WorldWideScience

Sample records for platinum metals group

  1. Development of radioactive platinum group metal catalysts

    International Nuclear Information System (INIS)

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

    1999-03-01

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

  2. Development of radioactive platinum group metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-03-01

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

  3. Bioaccumulation of platinum group metals in dolphins, Stenella sp ...

    African Journals Online (AJOL)

    Platinum group metals (PGMs) concentrations were measured in the tissues= of dolphins (Stenella sp.) caught along the Ghanaian coastline. Tissues from specimens caught by fishermen from Dixcove, western Ghana, were analysed in 2006 for palladium (Pd), platinum (Pt) and rhodium (Rh) using the Neutron Activation ...

  4. Activation analysis for platinum in gold and metals of the platinum group through 199Au

    International Nuclear Information System (INIS)

    Foerster, H.

    1976-01-01

    Platinum was determined in gold and in metals of the platinum group through 199 Au by activation analysis. The matrix was separated at the end of irradiation before the daughter nuclide was formed. Gold was separated by extraction with MIBK from 1

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

    International Nuclear Information System (INIS)

    Ivanovskii, Alexander L

    2009-01-01

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

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

    Science.gov (United States)

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

    2012-01-01

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

  7. Recycling of platinum group metals from the automotive catalysts

    International Nuclear Information System (INIS)

    Benevit, Mariana; Petter, Patricia Melo Halmenschlager; Veit, Hugo Marcelo

    2014-01-01

    Currently it is very important to use alternative sources of raw material for obtaining metals, avoiding the traditional mining. This work aims to characterize and evaluate the recoverability of platinum group metals present in automotive catalysts. Thus, the catalysts were divided into two groups: the first was catalysts used in 1.0 cars and the second was catalyst used in 2.0 cars. DRX and FRX techniques and chemical analysis performed by ICP/OES was used to characterized these materials. The results showed that there is a significant amount of platinum group elements in catalyst waste, which can be separated and reused. In the next step, hydro and pyrometallurgical routes, for metals extraction from catalyst waste, will be studied. (author)

  8. Effect of Platinum Group Metal Doping in Magnesium Diboride Wires

    DEFF Research Database (Denmark)

    Grivel, Jean-Claude; Alexiou, Aikaterini; Namazkar, Shahla

    2016-01-01

    The effect of some platinum group metals(PGM = Rh, Pd, and Pt) on the microstructure and critical current density of Cu/Nb-sheathed MgB2 wires has been studied using Mg1-x PGMxB2 powders with low doping levels. It was found that Pt and Pd do not enter the MgB2 lattice and have only limited influe...

  9. Platinum-group elements and gold in base metal sulfides, platinum-group minerals, and Re-Os isotope compositions of the Uitkomst complex, South Africa

    Czech Academy of Sciences Publication Activity Database

    Trubač, Jakub; Ackerman, Lukáš; Gauert, Ch.; Ďurišová, Jana; Hrstka, Tomáš

    2018-01-01

    Roč. 113, č. 2 (2018), s. 439-461 ISSN 0361-0128 R&D Projects: GA ČR GA13-15390S Institutional support: RVO:67985831 Keywords : binary alloys * copper compounds * economic geology * gold * iridium * isotopes * ore deposits * osmium * palladium * platinum * platinum metals * pyrites * Rhenium * rhenium alloys * ruthenium * solid solutions * sulfur compounds * crustal materials * mass-balance calculations * massive sulfides * mineralized zone * monosulfide solid solutions * platinum group elements * platinum group elements (PGEs) * platinum group minerals Subject RIV: DB - Geology ; Mineralogy; AC - Archeology, Anthropology, Ethnology (ARUB-Q) OBOR OECD: Geology; Archaeology (ARUB-Q) Impact factor: 2.519, year: 2016

  10. Platinum group metal recovery and catalyst manufacturing process

    Energy Technology Data Exchange (ETDEWEB)

    Chung, H. S.; Kim, Y. S.; Yoo, J. H.; Lee, H. S.; Ahn, D. H.; Kim, K. R.; Lee, S. H.; Paek, S. W.; Kang, H. S.

    1998-03-01

    The fission product nuclides generated during the irradiation of reactor fuel include many useful elements, among them platinum group metal such as ruthenium, rhodium and palladium which are of great industrial importance, occur rarely in nature and are highly valuable. In this research, the authors reviewed various PGM recovery methods. Recovery of palladium from seven-component simulated waste solution was conducted by selective precipitation method. The recovery yield was more than 99.5% and the purity of the product was more than 99%. Wet-proof catalyst was prepared with the recovered palladium. The specific surface area of the catalyst support was more than 400 m{sup 2}/g. The content of palladium impregnated on the support was 10 wt.%. Hydrogen isotope exchange efficiency of 93 % to equilibrium with small amount of the catalyst was obtained. It was turned out possible to consider using such palladium or other very low active PGM materials in applications where its actively is unimportant as in nuclear industries. (author). 63 refs., 38 tabs., 36 figs.

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

    International Nuclear Information System (INIS)

    Jensen, G.A.

    1985-03-01

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

  12. Investigations of radiochemical methods for the platinum group metals for NAA

    International Nuclear Information System (INIS)

    Tredoux, M.

    A radiochemical procedure for the determination of the platinum group metals and gold is outlined in this report. The sample is irradiated, treated with acids and passed through anion-exchange columns before being determined by gamma spectrometry

  13. Peruvian perovskite Between Transition-metal to PGM/PlatinumGroupMetal Catalytic Fusion

    Science.gov (United States)

    Maksoed, Wh-

    2016-11-01

    Strongly correlated electronic materials made of simple building blocks, such as a transition-metal ion in an octahedral oxygen cage forming a perovskite structure- Dagotto & Tokura for examples are the high-temperature superconductivity & the CMR/Colossal Magnetoresistance . Helium-4 denotes from LC Case,ScD: "Catalytic Fusion of Deuterium into Helium-4"- 1998 dealt with gaseous D2- "contacted with a supported metallic catalyst at superatmospheric pressure". The catalyst is a platinum-group metal, at about 0.5% - 1% by weight, on activated C. Accompanies Stephen J Geier, 2010 quotes "transition metal complexes", the Energy thus produced is enormous, and because the deuterium is very cheap in the form of heavy water (less than US 1/g), the fuel cost is very low (seas &Deuteronomy to be eternally preserves. Heartfelt Gratitudes to HE. Mr. Prof. Ir. HANDOJO.

  14. Determination of platinum group metals by ICP-AES in environmental samples after preconcentration

    International Nuclear Information System (INIS)

    Vlasankova, R.; Sommer, L.

    1999-01-01

    Platinum group metal (PGM) may have toxic properties and their presence in the environment represent danger for human health. With the introduction of automobile catalytic converters containing PGM, the emission of these noble metals into atmosphere has increased. Platinum, palladium and rhodium are used in this catalytic converters to decrease toxic emissions of carbon monoxide, unburnt hydrocarbons and nitrogen oxides in vehicles exhaust gases. These catalysts are mobile sources of PGM into the environment. Thus, increased platinum concentrations have been found in various objects of environment because of the massive introduction of such catalytic converters are present. The preconcentration and separation of PGM and their determination by ICP-AES in environmental samples are described

  15. Platinum Group Metal Recycling Technology Development - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Lawrence Shore

    2009-08-19

    BASF Catalysts LLC, formerly Engelhard Corporation, has completed a project to recover Pt from PEM fuel cell membrane electrode assemblies. The project, which began in 2003, has met the project objective of an environmentally-friendly, cost-effective method for recovery of platinum without release of hydrogen fluoride. This has been achieved using a combination of milling, dispersion and acid leaching. 99% recovery of Pt was achieved, and this high yield can be scaled up using one vessel for a single leach and rinse. Leaching was been successfully achieved using a 10% solids level, double the original target. At this solids content, the reagent and utility costs represent ~0.35% of the Pt value of a lot, using very conservative assumptions. The main cost of the process is capital depreciation, followed by labor.

  16. Platinum metals in the environment

    Energy Technology Data Exchange (ETDEWEB)

    Zereini, Fathi [Frankfurt Univ. (Germany). Dept. of Environmental Analytical Chemistry; Wiseman, Clare L.S. (ed.) [Toronto Univ. (Canada). School of the Environment

    2015-03-01

    This book contains the five chapters with the following topics: 1. SOURCES OF PGE EMISSIONS ELEMENTS: Sources of Platinum Group Elements (PGE) in the Environment; Impact of Platinum Group Element Emissions from Mining and Production Activities. 2. ANALYTICAL METHODS FOR THE DETERMINATION OF PGE IN BIOLOGICAL AND ENVIRONMENTAL MATRICES: Appraisal of Biosorption for Recovery, Separation and Determination of Platinum, Palladium and Rhodium in Environmental Samples; On the Underestimated Factors Influencing the Accuracy of Determination of Pt and Pd by Electrothermal Atomic Absorption Spectrometry in Road Dust Samples; Application of Solid Sorbents for Enrichment and Separation of Platinum Metal Ions; Voltammetric Analysis of Platinum in Environmental Matrices; Speciation Analysis of Chloroplatinates; Analysis of Platinum Group Elements in Environmental Samples: A Review. 3. OCCURRENCE, CHEMICAL BEHAVIOR AND FATE OF PGE IN THE ENVIRONMENT: Brazilian PGE Research Data Survey on Urban and Roadside Soils; Platinum, Palladium and Rhodium in a Bavarian Roadside Soil; Increase of Platinum Group Element Concentrations in Soils and Airborne Dust During the Period of Vehicular Exhaust Catalysts Introduction; Platinum-Group Elements in Urban Fluvial Bed Sediments-Hawaii; Long-Term Monitoring of Palladium and Platinum Contents in Road Dust of the City of Munich, Germany; Characterization of PGEs and Other Elements in Road Dusts and Airborne Particles in Houston, Texas; Accumulation and Distribution of Pt and Pd in Roadside Dust, Soil and Vegetation in Bulgaria; Increase of the Environmental Pt Concentration in the Metropolitan Area of Mexico City Associated to the Use of Automobile Catalytic Converters; Solubility of Emitted Platinum Group Elements (Pt, Pd and Rh) in Airborne Particulate Matter (PM10) in the Presence of Organic Complexing Agents; The Influence of Anionic Species (Cl{sup -}, NO{sub 3}{sup -}, SO{sub 4}{sup 2-}) on the Transformation and Solubility of Platinum in

  17. Automated installation for atomic emission determination of gold, silver and platinum group metals

    International Nuclear Information System (INIS)

    Zayakina, S.B.; Anoshin, G.N.; Gerasimov, P.A.; Smirnov, A.V.

    1999-01-01

    An automated installation for the direct atomic emission determination of silver, gold and platinum-group metals (Ru) in geological and geochemical materials with software for automated data acquisition and handling is designed and developed. The installation consists of a DFS-458 diffraction spectrograph, a MAES-10 multichannel analyzer of emission spectra, and a dual-jet plasmatron. A library of spectral lines of almost all elements excited in the dual-jet plasmatron is complied [ru

  18. Platinum-group elements

    Science.gov (United States)

    Zientek, Michael L.; Loferski, Patricia J.; Parks, Heather L.; Schulte, Ruth F.; Seal, Robert R.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    The platinum-group elements (PGEs)—platinum, palladium, rhodium, ruthenium, iridium, and osmium—are metals that have similar physical and chemical properties and tend to occur together in nature. PGEs are indispensable to many industrial applications but are mined in only a few places. The availability and accessibility of PGEs could be disrupted by economic, environmental, political, and social events. The United States net import reliance as a percentage of apparent consumption is about 90 percent.PGEs have many industrial applications. They are used in catalytic converters to reduce carbon monoxide, hydrocarbon, and nitrous oxide emissions in automobile exhaust. The chemical industry requires platinum or platinum-rhodium alloys to manufacture nitric oxide, which is the raw material used to manufacture explosives, fertilizers, and nitric acid. In the petrochemical industry, platinum-supported catalysts are needed to refine crude oil and to produce aromatic compounds and high-octane gasoline. Alloys of PGEs are exceptionally hard and durable, making them the best known coating for industrial crucibles used in the manufacture of chemicals and synthetic materials. PGEs are used by the glass manufacturing industry in the production of fiberglass and flat-panel and liquid crystal displays. In the electronics industry, PGEs are used in computer hard disks, hybridized integrated circuits, and multilayer ceramic capacitors.Aside from their industrial applications, PGEs are used in such other fields as health, consumer goods, and finance. Platinum, for example, is used in medical implants, such as pacemakers, and PGEs are used in cancer-fighting drugs. Platinum alloys are an ideal choice for jewelry because of their white color, strength, and resistance to tarnish. Platinum, palladium, and rhodium in the form of coins and bars are also used as investment commodities, and various financial instruments based on the value of these PGEs are traded on major exchanges

  19. HIGHLY REFRACTORY CRUCIBLES OF STABILIZED ZIRCONIA FOR INDUCTION MELTING OF THE PLATINUM GROUP METALS, FABRICATED BY VIBROCASTING

    Directory of Open Access Journals (Sweden)

    V. V. Primachenko

    2012-01-01

    Full Text Available As the result of the studies at PJSC « UKRNIIO them. A.S.Berezhnogo» the technology and commercial production of crucibles from stabilized zirconia for the smelting of platinum group metals are develop

  20. HIGHLY REFRACTORY CRUCIBLES OF STABILIZED ZIRCONIA FOR INDUCTION MELTING OF THE PLATINUM GROUP METALS, FABRICATED BY VIBROCASTING

    OpenAIRE

    V. V. Primachenko; V. V. Martynenko; I. G. Szulik; I. A. Kushchenko

    2012-01-01

    As the result of the studies at PJSC « UKRNIIO them. A.S.Berezhnogo» the technology and commercial production of crucibles from stabilized zirconia for the smelting of platinum group metals are develop

  1. Real life experimental determination of platinum group metals content in automotive catalytic converters

    Science.gov (United States)

    Yakoumis, I.; Moschovi, A. M.; Giannopoulou, I.; Panias, D.

    2018-03-01

    The real life experimental protocol for the preparation of spent automobile catalyst samples for elemental analysis is thoroughly described in the following study. Collection, sorting and dismantling, homogenization and sample preparation for X-Ray fluorescence spectroscopy and Atomic Adsorption Spectroscopy combined with Inductive coupled plasma mass spectrometry are discussed in detail for both ceramic and metallic spent catalysts. The concentrations of Platinum Group Metals (PGMs) in spent catalytic converters are presented based on typical consignments of recycled converters (more than 45,000 pieces) from the Greek Market. The conclusions clearly denoted commercial metallic catalytic foil contains higher PGMs loading than ceramic honeycombs. On the other hand, the total PGMs loading in spent ceramic catalytic converters has been found higher than the corresponding value for the metallic ones.

  2. Thermochemical Properties of Group IVB and VB Transition Metal Alloys with Platinum Group Metals: Acid - Stabilization.

    Science.gov (United States)

    Cima, Michael John

    Solid-state galvanic cell measurements and oxide equilibration experiments are used to derive thermochemical quantities for a variety of acid-base stabilized alloys such as Nb-Pd, Nb-Rh, Ti-Pd, and Ti-Rh. The experiments have effectively resulted in the titration of palladium by niobium metal. The excess partial molar Gibbs energy of niobium at infinite dilution was determined to be -62 kcal/mole at 1000^circ C and the Gibbs energy of formation of {rm NbPd}_{3.55} is -42 kcal/mole. These results and those for the other systems are used to assess the importance of crystal field effects in the context of the generalized Lewis acid-base theory.

  3. High Performance Platinum Group Metal Free Membrane Electrode Assemblies through Control of Interfacial Processes

    Energy Technology Data Exchange (ETDEWEB)

    Ayers, Katherine [Proton Energy Systems, Wallingford, CT (United States); Capuano, Christopher [Proton Energy Systems, Wallingford, CT (United States); Atanassov, Plamen [Univ. of New Mexico, Albuquerque, NM (United States); Mukerjee, Sanjeev [Northeastern Univ., Boston, MA (United States); Hickner, Michael [Pennsylvania State Univ., University Park, PA (United States)

    2017-11-29

    The quantitative goal of this project was to produce a high-performance anion exchange membrane water electrolyzer (AEM-WE) completely free of platinum group metals (PGMs), which could operate for at least 500 hours with less than 50 microV/hour degradation, at 500 mA/cm2. To achieve this goal, work focused on the optimization of electrocatalyst conductivity, with dispersion and utilization in the membrane electrode assembly (MEA) improved through refinement of deposition techniques. Critical factors were also explored with significant work undertaken by Northeastern University to further understand catalyst-membrane-ionomer interfaces and how they differ from liquid electrolyte. Water management and optimal cell operational parameters were established through the design, fabrication, and test of a new test station at Proton specific for AEM evaluation. Additionally, AEM material stability and robustness at high potentials and gas evolution conditions were advanced at Penn State.

  4. Removal of platinum group metals contained in molten glass using copper

    International Nuclear Information System (INIS)

    Uruga, Kazuyoshi; Sawada, Kayo; Arita, Yuji; Enokida, Youichi; Yamamoto, Ichiro

    2007-01-01

    Removal of platinum group metals (PGMs) such as Pd, Ru, and RuO 2 from molten glass by using various amounts of liquid Cu was done as a basic study on a new vitrification process for a high-level radio-active waste. We prepared two types of borosilicate glasses containing PGMs and Cu, respectively. These glasses were mixed together and heated at 1,473 K for 4h in Ar atmosphere. More than 95% of Pd were removed as a spherical metal button composed of Pd-Cu alloy when Cu was added in an amount 0.5 times the weight of Pd. Nearly 95% of Ru was also removed as a spherical button with 2.5-5 times as much Cu addition as Ru in weight. Ruthenium oxide was reduced to metallic Ru by a reaction with Cu in the molten glass. The removal fraction was increased by increasing the amount of Cu and reached 63% when Cu addition was 7.5 times as much as RuO 2 in weight. By addition of Si as a reducing agent, nearly 90% of Pd and Ru were removed with Cu and Si metal composites even under O 2 :Ar=20:80 (v/v) condition. (author)

  5. Teaching - methodical and research center of hydrogen power engineering and platinum group metals in the former Soviet Union countries

    International Nuclear Information System (INIS)

    Evdokimov, A.A; Sigov, A.S; Shinkarenko, V.V.

    2005-01-01

    Full text: Teaching - Methodical and Research Center (TMRC) 'Sokolinaja Gora' is founded in order to provide methodical-information and scientific support of institutes of higher education in the field of hydrogen power engineering and platinum group metals in Russia and in the countries of the Former Soviet union. It is independent association of creative communities of scientist of higher educational specialists. The main directions of the Center activity are: 1. Teaching-methodological support and development of teaching in the field of hydrogen power engineering and platinum group metals in Russia in the countries of the Former Soviet Union. Themes of teaching includes the basic of safe using of hydrogen technologies and devices, ecological, economic and law aspects of new hydrogen power engineering, transition to which in 21 century is one of the central problems of mankind survival; 2. Organizing of joint researches by independent creative communities of scientists in the field of hydrogen power engineering and platinum group metal; 3. Independent scientific examination, which is made by Advisory Committee of High Technologies consisting of representatives of the countries of Former Soviet Union, which are standing participants of an Annual International Symposia 'Hydrogen Power Engineering and Platinum Group Metals in the Former Soviet Union Countries'. Structure of the Center: 1. Center of strategic development in the field of high technologies; 2. Scientific Research Institute of Hydrogen Power Engineering and Platinum Group Metals; 3. Teaching-Methodical Association in specialization 'Hydrogen Power Engineering and economics' and hydrogen wide spread training; 4. Media Center 'Hydrogen Power Engineering and Platinum Group Metals', 5. Organizational Center; 6. Administrative Center. The Center will be established step-by-step in 2005-2010 on the basis of the following programs: Teaching-methodological program. On the basis of this program it is planned to

  6. Global exploration and production capacity for platinum-group metals from 1995 through 2015

    Science.gov (United States)

    Wilburn, David R.

    2012-01-01

    Platinum-group metals (PGMs) are required in a variety of commercial, industrial, and military applications for many existing and emerging technologies, yet the United States is highly dependent on foreign sources of PGMs. Information on global exploration for PGMs since 1995 has been used in this study as a basis for identifying locations where the industry has determined that exploration has provided data sufficient to warrant development of a new mine or expansion of an existing operation or where a significant increase in capacity for PGMs is anticipated by 2015. Discussions include an overview of the industry and the selected sites, factors affecting mineral supply, and circumstances leading to the development of mineral properties with the potential to affect mineral supply. Of the 52 sites or regional operations that were considered in this analysis, 16 sites were producing before 1995, 28 sites commenced production from 1995 through 2010, and 8 sites were expected to begin production from 2011 through 2015 if development plans came to fruition. The United States imports PGMs primarily from Canada, Russia, South Africa, and Zimbabwe to meet increasing demand for these materials in a variety of specialized and high-tech applications. Feed sources of PGMs are changing in South Africa and Russia, which together accounted for about 89 percent of platinum production and 82 percent of palladium production in 2009. A greater amount of South African PGM capacity is likely to come from deeper, higher cost Upper Group Reef seam 2 deposits and deposits in the Eastern Bushveld area. Future Russian PGM capacity is likely to come from ore zones with generally lower PGM content and different platinum-to-palladium ratios than the nickel-rich ore that dominated PGM supply in the 1990s. Because PGM supply from Canada and Russia is derived as a byproduct of copper and nickel mining, the PGM supply from these countries is influenced by economic, environmental, political, and

  7. Influence of platinum group metal-free catalyst synthesis on microbial fuel cell performance

    Science.gov (United States)

    Santoro, Carlo; Rojas-Carbonell, Santiago; Awais, Roxanne; Gokhale, Rohan; Kodali, Mounika; Serov, Alexey; Artyushkova, Kateryna; Atanassov, Plamen

    2018-01-01

    Platinum group metal-free (PGM-free) ORR catalysts from the Fe-N-C family were synthesized using sacrificial support method (SSM) technique. Six experimental steps were used during the synthesis: 1) mixing the precursor, the metal salt, and the silica template; 2) first pyrolysis in hydrogen rich atmosphere; 3) ball milling; 4) etching the silica template using harsh acids environment; 5) the second pyrolysis in ammonia rich atmosphere; 6) final ball milling. Three independent batches were fabricated following the same procedure. The effect of each synthetic parameters on the surface chemistry and the electrocatalytic performance in neutral media was studied. Rotating ring disk electrode (RRDE) experiment showed an increase in half wave potential and limiting current after the pyrolysis steps. The additional improvement was observed after etching and performing the second pyrolysis. A similar trend was seen in microbial fuel cells (MFCs), in which the power output increased from 167 ± 2 μW cm-2 to 214 ± 5 μW cm-2. X-ray Photoelectron Spectroscopy (XPS) was used to evaluate surface chemistry of catalysts obtained after each synthetic step. The changes in chemical composition were directly correlated with the improvements in performance. We report outstanding reproducibility in both composition and performance among the three different batches.

  8. Recycling of platinum group metals from the automotive catalysts; Reciclagem de metais do grupo da platina proveniente de catalisadores automotivos

    Energy Technology Data Exchange (ETDEWEB)

    Benevit, Mariana; Petter, Patricia Melo Halmenschlager; Veit, Hugo Marcelo, E-mail: patymhp@yahoo.com.br [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Faculdade de Engenharia. Departamento de Materiais

    2014-07-01

    Currently it is very important to use alternative sources of raw material for obtaining metals, avoiding the traditional mining. This work aims to characterize and evaluate the recoverability of platinum group metals present in automotive catalysts. Thus, the catalysts were divided into two groups: the first was catalysts used in 1.0 cars and the second was catalyst used in 2.0 cars. DRX and FRX techniques and chemical analysis performed by ICP/OES was used to characterized these materials. The results showed that there is a significant amount of platinum group elements in catalyst waste, which can be separated and reused. In the next step, hydro and pyrometallurgical routes, for metals extraction from catalyst waste, will be studied. (author)

  9. Direct alcohol fuel cells: Increasing platinum performance by modification with sp-group metals

    Science.gov (United States)

    Figueiredo, Marta C.; Sorsa, Olli; Doan, Nguyet; Pohjalainen, Elina; Hildebrand, Helga; Schmuki, Patrik; Wilson, Benjamin P.; Kallio, Tanja

    2015-02-01

    By using sp group metals as modifiers, the catalytic properties of Pt can be improved toward alcohols oxidation. In this work we report the performance increase of direct alcohol fuel cells (DAFC) fuelled with ethanol or 2-propanol with platinum based anode electrodes modified with Bi and Sb adatoms. For example, by simply adding Sb to the Pt/C based anode ink during membrane electrode assembly fabrication of a direct ethanol fuel cell (DEFC) its performance is improved three-fold, with more than 100 mV increase in the open circuit potential. For the fuel cell fuelled with 2-propanol high power densities are obtained at very high potentials with these catalyst materials suggesting a great improvement for practical applications. Particularly in the case of Pt/C-Bi, the improvement is such that within 0.6 V (from 0.7 to 0.1 V) the power densities are between 7 and 9 mW/cm2. The results obtained with these catalysts are in the same range as those obtained with other bimetallic catalysts comprising of PtRu and PtSn, which are currently considered to be the best for these type of fuel cells and that are obtained by more complicated (and consequently more expensive) methods.

  10. Enhanced Dissolution of Platinum Group Metals Using Electroless Iron Deposition Pretreatment

    Science.gov (United States)

    Taninouchi, Yu-ki; Okabe, Toru H.

    2017-12-01

    In order to develop a new method for efficiently recovering platinum group metals (PGMs) from catalyst scraps, the authors investigated an efficient dissolution process where the material was pretreated by electroless Fe deposition. When Rh-loaded alumina powder was kept in aqua regia at 313 K (40 °C) for 30 to 60 minutes, the Rh hardly dissolved. Meanwhile, after electroless Fe plating using a bath containing sodium borohydride and potassium sodium tartrate as the reducing and complexing agents, respectively, approximately 60 pct of Rh was extracted by aqua regia at 313 K (40 °C) after 30 minutes. Furthermore, when heat treatment was performed at 1200 K (927 °C) for 60 minutes in vacuum after electroless plating, the extraction of Rh approached 100 pct for the same leaching conditions. The authors also confirmed that the Fe deposition pretreatment enhanced the dissolution of Pt and Pd. These results indicate that an effective and environmentally friendly process for the separation and extraction of PGMs from catalyst scraps can be developed utilizing this Fe deposition pretreatment.

  11. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells

    Science.gov (United States)

    Setzler, Brian P.; Zhuang, Zhongbin; Wittkopf, Jarrid A.; Yan, Yushan

    2016-12-01

    Fuel cells are the zero-emission automotive power source that best preserves the advantages of gasoline automobiles: low upfront cost, long driving range and fast refuelling. To make fuel-cell cars a reality, the US Department of Energy has set a fuel cell system cost target of US$30 kW-1 in the long-term, which equates to US$2,400 per vehicle, excluding several major powertrain components (in comparison, a basic, but complete, internal combustion engine system costs approximately US$3,000). To date, most research for automotive applications has focused on proton exchange membrane fuel cells (PEMFCs), because these systems have demonstrated the highest power density. Recently, however, an alternative technology, hydroxide exchange membrane fuel cells (HEMFCs), has gained significant attention, because of the possibility to use stable platinum-group-metal-free catalysts, with inherent, long-term cost advantages. In this Perspective, we discuss the cost profile of PEMFCs and the advantages offered by HEMFCs. In particular, we discuss catalyst development needs for HEMFCs and set catalyst activity targets to achieve performance parity with state-of-the-art automotive PEMFCs. Meeting these targets requires careful optimization of nanostructures to pack high surface areas into a small volume, while maintaining high area-specific activity and favourable pore-transport properties.

  12. Chemical reactions on platinum-group metal surfaces studied by synchrotron-radiation-based spectroscopy

    International Nuclear Information System (INIS)

    Kondoh, Hiroshi; Nakai, Ikuyo; Nagasaka, Masanari; Amemiya, Kenta; Ohta, Toshiaki

    2009-01-01

    A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111), and H 2 O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions. (author)

  13. Recovery of Platinum Group Metals from Spent Catalysts Using Iron Chloride Vapor Treatment

    Science.gov (United States)

    Taninouchi, Yu-ki; Okabe, Toru H.

    2018-05-01

    The recovery of platinum group metals (PGMs) from spent automobile catalysts is a difficult process because of their relatively low contents in the scrap. In this study, to improve the efficiency of the existing recycling techniques, a novel physical concentration method involving treatment with FeCl2 vapor has been examined. The reactions occurring between typical catalyst components and FeCl2 vapor are discussed from the thermodynamic point of view, and the validity of the proposed technique was experimentally verified. The obtained results indicate that the vapor treatment at around 1200 K (927 °C) can effectively alloy PGMs (Pt, Pd, and Rh) with Fe, resulting in the formation of a ferromagnetic alloy. It was also confirmed that cordierite and alumina (the major catalyst components) remained unreacted after the vapor treatment, while ceria species were converted into oxychlorides. The samples simulating the automobile catalyst were also subjected to magnetic separation after the treatment with FeCl2 vapor; as a result, PGMs were successfully extracted and concentrated in the form of a magnetic powder. Thus, the FeCl2 vapor treatment followed by magnetic separation can be utilized for recovering PGMs directly from spent catalysts as an effective pretreatment for the currently used recycling methods.

  14. Competitive platinum-group-metal (PGM) supply from the Eastern Limb, Bushveld Complex: Geological, mining and mineral economic aspects

    CSIR Research Space (South Africa)

    McGill, JE

    2011-08-01

    Full Text Available -GROUP-METAL (PGM) SUPPLY FROM THE EASTERN LIMB, BUSHVELD COMPLEX: GEOLOGICAL, MINING, AND MINERAL ECONOMIC ASPECTS Dr. Jeannette E. McGill & Prof. Murray W. Hitzman ACKNOWLEDGEMENTS ? COUNCIL FOR SCIENTIFIC AND INDUSTRIAL RESEARCH (CSIR) ? Centre for Mining... Innovation ? Office of Graduate Studies, Fogarty Endowment ? Mr. VISHNU PILLAY (EXECUTIVE HEAD: JV?S ? Anglo Platinum) ? ACADEMIC ADVISORS Prof. Murray Hitzman (Economic Geology); Dr. Hugh Miller (Mining Engineering); Prof. Rodderick Eggert (Mineral...

  15. First determination of the levels of platinum group metals in Manta birostris (manta ray) caught along the Ghanaian coastline.

    Science.gov (United States)

    Essumang, D K

    2010-06-01

    Tissues from Manta birostris caught by fishermen from Dixcove in the western part of Ghana were analyzed for their Platinum, palladium and rhodium concentrations (PGM). The use of chondrichthyan fish has permitted the study of trace levels of Platinum group metals (PGMs) which have travelled very far into the sea. The analysis showed that Ghana's coastline is fairly polluted with these platinum group metals (PGMs). PGM concentration in manta ray recorded a range of (0.15-0.85) microg/g for Pt, (0.033-0.67) microg/g for Pd and (0.007-0.145) microg/g for Rh. Comparing these values to the UK dietary intake of 0.2 microg/day for Pt and Rh and 1.0 microg/day for Pd, its indicates that the values obtained from the analysis for Pt was above the required level. This is the first study to show the accumulation of PGM in chondrichthyan fish, although the sources of this pollution are not clear as manta birostris is migratory and therefore need to be investigated further. The presence of the PGM is very significant, since manta ray meat is consumed in Ghana. This may presents a health risk, due to a possible accumulation of PGMs in humans.

  16. Uptake of traffic-related heavy metals and platinum group elements (PGE) by plants

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, J.; Hannker, D.; Eckhardt, J.D.; Stueben, D. [Institute of Petrography and Geochemistry, University of Karlsruhe, Karlsruhe (Germany)

    1998-04-23

    The distribution of the platinum group elements (PGE) caused by traffic emissions from autoexhaust catalysts has been determined in soils and different types of plants. The plants (spinach, cress, phacelia, stinging nettle) were cultivated on different soils collected from areas adjacent to a German highway and on uncontaminated sandy and clayey soils. The main result of the experiments was a measurable transfer of PGE from contaminated soil to plants. Following the definition of Sauerbeck (Beurteilung von Schwermetallkontaminationen im Boden. Frankfurt/Main: Dechema-Fachgespraeche, 1989:281-316), Pt, Rh and Pd transfer coefficients are within the range of immobile to moderately mobile elements, such as Cu. The transfer coefficient decreases from Pd>Pt{>=}Rh. Palladium therefore is the most biologically available of this element group

  17. Novel non-platinum metal catalyst material

    DEFF Research Database (Denmark)

    2014-01-01

    The present invention relates to a novel non-platinum metal catalyst material for use in low temperature fuel cells and electrolysers and to fuel cells and electrolysers comprising the novel non-platinum metal catalyst material. The present invention also relates to a novel method for synthesizing...... the novel non-platinum metal catalyst material....

  18. Contamination from gold and platinum-group metals mining in the Gulf of Darién, Colombia

    Science.gov (United States)

    Vasquez-Bedoya, L.; Palacio Baena, J.

    2013-12-01

    Gulf of Darién, triangular southernmost extension of the Caribbean Sea, bounded by Panama on the southwest and by Colombia on the southeast and east. The Gulf is made up of 17 municipalities in the department of Choco and Antioquia. The Gulf of Darién is a geostrategic region, rich in biodiversity, known for its natural resources of minerals, oil, lumber as well as its water and fertile land. The Darién also acts as the bridge between South America and Central America and has access to the Pacific Ocean and the Caribbean Sea. The economy in the region is based mainly on agribusinesses, tourism and mining activities, mainly the 'mining of gold and platinum-group metals'. In our study we determined the degree of trace element contamination in estuarine sediment samples originated from mining activities and municipal waste water discharges of effluents on the gulf of Darién. . Surface samples were taken from 17 locations through the entire Gulf. Grain size, Corg, Ag, Al, Ca , Cr, Cu, Fe, Mg, Mn, Na, Ni, Pb and Zn concentrations were analyzed, and enrichment factors (EF) as well as geo-accumulation indices (Igeo) were calculated. Concentrations of Pb, Zn, Ni, Cu and Cr show levels that are consistent with those typically found in urbanized marine environments. EF and Igeo values revealed that the Gulf is extremely contaminated with Ag and moderately contaminated with Cr and Zn. The sources of Cr, Ag, Hg and Zn are associated with the development of mining activities in the Atrato River basin. The observed enrichment of Ag may be explained as a residue of the extraction of gold and platinum-group metals.

  19. Lipid solubility of the platinum group metals Pt, Pd and Rh in dependence on the presence of complexing agents

    International Nuclear Information System (INIS)

    Zimmermann, Sonja; Menzel, Christoph M.; Stueben, Doris; Taraschewski, Horst; Sures, Bernd

    2003-01-01

    All complexing agents had a significant influence on octanol solubility of PGM. - Investigations on the bioaccumulation of the platinum group metals (PGM) Pt, Pd and Rh in aquatic organisms are of growing interest in environmental research due to the increasing emission of these metals by motor vehicles with catalytic converters. Until now, nothing is known about the possible influence of complexing agents on the bioaccumulation capacity of these precious metals. According to the partition coefficient between 1-octanol and water (P OW ) as a measure of bioaccumulation, in this study a simple shaking method was performed in order to investigate the effects of different complexing agents (L-methionine, thio urea, EDTA, humic substances, bile compounds) on the octanol solubility of the PGM. The results demonstrated a significant influence of all agents used. L-Methionine and thio urea decreased the lipid solubility. In contrast, the presence of EDTA, humic substances and especially bile caused a higher transfer of metals in the octanol phase. For most complexing agents tested, the transfer of Pd to the lipid phase was significantly higher compared with Rh and Pt, except for bile acid where the highest octanol solubility was found for Pt. Recent experimental results on PGM accumulation in zebra mussels confirm a high bioaccumulation of Pd which could be predicted from the lipid solubility

  20. Lipid solubility of the platinum group metals Pt, Pd and Rh in dependence on the presence of complexing agents

    Energy Technology Data Exchange (ETDEWEB)

    Zimmermann, Sonja; Menzel, Christoph M.; Stueben, Doris; Taraschewski, Horst; Sures, Bernd

    2003-07-01

    All complexing agents had a significant influence on octanol solubility of PGM. - Investigations on the bioaccumulation of the platinum group metals (PGM) Pt, Pd and Rh in aquatic organisms are of growing interest in environmental research due to the increasing emission of these metals by motor vehicles with catalytic converters. Until now, nothing is known about the possible influence of complexing agents on the bioaccumulation capacity of these precious metals. According to the partition coefficient between 1-octanol and water (P{sub OW}) as a measure of bioaccumulation, in this study a simple shaking method was performed in order to investigate the effects of different complexing agents (L-methionine, thio urea, EDTA, humic substances, bile compounds) on the octanol solubility of the PGM. The results demonstrated a significant influence of all agents used. L-Methionine and thio urea decreased the lipid solubility. In contrast, the presence of EDTA, humic substances and especially bile caused a higher transfer of metals in the octanol phase. For most complexing agents tested, the transfer of Pd to the lipid phase was significantly higher compared with Rh and Pt, except for bile acid where the highest octanol solubility was found for Pt. Recent experimental results on PGM accumulation in zebra mussels confirm a high bioaccumulation of Pd which could be predicted from the lipid solubility.

  1. Determination of platinum group metal catalyst residues in active pharmaceutical ingredients by means of total reflection X-ray spectrometry

    International Nuclear Information System (INIS)

    Marguí, Eva; Queralt, Ignasi; Hidalgo, Manuela

    2013-01-01

    The control of metal catalyst residues (i.e., platinum group metals (PGMs)) in different stages of the manufacturing processes of the active pharmaceutical ingredients (APIs) and, especially, in the final product is crucial. For API specimens, there are strict guidelines to limit the levels of metal residues based on their individual levels of safety concern. For PGMs the concentration limit has been established at 10 mg/kg in the API. Therefore great effort is currently being devoted to the development of new and simple procedures to control metals in pharmaceuticals. In the present work, an analytical methodology based on benchtop total reflection X-ray fluorescence spectrometry (TXRF) has been developed for the rapid and simple determination of some PGM catalyst impurities (Rh, Pd, Ir and Pt) in different types of API samples. An evaluation of different sample treatments (dissolution and digestion of the solid pharmaceutical samples) has been carried out and the developed methodologies have been validated according to the analytical parameters to be considered and acceptance criteria for PGM determination according to the United States Pharmacopeia (USP). Limits of quantification obtained for PGM metals were in the range of 2–4 mg/kg which are satisfactory according to current legislation. From the obtained results it is shown that the developed TXRF method can be implemented in the pharmaceutical industries to increase productivity of the laboratory; offering an interesting and complementary analytical tool to other atomic spectroscopic methods. - Highlights: • A TXRF method for PGM catalyst residue determination in API samples is presented. • Analysis can be performed using 10 μL of the internal standardized dissolved API. • The method is rapid, simple and suitable according to the USP requirements

  2. η5 and η6 - cyclic π-perimeter hydrocarbon platinum group metal ...

    Indian Academy of Sciences (India)

    The SMART20 software was used for data acquisition. ... were undertaken with the SAINT20 software. Structures ..... the change in electron density around the metal centre. .... request@ccdc.cam.ac.uk, or by contacting The Cambridge.

  3. Metals in environmental media: A study of trace and platinum group ...

    African Journals Online (AJOL)

    A detailed study has been conducted to determine the contamination of Thohoyandou roadside soils, vegetation, sewage and river waters by Zn, Cu, Cr, Pb, Cd, Fe, Pt and Pd. The study further investigated the correlation between these trace metals in roadside soils and vegetation in order to infer the potential impacts of ...

  4. Platinum Group Metal-free Catalysts for Hydrogen Evolution Reaction in Microbial Electrolysis Cells.

    Science.gov (United States)

    Yuan, Heyang; He, Zhen

    2017-07-01

    Hydrogen gas is a green energy carrier with great environmental benefits. Microbial electrolysis cells (MECs) can convert low-grade organic matter to hydrogen gas with low energy consumption and have gained a growing interest in the past decade. Cathode catalysts for the hydrogen evolution reaction (HER) present a major challenge for the development and future applications of MECs. An ideal cathode catalyst should be catalytically active, simple to synthesize, durable in a complex environment, and cost-effective. A variety of noble-metal free catalysts have been developed and investigated for HER in MECs, including Nickel and its alloys, MoS 2 , carbon-based catalysts and biocatalysts. MECs in turn can serve as a research platform to study the durability of the HER catalysts. This personal account has reviewed, analyzed, and discussed those catalysts with an emphasis on synthesis and modification, system performance and potential for practical applications. It is expected to provide insights into the development of HER catalysts towards MEC applications. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Platinum-group element mineralization

    International Nuclear Information System (INIS)

    Gruenewaldt, G.

    1985-01-01

    The purpose of this investigation is to determine the geological processes responsible for the abnormal enrichment of the platinum-group elements (PGE) in the mineralized layers of the Bushveld Complex. Questions asked are: what processes caused enrichment of the Bushveld magma in the PGE ; by what processes were these PGE concentrated in the mineralized layers ; was contamination of the Bushveld magma from external sources important in the formation of the PGE enriched layers ; what are the effects of fractional crystallization on the PGE ratios

  6. Probing Interaction Between Platinum Group Metal (PGM) and Non-PGM Support Through Surface Characterization and Device Performance

    Science.gov (United States)

    Saha, Shibely

    High cost and limited abundance of Platinum (Pt) have hindered effective commercialization of Proton Exchange Membrane Fuel Cell and Electrolyzer. Efforts have been undertaken to reduce precious group metal (PGM) requirement for these devices without compromising the activity of the catalyst by using transition metal carbides (TMC) as non-PGM support thanks to their similar electronic and geometric structures as Pt. In this work Mo2C was selected as non-PGM support and Pt was used as the PGM of interest. We hypothesize that the hollow nanotube morphology of Mo2C support combined with Pt nano particles deposited on it via atomic layer deposition (ALD) technique would allow increased interaction between them which may increase the activity of Pt and Mo2C as well as maximize the Pt active surface area. Specifically, a rotary ALD equipment was used to grow Pt particles from atomic level to 2--3 nanometers by simply adjusting number of ALD cycles in order to probe the interaction between the deposited Pt nanoparticles and Mo2C nanotube support. Interaction between the Pt and Mo2 C was analyzed via surface characterization and electrochemical characterization. Interaction between Pt and Mo2C arises due to the lattice mismatch between Pt and Mo2C as well as electron migration between them. Lattice spacing analysis using high resolution transmission electron microscopy (HRTEM) images, combined with Pt binding energy shift in XPS results, clearly showed strong bonding between Pt nanoparticles and the Mo2C nanotube support in all the resultant Pt/Mo2C samples. We postulate that this strong interaction is responsible for the significantly enhanced durability observed in our constant potential electrolysis (CPE) and accelerated degradation testing (ADT). Of the three samples from different ALD cycles (15, 50 and 100), Mo2C nanotubes modified by 50 (1.07 wt% Pt loading) and 100 cycles (4.4 wt% Pt) of Pt deposition, showed higher HER and HOR activity per Pt mass than commercial

  7. Induction of heat shock proteins (hsp70) in the zebra mussel (Dreissena polymorpha) following exposure to platinum group metals (platinum, palladium and rhodium): Comparison with lead and cadmium exposures

    Energy Technology Data Exchange (ETDEWEB)

    Singer, Christoph [Zoologisches Institut I-Oekologie, Universitaet Karlsruhe, Geb. 07.01, Kornblumenstrasse 13, D-76131 Karlsruhe (Germany); Zimmermann, Sonja [Zoologisches Institut I-Oekologie, Universitaet Karlsruhe, Geb. 07.01, Kornblumenstrasse 13, D-76131 Karlsruhe (Germany); Sures, Bernd [Zoologisches Institut I-Oekologie, Universitaet Karlsruhe, Geb. 07.01, Kornblumenstrasse 13, D-76131 Karlsruhe (Germany)]. E-mail: dc11@rz.uni-karlsruhe.de

    2005-10-05

    An increasing number of papers concentrate on the availability and uptake of platinum group elements (PGE) by different organisms. These metals are discharged into the environment from different anthropogenic sources, such as automobile catalytic converters, hospitals and other medical institutions. As the effects of these precious metals on organisms remain unclear, the induction of heat shock proteins (hsp70) in zebra mussels (Dreissena polymorpha) following exposure to soluble salts of platinum, palladium and rhodium was compared with the hsp70 induction in mussels following exposure to cadmium and lead. Mussels were sampled weekly during a period of 10 weeks and analyzed for their metal concentration and their hsp70 level. Highest metal uptake was found for Cd, followed by Pt, Pb and Pd. Rh demonstrated the lowest uptake rate. A clear time-dependent increase of hsp70 levels occurred in all exposed mussels. Concentrations of hsp70 started to rise between days 18 and 25, except for the Pt-exposed group, where the initial increase was between days 25 and 32. All groups reached maximal hsp70 concentrations at day 39. Subsequently, hsp70 levels decreased to initial levels for the remaining exposure period. Threshold metal levels for the hsp70 induction varied among the metals and increased in the order: Rh < Pd {<=} Pb < Pt < Cd. Highest hsp70 values were found for mussels exposed to Pd, with a 25-fold higher level than in the controls, followed by Pt- and Rh-exposed mussels, which showed a 19-fold increase. The hsp70 levels of the mussels exposed to Cd and Pb were much lower, showing 6- and 12-fold higher values than the control, respectively. The clear induction of hsp70 due to exposure to Pt, Pd and Rh gives evidence for strong cellular effects of these metals, especially, when compared with lead and cadmium. Among the metals tested, Pd seems to have the highest potential as inducer for hsp70 production due to its low threshold level in combination with the

  8. Induction of heat shock proteins (hsp70) in the zebra mussel (Dreissena polymorpha) following exposure to platinum group metals (platinum, palladium and rhodium): Comparison with lead and cadmium exposures

    International Nuclear Information System (INIS)

    Singer, Christoph; Zimmermann, Sonja; Sures, Bernd

    2005-01-01

    An increasing number of papers concentrate on the availability and uptake of platinum group elements (PGE) by different organisms. These metals are discharged into the environment from different anthropogenic sources, such as automobile catalytic converters, hospitals and other medical institutions. As the effects of these precious metals on organisms remain unclear, the induction of heat shock proteins (hsp70) in zebra mussels (Dreissena polymorpha) following exposure to soluble salts of platinum, palladium and rhodium was compared with the hsp70 induction in mussels following exposure to cadmium and lead. Mussels were sampled weekly during a period of 10 weeks and analyzed for their metal concentration and their hsp70 level. Highest metal uptake was found for Cd, followed by Pt, Pb and Pd. Rh demonstrated the lowest uptake rate. A clear time-dependent increase of hsp70 levels occurred in all exposed mussels. Concentrations of hsp70 started to rise between days 18 and 25, except for the Pt-exposed group, where the initial increase was between days 25 and 32. All groups reached maximal hsp70 concentrations at day 39. Subsequently, hsp70 levels decreased to initial levels for the remaining exposure period. Threshold metal levels for the hsp70 induction varied among the metals and increased in the order: Rh < Pd ≤ Pb < Pt < Cd. Highest hsp70 values were found for mussels exposed to Pd, with a 25-fold higher level than in the controls, followed by Pt- and Rh-exposed mussels, which showed a 19-fold increase. The hsp70 levels of the mussels exposed to Cd and Pb were much lower, showing 6- and 12-fold higher values than the control, respectively. The clear induction of hsp70 due to exposure to Pt, Pd and Rh gives evidence for strong cellular effects of these metals, especially, when compared with lead and cadmium. Among the metals tested, Pd seems to have the highest potential as inducer for hsp70 production due to its low threshold level in combination with the

  9. Biological role in the transformation of platinum-group mineral grains

    Science.gov (United States)

    Reith, Frank; Zammit, Carla M.; Shar, Sahar S.; Etschmann, Barbara; Bottrill, Ralph; Southam, Gordon; Ta, Christine; Kilburn, Matthew; Oberthür, Thomas; Ball, Andrew S.; Brugger, Joël

    2016-04-01

    Platinum-group elements are strategically important metals. Finding new deposits is becoming increasingly difficult owing to our limited understanding of the processes that affect their mobility in surface environments. Microorganisms have been shown to promote the mobility of metals around ore deposits. Here we show that microorganisms influence the mobility of platinum-group elements in mineral grains collected from Brazil, Australia and Colombia. Scanning electron microscopy showed biofilms covering the platinum-group mineral grains. The biofilms contained abundant platinum-group element nanoparticles and microcrystalline aggregates, and were dominated by Proteobacteria, many of which were closely related to known metal-resistant species. Some platinum-group mineral grains contained carbon, nitrogen, sulfur, selenium and iodine, suggesting the grains may be biogenic in origin. Molecular analyses show that Brazilian platinum-palladium grains hosted specific bacterial communities, which were different in composition from communities associated with gold grains, or communities in surrounding soils and sediments. Nano-phase metallic platinum accumulated when a metallophillic bacterium was incubated with a percolating platinum-containing medium, suggesting that biofilms can cause the precipitation of mobile platinum complexes. We conclude that biofilms are capable of forming or transforming platinum-group mineral grains, and may play an important role for platinum-group element dispersion and re-concentration in surface environments.

  10. Universal dependence of hydrogen oxidation and evolution reaction activity of platinum-group metals on pH and hydrogen binding energy.

    Science.gov (United States)

    Zheng, Jie; Sheng, Wenchao; Zhuang, Zhongbin; Xu, Bingjun; Yan, Yushan

    2016-03-01

    Understanding how pH affects the activity of hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) is key to developing active, stable, and affordable HOR/HER catalysts for hydroxide exchange membrane fuel cells and electrolyzers. A common linear correlation between hydrogen binding energy (HBE) and pH is observed for four supported platinum-group metal catalysts (Pt/C, Ir/C, Pd/C, and Rh/C) over a broad pH range (0 to 13), suggesting that the pH dependence of HBE is metal-independent. A universal correlation between exchange current density and HBE is also observed on the four metals, indicating that they may share the same elementary steps and rate-determining steps and that the HBE is the dominant descriptor for HOR/HER activities. The onset potential of CO stripping on the four metals decreases with pH, indicating a stronger OH adsorption, which provides evidence against the promoting effect of adsorbed OH on HOR/HER.

  11. Levels of Platinum Group Metals in Selected Species (Sarotherodon melanotheron, Chonophorus lateristriga, Macrobrachium vollenhovenii and Crassostrea tulipa in Some Estuaries and Lagoons Along the Coast of Ghana

    Directory of Open Access Journals (Sweden)

    D. K. Essumang

    2010-01-01

    Full Text Available The use of some biota as bioindicators of heavy metal pollution has been demonstrated as particularly adequate due to their capacity of bioconcentration. This study evaluated the levels of platinum group metals (PGMs in some selected species along the coastal belt of Ghana, using the neutron activation analysis (NAA method. The result was processed to evaluate pollution indices in order to map the distribution of the metals in those species in the lagoons and estuaries along the costal belt of Ghana. The analysis showed significant levels of all PGMs in blackchin tilapia (Sarotherodon melanotheron Cichlidae, brown goby (Chonophorus lateristriga Gobiidae, shrimp (Macrobrachium vollenhovenii Palaemonidae, and mangrove oysters (Crassostrea tulipa Ostreidae in the lagoons and river Pra estuary. However, the oysters showed an elevated mean concentration of 0.13 μ/g (dry weight Pd. From the pollution indices, most of the sampling sites registered mean contamination factor (CF values between 1.20 and 3.00 for Pt, Pd, and Rh. The pollution load index (PLI conducted also gave an average pollution index between 0.79 and 2.37, indicating progressive contamination levels. The results revealed that anthropogenic sources, industrial and hospital effluent, etc., together with vehicular emissions, could be the contributing factors to the deposition of PGMs along the Ghanaian coast.

  12. Recovery of platinum-group metals (PGMS from spent automotive catalysts: Part II: Automotive catalysts: Structures and principle of operation

    Directory of Open Access Journals (Sweden)

    Dimitrijević Mile D.

    2015-01-01

    Full Text Available Catalytic converters are incorporated into motor vehicle emission systems (passenger cars, trucks and other motor vehicles, as well as civil and agricultural machines, as of lately to reduce air pollution as well as to meet the emission standards. Their purpose is to convert toxic emissions generated by combustion of liquid fossil fuels into less harmful products. In catalytic converters, rhodium is used for the reduction of gasses, whereas platinum and palladium are used for the oxidation of gasses. This paper presents the structure and operating principle of automotive catalysts in view of the fact that cars are the most prevalent motor vehicles worldwide and due to the fact that the production of cars with gasoline and diesel engines will dominate until at least 2020.

  13. Power generation in microbial fuel cells using platinum group metal-free cathode catalyst: Effect of the catalyst loading on performance and costs.

    Science.gov (United States)

    Santoro, Carlo; Kodali, Mounika; Herrera, Sergio; Serov, Alexey; Ieropoulos, Ioannis; Atanassov, Plamen

    2018-02-28

    Platinum group metal-free (PGM-free) catalyst with different loadings was investigated in air breathing electrodes microbial fuel cells (MFCs). Firstly, the electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalyst was investigated by rotating ring disk electrode (RRDE) setup with different catalyst loadings. The results showed that higher loading led to an increased in the half wave potential and the limiting current and to a further decrease in the peroxide production. The electrons transferred also slightly increased with the catalyst loading up to the value of ≈3.75. This variation probably indicates that the catalyst investigated follow a 2x2e - transfer mechanism. The catalyst was integrated within activated carbon pellet-like air-breathing cathode in eight different loadings varying between 0.1 mgcm -2 and 10 mgcm -2 . Performance were enhanced gradually with the increase in catalyst content. Power densities varied between 90 ± 9 μWcm -2 and 262 ± 4 μWcm -2 with catalyst loading of 0.1 mgcm -2 and 10 mgcm -2 respectively. Cost assessments related to the catalyst performance are presented. An increase in catalyst utilization led to an increase in power generated with a substantial increase in the whole costs. Also a decrease in performance due to cathode/catalyst deterioration over time led to a further increase in the costs.

  14. Catalytic transformations of fatty acids derivatives for food, oleochemicals and fuels over carbon supported platinum group metals

    Energy Technology Data Exchange (ETDEWEB)

    Simakova, I.

    2010-07-01

    prominent in linoleic acid deoxygenation giving only 3 % conversion of fatty acids in 330 min. The deactivation originated from the formation of C17 aromatic compounds and fatty acid dimers via Diels-Alder reaction. Thus hydrogenation of unsaturated fatty acids can be considered as preliminary chemical modification step in the green diesel production. In this work particular care was taken to strengthen the nano level understanding of the Pd role, in particular metal size effect, in the catalytic hydrogenation and deoxygenation. Pd/C catalysts were synthesized with the same Pd loading and systematically varied metal dispersion via the controllable formation of Pd particles over carbon support surface. The effect of metal dispersion on hydrogenation rate and trans/cis ratio was revealed. An optimum metal dispersion giving the highest decarboxylation reaction rate was observed. In addition to the particle size effect, the impact of mass transfer was elucidated and detail discussions on temperature programmed desorption of CO from the fresh and spent samples was provided. Hydrogenation of vegetable feedstocks was performed in batch and continuous modes, using powdered and granulated Pd/C catalysts correspondingly. One of the main focuses of the work was put on the scale-up of the hydrogenation process. There are several challenges attributed to the scale-up of a chemical process which have to be recognized before progressing to an industrial application. In terms of the high production volumes the logical step is to investigate the performance of hydrogenation as a continuous process. A laboratory study in a continuous fixed bed reactor was performed, giving crucial information about the catalyst long-term stability and catalyst deactivation. Furthermore, the impact of using free fatty acids or triglycerides feedstocks as well as the effect of catalyst particle size and Pd loading were investigated in continuous mode. Finally, the production capacities for different operation

  15. Invited: Tailoring Platinum Group Metals Towards Optimal Activity for Oxygen Electroreduction to H2o and H2O2: From Extended Surfaces to Nanoparticles

    DEFF Research Database (Denmark)

    Stephens, Ifan

    2014-01-01

    ). The figure shows transmission electron miscroscopy images of 9 nm diameter PtxY nanoparticles, based on high angle annular dark field –scanning transmission electron microscopy (left) and Y, Pt and combined Pt+Y X-ray energy dispersive X-ray spectroscopy elemental maps. (a) as-prepared catalyst and (b) after......The slow kinetics of the 4-electron reduction of oxygen to H2O imposes a bottleneck against the widespread uptake of low temperature fuel cells in automotive vehicles. High loadings of platinum are required to drive the reaction; the limited supply of this precious metal limits the extent to which...... fuel cell technology could be scaled up.(1) The most widely used strategy towards decreasing the Pt loading is to alloy Pt with other late transition metals, in particular Ni or Co. (2-5) However, when tested in a fuel cell, these alloys are often susceptible towards degradation via dealloying.(6, 7...

  16. Thiosemicarbazone complexes of the platinum metals. A story of ...

    Indian Academy of Sciences (India)

    Unknown

    Thiosemicarbazone complexes; platinum metals; variable coordination; ... carbonylic carbon via one or two intervening atoms, D,N,S tricoordination usually takes .... modelling studies show that in this coordination mode, the phenyl ring of the.

  17. Electrodeposition of platinum metals and alloys from chloride melts

    Directory of Open Access Journals (Sweden)

    Saltykova N.A.

    2003-01-01

    Full Text Available The structure of platinum metals and their alloys deposited by the electrolysis of chloride melts have been investigated. The cathodic deposits were both in the form of compact layers and dendrites. All the alloys of platinum metals obtained are solid solutions in the whole range of composition. Depending on the experimental conditions the layers had columnar, stratum and spiral (dissipative structures. The stratum and dissipative structures were observed in the case of alloys only.

  18. Nuclear analytical methods for platinum group elements

    International Nuclear Information System (INIS)

    2005-04-01

    Platinum group elements (PGE) are of special interest for analytical research due to their economic importance like chemical peculiarities as catalysts, medical applications as anticancer drugs, and possible environmental detrimental impact as exhaust from automobile catalyzers. Natural levels of PGE are so low in concentration that most of the current analytical techniques approach their limit of detection capacity. In addition, Ru, Rh, Pd, Re, Os, Ir, and Pt analyses still constitute a challenge in accuracy and precision of quantification in natural matrices. Nuclear analytical techniques, such as neutron activation analysis, X ray fluorescence, or proton-induced X ray emission (PIXE), which are generally considered as reference methods for many analytical problems, are useful as well. However, due to methodological restrictions, they can, in most cases, only be applied after pre-concentration and under special irradiation conditions. This report was prepared following a coordinated research project and a consultants meeting addressing the subject from different viewpoints. The experts involved suggested to discuss the issue according to the (1) application, hence, the concentration levels encountered, and (2) method applied for analysis. Each of the different fields of application needs special consideration for sample preparation, PGE pre-concentration, and determination. Additionally, each analytical method requires special attention regarding the sensitivity and sample type. Quality assurance/quality control aspects are considered towards the end of the report. It is intended to provide the reader of this publication with state-of-the-art information on the various aspects of PGE analysis and to advise which technique might be most suitable for a particular analytical problem related to platinum group elements. In particular, many case studies described in detail from the authors' laboratory experience might help to decide which way to go. As in many cases

  19. Platinum-group elements in the Eastern Deccan volcanic province ...

    Indian Academy of Sciences (India)

    This study is the first detailed investigation of the platinum-group elements (PGE) at the eastern mar- ... A Zr vs. Pd scattergram found a strong positive correlation for these two elements ..... and the PGE and Au collected by co-precipitation.

  20. A survey of the determination of the platinum group elements.

    Science.gov (United States)

    Kallmann, S

    1987-08-01

    The platinum-group metals (PGMs), Ru, Rh, Pd, Os, Ir and Pt, are widely used as catalysts in petroleum and chemical processes. They find wide applications in automotive exhaust-gas control converters and are of immense importance to the electronics industry. They are found in many items of jewellery and serve to an increasing extent as a form of investment. The PGMs are extracted in minute quantities from a limited number of ores, found mainly in S. Africa and the USSR. They are concentrated and separated from each other by elaborate chemical processes. Because of their great intrinsic value (Pt $650 per oz; Rh $1400 per oz), the recycling of the PGMs from literally hundreds of different forms of scrap is an essential factor in the overall management of the PGM economy. In this survey emphasis is placed on the need to tailor the analytical method according to (a) the environment in which the PGMs occur, (b) the individual PGM concentrations, and (c) the desired sensitivity and precision. The factors which determine the choice of chemical, physicochemical and/or instrumental approaches are discussed. They are further commented on in extensive presentations of dissolution and separation techniques and methods for the final measurement of individual PGMs. Appendices are provided which present the compositions and sources of the products most frequently encountered in PGM analysis, along with information on methods of decomposition, separations required, type of separation, and final determination.

  1. Platinum redispersion on metal oxides in low temperature fuel cells

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Cerri, Isotta; Nagami, Tetsuo

    2013-01-01

    We have analyzed the aptitude of several metal oxide supports (TiO2, SnO2, NbO2, ZrO2, SiO2, Ta2O5 and Nb2O5) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in ...

  2. Platinum redispersion on metal oxides in low temperature fuel cells.

    Science.gov (United States)

    Tripković, Vladimir; Cerri, Isotta; Nagami, Tetsuo; Bligaard, Thomas; Rossmeisl, Jan

    2013-03-07

    We have analyzed the aptitude of several metal oxide supports (TiO(2), SnO(2), NbO(2), ZrO(2), SiO(2), Ta(2)O(5) and Nb(2)O(5)) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in detail; however, due to different operating conditions it is not straightforward to link the chemical and the electrochemical environment. The largest differences reflect in (1) the oxidation state of the surface (the oxygen species coverage), (2) temperature and (3) the possibility of platinum dissolution at high potentials and the interference of redispersion with normal working potential of the PEMFC cathode. We have calculated the PtO(x) (x = 0, 1, 2) adsorption energies on different metal oxides' surface terminations as well as inside the metal oxides' bulk, and we have concluded that NbO(2) might be a good support for platinum redispersion at PEMFC cathodes.

  3. Accumulation of platinum group elements by the marine gastropod Littorina littorea

    Energy Technology Data Exchange (ETDEWEB)

    Mulholland, Rachel [School of Geography, Earth and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Turner, Andrew, E-mail: aturner@plymouth.ac.uk [School of Geography, Earth and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)

    2011-04-15

    The accumulation and trophic transfer of the platinum group elements (PGE): Rh, Pd and Pt; have been studied in short-term (5 day) exposures conducted in aquaria containing the marine macroalga, Ulva lactuca, and/or the grazing mollusc, Littorina littorea. Metals added to sea water (to concentrations of 20 {mu}g L{sup -1}) were taken up by U. lactuca in the order Rh, Pt > Pd and by L. littorea in the order Pd {>=} Pt {>=} Rh, with greatest metal accumulation in the latter generally occurring in the visceral complex and kidney. When fed contaminated alga, accumulation of Rh and Pd by L. littorea, relative to total available metal, increased by an order of magnitude, while accumulation of Pt was not readily detected. We conclude that the diet is the most important vector for accumulation of Rh and Pd, while accumulation of Pt appears to proceed mainly from the aqueous phase. - Research highlights: > Platinum group elements are accumulated by, Littorina littorea. > The aqueous phase and diet are important vehicles for Rh and Pd accumulation by the snail. > Grazing molluscs may serve as biomonitors of coastal PGE contamination. - Platinum group elements are accumulated by the marine snail, Littorina littorea, from both the aqueous phase and the diet.

  4. Multi-elemental characterization of tunnel and road dusts in Houston, Texas using dynamic reaction cell-quadrupole-inductively coupled plasma–mass spectrometry: Evidence for the release of platinum group and anthropogenic metals from motor vehicles

    International Nuclear Information System (INIS)

    Spada, Nicholas; Bozlaker, Ayse; Chellam, Shankararaman

    2012-01-01

    Highlights: ► Analytical method for PGEs, main group, transition and rare earth metals developed. ► Comprehensive characterization of road and tunnel dust samples was accomplished. ► PGEs in dusts arise from autocatalyst attrition. ► Mobile sources also contributed to Cu, Zn, Ga, As, Mo, Cd, Sn, Sb, Ba, W and Pb. ► All other elements, including rare earths arose from crustal sources. - Abstract: Platinum group elements (PGEs) including Rh, Pd, and Pt are important tracers for vehicular emissions, though their measurement is often challenging and difficult to replicate in environmental campaigns. These challenges arise from sample preparation steps required for PGE quantitation, which often cause severe isobaric interferences and spectral overlaps from polyatomic species of other anthropogenically emitted metals. Consequently, most previous road dust studies have either only quantified PGEs or included a small number of anthropogenic elements. Therefore a novel analytical method was developed to simultaneously measure PGEs, lanthanoids, transition and main group elements to comprehensively characterize the elemental composition of urban road and tunnel dusts. Dust samples collected from the vicinity of high-traffic roadways and a busy underwater tunnel restricted to single-axle (predominantly gasoline-driven) vehicles in Houston, TX were analyzed for 45 metals with the newly developed method using dynamic reaction cell-quadrupole-inductively coupled plasma–mass spectrometry (DRC-q-ICP–MS). Average Rh, Pd and Pt concentrations were 152 ± 52, 770 ± 208 and 529 ± 130 ng g −1 respectively in tunnel dusts while they varied between 6 and 8 ng g −1 , 10 and 88 ng g −1 and 35 and 131 ng g −1 in surface road dusts. Elemental ratios and enrichment factors demonstrated that PGEs in dusts originated from autocatalyst attrition/abrasion. Strong evidence is also presented for mobile source emissions of Cu, Zn, Ga, As, Mo, Cd, Sn, Sb, Ba, W and Pb. However

  5. Amperometric and coulometric methods of platinum metal determination. (Review)

    International Nuclear Information System (INIS)

    Ezerskaya, N.A.

    1981-01-01

    Reviewed are works published in the period from 1957-1979, on amperometric and coulometric (potentiostatistic and amperostatistic variant) determination of platinum metals, Ru in particular. During amperometric titration of Ru the following titrantes are used: hydroquinone, thioxne thiourea, Na 2 S 2 O 3 . It is proposed to titrate Ru in the form of ruthenate-ion with hydrazine sulphate in alkal: medium according to the current of reagent oxidation. During coulometric determination of Ru the electrogenerating titrant TiCl 3 or Ti 2 (SO 4 ) 3 (for initial form of Ru [RuCl 6 ] 2- ) is used [ru

  6. Separation of platinum metals by theirs extraction as sulfides

    International Nuclear Information System (INIS)

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

    1978-01-01

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

  7. Same-Side Platinum Electrodes for Metal Assisted Etching of Porous Silicon

    Science.gov (United States)

    2015-11-01

    Platinum Electrodes for Metal Assisted Etching of Porous Silicon by Matthew H Ervin and Brian Isaacson Sensors and Electron Devices Directorate...SUBTITLE Same-Side Platinum Electrodes for Metal Assisted Etching of Porous Silicon 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT

  8. Platinum-Group Elements in Soils and Street Dust of the Southeastern Administrative District of Moscow

    Science.gov (United States)

    Ladonin, D. V.

    2018-03-01

    The contents of five platinum-group metals (Ru, Rh, Pd, Ir, and Pt) in soils and street dust of the Southeastern administrative district (SEAD) of Moscow have been determined. The contents of these elements in soils may considerably exceed their natural abundances in the lithosphere and are characterized by considerable variability and asymmetric frequency distribution. A close correlation between Rh, Pd, and Pt contents in soils and street dust has been shown. The data on the contents of the elements and the ratios between them suggest that motor vehicles are the major source of pollution of soils and street dust in the studied district.

  9. Segregation of the elements of the platinum group in a simulated high-level waste glass

    International Nuclear Information System (INIS)

    Mitamura, H.; Banba, T.; Kamizono, H.; Kiriyama, Y.; Kumata, M.; Murakami, T.; Tashiro, S.

    1983-01-01

    Segregation of the elements of the platinum group occurred during vitrification of the borosilicate glass containing 20 wt% simulated high-level waste oxides. The segregated materials were composed of two crystalline phases: one was the solid solution of ruthenium and rhodium dioxides and the other was that of palladium and rhodium metals also with tellurium. The segregated materials were not distributed homogeneously throughout the glass: (i) on the surface of the glass, there occurred palladium, rhodium and tellurium alloy alone; and (ii) at the inner part of the glass, the agglomerates of the two phases were concentrated in one part and dispersed in the other

  10. Metal Oxide-Supported Platinum Overlayers as Proton-Exchange Membrane Fuel Cell Cathodes

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Abild-Pedersen, Frank; Studt, Felix

    2012-01-01

    We investigated the activity and stability of n=(1, 2, 3) platinum layers supported on a number of rutile metal oxides (MO2; M=Ti, Sn, Ta, Nb, Hf and Zr). A suitable oxide support can alleviate the problem of carbon corrosion and platinum dissolution in Pt/C catalysts. Moreover, it can increase t...

  11. Concentration and measuring Platinum Group Elements (PGE) Transfer Factor in soil and vegetations

    International Nuclear Information System (INIS)

    Adibah Sakinah Oyub

    2012-01-01

    This study was conducted to determine the concentration and to measure platinum group elements (PGE) transfer factor in environmental samples of roadside soil and vegetation. The use of vehicle catalytic converter has released platinum group elements (PGE) and other gases into the environment. Thus, roadside soil and plants were exposed to this element and has become the medium for the movement of this elements. Samples of roadside soil and vegetation were taken at various locations in UKM Bangi Toll and the concentration of platinum group elements (PGE) is determined using mass spectrometry-inductively coupled plasma (ICP-MS). Overall, the concentrations of platinum group elements (PGE), which is the element platinum (Pt) in soil was 0.016 ± 0.036 μgg -1 . While the concentration of the elements palladium (Pd) was 0.079 ± 0.019 μgg -1 and element rhodium (Rh) is at a concentration of 0.013 ± 0.020 μgg -1 . Overall, the transfer factor for the element platinum (Pt) is 1. While the transfer factor of the element palladium (Pd) is 0.96 and the element rhodium (Rh) is 1.11. In conclusion, the concentration of platinum group elements (PGE) in soils have increased. (author)

  12. Study of sorption of platinum metals, gold and silver by phosphonium hydroxide antonite

    International Nuclear Information System (INIS)

    Khudaybergenov, U.; Tajibaev, D.; Yuldasheva, K.T.

    2002-01-01

    The aim of the work was to study and to use a phosphonium hydroxide anionite for concentrating of trace amounts of platinum metals, gold and silver from the mixed solutions composed of copper, nickel, cobalt, iron and zinc. The experiments were done using radionuclides of determined and interfered elements. Conditions for sorption concentrating of the noble metals by phosphonium hydroxide were determined by the selectivity of the phosphonium hydroxide to the noble metals from acid solutions. A noble metal sorption degree was observed from the experiments to be rather high at the acid concentration level of 0.1-0.5 M. At higher than 0.5 M acid concentration sorption activity decreased. With increase of chlorine acid-concentration sorption of palladium was observed to considerably decrease, while iridium sorption was increased. The latter fact can be caused by lowering of hydration of iridium ions. A considerable decrease of capability of the noble metal sorption from nitric acid solutions was observed. It is possible that HNO 3 anions are strongly bound with the anionite functional group. Thus, nitric acid reduces sorption of the noble metals in the following order: Ir>Ru>Pd>Pt>Os, and it does not have effect on the sorption activity of Au and Ag. Increase of H 2 SO 4 concentration in the solution has slightly reduced noble metal sorption activity. Copper, nickel, iron and other metals accompanying the noble metals, at concentration ratio of 1:1000 have resulted in decrease of sorption activity of the noble metals, although sorption of iridium was increased in the presence of copper, silver and nickel. We suggest that copper, silver and nickel have formed the complex functional compounds, which can probably undergo an anion exchange

  13. Toxicity of platinum, palladium and rhodium to Daphnia magna in single and binary metal exposure experiments.

    Science.gov (United States)

    Zimmermann, Sonja; Wolff, Carolina; Sures, Bernd

    2017-05-01

    Mainly due to automobile traffic, but also due to other sources, the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) are introduced into aquatic biotopes where they accumulate in sediments of lakes and rivers. However, the toxicity of these noble metals to aquatic organisms is not well understood and especially toxicity studies under standardized condition are lacking. Thus, the toxicity of Pt, Pd and Rh to Daphnia magna was tested in single metal exposure experiments according to OECD guideline 202. Immobility and lethality was recorded after 24 h and 48 h of exposure and EC 50 and LC 50 , respectively, were determined. As the nominal exposure concentration of Pd differed significantly from the quantified concentration, the control of the real exposure concentration by chemical analysis is mandatory, especially for Pd. The toxicity decreased in the order Pd > Pt ≫ Rh with e.g. LC 50 (48 h) values of 14 μg/L for Pd, 157 μg/L for Pt and 56,800 μg/L for Rh. The exposure period had a clear effect on the toxicity of Pt, Pd and Rh. For Pt and Rh the endpoint immobility was more sensitive than the endpoint lethality whereas Pd toxicity was similar for both endpoints. The Hill slopes, which are a measure for the steepness of the concentration-response curves, showed no significant discrepancies between the different metals. The binary metal exposure to Pt and Pd revealed a more-than-additive, i.e. a synergistic toxicity using the toxic unit approach. The present study is a start to understand the toxicity of interacting PGE. The modes of action behind the synergistic effect are unclear. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Factors Governing concentration of platinum group elements in layered complexes

    DEFF Research Database (Denmark)

    Makovicky, E.; Rose-Hansen, J.; Karup-Møller, Sven

    1996-01-01

    This report covers the synthetic research results obtained by the Danish group on: (1) The phase system Fe-Ir-S at 1100o, 1000o and 800oC, (2) Metal-rich portions of the phase system Pt-Ir-Fe-S: Pt-Fe-Ir alloys and associated sulfides at 1000oC and 1100oC, (3) The Fe (Cu)-Pt-Rh-S system: alloys...

  15. Platinum group elements in the environment: emissions and exposure.

    Science.gov (United States)

    Dubiella-Jackowska, Aleksandra; Polkowska, Zaneta; Namieńnik, Jacek

    2009-01-01

    PGEs (Pt, Pd, Ru, Ir, and Os) are a relatively new group of anthropogenic pollutants. Specific useful properties of these metals (high resistance to chemical corrosion over a wide range of temperatures, high melting point, high mechanical resistance, and high plasticity) have fomented rapid growth of new and existing applications in various economic and industrial sectors. These metals are not only used in the chemical, petrochemical, electrical, and electronics industries but also PGE use, in various industries, has dramatically increased emissions of these metals to the environment; emissions from vehicle catalytic converters and hospital wastewater discharges are particularly significant. The environmental benefits of using PGEs in vehicle catalytic converters are clear. These metals catalyze the conversion of toxic constituents of exhaust fumes (CO, HCs, NOxs) to water, CO2, and molecular nitrogen. As a result of adverse physico-chemical and mechanical influences on the catalyst surface, PGEs are released from this layer and are emitted into the environment in exhaust fumes. Research results indicate that the levels of such emissions are rather low (ng km(-1)). However, recent data show that certain chemical forms of PGEs emitted from vehicles are, or may be, bioavailable. Hence, the potential for PGEs to bioaccumulate in different environmental compartments should be studied, and, if necessary, addressed. The use of Pt in anticancerous drug preparations also contributes to environmental burdens. Pt, when administered as a drug, is excreted in a patient's urine and, as a consequence, has been observed in hospital and communal wastewater discharges. Few studies have been published that address bioavailability, mode of penetration into live organisms, or environmental fate of PGEs. The toxic effect of these metals on living organisms, including humans, is still in dispute and incompletely elucidated. Contrary to some chlorine complexes of Pt, which most

  16. Column liquid chromatography applied to concentrating, separating, and determining platinum metals

    International Nuclear Information System (INIS)

    Alimarin, I.P.; Basova, E.M.; Bol'shova, T.A.; Ivanov, V.M.

    1986-01-01

    The present survey deals with high-performance liquid chromatography (HPLC) in relation to the chromatographic behavior of the platinum metals, including separation and determination. The data shows that HPLC is the most promising and effective method of separating metals, including platinum ones. The method provides efficient separation of microgram amoounts of mixtures with a resolving power 3-20 times that of thin-layer chromatography. It is shown that the most promising line of advance in HPLC for inorganic systems lies in the separation and determination of metals as chelates by absorption or ion-pair chromatography. Examples of using HPLC for determining noble metals in particular cases indicate that the metrological characteristics are favorable

  17. Accumulation and distribution characteristics of platinum group elements in roadside dusts in Beijing, China.

    Science.gov (United States)

    Gao, Bo; Yu, Yanke; Zhou, Huaidong; Lu, Jin

    2012-06-01

    The concentrations, distribution, and accumulation of platinum group elements (PGEs) were investigated in roadside dusts collected in four different foundational areas in Beijing during February to May 2010. The results showed that PGE levels in all samples were above the average upper crust values, with mean concentrations of 57.5 ng · g(-1) Pd, 28.2 ng · g(-1) Pt, and 9.8 ng · g(-1) Rh, respectively. Palladium concentration has increased rapidly in recent years. The rank of PGE levels in four different functional regions for roadside dusts was: heavy density traffic area > residential area > educational area > tourism area. Palladium, Pt, and Rh concentrations in dusts showed strong positive correlations, indicating a common traffic-related source of these metals. Meanwhile, PGEs in these samples were not correlated with other traffic-related metals except for Cr. The average PGE ratios of road dusts from Beijing were consistent with those in Germany and Western Australia, but lower than those in the United States and Mexico, indicating that various catalyst productions were used in different countries. In addition, grain-size partitioning of PGEs in dusts indicated that concentrations of PGEs differed from one particle size to another. The coarse fraction had higher PGE concentrations than the fine fraction in roadside dusts. These results showed that autocatalyst PGE contamination estimates in the environment would be significantly underestimated if only a fine-grain size fraction (<0.063 mm) is analyzed. Copyright © 2012 SETAC.

  18. High salinity volatile phases in magmatic Ni-Cu-platinum group element deposits

    Science.gov (United States)

    Hanley, J. J.; Mungall, J. E.

    2004-12-01

    The role of "deuteric" fluids (exsolved magmatic volatile phases) in the development of Ni-Cu-PGE (platinum group element) deposits in mafic-ultramafic igneous systems is poorly understood. Although considerable field evidence demonstrates unambiguously that fluids modified most large primary Ni-Cu-PGE concentrations, models which hypothesize that fluids alone were largely responsible for the economic concentration of the base and precious metals are not widely accepted. Determination of the trace element composition of magmatic volatile phases in such ore-forming systems can offer considerable insight into the origin of potentially mineralizing fluids in such igneous environments. Laser ablation ICP-MS microanalysis allows researchers to confirm the original metal budget of magmatic volatile phases and quantify the behavior of trace ore metals in the fluid phase in the absence of well-constrained theoretical or experimental predictions of ore metal solubility. In this study, we present new evidence from major deposits (Sudbury, Ontario, Canada; Stillwater Complex, Montana, U.S.A.) that compositionally distinct magmatic brines and halide melt phases were exsolved from crystallizing residual silicate melt and trapped within high-T fluid conduits now comprised of evolved rock compositions (albite-quartz graphic granite, orthoclase-quartz granophyre). Petrographic evidence demonstrates that brines and halide melts coexisted with immiscible carbonic phases at the time of entrapment (light aliphatic hydrocarbons, CO2). Brine and halide melt inclusions are rich in Na, Fe, Mn, K, Pb, Zn, Ba, Sr, Al and Cl, and homogenize by either halite dissolution at high T ( ˜450-700° C) or by melting of the salt phase (700-800° C). LA-ICPMS analyses of single inclusions demonstrate that high salinity volatile phases contained abundant base metals (Cu, Fe, Sn, Bi) and precious metals (Pt, Pd, Au, Ag) at the time of entrapment. Notably, precious metal concentrations in the inclusions

  19. Outstanding low temperature HC-SCR of NOx over platinum-group catalysts supported on mesoporous materials expecting diesel-auto emission regulation

    International Nuclear Information System (INIS)

    Komatsu, Tamikuni; Tomokuni, Keizou; Yamada, Issaku

    2006-01-01

    Outstanding low temperature HC-SCR of NOx over platinum-group catalysts supported on mesoporous materials, which does not rely on the conventional NOx-absorption-reduction-catalysts, is presented for the purpose of de-NOx of diesel-auto emissions. The established catalysts basically consist of mesoporous silica or metal-substituted mesoporous silicates for supports and platinum for active species, which is operated under lean- and rich-conditions. The new catalysts are very active at 150-200 o C and free from difficult problems of SOx-deactivation and hydrothermal ageing of the NOx-absorption-reduction catalyst. (author)

  20. Silica Supported Platinum Catalysts for Total Oxidation of the Polyaromatic Hydrocarbon Naphthalene: An Investigation of Metal Loading and Calcination Temperature

    Directory of Open Access Journals (Sweden)

    David R. Sellick

    2015-04-01

    Full Text Available A range of catalysts comprising of platinum supported on silica, prepared by an impregnation method, have been studied for the total oxidation of naphthalene, which is a representative Polycyclic Aromatic Hydrocarbon. The influence of platinum loading and calcination temperature on oxidation activity was evaluated. Increasing the platinum loading up to 2.5 wt.% increased the catalyst activity, whilst a 5.0 wt.% catalyst was slightly less active. The catalyst containing the optimum 2.5 wt.% loading was most active after calcination in air at 550 °C. Characterisation by carbon monoxide chemisorption and X-ray photoelectron spectroscopy showed that low platinum dispersion to form large platinum particles, in combination with platinum in metallic and oxidised states was important for high catalyst activity. Catalyst performance improved after initial use in repeat cycles, whilst there was slight deactivation after prolonged time-on-stream.

  1. Alkali metals and group IIA metals

    International Nuclear Information System (INIS)

    Fenton, D.E.

    1987-01-01

    This chapter on the coordination complexes of the alkali metals of group IIA starts with a historical perspective of their chemistry, from simple monodentate ligands, metal-β-diketonates to the macrocyclic polyethers which act as ligands to the alkali and akaline earth metals. Other macrocyclic ligands include quarterenes, calixarenes, porphyrins, phthalocyanines and chlorophylls. A section on the naturally occurring ionophores and carboxylic ionophores is included. (UK)

  2. Gibbs Free Energy of Formation for Selected Platinum Group Minerals (PGM

    Directory of Open Access Journals (Sweden)

    Spiros Olivotos

    2016-01-01

    Full Text Available Thermodynamic data for platinum group (Os, Ir, Ru, Rh, Pd and Pt minerals are very limited. The present study is focused on the calculation of the Gibbs free energy of formation (ΔfG° for selected PGM occurring in layered intrusions and ophiolite complexes worldwide, applying available experimental data on their constituent elements at their standard state (ΔG = G(species − ΔG(elements, using the computer program HSC Chemistry software 6.0. The evaluation of the accuracy of the calculation method was made by the calculation of (ΔGf of rhodium sulfide phases. The calculated values were found to be ingood agreement with those measured in the binary system (Rh + S as a function of temperature by previous authors (Jacob and Gupta (2014. The calculated Gibbs free energy (ΔfG° followed the order RuS2 < (Ir,OsS2 < (Pt, PdS < (Pd, PtTe2, increasing from compatible to incompatible noble metals and from sulfides to tellurides.

  3. Impurities determination in precious metals like rhodium, palladium and platinum by neutron activation without separation

    International Nuclear Information System (INIS)

    May, S.; Piccot, D.; Pinte, G.

    1978-01-01

    The possibilities of the method explored using an installation of gamma or X ray spectrometry of good performance. The irradiations were realized in the reactors EL.3 (flux approximately 6.10 12 n.cm -2 .s -1 ) and Osiris (flux > 10 14 n.cm -2 .s -1 ) of the CEN Saclay. In rhodium the presence of iridium limits the analysis possibilities. However gold, silver and platinum are easily determined, just as the other elements (As, Br, Cl, Co, Mn, Na, Sb). In platinum it is possible to determine the elements of long period, especially antimony, silver, cobalt, iridium, tantalum and zinc. As for palladium the principal impurities are gold, silver and ruthenium for what is of precious metals and particularly zinc among the other metals. For the three matrices considered the detection limits of a certain number of elements are indicated [fr

  4. New exploration methods for platinum and rhodium deposits poor in base-metal sulphides

    DEFF Research Database (Denmark)

    Ohnenstetter, M.; Johan, Z.; Cocherie, A.

    1999-01-01

    Platinum-group elements (PGE) are typically associated with mafic and ultramafic intrusive rocks and the main exploration targets are layers and zones rich in PGE-bearing sulphides. Some PGE occurences, however, are in sulphide-poor situations and this raises the possibility that PGE deposits may...

  5. Platinum group elements geochemistry of ultramafic and associated ...

    Indian Academy of Sciences (India)

    group element (PGE) and associated gold mineralization in these ultramafic rocks. A mineral ... Paleoproterozoic age, mostly emplaced into the .... tified reference materials (CRM) from the US Geo- ..... Classification diagram (Barnes et al.

  6. SERS and DFT study of water on metal cathodes of silver, gold and platinum nanoparticles.

    Science.gov (United States)

    Li, Jian-Feng; Huang, Yi-Fan; Duan, Sai; Pang, Ran; Wu, De-Yin; Ren, Bin; Xu, Xin; Tian, Zhong-Qun

    2010-03-14

    The observed surface-enhanced Raman scattering (SERS) spectra of water adsorbed on metal film electrodes of silver, gold, and platinum nanoparticles were used to infer interfacial water structures on the basis of the change of the electrochemical vibrational Stark tuning rates and the relative Raman intensity of the stretching and bending modes. To explain the increase of the relative Raman intensity ratio of the bending and stretching vibrations at the very negative potential region, density functional theory calculations provide the conceptual model. The specific enhancement effect for the bending mode was closely associated with the water adsorption structure in a hydrogen bonded configuration through its H-end binding to surface sites with large polarizability due to strong cathodic polarization. The present results allow us to propose that interfacial water molecules exist on these metal cathodes with different hydrogen bonding interactions, i.e., the HO-HH-Pt dihydrogen bond for platinum and the HO-HAg(Au) for silver and gold. This dihydrogen bonding configuration on platinum is further supported from observation of the Pt-H stretching band. Furthermore, the influences of the pH effect on SERS intensity and vibrational Stark effect on the gold electrode indicate that the O-H stretching SERS signals are enhanced in the alkaline solutions because of the hydrated hydroxide surface species adsorbed on the gold cathode.

  7. Emerging airborne contaminants in India: Platinum Group Elements from catalytic converters in motor vehicles

    International Nuclear Information System (INIS)

    Sen, Indra S.; Mitra, Arijeet; Peucker-Ehrenbrink, Bernhard; Rothenberg, Sarah E.; Tripathi, Sachchida Nand; Bizimis, Michael

    2016-01-01

    Platinum Group Element (PGE) pollution on the Indian subcontinent is a growing concern because vehicle sales in India have rapidly increased over the last decade, and it is well known that automobile catalytic converters are one of the major source of anthropogenic PGE in the environment. Despite the rapid growth of the Indian automobile industry, the sources and magnitude of PGE contamination in Indian airborne particles are unknown. In this study we report PGE and mercury (Hg) concentrations, as well as osmium isotope ratios ( 187 Os/ 188 Os) of airborne particles (PM 10 ) collected in Kanpur, a large industrial city in India. We estimate that 61 ± 22%, 32 ± 24%, and 7 ± 3% of the total Os fraction are derived from eroding upper continental crust, catalytic converters fitted in the exhaust system of motor vehicles, and fossil fuel combustion, respectively. Only one sample had a ten times higher (∼76%) than average contribution from fossil fuel. Unlike Os, Pt is predominantly (84 ± 10%) derived from anthropogenic sources. Platinum Group Element and Hg concentrations are not well correlated. However, the highest concentration of particulate Hg corresponds to the most radiogenic 187 Os/ 188 Os isotope ratios (4.6). Our results further indicated that PGE/Ir ratios could be successfully used to quantify the relative proportions of natural and anthropogenic PGE sources in aerosol samples. Since PGE and Hg data on Indian environmental samples are scarce, this study provides an interpretive framework that calls for additional assessments of PGE and Hg concentrations in environmental samples from India. - Highlights: • Platinum Group Element Pollution is a growing concern in Asia. • Osmium isotopes as tracers of PGE sources is proposed. • Platinum Group Element pollution in India.

  8. High pressure stability of the monosilicides of cobalt and the platinum group elements

    International Nuclear Information System (INIS)

    Hernandez, J.A.; Vočadlo, L.; Wood, I.G.

    2015-01-01

    Highlights: • We model the high-pressure phases of cobalt- and platinum-group-monosilicides. • CoSi, RuSi, OsSi transform with pressure from the ε-FeSi to the CsCl structure. • RhSi and IrSi transform with pressure from the MnP structure to the ε-FeSi structure. • PdSi and PtSi transform with pressure from the MnP structure to the CuTi structure. - Abstract: The high pressure stability of CoSi, RuSi, RhSi, PdSi, OsSi, IrSi and PtSi was investigated by static first-principles calculations up to 300 GPa at 0 K. As found experimentally, at atmospheric pressure, CoSi, RuSi and OsSi were found to adopt the cubic ε-FeSi structure (P2 1 3) whereas RhSi, PdSi, IrSi and PtSi were found to adopt the orthorhombic MnP (Pnma) structure. At high pressure, CoSi, RuSi and OsSi show a phase transition to the CsCl structure (Pm3 ¯ m) structure at 270 GPa, 7 GPa and 6 GPa respectively. RhSi and IrSi were found to transform to an ε-FeSi structure at 10 GPa and 25 GPa. For PdSi and PtSi, a transformation from the MnP structure to the tetragonal CuTi structure (P4/nmm) occurs at 13 GPa and 20 GPa. The pressure dependence of the electronic density of states reveals that RuSi and OsSi are semiconductors in the ε-FeSi structure and become metallic in the CsCl structure. RhSi and IrSi are metals in the MnP structure and become semimetals in their high pressure ε-FeSi form. CoSi in the ε-FeSi configuration is a semimetal. PdSi and PtSi remain metallic throughout up to 300 GPa

  9. Separation and preconcentration of platinum-group metals from spent autocatalysts solutions using a hetero-polymeric S, N-containing sorbent and determination by high-resolution continuum source graphite furnace atomic absorption spectrometry.

    Science.gov (United States)

    Eskina, Vasilina V; Dalnova, Olga A; Filatova, Daria G; Baranovskaya, Vasilisa B; Karpov, Yuri A

    2016-10-01

    This paper describes the potential of high-resolution continuum source graphite furnace atomic absorption spectrometry for determination of Pt, Pd and Rh after separation and concentration by original in-house developed heterochain polymer S, N-containing sorbent. The methods of sample preparation of spent ceramic-based autocatalysts were considered, two of which were used: autoclave decomposition in mixture of acids HCl:HNO3 (3:1) and high-temperature melting with K2S2O7. Both methods anyway limit the direct determination of analytes by HR CS GFAAS. Using the first method it is an incomplete digestion of spent autocatalysts samples, since the precipitate is Si, and the rhodium metal dissolves with difficulty and partially passes into solution. In contrast to the first method, the second method allow to completely transfer analytes into solution, however, the background signal produced by the chemical composition of the flux, overlaps the analytical zone. It was found, that Pt, Pd and Rh contained in the spent ceramic automotive catalysts could be effectively separated and concentrated by heterochain polymer S, N-containing sorbent, which has high sorption capacity, selectivity and resistant to dilute acids. The chosen HR CS GFAAS analysis conditions enable us to determine Pt, Pd and Rh with good metrological characteristics. The concentrations of Pt, Pd and Rh in two samples of automobile exhaust catalysts were found in range of 0.00015-0.00050; 0.170-0.189; 0.0180-0.0210wt%, respectively. The relative standard deviation obtained by HR CS GFAAS was not more than 5%. Limits of detection by HR CS GFAAS achieved were 6.2·10(-6)wt% for Pt, 1.8·10(-6)wt% for Pd, and 3.4·10(-6)wt% for Rh. Limits of determination achieved by HR CS GFAAS were 1.1·10(-5)wt% for Pt, 6.9·10(-5)wt% for Pd, and 8.3·10(-5)wt% for Rh. To control the accuracy of PGM in sorption concentrates by HR CS GFAAS method, it was appropriate to conduct an inter-method comparative experiment. The

  10. Platinum recycling in the United States in 1998

    Science.gov (United States)

    Hilliard, Henry E.

    2001-01-01

    In the United States, catalytic converters are the major source of secondary platinum for recycling. Other sources of platinum scrap include reforming and chemical process catalysts. The glass industry is a small but significant source of platinum scrap. In North America, it has been estimated that in 1998 more than 20,000 kilograms per year of platinum-group metals from automobile catalysts were available for recycling. In 1998, an estimated 7,690 kilograms of platinum were recycled in the United States. U.S. recycling efficiency was calculated to have been 76 percent in 1998; the recycling rate was estimated at 16 percent.

  11. Platinum-group elements fractionation by selective complexing, the Os, Ir, Ru, Rh-arsenide-sulfide systems above 1020 °C

    Science.gov (United States)

    Helmy, Hassan M.; Bragagni, Alessandro

    2017-11-01

    The platinum-group element (PGE) contents in magmatic ores and rocks are normally in the low μg/g (even in the ng/g) level, yet they form discrete platinum-group mineral (PGM) phases. IPGE (Os, Ir, Ru) + Rh form alloys, sulfides, and sulfarsenides while Pt and Pd form arsenides, tellurides, bismuthoids and antimonides. We experimentally investigate the behavior of Os, Ru, Ir and Rh in As-bearing sulfide system between 1300 and 1020 °C and show that the prominent mineralogical difference between IPGE (+Rh) and Pt and Pd reflects different chemical preference in the sulfide melt. At temperatures above 1200 °C, Os shows a tendency to form alloys. Ruthenium forms a sulfide (laurite RuS2) while Ir and Rh form sulfarsenides (irarsite IrAsS and hollingworthite RhAsS, respectively). The chemical preference of PGE is selective: IPGE + Rh form metal-metal, metal-S and metal-AsS complexes while Pt and Pd form semimetal complexes. Selective complexing followed by mechanical separation of IPGE (and Rh)-ligand from Pt- and Pd-ligand associations lead to PGE fractionation.

  12. Platinum Group Thiophenoxyimine Complexes: Syntheses,Crystallographic and Computational Studies of Structural Properties

    Energy Technology Data Exchange (ETDEWEB)

    Krinsky, Jamin L.; Arnold, John; Bergman, Robert G.

    2006-10-03

    Monomeric thiosalicylaldiminate complexes of rhodium(I) and iridium(I) were prepared by ligand transfer from the homoleptic zinc(II) species. In the presence of strongly donating ligands, the iridium complexes undergo insertion of the metal into the imine carbon-hydrogen bond. Thiophenoxyketimines were prepared by non-templated reaction of o-mercaptoacetophenone with anilines, and were complexed with rhodium(I), iridium(I), nickel(II) and platinum(II). X-ray crystallographic studies showed that while the thiosalicylaldiminate complexes display planar ligand conformations, those of the thiophenoxyketiminates are strongly distorted. Results of a computational study were consistent with a steric-strain interpretation of the difference in preferred ligand geometries.

  13. Environmental routes for platinum group elements to biological materials. A review

    Energy Technology Data Exchange (ETDEWEB)

    Ek, Kristine H.; Morrison, Gregory M. [Water Environment Transport, Chalmers University of Technology, SE 412 96 Goteborg (Sweden); Rauch, Sebastien [R.M. Parsons Laboratory 48-108, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

    2004-12-01

    The increased use of platinum group elements (PGE) in automobile catalysts has led to concern over potential environmental and biological accumulation. Platinum (Pt), palladium (Pd) and rhodium (Rh) concentrations have increased in the environment since the introduction of automobile catalysts. This review summarises current knowledge concerning the environmental mobility, speciation and bioavailability of Pt, Pd and Rh. The greater proportion of PGE emissions is from automobile catalysts, in the form of nanometer-sized catalyst particles, which deposit on roadside surfaces, as evidenced in samples of road dust, grass and soil. In soil, PGE can be transformed into more mobile species through complexation with organic matter and can be solubilised in low pH rainwater. There are indications that environmentally formed Pd species are more soluble and hence more mobile in the environment than Rh and Pt. PGE can reach waterbodies through stormwater transport and deposition in sediments. Besides external contamination of grass close to roads, internal PGE uptake has been observed for plants growing on soil contaminated with automobile catalyst PGE. Fine particles of PGE were also detected on the surface of feathers sampled from passerines and raptors in their natural habitat, and internal organs of these birds also contained PGE. Uptake has been observed in sediment-dwelling invertebrates, and laboratory studies have shown an uptake of PGE in eel and fish exposed to water containing road dust.The available evidence indicates that the PGE, especially Pd, are transported to biological materials through deposition in roots by binding to sulphur-rich low molecular weight species in plants. PGE uptake to exposed animals have uptake rates in the following order: Pd>Pt>Rh. The liver and kidney accumulate the highest levels of PGE, especially Pd. Urinary Pd and Rh, but not Pt, levels are correlated with traffic intensity. Dental alloys may lead to elevated urinary Pt levels

  14. pH-dependent release of trace elements including platinum group elements (PGEs) from gasoline and diesel catalysts

    Science.gov (United States)

    Sucha, Veronika; Mihaljevic, Martin; Ettler, Vojtech; Strnad, Ladislav

    2014-05-01

    The release of trace metals and platinum group elements (PGEs) from automobile exhaust catalysts represents a remarkable source of higly dispersed environmental contamination. Especially, PGEs have shown increasing research interest due to their possible bioaccessibility. In our research, we focused on leaching behaviour of trace metals from gasoline and diesel automobile catalysts. While catalysts for gasoline engines contain a mixture of Pt-Pd-Rh or Pd-Rh, catalysts for diesel engines are composed only of Pt. We used dust from two crushed gasoline and two crushed diesel catalysts (new and aged). The dust of gasoline catalysts contains significant concentrations of Pt (700 mg.kg-1), Pd (11 000 mg.kg-1) and Rh (700 mg.kg-1). And the dust of diesel catalysts are composed of Pt (3 900 mg.kg-1) and they contains negligible amounts of Pd dan Rh (leaching of trace metals from dust we used pH-stat leaching test according to the European standard CEN/TS 14997. The concentrations of cations: PGEs (Pt, Pd a Rh), K, Na, Ca, Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, La and Ce were determined by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS), and anions: F-, Cl-, SO42- and NO3- by high-performance liquid chromatography. Although the dusts from catalysts were relatively stable to acid/base influence, the leaching of trace metals from catalysts showed a dependence on pH. Generally, the highest concentrations were released under acidic conditions. The leaching of PGEs was higher for Pt in diesel catalysts and for Pd and Rh in gasoline catalysts. The highest concentrations of Zn and Pb were observed in old catalysts. The rare earth metals were released more from gasoline catalysts. Catalysts particles represent health risk especially with respect to their PGEs contents.

  15. Urinary excretion of platinum from South African precious metals refinery workers.

    Science.gov (United States)

    Linde, Stephanus J L; Franken, Anja; du Plessis, Johannes L

    2018-03-30

    Urinary platinum (Pt) excretion is a reliable biomarker for occupational Pt exposure and has been previously reported for precious metals refinery workers in Europe but not for South Africa, the world's largest producer of Pt. This study aimed to quantify the urinary Pt excretion of South African precious metals refinery workers. Spot urine samples were collected from 40 workers (directly and indirectly exposed to Pt) at two South African precious metals refineries on three consecutive mornings prior to their shifts. Urine samples were analysed for Pt using inductively coupled plasma-mass spectrometry and were corrected for creatinine content. The urinary Pt excretion of workers did not differ significantly between sampling days. Urinary Pt excretions ranged from work area (P=0.0006; η 2 =0.567) and the number of years workers were employed at the refineries (P=0.003; η 2 =0.261) influenced their urinary Pt excretion according to effect size analyses. Directly exposed workers had significantly higher urinary Pt excretion compared with indirectly exposed workers (P=0.007). The urinary Pt excretion of South African precious metals refinery workers reported in this study is comparable with that of seven other studies conducted in precious metals refineries and automotive catalyst plants in Europe. The Pt body burden of workers is predominantly determined by their work area, years of employment in the refineries and whether they are directly or indirectly exposed to Pt. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  16. Determination of platinum-group elements in the geological standard reference materials by isotope dilution-ICPMS

    Energy Technology Data Exchange (ETDEWEB)

    Mingyue, Hu; Hongliao, He [National Research Center for Geoanalysis, Beijing (China)

    2005-10-15

    Platinum group elements (PGEs) includes platinum, palladium, iridium, osmium, rhodium and ruthenium. It has very high economic and scientific value in the field of geoscience and environmental science. But the analysis data referred by the different lab are very disperse because of the difficulty of the determination of PGEs. It makes very difficult to fix the value of the PGEs in the standard reference materials. In the article, the values of the PGEs in the standard reference materials of ocean sediment are determined by isotope dilution technique and dependable values of these elements are provided. (authors)

  17. Determination of platinum-group elements in the geological standard reference materials by isotope dilution-ICPMS

    International Nuclear Information System (INIS)

    Hu Mingyue; He Hongliao

    2005-01-01

    Platinum group elements (PGEs) includes platinum, palladium, iridium, osmium, rhodium and ruthenium. It has very high economic and scientific value in the field of geoscience and environmental science. But the analysis data referred by the different lab are very disperse because of the difficulty of the determination of PGEs. It makes very difficult to fix the value of the PGEs in the standard reference materials. In the article, the values of the PGEs in the standard reference materials of ocean sediment are determined by isotope dilution technique and dependable values of these elements are provided. (authors)

  18. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

    Science.gov (United States)

    Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

    2018-01-22

    Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Micrometer- and nanometer-sized platinum group nuggets in micrometeorites from deep-sea sediments of the Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; Parashar, K.; ShyamPrasad, M.

    We examined 378 micrometeorites collected from deep-sea sediments of the Indian Ocean of which 175, 180, and 23 are I-type, S-type, and G-type, respectively. Of the 175 I-type spherules, 13 contained platinum group element nuggets (PGNs...

  20. The influence of platinum washing-out time on its recovery from used auto catalytic converters

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk

    2014-07-01

    Full Text Available The used catalytic converters contain small amounts of precious metals. Recovery of these metals is essential for environmental and economic reasons. This work presents a method of Platinum Group Metals (PGM recovery from auto catalytic converters in which they are washed out by a liquid metal. The magneto-hydro-dynamic pump was used to force circulation of liquid metal under the influence of electromagnetic fields The influence of process time on platinum recovery was also carried out.

  1. Revisiting platinum group elements of Late Permian coals from western Guizhou Province, SW China

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Liang [State Key Lab of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550002 (China); Gao, Jianfeng [Department of Earth Sciences, The University of Hong Kong, Pokfulam Road, Hong Kong SAR (China)

    2008-08-05

    Twenty five coal samples from the Late Permian coal-bearing strata in Weining, Nayong, and Zhijin, western Guizhou Province, SW, China, were analyzed for platinum group elements (PGEs). The coal ashes were digested by the Carius tube technique and accurately measured by isotope dilution-inductively coupled plasma mass spectrometry (ID-ICP-MS) for all PGEs. The results are much lower than the previous reported values. Our study suggested that the previously reported PGE values are incorrect and may due to the polyatomic interferences in ICP-MS measurements. In our study, samples from the Weining coalfield have the lowest PGE contents (from 0.019 Ir to 0.42 ng/g Pd), which represent the PGE background value in coal in western Guizhou province. Some of the coals have Pt and Pd contents about 20-times higher than the background value, indicating PGEs are concentrated. We also reported new and reliable PGE data and background value of coal in western Guizhou province, SW, China, and suggested to rework the PGE background values of Chinese coals. (author)

  2. Material and Energy Flows Associated with Select Metals in GREET 2. Molybdenum, Platinum, Zinc, Nickel, Silicon

    Energy Technology Data Exchange (ETDEWEB)

    Benavides, Pahola T. [Argonne National Lab. (ANL), Argonne, IL (United States); Dai, Qiang [Argonne National Lab. (ANL), Argonne, IL (United States); Sullivan, John L. [Argonne National Lab. (ANL), Argonne, IL (United States); Kelly, Jarod C. [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2015-09-01

    In this work, we analyzed the material and energy consumption from mining to production of molybdenum, platinum, zinc, and nickel. We also analyzed the production of solar- and semiconductor-grade silicon. We described new additions to and expansions of the data in GREET 2. In some cases, we used operating permits and sustainability reports to estimate the material and energy flows for molybdenum, platinum, and nickel, while for zinc and silicon we relied on information provided in the literature.

  3. Platinum-group elements in southern Africa: mineral inventory and an assessment of undiscovered mineral resources: Chapter Q in Global mineral resource assessment

    Science.gov (United States)

    Zientek, Michael L.; Causey, J. Douglas; Parks, Heather L.; Miller, Robert J.

    2014-01-01

    The platinum-group elements, platinum, palladium, rhodium, ruthenium, iridium, and osmium, possess unique physical and chemical characteristics that make them indispensable to modern technology and industry. However, mineral deposits that are the main sources of these elements occur only in three countries in the world, raising concerns about potential disruption in mineral supply. Using information in the public domain, mineral resource and reserve information has been compiled for mafic and ultramafic rocks in South Africa and Zimbabwe that host most of the world’s platinum-group element resources.

  4. Low platinum catalyst and method of preparation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Di-Jia; Chong, Lina

    2017-11-21

    A low platinum catalyst and method for making same. The catalyst comprises platinum-transition metal bimetallic alloy microcrystallites over a transition metal-nitrogen-carbon composite. A method of making a catalyst comprises preparation of transition metal organic frameworks, infusion of platinum, thermal treatment, and reduction to form the microcrystallites and composite.

  5. Empirical constraints on partitioning of platinum group elements between Cr-spinel and primitive terrestrial magmas

    Science.gov (United States)

    Park, Jung-Woo; Kamenetsky, Vadim; Campbell, Ian; Park, Gyuseung; Hanski, Eero; Pushkarev, Evgeny

    2017-11-01

    Recent experimental studies and in situ LA-ICP-MS analysis on natural Cr-spinel have shown that Rh and IPGEs (Ir-group platinum group elements: Ru, Ir, Os) are enriched in the lattice of Cr-spinel. However, the factors controlling the partitioning behaviour of these elements are not well constrained. In this study, we report the Rh, IPGE, and trace element contents in primitive Cr-spinel, measured by LA-ICP-MS, from nine volcanic suites covering various tectonic settings including island arc picrites, boninites, large igneous province picrites and mid-ocean ridge basalts. The aim is to understand the factors controlling the enrichment of Rh and IPGEs in Cr-spinels, to estimate empirical partition coefficients between Cr-spinel and silicate melts, and to investigate the role of Cr-spinel fractional crystallization on the PGE geochemistry of primitive magmas during the early stages of fractional crystallization. There are systematic differences in trace elements, Rh and IPGEs in Cr-spinels from arc-related magmas (Arc Group Cr-spinel), intraplate magmas (Intraplate Group Cr-spinel), and mid-ocean ridge magmas (MORB Group Cr-spinel). Arc Group Cr-spinels are systematically enriched in Sc, Co and Mn and depleted in Ni compared to the MORB Group Cr-spinels. Intraplate Group Cr-spinels are distinguished from the Arc Group Cr-spinels by their high Ni contents. Both the Arc and Intraplate Group Cr-spinels have total Rh and IPGE contents of 22-689 ppb whereas the MORB Group Cr-spinels are depleted in Rh and IPGE (total time-resolved spectra of LA-ICP-MS data for Cr-spinels mostly show constant count rates for trace element and Rh and IPGEs, suggesting homogeneous distribution of these elements in Cr-spinels. The PGE spikes observed in several Cr-spinels were interpreted to be PGE-bearing mineral inclusions and excluded from calculating the PGE contents of the Cr-spinels. On primitive mantle normalized diagrams the Arc Group Cr-spinels are characterized by a fractionated

  6. The fire assay preconcentration of the platinum group elements for the neutron activation analysis of geological material

    International Nuclear Information System (INIS)

    Parry, S.J.

    1994-01-01

    This paper describes the work that has been carried out using neutron activation analysis (NAA) to develop a rapid and reliable method for the determination of the platinum group elements (PGE: Pt, Pd, Ir, Ru, Rh, and Os) and Au in geological, environmental and industrial samples. The method is based on the now established method of preconcentration with fire assay, followed by NAA of the separated PGE and Au. Recent developments have seen improvements in the technique to eliminate losses due to dissolution procedures, and complete recovery of the elements prior to analysis. The method is now being used to validate inductively coupled plasma-mass spectroscopy methods for analysis of the PGE

  7. Study of half-sandwich mono and dinuclear complexes of platinum ...

    Indian Academy of Sciences (India)

    of platinum group metals containing pyrazolyl pyridine analogues: Synthesis ... sis for specific reactions. Inclusion of ... was poured in to 100 ml of water, resulted in whitish precipitate ..... condition in the presence of potassium carbonate and.

  8. Optimization of a polarized source for in vivo x-ray fluorescence analysis of platinum and other heavy metals

    International Nuclear Information System (INIS)

    Lewis, D.G.

    1994-01-01

    The Monte Carlo method was used to optimize a polarized photon source for the x-ray fluorescence analysis of platinum and other heavy metals in vivo. The source consisted of a 140 kVp, 25 mA x-ray tube with the photons plane-polarized by 90 o scattering. The use of plane-polarized photons results in a significant reduction in background when the fluorescent radiation is measured along the direction of polarization. A Monte Carlo computer programme was written to simulate the production and interaction of polarized photons in order to determine the optimal polarizing material and dimensions, together with beam width and geometrical arrangement of source, polarizer and beam collimators. Calculated photon energy distributions are compared with experimental data to test the validity of the model. (author)

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

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  10. On the nature of oxygen-containing surface groups on carbon nanofibers and their role for platinum deposition—an xps and titration study

    NARCIS (Netherlands)

    Plomp, A.J.; Su, D.S.; de Jong, K.P.; Bitter, J.H.

    2009-01-01

    XPS and acid−base titrations were used to investigate the nature and stability of oxygen-containing surface groups on carbon nanofibers (CNF) and platinum-containing CNF. During heat treatments in inert atmosphere at 973 K all acidic (carboxylic) oxygen surface groups were removed for CNF.

  11. Synthesis of Platinum Nanotubes and Nanorings via Simultaneous Metal Alloying and Etching

    KAUST Repository

    Huang, Zhiqi; Raciti, David; Yu, Shengnan; Zhang, Lei; Deng, Lin; He, Jie; Liu, Yijing; Khashab, Niveen M.; Wang, Chao; Gong, Jinlong; Nie, Zhihong

    2016-01-01

    Metallic nanotubes represent a class of hollow nanostructures with unique catalytic properties. However, the wet-chemical synthesis of metallic nanotubes remains a substantial challenge, especially for those with dimensions below 50 nm

  12. Instrumental neutron activation analysis of a nickel sulfide fire assay button to determine the platinum group elements and gold

    Energy Technology Data Exchange (ETDEWEB)

    Asif, M.; Parry, S.J.; Malik, H. (Imperial College of Science, Technology and Medicine, Silwood Park, Ascot (United Kingdom). Centre for Analytical Research in the Environment)

    1992-08-01

    Platinum group elements and gold were determined in reference materials SARM 7 and MA 1b using fire assay with 0.5 g of nickel prior to neutron activation analysis. The method is simple and rapid, avoiding the dissolution step where losses occur, particularly of gold. The problem of standardizing the button mass was overcome by using a spiking technique. The method is best suited to samples with little or no copper, when the detection limits can be as low as 0.002, 0.025, 0.018, 0.0002, 0.002, 0.020 and 0.2 mg kg[sup -1] for Rh, Pd, Pt, Ir, Au, Os and Ru, respectively. (author).

  13. Fibrous Platinum-Group Minerals in “Floating Chromitites” from the Loma Larga Ni-Laterite Deposit, Dominican Republic

    Directory of Open Access Journals (Sweden)

    Thomas Aiglsperger

    2016-11-01

    Full Text Available This contribution reports on the observation of enigmatic fibrous platinum-group minerals (PGM found within a chromitite body included in limonite (“floating chromitite” from Ni-laterites in the Dominican Republic. Fibrous PGM have a Ru-Os-Ir-Fe dominated composition and are characterized by fibrous textures explained by grain-forming fibers which are significantly longer (1–5 µm than they are wide (~100 nm. Back-scattered electron (BSE images suggest that these nanofibers are platinum-group elements (PGE-bearing and form <5 µm thick layers of bundles which are oriented orthogonal to grains’ surfaces. Trace amounts of Si are most likely associated with PGE-bearing nanofibers. One characteristic fibrous PGM was studied in detail: XRD analyses point to ruthenian hexaferrum. However, the unpolished fibrous PGM shows numerous complex textures on its surface which are suggestive for neoformation processes: (i features suggesting growth of PGE-bearing nanofibers; (ii occurrence of PGM nanoparticles within film material (biofilm? associated with PGE-bearing nanofibers; (iii a Si-rich and crater-like texture hosting PGM nanoparticles and an Ir-rich accumulation of irregular shape; (iv complex PGM nanoparticles with ragged morphologies, resembling sponge spicules and (v oval forms (<1 µm in diameter with included PGM nanoparticles, similar to those observed in experiments with PGE-reducing bacteria. Fibrous PGM found in the limonite may have formed due to supergene (bio-weathering of fibrous Mg-silicates which were incorporated into desulphurized laurite during stages of serpentinization.

  14. Exposure of the German general population to platinum and rhodium - Urinary levels and determining factors.

    Science.gov (United States)

    Munker, Sven; Kilo, Sonja; Röß, Christoph; Jeitner, Peter; Schierl, Rudolf; Göen, Thomas; Drexler, Hans

    2016-11-01

    In this study the exposure of the general population in Germany to platinum and rhodium and its determinants was investigated in 259 participants (subdivided in three groups) by urine analyses and assessment of the dental status. Complementary, an interview including questions characterising possible exposure to traffic exhaust was conducted. The median excretion was 2.42ng platinum/g creatinine and 7.27ng rhodium/g creatinine. The detailed analysis of the collected data showed significant higher platinum excretion values with increasing number of surfaces covered with restorations containing precious metals (R=0.389; prhodium excretion values (median=7.27ng/g; 95th percentile=13.5 ng/g). In summary, the study showed that exhaust emissions have an influence on platinum and rhodium excretion, but for platinum this influence is rather low compared to the influence of precious metals containing restorations. Copyright © 2016 Elsevier GmbH. All rights reserved.

  15. Application of liquid column chromatography to preconcentration, separation and determination of platinum metals

    International Nuclear Information System (INIS)

    Alimarin, I.P.; Basova, E.M.; Bol'shova, T.A.; Ivanov, V.M.

    1986-01-01

    Separation and determination of platimum metals using the methods of adsorption, ion-pair, ion-exchange, distributing and sieve chromatography are discussed in the review of literature in 1971-1984. Separation and determination of metals as chelates using the method of adsorption and ion-pair chromatograpy are noted to be most perspective directions of developing highly effective liquid chromatography of inorganic systems

  16. Platinum Group Elements (PGE) geochemistry of komatiites and boninites from Dharwar Craton, India: Implications for mantle melting processes

    Science.gov (United States)

    Saha, Abhishek; Manikyamba, C.; Santosh, M.; Ganguly, Sohini; Khelen, Arubam C.; Subramanyam, K. S. V.

    2015-06-01

    High MgO volcanic rocks having elevated concentrations of Ni and Cr are potential hosts for platinum group elements (PGE) owing to their primitive mantle origin and eruption at high temperatures. Though their higher PGE abundance is economically significant in mineral exploration studies, their lower concentrations are also valuable geochemical tools to evaluate petrogenetic processes. In this paper an attempt has been made to evaluate the PGE geochemistry of high MgO volcanic rocks from two greenstone belts of western and eastern Dharwar Craton and to discuss different mantle processes operative at diverse geodynamic settings during the Neoarchean time. The Bababudan greenstone belt of western and Gadwal greenstone belt of eastern Dharwar Cratons are dominantly composed of high MgO volcanic rocks which, based on distinct geochemical characteristics, have been identified as komatiites and boninites respectively. The Bababudan komatiites are essentially composed of olivine and clinopyroxene with rare plagioclase tending towards komatiitic basalts. The Gadwal boninites contain clinopyroxene, recrystallized hornblende with minor orthopyroxene, plagioclase and sulphide minerals. The Bababudan komatiites are Al-undepleted type (Al2O3/TiO2 = 23-59) with distinctly high MgO (27.4-35.8 wt.%), Ni (509-1066 ppm) and Cr (136-3036 ppm) contents. These rocks have low ΣPGE (9-42 ppb) contents with 0.2-2.4 ppb Iridium (Ir), 0.2-1.4 ppb Osmium (Os) and 0.4-4.4 ppb Ruthenium (Ru) among Iridium group PGE (IPGE); and 1.4-16.2 ppb Platinum (Pt), 2.8-19 ppb Palladium (Pd) and 0.2-9.8 ppb Rhodium (Rh) among Platinum group PGE (PPGE). The Gadwal boninites are high-Ca boninites with CaO/Al2O3 ratios varying between 0.8 and 1.0, with 12-24 wt.% MgO, 821-1168 ppm Ni and 2307-2765 ppm Cr. They show higher concentration of total PGE (82-207 ppb) with Pt concentration ranging from 13 to 19 ppb, Pd between 65 and 180 ppb and Rh in the range of 1.4-3 ppb compared to the Bababudan komatiites. Ir

  17. Platinum-Group Minerals and Other Accessory Phases in Chromite Deposits of the Alapaevsk Ophiolite, Central Urals, Russia

    Directory of Open Access Journals (Sweden)

    Federica Zaccarini

    2016-10-01

    Full Text Available An electron microprobe study has been carried out on platinum-group minerals, accessory phases, and chromite in several chromite deposits of the Alapaevsk ophiolite (Central Urals, Russia namely the Bakanov Kluch, Kurmanovskoe, Lesnoe, 3-d Podyony Rudnik, Bol’shaya Kruglyshka, and Krest deposits. These deposits occur in partially to totally serpentinized peridotites. The microprobe data shows that the chromite composition varies from Cr-rich to Al-rich. Tiny platinum-group minerals (PGM, 1–10 µm in size, have been found in the chromitites. The most abundant PGM is laurite, accompanied by minor cuproiridsite and alloys in the system Os–Ir–Ru. A small grain (about 20 μm was found in the interstitial serpentine of the Bakanov Kluch chromitite, and its calculated stoichiometry corresponds to (Ni,Fe5P. Olivine, occurring in the silicate matrix or included in fresh chromite, has a mantle-compatible composition in terms of major and minor elements. Several inclusions of amphibole, Na-rich phlogopite, and clinopyroxene have been identified. The bimodal Cr–Al composition of chromite probably corresponds to a vertical distribution in the ophiolite sequence, implying formation of Cr-rich chromitites in the deep mantle, and Al-rich chromitites close to the Moho-transition zone, in a supra-subduction setting. The presence of abundant hydrous silicate inclusions, such as amphibole and phlogopite, suggests that the Alapaevsk chromitites crystallized as a result of the interaction between a melt enriched in fluids and peridotites. Laurite and cuproiridsite are considered to be magmatic in origin, i.e., entrapped as solid phases during the crystallization of chromite at high temperatures. The sulfur fugacity was relatively high to allow the precipitation of Ir-bearing sulfides, but below the Os–OsS2 buffer. The alloys in the system Os–Ir–Ru are classified as secondary PGM, i.e., formed at low temperature during the serpentinization process. The

  18. In vitro permeation of platinum and rhodium through Caucasian skin.

    Science.gov (United States)

    Franken, A; Eloff, F C; Du Plessis, J; Badenhorst, C J; Jordaan, A; Du Plessis, J L

    2014-12-01

    During platinum group metals (PGMs) refining the possibility exists for dermal exposure to PGM salts. The dermal route has been questioned as an alternative route of exposure that could contribute to employee sensitisation, even though literature has been focused on respiratory exposure. This study aimed to investigate the in vitro permeation of platinum and rhodium through intact Caucasian skin. A donor solution of 0.3mg/ml of metal, K2PtCl4 and RhCl3 respectively, was applied to the vertical Franz diffusion cells with full thickness abdominal skin. The receptor solution was removed at various intervals during the 24h experiment, and analysed with high resolution ICP-MS. Skin was digested and analysed by ICP-OES. Results indicated cumulative permeation with prolonged exposure, with a significantly higher mass of platinum permeating after 24h when compared to rhodium. The mass of platinum retained inside the skin and the flux of platinum across the skin was significantly higher than that of rhodium. Permeated and skin retained platinum and rhodium may therefore contribute to sensitisation and indicates a health risk associated with dermal exposure in the workplace. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Alkali metal-refractory metal biphase electrode for AMTEC

    Science.gov (United States)

    Williams, Roger M. (Inventor); Bankston, Clyde P. (Inventor); Cole, Terry (Inventor); Khanna, Satish K. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Wheeler, Bob L. (Inventor)

    1989-01-01

    An electrode having increased output with slower degradation is formed of a film applied to a beta-alumina solid electrolyte (BASE). The film comprises a refractory first metal M.sup.1 such as a platinum group metal, suitably platinum or rhodium, capable of forming a liquid or a strong surface adsorption phase with sodium at the operating temperature of an alkali metal thermoelectric converter (AMTEC) and a second refractory metal insoluble in sodium or the NaM.sup.1 liquid phase such as a Group IVB, VB or VIB metal, suitably tungsten, molybdenum, tantalum or niobium. The liquid phase or surface film provides fast transport through the electrode while the insoluble refractory metal provides a structural matrix for the electrode during operation. A trilayer structure that is stable and not subject to deadhesion comprises a first, thin layer of tungsten, an intermediate co-deposited layer of tungsten-platinum and a thin surface layer of platinum.

  20. Identification of the formation of metal-vinylidene interfacial bonds of alkyne-capped platinum nanoparticles by isotopic labeling.

    Science.gov (United States)

    Hu, Peiguang; Chen, Limei; Deming, Christopher P; Bonny, Lewis W; Lee, Hsiau-Wei; Chen, Shaowei

    2016-10-07

    Stable platinum nanoparticles were prepared by the self-assembly of 1-dodecyne and dodec-1-deuteroyne onto bare platinum colloid surfaces. The nanoparticles exhibited consistent core size and optical properties. FTIR and NMR measurements confirmed the formation of Pt-vinylidene (Pt[double bond, length as m-dash]C[double bond, length as m-dash]CH-) interfacial linkages rather than Pt-acetylide (Pt-C[triple bond, length as m-dash]C-) and platinum-hydride (Pt-H) bonds.

  1. Platinum group element enrichments and possible chondritic Ru:Ir across the Frasnian-Famennian boundary, western New York State.

    Science.gov (United States)

    Over, D J; Conaway, C A; Katz, D J; Goodfellow, W D; Gregoire, D C

    1997-08-01

    The Frasnian-Famennian boundary is recognized as the culmination of a global mass extinction in the Late Devonian. In western New York State the boundary is a distinct horizon within a pyritic black shale bed of the upper Hanover Shale defined by the first occurrence of Palmatolepis triangularis in the absence of Frasnian conodonts. The boundary is characterized by a minor disconformity marked by a lag concentration of conodonts. Iridium at the boundary is 0.11-0.24 ng/g, two to five times background levels of <0.05 ng/g; other Ir enrichments of 0.38 ng/g and 0.49 ng/g occur within 50 cm of the conodont-constrained boundary. Numerous Ir enrichments in the boundary interval suggest extraterrestrial accretion and platinum group element (PGE) concentration at disconformities, or mobilization and concentration in organic-rich/pyritic-rich laminations from cosmic or terrestrial sources. PGE ratios of Pt/Pd and Ku/Ir at the boundary horizon approximate chondritic ratios and are suggestive of an unaltered extraterrestrial source. These values do not conclusively establish a single extraterrestrial impact as the ultimate cause of the Frasnian-Famennian mass extinction, especially given the presence of similar Ir enrichments elsewhere in the section and the absence at the boundary of microtektites and shocked mineral grains.

  2. Reliability assessment of MVP-BURN and JENDL-4.0 related to nuclear transmutation of light platinum group elements

    Directory of Open Access Journals (Sweden)

    Terashima Atsunori

    2017-01-01

    Full Text Available The Aprés ORIENT research program, as a concept of advanced nuclear fuel cycle, was initiated in FY2011 aiming at creating stable, highly-valuable elements by nuclear transmutation from ↓ssion products. In order to simulate creation of such elements by (n, γ reaction succeeded by β− decay in reactors, a continuous-energy Monte Carlo burnup calculation code MVP-BURN was employed. Then, it is one of the most important tasks to con↓rm the reliability of MVP-BURN code and evaluated neutron cross section library. In this study, both an experiment of neutron activation analysis in TRIGA Mark I reactor at University of California, Irvine and the corresponding burnup calculation using MVP-BURN code were performed for validation of the simulation on transmutation of light platinum group elements. Especially, some neutron capture reactions such as 102Ru(n, γ103Ru, 104Ru(n, γ105Ru, and 108Pd(n, γ109Pd were dealt with in this study. From a comparison between the calculation (C and the experiment (E about 102Ru(n, γ103Ru, the deviation (C/E-1 was signi↓cantly large. Then, it is strongly suspected that not MVP-BURN code but the neutron capture cross section of 102Ru belonging to JENDL-4.0 used in this simulation have made the big di↑erence as (C/E-1 >20%.

  3. Reliability assessment of MVP-BURN and JENDL-4.0 related to nuclear transmutation of light platinum group elements

    Science.gov (United States)

    Terashima, Atsunori; Nilsson, Mikael; Ozawa, Masaki; Chiba, Satoshi

    2017-09-01

    The Aprés ORIENT research program, as a concept of advanced nuclear fuel cycle, was initiated in FY2011 aiming at creating stable, highly-valuable elements by nuclear transmutation from ↓ssion products. In order to simulate creation of such elements by (n, γ) reaction succeeded by β- decay in reactors, a continuous-energy Monte Carlo burnup calculation code MVP-BURN was employed. Then, it is one of the most important tasks to con↓rm the reliability of MVP-BURN code and evaluated neutron cross section library. In this study, both an experiment of neutron activation analysis in TRIGA Mark I reactor at University of California, Irvine and the corresponding burnup calculation using MVP-BURN code were performed for validation of the simulation on transmutation of light platinum group elements. Especially, some neutron capture reactions such as 102Ru(n, γ)103Ru, 104Ru(n, γ)105Ru, and 108Pd(n, γ)109Pd were dealt with in this study. From a comparison between the calculation (C) and the experiment (E) about 102Ru(n, γ)103Ru, the deviation (C/E-1) was signi↓cantly large. Then, it is strongly suspected that not MVP-BURN code but the neutron capture cross section of 102Ru belonging to JENDL-4.0 used in this simulation have made the big di↑erence as (C/E-1) >20%.

  4. Gibbs energies of protonation and complexation of platinum and vanadate metal ions with naringenin and phenolic acids: Theoretical calculations associated with experimental values

    International Nuclear Information System (INIS)

    Fazary, Ahmed E.; Alshihri, Ayed S.; Alfaifi, Mohammad Y.; Saleh, Kamel A.; Elbehairi, Serag Eldin I.; Fawy, Khaled F.; Abd-Rabboh, Hisham S.M.

    2016-01-01

    Highlights: • The experimental thermodynamic equilibrium and stability constants of vanadium and platinum complexes involving naringin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid were determined. • The theoretical calculations of the free energy changes associated with the ligand protonation, and metal ion–ligand complex formation equilibria using density function theory calculations, providing a complete picture of the microscopic equilibria of the studied complex systems. - Abstract: The Experimental thermodynamic equilibrium (pK_a values) and stability (log β) constants of vanadium and platinum binary and mixed ligand complexes involving naringenin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid were determined at 310.15 K in 0.16 mol·dm"−"3 KCl aqueous solutions using pH-potentiometric technique and by means of two estimation models (HYPERQUAD 2008 and Bjerrum–Calvin). The theoretical calculations of overall protonation and stability constants of the metal complex species in solution were predicted as the free energy change associated with the ligand protonation, and metal ion–ligand complex formation equilibria (species solvation/de-solvation) using ab initio and density function theory (DFT) calculations. The usage of the experimental potentiometry technique and theoretical predictions provides a complete picture of the microscopic equilibria of the studied systems (vanadium/platinum–naringenin–phenolic acid). Specifically, this theoretically DFT predications would be useful to determine the most real protonation constants of the studied bioligands in which the binding sites changes due to the ligand protonation/deprotonation equilibria. Also, the complexing capacities of vanadium and platinum towards naringenin, ferulic acid, p-coumaric acid, caffeic acid, vanillic acid, sinapic acid, and gallic acid in solutions were evaluated and discussed. From the

  5. Graphite-supported platinum catalysts: Effects of gas and aqueous phase treatments

    Energy Technology Data Exchange (ETDEWEB)

    Vleeming, J.H.; Kuster, B.F.M.; Marin, G.B. [Eindhoven Univ. of Technology (Netherlands)] [and others

    1997-03-01

    The effects on the platinum particle diameter and the available platinum surface area of a graphite-supported platinum catalyst resulting from pretreatments and from performing a selective oxidation reaction are investigated. In the gas phase considerable catalyst sintering occurs only in the presence of oxygen at 773 K due to extensive carbon burn-off, whereas in an aqueous phase platinum particle growth is limited upon oxidative treatment. A hydrogen treatment in aqueous phase at 363 K causes platinum particle growth, aggregate formation, and covering of metal sites. These phenomena become more important with increasing pH. Platinum particle growth and aggregate formation are attributed to platinum particle rather than platinum adatom mobility and is caused by the destruction of the oxygen-containing surface groups on the graphite support, which serve as anchorage sites for the platinum particles. Site covering is caused by products originating from the graphite support, which are formed as a result of the reductive treatments. When performing the aqueous phase oxidation of methyl {alpha}-D-glucopyranoside at 323 K and a pH of 9, catalyst modifications are small under oxidative conditions. Exposure of the catalyst for several hours to methyl {alpha}-D-glucopyranoside under the same conditions but in the absence of oxygen causes site covering. 50 refs., 9 figs., 1 tab.

  6. Synthesis of Platinum Nanotubes and Nanorings via Simultaneous Metal Alloying and Etching

    KAUST Repository

    Huang, Zhiqi

    2016-04-19

    Metallic nanotubes represent a class of hollow nanostructures with unique catalytic properties. However, the wet-chemical synthesis of metallic nanotubes remains a substantial challenge, especially for those with dimensions below 50 nm. This communication describes a simultaneous alloying-etching strategy for the synthesis of Pt nanotubes with open ends by selective etching Au core from coaxial Au/Pt nanorods. This approach can be extended for the preparation of Pt nanorings when Saturn-like Au core/Pt shell nanoparticles are used. The diameter and wall thickness of both nanotubes and nanorings can be readily controlled in the range of 14-37 nm and 2-32 nm, respectively. We further demonstrated that the nanotubes with ultrathin side walls showed superior catalytic performance in oxygen reduction reaction. © 2016 American Chemical Society.

  7. Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Kim, In Soo [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Nanophotonics Center, Korea Institute of Science and Technology, Seoul 02792 South Korea; Li, Zhanyong [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Zheng, Jian [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Platero-Prats, Ana E. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Mavrandonakis, Andreas [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Pellizzeri, Steven [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Ferrandon, Magali [Chemical Sciences and Engineering Division, Argonne National Lab, 9700 S. Cass Ave. Argonne IL 60439 USA; Vjunov, Aleksei [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Gallington, Leighanne C. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Webber, Thomas E. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Vermeulen, Nicolaas A. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Penn, R. Lee [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Getman, Rachel B. [Chemical and Biomolecular Engineering, Clemson University, 205 Earle Hall Clemson SC 29634 USA; Cramer, Christopher J. [Department of Chemistry, University of Minnesota, 207 Pleasant St. SE Minneapolis MN 55455 USA; Chapman, Karena W. [X-ray Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Fulton, John L. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Lab, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, Technische Universität München, Lichtenbergstrasse 4 85748 Garching Germany; Farha, Omar K. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Hupp, Joseph T. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA; Department of Chemistry, Northwestern University, 2145 Sheridan Rd. Evanston IL 60208 USA; Martinson, Alex B. F. [Materials Science Division, Argonne National Lab, 9700 S Cass Ave. Argonne IL 60439 USA

    2018-01-02

    Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

  8. Anchoring platinum on graphene using metallic adatoms: a first principles investigation

    International Nuclear Information System (INIS)

    Sen, F G; Alpas, A T; Qi, Y

    2012-01-01

    First principles calculations based on spin-polarized density functional theory were used to identify metallic adatoms that would strengthen the Pt(111)/graphene interface (with a low work of separation of 0.009 J m -2 ), when the adatom was placed between the Pt(111) and the graphene. It was shown that the strength of the Pt-adatom bond, which had a metallic character, increased with the amount of charge transferred from the adatom to the Pt. The carbon-adatom bond, on the other hand, had a mixed ionic and covalent character and was weaker than the Pt-adatom bond for each of the 25 elements considered. Consequently, the total Pt(111)/graphene interface strength and, hence, the anchoring effect of the adatom were controlled by the carbon-adatom bond strength. Metals with unfilled d orbitals increased the Pt/graphene interface strength to above 0.5 J m -2 . The carbon-adatom bond strength was proportional to the ratio between the charge transferred from the adatom to the graphene (ΔZ C ) and the charge transferred to the Pt surface (ΔZ Pt ); i.e., the ΔZ C /ΔZ Pt ratio defined the ability of an adatom to anchor Pt to graphene. For Ir, Os, Ru, Rh and Re, ΔZ C /ΔZ Pt > 1.0, making these elements the most effective adatoms for anchoring Pt to graphene. (paper)

  9. Intrinsic thermoelectric power of group VB metals

    Directory of Open Access Journals (Sweden)

    Gunadhor Singh Okram

    2012-03-01

    Full Text Available We have reinvestigated the thermopower of group VB metals in polycrystalline forms in the temperature range of 6-300K, taking into account the critical nature of the sample surface and heat treatment especially for niobium. Strikingly small magnitude, negative sign, phonon drag dip and superconductivity not reported previously were observed in surface-cleaned single crystalline Nb. However, while thermopower magnitudes are small, mixed signs were found in the polycrystalline V, Nb and Ta samples. These properties were therefore interpreted as their intrinsic properties and were briefly discussed taking into account of the existing theory by fitting also the data that give the Fermi energies of 10.94 eV, 5.08 eV and 1.86eV, respectively.

  10. Developments in platinum anticancer drugs

    Science.gov (United States)

    Tylkowski, Bartosz; Jastrząb, Renata; Odani, Akira

    2018-01-01

    Platinum compounds represent one of the great success stories of metals in medicine. Following the unexpected discovery of the anticancer activity of cisplatin (Fig. 1) in 1965 by Prof. Rosenberg [1], a large number of its variants have been prepared and tested for their ability to kill cancer cells and inhibit tumor growth. Although cisplatin has been in use for over four decades, new and more effective platinum-based therapeutics are finally on the horizon. A wide introduction to anticancer studies is given by the authors of the previous chapter. This chapter aims at providing the readers with a comprehensive and in-depth understanding of recent developments of platinum anticancer drugs and to review the state of the art. The chapter is divided into two parts. In the first part we present a historical aspect of platinum and its complexes, while in the second part we give an overview of developments in the field of platinum anticancer agents.

  11. Implantation of titanium, chromium, yttrium, molybdenum, silver, hafnium, tantalum, tungsten and platinum ions generated by a metal vapor vacuum ion source into 440C stainless steel

    International Nuclear Information System (INIS)

    Sasaki, Jun; Hayashi, Kazunori; Sugiyama, Kenji; Ichiko, Osami; Hashiguchi, Yoshihiro

    1992-01-01

    Titanium, yttrium, molybdenum, silver, chromium, hafnium, tantalum, tungsten and platinum ions generated by a metal vapor vacuum arc (MEVVA) ion source were implanted into 440C stainless steel in the dose region 10 17 ions cm -2 with extraction voltages of up to 70 kV. Glow discharge spectroscopy (GDS), friction coefficient, and Vickers microhardness of the specimens were studied. Grooves made by friction tests were investigated by electron probe microanalysis (EPMA). GDS showed incorporation of carbon in the yttrium, hafnium, tantalum, tungsten and platinum implanted specimens, as well as titanium implanted samples. A large amount of oxygen was observed in the yttrium implanted specimen. The friction coefficient was measured by reciprocating sliding of an unimplanted 440C ball without lubricant at a load of 0.245 N. The friction decreased and achieved a stable state after implantation of titanium, hafnium and tantalum. The friction coefficient of the platinum implanted specimen showed a gradual decrease after several cycles of sliding at high friction coefficient. The yttrium implanted sample exhibited a decreased but slightly unstable friction coefficient. Results from EPMA showed that the implanted elements, which gave decreased friction, remained even after sliding of 200 cycles. Implantation of chromium, molybdenum, silver and tungsten did not provide a decrease in friction and the implants were gone from the wear grooves after the sliding tests. (orig.)

  12. Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins

    Energy Technology Data Exchange (ETDEWEB)

    Matsubara, I. [Lab. of Chemistry, Tokyo Women' s Medical Univ. (Japan); Takeda, Y.; Ishida, K. [Lab. of Chemistry, Nippon Medical School, Kawasaki-shi, Kanagawa-ken (Japan)

    2000-02-01

    The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 {mu}g of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios. (orig.)

  13. Re-Os isotope and platinum group elements of a FOcal ZOne mantle source, Louisville Seamounts Chain, Pacific ocean

    Science.gov (United States)

    Tejada, Maria Luisa G.; Hanyu, Takeshi; Ishikawa, Akira; Senda, Ryoko; Suzuki, Katsuhiko; Fitton, Godfrey; Williams, Rebecca

    2015-02-01

    The Louisville Seamount Chain (LSC) is, besides the Hawaiian-Emperor Chain, one of the longest-lived hotspot traces. We report here the first Re-Os isotope and platinum group element (PGE) data for Canopus, Rigil, and Burton Guyots along the chain, which were drilled during IODP Expedition 330. The LSC basalts possess (187Os/188Os)i = 0.1245-0.1314 that are remarkably homogeneous and do not vary with age. A Re-Os isochron age of 64.9 ± 3.2 Ma was obtained for Burton seamount (the youngest of the three seamounts drilled), consistent with 40Ar-39Ar data. Isochron-derived initial 187Os/188Os ratio of 0.1272 ± 0.0008, together with data for olivines (0.1271-0.1275), are within the estimated primitive mantle values. This (187Os/188Os)i range is similar to those of Rarotonga (0.124-0.139) and Samoan shield (0.1276-0.1313) basalts and lower than those of Cook-Austral (0.136-0.155) and Hawaiian shield (0.1283-0.1578) basalts, suggesting little or no recycled component in the LSC mantle source. The PGE data of LSC basalts are distinct from those of oceanic lower crust. Variation in PGE patterns can be largely explained by different low degrees of melting under sulfide-saturated conditions of the same relatively fertile mantle source, consistent with their primitive mantle-like Os and primordial Ne isotope signatures. The PGE patterns and the low 187Os/188Os composition of LSC basalts contrast with those of Ontong Java Plateau (OJP) tholeiites. We conclude that the Re-Os isotope and PGE composition of LSC basalts reflect a relatively pure deep-sourced common mantle sampled by some ocean island basalts but is not discernible in the composition of OJP tholeiites.

  14. Global mining risk footprint of critical metals necessary for low-carbon technologies: the case of neodymium, cobalt, and platinum in Japan.

    Science.gov (United States)

    Nansai, Keisuke; Nakajima, Kenichi; Kagawa, Shigemi; Kondo, Yasushi; Shigetomi, Yosuke; Suh, Sangwon

    2015-02-17

    Meeting the 2-degree global warming target requires wide adoption of low-carbon energy technologies. Many such technologies rely on the use of precious metals, however, increasing the dependence of national economies on these resources. Among such metals, those with supply security concerns are referred to as critical metals. Using the Policy Potential Index developed by the Fraser Institute, this study developed a new footprint indicator, the mining risk footprint (MRF), to quantify the mining risk directly and indirectly affecting a national economy through its consumption of critical metals. We formulated the MRF as a product of the material footprint (MF) of the consuming country and the mining risks of the countries where the materials are mined. A case study was conducted for the 2005 Japanese economy to determine the MF and MRF for three critical metals essential for emerging energy technologies: neodymium, cobalt and platinum. The results indicate that in 2005 the MFs generated by Japanese domestic final demand, that is, the consumption-based metal output of Japan, were 1.0 × 10(3) t for neodymium, 9.4 × 10(3) t for cobalt, and 2.1 × 10 t for platinum. Export demand contributes most to the MF, accounting for 3.0 × 10(3) t, 1.3 × 10(5) t, and 3.1 × 10 t, respectively. The MRFs of Japanese total final demand (domestic plus export) were calculated to be 1.7 × 10 points for neodymium, 4.5 × 10(-2) points for cobalt, and 5.6 points for platinum, implying that the Japanese economy is incurring a high mining risk through its use of neodymium. This country's MRFs are all dominated by export demand. The paper concludes by discussing the policy implications and future research directions for measuring the MFs and MRFs of critical metals. For countries poorly endowed with mineral resources, adopting low-carbon energy technologies may imply a shifting of risk from carbon resources to other natural resources, in particular critical metals, and a trade

  15. Levels of platinum group elements and rare-earth elements in wild mushroom species growing in Poland.

    Science.gov (United States)

    Mleczek, Mirosław; Niedzielski, Przemysław; Kalač, Pavel; Siwulski, Marek; Rzymski, Piotr; Gąsecka, Monika

    2016-01-01

    Due to limited data-describing abilities of mushrooms to accumulate platinum group elements (PGEs) and rare-earth elements (REEs), the aim of this study was to determine, by inductively coupled plasma optical emission spectrometry followed by microwave-assisted sample digestion by nitric acid, the content of these elements in 20 mushroom species (10 above ground and 10 growing on wood), mostly edible, collected near a busy trunk road. The highest content of PGEs in above-ground mushroom species was observed in Lepista gilva and Suillus bovinus fruit bodies (0.38 ± 0.05 and 0.37 ± 0.03 mg kg(-1) DW, respectively), while in mushrooms growing on wood, the highest content was observed in Pleurotus ostreatus (0.35 ± 0.04 mg kg(-1) DW). The mean content of PGEs for both these groups was 0.23 ± 0.08 and 0.26 ± 0.07 mg kg(-1) DW, respectively. The highest content of REEs in Suillus luteus and Tricholoma equestra was 5.03 ± 0.50 and 2.18 ± 0.56 mg kg(-1) DW, respectively, but within mushrooms growing on wood in Ganoderma applanatum fruiting bodies it was 4.19 ± 0.78 mg kg(-1) DW. Mean contents of REEs were 1.39 ± 1.21 and 1.61 ± 0.97 mg kg(-1) DW in above-ground species and species growing on wood, respectively. Generally, the group of mushroom species growing on wood was capable of slightly higher accumulation of both REEs and PGEs. No limits have been established for both the groups until now.

  16. Determination of the platinum - group elements (PGE) and gold (Au) in the manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with ICP-MS

    Digital Repository Service at National Institute of Oceanography (India)

    Balaram, V.; Mathur, R.; Banakar, V.K.; Hein, J.R.; Rao, C.R.M.; Rao, T.G.; Dasaram, B.

    Platinum group elements (PGE) and Au data in polymetallic oceanic ferromanganese nodule reference samples and crust samples obtained by inductively coupled plasma mass spectrometry (ICP-MS), after separation and pre-concentration by nickel sulfide...

  17. Platinum stable isotopes in ferromanganese crust and nodules

    Science.gov (United States)

    Corcoran, Loretta; Seward, Terry; Handler, Monica R.

    2015-04-01

    Hydrogenetic ferromanganese (Fe-Mn) crust and nodules are slow-growing chemical sediments that form by direct precipitation from seawater, resulting in a record of changing seawater chemistry. These sediments are the primary sink for platinum in the modern oxic marine environment, hosting well-documented enrichments over other platinum-group elements (PGEs): the Pt anomaly [1]. Platinum is a non-bio-essential, highly siderophile, transition metal with six stable isotopes (190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt) with several oxidation states (Pt0, Pt2+ and Pt4+). Platinum is generally considered to exist in the hydrosphere as Pt2+ although its behaviour in the marine environment is poorly constrained, and Pt4+may also be present. Variations in ocean redox state, together with changes in source fluxes to the oceans, may therefore lead to small variations (Leaching experiments conducted on platinum rich terrestrial materials underwent platinum stable isotopic measurement as an analogue for the Pt isotopic fractionation associated with continental weathering. [1] Hodge, V.F. et al. (1985) Earth and Planetary Science Letters, 72, 158-162. [2] Creech, J. et al. (2013) Journal of Analytical Atomic Spectrometry, 28. 853-865.

  18. Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii

    Science.gov (United States)

    Pitcher, L.; Helz, R.T.; Walker, R.J.; Piccoli, P.

    2009-01-01

    Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35??years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9??wt.%, with temperatures prior to quench ranging from 1140????C to ambient (110????C). Five eruption samples were also analyzed. Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006-1.40??ppb for Os and 0.0006-2.01??ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF6 in some of the most magnesian samples. Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values

  19. Concentrations of Platinum Group Elements (Pt, Pd, Rh) in Airborne Particulate Matter (PM2.5 and PM10-2.5) Collected at Selected Canadian Urban Sites: a Case Study

    OpenAIRE

    Celo V.; Zhao J. J.; Dabek-Zlotorzynska E.

    2013-01-01

    Increasing environmental concentrations of platinum group elements (PGEs), in particular platinum (Pt), palladium (Pd) and rhodium (Rh), from catalytic converters has been reported worldwide. Initially it was believed that the emitted PGEs remain in the roadside environment, but recent studies have shown that fine PGE-containing particles can be transported and distributed at regional and long-range levels. Therefore, the monitoring of PGEs in airborne particulate matter (PM) is important for...

  20. Half-sandwich pentamethylcyclopentadienyl group 9 metal ...

    Indian Academy of Sciences (India)

    453 and LS-174) revealed low anti-proliferative activity. Replacement of substituted pyridine ligand in complexes such as picolinic acid exhibits better DNA binding affinity and cytotoxicity.7–10. Till now, a few reports are available for metal com-.

  1. Strategic and tactical determinants for South African platinum-group-metals supply

    CSIR Research Space (South Africa)

    McGill, JE

    2011-11-01

    Full Text Available continue deep development on the western limb, move to open shallower mines in the eastern limb, or adopt a combination of both approaches. To investigate the viability of eastern limb resources, and reserves, three main issues require consideration...-run forecast of demand and supply dynamics, and commodity prices, underpin a continued need for PGM production. National policy framework Strategic 2 Legislative environment supports the development of PGM resources in South Africa. Direct eastern limb...

  2. Borides of the group 1 metals of the periodic system

    International Nuclear Information System (INIS)

    Samsonov, G.V.; Serebryakova, T.I.; Neronov, V.A.

    1975-01-01

    The borides of alkali metals (lithium, sodium, potassium) and the metals of a copper subgroup (copper, silver, gold) are described. Consideration is given to the crystalline structure and state diagrams of the metal systems within the first group of the Periodic Table with boron. Existence, formation conditions and physico-chemical properties of binary boride phases are characterized. Conclusion is made as to the absence of interaction between boron and silver. Information on the interaction between gold and boron is scanty and conflicting. Methods are described suitable for the production of the borides of the metals within the first group of the Periodic Table [ru

  3. Interaction of terbium group metal oxides with carbon

    International Nuclear Information System (INIS)

    Vodop'yanov, A.G.; Baranov, S.V.; Kozhevnikov, G.N.

    1990-01-01

    Mechanism of carbothermal reduction of terbium group metals from oxides is investigated using thermodynamic and kinetic analyses. Interaction of metal oxides with carbon covers dissociation of metal oxides and reduction by carbon monoxide, which contribution into general reduction depends on CO pressure. Temperatures of reaction beginning for batch initial components at P=1.3x10 -4 and P CO =0.1 MPa and of formation of oxycarbide melts are determined

  4. Nuclear magnetic resonance study of the structure of simple molecules adsorbed on metal surfaces: acetylene on platinum

    International Nuclear Information System (INIS)

    Wang, P.K.

    1984-01-01

    We have used NMR to determine the structure of acetylene (HC - CH) adsorbed at room temperature on small platinum particles by studying the 13 C- 13 C, 13 C- 1 H, and 1 H- 1 H dipolar interactions among the nuclei in the adsorbed molecules. We find a model of 77% CCH 2 and 23% HCCH to be the only one consistent with all of our data. The C-C bond length of the majority species, CCH 2 , is determined as 1.44 +- 0.02 A, midway between a single and double bond, suggesting that both carbon atoms bond to the surface. 36 references, 29 figures, 1 table

  5. Phosphors containing boron and metals of Group IIIA and IIIB

    Science.gov (United States)

    Setlur, Anant Achyut; Srivastava, Alok Mani; Comanzo, Holly Ann; Manivannan, Venkatesan

    2006-10-31

    A phosphor comprises: (a) at least a first metal selected from the group consisting of yttrium and elements of lanthanide series other than europium; (b) at least a second metal selected from the group consisting of aluminum, gallium, indium, and scandium; (c) boron; and (d) europium. The phosphor is used in light source that comprises a UV radiation source to convert UV radiation to visible light.

  6. Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

    KAUST Repository

    Goswami, Subhadip

    2014-12-18

    A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores\\' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores\\' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).

  7. Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

    KAUST Repository

    Goswami, Subhadip; Winkel, Russell W.; Alarousu, Erkki; Ghiviriga, Ion; Mohammed, Omar F.; Schanze, Kirk S.

    2014-01-01

    A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).

  8. The platinum group elements and gold: analysis by radiochemical and instrumental neutron activation analysis and relevance to geological exploration and related problems

    Energy Technology Data Exchange (ETDEWEB)

    Reeves, S.; Plimer, I. R. [Melbourne Univ., Parkville, VIC (Australia). School of Physics

    1996-12-31

    This paper presents an overview of research conducted with the support of the Australian Institute of Nuclear Science and Engineering, at the University of Melbourne, School of Earth Sciences, Radiochemical Neutron Activation Laboratory. The primary objective of this research is to realize the high potential of the platinum group elements (PGE) and gold to the solution of petrogenetic problems, the study of magma generation and magmatic processes in mafic/ultramafic rock suites, as tracers in hydrothermal ore formation. The PGEs (Os, Ru, Ir, Pt, Pd and Rh) are among the least abundant of all elements on earth with unique properties such as high melting points, high electrical and thermal conductivity, high density, strength and toughness as alloys. They exhibit both siderophile and chalcophile characteristics and are valuable tools in providing information about magmatic processes, in particular S-saturation, as well as crystal fractionation trends. Two distinct groups of PGEs are discerned; the IPGEs (Ru, Os, Ir) and the PPGEs (Pt, Pd, Rh, Au) on the basis of their behaviour during fractionation processes. Using chondrite normalized PGE patterns it is possible to distinguish between sulphides that segregated from primitive magmas, such as komatiites, and sulphides which segregated from more fractionated magmas, such as tholeiites. It is critical to the understanding of these processes to be able to analyse key elements, such as the PGE and gold, in the parts per billion to parts per trillion range. Platinum group elements and Au were determined by radiochemical neutron activation analysis using a modified NiS fire-assay preconcentration technique, adapted from procedures first used by Robert, R.V. D. and van Wyk, E. (1975) . Detection limits are generally 0.005-0.01 ppb (Au and Ir), 0.1-0.2 ppb (Pd and Pt), and 0.1-0.5 ppb for Ru. 9 refs.

  9. The platinum group elements and gold: analysis by radiochemical and instrumental neutron activation analysis and relevance to geological exploration and related problems

    International Nuclear Information System (INIS)

    Reeves, S.; Plimer, I. R.

    1996-01-01

    This paper presents an overview of research conducted with the support of the Australian Institute of Nuclear Science and Engineering, at the University of Melbourne, School of Earth Sciences, Radiochemical Neutron Activation Laboratory. The primary objective of this research is to realize the high potential of the platinum group elements (PGE) and gold to the solution of petrogenetic problems, the study of magma generation and magmatic processes in mafic/ultramafic rock suites, as tracers in hydrothermal ore formation. The PGEs (Os, Ru, Ir, Pt, Pd and Rh) are among the least abundant of all elements on earth with unique properties such as high melting points, high electrical and thermal conductivity, high density, strength and toughness as alloys. They exhibit both siderophile and chalcophile characteristics and are valuable tools in providing information about magmatic processes, in particular S-saturation, as well as crystal fractionation trends. Two distinct groups of PGEs are discerned; the IPGEs (Ru, Os, Ir) and the PPGEs (Pt, Pd, Rh, Au) on the basis of their behaviour during fractionation processes. Using chondrite normalized PGE patterns it is possible to distinguish between sulphides that segregated from primitive magmas, such as komatiites, and sulphides which segregated from more fractionated magmas, such as tholeiites. It is critical to the understanding of these processes to be able to analyse key elements, such as the PGE and gold, in the parts per billion to parts per trillion range. Platinum group elements and Au were determined by radiochemical neutron activation analysis using a modified NiS fire-assay preconcentration technique, adapted from procedures first used by Robert, R.V. D. and van Wyk, E. (1975) . Detection limits are generally 0.005-0.01 ppb (Au and Ir), 0.1-0.2 ppb (Pd and Pt), and 0.1-0.5 ppb for Ru. 9 refs

  10. The platinum group elements and gold: analysis by radiochemical and instrumental neutron activation analysis and relevance to geological exploration and related problems

    Energy Technology Data Exchange (ETDEWEB)

    Reeves, S; Plimer, I R [Melbourne Univ., Parkville, VIC (Australia). School of Physics

    1997-12-31

    This paper presents an overview of research conducted with the support of the Australian Institute of Nuclear Science and Engineering, at the University of Melbourne, School of Earth Sciences, Radiochemical Neutron Activation Laboratory. The primary objective of this research is to realize the high potential of the platinum group elements (PGE) and gold to the solution of petrogenetic problems, the study of magma generation and magmatic processes in mafic/ultramafic rock suites, as tracers in hydrothermal ore formation. The PGEs (Os, Ru, Ir, Pt, Pd and Rh) are among the least abundant of all elements on earth with unique properties such as high melting points, high electrical and thermal conductivity, high density, strength and toughness as alloys. They exhibit both siderophile and chalcophile characteristics and are valuable tools in providing information about magmatic processes, in particular S-saturation, as well as crystal fractionation trends. Two distinct groups of PGEs are discerned; the IPGEs (Ru, Os, Ir) and the PPGEs (Pt, Pd, Rh, Au) on the basis of their behaviour during fractionation processes. Using chondrite normalized PGE patterns it is possible to distinguish between sulphides that segregated from primitive magmas, such as komatiites, and sulphides which segregated from more fractionated magmas, such as tholeiites. It is critical to the understanding of these processes to be able to analyse key elements, such as the PGE and gold, in the parts per billion to parts per trillion range. Platinum group elements and Au were determined by radiochemical neutron activation analysis using a modified NiS fire-assay preconcentration technique, adapted from procedures first used by Robert, R.V. D. and van Wyk, E. (1975) . Detection limits are generally 0.005-0.01 ppb (Au and Ir), 0.1-0.2 ppb (Pd and Pt), and 0.1-0.5 ppb for Ru. 9 refs.

  11. Synthesis of IV-VI Transition Metal Carbide and Nitride Nanoparticles Using a Reactive Mesoporous Template for Electrochemical Hydrogen Evolution Reaction

    KAUST Repository

    Alhajri, Nawal Saad

    2016-01-01

    Interstitial carbides and nitrides of early transition metals in Groups IV-VI exhibit platinum-like behavior which makes them a promising candidate to replace noble metals in a wide variety of reactions. Most synthetic methods used to prepare

  12. The architecture of metal coordination groups in proteins.

    Science.gov (United States)

    Harding, Marjorie M

    2004-05-01

    A set of tables is presented and a survey given of the architecture of metal coordination groups in a representative set of protein structures from the Protein Data Bank [Bernstein et al. (1977), J. Mol. Biol. 112, 535-542; Berman et al. (2000), Nucleic Acids Res. 28, 235-242]. The structures have been determined to a resolution of 2.5 A or better; the metals considered are Ca, Mg, Mn, Fe, Cu, Zn, Na and K, with particular emphasis on Ca and Zn and the exclusion of haem groups and Fe/S clusters; the proteins are a representative set in which none has more than 30% sequence identity with any other. In them the metal is coordinated by several donor groups from different amino-acid residues in the protein chain and often also by water or other small molecules. The tables, for approximately 600 metal coordination groups, include information on the conformations of the protein chain in the region around the metal and reliability indicators. They illustrate the wide variety of coordination numbers, chelate-loop sizes and other properties and the different characteristics of different metals. They show that glycine has a particular significance in the position adjacent to a donor residue, especially in Ca coordination groups. They also show that metal coordination does not appear to lead to significant distortions of the torsion angles phi, psi from their normally allowed values. Very few metal coordination groups occur more than once in the representative set and when they do they are usually related in fold and function; they have similar but not necessarily identical conformations. However, individual chelate loops, for example Zn(-C-X-X'-C-), in which both cysteines are coordinated to Zn through S, and X and X' are any amino acids, are repeated frequently in many different and unrelated proteins. Not all chelate loops with the same composition have the same conformation, but for smaller loops there are usually one or two strongly preferred and well defined

  13. Komatiites and nickel sulfide ores of the Black Swan area, Yilgarn Craton, Western Australia. 4. Platinum group element distribution in the ores, and genetic implications

    Science.gov (United States)

    Barnes, Stephen J.

    2004-11-01

    The Black Swan komatiite sequence, in the Eastern Goldfields province of the Archaean Yilgarn Craton in Western Australia, is a body of dominantly olivine-rich cumulates with lesser volumes of spinifex textured rocks, interpreted as a section through an extensive komatiite lava flow field. The sequence hosts a number of nickel sulfide orebodies, including the Silver Swan massive shoot and the Cygnet and Black Swan disseminated orebodies. The massive sulfide orebodies of the Black Swan Succession are pervasively depleted in all platinum group elements (PGEs), particularly Pt and Pd, despite very high Ni contents. This depletion cannot be explained by R-factor variations, which would also require relatively low Ni tenors. The PGE depletion could be explained in part if the ores are enriched in a monosulfide solid solution (MSS) cumulate component, but requires some additional fractional segregation of sulfide melt upstream from the site of deposition. The Silver Swan orebody shows a remarkably consistent vertical zonation in PGE contents, particularly in Ir, Ru, Rh, Os, which increase systematically from very low levels at the stratigraphic base of the sulfide body to maxima corresponding roughly with the top of a lower layer of the orebody rich in silicate inclusions. Platinum shows the opposite trend, but is somewhat modified by remobilisation during talc carbonate alteration. A similar pattern is also observed in the adjacent White Swan orebody. This zonation is interpreted and modelled as the result of fractional crystallisation of MSS from the molten sulfide pool. The strong IPGE depletion towards the base of the orebody may be a consequence of sulfide liquid crystallisation in an inverted thermal gradient, between a thin rapidly cooling upper rind of komatiite lava and a hot substrate.

  14. Platinum, palladium, and rhodium in volcanic and plutonic rocks from the Gravina-Nutzotin belt, Alaska

    Science.gov (United States)

    Page, Norman J; Berg, Henry C.; Haffty, Joseph

    1977-01-01

    The Gravina-Nutzotin belt of Middle (?) Jurassic to middle Cretaceous sedimentary and volcanic rocks in south and southeastern Alaska includes concentrically zoned ultramafic complexes known to contain platinum-group metals. Previous isotopic, petrologic, and geologic studies suggested a close relation in time and space between the volcanic rocks and the ultramafic complexes. Interpretation of 40 analyses for platinum, palladium, and rhodium in volcanic and plutonic rocks of the belt indicates a strong geochemical correlation between the two groups of rocks and is in support of their being cogenetic either from directly connected magma chambers and flows or indirectly by selective concentration processes from similar mantle material.

  15. Biohydrometallurgical methods for metals recovery from waste materials

    OpenAIRE

    J. Willner; J. Kadukova; A. Fornalczyk; M. Saternus

    2015-01-01

    The article draws attention to recently conducted research of bacterial leaching of metals from various polymetallic waste. These wastes are the carriers of valuable metals: base metals, precious and platinum group metals (e.g. electronic waste, spent catalysts) or rare earth elements.

  16. Biohydrometallurgical methods for metals recovery from waste materials

    Directory of Open Access Journals (Sweden)

    J. Willner

    2015-01-01

    Full Text Available The article draws attention to recently conducted research of bacterial leaching of metals from various polymetallic waste. These wastes are the carriers of valuable metals: base metals, precious and platinum group metals (e.g. electronic waste, spent catalysts or rare earth elements.

  17. Primary endpoint results of the OMEGA Study: One-year clinical outcomes after implantation of a novel platinum chromium bare metal stent

    Energy Technology Data Exchange (ETDEWEB)

    Wang, John C., E-mail: john.wang@medstar.net [MedStar Union Memorial Hospital, Baltimore MD (United States); Carrié, Didier, E-mail: carrie.didier@chu-toulouse.fr [Centre Hôpital Universitaire Rangueil, Toulouse (France); Masotti, Monica, E-mail: MASOTTI@clinic.ub.es [Hospital Clinic, University of Barcelona (Spain); Erglis, Andrejs, E-mail: a.a.erglis@stradini.lv [Pauls Stradins Clinical University Hospital, University of Latvia, Riga (Latvia); Mego, David, E-mail: David.Mego@arheart.com [Arkansas Heart Hospital, Little Rock, AR (United States); Watkins, Matthew W., E-mail: Matthew.Watkins@vtmednet.org [University of Vermont Medical Center, Burlington VT (United States); Underwood, Paul, E-mail: Paul.underwood@bsci.com [Boston Scientific, Marlborough MA USA (United States); Allocco, Dominic J., E-mail: Dominic.allocco@bsci.com [Boston Scientific, Marlborough MA USA (United States); Hamm, Christian W., E-mail: C.Hamm@kerckhoff-klinik.de [Kerckhoff Heart and Thoraxcenter, Bad Nauheim (Germany)

    2015-03-15

    Background/purpose: Bare metal stents (BMS) have similar rates of death and myocardial infarction (MI) compared to drug-eluting stents (DES). DES lower repeat revascularization rates compared to BMS, but may have higher rates of late stent thrombosis (ST) potentially due to impaired endothelialization requiring longer dual anti-platelet therapy (DAPT). OMEGA evaluated a novel BMS designed to have improved deliverability and radiopacity, in comparison to currently available platforms. Methods/materials: OMEGA was a prospective, multicenter, single-arm study enrolling 328 patients at 37 sites (US and Europe). Patients received the OMEGA stent (bare platinum chromium element stent) for the treatment of de novo native coronary artery lesions (≤ 28 mm long; diameter ≥ 2.25 mm to ≤ 4.50 mm). The primary endpoint was 9-month target lesion failure (TLF: cardiac death, target vessel-related MI, target lesion revascularization [TLR]) compared to a prespecified performance goal (PG) based on prior generation BMS. All major cardiac events were independently adjudicated. DAPT was required for a minimum of 1 month post procedure. Results: In the OMEGA study, the mean age was 65; 17% had diabetes mellitus. The primary endpoint was met; 9 month TLF rate was 11.5%, and the upper 1-sided 95% confidence bound of 14.79% was less than the prespecified PG of 21.2% (p < 0.0001). One-year event rates were low including a TLF rate of 12.8% and an ST rate of 0.6% at 12 months. Conclusions: One-year outcomes of OMEGA show low rates of TLF, revascularization and ST. This supports safety and efficacy of the OMEGA BMS for the treatment of coronary artery disease. - Highlights: • The OMEGA study evaluated a novel platinum chromium bare metal stent. • OMEGA enrolled 328 patients at 37 sites (US and Europe). • The primary endpoint of 9 month target lesion failure was 11.5%. • One-year event rates were low including an ST rate of 0.6% at 12 months.

  18. Primary endpoint results of the OMEGA Study: One-year clinical outcomes after implantation of a novel platinum chromium bare metal stent

    International Nuclear Information System (INIS)

    Wang, John C.; Carrié, Didier; Masotti, Monica; Erglis, Andrejs; Mego, David; Watkins, Matthew W.; Underwood, Paul; Allocco, Dominic J.; Hamm, Christian W.

    2015-01-01

    Background/purpose: Bare metal stents (BMS) have similar rates of death and myocardial infarction (MI) compared to drug-eluting stents (DES). DES lower repeat revascularization rates compared to BMS, but may have higher rates of late stent thrombosis (ST) potentially due to impaired endothelialization requiring longer dual anti-platelet therapy (DAPT). OMEGA evaluated a novel BMS designed to have improved deliverability and radiopacity, in comparison to currently available platforms. Methods/materials: OMEGA was a prospective, multicenter, single-arm study enrolling 328 patients at 37 sites (US and Europe). Patients received the OMEGA stent (bare platinum chromium element stent) for the treatment of de novo native coronary artery lesions (≤ 28 mm long; diameter ≥ 2.25 mm to ≤ 4.50 mm). The primary endpoint was 9-month target lesion failure (TLF: cardiac death, target vessel-related MI, target lesion revascularization [TLR]) compared to a prespecified performance goal (PG) based on prior generation BMS. All major cardiac events were independently adjudicated. DAPT was required for a minimum of 1 month post procedure. Results: In the OMEGA study, the mean age was 65; 17% had diabetes mellitus. The primary endpoint was met; 9 month TLF rate was 11.5%, and the upper 1-sided 95% confidence bound of 14.79% was less than the prespecified PG of 21.2% (p < 0.0001). One-year event rates were low including a TLF rate of 12.8% and an ST rate of 0.6% at 12 months. Conclusions: One-year outcomes of OMEGA show low rates of TLF, revascularization and ST. This supports safety and efficacy of the OMEGA BMS for the treatment of coronary artery disease. - Highlights: • The OMEGA study evaluated a novel platinum chromium bare metal stent. • OMEGA enrolled 328 patients at 37 sites (US and Europe). • The primary endpoint of 9 month target lesion failure was 11.5%. • One-year event rates were low including an ST rate of 0.6% at 12 months

  19. Simultaneous determination of platinum group elements and rhenium in rock samples using isotope dilution inductively coupled plasma mass spectrometry after cation exchange separation followed by solvent extraction

    International Nuclear Information System (INIS)

    Shinotsuka, Kazunori; Suzuki, Katsuhiko

    2007-01-01

    A simple and precise determination method for platinum group elements (PGEs) and Re in rock samples was developed using isotope dilution coupled with inductively coupled plasma mass spectrometry (ID-ICP-MS). Cation exchange separation was employed for simplicity, because it is applicable to group separation and simultaneous isotopic measurement in contrast with the widely used anion exchange separation which entails separate elution. However, its application to ID-ICP-MS has been limited due to spectral interferences from impurities retained in the PGE fraction even after ion chromatography. To overcome this limitation, solvent extraction using N-benzoyl-N-phenylhydroxylamine (BPHA) in chloroform was successfully applied for further purification. After the examination of optimum experimental parameters in cation exchange separation and solvent extraction using synthetic PGE solution, the established procedure was applied to the determination of PGEs and Re in some geochemical reference materials. The obtained results agreed well with the literature data determined using the different digestion methods (NiS fire assay and the use of a high-pressure asher) within the analytical uncertainties of each other. Significant difference in reproducibility between Ru, Ir, Pt and Os group, and Pd and Re group was observed in the results for BHVO-2 and JA-2. By considering the error factors affecting analytical reproducibility, we concluded that the difference is ascribed to the sample heterogeneity of minor minerals enriched in Ru, Ir, Pt and Os

  20. Radiochemical neutron activation analysis of high pure palladium and platinum by ion exchange chromatography

    International Nuclear Information System (INIS)

    Sadikov, I.I.; Zinov'ev, V.G.; Sadikova, Z.O.; Salimov, M.I.

    2006-01-01

    Full text: The palladium and platinum are widely used for jewel manufacture because of their beautiful white color. However the most part of these metals are widely adopted in the world as catalysts. Many works on analytical chemistry of platinum group elements published during last years are devoted to determination of platinum and palladium in other materials. There are no articles on analysis technique of the palladium and platinum purity published during last 20 years. Available publications are very old and are published till 70th of the last century, and implement chemical and spectral methods. At the same time, the palladium and platinum are very suitable for NAA. Therefore the purpose of our research was development of high-sensitivity and multielement techniques of radiochemical neutron activation analysis of a high pure palladium and platinum. Research of nuclear characteristics of palladium and platinum has shown that radioactive nuclides with different yields are formed under the reactor neutrons. 109 , 111 , 111m Pd, 109m , 111 Ag, 191 , 197 , 199 Pt, 199 Au are the most important among them. 109Pd separation factor is equal to 1*10 5 at palladium analysis, whereas 197 Pt and 199 Au separation factor is equal to 1*10 4 at the platinum analysis every other day after irradiation. Palladium and platinum can be separated by precipitation, extraction and ion exchange methods. For separation of radioactive nuclide of the matrix elements from the impurity elements we used ion exchange chromatography system Dowex-1x8 - 1 M HNO 3 for palladium and Dowex-1x8 - 0.1 M HNO 3 for platinum. At the HNO 3 acid concentrations variation from 0,1 M to 1 M more then 25 elements have distribution factors less than 1 and 10 elements have distribution factors 5 while matrix elements have distribution factors higher than 100. It allows an effective separation of these elements from palladium and platinum. Optimum sizes of the chromatographic column and the column effluent

  1. Group 4 Metal Complexes of Chelating Cyclopentadienyl-ketimide Ligands

    Czech Academy of Sciences Publication Activity Database

    Večeřa, M.; Varga, Vojtěch; Císařová, I.; Pinkas, Jiří; Kucharczyk, P.; Sedlařík, V.; Lamač, Martin

    2016-01-01

    Roč. 35, č. 5 (2016), s. 785-798 ISSN 0276-7333 R&D Projects: GA ČR(CZ) GA14-08531S; GA MŠk(CZ) LO1504 Institutional support: RVO:61388955 Keywords : group 4 metal complexes * cyclopentadienyl-ketimide ligands * metallocenes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.862, year: 2016

  2. Investigations on the bioavailability of traffic-related platinum group elements (PGE) to the aquatic fauna with special consideration being given to palladium; Untersuchungen zur Bioverfuegbarkeit Kfz-emittierter Platingruppenelemente (PGE) fuer die aquatische Fauna unter besonderer Beruecksichtigung von Palladium

    Energy Technology Data Exchange (ETDEWEB)

    Sures, B.; Thielen, F.; Zimmermann, S. [Karlsruhe Univ. (T.H.) (Germany). Zoologisches Inst.

    2002-07-01

    The uptake and accumulation of the traffic-related platinum group elements (PGE) Pt, Pd and Rh by the aquatic fauna was investigated. Zebra mussels, eels and barbels were maintained in water containing either road dust or ground catalytic converter material. Following the exposure, samples of fish liver and kidney, as well as the soft tissues of the mussels, were analysed. Our results revealed that all three catalytic noble metals were accumulated by aquatic organisms. The highest bioavailability was found for Pd, followed by Pt and Rh. The concentration factor of Pd for Dreissena polymorpha was 5 times higher compared with Pb and only 6 times lower than the essential element Cu. With regard to the increasing emission of Pd the level of this metal has to be monitored very carefully in the environment. (orig.) [German] Die Aufnahme und Anreicherung der Kfz-buertigen Platingruppenelemente (PGE) Pt, Pd und Rh durch aquatische Tiere wurde an Dreikantmuscheln, Aalen und Barben untersucht. Hierzu wurden die Testorganismen in Wasser mit Strassenstaub einer stark befahrenen Strasse oder mit zerriebenem Autokatalysatormaterial ueber mehrere Wochen exponiert und anschliessend Leber und Niere der Fische sowie das Weichgewebe der Muscheln analysiert. Im Rahmen dieser Studien konnte nachgewiesen werden, dass alle drei Edelmetalle durch Fische wie durch Muscheln aufgenommen und angereichert werden. Fuer Pd fand sich die hoechste Bioverfuegbarkeit, gefolgt von Pt und Rh. Das Ausmass der Aufnahme von Pd durch Dreissena polymorpha war ca. 5fach hoeher als von Pb und 6fach niedriger verglichen mit dem essenziellen Element Cu. In Anbetracht der steigenden Emission von Pd sollte ein Umweltmonitoring die Verbreitung von Pd in der Umwelt klaeren. (orig.)

  3. Platinum-group element geochemistry used to determine Cu and Au fertility in the Northparkes igneous suites, New South Wales, Australia

    Science.gov (United States)

    Hao, Hongda; Campbell, Ian H.; Park, Jung-Woo; Cooke, David R.

    2017-11-01

    Recent studies have shown that platinum-group elements (PGE) can be used to constrain the timing of sulfide saturation in evolving felsic systems. In this study, we report trace-element, PGE, Re and Au data for the barren and ore-associated suites of intermediate to felsic rocks from the Northparkes Cu-Au porphyry region, emphasizing the timing of sulfide saturation and its influence on the tenor of the associated hydrothermal mineralization. Two barren suites, the Goonumbla and Wombin Volcanics and associate intrusive rocks, are found in the region. Geochemical modelling shows that the barren suites are dominated by plagioclase-pyroxene fractionation, whereas the ore-associated Northparkes Cu-Au porphyry suite is characterized by plagioclase-amphibole fractionation, which requires the ore-bearing suite to have crystallized from a wetter magma than barren suites. The concentrations of PGE, Re and Au in the barren suites decrease continuously during fractional crystallization. This is attributed to early sulfide saturation with the fraction of immiscible sulfide precipitation required to produce the observed trend, being 0.13 and 0.16 wt.% for the Goonumbla and Wombin suites, respectively. The calculated partition coefficients for Au and Pd required to model the observed change in these elements with MgO are well below published values, indicating that R, the mass ratio of silicate to sulfide melt, played a significant role in controlling the rate of decline of these elements with fractionation. Palladium in the ore-associated suite, in contrast, first increases with fractionation then decreases abruptly at 1.2 wt.% MgO. The sharp decrease is attributed to the onset of sulfide precipitation. Platinum on the other hand shows a moderate decrease, starting from the highest MgO sample analysed, but then decreasing strongly from 1.2 wt.% MgO. The initial Pt decrease is attributed to precipitation of a platinum-group mineral (PGM), probably a Pt-Fe alloy, and the sharp

  4. Noble metal extraction and sorption concentrating

    International Nuclear Information System (INIS)

    Petrukhin, O.M.; Malofeeva, G.I.

    1985-01-01

    Works performed in the USSR Academy of Sciences GEOCHI laboratory of extraction methods and devoted to selectivity problems of extraction and sorption methods of platinum metal, cadmium and indium concentrating in analytical chemistry are discussed. On choosing complexino. reagent main attention is paid to the selectivity variation based on different stability of metal complexes. Platinum metals are extracted in the form of ion associates when usinq hard, mainly oxyqen-containing, extractants. Coordination-solvated metal complexes are extracted white usinq extractants containing sulfur, trivalent phosphorus and aromatic nitroqen as donor anions. Selectivity is maximum for sulfur- and nitroren-containinq extractants and sorbents. In case of the group extraction of platinum metals sorption is preferable and in case of selective extraction of individual metals, especially, in case of need of relative concentratinq extraction is preferable

  5. Contributions to the determination of the noble metals gold, iridium, palladium, platinum, rhodium and application to environmentally relevant samples

    International Nuclear Information System (INIS)

    Zischka, M.

    1998-11-01

    The concentrations of noble metals in the environment are still very low (low ng/g and sub ng/g range), although they are emitted to an increasing extent as components of catalytic exhaust emission converters into the environment. The determination of these elements can be error prone even when the determinations are carried out by use of highly sensitive methods in combination with high performance sample preparation techniques. Accurate data with smallest possible measurement uncertainties are a prerequisite for the interpretation of the distribution of noble metals in the environment and their possible toxicological effects. Difficulties related to the determination of the noble metals could be the incomplete recovery after sample preparation, sample digestion and interferences arising in subsequent instrumental determination methods. For this reason two different sample decomposition methods in combination with powerful instrumental techniques are checked for suitability for the determination of the noble metals in environmentally relevant samples. Digestion methods under evaluation are the NiS fire assay and the leaching with aqua regia in closed vessels under high pressure and high temperature. The NiS fire assay provides pre-concentration of the noble-metals and matrix separation of most of the remaining matrix elements. Disadvantages of this method are the need for experienced analysts, the awkward handling and the time-consuming procedure. On the other hand leaching with aqua regia under high pressure at high temperatures is easy to handle and not time-consuming with the crucial disadvantage that neither a pre-concentration of the noble metals nor a matrix separation can be achieved. Investigated instrumental techniques are the ICP-AES (inductively coupled plasma atomic emission spectrometry) with an axially arranged plasma either with a cross-flow or with an ultrasonic nebulizer, the quadrupole ICP-MS (inductively coupled plasma mass spectrometry) and the

  6. Core-Shell Structuring of Pure Metallic Aerogels towards Highly Efficient Platinum Utilization for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Cai, Bin; Hübner, René; Sasaki, Kotaro; Zhang, Yuanzhe; Su, Dong; Ziegler, Christoph; Vukmirovic, Miomir B; Rellinghaus, Bernd; Adzic, Radoslav R; Eychmüller, Alexander

    2018-03-05

    The development of core-shell structures remains a fundamental challenge for pure metallic aerogels. Here we report the synthesis of Pd x Au-Pt core-shell aerogels composed of an ultrathin Pt shell and a composition-tunable Pd x Au alloy core. The universality of this strategy ensures the extension of core compositions to Pd transition-metal alloys. The core-shell aerogels exhibited largely improved Pt utilization efficiencies for the oxygen reduction reaction and their activities show a volcano-type relationship as a function of the lattice parameter of the core substrate. The maximum mass and specific activities are 5.25 A mg Pt -1 and 2.53 mA cm -2 , which are 18.7 and 4.1 times higher than those of Pt/C, respectively, demonstrating the superiority of the core-shell metallic aerogels. The proposed core-based activity descriptor provides a new possible strategy for the design of future core-shell electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Solvent extraction of platinum with thiobenzanilide. Separation of platinum from copper

    International Nuclear Information System (INIS)

    Shkil', A.N.; Zolotov, Yu.A.

    1989-01-01

    The solvent extraction of micro concentrations of platinum has been investigated from hydrochloric acid media using thiobenzanilide in the presence of SnCl 2 and KI. In the presence of SnCl 2 platinum is extracted rapidly and to significant completion. Conditions have been developed for the quantitative extraction of platinum. The authors have also examined the solvent extraction of copper(II) using thiobenzanilide, interference due to copper(II) and iron(III) on solvent extraction of platinum, and methods to suppress this interference. A procedure has also been developed for the separation of platinum from copper. Solvent extraction of metals was studied using radioactive isotopes: 197 Pt, 64 Cu, 59 Fe, 198 Au, 109 Pd, 110m Ag

  8. Characterization of electrochemically modified polycrystalline platinum surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Krebs, L.C.; Ishida, Takanobu.

    1991-12-01

    The characterization of electrochemically modified polycrystalline platinum surfaces has been accomplished through the use of four major electrochemical techniques. These were chronoamperometry, chronopotentiommetry, cyclic voltammetry, and linear sweep voltammetry. A systematic study on the under-potential deposition of several transition metals has been performed. The most interesting of these were: Ag, Cu, Cd, and Pb. It was determined, by subjecting the platinum electrode surface to a single potential scan between {minus}0.24 and +1.25 V{sub SCE} while stirring the solution, that the electrocatalytic activity would be regenerated. As a consequence of this study, a much simpler method for producing ultra high purity water from acidic permanganate has been developed. This method results in water that surpasses the water produced by pyrocatalytic distillation. It has also been seen that the wettability of polycrystalline platinum surfaces is greatly dependent on the quantity of oxide present. Oxide-free platinum is hydrophobic and gives a contact angle in the range of 55 to 62 degrees. We have also modified polycrystalline platinum surface with the electrically conducting polymer poly-{rho}-phenylene. This polymer is very stable in dilute sulfuric acid solutions, even under applied oxidative potentials. It is also highly resistant to electrochemical hydrogenation. The wettability of the polymer modified platinum surface is severely dependent on the choice of supporting electrolyte chosen for the electrochemical polymerization. Tetraethylammonium tetrafluoroborate produces a film that is as hydrophobic as Teflon, whereas tetraethylammonium perchlorate produces a film that is more hydrophilic than oxide-free platinum.

  9. Characterization of electrochemically modified polycrystalline platinum surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Krebs, Leonard C. [State Univ. of New York (SUNY), Stony Brook, NY (United States); Ishida, Takanobu [State Univ. of New York (SUNY), Stony Brook, NY (United States)

    1991-12-01

    The characterization of electrochemically modified polycrystalline platinum surfaces has been accomplished through the use of four major electrochemical techniques. These were chronoamperometry, chronopotentiommetry, cyclic voltammetry, and linear sweep voltammetry. A systematic study on the under-potential deposition of several transition metals has been performed. The most interesting of these were: Ag, Cu, Cd, and Pb. It was determined, by subjecting the platinum electrode surface to a single potential scan between -0.24 and +1.25 VSCE while stirring the solution, that the electrocatalytic activity would be regenerated. As a consequence of this study, a much simpler method for producing ultra high purity water from acidic permanganate has been developed. This method results in water that surpasses the water produced by pyrocatalytic distillation. It has also been seen that the wettability of polycrystalline platinum surfaces is greatly dependent on the quantity of oxide present. Oxide-free platinum is hydrophobic and gives a contact angle in the range of 55 to 62 degrees. We have also modified polycrystalline platinum surface with the electrically conducting polymer poly-ρ-phenylene. This polymer is very stable in dilute sulfuric acid solutions, even under applied oxidative potentials. It is also highly resistant to electrochemical hydrogenation. The wettability of the polymer modified platinum surface is severely dependent on the choice of supporting electrolyte chosen for the electrochemical polymerization. Tetraethylammonium tetrafluoroborate produces a film that is as hydrophobic as Teflon, whereas tetraethylammonium perchlorate produces a film that is more hydrophilic than oxide-free platinum.

  10. Design of supported bi-metallic nanoparticles based on Platinum and Palladium using Surface Organometallic Chemistry (SOMC)

    KAUST Repository

    Al-Shareef, Reem A.

    2017-11-01

    Well-defined silica supported bimetallic catalysts Pt100-x Pdx (where x is the molar ratio of Pd) are prepared by Surface Organometallic Chemistry (SOMC) via controlled decomposition of Pd2(allyl)2Cl2 on Pt/SiO2. For comparison purposes, Pt100-x Pdx bimetallic catalysts is also prepared by ion-exchange (IE). According to the results of STEM, XAS and H2 chemisorption, all bimetallic nanoparticles, prepared using neither SOMC nor IE, produce discrete formation of monometallic species (either Pt or Pd). Most catalysts exhibit a narrow particle size distribution with an average diameter ranging from 1 to 3 nm for samples prepared by IE and from 2 to 5 nm for the ones synthesized by SOMC. For all catalysts investigated in the present work, iso-butane reaction with hydrogen under differential conditions (conversions below 5%) leads to the formation of methane and propane (hydrogenolysis), n-butane (isomerization), and traces of iso-butylene (dehydrogenation). The total rate of reaction decreases with increasing the Pd loading for both catalysts series as a result of decreasing turnover rate (expressed as moles converted per total surface metal per second) of both isomerization and hydrogenolysis. In the case of Pt100-x Pdx(SOMC) catalysts, the results suggest a selective coverage of Pt (100) surface by a Pd layer, followed by a buildup of Pd overcoat onto a Pd layer assuming that each metal keeps its intrinsic catalytic properties. There is no mutual electronic charge transfer between the two metals (DFT). For the PtPd catalysts prepared by IE, the catalytic behavior cannot simply be explained by a surface coverage of highly active Pt metal by less active Pd (not observed), suggesting there is formation of a surface alloy between Pt and Pd collaborated by EXAFS and DFT. The catalytic results are explained by a simple structure activity relationship based on the previously proposed mechanism of C-H bond and C-C Bond activation and cleavage for iso-butane hydrogenolysis

  11. Platinum-group element contents of Karelian kimberlites: Implications for the PGE budget of the sub-continental lithospheric mantle

    Science.gov (United States)

    Maier, W. D.; O'Brien, H.; Peltonen, P.; Barnes, Sarah-Jane

    2017-11-01

    We present high-precision isotope dilution data for Os, Ir, Ru, Pt, Pd and Re in Group I and Group II kimberlites from the Karelian craton, as well as 2 samples of the Premier Group I kimberlite pipe from the Kaapvaal craton. The samples have, on average, 1.38 ppb Pt and 1.33 ppb Pd, with Pt/Pd around unity. These PGE levels are markedly lower, by as much as 80%, than those reported previously for kimberlites from South Africa, Brazil and India, but overlap with PGE results reported recently from Canadian kimberlites. Primitive-mantle-normalised chalcophile element patterns are relatively flat from Os to Pt, but Cu, Ni and, somewhat less so, Au are enriched relative to the PGE (e.g., Cu/Pd > 25.000). Pd/Ir ratios are 3,6 on average, lower than in most other mantle melts. The PGE systematics can be largely explained by two components, (i) harzburgite/lherzolite detritus of the SCLM with relatively high IPGE (Os-Ir-Ru)/PPGE (Rh-Pt-Pd) ratios, and (ii) a melt component that has high PPGE/IPGE ratios. By using the concentrations of iridium in the kimberlites as a proxy for the proportion of mantle detritus in the magma, we estimate that the analysed kimberlites contain 3-27% entrained and partially dissolved detritus from the sub-continental lithospheric mantle, consistent with previous estimates of kimberlites elsewhere (Tappe S. et al., 2016, Chem. Geol. 10.1016/j.chemgeo.2016.08.019).

  12. Separation of palladium from high-level waste using metal ferro cyanide loaded resins

    International Nuclear Information System (INIS)

    Valsala, T.P.; Joseph, Annie; Yeotikar, R.G.

    2005-01-01

    High-level waste (HLW) is generated during reprocessing of spent fuel. HLW contains corrosion products, unextracted actinides, process chemicals and fission products. A recent trend is there to consider waste as a source of wealth. Among the fission products separation and recovery of platinum group metals have gained great attention. HLW is a good source of palladium of the platinum group metal. The present study shows the feasibility of ion exchange separation of Pd from HLW. (author)

  13. Platinum-group elements, S, Se and Cu in highly depleted abyssal peridotites from the Mid-Atlantic Ocean Ridge (ODP Hole 1274A): Influence of hydrothermal and magmatic processes

    Science.gov (United States)

    Marchesi, Claudio; Garrido, Carlos J.; Harvey, Jason; González-Jiménez, José María; Hidas, Károly; Lorand, Jean-Pierre; Gervilla, Fernando

    2013-11-01

    Highly depleted harzburgites and dunites were recovered from ODP Hole 1274A, near the intersection between the Mid-Atlantic Ocean Ridge and the 15°20'N Fracture Zone. In addition to high degrees of partial melting, these peridotites underwent multiple episodes of melt-rock reaction and intense serpentinization and seawater alteration close to the seafloor. Low concentrations of Se, Cu and platinum-group elements (PGE) in harzburgites drilled at around 35-85 m below seafloor are consistent with the consumption of mantle sulfides after high degrees (>15-20 %) of partial melting and redistribution of chalcophile and siderophile elements into PGE-rich residual microphases. Higher concentrations of Cu, Se, Ru, Rh and Pd in harzburgites from the uppermost and lowest cores testify to late reaction with a sulfide melt. Dunites were formed by percolation of silica- and sulfur-undersaturated melts into low-Se harzburgites. Platinum-group and chalcophile elements were not mobilized during dunite formation and mostly preserve the signature of precursor harzburgites, except for higher Ru and lower Pt contents caused by precipitation and removal of platinum-group minerals. During serpentinization at low temperature (desulfurization to S-poor sulfides (mainly heazlewoodite) and awaruite. Contrary to Se and Cu, sulfur does not record the magmatic evolution of peridotites but was mostly added in hydrothermal sulfides and sulfate from seawater. Platinum-group elements were unaffected by post-magmatic low-temperature processes, except Pt and Pd that may have been slightly remobilized during oxidative seawater alteration.

  14. Concentrations of platinum-group elements (PGE), Re and Au in arsenian pyrite and millerite from Mo–Ni–PGE-Au black shales (Zunyi region, Guizhou Province, China): results from LA-ICPMS study

    Czech Academy of Sciences Publication Activity Database

    Pašava, J.; Ackerman, Lukáš; Halodová, P.; Pour, O.; Ďurišová, Jana; Zaccarini, F.; Aiglsperger, T.; Vymazalová, A.

    2017-01-01

    Roč. 29, č. 4 (2017), s. 623-633 ISSN 0935-1221 R&D Projects: GA ČR GA13-15390S Institutional support: RVO:67985831 Keywords : Mo–Ni–PGE-Au black shale * south China * hydroseparation * arsenian pyrite * millerite * LA-ICPMS analysis * platinum-group elements * PGE * Re * Au and As concentrations Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 1.362, year: 2016

  15. Behaviour of palladium(II), platinum(IV), and rhodium(III) in artificial and natural waters: Influence of reactor surface and geochemistry on metal recovery

    Energy Technology Data Exchange (ETDEWEB)

    Cobelo-Garcia, Antonio [School of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)]. E-mail: antonio.cobelo-garcia@plymouth.ac.uk; Turner, Andrew [School of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Millward, Geoffrey E. [School of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Couceiro, Fay [School of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)

    2007-03-07

    The recovery of dissolved platinum group elements (PGE: Pd(II), Pt(IV) and Rh(III)) added to Milli-Q[reg] water, artificial freshwater and seawater and filtered natural waters has been studied, as a function of pH and PGE concentration, in containers of varying synthetic composition. The least adsorptive and/or precipitative loss was obtained for borosilicate glass under most of the conditions employed, whereas the greatest loss was obtained for low-density polyethylene. Of the polymeric materials tested, the adsorptive and/or precipitative loss of PGE was lowest for fluorinated ethylene propylene (Teflon[reg]). The loss of Pd(II) in freshwater was significant due to its affinity for surface adsorption and its relatively low solubility. The presence of natural dissolved organic matter increases the recovery of Pd(II) but enhances the loss of Pt(IV). The loss of Rh(III) in seawater was significant and was mainly due to precipitation, whereas Pd(II) recovery was enhanced, compared to freshwater, because of its complexation with chloride. The results have important implications regarding protocols employed for sample preservation and controlled laboratory experiments used in the study of the speciation and biogeochemical behaviour of PGE.

  16. Bioavailability of very finely distributed metallic platinum in the lungs and first orienting studies on effects. Part 1; Bioverfuegbarkeit von feinstverteiltem metallischem Platin in der Lunge und erste orientierende Wirkungsuntersuchungen (VPT 09; 1. Teil)

    Energy Technology Data Exchange (ETDEWEB)

    Artelt, S [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung, Hannover (Germany)

    1998-12-31

    Projects 07 VPT 08 and 07 VPT 08A revealed that platinum from automotive catalytic converters are largely emitted in metallic form as bound to the support material (aluminium oxide). Platinum emissions from this source are on the order of ng per km. The aim of the still ongoing project 07 VPT 09 is to estimate any health hazards that might grow from the deposition in the human lung by inhalation of very fine platinum particles. To answer this question it is necessary to have sufficient quantities of abraded material at one`s disposal. [Deutsch] Im Rahmen des Projektes 07 VPT 08 und 07 VPT 08A wurde festgestellt, dass Platin aus Automobilabgaskatalysatoren zum ueberwiegenden Teil in metallischer Form, gebunden an Traegermaterial (Aluminiumoxid), emittiert wird. Dabei liegt die Platinemission in der Groessenordnung von ng Platin/km. Im noch laufenden Vorhaben 07 VPT 09 soll ein eventuell auftretendes gesundheitliches Risiko, das durch die inhalative Aufnahme von sehr feinen Platinpartikeln in die Lunge des Menschen entstehen koennte, abgeschaetzt werden. Versuche zur Beantwortung dieser Frage setzen voraus, dass eine genuegend grosse Menge an Abriebmaterial zur Verfuegung steht. (orig.)

  17. Bioavailability of very finely distributed metallic platinum in the lungs and first orienting studies on effects. Part 1; Bioverfuegbarkeit von feinstverteiltem metallischem Platin in der Lunge und erste orientierende Wirkungsuntersuchungen (VPT 09; 1. Teil)

    Energy Technology Data Exchange (ETDEWEB)

    Artelt, S. [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung, Hannover (Germany)

    1997-12-31

    Projects 07 VPT 08 and 07 VPT 08A revealed that platinum from automotive catalytic converters are largely emitted in metallic form as bound to the support material (aluminium oxide). Platinum emissions from this source are on the order of ng per km. The aim of the still ongoing project 07 VPT 09 is to estimate any health hazards that might grow from the deposition in the human lung by inhalation of very fine platinum particles. To answer this question it is necessary to have sufficient quantities of abraded material at one`s disposal. [Deutsch] Im Rahmen des Projektes 07 VPT 08 und 07 VPT 08A wurde festgestellt, dass Platin aus Automobilabgaskatalysatoren zum ueberwiegenden Teil in metallischer Form, gebunden an Traegermaterial (Aluminiumoxid), emittiert wird. Dabei liegt die Platinemission in der Groessenordnung von ng Platin/km. Im noch laufenden Vorhaben 07 VPT 09 soll ein eventuell auftretendes gesundheitliches Risiko, das durch die inhalative Aufnahme von sehr feinen Platinpartikeln in die Lunge des Menschen entstehen koennte, abgeschaetzt werden. Versuche zur Beantwortung dieser Frage setzen voraus, dass eine genuegend grosse Menge an Abriebmaterial zur Verfuegung steht. (orig.)

  18. Preparation of platinum/iridium scanning probe microscopy tips

    DEFF Research Database (Denmark)

    Sørensen, Alexis Hammer; Hvid, U.; Mortensen, M.W.

    1999-01-01

    oxide layer. In order to explain the relatively high etching rates observed for the otherwise noble metal platinum we suggest that besides anodic corrosion of the platinum by the electrolyte containing chloride ions, a different etching mechanism causes a substantial increase of the etching rate...

  19. Direct determination of platinum group elements and their distributions in geological and environmental samples at the ng g{sup -1} level using LA-ICP-IDMS

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, Sergei F.; Heumann, Klaus G. [Johannes Gutenberg-University Mainz, Institute of Inorganic Chemistry and Analytical Chemistry, Mainz (Germany)

    2005-10-01

    Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) was applied to the direct and simultaneous determination of the platinum group elements (PGEs) Pt, Pd, Ru, and Ir in geological and environmental samples. A special laser ablation system with high ablation rates was used, along with sector field ICP-MS. Special attention was paid to deriving the distributions of PGEs in the pulverized samples. IDMS could not be applied to the (mono-isotopic) Rh, but the similar ablation behavior of Ru and Rh allowed Rh to be simultaneously determined via relative sensitivity coefficients. The laser ablation process produces hardly any oxide ions (which usually cause interference in PGE analysis with liquid sample injection), so the ICP-MS can be run in its low mass resolution but high-sensitivity mode. The detection limits obtained for the geological samples were 0.16 ng g{sup -1}, 0.14 ng g{sup -1}, 0.08 ng g{sup -1}, 0.01 ng g{sup -1} and 0.06 ng g{sup -1} for Ru, Rh, Pd, Ir and Pt, respectively. LA-ICP-IDMS was applied to different geological reference materials (TDB-1, WGB-1, UMT-1, WMG-1, SARM-7) and the road dust reference material BCR-723, which are only certified for some of the PGEs. Comparisons with certified values as well as with indicative values from the literature demonstrated the validity of the LA-ICP-IDMS method. The PGE concentrations in subsamples of the road dust reference material correspond to a normal distribution, whereas the distributions in the geological reference materials TDB-1, WGB-1, UMT-1, WMG-1, and SARM-7 are more complex. For example, in the case of Ru, a logarithmic normal distribution best fits the analyzed concentrations in TDB-1 subsamples, whereas a pronounced nugget effect was found for Pt in most geological samples. (orig.)

  20. Direct determination of platinum group elements and their distributions in geological and environmental samples at the ng g(-1) level using LA-ICP-IDMS.

    Science.gov (United States)

    Boulyga, Sergei F; Heumann, Klaus G

    2005-10-01

    Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) was applied to the direct and simultaneous determination of the platinum group elements (PGEs) Pt, Pd, Ru, and Ir in geological and environmental samples. A special laser ablation system with high ablation rates was used, along with sector field ICP-MS. Special attention was paid to deriving the distributions of PGEs in the pulverized samples. IDMS could not be applied to the (mono-isotopic) Rh, but the similar ablation behavior of Ru and Rh allowed Rh to be simultaneously determined via relative sensitivity coefficients. The laser ablation process produces hardly any oxide ions (which usually cause interference in PGE analysis with liquid sample injection), so the ICP-MS can be run in its low mass resolution but high-sensitivity mode. The detection limits obtained for the geological samples were 0.16 ng g(-1), 0.14 ng g(-1), 0.08 ng g(-1), 0.01 ng g(-1) and 0.06 ng g(-1) for Ru, Rh, Pd, Ir and Pt, respectively. LA-ICP-IDMS was applied to different geological reference materials (TDB-1, WGB-1, UMT-1, WMG-1, SARM-7) and the road dust reference material BCR-723, which are only certified for some of the PGEs. Comparisons with certified values as well as with indicative values from the literature demonstrated the validity of the LA-ICP-IDMS method. The PGE concentrations in subsamples of the road dust reference material correspond to a normal distribution, whereas the distributions in the geological reference materials TDB-1, WGB-1, UMT-1, WMG-1, and SARM-7 are more complex. For example, in the case of Ru, a logarithmic normal distribution best fits the analyzed concentrations in TDB-1 subsamples, whereas a pronounced nugget effect was found for Pt in most geological samples.

  1. Structural property of platinum mononitride

    International Nuclear Information System (INIS)

    Yu, L.H.; Yao, K.L.; Liu, Z.L.; Zhang, Y.S.

    2007-01-01

    The structural stability and pressure-induced structural phase transition of platinum mononitride (PtN), as well as its electronic structure, were studied using the full potential augmented plane wave plus local orbitals method with the generalized gradient approximation (GGA) exchange-correlation functional. The total energy calculations show that the optimized wurtzite structure is most stable energetically among four structures: zinc blende, rocksalt, CsCl and wurtzite, which reveals the platinum mononitride PtN perhaps crystallizes in the wurtzite structure; the pressure of phase transition from wurtzite to rocksalt is predicted to be 41.4 GPa.The calculated bulk modulus of the wurtzite structure is 99.41 GPa, which is smaller than that of the other three structures and face-centered cubic Pt. The band structure calculations show wurtzite PtN is metallic

  2. Rhenium–platinum antitumor systems

    Directory of Open Access Journals (Sweden)

    A. V. Shtemenko

    2017-04-01

    Full Text Available This review provides an overlook of design (in short, antitumor and other biological activity of quadruple-bonded cluster dirhenium(III compounds and their synergism with cisplatin. In particular, we describe the work of the rhenium-platinum antitumor system (introduction of rhenium and platinum compounds. Among known metal-based anticancer drugs and drug candidates dirhenium(III compounds differ profoundly due to their strong antiradical and antioxidant properties determined by quadruple bond unsaturation. Such advantages of metal complexes as more expressed redox chemical propertie should be exploited for creating more efficient anticancer drugs. Combination of drugs leads to synergistic effects and/or to lowe­ring toxicity of platinides and is very promising in cancer chemotherapy. The review covers the follo­wing items: design of quadruple bonded dirhenium(III clusters, their spectral and antiradical properties (in short; interaction of the dirhenium(III compounds with lipids and formation of liposomes; interaction of the dirhenium(III compounds with erythrocytes and their antihemolytic activity in the models of hemolytic anemia; anticancer activity of dirhenium clusters and work of the rhenium-platinum antitumor system; antianemic and antioxidant properties of the dirhenium(III compounds in the model of tumor growth; interaction of the dirhenium(III compounds with nucleobases and DNA. Some modern trends in the field of bioinorganic and medicinal chemi­stry are also considered regarding their connection to the rhenium-platinum system efficiency: use of combinational therapy and nanomaterials; involvement of some biologically active ligands and redox-activation strategy, etc.

  3. Replacement of a thiourea with an amidine group in a monofunctional platinum-acridine antitumor agent. Effect on DNA interactions, DNA adduct recognition and repair

    Czech Academy of Sciences Publication Activity Database

    Kostrhunová, Hana; Malina, Jaroslav; Pickard, A.J.; Štěpánková, Jana; Vojtíšková, Marie; Kašpárková, Jana; Muchová, T.; Rohlfing, M.L.; Bierbach, U.; Brabec, Viktor

    2011-01-01

    Roč. 8, č. 5 (2011), s. 1941-1954 ISSN 1543-8384 R&D Projects: GA ČR(CZ) GAP205/11/0856 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : platinum * DNA binding * anticancer effects Subject RIV: BO - Biophysics Impact factor: 4.782, year: 2011

  4. Isotope dilution inductively coupled plasma quadrupole mass spectrometry in connection with a chromatographic separation for ultra trace determinations of platinum group elements (Pt, Pd, Ru, Ir) in environmental samples.

    Science.gov (United States)

    Müller, M; Heumann, K G

    2000-09-01

    An isotope dilution inductively coupled plasma quadrupole mass spectrometric (ID-ICP-QMS) method was developed for the simultaneous determination of the platinum group elements Pt, Pd, Ru, and Ir in environmental samples. Spike solutions, enriched with the isotopes 194Pt, 108Pd, 99Ru, and 191Ir, were used for the isotope dilution step. Interfering elements were eliminated by chromatographic separation using an anion-exchange resin. Samples were dissolved with aqua regia in a high pressure asher. Additional dissolution of possible silicate portions by hydrofluoric acid was usually not necessary. Detection limits of 0.15 ng x g(-1), 0.075 ng x g(-1), and 0.015 ng x g(-1) were achieved for Pt, Pd, Ru, and Ir, respectively, using sample weights of only 0.2 g. The reliability of the ID-ICP-QMS method was demonstrated by analyzing a Canadian geological reference material and by participating in an interlaboratory study for the determination of platinum and palladium in a homogenized road dust sample. Surface soil, sampled at different distances from a highway, showed concentrations in the range of 0.1-87 ng x g(-1). An exponential decrease of the platinum and palladium concentration with increasing distance and a small anthropogenic contribution to the natural background concentration of ruthenium and iridium was found in these samples.

  5. Modification of the sulphur resistance of platinum by addition of metals for aromatics hydrogenation; Modification de la thioresistance du platine par ajouts d'elements metalliques pour l'hydrogenation d'aromatiques

    Energy Technology Data Exchange (ETDEWEB)

    Guillon, E

    1999-09-15

    The aim of this study is based on the understanding of sulphur resistance of platinum catalytic systems. In this work, bimetallic systems (Pt-Ge, Pt-Au and Pt-Pd) supported on {gamma}-alumina have been studied. Preparation methods have been chosen to give the best control of the physicochemical properties of final system. Electronic and geometrical properties of the metallic phase were characterised by various techniques (TPR, infrared spectroscopy of adsorbed CO (IR(CO)), EXAFS, LEIS). Ortho-xylene hydrogenation in presence of 100 ppm of sulphur was used as model catalytic test in order to study the sulphur resistance of the catalysts. It has been shown that germanium and palladium act as electro-acceptors toward platinum. The ranking of catalytic activity in presence of sulphur is as followed: Pt-Pd > Pt-Au {approx_equal} Pt >> Pt-Ge {approx_equal} 0. The best sulphur resistance for Pt-Pd was obtained for the composition Pt{sub 20}Pd{sub 80} (Pd/Pt=4). An eggshell PdS structure with Pt (sulfur free) core is proposed. These works show that the sulphur resistance of platinum is not only linked with its electronic properties. They allow us to propose an original concept of sulphur resistant catalyst taking into account each catalytic parameters such as chemical bonding of S and aromatic compounds on the metallic site, physico-chemical characteristics of the bimetallic aggregates (particle size, structure, surface composition) and electronic modification of surface atoms in bimetallic catalysts. (author)

  6. Modification of the sulphur resistance of platinum by addition of metals for aromatics hydrogenation; Modification de la thioresistance du platine par ajouts d'elements metalliques pour l'hydrogenation d'aromatiques

    Energy Technology Data Exchange (ETDEWEB)

    Guillon, E.

    1999-09-15

    The aim of this study is based on the understanding of sulphur resistance of platinum catalytic systems. In this work, bimetallic systems (Pt-Ge, Pt-Au and Pt-Pd) supported on {gamma}-alumina have been studied. Preparation methods have been chosen to give the best control of the physicochemical properties of final system. Electronic and geometrical properties of the metallic phase were characterised by various techniques (TPR, infrared spectroscopy of adsorbed CO (IR(CO)), EXAFS, LEIS). Ortho-xylene hydrogenation in presence of 100 ppm of sulphur was used as model catalytic test in order to study the sulphur resistance of the catalysts. It has been shown that germanium and palladium act as electro-acceptors toward platinum. The ranking of catalytic activity in presence of sulphur is as followed: Pt-Pd > Pt-Au {approx_equal} Pt >> Pt-Ge {approx_equal} 0. The best sulphur resistance for Pt-Pd was obtained for the composition Pt{sub 20}Pd{sub 80} (Pd/Pt=4). An eggshell PdS structure with Pt (sulfur free) core is proposed. These works show that the sulphur resistance of platinum is not only linked with its electronic properties. They allow us to propose an original concept of sulphur resistant catalyst taking into account each catalytic parameters such as chemical bonding of S and aromatic compounds on the metallic site, physico-chemical characteristics of the bimetallic aggregates (particle size, structure, surface composition) and electronic modification of surface atoms in bimetallic catalysts. (author)

  7. Kohn Anomaly and Phase Stability in Group VB Transition Metals

    Directory of Open Access Journals (Sweden)

    Alexander Landa

    2018-03-01

    Full Text Available In the periodic table, only a few pure metals exhibit lattice or magnetic instabilities associated with Fermi surface nesting, the classical examples being α-U and Cr. Whereas α-U displays a strong Kohn anomaly in the phonon spectrum that ultimately leads to the formation of charge density waves (CDWs, Cr is known for its nesting-induced spin density waves (SDWs. Recently, it has become clear that a pronounced Kohn anomaly and the corresponding softening in the elastic constants is also the key factor that controls structural transformations and mechanical properties in compressed group VB metals—materials with relatively high superconducting critical temperatures. This article reviews the current understanding of the structural and mechanical behavior of these metals under pressure with an introduction to the concept of the Kohn anomaly and how it is related to the important concept of Peierls instability. We review both experimental and theoretical results showing different manifestations of the Kohn anomaly in the transverse acoustic phonon mode TA (ξ00 in V, Nb, and Ta. Specifically, in V the anomaly triggers a structural transition to a rhombohedral phase, whereas in Nb and Ta it leads to an anomalous reduction in yield strength.

  8. In vitro permeation of platinum through African and Caucasian skin.

    Science.gov (United States)

    Franken, A; Eloff, F C; du Plessis, J; Badenhorst, C J; Du Plessis, J L

    2015-02-03

    The majority of the South African workforce are Africans, therefore potential racial differences should be considered in risk and exposure assessments in the workplace. Literature suggests African skin to be a superior barrier against permeation and irritants. Previous in vitro studies on metals only included skin from Caucasian donors, whereas this study compared the permeation of platinum through African and Caucasian skin. A donor solution of 0.3 mg/ml of potassium tetrachloroplatinate (K₂PtCl₄) dissolved in synthetic sweat was applied to the vertical Franz diffusion cells with full thickness abdominal skin. Skin from three female African and three female Caucasian donors were included (n=21). The receptor solution was removed at various intervals during the 24 h experiment, and analysed with high resolution inductively coupled plasma-mass spectrometry (ICP-MS). Skin was digested and analysed by inductively coupled plasma-optical emission spectrometry (ICP-OES). Significantly higher permeation of platinum through intact African skin (p=0.044), as well as a significantly higher mass of platinum retention in African skin in comparison with Caucasian skin (p=0.002) occurred. Significant inter-donor variation was found in both racial groups (pskin and further investigation is necessary to explain the higher permeation through African skin. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  9. Testing the Younger Dryas impact hypothesis with platinum-group elements (PGE), Re, and Os isotopes in sediments from Hall's Cave and Freidken Archaeological site, Texas

    Science.gov (United States)

    Sun, N.; Brandon, A. D.; Forman, S. L.

    2017-12-01

    The Younger Dryas impact hypothesis suggests that extraterrestrial (ET) object(s) hit and exploded over North America 12,900 years ago and triggered the onset of Younger Dryas (YD) cooling and widespread megafaunal extinctions and the demise of the Clovis archeological culture. Supporting signatures such as concentrated carbon spherules and enlogaes, magnetic grains and spherules, nanodiamonds, and Ir-enrichment have been reported, but over time their lack of reproducibility of results at different locations have brought into question the impact hypothesis. Among the impact signatures investigated by previous studies, only few researchers included Re and platinum group element (PGE: Os, Ir, Ru, Rh, Pt, and Pd) characteristic concentrations, and 187Os/188Os ratios for ET mixing in terrestrial materials. Less than 1% of ET materials can provide enriched PGE concentrations, such that PGE are a sensitive tool to identify ET input in terrestrial materials. Because of the large difference between chondritic and continental crust 187Os/188Os ratios, 0.127 and >1.4, respectively, the 187Os/188Os ratios are also highly sensitive indicators of an extraterrestrial component in terrestrial and marine sediments. In this study, we examine sediments associated with the YD from two reported sites in North America, Hall's Cave and the Freidken Archaeological site in Central Texas, using the PGE and Re geochemical approach to test the evidence of the extraterrestrial projectiles during Younger Dryas period. Our current data show at Hall's Cave the PGE concentrations and patterns do not confirm the presence of an elevated meteoritic contribution. However, the 187Os/188Os depth profile shows a sudden 187Os/188Os decrease from 2.28 2.45 to 1.64 at the YD boundary layer, consistent with an increase in material derived from ET projectiles with chondritic 187Os/188Os ratios contaminating the Earth surface at the time of the YD extinction. Additional samples from the YD boundary at the

  10. Metal cluster compounds - chemistry and importance; clusters containing isolated main group element atoms, large metal cluster compounds, cluster fluxionality

    International Nuclear Information System (INIS)

    Walther, B.

    1988-01-01

    This part of the review on metal cluster compounds deals with clusters containing isolated main group element atoms, with high nuclearity clusters and metal cluster fluxionality. It will be obvious that main group element atoms strongly influence the geometry, stability and reactivity of the clusters. High nuclearity clusters are of interest in there own due to the diversity of the structures adopted, but their intermediate position between molecules and the metallic state makes them a fascinating research object too. These both sites of the metal cluster chemistry as well as the frequently observed ligand and core fluxionality are related to the cluster metal and surface analogy. (author)

  11. Strategies for the fabrication of porous platinum electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Kloke, Arne; Stetten, Felix von; Kerzenmacher, Sven [Laboratory for MEMS Applications, Department of Microsystems Engineering-IMTEK, University of Freiburg, Freiburg (Germany); Zengerle, Roland [Laboratory for MEMS Applications, Department of Microsystems Engineering-IMTEK, University of Freiburg, Freiburg (Germany); BIOSS Centre for Biological Signalling Studies, Albert-Ludwigs-Universitaet Freiburg (Germany)

    2011-11-16

    Porous platinum is of high technological importance due to its various applications in fuel cells, sensors, stimulation electrodes, mechanical actuators and catalysis in general. Based on a discussion of the general principles behind the reduction of platinum salts and corresponding deposition processes this article discusses techniques available for platinum electrode fabrication. The numerous, different strategies available to fabricate platinum electrodes are reviewed and discussed in the context of their tuning parameters, strengths and weaknesses. These strategies comprise bottom-up approaches as well as top-down approaches. In bottom-up approaches nanoparticles are synthesized in a first step by chemical, photochemical or sonochemical means followed by an electrode formation step by e.g. thin film technology or network formation to create a contiguous and conducting solid electrode structure. In top-down approaches fabrication starts with an already conductive electrode substrate. Corresponding strategies enable the fabrication of substrate-based electrodes by e.g. electrodeposition or the fabrication of self-supporting electrodes by dealloying. As a further top-down strategy, this review describes methods to decorate porous metals other than platinum with a surface layer of platinum. This way, fabrication methods not performable with platinum can be applied to the fabrication of platinum electrodes with the special benefit of low platinum consumption. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. BOWIEITE: A NEW RHODIUM-IRIDIUM-PLATINUM SULFIDE IN PLATINUM-ALLOY NUGGETS, GOODNEWS BAY, ALASKA.

    Science.gov (United States)

    Desborough, George A.; Criddle, Alan J.

    1984-01-01

    Bowieite (Rh,Ir,Pt)//2S//3, a new mineral species, is found in three nuggets of platinum from Goodnews Bay, Alaska. In linearly polarized reflected light, and compared to the host, higher reflecting white platinum-iridium alloy, bowieite is pale gray to pale gray-brown; neither bireflectance nor reflectance pleochroism is apparent. With polars crossed, its anisotropic rotation tints vary from gray to dark brown. Luminance values (relative to the CIE illuminant C) for R//1 and R//2, computed from full spectral data for the most bireflectant grain, are 45. 8% and 48. 2% in air, and 30. 5% and 33. 0% in oil, respectively. VHN//1//0//0 1288 (858 to 1635). Bowieite is orthorhombic, space group Pnca, with a 8. 454(7) -8. 473(8), b 5. 995(1)-6. 002(7), c 6. 143(1)-6. 121(8) A, Z equals 4. Some grains that are 2. 6 to 3. 8 atomic % metal-deficient occur as an optically coherent rim on bowieite; the rim and the bowieite grain are not optically continuous.

  13. Organodioxygen complexes of some group 4B metal ions

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Akhter Hossain; Gino Mariotto

    2003-09-01

    Organodioxygen complexes of some group 4B metal ions, viz., zirconium(IV), tin(IV) and lead(II) containing monodentate, bidentate and tridentate ligands were synthesized and characterized. The complexes have the compositions of [Zr(O)(O 2 )2C 5 H 5 N.H 2 O], [Zr(O)(O 2 - ) 2 .2OPPh 3 ], [Sn(O 2 )(C 9 H 6 NO) 2 ], [Sn(0 2 ) 2 .(CH 2 ) 2 (NH 2 ) 2 ], [Pb(O 2 - )(C 5 H 5 N) 2 NO 3 ], [Pb(O 2 )(C 8 H 6 NOH)], [Pb(O 2 - )(det)NO 3 ] and [PbO 2 - ) (C 5 H 4 NCOOH)NO 3 .H 2 O]. Because of apparent linearity of M- O 2 grouping, the V 1 (O-O) stretching modes were only Raman active, giving bands at 810- 841 cm 1 for the peroxo complexes (1, 3, ,4 and 6), while the bands in the superoxo complexes (2, 5, 7 and 8) appeared at 1020- 1100 cm -1 . The peroxo complex of Zr(IV) containing monodentate ligands were found to oxidize trans-stilbene to trans-stilbene oxide under stoichiometric conditions. The organoperoxo complexes of tin and lead were insensitive to oxidative processes. (author)

  14. The synthesis and properties of some organometallic compounds containing group IV (Ge, Sn)-group II (Zn, Cd) metal---metal bonds

    NARCIS (Netherlands)

    Des Tombe, F.J.A.; Kerk, G.J.M. van der; Creemers, H.M.J.C.; Carey, N.A.D.; Noltes, J.G.

    1972-01-01

    The reactions of triphenylgermane and triphenyltin hydride with coordinatively saturated organozinc or organocadmium compounds give organometallic complexes containing Group IV (Ge, Sn)-Group II(Zn, Cd) metal---metal bonds. The 2,2′-bipyridine complexes show solvent-dependent charge-transfer

  15. A randomized phase II study of carboplatin plus pegylated liposomal doxorubicin versus carboplatin plus paclitaxel in platinum sensitive ovarian cancer patients: a Hellenic Cooperative Oncology Group study

    Directory of Open Access Journals (Sweden)

    Briasoulis Evangelos

    2010-01-01

    Full Text Available Abstract Background Platinum-based combinations are the standard second-line treatment for platinum-sensitive ovarian cancer (OC. This randomized phase II study was undertaken in order to compare the combination of carboplatin and pegylated liposomal doxorubicin (LD with carboplatin and paclitaxel (CP in this setting. Methods Patients with histologically confirmed recurrent OC, at the time of or more than 6 months after platinum-based chemotherapy, were randomized to six cycles of CP (carboplatin AUC5 + paclitaxel 175 mg/m2, d1q21 or CLD (carboplatin AUC5 + pegylated LD 45 mg/m2, d1q28. Results A total of 189 eligible patients (CP 96, CLD 93, with a median age of 63 years, median Performance Status (PS 0 and a median platinum free interval (PFI of 16.5 months, entered the study. Discontinuation due to toxicity was higher in the CP patients (13.5% versus 3%, P = 0.016. The overall response rate was similar: CP 58% versus CLD 51%, P = 0.309 (Complete Response; CR 34% versus 23% and there was no statistical difference in time-to-progression (TTP or overall survival (OS; TTP 10.8 months CP versus 11.8 CLD, P = 0.904; OS 29.4 months CP versus 24.7 CLD, P = 0.454. No toxic deaths were recorded. Neutropenia was the most commonly seen severe toxicity (CP 30% versus CLD 35%. More frequent in CLD were severe thrombocytopenia (11% versus 2%, P = 0.016, skin toxicity and Palmar-plantar erythrodysesthesia (PPE grade 1-2 (38% versus 9%, PP = 0.029, 20% versus 5%, P = 0.003. PS and PFI were independent prognostic factors for TTP and OS. Conclusions The combination of pegylated LD with carboplatin is effective, showing less neurotoxicity and alopecia than paclitaxel-carboplatin. It thus warrants a further phase III evaluation as an alternative treatment option for platinum-sensitive OC patients. Trial Registration Australian New Zealand Clinical Trials Registry: ACTRN12609000436279

  16. Sulfide precipitation method of separating uranium from Group II and Group III metal ions

    International Nuclear Information System (INIS)

    Sundar, P.S.

    1977-01-01

    Uranium is separated from analytical Group II and Group III metal ions in an aqueous liquor containing uranyl ions. The liquor is extracted with a non-interfering, water-immiscible, organic solvent containing a reagent which will react with the uranyl ions to form a complex soluble in the solvent. If the liquor is acidic, the solvent is washed with water. Then to the solvent is added an aqueous solution containing about 0.5 to 1.0 mole per liter of (NH 4 ) 2 CO 3 or NH 4 HCO 3 ions and sufficient sulfide ions to precipitate the metal ions as sulfides. The solvent and the aqueous solution are separated and the sulfides filtered from the aqueous solution. The ammonium-uranyl-tricarbonate in the aqueous solution can then be precipitated by increasing the concentration of (NH 4 ) 2 CO 3 or NH 4 HCO 3 ions to about 1.5 to 2.5 moles per liter. The precipitate is filtered and calcined to obtain U 3 O 8 or UO 2 . 21 claims, 1 figure

  17. Occurrence model for magmatic sulfide-rich nickel-copper-(platinum-group element) deposits related to mafic and ultramafic dike-sill complexes: Chapter I in Mineral deposit models for resource assessment

    Science.gov (United States)

    Schulz, Klaus J.; Woodruff, Laurel G.; Nicholson, Suzanne W.; Seal, Robert R.; Piatak, Nadine M.; Chandler, Val W.; Mars, John L.

    2014-01-01

    Magmatic sulfide deposits containing nickel (Ni) and copper (Cu), with or without (±) platinum-group elements (PGE), account for approximately 60 percent of the world’s nickel production. Most of the remainder of the Ni production is derived from lateritic deposits, which form by weathering of ultramafic rocks in humid tropical conditions. Magmatic Ni-Cu±PGE sulfide deposits are spatially and genetically related to bodies of mafic and/or ultramafic rocks. The sulfide deposits form when the mantle-derived mafic and/or ultramafic magmas become sulfide-saturated and segregate immiscible sulfide liquid, commonly following interaction with continental crustal rocks.

  18. Development of an ultratrace analysis method for elements of the platinum group contained in environmental and geological samples using an ICP-QMS with isotope dilution analysis and suitable separation techniques; Entwicklung eines Verfahrens zur Ultraspurenbestimmung der Platingruppenelemente in Umwelt- und geologischen Proben mit einem ICP-QMS unter Verwendung der Isotopenverduennungsanalyse sowie geeigneter Separationstechniken

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, M.

    2001-07-01

    This study focussed on developing a method of ultratrace analysis for elements of the platinum group contained in environmental or geological samples using mass spectroscopic isotope dilution analysis followed by measurement on a quadrupol ICP-MS (ICP-QMSIVA). This method was subsequently used for the certification of two reference materials for environmental sampling as part of a EU project titled ''Production and certification of a road dust reference material for platinum, palladium and rhodium (PGEs) in automotive catalytic converters (PACEPAC)''. In the intercomparison round the results obtained were found to be in very good agreement with the weighted mean values of the results obtained by the other participating laboratories. The results obtained with the method developed in this study were used for the preliminary certification procedure across all elements under study without exception. In this way the present study made a substantial contribution to the successful completion of this project, and prior expectations concerning the correctness and consistency of the developed method were satisfied to the full. This is renewed confirmation of the great significance of the isotope dilution technique for the certification of reference materials, which is attributable to the highly accurate results it yields when handled properly. Comparison between CNiS dokimasia and NAA on the one hand, which was carried out in cooperation with the Nuclear Chemical Institute of Mainz University, and the present method on the other showed good agreement in terms of the decrease in Pd and Pt concentrations with growing distance from the motorway. In conjunction with the research results obtained with NAA, a well-established technique, this study shows that elements of the platinum group from automotive catalytic converters are largely emitted in metallic form. ICP-QMSIVA thus represents a very good means of keeping track of the anthropogenic deposition in the

  19. Adsorption of volatile polonium species on metals in various gas atmospheres. Pt. II. Adsorption of volatile polonium on platinum, silver and palladium

    Energy Technology Data Exchange (ETDEWEB)

    Maugeri, Emilio Andrea; Joerg Neuhausen; Dressler, Rugard; Piguet, David; Voegele, Alexander; Schumann, Dorothea [Paul Scherrer Institut (PSI), Villigen (Switzerland). Lab. for Radiochemistry; Misiak, Ryszard [The Henryk Niewodniczanski Institute of Nuclear Physics, Krakow (Poland); Eichler, Robert [Paul Scherrer Institut (PSI), Villigen (Switzerland). Lab. for Radiochemistry; Bern Univ. (Switzerland). Dept. for Chemistry and Biochemistry

    2016-07-01

    This work presents the results obtained from studying the interaction between polonium compounds formed in different atmospheres and platinum, palladium and silver surfaces obtained by thermochromatography. These results are of crucial importance for the design of cover gas filter systems for lead-bismuth eutectic (LBE)-based nuclear facilities such as accelerator driven systems (ADS). The results obtained from studying the interaction of polonium and platinum under inert atmosphere and reducing atmospheres with and without addition of moisture show that polonium is deposited at temperatures between 993 and 1221 K, with adsorption enthalpies ranging from -235 to -291 kJ mol{sup -1}, indicating a very strong adsorption of the polonium species present on platinum surfaces. The interaction between polonium and silver was investigated using purified inert, reducing and oxidizing carrier gases. Results show a deposition temperature between 867 and 990 K, with adsorption enthalpies ranging from -205 to -234 kJ mol{sup -1}. The interaction of polonium and palladium was studied in purified helium and purified hydrogen. For both conditions a deposition temperature of 1221 K was observed corresponding to an adsorption enthalpy of -340 kJ mol{sup -1}. No highly volatile polonium species was formed at any of the applied experimental conditions.

  20. Synthesis of platinum nanowheels using a bicellar template.

    Science.gov (United States)

    Song, Yujiang; Dorin, Rachel M; Garcia, Robert M; Jiang, Ying-Bing; Wang, Haorong; Li, Peng; Qiu, Yan; van Swol, Frank; Miller, James E; Shelnutt, John A

    2008-09-24

    Disk-like surfactant bicelles provide a unique meso-structured reaction environment for templating the wet-chemical reduction of platinum(II) salt by ascorbic acid to produce platinum nanowheels. The Pt wheels are 496 +/-55 nm in diameter and possess thickened centers and radial dendritic nanosheets (about 2-nm in thickness) culminating in flared dendritic rims. The structural features of the platinum wheels arise from confined growth of platinum within the bilayer that is also limited at edges of the bicelles. The size of CTAB/FC7 bicelles is observed to evolve with the addition of Pt(II) complex and ascorbic acid. Synthetic control is demonstrated by varying the reaction parameters including metal salt concentration, temperature, and total surfactant concentration. This study opens up opportunities for the use of other inhomogeneous soft templates for synthesizing metals, metal alloys, and possibly semiconductors with complex nanostructures.

  1. Platinum single crystal electrodes for the electrocatalysis of methane oxidation

    Directory of Open Access Journals (Sweden)

    Mayara Munaretto

    2011-03-01

    Full Text Available The main objective of this paper is to characterize the voltammetric profiles of platinum single crystals of low Miller indexes Pt(100 and Pt(110 and study their catalytic activities on the oxidation of methane. In this way, it was developed a metallic surface modified by presence of other metal oxide, which presents catalytic activity for this reaction. It is well known that the electrooxidation of methane (CH4 leads mainly to the formation of CO2 and H2O, however, the oxidation can also lead to the formation of CO, a reaction intermediate that has strong interaction with metal surfaces, such as platinum. This molecule tends to accumulate on the platinum surface and to passive it, due to the self-poisoning, decreasing its catalytic activity. Therefore, the main aim of this work was the development of a platinum electrode modified by deposition of titanium oxide, which presented electrocatalytic properties for the oxidation of methane.

  2. Synthesis of Group IVB Metals Oxicarbides by Carboreduction Reactions

    Directory of Open Access Journals (Sweden)

    A.D. Mazzoni

    2002-10-01

    Full Text Available The metals of the group IV B (Ti, Zr, Hf present a series of carbides and oxicarbides with scientific and technological interest. Many of these compounds belong to the subsystem "MO - MC" of the pseudoternary "MO - MN - MC" system (where M = Ti, Zr or Hf. In this work carboreduction reactions of TiO2 and ZrO2 were performed in argon atmosphere, using temperatures from 1250° to 1650° and reaction times of 120 min. The oxicarbides obtained were in the range TiC0.16O0.84 to TiC0.73O0.27 and ZrC0.46O0.54 to ZrC0.90O0.10. respectively. The reaction products were characterized by X-ray diffraction (XRD, with the calculation of their cell constants by means of the Rietveld method. Scanning Electron Microscopy (SEM was used in the characterization of powdered materials. Additionally, the carborreduction reaction was followed by weight loss.

  3. Synthesis of graphite intercalation compound of group VI metals and uranium hexafluorides

    International Nuclear Information System (INIS)

    Fukui, Toshihiro; Hagiwara, Rika; Ema, Keiko; Ito, Yasuhiko

    1993-01-01

    Systematic investigations were made on the synthesis of graphite intercalation compounds of group VI transition metals (W and Mo) and uranium hexafluorides. The reactions were performed by interacting liquid or gaseous metal hexafluorides with or without elemental fluorine at ambient temperature. The degree of intercalation of these metal fluorides depends on the formation enthalpy of fluorometallate anion from the original metal hexafluoride, as has been found for other intercalation reactions of metal fluorides. (author)

  4. Aromatic polyetherketones and polyethersulfones containing 6 group metals

    International Nuclear Information System (INIS)

    Agapov, V.M.; Salazkin, S.N.; Sergeev, V.A.; Komarova, L.I.; Petrovskij, P.V.

    1991-01-01

    Molybdenum- and tungsten-containing polyaryleneetherketones and polyaryleneethersulfones were prepared by the method of chemical modification. Metal content in the polymers constitutes from 0.7 to 12 mass %. The structure of the metal-containing polymers prepared was studied by the methods of 1 H and 13 C NMR and IR spectroscopy. Their properties were analyzed

  5. Enhanced catalytic activity of nanoscale platinum islands loaded ...

    Indian Academy of Sciences (India)

    2016-08-26

    Aug 26, 2016 ... In the present study, different catalysts (∼ 10 nm thick) including metals, noble metals and metal oxides, were loaded in dotted island form over SnO2 thin film for LPG gas detection. A comparison of various catalysts indicated that the presence of platinum dotted islands over SnO2 thin film deposited by r.f. ...

  6. Photoacidic and Photobasic Behavior of Transition Metal Compounds with Carboxylic Acid Group(s)

    Energy Technology Data Exchange (ETDEWEB)

    O’Donnell, Ryan M. [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States; Sampaio, Renato N. [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States; Li, Guocan [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States; Johansson, Patrik G. [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States; Ward, Cassandra L. [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States; Meyer, Gerald J. [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States

    2016-03-10

    Excited state proton transfer studies of six Ru polypyridyl compounds with carboxylic acid/carboxylate group(s) revealed that some were photoacids and some were photobases. The compounds [RuII(btfmb)2(LL)]2+, [RuII(dtb)2(LL)]2+, and [RuII(bpy)2(LL)]2+, where bpy is 2,2'-bipyridine, btfmb is 4,4'-(CF3)2-bpy, and dtb is 4,4'-((CH3)3C)2-bpy, and LL is either dcb = 4,4'-(CO2H)2-bpy or mcb = 4-(CO2H),4'-(CO2Et)-2,2'-bpy, were synthesized and characterized. The compounds exhibited intense metal-to-ligand charge-transfer (MLCT) absorption bands in the visible region and room temperature photoluminescence (PL) with long τ > 100 ns excited state lifetimes. The mcb compounds had very similar ground state pKa’s of 2.31 ± 0.07, and their characterization enabled accurate determination of the two pKa values for the commonly utilized dcb ligand, pKa1 = 2.1 ± 0.1 and pKa2 = 3.0 ± 0.2. Compounds with the btfmb ligand were photoacidic, and the other compounds were photobasic. Transient absorption spectra indicated that btfmb compounds displayed a [RuIII(btfmb–)L2]2+* localized excited state and a [RuIII(dcb–)L2]2+* formulation for all the other excited states. Time dependent PL spectral shifts provided the first kinetic data for excited state proton transfer in a transition metal compound. PL titrations, thermochemical cycles, and kinetic analysis (for the mcb compounds) provided self-consistent pKa* values. The ability to make a single ionizable group photobasic or photoacidic through ligand design was unprecedented and was understood based on the orientation of the lowest-lying MLCT excited state dipole relative to the ligand that contained the carboxylic acid group(s).

  7. Possibilities Of Metals Extracton From Spent Metallic Automotive Catalytic Converters By Using Biometallurgical Method

    Directory of Open Access Journals (Sweden)

    Willner J.

    2015-09-01

    Full Text Available The main task of automotive catalytic converters is reducing the amount of harmful components of exhaust gases. Metallic catalytic converters are an alternative to standard ceramic catalytic converters. Metallic carriers are usually made from FeCrAl steel, which is covered by a layer of Precious Group Metals (PGMs acting as a catalyst. There are many methods used for recovery of platinum from ceramic carriers in the world, but the issue of platinum and other metals recovery from metallic carriers is poorly described. The article presents results of preliminary experiments of metals biooxidation (Fe, Cr and Al from spent catalytic converters with metallic carrier, using bacteria of the Acidithiobacillus genus.

  8. The RSC Faraday prize lecture of 1989 on platinum.

    Science.gov (United States)

    Thomas, John Meurig

    2017-08-25

    In 1861, Michael Faraday gave one of his last Friday Evening Discourses at the Royal Institution of Great Britain, London, on platinum, which he described as "this beautiful, magnificent and valuable metal". More than a hundred and twenty years later (in 1989), the author re-enacted, at the Royal Institution, many of the demonstrations that Faraday carried out in his memorable Discourse. This article outlines many of Faraday's views on, and experiments with, platinum. It also describes the continuing importance and utilization of platinum, both as perceived in 1989 and from present perspectives.

  9. METALLICITY DISTRIBUTION FUNCTIONS OF FOUR LOCAL GROUP DWARF GALAXIES

    Energy Technology Data Exchange (ETDEWEB)

    Ross, Teresa L.; Holtzman, Jon [Department of Astronomy, New Mexico State University, P.O. Box 30001, MSC 4500, Las Cruces, NM 88003-8001 (United States); Saha, Abhijit [NOAO, 950 Cherry Avenue, Tucson, AZ 85726-6732 (United States); Anthony-Twarog, Barbara J., E-mail: rosst@nmsu.edu, E-mail: holtz@nmsu.edu, E-mail: bjat@ku.edu [Department of Physics and Astronomy, University of Kansas, Lawrence, KS 66045-7582 (United States)

    2015-06-15

    We present stellar metallicities in Leo I, Leo II, IC 1613, and Phoenix dwarf galaxies derived from medium (F390M) and broad (F555W, F814W) band photometry using the Wide Field Camera 3 instrument on board the Hubble Space Telescope. We measured metallicity distribution functions (MDFs) in two ways, (1) matching stars to isochrones in color–color diagrams and (2) solving for the best linear combination of synthetic populations to match the observed color–color diagram. The synthetic technique reduces the effect of photometric scatter and produces MDFs 30%–50% narrower than the MDFs produced from individually matched stars. We fit the synthetic and individual MDFs to analytical chemical evolution models (CEMs) to quantify the enrichment and the effect of gas flows within the galaxies. Additionally, we measure stellar metallicity gradients in Leo I and II. For IC 1613 and Phoenix our data do not have the radial extent to confirm a metallicity gradient for either galaxy. We find the MDF of Leo I (dwarf spheroidal) to be very peaked with a steep metal-rich cutoff and an extended metal-poor tail, while Leo II (dwarf spheroidal), Phoenix (dwarf transition), and IC 1613 (dwarf irregular) have wider, less peaked MDFs than Leo I. A simple CEM is not the best fit for any of our galaxies; therefore we also fit the “Best Accretion Model” of Lynden-Bell. For Leo II, IC 1613, and Phoenix we find similar accretion parameters for the CEM even though they all have different effective yields, masses, star formation histories, and morphologies. We suggest that the dynamical history of a galaxy is reflected in the MDF, where broad MDFs are seen in galaxies that have chemically evolved in relative isolation and narrowly peaked MDFs are seen in galaxies that have experienced more complicated dynamical interactions concurrent with their chemical evolution.

  10. Concentrations of Platinum Group Elements (Pt, Pd, Rh in Airborne Particulate Matter (PM2.5 and PM10-2.5 Collected at Selected Canadian Urban Sites: a Case Study

    Directory of Open Access Journals (Sweden)

    Celo V.

    2013-04-01

    Full Text Available Increasing environmental concentrations of platinum group elements (PGEs, in particular platinum (Pt, palladium (Pd and rhodium (Rh, from catalytic converters has been reported worldwide. Initially it was believed that the emitted PGEs remain in the roadside environment, but recent studies have shown that fine PGE-containing particles can be transported and distributed at regional and long-range levels. Therefore, the monitoring of PGEs in airborne particulate matter (PM is important for the estimation of potential risks to human health and to the ecosystem. The aim of this study is to present the first results from an analysis on the concentration and distribution of Pt, Pd and Rh in PM collected on Teflon filters at two selected urban sites (Toronto, Ontario; Edmonton, Alberta collected within the Canadian National Air Pollution Surveillance (NAPS network. In this work, a quadruple inductively coupled plasma mass spectrometry (ICP-MS, combined with microwave assisted acid digestion using aqua regia was used. A cation exchange separation was used to alleviate the matrix-induced spectral and nonspectral interferences prior to ICP-MS analysis. To obtain sufficient material needed for PGEs analysis, fine PM (particles with aerodynamic diameter less than 2.5 mm; PM2.5 and coarse PM (with aerodynamic diameter between 2.5 and 10 mm; PM10-2.5 samples were combined into composite samples on a seasonal basis. The obtained results will be discussed and compared with literature data.

  11. The effect of gamma radiation on reference electrodes and platinum and carbon steel bare metal electrodes in a simulated waste solution

    International Nuclear Information System (INIS)

    Danielson, M.J.

    1993-09-01

    Electrochemical potential measurements of materials in waste tanks are important in determining if the materials have a propensity for stress corrosion cracking and pitting. Potential measurement requires a reference electrode, but the effect of radiation on the potential generated by the reference electrode has been an unknown quantity. To determine the significance of the radiation effect, Pacific Northwest Laboratory conducted studies of five types of electrodes under gamma radiation at room temperature. The subjects were two types of silver/silver chloride reference electrodes (Fisher and Lazaran), a mercury/calomel reference electrode, a platinum ''flag,'' and a piece of A-537 carbon steel; the electrodes were exposed to a simulated caustic tank environment. The Fisher silver/silver chloride and mercury/calomel reference electrodes showed essentially no radiation effects up to a flux of 2.1E6 R/h and fluence of 9.4E8 R, indicating they would be useful reference electrodes for in-tank studies. The Lazaran reg-sign silver/silver chloride electrode showed serious potential deviations at fluences of 2.E8 R, but it would be the electrode of choice in many situations because it is simple to maintain. Radiation affected the open circuit potential of both the platinum and carbon steel electrodes. This effect indicates that corrosion studies without radiation may not duplicate the corrosion processes expected in a waste tank. Mixed-potential theory was used to explain the radiation effects

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1976-07-01

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

  13. A novel reusable platinum nanocatalyst

    International Nuclear Information System (INIS)

    Zhou Weiqiang; Wang Jing; Wang Chuanyi; Du Yukou; Xu Jingkun; Yang Ping

    2010-01-01

    Recyclability of noble metal catalysts is a challenging issue when dealing with their industrial applications. Smart pH-sensitive Pt nanoparticles were successfully prepared for the first time by using octa(N,N-diacetic acid phenylamine)silsesquioxane (OAPAS) as a macromolecular protective agent. As-prepared Pt nanoparticles can self-aggregate or redisperse by only changing the pH of the system solution. In the weak acidic or alkaline solution (pH > 4.0), the Pt nanoparticles dispersed homogenously; while in the acidic solution (pH = 2.5), they self-aggregated. The dynamic self-aggregation and redispersion processes of the Pt nanoparticles driven by pH changes were revealed by transmission electron microscopy measurements. Electrocatalytic experiments proved that the platinum nanoparticles as a recyclable catalyst showed excellent activity for the hydrogenation of aldehyde after runs of five times. Such platinum nanoparticles are thereby anticipated to have great potential functioning as 'smart' catalysts for industrial applications.

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

    International Nuclear Information System (INIS)

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

    1982-01-01

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

  15. Excision repair cross-complementation group 1 (ERCC1) in platinum-based treatment of non-small cell lung cancer with special emphasis on carboplatin: a review of current literature

    DEFF Research Database (Denmark)

    Vilmar, A.; Sorensen, J.B.

    2009-01-01

    on carboplatin based on the current literature. Research on the development of a reliable methodology is warranted followed by validation in large, prospective, randomized trials as ERCC1 may possibly play an important role as tumour marker in tailored chemotherapy for NSCLC Udgivelsesdato: 2009/5......-complementation group 1 (ERCC1) has shown potential as a predictive marker in patients with NSCLC treated with cisplatin-based chemotherapy. Carboplatin has gained widespread use in the treatment of advanced NSCLC and its mechanisms of action are likely similar to that of cisplatin. MATERIALS AND METHODS: A literature...... review on ERCC1 was conducted as predictor in NSCLC patients receiving platinum-based treatment with emphasis on carboplatin. English language publications from January 1996 to February 2008 were eligible and data on methodology and outcome were recorded. RESULTS: Eight preclinical articles, 25 clinical...

  16. The effect of complexation with platinum in polyfluorene derivatives: A photo- and electro-luminescence study

    International Nuclear Information System (INIS)

    Assaka, Andressa M.; Hu Bin; Mays, Jimmy; Iamazaki, Eduardo T.; Atvars, Teresa D.Z.; Akcelrud, Leni

    2011-01-01

    The synthesis and characterization of a polymeric structure containing fluorene units statistically linked to 3-cyclohexyl-thiophene and bipyridine PFOTBipy-poly[(4-hexylthiophene-2,5-diyl)(9,9-dihexyl-fluoren-2,7-diyl) -co-(bipyridine-5.5'-diyl)(9,9-dihexyl-fluoren-2,7-diyl)], is reported. The complexation with platinum was possible through the bipyridil units present in 10%, 50% and 100% content. The structure has a fluorenyl moiety between each bipyridine and thiophene groups resulting in a stable and efficient light-emitting polymeric material combining the well known emissive properties of fluorene, the charge mobility generated by thiophene and the electron-transfer properties of a metal complex as well. All the polymers were photo and electroluminescent materials, and showed phosphorescence at low temperatures. Photoluminescence properties were studied by steady state and time resolved spectroscopy and showed changes of both emission peak and relative intensity of the emission bands depending on the relative amount of the platinum complex. The electroluminescence followed the trends found for photoluminescence. The blue emission of the copolymer without platinum is due to the fluorenyl segments and for higher complex contents the emission is characteristic of the aggregates involving the bipyridinyl moieties. Therefore, emission color can be tuned by the complex content. The turn-on voltage was strongly reduced from 22 to 8 V for the 100% complexed copolymer, as compared to the device made with the non complexed one, but the luminance decreased, due to quenching or trapping effects. - Research Highlights: →Statistic copolymer containing fluorine, thiophene and bipyridine. →Complexation of platinum with platinum with bipyridine. →Electroluminescence and electrophosphorescence at low temperatures. →Emission color can be tuned by the complex content.

  17. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  18. Neutron activation analysis for noble metals in matte leach residues

    International Nuclear Information System (INIS)

    Hart, R.J.

    1978-01-01

    The development of the neutron activation analysis technique as a method for rapid and precise determinations of platinum group metals in matte leach residues depends on obtaining a method for effecting complete and homogeneous sample dilution. A simple method for solid dilution of metal samples is outlined in this study, which provided a basis for the accurate determination of all the noble metals by the Neutron Activation Analysis technique

  19. Tripodal osmium polypyridyl complexes for self-assembly on platinum nanoparticles

    NARCIS (Netherlands)

    Contreras-Carballada, P.; Edafe, F.; Tichelaar, F.D.; Belser, P.; De Cola, L.; Williams, R.M.

    2011-01-01

    The combination of platinum nanoparticles with a tripodal osmium complex that anchors to the metal surface leads, under visible light irradiation, to the formation of solvated electrons. The formation kinetics is limited by the detachment of the electron from the platinum surface into the solution,

  20. Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Jennifer N. [Univ. of California, San Diego, CA (United States); Wang, Joseph [Univ. of California, San Diego, CA (United States)

    2014-08-31

    controlled, the nanocrystals boast a defined shape, morphology, orientation and size and are synthesized at benign reaction conditions. Adapting the methods of biomineralization towards the synthesis of platinum nanocrystals will allow effective control at a molecular level of the synthesis of highly active metal electrocatalysts, with readily tailored properties, through tuning of the biochemical inputs. The proposed research will incorporate many facets of biomineralization by: (1) isolating peptides that selectively bind particular crystal faces of platinum (2) isolating peptides that promote the nucleation and growth of particular nanocrystal morphologies (3) using two-dimensional DNA scaffolds to control the spatial orientation and density of the platinum nucleating peptides, and (4) combining bio-templating and soluble peptides to control crystal nucleation, orientation, and morphology. The resulting platinum nanocrystals will be evaluated for their electrocatalytic behavior (on common carbon supports) to determine their optimal size, morphology and crystal structure. We expect that such rational biochemical design will lead to highly uniform and efficient platinum nanocrystal catalysts for fuel cell applications.

  1. Melt cationic and anionic composition effect on titanium group metal corrosion in halogenides of alkali earths

    International Nuclear Information System (INIS)

    Tkhaj, V.; Kovalik, O.Yu.; Dikunov, Yu.G.; P'yankova, S.P.

    1997-01-01

    A study was made on interaction of titanium group metals with melts of chlorides and chloride-fluorides of alkaline earth metals and magnesium. It was revealed that the rate of metal corrosion increased from BaCl 2 2 2 2 in chloride series. It is explained by amplification of oxidation activity of salt cation in the series: Ba 2+ 2+ 2+ 2+ . It was also determined that corrosion rate of titanium exceeded the one of zirconium and hafnium, became reducing power of titanium was the highest in the given group

  2. Point defects in platinum

    International Nuclear Information System (INIS)

    Piercy, G.R.

    1960-01-01

    An investigation was made of the mobility and types of point defect introduced in platinum by deformation in liquid nitrogen, quenching into water from 1600 o C, or reactor irradiation at 50 o C. In all cases the activation energy for motion of the defect was determined from measurements of electrical resistivity. Measurements of density, hardness, and x-ray line broadening were also made there applicable. These experiments indicated that the principal defects remaining in platinum after irradiation were single vacant lattice sites and after quenching were pairs of vacant lattice sites. Those present after deformation In liquid nitrogen were single vacant lattice sites and another type of defect, perhaps interstitial atoms. (author)

  3. Binding of dioxouranium(VI) and platinum(II) to ribonuclease-S

    Energy Technology Data Exchange (ETDEWEB)

    Marzotto, A [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

    1976-12-01

    The preferred binding sites of RNase-S to dioxouranium(VI) and platinum(II) has been determined by Wyckoff et al., (J.Biol.Chem., v242, 1967, p.3749; ibid p.3984; ibid v245, 1970, p.305) elaborating protein and of heavy-atom derivatives reported by Wyckoff and coworkers. The major sites are exposed at the surface of the protein molecule and are not directly involved in the biological properties; the coordination geometry of the groups bound to the metal ions have been examined in comparison with model compounds.

  4. Bi-metallic nanoparticles as cathode electrocatalysts

    Science.gov (United States)

    Lu, Jun; Amine, Khalil; Wang, Xiaoping; Luo, Xiangyi; Myers, Deborah J.

    2018-03-27

    A lithium-air battery cathode catalyst includes core-shell nanoparticles on a carbon support, wherein: a core of the core-shell nanoparticles is platinum metal; and a shell of the core-shell nanoparticles is copper metal; wherein: the core-shell nanoparticles have a weight ratio of the copper metal to the platinum metal from about 4% to about 6% copper to from about 2% to about 12% platinum, with a remaining percentage being the carbon support.

  5. Incorporation of transition and platinum group elements (PGE) in Co-rich Mn crusts at Afanasiy-Nikitin Seamount (AFS) in the equatorial S Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Glasby, G.P.

    in the western Pacific. These mineral grains are typically in the size range 10–20 mm but large grains of sulfides up to 1 mm were found in some cases. These authors also noted that ferromanganese crusts have rough surfaces with low relief (0.1–0.15 mm...-ferrous metals of different composition. Native silver was a major constituent but small amounts of gold, iron, copper, tungsten, Fe-Sb oxides, Zn-Ag-Cu sulfides, rare earth phosphates as well as intermetallic Cu-Zn, Cu-Ni, Sn-Pb-Cu-Ni, Ni-Cr-Mo, Fe-Cr-Ni and Au...

  6. Measurement of activation yields for platinum group elements using Bremsstrahlung radiation with end-point energies in the range 11-14 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Tickner, James, E-mail: james.tickner@csiro.a [CSIRO Process Science and Engineering, PMB 5, Menai, NSW 2234 (Australia); Bencardino, Raffaele; Roach, Greg [CSIRO Process Science and Engineering, PMB 5, Menai, NSW 2234 (Australia)

    2010-01-15

    Activation yields have been measured for (gamma,n) reactions of the elements Ru, Rh, Pd, Ir and Pt. Metallic foils of natural isotopic composition were irradiated using Bremsstrahlung radiation produced from an electron linear accelerator operated with electron beam energies in the range 11-14 MeV. Activation products, including both unstable ground states and metastates were measured using a high-purity germanium detector. Cross-sections were estimated from the yield data by assuming a simple two-parameter model for the shape of the cross-section with energy.

  7. Measurement of activation yields for platinum group elements using Bremsstrahlung radiation with end-point energies in the range 11-14 MeV

    International Nuclear Information System (INIS)

    Tickner, James; Bencardino, Raffaele; Roach, Greg

    2010-01-01

    Activation yields have been measured for (γ,n) reactions of the elements Ru, Rh, Pd, Ir and Pt. Metallic foils of natural isotopic composition were irradiated using Bremsstrahlung radiation produced from an electron linear accelerator operated with electron beam energies in the range 11-14 MeV. Activation products, including both unstable ground states and metastates were measured using a high-purity germanium detector. Cross-sections were estimated from the yield data by assuming a simple two-parameter model for the shape of the cross-section with energy.

  8. Dissolution of Metal Supported Spent Auto Catalysts in Acids

    Directory of Open Access Journals (Sweden)

    Fornalczyk A.

    2016-03-01

    Full Text Available Metal supported auto catalysts, have been used in sports and racing cars initially, but nowadays their application systematically increases. In Metal Substrate (supported Converters (MSC, catalytic functions are performed by the Platinum Group Metals (PGM: Pt, Pd, Rh, similarly to the catalysts on ceramic carriers. The contents of these metals make that spent catalytic converters are valuable source of precious metals. All over the world there are many methods for the metals recovery from the ceramic carriers, however, the issue of platinum recovery from metal supported catalysts has not been studied sufficiently yet. The paper presents preliminary results of dissolution of spent automotive catalyst on a metal carrier by means of acids: H2SO4, HCl, HNO3, H3PO4. The main assumption of the research was the dissolution of base metals (Fe, Cr, Al from metallic carrier of catalyst, avoiding dissolution of PGMs. Dissolution was the most effective when concentrated hydrochloric acid, and 2M sulfuric acid (VI was used. It was observed that the dust, remaining after leaching, contained platinum in the level of 0.8% and 0.7%, respectively.

  9. Synthesis of platinum nanowire networks using a soft template.

    Science.gov (United States)

    Song, Yujiang; Garcia, Robert M; Dorin, Rachel M; Wang, Haorong; Qiu, Yan; Coker, Eric N; Steen, William A; Miller, James E; Shelnutt, John A

    2007-12-01

    Platinum nanowire networks have been synthesized by chemical reduction of a platinum complex using sodium borohydride in the presence of a soft template formed by cetyltrimethylammonium bromide in a two-phase water-chloroform system. The interconnected polycrystalline nanowires possess the highest surface area (53 +/- 1 m2/g) and electroactive surface area (32.4 +/- 3.6 m2/g) reported for unsupported platinum nanomaterials; the high surface area results from the small average diameter of the nanowires (2.2 nm) and the 2-10 nm pores determined by nitrogen adsorption measurements. Synthetic control over the network was achieved simply by varying the stirring rate and reagent concentrations, in some cases leading to other types of nanostructures including wormlike platinum nanoparticles. Similarly, substitution of a palladium complex for platinum gives palladium nanowire networks. A mechanism of formation of the metal nanowire networks is proposed based on confined metal growth within a soft template consisting of a network of swollen inverse wormlike micelles.

  10. Erosion of the 4-6- and 8 group transition metals under intense laser radiation

    International Nuclear Information System (INIS)

    Samsonov, G.V.; Verkhoturov, A.D.; Roshchina, A.I.; Vasil'ev, A.V.; Klimenko, V.P.

    1976-01-01

    The erosion resistance is studied of transition metals of Groups 4-6 and 8 at laser emission of approximately 6x1O 7 W/cm 2 . It is shown that as the emission power increases from 10 6 to 6x10 7 W/cm 2 the erosion values show an increase over tenfold without any subsequent filling of the craters. The growth of the metallic erosion is largely caused by a greater crater diameter. The erosion resistance of metals enhances in the following series: Ti-Zr-Co-Ni-Fe, Hf-V-Nb-Mo-Cr-Ta-W-Cu

  11. Structural Mimics of the [Fe]-Hydrogenase: A Complete Set for Group VIII Metals.

    Science.gov (United States)

    Barik, Chandan Kr; Ganguly, Rakesh; Li, Yongxin; Leong, Weng Kee

    2018-06-18

    A set of structural mimics of the [Fe]-hydrogenase active site comprising all the group VIII metals, viz., [M(2-NHC(O)C 5 H 4 N)(CO) 2 (2-S-C 5 H 4 N)], has been synthesized. They exist as a mixture of isomers in solution, and the relative stability of the isomers depends on the nature of the metal and the substituent at the 6-position of the pyridine ligand.

  12. Annotated bibliography for liquid metal surface tensions of groups III-A, IV-A, and V-A metals

    International Nuclear Information System (INIS)

    Murtha, M.J.; Burnet, G.

    1976-04-01

    An annotated bibliography has been prepared which includes summaries of 82 publications dating from 1920 and dealing with the measurement of the surface tensions of Groups III-A, IV-A, and V-A metals in the liquid state. The bibliography is organized by key element investigated, and contains a tabulation of correlations for surface tension as a function of temperature. A brief discussion dealing with variables and methods has been included

  13. A 50-year record of platinum, iridium, and rhodium in Antarctic snow: volcanic and anthropogenic sources.

    Science.gov (United States)

    Soyol-Erdene, Tseren-Ochir; Huh, Youngsook; Hong, Sungmin; Hur, Soon Do

    2011-07-15

    Antarctic snow preserves an atmospheric archive that enables the study of global atmospheric changes and anthropogenic disturbances from the past. We report atmospheric deposition rates of platinum group elements (PGEs) in Antarctica during the last ∼ 50 years based on determinations of Pt, Ir, and Rh in snow samples collected from Queen Maud Land, East Antarctica to evaluate changes in the global atmospheric budget of these noble metals. The 50-year average PGE concentrations in Antarctic snow were 17 fg g(-1) (4.7-76 fg g(-1)) for Pt, 0.12 fg g(-1) (pollution for Pt and probably for Rh since the 1980s, which may be attributed to the increasing emissions of these metals from anthropogenic sources such as automobile catalysts and metal production processes.

  14. The use of cation exchange matrix separation coupled with ICP-MS to directly determine platinum group element (PGE) and other trace element emissions from passenger cars equipped with diesel particulate filters (DPF)

    Energy Technology Data Exchange (ETDEWEB)

    Cairns, Warren R.L.; Cozzi, Giulio [Institute for the Dynamics of Environmental Processes-CNR, Venice (Italy); De Boni, Antonella; Gabrieli, Jacopo [University of Venice, Department of Environmental Science, Venice (Italy); Asti, Massimo; Merlone Borla, Edoardo; Parussa, Flavio [Centro Ricerche Fiat, Orbassano (Italy); Moretto, Ezio [FIAT Powertrain Technologies S.p.A, Turin (Italy); Cescon, Paolo; Barbante, Carlo [University of Venice, Department of Environmental Science, Venice (Italy); Institute for the Dynamics of Environmental Processes-CNR, Venice (Italy); Boutron, Claude [Laboratoire de Glaciologie et Geophysique de l' Environnement, UMR CNRS 5183, B.P. 96, Saint Martin d' Heres Cedex (France)

    2011-03-15

    Inductively coupled plasma-mass spectrometry coupled with cation exchange matrix separation has been optimised for the direct determination of platinum group element (PGE) and trace element emissions from a diesel engine car. After matrix separation method detection limits of 1.6 ng g{sup -1} for Pd, 0.4 ng g{sup -1} for Rh and 4.3 ng g{sup -1} for Pt were achieved, the method was validated against the certified reference material BCR 723, urban road dust. The test vehicle was fitted with new and aged catalytic converters with and without diesel particulate filters (DPF). Samples were collected after three consecutive New European Driving Cycle (NEDC) of the particulate and ''soluble'' phases using a home-made sampler optimised for trace element analysis. Emission factors for the PGEs ranged from 0.021 ng km{sup -1} for Rh to 70.5 ng km{sup -1} for Pt; when a DPF was fitted, the emission factors for the PGEs actually used in the catalysts dropped by up to 97% (for Pt). Trace element emission factors were found to drop by a maximum of 92% for Ni to a minimum of 18% for Y when a DPF was fitted; a new DPF was also found to cause a reduction of up to 86% in the emission of particulate matter. (orig.)

  15. Platinum-Group Minerals in Chromitites of the Niquelândia Layered Intrusion (Central Goias, Brazil: Their Magmatic Origin and Low-Temperature Reworking during Serpentinization and Lateritic Weathering

    Directory of Open Access Journals (Sweden)

    Nelson Angeli

    2012-10-01

    Full Text Available A variety of platinum-group-minerals (PGM have been found to occur associated with the chromitite and dunite layers in the Niquelândia igneous complex. Two genetically distinct populations of PGM have been identified corresponding to phases crystallized at high temperatures (primary, and others formed or modified during post-magmatic serpentinization and lateritic weathering (secondary. Primary PGM have been found in moderately serpentinized chromitite and dunite, usually included in fresh chromite grains or partially oxidized interstitial sulfides. Due to topographically controlled lateritic weathering, the silicate rocks are totally transformed to a smectite-kaolinite-garnierite-amorphous silica assemblage, while the chromite is changed into a massive aggregate of a spinel phase having low-Mg and a low Fe3+/Fe2+ ratio, intimately associated with Ti-minerals, amorphous Fe-hydroxides, goethite, hematite and magnetite. The PGM in part survive alteration, and in part are corroded as a result of deep chemical weathering. Laurite is altered to Ru-oxides or re-crystallizes together with secondary Mg-ilmenite. Other PGM, especially the Pt-Fe alloys, re-precipitate within the altered chromite together with kaolinite and Fe-hydroxides. Textural evidence suggests that re-deposition of secondary PGM took place during chromite alteration, controlled by variation of the redox conditions on a microscopic scale.

  16. Dose-response relationships determined in growing rats for various platinum compounds administered with the food. Untersuchungen zu Dosis-Wirkungsbeziehungen verschiedener alimentaer zugefuehrter Platinverbindungen bei wachsenden Ratten

    Energy Technology Data Exchange (ETDEWEB)

    Bader, R.

    1991-02-08

    Forming part of a research project entitled 'Emissions of Precious Metals', this study had the aim to describe dose-related responses that occur in growing rats following administration of platinum with the food. The oral intake of diets containing up to to 50 mg platinum/kg food had no detectable influence on the food consumption of the animals, nor were there any deviations from the normal growth curves that could be related to the addition of platinum. Comparisons with the control group pointed to a decline in erythrocytes from 5.88 {+-} 0.55 x 10{sup 6}/{mu}l to 5.11 {+-} 0.50 x 10{sup 6}/{mu}l following administration of 50 ppm PtCl{sub 4} over a period of four weeks. There were no other changes in hematological parameters that attained statistical significance. The treatment group receiving platinum amounts of 50 mg/kg with the diet showed a plasma creatinine value of 1.45 {+-} 0.19 {mu}g/dl, which significantly (p < 0.05) exceeded that of the control group, where creatinine levels remained at 0.70 {+-} 0.50 {mu}g/dl. This leads to the conclusion that the possibility of renal impairment after high oral doses of PtCl{sub 4} is not very remote. (orig./VT).

  17. Roadside Accumulation of Pt, Pd, Rh and Other Trace Elements From Automobiles: Catalytic Converter Attrition and Platinum-Group Element Mobility in the Roadside Environment.

    Science.gov (United States)

    Ely, J. C.; Dahlheimer, S. R.; Neal, C. R.

    2003-12-01

    Elemental abundances of Pt, Pd and Rh have been documented across the industrialized world in roadside environments due to attrition of automotive catalytic converters (Zereini and Alt, 2000, Anthropogenic PGE Emissions, Springer, 308pp; Ely et al., 2001, EnvSci&Tech, 35:3816-3822; Whiteley and Murray, 2003, SciTotEnv, in press). In our ongoing study, the highest reported roadside Pt abundance 1.8 ppm has been found immediately adjacent to the road at a field site in South Bend, IN, USA. Furthermore, initial studies show positive correlations of Pt, Pd and Rh with some trace elements (Ni, Cu, Zn and Pb), which has been confirmed by further analysis for these and other elements (Ce, Cr). It has been demonstrated that elements such as Ce are present in catalytic converters at concentrations of 100's ppm to 3-wt.%. These elements are also being attrited with Pt, Pd and Rh and aerially transported and deposited. Our field site was established next to US-933 adjacent to the Notre Dame campus. Areas were cleared of the top 2-4 cm of soil (removing surficial Pt, Pd and Rh) at 1, 5, 10 and 50 meters from the roadside. Within 3 months the 1-meter site contained 67% of the initial Rh and Pt concentrations and 100% of the initial Pd concentration. The sites at 5, 10 and 50 meters showed similar results, in some cases exceeding the initial concentrations. After 6 months the concentrations of Pt, Pd and Rh were all within error of the initial concentrations, indicating steady state abundances had probably been reached. Grass samples from each site showed that washed vs. unwashed samples were within error of each other, and there may be a slight enrichment (approx. 1 ppb) in the grasses of Pd and Pt, but this enrichment was independent of distance from the road. The steady-state situation suggests that the PGEs are being removed from the immediate roadside environment, which requires that the metals are being oxidized and/or complexed in such a way to facilitate transport. The

  18. Features of proteolytic properties of tetraphenylporphyrin complex with lanthanide group metals

    Science.gov (United States)

    Tobolkina, Elena A.; Skripnikova, Tatiana A.; Starikova, Anna A.; Shumilova, Galina I.; Pendin, Andrey A.

    2018-01-01

    Demetallation of metalloporphyrin molecules is one of the essential degradation reactions in photosynthesis. The effect of metalloporphyrin nature on removal of central metals from tetraphenylporphyrin complexes based on lanthanide group metals (Dy, Er, Lu, Ho) has been studied. pH values, at which the metal ions leave the metalloporphyrin complex were established using two-phase spectrophotometric titration with potentiometric pH-control. The pH values decrease with the increase of atomic numbers of lanthanide groups, as well as with increase of 4f-electrons. The reaction of an extra ligand exchange for the hydroxide ion was studied. For Dy-, Er- and Ho-tetraphenylporphyrin complexes one particle of extra ligand coordinates with one porphyrin complex. A complex with dimeric particles can be formed for the system of Lu-tetraphenylporphyrin. Constants of the ion exchange reactions were calculated.

  19. TP53 status and taxane-platinum versus platinum-based therapy in ovarian cancer patients: A non-randomized retrospective study

    Directory of Open Access Journals (Sweden)

    Markowska Janina

    2008-01-01

    Full Text Available Abstract Background Taxane-platinum therapy (TP has replaced platinum-based therapy (PC or PAC, DNA damaging chemotherapy in the postoperative treatment of ovarian cancer patients; however, it is not always effective. TP53 protein plays a differential role in response to DNA-damaging agents and taxanes. We sought to define profiles of patients who benefit the most from TP and also of those who can be treated with PC. Methods We compared the effectiveness of PC/PAC (n = 253 and TP (n = 199 with respect to tumor TP53 accumulation in ovarian cancer patients with FIGO stage IIB-IV disease; this was a non-randomized retrospective study. Immunohistochemical analysis was performed on 452 archival tumors; univariate and multivariate analysis by the Cox's and logistic regression models was performed in all patients and in subgroups with [TP53(+] and without TP53 accumulation [TP53(-]. Results The advantage of taxane-platinum therapy over platinum-based therapy was seen in the TP53(+, and not in the TP53(- group. In the TP53(+ group taxane-platinum therapy enhanced the probability of complete remission (p = .018, platinum sensitivity (p = .014, platinum highly sensitive response (p = .038 and longer survival (OS, p = .008. Poor tumor differentiation diminished the advantage from taxane-platinum therapy in the TP53(+ group. In the TP53(- group PC/PAC was at least equally efficient as taxane-platinum therapy and it enhanced the chance of platinum highly sensitive response (p = .010. However, in the TP53(- group taxane-platinum therapy possibly diminished the risk of death in patients over 53 yrs (p = .077. Among factors that positively interacted with taxane-platinum therapy in some analyses were endometrioid and clear cell type, FIGO III stage, bulky residual tumor, more advanced age of patient and moderate tumor differentiation. Conclusion Our results suggest that taxane-platinum therapy is particularly justified in patients with TP53(+ tumors or older

  20. Material efficiency: rare and critical metals.

    Science.gov (United States)

    Ayres, Robert U; Peiró, Laura Talens

    2013-03-13

    In the last few decades, progress in electronics, especially, has resulted in important new uses for a number of geologically rare metals, some of which were mere curiosities in the past. Most of them are not mined for their own sake (gold, the platinum group metals and the rare Earth elements are exceptions) but are found mainly in the ores of the major industrial metals, such as aluminium, copper, zinc and nickel. We call these major metals 'attractors' and the rare accompanying metals 'hitch-hikers'. The key implication is that rising prices do not necessarily call forth greater output because that would normally require greater output of the attractor metal. We trace the geological relationships and the functional uses of these metals. Some of these metals appear to be irreplaceable in the sense that there are no known substitutes for them in their current functional uses. Recycling is going to be increasingly important, notwithstanding a number of barriers.

  1. Infrared multiple photon dissociation spectroscopy of group I and group II metal complexes with Boc-hydroxylamine.

    Science.gov (United States)

    Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; Van Stipdonk, Michael J

    2013-08-30

    Hydroxamates are essential growth factors for some microbes, acting primarily as siderophores that solubilize iron for transport into a cell. Here we determined the intrinsic structure of 1:1 complexes between Boc-protected hydroxylamine and group I ([M(L)](+)) and group II ([M(L-H)](+)) cations, where M and L are the cation and ligand, respectively, which are convenient models for the functional unit of hydroxamate siderphores. The relevant complex ions were generated by electrospray ionization (ESI) and isolated and stored in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Infrared spectra of the isolated complexes were collected by monitoring (infrared) photodissociation yield as a function of photon energy. Experimental spectra were then compared to those predicted by density functional theory (DFT) calculations. The infrared multiple photon dissociation (IRMPD) spectra collected are in good agreement with those predicted to be lowest-energy by DFT. The spectra for the group I complexes contain six resolved absorptions that can be attributed to amide I and II type and hydroxylamine N-OH vibrations. Similar absorptions are observed for the group II cation complexes, with shifts of the amide I and amide II vibrations due to the change in structure with deprotonation of the hydroxylamine group. IRMPD spectroscopy unequivocally shows that the intrinsic binding mode for the group I cations involves the O atoms of the amide carbonyl and hydroxylamine groups of Boc-hydroxylamine. A similar binding mode is preferred for the group II cations, except that in this case the metal ion is coordinated by the O atom of the deprotonated hydroxylamine group. Copyright © 2013 John Wiley & Sons, Ltd.

  2. Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

    Directory of Open Access Journals (Sweden)

    Yedil Yergozhin

    2013-05-01

    Full Text Available The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

  3. Effect of functionalization of boron nitride flakes by main group metal clusters on their optoelectronic properties

    Science.gov (United States)

    Chakraborty, Debdutta; Chattaraj, Pratim Kumar

    2017-10-01

    The possibility of functionalizing boron nitride flakes (BNFs) with some selected main group metal clusters, viz. OLi4, NLi5, CLi6, BLI7 and Al12Be, has been analyzed with the aid of density functional theory (DFT) based computations. Thermochemical as well as energetic considerations suggest that all the metal clusters interact with the BNF moiety in a favorable fashion. As a result of functionalization, the static (first) hyperpolarizability (β ) values of the metal cluster supported BNF moieties increase quite significantly as compared to that in the case of pristine BNF. Time dependent DFT analysis reveals that the metal clusters can lower the transition energies associated with the dominant electronic transitions quite significantly thereby enabling the metal cluster supported BNF moieties to exhibit significant non-linear optical activity. Moreover, the studied systems demonstrate broad band absorption capability spanning the UV-visible as well as infra-red domains. Energy decomposition analysis reveals that the electrostatic interactions principally stabilize the metal cluster supported BNF moieties.

  4. The relationship between debt levels and total shareholder return of JSE-listed platinum companies

    Directory of Open Access Journals (Sweden)

    Sandra Jooste

    2016-02-01

    Full Text Available The purpose of this study is to investigate empirically whether there is a positive correlation between debt levels and total shareholder return (TSR of platinum JSE-listed companies. The study field comprised annual analyses for 12 companies listed under the Platinum and Precious Metals sector on the JSE Ltd for the 14-year period 2000 to 2013. The results of the study were inconclusive as a statistically significant positive correlation between changes in debt levels and changes in TSR could only be found in two of these years. The core audience of the study will be the management of South African platinum companies considering changes in their capital structure, and investors considering investment in a listed platinum company. The contribution of the study is therefore to add to the body of literature on capital structure decisions from a South African platinum mine context

  5. Influence of prognostic groupings and treatment results in the management of unresectable hepatoma: experience with cis-platinum-based chemoradiotherapy in 76 patients

    International Nuclear Information System (INIS)

    Abrams, Ross A.; Cardinale, Robert M.; Enger, Cheryl; Haulk, Thomas L.; Hurwitz, Herbert; Osterman, Floyd; Sitzmann, James V.

    1997-01-01

    Purpose: Internationally, hepatoma is a common cause of cancer death. Although the only curative therapy is surgical, most tumors are unresectable and cause death. The value of nonsurgical, antineoplastic therapy for such tumors is controversial. This study was undertaken to extend and confirm promising, but preliminary, treatment observations in the unresectable context. Methods and Materials: From 1988 to 1993, 76 patients with unresectable, biopsy proven, hepatoma underwent uniform pretreatment assessment followed by induction therapy with external beam radiotherapy (21 Gy/7 fractions/10 days) and intravenous Cisplatinum, 50 mg/m 2 . One month later patients began monthly intrahepatic artery Cisplatinum, 50 mg/m 2 . Clinical course and treatment outcomes were correlated with previously published prognostic factors and groupings (Nomura et al., Okuda et al., Stillwagon, et al.). Results: The toxicity of this therapy was modest and nonlimiting. Twenty-four patients (32%) progressed during induction and prior to receiving two cycles of intrahepatic artery Cisplatinum without evidence of benefit. Patients showing this early progression were more likely to be Stillwagon unfavorable than favorable (p = 0.013), Okuda Stage II than Stage I (p = 0.024), and slightly but not statistically more likely to be alpha-fetoprotein positive than alpha-fetoprotein negative (p = 0.098). The overall objective response rate was 43% (38% among AFP positive and 62% among AFP negative patients) (p = 0.15). Although 21 patients had evidence of extra hepatic metastases, survival for these patients did not differ from patients without metastases (p = 0.09) and patients with extra hepatic metastases were just as likely to show intrahepatic response (p = 0.84). Conclusion: The chemoradiotherapy program utilized produced objective response and minimal toxicity. One-third of patients progressed rapidly in spite of treatment. Among the remaining patients, response occurred frequently. This

  6. Determination of platinum group elements and gold in reference materials by instrumental neutron activation analysis and inductively coupled plasma-mass spectrometry with nickel sulphide fire-assay collection

    International Nuclear Information System (INIS)

    Morcelli, C.P.R.; Figueiredo, A.M.G.; Sarkis, J.E.S.; Kakazu, M.; Enzweiler, J.

    2002-01-01

    Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) after NiS fire assay were used to determine platinum group elements (PGE) and Au in the geological reference materials peridotite GPt-3 and pyroxene peridotite GPt-4 (IGGE, China). INAA has been one of the most useful analytical techniques for PGEs and Au determination, due to its high sensitivity and accuracy. After the fire assay, the NiS button is dissolved in concentrated hydrochloric acid, leaving a residue of insoluble PGE sulphides; the solution is filtered and the filter is directly irradiated with neutrons. In more recent years, ICP-MS with nickel fire assay collection and tellurium coprecipitation has been used as a mean of analysing PGE, with the main advantage of avoiding problems of losses of PGE during the HCl digestion of the NiS button. Buttons were prepared by mixing the sample (10-15 g) with fluxes, nickel and sulphur in a fire clay crucible and fused at temperatures around 1000 deg C. For NAA, the filters containing the PGEs and Au were irradiated at the IEA-R1 research nuclear reactor at IPEN. The measurements of the induced gamma-ray activity were carried out in an hyperpure Ge detector. In general, the results obtained by the two techniques were in good agreement with recommended values. INAA results exhibited higher values than the recommended values for Pd and Pt in GPt-3, while the opposite effect was observed for GPt-4 sample. Ru was not detected by INAA. On the other hand, Rh and Ir were determined more accurately by INAA (relative errors better than 10%). The ICP-MS analytical technique showed better detection limits, and all the PGE were determined. Results obtained for Pt and Pd presented accuracy better than 5% while losses were observed for Os and Ir. (author)

  7. Supramolecular assembly of group 11 phosphorescent metal complexes for chemosensors of alcohol derivatives

    Science.gov (United States)

    Lintang, H. O.; Ghazalli, N. F.; Yuliati, L.

    2018-04-01

    We report on systematic study on vapochromic sensing of ethanol by using phosphorescent trinuclear metal pyrazolate complexes with supramolecular assembly of weak intermolecular metal-metal interactions using 4-(3,5-dimethoxybenzyl)-3,5-dimethyl pyrazole ligand (1) and group 11 metal ions (Cu(I), Ag(I), Au(I)). Upon excitation at 284, the resulting complexes showed emission bands with a peak centered at 616, 473 and 612 nm for 2(Cu), 2(Ag) and 2(Au), respectively. Chemosensor 2(Cu) showed positive response to ethanol vapors in 5 mins by blue-shifting its emission band from 616 to 555 nm and emitting bright orange to green. Otherwise 2(Au) gave shifting from its emission band centered at 612 to 587 nm with Δλ of 25 nm (41%) and color changes from red-orange to light green-orange while 2(Ag) showed quenching in its original emission intensity at 473 nm in 40% with color changes from dark green to less emissive. These results demonstrate that sensing capability of chemosensor 2(Cu) with suitable molecular design of ligand and metal ion in the complex is due to the formation of a weak intermolecular hydrogen bonding interaction of O atom at the methoxy of the benzyl ring with the OH of the vapors at the outside of the molecules.

  8. Preparation and Characterization of Styrene Bearing Diethanolamine Side Group, Styrene Copolymer Systems, and Their Metal Complexes

    Directory of Open Access Journals (Sweden)

    Aslışah Açıkses

    2018-01-01

    Full Text Available The two copolymer systems of styrene bearing diethanol amine side group and styrene were prepared by free radical polymerization method at 60°C in presence of 1,4-dioxane as solvent and AIBN as initiator. Their metal complexes were prepared by reaction of the copolymer used as ligand P(DEAMSt-co-StL′′ and Ni(II and Co(II metal ions, which was carried out in presence of ethanol and NaOH at 65°C for 48 h in pH = 7.5. The structures of the copolymers used as ligand and metal complexes were identified by FT-IR, 1H-NMR spectra, and elemental analysis. The properties of the copolymers used as ligand and metal complexes were characterized by SEM-EDX, AAS, DSC, TGA, and DTA techniques. Then, the electrical properties of the copolymers and metal complexes were examined as a function of the temperature and frequency, and the activation energies (Ea were estimated with conductivity measurements.

  9. Rapid and Efficient Collection of Platinum from Karstedt's Catalyst Solution via Ligands-Exchange-Induced Assembly.

    Science.gov (United States)

    Yang, Gonghua; Wei, Yanlong; Huang, Zhenzhu; Hu, Jiwen; Liu, Guojun; Ou, Ming; Lin, Shudong; Tu, Yuanyuan

    2018-02-21

    Reported herein is a novel strategy for the rapid and efficient collection of platinum from Karstedt's catalyst solution. By taking advantage of a ligand-exchange reaction between alkynols and the 1,3-divinyltetramethyldisiloxane ligand (M Vi M Vi ) that coordinated with platinum (Pt(0)), the Karstedt's catalyst particles with a size of approximately 2.5 ± 0.7 nm could be reconstructed and assembled into larger particles with a size of 150 ± 35 nm due to the hydrogen bonding between the hydroxyl groups of the alkynol. In addition, because the silicone-soluble M Vi M Vi ligand of the Karstedt's catalyst was replaced by water-soluble alkynol ligands, the resultant large particles were readily dispersed in water, resulting in rapid, efficient, and complete collection of platinum from the Karstedt's catalyst solutions with platinum concentrations in the range from ∼20 000 to 0.05 ppm. Our current strategy not only was used for the rapid and efficient collection of platinum from the Karstedt's catalyst solutions, but it also enabled the precise evaluation of the platinum content in the Karstedt's catalysts, even if this platinum content was extremely low (i.e., 0.05 ppm). Moreover, these platinum specimens that were efficiently collected from the Karstedt's catalyst solutions could be directly used for the evaluation of platinum without the need for pretreatment processes, such as calcination and digestion with hydrofluoric acid, that were traditionally used prior to testing via inductively coupled plasma mass spectrometry in conventional methods.

  10. Report on generation IV technical working group 3 : liquid metal reactors

    International Nuclear Information System (INIS)

    Lineberry, M. J.; Rosen, S. L.; Sagayama, Y.

    2002-01-01

    This paper reports on the first round of R and D roadmap activities of the Generation IV (Gen IV) Technical Working Group (TWG) 3, on liquid metal-cooled reactors. Liquid metal coolants give rise to fast spectrum systems, and thus the reactor systems considered in this TWG are all fast reactors. Gas-cooled fast reactors are considered in the context of TWG 2. As is noted in other Gen IV papers, this first round activity is termed ''screening for potential'', and includes collecting the most complete set of liquid metal reactor/fuel cycle system concepts possible and evaluating the concepts against the Gen IV principles and goals. Those concepts or concept groups that meet the Gen IV principles and which are deemed to have reasonable potential to meet the Gen IV goals will pass to the next round of evaluation. Although we sometimes use the terms ''reactor'' or ''reactor system'' by themselves, the scope of the investigation by TWG 3 includes not only the reactor systems, but very importantly the closed fuel recycle system inevitably required by fast reactors. The response to the DOE Request for Information (RFI) on liquid metal reactor/fuel cycle systems from principal investigators, laboratories, corporations, and other institutions, was robust and gratifying. Thirty three liquid metal concept descriptions, from eight different countries, were ultimately received. The variation in the scope, depth, and completeness of the responses created a significant challenge for the group, but the TWG made a very significant effort not to screen out concepts early in the process

  11. Redeposition of electrochemically dissolved platinum as nanoparticles on carbon

    DEFF Research Database (Denmark)

    Norgaard, C. F.; Stamatin, S. N.; Skou, E. M.

    2014-01-01

    communication reports a simple chemical method for reprecipitating platinum as nanoparticles of reasonable particle size on a carbon substrate without intermediary separation and handling of solid platinum salt. After electrochemical dissolution, platinum was reprecipitated using a polyol based method. Platinum...

  12. A study of new rare-earth metal group-13 chalcohalides. Structures, chemistry, and optical properties

    International Nuclear Information System (INIS)

    Dorhout, P.K.; Van Calcar, P.M.

    1998-01-01

    Full text: Several new quaternary compounds from the rare-earth metal group-13 chalcohalide family have been prepared from alkaline earth halide flux reactions of binary and elemental starting materials. One compound, for example, Ca 2 La 6G a 2 S 1 4 , crystallizes as needles in an hexagonal cell while another, more disordered structure, La 11 Ga 19 Cl 6 S 42 , crystallizes as monoclinic plates. The former is a condensed structure with channels that contain the alkaline earth element while the latter forms a layered structure containing rare-earth halide clusters within interlayer galleries. These compounds are new members of a family of rare-earth metal main-group chalcogenides which show promise as electroluminescent materials. Structural and spectroscopic studies of these and related compounds will be discussed

  13. Investigation of mechanical and structural characteristics of platinum and palladium at high temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Trumie, B. T.; Gomidzelovie, L.; Marjanovic, S. R.; Krstic, V. R.

    2015-03-30

    In order to broaden future application of products based on platinum and palladium a comparative analysis of their high-temperature mechanical properties was performed. Platinum and palladium are of great importance and are widely used in chemical industry, electronics, for making laboratory dishes, to name a few. Mechanical properties of pure metals, such as: tensile strength, creep rate and rupture time were investigated using universal testing machine for tensile testing of materials. Microstructure of samples was investigated by optical microscopy. Based on obtained results it can be concluded that the platinum, compared to palladium, is superior for high-temperature applications. (Author)

  14. Investigation of mechanical and structural characteristics of platinum and palladium at high temperatures

    International Nuclear Information System (INIS)

    Trumie, B. T.; Gomidzelovie, L.; Marjanovic, S. R.; Krstic, V. R.

    2015-01-01

    In order to broaden future application of products based on platinum and palladium a comparative analysis of their high-temperature mechanical properties was performed. Platinum and palladium are of great importance and are widely used in chemical industry, electronics, for making laboratory dishes, to name a few. Mechanical properties of pure metals, such as: tensile strength, creep rate and rupture time were investigated using universal testing machine for tensile testing of materials. Microstructure of samples was investigated by optical microscopy. Based on obtained results it can be concluded that the platinum, compared to palladium, is superior for high-temperature applications. (Author)

  15. Ethanol oxidation on a nichrome-supported spherical platinum microparticle electrocatalyst prepared by electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhen-Hui; Li, Jing; Dong, Xiaoya; Wang, Dong; Chen, Tiwei; Qiao, Haiyan; Huang, Aiping [College of Chemistry and Environmental Science, Henan Key Laboratory for Environmental Pollution Control, Henan Normal University, Jianshe Road, Xinxiang 453007 (China)

    2008-11-15

    A novel electrode was rapidly prepared by depositing microparticle platinum onto a nichrome substrate in dilute chloroplatinic acid solution by cyclic voltammetry. The SEM results revealed that the deposits were composed of spherical Pt microparticles. Cyclic voltammetry and chronoamperometry were used for the characterization of the electrodes. Results of the electrochemical measurements showed that the spherical Pt microparticle electrodes retained the properties of metal platinum, increased the catalytic activity and promoted the electrocatalytic oxidation of ethanol. Moreover, the deposited Pt microparticles improved the electrochemical properties of the support material and reduced the dosage of noble metal platinum remarkably. The cost could be reduced dramatically by decreasing the contents of platinum. The spherical Pt microparticles deposited on the nichrome supports are likely a potential electrocatalyst for ethanol electrooxidation. (author)

  16. Study of gold-platinum and platinum-gold surface modification and its influence on hydrogen evolution and oxygen reduction

    Directory of Open Access Journals (Sweden)

    BRANIMIR N. GRGUR

    2005-02-01

    Full Text Available Surface modification of the electrodes was conducted from sulfuric acid solutions containing the corresponding metal–chloride complexes using cyclic voltammetry. Comparing the charges of the hydrogen underpotential deposition region, and the corresponding oxide reduction regions, it is concluded that a platinum overlayer on gold forms 3D islands, while gold on platinum forms 2D islands. Foreign metals present in an amount of up to one monolayer exert an influence on the change in reaction rate with respect to both hydrogen evolution (HER and oxygen reduction (ORR reactions. Aplatinum overlayer on a gold substrate increases the activity forHER and for ORR, compared with pure gold. These results can be understood in terms of a simple model, in which the change in the H and OH binding energies are directly proportional to the shift of the d-bond center of the overlayer. On the contrary, a gold layer on platinum slightly decreases the activity for both reactions compared with pure platinum.

  17. Electrochemical DNA biosensors based on platinum nanoparticles combined carbon nanotubes

    International Nuclear Information System (INIS)

    Zhu Ningning; Chang Zhu; He Pingang; Fang Yuzhi

    2005-01-01

    Platinum nanoparticles were used in combination with multi-walled carbon nanotubes (MWCNTs) for fabricating sensitivity-enhanced electrochemical DNA biosensor. Multi-walled carbon nanotubes and platinum nanoparticles were dispersed in Nafion, which were used to fabricate the modification of the glassy carbon electrode (GCE) surface. Oligonucleotides with amino groups at the 5' end were covalently linked onto carboxylic groups of MWCNTs on the electrode. The hybridization events were monitored by differential pulse voltammetry (DPV) measurement of the intercalated daunomycin. Due to the ability of carbon nanotubes to promote electron-transfer reactions, the high catalytic activities of platinum nanoparticles for chemical reactions, the sensitivity of presented electrochemical DNA biosensors was remarkably improved. The detection limit of the method for target DNA was 1.0 x 10 -11 mol l -1

  18. Designer ligands: The search for metal ion selectivity

    Directory of Open Access Journals (Sweden)

    Perry T. Kaye

    2011-03-01

    Full Text Available The paper reviews research conducted at Rhodes University towards the development of metal-selective ligands. The research has focused on the rational design, synthesis and evaluation of novel ligands for use in the formation of copper complexes as biomimetic models of the metalloenzyme, tyrosinase, and for the selective extraction of silver, nickel and platinum group metal ions in the presence of contaminating metal ions. Attention has also been given to the development of efficient, metal-selective molecular imprinted polymers.

  19. Selective hydrogenation of halogenated arenes using porous manganese oxide (OMS-2) and platinum supported OMS-2 catalysts.

    Science.gov (United States)

    McManus, Iain J; Daly, Helen; Manyar, Haresh G; Taylor, S F Rebecca; Thompson, Jillian M; Hardacre, Christopher

    2016-07-04

    Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group in chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 °C and, although the rate of reaction increased with increasing temperature up to 100 °C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 °C and 2 bar hydrogen pressure giving a selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate hydrogen. In the case of Pd/OMS-2 both the hydrogenation and hydrogen adsorption occur on the metal sites.

  20. Carbide-forming groups IVB-VIB metals: a new territory in the periodic table for CVD growth of graphene.

    Science.gov (United States)

    Zou, Zhiyu; Fu, Lei; Song, Xiuju; Zhang, Yanfeng; Liu, Zhongfan

    2014-07-09

    Early transition metals, especially groups IVB-VIB metals, can form stable carbides, which are known to exhibit excellent "noble-metal-like" catalytic activities. We demonstrate herein the applications of groups IVB-VIB metals in graphene growth using atmospheric pressure chemical vapor deposition technique. Similar to the extensively studied Cu, Ni, and noble metals, these transition-metal foils facilitate the catalytic growth of single- to few-layer graphene. The most attractive advantage over the existing catalysts is their perfect control of layer thickness and uniformity with highly flexible experimental conditions by in situ converting the dissolved carbons into stable carbides to fully suppress the upward segregation/precipitation effect. The growth performance of graphene on these transition metals can be well explained by the periodic physicochemical properties of elements. Our work has disclosed a new territory of catalysts in the periodic table for graphene growth and is expected to trigger more interest in graphene research.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2002-04-01

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

  2. WITNESSING GAS MIXING IN THE METAL DISTRIBUTION OF THE HICKSON COMPACT GROUP HCG 31

    International Nuclear Information System (INIS)

    Torres-Flores, S.; Alfaro-Cuello, M.; De Oliveira, C. Mendes; Amram, P.; Carrasco, E. R.; De Mello, D. F.

    2015-01-01

    We present for the first time direct evidence that in a merger of disk galaxies, the pre-existing central metallicities will mix as a result of gas being transported in the merger interface region along the line that joins the two coalescing nuclei. This is shown using detailed two-dimensional kinematics as well as metallicity measurements for the nearby ongoing merger in the center of the compact group HCG 31. We focus on the emission line gas, which is extensive in the system. The two coalescing cores display similar oxygen abundances. While in between the two nuclei, the metallicity changes smoothly from one nucleus to the other indicating a mix of metals in this region, which is confirmed by the high-resolution Hα kinematics (R = 45,900). This nearby system is especially important because it involves the merging of two fairly low-mass and clumpy galaxies (LMC-like galaxies), making it an important system for comparison with high-redshift galaxies

  3. WITNESSING GAS MIXING IN THE METAL DISTRIBUTION OF THE HICKSON COMPACT GROUP HCG 31

    Energy Technology Data Exchange (ETDEWEB)

    Torres-Flores, S.; Alfaro-Cuello, M. [Departamento de Física, Universidad de La Serena, Av. Cisternas 1200, La Serena (Chile); De Oliveira, C. Mendes [Instituto de Astronomia, Geofísica e Ciências Atmosféricas da Universidade de São Paulo, Cidade Universitária, CEP:05508-900, São Paulo, SP (Brazil); Amram, P. [Aix Marseille Université, CNRS, LAM (Laboratoire d' Astrophysique de Marseille) UMR 7326, F-13388, Marseille (France); Carrasco, E. R. [Gemini Observatory/AURA, Southern Operations Center, Casilla 603, La Serena (Chile); De Mello, D. F., E-mail: storres@dfuls.cl [Catholic University of America, Washington, DC 20064 (United States)

    2015-01-01

    We present for the first time direct evidence that in a merger of disk galaxies, the pre-existing central metallicities will mix as a result of gas being transported in the merger interface region along the line that joins the two coalescing nuclei. This is shown using detailed two-dimensional kinematics as well as metallicity measurements for the nearby ongoing merger in the center of the compact group HCG 31. We focus on the emission line gas, which is extensive in the system. The two coalescing cores display similar oxygen abundances. While in between the two nuclei, the metallicity changes smoothly from one nucleus to the other indicating a mix of metals in this region, which is confirmed by the high-resolution Hα kinematics (R = 45,900). This nearby system is especially important because it involves the merging of two fairly low-mass and clumpy galaxies (LMC-like galaxies), making it an important system for comparison with high-redshift galaxies.

  4. Synthesis of Hydrophilic Sulfur-Containing Adsorbents for Noble Metals Having Thiocarbonyl Group Based on a Methacrylate Bearing Dithiocarbonate Moieties

    Directory of Open Access Journals (Sweden)

    Haruki Kinemuchi

    2018-01-01

    Full Text Available Novel hydrophilic sulfur-containing adsorbents for noble metals were prepared by the radical terpolymerization of a methacrylate bearing dithiocarbonate moieties (DTCMMA, hydrophilic monomers, and a cross-linker. The resulting adsorbents efficiently and selectively adsorbed noble metals (Au, Ag, and Pd from various multielement aqueous solutions at room temperature owing to the thiocarbonyl group having high affinity toward noble metals. The metal adsorption by the adsorbents was proceeded by simple mixing followed by filtration. The noble metal selectivity of the adsorbent obtained from DTCMMA and N-isopropylacrylamide was higher than that of the adsorbent obtained from DTCMMA and N,N-dimethylacrylamide due to the lower nonspecific adsorption.

  5. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.

    2008-02-11

    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.

  6. Cycloadditions to Epoxides Catalyzed by GroupIII-V Transition-Metal Complexes

    KAUST Repository

    D'Elia, Valerio

    2015-05-25

    Complexes of groupIII-V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (C-C versus C-O) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (C-O bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of groupIII-V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (C-C bond cleavage). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Cycloadditions to Epoxides Catalyzed by GroupIII-V Transition-Metal Complexes

    KAUST Repository

    D'Elia, Valerio; Pelletier, Jeremie; Basset, Jean-Marie

    2015-01-01

    Complexes of groupIII-V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (C-C versus C-O) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (C-O bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of groupIII-V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (C-C bond cleavage). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Nanostructured gold and platinum electrodes on silicon structures for biosensing

    International Nuclear Information System (INIS)

    Ogurtsov, V I; Sheehan, M M

    2005-01-01

    Gold and platinum metal electrodes on Si/SiO 2 having undergone anisotropic potassium hydroxide (KOH) etch treatment are considered. This treatment etches at different rates and directions in the material resulting in creation of numerous pyramid shaped holes in the silicon substrate. This surface is used to make metal electrodes with increased electrode efficiency. The electrodes can serve as the sensors or as the sensor substrates (for surface polymer modification) and because both gold and platinum are inert they have applications for food safety biosensing. Wine, an economically significant food product, was chosen as a matrix, and impedance spectroscopy (EIS) was selected as a method of investigation of electrode behaviour. Based on results of EIS, different complexity equivalent circuits were determined by applying fitting mean square root optimisation of sensor complex impedance measurements

  9. A comparative study of electrochemical and optical properties of rhenium deposited on gold and platinum

    Energy Technology Data Exchange (ETDEWEB)

    Zerbino, Jorge O.; Castro Luna, Ana M.; Martins, M. E. [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Buenos Aires (Argentina). Inst. de Investigaciones Fisico-Quimicas, Teoricas y Aplicadas (INIFTA)]. E-mail: mmartins@inifta.unlp.edu.ar; Zinola, Carlos F.; Mendez, Eduardo [Universidad de la Republica, Montevideo (Uruguay). Facultad de Ciencias. Lab. de Electroquimica Fundamental

    2002-08-01

    Rhenium-containing films were grown on gold and platinum after different potentiostatic and potentiodynamic polarizations in the - 0.20 V to 0.70 V range (vs rhe) in aqueous acid perrhenate. Experimental data were obtained using cyclic voltammetry and ellipsometry, from which the thickness and optical indices of the electrodeposited rhenium layer were calculated. Metallic rhenium deposition on gold takes place at potentials within the hydrogen evolution reaction. Rhenium oxide on platinum is formed in the hydrogen adatom potential domain, whereas metallic rhenium is deposited concurrently with the hydrogen adsorption and evolution reactions on the same metal. (author)

  10. A comparative study of electrochemical and optical properties of rhenium deposited on gold and platinum

    Directory of Open Access Journals (Sweden)

    Zerbino Jorge O.

    2002-01-01

    Full Text Available Rhenium-containing films were grown on gold and platinum after different potentiostatic and potentiodynamic polarizations in the - 0.20 V to 0.70 V range (vs rhe in aqueous acid perrhenate. Experimental data were obtained using cyclic voltammetry and ellipsometry, from which the thickness and optical indices of the electrodeposited rhenium layer were calculated. Metallic rhenium deposition on gold takes place at potentials within the hydrogen evolution reaction. Rhenium oxide on platinum is formed in the hydrogen adatom potential domain, whereas metallic rhenium is deposited concurrently with the hydrogen adsorption and evolution reactions on the same metal.

  11. A combined radiation and platinum chemotherapy for esophageal carcinoma

    International Nuclear Information System (INIS)

    Takamura, Akio; Saito, Hiroya; Sakurai, Yasuo; Horio, Keiji; Mizoe, Junetsu.

    1993-01-01

    The prognosis of the patients with advanced esophageal carcinoma treated by definitive radiotherapy is still dismal with a reported 5-year survival rate of 5-10% in most series. Since 1986, combined radiotherapy with chemotherapy using platinum analogue was initiated at Asahikawa and Obihiro Kosei Hospitals in order to improve local-regional control and the survival of the patients. From 1980 to 1992, 81 patients with unresectable esophageal carcinoma were treated with radiotherapy. Since April 1986, 37 out of the 81 patients received both radiotherapy and chemotherapy with platinum. Platinum was used during the course of radiotherapy. The method of administration of platinum was as follows; Cisplatin intravenously (50 mg, weekly, total 200 mg) in 9 patients, Carboplatin intravenously (100-150 mg, weekly, total 400-900 mg) in 11 patients and Cisplatin intraarterially (100 mg, at a 3-4 week interval, total 100-300 mg) in 17 patients. These 37 patients (Group A) were compared to 44 patients treated by radiotherapy alone (Group B) with respect to initial response and survival rate. Response was defined according to the guidelines recommended by Japanese Society for Esophageal Diseases. Response rates were 59.1% (19 CR and 7 PR) in Group B and 70.3% (7 CR and 19 PR) in Group A. Primary relapse-free rates were 36.4% in Group B and 37.8% in Group A. The cumulative survival at 3 years were 11.7% in Group B and 10.6% in Group A. Enhancement of side effects by chemotherapy was minimal and acceptable. Improvement of local-regional control and survival was not obvious by adding a concomitant platinum-chemotherapy. A definite conclusion, however, could not be drawn because of the retrospective, non-controlled nature of this study. Introduction of more intensive, multiple agents chemotherapy seems necessary if one aims at improving the results. (author)

  12. Oscillatory instabilities in the electrooxidation of borohydride on platinum

    Energy Technology Data Exchange (ETDEWEB)

    Machado, Eduardo G.; Varela, Hamilton, E-mail: varela@iqsc.usp.br [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Instituto de Quimica

    2014-03-15

    The borohydride ion has been pointed as a promising alternative fuel. Most of the investigation on its electrochemistry is devoted to the electrocatalytic aspects of its electrooxidation on platinum and gold surfaces. Besides the known kinetic limitations and intricate mechanism, our Group has recently found the occurrence of two regions of bi-stability and autocatalysis in the electrode potential during the open circuit interaction of borohydride and oxidized platinum surfaces. Following this previous contribution, the occurrence of more complicated phenomena is here presented: namely the presence of electrochemical oscillations during the electrooxidation of borohydride on platinum in alkaline media. Current oscillations were found to be associated to two distinct instability windows and characterized in the resistance-potential parameter plane. The dynamic features of such oscillations suggest the existence of distinct mechanisms according to the potential region. Previously published results obtained under non-oscillatory regime were used to give some hints on the surface chemistry behind the observed dynamics. (author)

  13. Niraparib Maintenance Therapy in Platinum-Sensitive, Recurrent Ovarian Cancer

    DEFF Research Database (Denmark)

    Mirza, Mansoor R; Monk, Bradley J; Herrstedt, Jørn

    2016-01-01

    Background Niraparib is an oral poly(adenosine diphosphate [ADP]-ribose) polymerase (PARP) 1/2 inhibitor that has shown clinical activity in patients with ovarian cancer. We sought to evaluate the efficacy of niraparib versus placebo as maintenance treatment for patients with platinum-sensitive, ......Background Niraparib is an oral poly(adenosine diphosphate [ADP]-ribose) polymerase (PARP) 1/2 inhibitor that has shown clinical activity in patients with ovarian cancer. We sought to evaluate the efficacy of niraparib versus placebo as maintenance treatment for patients with platinum...... or 4 adverse events that were reported in the niraparib group were thrombocytopenia (in 33.8%), anemia (in 25.3%), and neutropenia (in 19.6%), which were managed with dose modifications. Conclusions Among patients with platinum-sensitive, recurrent ovarian cancer, the median duration of progression...

  14. Cytotoxic evaluation upon cis-platinum aminodiacetic acid complexes

    International Nuclear Information System (INIS)

    Almah binti Awaluddin; Parsons, Peter G.; Lean, Jenny M.; Jacobs, Jeffrey J.

    1990-01-01

    Cytoxic study of cis-platinum aminodiacetic acid complexes. Three novel platinum complexes have been synthesised and characterised by Awaluddin et. al (1987). This introduces a new area of radiopharmaceuticals based on technician and platinum. Cytotoxic studies were conducted on these complexes using four different types of cell lines. The para amina was found to be highly active against multi-resistant ovarian tumor cells compared to normal cells (fibroblast) and other tumor cells. The chemical structure of para-amina appears to be devoid of any functional group resembling current antitumor drugs except for a distant similarity to metotrexate with respect to the p-aminobenzoic type structure. However cell lines such as Hela and MM 253c-1, which is sensitive to metotrexate, were not sensitive to the para amina. Preliminary studies have shown that cells are blocked in the G phase of the cell cycle, suggesting an antimetabolite effect

  15. Responses of fibroblasts and glial cells to nanostructured platinum surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Pennisi, C P; Sevcencu, C; Yoshida, K [Center for Sensory-Motor Interaction (SMI), Aalborg University, Aalborg (Denmark); Dolatshahi-Pirouz, A; Foss, M; Larsen, A Nylandsted; Besenbacher, F [Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Aarhus (Denmark); Hansen, J Lundsgaard [Department of Physics and Astronomy, Aarhus University, Aarhus (Denmark); Zachar, V, E-mail: cpennisi@hst.aau.d [Laboratory for Stem Cell Research, Aalborg University (Denmark)

    2009-09-23

    The chronic performance of implantable neural prostheses is affected by the growth of encapsulation tissue onto the stimulation electrodes. Encapsulation is associated with activation of connective tissue cells at the electrode's metallic contacts, usually made of platinum. Since surface nanotopography can modulate the cellular responses to materials, the aim of the present work was to evaluate the 'in vitro' responses of connective tissue cells to platinum strictly by modulating its surface nanoroughness. Using molecular beam epitaxy combined with sputtering, we produced platinum nanostructured substrates consisting of irregularly distributed nanopyramids and investigated their effect on the proliferation, cytoskeletal organization and cellular morphology of primary fibroblasts and transformed glial cells. Cells were cultured on these substrates and their responses to surface roughness were studied. After one day in culture, the fibroblasts were more elongated and their cytoskeleton less mature when cultured on rough substrates. This effect increased as the roughness of the surface increased and was associated with reduced cell proliferation throughout the observation period (4 days). Morphological changes also occurred in glial cells, but they were triggered by a different roughness scale and did not affect cellular proliferation. In conclusion, surface nanotopography modulates the responses of fibroblasts and glial cells to platinum, which may be an important factor in optimizing the tissue response to implanted neural electrodes.

  16. Understanding hydrogen sorption in a metal-organic framework with open-metal sites and amide functional groups

    KAUST Repository

    Pham, Tony T.

    2013-05-09

    Grand canonical Monte Carlo (GCMC) studies of the mechanism of hydrogen sorption in an rht-MOF known as Cu-TPBTM are presented. The MOF is a decorated/substituted isostructural analogue to the unembellished rht-MOF, PCN-61, that was studied previously [ Forrest, K. A.J. Phys. Chem. C 2012, 116, 15538-15549. ]. The simulations were performed using three different hydrogen potentials of increasing complexity. Simulated hydrogen sorption isotherms and calculated isosteric heat of adsorption, Qst, values were in excellent agreement with the reported experimental data for only a polarizable model in one of four experimentally observed crystal structure configurations. The study demonstrates the ability of modeling to distinguish the differential sorption of distinct strucures; one configuration is found to be dominant due to favorable interactions with substrates. In addition, it was discovered that the presence of polar amide groups had a significant effect on the electrostatics of the Cu2+ ions and directs the low-pressure physisorption of hydrogen in the MOF. This is in contrast to what was observed in PCN-61, where an exterior copper ion had a higher relative charge and was the favored loading site. This tunability of the electrostatics of the copper ions via chemical substitution on the MOF framework can be explained by the presence of the negatively charged oxygen atom of the amide group that causes the interior Cu2+ ion to exhibit a higher positive charge through an inductive effect. Further, control simulations, taking advantage of the flexibility afforded by theoretical modeling, include artificially modified charges for both Cu2+ ions chosen equal to or with a higher charge on the exterior Cu2+ ion. This choice resulted in distinctly different hydrogen sorption characteristics in Cu-TPBTM with no direct sorption on the open-metal sites. Thus, this study demonstrates both the tunable nature of MOF platforms and the possibility for rational design of sorption

  17. Electron momentum spectroscopy of the group I and Il metal and oxides

    International Nuclear Information System (INIS)

    Ford, M.J.; Dorsett, H.E.; Sashin, V.A.; Bolorizadeh, M.A.; Mikajlo, E.A.; Soule de Bas, B.; Nixon, K.L.; Coleman, V.A.

    2002-01-01

    Full text: The group I and Il metals and oxides are relatively simple condensed phase systems that are easily accessible to theoretical studies. For this reason they have been the subject of a number of studies using a range of theoretical techniques. Calculated electronic band structures have traditionally been compared with optical, X-ray and photo emissions measurements. While these techniques provide excellent data for testing theoretical predictions they generally probe certain aspects of the electronic structure, such as special point energies or densities of states, or require considerable theoretical input for their interpretation. In this paper we present our electron momentum spectroscopy (EMS) measurements for the lighter group Il metals and oxides and group I oxides. EMS can measure directly the full band dispersions and intensities and provides a sensitive test of theoretical predictions. We compare our measurements with Hartree-Fock (HF) and density functional theory (DFT) calculations carried out within the linear combination of atomic orbitals approximation. As expected HF significantly overestimates the bandwidths and bandgaps. DFT gives reasonable overall agreement, albeit with slight overestimation of bandwidths for the oxides. The intensity distribution for the oxides show a systematic difference from all the calculations which cannot easily be explained by experimental effects such as multiple scattering in the target. This work was funded by the Australian Research Council and Flinders University. EA Mikajlo and K L Nixon acknowledge receipt of SENRAC and Ferry scholarships respectively

  18. Bioavailability of very finely distributed metallic platinum in the lungs and first orienting studies on effects. Part 2; Bioverfuegbarkeit von feinstverteiltem metallischem Platin in der Lunge und erste orientierende Wirkungsuntersuchungen (VPT 09; 2. Teil)

    Energy Technology Data Exchange (ETDEWEB)

    Emmendoerffer, A [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung, Hannover (Germany)

    1998-12-31

    Platinum is emitted from automotive catalytic converters in particulate form. The first organ to be exposed to it after its uptake by the organism is the lung. Lung macrophages therefore constitute the first barrier of the immune system which can to react to platinum. In this study the production of nitrogen oxides and cytokines was studied. These parameters play an important role in the initiation of inflammation and in the maintenance of chronic inflammatory processes that can lead to fibrosis of the lung. [Deutsch] Platin wird partikulaer aus Automobilabgaskatalysatoren emittiert. Das erste Zielorgan fuer eine Aufnahme im Organismus ist deshalb die Lunge. Die Lungenmakrophagen stellen also die erste Barriere des Immunsystems dar, das auf Platin reagieren kann. In vitro wurde die Produktion von Stickoxiden und Zytokinen untersucht. Diese Parameter spielen eine Rolle bei der Initiation von Entzuendungen und auch bei der Aufrechterhaltung chronisch entzuendlicher Prozesse, die in der Lunge zu einer Fibrose fuehren koennen. (orig.)

  19. Bioavailability of very finely distributed metallic platinum in the lungs and first orienting studies on effects. Part 2; Bioverfuegbarkeit von feinstverteiltem metallischem Platin in der Lunge und erste orientierende Wirkungsuntersuchungen (VPT 09; 2. Teil)

    Energy Technology Data Exchange (ETDEWEB)

    Emmendoerffer, A. [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung, Hannover (Germany)

    1997-12-31

    Platinum is emitted from automotive catalytic converters in particulate form. The first organ to be exposed to it after its uptake by the organism is the lung. Lung macrophages therefore constitute the first barrier of the immune system which can to react to platinum. In this study the production of nitrogen oxides and cytokines was studied. These parameters play an important role in the initiation of inflammation and in the maintenance of chronic inflammatory processes that can lead to fibrosis of the lung. [Deutsch] Platin wird partikulaer aus Automobilabgaskatalysatoren emittiert. Das erste Zielorgan fuer eine Aufnahme im Organismus ist deshalb die Lunge. Die Lungenmakrophagen stellen also die erste Barriere des Immunsystems dar, das auf Platin reagieren kann. In vitro wurde die Produktion von Stickoxiden und Zytokinen untersucht. Diese Parameter spielen eine Rolle bei der Initiation von Entzuendungen und auch bei der Aufrechterhaltung chronisch entzuendlicher Prozesse, die in der Lunge zu einer Fibrose fuehren koennen. (orig.)

  20. Room-Temperature Synthesis of Transition Metal Clusters and Main Group Polycations from Ionic Liquids

    OpenAIRE

    Ahmed, Ejaz

    2011-01-01

    Main group polycations and transition metal clusters had traditionally been synthesized via high-temperature routes by performing reactions in melts or by CTR, at room-temperature or lower temperature by using so-called superacid solvents, and at room-temperature in benzene–GaX3 media. Considering the major problems associated with higher temperature routes (e.g. long annealing time, risk of product decomposition, and low yield) and taking into account the toxicity of benzene and liquid SO2 i...

  1. Separation of gold, palladium and platinum in chromite by anion exchange chromatography for inductively coupled plasma atomic emission spectrometric analysis

    International Nuclear Information System (INIS)

    Choi, Kwang Soon; Lee, Chang Heon; Park, Yeong Jae; Joe, Kih Soo; Kim, Won Ho

    2001-01-01

    A study has been carried out on the separation of gold, iridium, palladium, rhodium, ruthenium and platinum in chromite samples and their quantitative determination using inductively coupled plasma atomic emission spectrometry (ICP-AES). The dissolution condition of the minerals by fusion with sodium peroxide was optimized and chromatographic elution behavior of the rare metals was investigated by anion exchange chromatography. Spectral interference of chromium, a matrix of the minerals, was investigated on determination of gold. Chromium interfered on determination of gold at the concentration of 500 mg/L and higher. Gold plus trace amounts of iridium, palladium, rhodium and ruthenium, which must be preconcentrated before ICP-AES was separated by anion exchange chromatography after reducing Cr(VI) to Cr(III) by H 2 O 2 . AuCl - 4 retained on the resin column was selectively eluted with acetone- HNO 3 -H 2 O as an eluent. In addition, iridium, palladium, rhodium and ruthenium remaining on the resin column were eluted as a group with concentrated HCl. However, platinum was eluted with concentrated HNO 3 . The recovery yield of gold with acetone-HNO 3 -H 2 O was 100.7 ± 2.0 % , and the yields of palladium and platinum with concentrated HCl and HNO 3 were 96.1 ± 1.8% and 96.6 ± 1.3%, respectively. The contents of gold and platinum in a Mongolian chromite sample were 32.6 ± 2.2 μg/g and 1.6 ± 0.14 μg/g, respectively. Palladium was not detected

  2. Surface layers in the 4A group metals with implanted silicon ions

    International Nuclear Information System (INIS)

    Kovneristyj, Yu.K.; Vavilova, V.V.; Krasnopevtsev, V.V.; Galkin, L.N.; Kudyshev, A.N.; Klechkovskaya, V.V.

    1987-01-01

    A study was made on the change of structure and phase composition of fine near the surface layers of 4A group metals (Hf, Zr, Ti) during ion Si implantation and successive thermal annealing at elevated temperatures. Implantation of Si + ions with 30 or 16 keV energy in Ti, Zr and Hf at room temperature results to amorphization of metal surface layer. The surface hafnium and titanium layer with implanted Si atoms due to interaction with residual atmosphere of oxygen turns during annealing at 870 K to amorphous solid solution of HfO 2m or TiO 2 with Si, preventing further metal oxidation; layers of amorphous alloy are characterized by thermal stability up to 1270 K. Oxidation of the surface amorphous layer in residual oxygen atmosphere and its crystallization in ZrO 2 take place in result of Zr annealing with implanted Si ions at temperature not exceeding 870 K. Similar phenomena are observed in the case of hafnium with implanted oxygen ions or small dose of silicon ions. Thermal stability of amorphous layers produced during ion implantation of Si in Ti, Zr and Hf corresponds to scale resistance of monolithic alloys in Ti-Si, Zr-Si and Hf-Si systems

  3. Modulation of individual steps in group I intron catalysis by a peripheral metal ion.

    Science.gov (United States)

    Forconi, Marcello; Piccirilli, Joseph A; Herschlag, Daniel

    2007-10-01

    Enzymes are complex macromolecules that catalyze chemical reactions at their active sites. Important information about catalytic interactions is commonly gathered by perturbation or mutation of active site residues that directly contact substrates. However, active sites are engaged in intricate networks of interactions within the overall structure of the macromolecule, and there is a growing body of evidence about the importance of peripheral interactions in the precise structural organization of the active site. Here, we use functional studies, in conjunction with published structural information, to determine the effect of perturbation of a peripheral metal ion binding site on catalysis in a well-characterized catalytic RNA, the Tetrahymena thermophila group I ribozyme. We perturbed the metal ion binding site by site-specifically introducing a phosphorothioate substitution in the ribozyme's backbone, replacing the native ligands (the pro-R (P) oxygen atoms at positions 307 and 308) with sulfur atoms. Our data reveal that these perturbations affect several reaction steps, including the chemical step, despite the absence of direct contacts of this metal ion with the atoms involved in the chemical transformation. As structural probing with hydroxyl radicals did not reveal significant change in the three-dimensional structure upon phosphorothioate substitution, the effects are likely transmitted through local, rather subtle conformational rearrangements. Addition of Cd(2+), a thiophilic metal ion, rescues some reaction steps but has deleterious effects on other steps. These results suggest that native interactions in the active site may have been aligned by the naturally occurring peripheral residues and interactions to optimize the overall catalytic cycle.

  4. Characterization of Platinum Nanoparticles Deposited on Functionalized Graphene Sheets

    Directory of Open Access Journals (Sweden)

    Yu-Chun Chiang

    2015-09-01

    Full Text Available Due to its special electronic and ballistic transport properties, graphene has attracted much interest from researchers. In this study, platinum (Pt nanoparticles were deposited on oxidized graphene sheets (cG. The graphene sheets were applied to overcome the corrosion problems of carbon black at operating conditions of proton exchange membrane fuel cells. To enhance the interfacial interactions between the graphene sheets and the Pt nanoparticles, the oxygen-containing functional groups were introduced onto the surface of graphene sheets. The results showed the Pt nanoparticles were uniformly dispersed on the surface of graphene sheets with a mean Pt particle size of 2.08 nm. The Pt nanoparticles deposited on graphene sheets exhibited better crystallinity and higher oxygen resistance. The metal Pt was the predominant Pt chemical state on Pt/cG (60.4%. The results from the cyclic voltammetry analysis showed the value of the electrochemical surface area (ECSA was 88 m2/g (Pt/cG, much higher than that of Pt/C (46 m2/g. The long-term test illustrated the degradation in ECSA exhibited the order of Pt/C (33% > Pt/cG (7%. The values of the utilization efficiency were calculated to be 64% for Pt/cG and 32% for Pt/C.

  5. Dansyl-naphthalimide dyads as molecular probes: effect of spacer group on metal ion binding properties.

    Science.gov (United States)

    Shankar, Balaraman H; Ramaiah, Danaboyina

    2011-11-17

    Interaction of a few dansyl-naphthalimide conjugates 1a-e linked through polymethylene spacer groups with various metal ions was investigated through absorption, fluorescence, NMR, isothermal calorimetric (ITC), and laser flash photolysis techniques. The characteristic feature of these dyads is that they exhibit competing singlet-singlet energy transfer (SSET) and photoinduced electron transfer (PET) processes, both of which decrease with the increase in spacer length. Depending on the spacer group, these dyads interact selectively with divalent Cu(2+) and Zn(2+) ions, as compared to other mono- and divalent metal ions. Jobs plot analysis showed that these dyads form 2:3 complexes with Cu(2+) ions, while 1:1 complexes were observed with Zn(2+) ions. The association constants for the Zn(2+) and Cu(2+) complexes were determined and are found to be in the order 10(3)-10(5) M(-1). Irrespective of the length of the spacer group, these dyads interestingly act as fluorescence ratiometric molecular probes for Cu(2+) ions by altering the emission intensity of both dansyl and naphthalimide chromophores. In contrast, only the fluorescence intensity of the naphthalimide chromophore of the lower homologues (n = 1-3) was altered by Zn(2+) ions. (1)H NMR and ITC measurements confirmed the involvement of both sulfonamide and dimethylamine groups in the complexation with Cu(2+) ions, while only the latter group was involved with Zn(2+) ions. Laser excitation of the dyads 1a-e showed formation of a transient absorption which can be attributed to the radical cation of the naphthalimide chromophore, whereas only the triplet excited state of the dyads 1a-e was observed in the presence of Cu(2+) ions. Uniquely, the complexation of 1a-e with Cu(2+) ions affects both PET and SSET processes, while only the PET process was partially inhibited by Zn(2+) ions in the lower homologues (n = 1-3) and the higher homologues exhibited negligible changes in their emission properties. Our results

  6. Determination of phosphorus traces in platinum alloys by two-phase isotope exchange

    International Nuclear Information System (INIS)

    Vlacil, F.

    1980-01-01

    The method of ZEMAN and KRATZER for the determination of phosphorus traces by means of two-phase isotope exchange was modified for the determination of phosphorus in pure platinum or pure platinum alloys. It was found that Pt, Rh, Ag and As do not interfere with the determination. Among the elements usually present in platinum metal or platinum alloys, only gold interferes. It was removed by extraction from 7M HCl by MIBK and AmOAc. Hydrochloric acid also interferes but it can be removed by evaporation. The analytical procedure is given for the solution obtained by pressure decomposition of the sample (0.5 g) in a steel bomb with PTFE inlay. It is possible to determine > 2 ppm P (approximate error -10%). If using calibration dependence instead of the well known equation for isotope exchange it is not necessary to know the content of P in the standard solution labelled with 32 P. (author)

  7. Conducting metal dithiolate complexes

    DEFF Research Database (Denmark)

    Underhill, A. E.; Ahmad, M. M.; Turner, D. J.

    1985-01-01

    Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound......Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound...

  8. Platinum-bearing chromite layers are caused by pressure reduction during magma ascent.

    Science.gov (United States)

    Latypov, Rais; Costin, Gelu; Chistyakova, Sofya; Hunt, Emma J; Mukherjee, Ria; Naldrett, Tony

    2018-01-31

    Platinum-bearing chromitites in mafic-ultramafic intrusions such as the Bushveld Complex are key repositories of strategically important metals for human society. Basaltic melts saturated in chromite alone are crucial to their generation, but the origin of such melts is controversial. One concept holds that they are produced by processes operating within the magma chamber, whereas another argues that melts entering the chamber were already saturated in chromite. Here we address the problem by examining the pressure-related changes in the topology of a Mg 2 SiO 4 -CaAl 2 Si 2 O 8 -SiO 2 -MgCr 2 O 4 quaternary system and by thermodynamic modelling of crystallisation sequences of basaltic melts at 1-10 kbar pressures. We show that basaltic melts located adjacent to a so-called chromite topological trough in deep-seated reservoirs become saturated in chromite alone upon their ascent towards the Earth's surface and subsequent cooling in shallow-level chambers. Large volumes of these chromite-only-saturated melts replenishing these chambers are responsible for monomineralic layers of massive chromitites with associated platinum-group elements.

  9. Study of the influence of platinum, palladium and rhodium on duckweed (Lemna minor).

    Science.gov (United States)

    Bednarova, Ivana; Mikulaskova, Hana; Havelkova, Barbora; Strakova, Lenka; Beklova, Miroslava; Sochor, Jiri; Hynek, David; Adam, Vojtech; Kizek, Rene

    2014-01-01

    Road traffic pollutants and the residues of cytostatics that are widely used in anti-cancer therapy are a significant sources of platinum group elements (PGE; Pt, Pd and Rh) in environment. These metals can migrate into sewage and thus pollute surface waters. The purpose of our study was to evaluate the effect of PtCl4 on the antioxidant and enzymatic activity of duckweed (Lemna minor), a bioindicator of the aquatic environment. The study was performed using a 7-day conventional test based on the OECD 221 (CSN EN ISO 20079)--Lemna sp. Growth Inhibition Test. We also conducted a microbiotest to analyse the effects of PtC4, PdCl2 and RhCl3 on the morphology and vegetative growth of colonies of this plant and compared their inhibitory effects during the microbiotest. We observed inhibition of colony growth and clear morphological changes. Antioxidant and enzymatic activities increased with platinum doses increased. The 168hEC50 of PtCl4 was 12.16 μM (95% confidence interval = 9.88-14.44) and the 168hEC50 of PdCl2 was 50.39 (95% confidence interval = 23.83-76.96). The greatest inhibition of growth by RhCl3 was observed at 25 μM. The obtained results suggest that L. minor phytotoxicity tests should be widely used in the biomonitoring.

  10. Synthesis and properties of platinum on multiwall carbon nanotube modified by chitosan

    Science.gov (United States)

    Fikriyyah, A. K.; Chaldun, E. R.; Indriyati

    2018-03-01

    Platinum nanoparticles on multiwall carbon nanotubes (Pt/MWCNT) play an important role in fuel cell to convert the chemical energy from a fuel into electricity. In this study, Pt/MWCNT electrocatalysts were prepared by chemical reduction of the metal salts in chitosan as the support. Firstly, commercial MWCNTs were functionalized by oxidative process using a mixture of nitric acid and sulfuric acid. Then, functionalized MWCNTs were mixed with chitosan-acetic acid solution to conduct grafting reaction with NH2 groups in chitosan by solution polymerization method. Platinum nanoparticles were loaded onto the surface of the MWCNTs after hexachloroplatinic acid was reduced by sodium hydroxide solution. The result showed that Pt was attached on MWCNT based on analysis from EDS, XRD, and UV Vis Spectroscopy. UV Vis analysis indicates the plasmon absorbance band of Pt nanoparticles in Pt/MWCNT, while XRD analysis confirmed the size of Pt particle in nanometer. This elucidates the potential procedure to synthesize Pt/MWCNT using chitosan.

  11. Effect of heavy metal on survival of certain groups of indigenous soil ...

    African Journals Online (AJOL)

    Heavy metal pollution of soil is known to adversely effect microbial activities at elevated concentration. However, response of indigenous soil bacterial population to added heavy metal and metal combinations is poorly understood. In the present study salts of heavy metals like Cu, Cd, Cr, Hg, Mn, Ni, Pb and Zn were added ...

  12. Effect of the platinum content on the microstructure and micropore size distribution of Pt/alumina-pillared clays.

    Science.gov (United States)

    Barrera-Vargas, M; Valencia-Rios, J; Vicente, M A; Korili, S A; Gil, A

    2005-12-15

    The aim of this work is to study the effect of the platinum content (0-1.8 wt % Pt) on the microstructure of an alumina-pillared clay. For this purpose, the nitrogen physisorption data at -196 degrees C, the micropore size distributions of the supported platinum catalysts, and the hydrogen chemisorption results at 30 degrees C have been analyzed and compared. The preparation of the catalysts has modified the textural properties of the Al-pillared clay support, giving rise to a loss of surface area and micropore volume. After reduction at 420 degrees C, the presence of dispersed metallic platinum with mean crystallite size in the 22-55 A range has been found by hydrogen adsorption. Comparison of all results reveals that the platinum species block the micropore entrances by steric hindrance to nitrogen access as the platinum content increases.

  13. The Origin of Sulfur Tolerance in Supported Platinum Catalysts: The Relationship between Structural and Catalytic Properties in Acidic and Alkaline Pt/LTL.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Miller, J.T.

    1996-01-01

    The reactivity, structure, and sulfur tolerance is compared for platinum supported on acidic and alkaline LTL zeolite. In the absence of sulfur, EXAFS spectroscopy indicates that small metallic platinum particles of approximately 6 to 14 atoms/cluster are present. The TOF for neopentane

  14. Synthesis and characterization of platinum supported on alumina doped with cerium catalyst

    International Nuclear Information System (INIS)

    Yusof Abdullah; Abd Fatah Awang Mat; Mohd Ali Sufi; Sarimah Mahat; Razali Kassim; Nurhaslinda Abdullah.

    1996-03-01

    The synthesis and characterization of gamma-alumina doped with cerium as platinum support for the automobile exhaust catalyst are described. Platinum/alumina/ceria catalyst were prepared by impregnation of hexachloroplatinic acid and sintered at 500 degree Celsius to obtain metal dispersions of 1.0 wt%. Catalyst distribution inside the powder and the effects of the addition of cerium to alumina were analyzed by the scanning electron microscopy (SEM) and x-ray fluorescence spectroscopy (XRF). The results showed that the alumina - supported catalysts contained well dispersion of the noble metal

  15. Water growth on metals and oxides: binding, dissociation and role of hydroxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Salmeron, M.; Bluhm, H.; Tatarkhanov, M.; Ketteler, G.; Shimizu, T.K.; Mugarza, A.; Deng, Xingyi; Herranz, T.; Yamamoto, S.; Nilsson, A.

    2008-09-01

    The authors discuss the role of the presence of dangling H bonds from water or from surface hydroxyl species on the wetting behavior of surfaces. Using Scanning Tunneling and Atomic Force Microscopies, and Photoelectron Spectroscopy, they have examined a variety of surfaces, including mica, oxides, and pure metals. They find that in all cases, the availability of free, dangling H-bonds at the surface is crucial for the subsequent growth of wetting water films. In the case of mica electrostatic forces and H-bonding to surface O atoms determine the water orientation in the first layer and also in subsequent layers with a strong influence in its wetting characteristics. In the case of oxides like TiO{sub 2}, Cu{sub 2}O, SiO{sub 2} and Al{sub 2}O{sub 3}, surface hydroxyls form readily on defects upon exposure to water vapor and help nucleate the subsequent growth of molecular water films. On pure metals, such as Pt, Pd, and Ru, the structure of the first water layer and whether or not it exhibits dangling H bonds is again crucial. Dangling H-bonds are provided by molecules with their plane oriented vertically, or by OH groups formed by the partial dissociation of water. By tying the two II atoms of the water molecules into strong H-bonds with pre-adsorbed O on Ru can also quench the wettability of the surface.

  16. Process for Making a Noble Metal on Tin Oxide Catalyst

    Science.gov (United States)

    Davis, Patricia; Miller, Irvin; Upchurch, Billy

    2010-01-01

    To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

  17. On salting in effect of the second group metal rhodanides on aqueous-amine solutions

    International Nuclear Information System (INIS)

    Krupatkin, I.L.; Ostrovskaya, E.M.; Vorob'eva, L.D.; Kamyshnikova, G.V.

    1978-01-01

    The ''salting in'' effect of rhodanides of Group 2 metals (magnesium, calcium, strontium, barium) on aqueous-amine solutions (water-aniline, and water-o-toluidine systems) is studied. The solubility in these systems has been determined by the isothermal method at 25 deg C. Compositions of the co-existing liquid phases have been determined by refractometry. The phase diagrams of water-aniline-rhodanide of magnesium, calcium and strontium systems have the same qualitative view. These rhodanides ''salt in'' the water-aniline system so strongly that the systems are completely homogenized. According to the decreasing homogenization effect on the water-aniline and water-o-toluidine systems the salts may be arranged into the following series Mg(NCS) 2 >Ca(NCS) 2 >Sr(NCS) 2 >Ba(NCS) 2 . The ''salting in'. effect is weaker in the water-o-toluidine system rather than in the water-aniline one

  18. Assessment of Typical Heavy Metals in Human Hair of Different Age Groups and Foodstuffs in Beijing, China.

    Science.gov (United States)

    Liang, Gang; Pan, Ligang; Liu, Xinhui

    2017-08-14

    Human hair of different age groups and foodstuff samples were collected in Beijing, China. The concerned metals-Cd, Cr, Pb, As, and Hg-were analyzed, and the metal levels in relation to age, gender, and dietary intake were further assessed. Results showed the highest level of the metals was shown by Pb, with an average concentration of 1.557 ± 0.779 mg/kg, followed by Cr (0.782 ± 0.394), Hg (0.284 ± 0.094), As (0.127 ± 0.078), and Cd (0.071 ± 0.032), following a decreasing order of Pb > Cr > Hg > As > Cd, which were all below the upper limit of normal values in China. The heavy metal concentrations varied greatly among different age groups, and higher concentrations for Cd, Cr, Pb, and As appeared in female hair, whereas higher Hg concentration were found in male hair, suggesting that age and gender were not crucial factors for assessing metal concentrations in human hair. The ingestion of cereals and vegetables were the main route by which heavy metals in the environment create hazardous health effects for local inhabitants, but the estimated metal intakes through food consumption were all lower than the proposed limit of Provisional Tolerable Weekly Intake (PTWI), indicating that heavy metals posed no health risks for the inhabitants. Furthermore, little relationship was found between metal intakes and the corresponding metal levels in hair. Nevertheless, the results of this study can be used to analyze the internal heavy metal burden in the resident population of Beijing area and can also serve as reference for further studies.

  19. Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics.

    Science.gov (United States)

    Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura

    2015-01-13

    Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy.

  20. Investigations in anhydrous liquid ammonia. Reaction of group 2, 4, 5, 11 metal and actinoids compounds

    International Nuclear Information System (INIS)

    Woidy, Patrick

    2014-01-01

    compounds led to the characterization of pentaammine complexes of the dioxidouranium cation which also was shown to form di-, tetra- or octanuclear networks via oxygen bridges. In the tetra- and octanuclear compounds, penta- and hexavalent uranyl cations seem to be present in one compound. The reactions of TiCl 3 and UF 4 and the reaction of Cs[UO 2 (NO 3 ) 3 ] and CuF 2 , yielded the new compounds [UF(NH 3 ) 8 ]Cl 3 . 3,5 NH 3 and Cs[UO 2 F 3 (NH 3 ) 2 ], respectively. Both compounds demonstrated on the one hand the possibility of the exchange of halides and on the other hand the ability to accept fluoride ions. Additionally, a new method for the synthesis of uranyl chloride is presented. Experiments regarding the solubility of metal halides of group 2, 4, and 5 of the periodic table yielded the ammonia complexes of [Ca(NH 3 ) 8 ]X 2 (X = Br and I), [Ti(NH 3 ) 8 ]Cl 3 . 6 NH 3 , and mer-[VF 3 (NH 3 ) 3 ]. Instead of the expected tetragonal antiprism for the eightfold coordinated Ca 2+ ion, a coordination polyhedron best described as a twofold capped trigonal prism and for the Ti 3+ ion an untypical eightfold coordination can be observed. Characterization of the novel compounds was carried out by single crystal and powder X-ray diffraction, infrared and Raman spectroscopy, thermogravimetry and mass spectrometry.

  1. Overexpression of BLM promotes DNA damage and increased sensitivity to platinum salts in triple negative breast and serous ovarian cancers

    DEFF Research Database (Denmark)

    Birkbak, N. J.; Li, Y.; Pathania, S

    2018-01-01

    inhibitor treatment. We identified two genes, the Bloom helicase (BLM) and Fanconi anemia complementation group I (FANCI), that have both increased DNA copy number and gene expression in the platinum sensitive cases. Increased level of expression of these two genes was also associated with platinum...

  2. Explorations of new selenites of the group IIIA and IVA metals

    International Nuclear Information System (INIS)

    Kong Fang; Li Peicin; Zhang Suyun; Mao Jianggao

    2012-01-01

    Systematic explorations of new phases in the Ga III /In III /Ge IV –Se IV –O systems by hydrothermal syntheses or solid-state reactions at high-temperature led to six new ternary compounds, namely, M 2 Se 2 O 7 (M=Ga 1, In 2), M(OH)(SeO 3 ) (M=Ga 3, In 4), α-Ge(SeO 3 ) 2 5 and β-Ge(SeO 3 ) 2 6. Ga 2 Se 2 O 7 1 displays a 3D open framework composed of 2D gallium oxide layers being further bridged and capped by SeO 3 groups. In 2 Se 2 O 7 2 features a 3D indium oxide framework formed by corner- and edge- sharing InO 6 octahedra with SeO 3 groups attached on the cavities and the 8-member ring tunnels of the structure. The isostructural of M(OH)(SeO 3 ) (M=Ga 3, In 4) exhibit a 2D metal selenite layer composed of 1D edge-sharing MO 6 octahedral chains that are interconnected by SeO 3 groups. α-Ge(SeO 3 ) 2 (P2 1 /n) 5 displays a 3D open framework with 1D 8-member ring tunnels along the a-axis while β-Ge(SeO 3 ) 2 (Pa-3) 6 exhibits a condensed 3D network. - Graphical abstract: Highlights: ► Up to now, selenites of the group IIIA and IVA metals are still rare. ► Hydrothermal or solid state reactions yielded six new compounds in this system. ► They are M 2 Se 2 O 7 (M=Ga, In), M(OH)(SeO 3 ) (M=Ga, In), α-Ge(SeO 3 ) 2 and β-Ge(SeO 3 ) 2 . ► They exhibit four different 3D and one 2D structural types. ► α-Ge(SeO 3 ) 2 and β-Ge(SeO 3 ) 2 represent the first examples of germanium selenites.

  3. Radiation and platinum drug interaction

    International Nuclear Information System (INIS)

    Nias, A.H.W.

    1985-01-01

    The ideal platinum drug-radiation interaction would achieve radiosensitization of hypoxic tumour cells with the use of a dose of drug which is completely non-toxic to normal tissues. Electron-affinic agents are employed with this aim, but the commoner platinum drugs are only weakly electron-affinic. They do have a quasi-alkylating action however, and this DNA targeting may account for the radiosensitizing effect which occurs with both pre- and post-radiation treatments. Because toxic drug dosage is usually required for this, the evidence of the biological responses to the drug and to the radiation, as well as to the combination, requires critical analysis before any claim of true enhancement, rather than simple additivity, can be accepted. The amount of enhancement will vary with both the platinum drug dose and the time interval between drug administration and radiation. Clinical schedules may produce an increase in tumour response and/or morbidity, depending upon such dose and time relationships. (author)

  4. Bibliography of the technical literature of the Materials Joining Group, Metals and Ceramics Division, 1951 through June 1987

    International Nuclear Information System (INIS)

    David, S.A.; Goodwin, G.M.; Gardner, K.

    1987-08-01

    This document contains a listing of the written scientific information originating in the Materials Joining Group (formerly the Welding and Brazing Group), Metals and Ceramics Division, Oak Ridge National Laboratory during 1951 through June 1987. It is a registry of about 400 documents as nearly as possible in the order in which they were issued

  5. Phosphoric acid fuel cell platinum use study

    Science.gov (United States)

    Lundblad, H. L.

    1983-05-01

    The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1986-12-15

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

  7. Distribution of rare-earth (Y, La, Ce) and other heavy metals in the profiles of the podzolic soil group

    Science.gov (United States)

    Vodyanitskii, Yu. N.; Goryachkin, S. V.; Savichev, A. T.

    2011-05-01

    Along with Fe and Al, many heavy metals (Mn, Cr, Zn, Cu, and Ni) show a markedly pronounced eluvial-illuvial redistribution in the profiles of soils of the podzolic group. The intensity of the redistribution of the bulk forms of these metals is comparable with that of Fe and exceeds that of Al. Although the podzolic soils are depleted of rare-earth metals, the latter respond readily to soil podzolization. The inactive participation of Al is explained by an insignificant portion of the active reaction-capable fraction. Podzolization does not influence the profile distribution of Sr and Ba. The leaching degree of heavy metals such as Mn, Cr, Zn, Ni, and Zr is noticeably higher in the sandy podzols than in the loamy podzolic soils. Leaching of heavy metals from the podzolic horizons is of geochemical importance, whereas the depletion of metals participating in plant nutrition and biota development is of ecological importance. The leaching of heavy metals is related to the destruction of clay particles in the heavy-textured podzolic soils; the effect of the soil acidity on the leaching of heavy metals is less significant.

  8. Slow and stopped light in active gain composite materials of metal nanoparticles. Ultralarge group index-bandwidth product predicted

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kwang-Hyon; Choe, Song-Hyok [Institute of Lasers, State Academy of Sciences, Unjong District, Pyongyang (Korea, Democratic People' s Republic of)

    2017-08-15

    Chip-compatible slow light devices with large group index-bandwidth products and low losses are of great interest in the community of modern photonics. In this work, active gain materials containing metal nanoparticles are proposed as the slow and stopped light materials. Gain-assisted high field enhancement in metal nanoparticles and the resultant strong dispersion lead to such phenomena. From the Maxwell-Garnett model, it is revealed that the metal nanocomposite exhibits the infinitely large group index when the gain of the host medium and the filling factor of metal nanoparticles satisfy a critical condition. For the gain of the host above the critical value, one can observe slowing down effect with amplification of light pulses. Significantly large group index-bandwidth products, which vary from a few to several thousand or even infinity depending on the gain value of the host medium, have been numerically predicted in active silica glasses containing spheroidal metal nanoparticles, as examples. The proposed scheme inherently provides the widely varying operating spectral range by changing the aspect ratio of metal nanoparticles and chip-compatibility with low cost. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Platinum catalysts recovery of the proton exchange membrane fuel cell; Recuperacao de catalisadores de platina da celula a combustibel de membrana polimerica trocadora de protons

    Energy Technology Data Exchange (ETDEWEB)

    Fukurozaki, S.H.; Seo, E.S.M. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Ciencia e Tecnologia de Materiais. Lab. de Processamento de Residuos

    2006-07-01

    Currently, platinum is the most feasible catalyst for the Proton Exchange Membrane Fuel Cells - PEMFC. Along with platinum's significant importance in this energy system are the high cost of this noble metal and its detrimental effects on the environment. Therefore, recycling this material seems as an alternative to decrease its impacts on the environment and, at the same time, to provide a reduction of the system's costs. A search was conducted for literature and studies about platinum recycling methods. However, only two techniques of platinum recovery, which are still in development, were found. In face of this situation, a recovery method of platinum from deactivated Membrane Electrode Assembly - MEA's was developed, with attention to aspects related to the environment and the necessary requirements for its primary recycling. The results found showed a high recovery ratio and a possibility to reintroduce this metal into the production cycle. (author)

  10. Method for the preparation of metal colloids in inverse micelles and product preferred by the method

    Science.gov (United States)

    Wilcoxon, Jess P.

    1992-01-01

    A method is provided for preparing catalytic elemental metal colloidal particles (e.g. gold, palladium, silver, rhodium, iridium, nickel, iron, platinum, molybdenum) or colloidal alloy particles (silver/iridium or platinum/gold). A homogeneous inverse micelle solution of a metal salt is first formed in a metal-salt solvent comprised of a surfactant (e.g. a nonionic or cationic surfactant) and an organic solvent. The size and number of inverse micelles is controlled by the proportions of the surfactant and the solvent. Then, the metal salt is reduced (by chemical reduction or by a pulsed or continuous wave UV laser) to colloidal particles of elemental metal. After their formation, the colloidal metal particles can be stabilized by reaction with materials that permanently add surface stabilizing groups to the surface of the colloidal metal particles. The sizes of the colloidal elemental metal particles and their size distribution is determined by the size and number of the inverse micelles. A second salt can be added with further reduction to form the colloidal alloy particles. After the colloidal elemental metal particles are formed, the homogeneous solution distributes to two phases, one phase rich in colloidal elemental metal particles and the other phase rich in surfactant. The colloidal elemental metal particles from one phase can be dried to form a powder useful as a catalyst. Surfactant can be recovered and recycled from the phase rich in surfactant.

  11. Infrared multiple photon dissociation spectroscopy of group I and group II metal complexes with Boc-hydroxylamine

    NARCIS (Netherlands)

    Dain, R.P.; Gresham, G.; Groenewold, G.S.; Steill, J.D.; Oomens, J.; van Stipdonk, M.J.

    2013-01-01

    RATIONALE: Hydroxamates are essential growth factors for some microbes, acting primarily as siderophores that solubilize iron for transport into a cell. Here we determined the intrinsic structure of 1:1 complexes between Boc-protected hydroxylamine and group I ([M(L)](+)) and group II ([M(L-H)](+))

  12. Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

    Science.gov (United States)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2017-10-05

    We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n-1 - ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Room temperature synthesis of colloidal platinum nanoparticles

    Indian Academy of Sciences (India)

    Unknown

    platinum cation used. ... Particle size increased with low reagent concentration. ... 2,100) was added separately to the starting solution. Argon gas was bubbled in the solution for 20 min. Later, reduction of platinum ions was carried out by bubbling hydrogen gas ... plex to aquate (Cl– → H2O ligand exchange). ... copper grid.

  14. A Change to the Platinum Publications | Poster

    Science.gov (United States)

    Please be advised that the Poster will no longer publish the “Platinum Publications” series listing recent NCI at Frederick publications. All published research represents a valuable addition to the fight against cancer, AIDS, and infectious diseases—thus, the “Platinum Publications” did not adequately commend all of the important work done by NCI at Frederick researchers.

  15. Collective Behavior of Water on Platinum

    Science.gov (United States)

    Limmer, David; Willard, Adam; Chandler, David

    2012-02-01

    We present the results of molecular dynamics simulations of a interface between water and a platinum electrode. Using importance sampling techniques we probe a variety of collective phenomenon that emerge at the interface. We consider platinum electrodes with two different geometries and discuss how different behaviors result from a competition between geometrical frustration and favorable local interactions.

  16. Investigation of morphological changes in platinum-containing nanostructures created by electron-beam-induced deposition

    NARCIS (Netherlands)

    Botman, A.; Hesselberth, M.; Mulders, J.J.L.

    2008-01-01

    Focused electron-beam-induced deposition (EBID) allows the rapid fabrication of three-dimensional nanodevices and metallic wiring of nanostructures, and is a promising technique for many applications in nanoresearch. The authors present two topics on platinum-containing nanostructures created by

  17. Reversible, high molecular weight palladium and platinum coordination polymers based on phosphorus ligands

    NARCIS (Netherlands)

    Paulusse, J.M.J.; Huijbers, J.P.J.; Sijbesma, R.P.

    2005-01-01

    A general strategy for the preparation and characterization of high molecular weight coordination polymers based on bifunctional phosphorus ligands and palladium or platinum dichloride is described. Metal-to-ligand stoichiometry is of key importance for the formation of linear coordination polymers

  18. Reversible, High Molecular Weight Palladium and Platinum Coordination Polymers Based on Phosphorus Ligands

    NARCIS (Netherlands)

    Paulusse, Jos Marie Johannes; Huijbers, Jeroen P.J.; Sijbesma, Rint P.

    2005-01-01

    A general strategy for the preparation and characterization of high molecular weight coordination polymers based on bifunctional phosphorus ligands and palladium or platinum dichloride is described. Metal-to-ligand stoichiometry is of key importance for the formation of linear coordination polymers

  19. The role of support and promoter on the oxidation of sulfur dioxide using platinum based catalysts

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Rasmussen, Søren Birk; Eriksen, Kim Michael

    2006-01-01

    The catalytic oxidation of SO2 to SO3 was studied over platinum based catalysts in the absence and the presence of dopants. The active metal was supported on silica gel or titania (anatase) by impregnation. The activities of the silica supported catalysts were found to follow the order PtRh/SiO2 ...

  20. Platinum(II) complexes as spectroscopic probes for biomolecules

    Energy Technology Data Exchange (ETDEWEB)

    Ratilla, E.

    1990-09-21

    The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the environment of the tag. Increasing the pH to 7.0 led to the modification by Pt(trpy)Cl{sup +}of Arg 91 in cytochrome c. Further studies with guanidine-containing ligands as models for arginine modification by Pt(trpy)Cl{sup +} showed that guanidine can act as a terminal ligand and as a bridging ligand. Owing to the potential utility of Pt(trpy)L{sup n+} as electron dense probes of nucleic acid structure, interactions of this bis-Pt(trpy){sup 2+} complex with nucleic acids was evaluated. Indeed, the complex interacts non-covalently with nucleic acids. Its interactions with DNA are not exactly the same as those of its precedents. Most striking is its ability to form highly immobile bands of DNA upon gel electrophoresis. 232 refs.

  1. Metal toxicity affects predatory stream invertebrates less than other functional feeding groups

    International Nuclear Information System (INIS)

    Liess, Matthias; Gerner, Nadine V.; Kefford, Ben J.

    2017-01-01

    Ecosystem effects of heavy metals need to be identified for a retrospective risk assessment, and potential impacts need to be predicted for a prospective risk assessment. In this study, we established a strong correlation between the toxic pressure of dissolved metals and invertebrate species. We compiled available data from a wide geographical range of Australian streams that were contaminated with heavy metals [mainly copper (Cu) and zinc (Zn)] and the corresponding invertebrate communities. Heavy metal toxicity is positively related to the proportion of predators within the invertebrate community, represented by the predator ratio , with an effect threshold range of 2.6 μg/L - 26 μg/L for Cu and 62 μg/L - 617 μg/L for Zn. These effect concentrations are in the ranges of the concentrations identified in model ecosystems and other field investigations and are just above the existing guideline limits. Heavy metals also affects the taxa richness negatively. Other community measures, such as the evenness, number of EPT (Ephemeroptera, Plecoptera, and Trichoptera) taxa, SPEcies At Risk (SPEAR) pesticides or SPEAR salinity were relatively poorly correlated with heavy metal toxicity in the streams. Therefore, we suggest applying the predator ratio within the community as a starting point for an indicator of the dissolved metal toxicity, the SPEAR metals . - Highlights: • Data on dissolved metals and invertebrates were compiled for a wide geographical range. • Heavy metal toxicity was strongly related to the predator ratio. • Ecologically relevant thresholds identified for Cu and Zn were above the guideline limits. - Increasing metal toxicity for Cu and Zn in streams could be related to an increasing predator ratio within the invertebrate community.

  2. Stabilization of 200-atom platinum nanoparticles by organosilane fragments

    KAUST Repository

    Pelzer, Katrin

    2011-04-19

    Three\\'s a charm: Platinum nanoparticles of 2 nm diameter and containing approximately 200 atoms covered with n-octylsilyl groups (see picture, right; Pt blue, Si red, C gray, H turquoise) form when [Pt(dba)2] (dba=dibenzylideneacetone) decomposes in the presence of n-octylsilane. The particles adopt a cuboctahedral structure with an edge length of three atoms. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Stabilization of 200-atom platinum nanoparticles by organosilane fragments

    KAUST Repository

    Pelzer, Katrin; Hä vecker, Michael; Boualleg, Malika; Candy, Jean Pierre; Basset, Jean-Marie

    2011-01-01

    Three's a charm: Platinum nanoparticles of 2 nm diameter and containing approximately 200 atoms covered with n-octylsilyl groups (see picture, right; Pt blue, Si red, C gray, H turquoise) form when [Pt(dba)2] (dba=dibenzylideneacetone) decomposes in the presence of n-octylsilane. The particles adopt a cuboctahedral structure with an edge length of three atoms. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Tin-Platinum catalysts interactions on titania and silica

    International Nuclear Information System (INIS)

    Nava, N.; Del Angel, P.; Salmones, J.; Baggio-Saitovitch, E.; Santiago, P.

    2007-01-01

    Pt-Sn was supported on titania and silica, and the resulting interactions between the components in prepared samples and the resulting interactions between the components before and after treatment with hydrogen were characterized by Moessbauer spectroscopy, X-ray diffraction, Rietveld refinement, high-resolution transmission electron microscopy (HRTEM) and catalytic tests data. Results show the presence of Pt and SnO 2 after calcinations, and Pt 3 Sn, PtSn and PtSn 3 after reduction. Rietveld analysis shows that some Ti 4+ are replaced by Sn 4+ atoms in the titania structure. Finally, HRTEM and the practically absence of activity observed confirms that metallic platinum is encapsulated

  5. Synthesis, characterization, vibrational spectroscopy, and factor group analysis of partially metal-doped phosphate materials

    Science.gov (United States)

    Sronsri, Chuchai; Boonchom, Banjong

    2018-04-01

    A simple precipitating method was used to synthesize effectively a partially metal-doped phosphate hydrate (Mn0.9Mg0.1HPO4·3H2O), whereas the thermal decomposition process of the above hydrate precursor was used to obtain Mn1.8Mg0.2P2O7 and LiMn0.9Mg0.1PO4 compounds under different conditions. To separate the overlapping thermal decomposition peak, a deconvolution technique was used, and the separated peak was applied to calculate the water content. The factor group splitting analysis was used to exemplify their vibrational spectra obtained from normal vibrations of HPO42-, H2O, P2O74- and PO43- functional groups. Further, the deconvoluted bending mode of water was clearly observed. Mn0.9Mg0.1HPO4·3H2O was observed in the orthorhombic crystal system with the space group of Pbca (D2h15). The formula units per unit cell were found to be eight (Z = 8), and the site symmetric type of HPO42- was observed as Cs. For the HPO42- unit, the correlation filed splitting analysis of type C3v - Cs - D2h15 was calculated and had 96 internal modes, whereas H2O in the above hydrate was symbolized as C2v - Cs - D2h15 and had 24 modes. The symbol C2v - Cs - C2h3 was used for the correlation filed splitting analysis of P2O74- in Mn1.8Mg0.2P2O7 (monoclinic, C2/m (C2h3), Z = 2, and 42 modes). Finally, the symbol Td - Cs - D2h16 was used for the correlation filed splitting analysis of PO43- in LiMn0.9Mg0.1PO4 (orthorhombic, Pnma (D2h16), Z = 4, and 36 modes).

  6. Hall Measurements on Carbon Nanotube Paper Modified With Electroless Deposited Platinum

    Directory of Open Access Journals (Sweden)

    Iwuoha Emmanuel

    2009-01-01

    Full Text Available Abstract Carbon nanotube paper, sometimes referred to as bucky paper, is a random arrangement of carbon nanotubes meshed into a single robust structure, which can be manipulated with relative ease. Multi-walled carbon nanotubes were used to make the nanotube paper, and were subsequently modified with platinum using an electroless deposition method based on substrate enhanced electroless deposition. This involves the use of a sacrificial metal substrate that undergoes electro-dissolution while the platinum metal deposits out of solution onto the nanotube paper via a galvanic displacement reaction. The samples were characterized using SEM/EDS, and Hall-effect measurements. The SEM/EDS analysis clearly revealed deposits of platinum (Pt distributed over the nanotube paper surface, and the qualitative elemental analysis revealed co-deposition of other elements from the metal substrates used. When stainless steel was used as sacrificial metal a large degree of Pt contamination with various other metals was observed. Whereas when pure sacrificial metals were used bimetallic Pt clusters resulted. The co-deposition of a bimetallic system upon carbon nanotubes was a function of the metal type and the time of exposure. Hall-effect measurements revealed some interesting fluctuations in sheet carrier density and the dominant carrier switched from N- to P-type when Pt was deposited onto the nanotube paper. Perspectives on the use of the nanotube paper as a replacement to traditional carbon cloth in water electrolysis systems are also discussed.

  7. Multiplicity dependence of matrix-induced frequency shifts for atomic transitions of the group 12 metals in rare gas solids

    International Nuclear Information System (INIS)

    Laursen, S.L.; Cartland, H.E.

    1991-01-01

    Atomic resonances of the group 12 metal atoms, Hg, Cd, and Zn, undergo frequency shifts from the gas phase atomic line when trapped in rare gas matrices of Ar, Kr, and Xe at 12 K. As expected, the shifts are approximately linear in polarizability of the rare gas, but the slope of this line depends on whether the transition in question is 1 P 1 left-arrow 1 S 0 or 3 P 1 left-arrow 1 S 0 . Thus the matrix-induced frequency shift is dependent on the singlet or triplet nature of the excited state as well as on the matrix material. This dependence on multiplicity is discussed in terms of interactions between the excited-state atomic orbitals and the matrix. The results are compared to matrix studies of other metals and to related gas-phase work on diatomic van der Waals complexes of group 12 metals with rare gases

  8. Near-Earth asteroids: Metals occurrence, extraction, and fabrication

    Science.gov (United States)

    Westfall, Richard

    Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

  9. Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

    International Nuclear Information System (INIS)

    Abdullah, Mohd Zamri; Ismail, Siti Salwa

    2015-01-01

    The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature

  10. Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

    Energy Technology Data Exchange (ETDEWEB)

    Abdullah, Mohd Zamri, E-mail: zamriab@petronas.com.my; Ismail, Siti Salwa [Chemical Engineering Department, Universiti Teknologi PETRONAS, 31750 Bandar Seri Iskandar, Perak (Malaysia)

    2015-07-22

    The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.

  11. Nanolithographic Fabrication and Heterogeneous Reaction Studies ofTwo-Dimensional Platinum Model Catalyst Systems

    Energy Technology Data Exchange (ETDEWEB)

    Contreras, Anthony Marshall [Univ. of California, Berkeley, CA (United States)

    2006-05-20

    In order to better understand the fundamental components that govern catalytic activity, two-dimensional model platinum nanocatalyst arrays have been designed and fabricated. These catalysts arrays are meant to model the interplay of the metal and support important to industrial heterogeneous catalytic reactions. Photolithography and sub-lithographic techniques such as electron beam lithography, size reduction lithography and nanoimprint lithography have been employed to create these platinum nanoarrays. Both in-situ and ex-situ surface science techniques and catalytic reaction measurements were used to correlate the structural parameters of the system to catalytic activity.

  12. TEM and EELS studies of microwave-irradiation synthesis of bimetallic platinum nanocatalysts

    International Nuclear Information System (INIS)

    Mathe, N R; Scriba, M R; Coville, N J; Olivier, J E

    2014-01-01

    Microwave-irradiation (MW) synthesis of nanostructured materials provides for the synthesis of metal nanoparticles, using fast and uniform heating rates. This procedure affords better control of the shape and size of the nanoparticles when compared to conventional methods. In this work, microwave-irradiation was used to produce platinum-cobalt (Pt-Co) and platinum-nickel (Pt-Ni) nanoparticles for use as electrocatalysts in the methanol oxidation reaction. High resolution TEM imaging and EELS studies revealed that these bimetallic nanoparticles form islands or hetero-structures

  13. Preparation of New Adsorbent Containing Hydroxamic Acid Groups by Electron Beam-Induced Grafting for Metal Ion Adsorption

    International Nuclear Information System (INIS)

    Suwanmala, Phiriyatorn; Hoshina, Hiroyuki; Seko, Noriaki; Tamada, Masao

    2007-08-01

    Full text: A new adsorbent containing hydroxamic acid groups was synthesized by electron beam-induced graft copolymerization of methyl acrylate (MA) onto nonwoven fabric composed of polyethylene-coated polypropylene fiber. Conversion of ester groups of the grafted copolymer into the hydroxamic groups was performed by treatment with an alkaline solution of hydroxylamine (HA). Adsorbent containing hydroxamic acid groups can adsorb 99% of UO2 2+ , 98% of V5+, 97% of Pb2+ and 96% of Al3+ at pH, 5, 4, 6, and 4, respectively, after coming into contact with 100 ppb metal solution for 24 h

  14. Metal Separations and Recovery in the Mining Industry

    Science.gov (United States)

    Izatt, Steven R.; Bruening, Ronald L.; Izatt, Neil E.

    2012-11-01

    Molecular Recognition Technology (MRT) plays an important role in the hydrometallurgical processing dissolved entities in solutions in the mining industry. The status of this industry with respect to sustainability and environmental issues is presented and discussed. The roles of MRT and ion exchange in metal separation and recovery processes in the mining industry are discussed and evaluated. Examples of MRT separation processes of interest to the mining community are given involving gold, cobalt purification by extraction of trace cadmium, rhenium, and platinum group metals (PGMs). MRT processes are shown to be sustainable, economically viable, energy efficient, and environmentally friendly, and to have a low carbon footprint.

  15. Biosorption of platinum and palladium for their separation/preconcentration prior to graphite furnace atomic absorption spectrometric determination

    Energy Technology Data Exchange (ETDEWEB)

    Godlewska-Zylkiewicz, Beata E-mail: bgodlew@uwb.edu.pl

    2003-08-15

    Inexpensive baker's yeast Saccharomyces cerevisiae and green algae Chlorella vulgaris, either free or immobilized on silica gel have been shown to selectively accumulate platinum and palladium from water samples in acidic medium (pH 1.6-1.8). Optimization of conditions of metals biosorption (sample pH, algae and yeast masses, adsorption time, temperature) was performed in batch mode. The procedure of matrix separation based on biosorption of platinum and palladium on algae C. vulgaris covalently immobilized on silica gel in flow mode was developed. The use of algae in flow procedure offers several advantages compared with its use in the batch mode. The procedure shows better reproducibility (<2%), improved efficiency of platinum retention on the column (93.3{+-}1.6%), is less laborious and less time consuming. The best recovery of biosorbed metals from column (87.7{+-}3.3% for platinum and 96.8{+-}1.1 for palladium) was obtained with solution of 0.3 mol l{sup -1} thiourea in 1 mol l{sup -1} hydrochloric acid. The influence of thiourea on analytical signals of examined metals during GFAAS determination is discussed. The procedure has been applied for separation of noble metals from tap and waste water samples spiked with platinum and palladium.

  16. Platinum incorporation in the Na Y zeolite through impregnation method, and characterization by XRD, FTIR and nitrogen adsorption

    International Nuclear Information System (INIS)

    Araujo, A.S.; Sousa, B.V.; Andrade, A.C.C.; Rodrigues, M.G.F.; Rangel, M.C.

    2007-01-01

    Supported metal catalysts are widely used in petroleum refining, chemical and petroleum industries. These catalysts are important in ammonia synthesis, conversion of hydrocarbons with water vapor to synthesis gas, reforming, hydrocracking, ... Platinum has long been used in cracking, hydrogenation and dehydrogenation processes. The aim of this project is the Na Y zeolitic sample preparation through impregnation for incipient humidity, with 0,5% concentration of platinum, aiming its use as a catalyst in the steam reforming reaction. The characterization techniques used were: X Rays Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR) and Nitrogen Adsorption (BET Method). From the obtained results through the techniques mentioned previously it is possible to evidence that the platinum impregnation process did not change the Na Y zeolite structure. Through the superficial specific area (BET) it was possible to observe that the platinum impregnation process caused a decrease in the specific area due to the reduction to the accessibility to the micropores of the zeolitic structure. (author)

  17. Ion mobility studies of carbohydrates as group I adducts: isomer specific collisional cross section dependence on metal ion radius.

    Science.gov (United States)

    Huang, Yuting; Dodds, Eric D

    2013-10-15

    Carbohydrates play numerous critical roles in biological systems. Characterization of oligosaccharide structures is essential to a complete understanding of their functions in biological processes; nevertheless, their structural determination remains challenging in part due to isomerism. Ion mobility spectrometry provides the means to resolve gas phase ions on the basis of their shape-to-charge ratios, thus providing significant potential for separation and differentiation of carbohydrate isomers. Here, we report on the determination of collisional cross sections for four groups of isomeric carbohydrates (including five isomeric disaccharides, four isomeric trisaccharides, two isomeric pentasaccharides, and two isomeric hexasaccharides) as their group I metal ion adducts (i.e., [M + Li](+), [M + Na](+), [M + K](+), [M + Rb](+), and [M + Cs](+)). In all, 65 collisional cross sections were measured, the great majority of which have not been previously reported. As anticipated, the collisional cross sections of the carbohydrate metal ion adducts generally increase with increasing metal ion radius; however, the collisional cross sections were found to scale with the group I cation size in isomer specific manners. Such measurements are of substantial analytical value, as they illustrate how the selection of charge carrier influences carbohydrate ion mobility determinations. For example, certain pairs of isomeric carbohydrates assume unique collisional cross sections upon binding one metal ion, but not another. On the whole, these data suggest a role for the charge carrier as a probe of carbohydrate structure and thus have significant implications for the continued development and application of ion mobility spectrometry for the distinction and resolution of isomeric carbohydrates.

  18. Understanding hydrogen sorption in a metal-organic framework with open-metal sites and amide functional groups

    KAUST Repository

    Pham, Tony T.; Forrest, Katherine A.; Nugent, Patrick S.; Belmabkhout, Youssef; Luebke, Ryan; Eddaoudi, Mohamed; Zaworotko, Michael J.; Space, Brian

    2013-01-01

    of the copper ions via chemical substitution on the MOF framework can be explained by the presence of the negatively charged oxygen atom of the amide group that causes the interior Cu2+ ion to exhibit a higher positive charge through an inductive effect. Further

  19. Mechanism of Platinum Derivatives Induced Kidney Injury

    Directory of Open Access Journals (Sweden)

    Feifei YAN

    2015-09-01

    Full Text Available Platinum derivatives are the most widely used chemotherapeutic agents to treat solid tumors including ovarian, head and neck, and testicular germ cell tumors, lung cancer, and colorectal cancer. Two major problems exist, however, in the clinic use of platinum derivatives. One is the development of tumor resistance to the drug during therapy, leading to treatment failure. The other is the drug’s toxicity such as the cisplatin’s nephrotoxicity, which limits the dose that can be administered. This paper describes the mechanism of platinum derivatives induced kidney injury.

  20. Improved oxidation resistance of group VB refractory metals by Al+ ion implantation

    International Nuclear Information System (INIS)

    Hampikian, J.M.

    1996-01-01

    Aluminum ion implantation of vanadium, niobium, and tantalum improved the metals' oxidation resistances at 500 C and 735 C. Implanted vanadium oxidized only to one-third the extent of unimplanted vanadium when exposed at 500 C to air. The oxidative weight gains of implanted niobium and tantalum proved negligible when measured at 500 C and for times sufficient to fully convert the untreated metals to their pentoxides. At 735 C, implantation of vanadium only slightly retarded its oxidation, while oxidative weight gains of niobium and tantalum were reduced by factors of 3 or more. Implanted niobium exhibited weight gain in direct proportion to oxidation time squared at 735 C. Microstructural examination of the metals implanted with selected fluences of the 180 kV aluminum ions showed the following. The solubility limit of aluminum is extended by implantation, the body centered cubic (bcc) phases being retained to ∼60 at. pct Al in all three metals. The highest fluence investigated, 2.4 x 10 22 ions/m 2 , produced an ∼400-nm layer of VAl 3 beneath the surface of vanadium, and ∼300-nm layers of an amorphous phase containing ∼70 at. pct Al beneath the niobium and tantalum surfaces. All three metals, implanted to this fluence and annealed at 600 C, contained tri-aluminides, intermetallic compounds known for their oxidation resistances. Specimens implanted to this fluence were thus selected for the oxidation measurements

  1. Synthesis and characterization of group V metal carbide and nitride catalysts

    Science.gov (United States)

    Kwon, Heock-Hoi

    1998-11-01

    Group V transition metal carbides and nitrides were prepared via the temperature programmed reaction (TPR) of corresponding oxides with NHsb3 or a CHsb4/Hsb2 mixture. Except for the tantalum compounds, phase-pure carbides and nitrides were prepared. The vanadium carbides and nitrides were the most active and selective catalysts. Therefore the principal focus of the research was the preparation, characterization, and evaluation of high surface area vanadium nitride catalysts. A series of vanadium nitrides with surface areas up to 60 msp2/g was prepared. Thermal gravimetric analysis coupled with x-ray diffraction and scanning electron microscopy indicated that the solid-state reaction proceeded by the sequential reduction of Vsb2Osb5 to VOsb{0.9} and concluded with the topotactic substitution of nitrogen for oxygen in VOsb{0.9}. The transformation of Vsb2Osb5 to VN was pseudomorphic. An experimental design was executed to determine effects of the heating rates and space velocities on the VN microstructures. The heating rates had minor effects on the surface areas and pore size distributions; however, increasing the space velocity significantly increased the surface area. The materials were mostly mesoporous. Oxygen chemisorption on the vanadium nitrides scaled linearly with the surface area. The corresponding O/Vsbsurface ratio was ≈0.6. The vanadium nitrides were active for butane activation and pyridine hydrodenitrogenation. During butane activation, their selectivities towards dehydrogenation products were as high as 98%. The major product in pyridine hydrodenitrogenation was pentane. The reaction rates increased almost linearly with the surface area suggesting that these reactions were structure insensitive. The vanadium nitrides were not active for crotonaldehyde hydrogenation; however, they catalyzed an interesting ring formation reaction that produced methylbenzaldehyde and xylene from crotonaldehyde. A new method was demonstrated for the production of very

  2. Electrochemical sensors and devices for heavy metals assay in water: the French groups' contribution

    Directory of Open Access Journals (Sweden)

    Luca ePUJOL

    2014-04-01

    Full Text Available A great challenge in the area of heavy metal trace detection is the development of electrochemical techniques and devices which are user-friendly, robust, selective, with low detection limits and allowing fast analyses. This review presents the major contribution of the French scientific academic community in the field of electrochemical sensors and electroanalytical methods within the last 20 years. From the well-known polarography to the up-to-date generation of functionalized interfaces, the different strategies dedicated to analytical performances improvement are exposed: stripping voltammetry, solid mercury-free electrode, ion selective sensor, carbon based materials, chemically modified electrodes, nano-structured surfaces. The paper particularly emphasizes their advantages and limits face to the last Water Frame Directive devoted to the Environmental Quality Standards for heavy metals. Recent trends on trace metal speciation as well as on automatic on line monitoring devices are also evoked.

  3. Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones

    Science.gov (United States)

    Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

    2010-04-27

    The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen. The invention also relates to methods of making the metal-metal oxide composites.

  4. Adsorption and temperature-programmed desorption of hydrogen with dispersed platinum and platinum-gold catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, J.R.; Foger, K.; Breakspere, R.J.

    1979-05-01

    Adsorption and temperature-programmed desorption of hydrogen with dispersed platinum and platinum-gold catalysts was studied with 0.9-3Vertical Bar3< platinum on silica gel, aerosil, sodium and lanthanum Y zeolites, and ..gamma..-alumina, and on aerosil-supported gold-platinum alloys containing 2, 10, 24, 33, and 85Vertical Bar3< gold. Surface enrichment with gold in the alloy systems, as derived from hydrogen adsorption data and predicted from surface enrichment theory and electron microscopic measurements of particle size, were in good agreement, which indicated that equilibrium was achieved by the thermal treatment (oxygen at 573/sup 0/K, hydrogen at 620/sup 0/K, repeated cycles) used. Hydrogen spillover to gold was observed at the higher hydrogen pressures tested on the alloys with high gold content, and to the zeolite supports. The temperature-programed desorption profiles were independent of gold content, which indicated that gold acts only as diluent, and that isolated surface platinum atoms become populated with hydrogen atoms either by hydrogen atom spillover from platinum ensembles to gold and from the gold to the isolated platinum, and/or by adsorption of a molecule directly on the isolated platinum and chemisorption of one H atom at an adjacent gold atom. The distribution of surface platinum ensembles was evaluated by a computer simulation method.

  5. Hydrogenation of hexene over platinum on alumina vs. platinum in a Na-Y zeolite

    International Nuclear Information System (INIS)

    Miner, R.S. Jr.; Ione, K.G.; Namba, S.; Turkevich, J.

    1978-01-01

    In order to study the efficacy of zeolites as supports, several platinum H--Y zeolites were prepared by ion exchanging an H--Y zeolite with Pt(NH 3 ) 4 Cl 2 and reducing these products with hydrazine hydrate (A, B, C). Another preparation was made by adsorbing 32-A platinum sol on the zeolite crystallites (D). These catalysts were studied for hydrogenation and isomerization of hexene-1, ethylene hydrogenation, hydrogen chemisorption, and poison titration. They were compared with monodisperse Pt (32 A diameter) on alumina. A marked difference was found between the behavior of hexene-1 with the platinum-in-zeolite and with the platinum-on-alumina

  6. Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework.

    Science.gov (United States)

    Mohideen, M Infas H; Xiao, Bo; Wheatley, Paul S; McKinlay, Alistair C; Li, Yang; Slawin, Alexandra M Z; Aldous, David W; Cessford, Naomi F; Düren, Tina; Zhao, Xuebo; Gill, Rachel; Thomas, K Mark; Griffin, John M; Ashbrook, Sharon E; Morris, Russell E

    2011-04-01

    Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

  7. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Du, Guodong [Iowa State Univ., Ames, IA (United States)

    2003-01-01

    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti(η2-PhC≡CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti(η2-PhC≡CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph)2C(Ph)2O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti(η2-PhC≡CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and α-hydroxy ketones to benzaldehyde and α-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono

  8. VB Platinum Tile & Carpet, Inc. Information Sheet

    Science.gov (United States)

    VB Platinum Tile & Carpet, Inc. (the Company) is located in Bristow, Virginia. The settlement involves renovation activities conducted at a property constructed prior to 1978, located in Washington, DC.

  9. Platinum-Resistor Differential Temperature Sensor

    Science.gov (United States)

    Kolbly, R. B.; Britcliffe, M. J.

    1985-01-01

    Platinum resistance elements used in bridge circuit for measuring temperature difference between two flowing liquids. Temperature errors with circuit are less than 0.01 degrees C over range of 100 degrees C.

  10. Soil microbial activity, mycelial lengths and physiological groups of bacteria in a heavy metal polluted area

    Energy Technology Data Exchange (ETDEWEB)

    Nordgren, A; Kauri, T; Baeaeth, E; Soederstroem, B

    1986-01-01

    The biological effects of heavy metal contamination of coniferous forest soils were studied in the A/sub 01//A/sub 02/ layer around a primary smelter in Northern Sweden. Soil concentrations of 17 elements were determined. Smelter-emitted heavy metals were 5 to 75 times higher in the plot closest to the smelter compared with background levels. Despite emission of sulfur no decrease in pH was found. Bacteria producing acid from maltose, cellobiose, arabinose or xylose and bacteria hydrolyzing starch, pectin, xyland or cellulose decreased 8- to 11-fold due to the soil contamination. Chitin hydrolyzers were 5 times less abundant at the most polluted site compared with background levels. Soil respiration rate and urease activity decreased by about a factor of 4, but phosphatase activity and mycelial lengths were unaffected by the soil contamination. Soil bacteria showed a sigmoidal response to the log of metal concentration in the soil and were affected at a lower pollution level than the other biological variables in the study. A multivariate analysis (partial least squares) showed that soil metal contamination and soil pH were the two environmental factors influencing the soil microorganisms.

  11. Group 4 Transition-Metal Complexes of an Aniline–Carbene–Phenol Ligand

    KAUST Repository

    Despagnet-Ayoub, Emmanuelle

    2013-05-24

    Attempts to install a tridentate aniline-NHC-phenol (NCO) ligand on titanium and zirconium led instead to complexes resulting from unexpected rearrangement pathways that illustrate common behavior in carbene-early- transition-metal chemistry. © 2013 American Chemical Society.

  12. Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table

    NARCIS (Netherlands)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F. Matthias

    2017-01-01

    We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium,

  13. Facile solid-state synthesis of oxidation-resistant metal nanoparticles at ambient conditions

    Science.gov (United States)

    Lee, Kyu Hyung; Jung, Hyuk Joon; Lee, Ju Hee; Kim, Kyungtae; Lee, Byeongno; Nam, Dohyun; Kim, Chung Man; Jung, Myung-Hwa; Hur, Nam Hwi

    2018-05-01

    A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

  14. Elaboration, physical and electrochemical characterizations of CO tolerant PEMFC anode materials. Study of platinum-molybdenum and platinum-tungsten alloys and composites; Elaborations et caracterisations electrochimiques et physiques de materiaux d'anode de PEMFC peu sensibles a l'empoisonnement par CO: etude d'alliages et de composites a base de platine-molybdene et de platine-tungstene

    Energy Technology Data Exchange (ETDEWEB)

    Peyrelade, E.

    2005-06-15

    PEMFC development is hindered by the CO poisoning ability of the anode platinum catalyst. It has been previously shown that the oxidation potential of carbon monoxide adsorbed on the platinum atoms can be lowered using specific Pt based catalysts, either metallic alloys or composites. The objective is then to realize a catalyst for which the CO oxidation is compatible with the working potential of a PEMFC anode. In our approach, to enhance the CO tolerance of platinum based catalyst supported on carbon, we studied platinum-tungsten and platinum-molybdenum alloys and platinum-metal oxide materials (Pt-WO{sub x} and Pt-MoO{sub x}). The platinum based alloys demonstrate a small effect of the second metal towards the oxidation of carbon monoxide. The platinum composites show a better tolerance to carbon monoxide. Electrochemical studies on both Pt-MoO{sub x} and Pt-WO{sub x} demonstrate the ability of the metal-oxides to promote the ability of Pt to oxidize CO at low potentials. However, chrono-amperometric tests reveal a bigger influence of the tungsten oxide. Complex chemistry reactions on the molybdenum oxide surface make it more difficult to observe. (author)

  15. Enhancement of oxidative electrocatalytic properties of platinum nanoparticles by supporting onto mixed WO{sub 3}/ZrO{sub 2} matrix

    Energy Technology Data Exchange (ETDEWEB)

    Rutkowska, Iwona A., E-mail: ilinek@chem.uw.edu.pl; Wadas, Anna; Kulesza, Pawel J., E-mail: pkulesza@chem.uw.edu.pl

    2016-12-01

    Highlights: • The electrocatalytic system utilizing Pt nanoparticles dispersed on mixed metal oxide (WO{sub 3}/ZrO{sub 2}) system is proposed. • The system is characterized by high activity toward oxidations of ethanol, methanol and acetaldehyde in acid medium. • The enhancement effect is facilitated by presence of hydroxyl groups, high mobility of protons and improved distribution of electrons. • Strong interactions between Pt and the mixed oxide WO{sub 3}/ZrO{sub 2} support are postulated. - Abstract: Nanostructured mixed metal (W, Zr) oxide matrices (in a form of layered intercalated films of WO{sub 3} and ZrO{sub 2}) are considered here for supporting and activating catalytic platinum nanoparticles toward electrooxidation of ethanol. Remarkable increases of electrocatalytic (voltammetric, chronoamperometric) currents measured in 0.5 mol dm{sup −3} H{sub 2}SO{sub 4} (containing 0.5 mol dm{sup −3} ethanol) have been observed. Comparison has been made to the behavior of methanol and acetaldehyde under analogous conditions. The enhancement effects are interpreted in terms of specific interactions between platinum nanoparticles and the metal oxide species, high acidity of the mixed oxide sites, as well as high population of surface hydroxyl groups and high mobility of protons existing in close vicinity of Pt catalytic sites. The metal oxide nanostructures are expected to interact competitively (via the surface hydroxyl groups) with adsorbates of the undesirable reaction intermediates, including CO, facilitating their desorption (“third body effect”), or even oxidative removal (e.g., of CO to CO{sub 2}). The fact that the partially reduced tungsten oxide (H{sub x}WO{sub 3}) component is characterized by fast electron transfers coupled to proton displacements tends to improve the overall charge propagation at the electrocatalytic interface.

  16. Comparison of different sample preparation methods for platinum determination in cultured cells by graphite furnace atomic absorption spectrometry

    Directory of Open Access Journals (Sweden)

    Man Xiao

    2017-01-01

    Full Text Available Background Platinum-based agents are widely used in chemotherapy against solid tumors and insufficient intracellular drug accumulation is one of the leading causes of platinum resistance which is associated with poor survival of tumor patients. Thus, the detection of intracellular platinum is pivotal for studies aiming to overcome platinum resistance. In the present study, we aimed to establish a reliable graphite furnace atomic absorption spectrometry (GFAAS-based assay to quantify the intracellular platinum content for cultured cells. Methods Several most commonly applied cell preparation methods, including 0.2% HNO3, 0.2% Triton X-100, concentrated nitric acid, RIPA combined with concentrated nitric acid and hydroxide, followed by GFAAS for platinum detection were compared in ovarian, cervical and liver cancer cell lines to obtain the optimal one, and parameters regarding linearity, accuracy, precision and sensitivity were evaluated. Influence of other metals on platinum detection and the storage conditions of samples were also determined. Results The treatment of cells with 0.2% HNO3 was superior to other approaches with fewer platinum loss and better repeatability. The recovery rate and precision of this method were 97.3%–103.0% and 1.4%–3.8%, respectively. The average recoveries in the presence of other metals were 95.1%–103.1%. The detection limit was 13.23 ug/L. The recovery rate of platinum remained acceptable even in cell samples stored in −20 °C or −80 °C for two months. Discussion After comparison, we found that 0.2% HNO3 was optimal for intracellular platinum quantification based on GFAAS, which presented values compatible with that of inductively-coupled plasma mass-spectrometry (ICP-MS, and this is partially attributed to the simplicity of this method. Moreover, the assay was proved to be accurate, sensitive, cost-effective and suitable for the research of platinum-based antitumor therapy.

  17. Development of Novel Non-Pt Group Metal Electrocatalysts for PEM Fuel Cell Applications

    Energy Technology Data Exchange (ETDEWEB)

    Mukerjee, Sanjeev [Northeastern Univ., Boston, MA (United States). Dept. of Chemistry and Chemical Biology; Atanassov, Plamen [Univ. of New Mexico, Albuquerque, NM (United States); Barton, Scott [Michigan State Univ., East Lansing, MI (United States); Dale, Nilesh [Nissan Technical Center North America (NTCNA), Farmington Hills, MI (United States); Halevi, Bar [Pajarito Powder LLC, Albuquerque, NM (United States)

    2016-01-04

    The objective of this multi-institutional effort was to comprehensively pursue the goal of eliminating noble metal (Pt group metals, PGM) from the cathodic oxygen reduction reaction (ORR) electrode thereby providing a quantum leap in lowering the overall PGM loading in a polymer electrolyte fuel cell (PEMFC). The overall project scope encompassed (a) comprehensive materials discovery effort, (b) a concomitant effort to scale up these materials with very high ( ±5%) reproducibility, both intra and inter, (c) understanding mass transport in porous medium both in gas diffusion and micro-porous layers for enhanced areal activity, (d) understanding mechanistic aspects of active site structure and ORR electrocatalytic pathway. Overall project milestones and metrics were (a) first phase effort based on performance in oxygen where the project’s Go/No-Go decision point milestone of 100 mA/cm2 at 0.8 V (internal resistance-free, iR-free) at 80°C, pure H2/O2, with 1.5 bar total pressure was met. Subsequently, the principle objectives were to (a) transition the project from H2/O2 to H2/Air with slated target of exceeding 30 mA/cm2 @ 0.8 V, 2.5 bar total pressure and an end of the project target of 1 A/cm2 @ 0.4 V (same total pressure), both under 100% relative humidity. The target for catalyst material scale up was to achieve 100 g batch size at the end of the program. This scale up target had a quality control milestone of less than 5% variation of activity measured with H2/Air (2.5 bar total pressure) at 0.8 V. In addition, the project also aimed at arriving at a unified understanding of the nature of active sites in these catalysts as well as some preliminary understanding of the mechanistic pathway. Also addressed is the development of an integrated method for determination of mass transport parameters using a combination of Helox experiments and modeling of the gas

  18. Iodometric determination of platinum(4) using amperometry

    International Nuclear Information System (INIS)

    Zakharov, V.A.; Gavva, N.F.; Songina, O.A.

    1976-01-01

    The possibility of iodometric determination of platinum (4) by amperometric titration has been investigated. Titration has been conducted at zero potential of platinum reference electrode. Voltampere curves and absorption spectra of the solutions have been recorded to elucidate the nature of platinum (4) interaction with iodide-ion. It has been established that in the case of small excess of iodide complex [PtI 6 ] 2- is formed. When there is a considerable excess of KI, platinum (4) is reduced to Pt(2) with the formation of [PtI 4 ] 2 - and liberation of free iodine. Optimal for iodometric titration of Pt(4) is the use of acetate ot phosphate background solution with pH 6-8 with respect to 1M KI which is attained by adding 3 g of solid KI to 20 ml of the solution being titrated. Under these conditions the limit of platinum detection is 0.5 mkg/ml. Determination of Pt (4) is not hindered by the presence of 200-fold amounts of Cr(6), V(5), and Ni(2) as well as by 20-10-fold amounts of As(5), Sb(5), Se(4), Te(4), Rh(3), and Ir(3), Determination is hindered by the presence of Pd(2), Fe(3), Ir(4), and Cu(2) which, however, can easily be overcome. The possibility has been shown of using the developed technique for analysis of platinum catalysts and alloys

  19. Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

    Science.gov (United States)

    Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

    2016-07-01

    For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

  20. Glycolate adsorption at gold and platinum electrodes: A theoretical and in situ spectroelectrochemical study

    International Nuclear Information System (INIS)

    Delgado, Jose Manuel; Blanco, Raquel; Orts, Jose Manuel; Perez, Juan Manuel; Rodes, Antonio

    2010-01-01

    The adsorption of glycolate anions at sputtered gold thin-film electrodes was studied in perchloric acid solutions by cyclic voltammetry experiments combined with in situ Surface Enhanced Raman Scattering (SERS) and Surface Enhanced Infrared Reflection Absorption Spectroscopy under attenuated total reflection conditions (ATR-SEIRAS). Theoretical harmonic vibrational frequencies and band intensities obtained from B3LYP/LANL2DZ,6-31+G(d) calculations for glycolate species adsorbed on Au clusters with (1 1 1) orientation were used to interpret the experimental spectra. Vibrational data confirm the bidentate bonding of glycolate anions through the oxygen atoms of the carboxylate group, in a bridge configuration with the OCO plane perpendicular to the metal surface. The DFT calculations show no significant effect of the total charge of the metal cluster-adsorbate adduct on the vibrational frequencies of adsorbed glycolate species. The infrared experimental study is extended to platinum films electrochemically deposited onto sputtered gold thin-film electrodes showing the potential-dependent formation of adsorbed CO upon dissociative adsorption of glycolate anions. As in the case of gold, the reversible adsorption of glycolate anions takes place in a bidentate configuration as predicted by DFT calculations for glycolate adsorbed on Pt(1 1 1) clusters. At low glycolic acid concentration, the in situ ATR-SEIRA spectra evidence the formation of adsorbed oxalate as reaction intermediate.

  1. Expression of Drug-Resistant Factor Genes in Hepatocellular Carcinoma Patients Undergoing Chemotherapy with Platinum Complex by Arterial Infusion

    Directory of Open Access Journals (Sweden)

    Shiro Ueda

    2010-09-01

    Full Text Available This study investigated gene expression of drug resistance factors in biopsy tissue samples from hepatocellular carcinoma (HCC patients undergoing chemotherapy by platinum complex. Liver biopsy was performed to collect tissue from the tumor site (T and the non-tumor site (NT prior to the start of treatment. For drug-resistant factors, drug excretion transporters cMOAT and MDR-1, intracellular metal binding protein MT2, DNA repair enzyme ERCC-l and inter-nucleic cell transport protein MVP, were investigated. The comparison of the expression between T and NT indicated a significant decrease of MT2 and MDR-1 in T while a significant increase in ERCC-1 was noted in T. Further, expression was compared between the response cases and non-response cases using the ratios of expression in T to those in NT. The response rate was significantly low in the high expression group when the cutoff value of cMOAT and MT2 was set at 1.5 and 1.0, respectively. Furthermore, when the patients were classified into A group (cMOAT ≧ 1.5 or MT2 ≧ 1.0 and B group (cMOAT < 1.5 and MT2 < 1.0, the response rate of A group was significantly lower than B group when we combined the cutoff values of cMOAT and MT2. It is considered possible to estimate the therapeutic effect of platinum complex at a high probability by combining the expression condition of these two genes.

  2. Fabrication of three-dimensional platinum microstructures with laser irradiation and electrochemical technique

    International Nuclear Information System (INIS)

    Kikuchi, T.; Takahashi, H.; Maruko, T.

    2007-01-01

    Three-dimensional (3D) platinum microstructures were fabricated by successive procedures: aluminum anodizing, laser irradiation, nickel/platinum electroplating, and removal of the aluminum substrate, the oxide films, and the nickel metal layer. Aluminum plates and rods were anodized in an oxalic acid solution to form porous type oxide films. The anodized specimens were immersed in a nickel electroplating solution, and then irradiated with a pulsed Nd-yttrium aluminum garnet (YAG) laser beam to remove the anodic oxide film with a three-dimensional XYZθ stage. The specimens were cathodically polarized in the nickel and a platinum electroplating solution to form the metal micropattern at the laser-irradiated area. The electroplated specimens were immersed in NaOH solution to dissolve the aluminum substrate and the oxide films, and then immersed in HCl solution to dissolve the nickel deposits. A platinum grid-shaped microstructure, a microspring, and a cylindrical network microstructure with 50-100 μm line width were obtained successfully

  3. Fabrication of three-dimensional platinum microstructures with laser irradiation and electrochemical technique

    Energy Technology Data Exchange (ETDEWEB)

    Kikuchi, T. [Graduate School of Engineering, Hokkaido University, N13, W8, Kita-Ku, Sapporo (Japan)]. E-mail: kiku@elechem1-mc.eng.hokudai.ac.jp; Takahashi, H. [Graduate School of Engineering, Hokkaido University, N13, W8, Kita-Ku, Sapporo (Japan); Maruko, T. [Furuya Metal Co. Ltd., R and D Group, Shimodate Daiichi Kogyodanchi 1915, Morisoejima, Chikusei, Ibaraki (Japan)

    2007-02-01

    Three-dimensional (3D) platinum microstructures were fabricated by successive procedures: aluminum anodizing, laser irradiation, nickel/platinum electroplating, and removal of the aluminum substrate, the oxide films, and the nickel metal layer. Aluminum plates and rods were anodized in an oxalic acid solution to form porous type oxide films. The anodized specimens were immersed in a nickel electroplating solution, and then irradiated with a pulsed Nd-yttrium aluminum garnet (YAG) laser beam to remove the anodic oxide film with a three-dimensional XYZ{theta} stage. The specimens were cathodically polarized in the nickel and a platinum electroplating solution to form the metal micropattern at the laser-irradiated area. The electroplated specimens were immersed in NaOH solution to dissolve the aluminum substrate and the oxide films, and then immersed in HCl solution to dissolve the nickel deposits. A platinum grid-shaped microstructure, a microspring, and a cylindrical network microstructure with 50-100 {mu}m line width were obtained successfully.

  4. Platinum clusters with precise numbers of atoms for preparative-scale catalysis.

    Science.gov (United States)

    Imaoka, Takane; Akanuma, Yuki; Haruta, Naoki; Tsuchiya, Shogo; Ishihara, Kentaro; Okayasu, Takeshi; Chun, Wang-Jae; Takahashi, Masaki; Yamamoto, Kimihisa

    2017-09-25

    Subnanometer noble metal clusters have enormous potential, mainly for catalytic applications. Because a difference of only one atom may cause significant changes in their reactivity, a preparation method with atomic-level precision is essential. Although such a precision with enough scalability has been achieved by gas-phase synthesis, large-scale preparation is still at the frontier, hampering practical applications. We now show the atom-precise and fully scalable synthesis of platinum clusters on a milligram scale from tiara-like platinum complexes with various ring numbers (n = 5-13). Low-temperature calcination of the complexes on a carbon support under hydrogen stream affords monodispersed platinum clusters, whose atomicity is equivalent to that of the precursor complex. One of the clusters (Pt 10 ) exhibits high catalytic activity in the hydrogenation of styrene compared to that of the other clusters. This method opens an avenue for the application of these clusters to preparative-scale catalysis.The catalytic activity of a noble metal nanocluster is tied to its atomicity. Here, the authors report an atom-precise, fully scalable synthesis of platinum clusters from molecular ring precursors, and show that a variation of only one atom can dramatically change a cluster's reactivity.

  5. Rationalizing the structural variability of the exocyclic amino groups in nucleobases and their metal complexes: cytosine and adenine.

    Science.gov (United States)

    Fonseca Guerra, Célia; Sanz Miguel, Pablo J; Cebollada, Andrea; Bickelhaupt, F Matthias; Lippert, Bernhard

    2014-07-28

    The exocyclic amino groups of cytosine and adenine nucleobases are normally almost flat, with the N atoms essentially sp(2) hybridized and the lone pair largely delocalized into the heterocyclic rings. However, a change to marked pyramidality of the amino group (N then sp(3) hybridized, lone pair essentially localized at N) occurs during i) involvement of an amino proton in strong hydrogen bonding donor conditions or ii) with monofunctional metal coordination following removal of one of the two protons. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Modelling chemical abundance distributions for dwarf galaxies in the Local Group: the impact of turbulent metal diffusion

    Science.gov (United States)

    Escala, Ivanna; Wetzel, Andrew; Kirby, Evan N.; Hopkins, Philip F.; Ma, Xiangcheng; Wheeler, Coral; Kereš, Dušan; Faucher-Giguère, Claude-André; Quataert, Eliot

    2018-02-01

    We investigate stellar metallicity distribution functions (MDFs), including Fe and α-element abundances, in dwarf galaxies from the Feedback in Realistic Environment (FIRE) project. We examine both isolated dwarf galaxies and those that are satellites of a Milky Way-mass galaxy. In particular, we study the effects of including a sub-grid turbulent model for the diffusion of metals in gas. Simulations that include diffusion have narrower MDFs and abundance ratio distributions, because diffusion drives individual gas and star particles towards the average metallicity. This effect provides significantly better agreement with observed abundance distributions in dwarf galaxies in the Local Group, including small intrinsic scatter in [α/Fe] versus [Fe/H] of ≲0.1 dex. This small intrinsic scatter arises in our simulations because the interstellar medium in dwarf galaxies is well mixed at nearly all cosmic times, such that stars that form at a given time have similar abundances to ≲0.1 dex. Thus, most of the scatter in abundances at z = 0 arises from redshift evolution and not from instantaneous scatter in the ISM. We find similar MDF widths and intrinsic scatter for satellite and isolated dwarf galaxies, which suggests that environmental effects play a minor role compared with internal chemical evolution in our simulations. Overall, with the inclusion of metal diffusion, our simulations reproduce abundance distribution widths of observed low-mass galaxies, enabling detailed studies of chemical evolution in galaxy formation.

  7. Palladium, platinum, and rhodium contents of rocks near the lower margin of the Stillwater complex, Montana.

    Science.gov (United States)

    Zientek, M.L.; Foose, M.P.; Leung, Mei

    1986-01-01

    Statistical summaries are reported for Pd, Pt and Rh contents of rocks from the lower part of the Stillwater complex, the underlying contact-metamorphosed sediments, and post-metamorphic dykes and sills wholly within the hornfelses. Variability of the data among the rock types is attributed largely to differences in sulphide content. Non-correlation of sulphur with platinum-group assays of many rock types leads to the suggestion that the immiscible sulphide and silicate liquids did not completely equilibrate with respect to platinum-group elements. -G.J.N.

  8. Platinum nanoparticles: a non-toxic, effective and thermally stable alternative plasmonic material for cancer therapy and bioengineering.

    Science.gov (United States)

    Samadi, Akbar; Klingberg, Henrik; Jauffred, Liselotte; Kjær, Andreas; Bendix, Poul Martin; Oddershede, Lene B

    2018-05-17

    Absorption of near infrared (NIR) light by metallic nanoparticles can cause extreme heating and is of interest for instance in cancer treatment since NIR light has a relatively large penetration depth into biological tissue. Here, we quantify the extraordinary thermoplasmonic properties of platinum nanoparticles and demonstrate their efficiency in photothermal cancer therapy. Although platinum nanoparticles are extensively used for catalysis, they are much overlooked in a biological context. Via direct measurements based on a biological matrix we show that individual irradiated platinum nanoparticles with diameters of 50-70 nm can easily reach surface temperatures up to 900 K. In contrast to gold nanoshells, which are often used for photothermal purposes, we demonstrate that the platinum particles remain stable at these extreme temperatures. The experiments are paralleled by finite element modeling confirming the experimental results and establishing a theoretical understanding of the particles' thermoplasmonic properties. At extreme temperatures it is likely that a vapor layer will form around the plasmonic particle, and we show this scenario to be consistent with direct measurements and simulations. Viability studies demonstrate that platinum nanoparticles themselves are non-toxic at therapeutically relevant concentrations, however, upon laser irradiation we show that they efficiently kill human cancer cells. Therefore, platinum nanoparticles are highly promising candidates for thermoplasmonic applications in the life sciences, in nano-medicine, and for bio-medical engineering.

  9. Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms.

    Science.gov (United States)

    Yu, Haoyu; Truhlar, Donald G

    2015-07-14

    Although many transition metal complexes are known to have high multireference character, the multireference character of main-group closed-shell singlet diatomic molecules like BeF, CaO, and MgO has been less studied. However, many group-1 and group-2 diatomic molecules do have multireference character, and they provide informative systems for studying multireference character because they are simpler than transition metal compounds. The goal of the present work is to understand these multireference systems better so that, ultimately, we can apply what we learn to more complicated multireference systems and to the design of new exchange-correlation functionals for treating multireference systems more adequately. Fourteen main-group diatomic molecules and one triatomic molecule (including radicals, cations, and anions, as well as neutral closed-shell species) have been studied for this article. Eight of these molecules contain a group-1 element, and six contain a group-2 element. Seven of these molecules are multireference systems, and eight of them are single-reference systems. Fifty-three exchange-correlation functionals of 11 types [local spin-density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)] and the Hartree-Fock method have been applied to calculate the bond distance, bond dissociation energy (BDE), and dipole moment of these molecules. All of the calculations are converged to a stable solution by allowing the symmetry of the Slater determinant to be broken. A reliable functional should not only predict an accurate BDE but also predict accurate components of the BDE, so each bond dissociation energy has been decomposed into ionization potential (IP) of the electropositive

  10. Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

    Science.gov (United States)

    Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani; Manivannan, Venkatesan

    2004-07-13

    Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

  11. Transition-metal-doped group-IV monochalcogenides: a combination of two-dimensional triferroics and diluted magnetic semiconductors

    Science.gov (United States)

    Yang, Liu; Wu, Menghao; Yao, Kailun

    2018-05-01

    We report the first-principles evidence of a series of two-dimensional triferroics (ferromagnetic + ferroelectric + ferroelastic), which can be obtained by doping transition-metal ions in group-IV monochalcogenide (SnS, SnSe, GeS, GeSe) monolayers, noting that a ferromagnetic Fe-doped SnS2 monolayer has recently been realized (Li B et al 2017 Nat. Commun. 8 1958). The ferroelectricity, ferroelasticity and ferromagnetism can be coupled and the magnetization direction may be switched upon ferroelectric/ferroelastic switching, rendering electrical writing + magnetic reading possible. They can be also two-dimensional half-metals or diluted magnetic semiconductors, where p/n channels or even multiferroic tunneling junctions can be designed by variation in doping and incorporated into a monolayer wafer.

  12. Sulfur tolerant zeolite supported platinum catalysts for aromatics hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Bergem, Haakon

    1997-12-31

    The increased demand for transportation fuels at the expence of heavier fuel oil has forced the refinery industry to expand their conversion capacity with hydrotreating as one of the key processes. A shift towards more diesel powered vehicles along with tightening fuel regulations demanding cleaner fuels has lead to increasing interest in catalytic processes for the manufacturing of such environmentally acceptable fuels. This provides the motivation for this thesis. Its main objective was to study possible catalysts active for desulfurization, hydrogenation, and ring-opening of aromatics all in the presence of sulfur. A close examination of the physical properties and kinetical behaviour of the chosen catalysts has been performed. A high pressure reactor setup was designed and built for activity measurements. Zeolite supported platinum catalysts were prepared and both the metal and acid functions were characterized utilizing various experimental techniques. Hydrogenation of toluene was used as a model reaction and the effect of sulfur adsorption on the activity and kinetic behaviour of the catalysts was investigated. The catalyst samples showed hydrogenation activities comparable to a commercial Pt/Al2O3 catalyst. There were no clear differences in the effect of the various sulfur compounds studied. Platinum supported on zeolite Y gave considerably more sulfur tolerant catalysts compared to Al2O3 as support. 155 refs., 58 figs., 36 tabs.

  13. Formic Acid Electrooxidation by a Platinum Nanotubule Array Electrode

    Directory of Open Access Journals (Sweden)

    Eric Broaddus

    2013-01-01

    Full Text Available One-dimensional metallic nanostructures such as nanowires, rods, and tubes have drawn much attention for electrocatalytic applications due to potential advantages that include fewer diffusion impeding interfaces with polymeric binders, more facile pathways for electron transfer, and more effective exposure of active surface sites. 1D nanostructured electrodes have been fabricated using a variety of methods, typically showing improved current response which has been attributed to improved CO tolerance, enhanced surface activity, and/or improved transport characteristics. A template wetting approach was used to fabricate an array of platinum nanotubules which were examined electrochemically with regard to the electrooxidation of formic acid. Arrays of 100 and 200 nm nanotubules were compared to a traditional platinum black catalyst, all of which were found to have similar surface areas. Peak formic acid oxidation current was observed to be highest for the 100 nm nanotubule array, followed by the 200 nm array and the Pt black; however, CO tolerance of all electrodes was similar, as were the onset potentials of the oxidation and reduction peaks. The higher current response was attributed to enhanced mass transfer in the nanotubule electrodes, likely due to a combination of both the more open nanostructure as well as the lack of a polymeric binder in the catalyst layer.

  14. The Oldest Stars of the Extremely Metal-Poor Local Group Dwarf Irregular Galaxy Leo A

    Science.gov (United States)

    Schulte-Ladbeck, Regina E.; Hopp, Ulrich; Drozdovsky, Igor O.; Greggio, Laura; Crone, Mary M.

    2002-08-01

    We present deep Hubble Space Telescope (HST) single-star photometry of Leo A in B, V, and I. Our new field of view is offset from the centrally located field observed by Tolstoy et al. in order to expose the halo population of this galaxy. We report the detection of metal-poor red horizontal branch stars, which demonstrate that Leo A is not a young galaxy. In fact, Leo A is as least as old as metal-poor Galactic Globular Clusters that exhibit red horizontal branches and are considered to have a minimum age of about 9 Gyr. We discuss the distance to Leo A and perform an extensive comparison of the data with stellar isochrones. For a distance modulus of 24.5, the data are better than 50% complete down to absolute magnitudes of 2 or more. We can easily identify stars with metallicities between 0.0001 and 0.0004, and ages between about 5 and 10 Gyr, in their post-main-sequence phases, but we lack the detection of main-sequence turnoffs that would provide unambiguous proof of ancient (>10 Gyr) stellar generations. Blue horizontal branch stars are above the detection limits but difficult to distinguish from young stars with similar colors and magnitudes. Synthetic color-magnitude diagrams show it is possible to populate the blue horizontal branch in the halo of Leo A. The models also suggest ~50% of the total astrated mass in our pointing to be attributed to an ancient (>10 Gyr) stellar population. We conclude that Leo A started to form stars at least about 9 Gyr ago. Leo A exhibits an extremely low oxygen abundance, only 3% of solar, in its ionized interstellar medium. The existence of old stars in this very oxygen-deficient galaxy illustrates that a low oxygen abundance does not preclude a history of early star formation. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained from the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., under NASA contract NAS 5-26555.

  15. Platinum uptake from chloride solutions using biosorbents

    Directory of Open Access Journals (Sweden)

    Mehmet Hakan Morcali

    2013-04-01

    Full Text Available Present work investigates platinum uptake from synthetically prepared, dilute platinum-bearing solutions using biomass residues, i.e. pistachio nut shell and rice husk, which are abundant in Turkey, and provides a comparison between these two biosorbents. Effects of the different uptake parameters, sorbent dosage, contact time, temperature and pH of solution on platinum uptake (% were studied in detail on a batch sorption. Before the pistachio nut shell was activated, platinum uptake (% was poor compared to the rice husk. However, after the pistachio nut shell was activated at 1000 °C under an argon atmosphere, the platinum uptake (% increased two-fold. The pistachio nut shell (original and activated and rice husk were shown to be better than commercially available activated carbon in terms of adsorption capacity. These two sorbents have also been characterized by FTIR and SEM. Adsorption equilibrium data best complied with the Langmuir isotherm model. Maximum adsorption capacities, Qmax, at 25 °C were found to be 38.31 and 42.02 mg.g- 1for the activated pistachio nut shell and rice husk, respectively. Thermodynamic calculations using the measured ∆H°, ∆S° and ∆G° values indicate that the uptake process was spontaneous and endothermic. The experimental data were shown to be fit the pseudo-second-order kinetic model.

  16. Performance of Platinum Nanoparticles / Multiwalled Carbon Nanotubes / Bacterial Cellulose Composite as Anode Catalyst for Proton Exchange Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Henry Fonda Aritonang

    2017-05-01

    Full Text Available Highly dispersed platinum (Pt nanoparticles / multiwalled carbon nanotubes (MWCNTs on bacterial cellulose (BC as anode catalysts for proton exchange membrane fuel cells (PEMFC were prepared with various precursors and their electro-catalytic activities towards hydrogen oxidation at 70 oC under non-humidified conditions. The composite was prepared by deposition of Pt nanoparticles and MWCNTs on BC gel by impregnation method using a water solution of metal precursors and MWCNTs followed by reducing reaction using a hydrogen gas. The composite was characterized by using TEM (transmission electron microscopy, EDS (energy dispersive spectroscopy, and XRD (X-ray diffractometry techniques. TEM images and XRD patterns both lead to the observation of spherical metallic Pt nanoparticles with mean diameter of 3-11 nm well impregnated into the BC fibrils. Preliminary tests on a single cell indicate that renewable BC is a good prospect to be explored as a membrane in fuel cell field. Copyright © 2017 BCREC Group. All rights reserved Received: 21st November 2016; Revised: 26th February 2017; Accepted: 27th February 2017 How to Cite: Aritonang, H.F., Kamu, V.S., Ciptati, C., Onggo, D., Radiman, C.L. (2017. Performance of Platinum Nanoparticles / Multiwalled Carbon Nanotubes / Bacterial Cellulose Composite as Anode Catalyst for Proton Exchange Membrane Fuel Cells. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (2: 287-292 (doi:10.9767/bcrec.12.2.803.287-292 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.2.803.287-292

  17. Phosphorescent Organic Light Emitting Diodes Implementing Platinum Complexes

    Science.gov (United States)

    Ecton, Jeremy Exton

    Organic light emitting diodes (OLEDs) are a promising approach for display and solid state lighting applications. However, further work is needed in establishing the availability of efficient and stable materials for OLEDs with high external quantum efficiency's (EQE) and high operational lifetimes. Recently, significant improvements in the internal quantum efficiency or ratio of generated photons to injected electrons have been achieved with the advent of phosphorescent complexes with the ability to harvest both singlet and triplet excitons. Since then, a variety of phosphorescent complexes containing heavy metal centers including Os, Ni, Ir, Pd, and Pt have been developed. Thus far, the majority of the work in the field has focused on iridium based complexes. Platinum based complexes, however, have received considerably less attention despite demonstrating efficiency's equal to or better than their iridium analogs. In this study, a series of OLEDs implementing newly developed platinum based complexes were demonstrated with efficiency's or operational lifetimes equal to or better than their iridium analogs for select cases. In addition to demonstrating excellent device performance in OLEDs, platinum based complexes exhibit unique photophysical properties including the ability to form excimer emission capable of generating broad white light emission from a single emitter and the ability to form narrow band emission from a rigid, tetradentate molecular structure for select cases. These unique photophysical properties were exploited and their optical and electrical properties in a device setting were elucidated. Utilizing the unique properties of a tridentate Pt complex, Pt-16, a highly efficient white device employing a single emissive layer exhibited a peak EQE of over 20% and high color quality with a CRI of 80 and color coordinates CIE(x=0.33, y=0.33). Furthermore, by employing a rigid, tetradentate platinum complex, PtN1N, with a narrow band emission into a

  18. Novel platinum black electroplating technique improving mechanical stability.

    Science.gov (United States)

    Kim, Raeyoung; Nam, Yoonkey

    2013-01-01

    Platinum black microelectrodes are widely used as an effective neural signal recording sensor. The simple fabrication process, high quality signal recording and proper biocompatibility are the main advantages of platinum black microelectrodes. When microelectrodes are exposed to actual biological system, various physical stimuli are applied. However, the porous structure of platinum black is vulnerable to external stimuli and destroyed easily. The impedance level of the microelectrode increases when the microelectrodes are damaged resulting in decreased recording performance. In this study, we developed mechanically stable platinum black microelectrodes by adding polydopamine. The polydopamine layer was added between the platinum black structures by electrodeposition method. The initial impedance level of platinum black only microelectrodes and polydopamine added microelectrodes were similar but after applying ultrasonication the impedance value dramatically increased for platinum black only microelectrodes, whereas polydopamine added microelectrodes showed little increase which were nearly retained initial values. Polydopamine added platinum black microelectrodes are expected to extend the availability as neural sensors.

  19. NanoSIMS multi-element imaging reveals internalisation and nucleolar targeting for a highly-charged polynuclear platinum compound.

    Science.gov (United States)

    Wedlock, Louise E; Kilburn, Matt R; Liu, Rong; Shaw, Jeremy A; Berners-Price, Susan J; Farrell, Nicholas P

    2013-08-11

    Simultaneous multi-element imaging using NanoSIMS (nano-scale secondary ion mass spectrometry), exploiting the novel combination of (195)Pt and (15)N in platinum-am(m)ine antitumour drugs, provides information on the internalisation and subcellular localisation of both metal and ligands, and allows identification of ligand exchange.

  20. The Neoproterozoic Lavalleja group in Uruguay: geology and base metal deposits

    International Nuclear Information System (INIS)

    Sánchez-Bettucci, L.; Preciozzi, F.; Ramos, V.; Basei, M.

    2003-01-01

    The Lavalleja Group, which is exposed along the Dom Feliciano Belt is located in the southeast of Uruguay and is represented by metavolcano-sedimentary rocks. It is developed during late Proterozoic-Early Paleozoic Brasiliano orogeny. Based on geochemical signature of the rocks of the Lavalleja Group, mainly metagabbros, basic and acidic metavolcanic rocks, a back-arc basin tectonic setting is suggested by Sánchez-Bettucci et al. (2001). The metamorphic grade increases to the southeast, ranging from lower greenschist facies to lower amphibolite facies in the Fuente del Puma and Zanja del Tigre Formations (Sánchez-Bettucci et al., 2001). The non-metamorphic to anchimetamorphic Minas Formation of Sánchez-Bettucci et al. (2001) is a junior synonim of the Arroyo del Soldado Group, previously defined by Gaucher et al. (1996). The metamorphic mineral assemblages correspond to a low-pressure regional metamorphism associated with a high thermal gradient (Sánchez-Bettucci et al., 2001).A compressive deformational event, that probably corresponds to the basin closure of the Lavalleja Group during a continental collision was recognized. The petrology, geochemistry, metamorphism grade, and tectonic setting are consistent with a back-arc basin for the Lavalleja Group (Sánchez-Bettucci et al., 2001)

  1. Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grass, Michael Edward [Univ. of California, Berkeley, CA (United States)

    2008-09-01

    Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.

  2. Nano carbon supported platinum catalyst interaction behavior with perfluorosulfonic acid ionomer and their interface structures

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma

    2016-01-01

    behavior of Nafion ionomer on platinized carbon nano fibers (CNFs), carbon nano tubes (CNTs) and amorphous carbon (Vulcan). The interaction is affected by the catalyst surface oxygen groups as well as porosity. Comparisons between the carbon supports and platinized equivalents are carried out. It reveals......The interaction between perfluorosulfonic acid ionomer and supported platinum catalyst is essential. It directly influences platinum accessibility, stability of carbon support and platinum, proton conductivity and electron conductivity in an electrode. In this study, we compare the adsorption...... that the platinization step modifies the surface nature of the carbon supports in terms of specific surface area, crystallinity and especially porosity; therefore, ionomer adsorption over carbon is not always representative for the ionomer adsorption over carbon supported catalyst, though indicative. Moreover...

  3. Arresting mantle formation and redirecting embryonic shell gland tissue by platinum2+ leads to body plan modifications in Marisa cornuarietis (Gastropoda, Ampullariidae).

    Science.gov (United States)

    Marschner, Leonie; Triebskorn, Rita; Köhler, Heinz-R

    2012-08-01

    To evaluate the threat that anthropogenic substances pose to animals when they are emitted into the environment, tests like the invertebrate embryo toxicity test with the ramshorn snail Marisa cornuarietis have been developed. These tests are used to investigate substances like the heavy metal platinum (Pt) that is used in catalytic converters and is gradually released in car exhausts. In 2010, our group reported that high Pt concentrations cause body plan alterations in snails and prevent the formation of an external shell during M. cornuarietis embryogenesis. Now, this study presents scanning-electron micrographs and histological sections of platinum(2+) (Pt(2+))-treated and untreated M. cornuarietis embryos and compares "normally" developing and "shell-less" embryos during embryogenesis, to reveal the exact course of events that lead to this body plan shift. Both groups showed similar development until the onset of torsion 70- to 82-h postfertilization. In the Pt(2+)-exposed embryos, the rudimentary shell gland (=anlage of both shell gland and mantle, which usually evaginates, grows, and eventually covers the visceral sac) does not spread across the visceral sac but remains on its ventral side. Without the excessive growth of the shell gland, a horizontal rotation of the visceral sac relative to head and foot does not occur, as being normal during the process of torsion. Copyright © 2012 Wiley Periodicals, Inc.

  4. Metal oxide, Group V-VI chalcogenides and GaN/AlGaN photodetectors

    Science.gov (United States)

    Hasan, Md. Rezaul

    In this work, a simple, low-cost and catalyst free one-step solution processing of onedimensional Sb2S3 nanostructures on polyimide substrates was done. This structure demonstrated its potential application as a photoconductor in the UV and visible regime. Using-field emission scanning electron microscopy (SEM), grazing incidence X-Ray diffraction, Raman spectra and transmission electron microscopy measurements, it was shown that the Sb 2S3 films have high crystallinity, uniform morphology and nearstoichiometric composition. Further, using tauc plot, it was found that the films have a direct bandgap of 1.67 eV. MSM photodetectors, fabricated using these films showed a clear photo response in both UV as well as visible wavelength. These devices showed UV on/off ratio as high as 160 under the light intensity of 30 mW/cm2 and a small rise time and fall time of 44 ms 28 ms respectively. The effect of geometry of metal pad and bonding wire orientation of a multi-channel FET on the coupling of THz radiation was studied. The spatial variation images were taken by raster scan with the resolution of 0.07 mm steps in both x and y directions. An effective gate bias, where the effect of noise is minimum and photoresponse is maximum, was used for imaging. By applying VGS =-2.8V and VDS =380mV, the images were taken for all different combinations of activated bonding wires and metal pads. It was observed that, effect of bonding wire orientation is negligible for the large source pad as the radiation is coupled basically between drain and gate pad. Effect of drain bonding wire on coupling depends on the maximum width or diameter of metal pad and the incoming wavelength. In this work, Position of activated Drain pad and orientation of respective bonding wire defined the image tilting angle. Voltage drop across the shorting metal between drain pads, also played a role in increasing the asymmetry by selectively exciting a certain portion of FET Channels more than the other portion

  5. Fabrication of isolated platinum nanowire gratings and nanoparticles on silica substrate by femtosecond laser irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Nakajima, Yasutaka [School of Integrated Design Engineering, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223- 8522 (Japan); Nedyalkov, Nikolay [Institute of Electronics, Bulgarian Academy of Sciences, Tzarigradsko shouse 72, Sofia 1784 (Bulgaria); Department of Electronics and Electrical Engineering, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama, 223-8522 (Japan); Takami, Akihiro [School of Integrated Design Engineering, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223- 8522 (Japan); Terakawa, Mitsuhiro, E-mail: terakawa@elec.keio.ac.jp [School of Integrated Design Engineering, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223- 8522 (Japan); Department of Electronics and Electrical Engineering, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama, 223-8522 (Japan)

    2017-02-01

    Highlights: • Formation of HSFL with periodicities shorter than 100 nm. • Structural evolution from platinum nanowire gratings to platinum nanoparticles only by increasing the number of pulses. • Melting and fragmentation of the nanowire gratings would play a key role in structural evolution. - Abstract: We demonstrate the fabrication of isolated platinum nanostructures on a silica substrate by using femtosecond laser. Nanowire gratings which have short periodicities of approximately 50 nm were formed by irradiating a platinum thin film deposited on a fused silica substrate with 800-nm wavelength femtosecond laser pulses. The structural evolution from the nanowire gratings to nanoparticles was observed only by increasing the number of pulses. The periodicities or diameters of the structures showed good uniformity. Scanning electron microscopy of the surfaces and theoretical calculation of temperature profile using a two-temperature model revealed that the structural evolution can be attributed to the fragmentation of the formed nanowires. The presented method provides a simple and high-throughput technique for fabricating both metal nanowire gratings and nanoparticles, which have the potential to be used for the fabrication of optical, electrical and biomedical devices.

  6. Tin-Platinum catalysts interactions on titania and silica

    Energy Technology Data Exchange (ETDEWEB)

    Nava, N. [Instituto Mexicano del Petroleo Lazaro Cardenas 152, 07730 Mexico, D.F. (Mexico)], E-mail: tnava@imp.mx; Del Angel, P. [Instituto Mexicano del Petroleo Lazaro Cardenas 152, 07730 Mexico, D.F. (Mexico); Salmones, J. [Instituto Politecnico Nacional-ESIQIE UPALM, 07738 Mexico, D.F. (Mexico); Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Fisicas, Rua Dr. Xavier Sigaud 150, 22290-180 Rio de Janeiro, Brasil (Brazil); Santiago, P. [Instituto de Fisica, UNAM, Mexico, D. F., 04510 Mexico (Mexico)

    2007-09-30

    Pt-Sn was supported on titania and silica, and the resulting interactions between the components in prepared samples and the resulting interactions between the components before and after treatment with hydrogen were characterized by Moessbauer spectroscopy, X-ray diffraction, Rietveld refinement, high-resolution transmission electron microscopy (HRTEM) and catalytic tests data. Results show the presence of Pt and SnO{sub 2} after calcinations, and Pt{sub 3}Sn, PtSn and PtSn{sub 3} after reduction. Rietveld analysis shows that some Ti{sup 4+} are replaced by Sn{sup 4+} atoms in the titania structure. Finally, HRTEM and the practically absence of activity observed confirms that metallic platinum is encapsulated.

  7. Determining the selectivity of divalent metal cations for the carboxyl group of alginate hydrogel beads during competitive sorption.

    Science.gov (United States)

    An, Byungryul; Lee, Healim; Lee, Soonjae; Lee, Sang-Hyup; Choi, Jae-Woo

    2015-11-15

    To investigate the competitive sorption of divalent metal ions such as Ca(2+), Cu(2+), Ni(2+), and Pb(2+) on alginate hydrogel beads, batch and column tests were conducted. The concentration of carboxyl group was found to be limited in the preparation of spherical hydrogel beads. From kinetic test results, 80% of sorption was observed within 4h, and equilibrium was attained in 48 h. According to the comparison of the total uptake and release, divalent metal ions were found to stoichiometrically interact with the carboxyl group in the alginate polymer chain. From the Langmuir equation, the maximum capacities of Pb(2+), Cu(2+), and Ni(2+) were calculated to be 1.1, 0.48, and 0.13 mmol/g, respectively. The separation factor (α) values for αPb/Cu, αPb/Ni, and αCu/Ni were 14.0, 98.9, and 7.1, respectively. The sorption capacity of Pb(2+) was not affected by the solution pH; however, the sorption capacities of Cu(2+) and Ni(2+) decreased with increasing solution pH, caused by competition with hydrogen. According to the result from the fixed column test, Pb(2+) exhibited the highest affinity, followed by Cu(2+) and Ni(2+), which is in exact agreement with those of kinetic and isotherm tests. The sorbent could be regenerated using 4% HCl, and the regenerated sorbent exhibited 90% capacity upto 9 cycles. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. The stability boundary of group-III transition metal diboride ScB 2 (0 0 0 1) surfaces

    Science.gov (United States)

    Zhao, Hui; Qin, Na

    2012-01-01

    Experimental observations and theoretical investigations exhibit that a group-IV(V) transition metal diboride (0 0 0 1) surface is terminated with a 1 × 1 TM(B) layer. As to a group-III transition metal diboride, we have investigated the stability boundary of ScB2 (0 0 0 1) surfaces using first principles total energy plane-wave pseudopotential method based on density functional theory. The Mulliken charge population analysis shows that Sc atoms in the second layer cannot provide B atoms in the first layer with sufficient electrons to form a complete graphene-like boron layer. We also found that the charge transfer between the first and the second layer for the B-terminated surface is more than that for Sc-terminated surface. It elucidates the reason that the outermost interlayer spacing contract more strongly in the B-terminated surface than in the Sc-terminated surface. The surface energies of both terminated ScB2 (0 0 0 1) surfaces as a function of the chemical potential of B are also calculated to check the relative stability of the two surface structures.

  9. Engineering Platinum Alloy Electrocatalysts in Nanoscale for PEMFC Application

    Energy Technology Data Exchange (ETDEWEB)

    He, Ting [Idaho National Laboratory

    2016-03-01

    Fuel cells are expected to be a key next-generation energy source used for vehicles and homes, offering high energy conversion efficiency and minimal pollutant emissions. However, due to large overpotentials on anode and cathode, the efficiency is still much lower than theoretically predicted. During the past decades, considerable efforts have been made to investigate synergy effect of platinum alloyed with base metals. But, engineering the alloy particles in nanoscale has been a challenge. Most important challenges in developing nanostructured materials are the abilities to control size, monodispersity, microcomposition, and even morphology or self-assembly capability, so called Nanomaterials-by-Design, which requires interdisciplinary collaborations among computational modeling, chemical synthesis, nanoscale characterization as well as manufacturing processing. Electrocatalysts, particularly fuel cell catalysts, are dramatically different from heterogeneous catalysts because the surface area in micropores cannot be electrochemically controlled on the same time scale as more transport accessible surfaces. Therefore, electrocatalytic architectures need minimal microporous surface area while maximizing surfaces accessible through mesopores or macropores, and to "pin" the most active, highest performance physicochemical state of the materials even when exposed to thermodynamic forces, which would otherwise drive restructuring, crystallization, or densification of the nanoscale materials. In this presentation, results of engineering nanoscale platinum alloy particles down to 2 ~ 4 nm will be discussed. Based on nature of alloyed base metals, various synthesis technologies have been studied and developed to achieve capabilities of controlling particle size and particle microcomposition, namely, core-shell synthesis, microemulsion technique, thermal decomposition process, surface organometallic chemical method, etc. The results show that by careful engineering the

  10. The attachment of metal-chelating groups to proteins: tagging of albumin by diazonium coupling and use of the products as radiopharmaceuticals

    International Nuclear Information System (INIS)

    Leung, C.S.H.; Meares, C.F.; Goodwin, D.A.

    1978-01-01

    The ability to attach firmly chelated metal ions or powerful chelating agents to sites on biological molecules can enhance the utility of a number of physical techniques now used in the study of biological systems. A 'bifunctional' chelating agent, containing both an EDTA group and a diazonium group, has been prepared and coupled to human serum albumin. The extent of labeling under various conditions and the amino-acid sidechains labeled have been investigated. The reaction of protein-bound chelating groups with added metal ions has been studied, with the finding that only about 40-50% of these groups are available to bind metal ions. Proteolysis of the products leads to recovery of full metal-binding capacity. Properties of the products in vivo are discussed. (author)

  11. Determination of trace level of palladium and platinum content in anticancer drug Imatinib base by ICP-MS

    International Nuclear Information System (INIS)

    Yadav, Ravi; Salunke-Gawali, Sunita

    2013-01-01

    Metal impurities in Pharmaceutical drug substance is of great concern not only because of the intrinsic toxicity of certain contaminants but also due to the opposite effect that the contaminants which may have on drug stability and shelf life. Therefore it is necessary to monitor the organic as well as inorganic impurities throughout the process of manufacturing process at every stage from raw material, intermediate and finished products. An Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) method has been developed for Palladium and Platinum content in the anticancer drug, Imatinib mesylate. Rhodium (Rh) was used as internal standard for determination of Palladium and Platinum content on in Imatinib mesylate. (author)

  12. De-alloyed platinum nanoparticles

    Science.gov (United States)

    Strasser, Peter [Houston, TX; Koh, Shirlaine [Houston, TX; Mani, Prasanna [Houston, TX; Ratndeep, Srivastava [Houston, TX

    2011-08-09

    A method of producing de-alloyed nanoparticles. In an embodiment, the method comprises admixing metal precursors, freeze-drying, annealing, and de-alloying the nanoparticles in situ. Further, in an embodiment de-alloyed nanoparticle formed by the method, wherein the nanoparticle further comprises a core-shell arrangement. The nanoparticle is suitable for electrocatalytic processes and devices.

  13. Outpatient desensitization in selected patients with platinum hypersensitivity reactions.

    Science.gov (United States)

    O'Malley, David M; Vetter, Monica Hagan; Cohn, David E; Khan, Ambar; Hays, John L

    2017-06-01

    Platinum-based chemotherapies are a standard treatment for both initial and recurrent gynecologic cancers. Given this widespread use, it is important to be aware of the features of platinum hypersensitivity reactions and the subsequent treatment of these reactions. There is also increasing interest in the development of desensitization protocols to allow patients with a history of platinum hypersensitivity to receive further platinum based therapy. In this review, we describe the management of platinum hypersensitivity reactions and the desensitization protocols utilized at our institution. We also describe the clinical categorizations utilized to triage patients to appropriate desensitization protocols. Copyright © 2017 Elsevier Inc. All rights reserved.

  14. Influence of group II metals on Radium-226 concentration ratios in the native green plum (Buchanania obovata) from the Alligator Rivers Region, Northern Territory, Australia

    International Nuclear Information System (INIS)

    Medley, Peter; Bollhöfer, Andreas

    2016-01-01

    In this study, uptake of Ra from soil, and the influence of group II metals on Ra uptake, into the stones and edible flesh of the fruit of the wild green plum, Buchanania obovata, was investigated. Selective extraction of the exchangeable fraction of the soil samples was undertaken but was not shown to more reliably predict Ra uptake than total soil Ra activity concentration. Comparison of the group II metal to Ca ratios (i.e. Sr/Ca, Ba/Ca, Ra/Ca) in the flesh with exchangeable Ca shows that Ca outcompetes group II metals for root uptake and that the uptake pathway discriminated against group II metals relative to ionic radius, with uptake of Ca > Sr > Ba >> Ra. Flesh and stone analysis showed that movement of group II metals to these components of the plant, after root uptake, was strongly related. This supports the hypothesis that Sr, Ba and Ra are being taken up as analogue elements, and follow the same uptake and translocation pathways, with Ca. Comparison with previously reported data from a native passion fruit supports the use of total soil CRs on natural, undisturbed sites. As exchangeable CRs for Ra reach a saturation value it may be possible to make more precise predictions using selective extraction techniques for contaminated or disturbed sites. - Highlights: • We studied uptake of Ra-226 from soil into Buchanania obovata. • The influence of group II metals (Sr, Ba and Ca) on Ra uptake was investigated. • The exchangeable Ra fraction of the soil was not a more reliable predictor of Ra uptake than total soil Ra. • Ca outcompetes group II metals Sr, Ba and Ra for root uptake. • Uptake discriminated against group II metals relative to ionic radius, with uptake of Ca > Sr > Ba >> Ra.

  15. On the enzymatic formation of platinum nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Govender, Y.; Riddin, T. L. [Rhodes University, Department of Biochemistry, Microbiology and Biotechnology (South Africa); Gericke, M. [MINTEK (South Africa); Whiteley, C. G., E-mail: C.Whiteley@ru.ac.z [Rhodes University, Department of Biochemistry, Microbiology and Biotechnology (South Africa)

    2010-01-15

    A dimeric hydrogenase enzyme (44.5 and 39.4 kDa sub units) was isolated in a 39.5% yield from the fungus Fusarium oxysporum and purified 4.64-fold by ion exchange chromatography on Sephacryl S-200. Characterisation of the enzyme afforded pH and temperature optima of 7.5 and 38 {sup o}C, respectively, a half-life stability of 36 min and a V{sub max} and K{sub m} of 3.57 nmol min{sup -1} mL{sup -1} and 2.25 mM, respectively. This enzyme was inhibited (non-competitively) by hydrogen hexachloroplatinic acid (H{sub 2}PtCl{sub 6}) at 1 or 2 mM with a K{sub i} value of 118 {mu}M. Incubation of the platinum salt with the pure enzyme under an atmosphere of hydrogen and optimum enzyme conditions (pH 7.5, 38 {sup o}C) afforded <10% bioreduction after 8 h while at conditions suitable for platinum nanoparticle formation (pH 9, 65 {sup o}C) over 90% reduction took place after the same length of time. Cell-free extract from the fungal isolates produced nearly 90% bioreduction of the platinum salt under both pH and temperature conditions. The bioreduction of the platinum salt by a hydrogenase enzyme takes place by a passive process and not an active one as previously understood.

  16. Rockburst damage mechanism at Impala Platinum Mine

    CSIR Research Space (South Africa)

    Ledwaba, LS

    2012-05-01

    Full Text Available Impala Platinum Mine (Impala), situated north of the town of Rustenburg in the North West Province of South Africa, has experienced an increase in seismicity from ~841 seismic events in the year 2005 to ~1588 seismic events in 2008...

  17. Conducting metal oxide and metal nitride nanoparticles

    Science.gov (United States)

    DiSalvo, Jr., Francis J.; Subban, Chinmayee V.

    2017-12-26

    Conducting metal oxide and nitride nanoparticles that can be used in fuel cell applications. The metal oxide nanoparticles are comprised of for example, titanium, niobium, tantalum, tungsten and combinations thereof. The metal nitride nanoparticles are comprised of, for example, titanium, niobium, tantalum, tungsten, zirconium, and combinations thereof. The nanoparticles can be sintered to provide conducting porous agglomerates of the nanoparticles which can be used as a catalyst support in fuel cell applications. Further, platinum nanoparticles, for example, can be deposited on the agglomerates to provide a material that can be used as both an anode and a cathode catalyst support in a fuel cell.

  18. Search for and identification of gaseous noble metal emissions from catalytic converters. Quantitative and statistic screening of platinum metal aerosols emitted by automotive catalytic converters; Suche und Identifizierung von gasfoermigen katalysatorbuertigen Edelmetallemissionen (VPT 06). Quantitative und statistische Reihenuntersuchungen ueber emittierte Platinmetallaerosole aus Automobilkatalysatoren (VPT 08)

    Energy Technology Data Exchange (ETDEWEB)

    Artelt, S [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung, Hannover (Germany)

    1998-12-31

    The aim of these two projects was to determine whether platinum is contained in catalysed automobile exhaust fumes and in what quantities it is emitted. A further task was to determine the particle size and particle size distribution of emitted particles. For this purpose an engine test stand was set up at the Fraunhofer Institute for Toxicology and Aerosol Research and two different sampling techniques were developed. [Deutsch] Im Rahmen dieser beiden Vorhaben sollte untersucht werden, ob Platin im katalysierten Automobilabgas vorhanden ist und in welcher Menge es emittiert wird. Weiterhin sollte die Partikelgroesse der emittierten Partikel und ihre Verteilung bestimmt werden. Im Fraunhofer-Institut fuer Toxikologie und Aerosolforschung wurde dazu ein Motorstand aufgebaut und zwei unterschiedliche Probenahmetechniken entwickelt. (orig.)

  19. Search for and identification of gaseous noble metal emissions from catalytic converters. Quantitative and statistic screening of platinum metal aerosols emitted by automotive catalytic converters; Suche und Identifizierung von gasfoermigen katalysatorbuertigen Edelmetallemissionen (VPT 06). Quantitative und statistische Reihenuntersuchungen ueber emittierte Platinmetallaerosole aus Automobilkatalysatoren (VPT 08)

    Energy Technology Data Exchange (ETDEWEB)

    Artelt, S. [Fraunhofer-Institut fuer Toxikologie und Aerosolforschung, Hannover (Germany)

    1997-12-31

    The aim of these two projects was to determine whether platinum is contained in catalysed automobile exhaust fumes and in what quantities it is emitted. A further task was to determine the particle size and particle size distribution of emitted particles. For this purpose an engine test stand was set up at the Fraunhofer Institute for Toxicology and Aerosol Research and two different sampling techniques were developed. [Deutsch] Im Rahmen dieser beiden Vorhaben sollte untersucht werden, ob Platin im katalysierten Automobilabgas vorhanden ist und in welcher Menge es emittiert wird. Weiterhin sollte die Partikelgroesse der emittierten Partikel und ihre Verteilung bestimmt werden. Im Fraunhofer-Institut fuer Toxikologie und Aerosolforschung wurde dazu ein Motorstand aufgebaut und zwei unterschiedliche Probenahmetechniken entwickelt. (orig.)

  20. Novel bacterial gas sensor proteins with transition metal-containing prosthetic groups as active sites.

    Science.gov (United States)

    Aono, Shigetoshi

    2012-04-01

    Gas molecules function as signaling molecules in many biological regulatory systems responsible for transcription, chemotaxis, and other complex physiological processes. Gas sensor proteins play a crucial role in regulating such biological systems in response to gas molecules. New sensor proteins that sense oxygen or nitric oxide have recently been found, and they have been characterized by X-ray crystallographic and/or spectroscopic analysis. It has become clear that the interaction between a prosthetic group and gas molecules triggers dynamic structural changes in the protein backbone when a gas sensor protein senses gas molecules. Gas sensor proteins employ novel mechanisms to trigger conformational changes in the presence of a gas. In gas sensor proteins that have iron-sulfur clusters as active sites, the iron-sulfur clusters undergo structural changes, which trigger a conformational change. Heme-based gas sensor proteins reconstruct hydrogen-bonding networks around the heme and heme-bound ligand. Gas sensor proteins have two functional states, on and off, which are active and inactive, respectively, for subsequent signal transduction in response to their physiological effector molecules. To fully understand the structure-function relationships of gas sensor proteins, it is vital to perform X-ray crystal structure analyses of full-length proteins in both the on and off states.

  1. Spectrophotometric and electrochemical study for metal ion binding of azocalix[4]arene bearing p-ethylester group

    Science.gov (United States)

    Kim, Tae Hyun

    2017-05-01

    The complexation behavior of diazophenylcalix[4]arene bearing para-ethylester group (p-EAC) for alkali, alkaline earth, various heavy and transition metal ions (Li+, Na+, K+, Rb+, Cs+, Mg2 +, Ca2 +, Sr2 +, Ba2 +, Cr3 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Zn2 +, Pb2 +) was investigated by spectrophotometric and electrochemical methods in CH3CN. p-EAC exhibits decreased absorbance at 353 nm in the presence of Cr3 +, Fe2 +, Pb2 +, and Cu2 +. The spectra of p-EAC showed bathochromic shift in absorption maximum on the addition of Cr3 +, Fe2 +, or Pb2 + with decreasing order of absorbance (Cr3 + > Fe2 + > Pb2 +), and on the other hand, hypsochromic shift on the addition of Cu2 +. This leads to the selective coloration from light green to orange and colorless for Cr3 + and Cu2 + that can be detected by the naked eye, respectively. In electrochemistry experiments, p-EAC also showed two different types of voltammetric changes toward Cr3 +, Fe2 +, or Pb2 +, and toward Cu2 +, whereas no significant changes occurred in the presence of the other metal ions. Nonlinear fitting curve procedure was used to determine a logarithmic value of 5.20, 4.92, 3.54 and 4.80 for the stability constants of the complex of p-EAC with Cr3 +, Fe2 +, Pb2 +, and Cu2 +, respectively.

  2. Metal-ligand interactions

    Science.gov (United States)

    Ervin, Kent M.

    Experimental studies of the interactions of small transition-metal cluster anions with carbonyl ligands are reviewed and compared with neutral and cationic clusters. Under thermal conditions, the reaction rates of transition-metal clusters with carbon monoxide are measured as a function of cluster size. Saturation limits for carbon monoxide addition can be related to the geometric structures of the clusters. Both energy-resolved threshold collision-induced dissociation experiments and time-resolved photodissociation experiments are used to measure metal-carbonyl binding energies. For platinum and palladium trimer anions, the carbonyl binding energies are assigned to different geometric binding sites. Platinum and palladium cluster anions catalyse the oxidation of carbon monoxide to carbon dioxide in a full catalytic cycle at thermal energies.

  3. Quantitative electrochromatography of uranium and platinum on papers impregnated with thorium and antimony based cation exchanger

    International Nuclear Information System (INIS)

    Misra, A.K.

    1992-01-01

    Electrochromatography of 32 metal ions have been studied on papers impregnated with thorium antimonate cation exchanger in aq. organic acids, aq. nitric acid as well as in EDTA buffers. On the basis of differential migration which depends on the ion exchange properties of thorium antimonate and nature of complexes formed with the electrolytes, some useful qualitative and quantitative separations of synthetic mixtures of metal ions have been achieved. The effect of some other physical parameter has also been discussed. Quantitative separation of platinum and uranium has been developed. (author). 13 refs., 2 figs., 5 tabs

  4. Half-metallicity and electronic structures for carbon-doped group III-nitrides: Calculated with a modified Becke-Johnson potential

    Science.gov (United States)

    Fan, Shuai-wei; Wang, Ri-gao; Xu, Pemg

    2016-09-01

    The electronic structures and magnetism for carbon-doped group III-nitrides are investigated by utilizing the first principle method with the modified Becke-Johnson potential. Calculations show that carbon substituting cations (anions) would induce the group III-nitrides to be paramagnetic metals (half-metallic ferromagnets). Single carbon substituting nitrogen could produce 1.00μB magnetic moment. Electronic structures indicate that the carriers-mediated double-exchange interaction plays a crucial role in forming the ferromagnetism. Based on the mean-field theory, the Curie temperature for carbon-doped group III-nitrides would be above the room temperature. Negative chemical pair interactions imply that carbon dopants tend to form clustering distribution in group III-nitrides. The nitrogen vacancy would make the carbon-doped group III-nitrides lose the half-metallic ferromagnetism.

  5. Electrochemically Smart Bimetallic Materials Featuring Group 11 Metals: In-situ Conductive Network Generation and Its Impact on Cell Capacity

    Energy Technology Data Exchange (ETDEWEB)

    Takeuchi, Esther [Stony Brook Univ., NY (United States)

    2016-11-30

    Our results for this program “Electrochemically smart bimetallic materials featuring Group 11 metals: in-situ conductive matrix generation and its impact on battery capacity, power and reversibility” have been highly successful: 1) we demonstrated material structures which generated in-situ conductive networks through electrochemical activation with increases in conductivity up to 10,000 fold, 2) we pioneered in situ analytical methodology to map the cathodes at several stages of discharge through the use of Energy Dispersive X-ray Diffraction (EDXRD) to elucidate the kinetic dependence of the conductive network formation, and 3) we successfully designed synthetic methodology for direct control of material properties including crystallite size and surface area which showed significant impact on electrochemical behavior.

  6. Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: a Tool for Molecular Mass Prediction

    KAUST Repository

    Falivene, Laura; Cavallo, Luigi; Talarico, Giovanni

    2015-01-01

    A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%VBur) as molecular descriptor is reported. The %VBur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by DFT methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr and Hf confirm not only that the %VBur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.

  7. Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: a Tool for Molecular Mass Prediction

    KAUST Repository

    Falivene, Laura

    2015-10-02

    A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%VBur) as molecular descriptor is reported. The %VBur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by DFT methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr and Hf confirm not only that the %VBur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.

  8. Group 13 ligand supported heavy-metal complexes: first structural evidence for gallium-lead and gallium-mercury bonds.

    Science.gov (United States)

    Prabusankar, Ganesan; Gemel, Christian; Winter, Manuela; Seidel, Rüdiger W; Fischer, Roland A

    2010-05-25

    Heavy-metal complexes of lead and mercury stabilized by Group 13 ligands were derived from the oxidative addition of Ga(ddp) (ddp=HC(CMeNC(6)H(3)-2,6-iPr(2))(2), 2-diisopropylphenylamino-4-diisopropyl phenylimino-2-pentene) with corresponding metal precursors. The reaction of Me(3)PbCl and Ga(ddp) afforded compound [{(ddp)Ga(Cl)}PbMe(3)] (1) composed of Ga-Pb(IV) bonds. In addition, the monomeric plumbylene-type compound [{(ddp)Ga(OSO(2)CF(3))}(2)Pb(thf)] (2a) with an unsupported Ga-Pb(II)-Ga linkage was obtained by the reaction of [Pb(OSO(2)CF(3))(3)] with Ga(ddp) (2 equiv). Compound 2a falls under the rare example of a discrete plumbylene-type compound supported by a nonclassical ligand. Interesting structural changes were observed when [Pb(OSO(2)CF(3))(3)]2.H(2)O was treated with Ga(ddp) in a 1:2 ratio to yield [{(ddp)Ga(mu-OSO(2)CF(3))}(2)(OH(2))Pb] (2b) at below -10 degrees C. Compound 2b consists of a bent Ga-Pb-Ga backbone with a bridging triflate group between the Ga-Pb bond and a weakly interacting water molecule at the gallium center. Similarly, the reaction of mercury thiolate Hg(SC(6)F(5)) with Ga(ddp) (2 equiv) produced the bimetallic homoleptic compounds anti-[{(ddp)Ga(SC(6)F(5))}(2)Hg] (3a) and gauche-[{(ddp)Ga(SC(6)F(5))}(2)Hg] (3b), respectively, with a linear Ga-Hg-Ga linkage. Compounds 1-3 were structurally characterized and these are the first examples of compounds comprised of Ga-Pb(II), Ga-Pb(IV), and Ga-Hg bonds.

  9. Prevention of blood transfusion with intravenous iron in gynecologic cancer patients receiving platinum-based chemotherapy.

    Science.gov (United States)

    Athibovonsuk, Punnada; Manchana, Tarinee; Sirisabya, Nakarin

    2013-12-01

    To compare the efficacy of intravenous iron and oral iron for prevention of blood transfusions in gynecologic cancer patients receiving platinum-based chemotherapy. Sixty-four non anemic gynecologic cancer patients receiving adjuvant platinum-based chemotherapy were stratified and randomized according to baseline hemoglobin levels and chemotherapy regimen. The study group received 200mg of intravenous iron sucrose immediately after each chemotherapy infusion. The control group received oral ferrous fumarate at a dose of 200mg three times a day. Complete blood count was monitored before each chemotherapy infusion. Blood transfusions were given if hemoglobin level was below 10mg/dl. There were 32 patients in each group. No significant differences in baseline hemoglobin levels and baseline characteristics were demonstrated between both groups. Nine patients (28.1%) in the study group and 18 patients (56.3%) in the control group required blood transfusion through 6 cycles of chemotherapy (p=0.02). Fewer median number of total packed red cell units were required in the study group compared to the control group (0 and 0.5 unit, respectively, p=0.04). Serious adverse events and hypersensitivity reactions were not reported. However, constipation was significantly higher in the control group (3.1% and 40.6%, p=gynecologic cancer patients receiving platinum-based chemotherapy, associated with less constipation than the oral formulation. © 2013 Elsevier Inc. All rights reserved.

  10. Principles for prevention of toxic effects from metals

    DEFF Research Database (Denmark)

    Landrigan, Philip J.; Kotelchuk, David; Grandjean, Philippe

    2007-01-01

    of the Toxic Effects of Metals Aluminum Antimony Arsenic Barium Beryllium Bismuth Cadmium Chromium Cobalt Copper Gallium and Semiconductor Compounds Germanium Indium Iron Lead Manganese Mercury Molybdenum Nickel Palladium Platinum Selenium Silver Tellurium Thallium Tin Titanium Tungsten Uranium Vanadium Zinc...

  11. Investigation of the origin and distribution of heavy metals around ...

    African Journals Online (AJOL)

    2010-04-28

    Apr 28, 2010 ... JS Ogola1*, HR Mundalamo1 and G Brandl2. 1Department of Mining and ..... CSIR, Environmental Services, Pretoria,. South Africa. ... chemical orientation studies and the platinum potential of Jamaica. Trans. Inst. Min. Metall.

  12. A review on transition-metal mediated synthesis of quinolines

    Indian Academy of Sciences (India)

    Rashmi Sharma

    2018-06-14

    Jun 14, 2018 ... Special Section on Transition Metal Catalyzed Synthesis of Medicinally Relevant Molecules. A review on ...... iron(III) chloride and TEMPO oxoammonium salt as an .... propyl-3-ethylquinoline (209) in presence of platinum.

  13. Forging Unsupported Metal-Boryl Bonds with Icosahedral Carboranes.

    Science.gov (United States)

    Saleh, Liban M A; Dziedzic, Rafal M; Khan, Saeed I; Spokoyny, Alexander M

    2016-06-13

    In contrast to the plethora of metal-catalyzed cross-coupling methods available for the installation of functional groups on aromatic hydrocarbons, a comparable variety of methods are currently not available for icosahedral carboranes, which are boron-rich three-dimensional aromatic analogues of aryl groups. Part of this is due to the limited understanding of the elementary steps for cross-coupling involving carboranes. Here, we report our efforts in isolating metal-boryl complexes to further our understanding of one of these elementary steps, oxidative addition. Structurally characterized examples of group 10 M-B bonds featuring icosahedral carboranes are completely unknown. Use of mercurocarboranes as a reagent to deliver M-B bonds saw divergent reactivity for platinum and palladium, with a Pt-B bond being isolated for the former, and a rare Pd-Hg bond being formed for the latter. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. A rapid and practical strategy for the determination of platinum, palladium, ruthenium, rhodium, iridium and gold in large amounts of ultrabasic rock by inductively coupled plasma optical emission spectrometry combined with ultrasound extraction

    Science.gov (United States)

    Zhang, Gai; Tian, Min

    2015-04-01

    This proposed method regulated the determination of platinum, palladium, ruthenium, rhodium, iridium and gold in platinum-group ores by nickel sulfide fire assay—inductively coupled plasma optical emission spectrometry (ICP-OES) combined with ultrasound extraction for the first time. The quantitative limits were 0.013-0.023μg/g. The samples were fused to separate the platinum-group elements from matrix. The nickel sulfide button was then dissolved with hydrochloric acid and the insoluble platinum-group sulfide residue was dissolved with aqua regia by ultrasound bath and finally determined by ICP-OES. The proposed method has been applied into the determination of platinum-group element and gold in large amounts of ultrabasic rocks from the Great Dyke of Zimbabwe.

  15. Assessment of sublethal endpoints after chronic exposure of the nematode Caenorhabditis elegans to palladium, platinum and rhodium.

    Science.gov (United States)

    Schertzinger, Gerhard; Zimmermann, Sonja; Grabner, Daniel; Sures, Bernd

    2017-11-01

    The aim of this study was to investigate chronic effects of the platinum-group elements (PGE) palladium (Pd), platinum (Pt) and rhodium (Rh) on the nematode Caenorhabditis elegans. Aquatic toxicity testing was carried out according to ISO 10872 by determining 96 h EC 50 values for sublethal endpoints, including growth, fertility and reproduction. Single PGE standard solutions were used as metal source. Based on the EC 50 values for Pt, reproduction (96 h EC 50  = 497 μg/L) was the most sensitive endpoint followed by fertility (96 h EC 50  = 726 μg/L) and growth (96 h EC 50  = 808 μg/L). For Pd, no precise EC 50 values could be calculated due to bell-shaped concentration response curves, but the 96 h EC 50 for reproduction ranged between 10 and 100 μg/L. Pd and Pt had effects on all endpoints. With raising element concentrations reproduction was inhibited first. At a certain concentration, fertility was also affected, which in turn had an additional effect on reproduction. Growth inhibition can also lead to a loss of fertility if the worms do not reach an appropriate body size to become fertile. Rhodium showed no inhibition of any endpoint between concentrations of 100 to 10,000 μg Rh/L. The results of this study allow the following order of PGE with respect to decreasing toxicity to C. elegans: Pd > Pt » Rh. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases.

    Science.gov (United States)

    Fu, Wei; Li, Xin-Hao; Bao, Hong-Liang; Wang, Kai-Xue; Wei, Xiao; Cai, Yi-Yu; Chen, Jie-Sheng

    2013-01-01

    The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay.

  17. Structure, activity, and stability of platinum alloys as catalysts for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Vej-Hansen, Ulrik Grønbjerg

    In this thesis I present our work on theoretical modelling of platinum alloys as catalysts for the Oxygen Reduction Reaction (ORR). The losses associated with the kinetics of the ORR is the main bottleneck in low-temperature fuel cells for transport applications, and more active catalysts...... are essential for wide-spread use of this technology. platinum alloys have shown great promise as more active catalysts, which are still stable under reaction conditions. We have investigated these systems on multiple scales, using either Density Functional Theory (DFT) or Effective Medium Theory (EMT......), depending on the length and time scales involved. Using DFT, we show how diffusion barriers in transition metal alloys in the L12 structure depend on the alloying energy, supporting the assumption that an intrinsically more stable alloy is also more stable towards diffusion-related degradation...

  18. Synergistic effect of Brønsted acid and platinum on purification of automobile exhaust gases

    Science.gov (United States)

    Fu, Wei; Li, Xin-Hao; Bao, Hong-Liang; Wang, Kai-Xue; Wei, Xiao; Cai, Yi-Yu; Chen, Jie-Sheng

    2013-01-01

    The catalytic purification of automobile exhaust gases (CO, NOx and hydrocarbons) is one of the most practiced conversion processes used to lower the emissions and to reduce the air pollution. Nevertheless, the good performance of exhaust gas purification catalysts often requires the high consumption of noble metals such as platinum. Here we report that the Brønsted acid sites on the external surface of a microporous silicoaluminophosphate (SAPO) act as a promoter for exhaust gas purification, effectively cutting the loading amount of platinum in the catalyst without sacrifice of performance. It is revealed that in the Pt-loaded SAPO-CHA catalyst, there exists a remarkable synergistic effect between the Brønsted acid sites and the Pt nanoparticles, the former helping to adsorb and activate the hydrocarbon molecules for NO reduction during the catalytic process. The thermal stability of SAPO-CHA also makes the composite catalyst stable and reusable without activity decay. PMID:23907148

  19. Formic acid oxidation at platinum-bismuth catalysts

    Directory of Open Access Journals (Sweden)

    Popović Ksenija Đ.

    2015-01-01

    Full Text Available The field of heterogeneous catalysis, specifically catalysis on bimetallic surfaces, has seen many advances over the past few decades. Bimetallic catalysts, which often show electronic and chemical properties that are distinct from those of their parent metals, offer the opportunity to obtain new catalysts with enhanced selectivity, activity, and stability. The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small organic molecules and because of its technical relevance for fuel cell applications. Platinum is one of the most commonly used catalysts for this reaction, despite the fact that it shows a few significant disadvantages: high cost and extreme susceptibility to poisoning by CO. To solve this problem, several approaches have been used, but generally, they all consist in the modification of platinum with a second element. Especially, bismuth has received significant attention as Pt modifier. According to the results presented in this survey dealing with the effects influencing the formic acid oxidation it was found that two types of Pt-Bi bimetallic catalysts (bulk and low loading deposits on GC showed superior catalytic activity in terms of the lower onset potential and oxidation current density, as well as exceptional stability compared to Pt. The findings in this report are important for the understanding of mechanism of formic acid electrooxidation on a bulk alloy and decorated surface, for the development of advanced anode catalysts for direct formic acid fuel cells, as well as for the synthesis of novel low-loading bimetallic catalysts. The use of bimetallic compounds as the anode catalysts is an effective solution to overcoming the problems of the formic acid oxidation current stability for long term applications. In the future, the tolerance of both CO poisoning and electrochemical leaching should be considered as the key factors in the development

  20. A Meta-Analysis of Platinum Plus Gemcitabine or Vinorelbine for Advanced Non-small Cell Lung Cancer

    Directory of Open Access Journals (Sweden)

    Guanghui GAO

    2009-01-01

    Full Text Available Background and objective Platinum plus the third-generation agent doublet chemotherapy is the standard regimens and first line chemotherapy for advanced non-small cell lung cancer (NSCLC. The aim of this study is to determine the benefits and harms of platinum plus gemcitabine or vinorelbine for advanced NSCLC. Methods Thedatabases PubMed, CENTRAL, EMBASE and Chinese Biomedical Literature database were retrieved by using the key words "non small cell lung cancer" or "Carcinoma, Non Small Cell Lung" so as to search the studies about the randomized controlled clinical trials (RCT that had compared the gemcitabine plus platinum versus vinorelbine plus platinum for advanced NSCLC. A meta-analysis was conducted. Results Nine randomized controlled trials, with total 2 186 patients,were included. The overall response rate and one-year survival rate of the gemcitabine group were not significantly different from that of vinorelbine regimen (RR=0.91, 95%CI: 0.81-1.03, P =0.15; RR=1.06, 95%CI: 0.96-1.18, P =0.27, respectively. The incidence rate of grade 3-4 netropenia, constipation, phlebitis and grade 1-4 neuropathy were higher in vinorelbine group, just like higher incidence rate of grade 3-4 thrombocytopenia in the gemcitabine group. Conclusion The curative effects of the gemcitabine or vinorelbine plus platinum regimens are similar. The choice of gemcitabine or vinorelbine depends on the toxicity of the drugs and patients' tolerance.

  1. Reactions of neopentane and neohexane on platinum/Y-zeolite and platinum/silica catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Foger, K.; Anderson, J.R.

    1978-10-13

    The hydrocracking/hydroisomerization reaction of 20:1 hydrogen/neopentane at 455-625/sup 0/K was studied on platinum-exchanged sodium, calcium, and lanthanum Y zeolites and Aerosil-supported platinum of 1-20 nm average platinum particle size, by analysis of the product distribution, ESCA, and temperature-programed desorption. The results suggested that the reaction occurs only on platinum and that it proceeds by two parallel pathways which have different activation energies and whose relative proportion depends on the particle size. One pathway is the conventionally accepted one on low-index crystallite facets; the other proceeds on single-surface platinum atoms of low coordination (corner or edge atoms) which become more abundant at lower crystallite size. In both cases, the adsorbed intermediate may undergo either isomerization or hydrogenolysis; the selectivity depends on the hydrogen partial pressure and the relative strength of adsorption of hydrogen and neopentane. Neohexane isomerization selectivity on the same catalysts is consistent with a carbonium ion mechanism on a dual-function catalyst.

  2. Platinum group elements and gold in ferromanganese crusts from ...

    Indian Academy of Sciences (India)

    The strong enrichment of Pt (up to 1 ppm) relative to the other PGE and its pos- itive correlations with ... around Late Miocene as indicated by the contin- uous growth of ...... 198. 331–351. Koschinsky A and Halbach P 1995 Sequential leaching.

  3. Beyond alkyl transfer: Synthesis of main group metal (Mg, Ca, Zn) silyl and tris(oxazolinyl)borato complexes and their stoichiometric and catalytic reactions with borane Lewis acids and carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Lampland, Nicole Lynn [Iowa State Univ., Ames, IA (United States)

    2015-05-09

    Recently, the fundamental knowledge of main group metal chemistry has grown. This progress is crucial for the further development of main group metal compounds in silicon chemistry and catalysis and for advancing their applications as green alternatives to many rare earth and transition metal compounds. This thesis focuses on reactivity beyond the welldocumented alkyl-transfer applications for main group metals, and it highlights examples of reactions with Lewis acids and the reduction of carbonyls.

  4. Electrochemical behavior of titanium implanted with platinum

    International Nuclear Information System (INIS)

    Thompson, N.G.; Lichter, B.D.; Appleton, B.R.; Kelly, E.J.; White, C.W.

    1979-01-01

    The following conclusions apply to Ti(Pt) near-surface alloys studied. (1) Open-circuit corrosion measurements show that accumulation of platinum may occur at a surface concentration of 0.32 atomic percent Pt while no accumulation occurs at 0.16 atomic percent Pt. However, these results do not allow a distinction as to cause of accumulation to be made between concentration effects and effects due to the presence of an oxide film. (2) Potentiostatic corrosion at -0.450 V (active corrosion) establish that little or no accumulation of platinum occurs at an oxide-free surface for concentrations less than 0.086 atomic percent Pt; whereas, a large amount of accumulation occurs for a distribution with a peak concentration of 0.83 atomic percent Pt. (3) An initial distribution having a peak concentration of 0.32 atomic percent platinum is sufficient to induce natural passivity in titanium and bring a freely corroding sample to a potential of 0.269 V. This is nearly the applicable reversible potential (-0.260 V) for the hydrogen reaction in 1N H 2 SO 4 . (4) Of three samples which showed accumulation, platinum was eventually lost for two of these samples (0.32 atomic percent, open-circuit corrosion; 0.83 atomic percent, potentiostatic corrosion). The remaining sample (9.1 atomic percent, open-circuit corrosion) maintained the maximum possible potential of -0.260 V for the length of the experiment (approx. 30 days). (5) For samples which had been polarized at -0.300 to -0.340 V and which had eventually reverted to the behavior of pure Ti, post corrosion RBS measurements reveal that a substantial fraction of the Pt fluence is retained on the surface in an electrochemically inactive state

  5. Effect of pendant group length upon metal ion complexation in acetonitrile by di-ionized calix[4]arenes bearing two dansyl fluorophores.

    Science.gov (United States)

    Ocak, Ummühan; Ocak, Miraç; Shen, Xin; Surowiec, Kazimierz; Bartsch, Richard A

    2009-11-01

    A series of three di-ionizable calix[4]arenes with two pendant dansyl (1-dimethylaminonaphthalene-5-sulfonyl) groups linked to the lower rims was synthesized. Structures of the three ligands were identical except for the length of the spacers which connected the two dansyl groups to the calix[4]arene scaffold. Following conversion of the ligands into their di-ionized di(tetramethylammonium) salts, absorption and emission spectrophotometry were utilized to probe the influence of metal cation (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Ag+, Cd2+, Co2+, Fe2+, Hg2+, Mn2+, Pb2+, Zn2+ and Fe3+) complexation in acetonitrile. Upon complexation with these metal cations, emission spectra underwent marked red shifts and quenching of the dansyl group fluorescence for the di-ionized ligand with the shortest spacer. A similar effect was noted for the di-ionized ligand with an intermediate spacer for all of the metal ions, except Ba2+. For the di-ionized ligand with the longest spacer, the metal cations showed different effects on the emission spectrum. Li+, Mg2+, Ca2+ and Ba2+ caused enhancement of emission intensity with a red shift. Other metal cations produce quenching with red shifts in the emission spectra. Transition metal cations interacted strongly with all three di-ionized ligands. In particular, Fe3+ and Hg2+ caused greater than 99% quenching of the dansyl fluorescence in the di-ionized ligands.

  6. On the enzymatic formation of platinum nanoparticles

    International Nuclear Information System (INIS)

    Govender, Y.; Riddin, T. L.; Gericke, M.; Whiteley, C. G.

    2010-01-01

    A dimeric hydrogenase enzyme (44.5 and 39.4 kDa sub units) was isolated in a 39.5% yield from the fungus Fusarium oxysporum and purified 4.64-fold by ion exchange chromatography on Sephacryl S-200. Characterisation of the enzyme afforded pH and temperature optima of 7.5 and 38 o C, respectively, a half-life stability of 36 min and a V max and K m of 3.57 nmol min -1 mL -1 and 2.25 mM, respectively. This enzyme was inhibited (non-competitively) by hydrogen hexachloroplatinic acid (H 2 PtCl 6 ) at 1 or 2 mM with a K i value of 118 μM. Incubation of the platinum salt with the pure enzyme under an atmosphere of hydrogen and optimum enzyme conditions (pH 7.5, 38 o C) afforded o C) over 90% reduction took place after the same length of time. Cell-free extract from the fungal isolates produced nearly 90% bioreduction of the platinum salt under both pH and temperature conditions. The bioreduction of the platinum salt by a hydrogenase enzyme takes place by a passive process and not an active one as previously understood.

  7. Platinum boride nanowires: Synthesis and characterization

    International Nuclear Information System (INIS)

    Ding Zhanhui; Qiu Lixia; Zhang Jian; Yao Bin; Cui Tian; Guan Weiming; Zheng Weitao; Wang Wenquan; Zhao Xudong; Liu Xiaoyang

    2012-01-01

    Highlights: ► Platinum boride nanowires have been synthesized via the direct current arc discharge method. ► XRD, TEM and SAED indicate that the nanowires are single-crystal PtB. ► Two broad photoluminescence emission peaks at about 586 nm and 626 nm have been observed in the PL spectroscopy of PtB nanowires. - Abstract: Platinum boride (PtB) nanowires have been successfully fabricated with direct current arc discharge method using a milled mixture of platinum (Pt) and boron nitride (BN) powders. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the compositions, morphology, and structures of the samples. The results show that PtB nanowires are 30–50 nm thick and 20–30 μm long. TEM and selected area electron diffraction (SAED) patterns identify that the PtB nanowires are single-crystalline in nature. A growth mechanism based on vapor–liquid–solid (VLS) process is proposed for the formation of nanowires.

  8. HydroCoil as an adjuvant to bare platinum coil treatment of 100 cerebral aneurysms

    International Nuclear Information System (INIS)

    Fanning, Noel F.; Berentei, Zsolt; Brennan, Paul R.; Thornton, John

    2007-01-01

    Introduction The overall safety of the HydroCoil, an expansile hybrid hydrogel-platinum coil, is unknown. We report a prospective observational study of our first 100 cerebral aneurysms treated with HydroCoils, focusing on safety and initial efficacy.Methods Indications, procedural complications, clinical and angiographic outcomes were recorded. Packing density, number of coils deployed and angiographic results were compared with those in a matched control group of 100 aneurysms treated solely with bare platinum coils. HydroCoil complication rates were compared to bare platinum coil rates at our institution and in published series. Results Adjuvant HydroCoil treatment led to increased mean percentage aneurysm filling compared to controls (50 ± 21% versus 27 ± 13%, P < 0.001). Immediate posttreatment angiographic results showed significantly (P < 0.001) more complete occlusions and fewer incomplete (<95%) occlusions compared to controls. Intermediate follow-up angiograms (median 7.5 months) in 63 aneurysms showed a trend towards fewer incomplete occlusions with HydroCoil treatment. There were significantly fewer major recurrences with HydroCoil treatment compared to the control treatment (9.5% versus 22.6%, P 0.046). In the adjuvant HydroCoil group, major recurrent aneurysms had significantly less percentage volume packing with HydroCoils than non-recurrent aneurysms (50.3 ± 5.0% versus 65.3 ± 18.0%, P = 0.04). There was a 12% procedural complication rate, 6% procedural morbidity and 1% mortality rate, similar to institutional and reported bare platinum coil complication rates.Conclusion HydroCoils can be safely deployed with a similar complication rate to bare platinum coils. They result in improved aneurysm filling. Intermediate follow-up angiography showed significantly fewer major recurrences. Long-term follow-up is required to confirm initial improved stability. (orig.)

  9. Life cycle assessment of metals: a scientific synthesis.

    Directory of Open Access Journals (Sweden)

    Philip Nuss

    Full Text Available We have assembled extensive information on the cradle-to-gate environmental burdens of 63 metals in their major use forms, and illustrated the interconnectedness of metal production systems. Related cumulative energy use, global warming potential, human health implications and ecosystem damage are estimated by metal life cycle stage (i.e., mining, purification, and refining. For some elements, these are the first life cycle estimates of environmental impacts reported in the literature. We show that, if compared on a per kilogram basis, the platinum group metals and gold display the highest environmental burdens, while many of the major industrial metals (e.g., iron, manganese, titanium are found at the lower end of the environmental impacts scale. If compared on the basis of their global annual production in 2008, iron and aluminum display the largest impacts, and thallium and tellurium the lowest. With the exception of a few metals, environmental impacts of the majority of elements are dominated by the purification and refining stages in which metals are transformed from a concentrate into their metallic form. Out of the 63 metals investigated, 42 metals are obtained as co-products in multi output processes. We test the sensitivity of varying allocation rationales, in which the environmental burden are allocated to the various metal and mineral products, on the overall results. Monte-Carlo simulation is applied to further investigate the stability of our results. This analysis is the most comprehensive life cycle comparison of metals to date and allows for the first time a complete bottom-up estimate of life cycle impacts of the metals and mining sector globally. We estimate global direct and indirect greenhouse gas emissions in 2008 at 3.4 Gt CO2-eq per year and primary energy use at 49 EJ per year (9.5% of global use, and report the shares for all metals to both impact categories.

  10. Recovery of Platinum from Dilute Chloride Media Using Biosorbents

    Science.gov (United States)

    Zeytuncu, B.; Morcali, M. H.; Yucel, O.

    Pistachio nut shells and Rice husk, a biomass residue, were investigated as adsorbents for the platinum uptake from synthetically prepared dilute chloroplatinic acid solutions. The effects of the different uptake parameters on platinum uptake (%) were studied in detail on a batch sorption. Before the pistachio nut shell material was activated, platinum uptake (%) was poor compared with rice husk. However, after the pistachio nut shell material was activated at 1000°C under an argon atmosphere, the platinum uptake (%) increased two-fold. The pistachio nut shell (inactivated and activated) and rice husk were characterized by Attenuated Total Reflection-Fourier transform infrared spectroscopy (ATR-FTIR).

  11. The application of the inductively coupled plasma system to the simultaneous determination of precious metals

    International Nuclear Information System (INIS)

    Watson, A.E.; Russell, G.M.; Middleton, H.R.; Davenport, F.F.

    1983-01-01

    This report describes the development of a spectrochemical technique using excitation by an inducticely coupled plasma (ICP) source for the simultaneous determination of the precious metals (defined here as gold, silver, and all the platinum-group metals except osmium) in a wide variety of samples from a plant for the extraction and refining of platinum metal. The limits of detection for the analytes were determined in various acid and salt media and, under the conditions used, ranged from 20 to 100ng/l. The analytes were determined in the presence of a thousandfold excess of each of the other precious metals used as a matrix element. Some severe interferences were noted but were ascribed to spectral-line overlap or to contamination of the matrix material. Various dissolution techniques, based upon standard procedures applied in the precious-metals industry, were used, depending on the particular type of material treated. The spectrometer was calibrated by the use of solutions containing the analytes, sodium chloride, and acid, with scandium as the internal standard. The accuracy and precision of the technique, established by the analysis of many samples of each type, were found to be satisfactory when close attention was paid to detail in the preparation of the analytical solution. The relative standard deviation of the method ranges from 0,005 to 0,05, depending on the element being determined

  12. A DFT investigation on group 8B transition metal-doped silicon carbide nanotubes for hydrogen storage application

    Science.gov (United States)

    Tabtimsai, Chanukorn; Ruangpornvisuti, Vithaya; Tontapha, Sarawut; Wanno, Banchob

    2018-05-01

    The binding of group 8B transition metal (TMs) on silicon carbide nanotubes (SiCNT) hydrogenated edges and the adsorption of hydrogen molecule on the pristine and TM-doped SiCNTs were investigated using the density functional theory method. The B3LYP/LanL2DZ method was employed in all calculations for the considered structural, adsorption, and electronic properties. The Os atom doping on the SiCNT is found to be the strongest binding. The hydrogen molecule displays a weak interaction with pristine SiCNT, whereas it has a strong interaction with TM-doped SiCNTs in which the Os-doped SiCNT shows the strongest interaction with the hydrogen molecule. The improvement in the adsorption abilities of hydrogen molecule onto TM-doped SiCNTs is due to the protruding structure and the induced charge transfer between TM-doped SiCNT and hydrogen molecule. These observations point out that TM-doped SiCNTs are highly sensitive toward hydrogen molecule. Moreover, the adsorptions of 2-5 hydrogen molecules on TM-doped SiCNT were also investigated. The maximum storage number of hydrogen molecules adsorbed on the first layer of TM-doped SiCNTs is 3 hydrogen molecules. Therefore, TM-doped SiCNTs are suitable to be sensing and storage materials for hydrogen gas.

  13. First-Principles Momentum Dependent Local Ansatz Approach to the Momentum Distribution Function in Iron-Group Transition Metals

    Science.gov (United States)

    Kakehashi, Yoshiro; Chandra, Sumal

    2017-03-01

    The momentum distribution function (MDF) bands of iron-group transition metals from Sc to Cu have been investigated on the basis of the first-principles momentum dependent local ansatz wavefunction method. It is found that the MDF for d electrons show a strong momentum dependence and a large deviation from the Fermi-Dirac distribution function along high-symmetry lines of the first Brillouin zone, while the sp electrons behave as independent electrons. In particular, the deviation in bcc Fe (fcc Ni) is shown to be enhanced by the narrow eg (t2g) bands with flat dispersion in the vicinity of the Fermi level. Mass enhancement factors (MEF) calculated from the jump on the Fermi surface are also shown to be momentum dependent. Large mass enhancements of Mn and Fe are found to be caused by spin fluctuations due to d electrons, while that for Ni is mainly caused by charge fluctuations. Calculated MEF are consistent with electronic specific heat data as well as recent angle resolved photoemission spectroscopy data.

  14. Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces

    Science.gov (United States)

    Hu, Peiguang; Chen, Limei; Deming, Christopher P.; Lu, Jia-En; Bonny, Lewis W.; Chen, Shaowei

    2016-06-01

    Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent

  15. Metal complexes in cancer therapy – an update from drug design perspective

    Directory of Open Access Journals (Sweden)

    Ndagi U

    2017-03-01

    Full Text Available Umar Ndagi, Ndumiso Mhlongo, Mahmoud E Soliman Molecular Modelling and Drug Design Research Group, School of Health Sciences, University of KwaZulu-Natal, Westville, Durban, South Africa Abstract: In the past, metal-based compounds were widely used in the treatment of disease conditions, but the lack of clear distinction between the therapeutic and toxic doses was a major challenge. With the discovery of cisplatin by Barnett Rosenberg in 1960, a milestone in the history of metal-based compounds used in the treatment of cancers was witnessed. This forms the foundation for the modern era of the metal-based anticancer drugs. Platinum drugs, such as cisplatin, carboplatin and oxaliplatin, are the mainstay of the metal-based compounds in the treatment of cancer, but the delay in the therapeutic accomplishment of other metal-based compounds hampered the progress of research in this field. Recently, however, there has been an upsurge of activities relying on the structural information, aimed at improving and developing other forms of metal-based compounds and nonclassical platinum complexes whose mechanism of action is distinct from known drugs such as cisplatin. In line with this, many more metal-based compounds have been synthesized by redesigning the existing chemical structure through ligand substitution or building the entire new compound with enhanced safety and cytotoxic profile. However, because of increased emphasis on the clinical relevance of metal-based complexes, a few of these drugs are currently on clinical trial and many more are awaiting ethical approval to join the trial. In this review, we seek to give an overview of previous reviews on the cytotoxic effect of metal-based complexes while focusing more on newly designed metal-based complexes and their cytotoxic effect on the cancer cell lines, as well as on new approach to metal-based drug design and molecular target in cancer therapy. We are optimistic that the concept of selective

  16. Release of low molecular weight silicones and platinum from silicone breast implants.

    Science.gov (United States)

    Lykissa, E D; Kala, S V; Hurley, J B; Lebovitz, R M

    1997-12-01

    We have conducted a series of studies addressing the chemical composition of silicone gels from breast implants as well as the diffusion of low molecular weight silicones (LM-silicones) and heavy metals from intact implants into various surrounding media, namely, lipid-rich medium (soy oil), aqueous tissue culture medium (modified Dulbecco's medium, DMEM), or an emulsion consisting of DMEM plus 10% soy oil. LM-silicones in both implants and surrounding media were detected and quantitated using gas chromatography (GC) coupled with atomic emission (GC-AED) as well as mass spectrometric (GC/MS) detectors, which can detect silicones in the nanogram range. Platinum, a catalyst used in the preparation of silicone gels, was detected and quantitated using inductive argon-coupled plasma/mass spectrometry (ICP-MS), which can detect platinum in the parts per trillion range. Our results indicate that GC-detectable low molecular weight silicones contribute approximately 1-2% to the total gel mass and consist predominantly of cyclic and linear poly-(dimethylsiloxanes) ranging from 3 to 20 siloxane [(CH3)2-Si-O] units (molecular weight 200-1500). Platinum can be detected in implant gels at levels of approximately 700 micrograms/kg by ICP-MS. The major component of implant gels appears to be high molecular weight silicone polymers (HM-silicones) too large to be detected by GC. However, these HM-silicones can be converted almost quantitatively (80% by mass) to LM-silicones by heating implant gels at 150-180 degrees C for several hours. We also studied the rates at which LM-silicones and platinum leak through the intact implant outer shell into the surrounding media under a variety of conditions. Leakage of silicones was greatest when the surrounding medium was lipid-rich, and up to 10 mg/day LM-silicones was observed to diffuse into a lipid-rich medium per 250 g of implant at 37 degrees C. This rate of leakage was maintained over a 7-day experimental period. Similarly, platinum was

  17. Noble Metal/Ceramic Composites in Flame Processes

    DEFF Research Database (Denmark)

    Schultz, Heiko; Madler, Lutz; Strobel, Reto

    conditions influence the resulting noble metal particles size in those systems [1]. For every specific application the particle size and the metal/metal oxide interaction affect the performance of these nano-composite materials [2]. Recently, aerosol processes have been successfully used to produce platinum...

  18. Green synthesis and characterisation of platinum nanoparticles using quail egg yolk

    Science.gov (United States)

    Nadaroglu, Hayrunnisa; Gungor, Azize Alayli; Ince, Selvi; Babagil, Aynur

    2017-02-01

    Nanotechnology is extensively used in all parts today. Therefore, nano synthesis is also significant in all explored areas. The results of studies conducted have revealed that nanoparticle synthesis is performed by using both chemical and physical methods. It is well known that these syntheses are carried out at high charge, pressure and temperature in harsh environments. Therefore, this study investigated green synthesis method that sustains more mild conditions. In this study, quail egg yolk having high vitamin and protein content was prepared for green synthesis reaction and used for the synthesis of platinum nanoparticles in the reaction medium. Reaction situations were optimised as a function of pH, temperature, time and concentration by using quail egg yolk. The results showed that the highest platinum nanoparticles were synthesised at 20 °C and pH 6.0 for 4 h. Also, optimal concentration of metal ions was established as 0.5 mM. The synthesised platinum nanoparticles were characterised by using UV spectrum, X-ray diffraction and scanning electron microscope.

  19. 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.

  20. Modeling of Platinum-Aryl Interaction with Amyloid-β Peptide.

    Science.gov (United States)

    Turner, Matthew; Platts, James A; Deeth, Robert J

    2016-03-08

    Ligand field molecular mechanics (LFMM), density functional theory (DFT), and semiempirical PM7 methods are used to study the binding of two Pt(II)-L systems to an N-terminal fragment of the amyloid-β peptide, where L = 2,2-bipyridyl or 1,10-phenanthroline. Molecular dynamics simulations are used to explore the conformational freedom of the peptide using LFMM combined with AMBER molecular mechanics parameters. We establish a modeling protocol, allowing for identification and analysis of favorable platinum-binding modes and peptide conformations. Preferred binding modes are identified for each ligand investigated; metal coordination occurs via Nε in His residues for both ligands--His6ε-His13ε and His6ε-His14ε for the bipyridyl and phenanthroline ligands, respectively. The observed change in binding mode for the different ligands suggests that the binding mode of these platinum-based structures can be controlled by the choice of ligand. In the bipy systems, Boltzmann population at 310 K is dominated by a single conformer, while in the phenanthroline case, three conformations make significant contributions to the ensemble. The relative stability of these conformations is due to the inherent stability of binding platinum via Nε in addition to subtle H-bonding effects.

  1. Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes

    International Nuclear Information System (INIS)

    Cunha, M.C.P.M. da; De Souza, J.P.I.; Nart, F.C.

    2000-01-01

    The reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes has been investigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For 3 M HNO 3 concentration it has been found that nitrate starts the reduction with partial N-O bond dissociation and N-N bond formation generating NO and N 2 O. At potentials lower than 0.2 V the reaction proceeds forming dissolved NH 4 + . For potentials lower than 0 V the reduction continues via a multiple pathway reaction leading to the nonselective production of N 2 , NH 2 OH, and N 2 H 2 . On the alloyed electrodes, the production of NO and N 2 O has been observed in both cathodic and anodic scans, while on pure platinum and rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting with the pure platinum and rhodium alloys, where the N-O bond break starts forming NO and N 2 O, on the alloys HNO 2 has been observed as the first reaction step. For alloys with higher rhodium composition, like Pt 75 Rh 25 , no N 2 has been detected for potentials lower than 0 V

  2. Separation of Acetylene from Carbon Dioxide and Ethylene by a Water-Stable Microporous Metal-Organic Framework with Aligned Imidazolium Groups inside the Channels.

    Science.gov (United States)

    Lee, Jaechul; Chuah, Chong Yang; Kim, Jaheon; Kim, Youngsuk; Ko, Nakeun; Seo, Younggyu; Kim, Kimoon; Bae, Tae Hyun; Lee, Eunsung

    2018-04-24

    Separation of acetylene from carbon dioxide and ethylene is challenging in view of their similar sizes and physical properties. Metal-organic frameworks (MOFs) in general are strong candidates for these separations owing to the presence of functional pore surfaces that can selectively capture a specific target molecule. Here, we report a novel 3D microporous cationic framework named JCM-1. This structure possesses imidazolium functional groups on the pore surfaces and pyrazolate as a metal binding group, which is well known to form strong metal-to-ligand bonds. The selective sorption of acetylene over carbon dioxide and ethylene in JCM-1 was successfully demonstrated by equilibrium gas adsorption analysis as well as dynamic breakthrough measurement. Furthermore, its excellent hydrolytic stability makes the separation processes highly recyclable without a substantial loss in acetylene uptake capacity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Evaluation of the antitumor activity of platinum nanoparticles in the treatment of hepatocellular carcinoma induced in rats.

    Science.gov (United States)

    Medhat, Amina; Mansour, Somaya; El-Sonbaty, Sawsan; Kandil, Eman; Mahmoud, Mustafa

    2017-07-01

    This study aimed to evaluate the antitumor activity of platinum nanoparticles compared with cis-platin both in vitro and in vivo in the treatment of hepatocellular carcinoma induced in rats. The treatment efficacy of platinum nanoparticles was evaluated by measuring antioxidant activities against oxidative stress caused by diethylnitrosamine in liver tissue. The measurements included reduced glutathione content and superoxide dismutase activity, as well as malondialdehyde level. Liver function tests were also determined, in addition to the evaluation of serum alpha-fetoprotein, caspase-3, and cytochrome c in liver tissue. Total RNA extraction from liver tissue samples was also done for the relative quantification of B-cell lymphoma 2, matrix metallopeptidase 9, and tumor protein p53 genes. Histopathological examination was also performed for liver tissue. Results showed that platinum nanoparticles are more potent than cis-platin in treatment of hepatocellular carcinoma induced by diethylnitrosamine in rats as it ameliorated the investigated parameters toward normal control animals. These findings were well appreciated with histopathological studies of diethylnitrosamine group treated with platinum nanoparticles, suggesting that platinum nanoparticles can serve as a good therapeutic agent for the treatment of hepatocellular carcinoma which should attract further studies.

  4. A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes

    International Nuclear Information System (INIS)

    Selvarani, G.; Sahu, A.K.; Choudhury, N.A.; Sridhar, P.; Pitchumani, S.; Shukla, A.K.

    2007-01-01

    A method, to anchor phenyl-sulfonic acid functional groups with the platinum catalyst supported onto a high surface-area carbon substrate, is reported. The use of the catalyst in the electrodes of a polymer electrolyte fuel cell (PEFC) helps enhancing its performance. Characterization of the catalyst by Fourier transform infra red (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and point-of-zero-charge (PZC) studies suggests that the improvement in performance of the PEFC is facilitated not only by enlarging the three-phase boundary in the catalyst layer but also by providing ionic-conduction paths as well as by imparting negative charge to platinum sites with concomitant oxidation of sulfur present in the carbon support. It is argued that the negatively charged platinum sites help repel water facilitating oxygen to access the catalyst sites. The PEFC with modified carbon-supported platinum catalyst electrodes exhibits 40% enhancement in its power density as compared to the one with unmodified carbon-supported platinum catalyst electrodes

  5. Bimetallic alloy electrocatalysts with multilayered platinum-skin surfaces

    Science.gov (United States)

    Stamenkovic, Vojislav R.; Wang, Chao; Markovic, Nenad M.

    2016-01-26

    Compositions and methods of preparing a bimetallic alloy having enhanced electrocatalytic properties are provided. The composition comprises a PtNi substrate having a surface layer, a near-surface layer, and an inner layer, where the surface layer comprises a nickel-depleted composition, such that the surface layer comprises a platinum skin having at least one atomic layer of platinum.

  6. Atomically flat platinum films grown on synthetic mica

    Science.gov (United States)

    Tanaka, Hiroyuki; Taniguchi, Masateru

    2018-04-01

    Atomically flat platinum thin films were heteroepitaxially grown on synthetic fluorophlogopite mica [KMg3(AlSi3O10)F2] by van der Waals epitaxy. Platinum films deposited on a fluorophlogopite mica substrate by inductively coupled plasma-assisted sputtering with oxygen introduction on a synthetic mica substrate resulted in the growth of twin single-crystalline epitaxial Pt(111) films.

  7. Enzymatic recovery of platinum (IV) from industrial wastewater using ...

    African Journals Online (AJOL)

    highest hydrogen-dependent platinum (IV) reducing activity in the presence of hydrogenase and its physiological electron carrier, cytochrome c3. When the purified hydrogenase enzyme (with and without cytochrome c3) was used with the industrial effluent, containing 7.9 mg.l-1 platinum, only 10 – 15% recovery was noted ...

  8. Platinum-TM (TM = Fe, Co) alloy nanoparticles dispersed nitrogen doped (reduced graphene oxide-multiwalled carbon nanotube) hybrid structure cathode electrocatalysts for high performance PEMFC applications.

    Science.gov (United States)

    Vinayan, B P; Ramaprabhu, S

    2013-06-07

    The efforts to push proton exchange membrane fuel cells (PEMFC) for commercial applications are being undertaken globally. In PEMFC, the sluggish kinetics of oxygen reduction reactions (ORR) at the cathode can be improved by the alloying of platinum with 3d-transition metals (TM = Fe, Co, etc.) and with nitrogen doping, and in the present work we have combined both of these aspects. We describe a facile method for the synthesis of a nitrogen doped (reduced graphene oxide (rGO)-multiwalled carbon nanotubes (MWNTs)) hybrid structure (N-(G-MWNTs)) by the uniform coating of a nitrogen containing polymer over the surface of the hybrid structure (positively surface charged rGO-negatively surface charged MWNTs) followed by the pyrolysis of these (rGO-MWNTs) hybrid structure-polymer composites. The N-(G-MWNTs) hybrid structure is used as a catalyst support for the dispersion of platinum (Pt), platinum-iron (Pt3Fe) and platinum-cobalt (Pt3Co) alloy nanoparticles. The PEMFC performances of Pt-TM alloy nanoparticle dispersed N-(G-MWNTs) hybrid structure electrocatalysts are 5.0 times higher than that of commercial Pt-C electrocatalysts along with very good stability under acidic environment conditions. This work demonstrates a considerable improvement in performance compared to existing cathode electrocatalysts being used in PEMFC and can be extended to the synthesis of metal, metal oxides or metal alloy nanoparticle decorated nitrogen doped carbon nanostructures for various electrochemical energy applications.

  9. Synthesis of group 10 metal complexes with a new unsymmetrical PN3P-pincer ligand through ligand post-modification: Structure and reactivity

    KAUST Repository

    Wang, Xiufang

    2017-01-01

    A post-modification strategy are used to synthesize a new class of diimine-amido PN3P-pincer group-10 transition metal complexes. The coordination chemistry and the thermal stabilities of their organometallic derivatives are characterized and investigated.

  10. The effects of thermal-neutron irradiation on platinum and dilute platinum-gold alloys

    International Nuclear Information System (INIS)

    Piani, C.S.B.

    1978-12-01

    The effect of varying defect concentrations on the recovery spectrum of thermal-neutron-irradiated pure platinum after isochronal anneals was investigated. The dose-independence of substages I(A), I(B) and I(C), and the dose dependence of substage I(D) and I(E), were observed to be in agreement with electron-irradiated studies. The 120 K substage in pure platinum was shown not to be due to interstitial-interstitial reactions, but could possibly be accounted for in terms of detrapping of interstitials from impurities or intrinsic immobile defects. The 360 K stage was shown to shift and was suppressed with increasing defect concentration. The possible conversion of the crowdion to a dumbbell near 160 K in Stage ll in platinum, as predicted by the two-interstitial model, was investigated by consideration of the initial slopes of the production curves between 80 K and 300 K. A minimum in these slopes was observed near 160 K and could be interpreted as due to the conversion of the highly mobile crowdion to an immobile dumbbell at this temperature. The influence of varying gold concentrations on the recovery spectrum of platinum was investigated in dilute platinum-gold alloys. The characteristics of several additional substages in Stage ll, due to the gold alloying were comparable to the results of electron-irradiation experiments. The observations made with regard to the impurity (gold) dependence of these substages could be interpreted in terms of the concentrations of the interstitials, vacancies and impurities present in the material. The interpretation of these substages was found to be consistent, if the recovery spectrum was investigated as a function of defect concentration [af

  11. Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

    International Nuclear Information System (INIS)

    Mauro, Marcella; Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo; Jaganjac, Morana; Bovenzi, Massimo; Filon, Francesca Larese

    2015-01-01

    The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na 2 PtC l6 and RhCl 3 ·3H 2 O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm −2  h −1 and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration

  12. Permeation of platinum and rhodium nanoparticles through intact and damaged human skin

    Energy Technology Data Exchange (ETDEWEB)

    Mauro, Marcella [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy); Crosera, Matteo; Bianco, Carlotta; Adami, Gianpiero; Montini, Tiziano; Fornasiero, Paolo [University of Trieste, Department of Chemical and Pharmaceutical Sciences (Italy); Jaganjac, Morana [Rudjer Boskovic Institute, Laboratory for Oxidative Stress, Department of Molecular Medicine (Croatia); Bovenzi, Massimo; Filon, Francesca Larese, E-mail: larese@units.it [University of Trieste, Clinical Unit of Occupational Medicine, Department of Medical Sciences (Italy)

    2015-06-15

    The aim of the study was to evaluate percutaneous penetration of platinum and rhodium nanoparticles (PtNPs: 5.8 ± 0.9 nm, RhNPs: 5.3 ± 1.9 nm) through human skin. Salts compounds of these metals are sensitizers and some also carcinogenic agents. In vitro permeation experiments were performed using Franz diffusion cells with intact and damaged skin. PtNPs and RhNPs, stabilized with polyvinylpyrrolidone, were synthesized by reduction of Na{sub 2}PtC{sub l6} and RhCl{sub 3}·3H{sub 2}O respectively. Suspensions with a concentration of 2.0 g/L of PtNPs and RhNPs were dispersed separately in synthetic sweat at pH 4.5 and applied as donor phases to the outer surface of the skin for 24 h. Measurements of the content of the metals in the receiving solution and in the skin were performed subsequently. Rhodium skin permeation was demonstrated through damaged skin, with a permeation flux of 0.04 ± 0.04 μg cm{sup −2} h{sup −1} and a lag time of 7.9 ± 1.1 h, while no traces of platinum were found in receiving solutions. Platinum and rhodium skin-analysis showed significantly higher concentrations of the metals in damaged skin. Rh and Pt applied as NPs can penetrate the skin barrier and Rh can be found in receiving solutions. These experiments pointed out the need for skin contamination prevention, since even a minor injury to the skin barrier can significantly increase penetration.

  13. Chiral discrimination in platinum anticancer drugs

    Czech Academy of Sciences Publication Activity Database

    Benedetti, M.; Malina, Jaroslav; Kašpárková, Jana; Brabec, Viktor; Natile, G.

    2002-01-01

    Roč. 110, Suppl. 5 (2002), s. 779-782 ISSN 0091-6765 R&D Projects: GA ČR GA301/00/0556; GA ČR GA305/02/1552; GA AV ČR IAA7004805; GA AV ČR IBS5004107; GA MŠk OC D20.001 Institutional research plan: CEZ:AV0Z5004920 Keywords : DNA * platinum * cancer Subject RIV: BO - Biophysics Impact factor: 3.452, year: 2002

  14. Spin Hall magnetoresistance at the interface between platinum and cobalt ferrite thin films with large magnetic anisotropy

    Directory of Open Access Journals (Sweden)

    Takeshi Tainosho

    2017-05-01

    Full Text Available The recently discovered spin Hall magnetoresistance (SMR effect is a useful means to obtain information on the magnetization process at the interface between a nonmagnetic metal and ferromagnetic insulators. We report the SMR measurements at the interface between platinum and cobalt ferrite thin films for samples with two different preferential directions of magnetization (out-of-plane and in-plane. The directional difference of the magnetic easy axis does not seem to influence the value of SMR.

  15. Surplus Cost Potential as a Life Cycle Impact Indicator for Metal Extraction

    Directory of Open Access Journals (Sweden)

    Marisa D.M. Vieira

    2016-01-01

    Full Text Available In the evaluation of product life cycles, methods to assess the increase in scarcity of resources are still under development. Indicators that can express the importance of an increase in scarcity of metals extracted include surplus ore produced, surplus energy required, and surplus costs in the mining and the milling stage. Particularly the quantification of surplus costs per unit of metal extracted as an indicator is still in an early stage of development. Here, we developed a method that quantifies the surplus cost potential of mining and milling activities per unit of metal extracted, fully accounting for mine-specific differences in costs. The surplus cost potential indicator is calculated as the average cost increase resulting from all future metal extractions, as quantified via cumulative cost-tonnage relationships. We tested the calculation procedure with 12 metals and platinum-group metals as a separate group. We found that the surplus costs range six orders of magnitude between the metals included, i.e., between $0.01–$0.02 (iron and $13,533–$17,098 (rhodium USD (year 2013 per kilogram of metal extracted. The choice of the reserve estimate (reserves vs. ultimate recoverable resource influenced the surplus costs only to a limited extent, i.e., between a factor of 0.7 and 3.2 for the metals included. Our results provide a good basis to regularly include surplus cost estimates as resource scarcity indicator in life cycle assessment.

  16. A NEW EMPIRICAL INVESTIGATION OF THE PLATINUM SPOT RETURNS

    Directory of Open Access Journals (Sweden)

    Simone Kruse

    2017-08-01

    Full Text Available The global platinum market has been in downturn and unstable for five consecutive years, and thus market participants are demanding effective quantitative risk management tools. Since platinum is so widely used and serves as an important investment vehicle, the importance of risk management of platinum spot returns cannot be understated. In this paper, we take advantage of a very popular econometric model, the generalized autoregressive conditional heteroscedasticity (GARCH model, for platinum returns. We received two important findings by using the conventional GARCH models in explain daily platinum spot returns. First, it is crucial to introduce heavy-tailed distribution to explain conditional heavy tails; and second, the NRIG distribution performs better than the most widely-used heavy-tailed distribution, the Student’s t distribution.

  17. Tunable electronic and magnetic properties in germanene by alkali, alkaline-earth, group III and 3d transition metal atom adsorption.

    Science.gov (United States)

    Li, Sheng-shi; Zhang, Chang-wen; Ji, Wei-xiao; Li, Feng; Wang, Pei-ji; Hu, Shu-jun; Yan, Shi-shen; Liu, Yu-shen

    2014-08-14

    We performed first-principles calculations to study the adsorption characteristics of alkali, alkali-earth, group III, and 3d transition-metal (TM) adatoms on germanene. We find that the adsorption of alkali or alkali-earth adatoms on germanene has minimal effects on geometry of germanene. The significant charge transfer from alkali adatoms to germanene leads to metallization of germanene, whereas alkali-earth adatom adsorption, whose interaction is a mixture of ionic and covalent, results in semiconducting behavior with an energy gap of 17-29 meV. For group III adatoms, they also bind germanene with mixed covalent and ionic bonding character. Adsorption characteristics of the transition metals (TMs) are rather complicated, though all TM adsorptions on germanene exhibit strong covalent bonding with germanene. The main contributions to the strong bonding are from the hybridization between the TM 3d and Ge pz orbitals. Depending on the induced-TM type, the adsorbed systems can exhibit metallic, half-metallic, or semiconducting behavior. Also, the variation trends of the dipole moment and work function with the adsorption energy across the different adatoms are discussed. These findings may provide a potential avenue to design new germanene-based devices in nanoelectronics.

  18. Methods for recovering precious metals from industrial waste

    Science.gov (United States)

    Canda, L.; Heput, T.; Ardelean, E.

    2016-02-01

    The accelerated rate of industrialization increases the demand for precious metals, while high quality natural resources are diminished quantitatively, with significant operating costs. Precious metals recovery can be successfully made from waste, considered to be secondary sources of raw material. In recent years, concerns and interest of researchers for more increasing efficient methods to recover these metals, taking into account the more severe environmental protection legislation. Precious metals are used in a wide range of applications, both in electronic and communications equipment, spacecraft and jet aircraft engines and for mobile phones or catalytic converters. The most commonly recovered precious metals are: gold from jewellery and electronics, silver from X- ray films and photographic emulsions, industrial applications (catalysts, batteries, glass/mirrors), jewellery; platinum group metals from catalytic converters, catalysts for the refining of crude oil, industrial catalysts, nitric acid manufacturing plant, the carbon-based catalyst, e-waste. An important aspect is the economic viability of recycling processes related to complex waste flows. Hydrometallurgical and pyrometallurgical routes are the most important ways of processing electrical and electronic equipment waste. The necessity of recovering precious metals has opened new opportunities for future research.

  19. Determination of platinum in urine and serum after the administration of cisplatin by neutron activation analysis

    International Nuclear Information System (INIS)

    Kucera, J.; Drobnik, J.

    1982-01-01

    A simple neutron activation method is described for platinum determination in urine and serum of dogs when studying the pharmacokinetics of cisplatin, an antitumour drug. The procedure is based on the nuclear reaction 198 Pt(n,ν,ν) 199 Au, a radiochemical separation of gold, and gamma-spectrometry of the radionuclide 199 Au. Gold is separated as metal by coprecipitation with selenium after the addition of ascorbic acid in a highly acidic medium. The interference contribution of 199 Au originating from stable gold is evaluated, too. (author)

  20. Scaling Behavior of the Spin Pumping Effect in Ferromagnet-Platinum Bilayers

    Science.gov (United States)

    Czeschka, F. D.; Dreher, L.; Brandt, M. S.; Weiler, M.; Althammer, M.; Imort, I.-M.; Reiss, G.; Thomas, A.; Schoch, W.; Limmer, W.; Huebl, H.; Gross, R.; Goennenwein, S. T. B.

    2011-07-01

    We systematically measured the dc voltage VISH induced by spin pumping together with the inverse spin Hall effect in ferromagnet-platinum bilayer films. In all our samples, comprising ferromagnetic 3d transition metals, Heusler compounds, ferrite spinel oxides, and magnetic semiconductors, VISH invariably has the same polarity, and scales with the magnetization precession cone angle. These findings, together with the spin mixing conductance derived from the experimental data, quantitatively corroborate the present theoretical understanding of spin pumping in combination with the inverse spin Hall effect.

  1. Non-platinum electrocatalysts for PEM fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Lee, K.; Zhang, L.; Shi, Z.; Hui, R.; Zhang, J. [National Research Council of Canada, Vancouver, BC (Canada). Inst. For Fuel Cell Innovation

    2008-07-01

    High cost, low reliability and durability are the main barriers preventing widespread commercialization of fuel cells. In particular, the platinum (Pt)-based electrocatalysts used in proton exchange membrane (PEM) fuel cells, including direct methanol fuel cells (DMFCs) are major contributors to the high cost of PEM fuel cells. The Institute for Fuel Cell Innovation at the National Research Council of Canada has developed several new non-Pt electrocatalysts for PEM fuel cell applications. This paper presented the research results on these catalysts, including transition metal macrocycles, chalcogenides, and Ir- or Pd-based alloys. It also described catalyst structure modes via theoretical density functional theory (DFT) calculations. Research activities on these electrocatalysts was summarized in terms of catalytic activity and the oxygen reduction reaction (ORR). Typical catalysts such as cobalt(Co)-polypyrrole (PPy) and the chalcogenides show promising results in terms of catalytic activity and a 4-electron reaction mechanism. Efforts are underway to modify both catalyst structure and synthesis methods in order to further improve catalyst performance. 4 refs., 2 figs.

  2. Characterization and Catalytic Activity for the Oxidation of Ethane and Propane on Platinum and Copper Supported on CeO2/Al2O3

    Directory of Open Access Journals (Sweden)

    Cataluña R.

    1998-01-01

    Full Text Available Ethane and propane oxidation on platinum and copper supported on Al2O3 and CeO2/Al2O3 catalysts were studied comparatively by examining reaction rates as a function of temperature. Results show that the addition of cerium oxide shifts the catalytic activity to higher temperatures. This negative influence is less pronounced in the case of supported copper samples, which on the basis of EPR and FTIR of adsorbed CO results is attributed to the low relative amount of this metal is in contact with ceria. The decrease in activity the presence of ceria might be due to changes in metal particle size or to the stabilization of the oxidized states of the metals, induced by their interactions with cerium oxide. The higher activity of platinum, in comparison with copper, is attributed to its higher reducibility along with an easier hydrocarbon activation on that metal.

  3. Cellulose bearing Schiff base and carboxylic acid chelating groups: a low cost and green adsorbent for heavy metal ion removal from aqueous solution.

    Science.gov (United States)

    Saravanan, R; Ravikumar, L

    2016-10-01

    Chemically modified cellulose bearing metal binding sites like Schiff base and carboxylic acid groups was synthesized and characterized through Fourier transform infrared and solid state 13 C-nuclear magnetic resonance (NMR) analysis. The chemically modified cellulose (Cell-PA) adsorbent was examined for its metal ion uptake ability for Cu(II) and Pb(II) ions from aqueous solution. Kinetic and isotherm studies were carried out under optimum conditions. Pseudo-second-order kinetics and Langmuir isotherm fit well with the experimental data. Thermodynamic studies were also performed along with adsorption regeneration performance studies. The adsorbent (Cell-PA) shows high potential for the removal of Cu(II) and Pb(II) metal ions, and it shows antibacterial activity towards selected microorganisms.

  4. Nickel group cluster anion reactions with carbon monoxide: Rate coefficients and chemisorption efficiency

    Science.gov (United States)

    Hintz, Paul A.; Ervin, Kent M.

    1994-04-01

    Reactions of Ni-n(n=3-10), Pd-n(n=3-8), and Pt-n(n=3-7) with CO are studied in a flow tube reactor. Bimolecular rate coefficients are measured for the association reaction of CO adsorbing on the cluster surface. The rate coefficients range from about 10% of the collision rate for the trimer anions to near the collision rate for clusters larger than four atoms. The maximum number of CO molecules that bind to each cluster is determined. Whereas the saturation limits for nickel are typical for an 18 electron transition metal, the limits for platinum are lower, reflecting the electron deficient structures observed in condensed phase chemistry. The CO saturated palladium clusters represent the first examples of saturated binary palladium carbonyl compounds. Comparisons are made to similar studies on metal cation and neutral clusters and also to surface scattering studies of nickel group metals.

  5. Corrosion Studies of Platinum Nano-Particles for Fuel Cells

    DEFF Research Database (Denmark)

    Shim, Signe Sarah

    The main focus of the present thesis is on corrosion and prevention of corrosion of platinum particles supported on carbon. This is important for instance in connection with start up and shutdown of fuel cells. The degradation mechanism of platinum particles supported on carbon has been character......The main focus of the present thesis is on corrosion and prevention of corrosion of platinum particles supported on carbon. This is important for instance in connection with start up and shutdown of fuel cells. The degradation mechanism of platinum particles supported on carbon has been...... characterized during oxygen reduction reaction (ORR) condition using identical location (IL) transmission electron microscopy (TEM). A TEM grid was used as the working electrode in an electrochemical setup allowing a direct correlation between the electrochemical response and the TEM analysis. The main results...... thirds and one monolayer of gold on platinum supported on carbon were synthesized by an inverse micelle method. The results obtained appear independent of the gold coverage. It has been shown that the electrochemical active surface areas of the platinum and platinum gold particles synthesized...

  6. Comparison of adaptability to heavy metals among crop plants (part 2). Adaptability to zinc group metals-studies on the comparative plant nutrition

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, A; Tadano, T; Muto, K

    1975-01-01

    Eighteen crop species were grown in culture solution having graded levels of Zn, Cd and Hg, and the differences among species in response to these elements were discussed. As the average of all species tested, the metal content of the shoot is Ca > Mn > Zn > Cd > Hg, and the root-to-shoot content ratio is reversed at equivalent levels. These values increase with an increase in the level of respective ions in the culture solution. The metal concentration in the shoot among species does not change significantly with the level of that element. There is a positive correlation among species between Zn and Cd, but Hg shows a different trend. The tolerance to Zn is weak in many species of Gramineae and Curciferae, and strong Solanaceae and Umbelliferae. Many species of Gramineae are very tolerant to high levels of Zn or Cd due to a high excluding power of the roots, but possess a weak tolerance to high Hg levels. Egg-plant, soybean, and pea are susceptible to high levels of all three elements.

  7. Evidence of Increased Anthropogenic Emissions of Platinum in Coastal Systems from Time-Series Analysis of Mussels Samples (1991-2011

    Directory of Open Access Journals (Sweden)

    Patricia Neira Del Río

    2014-06-01

    Full Text Available The Platinum Group Elements (PGEs, which include platinum (Pt, palladium (Pd, iridium (Ir, rhodium (Rh, osmium (Os and ruthenium (Ru, are amongst the rarest trace elements in the Earth’s crust. They have similar physical and chemical properties, and tend to occur together in the same mineral deposits. Their properties are resistance to chemical corrosion over a wide temperature range, high melting point, high mechanical strength and good ductility, as well as outstanding catalytic properties, being therefore critical in many emerging technologies. Although natural environmental concentrations of PGEs are extremely low – generally at or below the ng/g –, levels of Pt, Pd and Rh are increasing, mainly because of their use in catalytic converters of motor vehicles (Zereini et al., 2007. The automobile catalysts converters use noble metals as active components, and were developed with the aim of reducing emissions of hydrocarbons, carbon monoxide and nitrogen oxides (Sures et al., 2005. Since the beginning of the 1980s, the PGEs represent a relatively new category of trace metals in the environment, especially in relation to automobile traffic (Haus et al., 2007. The PGEs of automobile catalytic converters are eroded from the surface of the catalyst and subsequently emitted in metallic form or as oxides (Turner and Price, 2008. The PGEs are subject to various physical and chemical transformations after deposition, and can potentially result in migration into environmental compartments (Moldovan et al., 2001; Vaughan and Florence, 1992. The concentration of PGEs has much increased in traffic exposed environmental samples (Lesniewska et al., 2004; Ely et al., 2001; Zereini et al., 2001; Schäfer et al., 1999; Fritsche and Meisel, 2004. However, what constituted a decrease in greenhouse gas emissions has resulted in increased levels of PGEs in the environment as shown in some studies in the dust of the road, roadsides, river sediments, sewage

  8. Electrochemical behaviour of gamma hydroxybutyric acid at a platinum electrode in acidic medium

    International Nuclear Information System (INIS)

    Jiménez-Pérez, R.; Sevilla, J.M.; Pineda, T.; Blázquez, M.; González-Rodríguez, J.

    2013-01-01

    Highlights: • This is the first reported electrochemical study of the behaviour of GHB. • The first study of the interaction of GHB on solid electrodes. • The GHB oxidation process in platinum electrodes is a complex process. • Re-dissolution and reduction of Pt oxides and oxidation of the GHB OH group. • The oxidation process is also influenced by pH and GHB concentration. -- Abstract: The electrooxidation of gamma hydroxybutyric acid (GHB) on a polycrystalline platinum electrode is studied by cyclic voltammetry in acidic medium. Two oxidation peaks, A and B, are obtained in the positive scan within the potential range of the double layer region and of the platinum oxide region, respectively. In the negative going potential sweep an inverted oxidation peak with an onset partially overlapping with the tail of the cathodic peak for the reduction of the platinum oxide formed during the anodic scan is obtained (peak C). This inverted peak can be observed at a potential close to +0.2 V (vs Ag/AgCl at pH 2) and separated 0.4 and 0.8 V from the two other oxidation peaks obtained during the anodic scan and in such conditions that the surface is particularly activated to favour this electrochemical process. The response obtained in the electronic current for the different peaks when GHB concentration and scan rate were changed to allows inferring that these are the result of a potential dependent mechanism. The behaviour observed is according with the oxidation of the alcohol group to the corresponding aldehyde and carboxylic acid (succinic acid) as main products

  9. Multi-metallic Nanomaterials From Ni, Ag, Pd With Pt's Catalytic Activity

    KAUST Repository

    Huang, Kuo-Wei

    2015-06-04

    A trimetallic catalyst that is a combination of nickel, silver and palladium metal is described. The trimetallic catalyst can be used to produce hydrogen and is useful as a replacement for platinum in hydrogenation reactions.

  10. Multi-metallic Nanomaterials From Ni, Ag, Pd With Pt's Catalytic Activity

    KAUST Repository

    Huang, Kuo-Wei; Lai, Zhiping; Hu, Lei

    2015-01-01

    A trimetallic catalyst that is a combination of nickel, silver and palladium metal is described. The trimetallic catalyst can be used to produce hydrogen and is useful as a replacement for platinum in hydrogenation reactions.

  11. Dissolution of Platinum in Hydrochloric Acid Under Industrial-Scale Alternating Current Polarization

    Science.gov (United States)

    Myrzabekov, B. E.; Bayeshov, A. B.; Makhanbetov, A. B.; Mishra, B.; Baigenzhenov, O. S.

    2018-02-01

    The electrochemical behavior of platinum in a hydrochloric acid solution under polarization by an industrial-scale alternating current has been investigated. For the electrical dissolution of platinum, titanium is used as an auxiliary electrode, which increases the yield of platinum dissolution by 12.5 pct. The influence of the concentration of hydrochloric acid, the current densities of the platinum and titanium electrodes, and the temperature of the electrolyte on the efficiency of the process of dissolving platinum have all been studied.

  12. Platinum nanoparticles embedded in layer-by-layer films from SnO{sub 2}/polyallylamine for ethanol electrooxidation

    Energy Technology Data Exchange (ETDEWEB)

    Barretto, Caroline B.; Parreira, Renato L.T.; Goncalves, Rogeria R.; Huguenin, Fritz [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, 14040-901 Ribeirao Preto SP (Brazil); de Azevedo, Dayse C. [NovoCell Energy Systems S.A., 13478-722 Americana SP (Brazil)

    2008-10-15

    Self-assembled films from SnO{sub 2} and polyallylamine (PAH) were deposited on gold via ionic attraction by the layer-by-layer (LbL) method. The modified electrodes were immersed into a H{sub 2}PtCl{sub 6} solution, a current of 100 {mu}A was applied, and different electrodeposition times were used. The SnO{sub 2}/PAH layers served as templates to yield metallic platinum with different particle sizes. The scanning tunnel microscopy images show that the particle size increases as a function of electrodeposition time. The potentiodynamic profile of the electrodes changes as a function of the electrodeposition time in 0.5 mol L{sup -1} H{sub 2}SO{sub 4}, at a sweeping rate of 50 mV s{sup -1}. Oxygen-like species are formed at less positive potentials for the Pt-SnO{sub 2}/PAH film in the case of the smallest platinum particles. Electrochemical impedance spectroscopy measurements in acid medium at 0.7 V show that the charge transfer resistance normalized by the exposed platinum area is 750 times greater for platinum electrode (300 k{omega} cm{sup 2}) compared with the Pt-SnO{sub 2}/PAH film with 1 min of electrodeposition (0.4 k{omega} cm{sup 2}). According to the Langmuir-Hinshelwood bifunctional mechanism, the high degree of coverage with oxygen-like species on the platinum nanoparticles is responsible for the electrocatalytic activity of the Pt-SnO{sub 2}/PAH concerning ethanol electrooxidation. With these features, this Pt-SnO{sub 2}/PAH film may be grown on a proton exchange membrane (PEM) in direct ethanol fuel cells (DEFC). (author)

  13. Effect of coexistent hydrogen isotopes on tracer diffusion of tritium in alpha phase of group-V metal-hydrogen systems

    International Nuclear Information System (INIS)

    Sakamoto, Kan; Hashizume, Kenichi; Sugisaki, Masayasu

    2009-01-01

    Tracer diffusion coefficients of tritium in the alpha phase of group-V metal-hydrogen systems, α-MH(D)xTy (M=V and Ta; x>>y), were measured in order to clarify the effects of coexistent hydrogen isotopes on the tritium diffusion behavior. The hydrogen concentration dependence of such behavior and the effects of the coexistent hydrogen isotopes (protium and deuterium) were determined. The results obtained in the present (for V and Ta) and previous (for Nb) studies revealed that tritium diffusion was definitely dependent on hydrogen concentration but was not so sensitive to the kind of coexistent hydrogen isotopes. By summarizing those data, it was found that the hydrogen concentration dependence of the tracer diffusion coefficient of tritium in the alpha phase of group-V metals could be roughly expressed by a single empirical curve. (author)

  14. Liquid-liquid extraction/separation of platinum(IV) and rhodium(III) from acidic chloride solutions using tri-iso-octylamine

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jin-Young, E-mail: jinlee@kigam.re.kr [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of); Rajesh Kumar, J., E-mail: rajeshkumarphd@rediffmail.com [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of); Kim, Joon-Soo; Park, Hyung-Kyu; Yoon, Ho-Sung [Metals Recovery Department, Minerals Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 92 Gahangno, Yuesong-gu, Daejeon 305-350 (Korea, Republic of)

    2009-08-30

    Liquid-liquid extraction/separation of platinum(IV) and rhodium(III) from acidic chloride solutions was carried out using tri-iso-octylamine (Alamine 308) as an extractant diluted in kerosene. The percentage extraction of platinum(IV) and rhodium(III) increased with increase in acid concentration up to 8 mol L{sup -1}. However, at 10 mol L{sup -1} HCl concentration, the extraction behavior was reversed, indicating the solvation type mechanism during extraction. The quantitative extraction of {approx}98% platinum(IV) and 36% rhodium(III) was achieved with 0.01 mol L{sup -1} Alamine 308. The highest separation factor (S.F. = 184.7) of platinum(IV) and rhodium(III) was achieved with 0.01 mol L{sup -1} Alamine 308 at 1.0 mol L{sup -1} of hydrochloric acid concentration. Alkaline metal salts like sodium chloride, sodium nitrate, sodium thiocyanate, lithium chloride, lithium nitrate, potassium chloride and potassium thiocyanate used for the salting-out effect. LiCl proved as best salt for the extraction of platinum(IV). Temperature effect demonstrates that the extraction process is exothermic. Hydrochloric acid and thiourea mixture proved to be better stripping reagents when compared with other mineral acids and bases.

  15. Platinum dendritic nanoparticles with magnetic behavior

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wenxian, E-mail: wl240@uowmail.edu.au [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); Solar Energy Technologies, School of Computing, Engineering, and Mathematics, University of Western Sydney, Penrith NSW 2751 (Australia); Sun, Ziqi; Nevirkovets, Ivan P.; Dou, Shi-Xue [Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522 (Australia); Tian, Dongliang [Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of the Ministry of Education, School of Chemistry and the Environment, Beihang University, Beijing 100191 (China)

    2014-07-21

    Magnetic nanoparticles have attracted increasing attention for biomedical applications in magnetic resonance imaging, high frequency magnetic field hyperthermia therapies, and magnetic-field-gradient-targeted drug delivery. In this study, three-dimensional (3D) platinum nanostructures with large surface area that features magnetic behavior have been demonstrated. The well-developed 3D nanodendrites consist of plentiful interconnected nano-arms ∼4 nm in size. The magnetic behavior of the 3D dendritic Pt nanoparticles is contributed by the localization of surface electrons due to strongly bonded oxygen/Pluronic F127 and the local magnetic moment induced by oxygen vacancies on the neighboring Pt and O atoms. The magnetization of the nanoparticles exhibits a mixed paramagnetic and ferromagnetic state, originating from the core and surface, respectively. The 3D nanodendrite structure is suitable for surface modification and high amounts of drug loading if the transition temperature was enhanced to room temperature properly.

  16. Superconductivity observed in platinum-silicon interface

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, Pai-Chia, E-mail: paichia@phys.sinica.edu.tw [Research Program on Nanoscience and Nanotechnology, Academia Sinica, Taipei 11529, Taiwan (China); Institute of Physics, Academia Sinica, Taipei 11529, Taiwan (China); Department of Materials Science and Engineering, National Taiwan University, Taipei 10617, Taiwan (China); Chen, Chun-Wei [Department of Materials Science and Engineering, National Taiwan University, Taipei 10617, Taiwan (China); Lee, Ku-Pin; Shiue, Jessie, E-mail: yshiue@phys.sinica.edu.tw [Research Program on Nanoscience and Nanotechnology, Academia Sinica, Taipei 11529, Taiwan (China); Institute of Physics, Academia Sinica, Taipei 11529, Taiwan (China)

    2014-05-26

    We report the discovery of superconductivity with an onset temperature of ∼0.6 K in a platinum-silicon interface. The interface was formed by using a unique focused ion beam sputtering micro-deposition method in which the energies of most sputtered Pt atoms are ∼2.5 eV. Structural and elemental analysis by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy reveal a ∼ 7 nm interface layer with abundant Pt, which is the layer likely responsible for the superconducting transport behavior. Similar transport behavior was also observed in a gold-silicon interface prepared by the same technique, indicating the possible generality of this phenomenon.

  17. A platinum in-core flux detector

    International Nuclear Information System (INIS)

    Shields, R.B.

    1976-01-01

    The performance is described of a platinum emitter self-powered detector having the following parameters: emitter diameter 0.51 mm, Inconel 600 collector of 1.5 mm outer diameter and 0.25 mm wall thickness, compacted powder MgO insulant, thermal neutron flux 10 14 n.cm -2 .s -1 and gamma radiation dose rate 1.2 x 10 8 rad.h -1 . The advantage of the detector is its sensitivity to both neutrons and gamma radiation. A comparison is made with other types of detectors using Ce, Ta, Os, Rh, V, Co, Zr as emitters, especially in relation to the emitter response time to neutrons or gammas, the output signal amplitude, sensitivity, and the emitter half-life. Extensive tests of the detectors proceeded for two years on the NRU and CANDU-BLW reactors in Gentilly, Canada. (J.B.)

  18. Platinum dendritic nanoparticles with magnetic behavior

    International Nuclear Information System (INIS)

    Li, Wenxian; Sun, Ziqi; Nevirkovets, Ivan P.; Dou, Shi-Xue; Tian, Dongliang

    2014-01-01

    Magnetic nanoparticles have attracted increasing attention for biomedical applications in magnetic resonance imaging, high frequency magnetic field hyperthermia therapies, and magnetic-field-gradient-targeted drug delivery. In this study, three-dimensional (3D) platinum nanostructures with large surface area that features magnetic behavior have been demonstrated. The well-developed 3D nanodendrites consist of plentiful interconnected nano-arms ∼4 nm in size. The magnetic behavior of the 3D dendritic Pt nanoparticles is contributed by the localization of surface electrons due to strongly bonded oxygen/Pluronic F127 and the local magnetic moment induced by oxygen vacancies on the neighboring Pt and O atoms. The magnetization of the nanoparticles exhibits a mixed paramagnetic and ferromagnetic state, originating from the core and surface, respectively. The 3D nanodendrite structure is suitable for surface modification and high amounts of drug loading if the transition temperature was enhanced to room temperature properly.

  19. Cobalt- and platinum-rich ferromanganese crusts and associated substrate rocks from the Marshall Islands

    Science.gov (United States)

    Hein, J.R.; Schwab, W.C.; Davis, A.

    1988-01-01

    Ferromanganese crusts cover most hard substrates on seafloor edifices in the central Pacific basin. Crust samples and their associated substrates from seven volcanic edifices of Cretaceous age along the Ratak chain of the Marshall Islands are discussed. The two most abundant substrate lithologies recovered were limestone, dominantly fore-reef slope deposits, and volcanic breccia composed primarily of differentiated alkalic basalt and hawaiite clasts in a phosphatized carbonate matrix. The degree of mass wasting on the slopes of these seamounts is inversely correlated with the thickness of crusts. Crusts are generally thin on limestone substrate. Away from areas of active mass-wasting processes, and large atolls, crusts may be as thick as 10 cm maximum. The dominant crystalline phase in the Marshall Islands crusts is ??-MnO2 (vernadite). High concentrations of cobalt, platinum and rhodium strongly suggest that the Marshall Islands crusts are a viable source for these important metals. Many metals and the rare earth elements vary significantly on a fine scale through most crusts, thus reflecting the abundances of different host mineral phases in the crusts and changes in seawater composition with time. High concentrations of cobalt, nickel, titanium, zinc, lead, cerium and platinum result from a combination of their substitution in the iron and manganese phases and their oxidation potential. ?? 1988.

  20. Design, synthesis and DNA interactions of a chimera between a platinum complex and an IHF mimicking peptide.

    Science.gov (United States)

    Rao, Harita; Damian, Mariana S; Alshiekh, Alak; Elmroth, Sofi K C; Diederichsen, Ulf

    2015-12-28

    Conjugation of metal complexes with peptide scaffolds possessing high DNA binding affinity has shown to modulate their biological activities and to enhance their interaction with DNA. In this work, a platinum complex/peptide chimera was synthesized based on a model of the Integration Host Factor (IHF), an architectural protein possessing sequence specific DNA binding and bending abilities through its interaction with a minor groove. The model peptide consists of a cyclic unit resembling the minor grove binding subdomain of IHF, a positively charged lysine dendrimer for electrostatic interactions with the DNA phosphate backbone and a flexible glycine linker tethering the two units. A norvaline derived artificial amino acid was designed to contain a dimethylethylenediamine as a bidentate platinum chelating unit, and introduced into the IHF mimicking peptides. The interaction of the chimeric peptides with various DNA sequences was studied by utilizing the following experiments: thermal melting studies, agarose gel electrophoresis for plasmid DNA unwinding experiments, and native and denaturing gel electrophoresis to visualize non-covalent and covalent peptide-DNA adducts, respectively. By incorporation of the platinum metal center within the model peptide mimicking IHF we have attempted to improve its specificity and DNA targeting ability, particularly towards those sequences containing adjacent guanine residues.

  1. Procedure of Destructive Chemical Recovery of Precious Metals in Nitric Acid Production

    Directory of Open Access Journals (Sweden)

    Ljubičić, M.

    2012-07-01

    Full Text Available The heart of the nitric acid production process is the chemical reactor containing a platinum-based catalyst pack and an associated catchment system, which allows the ammonia oxidation reaction to take place efficiently. Under the severe operating conditions imposed by the high-pressure ammonia oxidation process, the catalyst gauzes experience progressive deterioration, as shown by the restricted surface of the catalyst wires, the loss of catalytic activity and the loss of catalytic materials. The higher the pressure of gaseous ammonia oxidation, the greater the loss of platinum group metals from the surface of the applied selective heterogeneous catalysts. Total losses for one batch over the whole period of using selective heterogeneous catalysts may account in the range from 20 to 40 % of the total installed quantity of precious metals. An important part of the platinum removed from the platinum-rhodium alloy wires can be recovered at the outlet of the reactor by means of palladium catchment gauzes. However, this catchment process, which is based on the great ability of palladium to alloy with platinum, is not 100 % effective and a fraction of the platinum and practically all of the rhodium lost by the catalyst wires, evades the catchment package and is then deposited in other parts of the plant, especially heat exchangers. From the above mentioned operating equipment, the retained mass of precious metals can be recovered by the technical procedure of non-destructive and destructive chemical solid-liquid extraction.Shown is the technical procedure of destructive chemical recovery of preheater and boiler for preheating and production of steam by applying sulfuric acid (w = 20 % and subsequent procedure of raffination of derived sludge, to the final recovery of precious metals. The technical procedure of destructive chemical recovery of precious metals from preheater and boiler for preheating and production of steam in nitric acid production is

  2. Spatial and temporal distribution of platinum, palladium and rhodium in Zagreb air.

    Science.gov (United States)

    Rinkovec, Jasmina; Pehnec, Gordana; Godec, Ranka; Davila, Silvije; Bešlić, Ivan

    2018-09-15

    Platinum (Pt), palladium (Pd) and rhodium (Rh) are most widely used in the production of automotive catalytic converters that serve to reduce toxic emissions from motor vehicles. The aim of this study was to quantitatively determine the levels of platinum, palladium and rhodium in the PM 10 and PM 2.5 fraction of airborne particle matter and find their spatial and temporal distribution at different polluted areas of the city of Zagreb, Croatia. The method used in this paper included weekly sampling of airborne particle matter on quartz filters, microwave digestion in acid under high pressure and temperature, and analysis by inductively coupled plasma mass spectrometry (ICP MS). The results have shown that the highest mean values at all three sampling stations (North, Center, South) were obtained for palladium (3.856 pg m -3 , 5.396 pg m -3 , 5.600 pg m -3 ) and the lowest for rhodium (0.444 pg m -3 , 0.643 pg m -3 , 0.750 pg m -3 ). The average mass concentrations of platinum group elements (PGE) in PM 10 increased for all three elements in the direction North Zagreb are the first results of their kind for this area and will provide insights into the contribution of catalytic converters to the presence of these elements in the environment. Copyright © 2018 Elsevier B.V. All rights reserved.

  3. Wireless gas sensing in South African underground platinum mines

    CSIR Research Space (South Africa)

    Abu-Mahfouz, Adnan M

    2014-04-01

    Full Text Available Approximately 70% of South African mines are classified as fiery, where methane gas potentially could cause explosions. The number of flammable gas reports and accidents are increasing steadily for both gold and platinum mines. However...

  4. Nanoparticulate platinum films on gold using dendrimer-based wet ...

    Indian Academy of Sciences (India)

    Central Electrochemical Research Institute, Karaikudi 630 006, India. E-mail: ... deposition methods for applications involving thin films, e.g., catalysis. Deposition of platinum .... The spectrum recorded at 0.3 V shows a mixed control behaviour ...

  5. Study of dopamine reactivity on platinum single crystal electrode surfaces

    International Nuclear Information System (INIS)

    Chumillas, Sara; Figueiredo, Marta C.; Climent, Víctor; Feliu, Juan M.

    2013-01-01

    Dopamine is the biological molecule responsible, among other functions, of the heart beat and blood pressure regulation. Its loss, in the human body, can result in serious diseases such as Parkinson's, schizophrenia or depression. Structurally, this molecule belongs to the group of catecholamines, together with epinephrine (adrenaline) and norepinephrine (noradrenaline). The hydroquinone moiety of the molecule can be easily oxidized to quinone, rendering the electrochemical methods a convenient approach for the development of dopamine biosensors. The reactivity of similar aromatic molecules, such as catechol and hydroquinone, at well-ordered platinum surfaces, has recently been investigated in our group. In this paper, we extend these studies to the structurally related molecule dopamine. The study has been performed in neutral pH, since this is closer to the natural conditions for these molecules in biological media. Cyclic voltammetry and in situ infra-red spectroscopy have been combined to extract information about the behavior of this molecule on well-defined platinum surfaces. Dopamine appears to be electrochemically active and reveals interesting adsorption phenomena at low potentials (0.15–0.25 V vs RHE), sensitive to the single crystal orientation. The adsorption of dopamine on these surfaces is very strong, taking place at much lower potentials than the electron transfer from solution species. Specifically, the voltammetry of Pt(1 1 1) and Pt(1 0 0) in dopamine solutions shows an oxidation peak at potentials close to the onset of hydrogen evolution, which is related to the desorption of hydrogen and the adsorption of dopamine. On the other hand, adsorption on Pt(1 1 0) is irreversible and the surface appears totally blocked. Spectroscopic results indicate that dopamine is adsorbed flat on the surface. At potentials higher than 0.6 V vs RHE the three basal planes show a common redox process. The initial formation of the quinone moiety is followed by a

  6. Platinum stable isotope analysis of geological standard reference materials by double-spike MC-ICPMS.

    Science.gov (United States)

    Creech, J B; Baker, J A; Handler, M R; Bizzarro, M

    2014-01-10

    We report a method for the chemical purification of Pt from geological materials by ion-exchange chromatography for subsequent Pt stable isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using a 196 Pt- 198 Pt double-spike to correct for instrumental mass bias. Double-spiking of samples was carried out prior to digestion and chemical separation to correct for any mass-dependent fractionation that may occur due to incomplete recovery of Pt. Samples were digested using a NiS fire assay method, which pre-concentrates Pt into a metallic bead that is readily dissolved in acid in preparation for anion-exchange chemistry. Pt was recovered from anion-exchange resin in concentrated HNO 3 acid after elution of matrix elements, including the other platinum group elements (PGE), in dilute HCl and HNO 3 acids. The separation method has been calibrated using a precious metal standard solution doped with a range of synthetic matrices and results in Pt yields of ≥90% with purity of ≥95%. Using this chemical separation technique, we have separated Pt from 11 international geological standard reference materials comprising of PGE ores, mantle rocks, igneous rocks and one sample from the Cretaceous-Paleogene boundary layer. Pt concentrations in these samples range from ca. 5 ng g -1 to 4 μg g -1 . This analytical method has been shown to have an external reproducibility on δ 198 Pt (permil difference in the 198 Pt/ 194 Pt ratio from the IRMM-010 standard) of ±0.040 (2 sd) on Pt solution standards (Creech et al., 2013, J. Anal. At. Spectrom. 28, 853-865). The reproducibility in natural samples is evaluated by processing multiple replicates of four standard reference materials, and is conservatively taken to be ca. ±0.088 (2 sd). Pt stable isotope data for the full set of reference materials have a range of δ 198 Pt values with offsets of up to 0.4‰ from the IRMM-010 standard, which are readily resolved with this technique. These

  7. Determination of microquantities of silver in platinum by isotope dilution

    International Nuclear Information System (INIS)

    Yedinakova, V.; Sladkovska, Y.

    1980-01-01

    A method is described for determining microquantities of silver in platinum. It is based on isotope dilution by means of substoichiometric extraction of dithizonates with carbon tetrachloride. The determination of silver according to this technique is not interfered by zinc or gold in quantities exceeding the silver content by one order of magnitude nor by a great excess of platinum. In the presence of copper the addition of complexon is necessary. (author)

  8. Platinum-Bismuth Bimetallic Catalysts: Synthesis, Characterization and Applications

    OpenAIRE

    Saucedo, Jose A, Jr; Xiao, Yang; Varma, Arvind

    2015-01-01

    Bimetallic catalysts have been explored and shown to exhibit unique characteristics which are not present in monometallic catalysts. Platinum is well known as an effective catalyst for oxidation and reduction reactions, and it can be made more effective when bismuth is introduced as a promotor. Thus, the effectiveness of the Pt-Bi catalyst was demonstrated in prior work. What is not clear, however, is the mechanism behind the catalyst function; why addition of bismuth to platinum decreases de...

  9. Growth of uniform nanoparticles of platinum by an economical approach at relatively low temperature

    KAUST Repository

    Shah, M.A.

    2012-01-01

    Current chemical methods of synthesis have shown limited success in the fabrication of nanomaterials, which involves environmentally malignant chemicals. Environmental friendly synthesis requires alternative solvents, and it is expected that the use of soft options of green approaches may overcome these obstacles. Water, which is regarded as a benign solvent, has been used in the present work for the preparation of platinum nanoparticles. The average particle diameter is in the range of ∼13±5 nm and particles are largely agglomerated. The advantages of preparing nanoparticles with this method include ease, flexibility and cost effectiveness. The prospects of the process are bright, and the technique could be extended to prepare many other important metal and metal oxide nanostructures. © 2012 Sharif University of Technology. Production and hosting by Elsevier B.V. All rights reserved.

  10. Growth of uniform nanoparticles of platinum by an economical approach at relatively low temperature

    KAUST Repository

    Shah, M.A.

    2012-06-01

    Current chemical methods of synthesis have shown limited success in the fabrication of nanomaterials, which involves environmentally malignant chemicals. Environmental friendly synthesis requires alternative solvents, and it is expected that the use of soft options of green approaches may overcome these obstacles. Water, which is regarded as a benign solvent, has been used in the present work for the preparation of platinum nanoparticles. The average particle diameter is in the range of ∼13±5 nm and particles are largely agglomerated. The advantages of preparing nanoparticles with this method include ease, flexibility and cost effectiveness. The prospects of the process are bright, and the technique could be extended to prepare many other important metal and metal oxide nanostructures. © 2012 Sharif University of Technology. Production and hosting by Elsevier B.V. All rights reserved.

  11. Platinum-gold nanoclusters as catalyst for direct methanol fuel cells.

    Science.gov (United States)

    Giorgi, L; Giorgi, R; Gagliardi, S; Serra, E; Alvisi, M; Signore, M A; Piscopiello, E

    2011-10-01

    Nanosized platinum-gold alloys clusters have been deposited on gas diffusion electrode by sputter deposition. The deposits were characterized by FE-SEM, TEM and XPS in order to verify the formation of alloy nanoparticles and to study the influence of deposition technique on the nanomorphology. The deposition by sputtering process allowed a uniform distribution of metal particles on porous surface of carbon supports. Typical island growth mode was observed with the formation of a dispersed metal nanoclusters (mean size about 5 nm). Cyclic voltammetry was used to determine the electrochemical active surface and the electrocatalytic performance of the PtAu electrocatalysts for methanol oxidation reaction. The data were re-calculated in the form of mass specific activity (MSA). The sputter-catalyzed electrodes showed higher performance and stability compared to commercial catalysts.

  12. Effect of titania on the characteristics of a Tin-Platinum catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Morales-Gil, P., E-mail: moralesp@imp.mx; Nava, N. [Instituto Mexicano del Petróleo (Mexico); Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Físicas (Brazil)

    2015-06-15

    Pt-Sn bimetallic catalysts dispersed on alumina are commonly used for reforming and dehydrogenation reactions. In this research work, Pt and Sn were supported on titania. The resulting interactions between the components in the prepared samples, before and after treatment with hydrogen, were studied by Mössbauer spectroscopy, X-ray diffraction and Rietveld refinement. The results show the presence of Pt and SnO{sub 2} after calcinations. After the reduction process, metallic Pt, PtSn, and Pt{sub 3}Sn alloys were identified. The Rietveld refinement analysis shows that some Ti{sup 4+} atoms were replaced by Sn{sup 4+} atoms in the titania structure. Finally, the Mössbauer spectroscopy and X-ray diffraction results indicate that metallic platinum and SnO{sub 2} are encapsulated by a TiOx layer.

  13. Exosomes as mediators of platinum resistance in ovarian cancer.

    Science.gov (United States)

    Crow, Jennifer; Atay, Safinur; Banskota, Samagya; Artale, Brittany; Schmitt, Sarah; Godwin, Andrew K

    2017-02-14

    Exosomes have been implicated in the cell-cell transfer of oncogenic proteins and genetic material. We speculated this may be one mechanism by which an intrinsically platinum-resistant population of epithelial ovarian cancer (EOC) cells imparts its influence on surrounding tumor cells. To explore this possibility we utilized a platinum-sensitive cell line, A2780 and exosomes derived from its resistant subclones, and an unselected, platinum-resistant EOC line, OVCAR10. A2780 cells demonstrate a ~2-fold increase in viability upon treatment with carboplatin when pre-exposed to exosomes from platinum-resistant cells as compared to controls. This coincided with increased epithelial to mesenchymal transition (EMT). DNA sequencing of EOC cell lines revealed previously unreported somatic mutations in the Mothers Against Decapentaplegic Homolog 4 (SMAD4) within platinum-resistant cells. A2780 cells engineered to exogenously express these SMAD4 mutations demonstrate up-regulation of EMT markers following carboplatin treatment, are more resistant to carboplatin, and release exosomes which impart a ~1.7-fold increase in resistance in naive A2780 recipient cells as compared to controls. These studies provide the first evidence that acquired SMAD4 mutations enhance the chemo-resistance profile of EOC and present a novel mechanism in which exchange of tumor-derived exosomes perpetuates an EMT phenotype, leading to the development of subpopulations of platinum-refractory cells.

  14. High performance platinum single atom electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

    2017-07-01

    For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

  15. Structure-activity relationships of carbon-supported platinum-bismuth and platinum-antimony oxidation catalysts

    CSIR Research Space (South Africa)

    Maphoru, MV

    2017-04-01

    Full Text Available Compositional and morphological studies on supported platinum are important for the improvement and expanded use of catalysts for oxidative coupling reactions. Nanocomposites consisting of 5% Pt supported on activated carbon and promoted with 5% Bi...

  16. Synthesis of main group, rare-earth, and d{sup 0} metal complexes containing beta-hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Ka King [Iowa State Univ., Ames, IA (United States)

    2013-01-01

    A series of organometallic compounds containing the tris(dimethylsilyl)methyl ligand are described. The potassium carbanions KC(SiHMe2)3 and KC(SiHMe2})3TMEDA are synthesized by deprotonation of the hydrocarbon HC(SiHMe2)3 with potassium benzyl. KC(SiHMe2)3TMEDA crystallizes as a dimer with two types of three-center-two-electron KH- Si interactions. Homoleptic Ln(III) tris(silylalkyl) complexes containing β-SiH groups M{C(SiHMe2)3}3 (Ln = Y, Lu, La) are synthesized from salt elimination of the corresponding lanthanide halide and 3 equiv. of KC(SiHMe2)3. The related reactions with Sc yield bis(silylalkyl) ate-complexes containing either LiCl or KCl. The divalent calcium and ytterbium compounds M{C(SiHMe2)3}2L (M = Ca, Yb; L = THF2 or TMEDA) are prepared from MI2 and 2 equiv of KC(SiHMe2)3. The compounds M{C(SiHMe2)3}2L (M = Ca, Yb; L = THF2 or TMEDA) and La{C(SiHMe2)3}3 react with 1 equiv of B(C6F5)3 to give 1,3- disilacyclobutane {Me2Si-C(SiHMe2)2}2 and MC(SiHMe2)3HB(C6F5)3L, and La{C(SiHMe2)3}2HB(C6F5)3, respectively. The corresponding reactions of Ln{C(SiHMe2)3}3 (Ln = Y, Lu) give the β-SiH abstraction product [{(Me2HSi)3C}2LnC(SiHMe2)2SiMe2][HB(C6F5)3] (Ln = Y, Lu), but the silene remains associated with the Y or Lu center. The abstraction reactions of M{C(SiHMe2)3}2L (M = Ca, Yb; L = THF2or TMEDA) and Ln{C(SiHMe2)3}3 (Ln = Y, Lu, La) and 2 equiv of B(C6

  17. Thin-layer chromatography of ternary complexes of group-IIIA metals with 2-thenoyltrifluoroacetone and 2,2'-bipyridyl on cellulose layer

    Energy Technology Data Exchange (ETDEWEB)

    Chao, H E; Saitoh, K; Suzuki, N [Tohoku Univ., Sendai (Japan). Faculty of Science

    1980-11-11

    Normal phase thin-layer chromatographic behaviour of several ternary complexes of group-IIIA metals with 2-thenoyltrifluoroacetone (TTA) and 2,2'bipyridyl (bpy) has been investigated on cellulose layer. The ternary complexes of lanthanide metals show higher mutual separability than the complexes with TTA alone. Mutual separation of TTA complexes with La(III), Ce(III), Eu(III) or Y(III), Sc(III), Th(IV), and U(VI) has been successfully achieved by two-dimensional TLC, primarily with carbon tetrachloride-benzene (75:25) containing 0.02M TTA, and secondary with carbon tetrachloride-hexane (35:65) containing both 0.02M TTA and 0.02M bpy.

  18. Synthesis and characterization of near-IR absorbing metal-free and zinc(II phthalocyanines modified with aromatic azo groups

    Directory of Open Access Journals (Sweden)

    Mukaddes Özçeşmeci

    2015-05-01

    Full Text Available Metal-free and zinc(II phthalocyanine complexes bearing peripheral (E-4-((2-hydroxynaphthalen-1-yldiazenyl units have been synthesized. Novel phthalonitrile derivative required for the preparation of phthalocyanine complexes was prepared by coupling 4-aminophthalonitrile and 2-naphthol. The structures of these new compounds were characterized by using elemental analyses, proton nuclear magnetic resonance, fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, fluorescence spectroscopy and mass spectrometry. In the UV-Vis spectra a broad absorption band appears for phthalocyanine complexes at around 450–500 nm resulting from azo-group introduced onto the phthalocyanine ring. The photophysical properties of metal-free and zinc(II phthalocyanines were studied in tetrahydrofuran.

  19. Morphology Control of Platinum Nanoparticles and their Catalytic Properties

    International Nuclear Information System (INIS)

    Miyazaki, Akane; Balint, Ioan; Nakano, Yoshio

    2003-01-01

    Platinum nanoparticles with different morphology were prepared by reduction of K 2 PtCl 4 solution in the presence of different capping polymers. It was found that the shapes and the sizes of the Pt nanocrystals resulted were related to the kind of capping polymer used. When poly(vinylpyrrolidon) (PVP), poly(N-isopropylacrylamide) (NIPA) and sodium poly(acrylate) (SPA) were used as capping agents, the dominant shapes of the Pt nanocrystals observed by transmission electron microscopy were hexagonal (∼62%), square (∼67%) and triangular (∼41%), respectively. The average sizes of Pt nanocrystals were 6.9, 13.6 and 14.6 nm for capping polymers of PVP, NIPA and SPA, respectively. The colloidal Pt nanoparticles with different morphologies were supported on γ-Al 2 O 3 (1 wt.% Pt) and then their catalytic activity for NO reduction by CH 4 was tested in the 350-600 deg. C temperature range. Additionally, the catalytic activities of these alumina-supported Pt nanocrystals were compared with a conventional catalyst having the average size of Pt particles of ∼2.4 nm. Over the alumina-supported Pt nanocrystals as compared with the conventional Pt/Al 2 O 3 , it was observed that the NO/CH 4 reaction yields to NH 3 and CO decreased significantly and on the other hand, the yield to N 2 O increased. The experimental results are suggesting that the catalytic behavior can be tuned in a convenient way through the morphological control of the metal nanoparticles

  20. Morphology Control of Platinum Nanoparticles and their Catalytic Properties

    Energy Technology Data Exchange (ETDEWEB)

    Miyazaki, Akane [Tokyo Institute of Technology, Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Technology (Japan)], E-mail: akanem@chemenv.titech.ac.jp; Balint, Ioan [Institute of Physical Chemistry, Romanian Academy (Romania); Nakano, Yoshio [Tokyo Institute of Technology, Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of Science and Technology (Japan)

    2003-04-15

    Platinum nanoparticles with different morphology were prepared by reduction of K{sub 2}PtCl{sub 4} solution in the presence of different capping polymers. It was found that the shapes and the sizes of the Pt nanocrystals resulted were related to the kind of capping polymer used. When poly(vinylpyrrolidon) (PVP), poly(N-isopropylacrylamide) (NIPA) and sodium poly(acrylate) (SPA) were used as capping agents, the dominant shapes of the Pt nanocrystals observed by transmission electron microscopy were hexagonal ({approx}62%), square ({approx}67%) and triangular ({approx}41%), respectively. The average sizes of Pt nanocrystals were 6.9, 13.6 and 14.6 nm for capping polymers of PVP, NIPA and SPA, respectively. The colloidal Pt nanoparticles with different morphologies were supported on {gamma}-Al{sub 2}O{sub 3} (1 wt.% Pt) and then their catalytic activity for NO reduction by CH{sub 4} was tested in the 350-600 deg. C temperature range. Additionally, the catalytic activities of these alumina-supported Pt nanocrystals were compared with a conventional catalyst having the average size of Pt particles of {approx}2.4 nm. Over the alumina-supported Pt nanocrystals as compared with the conventional Pt/Al{sub 2}O{sub 3}, it was observed that the NO/CH{sub 4} reaction yields to NH{sub 3} and CO decreased significantly and on the other hand, the yield to N{sub 2}O increased. The experimental results are suggesting that the catalytic behavior can be tuned in a convenient way through the morphological control of the metal nanoparticles.