Hydrothermal synthesis of layered iron-chalcogenide superconductors and related compounds

International Nuclear Information System (INIS)

Pachmayr, Ursula Elisabeth

2017-01-01

This thesis provides a new preparative approach to iron-chalcogenide based superconductors. The hydrothermal synthesis of anti-PbO type FeSe, which can be seen as basis structure of the compounds of interest was successfully developed. Along with this, some insights regarding the influence of synthesis parameters were gained featuring a basis for further hydrothermal syntheses of new iron-chalcogenide compounds. The potential of this method, primarily the extension of the so far limited accessibility of iron-chalcogenide based superconductors by solid-state sythesis, was revealed within the present work. The solid-solution FeSe_1_-_xS_x was prepared for the whole substitution range, whereas solid-state synthesis exhibits a solubility limit at x = 0.3. Furthermore, the new compounds [(Li_0_._8Fe_0_._2)OH]FeX (X = Se, S) were synthesized which are exclusively accessible via hydrothermal method. The compounds, where layers of (Li_0_._8Fe_0_._2)OH alternate with FeX layers, feature exceptional physical properties, notably a coexistence of superconductivity and ferromagnetism. They were intensively studied within this work. By combination of solid-state and hydrothermal ion-exchange synthesis even large crystals necessary for subsequent physical measurements are accessible. Apart from these layered iron-chalcogenide superconductors, further compounds which likewise exhibit building blocks of edge-sharing FeSe_4 tetrahedra were found via this synthesis method. The iron selenides A_2Fe_4Se_6 (A = K, Rb, Cs) consist of double chains of [Fe_2Se_3]"1"-, whereas a new compound Na_6(H_2O)_1_8Fe_4Se_8 exhibits [Fe_4Se_8]"6"- 'stella quadrangula' clusters. This structural diversity as well as the associated physical properties of the compounds demonstrates the numerous capabilities of hydrothermal synthesis in the field of iron-chalcogenide compounds. In particular with regard to iron-chalcogenide based superconductors this synthesis strategy is encouraging. It seems probable

Hydrothermal synthesis of layered iron-chalcogenide superconductors and related compounds

Energy Technology Data Exchange (ETDEWEB)

Pachmayr, Ursula Elisabeth

2017-04-06

This thesis provides a new preparative approach to iron-chalcogenide based superconductors. The hydrothermal synthesis of anti-PbO type FeSe, which can be seen as basis structure of the compounds of interest was successfully developed. Along with this, some insights regarding the influence of synthesis parameters were gained featuring a basis for further hydrothermal syntheses of new iron-chalcogenide compounds. The potential of this method, primarily the extension of the so far limited accessibility of iron-chalcogenide based superconductors by solid-state sythesis, was revealed within the present work. The solid-solution FeSe{sub 1-x}S{sub x} was prepared for the whole substitution range, whereas solid-state synthesis exhibits a solubility limit at x = 0.3. Furthermore, the new compounds [(Li{sub 0.8}Fe{sub 0.2})OH]FeX (X = Se, S) were synthesized which are exclusively accessible via hydrothermal method. The compounds, where layers of (Li{sub 0.8}Fe{sub 0.2})OH alternate with FeX layers, feature exceptional physical properties, notably a coexistence of superconductivity and ferromagnetism. They were intensively studied within this work. By combination of solid-state and hydrothermal ion-exchange synthesis even large crystals necessary for subsequent physical measurements are accessible. Apart from these layered iron-chalcogenide superconductors, further compounds which likewise exhibit building blocks of edge-sharing FeSe{sub 4} tetrahedra were found via this synthesis method. The iron selenides A{sub 2}Fe{sub 4}Se{sub 6} (A = K, Rb, Cs) consist of double chains of [Fe{sub 2}Se{sub 3}]{sup 1-}, whereas a new compound Na{sub 6}(H{sub 2}O){sub 18}Fe{sub 4}Se{sub 8} exhibits [Fe{sub 4}Se{sub 8}]{sup 6-} 'stella quadrangula' clusters. This structural diversity as well as the associated physical properties of the compounds demonstrates the numerous capabilities of hydrothermal synthesis in the field of iron-chalcogenide compounds. In particular with regard

Chalcogenide glasses as optical and ion-conducting materials. Kogaku oyobi ion dendo zairyo toshite no chalcogenide glass

Energy Technology Data Exchange (ETDEWEB)

Toge, N.; Minami, T. (Univ. of Osaka Prefecture, Osaka (Japan))

1991-12-01

Nonoxide glasses whose main constituent are chalcogen elements like S, Se, or Te etc. show a lot of various properties, for instance, high infrared transmittancy and semi-conductivity which are already well known. Additionally, the optical properties change a lot along with the phase transition's happening between crystal and noncrystal under comparative low temperature. Further, it is also observed that the glasses containing proper cation appear high ion-conductivity. This paper supplies a brief reviews of chalcogenide glasses used as materials for infrared fiber, phase transition optical memory and superionic conductor, wherein the former two have already on the stage of utilization, particularly the realization of a rewritable optical memory is possible by using chalcogenide glasses film, and ion-conductor is in the phase to have shown the possibility of high conductivity while the development thereof is being expected. 22 refs., 8 figs.

Synthesis of ruthenium phosphides

International Nuclear Information System (INIS)

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

1977-01-01

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

Synthesis of cadmium chalcogenide nanotubes at room temperature

KAUST Repository

Pan, Jun; Qian, Yitai

2012-01-01

Cadmium chalcogenide (CdE, E=S, Se, Te) polycrystalline nanotubes have been synthesized from precursor of CdS/cadmium thiolate complex at room temperature. The precursor was hydrothermally synthesized at 180 °C using thioglycolic acid (TGA) and cadmium acetate as starting materials. The transformation from the rod-like precursor of CdS/cadmium thiolate complex to CdS, CdSe and CdTe nanotubes were performed under constant stirring at room temperature in aqueous solution containing S 2-, Se 2- and Te 2-, respectively. The nanotube diameter can be controlled from 150 to 400 nm related to the dimension of templates. The XRD patterns show the cadmium chalcogenide nanotubes all corresponding to face-centered cubic structure. © 2012 Elsevier B.V. All rights reserved.

Synthesis of cadmium chalcogenide nanotubes at room temperature

KAUST Repository

Pan, Jun

2012-10-01

Cadmium chalcogenide (CdE, E=S, Se, Te) polycrystalline nanotubes have been synthesized from precursor of CdS/cadmium thiolate complex at room temperature. The precursor was hydrothermally synthesized at 180 °C using thioglycolic acid (TGA) and cadmium acetate as starting materials. The transformation from the rod-like precursor of CdS/cadmium thiolate complex to CdS, CdSe and CdTe nanotubes were performed under constant stirring at room temperature in aqueous solution containing S 2-, Se 2- and Te 2-, respectively. The nanotube diameter can be controlled from 150 to 400 nm related to the dimension of templates. The XRD patterns show the cadmium chalcogenide nanotubes all corresponding to face-centered cubic structure. © 2012 Elsevier B.V. All rights reserved.

Magnetic chalcogenides in 3 and lower dimensions

Science.gov (United States)

Furdyna, J. K.; Dong, S.-N.; Lee, S.; Liu, X.; Dobrowolska, M.

2018-06-01

In this article we review magnetic phenomena that occur in the chalcogenide family involving transition metals. Magnetic properties displayed by bulk 3D chalcogenides compounds and alloys produced by equilibrium growth methods are discussed. 2D magnetic chalcogenide systems such as epitaxial films and more complex multilayers, whose formation is made possible by epitaxial methods and/or by van der Waals epitaxy, are presented in detail. We present a brief overview of magnetic effects emerging as the dimensionality of chalcogenide materialss is reduced to 1D (nanowires and related structures) and to zero-D (quantum dots formed by both top-down and bottom-up methods).

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

International Nuclear Information System (INIS)

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

2000-01-01

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

Polarographic determination of ruthenium

International Nuclear Information System (INIS)

Li Jifu; Duan Shirong; Wu Xi

1989-01-01

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

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.)

High-Purity Glasses Based on Arsenic Chalcogenides

Science.gov (United States)

2001-06-01

Chemical interaction of chalcogenides and some impurities (CS 2, TeO2 ) with the quartz glass at high temperature leads to the thin layers formation...UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADPO1 1523 TITLE: High-Purity Glasses Based on Arsenic Chalcogenides...Materials Vol. 3, No. 2, June 2001, p. 341 - 349 HIGH-PURITY GLASSES BASED ON ARSENIC CHALCOGENIDES M. F. Churbanov, I. V. Scripachev, G. E. Snopatin, V. S

The chemistry of copper chalcogenides in waste glasses

International Nuclear Information System (INIS)

Schreiber, H.D.; Lambert, H.W.

1994-01-01

The solubilities of copper chalcogenides (CuS, CuSe, CuTe) were measured in a glass melt which is representative of those proposed for nuclear waste immobilization and circuit board vitrification. CuTe is more soluble than CuS and CuSe in the glass melt under relatively oxidizing conditions. However, the solubilities of all the copper chalcogenides in the glass melt are virtually identical at reducing conditions, probably a result of the redox-controlled solubility of copper metal in all cases. The redox chemistry of a glass melt coexisting with an immiscible copper chalcogenide depends primarily on the prevailing oxygen fugacity, not on the identity of the chalcogenide. The target concentration of less than 0.3 to 0.5 wt% copper in the waste glass should eliminate the precipitation of copper chalcogenides during processing

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.)

Structure of bimetallic clusters. Extended x-ray absorption fine structure (EXAFS) studies of Rh--Cu clusters

International Nuclear Information System (INIS)

Meitzner, G.; Via, G.H.; Lytle, F.W.; Sinfelt, J.H.

1983-01-01

An investigation of the structure of the bimetallic clusters present in rhodium--copper catalysts was conducted with the use of extended x-ray absorption fine structure (EXAFS) measurements. Two catalysts were studied, both employing silica as a support for the clusters and both containing 1 wt. % rhodium. In one catalyst the Cu:Rh atomic ratio was 1:2 and in the other 1:1. Studies were made of the EXAFS associated with the K absorption edges of the rhodium and copper. The results of the EXAFS studies indicate that copper concentrates at the surface of the rhodium--copper clusters. In this regard the results are similar to our earlier reported results on ruthenium--copper clusters. However, the extent of surface segregation of the copper appears to be less pronounced for rhodium--copper clusters. This result is reasonable on the basis that rhodium and copper, unlike ruthenium and copper, exhibit at least some miscibility in the bulk

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

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

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.

Noble-Metal Chalcogenide Nanotubes

Directory of Open Access Journals (Sweden)

Nourdine Zibouche

2014-10-01

Full Text Available We explore the stability and the electronic properties of hypothetical noble-metal chalcogenide nanotubes PtS2, PtSe2, PdS2 and PdSe2 by means of density functional theory calculations. Our findings show that the strain energy decreases inverse quadratically with the tube diameter, as is typical for other nanotubes. Moreover, the strain energy is independent of the tube chirality and converges towards the same value for large diameters. The band-structure calculations show that all noble-metal chalcogenide nanotubes are indirect band gap semiconductors. The corresponding band gaps increase with the nanotube diameter rapidly approaching the respective pristine 2D monolayer limit.

High surface area graphene-supported metal chalcogenide assembly

Science.gov (United States)

Worsley, Marcus A.; Kuntz, Joshua D.; Orme, Christine A.

2017-04-25

Disclosed here is a method for hydrocarbon conversion, comprising contacting at least one graphene-supported assembly with at least one hydrocarbon feedstock, wherein the graphene-supported assembly comprises (i) a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds and (ii) at least one metal chalcogenide compound disposed on the graphene sheets, wherein the chalcogen of the metal chalcogenide compound is selected from S, Se and Te, and wherein the metal chalcogenide compound accounts for at least 20 wt. % of the graphene-supported assembly.

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.

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.

Solution synthesis of mixed-metal chalcogenide nanoparticles and spray deposition of precursor films

Science.gov (United States)

Schulz, Douglas L.; Curtis, Calvin J.; Ginley, David S.

2000-01-01

A colloidal suspension comprising metal chalcogenide nanoparticles and a volatile capping agent. The colloidal suspension is made by reacting a metal salt with a chalcogenide salt in an organic solvent to precipitate a metal chalcogenide, recovering the metal chalcogenide, and admixing the metal chalcogenide with a volatile capping agent. The colloidal suspension is spray deposited onto a substrate to produce a semiconductor precursor film which is substantially free of impurities.

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)

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.)

Metastable states in amorphous chalcogenide semiconductors

CERN Document Server

Mikla, Victor I

2009-01-01

This book addresses an interesting and technologically important class of materials, the amorphous chalcogenide semiconductors. Experimental results on the structural and electronic metastable states in Se-rich chalcogenides are presented. Special attention is paid to the states in the mobility gap and their sensitivity to various factors such as irradiation, annealing and composition. Photoinduced changes of structure and physical properties are also considered and structural transformation at photocrystallization is studied in detail. Finally, the authors discuss potential applications of th

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.

Terahertz-induced Kerr effect in amorphous chalcogenide glasses

DEFF Research Database (Denmark)

Zalkovskij, Maksim; Strikwerda, Andrew; Iwaszczuk, Krzysztof

2013-01-01

We have investigated the terahertz-induced third-order (Kerr) nonlinear optical properties of the amorphous chalcogenide glasses As2S3 and As2Se3. Chalcogenide glasses are known for their high optical Kerr nonlinearities which can be several hundred times greater than those of fused silica. We use...

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.

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.

Recent Advances in Layered Metal Chalcogenides as Superconductors and Thermoelectric Materials: Fe-Based and Bi-Based Chalcogenides.

Science.gov (United States)

Mizuguchi, Yoshikazu

2016-04-01

Recent advances in layered (Fe-based and Bi-based) chalcogenides as superconductors or functional materials are reviewed. The Fe-chalcogenide (FeCh) family are the simplest Fe-based high-Tc superconductors. The superconductivity in the FeCh family is sensitive to external or chemical pressure, and high Tc is attained when the local structure (anion height) is optimized. The Bi-chalcogenide (BiCh2) family are a new group of layered superconductors with a wide variety of stacking structures. Their physical properties are also sensitive to external or chemical pressure. Recently, we revealed that the emergence of superconductivity and the Tc in this family correlate with the in-plane chemical pressure. Since the flexibility of crystal structure and electronic states are an advantage of the BiCh2 family for designing functionalities, I briefly review recent developments in this family as not only superconductors but also other functional materials. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

All-optical tuning of EIT-like dielectric metasurfaces by means of chalcogenide phase change materials.

Science.gov (United States)

Petronijevic, E; Sibilia, C

2016-12-26

Electromagnetically induced transparency (EIT) is a pump-induced narrowband transparency window within an absorption line of the probe beam spectrum in an atomic system. In this paper we propose a way to bring together the all-dielectric metamaterials to have EIT-like effects and to optically tune the response by hybridizing them with a layer of a phase change material. We propose a design of the metamaterial based on Si nanoresonators that can support an EIT-like resonant response. On the top of the resonators we consider a thin layer of a chalcogenide phase change material, which we will use to tune the optical response. Our choice is Ge2Sb2Te5 (GST), since it has two stable phases at room temperature, namely amorphous and crystalline, between which it can be switched quickly, nonvolatively and reversibly, sustaining a large number of switching cycles. They differ in optical properties, while still having moderately low losses in telecom range. Since such dielectric resonators do not have non-radiative losses of metals around 1550nm, they can lead to a high-Q factor of the EIT-like response in this range. Firstly, we optimize the starting structure so that it gives an EIT-like response at 1550 nm when the GST layer is in the amorphous state. Our starting design uses glass as a substrate, but we also consider implementation in SOI technology. If we then switch the thin layer of GST to its crystalline phase, which has higher losses, the EIT-like response is red shifted, providing around 10:1 contrast at 1550nm. This reversible tuning can be done with an ns visible pulsed laser. We discuss the results of the simulation of the dielectric metasurface for different configurations and the tuning possibility.

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.

Chalcogenides Metastability and Phase Change Phenomena

CERN Document Server

Kolobov, Alexander V

2012-01-01

A state-of-the-art description of metastability observed in chalcogenide alloys is presented with the accent on the underlying physics. A comparison is made between sulphur(selenium)-based chalcogenide glasses, where numerous photo-induced phenomena take place entirely within the amorphous phase, and tellurides where a reversible crystal-to-amorphous phase-change transformation is a major effect. Applications of metastability in devices¿optical memories and nonvolatile electronic phase-change random-access memories among others are discussed, including the latest trends. Background material essential for understanding current research in the field is also provided.

Chalcogenide phase-change thin films used as grayscale photolithography materials.

Science.gov (United States)

Wang, Rui; Wei, Jingsong; Fan, Yongtao

2014-03-10

Chalcogenide phase-change thin films are used in many fields, such as optical information storage and solid-state memory. In this work, we present another application of chalcogenide phase-change thin films, i.e., as grayscale photolithgraphy materials. The grayscale patterns can be directly inscribed on the chalcogenide phase-change thin films by a single process through direct laser writing method. In grayscale photolithography, the laser pulse can induce the formation of bump structure, and the bump height and size can be precisely controlled by changing laser energy. Bumps with different height and size present different optical reflection and transmission spectra, leading to the different gray levels. For example, the continuous-tone grayscale images of lifelike bird and cat are successfully inscribed onto Sb(2)Te(3) chalcogenide phase-change thin films using a home-built laser direct writer, where the expression and appearance of the lifelike bird and cat are fully presented. This work provides a way to fabricate complicated grayscale patterns using laser-induced bump structures onto chalcogenide phase-change thin films, different from current techniques such as photolithography, electron beam lithography, and focused ion beam lithography. The ability to form grayscale patterns of chalcogenide phase-change thin films reveals many potential applications in high-resolution optical images for micro/nano image storage, microartworks, and grayscale photomasks.

Uptake of hazardous radionuclides within layered chalcogenide for environmental protection

Energy Technology Data Exchange (ETDEWEB)

Sengupta, Pranesh, E-mail: praneshsengupta@gmail.com [Materials Science Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Dudwadkar, N.L. [Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Vishwanadh, B. [Materials Science Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Pulhani, V. [Health Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Rao, Rekha [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Tripathi, S.C. [Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Dey, G.K. [Materials Science Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

2014-02-15

Highlights: • Layered chalcogenide with CdI{sub 2} crystal structure prepared by hydrothermal route. • Exploration of the possibilities for radionuclides’ uptake using layered chalcogenide. • Proposing ‘topotactic ionic substitution’ as major uptake mechanism. -- Abstract: Ensuring environmental protection in and around nuclear facilities is a matter of deep concern. Toward this, layered chalcogenide with CdI{sub 2} crystal structure has been prepared. Structural characterizations of layered chalcogenide suggest ‘topotactic ionic substitution’ as the dominant mechanism behind uptake of different cations within its lattice structure. An equilibration time of 45 min and volume to mass ratio of 30:1 are found to absorb {sup 233}U, {sup 239}Pu, {sup 106}Ru, {sup 85+89}Sr, {sup 137}Cs and {sup 241}Am radionuclides to the maximum extents.

Summary of Chalcogenide Glass Processing: Wet-Etching and Photolithography

Energy Technology Data Exchange (ETDEWEB)

Riley, Brian J.; Sundaram, S. K.; Johnson, Bradley R.; Saraf, Laxmikant V.

2006-12-01

This report describes a study designed to explore the different properties of two different chalcogenide materials, As2S3 and As24S38Se38, when subjected to photolithographic wet-etching techniques. Chalcogenide glasses are made by combining chalcogen elements S, Se, and Te with Group IV and/or V elements. The etchant was selected from the literature and was composed of sodium hydroxide, isopropyl alcohol, and deionized water and the types of chalcogenide glass for study were As2S3 and As24S38Se38. The main goals here were to obtain a single variable etch rate curve of etch depth per time versus NaOH overall solution concentration in M and to see the difference in etch rate between a given etchant when used on the different chalcogenide stoichiometries. Upon completion of these two goals, future studies will begin to explore creating complex, integrated photonic devices via these methods.

Effect of ruthenium cluster on the photoluminescence of chemically derivatized porous silicon

International Nuclear Information System (INIS)

Boukherroub, Rabah; Zargarian, Davit; Reber, Christian; Lockwood, David J.; Carty, Arthur J.; Wayner, Danial D.M.

2003-01-01

A green photoluminescent triruthenium cluster (I) has been chemisorbed on highly luminescent porous silicon (PSi) layers, either freshly prepared or chemically modified with 1-decene, ethyl undecylenate, or undecylenic acid, in order to study the influence of the cluster on the photoluminescence (PL) arising from the PSi. Immersing the hydrogen-terminated PSi in a hexane solution of (I) for several days at room temperature led to the quenching of PL arising from PSi; the only PL detected was due to the Ru cluster (I). A complete quenching of the PL due to PSi was also observed when derivatized PSi surfaces were exposed to the same solution of (I); in these cases, the PL of (I) also shifted to lower energies. Both the quenching of the PL arising from the PSi layers and the shift in the PL of the cluster (I) are likely due to the difference in the chemical interaction of the PO moiety and the CO groups of the Ru cluster with the terminal functional group of the organic monolayer

Effect of ruthenium cluster on the photoluminescence of chemically derivatized porous silicon

Energy Technology Data Exchange (ETDEWEB)

Boukherroub, Rabah; Zargarian, Davit; Reber, Christian; Lockwood, David J.; Carty, Arthur J.; Wayner, Danial D.M

2003-07-15

A green photoluminescent triruthenium cluster (I) has been chemisorbed on highly luminescent porous silicon (PSi) layers, either freshly prepared or chemically modified with 1-decene, ethyl undecylenate, or undecylenic acid, in order to study the influence of the cluster on the photoluminescence (PL) arising from the PSi. Immersing the hydrogen-terminated PSi in a hexane solution of (I) for several days at room temperature led to the quenching of PL arising from PSi; the only PL detected was due to the Ru cluster (I). A complete quenching of the PL due to PSi was also observed when derivatized PSi surfaces were exposed to the same solution of (I); in these cases, the PL of (I) also shifted to lower energies. Both the quenching of the PL arising from the PSi layers and the shift in the PL of the cluster (I) are likely due to the difference in the chemical interaction of the PO moiety and the CO groups of the Ru cluster with the terminal functional group of the organic monolayer.

Effect of ruthenium cluster on the photoluminescence of chemically derivatized porous silicon

Science.gov (United States)

Boukherroub, Rabah; Zargarian, Davit; Reber, Christian; Lockwood, David J.; Carty, Arthur J.; Wayner, Danial D. M.

2003-07-01

A green photoluminescent triruthenium cluster (I) has been chemisorbed on highly luminescent porous silicon (PSi) layers, either freshly prepared or chemically modified with 1-decene, ethyl undecylenate, or undecylenic acid, in order to study the influence of the cluster on the photoluminescence (PL) arising from the PSi. Immersing the hydrogen-terminated PSi in a hexane solution of (I) for several days at room temperature led to the quenching of PL arising from PSi; the only PL detected was due to the Ru cluster (I). A complete quenching of the PL due to PSi was also observed when derivatized PSi surfaces were exposed to the same solution of (I); in these cases, the PL of (I) also shifted to lower energies. Both the quenching of the PL arising from the PSi layers and the shift in the PL of the cluster (I) are likely due to the difference in the chemical interaction of the PO moiety and the CO groups of the Ru cluster with the terminal functional group of the organic monolayer.

Metal chalcogenide nanostructures for renewable energy applications

CERN Document Server

Qurashi, Ahsanulhaq

2014-01-01

This first ever reference book that focuses on metal chalcogenide semiconductor nanostructures for renewable energy applications encapsulates the state-of-the-art in multidisciplinary research on the metal chalcogenide semiconductor nanostructures (nanocrystals, nanoparticles, nanorods, nanowires,  nanobelts, nanoflowers, nanoribbons and more).  The properties and synthesis of a class of nanomaterials is essential to renewable energy manufacturing and this book focuses on the synthesis of metal chalcogendie nanostructures, their growth mechanism, optical, electrical, and other important prop

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

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)

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.)

Iron chalcogenide superconductors at high magnetic fields

Science.gov (United States)

Lei, Hechang; Wang, Kefeng; Hu, Rongwei; Ryu, Hyejin; Abeykoon, Milinda; Bozin, Emil S; Petrovic, Cedomir

2012-01-01

Iron chalcogenide superconductors have become one of the most investigated superconducting materials in recent years due to high upper critical fields, competing interactions and complex electronic and magnetic phase diagrams. The structural complexity, defects and atomic site occupancies significantly affect the normal and superconducting states in these compounds. In this work we review the vortex behavior, critical current density and high magnetic field pair-breaking mechanism in iron chalcogenide superconductors. We also point to relevant structural features and normal-state properties. PMID:27877518

Hybrid polymer photonic crystal fiber with integrated chalcogenide glass nanofilms

DEFF Research Database (Denmark)

Markos, Christos; Kubat, Irnis; Bang, Ole

2014-01-01

The combination of chalcogenide glasses with polymer photonic crystal fibers (PCFs) is a difficult and challenging task due to their different thermo-mechanical material properties. Here we report the first experimental realization of a hybrid polymer-chalcogenide PCF with integrated As2S3 glass...... nanofilms at the inner surface of the air-channels of a poly-methyl-methacrylate (PMMA) PCF. The integrated high refractive index glass films introduce distinct antiresonant transmission bands in the 480-900 nm wavelength region. We demonstrate that the ultra-high Kerr nonlinearity of the chalcogenide glass...

Nonlinear optical localization in embedded chalcogenide waveguide arrays

International Nuclear Information System (INIS)

Li, Mingshan; Huang, Sheng; Wang, Qingqing; Chen, Kevin P.; Petek, Hrvoje

2014-01-01

We report the nonlinear optical localization in an embedded waveguide array fabricated in chalcogenide glass. The array, which consists of seven waveguides with circularly symmetric cross sections, is realized by ultrafast laser writing. Light propagation in the chalcogenide waveguide array is studied with near infrared laser pulses centered at 1040 nm. The peak intensity required for nonlinear localization for the 1-cm long waveguide array was 35.1 GW/cm 2 , using 10-nJ pulses with 300-fs pulse width, which is 70 times lower than that reported in fused silica waveguide arrays and with over 7 times shorter interaction distance. Results reported in this paper demonstrated that ultrafast laser writing is a viable tool to produce 3D all-optical switching waveguide circuits in chalcogenide glass

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.)

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)

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%....

Solvent properties of hydrazine in the preparation of metal chalcogenide bulk materials and films.

Science.gov (United States)

Yuan, Min; Mitzi, David B

2009-08-21

A combination of unique solvent properties of hydrazine enables the direct dissolution of a range of metal chalcogenides at ambient temperature, rendering this an extraordinarily simple and soft synthetic approach to prepare new metal chalcogenide-based materials. The extended metal chalcogenide parent framework is broken up during this process, and the resulting metal chalcogenide building units are re-organized into network structures (from 0D to 3D) based upon their interactions with the hydrazine/hydrazinium moieties. This Perspective will review recent crystal and materials chemistry developments within this family of compounds and will briefly discuss the utility of this approach in metal chalcogenide thin-film deposition.

Carbon nanotube-chalcogenide composite

Czech Academy of Sciences Publication Activity Database

Stehlík, Š.; Orava, J.; Kohoutek, T.; Wágner, T.; Frumar, M.; Zima, Vítězslav; Hara, T.; Matsui, Y.; Ueda, K.; Pumera, M.

2010-01-01

Roč. 183, č. 1 (2010), s. 144-149 ISSN 0022-4596 R&D Projects: GA ČR GA203/08/0208 Institutional research plan: CEZ:AV0Z40500505 Keywords : carbon nanotubes * chalcogenide glasses * composites Subject RIV: CA - Inorganic Chemistry Impact factor: 2.261, year: 2010

Prediction of free-volume-type correlations in glassy chalcogenides from positron annihilation lifetime measurements

International Nuclear Information System (INIS)

Shpotyuk, O.; Ingram, A.; Shpotyuk, M.; Filipecki, J.

2014-01-01

Highlights: • Decisive role of specific chemical environment in free-volume correlations in glass. • Realistic free volumes in As–S/Se glass are defined by newly modified τ 2 -R formula. • Overestimated void sizes in chalcogenide glass as compared with molecular polymers. - Abstract: A newly modified correlation equation between defect-related positron lifetime determined within two-state trapping model and radius of corresponding free-volume-type defects was proposed to describe compositional variations in atomic-deficient structure of covalent-bonded chalcogenides like binary As–S/Se glasses. Specific chemical environment of free-volume voids around neighboring network-forming polyhedrons was shown to play a decisive role in this correlation, leading to systematically enhanced volumes in comparison with typical molecular substrates, such as polymers

Prediction of free-volume-type correlations in glassy chalcogenides from positron annihilation lifetime measurements

Energy Technology Data Exchange (ETDEWEB)

Shpotyuk, O., E-mail: shpotyuk@novas.lviv.ua [Institute of Materials of SRC “Carat”, 212 Stryjska Str., Lviv 79031 (Ukraine); Institute of Physics of Jan Dlugosz University, 13/15 al. Armii Krajowej, Czestcochowa 42200 (Poland); Ingram, A. [Opole University of Technology, 75 Ozimska Str., Opole 45370 (Poland); Shpotyuk, M. [Institute of Materials of SRC “Carat”, 212 Stryjska Str., Lviv 79031 (Ukraine); Lviv Polytechnic National University, 12 Bandery Str., Lviv 79013 (Ukraine); Filipecki, J. [Institute of Physics of Jan Dlugosz University, 13/15 al. Armii Krajowej, Czestcochowa 42200 (Poland)

2014-11-01

Highlights: • Decisive role of specific chemical environment in free-volume correlations in glass. • Realistic free volumes in As–S/Se glass are defined by newly modified τ{sub 2}-R formula. • Overestimated void sizes in chalcogenide glass as compared with molecular polymers. - Abstract: A newly modified correlation equation between defect-related positron lifetime determined within two-state trapping model and radius of corresponding free-volume-type defects was proposed to describe compositional variations in atomic-deficient structure of covalent-bonded chalcogenides like binary As–S/Se glasses. Specific chemical environment of free-volume voids around neighboring network-forming polyhedrons was shown to play a decisive role in this correlation, leading to systematically enhanced volumes in comparison with typical molecular substrates, such as polymers.

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

Dry etching of thin chalcogenide films

Energy Technology Data Exchange (ETDEWEB)

Petkov, Kiril [Acad. J. Malinowski Central Laboratory of Photoprocesses, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Bl. 109, 1113 Sofia (Bulgaria); Vassilev, Gergo; Vassilev, Venceslav, E-mail: kpetkov@clf.bas.b [Department of Semiconductors, University of Chemical Technology and Metallurgy, 8 Kl. Ohridsky Blvd., 1756 Sofia (Bulgaria)

2010-04-01

Fluorocarbon plasmas (pure and mixtures with Ar) were used to investigate the changes in the etching rate depending on the chalcogenide glasses composition and light exposure. The experiments were performed on modified commercial HZM-4 vacuum equipment in a diode electrode configuration. The surface microstructure of thin chalcogenide layers and its change after etching in CCl{sub 2}F{sub 2} and CF{sub 4} plasmas were studied by SEM. The dependence of the composition of As-S-Ge, As-Se and multicomponent Ge-Se-Sb-Ag-I layers on the etching rate was discussed. The selective etching of some glasses observed after light exposure opens opportunities for deep structure processing applications.

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)

Visible-active photocatalytic behaviors observed in nanostructured lead chalcogenides PbX (X = S, Se, Te)

International Nuclear Information System (INIS)

Qiao, Li-Na; Wang, H.C.; Shen, Y.; Lin, Yuan-Hua; Nan, Ce-Wen

2016-01-01

Nanostructured lead chalcogenides (PbX, X = Te, Se, S) were prepared via a simple hydrothermal method. The powder samples were characterized by XRD, SEM, SAED and DRS. Phase composition and microstructure analysis indicate that these samples are pure lead chalcogenides phases and have similar morphologies. These lead chalcogenides display efficient absorption in the UV-visible light range. The photocatalytic properties of lead chalcogenides nanoparticles were evaluated by the photodegradation of Congo red under UV-visible light irradiation in air atmosphere. The Congo red solution can be efficiently degraded under visible light in the presence of lead chalcogenides nanoparticles. The photocatalytic activities of lead chalcogenides generally increase with increasing their band gaps and shows no appreciable loss after repeated cycles. Our results may be useful for developing new photocatalyst systems responsive to visible light among narrow band gap semiconductors

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)

Low-loss, submicron chalcogenide integrated photonics with chlorine plasma etching

Energy Technology Data Exchange (ETDEWEB)

Chiles, Jeff; Malinowski, Marcin; Rao, Ashutosh [CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816 (United States); Novak, Spencer; Richardson, Kathleen [CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816 (United States); Department of Materials Science and Engineering, COMSET, Clemson University, Clemson, South Carolina 29634 (United States); Fathpour, Sasan, E-mail: fathpour@creol.ucf.edu [CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816 (United States); Department of Electrical Engineering and Computer Science, University of Central Florida, Orlando, Florida 32816 (United States)

2015-03-16

A chlorine plasma etching-based method for the fabrication of high-performance chalcogenide-based integrated photonics on silicon substrates is presented. By optimizing the etching conditions, chlorine plasma is employed to produce extremely low-roughness etched sidewalls on waveguides with minimal penalty to propagation loss. Using this fabrication method, microring resonators with record-high intrinsic Q-factors as high as 450 000 and a corresponding propagation loss as low as 0.42 dB/cm are demonstrated in submicron chalcogenide waveguides. Furthermore, the developed chlorine plasma etching process is utilized to demonstrate fiber-to-waveguide grating couplers in chalcogenide photonics with high power coupling efficiency of 37% for transverse-electric polarized modes.

Low-loss, submicron chalcogenide integrated photonics with chlorine plasma etching

International Nuclear Information System (INIS)

Chiles, Jeff; Malinowski, Marcin; Rao, Ashutosh; Novak, Spencer; Richardson, Kathleen; Fathpour, Sasan

2015-01-01

A chlorine plasma etching-based method for the fabrication of high-performance chalcogenide-based integrated photonics on silicon substrates is presented. By optimizing the etching conditions, chlorine plasma is employed to produce extremely low-roughness etched sidewalls on waveguides with minimal penalty to propagation loss. Using this fabrication method, microring resonators with record-high intrinsic Q-factors as high as 450 000 and a corresponding propagation loss as low as 0.42 dB/cm are demonstrated in submicron chalcogenide waveguides. Furthermore, the developed chlorine plasma etching process is utilized to demonstrate fiber-to-waveguide grating couplers in chalcogenide photonics with high power coupling efficiency of 37% for transverse-electric polarized modes

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)

Ruthenium/Graphene-like Layered Carbon Composite as an Efficient Hydrogen Evolution Reaction Electrocatalyst.

Science.gov (United States)

Chen, Zhe; Lu, Jinfeng; Ai, Yuejie; Ji, Yongfei; Adschiri, Tadafumi; Wan, Lijun

2016-12-28

Efficient water splitting through electrocatalysis has been studied extensively in modern energy devices, while the development of catalysts with activity and stability comparable to those of Pt is still a great challenge. In this work, we successfully developed a facile route to synthesize graphene-like layered carbon (GLC) from a layered silicate template. The obtained GLC has layered structure similar to that of the template and can be used as support to load ultrasmall Ru nanoparticles on it in supercritical water. The specific structure and surface properties of GLC enable Ru nanoparticles to disperse highly uniformly on it even at a large loading amount (62 wt %). When the novel Ru/GLC was used as catalyst on a glass carbon electrode for hydrogen evolution reaction (HER) in a 0.5 M H 2 SO 4 solution, it exhibits an extremely low onset potential of only 3 mV and a small Tafel slope of 46 mV/decade. The outstanding performance proved that Ru/GLC is highly active catalyst for HER, comparable with transition-metal dichalcogenides or selenides. As the price of ruthenium is much lower than platinum, our study shows that Ru/GLC might be a promising candidate as an HER catalyst in future energy applications.

Index change of chalcogenide materials from precision glass molding processes

Science.gov (United States)

Deegan, J.; Walsh, K.; Lindberg, G.; Benson, R.; Gibson, D.; Bayya, S.; Sanghera, J.; Stover, E.

2015-05-01

With the increase in demand for infrared optics for thermal applications and the use of glass molding of chalcogenide materials to support these higher volume optical designs, an investigation of changes to the optical properties of these materials is required. Typical precision glass molding requires specific thermal conditions for proper lens molding of any type of optical glass. With these conditions a change (reduction) of optical index occurs after molding of all oxide glass types and it is presumed that a similar behavior will happen with chalcogenide based materials. We will discuss the effects of a typical molding thermal cycle for use with commercially and newly developed chalcogenide materials and show results of index variation from nominally established material data.

Similarity in the superconducting properties of chalcogenides, cuprate oxides and fullerides

International Nuclear Information System (INIS)

Tsendin, K.D.; Popov, B.P.; Denisov, D.V.

2004-01-01

The idea of Anderson pairs has been put forward for explanation of many extraordinary properties of chalcogenides glassy semiconductors. Recent decades made obvious that these pairs localized on the centers with negative effective correlation energy (negative-U centers) really exist in chalcogenides. If the concentration of negative-U centers is enough to create the pair band states, this can lead to superconductivity because Anderson pairs are Bose particles. In the present paper we show that several puzzling superconductivity properties of chalcogenides, high-temperature cuprate superconductors and fullerides are similar for these three groups of materials and can be naturally explained in the frame of negative-U centers model of superconductivity

A feasibility study of unconventional planar ligand spacers in chalcogenide nanocrystals.

Science.gov (United States)

Lukose, Binit; Clancy, Paulette

2016-05-18

The solar cell efficiency of chalcogenide nanocrystals (quantum dots) has been limited in the past by the insulation between neighboring quantum dots caused by intervening, often long-chain, aliphatic ligands. We have conducted a computationally based feasibility study to investigate the use of ultra-thin, planar, charge-conducting ligands as an alternative to traditional long passive ligands. Not only might these radically unconventional ligands decrease the mean distance between adjacent quantum dots, but, since they are charge-conducting, they have the potential to actively enhance charge migration. Our ab initio studies compare the binding energies, electronic energy gaps, and absorption characteristics for both conventional and unconventional ligands, such as phthalocyanines, porphyrins and coronene. This comparison identified these unconventional ligands with the exception of titanyl phthalocyanine, that bind to themselves more strongly than to the surface of the quantum dot, which is likely to be less desirable for enhancing charge transport. The distribution of finite energy levels of the bound system is sensitive to the ligand's binding site and the levels correspond to delocalized states. We also observed a trap state localized on a single Pb atom when a sulfur-containing phenyldithiocarbamate (PTC) ligand is attached to a slightly off-stoichiometric dot in a manner that the sulfur of the ligand completes stoichiometry of the bound system. Hence, this is indicative of the source of trap state when thio-based ligands are bound to chalcogenide nanocrystals. We also predict that titanyl phthalocyanine in a mix with chalcogenide dots of diameter ∼1.5 Å can form a donor-acceptor system.

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

Pinning down high-performance Cu-chalcogenides as thin-film solar cell absorbers: A successive screening approach

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yubo; Zhang, Wenqing, E-mail: wqzhang@mail.sic.ac.cn, E-mail: pzhang3@buffalo.edu [Materials Genome Institute and Department of Physics, Shanghai University, Shanghai 200444 (China); State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Wang, Youwei; Zhang, Jiawei; Xi, Lili [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Zhang, Peihong, E-mail: wqzhang@mail.sic.ac.cn, E-mail: pzhang3@buffalo.edu [Materials Genome Institute and Department of Physics, Shanghai University, Shanghai 200444 (China); Department of Physics, University at Buffalo, SUNY, Buffalo, New York 14260 (United States)

2016-05-21

Photovoltaic performances of Cu-chalcogenides solar cells are strongly correlated with the absorber fundamental properties such as optimal bandgap, desired band alignment with window material, and high photon absorption ability. According to these criteria, we carry out a successive screening for 90 Cu-chalcogenides using efficient theoretical approaches. Besides the well-recognized CuInSe{sub 2} and Cu{sub 2}ZnSnSe{sub 4} materials, several novel candidates are identified to have optimal bandgaps of around 1.0–1.5 eV, spike-like band alignments with CdS window layer, sharp photon absorption edges, and high absorption coefficients. These new systems have great potential to be superior absorbers for photovolatic applications if their carrrier transport and defect properties are properly optimized.

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

Chalcogenide Glass Optical Waveguides for Infrared Biosensing

Directory of Open Access Journals (Sweden)

Bruno Bureau

2009-09-01

Full Text Available Due to the remarkable properties of chalcogenide (Chg glasses, Chg optical waveguides should play a significant role in the development of optical biosensors. This paper describes the fabrication and properties of chalcogenide fibres and planar waveguides. Using optical fibre transparent in the mid-infrared spectral range we have developed a biosensor that can collect information on whole metabolism alterations, rapidly and in situ. Thanks to this sensor it is possible to collect infrared spectra by remote spectroscopy, by simple contact with the sample. In this way, we tried to determine spectral modifications due, on the one hand, to cerebral metabolism alterations caused by a transient focal ischemia in the rat brain and, in the other hand, starvation in the mouse liver. We also applied a microdialysis method, a well known technique for in vivo brain metabolism studies, as reference. In the field of integrated microsensors, reactive ion etching was used to pattern rib waveguides between 2 and 300 μm wide. This technique was used to fabricate Y optical junctions for optical interconnections on chalcogenide amorphous films, which can potentially increase the sensitivity and stability of an optical micro-sensor. The first tests were also carried out to functionalise the Chg planar waveguides with the aim of using them as (biosensors.

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)

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

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.

Synthesis of 2D Metal Chalcogenide Thin Films through the Process Involving Solution-Phase Deposition.

Science.gov (United States)

Giri, Anupam; Park, Gyeongbae; Yang, Heeseung; Pal, Monalisa; Kwak, Junghyeok; Jeong, Unyong

2018-04-24

2D metal chalcogenide thin films have recently attracted considerable attention owing to their unique physicochemical properties and great potential in a variety of applications. Synthesis of large-area 2D metal chalcogenide thin films in controllable ways remains a key challenge in this research field. Recently, the solution-based synthesis of 2D metal chalcogenide thin films has emerged as an alternative approach to vacuum-based synthesis because it is relatively simple and easy to scale up for high-throughput production. In addition, solution-based thin films open new opportunities that cannot be achieved from vacuum-based thin films. Here, a comprehensive summary regarding the basic structures and properties of different types of 2D metal chalcogenides, the mechanistic details of the chemical reactions in the synthesis of the metal chalcogenide thin films, recent successes in the synthesis by different reaction approaches, and the applications and potential uses is provided. In the last perspective section, the technical challenges to be overcome and the future research directions in the solution-based synthesis of 2D metal chalcogenides are discussed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Breakthrough switching speed with an all-optical chalcogenide glass chip: 640 Gbit/s demultiplexing

DEFF Research Database (Denmark)

Galili, Michael; Xu, Jing; Mulvad, Hans Christian Hansen

2009-01-01

We report the first demonstration of error-free 640 Gbit/s demultiplexing using the Kerr non-linearity of an only 5 cm long chalcogenide glass waveguide chip. Our approach exploits four-wave mixing by the instantaneous nonlinear response of chalcogenide. Excellent performance is achieved with onl...... 2 dB average power penalty and no indication of error-floor. Characterisation of the FWM efficiency for the chalcogenide waveguide is given and confirms the good performance of the device....

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.)

Angle-resolved photoemission spectroscopy on iron-chalcogenide superconductors

Energy Technology Data Exchange (ETDEWEB)

Maletz, Janek; Zabolotnyy, Volodymyr; Evtushinsky, Daniil; Thirupathaiah, Setti; Wolter-Giraud, Anja; Harnagea, Luminita; Kordyuk, Alexander; Borisenko, Sergey [IFW Dresden (Germany); Yaresko, Alexander [MPI-FKF, Stuttgart (Germany); Vasiliev, Alexander [Moscow State University (Russian Federation); Chareev, Dimitri [RAS, Chernogolovka (Russian Federation); Rienks, Emile [Helmholtz-Zentrum Berlin (Germany); Buechner, Bernd [IFW Dresden (Germany); TU Dresden (Germany); Shermadini, Zurab; Luetkens, Hubertus; Sedlak, Kamil; Khasanov, Rustem; Amato, Alex; Krzton-Maziopa, Anna; Conder, Kazimierz; Pomjakushina, Ekaterina [Paul Scherrer Institute (Switzerland); Klauss, Hans-Henning [TU Dresden (Germany)

2014-07-01

The electronic structure of the iron chalcogenide superconductors FeSe{sub 1-x} and Rb{sub 0.77}Fe{sub 1.61}Se{sub 2} was investigated by high-resolution angle-resolved photoemission spectroscopy (ARPES). The results were compared to DFT calculations and μSR measurements. Both compounds share ''cigar-shaped'' Fermi surface sheets in their electronic structure, that can be found in almost all iron-pnictide superconductors. These features originate from a strong interplay of two hole- and electron-like bands in the Brillouin zone center, leading to a pronounced singularity in the density of states just below the Fermi level. This facilitates the coupling to a bosonic mode responsible for superconductivity.

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

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

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)

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

Superconducting properties of iron chalcogenide thin films

Directory of Open Access Journals (Sweden)

Paolo Mele

2012-01-01

Full Text Available Iron chalcogenides, binary FeSe, FeTe and ternary FeTexSe1−x, FeTexS1−x and FeTe:Ox, are the simplest compounds amongst the recently discovered iron-based superconductors. Thin films of iron chalcogenides present many attractive features that are covered in this review, such as: (i easy fabrication and epitaxial growth on common single-crystal substrates; (ii strong enhancement of superconducting transition temperature with respect to the bulk parent compounds (in FeTe0.5Se0.5, zero-resistance transition temperature Tc0bulk = 13.5 K, but Tc0film = 19 K on LaAlO3 substrate; (iii high critical current density (Jc ~ 0.5 ×106 A cm2 at 4.2 K and 0 T for FeTe0.5Se0.5 film deposited on CaF2, and similar values on flexible metallic substrates (Hastelloy tapes buffered by ion-beam assisted deposition with a weak dependence on magnetic field; (iv high upper critical field (~50 T for FeTe0.5Se0.5, Bc2(0, with a low anisotropy, γ ~ 2. These highlights explain why thin films of iron chalcogenides have been widely studied in recent years and are considered as promising materials for applications requiring high magnetic fields (20–50 T and low temperatures (2–10 K.

Transuranium element chalcogenides. Crystallochemistry and Moessbauer spectrometry of neptunium 237 chalcogenides

International Nuclear Information System (INIS)

Thevenin, T.; Pages, M.; Damien, D.

1981-09-01

To study actinide compounds , neptunium 237 has been studied by Moessbauer resonance. The different oxidation degrees of neptunium (7, 6, 5, 4 and 3) have a very important effect on isomeric displacements. In the study of chalcogenides, the isomeric displacement value of NpS 3 confirms the valency 4+ of neptunium in this compound. Results obtained with Np 3 S 5 show two valency state +3 and +4 in this compound. There is a good agreement with the two crystalline sites determined by crystallography [fr

Method to synthesize metal chalcogenide monolayer nanomaterials

Science.gov (United States)

Hernandez-Sanchez, Bernadette A.; Boyle, Timothy J.

2016-12-13

Metal chalcogenide monolayer nanomaterials can be synthesized from metal alkoxide precursors by solution precipitation or solvothermal processing. The synthesis routes are more scalable, less complex and easier to implement than other synthesis routes.

Forced Ion Migration for Chalcogenide Phase Change Memory Device

Science.gov (United States)

Campbell, Kristy A (Inventor)

2013-01-01

Non-volatile memory devices with two stacked layers of chalcogenide materials comprising the active memory device have been investigated for their potential as phase-change memories. The devices tested included GeTe/SnTe, Ge2Se3/SnTe, and Ge2Se3/SnSe stacks. All devices exhibited resistance switching behavior. The polarity of the applied voltage with respect to the SnTe or SnSe layer was critical to the memory switching properties, due to the electric field induced movement of either Sn or Te into the Ge-chalcogenide layer. One embodiment of the invention is a device comprising a stack of chalcogenide-containing layers which exhibit phase-change switching only after a reverse polarity voltage potential is applied across the stack causing ion movement into an adjacent layer and thus "activating" the device to act as a phase-change random access memory device or a reconfigurable electronics device when the applied voltage potential is returned to the normal polarity. Another embodiment of the invention is a device that is capable of exhibiting more than two data states.

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)

Scanning tunneling microscopy on iron-chalcogenide superconductor Fe(Se, Te) single crystal

International Nuclear Information System (INIS)

Ukita, R.; Sugimoto, A.; Ekino, T.

2011-01-01

We show scanning tunneling microscopy/spectroscopy (STM/STS) results of Fe(Se, Te). STM topography shows square arrangements of spots with the lattice spacing 0.37 nm. Te and Se atoms are randomly distributed in the STM topography. The STM topography of FeTe exhibits clusters of separated iron atoms. We have investigated the iron-chalcogenide superconductor Fe(Se, Te) using a low-temperature scanning tunneling microscopy/spectroscopy (STM/STS) technique. STM topography at 4.9 K shows clear regular square arrangements of spots with the lattice spacing ∼0.37 nm, from which what we observe are attributed to Se or Te atomic plane. In the topography, brighter and darker atomic spots are randomly distributed, which are most probably due to Te and Se atoms, respectively. For the FeTe compound, the topography exhibits clusters of the bright spots probably arising from separated iron atoms distributing over several Te lattice sites. The STS measurements clarify the existence of the large-size gap with 2Δ = 0.4-0.6 eV.

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.

New Trends in Amplifiers and Sources via Chalcogenide Photonic Crystal Fibers

Directory of Open Access Journals (Sweden)

L. Mescia

2012-01-01

Full Text Available Rare-earth-doped chalcogenide glass fiber lasers and amplifiers have great applicative potential in many fields since they are key elements in the near and medium-infrared (mid-IR wavelength range. In this paper, a review, even if not exhaustive, on amplification and lasing obtained by employing rare-earth-doped chalcogenide photonic crystal fibers is reported. Materials, devices, and feasible applications in the mid-IR are briefly mentioned.

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.

Mechanism for resistive switching in chalcogenide-based electrochemical metallization memory cells

Directory of Open Access Journals (Sweden)

Fei Zhuge

2015-05-01

Full Text Available It has been reported that in chalcogenide-based electrochemical metallization (ECM memory cells (e.g., As2S3:Ag, GeS:Cu, and Ag2S, the metal filament grows from the cathode (e.g., Pt and W towards the anode (e.g., Cu and Ag, whereas filament growth along the opposite direction has been observed in oxide-based ECM cells (e.g., ZnO, ZrO2, and SiO2. The growth direction difference has been ascribed to a high ion diffusion coefficient in chalcogenides in comparison with oxides. In this paper, upon analysis of OFF state I–V characteristics of ZnS-based ECM cells, we find that the metal filament grows from the anode towards the cathode and the filament rupture and rejuvenation occur at the cathodic interface, similar to the case of oxide-based ECM cells. It is inferred that in ECM cells based on the chalcogenides such as As2S3:Ag, GeS:Cu, and Ag2S, the filament growth from the cathode towards the anode is due to the existence of an abundance of ready-made mobile metal ions in the chalcogenides rather than to the high ion diffusion coefficient.

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

Size-controlled synthesis of chalcogen and chalcogenide nanoparticles using protic ionic liquids with imidazolium cation

International Nuclear Information System (INIS)

Meenatchi, Boominathan; Renuga, Velayutham; Manikandan, Ayyar

2016-01-01

Green synthesis of selenium (chalcogen) nanoparticles (SeNPs) has been successfully attained by simple wet chemical method that involves the reaction of six different protic ionic liquids with imidazolium cations and sodium hydrogen selenide (NaHSe) in the presence of poly ethylene glycol-600 (PEG-600) as an additional stabilizer. The obtained SeNPs were characterized using UV spectral (UV), Fourier transform infra-red (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron microscope (SEM) with energy dispersive X-ray (EDX) and high resolution transmission electron microscope (TEM) analysis. The results illustrate that the synthesized SeNPs are spherical in shape with size ranging 19-24 nm and possess good optical property with greater band gap energy, high thermal stability up to 330 .deg. C, low melting point of 218-220 .deg. C comparing to precursor selenium. Using the synthesized SeNPs, two chalcogenides such as ZnSe and CdSe semiconductor nanoparticles were synthesized and characterized using XRD, SEM with EDX and TEM analysis. The fabricated CdSe and ZnSe nanoparticles appeared like pebble and cluster structure with particle size of 29.97 nm and 22.73 nm respectively.

Size-controlled synthesis of chalcogen and chalcogenide nanoparticles using protic ionic liquids with imidazolium cation

Energy Technology Data Exchange (ETDEWEB)

Meenatchi, Boominathan [Cauvery College for Women, Tamilnadu (India); Renuga, Velayutham [National College, Tamilnadu (India); Manikandan, Ayyar [Bharath Institute of Higher Education and Research, Bharath University, Tamilnadu (India)

2016-03-15

Green synthesis of selenium (chalcogen) nanoparticles (SeNPs) has been successfully attained by simple wet chemical method that involves the reaction of six different protic ionic liquids with imidazolium cations and sodium hydrogen selenide (NaHSe) in the presence of poly ethylene glycol-600 (PEG-600) as an additional stabilizer. The obtained SeNPs were characterized using UV spectral (UV), Fourier transform infra-red (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron microscope (SEM) with energy dispersive X-ray (EDX) and high resolution transmission electron microscope (TEM) analysis. The results illustrate that the synthesized SeNPs are spherical in shape with size ranging 19-24 nm and possess good optical property with greater band gap energy, high thermal stability up to 330 .deg. C, low melting point of 218-220 .deg. C comparing to precursor selenium. Using the synthesized SeNPs, two chalcogenides such as ZnSe and CdSe semiconductor nanoparticles were synthesized and characterized using XRD, SEM with EDX and TEM analysis. The fabricated CdSe and ZnSe nanoparticles appeared like pebble and cluster structure with particle size of 29.97 nm and 22.73 nm respectively.

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

Interfacial scanning tunneling spectroscopy (STS) of chalcogenide/metal hybrid nanostructure

Energy Technology Data Exchange (ETDEWEB)

Saad, Mahmoud M.; Abdallah, Tamer [Physics Department, Faculty of Science, Ain Shams University, Abbassia, Cairo (Egypt); Easawi, Khalid; Negm, Sohair [Department of Physics and Mathematics, Faculty of Engineering (Shoubra), Benha University (Egypt); Talaat, Hassan, E-mail: hassantalaat@hotmail.com [Physics Department, Faculty of Science, Ain Shams University, Abbassia, Cairo (Egypt)

2015-05-15

Graphical abstract: - Highlights: • Comparing band gaps values obtained optically with STS. • Comparing direct imaging with calculated dimensions. • STS determination of the interfacial band bending of metal/chalcogenide. - Abstract: The electronic structure at the interface of chalcogenide/metal hybrid nanostructure (CdSe–Au tipped) had been studied by UHV scanning tunneling spectroscopy (STS) technique at room temperature. This nanostructure was synthesized by a phase transfer chemical method. The optical absorption of this hybrid nanostructure was recorded, and the application of the effective mass approximation (EMA) model gave dimensions that were confirmed by the direct measurements using the scanning tunneling microscopy (STM) as well as the high-resolution transmission electron microscope (HRTEM). The energy band gap obtained by STS agrees with the values obtained from the optical absorption. Moreover, the STS at the interface of CdSe–Au tipped hybrid nanostructure between CdSe of size about 4.1 ± 0.19 nm and Au tip of size about 3.5 ± 0.29 nm shows a band bending about 0.18 ± 0.03 eV in CdSe down in the direction of the interface. Such a result gives a direct observation of the electron accumulation at the interface of CdSe–Au tipped hybrid nanostructure, consistent with its energy band diagram. The presence of the electron accumulation at the interface of chalcogenides with metals has an important implication for hybrid nanoelectronic devices and the newly developed plasmon/chalcogenide photovoltaic solar energy conversion.

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)

Debye temperatures of uranium chalcogenides from their lattice ...

Indian Academy of Sciences (India)

Unknown

From the phonon frequencies, their Debye temperatures are evaluated. Further, ... Keywords. Uranium chalcogenides; p-wave electronic superconductor; phonon frequency; Debye tempera- ture; spin ... to the ionic crystals of similar structure.

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.

Modulation-instability biosensing using an As2S3 chalcogenide tapered fiber

DEFF Research Database (Denmark)

Markos, Christos; Bang, Ole

2016-01-01

We demonstrate an experimentally feasible biosensor design based on As2S3 chalcogenide tapered fiber. Pumping the fiber close to 1064 nm, a record sensitivity up to ~18 nm/nm was predicted.......We demonstrate an experimentally feasible biosensor design based on As2S3 chalcogenide tapered fiber. Pumping the fiber close to 1064 nm, a record sensitivity up to ~18 nm/nm was predicted....

Multimode supercontinuum generation in chalcogenide glass fibres

DEFF Research Database (Denmark)

Kubat, Irnis; Bang, Ole

2016-01-01

Mid-infrared supercontinuum generation is considered in chalcogenide fibres when taking into account both polarisations and the necessary higher order modes. In particular we focus on high pulse energy supercontinuum generation with long pump pulses. The modeling indicates that when only a single...

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

Ruthenium based redox flow battery for solar energy storage

International Nuclear Information System (INIS)

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

2011-01-01

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

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.

Ageing effects in As10Se90 chalcogenide glasses induced by gamma-irradiation

International Nuclear Information System (INIS)

Golovchak, R.; Shpotyuk, O.; Shpotyuk, M.; Gorecki, Cz.; Kozdras, A.

2005-01-01

The peculiarities of gamma-induced (Co 60 source, 1.85 MGy absorbed dose) ageing phenomena in As 10 Se 90 chalcogenide glasses are investigated for the first time. The analogy between the observed radiation-induced ageing and the thermally induced one in vitreous selenium is emphasized. Like to thermal treatment, gamma-irradiation leads to an increase in the glass transition temperature and the relaxation rate towards a thermodynamic equilibrium of supercooled liquid, the value of this increase being greater in the case of radiation influence

ZnO and copper indium chalcogenide heterojunctions prepared by inexpensive methods

International Nuclear Information System (INIS)

Berruet, M.; Di Iorio, Y.; Troviano, M.; Vázquez, M.

2014-01-01

Solution-based techniques were used to prepare ZnO/CuIn(Se, S) 2 heterojunctions that serve as solar cell prototypes. A duplex layer of ZnO (compact + porous) was electrodeposited. Chalcogenide thin films were deposited using successive ionic layer adsorption and reaction method (SILAR). By subsequent thermal treatments in two different atmospheres, CuInSe 2 (CISe) and CuInSe 2−x S x (CISeS) were obtained. The composition and morphology of the annealed films were characterized by GXRD, micro-Raman spectroscopy and SEM. Devices prepared with CISe and CISeS show a clear photo-response. The introduction of a buffer layer of TiO 2 into the ZnO/chalcogenide interface was necessary to detect photocurrent. The presence of CISeS improves the response of the cell, with higher values of short circuit current density, open circuit potential and fill factor. These promising results show that it is possible to prepare photovoltaic heterojunctions by depositing chalcogenides onto porous ZnO substrates using low-cost solution-based techniques. - Highlights: • Heterojunctions that serve as solar cell prototypes were prepared using solution-based techniques. • The devices comprised a double layer of ZnO and CuInSe 2 or CuInSe 0.4 S 1.6 . • A TiO 2 buffer layer in the ZnO/chalcogenide interface is necessary to detect photocurrent. • The incorporation of S improved the response of the photovoltaic heterojunction

Infrared emitting and photoconducting colloidal silver chalcogenide nanocrystal quantum dots from a silylamide-promoted synthesis.

Science.gov (United States)

Yarema, Maksym; Pichler, Stefan; Sytnyk, Mykhailo; Seyrkammer, Robert; Lechner, Rainer T; Fritz-Popovski, Gerhard; Jarzab, Dorota; Szendrei, Krisztina; Resel, Roland; Korovyanko, Oleksandra; Loi, Maria Antonietta; Paris, Oskar; Hesser, Günter; Heiss, Wolfgang

2011-05-24

Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag(2)Se, Ag(2)Te, and Ag(2)S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region, making these materials promising as environmentally benign alternatives to established infrared active nanocrystals containing toxic metals such as Hg, Cd, and Pb. We present Ag(2)Se nanocrystals in detail, giving size-tunable luminescence with quantum yields above 1.7%. The luminescence, with a decay time on the order of 130 ns, was shown to improve due to the growth of a monolayer thick ZnSe shell. Photoconductivity with a quantum efficiency of 27% was achieved by blending the Ag(2)Se nanocrystals with a soluble fullerene derivative. The co-injection of lithium silylamide was found to be crucial to the synthesis of Ag chalcogenide nanocrystals, which drastically increased their nucleation rate even at relatively low growth temperatures. Because the same observation was made for the nucleation of Cd chalcogenide nanocrystals, we conclude that the addition of lithium silylamide might generally promote wet-chemical synthesis of metal chalcogenide nanocrystals, including in as-yet unexplored materials.

Luminescent properties of fluorophosphate glasses with lead chalcogenides molecular clusters

International Nuclear Information System (INIS)

Kolobkova, E.V.; Kukushkin, D.S.; Nikonorov, N.V.; Shakhverdov, T.A.; Sidorov, A.I.; Vasiliev, V.N.

2015-01-01

Fluorophosphate glasses containing lead, selenium, and sulfur exhibit an intense luminescence in the 400–620 nm spectral region when excited by the 240–420 nm radiation. This luminescence is due to the presence of (PbSe) n and/or (PbS) n molecular clusters in the glasses, which appear in the as-prepared glasses before quantum dots formation. The thermal treatment at temperatures less than the glass transition temperature results in the red-shift of the luminescence bands and in an increase in the luminescence intensity. Heating the thermally treated glass samples leads to the reversible thermal quenching of the luminescence. - Highlights: • Fluorophosphate glasses with Pb, Se, and S ions contain (PbSe) n or (PbS) n molecular clusters. • (PbSe) n and (PbS) n molecular clusters possess luminescence in the visible with UV excitation. • Heating the glass leads to the reversible thermal quenching of the luminescence

Investigation of corrosion behavior of nitrogen doped and platinum/ruthenium doped diamond-like carbon thin films in Hank's solution

International Nuclear Information System (INIS)

Khun, N.W.; Liu, E.

2011-01-01

Undoped (DLC), nitrogen-doped (N-DLC) and platinum/ruthenium doped diamond-like carbon (PtRu-DLC) thin films were deposited on p-Si (100) substrates using a DC magnetron sputtering deposition system. The chemical composition, bonding structure, surface morphology and adhesion strength of the films were characterized using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM) and micro-scratch test, respectively. The corrosion behavior of the films in a Hank's solution was investigated using potentiodynamic polarization test. The corrosion results revealed that the PtRu-DLC film had the highest corrosion potential among the films used in this study. Highlights: → DLC thin films were deposited on Si substrates via dc magnetron sputtering. → Some DLC films were doped with N and/or Pt/Ru. → The film corrosion behavior was studied in a Hank solution with polarization test. → The PtRu-DLC film showed the highest corrosion potential among the films studied.

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

Fabrication and characterization of on-chip optical nonlinear chalcogenide nanofiber devices.

Science.gov (United States)

Zhang, Qiming; Li, Ming; Hao, Qiang; Deng, Dinghuan; Zhou, Hui; Zeng, Heping; Zhan, Li; Wu, Xiang; Liu, Liying; Xu, Lei

2010-11-15

Chalcogenide (As(2)S(3)) nanofibers as narrow as 200 nm in diameter are drawn by the fiber pulling method, are successfully embedded in SU8 polymer, and form on-chip waveguides and high-Q microknot resonators (Q = 3.9 × 10(4)) with smooth cleaved end faces. Resonance tuning of resonators is realized by localized laser irradiation. Strong supercontinuum generation with a bandwidth of 500 nm is achieved in a 7-cm-long on-chip chalcogenide waveguide. Our result provides a method for the development of compact, high-optical-quality, and robust photonic devices.

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

General Top-Down Ion Exchange Process for the Growth of Epitaxial Chalcogenide Thin Films and Devices

KAUST Repository

Xia, Chuan; Li, Peng; Li, Jun; Jiang, Qiu; Zhang, Xixiang; Alshareef, Husam N.

2016-01-01

) epitaxial chalcogenide metallic and semiconducting films and (2) free-standing chalcogenide films and (3) completed in situ formation of atomically sharp heterojunctions by selective ion exchange. Epitaxial NiCo2S4 thin films prepared by our process show 115

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

Limiting of photo induced changes in amorphous chalcogenide/alumino-silicate nanomultilayers

International Nuclear Information System (INIS)

Charnovych, S.; Nemec, P.; Nazabal, V.; Csik, A.; Allix, M.; Matzen, G.; Kokenyesi, S.

2011-01-01

Highlights: → Amorphous chalcogenides were investigated in this work. → Photo-induced effects were investigated in the created thin films. → Limiting of photo induced changes in amorphous chalcogenide/alumino-silicate nanomultilayers have been studied. - Abstract: Photo induced changes in amorphous As 20 Se 80 /alumino-silicate nanomultilayers (NML) produced by pulsed laser deposition (PLD) method have been studied in this work. The aim was to investigate the photo induced optical and surface relief changes due to the band gap illumination under the size- and hard cover limited conditions. It was observed that the hard cover layer on the surface of the uniform film or alumino-silicate sub-layers in the NML structure influences the photo darkening and restricts surface relief formations in As 20 Se 80 film or in the related NML compared with this effect in a pure chalcogenide layer. The influence of hard layers is supposed to be connected with limiting the free volume formation at the initial stage of the transformation process, which in turn limits the atomic movement and so the surface relief formation.

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.

Infrared Emitting and Photoconducting Colloidal Silver Chalcogenide Nanocrystal Quantum Dots from a Silylamide-Promoted Synthesis

NARCIS (Netherlands)

Yarema, Maksym; Pichler, Stefan; Sytnyk, Mykhailo; Seyrkammer, Robert; Lechner, Rainer T.; Fritz-Popovski, Gerhard; Jarzab, Dorota; Szendrei, Krisztina; Resel, Roland; Korovyanko, Oleksandra; Loi, Maria Antonietta; Paris, Oskar; Hesser, Guenter; Heiss, Wolfgang; Hesser, Günter

Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag(2)Se, Ag(2)Te, and Ag(2)S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region,

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

Pulsed laser deposited amorphous chalcogenide and alumino-silicate thin films and their multilayered structures for photonic applications

Energy Technology Data Exchange (ETDEWEB)

Němec, P. [Department of Graphic Arts and Photophysics, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 53210 Pardubice (Czech Republic); Charrier, J. [FOTON, UMR CNRS 6082, Enssat, 6 rue de Kerampont, BP 80518, 22305 Lannion (France); Cathelinaud, M. [Missions des Ressources et Compétences Technologiques, UPS CNRS 2274, 92195 Meudon (France); Allix, M. [CEMHTI-CNRS, Site Haute Température, Orléans (France); Adam, J.-L.; Zhang, S. [Equipe Verres et Céramiques, UMR-CNRS 6226, Sciences Chimiques de Rennes (SCR), Université de Rennes 1, 35042 Rennes Cedex (France); Nazabal, V., E-mail: virginie.nazabal@univ-rennes1.fr [Department of Graphic Arts and Photophysics, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 53210 Pardubice (Czech Republic); Equipe Verres et Céramiques, UMR-CNRS 6226, Sciences Chimiques de Rennes (SCR), Université de Rennes 1, 35042 Rennes Cedex (France)

2013-07-31

Amorphous chalcogenide and alumino-silicate thin films were fabricated by the pulsed laser deposition technique. Prepared films were characterized in terms of their morphology, chemical composition, and optical properties. Multilayered thin film stacks for reflectors and vertical microcavities were designed for telecommunication wavelength and the window of atmosphere transparency (band II) at 1.54 μm and 4.65 μm, respectively. Bearing in mind the benefit coming from the opportunity of an efficient wavelength tuning or, conversely, to stabilize the photoinduced effects in chalcogenide films as well as to improve their mechanical properties and/or their chemical durability, several pairs of materials from pure chalcogenide layers to chalcogenide/oxide layers were investigated. Different layer stacks were fabricated in order to check the compatibility between dissimilar materials which can have a strong influence on the interface roughness, adhesion, density, and homogeneity, for instance. Three different reflector designs were formulated and tested including all-chalcogenide layers (As{sub 40}Se{sub 60}/Ge{sub 25}Sb{sub 5}S{sub 70}) and mixed chalcogenide-oxide layers (As{sub 40}Se{sub 60}/alumino-silicate and Ga{sub 10}Ge{sub 15}Te{sub 75}/alumino-silicate). Prepared multilayers showed good compatibility between different material pairs deposited by laser ablation despite the diversity of chemical compositions. As{sub 40}Se{sub 60}/alumino-silicate reflector showed the best parameters; its stop band (R > 97% at 8° off-normal incidence) has a bandwidth of ∼ 100 nm and it is centered at 1490 nm. The quality of the different mirrors developed was good enough to try to obtain a microcavity structure for the 1.5 μm telecommunication wavelength made of chalcogenide layers. The microcavity structure consists of Ga{sub 5}Ge{sub 20}Sb{sub 10}S{sub 65} (doped with 5000 ppm of Er{sup 3+}) spacer surrounded by two 10-layer As{sub 40}Se{sub 60}/Ge{sub 25}Sb{sub 5}S{sub 70

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

Science.gov (United States)

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

2017-12-30

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

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.

ZnO and copper indium chalcogenide heterojunctions prepared by inexpensive methods

Energy Technology Data Exchange (ETDEWEB)

Berruet, M., E-mail: berruetm@gmail.com [División Electroquímica y Corrosión, Facultad de Ingeniería, INTEMA, CONICET, Universidad Nacional de Mar del Plata, Juan B. Justo 4302, B7608FDQ Mar del Plata (Argentina); Di Iorio, Y. [División Electroquímica y Corrosión, Facultad de Ingeniería, INTEMA, CONICET, Universidad Nacional de Mar del Plata, Juan B. Justo 4302, B7608FDQ Mar del Plata (Argentina); Troviano, M. [Instituto de Investigación y Desarrollo en Ingeniería de Procesos, Biotecnología y Energías Alternativas (PROBIEN, CONICET-UNCo), Buenos Aires 1400, Q8300IBX Neuquén (Argentina); Vázquez, M. [División Electroquímica y Corrosión, Facultad de Ingeniería, INTEMA, CONICET, Universidad Nacional de Mar del Plata, Juan B. Justo 4302, B7608FDQ Mar del Plata (Argentina)

2014-12-15

Solution-based techniques were used to prepare ZnO/CuIn(Se, S){sub 2} heterojunctions that serve as solar cell prototypes. A duplex layer of ZnO (compact + porous) was electrodeposited. Chalcogenide thin films were deposited using successive ionic layer adsorption and reaction method (SILAR). By subsequent thermal treatments in two different atmospheres, CuInSe{sub 2} (CISe) and CuInSe{sub 2−x}S{sub x} (CISeS) were obtained. The composition and morphology of the annealed films were characterized by GXRD, micro-Raman spectroscopy and SEM. Devices prepared with CISe and CISeS show a clear photo-response. The introduction of a buffer layer of TiO{sub 2} into the ZnO/chalcogenide interface was necessary to detect photocurrent. The presence of CISeS improves the response of the cell, with higher values of short circuit current density, open circuit potential and fill factor. These promising results show that it is possible to prepare photovoltaic heterojunctions by depositing chalcogenides onto porous ZnO substrates using low-cost solution-based techniques. - Highlights: • Heterojunctions that serve as solar cell prototypes were prepared using solution-based techniques. • The devices comprised a double layer of ZnO and CuInSe{sub 2} or CuInSe{sub 0.4}S{sub 1.6}. • A TiO{sub 2} buffer layer in the ZnO/chalcogenide interface is necessary to detect photocurrent. • The incorporation of S improved the response of the photovoltaic heterojunction.

Surfactant free metal chalcogenides microparticles consisting of ...

Indian Academy of Sciences (India)

SANYASINAIDU GOTTAPU

2017-11-11

Nov 11, 2017 ... Metal chalcogenides; copper sulphide; copper selenide; micro flowers. 1. Introduction .... adding calculated quantity (2.7 mmol) of each acid separately. .... salts (LiCl, LiNO3, and LiOAc), and then hydride ions from (BH. − ... Concentration of metal .... hait A and Lim J Y 2016 Cation exchange synthesis of.

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

The intercalation chemistry of layered iron chalcogenide superconductors

Energy Technology Data Exchange (ETDEWEB)

Vivanco, Hector K.; Rodriguez, Efrain E., E-mail: efrain@umd.edu

2016-10-15

The iron chalcogenides FeSe and FeS are superconductors composed of two-dimensional sheets held together by van der Waals interactions, which makes them prime candidates for the intercalation of various guest species. We review the intercalation chemistry of FeSe and FeS superconductors and discuss their synthesis, structure, and physical properties. Before we review the latest work in this area, we provide a brief background on the intercalation chemistry of other inorganic materials that exhibit enhanced superconducting properties upon intercalation, which include the transition metal dichalcogenides, fullerenes, and layered cobalt oxides. From past studies of these intercalated superconductors, we discuss the role of the intercalates in terms of charge doping, structural distortions, and Fermi surface reconstruction. We also briefly review the physical and chemical properties of the host materials—mackinawite-type FeS and β-FeSe. The three types of intercalates for the iron chalcogenides can be placed in three categories: 1.) alkali and alkaline earth cations intercalated through the liquid ammonia technique; 2.) cations intercalated with organic amines such as ethylenediamine; and 3.) layered hydroxides intercalated during hydrothermal conditions. A recurring theme in these studies is the role of the intercalated guest in electron doping the chalcogenide host and in enhancing the two-dimensionality of the electronic structure by spacing the FeSe layers apart. We end this review discussing possible new avenues in the intercalation chemistry of transition metal monochalcogenides, and the promise of these materials as a unique set of new inorganic two-dimensional systems.

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.

Dominant control region of the human β- like globin gene cluster

NARCIS (Netherlands)

Blom van Assendelft, Margaretha van

1989-01-01

The structure and regulation of the human β -like globin gene cluster has been studied extensively. Genetic disorders connected with this gene cluster are responsible for human diseases associated with high levels of morbidity and mortality, such as β-thalassaemia and sickle cell anaemia. The work

Inverse opal photonic crystal of chalcogenide glass by solution processing.

Science.gov (United States)

Kohoutek, Tomas; Orava, Jiri; Sawada, Tsutomu; Fudouzi, Hiroshi

2011-01-15

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors. Copyright © 2010 Elsevier Inc. All rights reserved.

Spatial correlations, clustering and percolation-like transitions in homicide crimes

Science.gov (United States)

Alves, L. G. A.; Lenzi, E. K.; Mendes, R. S.; Ribeiro, H. V.

2015-07-01

The spatial dynamics of criminal activities has been recently studied through statistical physics methods; however, models and results have been focusing on local scales (city level) and much less is known about these patterns at larger scales, e.g. at a country level. Here we report on a characterization of the spatial dynamics of the homicide crimes along the Brazilian territory using data from all cities (˜5000) in a period of more than thirty years. Our results show that the spatial correlation function in the per capita homicides decays exponentially with the distance between cities and that the characteristic correlation length displays an acute increasing trend in the latest years. We also investigate the formation of spatial clusters of cities via a percolation-like analysis, where clustering of cities and a phase-transition-like behavior describing the size of the largest cluster as a function of a homicide threshold are observed. This transition-like behavior presents evolutive features characterized by an increasing in the homicide threshold (where the transitions occur) and by a decreasing in the transition magnitudes (length of the jumps in the cluster size). We believe that our work sheds new light on the spatial patterns of criminal activities at large scales, which may contribute for better political decisions and resources allocation as well as opens new possibilities for modeling criminal activities by setting up fundamental empirical patterns at large scales.

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)

Electrochemistry of ruthenium acetate trigonal cluster with dimethylsulfoxide and pyridine

International Nuclear Information System (INIS)

Alexiou, A.D.P.; Toma, H.E.

1990-01-01

The electrochemical behaviour of asymetric cluster with two ligands, pyridine and dimethyl-sulfoxide is studied for determining the changes from cluster oxidation influence on DMSO-Ru ligand and for verifying the ligand isomers which were detected in two systems; [Ru(NHsub(3))dmso] sup(3+/2+) [9] and [Ru(edta)dmso] sup(1-/2-)[10]. (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)

Homogeneity and internal defects detect of infrared Se-based chalcogenide glass

Science.gov (United States)

Li, Zupana; Wu, Ligang; Lin, Changgui; Song, Bao'an; Wang, Xunsi; Shen, Xiang; Dai, Shixunb

2011-10-01

Ge-Sb-Se chalcogenide glasses is a kind of excellent infrared optical material, which has been enviromental friendly and widely used in infrared thermal imaging systems. However, due to the opaque feature of Se-based glasses in visible spectral region, it's difficult to measure their homogeneity and internal defect as the common oxide ones. In this study, a measurement was proposed to observe the homogeneity and internal defect of these glasses based on near-IR imaging technique and an effective measurement system was also constructed. The testing result indicated the method can gives the information of homogeneity and internal defect of infrared Se-based chalcogenide glass clearly and intuitionally.

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.)

Conductivity in Ag-As-S(Se,Te) chalcogenide glasses

Czech Academy of Sciences Publication Activity Database

Stehlík, Š.; Kolář, J.; Bartoš, M.; Vlček, Milan; Frumar, M.; Zima, Vítězslav; Wágner, T.

2010-01-01

Roč. 181, 37/38 (2010), s. 1625-1630 ISSN 0167-2738 Institutional research plan: CEZ:AV0Z40500505 Keywords : chalcogenide glasses * ionics conductivity * phase separation Subject RIV: CA - Inorganic Chemistry Impact factor: 2.496, year: 2010

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.

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...

Open-framework micro- and meso-structured chalcogenides and their ion exchange properties

Science.gov (United States)

Ding, Nan

2007-12-01

Micro- and meso- structured chalcogenides with open inorganic framework have driven tremendous attention and intense work during the last two decades. They belong to a special category of materials possessing multifunctional potential due to their large void space within the atomic skeletons and the novel physical properties brought by the chalcogen elements. The latter are not generally present in typical open-framework oxides. In addition, because of the different size and electronegativity of the chalcogen elements compared to oxygen, many new structural properties were expected to emerge when the work in this dissertation was undertaken. The major body of this work involves group 13 (e.g. Ga, In) or 14 (e.g. Ge, Sn) elements with chalcogen. Transition metals also are incorporated in a few examples. The first two groups of compounds reported belong to the latter case. Unique structure types have been obtained under hydrothermal conditions via the combination of M (M = Zn, Cd), Sn and Q (Q = S, Se) to build microporous A6M4Sn3Q13 (A = K, Rb) based on truncated penta-supertrahedral cluster [M4Sn4Q 17]10-. More surprisingly, the protonation of K 6Cd4Sn3Se13 led to another new compound K14Cd15Sn12Se46 which possesses a labyrinth-like void space within the compact [Cd15Sn12Se 46]14- anionic skeleton. This structural characteristic leads to an unusual stability of the compound in acid. Both the K6Cd 4Sn3Se13 and K14Cd15Sn 12Se46 are fast ion-exchangers and their K+ ions can be replaced by other alkali metal cations and even H+ for the latter. Other work reported was aimed at the heavier analogs of alumiophosphate, i.e. the open-frameworks based on group 13 (Ga, In), 15 (Sb) and chalcogen elements. Two groups of chalcoantimonates with two-dimensional architectures [M5Sb6S19]5- and polymorphic [M2Sb2Q7]2- (M = Ga, In; Q = S, Se) were obtained. With the help of bulky organic structure-directing agents, large windows were formed in some of these anionic slabs. The windows

Debye temperatures of uranium chalcogenides from their lattice ...

Indian Academy of Sciences (India)

Phonon dispersion relations in uranium chalcogenides have been investigated using a modified three-body force shell model. From the phonon frequencies, their Debye temperatures are evaluated. Further, on the basis of the spin fluctuation in the heavy fermion uranium compounds, UPt3 and UBe13, the possible ...

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.

Chalcogenide Sensitized Carbon Based TiO2 Nanomaterial For Solar Driven Applications

Science.gov (United States)

Pathak, Pawan

The demand for renewable energy is growing because fossils fuels are depleting at a rapid pace. Solar energy an abundant green energy resource. Utilizing this resource in a smart manner can resolve energy-crisis related issues. Sun light can be efficiently harvested using semiconductor based materials by utilizing photo-generated charges for numerous beneficial applications. The main goal of this thesis is to synthesize different nanostructures of TiO2, develop a novel method of coupling and synthesizing chalcogenide nanocrystals with TiO2 and to study the charge transportation effects of the various carbon allotropes in the chalcogenide nanocrystal sensitized TiO2 nanostructure. We have fabricated different nanostructures of TiO2 as solar energy harvesting materials. Effects of the different phases of TiO2 have also been studied. The anatase phase of TiO2 is more photoactive than the rutile phase of TiO2, and the higher dimension of the TiO2 can increase the surface area of the material which can produce higher photocurrent. Since TiO2 only absorbs in the UV range; to increase the absorbance TiO2 should be coupled to visible light absorbing materials. This dissertation presents a simple approach to synthesize and couple chalcogenide nanocrystals with TiO2 nanostructure to form a heterostructured composite. An atmospheric pressure based, single precursor, one-pot approach has been developed and tested to assemble chalcogenide nanocrystal on the TiO2 surface. Surface characterization using microscopy, X-ray diffraction, and elemental analysis indicates the formation of nanocrystals along the nanotube walls and inter-tubular spacing. Optical measurements indicate that the chalcogenide nanocrystals absorb in the visible region and demonstrate an increase in photocurrent in comparison to bare TiO2 nanostructure. The CdS synthesized TiO2 nanostructure produced the highest photocurrent as measured in the three electrode system. We have also assembled the PbS nanocrystal

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.

Theoretical study of phonon dispersion, elastic, mechanical and thermodynamic properties of barium chalcogenides

Science.gov (United States)

Musari, A. A.; Orukombo, S. A.

2018-03-01

Barium chalcogenides are known for their high-technological importance and great scientific interest. Detailed studies of their elastic, mechanical, dynamical and thermodynamic properties were carried out using density functional theory and plane-wave pseudo potential method within the generalized gradient approximation. The optimized lattice constants were in good agreement when compared with experimental data. The independent elastic constants, calculated from a linear fit of the computed stress-strain function, were used to determine the Young’s modulus (E), bulk modulus (B), shear modulus (G), Poisson’s ratio (σ) and Zener’s anisotropy factor (A). Also, the Debye temperature and sound velocities for barium chalcogenides were estimated from the three independent elastic constants. The calculations of phonon dispersion showed that there are no negative frequencies throughout the Brillouin zone. Hence barium chalcogenides have dynamically stable NaCl-type crystal structure. Finally, their thermodynamic properties were calculated in the temperature range of 0-1000 K and their constant-volume specific heat capacities at room-temperature were reported.

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.)

Amorphous chalcogenides advances and applications

CERN Document Server

Wang, Rong Ping

2014-01-01

This book provides a comprehensive overview of the chalcogenide glass science and various applications based on the glasses. It starts with a review on the glass-forming ability of various systems, followed by a discussion on the structural and physical properties of various chalcolgenide glasses and their application in integrated optics. The chapters have been contributed by prominent experts from all over the world, and therefore, the book presents the recent research advances in the area. This book will appeal to anyone who is involved in glass science and technology and glass application.

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

New functionality of chalcogenide glasses for radiation sensing of nuclear wastes

International Nuclear Information System (INIS)

Ailavajhala, M.S.; Gonzalez-Velo, Y.; Poweleit, C.D.; Barnaby, H.J.; Kozicki, M.N.; Butt, D.P.; Mitkova, M.

2014-01-01

Highlights: • Study of thin film chalcogenide glasses under gamma radiation and a proposed radiation sensor design. • Structural changes were observed at various radiation doses. • Formation of Ag 2 Se in Se depleted glasses with sufficient radiation dose. • In conventional semiconductor chip environment, the proposed sensor has a linear current vs. dose behavior up to 600 J/cm 2 . - Abstract: Data about gamma radiation induced effects in Ge 40 Se 60 chalcogenide thin films and radiation induced silver diffusion within these are presented. Blanket films and devices were created to study the structural changes, diffusion products, and device performance. Raman spectroscopy, X-ray diffraction, current vs. voltage (I–V) and impedance measurements expound the behavior of Ge 40 Se 60 glass and silver diffusion within this glass under radiation. Raman study shows that there is a decrease in the area ratio between edge shared and corner shared structural units revealing structural reorganization occurring in the glasses as a result of gamma radiation. X-ray diffraction studies revealed that with sufficiently radiation dose it is also possible to create Ag 2 Se in selenium-depleted systems. Oxidation of the Ge enriched chalcogenide backbone is confirmed through the electrical performance of the sensing elements based on these films. Combination of these structural and diffusion products influences the device performance. The I–V behavior is characterized by increase in current and then stabilization as a function of radiation dose. Additionally, device modeling is also presented using Silvaco software and analytical methods to shed light on the device behavior. This type of sensor design and material characterizations facilitate in improving the radiation sensing capabilities of silver containing chalcogenide glass thin films

New functionality of chalcogenide glasses for radiation sensing of nuclear wastes

Energy Technology Data Exchange (ETDEWEB)

Ailavajhala, M.S., E-mail: m.ailavajhala@gmail.com [Department of Electrical and Computer Engineering, Boise State University, Boise, ID 83725 (United States); Gonzalez-Velo, Y. [School of Electrical, Computer and Energy Engineering, Arizona State University, Tempe, AZ 85287-5706 (United States); Poweleit, C.D. [Department of Physics, Arizona State University, Tempe, AZ 85287-5706 (United States); Barnaby, H.J.; Kozicki, M.N. [School of Electrical, Computer and Energy Engineering, Arizona State University, Tempe, AZ 85287-5706 (United States); Butt, D.P. [Department of Materials Science and Engineering, Boise State University, Boise, ID 83725 (United States); Mitkova, M., E-mail: maheshailavajhala@u.boisestate.edu [Department of Electrical and Computer Engineering, Boise State University, Boise, ID 83725 (United States)

2014-03-01

Highlights: • Study of thin film chalcogenide glasses under gamma radiation and a proposed radiation sensor design. • Structural changes were observed at various radiation doses. • Formation of Ag{sub 2}Se in Se depleted glasses with sufficient radiation dose. • In conventional semiconductor chip environment, the proposed sensor has a linear current vs. dose behavior up to 600 J/cm{sup 2}. - Abstract: Data about gamma radiation induced effects in Ge{sub 40}Se{sub 60} chalcogenide thin films and radiation induced silver diffusion within these are presented. Blanket films and devices were created to study the structural changes, diffusion products, and device performance. Raman spectroscopy, X-ray diffraction, current vs. voltage (I–V) and impedance measurements expound the behavior of Ge{sub 40}Se{sub 60} glass and silver diffusion within this glass under radiation. Raman study shows that there is a decrease in the area ratio between edge shared and corner shared structural units revealing structural reorganization occurring in the glasses as a result of gamma radiation. X-ray diffraction studies revealed that with sufficiently radiation dose it is also possible to create Ag{sub 2}Se in selenium-depleted systems. Oxidation of the Ge enriched chalcogenide backbone is confirmed through the electrical performance of the sensing elements based on these films. Combination of these structural and diffusion products influences the device performance. The I–V behavior is characterized by increase in current and then stabilization as a function of radiation dose. Additionally, device modeling is also presented using Silvaco software and analytical methods to shed light on the device behavior. This type of sensor design and material characterizations facilitate in improving the radiation sensing capabilities of silver containing chalcogenide glass thin films.

Anchoring selenido-carbonyl ruthenium clusters to functionalized silica xerogels

International Nuclear Information System (INIS)

Cauzzi, Daniele; Graiff, Claudia; Pattacini, Roberto; Predieri, Giovanni; Tiripicchio, Antonio

2003-01-01

Silica Xerogels containing carbonyl Ru 3 Se 2 nido clusters were prepared in three different ways. The simple dispersion of [Ru 3 (μ 3 -Se) 2 (CO) 7 (PPh 3 ) 2 ] via sol gel process produces an inhomogeneous material; by contrast, homogeneous xerogels were obtained by reaction of [Ru 3 (μ 3 -Se) 2 (CO) 8 (PPh 3 )] with functionalized xerogels containing grafted diphenylphosphine moieties and by reaction of [Ru 3 (CO) 12 ] with a xerogel containing grafted phosphine-selenide groups. The reaction between [Ru 3 (CO) 12 ] and dodecyl diphenylphosphine selenide led to the formation of four selenido carbonyl clusters, which are soluble in hydrocarbon solvents and can be deposited as thin films from their solution by slow evaporation. (author)

Photoinduced Operation by Absorption of the Chalcogenide Nanocrystallite Containing Solar Cells

Directory of Open Access Journals (Sweden)

Elnaggar A.M.

2016-12-01

Full Text Available It is shown that for the solar cells containing chalcogenide nanocrystallites using external laser light, one can achieve some enhancement of the photovoltaic efficiency. Photoinduced treatment was carried out using two beams of splitted Er: glass laser operating at 1.54 μm. The light of the laser was incident at different angles and the angles between the beams also were varied. Also, the studies of nanocomposite effective structures have shown enhancement of effective nanocrystalline sizes during the laser treatment. Nanocrystallites of CuInS2 and CuZnSnS4 (CZTS were used as chalcogenide materials. The optimization of the laser beam intensities and nanoparticle sizes were explored.

Investigation of corrosion behavior of nitrogen doped and platinum/ruthenium doped diamond-like carbon thin films in Hank's solution

Energy Technology Data Exchange (ETDEWEB)

Khun, N.W.; Liu, E., E-mail: MEJLiu@ntu.edu.sg

2011-10-10

Undoped (DLC), nitrogen-doped (N-DLC) and platinum/ruthenium doped diamond-like carbon (PtRu-DLC) thin films were deposited on p-Si (100) substrates using a DC magnetron sputtering deposition system. The chemical composition, bonding structure, surface morphology and adhesion strength of the films were characterized using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM) and micro-scratch test, respectively. The corrosion behavior of the films in a Hank's solution was investigated using potentiodynamic polarization test. The corrosion results revealed that the PtRu-DLC film had the highest corrosion potential among the films used in this study. Highlights: {yields} DLC thin films were deposited on Si substrates via dc magnetron sputtering. {yields} Some DLC films were doped with N and/or Pt/Ru. {yields} The film corrosion behavior was studied in a Hank solution with polarization test. {yields} The PtRu-DLC film showed the highest corrosion potential among the films studied.

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)

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…

Dynamic stabilities of icosahedral-like clusters and their ability to form quasicrystals

Energy Technology Data Exchange (ETDEWEB)

Liang, Xiaogang; Hamid, Ilyar; Duan, Haiming, E-mail: dhm@xju.edu.cn [College of Physics Science and Technology. Xinjiang University, Urumqi 830046 (China)

2016-06-15

The dynamic stabilities of the icosahedral-like clusters containing up to 2200 atoms are investigated for 15 metal elements. The clusters originate from five different initial structures (icosahedron, truncated decahedron, octahedron, closed-shell fragment of an HCP structure, and non-closed-shell fragment of an HCP structure). The obtained order of the dynamic stabilities of the icosahedral-like clusters can be assigned to three groups, from stronger to weaker, according to the size ranges involved: (Zr, Al, Ti) > (Cu, Fe, Co, Ni, Mg, Ag) > (Pb, Au, Pd, Pt, Rh, Ir), which correspond to the predicted formation ability of the quasicrystals. The differences of the sequences can be explained by analyzing the parameters of the Gupta-type many-body inter-atomic potentials.

Recent Progress In Infrared Chalcogenide Glass Fibers

Science.gov (United States)

Bornstein, A.; Croitoru, N.; Marom, E.

1984-10-01

Chalcogenide glasses containing elements like As, Ge, Sb and Se have been prepared. A new technique of preparing the raw material and subsequently drawing fibers has been devel-oped in order to avoid the forming of oxygen compounds. The fibers have been drawn by cru-cible and rod method from oxygen free raw material inside an Ar atmosphere glove box. The fibers drawn to date with air and glass cladding have a diameter of 50-500 pm and length of several meterd. Preliminary attenuation measurements indicate that the attentuation is better than 0.1 dB/cm and it is not affected even when the fiber is bent to 2 cm circular radius. The fibes were testes a CO laser beam and were not damaged at power densities below 10 kW/2cm2 CW &100 kw/cm using short pulses 75 n sec. The transmitted power density was 0.8 kW/cm2 which is an appropriate value to the needed for cutting and ablation of human tissues.

Efficient Mid-Infrared Supercontinuum Generation in Tapered Large Mode Area Chalcogenide Photonic Crystal Fibers

DEFF Research Database (Denmark)

Petersen, Christian Rosenberg; Engelsholm, Rasmus Dybbro; Markos, Christos

2017-01-01

Mid-infrared supercontinuum spanning from 1.8-9  μm with an output power of 41.5 mW is demonstrated by pumping tapered large mode area chalcogenide photonic crystal fibers using a 4 μm optical parametric source.......Mid-infrared supercontinuum spanning from 1.8-9  μm with an output power of 41.5 mW is demonstrated by pumping tapered large mode area chalcogenide photonic crystal fibers using a 4 μm optical parametric source....

Towards efficient solar-to-hydrogen conversion: Fundamentals and recent progress in copper-based chalcogenide photocathodes

Directory of Open Access Journals (Sweden)

Chen Yubin

2016-09-01

Full Text Available Photoelectrochemical (PEC water splitting for hydrogen generation has been considered as a promising route to convert and store solar energy into chemical fuels. In terms of its large-scale application, seeking semiconductor photoelectrodes with high efficiency and good stability should be essential. Although an enormous number of materials have been explored for solar water splitting in the last several decades, challenges still remain for the practical application. P-type copper-based chalcogenides, such as Cu(In, GaSe2 and Cu2ZnSnS4, have shown impressive performance in photovoltaics due to narrow bandgaps, high absorption coefficients, and good carrier transport properties. The obtained high efficiencies in photovoltaics have promoted the utilization of these materials into the field of PEC water splitting. A comprehensive review on copper-based chalcogenides for solar-to-hydrogen conversion would help advance the research in this expanding area. This review will cover the physicochemical properties of copper-based chalco-genides, developments of various photocathodes, strategies to enhance the PEC activity and stability, introductions of tandem PEC cells, and finally, prospects on their potential for the practical solar-to-hydrogen conversion. We believe this review article can provide some insights of fundamentals and applications of copper-based chalco-genide thin films for PEC water splitting.

Theoretical prediction of the structural properties of uranium chalcogenides under high pressure

Science.gov (United States)

Kapoor, Shilpa; Yaduvanshi, Namrata; Singh, Sadhna

2018-05-01

Uranium chalcogenides crystallize in rock salt structure at normal condition and transform to Cesium Chloride structure at high pressure. We have investigated the transition pressure and volume drop of USe and UTe using three body potential model (TBIP). Present model includes long range Columbic, three body interaction forces and short range overlap forces operative up to next nearest neighbors. We have reported the phase transition pressure, relative volume collapses, the thermo physical properties such as molecular force constant (f), infrared absorption frequency (v0), Debye temperature (θD) and Gruneisen parameter (γ) of present chalcogenides and found that our results in general good agreement with experimental and other theoretical data.

Hydrazine-hydrothermal method to synthesize three-dimensional chalcogenide framework for photocatalytic hydrogen generation

International Nuclear Information System (INIS)

Liu Yi; Kanhere, Pushkar D.; Wong, Chui Ling; Tian Yuefeng; Feng Yuhua; Boey, Freddy; Wu, Tom; Chen Hongyu; White, Tim J.; Chen Zhong; Zhang Qichun

2010-01-01

A novel chalcogenide, [Mn 2 Sb 2 S 5 (N 2 H 4 ) 3 ] (1), has been synthesized by the hydrazine-hydrothermal method. X-ray crystallography study reveals that the new compound 1 crystallizes in space group P1-bar (no. 2) of the triclinic system. The structure features an open neutral three-dimensional framework, where two-dimensional mesh-like inorganic layers are bridged by intra- and inter-layer hydrazine ligands. Both two Mn1 and Mn2 sites adopt distorted octahedral coordination. While two Sb1 and Sb2 sites exhibit two different coordination geometries, the Sb1 site is coordinated with three S atoms to generate a SbS 3 trigonal-pyramidal geometry, and the Sb2 site adopts a SbS 4 trigonal bipyramidal coordination geometry. It has an optical band gap of about ∼2.09 eV, which was deduced from the diffuse reflectance spectrum, and displays photocatalytic behaviors under visible light irradiation. Magnetic susceptibility measurements show compound 1 obeys the Curie-Weiss law in the range of 50-300 K. -- Graphical abstract: A novel chalcogenide, [Mn 2 Sb 2 S 5 (N 2 H 4 ) 3 ] (1), synthesized by hydrazine-hydrothermal method, has a band gap of about ∼2.09 eV and displays photocatalytic behaviors under visible light irradiation. Display Omitted

Genomic and expression analysis of the vanG-like gene cluster of Clostridium difficile.

Science.gov (United States)

Peltier, Johann; Courtin, Pascal; El Meouche, Imane; Catel-Ferreira, Manuella; Chapot-Chartier, Marie-Pierre; Lemée, Ludovic; Pons, Jean-Louis

2013-07-01

Primary antibiotic treatment of Clostridium difficile intestinal diseases requires metronidazole or vancomycin therapy. A cluster of genes homologous to enterococcal glycopeptides resistance vanG genes was found in the genome of C. difficile 630, although this strain remains sensitive to vancomycin. This vanG-like gene cluster was found to consist of five ORFs: the regulatory region consisting of vanR and vanS and the effector region consisting of vanG, vanXY and vanT. We found that 57 out of 83 C. difficile strains, representative of the main lineages of the species, harbour this vanG-like cluster. The cluster is expressed as an operon and, when present, is found at the same genomic location in all strains. The vanG, vanXY and vanT homologues in C. difficile 630 are co-transcribed and expressed to a low level throughout the growth phases in the absence of vancomycin. Conversely, the expression of these genes is strongly induced in the presence of subinhibitory concentrations of vancomycin, indicating that the vanG-like operon is functional at the transcriptional level in C. difficile. Hydrophilic interaction liquid chromatography (HILIC-HPLC) and MS analysis of cytoplasmic peptidoglycan precursors of C. difficile 630 grown without vancomycin revealed the exclusive presence of a UDP-MurNAc-pentapeptide with an alanine at the C terminus. UDP-MurNAc-pentapeptide [d-Ala] was also the only peptidoglycan precursor detected in C. difficile grown in the presence of vancomycin, corroborating the lack of vancomycin resistance. Peptidoglycan structures of a vanG-like mutant strain and of a strain lacking the vanG-like cluster did not differ from the C. difficile 630 strain, indicating that the vanG-like cluster also has no impact on cell-wall composition.

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

Electrical conduction mechanism in GeSeSb chalcogenide glasses

Indian Academy of Sciences (India)

by melt quenching has been determined at different temperatures in bulk through the I–V characteristic curves ... DC conductivity; chalcogenide glass; Sb–Se bonding; Poole–Frenkel mechanism .... measurements were taken at room temperature as well as ele- .... age across the sample was continuued, the induced thermal.

2D Metal Chalcogenides Incorporated into Carbon and their Assembly for Energy Storage Applications.

Science.gov (United States)

Deng, Zongnan; Jiang, Hao; Li, Chunzhong

2018-05-01

2D metal chalcogenides have become a popular focus in the energy storage field because of their unique properties caused by their single-atom thicknesses. However, their high surface energy and van der Waals attraction easily cause serious stacking and restacking, leading to the generation of more inaccessible active sites with rapid capacity fading. The hybridization of 2D metal chalcogenides with highly conductive materials, particularly, incorporating ultrasmall and few-layered metal chalcogenides into carbon frameworks, can not only maximize the exposure of active sites but also effectively avoid their stacking and aggregation during the electrochemical reaction process. Therefore, a satisfactory specific capacity will be achieved with a long cycle life. In this Concept, the representative progress on such intriguing nanohybrids and their applications in energy storage devices are mainly summarized. Finally, an outlook of the future development and challenges of such nanohybrids for achieving an excellent energy storage capability is also provided. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

General Top-Down Ion Exchange Process for the Growth of Epitaxial Chalcogenide Thin Films and Devices

KAUST Repository

Xia, Chuan

2016-12-30

We demonstrate a versatile top-down ion exchange process, done at ambient temperature, to form epitaxial chalcogenide films and devices, with nanometer scale thickness control. To demonstrate the versatility of our process we have synthesized (1) epitaxial chalcogenide metallic and semiconducting films and (2) free-standing chalcogenide films and (3) completed in situ formation of atomically sharp heterojunctions by selective ion exchange. Epitaxial NiCo2S4 thin films prepared by our process show 115 times higher mobility than NiCo2S4 pellets (23 vs 0.2 cm(2) V-1 s(-1)) prepared by previous reports. By controlling the ion exchange process time, we made free-standing epitaxial films of NiCo2S4 and transferred them onto different substrates. We also demonstrate in situ formation of atomically sharp, lateral Schottky diodes based on NiCo2O4/NiCo2S4 heterojunction, using a single ion exchange step. Additionally, we show that our approach can be easily extended to other chalcogenide semiconductors. Specifically, we used our process to prepare Cu1.8S thin films with mobility that matches single crystal Cu1.8S (25 cm(2) V-1 s(-1)), which is ca. 28 times higher than the previously reported Cu1.8S thin film mobility (0.58 cm(2) V-1 s(-1)), thus demonstrating the universal nature of our process. This is the first report in which chalcogenide thin films retain the epitaxial nature of the precursor oxide films, an approach that will be useful in many applications.

Ge and As x-ray absorption fine structure spectroscopic study of homopolar bonding, chemical order, and topology in Ge-As-S chalcogenide glasses

International Nuclear Information System (INIS)

Sen, S.; Ponader, C.W.; Aitken, B.G.

2001-01-01

The coordination environments of Ge and As atoms in Ge x As y S 1-x-y glasses with x:y=1:2, 1:1, and 2.5:1 and with wide-ranging S contents have been studied with Ge and As K-edge x-ray absorption fine structure spectroscopy. The coordination numbers of Ge and As atoms are found to be 4 and 3, respectively, in all glasses. The first coordination shells of Ge and As atoms in the stoichiometric and S-excess glasses consist of S atoms only, implying the preservation of chemical order at least over the length scale of the first coordination shell. As-As homopolar bonds are found to appear at low and intermediate levels of S deficiency, whereas Ge-Ge bonds are formed only in strongly S-deficient glasses indicating clustering of metal atoms and violation of chemical order in S-deficient glasses. The composition-dependent variation in chemical order in chalcogenide glasses has been hypothesized to result in topological changes in the intermediate-range structural units. The role of such topological transitions in controlling the structure-property relationships in chalcogenide glasses is discussed

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.

Theory of small atomic-like 2D dust clusters

International Nuclear Information System (INIS)

Amiranashvili, Sh.G.; Gousein-zade, N.G.; Tsytovich, V.N.

2002-01-01

In several experiments atom-like dust clusters with parabolic confining potential were observed [1-3]. Here we present a general theory of 2D clusters confined by (1/2)m dω 0 2 r2 potential with arbitrary pair interaction potential depending on the inter-dust distance. It describes the equilibrium conditions, normal modes, their frequencies and possible instabilities of clusters with arbitrary N number of grains. The mono-layer clusters can have 2N frequencies of oscillations in the cluster plane among which 3 modes are trivial (ω = 0 and double degenerate frequency of oscillation in the potential well). The 2N - 3 non-trivial modes are considered. For example, for square dust cluster with potential V(r) the equilibrium is described by ω 0 2 = -(4/m) [V'(√(2)R) + V'(2R)], the frequency of radial oscillations is ω2 = (16R2/m) [V''(√(2)R) + 2V''(2R)], the two single modes frequencies are ω2 (32R2/m)V''(2R); ω2 = (16R2/m)V''(√(2)r) and one double degenerated mode frequency is ω2 = (1/m) [V'√(2)R) - V'(2R) + 4R2V''(√(2)R)] where ' corresponds to the differentiation of the potential V(r) with respect to √(r). The general stability criterion was found and investigated for N ≥ 4. The pair interaction potential V(r) is considered as a sum of different attraction and repulsion terms , including that which describe the non-screened collective and non collective attraction, the screened non-Coulomb interaction and the non-screened repulsion. The collective non-screened potential causes the absence of equilibria at certain dust cluster sizes. For screened Coulomb potential Vc(r) = (Z d 2 e2αscr/r)exp(-r/λscr) the clusters with the size R are considered. The pentagon cluster is found to be stable for R < 3.3λscr and the clusters with N ≥ 6 are found to be always unstable. The measurements of the frequencies of the cluster modes, the thresholds of cluster equilibria and the stability of the clusters can be used for detection of the dust

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

New functionality of chalcogenide glasses for radiation sensing of nuclear wastes.

Science.gov (United States)

Ailavajhala, M S; Gonzalez-Velo, Y; Poweleit, C D; Barnaby, H J; Kozicki, M N; Butt, D P; Mitkova, M

2014-03-30

Data about gamma radiation induced effects in Ge40Se60 chalcogenide thin films and radiation induced silver diffusion within these are presented. Blanket films and devices were created to study the structural changes, diffusion products, and device performance. Raman spectroscopy, X-ray diffraction, current vs. voltage (I-V) and impedance measurements expound the behavior of Ge40Se60 glass and silver diffusion within this glass under radiation. Raman study shows that there is a decrease in the area ratio between edge shared and corner shared structural units revealing structural reorganization occurring in the glasses as a result of gamma radiation. X-ray diffraction studies revealed that with sufficiently radiation dose it is also possible to create Ag2Se in selenium-depleted systems. Oxidation of the Ge enriched chalcogenide backbone is confirmed through the electrical performance of the sensing elements based on these films. Combination of these structural and diffusion products influences the device performance. The I-V behavior is characterized by increase in current and then stabilization as a function of radiation dose. Additionally, device modeling is also presented using Silvaco software and analytical methods to shed light on the device behavior. This type of sensor design and material characterizations facilitate in improving the radiation sensing capabilities of silver containing chalcogenide glass thin films. Copyright © 2013 Elsevier B.V. All rights reserved.

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

FEATURES OF ISLET-LIKE CLUSTERS GENERATION IN PANCREATIC DUCTAL CELL MOLOLAYER CULTURING

Directory of Open Access Journals (Sweden)

L. A. Kirsanova

2012-01-01

Full Text Available Newborn rabbit pancreatic cell monolayer was obtained as we described earlier.The cultivated epithelial cells were shown by immunofluorescence to express special ductal marker CK19 and were insulin-and glucagon- negative for 10–15 days. A few fusiforms of nestin-positive cells were found in monolayer. Over 2 weeks in serum-free medium the plaques of epithelial cells became crowded and formed 3-dimentional structures – islet- like clusters. Islet-like clusters contain some insulin- and glucagon-positive cells recognized by immunohysto- chemistry staining. Pancreatic endocrine cell generation in 3-dimentional structures is discussed. 

Case studies on the formation of chalcogenide self-assembled monolayers on surfaces and dissociative processes

Directory of Open Access Journals (Sweden)

Yongfeng Tong

2016-02-01

Full Text Available This report examines the assembly of chalcogenide organic molecules on various surfaces, focusing on cases when chemisorption is accompanied by carbon–chalcogen atom-bond scission. In the case of alkane and benzyl chalcogenides, this induces formation of a chalcogenized interface layer. This process can occur during the initial stages of adsorption and then, after passivation of the surface, molecular adsorption can proceed. The characteristics of the chalcogenized interface layer can be significantly different from the metal layer and can affect various properties such as electron conduction. For chalcogenophenes, the carbon–chalcogen atom-bond breaking can lead to opening of the ring and adsorption of an alkene chalcogenide. Such a disruption of the π-electron system affects charge transport along the chains. Awareness about these effects is of importance from the point of view of molecular electronics. We discuss some recent studies based on X-ray photoelectron spectroscopy that shed light on these aspects for a series of such organic molecules.

Study of third order nonlinearity of chalcogenide thin films using third harmonic generation measurements

Science.gov (United States)

Rani, Sunita; Mohan, Devendra; Kumar, Manish; Sanjay

2018-05-01

Third order nonlinear susceptibility of (GeSe3.5)100-xBix (x = 0, 10, 14) and ZnxSySe100-x-y (x = 2, y = 28; x = 4, y = 20; x = 6, y = 12; x = 8, y = 4) amorphous chalcogenide thin films prepared using thermal evaporation technique is estimated. The dielectric constant at incident and third harmonic wavelength is calculated using "PARAV" computer program. 1064 nm wavelength of Nd: YAG laser is incident on thin film and third harmonic signal at 355 nm wavelength alongwith fundamental light is obtained in reflection that is separated from 1064 nm using suitable optical filter. Reflected third harmonic signal is measured to trace the influence of Bi and Zn on third order nonlinear susceptibility and is found to increase with increase in Bi and Zn content in (GeSe3.5)100-xBix, and ZnxSySe100-x-y chalcogenide thin films respectively. The excellent optical nonlinear property shows the use of chalcogenide thin films in photonics for wavelength conversion and optical data processing.

THz waveguides, devices and hybrid polymer-chalcogenide photonic crystal fibers

DEFF Research Database (Denmark)

Bao, Hualong; Markos, Christos; Nielsen, Kristian

2014-01-01

In this contribution, we review our recent activities in the design, fabrication and characterization of polymer THz waveguides. Besides the THz waveguides, we finally will also briefly show some of our initial results on a novel hybrid polymer photonic crystal fiber with integrated chalcogenide...

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 ...

Differentiation of human multipotent dermal fibroblasts into islet-like cell clusters

Directory of Open Access Journals (Sweden)

Liu Wei

2010-06-01

Full Text Available Abstract Background We have previously obtained a clonal population of cells from human foreskin that is able to differentiate into mesodermal, ectodermal and endodermal progenies. It is of great interest to know whether these cells could be further differentiated into functional insulin-producing cells. Results Sixty-one single-cell-derived dermal fibroblast clones were established from human foreskin by limiting dilution culture. Of these, two clones could be differentiated into neuron-, adipocyte- or hepatocyte-like cells under certain culture conditions. In addition, those two clones were able to differentiate into islet-like clusters under pancreatic induction. Insulin, glucagon and somatostatin were detectable at the mRNA and protein levels after induction. Moreover, the islet-like clusters could release insulin in response to glucose in vitro. Conclusions This is the first study to demonstrate that dermal fibroblasts can differentiate into insulin-producing cells without genetic manipulation. This may offer a safer cell source for future stem cell-based therapies.

On the instability effects in radiation-sensitive chalcogenide glasses

International Nuclear Information System (INIS)

Balitska, V.; Kovalskiy, A.; Shpotyuk, O.; Vakiv, M.

2007-01-01

The features of application of radiation-sensitive media based on chalcogenide glasses of As-Ge-S system for registration of high-energy γ-radiation are analysed. It is shown that compositional features of the observed time-instability effect should be taken into account in order to ensure a higher accuracy of the developed dosimeters

On the instability effects in radiation-sensitive chalcogenide glasses

Energy Technology Data Exchange (ETDEWEB)

Balitska, V. [Lviv State University for Vital Activity Safety, 35 Kleparivska str., Lviv, UA-79007 (Ukraine); Lviv Institute of Materials of SRC ' Carat' , 202 Stryjska str., Lviv, UA-79031 (Ukraine); Kovalskiy, A. [Lviv Institute of Materials of SRC ' Carat' , 202 Stryjska str., Lviv, UA-79031 (Ukraine); International Materials Institute for New Functionality in Glass, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 (United States); Shpotyuk, O. [Lviv Institute of Materials of SRC ' Carat' , 202 Stryjska str., Lviv, UA-79031 (Ukraine); International Materials Institute for New Functionality in Glass, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 (United States)], E-mail: shpotyuk@novas.lviv.ua; Vakiv, M. [Lviv Institute of Materials of SRC ' Carat' , 202 Stryjska str., Lviv, UA-79031 (Ukraine)

2007-04-15

The features of application of radiation-sensitive media based on chalcogenide glasses of As-Ge-S system for registration of high-energy {gamma}-radiation are analysed. It is shown that compositional features of the observed time-instability effect should be taken into account in order to ensure a higher accuracy of the developed dosimeters.

Direct Electrospray Printing of Gradient Refractive Index Chalcogenide Glass Films.

Science.gov (United States)

Novak, Spencer; Lin, Pao Tai; Li, Cheng; Lumdee, Chatdanai; Hu, Juejun; Agarwal, Anuradha; Kik, Pieter G; Deng, Weiwei; Richardson, Kathleen

2017-08-16

A spatially varying effective refractive index gradient using chalcogenide glass layers is printed on a silicon wafer using an optimized electrospray (ES) deposition process. Using solution-derived glass precursors, IR-transparent Ge 23 Sb 7 S 70 and As 40 S 60 glass films of programmed thickness are fabricated to yield a bilayer structure, resulting in an effective gradient refractive index (GRIN) film. Optical and compositional analysis tools confirm the optical and physical nature of the gradient in the resulting high-optical-quality films, demonstrating the power of direct printing of multimaterial structures compatible with planar photonic fabrication protocols. The potential application of such tailorable materials and structures as they relate to the enhancement of sensitivity in chalcogenide glass based planar chemical sensor device design is presented. This method, applicable to a broad cross section of glass compositions, shows promise in directly depositing GRIN films with tunable refractive index profiles for bulk and planar optical components and devices.

Thermal, electronic and ductile properties of lead-chalcogenides under pressure.

Science.gov (United States)

Gupta, Dinesh C; Bhat, Idris Hamid

2013-09-01

Fully relativistic pseudo-potential ab-initio calculations have been performed to investigate the high pressure phase transition, elastic and electronic properties of lead-chalcogenides including the less known lead polonium. The calculated ground state parameters, for the rock-salt structure show good agreement with the experimental data. PbS, PbSe, PbTe and PbPo undergo a first-order phase transition from rock-salt to CsCl structure at 19.4, 15.5, 11.5 and 7.3 GPa, respectively. The elastic properties have also been calculated. The calculations successfully predicted the location of the band gap at L-point of Brillouin zone and the band gap for each material at ambient pressure. It is observed that unlike other lead-chalcogenides, PbPo is semi-metal at ambient pressure. The pressure variation of the energy gap indicates that these materials metalize under pressure. The electronic structures of these materials have been computed in parent as well as in high pressure B2 phase.

Synthesis of the first dimetallacarborane ruthenium-iridium cluster

International Nuclear Information System (INIS)

Lobanova, I.A.; Chizhevskij, I.T.; Petrovskij, P.V.; Bregadze, V.I.

1996-01-01

New electron-deficient dimetallic cluster (η 4 -C 8 H 12 )IrRu(μ-H)(PPh 3 ) 2 (η 5 -C 2 B 9 H 11 ) (1), has been prepared by the reaction of exo-nido-5,6,10-[Cl(PPh 3 ) 2 Ru]-5,6.10-(μ-H) 3 -10-H-7,8-C 2 B 9 H 8 with dimeric or acetylacetonate complexes of Ir in the presence of KOH in ethanol at 22 deg C. 1 H, 13 C, 31 P, 11 B NMR and IR spectral data for 1 are presented. 8 refs., 1 scheme

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)

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

International Nuclear Information System (INIS)

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

1980-01-01

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

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.

Reversibility windows in selenide-based chalcogenide glasses

International Nuclear Information System (INIS)

Shpotyuk, O.; Hyla, M.; Boyko, V.; Golovchak, R.

2008-01-01

A simple route for the estimation of the reversibility windows in the sense of non-ageing ability is developed for chalcogenide glasses obeying '8-N' rule at the example of As-Se, Ge-Se and Ge-As-Se glass systems. The low limit of their reversibility windows is determined at the average coordination number Z=2.4 in full agreement with rigidity percolation theory, while the upper limit is shown to be related to the glass preparation conditions and samples prehistory

Reversibility windows in selenide-based chalcogenide glasses

Energy Technology Data Exchange (ETDEWEB)

Shpotyuk, O. [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska Street, Lviv, UA 79031 (Ukraine); Institute of Physics of Jan Dlugosz University, 13/15, al. Armii Krajowej, Czestochowa, PL 42200 (Poland); Hyla, M. [Institute of Physics of Jan Dlugosz University, 13/15, al. Armii Krajowej, Czestochowa, PL 42200 (Poland); Boyko, V. [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska Street, Lviv, UA 79031 (Ukraine); Lviv National Polytechnic University, 12, Bandera Street, Lviv, UA 79013 (Ukraine); Golovchak, R. [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska Street, Lviv, UA 79031 (Ukraine)], E-mail: golovchak@novas.lviv.ua

2008-10-01

A simple route for the estimation of the reversibility windows in the sense of non-ageing ability is developed for chalcogenide glasses obeying '8-N' rule at the example of As-Se, Ge-Se and Ge-As-Se glass systems. The low limit of their reversibility windows is determined at the average coordination number Z=2.4 in full agreement with rigidity percolation theory, while the upper limit is shown to be related to the glass preparation conditions and samples prehistory.

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...

Prediction of operon-like gene clusters in the Arabidopsis thaliana genome based on co-expression analysis of neighboring genes.

Science.gov (United States)

Wada, Masayoshi; Takahashi, Hiroki; Altaf-Ul-Amin, Md; Nakamura, Kensuke; Hirai, Masami Y; Ohta, Daisaku; Kanaya, Shigehiko

2012-07-15

Operon-like arrangements of genes occur in eukaryotes ranging from yeasts and filamentous fungi to nematodes, plants, and mammals. In plants, several examples of operon-like gene clusters involved in metabolic pathways have recently been characterized, e.g. the cyclic hydroxamic acid pathways in maize, the avenacin biosynthesis gene clusters in oat, the thalianol pathway in Arabidopsis thaliana, and the diterpenoid momilactone cluster in rice. Such operon-like gene clusters are defined by their co-regulation or neighboring positions within immediate vicinity of chromosomal regions. A comprehensive analysis of the expression of neighboring genes therefore accounts a crucial step to reveal the complete set of operon-like gene clusters within a genome. Genome-wide prediction of operon-like gene clusters should contribute to functional annotation efforts and provide novel insight into evolutionary aspects acquiring certain biological functions as well. We predicted co-expressed gene clusters by comparing the Pearson correlation coefficient of neighboring genes and randomly selected gene pairs, based on a statistical method that takes false discovery rate (FDR) into consideration for 1469 microarray gene expression datasets of A. thaliana. We estimated that A. thaliana contains 100 operon-like gene clusters in total. We predicted 34 statistically significant gene clusters consisting of 3 to 22 genes each, based on a stringent FDR threshold of 0.1. Functional relationships among genes in individual clusters were estimated by sequence similarity and functional annotation of genes. Duplicated gene pairs (determined based on BLAST with a cutoff of EOperon-like clusters tend to include genes encoding bio-machinery associated with ribosomes, the ubiquitin/proteasome system, secondary metabolic pathways, lipid and fatty-acid metabolism, and the lipid transfer system. Copyright © 2012 Elsevier B.V. All rights reserved.

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)

The electronic structure of the antimony chalcogenide series: Prospects for optoelectronic applications

Energy Technology Data Exchange (ETDEWEB)

Carey, John J.; Allen, Jeremy P. [School of Chemistry and CRANN, Trinity College Dublin, Dublin 2 (Ireland); Scanlon, David O. [University College London, Kathleen Lonsdale Materials Chemistry, 20 Gordon Street, London WC1H 0AJ (United Kingdom); Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE (United Kingdom); Watson, Graeme W., E-mail: watsong@tcd.ie [School of Chemistry and CRANN, Trinity College Dublin, Dublin 2 (Ireland)

2014-05-01

In this study, density functional theory is used to evaluate the electronic structure of the antimony chalcogenide series. Analysis of the electronic density of states and charge density shows that asymmetric density, or ‘lone pairs’, forms on the Sb{sup III} cations in the distorted oxide, sulphide and selenide materials. The asymmetric density progressively weakens down the series, due to the increase in energy of valence p states from O to Te, and is absent for Sb{sub 2}Te{sub 3}. The fundamental and optical band gaps were calculated and Sb{sub 2}O{sub 3}, Sb{sub 2}S{sub 3} and Sb{sub 2}Se{sub 3} have indirect band gaps, while Sb{sub 2}Te{sub 3} was calculated to have a direct band gap at Γ. The band gaps are also seen to reduce from Sb{sub 2}O{sub 3} to Sb{sub 2}Te{sub 3}. The optical band gap for Sb{sub 2}O{sub 3} makes it a candidate as a transparent conducting oxide, while Sb{sub 2}S{sub 3} and Sb{sub 2}Se{sub 3} have suitable band gaps for thin film solar cell absorbers. - Graphical abstract: A schematic illustrating the interaction between the Sb{sup III} cations and the chalcogenide anions and the change in their respective energy levels down the series. - Highlights: • The electronic structure of the antimony chalcogenide series is modelled using DFT. • Asymmetric density is present on distorted systems and absent on the symmetric telluride system. • Asymmetric density is formed from the mixing of Sb 5s and anion p states, where the anti-bonding combination is stabilised by the Sb 5p states. • The asymmetric density weakens down the series due to the increase in energy of chalcogenide p states. • The increase in energy of the anion p states reduces the fundamental and optical band gaps.

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

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.

Deposition of Ge{sub 23}Sb{sub 7}S{sub 70} chalcogenide glass films by electrospray

Energy Technology Data Exchange (ETDEWEB)

Novak, Spencer, E-mail: spencen@g.clemson.edu [Department of Materials Science and Engineering, COMSET, Clemson University, Clemson, SC (United States); College of Optics and Photonics, CREOL, University of Central FL (United States); Johnston, Danvers E.; Li, Cheng; Deng, Weiwei [Department of Mechanical and Aerospace Engineering, University of Central FL (United States); Richardson, Kathleen [Department of Materials Science and Engineering, COMSET, Clemson University, Clemson, SC (United States); College of Optics and Photonics, CREOL, University of Central FL (United States)

2015-08-03

Solution-based chalcogenide glass films, traditionally deposited by spin-coating, are attractive for their potential use in chip-based devices operating in the mid-infrared and for ease of nanostructure incorporation. To overcome limitations of spin-coating such as excessive material waste and difficulty for scale-up, this paper introduces electrospray as a film deposition technique for solution-based chalcogenide glasses. Electrospray is shown to produce Ge{sub 23}Sb{sub 7}S{sub 70} films with similar surface quality and optical properties as films deposited by spin-coating. The advantages of electrospray deposition for nanoparticle dispersion, scalable and continuous manufacturing with little material waste, and comparable film quality to spin-coating make electrospray a promising deposition method for practical applications of chalcogenide glass films. - Highlights: • Electrospray film deposition processing of Ge{sub 23}Sb{sub 7}S{sub 70} films was developed. • Traditional spin-coated films were also fabricated in parallel. • Optical properties and surface quality found to be similar between two approaches.

1D - photonic crystals prepared from the amorphous chalcogenide films

Czech Academy of Sciences Publication Activity Database

Kohoutek, T.; Orava, J.; Wágner, T.; Hrdlička, M.; Vlček, Milan; Frumar, M.

2009-01-01

Roč. 20, - (2009), S346-S350 ISSN 0957-4522. [International Conference of Optical and Optoelectronic Materials and Applications. London, 29.07.2007-03.08.2007] Institutional research plan: CEZ:AV0Z40500505 Keywords : chalcogenide thin films Subject RIV: CA - Inorganic Chemistry Impact factor: 1.020, year: 2009

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)

Effects of cluster-shell competition and BCS-like pairing in 12C

Science.gov (United States)

Matsuno, H.; Itagaki, N.

2017-12-01

The antisymmetrized quasi-cluster model (AQCM) was proposed to describe α-cluster and jj-coupling shell models on the same footing. In this model, the cluster-shell transition is characterized by two parameters, R representing the distance between α clusters and Λ describing the breaking of α clusters, and the contribution of the spin-orbit interaction, very important in the jj-coupling shell model, can be taken into account starting with the α-cluster model wave function. Not only the closure configurations of the major shells but also the subclosure configurations of the jj-coupling shell model can be described starting with the α-cluster model wave functions; however, the particle-hole excitations of single particles have not been fully established yet. In this study we show that the framework of AQCM can be extended even to the states with the character of single-particle excitations. For ^{12}C, two-particle-two-hole (2p2h) excitations from the subclosure configuration of 0p_{3/2} corresponding to a BCS-like pairing are described, and these shell model states are coupled with the three α-cluster model wave functions. The correlation energy from the optimal configuration can be estimated not only in the cluster part but also in the shell model part. We try to pave the way to establish a generalized description of the nuclear structure.

The effect of diluting ruthenium by iron in RuxSey catalyst for oxygen reduction

International Nuclear Information System (INIS)

Delacote, Cyril; Lewera, Adam; Pisarek, Marcin; Kulesza, Pawel J.; Zelenay, Piotr; Alonso-Vante, Nicolas

2010-01-01

This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru x Se y . The catalysts were obtained by thermal decomposition of Ru 3 (CO) 12 and Fe(CO) 5 in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

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}.

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, ...

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

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

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.

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.

G0.253 + 0.016: A MOLECULAR CLOUD PROGENITOR OF AN ARCHES-LIKE CLUSTER

International Nuclear Information System (INIS)

Longmore, Steven N.; Ascenso, Joana; Testi, Leonardo; Bressert, Eli; Rathborne, Jill; Bastian, Nate; Alves, Joao; Meingast, Stefan; Bally, John; Battersby, Cara; Longmore, Andy; Purcell, Cormac; Walsh, Andrew; Jackson, James; Foster, Jonathan; Molinari, Sergio; Amorim, A.; Lima, J.; Marques, R.; Moitinho, A.

2012-01-01

Young massive clusters (YMCs) with stellar masses of 10 4 -10 5 M ☉ and core stellar densities of 10 4 -10 5 stars per cubic pc are thought to be the 'missing link' between open clusters and extreme extragalactic super star clusters and globular clusters. As such, studying the initial conditions of YMCs offers an opportunity to test cluster formation models across the full cluster mass range. G0.253 + 0.016 is an excellent candidate YMC progenitor. We make use of existing multi-wavelength data including recently available far-IR continuum (Herschel/Herschel Infrared Galactic Plane Survey) and mm spectral line (H 2 O Southern Galactic Plane Survey and Millimetre Astronomy Legacy Team 90 GHz Survey) data and present new, deep, multiple-filter, near-IR (Very Large Telescope/NACO) observations to study G0.253 + 0.016. These data show that G0.253 + 0.016 is a high-mass (1.3 × 10 5 M ☉ ), low-temperature (T dust ∼ 20 K), high-volume, and column density (n ∼ 8 × 10 4 cm –3 ; N H 2 ∼4×10 23 cm –2 ) molecular clump which is close to virial equilibrium (M dust ∼ M virial ) so is likely to be gravitationally bound. It is almost devoid of star formation and, thus, has exactly the properties expected for the initial conditions of a clump that may form an Arches-like massive cluster. We compare the properties of G0.253 + 0.016 to typical Galactic cluster-forming molecular clumps and find it is extreme, and possibly unique in the Galaxy. This uniqueness makes detailed studies of G0.253 + 0.016 extremely important for testing massive cluster formation models.

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

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.

Mid-infrared supercontinuum generation spanning more than 11 μm in a chalcogenide step-index fiber

DEFF Research Database (Denmark)

Petersen, Christian Rosenberg; Møller, Uffe Visbech; Kubat, Irnis

2015-01-01

Supercontinuum generation covering an ultra-broad spectrum from 1.5-11.7μm and 1.4-13.3μm is experimentally demonstrated by pumping an 85mm chalcogenide step-index fiber with 100fs pulses at a wavelength of 4.5μm and 6.3μm, respectively.......Supercontinuum generation covering an ultra-broad spectrum from 1.5-11.7μm and 1.4-13.3μm is experimentally demonstrated by pumping an 85mm chalcogenide step-index fiber with 100fs pulses at a wavelength of 4.5μm and 6.3μm, respectively....

Ultrafast Laser Fabrication of Bragg Waveguides in GLS Chalcogenide Glass

Directory of Open Access Journals (Sweden)

McMillen Ben

2013-11-01

Full Text Available We present work on the fabrication of Bragg waveguides in gallium-lanthanum-sulfide chalcogenide glass using an ultrafast laser. Waveguides were written with a single pass while modulating the writing beam. The spatial and temporal profile of the writing beam was ontrolled during waveguide fabrication in order to control the shape and size of the waveguide cross-section.

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.

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2018-02-05

Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 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

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

DEFF Research Database (Denmark)

Krebs, Frederik C; Biancardo, M.

2006-01-01

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

Synthesis and Characterization of Quaternary Metal Chalcogenide Aerogels for Gas Separation and Volatile Hydrocarbon Adsorption

KAUST Repository

Edhaim, Fatimah A.

2017-11-01

In this dissertation, the metathesis route of metal chalcogenide aerogel synthesis was expanded by conducting systematic studies between polysulfide building blocks and the 1st-row transition metal linkers. Resulting materials were screened as sorbents for selective gas separation and volatile organic compounds adsorption. They showed preferential adsorption of polarizable gases (CO2) and organic compounds (toluene). Ion exchange and heavy metal remediation properties have also been demonstrated. The effect of the presence of different counter-ion within chalcogel frameworks on the adsorption capacity of the chalcogels was studied on AFe3Zn3S17 (A= K, Na, and Rb) chalcogels. The highest adsorption capacity toward hydrocarbons and gases was observed on Rb based chalcogels. Adopting a new building block [BiTe3]3- with the 1st-row transition metal ions results in the formation of three high BET surface area chalcogels, KCrBiTe3, KZnBiTe3, and KFeBiTe3. The resulting chalcogels showed preferential adsorption of toluene vapor, and remarkable selectivity of CO2, indicating the potential future use of chalcogels in adsorption-based gas or hydrocarbon separation processes. The synthesis and characterization of the rare earth chalcogels NaYSnS4, NaGdSnS4, and NaTbSnS4 are also reported. Rare earth metal ions react with the thiostannate clusters in formamide solution forming extended polymeric networks by gelation. Obtained chalcogels have high BET surface areas, and showed notable adsorption capacity toward CO2 and toluene vapor. These chalcogels have also been engaged in the absorption of different organic molecules. The results reveal the ability of the chalcogels to distinguish among organic molecules on their electronic structures; hence, they could be used as sensors. Furthermore, the synthesis of metal chalcogenide aerogels Co0.5Sb0.33MoS4 and Co0.5Y0.33MoS4 by the sol-gel method is reported. In this system, the building blocks [MoS4]2- chelated with Co2+ and (Sb3

Iron based pnictide and chalcogenide superconductors studied by muon spin spectroscopy

International Nuclear Information System (INIS)

Shermadini, Zurab

2014-01-01

In the present thesis the superconducting properties of the Iron-based Ba 1-x Rb x Fe 2 As 2 arsenides, and A x Fe 2-y Se 2 (A=Cs,Rb,K) chalcogenides are investigated by means of Muon Spin Rotation Spectroscopy. The temperature and pressure dependence of the magnetic penetration depth is obtained form μSR experiments and analyzed to probe the superconducting gap-symmetries for each samples. The Ba 1-x Rb x Fe 2 As 2 system is described within the multi-gap s+s-wave scenario and results are discussed in the light of the suppression of inter-band processes upon hole doping. Due to the lowered upper critical field B c2 and reduced T c , a large section of B-T-p phase diagram is studied for the hole-overdoped x=1 case. By applying hydrostatic pressure, the RbFe 2 As 2 system exhibits a classical BCS superconducting characteristics. The A x Fe 2-y Se 2 chalcogenide represents a system containing magnetically ordered and superconducting phases simultaneously. In all investigated chalcogenide samples, about 90% of the total volume show the strong antiferromagnetic phase and 10% exhibit a paramagnetic behavior. Magnetization measurements reveal a 100% Meissner effect, while μSR clearly indicates that the paramagnetic phase is a perfect superconductor. Up to now, there is no clear evidence whether the antiferromagnetic phase is also superconducting. The microscopic coexistence and/or phase separation of superconductivity and magnetism is discussed. Moreover, a new hydrostatic double-wall pressure cell is developed and produced, satisfying the demands of μSR experiments. The designs and characteristics of the new pressure cell are reviewed in the present thesis.

Low-temperature photoluminescence in chalcogenide glasses doped with rare-earth ions

Czech Academy of Sciences Publication Activity Database

Kostka, Petr; Zavadil, Jiří; Iovu, M.S.; Ivanova, Z. G.; Furniss, D.; Seddon, A.B.

2015-01-01

Roč. 648, NOV 5 (2015), s. 237-243 ISSN 0925-8388 R&D Projects: GA ČR GAP106/12/2384 Institutional support: RVO:67985891 ; RVO:67985882 Keywords : chalcogenide glasses * rare earth ions * low-temperature photoluminescence * optical transmission Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass Impact factor: 3.014, year: 2015

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.

Silicon-based thin films as bottom electrodes in chalcogenide nonvolatile memories

Energy Technology Data Exchange (ETDEWEB)

Lee, Seung-Yun [IT Convergence and Components Laboratory, Electronics and Telecommunications Research Institute (ETRI), Yuseong-gu, Daejeon 305-350 (Korea, Republic of)], E-mail: seungyun@etri.re.kr; Yoon, Sung-Min; Choi, Kyu-Jeong; Lee, Nam-Yeal; Park, Young-Sam; Ryu, Sang-Ouk; Yu, Byoung-Gon; Kim, Sang-Hoon; Lee, Sang-Heung [IT Convergence and Components Laboratory, Electronics and Telecommunications Research Institute (ETRI), Yuseong-gu, Daejeon 305-350 (Korea, Republic of)

2007-10-31

The effect of the electrical resistivity of a silicon-germanium (SiGe) thin film on the phase transition in a GeSbTe (GST) chalcogenide alloy and the manufacturing aspect of the fabrication process of a chalcogenide memory device employing the SiGe film as bottom electrodes were investigated. While p-type SiGe bottom electrodes were formed using in situ doping techniques, n-type ones could be made in a different manner where phosphorus atoms diffused from highly doped silicon underlayers to undoped SiGe films. The p-n heterojunction did not form between the p-type GST and n-type SiGe layers, and the semiconduction type of the SiGe alloys did not influence the memory device switching. It was confirmed that an optimum resistivity value existed for memory operation in spite of proportionality of Joule heating to electrical resistivity. The very high resistivity of the SiGe film had no effect on the reduction of reset current, which might result from the resistance decrease of the SiGe alloy at high temperatures.

Half-Metallic Ferromagnetism and Stability of Transition Metal Pnictides and Chalcogenides

Science.gov (United States)

Liu, Bang-Gui

It is highly desirable to explore robust half-metallic ferromagnetic materials compatible with important semiconductors for spintronic applications. A state-of-the-art full potential augmented plane wave method within the densityfunctional theory is reliable enough for this purpose. In this chapter we review theoretical research on half-metallic ferromagnetism and structural stability of transition metal pnictides and chalcogenides. We show that some zincblende transition metal pnictides are half-metallic and the half-metallic gap can be fairly wide, which is consistent with experiment. Systematic calculations reveal that zincblende phases of CrTe, CrSe, and VTe are excellent half-metallic ferromagnets. These three materials have wide half-metallic gaps, are low in total energy with respect to the corresponding ground-state phases, and, importantly, are structurally stable. Halfmetallic ferromagnetism is also found in wurtzite transition metal pnictides and chalcogenides and in transition-metal doped semiconductors as well as deformed structures. Some of these half-metallic materials could be grown epitaxially in the form of ultrathin .lms or layers suitable for real spintronic applications.

Pressure dependence of crystal field splitting in Pr pnictides and chalcogenides

International Nuclear Information System (INIS)

Schirber, J.E.; Weaver, H.T.; Ginley, D.S.

1978-01-01

We have measured the pressure dependence of the Pr nuclear magnetic resonance shift in PrN, PrP, PrSb, PrAs, PrS and PrSe. The shifts in all the pnictides increase while in the chalcogenides the shifts decrease with pressure. The rare earth frequency shift is inversely proportional to the crystal field splitting in the context of the point charge model (PCM) so a decrease would be expected for all of these materials at a rate of 5/3 the volume compressibility. Our values for the pnictides tend to be considerably larger than the PCM value as well as the wrong sign. The chalcogenide values are much nearer in magnitude and are of the right sign for the PCM. Contrary to the report of Guertin et al. we see no anomaly in the pressure dependence of the susceptibility of PrS. The fact that PrN which is reported to be non-metallic also shows the wrong sign for the PCM presents difficulties for various conduction electron explanations for this unexpected behavior of the pnictides

Formation of surface nanolayers in chalcogenide crystals using coherent laser beams

Science.gov (United States)

Ozga, K.; Fedorchuk, A. O.; El-Naggar, A. M.; Albassam, A. A.; Kityk, V.

2018-03-01

We have shown a possibility to form laser modified surface nanolayers with thickness up to 60 nm in some ternary chalcogenide crystals (Ag3AsS3, Ag3SbS3, Tl3SbS3) The laser treatment was performed by two coherent laser beams split in a space. As the inducing lasers we have applied continuous wave (cw) Hesbnd Cd laser at wavelength 441 nm and doubled frequency cw Nd: YAG laser at 532 nm. The spectral energies of these lasers were higher with respect to the energy gaps of the studied crystals. The optical anisotropy was appeared and defected by monitoring of birefringence at probing wavelength of cw Hesbnd Ne laser at λ = 3390 nm. The changes of the laser stimulated near the surface layer morphology was monitored by TEM and AFM methods as well as by the reflected optical second harmonic generation at fundamental wavelength of microsecond CO2 laser generating at wavelength 10600 nm. This technique may open a new approach for the formation of the near the surface nanolayers in chalcogenides using external cw laser illumination.

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)

The Moessbauer effect in binary tin chalcogenides of tin 119

International Nuclear Information System (INIS)

Ortalli, I.; Fano, V.

1975-01-01

The values of the isomer shift, quadrupole splitting, Moessbauer coefficient, Debye temperature for the tin chalcogenides SnS. SnSe, SnTe are tabulated for the temperatures 80 and 300 K. Temperature dependences of the Moessbauer coefficient and of the effective Debye temperature for SnS, SnSe and SnTe in a temperature range of 78 to 300 K are presented. (Z.S.)

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.

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...

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.

Generation and Applications of High Average Power Mid-IR Supercontinuum in Chalcogenide Fibers

OpenAIRE

Petersen, Christian Rosenberg

2016-01-01

Mid-infrared supercontinuum with up to 54.8 mW average power, and maximum bandwidth of 1.77-8.66 μm is demonstrated as a result of pumping tapered chalcogenide photonic crystal fibers with a MHz parametric source at 4 μm

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-10-01

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

Automatic detection of multiple UXO-like targets using magnetic anomaly inversion and self-adaptive fuzzy c-means clustering

Science.gov (United States)

Yin, Gang; Zhang, Yingtang; Fan, Hongbo; Ren, Guoquan; Li, Zhining

2017-12-01

We have developed a method for automatically detecting UXO-like targets based on magnetic anomaly inversion and self-adaptive fuzzy c-means clustering. Magnetic anomaly inversion methods are used to estimate the initial locations of multiple UXO-like sources. Although these initial locations have some errors with respect to the real positions, they form dense clouds around the actual positions of the magnetic sources. Then we use the self-adaptive fuzzy c-means clustering algorithm to cluster these initial locations. The estimated number of cluster centroids represents the number of targets and the cluster centroids are regarded as the locations of magnetic targets. Effectiveness of the method has been demonstrated using synthetic datasets. Computational results show that the proposed method can be applied to the case of several UXO-like targets that are randomly scattered within in a confined, shallow subsurface, volume. A field test was carried out to test the validity of the proposed method and the experimental results show that the prearranged magnets can be detected unambiguously and located precisely.

Amplitudes of solar-like oscillations: Constraints from red giants in open clusters observed by Kepler

DEFF Research Database (Denmark)

Stello, Dennis; Huber, Daniel; Kallinger, Thomas

2011-01-01

implies that the stellar parameters can be measured to much higher precision than what is usually achievable for single stars. This makes clusters ideal for exploring the relation between the mode amplitude of solar-like oscillations and the global stellar properties. We have analyzed data obtained......Scaling relations that link asteroseismic quantities to global stellar properties are important for gaining understanding of the intricate physics that underpins stellar pulsations. The common notion that all stars in an open cluster have essentially the same distance, age, and initial composition...... with NASA's Kepler space telescope to study solar-like oscillations in 100 red giant stars located in either of the three open clusters, NGC 6791, NGC 6819, and NGC 6811. By fitting the measured amplitudes to predictions from simple scaling relations that depend on luminosity, mass, and effective...

Spectroscopic and electrochemical correlations in triangular ruthenium clusters containing N-heterocyclic ligands

International Nuclear Information System (INIS)

Cunha, C.J. da.

1989-01-01

A series of clusters of general formula [Ru sub(3) O (OOCCH sub(3)) sub(6) L sub(3)] sup(+), where L = N-heterocyclic ligands, were synthesized and characterized based on elemental analysis. UV-VIS and IR spectra. Voltametric studies revealed the existence of up to six acessible oxidation states, with a high degree of electronic delocalization. The Ru sub(3) O trigonal center possesses many delocalized electrons and can be visualized as a source of electrons. The ligands coordinated to the clusters tune their redox potentials, determine the differences in their electronic spectra, and are responsible for the special conditions required for their synthesis. (author)

Chalcogenide glasses for device application modified by high-energy irradiation

International Nuclear Information System (INIS)

Kavetskyy, T.; Shpotyuk, O.

2006-01-01

Full text: Chalcogenide glasses (ChG) or chemical compounds of chalcogen atoms (S, Se or Te, but not O) with some elements from IV-th and V-th groups of the Periodic Table (typically As, Ge, Sb, Bi, etc. ) obtained by melt quenching, are a perspective for application in modern optoelectronics, photonics, telecommunications, acoustic-optics, xerography, lithography, etc. This uniqueness is due to extremely high sensitivity of ChG to external influences, associated, presumably, with high steric flexibility proper to glassy-like network with low average atomic coordination (chalcogen atoms are typically two-fold coordinated in a glassy-like network), relatively large internal free volume and specific lp-character of electronic states localized at a valence-band top. However, at present, the further possibilities for conventional chemical/technological methods to prepare ChG are fully exhausted. One of the steps to resolve this problem is post-technological modification of ChG using possibilities of high-energy irradiation. This work is focused on new advanced radiation-modified ChG for device application in optoelectronics. The attractive practical use of these non-crystalline materials is tightly connected with radiation-induced defect formation processes. For the first time, we consider the possibilities of Raman scattering along with X-ray diffraction and positron annihilation lifetime spectroscopy to characterize microstructural mechanisms of radiation-induced effects in ChG. (authors)

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

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

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

Synthesis, crystal structure and electrical properties of the tetrahedral quaternary chalcogenides CuM{sub 2}InTe{sub 4} (M=Zn, Cd)

Energy Technology Data Exchange (ETDEWEB)

Nolas, George S., E-mail: gnolas@usf.edu [Department of Physics, University of South Florida, Tampa, FL 33620 (United States); Hassan, M. Shafiq; Dong, Yongkwan [Department of Physics, University of South Florida, Tampa, FL 33620 (United States); Martin, Joshua [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899 (United States)

2016-10-15

Quaternary chalcogenides form a large class of materials that continue to be of interest for energy-related applications. Certain compositions have recently been identified as possessing good thermoelectric properties however these materials typically have the kesterite structure type with limited variation in composition. In this study we report on the structural, optical and electrical properties of the quaternary chalcogenides CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} which crystallize in the modified zinc-blende crystal structure, and compare their properties with that of CuZn{sub 2}InSe{sub 4}. These p-type semiconductors have direct band gaps of about 1 eV resulting in relatively high Seebeck coefficient and resistivity values. This work expands on the research into quaternary chalcogenides with new compositions and structure types in order to further the fundamental investigation of multinary chalcogenides for potential thermoelectrics applications. - Graphical abstract: The structural, optical and electrical properties of the quaternary chalcogenides CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} are reported for the first time. The unique crystal structure allows for relatively good electrical transports and therefore potential for thermoelectric applications. - Highlights: • The physical properties of CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} are reported for the first time. • These materials have potential for thermoelectric applications. • Their direct band gaps also suggest potential for photovoltaics applications.

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

Short and medium range structures of 80GeSe2–20Ga2Se3 chalcogenide glasses

Science.gov (United States)

Petracovschi, Elena; Calvez, Laurent; Cormier, Laurent; Le Coq, David; Du, Jincheng

2018-05-01

The short and medium range structures of 80GeSe2–20Ga2Se3 (or Ge23.5Ga11.8Se64.7) chalcogenide glasses have been studied by combining ab initio molecular dynamics (AIMD) simulations and experimental neutron diffraction studies. The structure factor and total correlation function were calculated from glass structures generated from AIMD simulations and compared with neutron diffraction experiments showing reasonable agreement. The atomic structures of ternary chalcogenide glasses were analyzed in detail, and it was found that gallium atoms are four-fold coordinated by selenium (Se) and form [GaSe4] tetrahedra. Germanium atoms on average also have four-fold coordination, among which Se is 3.5 with the remaining being Ge–Ge homo-nuclear bonds. Ga and Ge tetrahedra link together mainly through corner-sharing and some edge-sharing of Se. No homo-nuclear bonds were observed among Ga atoms or between Ge and Ga. In addition, Se–Se homo-nuclear bonds and Se chains with various lengths were observed. A small fraction of Se atom triclusters that bond to three cations of Ge and Ga were also observed, confirming earlier proposals from 77Se solid state nuclear magnetic resonance studies. Furthermore, the electronic structures of ternary chalcogenide glasses were studied in terms of atomic charge and electronic density of states in order to gain insights into the chemical bonding and electronic properties, as well as to provide an explanation of the observed atomic structures in these ternary chalcogenide glasses.

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.

Structural and electronic properties of high pressure phases of lead chalcogenides

Science.gov (United States)

Petersen, John; Scolfaro, Luisa; Myers, Thomas

2012-10-01

Lead chalcogenides, most notably PbTe and PbSe, have become an active area of research due to their thermoelectric properties. The high figure of merit (ZT) of these materials has brought much attention to them, due to their ability to convert waste heat into electricity. Variation in synthesis conditions gives rise to a need for analysis of structural and thermoelectric properties of these materials at different pressures. In addition to the NaCl structure at ambient conditions, lead chalcogenides have a dynamic orthorhombic (Pnma) intermediate phase and a higher pressure yet stable CsCl phase. By altering the lattice constant, we simulate the application of external pressure; this has notable effects on ground state total energy, band gap, and structural phase. Using the General Gradient Approximation (GGA) in Density Functional Theory (DFT), we calculate the phase transition pressures by finding the differences in enthalpy from total energy calculations. For each phase, elastic constants, bulk modulus, shear modulus, Young's modulus, and hardness are calculated, using two different approaches. In addition to structural properties, we analyze the band structure and density of states at varying pressures, paying special note to thermoelectric implications.

Efficiency simulations of thin film chalcogenide photovoltaic cells for different indoor lighting conditions

International Nuclear Information System (INIS)

Minnaert, B.; Veelaert, P.

2011-01-01

Photovoltaic (PV) energy is an efficient natural energy source for outdoor applications. However, for indoor applications, the efficiency of PV cells is much lower. Typically, the light intensity under artificial lighting conditions is less than 10 W/m 2 as compared to 100-1000 W/m 2 under outdoor conditions. Moreover, the spectrum is different from the outdoor solar spectrum. In this context, the question arises whether thin film chalcogenide photovoltaic cells are suitable for indoor use. This paper contributes to answering that question by comparing the power output of different thin film chalcogenide solar cells with the classical crystalline silicon cell as reference. The comparisons are done by efficiency simulation based on the quantum efficiencies of the solar cells and the light spectra of typical artificial light sources i.e. an LED lamp, a 'warm' and a 'cool' fluorescent tube and a common incandescent and halogen lamp, which are compared to the outdoor AM 1.5 spectrum as reference.

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.

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)

Radiation-induced defects formation in Bi-containing vitreous chalcogenides

International Nuclear Information System (INIS)

Shpotyuk, O.; Vakiv, M.; Balitska, V.; Kovalskiy, A.

1997-01-01

Processes of formation and annihilation of coordination defects in As 2 Se 3 Bi y and (As 2 Se 3 )(Bi 2 Se 3 ) y amorphous chalcogenide semiconductors induced by influence of Co 60 gamma-irradiation are investigated by photoelectric spectroscopy method. It is obtained that radiation-induced changes of photoelectrical properties on bioconcentration of As 2 Se 3 Bi y glasses are characterized by anomalous concentration dependence. The nature of this effect is associated with diamagnetic coordination defects formation. (author). 19 refs, 3 figs

Investigations on the parent compounds of Fe-chalcogenide superconductors

International Nuclear Information System (INIS)

Koz, Cevriye

2015-01-01

This work is focused on the parent compounds of the Fe-chalcogenide superconductors. For this purpose poly- and single-crystalline forms of tetragonal β-Fe x Se, Fe 1+y Te, Fe 1+y Te 1-x Se x and Fe (1+y)-x M x Te (M = Ni, Co) have been prepared. Second focal points of this study are the low-temperature structural phase transitions and physical property changes in tetragonal Fe 1+y Te which are induced by composition, external pressure, and cationic substitution.

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.

Spin-glass-like dynamics of ferromagnetic clusters in La0.75Ba0.25CoO3

International Nuclear Information System (INIS)

Kumar, Devendra

2014-01-01

We report a magnetization study of the compound La 0.75 Ba 0.25 CoO 3 where the Ba 2+ doping is just above the critical limit for percolation of ferromagnetic clusters. The field cooled and zero-field cooled (ZFC) magnetization exhibit thermomagnetic irreversibility and the ac susceptibility shows a frequency dependent peak at the ferromagnetic ordering temperature (T C  ≈ 203 K) of the clusters. These features indicate the presence of a non-equilibrium state below T C . For the non-equilibrium state, the dynamic scaling of the imaginary part of the ac susceptibility and the static scaling of the nonlinear susceptibility clearly establish a spin-glass-like cooperative freezing of ferromagnetic clusters at 200.9(2) K. The assertion of the occurrence of spin-glass-like freezing of ferromagnetic clusters is further substantiated by ZFC ageing and memory experiments. We also observe certain dynamical features which are not present in a typical spin glass, such as: the initial magnetization after ZFC ageing first increases and then decreases with the waiting time; and there is an imperfect recovery of relaxation in negative temperature cycling experiments. This imperfect recovery transforms to perfect recovery for concurrent field cycling. Our analysis suggests that these additional dynamical features have their origin in the inter-cluster exchange interaction and cluster size distribution. The inter-cluster exchange interaction above the magnetic percolation level gives a superferromagnetic state in some granular thin films, but our results show the absence of a typical superferromagnetic-like state in La 0.75 Ba 0.25 CoO 3 . (paper)

The Effect of Indium Content on the Atomic Environment and Cluster Stability of GeSe4Inx=10,15 Glasses

Directory of Open Access Journals (Sweden)

Georgios S. E. Antipas

2015-01-01

Full Text Available The atomic environments of two chalcogenide glasses, with compositions GeSe4In10 and GeSe4In15, were studied via Reverse Monte Carlo and Density Functional Theory. Indium content demoted Ge–Se bonding in favor of Se-In while the contribution of Se–Se in the first coordination shell order was faint. Upon transition to the richer In glass, there was formation of rich Ge-centered clusters at radial distances further than 4 Å from the RMC box center, which was taken to signify a reduction of Ge–Se interactions. Cluster coordination by Se promoted stability while, very conclusively, In coordination lowered cluster stability by intervening in the Ge–Se and Se–Se networks.

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

Spectroscopic and electrochemical study of polynuclear clusters from ruthenium acetate

International Nuclear Information System (INIS)

Cipriano, C.

1989-01-01

The chemistry of the trinuclear clusters [Ru sub(3) O (CH sub(3) CO sub(2)) sub(4) L sub(3)] where L = imidazole, pyridine or pyrazine type of ligands, was investigated based on spectroscopic and electrochemical techniques. These complexes are of great interest from the point of view of their electronic and redox properties, providing multisite species for electron transfer processes. They were isolated in solid state, and characterized by means of elementary analyses and infrared spectra. The electrochemical behaviour in acetonitrile solution was typically reversible; the cyclic voltammograms exhibited a series of four or five mono electronic waves ascribed to the sucessive Ru sup(IV) Ru sup(III) Ru sup(III) / Ru sup(III) Ru sup(III) Ru sup(III)/ --- Ru sup(II) Ru sup(II) Ru sup(II) redox couples. The differences between the successive redox potentials were about 1 V, indicating strong metal-metal interaction in the trinuclear Ru sub(3) centre. The E values were strongly sensitive to the nature of the N-heterocyclic ligand, increasing with the pi-acceptor properties of the pyridine and pyrazine derivatives, but in a much less pronounced way in the case of the imidazole derivatives. Resonance Raman studies for the pyrazine cluster showed selective intensification of the vibrational modes of the Ru-pyrazine chromophore, and the trinuclear centre, using excitation wavelengths coinciding with the metal-to-pyrazine and metal-metal bands, respectively. (author)

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...

Neutron diffraction study on the medium and short-range order of ternary chalcogenide glasses

Czech Academy of Sciences Publication Activity Database

Neov, S.; Gerasimova, I.; Skordeva, E.; Arsova, D.; Pamukchieva, V.; Mikula, Pavol; Lukáš, Petr; Sonntag, R.

1999-01-01

Roč. 34, - (1999), s. 3669-3676 ISSN 0022-2461 R&D Projects: GA ČR GV202/97/K038 Keywords : neutron diffraction * short-range order * chalcogenide glasses Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.786, year: 1999

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.

Multi-layered Chalcogenides with potential for magnetism and superconductivity

Energy Technology Data Exchange (ETDEWEB)

Li, Li, E-mail: lil2@ornl.gov [Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Parker, David S. [Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Cruz, Clarina R. dela [Quantum Condensed Matter Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Sefat, Athena S., E-mail: sefata@ornl.gov [Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

2016-12-15

Highlights: • A comprehensive study on multi-layered thallium copper chalcogenides TlCu{sub 2n}Ch{sub n+1}. • All the TlCu{sub 2n}Ch{sub n+1} exhibit metallic behaviors with no long-range magnetism. • Calculations suggest a lack of Fermi-level spectral weight for magnetic instability. • Our results suggest a likelihood of magnetism for multiple structural layers with Fe. - Abstract: Layered thallium copper chalcogenides can form single, double, or triple layers of Cu–Ch separated by Tl sheets. Here we report on the preparation and properties of Tl-based materials of TlCu{sub 2}Se{sub 2}, TlCu{sub 4}S{sub 3}, TlCu{sub 4}Se{sub 3} and TlCu{sub 6}S{sub 4}. Having no long-range magnetism for these materials is quite surprising considering the possibilities of inter- and intra-layer exchange interactions through Cu 3d, and we measure by magnetic susceptibility and confirm by neutron diffraction. First principles density-functional theory calculations for both the single-layer TlCu{sub 2}Se{sub 2} (isostructural to the ‘122’ iron-based superconductors) and the double-layer TlCu{sub 4}Se{sub 3} suggest a lack of Fermi-level spectral weight that is needed to drive a magnetic or superconducting instability. However, for multiple structural layers with Fe, there is much greater likelihood for magnetism and superconductivity.

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.

Cosensitization Properties of Glutathione-Protected Au25 Cluster on Ruthenium Dye-Sensitized TiO2 Photoelectrode

Directory of Open Access Journals (Sweden)

Kazuya Nakata

2013-01-01

Full Text Available Cosensitization by glutathione-protected Au25 clusters on Ru complex, N719-sensitized TiO2 photoelectrodes is demonstrated. Glutathione-protected Au25 clusters showed no significant changes in properties after adsorption onto TiO2 particles, as confirmed by optical absorption spectroscopy, transmission electron microscopy, and laser desorption/ionization mass spectrometry. Adsorption property of the glutathione-protected Au25 clusters depends on the pH, which affects the incident photon-to-current conversion efficiency (IPCE of the TiO2 photoelectrode containing Au25 clusters. When pH 7. The IPCE of a TiO2 photoelectrode sensitized by both glutathione-protected Au25 clusters and N719 was increased compared with photoelectrodes containing either glutathione-protected Au25 clusters or N719, which suggests that glutathione-protected Au25 clusters act as a coadsorbent for N719 on TiO2 photoelectrodes. This is also supported by the results that the IPCE of N719-sensitized TiO2 photoelectrodes increased upon addition of glutathione. Furthermore, cosensitization by glutathione-protected Au25 clusters on N719-sensitized TiO2 photoelectrodes allows that wavelength of photoelectric conversion was extended to the near infrared (NIR region. These results suggest that glutathione-protected Au25 clusters act not only as a coadsorbent to increase IPCE but also as an NIR-active sensitizer.

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.

Diffusion of Ag ions under random potential barriers in silver-containing chalcogenide glasses

Czech Academy of Sciences Publication Activity Database

Stehlík, Štěpán; Shimakawa, K.; Wágner, T.; Frumar, M.

2012-01-01

Roč. 45, č. 20 (2012), s. 1-5 ISSN 0022-3727 Institutional research plan: CEZ:AV0Z10100521 Keywords : Ag ion diffusion * chalcogenide glass * Nyquist plots Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.528, year: 2012 http://iopscience.iop.org/0022-3727/45/20/205304/

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)

Magnetic and electronic properties of Neptunium chalcogenides from GGA + U + SOC and DFT investigations

Energy Technology Data Exchange (ETDEWEB)

Khan, Wilayat [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, 306 14 Pilsen (Czech Republic); Goumri-Said, Souraya, E-mail: sosaid@alfaisal.edu [College of Science, Physics Department, Alfaisal University, Riyadh 11533 (Saudi Arabia)

2017-06-15

Highlights: • Electronic and magnetic properties of Neptunium chalcogenides were explored theoretically using DFT approach. • Spin orbit coupling and GGA + U approach described successfully the f–f coupling. • Np{sub 2}X{sub 5} ate metallic with high magnetic character due to the Neptunium. • Fermi surfaces of Np{sub 2}Te{sub 5} have shown a greater electrical conductivity compared to Np{sub 2}Se{sub 5} and Np{sub 2}S{sub 5}. - Abstract: First-principles calculations techniques were employed to explore the structural, electronic and magnetic properties of Neptunium chalcogenides (Np{sub 2}X{sub 5}, X = S, Se and Te). No experimental or theoretical studies of their physical properties have been previously reported in the literature. The presence of highly localized f states has requested the employment of the spin orbit coupling and GGA + U approach in order to describe correctly the f–f coupling. Np{sub 2}X{sub 5} was found metallic with high magnetic character due to the Neptunium presence. Fermi surfaces of Np{sub 2}Te{sub 5} have shown a greater electrical conductivity compared to Np{sub 2}Se{sub 5} and Np{sub 2}S{sub 5}. The magnetic moment was found to be between 13.24 and 13.92μ{sub B}, principally induced by Np f and d-orbitals as well as the spin-polarization of the chalcogenes (Te, Se, S) induced by Np. Neptunium chalcogenides have shown interesting magnetic properties and should be manipulated with precaution due to their radioactive properties.

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.

Positronics of radiation-induced effects in chalcogenide glassy semiconductors

International Nuclear Information System (INIS)

Shpotyuk, O.; Kozyukhin, S. A.; Shpotyuk, M.; Ingram, A.; Szatanik, R.

2015-01-01

Using As 2 S 3 and AsS 2 glasses as an example, the principal possibility of using positron annihilation spectroscopy methods for studying the evolution of the free volume of hollow nanoobjects in chalcogenide glassy semiconductors exposed to radiation is shown. The results obtained by measurements of the positron annihilation lifetime and Doppler broadening of the annihilation line in reverse chronological order are in full agreement with the optical spectroscopy data in the region of the fundamental absorption edge, being adequately described within coordination defect-formation and physical-aging models

Positronics of radiation-induced effects in chalcogenide glassy semiconductors

Energy Technology Data Exchange (ETDEWEB)

Shpotyuk, O. [Scientific Research Company “Carat” (Ukraine); Kozyukhin, S. A., E-mail: sergkoz@igic.ras.ru [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation); Shpotyuk, M. [Scientific Research Company “Carat” (Ukraine); Ingram, A. [Opole Technical University (Poland); Szatanik, R. [Opole University (Poland)

2015-03-15

Using As{sub 2}S{sub 3} and AsS{sub 2} glasses as an example, the principal possibility of using positron annihilation spectroscopy methods for studying the evolution of the free volume of hollow nanoobjects in chalcogenide glassy semiconductors exposed to radiation is shown. The results obtained by measurements of the positron annihilation lifetime and Doppler broadening of the annihilation line in reverse chronological order are in full agreement with the optical spectroscopy data in the region of the fundamental absorption edge, being adequately described within coordination defect-formation and physical-aging models.

DETECTION OF SOLAR-LIKE OSCILLATIONS FROM KEPLER PHOTOMETRY OF THE OPEN CLUSTER NGC 6819

International Nuclear Information System (INIS)

Stello, Dennis; Bedding, Timothy R.; Huber, Daniel; Basu, Sarbani; Bruntt, Hans; Mosser, BenoIt; Barban, Caroline; Goupil, Marie-Jo; Stevens, Ian R.; Chaplin, William J.; Elsworth, Yvonne P.; Hekker, Saskia; Brown, Timothy M.; Christensen-Dalsgaard, Joergen; Kjeldsen, Hans; Arentoft, Torben; Gilliland, Ronald L.; Ballot, Jerome; GarcIa, Rafael A.; Mathur, Savita

2010-01-01

Asteroseismology of stars in clusters has been a long-sought goal because the assumption of a common age, distance, and initial chemical composition allows strong tests of the theory of stellar evolution. We report results from the first 34 days of science data from the Kepler Mission for the open cluster NGC 6819-one of the four clusters in the field of view. We obtain the first clear detections of solar-like oscillations in the cluster red giants and are able to measure the large frequency separation, Δν, and the frequency of maximum oscillation power, ν max . We find that the asteroseismic parameters allow us to test cluster membership of the stars, and even with the limited seismic data in hand, we can already identify four possible non-members despite their having a better than 80% membership probability from radial velocity measurements. We are also able to determine the oscillation amplitudes for stars that span about 2 orders of magnitude in luminosity and find good agreement with the prediction that oscillation amplitudes scale as the luminosity to the power of 0.7. These early results demonstrate the unique potential of asteroseismology of the stellar clusters observed by Kepler.

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.

A Self-Templating Scheme for the Synthesis of Nanostructured Transition Metal Chalcogenide Electrodes for Capacitive Energy Storage

KAUST Repository

Xia, Chuan

2015-06-11

Due to their unique structural features including well-defined interior voids, low density, low coefficients of thermal expansion, large surface area and surface permeability, hollow micro/nanostructured transition metal sulfides with high conductivity have been investigated as new class of electrode materials for pseudocapacitor applications. Herein, we report a novel self-templating strategy to fabricate well-defined single and double-shell NiCo2S4 hollow spheres, as a promising electrode material for pseudocapacitors. The surfaces of the NiCo2S4 hollow spheres consist of self-assembled 2D mesoporous nanosheets. This unique morphology results in a high specific capacitance (1257 F g-1 at 2 A g-1), remarkable rate performance (76.4% retention of initial capacitance from 2 A g-1 to 60 A g-1) and exceptional reversibility with a cycling efficiency of 93.8% and 87% after 10,000 and 20,000 cycles, respectively, at a high current density of 10 A g-1. The cycling stability of our ternary chalcogenides is comparable to carbonaceous electrode materials, but with much higher specific capacitance (higher than any previously reported ternary chalcogenide), suggesting that these unique chalcogenide structures have potential application in next-generation commercial pseudocapacitors.

The effect of oxygen impurity on the electronic and optical properties of calcium, strontium and barium chalcogenide compounds

International Nuclear Information System (INIS)

Dadsetani, M.; Beiranvand, R.

2010-01-01

Electronic and optical properties of calcium, strontium and barium chalcogenide compounds in NaCl structure are studied using the band structure results obtained through the full potential linearized augmented palne wave method. Different linear relationships are observed between theoretical band gap and 1/a 2 (where a is lattice constant) for calcium, strontium and barium chalcogenide compounds with and without oxygen, respectively. An abnormal behavior of electronic and optical properties are found for compounds containing oxygen. These effects are ascribed to the special properties of Ca-O, Sr-O and Ba-O bonds, which are different from chemical bonds between Ca, Sr and Ba and other chalcogen atoms.

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

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

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)

The effect of diluting ruthenium by iron in Ru{sub x}Se{sub y} catalyst for oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Delacote, Cyril [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France); CEISAM, CNRS, University of Nantes, F-44322 Nantes Cedex 3 (France); Lewera, Adam [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Pisarek, Marcin [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw (Poland); Kulesza, Pawel J. [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Zelenay, Piotr [Materials Physics and Applications, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Alonso-Vante, Nicolas, E-mail: nicolas.alonso.vante@univ-poitiers.f [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France)

2010-11-01

This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru{sub x}Se{sub y}. The catalysts were obtained by thermal decomposition of Ru{sub 3}(CO){sub 12} and Fe(CO){sub 5} in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.

The electronic band structures of gadolinium chalcogenides: a first-principles prediction for neutron detecting.

Science.gov (United States)

Li, Kexue; Liu, Lei; Yu, Peter Y; Chen, Xiaobo; Shen, D Z

2016-05-11

By converting the energy of nuclear radiation to excited electrons and holes, semiconductor detectors have provided a highly efficient way for detecting them, such as photons or charged particles. However, for detecting the radiated neutrons, those conventional semiconductors hardly behave well, as few of them possess enough capability for capturing these neutral particles. While the element Gd has the highest nuclear cross section, here for searching proper neutron-detecting semiconductors, we investigate theoretically the Gd chalcogenides whose electronic band structures have never been characterized clearly. Among them, we identify that γ-phase Gd2Se3 should be the best candidate for neutron detecting since it possesses not only the right bandgap of 1.76 eV for devices working under room temperature but also the desired indirect gap nature for charge carriers surviving longer. We propose further that semiconductor neutron detectors with single-neutron sensitivity can be realized with such a Gd-chalcogenide on the condition that their crystals can be grown with good quality.

DNA mediated wire-like clusters of self-assembled TiO₂ nanomaterials: supercapacitor and dye sensitized solar cell applications.

Science.gov (United States)

Nithiyanantham, U; Ramadoss, Ananthakumar; Ede, Sivasankara Rao; Kundu, Subrata

2014-07-21

A new route for the formation of wire-like clusters of TiO₂ nanomaterials self-assembled in DNA scaffold within an hour of reaction time is reported. TiO₂ nanomaterials are synthesized by the reaction of titanium-isopropoxide with ethanol and water in the presence of DNA under continuous stirring and heating at 60 °C. The individual size of the TiO₂ NPs self-assembled in DNA and the diameter of the wires can be tuned by controlling the DNA to Ti-salt molar ratios and other reaction parameters. The eventual diameter of the individual particles varies between 15 ± 5 nm ranges, whereas the length of the nanowires varies in the 2-3 μm range. The synthesized wire-like DNA-TiO₂ nanomaterials are excellent materials for electrochemical supercapacitor and DSSC applications. From the electrochemical supercapacitor experiment, it was found that the TiO₂ nanomaterials showed different specific capacitance (Cs) values for the various nanowires, and the order of Cs values are as follows: wire-like clusters (small size) > wire-like clusters (large size). The highest Cs of 2.69 F g(-1) was observed for TiO₂ having wire-like structure with small sizes. The study of the long term cycling stability of wire-like clusters (small size) electrode were shown to be stable, retaining ca. 80% of the initial specific capacitance, even after 5000 cycles. The potentiality of the DNA-TiO₂ nanomaterials was also tested in photo-voltaic applications and the observed efficiency was found higher in the case of wire-like TiO₂ nanostructures with larger sizes compared to smaller sizes. In future, the described method can be extended for the synthesis of other oxide based materials on DNA scaffold and can be further used in other applications like sensors, Li-ion battery materials or treatment for environmental waste water.

SOLAR-LIKE OSCILLATIONS IN A METAL-POOR GLOBULAR CLUSTER WITH THE HUBBLE SPACE TELESCOPE

International Nuclear Information System (INIS)

Stello, Dennis; Gilliland, Ronald L.

2009-01-01

We present analyses of variability in the red giant stars in the metal-poor globular cluster NGC 6397, based on data obtained with the Hubble Space Telescope. We use a nonstandard data reduction approach to turn a 23 day observing run originally aimed at imaging the white dwarf population, into time-series photometry of the cluster's highly saturated red giant stars. With this technique we obtain noise levels in the final power spectra down to 50 parts per million, which allows us to search for low-amplitude solar-like oscillations. We compare the observed excess power seen in the power spectra with estimates of the typical frequency range, frequency spacing, and amplitude from scaling the solar oscillations. We see evidence that the detected variability is consistent with solar-like oscillations in at least one and perhaps up to four stars. With metallicities 2 orders of magnitude lower than those of the Sun, these stars present so far the best evidence of solar-like oscillations in such a low-metallicity environment.

Characterization and modeling of microstructured chalcogenide fibers for efficient mid-infrared wavelength conversion.

Science.gov (United States)

Xing, Sida; Grassani, Davide; Kharitonov, Svyatoslav; Billat, Adrien; Brès, Camille-Sophie

2016-05-02

We experimentally demonstrate wavelength conversion in the 2 µm region by four-wave mixing in an AsSe and a GeAsSe chalcogenide photonic crystal fibers. A maximum conversion efficiency of -25.4 dB is measured for 112 mW of coupled continuous wave pump in a 27 cm long fiber. We estimate the dispersion parameters and the nonlinear refractive indexes of the chalcogenide PCFs, establishing a good agreement with the values expected from simulations. The different fiber geometries and glass compositions are compared in terms of performance, showing that GeAsSe is a more suited candidate for nonlinear optics at 2 µm. Building from the fitted parameters we then propose a new tapered GeAsSe PCF geometry to tailor the waveguide dispersion and lower the zero dispersion wavelength (ZDW) closer to the 2 µm pump wavelength. Numerical simulations shows that the new design allows both an increased conversion efficiency and bandwidth, and the generation of idler waves further in the mid-IR regions, by tuning the pump wavelength in the vicinity of the fiber ZDW.

Electrical properties and figures of merit for new chalcogenide-based thermoelectric materials

Energy Technology Data Exchange (ETDEWEB)

Schindler, J L; Hogan, T P; Brazis, P W; Kannewurf, C R; Chung, D Y; Kanatzidis, M G

1997-07-01

New Bi-based chalcogenide compounds have been prepared using the polychalcogenide flux technique for crystal growth. These materials exhibit characteristics of good thermoelectric materials. Single crystals of the compound CsBi{sub 4}Te{sub 6} have shown conductivity as high as 2440 S/cm with a p-type thermoelectric power of {approx}+110 {micro}V/K at room temperature. A second compound, {beta}-K{sub 2}Bi{sub 8}Se{sub 13} shows lower conductivity {approx}240 S/cm, but a larger n-type thermopower {approx}{minus}200 {micro}V/K. Thermal transport measurements have been performed on hot-pressed pellets of these materials and the results show comparable or lower thermal conductivities than Bi{sub 2}Te{sub 3}. This improvement may reflect the reduced lattice symmetry of the new chalcogenide thermoelectrics. The thermoelectric figure of merit for CsBi{sub 4}Te{sub 6} reaches ZT {approx} 0.32 at 260 K and for {beta}-K{sub 2}Bi{sub 8}Se{sub 13} ZT {approx} 0.32 at room temperature, indicating that these compounds are viable candidates for thermoelectric refrigeration applications.

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

Structural phase transition and elastic properties of mercury chalcogenides

Energy Technology Data Exchange (ETDEWEB)

Varshney, Dinesh, E-mail: vdinesh33@rediffmail.com [School of Physics, Vigyan Bhavan, Devi Ahilya University, Khandwa Road Campus, Indore 452001 (India); Shriya, S. [School of Physics, Vigyan Bhavan, Devi Ahilya University, Khandwa Road Campus, Indore 452001 (India); Khenata, R. [Laboratoire de Physique Quantique et de Modelisation Mathematique (LPQ3M), Departement de Technologie, Universite de Mascara, 29000 Mascara (Algeria)

2012-08-15

Pressure induced structural transition and elastic properties of ZnS-type (B3) to NaCl-type (B1) structure in mercury chalcogenides (HgX; X = S, Se and Te) are presented. An effective interionic interaction potential (EIOP) with long-range Coulomb, as well charge transfer interactions, Hafemeister and Flygare type short-range overlap repulsion extended up to the second neighbor ions and van der Waals interactions are considered. Emphasis is on the evaluation of the pressure dependent Poisson's ratio {nu}, the ratio R{sub BT/G} of B (bulk modulus) over G (shear modulus), anisotropy parameter, Shear and Young's modulus, Lame constant, Kleinman parameter, elastic wave velocity and thermodynamical property as Debye temperature. The Poisson's ratio behavior infers that Mercury chalcogenides are brittle in nature. To our knowledge this is the first quantitative theoretical prediction of the pressure dependence of elastic and thermodynamical properties explicitly the ductile (brittle) nature of HgX and still awaits experimental confirmations. Highlights: Black-Right-Pointing-Pointer Vast volume discontinuity in phase diagram infers transition from ZnS to NaCl structure. Black-Right-Pointing-Pointer The shear elastic constant C{sub 44} is nonzero confirms the mechanical stability. Black-Right-Pointing-Pointer Pressure dependence of {theta}{sub D} infers the softening of lattice with increasing pressure. Black-Right-Pointing-Pointer Estimated bulk, shear and tetragonal moduli satisfied elastic stability criteria. Black-Right-Pointing-Pointer In both B3 and B1 phases, C{sub 11} and C{sub 12} increase linearly with pressure.

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.

Structural, optical and electrical properties of cadmium-doped lead chalcogenide (PbSe) thin films

International Nuclear Information System (INIS)

Khan, Shamshad A.; Khan, Zishan H.; El-Sebaii, A.A.; Al-Marzouki, F.M.; Al-Ghamdi, A.A.

2010-01-01

(PbSe) 100-x Cd x thin films of thickness 3000 A with variable concentrations of Cd (x=5, 10, 15 and 20) were prepared by thermal evaporation on glass substrates at room temperature at a base pressure of 10 -6 Torr. The structural, optical and electrical properties of these films were studied. X-ray diffraction patterns were used to determine the crystal structure of the films. Films were of polycrystalline texture over the whole range of study. Optical constants of all films were determined by absorbance and reflection measurements in a wavelength range 400-1200 nm. Analysis of the optical absorption data showed that the rule of direct transitions predominates. The values of the absorption coefficient (α), extinction coefficient (k) and imaginary part of the dielectric constant were found to increase with increasing Cd content in lead chalcogenides while the refractive index (n) and real part of dielectric constant were increased with increasing Cd concentration up to 15% and then they decreased with 20% of Cd content in PbSe. These results were interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. The dc conductivities and activation energies of the films were measured in the temperature range 298-398 K. It was observed that the dc conductivity increases at all temperatures with the increase of Cd content in lead chalcogenide system. The experimental data suggests that the conduction is due to the thermally assisted tunneling of the carriers in the localized states near the band edges. The activation energy and optical band gap were found to decrease with increasing Cd concentration in lead chalcogenide.

A study of Rh xS y/C and RuSe x/C as methanol-tolerant oxygen reduction catalysts for mixed-reactant fuel cell applications

International Nuclear Information System (INIS)

Papageorgopoulos, Dimitrios C.; Liu, Fang; Conrad, Olaf

2007-01-01

For efficient operation, mixed-reactant fuel cells utilise highly selective anode and cathode electrocatalysts. While platinum and its alloys are the most widely used ORR electrocatalysts in conventional DMFCs, they suffer from both their very high activity for methanol oxidation and their inherent cost. Platinum-free precious metal chalcogenides have been suggested as alternatives with comparable oxygen reduction activity in the presence of methanol. Of these, commercially available carbon supported rhodium sulphide and developmental ruthenium selenium were electrochemically tested and assessed for their potential as selective ORR cathode catalysts. Both materials exhibited oxygen reduction activity approaching that of platinum, albeit at potentials 150 and 80 mV more negative. The three materials' ability to maintain their oxygen reduction activity in the presence of methanol ranks ruthenium selenium > rhodium sulphide >> platinum

Amorphous chalcogenide semiconductors for solid state dosimetric systems of high-energetic ionizing radiation

International Nuclear Information System (INIS)

Shpotyuk, O.

1997-01-01

The application possibilities of amorphous chalcogenide semiconductors use as radiation-sensitive elements of high-energetic (E > 1 MeV) dosimetric systems are analysed. It is shown that investigated materials are characterized by more wide region of registered absorbed doses and low temperature threshold of radiation information bleaching in comparison with well-known analogies based on coloring oxide glasses. (author)

Islet-like clusters derived from mesenchymal stem cells in Wharton's Jelly of the human umbilical cord for transplantation to control type 1 diabetes.

Directory of Open Access Journals (Sweden)

Kuo Ching Chao

Full Text Available BACKGROUND: There is a widespread interest in developing renewable sources of islet-replacement tissue for type I diabetes mellitus. Human mesenchymal cells isolated from the Wharton's jelly of the umbilical cord (HUMSCs, which can be easily obtained and processed compared with embryonic and bone marrow stem cells, possess stem cell properties. HUMSCs may be a valuable source for the generation of islets. METHODOLOGY AND PRINCIPAL FINDINGS: HUMSCs were induced to transform into islet-like cell clusters in vitro through stepwise culturing in neuron-conditioned medium. To assess the functional stability of the islet-like cell clusters in vivo, these cell clusters were transplanted into the liver of streptozotocin-induced diabetic rats via laparotomy. Glucose tolerance was measured on week 12 after transplantation accompanied with immunohistochemistry and electron microscopy analysis. These islet-like cell clusters were shown to contain human C-peptide and release human insulin in response to physiological glucose levels. Real-time RT-PCR detected the expressions of insulin and other pancreatic beta-cell-related genes (Pdx1, Hlxb9, Nkx2.2, Nkx6.1, and Glut-2 in these islet-like cell clusters. The hyperglycemia and glucose intolerance in streptozotocin-induced diabetic rats was significantly alleviated after xenotransplantation of islet-like cell clusters, without the use of immunosuppressants. In addition to the existence of islet-like cell clusters in the liver, some special fused liver cells were also found, which characterized by human insulin and nuclei-positive staining and possessing secretory granules. CONCLUSIONS AND SIGNIFICANCE: In this study, we successfully differentiate HUMSCs into mature islet-like cell clusters, and these islet-like cell clusters possess insulin-producing ability in vitro and in vivo. HUMSCs in Wharton's Jelly of the umbilical cord seem to be the preferential source of stem cells to convert into insulin

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,.

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

Radiation-induced defects formation in Bi-containing vitreous chalcogenides

Energy Technology Data Exchange (ETDEWEB)

Shpotyuk, O.; Vakiv, M.; Balitska, V.; Kovalskiy, A. [Institute of Materials, Lvov (Ukraine)

1997-12-01

Processes of formation and annihilation of coordination defects in As{sub 2}Se{sub 3}Bi{sub y} and (As{sub 2}Se{sub 3})(Bi{sub 2}Se{sub 3}){sub y} amorphous chalcogenide semiconductors induced by influence of Co{sup 60} gamma-irradiation are investigated by photoelectric spectroscopy method. It is obtained that radiation-induced changes of photoelectrical properties on bioconcentration of As{sub 2}Se{sub 3}Bi{sub y} glasses are characterized by anomalous concentration dependence. The nature of this effect is associated with diamagnetic coordination defects formation. (author). 19 refs, 3 figs.

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

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,.

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...

Effect of the Copper on Thermo - Mechanical and Optical Properties of S-Se-Cu Chalcogenide Glasses

Science.gov (United States)

Samudrala, Kavitha; Babu Devarasetty, Suresh

2018-03-01

The S15Se85-xCux (x = 0, 2, 4, 6, 8) chalcogenide glasses are synthesized using melt quenching technique and the effect of Copper on thermal, mechanical and optical properties of chalcogenide glasses are investigated. The glassy natures of the prepared samples were verified by X-ray diffraction and DSC studies. The optical band gap of the samples is estimated and it is observed that optical band gap is decreased with increasing of the copper content and is discussed in terms of cohesive energy and coordination number. The basic thermo-mechanical parameters such as micro-hardness, Volume (Vh) and formation energy (Eh) of micro voids in the glassy network and the modulus of Elasticity (E) are calculated in present glasses. The composition dependence of micro hardness is discussed in terms of heat of atomization energy.

Chalcogenide glass-on-graphene photonics

Science.gov (United States)

Lin, Hongtao; Song, Yi; Huang, Yizhong; Kita, Derek; Deckoff-Jones, Skylar; Wang, Kaiqi; Li, Lan; Li, Junying; Zheng, Hanyu; Luo, Zhengqian; Wang, Haozhe; Novak, Spencer; Yadav, Anupama; Huang, Chung-Che; Shiue, Ren-Jye; Englund, Dirk; Gu, Tian; Hewak, Daniel; Richardson, Kathleen; Kong, Jing; Hu, Juejun

2017-12-01

Two-dimensional (2D) materials are of tremendous interest to integrated photonics, given their singular optical characteristics spanning light emission, modulation, saturable absorption and nonlinear optics. To harness their optical properties, these atomically thin materials are usually attached onto prefabricated devices via a transfer process. Here, we present a new route for 2D material integration with planar photonics. Central to this approach is the use of chalcogenide glass, a multifunctional material that can be directly deposited and patterned on a wide variety of 2D materials and can simultaneously function as the light-guiding medium, a gate dielectric and a passivation layer for 2D materials. Besides achieving improved fabrication yield and throughput compared with the traditional transfer process, our technique also enables unconventional multilayer device geometries optimally designed for enhancing light-matter interactions in the 2D layers. Capitalizing on this facile integration method, we demonstrate a series of high-performance glass-on-graphene devices including ultra-broadband on-chip polarizers, energy-efficient thermo-optic switches, as well as graphene-based mid-infrared waveguide-integrated photodetectors and modulators.

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

Amorphous chalcogenide semiconductors for solid state dosimetric systems of high-energetic ionizing radiation

Energy Technology Data Exchange (ETDEWEB)

Shpotyuk, O. [Pedagogical University, Czestochowa (Poland)]|[Institute of Materials, Lvov (Ukraine)

1997-12-31

The application possibilities of amorphous chalcogenide semiconductors use as radiation-sensitive elements of high-energetic (E > 1 MeV) dosimetric systems are analysed. It is shown that investigated materials are characterized by more wide region of registered absorbed doses and low temperature threshold of radiation information bleaching in comparison with well-known analogies based on coloring oxide glasses. (author). 16 refs, 1 tab.

Destruction-polymerization transformations as a source of radiation-induced extended defects in chalcogenide glassy semiconductors

International Nuclear Information System (INIS)

Shpotyuk, Oleh; Filipecki, Jacek; Shpotyuk, Mykhaylo

2013-01-01

Long-wave shift of the optical transmission spectrum in the region of fundamental optical absorption edge is registered for As 2 S 3 chalcogenide glassy semiconductors after γ-irradiation. This effect is explained in the frameworks of the destruction-polymerization transformations concept by accepting the switching of the heteropolar As-S covalent bonds into homopolar As-As ones. It is assumed that (As 4 + ; S 1 - ) defect pairs are created under such switching. Formula to calculate content of the induced defects in chalcogenide glassy semiconductors is proposed. It is assumed that defects concentration depends on energy of broken covalent bond, bond-switching energy balance, correlation energy, optical band-gap and energy of excitation light. It is shown that theoretically calculated maximally possible content of radiation-induced defects in As 2 S 3 is about 1.6% while concentration of native defects is negligible. (copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

Chalcogenide Glass Radiation Sensor; Materials Development, Design and Device Testing

Energy Technology Data Exchange (ETDEWEB)

Mitkova, Maria; Butt, Darryl; Kozicki, Michael; Barnaby, Hugo

2013-04-30

For many decades, various radiation detecting material have been extensively researched, to find a better material or mechanism for radiation sensing. Recently, there is a growing need for a smaller and effective material or device that can perform similar functions of bulkier Geiger counters and other measurement options, which fail the requirement for easy, cheap and accurate radiation dose measurement. Here arises the use of thin film chalcogenide glass, which has unique properties of high thermal stability along with high sensitivity towards short wavelength radiation. The unique properties of chalcogenide glasses are attributed to the lone pair p-shell electrons, which provide some distinctive optical properties when compared to crystalline material. These qualities are derived from the energy band diagram and the presence of localized states in the band gap. Chalcogenide glasses have band tail states and localized states, along with the two band states. These extra states are primarily due to the lone pair electrons as well as the amorphous structure of the glasses. The localized states between the conductance band (CB) and valence band (VB) are primarily due to the presence of the lone pair electrons, while the band tail states are attributed to the Van der Waal's forces between layers of atoms [1]. Localized states are trap locations within the band gap where electrons from the valence band can hop into, in their path towards the conduction band. Tail states on the other hand are locations near the band gap edges and are known as Urbach tail states (Eu). These states are occupied with many electrons that can participate in the various transformations due to interaction with photons. According to Y. Utsugi et. al.[2], the electron-phonon interactions are responsible for the generation of the Urbach tails. These states are responsible for setting the absorption edge for these glasses and photons with energy near the band gap affect these states. We have

Surface morphology of spin-coated As-S-Se chalcogenide thin films

Czech Academy of Sciences Publication Activity Database

Kohoutek, T.; Wágner, T.; Orava, J.; Krbal, M.; Fejfar, Antonín; Mates, Tomáš; Kasap, S. O.; Frumar, M.

2007-01-01

Roč. 353, - (2007), s. 1437-1440 ISSN 0022-3093 R&D Projects: GA AV ČR IAA1010316; GA AV ČR IAA1010413 Grant - others:GA ČR(CZ) GA203/05/0524; GAMŠk(CZ) LC523 Program:LC Institutional research plan: CEZ:AV0Z10100521 Keywords : chemical properties * spin coating * infrared glasses * chalcogenides * atomic force and scanning tunneling microscopy * scanning electron microscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.319, year: 2007

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.

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.

Hydrogen treatment as a detergent of electronic trap states in lead chalcogenide nanoparticles

Science.gov (United States)

Voros, Marton; Brawand, Nicholas; Galli, Giulia

Lead chalcogenide (PbX) nanoparticles are promising materials for solar energy conversion. However, the presence of trap states in their electronic gap limits their usability, and developing a universal strategy to remove trap states is a persistent challenge. Using calculations based on density functional theory, we show that hydrogen acts as an amphoteric impurity on PbX nanoparticle surfaces; hydrogen atoms may passivate defects arising from ligand imbalance or off-stoichiometric surface terminations, irrespective of whether they originate from cation or anion excess. In addition, we show, using constrained density functional theory calculations, that hydrogen treatment of defective nanoparticles is also beneficial for charge transport in films. We also find that hydrogen adsorption on stoichiometric nanoparticles leads to electronic doping, preferentially n-type. Our findings suggest that post-synthesis hydrogen treatment of lead chalcogenide nanoparticle films is a viable approach to reduce electronic trap states or to dope well-passivated films. Work supported by the Center for Advanced Solar Photophysics, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (NB) and U.S. DOE under Contract No. DE-AC02-06CH11357 (MV).

Self-assembly of Fe3O4 nanocrystal-clusters into cauliflower-like architectures: Synthesis and characterization

International Nuclear Information System (INIS)

Zhu Luping; Liao Guihong; Bing Naici; Wang Linlin; Xie Hongyong

2011-01-01

Large-scale cauliflower-like Fe 3 O 4 architectures consist of well-assembled magnetite nanocrystal clusters have been synthesized by a simple solvothermal process. The as-synthesized Fe 3 O 4 samples were characterized by XRD, XPS, FT-IR, SEM, TEM, etc. The results show that the samples exhibit cauliflower-like hierarchical microstructures. The influences of synthesis parameters on the morphology of the samples were experimentally investigated. Magnetic properties of the Fe 3 O 4 cauliflower-like hierarchical microstructures have been detected by VSM at room temperature, showing a relatively low saturation magnetization of 65 emu/g and an enhanced coercive force of 247 Oe. - Graphical Abstract: Cauliflower-like Fe 3 O 4 architectures consist of well-assembled magnetite nanocrystal clusters have been synthesized by a simple solvothermal process, using FeCl 3 .6H 2 O and EDA as the starting materials. Highlights: → Cauliflower-like Fe 3 O 4 architectures were successfully prepared by a simple solvothermal route. → The cauliflower-like Fe 3 O 4 architectures have a size in the range of 200-300 nm. → They show a low saturation magnetization of 65 emu/g and an enhanced coercive force of 247 Oe. → These Fe 3 O 4 architectures may have potential applications in catalysis and biological fields.

AMPLITUDES OF SOLAR-LIKE OSCILLATIONS: CONSTRAINTS FROM RED GIANTS IN OPEN CLUSTERS OBSERVED BY KEPLER

International Nuclear Information System (INIS)

Stello, Dennis; Huber, Daniel; Bedding, Timothy R.; Benomar, Othman; Kallinger, Thomas; Basu, Sarbani; Mosser, BenoIt; Hekker, Saskia; Mathur, Savita; GarcIa, Rafael A.; Kjeldsen, Hans; Grundahl, Frank; Christensen-Dalsgaard, Joergen; Gilliland, Ronald L.; Verner, Graham A.; Chaplin, William J.; Elsworth, Yvonne P.; Meibom, Soeren; Molenda-Zakowicz, Joanna; Szabo, Robert

2011-01-01

Scaling relations that link asteroseismic quantities to global stellar properties are important for gaining understanding of the intricate physics that underpins stellar pulsations. The common notion that all stars in an open cluster have essentially the same distance, age, and initial composition implies that the stellar parameters can be measured to much higher precision than what is usually achievable for single stars. This makes clusters ideal for exploring the relation between the mode amplitude of solar-like oscillations and the global stellar properties. We have analyzed data obtained with NASA's Kepler space telescope to study solar-like oscillations in 100 red giant stars located in either of the three open clusters, NGC 6791, NGC 6819, and NGC 6811. By fitting the measured amplitudes to predictions from simple scaling relations that depend on luminosity, mass, and effective temperature, we find that the data cannot be described by any power of the luminosity-to-mass ratio as previously assumed. As a result we provide a new improved empirical relation which treats luminosity and mass separately. This relation turns out to also work remarkably well for main-sequence and subgiant stars. In addition, the measured amplitudes reveal the potential presence of a number of previously unknown unresolved binaries in the red clump in NGC 6791 and NGC 6819, pointing to an interesting new application for asteroseismology as a probe into the formation history of open clusters.

Locally formation of Ag nanoparticles in chalcogenide phase change thin films induced by nanosecond laser pulses

International Nuclear Information System (INIS)

Huang, Huan; Zhang, Lei; Wang, Yang; Han, Xiaodong; Wu, Yiqun; Zhang, Ze; Gan, Fuxi

2012-01-01

A simple method to optically synthesize Ag nanoparticles in Ge 2 Sb 2 Te 5 phase change matrix is described. The fine structures of the locally formed phase change chalcogenide nanocomposite are characterized by high-resolution transmission electron microscopy. The formation mechanism of the nanocomposite is discussed with temperature evolution and distribution simulations. This easy-prepared metal nano-particle-embedded phase change microstructure will have great potential in nanophotonics applications, such as for plasmonic functional structures. This also provides a generalized approach to the preparation of well-dispersed nanoparticle-embedded composite thin films in principle. -- Highlights: ► We describe a method to prepare chalcogenide microstructures with Ag nanoparticles. ► We give the fine structural images of phase change nanocomposites. ► We discuss the laser-induced fusion mechanism by temperature simulation. ► This microstructure will have great potential in nanophotonics applications.

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)

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.

Copper Antimony Chalcogenide Thin Film PV Device Development

Energy Technology Data Exchange (ETDEWEB)

Welch, Adam W.; Baranowski, Lauryn L.; de Souza Lucas, Francisco Willian; Toberer, Eric S.; Wolden, Colin A.; Zakutayev, Andriy

2015-06-14

Emerging ternary chalcogenide thin film solar cell technologies, such as CuSbS2 and CuSbSe2, have recently attracted attention as simpler alternatives to quaternary Cu2ZnSnS4 (CZTS). Despite suitable photovoltaic properties, the initial energy conversion efficiency of CuSbS2 is rather low (0.3%). Here, we report on our progress towards improving the efficiency of CuSbS2 solar cells using a high throughput approach. The combinatorial methodology quickly results in baseline solar cell prototypes with 0.6% efficiency, and then modification of the back contact architecture leads to 1% PV devices. We then translate the optimal CuSbS2 synthesis parameters to CuSbSe2 devices, which show 3% efficiencies.

Electrocatalytic studies of osmium-ruthenium carbonyl cluster compounds for their application as methanol-tolerant cathodes for oxygen reduction reaction and carbon monoxide-tolerant anodes for hydrogen oxidation reaction

Energy Technology Data Exchange (ETDEWEB)

Borja-Arco, E.; Uribe-Godinez, J.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

2006-07-01

This paper provided details of an electrokinetic study of novel electrocatalytic materials capable of performing both the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR). Osmium-ruthenium carbonyl cluster compounds (Os{sub x}Ru{sub 3}(CO){sub n}) were synthesized by chemical condensation in non-polar organic solvents at different boiling points and refluxing temperatures. Three different non-polar organic solvents were used: (1) n-nonane; o-xylene; and 1,2-dichlorobenzene. The electrocatalysts were characterized by Fourier Transform Infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A rotating disk electrode technique was used to analyze the materials. Results of the analysis showed that the materials performed ORR in both the presence and absence of carbon monoxide (CO), and that electrocatalysts were not poisoned by the presence of CO. Cyclic voltamperometry for the disk electrodes showed that the electrochemical behaviour of the compounds in the acid electrolyte was similar in the presence or absence of methanol. The Tafel slope, exchange current density and the transfer coefficient were also investigated. The electrokinetic parameters for the ORR indicated that the materials with the highest electrocatalytic activity were synthesized in 1,2-dichlorobenzene. Electrocatalytic activity during HOR were prepared in n-nonane. It was concluded that the new materials are good candidates for use as both a cathode and an anode in proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). 7 refs., 2 tabs., 7 figs.

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.

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.

Uranium(VI) and ruthenium extraction by dialkyldithio-phosphoric acids

International Nuclear Information System (INIS)

Fitoussi, R.; Musikas, C.

1980-01-01

Oxygen donors like dialkylphosphoric acids are good extractants for actinide ions, but little is known about their sulfur homologs. Investigations of U(VI) and Ru extraction from various aqueous media are reported. This includes extraction of U(VI) from nitric, perchloric, and phosphoric acids by solutions of dialkyldithiophosphoric acids in dodecane or benzene. Extraction of U(VI) by synergistic mixtures, of which at least one of the components is a sulfur donor, has been investigated. The extracted species have been identified, and a comparison with the complexes obtained by extraction with the homologous oxygen donors is made. The sulfur-actinide bond is weaker than the oxygen-actinide one, but in some synergistic extractions the dialkyldithiophosphonates are more efficient than the oxygen donors. In addition to size effects, this behavior could be attributed to the weakness of the hydrogen bonds of the SH groups, which allows a greater variety of the ligands to enter the coordination sphere of the metal. Ruthenium, like the d-transition elements, gives strong bonds with the sulfur donors. However, its extraction from nitric acid is slow. We investigated the influence of several parameters on the distribution coefficients and found that the presence of a reagent which destroys nitrous ions is necessary to achieve quantitative extraction. The role of RuNO groups is also discussed

DNA mediated wire-like clusters of self-assembled TiO2 nanomaterials: supercapacitor and dye sensitized solar cell applications

Science.gov (United States)

Nithiyanantham, U.; Ramadoss, Ananthakumar; Ede, Sivasankara Rao; Kundu, Subrata

2014-06-01

A new route for the formation of wire-like clusters of TiO2 nanomaterials self-assembled in DNA scaffold within an hour of reaction time is reported. TiO2 nanomaterials are synthesized by the reaction of titanium-isopropoxide with ethanol and water in the presence of DNA under continuous stirring and heating at 60 °C. The individual size of the TiO2 NPs self-assembled in DNA and the diameter of the wires can be tuned by controlling the DNA to Ti-salt molar ratios and other reaction parameters. The eventual diameter of the individual particles varies between 15 +/- 5 nm ranges, whereas the length of the nanowires varies in the 2-3 μm range. The synthesized wire-like DNA-TiO2 nanomaterials are excellent materials for electrochemical supercapacitor and DSSC applications. From the electrochemical supercapacitor experiment, it was found that the TiO2 nanomaterials showed different specific capacitance (Cs) values for the various nanowires, and the order of Cs values are as follows: wire-like clusters (small size) > wire-like clusters (large size). The highest Cs of 2.69 F g-1 was observed for TiO2 having wire-like structure with small sizes. The study of the long term cycling stability of wire-like clusters (small size) electrode were shown to be stable, retaining ca. 80% of the initial specific capacitance, even after 5000 cycles. The potentiality of the DNA-TiO2 nanomaterials was also tested in photo-voltaic applications and the observed efficiency was found higher in the case of wire-like TiO2 nanostructures with larger sizes compared to smaller sizes. In future, the described method can be extended for the synthesis of other oxide based materials on DNA scaffold and can be further used in other applications like sensors, Li-ion battery materials or treatment for environmental waste water.A new route for the formation of wire-like clusters of TiO2 nanomaterials self-assembled in DNA scaffold within an hour of reaction time is reported. TiO2 nanomaterials are

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.

Origin of the frequency shift of Raman scattering in chalcogenide glasses

DEFF Research Database (Denmark)

Han, X.C.; Tao, H.Z.; Gong, L.J.

2014-01-01

of the shift is associated with the topological connectivity of global network and/or the local environment of structural units, (e.g., tetrahedral GeSe4). Here we show the compositional evolution of the main Raman scattering frequency in Ge(SxSe1−x)2 glasses, and then clarify its structural origin. We keep...... units such as GeS4 tetrahedra. The ab-initio calculations of normal Raman mode combined with group theory analysis provide insight into the structural evolution of chalcogenide glasses with varying composition....

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)

Evolution of the C-Type Lectin-Like Receptor Genes of the DECTIN-1 Cluster in the NK Gene Complex

Directory of Open Access Journals (Sweden)

Susanne Sattler

2012-01-01

Full Text Available Pattern recognition receptors are crucial in initiating and shaping innate and adaptive immune responses and often belong to families of structurally and evolutionarily related proteins. The human C-type lectin-like receptors encoded in the DECTIN-1 cluster within the NK gene complex contain prominent receptors with pattern recognition function, such as DECTIN-1 and LOX-1. All members of this cluster share significant homology and are considered to have arisen from subsequent gene duplications. Recent developments in sequencing and the availability of comprehensive sequence data comprising many species showed that the receptors of the DECTIN-1 cluster are not only homologous to each other but also highly conserved between species. Even in Caenorhabditis elegans, genes displaying homology to the mammalian C-type lectin-like receptors have been detected. In this paper, we conduct a comprehensive phylogenetic survey and give an up-to-date overview of the currently available data on the evolutionary emergence of the DECTIN-1 cluster genes.

Extraction and recovery of mercury and lead from aqueous waste streams using redox-active layered metal chalcogenides. Annual progress report, September 15, 1996 - September 14, 1997

International Nuclear Information System (INIS)

Dorhout, P.K.; Strauss, S.H.

1997-01-01

'The authors have begun to examine the extraction and recovery of heavy elements from aqueous waste streams using redox-active metal chalcogenides. They have been able to prepare extractants from known chalcogenide starting materials, studied the efficacy of the extractants for selective removal of soft metal ions from aqueous phases, studied the deactivation of extractants and the concomitant recovery of soft metal ions from the extractants, and characterized all of the solids and solutions thus far in the study. The study was proposed as two parallel tasks: Part 1 and Part 2 emphasize the study and development of known metal chalcogenide extractants and the synthesis and development of new metal chalcogenide extractants, respectively. The two tasks were divided into sub-sections that study the extractants and their chemistry as detailed below: Preparation and reactivity of metal chalcogenide host solids Extraction of target waste (guest) ions from simulated waste streams Examination of the guest-host solids recovery of the guest metal and reuse of extractant Each section of the two tasks was divided into focused subsections that detail the specific problems and solutions to those problems that were proposed. The extent to which those tasks have been accomplished and the continued efforts of the team are described in detail below. (b) Progress and Results. The DOE-supported research has proceeded largely as proposed and has been productive in its first 12 months. Two full-paper manuscripts were submitted and are currently under peer review. A third paper is in preparation and will be submitted shortly. In addition, 5 submitted or invited presentations have been made.'

Effect of pressure on the crystal field splitting in rare earth pnictides and chalcogenides

International Nuclear Information System (INIS)

Schirber, J.E.; Weaver, H.T.

1978-01-01

The experimental situation for the pressure dependence of the crystal field of praseodymium pnictides and chalcogenides is reviewed and compared with the predictions of the point charge model. The problem of separating exchange and crystal field contributions from the measured NMR frequency shift or susceptibility measurements is discussed as well as problems explaining these effects with conduction electron related models

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 ...

Thermoelectric performance of tellurium-reduced quaternary p-type lead–chalcogenide composites

International Nuclear Information System (INIS)

Aminorroaya Yamini, Sima; Wang, Heng; Gibbs, Zachary M.; Pei, Yanzhong; Mitchell, David R.G.; Dou, Shi Xue; Snyder, G. Jeffrey

2014-01-01

Graphical abstract: - Abstract: A long-standing technological challenge to the widespread application of thermoelectric generators is obtaining high-performance thermoelectric materials from abundant elements. Intensive study on PbTe alloys has resulted in a high figure of merit for the single-phase ternary PbTe–PbSe system through band structure engineering, and the low thermal conductivity achieved due to nanostructuring leads to high thermoelectric performance for ternary PbTe–PbS compounds. Recently, the single-phase p-type quaternary PbTe–PbSe–PbS alloys have been shown to provide thermoelectric performance superior to the binary and ternary lead chalcogenides. This occurs via tuning of the band structure and from an extraordinary low thermal conductivity resulting from high-contrast atomic mass solute atoms. Here, we present the thermoelectric efficiency of nanostructured p-type quaternary PbTe–PbSe–PbS composites and compare the results with corresponding single-phase quaternary lead chalcogenide alloys. We demonstrate that the very low lattice thermal conductivity achieved is attributed to phonon scattering at high-contrast atomic mass solute atoms rather than from the contribution of secondary phases. This results in a thermoelectric efficiency of ∼1.4 over a wide temperature range (650–850 K) in a p-type quaternary (PbTe) 0.65 (PbSe) 0.1 (PbS) 0.25 composite that is lower than that of single-phase (PbTe) 0.85 (PbSe) 0.1 (PbS) 0.05 alloy without secondary phases

Large magnetoresistance in non-magnetic silver chalcogenides and new class of magnetoresistive compounds

Science.gov (United States)

Saboungi, Marie-Louis; Price, David C. L.; Rosenbaum, Thomas F.; Xu, Rong; Husmann, Anke

2001-01-01

The heavily-doped silver chalcogenides, Ag.sub.2+.delta. Se and Ag.sub.2+.delta. Te, show magnetoresistance effects on a scale comparable to the "colossal" magnetoresistance (CMR) compounds. Hall coefficient, magnetoconductivity, and hydrostatic pressure experiments establish that elements of narrow-gap semiconductor physics apply, but both the size of the effects at room temperature and the linear field dependence down to fields of a few Oersteds are surprising new features.

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

Bonding properties of FCC-like Au ₄₄ (SR) ₂₈ clusters from X-ray absorption spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Yang, Rui [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.; Chevrier, Daniel M. [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.; Zeng, Chenjie [Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.; Jin, Rongchao [Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.; Zhang, Peng [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.

2017-11-01

Thiolate-protected gold clusters with precisely controlled atomic composition have recently emerged as promising candidates for a variety of applications because of their unique optical, electronic, and catalytic properties. The recent discovery of the Au44(SR)28 total structure is considered as an interesting finding in terms of the face-centered cubic (FCC)-like core structure in small gold-thiolate clusters. Herein, the unique bonding properties of Au44(SR)28 is analyzed using temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge and compared with other FCC-like clusters such as Au36(SR)24 and Au28(SR)20. A negative thermal expansion was detected for the Au–Au bonds of the metal core (the first Au–Au shell) and was interpreted based on the unique Au core structure consisting of the Au4 units. EXAFS fitting results from Au28(SR)20, Au36(SR)24, and Au44(SR)28 show a size-dependent negative thermal expansion behavior in the first Au–Au shell, further highlighting the importance of the Au4 units in determining the Au core bonding properties and shedding light on the growth mechanism of these FCC-like Au clusters.

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

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.

Microbial synthesis of chalcogenide semiconductor nanoparticles: a review.

Science.gov (United States)

Jacob, Jaya Mary; Lens, Piet N L; Balakrishnan, Raj Mohan

2016-01-01

Chalcogenide semiconductor quantum dots are emerging as promising nanomaterials due to their size tunable optoelectronic properties. The commercial synthesis and their subsequent integration for practical uses have, however, been contorted largely due to the toxicity and cost issues associated with the present chemical synthesis protocols. Accordingly, there is an immediate need to develop alternative environment-friendly synthesis procedures. Microbial factories hold immense potential to achieve this objective. Over the past few years, bacteria, fungi and yeasts have been experimented with as eco-friendly and cost-effective tools for the biosynthesis of semiconductor quantum dots. This review provides a detailed overview about the production of chalcogen-based semiconductor quantum particles using the inherent microbial machinery. © 2015 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Achievements in the field of thermophysics of pniktides and chalcogenides of transition elements

International Nuclear Information System (INIS)

Westrum, E.F.

1979-01-01

Thermophysical aspects of thermodynamics of chalcogenides of transition metals are analyzed briefly with the aim of development of concepts on connection of these compounds entropy with their structure, expressed by Grenvold and Westrum in 1962. In a more detail way discussed are the achievement in the field of low-temperature thermophysics of pniktides of transition metals permitting to consider the similarity and the differences in properties of the two compound classes mentioned above. The characteristics of chalcogenides and pniktides, obtained by the method of low-temperature calorimetry and by the method of high-temperature adiabatic calorimetry as well, are considered. A more detail estimate is made of the heat capacity component caused by expansion (that is of the most importance while considering the high-temperature data on heat capacity). The effect of energy levels of ions and atoms on heat capacity and a number of other problems are also considered. The approach to solution of these problems is illustrated on experimental data for a number of compounds, such as marcasite (FeS 2 ), low-temperature digenite (Csub(1.80)S), CoFe 2 , arsenides and antimonides of a number of metals (FeSb 2 , CrSb 2 , CrAs 2 , U 2 As 4 , U 3 Sb 4 , USb 2 , UAs 2 )

Synthesis, structure and properties of tellurium cubane clusters of niobium and tantalum [M4(μ4-O)(μ3-Te)4(CN)12]6- (M=Nb, Ta)

International Nuclear Information System (INIS)

Fedin, V.P.; Kalinina, I.V.; Virovets, A.V.; Fenske, D.

2001-01-01

A new cubane cluster complex K 6 [Ta 4 (μ 4 -O)(μ 3 -Te) 4 (CN) 12 ] · KOH · 4H 2 O was prepared by high-temperature synthesis from a mixture of TaTe 4 and KCN with subsequent crystallization from aqueous solutions. The compound was characterized by the methods of cyclic voltammetry, X-ray diffraction analysis, IR, Raman and absorption spectroscopies. Comparative study of clusters [M 4 OTe 4 (CN) 12 ] 6- (M=Nb, Ta) containing μ 4 -O-ligands and being the first examples of molecular chalcogenide cubane complexes for group 5 metals of the Periodic System, was made [ru

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 ...

Structural, optical and electrical characterization of Ag doped lead chalcogenide (PbSe) thin films

Energy Technology Data Exchange (ETDEWEB)

Al-Ghamdi, A.A., E-mail: aghamdi90@hotmail.com [Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah (Saudi Arabia); Al-Heniti, S. [Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah (Saudi Arabia); Khan, Shamshad A. [Department of Physics, St. Andrew' s College, Gorakhpur, UP (India)

2013-03-15

Research and development efforts are currently underway to fabricate a variety of solid state devices. A good deal of information regarding the synthesis, structural, optical and electrical properties of Ag doped lead chalcogenides have been revealed. The bulk polycrystalline (PbSe){sub 100-x}Ag{sub x} ternary chalcogenides are prepared by diffusion technique. The XRD patterns recorded for the (PbSe){sub 100-x}Ag{sub x} thin films prepared by vacuum deposition technique, show that these films are polycrystalline in nature. The optical measurements reveal that the (PbSe){sub 100-x}Ag{sub x} thin films possess direct band gap and the band gap energy decreases with an increase of Ag concentration. The extinction coefficient (k) and refractive index (n) are found to be changing by increasing Ag concentration in PbSe. These results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. The dc conductivities of (PbSe){sub 100-x}Ag{sub x} thin films are measured in temperature range 303-403 K. It is observed that the dc conductivity increases at all the temperatures with an increase of Ag content in PbSe system. The experimental data suggests that the conduction is due to thermally assisted tunneling of the charge carriers in the localized states near the band edges. The activation energy and optical band gap are found to decrease with increasing Ag concentration in lead chalcogenide and there are good agreements between these two values. - Highlights: Black-Right-Pointing-Pointer (PbSe){sub 100-x}Ag{sub x} thin films has been investigated. Black-Right-Pointing-Pointer Polycrystalline nature has been verified by X-ray diffraction. Black-Right-Pointing-Pointer Optical absorption data showed the rules of direct transitions predominate. Black-Right-Pointing-Pointer Dc conductivity increases with an increase of Ag content in PbSe system. Black-Right-Pointing-Pointer Increase of Ag concentration causes a decrease in E{sub g

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

Advances in Mid-IR Fiber Lasers: Tellurite, Fluoride and Chalcogenide

Directory of Open Access Journals (Sweden)

Mario Christian Falconi

2017-06-01

Full Text Available A review on the recent progress in modeling and fabrication of medium infrared (Mid-IR fiber lasers is reported. The main objective is to illustrate some recent examples of continuous wave optical sources at wavelengths longer than those commonly employed in telecom applications and allowing high beam quality. A small number of Mid-IR lasers, among the large variety of schemes, glasses, dopants and pumping schemes reported in literature, is selected on the basis of their slope efficiency and threshold pump power. In particular, tellurite, fluoride and chalcogenide fiber lasers are considered. More details are given with reference to the novel pumping schemes.

Cluster-cluster correlations in the two-dimensional stationary Ising-model

International Nuclear Information System (INIS)

Klassmann, A.

1997-01-01

In numerical integration of the Cahn-Hillard equation, which describes Oswald rising in a two-phase matrix, N. Masbaum showed that spatial correlations between clusters scale with respect to the mean cluster size (itself a function of time). T. B. Liverpool showed by Monte Carlo simulations for the Ising model that the analogous correlations have a similar form. Both demonstrated that immediately around each cluster there is some depletion area followed by something like a ring of clusters of the same size as the original one. More precisely, it has been shown that the distribution of clusters around a given cluster looks like a sinus-curve decaying exponentially with respect to the distance to a constant value

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....

Recent Advances in Metal Chalcogenides (MX; X = S, Se) Nanostructures for Electrochemical Supercapacitor Applications: A Brief Review

Science.gov (United States)

Theerthagiri, Jayaraman; Durai, Govindarajan; Rana, Abu ul Hassan Sarwar; Sangeetha, Kirubanandam; Kuppusami, Parasuraman; Kim, Hyun-Seok

2018-01-01

Supercapacitors (SCs) have received a great deal of attention and play an important role for future self-powered devices, mainly owing to their higher power density. Among all types of electrical energy storage devices, electrochemical supercapacitors are considered to be the most promising because of their superior performance characteristics, including short charging time, high power density, safety, easy fabrication procedures, and long operational life. An SC consists of two foremost components, namely electrode materials, and electrolyte. The selection of appropriate electrode materials with rational nanostructured designs has resulted in improved electrochemical properties for high performance and has reduced the cost of SCs. In this review, we mainly spotlight the non-metallic oxide, especially metal chalcogenides (MX; X = S, Se) based nanostructured electrode materials for electrochemical SCs. Different non-metallic oxide materials are highlighted in various categories, such as transition metal sulfides and selenides materials. Finally, the designing strategy and future improvements on metal chalcogenide materials for the application of electrochemical SCs are also discussed. PMID:29671823

Mid-infrared supercontinuum generation in chalcogenide step-index fibers pumped at 2.9 and 4.5µm

DEFF Research Database (Denmark)

Kubat, Irnis; Agger, Christian; Møller, Uffe Visbech

The Mid-InfraRed (MIR) spectral range (2-12µm) contains the spectral fingerprint of many organic molecules, which can be probed nondestructively for e.g. detection of skin cancer. For this SuperContinuum (SC) laser sources are good candidates since they can have broadband bandwidths together...... with high spectral densities. Here we consider a MIR SC laser sources based on chalcogenide step-index fibers with exceptionally high numerical aperture of ~1 pumped either with Er:ZBLAN and Pr:CHALC fiber laser operating at 2.9 and 4.5µm, respectively, having P0=1kW, T0=50ps, ν_R=4MHz and Pavg=200m......W. The optical properties of fibers (dispersion, nonlinearity and confinement loss) are modeled using the finite element tools based on measured refractive indices of the core and the cladding chalcogenide compositions. Generation of MIR SC is investigated using the Generalized Nonlinear Schrödinger Equation...

Room-temperature current blockade in atomically defined single-cluster junctions

Science.gov (United States)

Lovat, Giacomo; Choi, Bonnie; Paley, Daniel W.; Steigerwald, Michael L.; Venkataraman, Latha; Roy, Xavier

2017-11-01

Fabricating nanoscopic devices capable of manipulating and processing single units of charge is an essential step towards creating functional devices where quantum effects dominate transport characteristics. The archetypal single-electron transistor comprises a small conducting or semiconducting island separated from two metallic reservoirs by insulating barriers. By enabling the transfer of a well-defined number of charge carriers between the island and the reservoirs, such a device may enable discrete single-electron operations. Here, we describe a single-molecule junction comprising a redox-active, atomically precise cobalt chalcogenide cluster wired between two nanoscopic electrodes. We observe current blockade at room temperature in thousands of single-cluster junctions. Below a threshold voltage, charge transfer across the junction is suppressed. The device is turned on when the temporary occupation of the core states by a transiting carrier is energetically enabled, resulting in a sequential tunnelling process and an increase in current by a factor of ∼600. We perform in situ and ex situ cyclic voltammetry as well as density functional theory calculations to unveil a two-step process mediated by an orbital localized on the core of the cluster in which charge carriers reside before tunnelling to the collector reservoir. As the bias window of the junction is opened wide enough to include one of the cluster frontier orbitals, the current blockade is lifted and charge carriers can tunnel sequentially across the junction.

Solution processing of chalcogenide materials using thiol-amine "alkahest" solvent systems.

Science.gov (United States)

McCarthy, Carrie L; Brutchey, Richard L

2017-05-02

Macroelectronics is a major focus in electronics research and is driven by large area applications such as flat panel displays and thin film solar cells. Innovations for these technologies, such as flexible substrates and mass production, will require efficient and affordable semiconductor processing. Low-temperature solution processing offers mild deposition methods, inexpensive processing equipment, and the possibility of high-throughput processing. In recent years, the discovery that binary "alkahest" mixtures of ethylenediamine and short chain thiols possess the ability to dissolve bulk inorganic materials to yield molecular inks has lead to the wide study of such systems and the straightforward recovery of phase pure crystalline chalcogenide thin films upon solution processing and mild annealing of the inks. In this review, we recount the work that has been done toward elucidating the scope of this method for the solution processing of inorganic materials for use in applications such as photovoltaic devices, electrocatalysts, photodetectors, thermoelectrics, and nanocrystal ligand exchange. We also take stock of the wide range of bulk materials that can be used as soluble precursors, and discuss the work that has been done to reveal the nature of the dissolved species. This method has provided a vast toolbox of over 65 bulk precursors, which can be utilized to develop new routes to functional chalcogenide materials. Future studies in this area should work toward a better understanding of the mechanisms involved in the dissolution and recovery of bulk materials, as well as broadening the scope of soluble precursors and recoverable functional materials for innovative applications.

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...

Magnetic excitations in iron chalcogenide superconductors.

Science.gov (United States)

Kotegawa, Hisashi; Fujita, Masaki

2012-10-01

Nuclear magnetic resonance and neutron scattering experiments in iron chalcogenide superconductors are reviewed to make a survey of the magnetic excitations in FeSe, FeSe 1- x Te x and alkali-metal-doped A x Fe 2- y Se 2 ( A = K, Rb, Cs, etc). In FeSe, the intimate relationship between the spin fluctuations and superconductivity can be seen universally for the variations in the off-stoichiometry, the Co-substitution and applied pressure. The isovalent compound FeTe has a magnetic ordering with different wave vector from that of other Fe-based magnetic materials. The transition temperature T c of FeSe increases with Te substitution in FeSe 1- x Te x with small x , and decreases in the vicinity of the end member FeTe. The spin fluctuations are drastically modified by the Te substitution. In the vicinity of the end member FeTe, the low-energy part of the spin fluctuation is dominated by the wave vector of the ordered phase of FeTe; however, the reduction of T c shows that it does not support superconductivity. The presence of same wave vector as that of other Fe-based superconductors in FeSe 1- x Te x and the observation of the resonance mode demonstrate that FeSe 1- x Te x belongs to the same group as most of other Fe-based superconductors in the entire range of x , where superconductivity is mediated by the spin fluctuations whose wave vector is the same as the nesting vector between the hole pockets and the electron pockets. On the other hand, the spin fluctuations differ for alkali-metal-doped A x Fe 2- y Se 2 and FeSe or other Fe-based superconductors in their wave vector and strength in the low-energy part, most likely because of the different Fermi surfaces. The resonance mode with different wave vector suggests that A x Fe 2- y Se 2 has an exceptional superconducting symmetry among Fe-based superconductors.

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

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)

Zinc Antimonides and Copper Chalcogenides as Thermoelectric Materials

DEFF Research Database (Denmark)

Blichfeld, Anders Bank

2017-01-01

, and linked with the physical properties. The materials crystallography approach, relating physical properties with a structural understating, has been applied in this thesis for two highly interesting materials systems, zinc antimonides and copper chalcogenides. Both of these systems are high profiled....... The preparation parameters used, have a large influence on the homogeneity of the products, and new electric phases were identified and studied for ZnSb. For the samples prepared by physical vapor deposition, the growth takes place under non-thermodynamic conditions, making it possible to access kinetically...... intensity X-ray radiation at large international facilities, making it possible to measure pair distribution function data directly on thin-film samples in a normal incident setup, termed tfPDF. The tfPDF method was demonstrated on the iron antimony system. tfPDF was developed even further to include...

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

Metabolic Heterogeneity Evidenced by MRS among Patient-Derived Glioblastoma Multiforme Stem-Like Cells Accounts for Cell Clustering and Different Responses to Drugs

Directory of Open Access Journals (Sweden)

Sveva Grande

2018-01-01

Full Text Available Clustering of patient-derived glioma stem-like cells (GSCs through unsupervised analysis of metabolites detected by magnetic resonance spectroscopy (MRS evidenced three subgroups, namely clusters 1a and 1b, with high intergroup similarity and neural fingerprints, and cluster 2, with a metabolism typical of commercial tumor lines. In addition, subclones generated by the same GSC line showed different metabolic phenotypes. Aerobic glycolysis prevailed in cluster 2 cells as demonstrated by higher lactate production compared to cluster 1 cells. Oligomycin, a mitochondrial ATPase inhibitor, induced high lactate extrusion only in cluster 1 cells, where it produced neutral lipid accumulation detected as mobile lipid signals by MRS and lipid droplets by confocal microscopy. These results indicate a relevant role of mitochondrial fatty acid oxidation for energy production in GSCs. On the other hand, further metabolic differences, likely accounting for different therapy responsiveness observed after etomoxir treatment, suggest that caution must be used in considering patient treatment with mitochondria FAO blockers. Metabolomics and metabolic profiling may contribute to discover new diagnostic or prognostic biomarkers to be used for personalized therapies.

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 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.

A Novel Ruthenium-Decorating Polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH2]·24H2O: An Active Heterogeneous Oxidation Catalyst for Alcohols

Directory of Open Access Journals (Sweden)

Rong Wan

2018-01-01

Full Text Available The first example of wholly inorganic ruthenium-containing polyoxomolybdate Cs3Na6H[MoVI14RuIV2O50(OH2]·24H2O (1 was isolated and systematically characterized by element analysis, infrared spectroscopy (IR, thermogravimetric analyses (TGA, X-ray photoelectron spectroscopy (XPS, energy dispersive X-ray spectroscopy (EDX and single-crystal X-ray diffraction. Compound 1 is composed of an unprecedented {Mo14}-type isopolymolybdate with a di-ruthenium core precisely encapsulated in its center, exhibiting a three-tiered ladder-like structure. The title compound can act as an efficient heterogeneous catalyst in the transformation of 1-phenylethanol to acetophenone. This catalyst is also capable of being recycled and reused for at least ten cycles with its activity being retained under the optimal conditions.

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

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)

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

Science.gov (United States)

Schaefer, Michael; Schlaf, Rudy

2015-08-01

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

Diametrical clustering for identifying anti-correlated gene clusters.

Science.gov (United States)

Dhillon, Inderjit S; Marcotte, Edward M; Roshan, Usman

2003-09-01

Clustering genes based upon their expression patterns allows us to predict gene function. Most existing clustering algorithms cluster genes together when their expression patterns show high positive correlation. However, it has been observed that genes whose expression patterns are strongly anti-correlated can also be functionally similar. Biologically, this is not unintuitive-genes responding to the same stimuli, regardless of the nature of the response, are more likely to operate in the same pathways. We present a new diametrical clustering algorithm that explicitly identifies anti-correlated clusters of genes. Our algorithm proceeds by iteratively (i). re-partitioning the genes and (ii). computing the dominant singular vector of each gene cluster; each singular vector serving as the prototype of a 'diametric' cluster. We empirically show the effectiveness of the algorithm in identifying diametrical or anti-correlated clusters. Testing the algorithm on yeast cell cycle data, fibroblast gene expression data, and DNA microarray data from yeast mutants reveals that opposed cellular pathways can be discovered with this method. We present systems whose mRNA expression patterns, and likely their functions, oppose the yeast ribosome and proteosome, along with evidence for the inverse transcriptional regulation of a number of cellular systems.

A Structural Study of the Pseudo-Binary Mercury Chalcogenide Alloy HgSe_{0.7}S_{0.3} at High Pressure

CERN Document Server

Kozlenko, D P; Ehm, L; Knorr, K; Hull, S; Shchennikov, V V; Voronin, V I

2002-01-01

The structure of the pseudo-binary mercury chalcogenide alloy HgSe_{0.7}S_{0.3} has been studied by means of X-ray and neutron powder diffraction at pressure up to 8.5 GPa. A phase transition from the cubic zinc blende structure to the hexagonal cinnabar structure was observed at P{\\sim}1 GPa. The obtained structural parameters were used for the analysis of the geometrical relationship between the zinc blende and the cinnabar phases. The zinc blende-cinnabar phase transition is discussed in the framework of Landau theory of the phase transitions. It was found that the possible order parameter for the structural transformation is the spontaneous strain e_{4}. This assignment agrees with previously observed high pressure behaviour of the elastic constants of other mercury chalcogenides.

A structural study of the pseudo-binary mercury chalcogenide alloy HgSe0.7S0.3 at high pressure

International Nuclear Information System (INIS)

Kozlenko, D.P.; Savenko, B.N.; Ehm, L.; Knorr, K.; Hull, S.; Shchennikov, V.V.; Voronin, V.I.

2002-01-01

The structure of the pseudo-binary mercury chalcogenide alloy HgSe 0.7 S 0.3 has been studied by means of X-ray and neutron powder diffraction at pressure up to 8.5 GPa. A phase transition from the cubic zinc blende structure to the hexagonal cinnabar structure was observed at P∼1 GPa. The obtained structural parameters were used for the analysis of the geometrical relationship between the zinc blende and the cinnabar phases. The zinc blende-cinnabar phase transition is discussed in the framework of the Landau theory of phase transitions. It was found that the possible order parameter for the structural transformation is the spontaneous strain e 4 . This assignment agrees with previously observed high pressure behaviour of the elastic constants of other mercury chalcogenides

Temperature and frequency response of conductivity in Ag2S doped chalcogenide glassy semiconductor

Science.gov (United States)

Ojha, Swarupa; Das, Anindya Sundar; Roy, Madhab; Bhattacharya, Sanjib

2018-06-01

The electric conductivity of chalcogenide glassy semiconductor xAg2S-(1-x)(0.5S-0.5Te) has been presented here as a function of temperature and frequency. Formation of different nanocrystallites has been confirmed from X-ray diffraction study. It is also noteworthy that average size of nanocrystallites decreases with the increase of dislocation density. Dc conductivity data have been interpreted using Mott's model and Greaves's model in low and high temperature regions respectively. Ac conductivity above the room temperature has been analyzed using Meyer-Neldel (MN) conduction rule. It is interestingly noted that Correlated Barrier Hopping (CBH) model is the most appropriate conduction mechanism for x = 0.35, where pairs of charge carrier are considered to hop over the potential barrier between the sites via thermal activation. To interpret experimental data for x = 0.45, modified non-overlapping small polaron tunnelling (NSPT) model is supposed to be appropriate model due to tunnelling through grain boundary. The conductivity spectra at various temperatures have been analyzed using Almond-West Formalism (power law model). Scaling of conductivity spectra reveals that electrical relaxation process of charge carriers (polaron) is temperature independent but depends upon the composition of the present chalcogenide glassy system.

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

Mid-infrared supercontinuum generation to 12.5μm in large NA chalcogenide step-index fibres pumped at 4.5μm

DEFF Research Database (Denmark)

Kubat, Irnis; Agger, Christian; Møller, Uffe Visbech

2014-01-01

We present numerical modeling of mid-infrared (MIR) supercontinuum generation (SCG) in dispersion-optimized chalcogenide (CHALC) step-index fibres (SIFs) with exceptionally high numerical aperture (NA) around one, pumped with mode-locked praseodymium-doped (Pr3+) chalcogenide fibre lasers. The 4...... for the highest NA considered but required pumping at 4.7kW as well as up to 3m of fibre to compensate for the lower nonlinearities. The amount of power converted into the 8-10 μm band was 7.5 and 8.8mW for the 8 and 10μm fibres, respectively. For the 20μm core fibres up to 46mW was converted....

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.

Structural and optical investigation of Te-based chalcogenide thin films

Energy Technology Data Exchange (ETDEWEB)

Sharma, Rita, E-mail: reetasharma2012@gmail.com; Sharma, Shaveta; Thangaraj, R.; Mian, M. [Semiconductors Laboratory, Department of Physics, GND University, Amritsar (India); Chander, Ravi [Applied Science Deptt. Govt. Polytechnic College Amritsar (India); Kumar, Praveen [Department of Physics, DAV University, Sarmastipur, Jalandhar-144012 (India)

2015-05-15

We report the structural and optical properties of thermally evaporated Bi{sub 2}Te{sub 3}, In{sub 2}Te{sub 3} and InBiTe{sub 3} films by using X-ray diffraction, optical and Raman Spectroscopy techniques. The as-prepared thin films were found to be Semi-crystalline by X-ray diffraction. Particle Size and Strain has been calculated from XRD data. The optical constants, film thickness, refractive index and optical band gap (E{sub g}) has been reported for In{sub 2}Te{sub 3}, InBiTe{sub 3} films. Raman Spectroscopy was performed to investigate the effect of Bi, In, on lattice vibration and chemical bonding in Te based chalcogenide glassy alloys.

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.

Convex Clustering: An Attractive Alternative to Hierarchical Clustering

Science.gov (United States)

Chen, Gary K.; Chi, Eric C.; Ranola, John Michael O.; Lange, Kenneth

2015-01-01

The primary goal in cluster analysis is to discover natural groupings of objects. The field of cluster analysis is crowded with diverse methods that make special assumptions about data and address different scientific aims. Despite its shortcomings in accuracy, hierarchical clustering is the dominant clustering method in bioinformatics. Biologists find the trees constructed by hierarchical clustering visually appealing and in tune with their evolutionary perspective. Hierarchical clustering operates on multiple scales simultaneously. This is essential, for instance, in transcriptome data, where one may be interested in making qualitative inferences about how lower-order relationships like gene modules lead to higher-order relationships like pathways or biological processes. The recently developed method of convex clustering preserves the visual appeal of hierarchical clustering while ameliorating its propensity to make false inferences in the presence of outliers and noise. The solution paths generated by convex clustering reveal relationships between clusters that are hidden by static methods such as k-means clustering. The current paper derives and tests a novel proximal distance algorithm for minimizing the objective function of convex clustering. The algorithm separates parameters, accommodates missing data, and supports prior information on relationships. Our program CONVEXCLUSTER incorporating the algorithm is implemented on ATI and nVidia graphics processing units (GPUs) for maximal speed. Several biological examples illustrate the strengths of convex clustering and the ability of the proximal distance algorithm to handle high-dimensional problems. CONVEXCLUSTER can be freely downloaded from the UCLA Human Genetics web site at http://www.genetics.ucla.edu/software/ PMID:25965340

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)

Two-Dimensional Transition Metal Oxide and Chalcogenide-Based Photocatalysts

Science.gov (United States)

Haque, Farjana; Daeneke, Torben; Kalantar-zadeh, Kourosh; Ou, Jian Zhen

2018-06-01

Two-dimensional (2D) transition metal oxide and chalcogenide (TMO&C)-based photocatalysts have recently attracted significant attention for addressing the current worldwide challenges of energy shortage and environmental pollution. The ultrahigh surface area and unconventional physiochemical, electronic and optical properties of 2D TMO&Cs have been demonstrated to facilitate photocatalytic applications. This review provides a concise overview of properties, synthesis methods and applications of 2D TMO&C-based photocatalysts. Particular attention is paid on the emerging strategies to improve the abilities of light harvesting and photoinduced charge separation for enhancing photocatalytic performances, which include elemental doping, surface functionalization as well as heterojunctions with semiconducting and conductive materials. The future opportunities regarding the research pathways of 2D TMO&C-based photocatalysts are also presented. [Figure not available: see fulltext.

Diffusion of 64Cu in copper-containing chalcogenide glasses

International Nuclear Information System (INIS)

Vlasov, Yu.G.; Bychkov, E.A.; Bolotov, A.M.; Tsegel'nik, V.S.; Gavrilov, Yu.A.

1996-01-01

Diffusion experiments with 64 Cu radioactive tracer for a number of copper-containing chalcogenide glasses CuI-As 2 Se 3 , Cu-SbI 3 -As 2 Se 3 , CuI-PbI 2 -As 2 Se 3 , CuI-PbI 2 -SbI 3 -As 2 Se 3 and Cu 2 Se-As 2 Se 3 are carried out for the first time. The results of diffusion and electrodiffusion measurements are in correspondence with information on electroconductivity and diffusion in a limited space (cage diffusion) from the Moessbauer spectroscopy on 124 I. It is shown for the first time that the Cheivin factor index for copper-conducting glasses in by 2-3 times higher as compared to silver-conducting glasses with approximate diffusion coefficients indices. 27 refs., 3 figs., 1 tab

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

Enhanced complete photonic bandgap in a moderate refractive index contrast chalcogenide-air system with connected-annular-rods photonic crystals

KAUST Repository

Hou, Jin; Yang, Chunyong; Li, Xiaohang; Cao, Zhenzhou; Chen, Shaoping

2018-01-01

. For the typical chalcogenide-glass–air system with an index contrast of 2.8:1, the optimized square lattice CARPC exhibits a significantly larger normalized CPBG of about 13.50%, though the use of triangular lattice CARPC is unable to enhance the CPBG

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

Pancreatic islet-like clusters from bone marrow mesenchymal stem cells of human first-trimester abortus can cure streptozocin-induced mouse diabetes.

Science.gov (United States)

Zhang, Yihua; Shen, Wenzheng; Hua, Jinlian; Lei, Anmin; Lv, Changrong; Wang, Huayan; Yang, Chunrong; Gao, Zhimin; Dou, Zhongying

2010-12-01

Bone marrow mesenchymal stem cells (BMSCs) have been reported to possess low immunogenicity and cause immunosuppression of recipients when allografted. They can differentiate into insulin-producing cells and may be a valuable source for islet formation. However, the extremely low differentiating rate of adult BMSCs toward insulin-producing cells and the insufficient insulin secretion of the differentiated BMSCs in vitro prevent their clinical use in diabetes treatment. Little is known about the potential of cell replacement therapy with human BMSCs. Previously, we isolated and identified human first-trimester fetal BMSCs (hfBMSCs). Under a novel four-step induction procedure established in this study, the hfBMSCs effectively differentiated into functional pancreatic islet-like cell clusters that contained 62 ± 14% insulin-producing cells, expressed a broad gene profile related to pancreatic islet β-cell development, and released high levels of insulin (2.245 ± 0.222 pmol/100 clusters per 30 min) and C-peptide (2.200 ± 0.468 pmol/100 clusters per 30 min) in response to 25 mmol/L glucose stimulus in vitro. The pancreatic islet-like cell clusters normalized the blood glucose level of diabetic model mice for at least 9 weeks when xenografted; blood glucose levels in these mice rose abnormally again when the grafts were removed. Examination of the grafts indicated that the transplanted cells survived in recipients and produced human insulin and C-peptide in situ. These results demonstrate that hfBMSCs derived from a human first-trimester abortus can differentiate into pancreatic islet-like cell clusters following an established four-step induction. The insulin-producing clusters present advantages in cell replacement therapy of type 1 diabetic model mice.

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

Thermally controlled mid-IR band-gap engineering in all-glass chalcogenide microstructured fibers: a numerical study

DEFF Research Database (Denmark)

Barh, Ajanta; Varshney, Ravi K.; Pal, Bishnu P.

2017-01-01

Presence of photonic band-gap (PBG) in an all-glass low refractive index (RI) contrast chalcogenide (Ch) microstructured optical fibers (MOFs) is investigated numerically. The effect of external temperature on the position of band-gap is explored to realize potential fiber-based wavelength filters....... Then the temperature sensitivity of band-gaps is investigated to design fiber-based mid-IR wavelength filters/sensors....

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.

Theory of Two-Magnon Raman Scattering in Iron Pnictides and Chalcogenides

Energy Technology Data Exchange (ETDEWEB)

Chen, C. C.

2011-08-15

Although the parent iron-based pnictides and chalcogenides are itinerant antiferromagnets, the use of local moment picture to understand their magnetic properties is still widespread. We study magnetic Raman scattering from a local moment perspective for various quantum spin models proposed for this new class of superconductors. These models vary greatly in the level of magnetic frustration and show a vastly different two-magnon Raman response. Light scattering by two-magnon excitations thus provides a robust and independent measure of the underlying spin interactions. In accord with other recent experiments, our results indicate that the amount of magnetic frustration in these systems may be small.

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

Radiation-induced defects in chalcogenide glasses characterized by combined optical spectroscopy, XPS and PALS methods

International Nuclear Information System (INIS)

Shpotyuk, O.; Kovalskiy, A.; Jain, H.; Golovchak, R.; Zurawska, A.

2007-01-01

Temperature-dependent optical absorption spectroscopy, high-resolution X-ray photoelectron spectroscopy and positron annihilation lifetimes spectroscopy are utilized to understand radiation-induced changes in Ge-Sb-S chalcogenide glasses. Theoretically predicted topological scheme of γ-induced coordination defect formation in stoichiometric Ge 23.5 Sb 11.8 S 64.7 glass composition is supported by these measurements. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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.

Bismuth chalcogenide compounds Bi 2 × 3 (X=O, S, Se): Applications in electrochemical energy storage

Energy Technology Data Exchange (ETDEWEB)

Ni, Jiangfeng; Bi, Xuanxuan; Jiang, Yu; Li, Liang; Lu, Jun

2017-04-01

Bismuth chalcogenides Bi2×3 (X=O, S, Se) represent a unique type of materials in diverse polymorphs and configurations. Multiple intrinsic features of Bi2×3 such as narrow bandgap, ion conductivity, and environmental friendliness, have render them attractive materials for a wide array of energy applications. In particular, their rich structural voids and the alloying capability of Bi enable the chalcogenides to be alternative electrodes for energy storage such as hydrogen (H), lithium (Li), sodium (Na) storage and supercapacitors. However, the low conductivity and poor electrochemical cycling are two key challenges for the practical utilization of Bi2×3 electrodes. Great efforts have been devoted to mitigate these challenges and remarkable progresses have been achieved, mainly taking profit of nanotechnology and material compositing engineering. In this short review, we summarize state-of-the-art research advances in the rational design of diverse Bi2×3 electrodes and their electrochemical energy storage performance for H, Li, and Na and supercapacitors. We also highlight the key technical issues at present and provide insights for the future development of bismuth based materials in electrochemical energy storage devices.

Phosphorene for energy and catalytic application—filling the gap between graphene and 2D metal chalcogenides

Science.gov (United States)

Jain, Rishabh; Narayan, Rekha; Padmajan Sasikala, Suchithra; Lee, Kyung Eun; Jung, Hong Ju; Ouk Kim, Sang

2017-12-01

Phosphorene, a newly emerging graphene analogous 2D elemental material of phosphorous atoms, is unique on the grounds of its natural direct band gap opening, highly anisotropic and extraordinary physical properties. This review highlights the current status of phosphorene research in energy and catalytic applications. The initial part illustrates the typical physical properties of phosphorene, which successfully bridge the prolonged gap between graphene and 2D metal chalcogenides. Various synthetic methods available for black phosphorus (BP) and the exfoliation/growth techniques for single to few-layer phosphorene are also overviewed. The latter part of this review details the working mechanisms and performances of phosphorene/BP in batteries, supercapacitors, photocatalysis, and electrocatalysis. Special attention has been paid to the research efforts to overcome the inherent shortcomings faced by phosphorene based devices. The relevant device performances are compared with graphene and 2D metal chalcogenides based counterparts. Furthermore, the underlying mechanism behind the unstable nature of phosphorene under ambient condition is discussed along with the various approaches to avoid ambient degradation. Finally, comments are offered for the future prospective explorations and outlook as well as challenges lying in the road ahead for phosphorene research.

On clusters and clustering from atoms to fractals

CERN Document Server

Reynolds, PJ

1993-01-01

This book attempts to answer why there is so much interest in clusters. Clusters occur on all length scales, and as a result occur in a variety of fields. Clusters are interesting scientifically, but they also have important consequences technologically. The division of the book into three parts roughly separates the field into small, intermediate, and large-scale clusters. Small clusters are the regime of atomic and molecular physics and chemistry. The intermediate regime is the transitional regime, with its characteristics including the onset of bulk-like behavior, growth and aggregation, a

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...

Functions of chalcogenide electrodes in solutions of complexing reagents and interfering ions

International Nuclear Information System (INIS)

Kiyanskij, V.V.

1990-01-01

The possibility to modify chalcogenide electrodes and their behaviour in solutions of complexing reagents for the development of new methods of potentiometric titration has been studied. It is shown that complexing reagents (EDTA, cupferron, 8-hydroxyquinoline, sodium dithiocarbaminate) and Cu(2), Hg(2) produce a strong effect on the functions of Ag, Cu, Cd, Pb - selective electrodes, which is used for titration of potential-determining and non-potential-determining ions ions (Sr 2+ , La 3+ etc.) and also for modification of sulfide-selecting electrode. A method of potentiometric titration of sulfates and chlorides with modified Cd- and Ag-selective electrodes is suggested

Ion beam assisted synthesis of nano-crystals in glasses (silver and lead chalcogenides)

International Nuclear Information System (INIS)

Espiau de Lamaestre, R.

2005-04-01

This work deals with the interest in ion beams for controlling nano-crystals synthesis in glasses. We show two different ways to reach this aim, insisting on importance of redox phenomena induced by the penetration and implantation of ions in glasses. We first show that we can use the great energy density deposited by the ions to tailor reducing conditions, favorable to metallic nano-crystal precipitation. In particular, we show that microscopic mechanism of radiation induced silver precipitation in glasses are analogous to the ones of classical photography. Ion beams can also be used to overcome supersaturation of elements in a given matrix. In this work, we synthesized lead chalcogenide nano-crystals (PbS, PbSe, PbTe) whose optical properties are interesting for telecommunication applications. We demonstrate the influence of complex chalcogenide chemistry in oxide glasses, and its relationship with the observed loss of growth control when nano-crystals are synthesized by sequential implantation of Pb and S in pure silica. As a consequence of this understanding, we demonstrate a novel and controlled synthesis of PbS nano-crystals, consisting in implanting sulfur into a Pb-containing glass, before annealing. Choice of glass composition provides a better control of precipitation physico-chemistry, whereas the use of implantation allows high nano-crystal volume fractions to be reached. Our study of IR emission properties of these nano-crystals shows a very high excitation cross section, and evidence for a 'dark exciton' emitting level. (author)

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.

Radionuclides in diffusion probing of inorganic materials based on chalcogenides

International Nuclear Information System (INIS)

Firsova, L.P.

1994-01-01

Migration of tellurium-125m, selenium-75, sulfur-35 radionuclides in solid solutions Pb 1-y (Se 0.08 Te 0.92 ) y and (Pb 1-x Sn x ) y Te 1-y , where x=0.1 and 0.2, has been studied, the results are presented. Data on dependence of selenium and tellurium self-diffusion coefficients on temperature in the range of 600-750 deg C are given. The results of the study of self-diffusion coefficient isothermal dependences on lead and tellurium vapour pressure in equilibrium with solid phases have been considered. It is ascertained that a change in the temperature and p-n transitions initiate the change in self-diffusion mechanisms of chalcogenide atoms. 8 refs., 3 tabs

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-08-14

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

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

International Nuclear Information System (INIS)

Schaefer, Michael; Schlaf, Rudy

2015-01-01

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

Investigation of structure, adhesion strength, wear performance and corrosion behavior of platinum/ruthenium/nitrogen doped diamond-like carbon thin films with respect to film thickness

Energy Technology Data Exchange (ETDEWEB)

Khun, N.W. [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Liu, E., E-mail: MEJLiu@ntu.edu.sg [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

2011-03-15

Research highlights: {yields} Sputtered PtRuN-DLC thin films were fabricated with different film thicknesses. {yields} The graphitization of the films increased with increased film thickness. {yields} The wear resistance of the films increased though their adhesion strength decreased. {yields} The corrosion potentials of the films shifted to more negative values. {yields} However, the corrosion currents of the films decreased. - Abstract: In this study, the corrosion performance of platinum/ruthenium/nitrogen doped diamond-like carbon (PtRuN-DLC) thin films deposited on p-Si substrates using a DC magnetron sputtering deposition system in a 0.1 M NaCl solution was investigated using potentiodynamic polarization test in terms of film thickness. The effect of the film thickness on the chemical composition, bonding structure, surface morphology, adhesion strength and wear resistance of the PtRuN-DLC films was studied using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM), micro-scratch test and ball-on-disc tribotest, respectively. It was found that the wear resistance of the PtRuN-DLC films apparently increased with increased film thickness though the adhesion strength of the films decreased. The corrosion results revealed that the increased concentration of sp{sup 2} bonds in the PtRuN-DLC films with increased film thickness shifted the corrosion potentials of the films to more negative values but the decreased porosity density in the films significantly decreased the corrosion currents of the films.

Investigation of structure, adhesion strength, wear performance and corrosion behavior of platinum/ruthenium/nitrogen doped diamond-like carbon thin films with respect to film thickness

International Nuclear Information System (INIS)

Khun, N.W.; Liu, E.

2011-01-01

Research highlights: → Sputtered PtRuN-DLC thin films were fabricated with different film thicknesses. → The graphitization of the films increased with increased film thickness. → The wear resistance of the films increased though their adhesion strength decreased. → The corrosion potentials of the films shifted to more negative values. → However, the corrosion currents of the films decreased. - Abstract: In this study, the corrosion performance of platinum/ruthenium/nitrogen doped diamond-like carbon (PtRuN-DLC) thin films deposited on p-Si substrates using a DC magnetron sputtering deposition system in a 0.1 M NaCl solution was investigated using potentiodynamic polarization test in terms of film thickness. The effect of the film thickness on the chemical composition, bonding structure, surface morphology, adhesion strength and wear resistance of the PtRuN-DLC films was studied using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM), micro-scratch test and ball-on-disc tribotest, respectively. It was found that the wear resistance of the PtRuN-DLC films apparently increased with increased film thickness though the adhesion strength of the films decreased. The corrosion results revealed that the increased concentration of sp 2 bonds in the PtRuN-DLC films with increased film thickness shifted the corrosion potentials of the films to more negative values but the decreased porosity density in the films significantly decreased the corrosion currents of the films.

Unexpected Rotamerism at the Origin of a Chessboard Supramolecular Assembly of Ruthenium Phthalocyanine.

Science.gov (United States)

Mattioli, Giuseppe; Larciprete, Rosanna; Alippi, Paola; Bonapasta, Aldo Amore; Filippone, Francesco; Lacovig, Paolo; Lizzit, Silvano; Paoletti, Anna Maria; Pennesi, Giovanna; Ronci, Fabio; Zanotti, Gloria; Colonna, Stefano

2017-11-16

We have investigated the formation and the properties of ultrathin films of ruthenium phthalocyanine (RuPc) 2 vacuum deposited on graphite by scanning tunneling microscopy and synchrotron photoemission spectroscopy measurements, interpreted in close conjunction with ab initio simulations. Thanks to its unique dimeric structure connected by a direct Ru-Ru bond, (RuPc) 2 can be found in two stable rotameric forms separated by a low-energy barrier. Such isomerism leads to a peculiar organization of the molecules in flat, horizontal layers on the graphite surface, characterized by a chessboard-like alternation of the two rotamers. Moreover, the molecules are vertically connected to form π-stacked columnar pillars of akin rotamers, compatible with the high conductivity measured in (RuPc) 2 powders. Such features yield an unprecedented supramolecular assembly of phthalocyanine films, which could open interesting perspectives toward the realization of new architectures of organic electronic devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Enhanced complete photonic bandgap in a moderate refractive index contrast chalcogenide-air system with connected-annular-rods photonic crystals

KAUST Repository

Hou, Jin

2018-03-27

Connected-annular-rods photonic crystals (CARPCs) in both triangular and square lattices are proposed to enhance the two-dimensional complete photonic bandgap (CPBG) for chalcogenide material systems with moderate refractive index contrast. For the typical chalcogenide-glass–air system with an index contrast of 2.8:1, the optimized square lattice CARPC exhibits a significantly larger normalized CPBG of about 13.50%, though the use of triangular lattice CARPC is unable to enhance the CPBG. It is almost twice as large as our previously reported result [IEEE J. Sel. Top. Quantum Electron. 22, 4900108 (2016) [CrossRef] ]. Moreover, the CPBG of the square-lattice CARPC could remain until an index contrast as low as 2.24:1. The result not only favors wideband CPBG applications for index contrast systems near 2.8:1, but also makes various optical applications that are dependent on CPBG possible for more widely refractive index contrast systems.

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...

Radiation-induced defects in chalcogenide glasses characterized by combined optical spectroscopy, XPS and PALS methods

Energy Technology Data Exchange (ETDEWEB)

Shpotyuk, O. [Institute of Physics of Jan Dlugosz University, 13/15 al. Armii Krajowej, Czestochowa 42201 (Poland); Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 (United States); Lviv Institute of Materials of SRC ' ' Carat' ' , 202, Stryjska str., 79031 Lviv (Ukraine); Kovalskiy, A.; Jain, H. [Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 (United States); Golovchak, R. [Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195 (United States); Lviv Institute of Materials of SRC ' ' Carat' ' , 202, Stryjska str., 79031 Lviv (Ukraine); Zurawska, A. [Opole University of Technology, 75, Ozimska str., Opole 45370 (Poland)

2007-03-15

Temperature-dependent optical absorption spectroscopy, high-resolution X-ray photoelectron spectroscopy and positron annihilation lifetimes spectroscopy are utilized to understand radiation-induced changes in Ge-Sb-S chalcogenide glasses. Theoretically predicted topological scheme of {gamma}-induced coordination defect formation in stoichiometric Ge{sub 23.5}Sb{sub 11.8}S{sub 64.7} glass composition is supported by these measurements. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Structural modification of covalent-bonded networks: on some methodological resolutions for binary chalcogenide glasses

International Nuclear Information System (INIS)

Shpotyuk, M; Shpotyuk, Ya; Shpotyuk, O

2011-01-01

New methodology to estimate efficiency of externally-induced structural modification in chalcogenide glasses is developed. This approach is grounded on the assumption that externally-induced structural modification is fully associated with destruction-polymerization transformations, which reveal themselves as local misbalances in covalent bond distribution, normal atomic coordination and intrinsic electrical fields. The input of each of these components into the total value of structural modification efficiency was probed for quasibinary (As 2 S 3 ) 100-x (Sb 2 S 3 ) x ChG.

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

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

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)

A first principles study of phase stability, bonding, electronic and lattice dynamical properties of beryllium chalcogenides at high pressure

International Nuclear Information System (INIS)

Dabhi, Shweta; Mankad, Venu; Jha, Prafulla K.

2014-01-01

Highlights: • First principles calculations are performed for BeS, BeSe and BeTe in B3, B8 and B1 phases. • They are indirect wide band gap semiconductors stable in B3 phase at ambient condition. • Phonon calculations at ambient and high pressure are reported. • The NiAs phase is dynamically stable at high pressure. - Abstract: The present paper reports a detailed and systematic theoretical study of structural, mechanical, electronic, vibrational and thermodynamical properties of three beryllium chalcogenides BeS, BeSe and BeTe in zinc blende, NiAs and rock salt phases by performing ab initio calculations based on density-functional theory. The calculated value of lattice constants and bulk modulus are compared with the available experimental and other theoretical data and found to agree reasonably well. These compounds are indirect wide band gap semiconductors with a partially ionic contribution in all considered three phases. The zinc blende phase of these chalcogenides is found stable at ambient condition and phase transition from zinc blende to NiAs structure is found to occur. The bulk modulus, its pressure derivative, anisotropic factor, Poission’s ratio, Young’s modulus for these are also calculated and discussed. The phonon dispersion curves of these beryllium chalcogenides in zinc blende phase depict their dynamical stability in this phase at ambient condition. We have also estimated the temperature variation of specific heat at constant volume, entropy and Debye temperature for these compounds in zinc blende phase. The variation of lattice-specific heat with temperature obeys the classical Dulong–Petit’s law at high temperature, while at low-temperature it obeys the Debye’s T 3 law