partner at Tsinghua University (Beijing). (orig.)

A Study on Zinc-Iron Alloy Electrodeposition from a Chloride Electrolyte

DEFF Research Database (Denmark)

Jensen, Jens Dahl

1998-01-01

The electrodeposition of zinc-iron alloys from a chloride-based electrolyte has been studied using electrochemical polarisation techniques, Auger Electron Spectroscopy (AES), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDXA) and Computer Assisted Pulse Plating (CAPP...... this system ideal for production of compositional modulated alloy (CMA) electrodeposits. Chloride content, pH and agitation of the electrolyte have been observed to have a strong influence on the reaction at the cathode surface, just as the use of pulse reversal current during electrodeposition. A theory...

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.

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.

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...

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

Facile One-Pot Synthesis of Flower Like Cobalt Oxide Nanostructures on Nickel Plate and Its Supercapacitance Properties.

Science.gov (United States)

Kandasamy, N; Venugopal, T; Kannan, K

2018-06-01

A flower like cobalt oxide nanostructured thin film (Co2O3) on Nickel (Ni) plate as have been successfully developed via alcoholic Seed Layer assisted chemical bath Deposition (SLD) process. Through the controlled alkaline electrolytes, the flower and paddles like Co2O3 nanoarchitectures were formed. The prepared thin film was characterized by X-ray diffraction (XRD), scanning electron microscope with energy dispersive X-ray (SEM and EDX), Atomic Force Microscope (AFM), Raman spectroscopy techniques. Electron micrograph reveals the flower and paddles like nanostructured Co2O3 thin film deposited on Ni plates. The electrochemical characteristics were investigated using cyclic voltammetry (CV), charge-discharge and AC impedance spectroscopy in different aqueous electrolytes such as NaOH, KOH, and LiOH. The maximum specific capacitance of 856 Fg-1 was attained with 2 M KOH electrolyte with 2 mVs-1 of the Co2O3 thin film coated Ni plate at 80 °C using SLD method. The capacitance values obtained with various electrolytes are in the order of KOH > NaOH > LiOH. The results indicate that the present method is economical and the material is ecofriendly with enhanced capacitance property.

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

Macro- and microdistributions in electrodeposition of chromium and its alloys from electrolytes based on chronic acid: microdistribution and microdissipation ability of the electrolytes

International Nuclear Information System (INIS)

Kruglikov, S.S.; Kruglikova, E.S.

1996-01-01

The distribution of electrodeposited chromium and Cr-W, Cr-Mo, Cr-Ti, Cr-Zr alloys on a surface with a regular two-dimensional microprofile has been studied. The standard, self-regulating, supersulfate, tetrachromate and rough chrome-plating electrolytes, as well as electrolytes for Cr-Zr and Cr-Mo alloys production, feature practically uniform microdistribution. The conclusion is made that formation and effect of cathode film under stationary conditions of cathode process do not involve diffusion restrictions of cathode reaction rate, while the thickness of the cathode film is small as compared with the amplitude of the microprofiles studies. 6 refs., 4 figs., 3 tabs

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)

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.

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 ...

Electrochemiluminescent determination of nicotine based on tri(2,2'-bipyridyl) ruthenium (II) complex through flow injection analysis

International Nuclear Information System (INIS)

Lin Mengshan; Wang Junsheng; Lai Chienhung

2008-01-01

This paper describes the electrogenerated chemiluminescence (ECL) processes of Ru(bpy) 3 2+ /nicotine system at ITO working electrode. An ECL-based method for rapid and sensitive detection of nicotine in phosphate buffer solution at pH 8.0 is established. Strong ECL emission was observed at a positive potential of 1.4 V vs. Ag/AgCl. A possible ECL mechanism is proposed for the Ru(bpy) 3 2+ /nicotine system, the oxidation product of nicotine at the electrode surface reacts with the 3+ state of ruthenium bipyridyl (2+) complex and form ruthenium complex exited state ions and thus releases photons. Effect of pH (medium/electrolyte), working potential, buffer composition, buffer concentration, reactant and co-reactant (nicotine) concentration, flow rate and loop size on the ECL spectrum of the Ru(bpy) 3 2+ /nicotine were studied. At the optimized experimental conditions, lower detection limit for nicotine was observed as 1.2 nmol L -1 (S/N = 3). Linear relationship between ECL current and concentration of nicotine was observed (up to 100 μmol L -1 ) with R-value of 0.997. The relative standard deviation with 5 μmol L -1 concentration of nicotine for 20 analyses was only 1.4%. A 94% recovery rate was observed in a real sample analysis without any complications/disturbance in measurement. Interferences of humid acid, camphor and SDS were not observed in their presence in the sample solution. The established procedure for nicotine quantification manifests fascinating results and can be suggested for further applications

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)

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.

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)

Corrosion of Cast Iron Mill Plates in Wet Grinding

Directory of Open Access Journals (Sweden)

Anthony ANDREWS

2010-12-01

Full Text Available Corrosion studies were carried out on two different maize grinding plates. Maize was soaked in water for three days and the water decanted and used as electrolyte. Mass loss and pH measurements were carried out every 3 days for 15-day period. Results show that, for each plate, mass loss and pH increased with exposure time. Corrosion rates determined from mass loss data was found to be strongly dependent on pH. The observed behaviour may be explained in terms of the chemical composition and/or microstructures of the plates. Results are briefly discussed in terms of the contribution of corrosion to wear.

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...

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.

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.

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.

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...

Method to electrolytically precipitate metals onto zirconium objects

International Nuclear Information System (INIS)

Donaghy, R.E.

1978-01-01

Tubes and other formed bodies made of zirconium or zirconium alloys which serve to take up nuclear fuels, are plated by electrolytically depositing a metal film onto these in order to improve their mechanical and corrosion properties. The object is activated in a solution of ammonium bifluoride and sulphuric acid, whereby an electrically conducting solid and a loose layer is formed. This loose film is removed by using fluoboric acid or hydrofluoric silicic acid solution, ultrasonics, or strips of organic material (cotton, polyester, nylon). The plating of Cu, Ni, Cr is described in detail. The object is rinsed between the process steps with deionized water and finally degased at a temperature of 150-200 0 C. (IHOE) [de

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)

Performance of molten carbonate fuel cells with the electrolyte molded at low pressure (3) The stability of anode microlayers

Energy Technology Data Exchange (ETDEWEB)

Sonai, Atsuo; Suzuki, Nobukazu; Murata, Kenji; Shirogami, Tamotsu

1987-01-01

It is known that an addition of organic binder to the electrolyte layer which composes a fuel cell enables to produce a large plate of electrolyte even in low temperature and low pressure conditions. However, when the binder is volatilized, bores remain making poor performance as a sepa-rator plate of the reacting gas. In order to prevent the gas permeation, it is necessary to combine a double layered electrode with microporous layers on the electrode surface ajacent to the electrolyte layer. In this study, stability of microporous layers of the anode electrode was examined, and it was found that the microporous layers made by sintering Ni-powders was unstable and dissoluted, but the impregnation of such second element as Chromium oxide, Yttrium oxide, Aluminum oxide into the layer improved the stability. (10 figs, 1 tab, 6 refs)

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

Investigation of the effects of process sequence on the contact resistance characteristics of coated metallic bipolar plates for polymer electrolyte membrane fuel cells

Science.gov (United States)

Turan, Cabir; Cora, Ömer Necati; Koç, Muammer

2013-12-01

In this study, results of an investigation on the effects of manufacturing and coating process sequence on the contact resistance (ICR) of metallic bipolar plates (BPP) for polymer electrolyte membrane fuel cells (PEMFCs) are presented. Firstly, uncoated stainless steel 316L blanks were formed into BPP through hydroforming and stamping processes. Then, these formed BPP samples were coated with three different PVD coatings (CrN, TiN and ZrN) at three different thicknesses (0.1, 0.5 and 1 μm). Secondly, blanks of the same alloy were coated first with the same coatings, thickness and technique; then, they were formed into BPPs of the same shape and dimensions using the manufacturing methods as in the first group. Finally, these two groups of BPP samples were tested for their ICR to reveal the effect of process sequence. ICR tests were also conducted on the BPP plates both before and after exposure to corrosion to disclose the effect of corrosion on ICR. Coated-then-formed BPP samples exhibited similar or even better ICR performance than formed-then-coated BPP samples. Thus, manufacturing of coated blanks can be concluded to be more favorable and worth further investigation in quest of making cost effective BPPs for mass production of PEMFC.

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.

Electrochemiluminescent determination of nicotine based on tri(2,2'-bipyridyl) ruthenium (II) complex through flow injection analysis

Energy Technology Data Exchange (ETDEWEB)

Lin Mengshan [Department of Chemistry, Tamkang University, Tamsui 25137, Taiwan (China)], E-mail: mslin@mail.tku.edu.tw; Wang Junsheng; Lai Chienhung [Department of Chemistry, Tamkang University, Tamsui 25137, Taiwan (China)

2008-11-01

This paper describes the electrogenerated chemiluminescence (ECL) processes of Ru(bpy){sub 3}{sup 2+}/nicotine system at ITO working electrode. An ECL-based method for rapid and sensitive detection of nicotine in phosphate buffer solution at pH 8.0 is established. Strong ECL emission was observed at a positive potential of 1.4 V vs. Ag/AgCl. A possible ECL mechanism is proposed for the Ru(bpy){sub 3}{sup 2+}/nicotine system, the oxidation product of nicotine at the electrode surface reacts with the 3+ state of ruthenium bipyridyl (2+) complex and form ruthenium complex exited state ions and thus releases photons. Effect of pH (medium/electrolyte), working potential, buffer composition, buffer concentration, reactant and co-reactant (nicotine) concentration, flow rate and loop size on the ECL spectrum of the Ru(bpy){sub 3}{sup 2+}/nicotine were studied. At the optimized experimental conditions, lower detection limit for nicotine was observed as 1.2 nmol L{sup -1} (S/N = 3). Linear relationship between ECL current and concentration of nicotine was observed (up to 100 {mu}mol L{sup -1}) with R-value of 0.997. The relative standard deviation with 5 {mu}mol L{sup -1} concentration of nicotine for 20 analyses was only 1.4%. A 94% recovery rate was observed in a real sample analysis without any complications/disturbance in measurement. Interferences of humid acid, camphor and SDS were not observed in their presence in the sample solution. The established procedure for nicotine quantification manifests fascinating results and can be suggested for further applications.

Electrochemiluminescent determination of nicotine based on tri(2,2'-bipyridyl) ruthenium (II) complex through flow injection analysis

Energy Technology Data Exchange (ETDEWEB)

Lin, Meng Shan; Wang, Jun Sheng; Lai, Chien Hung [Department of Chemistry, Tamkang University, Tamsui 25137 (China)

2008-11-01

This paper describes the electrogenerated chemiluminescence (ECL) processes of Ru(bpy){sub 3}{sup 2+}/nicotine system at ITO working electrode. An ECL-based method for rapid and sensitive detection of nicotine in phosphate buffer solution at pH 8.0 is established. Strong ECL emission was observed at a positive potential of 1.4 V vs. Ag/AgCl. A possible ECL mechanism is proposed for the Ru(bpy){sub 3}{sup 2+}/nicotine system, the oxidation product of nicotine at the electrode surface reacts with the 3+ state of ruthenium bipyridyl (2+) complex and form ruthenium complex exited state ions and thus releases photons. Effect of pH (medium/electrolyte), working potential, buffer composition, buffer concentration, reactant and co-reactant (nicotine) concentration, flow rate and loop size on the ECL spectrum of the Ru(bpy){sub 3}{sup 2+}/nicotine were studied. At the optimized experimental conditions, lower detection limit for nicotine was observed as 1.2 nmol L{sup -1} (S/N = 3). Linear relationship between ECL current and concentration of nicotine was observed (up to 100 {mu}mol L{sup -1}) with R-value of 0.997. The relative standard deviation with 5 {mu}mol L{sup -1} concentration of nicotine for 20 analyses was only 1.4%. A 94% recovery rate was observed in a real sample analysis without any complications/disturbance in measurement. Interferences of humid acid, camphor and SDS were not observed in their presence in the sample solution. The established procedure for nicotine quantification manifests fascinating results and can be suggested for further applications. (author)

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.

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.

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)

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

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)

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.

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}.

Polymer Electrolytes

Science.gov (United States)

Hallinan, Daniel T.; Balsara, Nitash P.

2013-07-01

This review article covers applications in which polymer electrolytes are used: lithium batteries, fuel cells, and water desalination. The ideas of electrochemical potential, salt activity, and ion transport are presented in the context of these applications. Potential is defined, and we show how a cell potential measurement can be used to ascertain salt activity. The transport parameters needed to fully specify a binary electrolyte (salt + solvent) are presented. We define five fundamentally different types of homogeneous electrolytes: type I (classical liquid electrolytes), type II (gel electrolytes), type III (dry polymer electrolytes), type IV (dry single-ion-conducting polymer electrolytes), and type V (solvated single-ion-conducting polymer electrolytes). Typical values of transport parameters are provided for all types of electrolytes. Comparison among the values provides insight into the transport mechanisms occurring in polymer electrolytes. It is desirable to decouple the mechanical properties of polymer electrolyte membranes from the ionic conductivity. One way to accomplish this is through the development of microphase-separated polymers, wherein one of the microphases conducts ions while the other enhances the mechanical rigidity of the heterogeneous polymer electrolyte. We cover all three types of conducting polymer electrolyte phases (types III, IV, and V). We present a simple framework that relates the transport parameters of heterogeneous electrolytes to homogeneous analogs. We conclude by discussing electrochemical stability of electrolytes and the effects of water contamination because of their relevance to applications such as lithium ion batteries.

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

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, ...

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

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.

End plate for e.g. solid oxide fuel cell stack, sets thermal expansion coefficient of material to predetermined value

DEFF Research Database (Denmark)

2011-01-01

.05-0.3 mm. USE - End plate for solid oxide fuel cell stack (claimed). Can also be used in polymer electrolyte fuel cell stack and direct methanol fuel cell stack. ADVANTAGE - The robustness of the end plate is improved. The structure of the end plate is simplified. The risk of delamination of the stack...

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...

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

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.

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

Electrochemical deposition of Ni coating on Cu substrate in ethylene glycol + iCl/sub 2/.6H/sub 2/0 electrolyte characterization of Ni coatings

International Nuclear Information System (INIS)

Ghaffar, A.

2011-01-01

The primary objective of this work was to develop the technical know-how regarding the electrodeposition technique and the parameters affecting the quality of the electrodeposit such as electrolyte nature, its pH, current density, potential, substrate material etc. The ethylene glycol based organic electrolyte was employed to improve the aesthetics, surface and structural properties of nickel electroplatings. For the purpose of achieving improvements in nickel plating, a comparative work-study was carried out using aqueous and organic electrolytes. The voltammetric experiments were performed to find out the electroactive potential domain of ethylene glycol electrolyte, or in other words, to get the current density and potential ranges suitable for electrodeposition of nickel on copper substrate. Electroplating was carried out galvanostatically at different current densities and concentrations to find out the quality of Ni electrodeposit in both aqueous and organic electrolytes. The most suited electrolyte concentration (0.6 M hydrated nickel chloride dissolved in corresponding electrolytic solvent) and current density (1 mA/cm/sup 2/) were chosen to carry out nickel plating in aqueous electrolyte as well as in ethylene glycol electrolyte. Subsequently, current efficiencies were calculated for both electrolytes to find out the improvement in the quality of Ni deposit. Finally, the material characterization techniques such as X-ray diffraction, scanning electron microscopy, atomic force microscopy and adhesion testing were performed to fully access the composition, structure and surface morphology of nickel coating. (author)

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

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

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

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)

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)

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

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.

Electrolytic Recovery of Nickel from Spent Electroless Nickel Bath Solution

Directory of Open Access Journals (Sweden)

R. Idhayachander

2010-01-01

Full Text Available Plating industry is one of the largest polluting small scale industries and nickel plating is among the important surface finishing process in this industry. The waste generated during this operation contains toxic nickel. Nickel removal and recovery is of great interest from spent bath for environmental and economic reasons. Spent electroless nickel solution from a reed relay switch manufacturing industry situated in Chennai was taken for electrolytic recovery of nickel. Electrolytic experiment was carried out with mild steel and gold coated mild steel as cathode and the different parameters such as current density, time, mixing and pH of the solution were varied and recovery and current efficiency was studied. It was noticed that there was an increase in current efficiency up to 5 A/dm2 and after that it declines. There is no significant improvement with mixing but with modified cathode there was some improvement. Removal of nickel from the spent electroless nickel bath was 81.81% at 5 A/dm2 and pH 4.23. Under this condition, the content of nickel was reduced to 0.94 g/L from 5.16 g/L. with 62.97% current efficiency.

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

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.

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

Corrosion Behavior of Nickel-Plated Alloy 600 in High Temperature Water

International Nuclear Information System (INIS)

Kim, Ji Hyun; Hwang, Il Soon

2008-01-01

In this paper, electrochemical and microstructural characteristics of nickel-plated Alloy 600 wee investigated in order to identify the performance of electroless Ni-plating on Alloy 600 in high-temperature aqueous condition with the comparison of electrolytic nickel-plating. For high temperature corrosion test of nickel-plated Alloy 600, specimens were exposed for 770 hours to typical PWR primary water condition. During the test, open circuit potentials (OCP's) of all specimens were measured using a reference electrode. Also, resistance to flow accelerated corrosion (FAC) test was examined in order to check the durability of plated layers in high-velocity flow environment at high temperature. After exposures to high flow rate aqueous condition, the integrity of surfaces was confirmed by using both scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). For the field application, a remote process for electroless nickel-plating was demonstrated using a plate specimen with narrow gap on a laboratory scale. Finally, a practical seal design was suggested for more convenient application

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.

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.

Electrolyte Chemistry for Simultaneous Stabilization of Potassium Metal and Superoxide in K-O₂ Batteries.

Science.gov (United States)

Xiao, Neng; Gourdin, Gerald; Wu, Yiying

2018-05-22

In the superoxide batteries based on O2/O2- redox chemistry, identifying an electrolyte to stabilize both alkali metal and superoxide remains challenging due to their reactivity towards electrolyte components. Bis(fluorosulfonyl)imide (FSI-) has been recognized as a "magical anion" for passivating alkali metals. Herein, we illustrate the chemical reactions between FSI- and superoxide, and the resultant dilemma when considering an anode-compatible electrolyte vs. a cathode-compatible one in K-O2 batteries. On one side, the KFSI-dimethoxyethane (DME) electrolyte passivates the potassium metal anode via the cleavage of S-F bond and formation of a KF-rich solid electrolyte interface (SEI). Nevertheless, the KFSI salt is chemically unstable due to the nucleophilic attack by superoxide and/or hydroxide species. On the other hand, potassium bis(trifluorosulfonyl)imide (KTFSI) is stable for KO2, but results in mossy deposition and irreversible plating and stripping. In order to circumvent this dilemma, we develop an artificial SEI for K metal anode to achieve long cycle-life K-O2 batteries. This work contributes to the understanding of electrolyte chemistry and guides the development of stable electrolytes and artificial SEI in metal-O2 batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Electrolyte for batteries with regenerative solid electrolyte interface

Science.gov (United States)

Xiao, Jie; Lu, Dongping; Shao, Yuyan; Bennett, Wendy D.; Graff, Gordon L.; Liu, Jun; Zhang, Ji-Guang

2017-08-01

An energy storage device comprising: an anode; and a solute-containing electrolyte composition wherein the solute concentration in the electrolyte composition is sufficiently high to form a regenerative solid electrolyte interface layer on a surface of the anode only during charging of the energy storage device, wherein the regenerative layer comprises at least one solute or solvated solute from the electrolyte composition.

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.

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)

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

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.

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.

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 ...

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...

Introduction of a cation in aqueous solution by electrolytic dissolution of metal. Applications to the decontamination of radioactive effluents

International Nuclear Information System (INIS)

Gauchon, Jean-Paul

1979-01-01

This research thesis aims at comparing results obtained in chemical decontamination of radioactive effluents with a metallic cation introduced by metal electro-dissolution or by dose addition. After an overview of methods used for the purification of radioactive effluents and a more precise presentation of chemical co-precipitation, the author reports preliminary tests of the application of chemical co-precipitation to the decontamination of radioactive effluents, reports the analysis of iron, zinc and copper behaviour in aqueous environment by means of thermodynamic diagrams and current-voltage curves. He reports the design and use of two electro-dissolution sets, and the application of copper electrolytic dissolution to the elimination of ruthenium in radioactive effluents. He finally addresses the purification treatment of effluents of nuclear reactors

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.

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.

Fluoroethylene Carbonate-Based Electrolyte with 1 M Sodium Bis(fluorosulfonyl)imide Enables High-Performance Sodium Metal Electrodes.

Science.gov (United States)

Lee, Yongwon; Lee, Jaegi; Lee, Jeongmin; Kim, Koeun; Cha, Aming; Kang, Sujin; Wi, Taeung; Kang, Seok Ju; Lee, Hyun-Wook; Choi, Nam-Soon

2018-05-02

Sodium (Na) metal anodes with stable electrochemical cycling have attracted widespread attention because of their highest specific capacity and lowest potential among anode materials for Na batteries. The main challenges associated with Na metal anodes are dendritic formation and the low density of deposited Na during electrochemical plating. Here, we demonstrate a fluoroethylene carbonate (FEC)-based electrolyte with 1 M sodium bis(fluorosulfonyl)imide (NaFSI) salt for the stable and dense deposition of the Na metal during electrochemical cycling. The novel electrolyte combination developed here circumvents the dendritic Na deposition that is one of the primary concerns for battery safety and constructs the uniform ionic interlayer achieving highly reversible Na plating/stripping reactions. The FEC-NaFSI constructs the mechanically strong and ion-permeable interlayer containing NaF and ionic compounds such as Na 2 CO 3 and sodium alkylcarbonates.

Chemical stability of {gamma}-butyrolactone-based electrolytes for aluminium electrolytic capacitors

Energy Technology Data Exchange (ETDEWEB)

Ue, Makoto [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Takeda, Masayuki [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Suzuki, Yoko [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Mori, Shoichiro [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan)

1996-06-01

{gamma}-Butyrolactone-based electrolytes have been used as the operating electrolytes for aluminum electrolytic capacitors. The chemical stability of these electrolytes at elevated temperatures has been examined by monitoring the decrease in their electrolytic conductivities. The deteriorated electrolytes were analyzed by gas and liquid chromatography and the conductivity decrease was directly correlated with the loss of acid components. In quaternary ammonium hydrogen maleate/{gamma}-butyrolactone electrolytes, the maleate anion decomposed by decarboxylation resulting in a complex polymer containing polyester and polyacrylate structures. Quaternary ammonium benzoate/{gamma}-butyrolactone electrolytes decomposed by SN2 reactions giving alkyl benzoates and trialkylamines. The deterioration of the carboxylate salt/{gamma}-butyrolactone electrolytes was accelerated by electrolysis. (orig.)

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

Electrolyte creepage barrier for liquid electrolyte fuel cells

Science.gov (United States)

Li, Jian [Alberta, CA; Farooque, Mohammad [Danbury, CT; Yuh, Chao-Yi [New Milford, CT

2008-01-22

A dielectric assembly for electrically insulating a manifold or other component from a liquid electrolyte fuel cell stack wherein the dielectric assembly includes a substantially impermeable dielectric member over which electrolyte is able to flow and a barrier adjacent the dielectric member and having a porosity of less than 50% and greater than 10% so that the barrier is able to measurably absorb and chemically react with the liquid electrolyte flowing on the dielectric member to form solid products which are stable in the liquid electrolyte. In this way, the barrier inhibits flow or creepage of electrolyte from the dielectric member to the manifold or component to be electrically insulated from the fuel cell stack by the dielectric assembly.

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

Interfacial stability and electrochemical behavior of Li/LiFePO4 batteries using novel soft and weakly adhesive photo-ionogel electrolytes

Science.gov (United States)

Aidoud, D.; Etiemble, A.; Guy-Bouyssou, D.; Maire, E.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

2016-10-01

We have developed flexible polymer-gel electrolytes based on a polyacrylate cross-linked matrix that confines an ionic liquid doped with a lithium salt. Free-standing solid electrolyte membrane is obtained after UV photo-polymerization of acrylic monomers dissolved inside the ionic liquid/lithium salt mixture. The liquid precursor of the photo-ionogel may also be directly deposited onto porous composite electrode, which results in all-solid state electrode/electrolyte stacking after UV illumination. Minor variations in the polymer component of the electrolyte formulation significantly affect the electrochemical behavior in LiFePO4/lithium and lithium/lithium cells. The rate performance increases with an increase of the ionic conductivity, which decreases with the polymer content and decreases with increasing oxygen content in the polyacrylate matrix. Their fairly low modulus endow them weak and beneficial pressure-sensitive-adhesive character. X-Rays Tomography shows that the solid-state photo-ionogel electrolytes keep their integrity upon cycling and that their surface remains smooth. The coulombic efficiency of LiFePO4/lithium cells increases with an increase of the adhesive strength of the photo-ionogel, suggesting a relationship between the contact intimacy at the lithium/photo-ionogel interface and the efficiency of the lithium striping/plating. In lithium/lithium cells, only the photo-ionogels with the higher adhesion strength are able to allow the reversible striping/plating of lithium.

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.

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

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.

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.

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

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

New materials for polymer electrolyte membrane fuel cell current collectors

Science.gov (United States)

Hentall, Philip L.; Lakeman, J. Barry; Mepsted, Gary O.; Adcock, Paul L.; Moore, Jon M.

Polymer Electrolyte Membrane Fuel cells for automotive applications need to have high power density, and be inexpensive and robust to compete effectively with the internal combustion engine. Development of membranes and new electrodes and catalysts have increased power significantly, but further improvements may be achieved by the use of new materials and construction techniques in the manufacture of the bipolar plates. To show this, a variety of materials have been fabricated into flow field plates, both metallic and graphitic, and single fuel cell tests were conducted to determine the performance of each material. Maximum power was obtained with materials which had lowest contact resistance and good electrical conductivity. The performance of the best material was characterised as a function of cell compression and flow field geometry.

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.

Tailoring the electrode-electrolyte interface of Solid Oxide Fuel Cells (SOFC) by laser micro-patterning to improve their electrochemical performance

Science.gov (United States)

Cebollero, J. A.; Lahoz, R.; Laguna-Bercero, M. A.; Larrea, A.

2017-08-01

Cathode activation polarisation is one of the main contributions to the losses of a Solid Oxide Fuel Cell. To reduce this loss we use a pulsed laser to modify the surface of yttria stabilized zirconia (YSZ) electrolytes to make a corrugated micro-patterning in the mesoscale. The beam of the laser source, 5 ns pulse width and emitting at λ = 532 nm (green region), is computer-controlled to engrave the selected micro-pattern on the electrolyte surface. Several laser scanning procedures and geometries have been tested. Finally, we engrave a square array with 28 μm of lattice parameter and 7 μm in depth on YSZ plates. With these plates we prepare LSM-YSZ/YSZ/LSM-YSZ symmetrical cells (LSM: La1-xSrxMnO3) and determine their activation polarisation by Electrochemical Impedance Spectroscopy (EIS). To get good electrode-electrolyte contact after sintering it is necessary to use pressure-assisted sintering with low loads (about 5 kPa), which do not modify the electrode microstructure. The decrease in polarisation with respect to an unprocessed cell is about 30%. EIS analysis confirms that the reason for this decrease is an improvement in the activation processes at the electrode-electrolyte interface.

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.

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

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)

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.

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.

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

Fabrication of carbon-polymer composite bipolar plates for polymer electrolyte membrane fuel cells by compression moulding

International Nuclear Information System (INIS)

Raza, M.A.; Ahmed, R.; Saleem, A.; Din, R.U.

2009-01-01

Fuel cells are considered as one of the most important technologies to address the future energy and environmental pollution problems. These are the most promising power sources for road transportation and portable devices. A fuel cell is an electrochemical device that converts chemical energy into electrical energy. A fuel cell stack consists of bipolar plates and membrane electrode assemblies (MEA). The bipolar plate is by weight, volume and cost one of the most significant components of a fuel cell stack. Major functions of bipolar plates are to separate oxidant and fuel gas, provide flow channels, conduct electricity and provide heat transfer. Bipolar plates can be made from various materials including graphite, metals, carbon / carbon and carbon/ polymer composites. Materials for carbon-polymer composites are relatively inexpensive, less corrosive, strong and channels can be formed by means of a moulding process. Carbon-polymer composites are of two type i.e; thermosetting and thermoplastic. For thermosetting composite a bulk molding compound (BMC) was prepared by adding graphite, vinyl ester resin, methyl ethyl ketone peroxide and cobalt naphthalate. The BMC was thoroughly mixed, poured into a die mould of a bipolar plate with channels and hot pressed at a specific temperature and pressure. A bipolar plate was formed according to the die mould. Design of the mould is also discussed. Conducting polymers were also added to BMC to increase the conductivity of bipolar plates. Particle size of the graphite has also a significant effect on the conductivity of the bipolar plates. Thermoplastic composites were also prepared using polypropylene and graphite.

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...

Fundamental aspects of molecular plating and production of smooth crack-free Nd targets

International Nuclear Information System (INIS)

Vascon, A.; Reich, T.; Drebert, J.; Eberhardt, K.; Helmholtz Institute Mainz, Mainz; Duellmann, Ch.E.; GSI Helmholtzzentrum fuer Schwerionenforschung GmbH, Darmstadt; Helmholtz Institute Mainz, Mainz

2014-01-01

A general understanding of the molecular plating process was obtained recently, which serves as a first step towards further improvements of the method aiming, for example, at the production of smooth, crack-free targets for nuclear physics applications. Constant current density electrolysis experiments were performed in organic media containing the model electrolyte Nd(NO 3 ) 3 ·6H 2 O. The process was investigated by considering influences of the electrolyte concentration (0.11, 0.22, 0.44 mM), the surface roughness of the deposition substrates (a few tens of nm), and the plating solvent (an isopropanol/isobutanol mixture, and N,N-dimethylformamide). The response of the process to changes of these parameters was monitored by recording cell potential curves and by characterizing the obtained deposits with γ-ray spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. By changing the solvent from isopropanol/isobutanol mixtures to N,N-dimethylformamide, we have succeeded in producing smooth, crack-free Nd targets. (author)

Occupational exposure to nickel salts in electrolytic plating.

Science.gov (United States)

Kiilunen, M; Aitio, A; Tossavainen, A

1997-04-01

An occupational hygiene survey was made in 38 nickel plating shops in Finland and exposure to nickel was studied by means of biological measurements and, in three shops, by using air measurements. The average after-shift urinary nickel concentration of 163 workers was 0.16 mumol l.-1 (range 0.001-4.99 mumol l.-1). After the 1-5 week vacation the urinary nickel concentration was higher than the upper reference limit of non-exposed Finns indicating that a part of water-soluble nickel salts is accumulated in the body. Urinary nickel concentrations in the shops considered clean in the industrial hygiene walk-through were not different from those observed in the shops considered dirty. The correlation between the concentrations of nickel in the air and in the urine was low, and the amount of nickel excreted in the urine exceeded the calculated inhaled amounts, indicating exposure by other routes such as ingestion.

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.

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.

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.

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.

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)

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.)

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

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.

Simulation of electrochemical nucleation in the presence of additives under galvanostatic and pulsed plating conditions

International Nuclear Information System (INIS)

Emekli, Ugur; West, Alan C.

2010-01-01

Galvanostatic nucleation of copper onto pretreated ruthenium is investigated using experimental methods and numerical simulations in the presence of two different suppressor molecules; polyethylene glycol (PEG) and ethylene glycol-propylene glycol-ethylene glycol block copolymer (EPE). The model parameters have been largely determined from electrochemical characterization. Results suggest that a fast adsorption rate of the suppressor results in higher nucleus densities. Simulation results provide insight why EPE is more effective than PEG at increasing nucleus density. In addition, the simulations are used to predict the impact of pulse plating paramaters, showing that both the properties of the additive and the waveform need to be considered to optimize nucleus density enhancement.

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.

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

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

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

Electrophoretic deposition of thin film zirconia electrolyte on non-conducting NiO-YSZ substrate

International Nuclear Information System (INIS)

Das, Debasish; Basu, Rajendra N.

2014-01-01

Eight (8) mol% yttria stabilized zirconia (YSZ), an electrolyte material for solid oxide fuel cell (SOFC), has been deposited onto porous non-conducting NiO-YSZ substrate using electrophoretic deposition technique (EPD) from a stable non-aqueous suspension of YSZ. Normally, EPD cannot be performed on a non-conducting substrate, but, in this present study, YSZ particulate film has been successfully deposited on a non-conducting NiO-YSZ substrate following two different EPD approaches:(a) using a conducting metallic plate on the reverse side of the porous NiO-YSZ anode substrate and (b) using a conducting polymer coated NiO-YSZ substrate. The deposited films are then formed dense coatings of 5-15 μm after sintering at 1400℃ for 6 h in air. Surface and cross-sectional morphologies of green and sintered films deposited by different EPD approaches are investigated using SEM. La 0.65 Sr 0.3 MnO 3 (LSM), a cathode for SOFC, is then screen-printed onto the electrolyte layer of such sintered half cells (anode+electrolyte) prepared by both the above approaches to construct SOFC single cells. A maximum output power density of 0.37 W.cm -2 is obtained using single cells prepared by conducting metallic plate assisted EPD compared to that of 0.73 W.cm -2 for polymer coated at 800℃ using H 2 as fuel and O 2 as oxidant. (author)

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)

Bipolar plates for polymer electrolyte membrane fuel cells made of thermal and electrical high conductivity thermoplastics. Formulation, production, characterization and application; Bipolarplatten fuer Polymerelektrolytmembran-Brennstoffzellen aus thermisch und elektrisch hochleitfaehigen thermoplastischen Kunststoffen. Rezeptierung, Herstellung, Charakterisierung und Anwendung

Energy Technology Data Exchange (ETDEWEB)

Kaiser, Ralf Leonhard

2008-07-01

The upcoming lack of primary energy sources and the need of reducing the anthropogenic climate change led to increased research activities in the field of Fuel Cells (FC) technology within the last ten years in Europe, the USA and Japan. Especially the automotive industry is highly interested in developing zero emission cars as a replacement of nowadays cars within the next twenty years. Not only for mobile applications the Polymer Electrolyte Membrane Fuel Cell systems (PEM-FC systems) is the focus of research and development. Also stationary (PEM-) FC applications seem to be more and more interesting for a decentralized energy supply, producing electricity and heat (Vaillant FC-Systems, Bosch/Junkers). For this purpose, system miniaturizing and weight reduction (70-90 wt-% of the stack itself is due to bipolar- and endplate) is not that essential as it is for mobile appliance, resulting in earlier commercial market introduction of these systems within the next few years. Not only the weight reduction of the FC-stack itself, but also the cost cutting of its components is vital for the economic success of this technology. The three most expensive components of the stack are the perfluorsulfonated ion conducting Membranen (PEM: Nafion, Ashai, Ashai glass), the noble metal catalyst (Platinum and/or Ruthenium) and the Bipolar Plate (BPP). The moulding processes (injection and/or compression moulding) of polymer materials allow highly integrated, tool reduced mass production of tailored stack components like the BP, the endplate, cell frame and peripheral components. The objective of this thesis is to describe the development of an conductive functionalised material suitable for moulding BPP, to investigate compounding optimisation methods (DOE) and evaluate the best fit parameters, to analyse the rheological behaviour of these highly filled compounds, to discuss suitable polymer related manufacturing processes like hot pressing, injection moulding and profile

Nanoporous polymer electrolyte

Science.gov (United States)

Elliott, Brian [Wheat Ridge, CO; Nguyen, Vinh [Wheat Ridge, CO

2012-04-24

A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0.times.10.sup.-6 S/cm at 25.degree. C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

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

Electrolytic decontamination of stainless steel using a basic electrolyte

International Nuclear Information System (INIS)

Childs, E.L.; Long, J.L.

1981-01-01

An electrolytic plutonium decontamination process or stainless steel was developed for use as the final step in a proposed radioactive waste handling and decontamination facility to be construced at the Rockwell International Rocky Flats plutonium handling facility. This paper discusses test plan, which was executed to compare the basic electrolyte with phosphoric acid and nitric acid electrolytes. 1 ref

Electroless nickel-plating for the PWSCC mitigation of nickel-base alloys in nuclear power plants

International Nuclear Information System (INIS)

Kim, Ji Hyun; Hwang, Il Soon

2008-01-01

The feasibility study has been performed as an effort to apply the electroless nickel-plating method for a proposed countermeasure to mitigate primary water stress corrosion cracking (PWSCC) of nickel-base alloys in nuclear power plants. In order to understand the corrosion behavior of nickel-plating at high temperature water, the electrochemical properties of electroless nickel-plated alloy 600 specimens exposed to simulated pressurized water reactor (PWR) primary water were experimentally characterized in high temperature and high pressure water condition. And, the resistance to the flow accelerated corrosion (FAC) test was investigated to check the durability of plated layers in high-velocity water-flowing environment at high temperature. The plated surfaces were examined by using both scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) after exposures to the condition. From this study, it is found that the corrosion resistance of electroless nickel-plated Alloy 600 is higher than that of electrolytic plating in 290 deg. C water

Highly Quantitative Electrochemical Characterization of Non-Aqueous Electrolytes & Solid Electrolyte Interphases

Energy Technology Data Exchange (ETDEWEB)

Sergiy V. Sazhin; Kevin L. Gering; Mason K. Harrup; Harry W. Rollins

2012-10-01

The methods to measure solid electrolyte interphase (SEI) electrochemical properties and SEI formation capability of non-aqueous electrolyte solutions are not adequately addressed in the literature. And yet, there is a strong demand in new electrolyte generations that promote stabilized SEIs and have an influence to resolve safety, calendar life and other limitations of Li-ion batteries. To fill this gap, in situ electrochemical approach with new descriptive criteria for highly quantitative characterization of SEI and electrolytes is proposed. These criteria are: SEI formation capacity, SEI corrosion rate, SEI maintenance rate, and SEI kinetic stability. These criteria are associated with battery parameters like irreversible capacity, self-discharge, shelf-life, power, etc. Therefore, they are especially useful for electrolyte development and standard fast screening, allowing a skillful approach to narrow down the search for the best electrolyte. The characterization protocol also allows retrieving information on interfacial resistance for SEI layers and the electrochemical window of electrolytes, the other important metrics of characterization. The method validation was done on electrolyte blends containing phosphazenes, developed at Idaho National Laboratory, as 1.2M LiPF6 [80 % EC-MEC (2:8) (v/v) + 20% Phosphazene variety] (v/v), which were targeted for safer electrolyte variations.

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.

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,.

On direct and indirect methanol fuel cells for transportation applications

Energy Technology Data Exchange (ETDEWEB)

Gottesfield, S.

1996-04-01

Research on direct oxidation methanol fuel cells (DMFCs) and polymer electrolyte fuel cells (PEFCs) is discussed. Systems considered for transportation applications are addressed. The use of platinum/ruthenium anode electrocatalysts and platinum cathode electrocatalysts in polymer electrolyte DMFCs has resulted in significant performance enhancements.

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

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

Facile preparation of polymer electrolytes based on the polymerized ionic liquid poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)) for lithium secondary batteries

International Nuclear Information System (INIS)

Li, Mingtao; Wang, Lu; Yang, Bolun; Du, Tingting; Zhang, Ying

2014-01-01

Graphical abstract: (A) The main components of PIL electrolytes, (B) A PIL electrolyte sample. - Highlights: • A new polymer electrolyte incorporating a DEME-TFSI liquid is prepared. • The ionic conductivity of the electrolytes reaches 7.58 × 10 −4 S cm −1 at 60 °C. • Batteries discharge 130 mAh g −1 at 0.1 C rates with good capacity retention. - Abstract: The polymer electrolytes based on a novel poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)) polymeric ionic liquid (PIL) as polymer host and containing DEME-TFSI ionic liquid, LiTFSI salt and nano silica are prepared. The polymer electrolyte is chemically stable even at a higher temperature of 60 °C in contact with lithium anode. Particularly, the electrolyte exhibits high lithium ion conductivity, wide electrochemical stability window and good lithium stripping/plating performance. When the IL content reaches 60% (the weight ratio of DEME-TFSI/PIL), the PIL electrolyte presents a higher ionic conductivity, and it is 7.58 × 10 −4 S cm −1 at 60 °C. Preliminary battery tests show that Li/LiFePO 4 cells with the PIL electrolytes are capable to deliver above 130 mAh g −1 at 60 °C with very good capacity retention

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

Surface composition effect of nitriding Ni-free stainless steel as bipolar plate of polymer electrolyte fuel cell

Energy Technology Data Exchange (ETDEWEB)

Yu, Yang; Shironita, Sayoko [Nagaoka University of Technology, 1603-1, Kamitomioka, Nagaoka, Niigata 940-2188 (Japan); Nakatsuyama, Kunio [Nakatsuyama Heat Treatment Co., Ltd., 1-1089-10, Nanyou, Nagaoka, Niigata 940-1164 (Japan); Souma, Kenichi [Nagaoka University of Technology, 1603-1, Kamitomioka, Nagaoka, Niigata 940-2188 (Japan); Hitachi Industrial Equipment Systems Co., Ltd., 3 Kanda Neribei, Chiyoda, Tokyo 101-0022 (Japan); Umeda, Minoru, E-mail: mumeda@vos.nagaokaut.ac.jp [Nagaoka University of Technology, 1603-1, Kamitomioka, Nagaoka, Niigata 940-2188 (Japan)

2016-12-01

Graphical abstract: The anodic current densities in the passive region of nitrided SUS445-N stainless steel are lower than those of a non heat-treated SUS445 stainless steel and heat-treated SUS445-Ar stainless steel under an Ar atmosphere. It shows a better corrosion resistance for the SUS445 stainless steel after the nitriding heat treatment. - Highlights: • The nitriding heat treatment was carried out using Ni-free SUS445 stainless steel. • The corrosion resistance of the nitrided SUS445-N stainless steel was improved. • The structure of the nitrided SUS445-N stainless steel changed from α-Fe to γ-Fe. • The surface elemental components present in the steels affect the corrosion resistance. - Abstract: In order to increase the corrosion resistance of low cost Ni-free SUS445 stainless steel as the bipolar plate of a polymer electrolyte fuel cell, a nitriding surface treatment experiment was carried out in a nitrogen atmosphere under vacuum conditions, while an Ar atmosphere was used for comparison. The electrochemical performance, microstructure, surface chemical composition and morphology of the sample before and after the electrochemical measurements were investigated using linear sweep voltammetry (LSV), X-ray diffraction (XRD), glow discharge optical emission spectroscopy (GDS) and laser scanning microscopy (LSM) measurements. The results confirmed that the nitriding heat treatment not only increased the corrosion resistance, but also improved the surface conductivity of the Ni-free SUS445 stainless steel. In contrast, the corrosion resistance of the SUS445 stainless steel decreased after heat treatment in an Ar atmosphere. These results could be explained by the different surface compositions between these samples.

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

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,.

Debye length dependence of the anomalous dynamics of ionic double layers in a parallel plate capacitor

NARCIS (Netherlands)

Kortschot, R. J.; Philipse, A. P.; Erné, B. H.

2014-01-01

The electrical impedance spectrum of simple ionic solutions is measured in a parallel plate capacitor at small applied ac voltage. The influence of the ionic strength is investigated using several electrolytes at different concentrations in solvents of different dielectric constants. The electric

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...

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.

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 ...

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

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

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

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.

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

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)

High temperature polymer electrolyte membrane fuel cells: Approaches, status, and perspectives

DEFF Research Database (Denmark)

This book is a comprehensive review of high-temperature polymer electrolyte membrane fuel cells (PEMFCs). PEMFCs are the preferred fuel cells for a variety of applications such as automobiles, cogeneration of heat and power units, emergency power and portable electronics. The first 5 chapters...... of and motivated extensive research activity in the field. The last 11 chapters summarize the state-of-the-art of technological development of high temperature-PEMFCs based on acid doped PBI membranes including catalysts, electrodes, MEAs, bipolar plates, modelling, stacking, diagnostics and applications....

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.

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.

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.

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)

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.

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.

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)

An experimental and simulation study of novel channel designs for open-cathode high-temperature polymer electrolyte membrane fuel cells

DEFF Research Database (Denmark)

Thomas, Sobi; Bates, Alex; Park, Sam

2016-01-01

A minimum balance of plant (BOP) is desired for an open-cathode high temperature polymer electrolyte membrane (HTPEM) fuel cell to ensure low parasitic losses and a compact design. The advantage of an open-cathode system is the elimination of the coolant plate and incorporation of a blower for ox...

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 ...

High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks from Dense Functionalized Nanoparticle Composites

KAUST Repository

Schaefer, Jennifer L.

2013-03-26

High lithium transference number, tLi+, electrolytes are desired for use in both lithium-ion and lithium metal rechargeable battery technologies. Historically, low tLi+ electrolytes have hindered device performance by allowing ion concentration gradients within the cell, leading to high internal resistances that ultimately limit cell lifetime, charging rates, and energy density. Herein, we report on the synthesis and electrochemical features of electrolytes based on nanoparticle salts designed to provide high tLi+. The salts are created by cofunctionalization of metal oxide nanoparticles with neutral organic ligands and tethered lithium salts. When dispersed in a conducting fluid such as tetraglyme, they spontaneously form a charged, nanoporous network of particles at moderate nanoparticle loadings. Modification of the tethered anion chemistry from -SO3 - to -SO3BF3 - is shown to enhance ionic conductivity of the electrolytes by facilitating ion pair dissociation. At a particle volume fraction of 0.15, the electrolyte exists as a self-supported, nanoporous gel with an optimum ionic conductivity of 10 -4 S/cm at room temperature. Galvanostatic polarization measurements on symmetric lithium metal cells containing the electrolyte show that the cell short circuit time, tSC, is inversely proportional to the square of the applied current density tSC ∼ J-2, consistent with previously predicted results for traditional polymer-in-salt electrolytes with low tLi+. Our findings suggest that electrolytes with tLi+ ≈ 1 and good ion-pair dissociation delay lithium dendrite nucleation and may lead to improved lithium plating in rechargeable batteries with metallic lithium anodes. © 2013 American Chemical Society.

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

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)

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

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.

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

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

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

Evaluations of corrosion resistance of Ni-Cr plated and Zn-plated Fe Substrates Using an Electrolytic Corrosion Test

International Nuclear Information System (INIS)

Lee, Jaebong; Kim, Kyungwook; Park, Minwoo; Song, Taejun; Lee, Chaeseung; Lee, Euijong; Kim, Sangyeol

2013-01-01

An Eectrolytic Corrosion(EC) test method was evaluated by the comparison with Copper Accelerated Acetic Salt Spray(CASS) and Neutral Salt Spray(SS) tests. Those methods were applied in order to evaluate corrosion resistance of Ni-Cr plated and Zn-plated Fe substrates. The correlations between results obtained by different test methods were investigated. Results showed that the electrochemical method such as the EC test method was superior to the conventional methods such as CASS and SS, in terms of the quantitative accuracy and the test-time span. Furthermore, the EC test method provided the useful means to estimate the initiation of corrosion of each layer by monitoring the rest potentials of the coated layers such as Ni, Cr, and Zn on Fe substrate. With regard to test time spans, the EC test provided the 78 times and 182 times faster results than the CASS test in cases of Fe + 5μm Ni + 0.5 μm Cr and Fe + 20 μm Ni + 0.5 μm Cr respectively, while the EC test was 85 times faster results than the Salt Spray test in the case of Fe + 20 g/m 2 Zn. Therefore, the EC test can be the better method to evaluate the resistance to corrosion of coated layers than the conventional methods such as the SS test and the CASS

A novel flow battery: A lead acid battery based on an electrolyte with soluble lead(II). Part IX: Electrode and electrolyte conditioning with hydrogen peroxide

Science.gov (United States)

Collins, John; Li, Xiaohong; Pletcher, Derek; Tangirala, Ravichandra; Stratton-Campbell, Duncan; Walsh, Frank C.; Zhang, Caiping

Extended cycling of a soluble lead acid battery can lead to problems due to an imbalance in the coulombic efficiency leading to deposits of Pb and PbO2 on the electrodes. Periodic addition of hydrogen peroxide to the electrolyte of the soluble lead acid flow battery largely overcomes several operational problems seen during extended cycling, using a 10 cm × 10 cm parallel plate flow cell. It is shown that this treatment greatly extends the number of cycles that can be achieved with a reasonable energy-, voltage-, and charge efficiency of 54-66%, 71%, and 77-91%.

A novel flow battery: A lead acid battery based on an electrolyte with soluble lead(II). Part IX: Electrode and electrolyte conditioning with hydrogen peroxide

Energy Technology Data Exchange (ETDEWEB)

Collins, John; Stratton-Campbell, Duncan [C-Tech Innovation Ltd., Capenhurst, Chester CH1 6EH (United Kingdom); Li, Xiaohong; Tangirala, Ravichandra; Walsh, Frank C.; Zhang, Caiping [Energy Technology Research Group, School of Engineering Sciences, University of Southampton, Highfield, University Road, Southampton SO17 1BJ (United Kingdom); Pletcher, Derek [Electrochemistry and Surface Science Group, School of Chemistry, University of Southampton, Southampton SO17 1BJ (United Kingdom)

2010-05-01

Extended cycling of a soluble lead acid battery can lead to problems due to an imbalance in the coulombic efficiency leading to deposits of Pb and PbO2 on the electrodes. Periodic addition of hydrogen peroxide to the electrolyte of the soluble lead acid flow battery largely overcomes several operational problems seen during extended cycling, using a 10 cm x 10 cm parallel plate flow cell. It is shown that this treatment greatly extends the number of cycles that can be achieved with a reasonable energy-, voltage-, and charge efficiency of 54-66%, 71%, and 77-91%. (author)

Fuel cell plates with skewed process channels for uniform distribution of stack compression load

Science.gov (United States)

Granata, Jr., Samuel J.; Woodle, Boyd M.

1989-01-01

An electrochemical fuel cell includes an anode electrode, a cathode electrode, an electrolyte matrix sandwiched between electrodes, and a pair of plates above and below the electrodes. The plate above the electrodes has a lower surface with a first group of process gas flow channels formed thereon and the plate below the electrodes has an upper surface with a second group of process gas flow channels formed thereon. The channels of each group extend generally parallel to one another. The improvement comprises the process gas flow channels on the lower surface of the plate above the anode electrode and the process gas flow channels on the upper surface of the plate below the cathode electrode being skewed in opposite directions such that contact areas of the surfaces of the plates through the electrodes are formed in crisscross arrangements. Also, the plates have at least one groove in areas of the surfaces thereof where the channels are absent for holding process gas and increasing electrochemical activity of the fuel cell. The groove in each plate surface intersects with the process channels therein. Also, the opposite surfaces of a bipolar plate for a fuel cell contain first and second arrangements of process gas flow channels in the respective surfaces which are skewed the same amount in opposite directions relative to the longitudinal centerline of the plate.

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.

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

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.

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 ...

Quantitative Analysis of Oxygen Gas Exhausted from Anode through In Situ Measurement during Electrolytic Reduction

Directory of Open Access Journals (Sweden)

Eun-Young Choi

2017-01-01

Full Text Available Quantitative analysis by in situ measurement of oxygen gas evolved from an anode was employed to monitor the progress of electrolytic reduction of simulated oxide fuel in a molten Li2O–LiCl salt. The electrolytic reduction of 0.6 kg of simulated oxide fuel was performed in 5 kg of 1.5 wt.% Li2O–LiCl molten salt at 650°C. Porous cylindrical pellets of simulated oxide fuel were used as the cathode by loading a stainless steel wire mesh cathode basket. A platinum plate was employed as the anode. The oxygen gas evolved from the anode was exhausted to the instrumentation for in situ measurement during electrolytic reduction. The instrumentation consisted of a mass flow controller, pump, wet gas meter, and oxygen gas sensor. The oxygen gas was successfully measured using the instrumentation in real time. The measured volume of the oxygen gas was comparable to the theoretically calculated volume generated by the charge applied to the simulated oxide fuel.

Nanostructured ZnO films in forms of rod, plate and flower: Electrodeposition mechanisms and characterization

International Nuclear Information System (INIS)

Kıcır, Nur; Tüken, Tunç; Erken, Ozge; Gumus, Cebrail; Ufuktepe, Yuksel

2016-01-01

Highlights: • Electrosynthesis of ZnO nanostructures in the form of plate, rod and flower. • The role of type and concentration of supporting electrolytes on growth mechanism. • Detailed analysis of morphologies, in comparison with the Literature. • Nanoplate form of ZnO exhibits higher Fermi level and lower band gap. - Abstract: Uniformity and reproducibility of well-defined ZnO nanostructures are particularly important issues for fabrication and applications of these nanomaterials. In present study, we report selective morphology control during electrodeposition, by adjusting the hydroxyl generation rate and Zn(OH)_2 deposition. In presence of remarkably high chloride concentration (0.3 M) and −1.0 V deposition potential, slow precipitation conditions were provided in 5 mM Zn(NO_3)_2 solution. By doing so, we have obtained highly ordered, vertically aligned and uniformly spaced hexagon shaped nanoplates, on ITO surface. We have also investigated the mechanism for shifting the morphology from rod/plate to flower like structure of ZnO, for better understanding the reproducibility. For this reason, the influence of various supporting electrolytes (sodium/ammonium salts of acetate) has been investigated for interpretation of the influence of OH"− concentration nearby the surface. From rod to plate and flower nanostructures, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis were realized for characterization, also the optical properties were studied.

Nanostructured ZnO films in forms of rod, plate and flower: Electrodeposition mechanisms and characterization

Energy Technology Data Exchange (ETDEWEB)

Kıcır, Nur, E-mail: nurkicir@gmail.com [Chemistry Department, Çukurova University, 01330 Adana (Turkey); Tüken, Tunç [Chemistry Department, Çukurova University, 01330 Adana (Turkey); Erken, Ozge [Physics Department, Adiyaman University, 02040 Adıyaman (Turkey); Gumus, Cebrail; Ufuktepe, Yuksel [Physics Department, Çukurova University, 01330 Adana (Turkey)

2016-07-30

Highlights: • Electrosynthesis of ZnO nanostructures in the form of plate, rod and flower. • The role of type and concentration of supporting electrolytes on growth mechanism. • Detailed analysis of morphologies, in comparison with the Literature. • Nanoplate form of ZnO exhibits higher Fermi level and lower band gap. - Abstract: Uniformity and reproducibility of well-defined ZnO nanostructures are particularly important issues for fabrication and applications of these nanomaterials. In present study, we report selective morphology control during electrodeposition, by adjusting the hydroxyl generation rate and Zn(OH){sub 2} deposition. In presence of remarkably high chloride concentration (0.3 M) and −1.0 V deposition potential, slow precipitation conditions were provided in 5 mM Zn(NO{sub 3}){sub 2} solution. By doing so, we have obtained highly ordered, vertically aligned and uniformly spaced hexagon shaped nanoplates, on ITO surface. We have also investigated the mechanism for shifting the morphology from rod/plate to flower like structure of ZnO, for better understanding the reproducibility. For this reason, the influence of various supporting electrolytes (sodium/ammonium salts of acetate) has been investigated for interpretation of the influence of OH{sup −} concentration nearby the surface. From rod to plate and flower nanostructures, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis were realized for characterization, also the optical properties were studied.

Surface characteristic of chemically converted graphene coated low carbon steel by electro spray coating method for polymer electrolyte membrane fuel cell bipolar plate.

Science.gov (United States)

Kim, Jungsoo; Kim, Yang Do; Nam, Dae Geun

2013-05-01

Graphene was coated on low carbon steel (SS400) by electro spray coating method to improve its properties of corrosion resistance and contact resistance. Exfoliated graphite was made of the graphite by chemical treatment (Chemically Converted Graphene, CCG). CCG is distributed using dispersing agent, and low carbon steel was coated with diffuse graphene solution by electro spray coating method. The structure of the CCG was analyzed using XRD and the coating layer of surface was analyzed using SEM. Analysis showed that multi-layered graphite structure was destroyed and it was transformed in to fine layers graphene structure. And the result of SEM analysis on the surface and the cross section, graphene layer was uniformly formed with 3-5 microm thickness on the surface of substrate. Corrosion resistance test was applied in the corrosive solution which is similar to the polymer electrolyte membrane fuel cell (PEMFC) stack inside. And interfacial contact resistance (ICR) test was measured to simulate the internal operating conditions of PEMFC stack. As a result of measuring corrosion resistance and contact resistance, it could be confirmed that low carbon steel coated with CCG was revealed to be more effective in terms of its applicability as PEMFC bipolar plate.

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...

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.

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.)

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

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....

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...

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

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

Electrolyte materials - Issues and challenges

International Nuclear Information System (INIS)

Balbuena, Perla B.

2014-01-01

Electrolytes are vital components of an electrochemical energy storage device. They are usually composed of a solvent or mixture of solvents and a salt or a mixture of salts which provide the appropriate environment for ionic conduction. One of the main issues associated with the selection of a proper electrolyte is that its electronic properties have to be such that allow a wide electrochemical window - defined as the voltage range in which the electrolyte is not oxidized or reduced - suitable to the battery operating voltage. In addition, electrolytes must have high ionic conductivity and negligible electronic conductivity, be chemically stable with respect to the other battery components, have low flammability, and low cost. Weak stability of the electrolyte against oxidation or reduction leads to the formation of a solid-electrolyte interphase (SEI) layer at the surface of the cathode and anode respectively. Depending on the materials of the electrolyte and those of the electrode, the SEI layer may be composed by combinations of organic and inorganic species, and it may exert a passivating role. In this paper we discuss the current status of knowledge about electrolyte materials, including non-aqueous liquids, ionic liquids, solid ceramic and polymer electrolytes. We also review the basic knowledge about the SEI layer formation, and challenges for a rational design of stable electrolytes

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)

Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

Science.gov (United States)

Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

2014-12-21

Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

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

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.

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

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.

Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes.

Science.gov (United States)

Kabdaşli, Işik; Arslan, Tülin; Olmez-Hanci, Tuğba; Arslan-Alaton, Idil; Tünay, Olcay

2009-06-15

In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well as sludge production and specific energy consumption. The results indicated that increasing the applied current density from 2.25 to 9.0 mA/cm(2) appreciably enhanced TOC removal efficiency from 20% to 66%, but a further increase in the applied current density to 56.25 mA/cm(2) did not accelerate TOC removal rates. Electrolyte concentration did not affect the process performance significantly and the highest TOC reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride content ( approximately 1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating effluent were established as follows: an applied current density of 9 mA/cm(2), the effluent's original electrolyte concentration and pH of the composite sample. TOC removal rates obtained for all electrocoagulation runs fitted pseudo-first-order kinetics very well (R(2)>92-99).

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

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.

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

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

An Insoluble Titanium-Lead Anode for Sulfate Electrolytes

Energy Technology Data Exchange (ETDEWEB)

Ferdman, Alla

2005-05-11

The project is devoted to the development of novel insoluble anodes for copper electrowinning and electrolytic manganese dioxide (EMD) production. The anodes are made of titanium-lead composite material produced by techniques of powder metallurgy, compaction of titanium powder, sintering and subsequent lead infiltration. The titanium-lead anode combines beneficial electrochemical behavior of a lead anode with high mechanical properties and corrosion resistance of a titanium anode. In the titanium-lead anode, the titanium stabilizes the lead, preventing it from spalling, and the lead sheathes the titanium, protecting it from passivation. Interconnections between manufacturing process, structure, composition and properties of the titanium-lead composite material were investigated. The material containing 20-30 vol.% of lead had optimal combination of mechanical and electrochemical properties. Optimal process parameters to manufacture the anodes were identified. Prototypes having optimized composition and structure were produced for testing in operating conditions of copper electrowinning and EMD production. Bench-scale, mini-pilot scale and pilot scale tests were performed. The test anodes were of both a plate design and a flow-through cylindrical design. The cylindrical anodes were composed of cylinders containing titanium inner rods and fitting over titanium-lead bushings. The cylindrical design allows the electrolyte to flow through the anode, which enhances diffusion of the electrolyte reactants. The cylindrical anodes demonstrate higher mass transport capabilities and increased electrical efficiency compared to the plate anodes. Copper electrowinning represents the primary target market for the titanium-lead anode. A full-size cylindrical anode performance in copper electrowinning conditions was monitored over a year. The test anode to cathode voltage was stable in the 1.8 to 2.0 volt range. Copper cathode morphology was very smooth and uniform. There was no

How Solid-Electrolyte Interphase Forms in Aqueous Electrolytes.

Science.gov (United States)

Suo, Liumin; Oh, Dahyun; Lin, Yuxiao; Zhuo, Zengqing; Borodin, Oleg; Gao, Tao; Wang, Fei; Kushima, Akihiro; Wang, Ziqiang; Kim, Ho-Cheol; Qi, Yue; Yang, Wanli; Pan, Feng; Li, Ju; Xu, Kang; Wang, Chunsheng

2017-12-27

Solid-electrolyte interphase (SEI) is the key component that enables all advanced electrochemical devices, the best representative of which is Li-ion battery (LIB). It kinetically stabilizes electrolytes at potentials far beyond their thermodynamic stability limits, so that cell reactions could proceed reversibly. Its ad hoc chemistry and formation mechanism has been a topic under intensive investigation since the first commercialization of LIB 25 years ago. Traditionally SEI can only be formed in nonaqueous electrolytes. However, recent efforts successfully transplanted this concept into aqueous media, leading to significant expansion in the electrochemical stability window of aqueous electrolytes from 1.23 V to beyond 4.0 V. This not only made it possible to construct a series of high voltage/energy density aqueous LIBs with unprecedented safety, but also brought high flexibility and even "open configurations" that have been hitherto unavailable for any LIB chemistries. While this new class of aqueous electrolytes has been successfully demonstrated to support diversified battery chemistries, the chemistry and formation mechanism of the key component, an aqueous SEI, has remained virtually unknown. In this work, combining various spectroscopic, electrochemical and computational techniques, we rigorously examined this new interphase, and comprehensively characterized its chemical composition, microstructure and stability in battery environment. A dynamic picture obtained reveals how a dense and protective interphase forms on anode surface under competitive decompositions of salt anion, dissolved ambient gases and water molecule. By establishing basic laws governing the successful formation of an aqueous SEI, the in-depth understanding presented in this work will assist the efforts in tailor-designing better interphases that enable more energetic chemistries operating farther away from equilibria in aqueous media.

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)

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)

An investigation of ruthenium coating from LiCl–KCl eutectic melt

International Nuclear Information System (INIS)

Kartal Sireli, G.

2014-01-01

Graphical abstract: - Highlights: • A white/gray Ru coating was achieved via electrodeposition from LiCl–KCl melt. • Cathodic current efficiency (η) was increased as high as 99.68%. • A dense and 8.5 μm thick Ru coating was possible to be grown after 2 h. • “Faceted structure” was observed on the surface of Ru deposited at 3 and 7 mA/cm 2 . • The thickness of Ru increased with increasing both current density and time. - Abstract: In this study, electrodeposition of ruthenium (Ru) from LiCl–KCl eutectic melt was investigated in a systematic manner and the effects of process parameters namely current density, time and agitation of electrolyte on the thickness and morphology of Ru layer were explored. The presence of Ru on graphite substrates was confirmed by thin film X-ray diffraction method. The Ru coatings formed at all electrodeposition conditions appeared as a white/gray deposit. The typical “faceted structure” was observed on the surface of Ru deposited at 3 and 7 mA/cm 2 . Fracture cross-section examinations revealed the columnar morphology of Ru which was twinned with boundaries. The smooth appearance of Ru coating became uneven and rough with coarse nodules at 12 mA/cm 2 . The thickness of Ru increased with increasing both current density and time at stationary electrodeposition conditions. A dense and 7.5 μm thick Ru coating was possible to grow on graphite without any agitation at 3 mA/cm 2 for 2 h. The highest cathodic current efficiency (η), 99.68%, was achieved at 3 mA/cm 2 after 2 h of electrodeposition time with the rotating cathode speed of 50 rpm. The cross sectional micro-indentation studies indicated that the Ru layer has hardness as high as 450 ± 10 HV

An investigation of ruthenium coating from LiCl–KCl eutectic melt

Energy Technology Data Exchange (ETDEWEB)

Kartal Sireli, G., E-mail: kartalgu@itu.edu.tr

2014-10-30

Graphical abstract: - Highlights: • A white/gray Ru coating was achieved via electrodeposition from LiCl–KCl melt. • Cathodic current efficiency (η) was increased as high as 99.68%. • A dense and 8.5 μm thick Ru coating was possible to be grown after 2 h. • “Faceted structure” was observed on the surface of Ru deposited at 3 and 7 mA/cm{sup 2}. • The thickness of Ru increased with increasing both current density and time. - Abstract: In this study, electrodeposition of ruthenium (Ru) from LiCl–KCl eutectic melt was investigated in a systematic manner and the effects of process parameters namely current density, time and agitation of electrolyte on the thickness and morphology of Ru layer were explored. The presence of Ru on graphite substrates was confirmed by thin film X-ray diffraction method. The Ru coatings formed at all electrodeposition conditions appeared as a white/gray deposit. The typical “faceted structure” was observed on the surface of Ru deposited at 3 and 7 mA/cm{sup 2}. Fracture cross-section examinations revealed the columnar morphology of Ru which was twinned with boundaries. The smooth appearance of Ru coating became uneven and rough with coarse nodules at 12 mA/cm{sup 2}. The thickness of Ru increased with increasing both current density and time at stationary electrodeposition conditions. A dense and 7.5 μm thick Ru coating was possible to grow on graphite without any agitation at 3 mA/cm{sup 2} for 2 h. The highest cathodic current efficiency (η), 99.68%, was achieved at 3 mA/cm{sup 2} after 2 h of electrodeposition time with the rotating cathode speed of 50 rpm. The cross sectional micro-indentation studies indicated that the Ru layer has hardness as high as 450 ± 10 HV.

Constructions of aluminium electrolytic cells

International Nuclear Information System (INIS)

Galushkin, N.V.

1995-01-01

This chapter of monograph is devoted to constructions of aluminium electrolytic cells. Therefore, the general characteristic and classification of aluminium electrolytic cells was considered. The anode and cathode structure was studied. The lining of cathode casing, the process of collection of anode gases, electrolytic cell cover, and electrical insulation was studied as well. The installation and dismantling of aluminium electrolytic cells was described.

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

FY 1998 annual report on the development of fuel cell power generation techniques. Research and development of solid electrolyte fuel cells (research results); 1998 nendo nenryo denchi gijutsu kaihatsu. Kotai denkaishitsugata nenryo denchi no kenkyu kaihatsu

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

Described herein are the FY 1998 research and development results of solid electrolyte fuel cells. For R and D of the tubular type cell by the wet processing technique, the tests are conducted to evaluate the initial performance and long-term durability for continuous operation of the single tubular cell. For development of the several-kW class modules, computer-aided simulations are conducted. For R and D of material and substrate techniques, the thermal cycle characteristics, cell characteristics and stress of the cell modules are evaluated, in order to evaluate their reliability. The thermal cycle test results indicate that performance of the single-stage cell is unaffected by the thermal cycles. It is found by the stress evaluation that use of the separator plate having a higher thermal expansion coefficient than the electrolyte plate and use of the sealant having a thermal expansion coefficient close to that of the electrolyte plate are effective means to reduce stresses. For the research to reduce costs of the cell materials, their chemical, mechanical and thermal characteristics are evaluated. For the system research, the areas for which the compact systems are suitable and their optimization are studied. (NEDO)

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.

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.

Polymer electrolyte membrane fuel cell (PEMFC) flow field plate: design, materials and characterisation

Energy Technology Data Exchange (ETDEWEB)

Hamilton, P.J.; Pollet, B.G. [PEM Fuel Cell Research Group, School of Chemical Engineering, University of Birmingham, Edgbaston, B15 2TT (United Kingdom)

2010-08-15

This review describes some recent developments in the area of flow field plates (FFPs) for proton exchange membrane fuel cells (PEMFCs). The function, parameters and design of FFPs in PEM fuel cells are outlined and considered in light of their performance. FFP materials and manufacturing methods are discussed and current in situ and ex situ characterisation techniques are described. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Efficient Electrolytes for Lithium–Sulfur Batteries

International Nuclear Information System (INIS)

Angulakshmi, Natarajan; Stephan, Arul Manuel

2015-01-01

This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium–sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium–sulfur batteries. The electrolytes for lithium–sulfur batteries are broadly classified as (i) non-aqueous liquid electrolytes, (ii) ionic liquids, (iii) solid polymer, and (iv) glass-ceramic electrolytes. This article presents the properties, advantages, and limitations of each type of electrolytes. Also, the importance of electrolyte additives on the electrochemical performance of Li–S cells is discussed.

Efficient Electrolytes for Lithium-Sulfur Batteries

Directory of Open Access Journals (Sweden)

Natarajan eAngulakshmi

2015-05-01

Full Text Available This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium-sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium-sulfur batteries. The electrolytes for lithium-sulfur batteries are broadly classified as (i non-aqueous liquid electrolytes, (ii ionic liquids, (iii solid polymer and (iv glass-ceramic electrolytes. This article presents the properties, advantages and limitations of each type of electrolytes. Also the importance of electrolyte additives on the electrochemical performance of Li-S cells is discussed.

Efficient Electrolytes for Lithium–Sulfur Batteries

Energy Technology Data Exchange (ETDEWEB)

Angulakshmi, Natarajan [Department of Materials Science and Engineering, Politecnico di Torino, Turin (Italy); Stephan, Arul Manuel, E-mail: arulmanuel@gmail.com [Central Electrochemical Research Institute (CSIR-CECRI), Karaikudi (India)

2015-05-21

This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium–sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium–sulfur batteries. The electrolytes for lithium–sulfur batteries are broadly classified as (i) non-aqueous liquid electrolytes, (ii) ionic liquids, (iii) solid polymer, and (iv) glass-ceramic electrolytes. This article presents the properties, advantages, and limitations of each type of electrolytes. Also, the importance of electrolyte additives on the electrochemical performance of Li–S cells is discussed.

The preparation of Th-232 target by molecular plating method

International Nuclear Information System (INIS)

Yang Chunli; Wu Junde; Su Shuxin; Yang Jingling

2010-01-01

In order to measure the reaction cross-section of 232 Th(α,2n) 234 U, the preparation of uniform and adherent Th-232 targets on Al foils of thickness 2-8 μm fixed on target frame by molecular plating technique from isopropanol was described. The substrate of electrolytic cell was reconstructed and the optimum acidity for the deposition of thorium were investigated. Through deposition yield analysis, the target thickness of 100- 200μg/cm 2 was determined. The α-spectrometry for the Th-232 targets shows a good energy resolution. (authors)

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.

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.

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.

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

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)

Electrolyte for a lithium/thionyl chloride electric cell, a method of preparing said electrolyte and an electric cell which includes said electrolyte

Energy Technology Data Exchange (ETDEWEB)

Gabano, J.

1983-03-01

An electrolyte for an electric cell whose negative active material is constituted by lithium and whose positive active material is constituted by thionyl chloride. The electrolyte contains at least one solvent and at least one solute, said solvent being thionyl chloride and said solute being chosen from the group which includes lithium tetrachloroaluminate and lithium hexachloroantimonate. According to the invention said electrolyte further includes a complex chosen from the group which includes AlCl/sub 3/,SO/sub 2/ and SbCl/sub 5/,SO/sub 2/. The voltage rise of electric cells which include such an electrolyte takes negligible time.

Study of electrodeposition technique to prepare alpha-counting plates of uranium 233

International Nuclear Information System (INIS)

Mertzig, W.

1979-01-01

The electrodeposition technique to prepare alpha-counting plates of 233 U for its determination is presented. To determine the optimum conditions for plating 233 U the effects of such parameters as current density, pH of eletrotype, salt concentration, time of electrolysis and distance electrodes were studied. A carrier method was developed to attain a quantitative electrodeposition of 233 U from aqueous solutions into alpha counting paltes. A single and incremental addition of natural uranium and thorium as carrier were studied. All samples were prepared using a electrodeposition cell manufactured at the IPEN, especially for use in electroplating tracer actinides. This cell is made of a metal-lucite to contain the electrolyte, which bottom is a polished brass disk coated with a Ni film serving as the cathode. A Pt wire anode is fixed on the top of the cell. The electroplated samples were alpha-counted using a surface barrier detector. A recovery of more than 99% was obtained in specific conditions. The plating procedure produced deposits which were firmly distributed over the plate area. The method was applied to determine tracer amounts of 233 U from oxalate and nitrate solutions coming from chemical processing irradiated thorium. (Author) [pt

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

High-performance electrolyte in the presence of dextrose and its derivatives for aluminum electrolytic capacitors

Science.gov (United States)

Tsai, Ming-Liao; Lu, Yi-Fang; Do, Jing-Shan

Dextrose and its derivatives (e.g. glucose, gluconic acid and gluconic lactone) are added to modify the characteristics of electrolytes used in aluminum electrolytic capacitors. The results show that the conductivity and sparking voltage of the electrolytes are severely affected by the concentration of dextrose gluconic acid and gluconic lactone. In addition, the pH of the electrolyte is only slightly affected by the quantity of gluconic acid and gluconic lactone. The capacitance, dissipation factor, and leakage current of capacitors impregnated with the electrolytes prepared in this work are periodically measured under storage conditions and loading at 105 °C.

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

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

Ceramic solid electrolytes

Energy Technology Data Exchange (ETDEWEB)

Goodenough, John B. [Center for Materials Science and Engineering, University of Texas at Austin, Austin, TX (United States)

1997-02-15

Strategies for the design of ceramic solid electrolytes are reviewed. Problems associated with stoichiometric and doped compounds are compared. In the illustration of design principles, emphasis is given to oxide-ion electrolytes for use in solid-oxide fuel cells, oxygen pumps, and oxygen sensors

Gel polymer electrolytes for batteries

Science.gov (United States)

Balsara, Nitash Pervez; Eitouni, Hany Basam; Gur, Ilan; Singh, Mohit; Hudson, William

2014-11-18

Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at 25.degree. C.

Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

Energy Technology Data Exchange (ETDEWEB)

Andrieu, X.; Boudin, F. [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

1996-12-31

The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

Energy Technology Data Exchange (ETDEWEB)

Andrieu, X; Boudin, F [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

1997-12-31

The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

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.

Compatibility of a Conventional Non-aqueous Magnesium Electrolyte with a High Voltage V₂O₅ Cathode and Mg Anode

Energy Technology Data Exchange (ETDEWEB)

Sa, Niya [Argonne National Lab. (ANL), Argonne, IL (United States); Proffit, Danielle L. [Argonne National Lab. (ANL), Argonne, IL (United States); Lipson, Albert L. [Argonne National Lab. (ANL), Argonne, IL (United States); Liu, Miao [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Gautam, Gopalakrishnan Sai [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Hahn, Nathan [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Feng, Zhenxing [Argonne National Lab. (ANL), Argonne, IL (United States); Fister, Timothy T. [Argonne National Lab. (ANL), Argonne, IL (United States); Ren, Yang [Argonne National Lab. (ANL), Argonne, IL (United States); Sun, Cheng-Jun [Argonne National Lab. (ANL), Argonne, IL (United States); Vaughey, John T. [Argonne National Lab. (ANL), Argonne, IL (United States); Liao, Chen [Argonne National Lab. (ANL), Argonne, IL (United States); Fenter, Paul A. [Argonne National Lab. (ANL), Argonne, IL (United States); Ceder, Gerbrand [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Zavadil, Kevin R. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Burrell, Anthony K. [Argonne National Lab. (ANL), Argonne, IL (United States)

2015-08-01

A major roadblock for magnesium ion battery development is the availability of an electrolyte that can deposit Mg reversibly and at the same time is compatible with a high voltage cathode. We report a prospective full magnesium cell utilizing a simple, non-aqueous electrolyte composed of high concentration magnesium bis(trifluoromethane sulfonyl)imide in diglyme, which is compatible with a high voltage vanadium pentoxide (V₂O₅) cathode and a Mg metal anode. For this system, plating and stripping of Mg metal can be achieved with magnesium bis(trifluoromethane sulfonyl)imide in diglyme electrolyte over a wide concentration range, however, reversible insertion of Mg into V₂O₅ cathode can only be attained at high electrolyte concentrations. Reversible intercalation of Mg into V₂O₅ is characterized and confirmed by X-ray diffraction, X-ray absorption near edge spectroscopy and energy dispersive spectroscopy.

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

Electrophoretic deposits of boron on duralumin plates used for measuring neutron flux

International Nuclear Information System (INIS)

Lang, F.M.; Magnier, P.; Finck, C.

1956-01-01

Preparation of boron thin film deposits of around 1 mg per cm 2 on duralumin plates with a diameter of 8 cm. The boron coated plates for ionization chambers were originally prepared at the CEA by pulverization of boron carbides on sodium silicates. This method is not controlling precisely enough the quantity of boron deposit. Thus, an electrophoretic method is considered for a better control of the quantity of boron deposit in the scope of using in the future boron 10 which is costly and rare. The method described by O. Flint is not satisfying enough and a similar electrophoretic process has been developed. Full description of the method is given as well as explanation of the use of dried methanol as solvent, tannin as electrolyte and magnesium chloride to avoid alumina formation. (M.P.)

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.)

A Flexible Solid Electrolyte Interphase Layer for Long-Life Lithium Metal Anodes.

Science.gov (United States)

Li, Nian-Wu; Shi, Yang; Yin, Ya-Xia; Zeng, Xian-Xiang; Li, Jin-Yi; Li, Cong-Ju; Wan, Li-Jun; Wen, Rui; Guo, Yu-Guo

2018-02-05

Lithium (Li) metal is a promising anode material for high-energy density batteries. However, the unstable and static solid electrolyte interphase (SEI) can be destroyed by the dynamic Li plating/stripping behavior on the Li anode surface, leading to side reactions and Li dendrites growth. Herein, we design a smart Li polyacrylic acid (LiPAA) SEI layer high elasticity to address the dynamic Li plating/stripping processes by self-adapting interface regulation, which is demonstrated by in situ AFM. With the high binding ability and excellent stability of the LiPAA polymer, the smart SEI can significantly reduce the side reactions and improve battery safety markedly. Stable cycling of 700 h is achieved in the LiPAA-Li/LiPAA-Li symmetrical cell. The innovative strategy of self-adapting SEI design is broadly applicable, providing opportunities for use in Li metal anodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

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

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

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...

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.

Electron transfer across multiple hydrogen bonds: the case of ureapyrimidinedione-substituted vinyl ruthenium and osmium complexes.

Science.gov (United States)

Pichlmaier, Markus; Winter, Rainer F; Zabel, Manfred; Zális, Stanislav

2009-04-08

Ruthenium and osmium complexes 2a,b and 3a,b featuring the N-4,6-dioxo-5,5-dibutyl- or the N-4,6-dioxo-5,5-di-(2-propenyl)-1,4,5,6-tetrahydropyrimidin-2-yl-N'(4-ethenylphenyl)-urea ligand dimerize by a self-complementary quadruply hydrogen-bonding donor/donor/acceptor/acceptor (DDAA) motif. We provide evidence that the dimeric structures are maintained in nonpolar solvents and in 0.1 M NBu(4)PF(6)/CH(2)Cl(2) supporting electrolyte solution. All complexes are reversibly oxidized in two consecutive two-electron oxidations (DeltaE(1/2) approximately = 500 mV) without any discernible potential splitting for the oxidation of the individual hydrogen-bridged redox active moieties. IR and UV/vis/NIR spectroelectrochemistry show a one-step conversion of the neutral to the dication without any discernible features of an intermediate monooxidized radical cation. Oxidation-induced IR changes of the NH and CO groups that are involved in hydrogen bonding are restricted to the styryl-bonded urea NH function. IR band assignments are aided by quantum chemical calculations. Our experimental findings clearly show that, at least in the present systems, the ureapyrimidinedione (Upy) DDAA hydrogen-bonding motif does not support electron transfer. The apparent reason is that neither of the hydrogen-bonding functionalities contributes to the occupied frontier levels. This results in nearly degenerate pairs of MOs representing the in-phase and out-of-phase combinations of the individual monomeric building blocks.

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...

Enhancing Capacity Performance by Utilizing the Redox Chemistry of the Electrolyte in a Dual-Electrolyte Sodium-Ion Battery.

Science.gov (United States)

Senthilkumar, Sirugaloor Thangavel; Bae, Hyuntae; Han, Jinhyup; Kim, Youngsik

2018-05-04

A strategy is described to increase charge storage in a dual electrolyte Na-ion battery (DESIB) by combining the redox chemistry of the electrolyte with a Na + ion de-insertion/insertion cathode. Conventional electrolytes do not contribute to charge storage in battery systems, but redox-active electrolytes augment this property via charge transfer reactions at the electrode-electrolyte interface. The capacity of the cathode combined with that provided by the electrolyte redox reaction thus increases overall charge storage. An aqueous sodium hexacyanoferrate (Na 4 Fe(CN) 6 ) solution is employed as the redox-active electrolyte (Na-FC) and sodium nickel Prussian blue (Na x -NiBP) as the Na + ion insertion/de-insertion cathode. The capacity of DESIB with Na-FC electrolyte is twice that of a battery using a conventional (Na 2 SO 4 ) electrolyte. The use of redox-active electrolytes in batteries of any kind is an efficient and scalable approach to develop advanced high-energy-density storage systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

Science.gov (United States)

Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung

2016-11-09

Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

Microstructure, thickness and sheet resistivity of Cu/Ni thin film produced by electroplating technique on the variation of electrolyte temperature

Science.gov (United States)

Toifur, M.; Yuningsih, Y.; Khusnani, A.

2018-03-01

In this research, it has been made Cu/Ni thin film produced with electroplating technique. The deposition process was done in the plating bath using Cu and Ni as cathode and anode respectively. The electrolyte solution was made from the mixture of HBrO3 (7.5g), NiSO4 (100g), NiCl2 (15g), and aquadest (250 ml). Electrolyte temperature was varied from 40°C up to 80°C, to make the Ni ions in the solution easy to move to Cu cathode. The deposition was done during 2 minutes on the potential of 1.5 volt. Many characterizations were done including the thickness of Ni film, microstructure, and sheet resistivity. The results showed that at all samples Ni had attacked on the Cu substrate to form Cu/Ni. The raising of electrolyte temperature affected the increasing of Ni thickness that is the Ni thickness increase with the increasing electrolyte temperature. From the EDS spectrum, it can be informed that samples already contain Ni and Cu elements and NiO and CuO compounds. Addition element and compound are found for sample Cu/Ni resulted from 70° electrolyte temperature of Ni deposition, that are Pt and PtO2. From XRD pattern, there are several phases which have crystal structure i.e. Cu, Ni, and NiO, while CuO and PtO2 have amorphous structure. The sheet resistivity linearly decreases with the increasing electrolyte temperature.

Fabrication of ruthemium 106 sources for betatherapy of choroid cancer

International Nuclear Information System (INIS)

Bourges, J.; Robelin, B.; Desmouliere, F.; Massicot, A.; Lefebre, D.

1985-01-01

Three sources of ruthenium 106 intended to the betatherapy of eye's tumours have been made by electrodeposition on stainless steel supports prior plated with gold 30 microns thick. This report presents the different steps of this preparation: ruthenium 106 purification from a solution of fission products by RuO 4 volatilization with AgO acting agent; gilding of the supports; ruthenium 106 electrodeposition as metal; protection of the source by a thin film of epoxyde resin [fr

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.

Plated copper front side metallization on printed seed-layers for silicon solar cells

OpenAIRE

Kraft, Achim

2015-01-01

A novel copper front side metallization architecture for silicon solar cells based on a fine printed silver seed-layer, plated with nickel, copper and silver, is investigated. The work focuses on the printing of fine seed-layers with low silver consumption, the corrosion of the printed seed-layers by the interaction with electrolyte solutions and the encapsulation material on module level and on the long term stability of the cells due to copper migration. The investigation of the correlation...

Improved electroless plating method through ultrasonic spray atomization for depositing silver nanoparticles on multi-walled carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Zhao, Qi [School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China); Xie, Ming [Kunming Institute of Precious Metals, Kunming 650106 (China); Liu, Yichun, E-mail: liuyichun@kmust.edu.cn [School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China); Yi, Jianhong [School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093 (China)

2017-07-01

Highlights: • Electroless plating method assisted by ultrasonic spray atomization was developed. • This method leads to much more uniform silver coatings on MWCNTs. • The plating parameters affect the layer morphologies a lot. - Abstract: A novel method was developed to deposit nanosized silver particles on multi-walled carbon nanotubes (MWCNTs). The electroless plating of silver on MWCNTs accomplished in small solution drops generated by ultrasonic spray atomization, which inhibited excessive growth of silver particles and led to much more uniform nanometer grain-sized coatings. The results showed that pretreatment was essential for silver particles to deposit on the MWCNTs, and the electrolyte concentration and reaction temperature were important parameters which had a great influence on the morphology and structure of the silver coatings. Possible mechanisms of this method are also discussed in the paper.

Improved electroless plating method through ultrasonic spray atomization for depositing silver nanoparticles on multi-walled carbon nanotubes

International Nuclear Information System (INIS)

Zhao, Qi; Xie, Ming; Liu, Yichun; Yi, Jianhong

2017-01-01

Highlights: • Electroless plating method assisted by ultrasonic spray atomization was developed. • This method leads to much more uniform silver coatings on MWCNTs. • The plating parameters affect the layer morphologies a lot. - Abstract: A novel method was developed to deposit nanosized silver particles on multi-walled carbon nanotubes (MWCNTs). The electroless plating of silver on MWCNTs accomplished in small solution drops generated by ultrasonic spray atomization, which inhibited excessive growth of silver particles and led to much more uniform nanometer grain-sized coatings. The results showed that pretreatment was essential for silver particles to deposit on the MWCNTs, and the electrolyte concentration and reaction temperature were important parameters which had a great influence on the morphology and structure of the silver coatings. Possible mechanisms of this method are also discussed in the paper.

Double-membrane triple-electrolyte redox flow battery design

Science.gov (United States)

Yushan, Yan; Gu, Shuang; Gong, Ke

2018-03-13

A redox flow battery is provided having a double-membrane (one cation exchange membrane and one anion exchange membrane), triple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and one electrolyte positioned between and in contact with the two membranes). The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolyte and the positive or negative electrolyte. This design physically isolates, but ionically connects, the negative electrolyte and positive electrolyte. The physical isolation offers great freedom in choosing redox pairs in the negative electrolyte and positive electrolyte, making high voltage of redox flow batteries possible. The ionic conduction drastically reduces the overall ionic crossover between negative electrolyte and positive one, leading to high columbic efficiency.

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.

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.

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

POLYMER ELECTROLYTE MEMBRANE FUEL CELLS

DEFF Research Database (Denmark)

2001-01-01

A method for preparing polybenzimidazole or polybenzimidazole blend membranes and fabricating gas diffusion electrodes and membrane-electrode assemblies is provided for a high temperature polymer electrolyte membrane fuel cell. Blend polymer electrolyte membranes based on PBI and various...... thermoplastic polymers for high temperature polymer electrolyte fuel cells have also been developed. Miscible blends are used for solution casting of polymer membranes (solid electrolytes). High conductivity and enhanced mechanical strength were obtained for the blend polymer solid electrolytes....... With the thermally resistant polymer, e.g., polybenzimidazole or a mixture of polybenzimidazole and other thermoplastics as binder, the carbon-supported noble metal catalyst is tape-cast onto a hydrophobic supporting substrate. When doped with an acid mixture, electrodes are assembled with an acid doped solid...

Simulation of through via bottom—up copper plating with accelerator for the filling of TSVs

International Nuclear Information System (INIS)

Wu Heng; Tang Zhen'an; Wang Zhu; Cheng Wan; Yu Daquan

2013-01-01

Filling high aspect ratio through silicon vias (TSVs) without voids and seams by copper plating is one of the technical challenges for 3D integration. Bottom—up copper plating is an effective solution for TSV filling. In this paper, a new numerical model was developed to simulate the electrochemical deposition (ECD) process, and the influence of an accelerator in the electrolyte was investigated. The arbitrary Lagrange—Eulerian (ALE) method for solving moving boundaries in the finite element method (FEM) was used to simulate the electrochemical process. In the model, diffusion coefficient and adsorption coefficient were considered, and then the time-resolved evolution of electroplating profiles was simulated with ion concentration distribution and the electric current density. (semiconductor technology)

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...

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)

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

Multiple-membrane multiple-electrolyte redox flow battery design

Science.gov (United States)

Yan, Yushan; Gu, Shuang; Gong, Ke

2017-05-02

A redox flow battery is provided. The redox flow battery involves multiple-membrane (at least one cation exchange membrane and at least one anion exchange membrane), multiple-electrolyte (one electrolyte in contact with the negative electrode, one electrolyte in contact with the positive electrode, and at least one electrolyte disposed between the two membranes) as the basic characteristic, such as a double-membrane, triple electrolyte (DMTE) configuration or a triple-membrane, quadruple electrolyte (TMQE) configuration. The cation exchange membrane is used to separate the negative or positive electrolyte and the middle electrolyte, and the anion exchange membrane is used to separate the middle electrolyte and the positive or negative electrolyte.

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.

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

Lithium dendrite and solid electrolyte interphase investigation using OsO4

Science.gov (United States)

Zier, Martin; Scheiba, Frieder; Oswald, Steffen; Thomas, Jürgen; Goers, Dietrich; Scherer, Torsten; Klose, Markus; Ehrenberg, Helmut; Eckert, Jürgen

2014-11-01

Osmium tetroxide (OsO4) staining, commonly used to enhance scattering contrast in electron microscopy of biologic tissue and polymer blends, has been adopted for studies of graphite anodes in lithium-ion batteries. OsO4 shows a coordinated reaction with components of the solid electrolyte interphase (SEI) and lithium dendrites, thereby increasing material contrast for scanning electron microscopy investigations. Utilizing the high affinity of lithium metal to react with osmium tetroxide it was possible to localize even small lithium deposits on graphite electrodes. In spite of their reaction with the OsO4 fume, the lithium dendrite morphology remains almost untouched by the staining procedure, offering information on the dendrite growth process. Correlating the quantity of osmium detected with the amount of residual ("dead") lithium of a discharged electrode, it was possible to obtain a practical measure for lithium plating and stripping efficiencies. EDX mappings allowed for a localization of electrochemically stripped lithium dendrites by their residual stained SEI shells. Cross sections, prepared by focused ion beam (FIB) of cycled graphite electrodes treated with OsO4, revealed important information about deposition and distribution of metallic lithium and the electrolyte reduction layer across the electrode.

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

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)

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)

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)

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).

Electrolytic hydriding and hydride distribution in zircaloy-4

International Nuclear Information System (INIS)

Gomes, M.H.L.

1974-01-01

A study has been made of the electrolytic hydriding of zircaloy-4 in the range 20-80 0 C, for reaction times from 5 to 30 hours, and the effect of potential, pH and dissolved oxygen has been investigated. The hydriding reaction was more sensitive to time and temperature conditions than to the electrochemical variables. It has been shown that a controlled introduction of hydrides in zircaloy is feasible. Hydrides were found to be plate like shaped and distributed mainly along grain-boundaries. It has been shown that hydriding kinetics do not follow a simple law but may be described by a Johnson-Mehl empirical equation. On the basis of this equation an activation energy of 9.400 cal/mol has been determined, which is close to the activation energy for diffusion of hydrogen in the hydride. (author)

Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

Energy Technology Data Exchange (ETDEWEB)

Lu, Dongping; Tao, Jinhui; Yan, Pengfei; Henderson, Wesley A.; Li, Qiuyan; Shao, Yuyan; Helm, Monte L.; Borodin, Oleg; Graff, Gordon L.; Polzin, Bryant; Wang, Chong-Min; Engelhard, Mark; Zhang, Ji-Guang; De Yoreo, James J.; Liu, Jun; Xiao, Jie

2017-02-10

Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, in which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.

Effect of microstructure of TiN film on properties as bipolar plate coatings in polymer electrolyte membrane fuel cell prepared by inductively coupled plasma assisted magnetron sputtering

International Nuclear Information System (INIS)

Feng, Kai; Li, Zhuguo

2013-01-01

As potential application in bipolar plate of polymer electrolyte membrane fuel cell, the microstructure, corrosion resistance and the electrical conductivity of titanium nitride (TiN) and Si doped titanium nitride (Ti 0.9 Si 0.1 N) films deposited by magnetron sputtering with different bias voltages are investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM), electrochemical test and four-point probe method, respectively. XRD, SEM and AFM results reveal that the texture and topography of TiN film depend on the bias voltage and incorporation of Si. When the bias voltage is − 20 V and − 30 V, the TiN and Ti 0.9 Si 0.1 N films exhibit a dense (111) plane preferred growth, denser structure and smoother surface topography. The potentiodynamic test results indicate that the TiN and Ti 0.9 Si 0.1 N films have higher chemical inertness and better corrosion resistance. The films can satisfy the requirement of current density for bipolar plate materials. Incorporation of Si element into TiN film makes the passive current density more stable. Four-point probe measurement results show that the resistivity of both TiN and Ti 0.9 Si 0.1 N films reaches minimum when the deposition bias voltage is − 20 V. - Highlights: • Dense TiN and Ti 0.9 Si 0.1 N films are deposited by magnetron sputtering. • Preferred growth orientation of TiN depends on the bias voltage and Si doping. • TiN and Ti 0.9 Si 0.1 N films have excellent corrosion resistance. • Surface conductivity of TiN and Ti 0.9 Si 0.1 N films evolves with bias voltage

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

Substitution of Ethynyl-Thiophene Chromophores on Ruthenium Sensitizers: Influence on Thermal and Photovoltaic Performance of Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Malapaka Chandrasekharam

2012-01-01

Full Text Available A new high molar extinction coefficient ruthenium(II bipyridyl complex, “Ru(2,2-bipyridine-4,4′-dicarboxylic acid(4,4′-bis((3-hexylthiophen-2-ylethynyl-2,2′-bipyridine(NCS2 (N(C4H94, MC101” was synthesized and fully characterized by 1H-NMR, ESI-MASS, FT-IR, UV-Vis., and fluorescence spectroscopes. The dye showed relatively high molar extinction coefficient of 25.0 × 103 M-1 cm-1 at λ maximum of 544 nm, while the reference C101 has shown 15.8 × 103 M-1cm-1 at λ maximum 528 nm. The monochromatic incident photon-to-collected electron conversion efficiency of 44.1% was obtained for MC101 over the entire visible range, while the C101 sensitized solar cell fabricated and evaluated under identical conditions exhibited 40.1%. The DSSCs fabricated with 0.54 cm2 active area TiO2 electrodes and high efficient electrolyte (E01, from the sensitizers MC101 and C101 exhibited energy conversion efficiencies of 3.25% (short-circuit current density (JSC = 7.32 mA/cm2, VOC = 610 mV, ff = 0.725 and 2.94% (JSC = 6.60 mA/cm2; VOC = 630 mV; ff = 0.709, respectively, under air mass of 1.5 sunlight.

New polysaccharide-based polymer electrolytes; Nouveaux electrolytes polymeres a base de polysaccharides

Energy Technology Data Exchange (ETDEWEB)

Velasquez-Morales, P.; Le Nest, J.F.; Gandini, A. [Ecole Francaise de Papeterie et des Industries Graphique, 38 - Saint Martin d`Heres (France)

1996-12-31

Polysaccharides like cellulose and chitosan are known for their filmic properties. This paper concerns the synthesis and the study of chitosan-based polymer electrolytes. A preliminary work concerns the study of glucosamine reactivity. The poly-condensation of chitosan ethers (obtained by reaction with ethylene oxide or propylene oxide) with bifunctional and monofunctional oligo-ethers leads to the formation of thin lattices (10 {mu}m) having excellent mechanical properties. The presence of grafted polyether chains along the polysaccharide skeleton allows to modify the vitreous transition temperature and the molecular disorder of the system. Two type of polymer electrolytes have been synthesized: electrolytes carrying a dissolved alkaline metal salt and ionomers. The analysis of their thermal, dynamical mechanical, nuclear magnetic relaxation, electrical, and electrochemical properties shows that this new class of polymer electrolytes has the same performances as ethylene poly-oxide based amorphous lattices plus the advantage of having good filmic properties. Abstract only. (J.S.)

New polysaccharide-based polymer electrolytes; Nouveaux electrolytes polymeres a base de polysaccharides

Energy Technology Data Exchange (ETDEWEB)

Velasquez-Morales, P; Le Nest, J F; Gandini, A [Ecole Francaise de Papeterie et des Industries Graphique, 38 - Saint Martin d` Heres (France)

1997-12-31

Polysaccharides like cellulose and chitosan are known for their filmic properties. This paper concerns the synthesis and the study of chitosan-based polymer electrolytes. A preliminary work concerns the study of glucosamine reactivity. The poly-condensation of chitosan ethers (obtained by reaction with ethylene oxide or propylene oxide) with bifunctional and monofunctional oligo-ethers leads to the formation of thin lattices (10 {mu}m) having excellent mechanical properties. The presence of grafted polyether chains along the polysaccharide skeleton allows to modify the vitreous transition temperature and the molecular disorder of the system. Two type of polymer electrolytes have been synthesized: electrolytes carrying a dissolved alkaline metal salt and ionomers. The analysis of their thermal, dynamical mechanical, nuclear magnetic relaxation, electrical, and electrochemical properties shows that this new class of polymer electrolytes has the same performances as ethylene poly-oxide based amorphous lattices plus the advantage of having good filmic properties. Abstract only. (J.S.)

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.

Experimental Study of Hydroxy Gas (HHO) Production with Variation in Current, Voltage and Electrolyte Concentration

Science.gov (United States)

Alam, Noor; Pandey, K. M.

2017-08-01

In this paper, work has been carried out experimentally for the investigation of the effects of variation incurrent, voltage, temperature, chemical concentration and reaction time on the amount of hydroxy gas produced. Further effects on the overall electrolysis efficiency of advance alkaline water is also studied. The hydroxy gas (HHO) has been produced experimentally by the electrolysis of alkaline water with parallel plate electrode of 316L-grade stainless steel. The electrode has been selected on the basis of corrosion resistance and inertness with respect to electrolyte (KOH). The process used for the production of HHO is conventional as compared to the other production processes because of reduced energy consumption, less maintenance and low setup cost. From the experimental results, it has been observed that with increase in voltage, temperature and electrolyte concentration of alkaline solution, the production of hydroxy gas has increased about 30 to 40% with reduction in electrical energy consumption.

Polymer Electrolytes for Lithium/Sulfur Batteries

Directory of Open Access Journals (Sweden)

The Nam Long Doan

2012-08-01

Full Text Available This review evaluates the characteristics and advantages of employing polymer electrolytes in lithium/sulfur (Li/S batteries. The main highlights of this study constitute detailed information on the advanced developments for solid polymer electrolytes and gel polymer electrolytes, used in the lithium/sulfur battery. This includes an in-depth analysis conducted on the preparation and electrochemical characteristics of the Li/S batteries based on these polymer electrolytes.

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...

Nickel electroplating on copper pre-activated Al alloy in the electrolyte containing PEG1000 as an additive

Science.gov (United States)

Guan, Jie; Wang, Jinwei; Zhang, Dawei

2018-06-01

Ni coatings are prepared on Cu-pretreated anodic Al alloy by electroplating technique in environment-friendly electrolytes with PEG1000 as an additive. Some defects like pores, cracks and even uncovered areas are observed for the sample of the Cu-pretreated anodic Al alloy, and these defects seem to be remedied with the following Ni electroplating as observed from their SEM images; while the covering effect of Ni onto the Cu layer is rather limited as judged by their corrosion current data of polarization test. After adding PEG1000 in the Ni electroplating electrolyte, the obtained coating surfaces are seen smoother and thicker; and most of the tiny particles are seen closely packed together with some bigger particles on them. The diffusion of nickel particles into copper layer are confirmed by the line and mapping mode of EDS element analysis for the Ni-Cu composite coating. Their much lower corrosion current density ( I corr) and higher micro-hardness support the fact that the addition of PEG1000 in Ni plating electrolyte has a function of promoting the refinement of Ni particles and the formation of more compacter, thicker and smoother Ni-Cu composite coating.

Solid polymer electrolyte from phosphorylated chitosan

Energy Technology Data Exchange (ETDEWEB)

Fauzi, Iqbal, E-mail: arcana@chem.itb.ac.id; Arcana, I Made, E-mail: arcana@chem.itb.ac.id [Inorganic and Physical Chemistry Research Groups, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

2014-03-24

Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the component’s composition respectively on the properties of polymer electrolyte, was carried out by analyzed of it’s characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensile resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 × 10{sup −6} S/cm up to 6.01 × 10{sup −4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 × 10{sup −3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.

Composition of highly concentrated silicate electrolytes and ultrasound influencing the plasma electrolytic oxidation of magnesium

Science.gov (United States)

Simchen, F.; Rymer, L.-M.; Sieber, M.; Lampke, T.

2017-03-01

Magnesium and its alloys are increasingly in use as lightweight construction materials. However, their inappropriate corrosion and wear resistance often prevent their direct practical use. The plasma electrolytic oxidation (PEO) is a promising, environmentally friendly method to improve the surface characteristics of magnesium materials by the formation of oxide coatings. These PEO layers contain components of the applied electrolyte and can be shifted in their composition by increasing the concentration of the electrolyte constituents. Therefore, in contrast to the use of conventional low concentrated electrolytes, the process results in more stable protective coatings, in which electrolyte species are the dominating constitutes. In the present work, the influence of the composition of highly concentrated alkaline silicate electrolytes with additives of phosphate and glycerol on the quality of PEO layers on the magnesium alloy AZ31 was examined. The effect of ultrasound coupled into the electrolyte bath was also considered. The process was monitored by recording the electrical process variables with a transient recorder and by observation of the discharge phenomena on the sample surface with a camera. The study was conducted on the basis of a design of experiments. The effects of the process parameter variation are considered with regard to the coatings thickness, hardness and corrosion resistance. Information about the statistical significance of the effects of the parameters on the considered properties is obtained by an analysis of variance (ANOVA).

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

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)

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)

Hardening parts by chrome plating in manufacture and repair

Science.gov (United States)

Astanin, V. K.; Pukhov, E. V.; Stekolnikov, Y. A.; Emtsev, V. V.; Golikova, O. A.

2018-03-01

In the engineering industry, galvanic coatings are widely used to prolong the service life of the machines, which contribute to the increase in the strength of the parts and their resistance to environmental influences, temperature and pressure drops, wear and fretting corrosion. Galvanic coatings have been widely applied in engineering, including agriculture, aircraft building, mining, construction, and electronics. The article focuses on the manufacturing methods of new agricultural machinery parts and the repair techniques of worn parts by chrome plating. The main attention is paid to the unstable methods of chromium deposition (in pulsed and reversing modes) in low-concentration electrolytes, which makes it possible to increase the reliability and durability of the hardened parts operation by changing the conditions of electrocrystallization, that is, directed formation of the structure and texture, thickness, roughness and microhardness of chromium plating. The practical recommendations are given on the current and temperature regimes of chromium deposition and composition of baths used for the restoration and hardening of the machine parts. Moreover, the basic methods of machining allowances removal are analysed.

Mathematical modeling of the lithium, thionyl chloride static cell. I. Neutral electrolyte. II - Acid electrolyte

Energy Technology Data Exchange (ETDEWEB)

Tsaur, K.C.; Pollard, R.

1984-05-01

Mathematical models are presented for a Li-LiAlCl4/SOCl2-C static cell with neutral electrolyte and a Li/SOCl2-C static cell with acid electrolyte. The model for the Li-LiAlCl4/SOCl2-C cell with neutral solution predicts that high internal resistance can develop in the positive electrode as a result of low local porosities which are, in turn, caused by large-volume, solid reaction products. Consequently, the maximum usable cell capacity is dictated by the nonuniformity of the reaction distribution at the front of the positive electrode. In many respects, a cell with acid electrolyte can be regarded as a combination of an equivalent neutral electrolyte system and an acid reservoir. The model for the Li/SOCl2 cell suggests that the cell life depends primarily on the quantity of acid added to the electrolyte. 58 references.

Mathematical modeling of the lithium, thionyl chloride static cell. I - Neutral electrolyte. II - Acid electrolyte

Science.gov (United States)

Tsaur, K.-C.; Pollard, R.

1984-05-01

Mathematical models are presented for a Li-LiAlCl4/SOCl2-C static cell with neutral electrolyte and a Li/SOCl2-C static cell with acid electrolyte. The model for the Li-LiAlCl4/SOCl2-C cell with neutral solution predicts that high internal resistance can develop in the positive electrode as a result of low local porosities which are, in turn, caused by large-volume, solid reaction products. Consequently, the maximum usable cell capacity is dictated by the nonuniformity of the reaction distribution at the front of the positive electrode. In many respects, a cell with acid electrolyte can be regarded as a combination of an equivalent neutral electrolyte system and an acid reservoir. The model for the Li/SOCl2 cell suggests that the cell life depends primarily on the quantity of acid added to the electrolyte.

BFR Electrolyte Additive Safety and Flammability Characterization

Energy Technology Data Exchange (ETDEWEB)

Allcorn, Eric [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2017-10-13

Lithium-ion battery safety is a critical issue in the adoption of the chemistry to larger scale applications such as transportation and stationary storage. One of the critical components impacting the safety of lithium-ion batteries is their use of highly flammable organic electrolytes. In this work, brominated flame retardants (BFR’s) – an existing class of flame retardant materials – are incorporated as additives to lithium-ion battery electrolytes with the intention to reduce the electrolyte flammability and thereby improve safety. There are a few critical needs for a successful electrolyte additive: solubility in the electrolyte, electrochemical stability over the range of battery operation, and minimal detrimental effects on battery performance. Those detrimental effects can take the form of electrolyte specific impacts, such as a reduction in conductivity, or electrode impacts, such as SEI-layer modification or chemical instability to the active material. In addition to these needs, the electrolyte additive also needs to achieve its intended purpose, which in this case is to reduce the flammability of the electrolyte. For the work conducted as part of this SPP agreement three separate BFR materials were provided by Albemarle to be tested by Sandia as additives in a traditional lithium-ion battery electrolyte. The provided BFR materials were tribromo-neopentyl alcohol, tetrabromo bisphenol A, and tribromoethylene. These materials were incorporated as separate 4 wt.% additives into a traditional lithium-ion battery electrolyte and compared to said traditional electrolyte, designated Gen2.

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...

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

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.

Multivalent weak electrolytes - risky background electrolytes for capillary zone electrophoresis

Czech Academy of Sciences Publication Activity Database

Beckers, J. L.; Boček, Petr

2002-01-01

Roč. 23, č. 12 (2002), s. 1942-1946 ISSN 0173-0835 R&D Projects: GA ČR GA203/99/0044; GA ČR GA203/02/0023; GA ČR GA203/01/0401; GA AV ČR IAA4031703; GA AV ČR IAA4031103 Institutional research plan: CEZ:AV0Z4031919 Keywords : background electrolytes * capillary zone electrophoresis * multivalent electrolytes Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 4.325, year: 2002

Electrolyte Additives for Phosphoric Acid Fuel Cells

DEFF Research Database (Denmark)

Gang, Xiao; Hjuler, H.A.; Olsen, C.A.

1993-01-01

, as a fuel-cell performance with the modified electrolytes. Specific conductivity measurements of some of the modified phosphoric acid electrolytes are reported. At a given temperature, the conductivity of the C4F9SO3K-modified electrolyte decreases with an increasing amount of the additive; the conductivity...... of the remains at the same value as the conductivity of the pure phosphoric acid. At a given composition, the conductivity of any modified electrolyte increases with temperature. We conclude that the improved cell performance for modified electrolytes is not due to any increase in conductivity.......Electrochemical characteristics of a series of modified phosphoric acid electrolytes containing fluorinated car on compounds and silicone fluids as additives are presented. When used in phosphoric acid fuel cells, the modified electrolytes improve the performance due to the enhanced oxygen...

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.

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

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)

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.

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.

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).

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)

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.

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.

Molecular motion in polymer electrolytes. An investigation of methods for improving the conductivity of solid polymer electrolytes

International Nuclear Information System (INIS)

Webster, Mark Ian

2002-01-01

Three methods were explored with a view to enhancing the ionic conductivity of polymer electrolytes; namely the addition of an inert, inorganic filler, the addition of a plasticizer and the incorporation of the electrolyte in the pores of silica matrices. There have been a number of reports, which suggest the addition of nanocrystalline oxides to polymer electrolytes increases the ionic conductivities by about a factor of two. In this thesis studies of the polymer electrolyte NaSCN.P(EO) 8 with added nanocrystalline alumina powder are reported which show no evidence of enhanced conductivity. The addition of a plasticizer to polymer electrolytes will increase the ionic conductivity. A detailed study was made of the polymer electrolytes LiT.P(EO) 10 and LiClO 4 .P(EO) 10 with added ethylene carbonate plasticizer. The conductivities showed an enhancement, however this disappeared on heating under vacuum. The present work suggests that the plasticised system is not thermodynamically stable and will limit the applications of the material. A series of samples were prepared from the polymer electrolyte LiT.P(EO) 8 and a range of porous silicas. The silicas were selected to give a wide range of pore size and included Zeolite Y, ZSM5, mesoporous silica and a range of porous glasses. This gave pore sizes from less than one nm to 50 nm. A variety of experiments, including X-ray diffraction, DSC and NMR, showed that the polymer electrolyte entered to pores of the silica. As a result the polymer was amorphous and the room temperature conductivity was enhanced. The high temperature conductivity was not increased above that for the pure electrolyte. The results suggest that this could be employed in applications, however would require higher conducting electrolytes to be of practical benefit. (author)

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.

Long-Range Intramolecular Electronic Communication in a Trinuclear Ruthenium Tropolonate Complex.

Science.gov (United States)

Yoshida, Jun; Kuwahara, Kyohei; Suzuki, Kota; Yuge, Hidetaka

2017-02-20

Dinuclear and trinuclear ruthenium complexes, [Ru(trop) 2 (C 2 trop)Ru(dppe)Cp] [2b; trop = tropolonato, C 2 trop = ethynyltropolonato, dppe = 1,2-bis(diphenylphosphino)ethane] and [Ru(trop){(C 2 trop)Ru(dppe)Cp} 2 ] (3), were synthesized, and their electronic and electrochemical properties were investigated in comparison with our previously reported complex [Ru(acac) 2 (C 2 trop)Ru(dppe)Cp] (2a). The electron-donating Ru II (dppe)Cp unit and electron-accepting Ru III O 6 unit are connected by C 2 trop in these complexes. 2a incorporates acetylacetonate as an ancillary ligand, while 2b and 3 incorporate tropolonate as an ancillary ligand. Every complex, 2a, 2b, and 3, exhibits similar UV-vis-near-IR (NIR) absorption spectra, demonstrating the lack of explicit intramolecular electronic communication between the units at least in the neutral state. The weak NIR absorption in 2a further diminished upon electrochemical oxidation, indicating almost no electronic communication between the units. In contrast, 2b and 3 exhibit broad NIR absorptions upon oxidation. Additionally, 3 exhibits four stepwise redox couples in the electrochemical study, which are formally attributed to [Ru II (trop) 3 ] - /[Ru III (trop) 3 ], two [Ru II (dppe)Cp]/[Ru III (dppe)Cp] + , and [Ru III (trop) 3 ]/[Ru IV (trop) 3 ] + couples. Clear separation of the redox couples attributed to the two terminal [Ru(dppe)Cp] units demonstrates the thermodynamic stability of the intermediate oxidation states with respect to disproportionation. Further electrochemical studies using an electrolyte including perfluorinated weakly coordinating anions and density functional theory/time-dependent density functional theory calculations confirmed the effect of ancillary ligands, acetylacetonate and tropolonate. In the case of 2a, electronic delocalization over the whole complex, especially over the [Ru(acac) 2 (trop)] unit, appears to be small. In contrast, the electronic communication between [Ru(dppe)Cp] and [Ru

Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

Science.gov (United States)

Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

2011-12-13

Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

Human Water and Electrolyte Balance

National Research Council Canada - National Science Library

Montain, S. J; Cheuvront, S. N; Carter, R; Sawka, M. N

2006-01-01

.... Sweat losses, if not replaced, reduce body water volume and electrolyte content. Excessive body water or electrolyte losses can disrupt physiological homeostasis and threaten both health and performance...

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.

Electrolytic production of uranous nitrate

International Nuclear Information System (INIS)

Orebaugh, E.G.; Propst, R.C.

1980-04-01

Efficient production of uranous nitrate is important in nuclear fuel reprocessing because U(IV) acts as a plutonium reductant in solvent extraction and can be coprecipitated with plutonium and/or throium as oxalates during fuel reprocessing. Experimental conditions are described for the efficient electrolytic production of uranous nitrate for use as a reductant in the SRP Purex process. The bench-scale, continuous-flow, electrolysis cell exhibits a current efficiency approaching 100% in combination with high conversion rates of U(VI) to U(IV) in simulated and actual SRP Purex solutions. High current efficiency is achieved with a voltage-controlled mercury-plated platinum electrode and the use of hydrazine as a nitrite scavenger. Conversion of U(VI) to U(IV) proceeds at 100% efficiency. Cathodic gas generation is minimal. The low rate of gas generation permits a long residence time within the cathode, a necessary condition for high conversions on a continuous basis. Design proposals are given for a plant-scale, continuous-flow unit to meet SRP production requirements. Results from the bench-scale tests indicate that an 8-kW unit can supply sufficient uranous nitrate reductant to meet the needs of the Purex process at SRP

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.

Electrolytes for lithium and lithium-ion batteries

CERN Document Server

Jow, T Richard; Borodin, Oleg; Ue, Makoto

2014-01-01

Electrolytes for Lithium and Lithium-ion Batteries provides a comprehensive overview of the scientific understanding and technological development of electrolyte materials in the last?several years. This book covers key electrolytes such as LiPF6 salt in mixed-carbonate solvents with additives for the state-of-the-art Li-ion batteries as well as new electrolyte materials developed recently that lay the foundation for future advances.?This book also reviews the characterization of electrolyte materials for their transport properties, structures, phase relationships, stabilities, and impurities.

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

Development of new bi-polar plates based on electrically conductive filled polymers for PEMFC

Energy Technology Data Exchange (ETDEWEB)

Jousse, F.; Salas, J.F.; Giroud, F. [C.E.A., Le Ripault, Monts (France); Icard, B.; Laurent, J.Y.; Serre Combe, P.

2000-07-01

In polymer electrolyte membrane fuel cell technology, the bi-polar plates are dedicated to: the current collection, the separation and distribution of gas (hydrogen and oxygen) at the cathode and the anode. To achieve these functions, bi-polar plate materials must satisfy the following properties: high conductivity (higher than 10 S/cm), high chemical resistance to acid and water, very low permeability to hydrogen (permeability < Pe{sup H2}{sub Nafion} (20 C) = 7.10{sup -17} m{sup 2}/Pa/s). Traditionally bi-polar plates have been designed with stainless steel or graphite. However, the cost of these plates are incompatible to transport applications, principally because of the gas channel machining step. Recently, we have noticed the work of T.M. Besmann [1] on the manufacturing of bi-polar plates based on carbon fibres and phenolic resin, processed by pyrolisis and densification on surface by a chemical vapour infiltration process. However, this kind of process seems too expensive and complex for the needs of the road electric transportation industry. Organic composites based on conductive chemical resistant fillers and processed by molding could be an alternative solution. Bi-polar plates requirements can be achieved by controlling and optimising experimental parameters such as the nature and morphology of fillers, the resin characteristics, and the process conditions. To avoid corrosion of the composite material, and then, the contamination of the cell, we have selected non metallic fillers, based on graphite or carbon black. (orig.)

Flow channel shape optimum design for hydroformed metal bipolar plate in PEM fuel cell

Energy Technology Data Exchange (ETDEWEB)

Peng, Linfa; Lai, Xinmin; Liu, Dong' an; Hu, Peng [State Key Laboratory of Mechanical System and Vibration, Shanghai Jiao Tong University, Shanghai 200240 (China); Ni, Jun [Department of Mechanical Engineering and Applied Mechanics, University of Michigan, Ann Arbor, MI 48109 (United States)

2008-03-15

Bipolar plate is one of the most important and costliest components of polymer electrolyte membrane (PEM) fuel cells. Micro-hydroforming is a promising process to reduce the manufacturing cost of PEM fuel cell bipolar plates made of metal sheets. As for hydroformed bipolar plates, the main defect is the rupture because of the thinning of metal sheet during the forming process. The flow channel section decides whether high quality hydroformed bipolar plates can be successively achieved or not. Meanwhile, it is also the key factor that is related with the reaction efficiency of the fuel cell stacks. In order to obtain the optimum flow channel section design prior the experimental campaign, some key geometric dimensions (channel depth, channel width, rib width and transition radius) of flow channel section, which are related with both reaction efficiency and formability, are extracted and parameterized as the design variables. By design of experiments (DOE) methods and an adoptive simulated annealing (ASA) optimization method, an optimization model of flow channel section design for hydroformed metal bipolar plate is proposed. Optimization results show that the optimum dimension values for channel depth, channel width, rib width and transition radius are 0.5, 1.0, 1. 6 and 0.5 mm, respectively with the highest reaction efficiency (79%) and the acceptable formability (1.0). Consequently, their use would lead to improved fuel cell efficiency for low cost hydroformed metal bipolar plates. (author)

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Gao, Han [Chemical; Maglia, Filippo [BMW Group, Munich 80788, Germany; Lamp, Peter [BMW Group, Munich 80788, Germany; Amine, Khalil [Chemical; Chen, Zonghai [Chemical

2017-12-13

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi0.6Mn0.2Co0.2O2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.

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.

Effect upon biocompatibility and biocorrosion properties of plasma electrolytic oxidation in trisodium phosphate electrolytes.

Science.gov (United States)

Kim, Yu-Kyoung; Park, Il-Song; Lee, Kwang-Bok; Bae, Tae-Sung; Jang, Yong-Seok; Oh, Young-Min; Lee, Min-Ho

2016-03-01

Surface modification to improve the corrosion resistance and biocompatibility of the Mg-Al-Zn-Ca alloy was conducted via plasma electrolytic oxidation (PEO) in an electrolyte that included phosphate. Calcium phosphate can be easily induced on the surface of a PEO coating that includes phosphate in a physiological environment because Ca(2+) ions in body fluids can be combined with PO4 (3-). Cytotoxicity of the PEO coating formed in electrolytes with various amounts of Na3PO4 was identified. In particular, the effects that PEO films have upon oxidative stress and differentiation of osteoblast activity were studied. As the concentration of Na3PO4 in the electrolyte increased, the oxide layer was found to become thicker, which increased corrosion resistance. However, the PEO coating formed in electrolytes with over 0.2 M of added Na3PO4 exhibited more microcracks and larger pores than those formed in smaller Na3PO4 concentrations owing to a large spark discharge. A nonuniform oxide film that included more phosphate caused more cytotoxicity and oxidative stress, and overabundant phosphate content in the oxide layer interrupted the differentiation of osteoblasts. The corrosion resistance of the magnesium alloy and the thickness of the oxide layer were increased by the addition of Na3PO4 in the electrolyte for PEO treatment. However, excessive phosphate content in the oxide layer led to oxidative stress, which resulted in reduced cell viability and activity.

Non-aqueous electrolytes for lithium ion batteries

Science.gov (United States)

Chen, Zonghai; Amine, Khalil

2015-11-12

The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

Drug delivery device including electrolytic pump

KAUST Repository

Foulds, Ian G.; Buttner, Ulrich; Yi, Ying

2016-01-01

Systems and methods are provided for a drug delivery device and use of the device for drug delivery. In various aspects, the drug delivery device combines a “solid drug in reservoir” (SDR) system with an electrolytic pump. In various aspects an improved electrolytic pump is provided including, in particular, an improved electrolytic pump for use with a drug delivery device, for example an implantable drug delivery device. A catalytic reformer can be incorporated in a periodically pulsed electrolytic pump to provide stable pumping performance and reduced actuation cycle.

Drug delivery device including electrolytic pump

KAUST Repository

Foulds, Ian G.

2016-03-31

Systems and methods are provided for a drug delivery device and use of the device for drug delivery. In various aspects, the drug delivery device combines a “solid drug in reservoir” (SDR) system with an electrolytic pump. In various aspects an improved electrolytic pump is provided including, in particular, an improved electrolytic pump for use with a drug delivery device, for example an implantable drug delivery device. A catalytic reformer can be incorporated in a periodically pulsed electrolytic pump to provide stable pumping performance and reduced actuation cycle.

Electrolyte chemistry control in electrodialysis processing

Science.gov (United States)

Hayes, Thomas D.; Severin, Blaine F.

2017-12-26

Methods for controlling electrolyte chemistry in electrodialysis units having an anode and a cathode each in an electrolyte of a selected concentration and a membrane stack disposed therebetween. The membrane stack includes pairs of cationic selective and anionic membranes to segregate increasingly dilute salts streams from concentrated salts stream. Electrolyte chemistry control is via use of at least one of following techniques: a single calcium exclusionary cationic selective membrane at a cathode cell boundary, an exclusionary membrane configured as a hydraulically isolated scavenger cell, a multivalent scavenger co-electrolyte and combinations thereof.

Conductivity studies of PEG based polymer electrolyte for applications as electrolyte in ion batteries

Science.gov (United States)

Patil, Ravikumar V.; Praveen, D.; Damle, R.

2018-05-01

Development of lithium ion batteries employing solid polymer electrolytes as electrolyte material has led to efficient energy storage and usage in many portable devices. However, due to a few drawbacks like lower ionic conductivity of solid polymer electrolytes (SPEs), studies on SPEs for improvement in conductivity still have a good scope. In the present paper, we report the conductivity studies of a new SPE with low molecular weight poly ethylene glycol (PEG) as host polymer in which a salt with larger anion Lithium trifluro methane sulphonate (LTMS). XRD studies have revealed that the salt completely dissociates in the polymer giving a good stable electrolyte at lower salt concentration. Conductivity of the SPEs has been studied as a function of temperature and we reiterate that the conductivity is a thermally activated process and follows Arrhenius type behavior.

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.

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

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.)

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.

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.

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

Plasma electrolytic oxidation of titanium in a phosphate/silicate electrolyte and tribological performance of the coatings

International Nuclear Information System (INIS)

Aliasghari, S.; Skeldon, P.; Thompson, G.E.

2014-01-01

Highlights: • Plasma electrolytic oxidation performed of titanium in silicate/phosphate electrolyte. • Range of duty cycle, current density, positive-to-negative current ratio studied. • Coatings contain anatase, rutile, Ti 3 O 5 , and amorphous silica. • Ptfe incorporated into coatings by addition of ptfe emulsion to the electrolyte. • Fiction reduced but wear life relatively short due to porosity of coatings. - Abstract: Plasma electrolytic oxidation of titanium has been investigated using a phosphate/silicate electrolyte with a square waveform and a frequency of 50 Hz. A range of constant rms current densities, duty cycles and negative-to-positive current ratios was employed. The resultant coatings were examined by analytical scanning and transmission electron microscopies and X-ray diffraction. The coatings, which were limited in thickness to ∼40 to 50 μm, contained anatase, rutile, Ti 2 O 5 and silicon-rich, amorphous material. The tribological behaviour was investigated using a ball-on-disc test, revealing a coefficient of friction against steel of ∼0.8, which reduced to ∼0.4 by incorporation of ptfe particles from the electrolyte. However, due to the composition and morphology of the coatings, their wear life was relatively short

Solid electrolytes

Science.gov (United States)

Abraham, Kuzhikalail M.; Alamgir, Mohamed

1993-06-15

This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

Charge regulation at semiconductor-electrolyte interfaces.

Science.gov (United States)

Fleharty, Mark E; van Swol, Frank; Petsev, Dimiter N

2015-07-01

The interface between a semiconductor material and an electrolyte solution has interesting and complex electrostatic properties. Its behavior will depend on the density of mobile charge carriers that are present in both phases as well as on the surface chemistry at the interface through local charge regulation. The latter is driven by chemical equilibria involving the immobile surface groups and the potential determining ions in the electrolyte solution. All these lead to an electrostatic potential distribution that propagate such that the electrolyte and the semiconductor are dependent on each other. Hence, any variation in the charge density in one phase will lead to a response in the other. This has significant implications on the physical properties of single semiconductor-electrolyte interfaces and on the electrostatic interactions between semiconductor particles suspended in electrolyte solutions. The present paper expands on our previous publication (Fleharty et al., 2014) and offers new results on the electrostatics of single semiconductor interfaces as well as on the interaction of charged semiconductor colloids suspended in electrolyte solution. Copyright © 2014 Elsevier Inc. All rights reserved.

Modeling particulate removal in plate-plate and wire-plate electrostatic precipitators

Directory of Open Access Journals (Sweden)

S Ramechecandane

2016-09-01

Full Text Available The present study is concerned with the modeling of electrically charged particles in a model plate-plate and a single wire-plate electrostatic precipitator (ESP. The particle concentration distributions for both a plate-plate and a wire-plate ESP are calculated using a modified drift flux model. Numerical investigations are performed using the modified drift flux model for particle number concentration, in addition to the RNG k - ε model for the mean turbulent flow field and the Poisson equation for the electric field. The proposed model and the outlined methodology for coupling the flow field, electric field, charging kinetics and particle concentration is applied to two model precipitators that are truly representative of a wide class of commercialized ESPs. The present investigation is quite different from the earlier studies as it does not make assumptions like a homogeneous electric field or an infinite turbulent diffusivity. The electric field calculated is a strong function of position and controls the migration velocity of particles. Hence, the proposed model can be implemented in a flow solver to obtain a full-fledged solution for any kind of ESP with no limitations on the particle number concentration, as encountered in a Lagrangian approach. The effect of turbulent diffusivity on particle number concentration in a plate-plate ESP is investigated in detail and the results obtained are compared with available experimental data. Similarly, the effect of particle size/diameter and applied electric potential on the accumulative collection performance in the case of a wire-plate ESP is studied and the results obtained are compared with available numerical data. The numerical results obtained using the modified drift flux model for both the plate-plate and wire-plate ESP are in close agreement with available experimental and numerical data.

The installation and dismantling of electrolytic cells

International Nuclear Information System (INIS)

Galushkin, N.V.

1995-01-01

This chapter of monograph is devoted to construction of aluminium electrolytic cells, their installation and dismantling. Therefore, the general characteristic and classification of aluminium electrolytic cells was considered. The anode and cathode structure was studied. The lining of cathode casing, the process of collection of anode gases, electrolytic cell cover, and electrical insulation was studied as well. The installation and dismantling of aluminium electrolytic cells was described.

Underscreening in concentrated electrolytes.

Science.gov (United States)

Lee, Alpha A; Perez-Martinez, Carla S; Smith, Alexander M; Perkin, Susan

2017-07-01

Screening of a surface charge by an electrolyte and the resulting interaction energy between charged objects is of fundamental importance in scenarios from bio-molecular interactions to energy storage. The conventional wisdom is that the interaction energy decays exponentially with object separation and the decay length is a decreasing function of ion concentration; the interaction is thus negligible in a concentrated electrolyte. Contrary to this conventional wisdom, we have shown by surface force measurements that the decay length is an increasing function of ion concentration and Bjerrum length for concentrated electrolytes. In this paper we report surface force measurements to test directly the scaling of the screening length with Bjerrum length. Furthermore, we identify a relationship between the concentration dependence of this screening length and empirical measurements of activity coefficient and differential capacitance. The dependence of the screening length on the ion concentration and the Bjerrum length can be explained by a simple scaling conjecture based on the physical intuition that solvent molecules, rather than ions, are charge carriers in a concentrated electrolyte.

Heavy-water extraction from non-electrolytic hydrogen streams

International Nuclear Information System (INIS)

LeRoy, R.L.; Hammerli, M.; Butler, J.P.

1981-01-01

Heavy water may be produced from non-electrolytic hydrogen streams using a combined electrolysis and catalytic exchange process. The method comprises contacting feed water in a catalyst column with hydrogen gas originating partly from a non-electrolytic hydrogen stream and partly from an electrolytic hydrogen stream, so as to enrich the feed water with the deuterium extracted from both the non-electrolytic and electrolytic hydrogen gas, and passing the deuterium water to an electrolyser wherein the electrolytic hydrogen gas is generated and then fed through the catalyst column. (L.L.)

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

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

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.)

Nuclear electrolytic hydrogen

International Nuclear Information System (INIS)

Barnstaple, A.G.; Petrella, A.J.

1982-05-01

An extensive study of hydrogen supply has recently been carried out by Ontario Hydro which indicates that electrolytic hydrogen produced from nuclear electricity could offer the lowest cost option for any future large scale hydrogen supply in the Province of Ontario, Canada. This paper provides a synopsis of the Ontario Hydro study, a brief overview of the economic factors supporting the study conclusion and discussion of a number of issues concerning the supply of electrolytic hydrogen by electric power utilities

Electrolytic preconcentration in instrumental analysis.

Science.gov (United States)

Sioda, R E; Batley, G E; Lund, W; Wang, J; Leach, S C

1986-05-01

The use of electrolytic deposition as a separation and preconcentration step in trace metal analysis is reviewed. Both the principles and applications of the technique are dealt with in some detail. Electrolytic preconcentration can be combined with a variety of instrumental techniques. Special attention is given to stripping voltammetry, potentiometric stripping analysis, different combinations with atomic-absorption spectrometry, and the use of flow-through porous electrodes. It is pointed out that the electrolytic preconcentration technique deserves more extensive use as well as fundamental investigation.

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.

Thermodynamics of electrolytes. III. Activity and osmotic coefficients for 2-2 electrolytes

Energy Technology Data Exchange (ETDEWEB)

Pitzer, K.S.; Mayorga, G.

1974-01-01

The peculiar behavior of 2-2 and higher valence type electrolytes is discussed in terms of various theories some of which assume, while others do not, an equilibrium between separated ions and ion pairs as distinct chemical species. It is recognized that in some cases a distinct species of inner-shell ion pairs is indicated by spectroscopic or ultrasonic data. Nevertheless, there are many advantages in representing, if possible, the properties of these electrolytes by appropriate virial coefficients and without chemical association equilibria. It is shown that this is possible and is conveniently accomplished by the addition of these equations are given for nine solutes. It is also noted that these equations have been successfully applied to mixed electrolytes involving one component of the 2-2 type. 2 figures, 1 table.

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

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).

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.

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.

Plasma electrolytic oxidation of titanium in a phosphate/silicate electrolyte and tribological performance of the coatings

Energy Technology Data Exchange (ETDEWEB)

Aliasghari, S.; Skeldon, P., E-mail: p.skeldon@manchester.ac.uk; Thompson, G.E.

2014-10-15

Highlights: • Plasma electrolytic oxidation performed of titanium in silicate/phosphate electrolyte. • Range of duty cycle, current density, positive-to-negative current ratio studied. • Coatings contain anatase, rutile, Ti{sub 3}O{sub 5}, and amorphous silica. • Ptfe incorporated into coatings by addition of ptfe emulsion to the electrolyte. • Fiction reduced but wear life relatively short due to porosity of coatings. - Abstract: Plasma electrolytic oxidation of titanium has been investigated using a phosphate/silicate electrolyte with a square waveform and a frequency of 50 Hz. A range of constant rms current densities, duty cycles and negative-to-positive current ratios was employed. The resultant coatings were examined by analytical scanning and transmission electron microscopies and X-ray diffraction. The coatings, which were limited in thickness to ∼40 to 50 μm, contained anatase, rutile, Ti{sub 2}O{sub 5} and silicon-rich, amorphous material. The tribological behaviour was investigated using a ball-on-disc test, revealing a coefficient of friction against steel of ∼0.8, which reduced to ∼0.4 by incorporation of ptfe particles from the electrolyte. However, due to the composition and morphology of the coatings, their wear life was relatively short.

Nonflammable perfluoropolyether-based electrolytes for lithium batteries

Science.gov (United States)

Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao; Devaux, Didier; Pandya, Ashish A.; Battaglia, Vincent S.; Balsara, Nitash P.; DeSimone, Joseph M.

2014-01-01

The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200 °C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi1/3Co1/3Mn1/3O2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity. PMID:24516123

Electrolyte management considerations in modern nickel/hydrogen and nickel/cadmium cells and battery designs

Energy Technology Data Exchange (ETDEWEB)

Thaller, L.H. [The Aerospace Corporation, El Segundo, CA (United States); Zimmermann, A.H. [The Aerospace Corporation, El Segundo, CA (United States)

1996-11-01

While attention has been paid to understanding and modeling abnormal nickel/hydrogen cell behaviors, not enough attention has been paid to the potassium ion content in these cells, and more recently, in batteries. This paper will review three general areas where the potassium ion content can impact the performance and life of nickel/hydrogen and nickel/cadmium cells. Sample calculations of the concentration or volume changes that can take place within operating cells will be presented. With the aid of an accurate model of an operating cell or battery, the impact of changes of potassium ion content within a potential cell design can be estimated. All three of these areas are directly related to the volume tolerance and pore size engineering aspects of the components used in the cell or battery design. the three areas follow. (i) The gamma phase uptake of potassium ion can result in a lowering of the electrolyte concentration. This leads to a higher electrolyte resistance as well as electrolyte diffusional limitations on the discharge rate. This phenomenon also impacts the response of the cell to a reconditioning cycle. (ii) The transport of water vapor from a warmer to a cooler portion of the cell or battery under the driving force of a vapor pressure gradient has already impacted cells when water vapor condenses on a colder cell wall. This paper will explore the convective and diffusive movement of gases saturated with water vapor from a warmer plate pack to a cooler one, both with and without liquid communication. (iii) The impact of low level shunt currents in multicell configurations results in the net movement of potassium hydroxide from one part of the battery to another. This movement impacts the electrolyte volume/vapor pressure relationship within the cell or battery. (orig.)

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...

Lithium-ion transport in inorganic solid state electrolyte

International Nuclear Information System (INIS)

Gao Jian; Li Hong; Zhao Yu-Sheng; Shi Si-Qi

2016-01-01

An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and designing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell (to convey ions while isolate electrons), and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state electrolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes. (topical review)

Solid electrolyte fuel cells

Science.gov (United States)

Isaacs, H. S.

Progress in the development of functioning solid electrolyte fuel cells is summarized. The solid electrolyte cells perform at 1000 C, a temperature elevated enough to indicate high efficiencies are available, especially if the cell is combined with a steam generator/turbine system. The system is noted to be sulfur tolerant, so coal containing significant amounts of sulfur is expected to yield satisfactory performances with low parasitic losses for gasification and purification. Solid oxide systems are electrically reversible, and are usable in both fuel cell and electrolysis modes. Employing zirconium and yttrium in the electrolyte provides component stability with time, a feature not present with other fuel cells. The chemical reactions producing the cell current are reviewed, along with materials choices for the cathodes, anodes, and interconnections.

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.

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

Physics of failure based analysis of aluminium electrolytic capacitor

International Nuclear Information System (INIS)

Sahoo, Satya Ranjan; Behera, S.K.; Kumar, Sachin; Varde, P.V.; Ravi Kumar, G.

2016-01-01

Electrolytic capacitors are one of the important devices in various power electronic systems, such as motor drives, uninterruptible power supply, electric vehicles and dc power supply. Electrolytic capacitors are also the integral part of many other electronic devices. One of the primary function of electrolytic capacitors is the smoothing of voltage ripple and storing electrical energy. However, the electrolytic capacitor has the shortest lifespan of components in power electronics. Past experiences show that electrolytic capacitor tends to degrade and fail faster under high electrical or thermal stress conditions during operations. The primary failure mechanism of an electrolytic capacitor is the evaporation of the electrolyte due to electrical or thermal overstress. This leads to the drift in the values of two important parameters-capacitance and equivalent series resistance (ESR) of the electrolytic capacitor. An attempt has been made to age the electrolytic capacitor and validate the results. The overall goal is to derive the accurate degradation model of the electrolytic capacitor. (author)

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

Activity and Stability of RuOx Based Electrocatalysts for the Oxygen Evolution Reaction

DEFF Research Database (Denmark)

Paoli, Elisa Antares

. By coupling Electrochemical Quartz Crystal Microbalance (EQCM) measurements with Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) analyses of the electrolyte, we emphasize the importance of monitoring the mass loss. Finally, the thesis focuses on improving the stability of ruthenium dioxide under OER...... results show that an improvement of stability can be obtained, slightly decreasing the activity as well. Unfortunately, a drastic enhancement, as hoped, was not detected. Instead the results serve as a starting point from which the strategy and method for stability improvements can be further developed....... activity on oxides and studies on well-defined surfaces are required. Notably, industrial applications demand maximized surface-to-bulk ratio, hence fabrication of catalysts in nanoparticulate form. In this perspective, this project aimed at investigating well-defined mass-selected ruthenium and ruthenium...

Alkyl Chain Barriers for Kinetic Optimization in Dye-Sensitized Solar Cells

NARCIS (Netherlands)

Kroeze, J.E.; Hirata, N.; Koops, S.; Nazeeruddin, M.K.; Schmidt-Mende, L.; Grätzel, M.; Durrant, J.R.

2006-01-01

The optimization of interfacial charge transfer is crucial to the design of dye-sensitized solar cells. In this paper we address the dynamics of the charge separation and recombination in liquid-electrolyte and solid-state cells employing a series of amphiphilic ruthenium dyes with varying

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)

Aluminium Electroplating on Steel from a Fused Bromide Electrolyte

Energy Technology Data Exchange (ETDEWEB)

Prabhat Tripathy; Laura Wurth; Eric Dufek; Toni Y. Gutknecht; Natalie Gese; Paula Hahn; Steven Frank; Guy Fredrickson; J Stephen Herring

2014-08-01

A quaternary bromide bath (LiBr-KBr-CsBr-AlBr3) was used to electro-coat aluminium on steel substrates. The electrolyte was prepared by the addition of AlBr3 into the eutectic LiBr-KBr-CsBr melt. A smooth, thick, adherent and shiny aluminium coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminium coverage. Both salt immersion and open circuit potential measurement suggest that the coatings did display good corrosion-resistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminium coating in preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminium coating on both ferrous and non-ferrous metals, including complex surfaces/geometries.

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...

The potential role of electrolytic hydrogen in Canada

International Nuclear Information System (INIS)

Hammerli, M.

1982-03-01

The potential role of electrolytic hydrogen in Canada is assessed for the period 1980 to 2025 for large-scale uses only. Present uses of hydrogen, and specifically electrolytic hydrogen, are discussed briefly and hydrogen production processes are summarized. Only hydrogen derived from natural gas, coal, or electrolysis of sater are considered. Cost estimates of electrolytic hydrogen are obtained from a parametric equation, comparing values for unipolar water elecctrklyser technologies with those for bipolar electrolysers. Both by-products of electrolytic hydrogen production, namely heavy water and oxygen, are evaluated. Electrolytic hydrogen, based on non-fossil primary energy sources, is also considered as ankther 'liquid fuel option' for Canada along with the alcohols. The market potential for hydrogen in general and electrolytic hydrogen is assessed. Results show that the market potential for electrolytic hydrogen is large by the year 2025

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.

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...

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.

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.

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.

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.

Hydrogenation of esters catalyzed by ruthenium PN3-Pincer complexes containing an aminophosphine arm

KAUST Repository

Chen, Tao

2014-08-11

Hydrogenation of esters under mild conditions was achieved using air-stable ruthenium PN3-pincer complexes containing an aminophosphine arm. High efficiency was achieved even in the presence of water. DFT studies suggest a bimolecular proton shuttle mechanism which allows H2 to be activated by the relatively stable catalyst with a reasonably low transition state barrier. © 2014 American Chemical Society.

3D-Printing Electrolytes for Solid-State Batteries.

Science.gov (United States)

McOwen, Dennis W; Xu, Shaomao; Gong, Yunhui; Wen, Yang; Godbey, Griffin L; Gritton, Jack E; Hamann, Tanner R; Dai, Jiaqi; Hitz, Gregory T; Hu, Liangbing; Wachsman, Eric D

2018-05-01

Solid-state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid-state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D-print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li 7 La 3 Zr 2 O 12 solid electrolyte. Using these 3D-printing ink formulations to further study and optimize electrolyte structure could lead to solid-state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chapter 6. Operation of electrolytic cell in standard operating practices

International Nuclear Information System (INIS)

Yanko, E.A.; Kabirov, Sh.O.; Safiev, Kh.; Azizov, B.S.; Mirpochaev, Kh.A.

2011-01-01

This chapter is devoted to operation of electrolytic cell in standard operating practices. Therefore, the electrolyte temperature, the composition of electrolyte, including the level of metals was considered. The regulation of electrolyte composition by liquidus temperature and electrolyte overheating was studied. Damping of anode effects was studied as well. Maintenance of electrolytic cells was described. Heat and energy balances of aluminium electrolytic cells were considered.