Science.gov

Sample records for metals palladium platinum

  1. Noble Metal Catalysts for Mercury Oxidation in Utility Flue Gas: Gold, Palladium and Platinum Formulations

    SciTech Connect

    Presto, A.A.; Granite, E.J

    2008-07-01

    The use of noble metals as catalysts for mercury oxidation in flue gas remains an area of active study. To date, field studies have focused on gold and palladium catalysts installed at pilot scale. In this article, we introduce bench-scale experimental results for gold, palladium and platinum catalysts tested in realistic simulated flue gas. Our initial results reveal some intriguing characteristics of catalytic mercury oxidation and provide insight for future research into this potentially important process.

  2. PLATINUM-GROUP METALS

    EPA Science Inventory

    The document assembles, organizes, and evaluates all pertinent information (up to April 1976) about the effects on man and his environment that result either directly or indirectly from pollution by platinum-group metals: iridium (Ir), osmium (Os), palladium (Pd), platinum (Pt), ...

  3. Preparation of highly reactive metal powders: preparation, characterization, and chemistry of iron, cobalt, nickel, palladium, and platinum microparticles

    SciTech Connect

    Kavaliunas, A.V.; Taylor, A.; Rieke, R.D.

    1983-01-01

    Anhydrous metal halides of iron cobalt, nickel, palladium, and platinum are readily reduced in glyme or tetra-hydro-furan (THF) with lithium in the presence of a small amount of naphthalene and yield finely divided, black metal powders of exceptional reactivity. Metal powders of Fe and Co react with C/sub 6/F/sub 5/X (X = Br, I) to yield solvated M(C/sub 6/F/sub 5/)/sub 2/ and MX/sub 2/. Powders of palladium and platinum react with C/sub 6/F/sub 5/I to yield solvated M(C/sub 6/F/sub 5/)I (M = Pd, Pt). Nickel powder reacts with C/sub 6/F/sub 5/I to yield the solvated species Ni(C/sub 6/F/sub 5/)/sub 2/ and NiI/sub 2/, however, with C/sub 6/F/sub 5/Br the product is solvated Ni(C/sub 6/F/sub 5/)Br. In most cases the metal powders are sufficiently reactive that a stoichiometric amount of C/sub 6/F/sub 5/X to the metal powder is used. The coordinated ether of all of these organometallic compounds is exceptionally labile and is displaced with a variety of ligands: phosphines, amines, sulfides, isocyanides, diolefins, and carbon monoxide. Many of the resultant compounds are novel and most are obtained in high yields. Palladium metal powder to which has been added 2,2'-bipyridine (bpy) reacts with iodobenzene to yield Pd(C/sub 6/H/sub 5/)I(bpy). Surface analyses including ESCA (electron spectroscopy) and BET were performed on the highly reactive Ni, Pt, and Pd metal powders. 32 references, 4 tables.

  4. Relevance and analysis of traffic related platinum group metals (Pt, Pd, Rh) in the aquatic biosphere, with emphasis on palladium.

    PubMed

    Sures, Bernd; Zimmermann, Sonja; Messerschmidt, Jürgen; von Bohlen, Alex

    2002-10-01

    Following the introduction of automobile catalysts in the middle of the Eighties in Germany there is an increasing emission of the platinum-group-metals (PGM) platinum (Pt), palladium (Pd) and rhodium (Rh). Still, it remains unclear if these metals are bioavailable for aquatic animals and to which extent they accumulate in the aquatic biosphere. Zebra mussels (Dreissena polymorpha) were maintained in water containing road dust at a concentration of 1 kg/10 l. Following an exposure period of 26 weeks, soft tissues of the mussels were analysed applying adsorptive cathodic stripping voltammetry (ACSV) for the determination of Pt and Rh and total-reflection X-ray fluorescence analysis after co-precipitation of Pd with mercury. This experiment revealed for the first time that all the three catalyst emitted metals were accumulated by mussels. The bioaccumulation increased in the following manner: Rh < Pt < Pd. Thus, the application of sentinel organisms in combination with modern trace analytical procedures in environmental impact studies does allow an assessment of the distribution and the degree of bioaccumulation of PGM in the environment, which is highly appreciated. PMID:12463686

  5. Biological availability of traffic-related platinum-group elements (palladium, platinum, and rhodium) and other metals to the zebra mussel (Dreissena polymorpha) in water containing road dust.

    PubMed

    Zimmermann, Sonja; Alt, Friedrich; Messerschmidt, Jürgen; von Bohlen, Alex; Taraschewski, Horst; Sures, Bernd

    2002-12-01

    The uptake and bioaccumulation of 15 road dust metals by the zebra mussel (Dreissena polymorpha) were investigated in laboratory exposure studies with emphasis on the traffic-related platinum-group elements (PGEs) palladium (Pd), platinum (Pt), and rhodium (Rh). The biological availability of the metals may depend on water characteristics, so the mussels were maintained in two types of water: nonchlorinated tap water and humic water of a bog lake, both of which contained dust of a moderately frequented road. After an exposure period of 26 weeks, soft tissues of the mussels were freeze-dried and analyzed for the metals. The metal concentrations in the mussel soft tissue ranged from several hundred micrograms per gram (e.g., for iron [Fe]) to less than 10 ng/g (for PGEs). Metal uptake from the road dust by the mussels was found for the PGEs and silver (Ag), bismuth (Bi), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), Fe, lead (Pb), and antimony (Sb). After maintenance of mussels in road dust-contaminated tap water, bioaccumulation factors (BAF = (C(exposed mussels) - C(control mussels))/C(total metal, water), where c is concentration) decreased in the following order: Cu > Cd > Ag > Pd > Sb > Pb > Fe > Pt > Rh. The biological availability of most metals was enhanced by humic water as compared to tap water. Our results show a hitherto unrecognized high availability of Pd for the mussels. Thus, this metal should be monitored more intensively in the environment to assess its distribution in the biosphere. PMID:12463569

  6. Mineral resource of the month: platinum-group metals

    USGS Publications Warehouse

    Hilliard, Henry

    2003-01-01

    The precious metals commonly referred to as platinum-group metals (PGM) include iridium, osmium, palladium, platinum, rhodium and ruthenium. PGM are among the rarest of elements, and their market values — particularly for palladium, platinum and rhodium — are the highest of all precious metals.

  7. Monodisperse colloidal metal particle from nonaqueous solutions: catalytic behavior in hydrogenation of but-1-ene of platinum, palladium, and rhodium particles supported on pumice

    SciTech Connect

    Boutonnet, M.; Kizling, J.; Mintsa-Eya, V.; Choplin, A.; Touroude, R.; Maire, G.; Stenius, P.

    1987-01-01

    Metal catalysts have been prepared by depositing monodisperse particles of platinum (2-3 nm), rhodium (2-3 nm), or palladium (5 nm) prepared in reversed micellar solutions on pumice. The particles are well dispersed on the support whereas particles deposited from aqueous or alcoholic solution give large aggregates. The catalytic properties of these different catalysts in the deuteration, isomerization, and hydrogen-deuterium exchange of but-1-ene have been compared. The activities calculated per metal surface atom are similar. However, platinum prepared from microemulsions show unusually high selectivity in the isomerization reaction, and for such particles dehydrogenated species are active in the exchange reaction. The specificity of rhodium and palladium catalysts is independent of the mode of preparation. The reaction mechanisms are discussed.

  8. Platinum-ruthenium-palladium fuel cell electrocatalyst

    DOEpatents

    Gorer, Alexander

    2006-02-07

    A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum at a concentration that is between about 20 and about 60 atomic percent, ruthenium at a concentration that is between about 20 and about 60 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having an atomic ratio of platinum to ruthenium that is between about 0.7 and about 1.2. Alternatively, the catalyst may contain platinum at a concentration that is between about 25 and about 50 atomic percent, ruthenium at a concentration that is between about 25 and about 55 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having a difference between the concentrations of ruthenium and platinum that is no greater than about 20 atomic percent.

  9. Platinum-ruthenium-palladium alloys for use as a fuel cell catalyst

    DOEpatents

    Gorer, Alexander

    2002-01-01

    A noble metal alloy composition for a fuel cell catalyst, a ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

  10. Determination of palladium and platinum by atomic absorption

    USGS Publications Warehouse

    Schnepfe, M.M.; Grimaldi, F.S.

    1969-01-01

    Palladium and platinum are determined by atomic absorption after fire-assay concentration into a gold bead. The limit of determination is ~0??06 ppm in a 20-g sample. Serious depressive interelement interferences are removed by buffering the solutions with a mixture of cadmium and copper sulphates with cadmium and copper concentrations each at 0??5%. Substantial amounts of Ag, Al, Au, Bi, Ca, Co, Cr, Fe, Hg, K, La, Mg, Mn, Mo, Na, Ni, Pb, Te, Ti, V, Y, Zn, and the platinum metals do not interfere in the atomic-absorption determination. ?? 1969.

  11. Accumulation of the precious metals platinum, palladium and rhodium from automobile catalytic converters in Paratenuisentis ambiguus as compared with its fish host, Anguilla anguilla.

    PubMed

    Zimmermann, S; von Bohlen, A; Messerschmidt, J; Sures, B

    2005-03-01

    The platinum group metals (PGM) Pt, Pd and Rh are emitted into the environment mainly by catalytic exhaust gas converters of cars. As PGM accumulate in sediments of aquatic ecosystems, the study was focused on the uptake of the noble metals by European eels, Anguilla anguilla infected with the acanthocephalan Paratenuisentis ambiguus. Eels were exposed to ground catalytic converter material for six weeks. After exposure Pt and Pd were detected in the liver and kidney of the eels and in the parasites. Palladium was also found in fish muscle and intestine. No Rh uptake by the eel tissues and the parasites occurred. Paratenuisentis ambiguus contained the highest levels of both metals with 40 times higher Pt concentrations and four times higher Pd concentrations than the liver of its host. Due to its accumulation capacity for PGM, P. ambiguus can be applied as a sensitive accumulation indicator in field studies to assess the degree of environmental PGM contamination in aquatic ecosystems. PMID:15831118

  12. Platinum- and platinum alloy-coated palladium and palladium alloy particles and uses thereof

    DOEpatents

    Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir Branko

    2010-04-06

    The present invention relates to particle and nanoparticle composites useful as oxygen-reduction electrocatalysts. The particle composites are composed of a palladium or palladium-alloy particle or nanoparticle substrate coated with an atomic submonolayer, monolayer, bilayer, or trilayer of zerovalent platinum atoms. The invention also relates to a catalyst and a fuel cell containing the particle or nanoparticle composites of the invention. The invention additionally includes methods for oxygen reduction and production of electrical energy by using the particle and nanoparticle composites of the invention.

  13. Luminescent Cyclometalated Platinum and Palladium Complexes with Novel Photophysical Properties

    NASA Astrophysics Data System (ADS)

    Turner, Eric

    Organic light emitting diodes (OLEDs) is a rapidly emerging technology based on organic thin film semiconductors. Recently, there has been substantial investment in their use in displays. In less than a decade, OLEDs have grown from a promising academic curiosity into a multi-billion dollar global industry. At the heart of an OLED are emissive molecules that generate light in response to electrical stimulation. Ideal emitters are efficient, compatible with existing materials, long lived, and produce light predominantly at useful wavelengths. Developing an understanding of the photophysical processes that dictate the luminescent properties of emissive materials is vital to their continued development. Chapter 1 and Chapter 2 provide an introduction to the topics presented and the laboratory methods used to explore them. Chapter 3 discusses a series of tridentate platinum complexes. A synthetic method utilizing microwave irradiation was explored, as well as a study of the effects ligand structure had on the excited state properties. Results and techniques developed in this endeavor were used as a foundation for the work undertaken in later chapters. Chapter 4 introduces a series of tetradentate platinum complexes that share a phenoxy-pyridyl (popy) motif. The new molecular design improved efficiency through increased rigidity and modification of the excited state properties. This class of platinum complexes were markedly more efficient than those presented in Chapter 3, and devices employing a green emitting complex of the series achieved nearly 100% electron-to-photon conversion efficiency in an OLED device. Chapter 5 adapts the ligand structure developed in Chapter 4 to palladium. The resulting complexes exceed reported efficiencies of palladium complexes by an order of magnitude. This chapter also provides the first report of a palladium complex as an emitter in an OLED device. Chapter 6 discusses the continuation of development efforts to include carbazolyl

  14. Platinum group elements in gold-sulfide and base-metal ores of the Sayan-Baikal Fold Region and possible platinum and palladium speciation in sulfides

    NASA Astrophysics Data System (ADS)

    Mironov, A. G.; Zhmodik, S. M.; Kolesov, G. M.; Mit'kin, V. N.; Damdinov, B. B.; Zayakina, S. B.

    2008-02-01

    The concentration levels and distribution features of the platinum group elements (PGE) in quartz-sulfide and base-metal ores in deposits of the Sayan-Baikal Fold Region (SBFR) are discussed. Microfire assay neutron activation analysis (MF-NAA), which enables one to work on a nondestructive basis and allows one to avoid inaccuracies related to chemical sample preparation, was used as the main analytical technique. Three types of hydrothermal mineralization with elevated grades of PGE (especially Pt, Pd, and Ru) have been identified: (1) pyrite-pyrrhotite (massive sulfide) mineralization hosted in black shales of the Il’chir Sequence; (2) gold-sulfide ores of the Zun-Kholba, Tainsky, Kamenny, and some other gold deposits; and (3) silver-basemetal ores of the Dzhida-Vitim Zone. The PGE contents significantly vary, from global average values to tens of grams per ton. An absence of PGE minerals implies that these elements are finely dispersed in sulfide minerals and native gold. Taking into account difficulties in conversion of PGE into analytical forms, their nonuniform distribution in sulfide minerals, their high affinity to coordination compounds, and experimental results, cluster species of Pt and Pd in major minerals are suggested for the gold-sulfide and silver-base-metal ores in deposits, which are related to suprasubduction ophiolites and island-arc and intraplate settings in the SBFR.

  15. Superlattices of platinum and palladium nanoparticles

    SciTech Connect

    MARTIN,JAMES E.; WILCOXON,JESS P.; ODINEK,JUDY G.; PROVENCIO,PAULA P.

    2000-04-06

    The authors have used a nonionic inverse micelle synthesis technique to form nanoclusters of platinum and palladium. These nanoclusters can be rendered hydrophobic or hydrophilic by the appropriate choice of capping ligand. Unlike Au nanoclusters, Pt nanoclusters show great stability with thiol ligands in aqueous media. Alkane thiols, with alkane chains ranging from C{sub 6} to C{sub 18} were used as hydrophobic ligands, and with some of these they were able to form 2-D and/or 3-D superlattices of Pt nanoclusters as small as 2.7 nm in diameter. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function of the particle centers, from which they can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the gaps between particles within superlattice domains increases, but more slowly than one might expect, possibly indicating thiol chain interdigitation.

  16. Operation of platinum-palladium catalysts with leaded gasoline.

    PubMed Central

    Teague, D M; Clougherty, L B; Speca, A N

    1975-01-01

    The effect of various fuel additives on the ability of platinum-palladium catalytic converters to remove the carbon monoxide and hydrocarbon components of automotive exhaust has been examined. Engine dynamometer studies suggest that these catalysts may be successfully used in conjunction with fuels of relatively high tetraethyllead concentrations, provided the ethylene dibromide portion of the scavenger is excluded. PMID:50929

  17. Operation of platinum-palladium catalysts with leaded gasoline.

    PubMed

    Teague, D M; Clougherty, L B; Speca, A N

    1975-04-01

    The effect of various fuel additives on the ability of platinum-palladium catalytic converters to remove the carbon monoxide and hydrocarbon components of automotive exhaust has been examined. Engine dynamometer studies suggest that these catalysts may be successfully used in conjunction with fuels of relatively high tetraethyllead concentrations, provided the ethylene dibromide portion of the scavenger is excluded. PMID:50929

  18. Identification of platinum and palladium particles emitted from vehicles and dispersed into the surface environment.

    PubMed

    Prichard, Hazel M; Fisher, Peter C

    2012-03-20

    Platinum, palladium, and rhodium are emitted from vehicle catalytic converters. Until now, the form of precious metal particles in road dust and urban waste has not been identified. This study has located, imaged, and analyzed these particles in road dust and gully waste. Two fragments of catalytic converter have been observed in road dust. They are 40-80 μm in size and covered in many minute particles (<0.3 μm) of either platinum with minor rhodium or palladium. One fragment identified in gully sediment is smaller, 25 μm in diameter, hosting only one attached particle of palladium with minor rhodium. As fragments are washed off roads they begin to disintegrate and the precious metals become detached. Also precious metal-bearing particles have been located in incinerated sewage ash including a 20 μm diameter cluster of <3 μm sized platinum particles that may be the remains of a catalytic converter fragment that has survived incineration. The form of these precious metal-bearing particles described here reveals that as they are dispersed from roads they are likely to be present predominantly as two particle sizes. Either they are attached to larger fragments of catalytic converter or they are released as individual detached tiny <0.3 μm to nanoparticle sizes. PMID:22313190

  19. Metal-support interaction in platinum and palladium nanoparticles loaded on nitrogen-doped mesoporous carbon for oxygen reduction reaction.

    PubMed

    Perini, Lorenzo; Durante, Christian; Favaro, Marco; Perazzolo, Valentina; Agnoli, Stefano; Schneider, Oliver; Granozzi, Gaetano; Gennaro, Armando

    2015-01-21

    Mesoporous carbons are highly porous materials, which show large surface area, chemical inertness and electrochemical performances superior to traditional carbon material. In this study, we report the preparation of nitrogen-doped and undoped mesoporous carbons by an optimized hard template procedure employing silica as template, sucrose and ammonia as carbon and nitrogen source, respectively. Surface area measurements assert a value of 900 and 600 m(2) g(-1) for the best doped and undoped samples, respectively. Such supports were then thoroughly characterized by surface science and electron microscopy tools. Afterward, they were decorated with Pt and Pd nanoparticles, and it was found that the presence of nitrogen defects plays a significant role in improving the metal particles dimension and dispersion. In fact, when doped supports are used, the resulting metal nanoparticles are smaller (2-4 nm) and less prone to aggregation. Photoemission measurements give evidence of a binding energy shift, which is consistent with the presence of an electronic interaction between nitrogen atoms and the metal nanoparticles, especially in the case of Pd. The catalytic properties of electrodes decorated with such catalyst/support systems were investigated by linear sweep voltammetry and by rotating disk electrode measurements, revealing excellent stability and good activity toward oxygen reduction reaction (ORR). In particular, although Pd nanoparticles always result in lower activity than Pt ones, both Pt and Pd electrodes based on the N-doped supports show an increased activity toward ORR with respect to the undoped ones. At the same mass loading, the Tafel slope and the stability test of the Pt@N-doped electrocatalysts indicate superior performances to that of a commercial Pt@C catalysts (30 wt % Pt on Vulcan XC-72, Johnson Matthey). PMID:25525718

  20. Ambiphilic diphosphine-borane ligands: metal-->borane interactions within isoelectronic complexes of rhodium, platinum and palladium.

    PubMed

    Bontemps, Sébastien; Sircoglou, Marie; Bouhadir, Ghenwa; Puschmann, Horst; Howard, Judith A K; Dyer, Philip W; Miqueu, Karinne; Bourissou, Didier

    2008-01-01

    Coordination of an ambiphilic diphosphine-borane (DPB) ligand to the RhCl(CO) fragment affords two isomeric complexes. According to X-ray diffraction analysis, each complex adopts a square-pyramidal geometry with trans coordination of the two phosphine buttresses and axial RhB contacts, but the two differ in the relative orientations around the rhodium and boron centres. DFT calculations on the actual complexes provide insight into the influence of the pi-accepting CO co-ligand, compared with previously reported complexes [Rh(mu-Cl)(dpb)]2 and [RhCl(dmap)(dpb)]. In addition, comparison of the nu(CO) frequency of [RhCl(CO)(dpb)] with that of the related borane-free complex [RhCl(CO)(iPr2PPh)2] substantiates the significant electron-withdrawing effect that the sigma-accepting borane moiety exerts on the metal. Valence isoelectronic [PtCl2(dpb)] and [PdCl2(dpb)] complexes have also been prepared and characterized spectroscopically and structurally. The pronounced influence of the transition metal on the magnitude of the M-->B interaction is highlighted by geometric considerations and NBO analyses. PMID:17948327

  1. Biosorption of platinum and palladium for their separation/preconcentration prior to graphite furnace atomic absorption spectrometric determination

    NASA Astrophysics Data System (ADS)

    Godlewska-Żyłkiewicz, Beata

    2003-08-01

    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 -1 thiourea in 1 mol l -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.

  2. Determination of palladium, platinum and rhodium in geologic materials by fire assay and emission spectrography

    USGS Publications Warehouse

    Hapfty, J.; Riley, L.B.

    1968-01-01

    A method is described for the determination of palladium down to 4ppb (parts per billion, 109), platinum down to 10 ppb and rhodium down to 5 ppb in 15 g of sample. Fire-assay techniques are used to preconcentrate the platinum metals into a gold bead, then the bead is dissolved in aqua regia and diluted to volume with 1M hydrochloric acid. The solution is analysed by optical emission spectrography of the residue from 200 ??l of it evaporated on a pair of flat-top graphite electrodes. This method requires much less sample handling than most published methods for these elements. Data are presented for G-1, W-1, and six new standard rocks of the U.S. Geological Survey. The values for palladium in W-1 are in reasonable agreement with previously published data. ?? 1968.

  3. Mineral resource of the month: platinum group metals

    USGS Publications Warehouse

    Loferski, Patricia J.

    2010-01-01

    The article focuses on platinum group metals (PGMs) and their properties. According to the author, PGMs, which include iridium, osmium, palladium, platinum, rhodium, and ruthenium, are among the rarest mineral commodities in the Earth's crust. PGMs are primarily used as catalytic converters that clean harmful exhaust from vehicle engines. They are also used in the chemical industry as catalysts in the production of nitric acid and in the petroleum refining industry.

  4. ALLERGIC RESPONSE TO PLATINUM AND PALLADIUM COMPLEXES DETERMINATION OF NO-EFFECT LEVEL

    EPA Science Inventory

    Rabbits, guinea pigs and mice were subcutaneously injected with PtSO4 (with and without NH4Cl) and PdSO4 (with and without NH4Cl) in an attempt to sensitize the animals to platinum or palladium. No allergic induction was found. No allergic induction to platinum or palladium was f...

  5. Bulk synthesis of nanoporous palladium and platinum powders

    SciTech Connect

    Robinson, David B; Fares, Stephen J; Tran, Kim L; Langham, Mary E

    2014-04-15

    Disclosed is a method for providing nanoporous palladium and platinum powders. These materials were synthesized on milligram to gram scales by chemical reduction of tetrahalo-complexes with ascorbate in a concentrated aqueous surfactant at temperatures between -20.degree. C. and 30.degree. C. The prepared particles have diameters of approximately 50 nm, wherein each particle is perforated by pores having diameters of approximately 3 nm, as determined by electron tomography. These materials are of potential value for hydrogen and electrical charge storage applications.

  6. Bulk synthesis of nanoporous palladium and platinum powders

    SciTech Connect

    Robinson, David B.; Fares, Stephen J.; Tran, Kim L.; Langham, Mary E.

    2012-04-17

    Disclosed is a method for providing nanoporous palladium and platinum powders. These materials were synthesized on milligram to gram scales by chemical reduction of tetrahalo-complexes with ascorbate in a concentrated aqueous surfactant at temperatures between -20.degree. C. and 30.degree. C. The prepared particles have diameters of approximately 50 nm, wherein each particle is perforated by pores having diameters of approximately 3 nm, as determined by electron tomography. These materials are of potential value for hydrogen and electrical charge storage applications.

  7. 48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify...

  8. 48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify...

  9. 48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify...

  10. 48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify...

  11. 48 CFR 252.208-7000 - Intent to furnish precious metals as Government-furnished material.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... Offeror shall cite the type (silver, gold, platinum, palladium, iridium, rhodium, and ruthenium) and... metal* Quantity Deliverable item (NSN and nomenclature)!!rs *If platinum or palladium, specify...

  12. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium... marking or description misrepresents the product's true composition. The Platinum Group Metals (PGM)...

  13. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium... marking or description misrepresents the product's true composition. The Platinum Group Metals (PGM)...

  14. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium... marking or description misrepresents the product's true composition. The Platinum Group Metals (PGM)...

  15. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium... marking or description misrepresents the product's true composition. The Platinum Group Metals (PGM)...

  16. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.”

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium... marking or description misrepresents the product's true composition. The Platinum Group Metals (PGM)...

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

    USGS Publications Warehouse

    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.

  18. Hydrogen absorption induced metal deposition on palladium and palladium-alloy particles

    DOEpatents

    Wang, Jia X.; Adzic, Radoslav R.

    2009-03-24

    The present invention relates to methods for producing metal-coated palladium or palladium-alloy particles. The method includes contacting hydrogen-absorbed palladium or palladium-alloy particles with one or more metal salts to produce a sub-monoatomic or monoatomic metal- or metal-alloy coating on the surface of the hydrogen-absorbed palladium or palladium-alloy particles. The invention also relates to methods for producing catalysts and methods for producing electrical energy using the metal-coated palladium or palladium-alloy particles of the present invention.

  19. Biaxially textured metal substrate with palladium layer

    DOEpatents

    Robbins, William B [Maplewood, MN

    2002-12-31

    Described is an article comprising a biaxially textured metal substrate and a layer of palladium deposited on at least one major surface of the metal substrate; wherein the palladium layer has desired in-plane and out-of-plane crystallographic orientations, which allow subsequent layers that are applied on the article to also have the desired orientations.

  20. Palladium-platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-01

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  1. Preparation and study of binary compounds of actinides and lanthanides. X. Separation of the TPE and platinum (palladium) by extraction chromatography

    SciTech Connect

    Lebedeva, L.S.; Nezgovorov, N.Yu.; Radchenko, V.M.; Vasil'ev, V.Ya.

    1988-03-01

    The possibility of separation of TPE from compounds bearing platinum or palladium by extraction chromatography using D2EHPA has been explored. It has been found that TPE loss is practically nil. The coefficient of TPE isolation from platinum metals is above 10/sup 3/. It has been shown that macroamounts of platinum can be removed preliminarily by its precipitation as the sparingly soluble salt (NH/sub 4/)/sub 2/PtCl/sub 6/ without a significant loss of TPE. The technique can also be applied for regeneration of platinum group elements from compounds with TPE. The purity of regenerated platinum (palladium) is enough for repeated use as components of compounds with TPE.

  2. Determination of platinum and palladium in geological materials by neutron-activation analysis after fire-assay preconcentration

    USGS Publications Warehouse

    Rowe, J.J.; Simon, F.O.

    1971-01-01

    Fire-asay preconcentration followed by neutron-activation analysis permits the determination of as little as 0.5 ppM of platinum and 0.5 ppM of palladium on a 20-g sample. Platinum and palladium are separated with carriers and beta-counted. Results for the platinum and palladium content of seven U.S.G.S. standard rocks are presented. ?? 1971.

  3. [Simultaneous determination of platinum (IV) and palladium (II) using spectrophotometry method].

    PubMed

    Ma, Dong-Lan; Wang, Yun; Ma, Kuang-Biao; Wang, Jin-Ye

    2009-10-01

    The N-(m-methylphenyl)-N'-(sodium p-aminobenzenesulfonate)-thiourea (MMPT) was good reagent of water solubility. In the medium of an HAc-NaAc buffer solution and hexadecyltrimethylammonium bromide (CTMAB), MMPT can react with platinum (IV) and palladium (II) to form green and brown soluble complex. The maximum absorbance of the complex was at lambdaPt(max) = 754.4 nm and lambdaPD(max) = 304.6 nm. Beer's law was obeyed with the concentration in the range of 0-32.0 microg Pt(IV)/25 mL and 0-25.0 microg Pd(II)/25 mL for platinum (IV) and palladium(II) respectively. The correlated coefficient was r754.4 = 0.999 5 for platinum (IV); and r304.6 = 0.999 9 for palladium (II). Their molar absorption coefficients were epsilonPT(754.4 = 8.6 x 10(4) L x mol(-1) x cm(-1) and epsilonPd(304.6) = 7.4 x 10(4) L x mol(-1) x cm(-1) respectively. The contents of platinum (IV) and palladium (II) were converted by determination of the absorbency of mix solution of platinum (IV) and palladium (II) at 754.4 and 304.6 nm. Only Cu2+ and Co2+ interfered with the determination of palladium (II) among 50 coexistent ions, so the selectivity was good. It can be used for the determination of content of synthesis samples. The relative standard deviation (RSD) was less than 2.0%, and the recovery (%) was in the range of 96%-104%. The results are satisfactory. Because the reagent reacts with platinum (IV) and palladium (II) to form water soluble complex and does not require pre-separation for simultaneous determination of platinum (IV) and palladium (II), the method is easy to operate, rapid and environment-friendly. PMID:20038071

  4. Synthesis and properties of para-substituted NCN-pincer palladium and platinum complexes.

    PubMed

    Slagt, Martijn Q; Rodríguez, Gema; Grutters, Michiel M P; Klein Gebbink, Robertus J M; Klopper, Wim; Jenneskens, Leonardus W; Lutz, Martin; Spek, Anthony L; van Koten, Gerard

    2004-03-19

    A variety of para-substituted NCN-pincer palladium(II) and platinum(II) complexes [MX(NCN-Z)] (M=Pd(II), Pt(II); X=Cl, Br, I; NCN-Z=[2,6-(CH(2)NMe(2))(2)C(6)H(2)-4-Z](-); Z=NO(2), COOH, SO(3)H, PO(OEt)(2), PO(OH)(OEt), PO(OH)(2), CH(2)OH, SMe, NH(2)) were synthesised by routes involving substitution reactions, either prior to or, notably, after metalation of the ligand. The solubility of the pincer complexes is dominated by the nature of the para substituent Z, which renders several complexes water-soluble. The influence of the para substituent on the electronic properties of the metal centre was studied by (195)Pt NMR spectroscopy and DFT calculations. Both the (195)Pt chemical shift and the calculated natural population charge on platinum correlate linearly with the sigma(p) Hammett substituent constants, and thus the electronic properties of predesigned pincer complexes can be predicted. The sigma(p) value for the para-PtI group itself was determined to be -1.18 in methanol and -0.72 in water/methanol (1/1). Complexes substituted with protic functional groups (CH(2)OH, COOH) exist as dimers in the solid state due to intermolecular hydrogen-bonding interactions. PMID:15034878

  5. Platinum metallization for MEMS application

    PubMed Central

    Guarnieri, Vittorio; Biazi, Leonardo; Marchiori, Roberto; Lago, Alexandre

    2014-01-01

    The adherence of Platinum thin film on Si/SiO2 wafer was studies using Chromium, Titanium or Alumina (Cr, Ti, Al2O3) as interlayer. The adhesion of Pt is a fundamental property in different areas, for example in MEMS devices, which operate at high temperature conditions, as well as in biomedical applications, where the problem of adhesion of a Pt film to the substrate is known as a major challenge in several industrial applications health and in biomedical devices, such as for example in the stents.1-4 We investigated the properties of Chromium, Titanium, and Alumina (Cr, Ti, and Al2O3) used as adhesion layers of Platinum (Pt) electrode. Thin films of Chromium, Titanium and Alumina were deposited on Silicon/Silicon dioxide (Si/SiO2) wafer by electron beam. We introduced Al2O3 as a new adhesion layer to test the behavior of the Pt film at higher temperature using a ceramic adhesion thin film. Electric behaviors were measured for different annealing temperatures to know the performance for Cr/Pt, Ti/Pt, and Al2O3/Pt metallic film in the gas sensor application. All these metal layers showed a good adhesion onto Si/SiO2 and also good Au wire bondability at room temperature, but for higher temperature than 400 °C the thin Cr/Pt and Ti/Pt films showed poor adhesion due to the atomic inter-diffusion between Platinum and the metal adhesion layers.5 The proposed Al2O3/Pt ceramic-metal layers confirmed a better adherence for the higher temperatures tested. PMID:24743057

  6. Antiviral activity of platinum (II) and palladium (II) complexes of pyridine-2-carbaldehyde thiosemicarbazone.

    PubMed

    Varadinova, T; Kovala-Demertzi, D; Rupelieva, M; Demertzis, M; Genova, P

    2001-04-01

    A heterocyclic compound, pyridine-2-carbaldehyde thiosemicarbazone (HFoTsc), and its six metal coordinated bound complexes, three with platinum (II) and three with palladium (II), were studied for their activity against herpes simplex virus 1 (HSV-1) infection in cultured cells. According to their cytotoxicity the compounds were divided into two groups. Group I (cytotoxic compounds) included all three palladium complexes and [Pt(HFoTsc)2] Cl2, with maximum non-toxic concentration (MNC) of 1-10 micromol/l and a 50% cytotoxic concentration (CC50) of 20-100 micromol/l. Group 2 (low cytotoxic compounds) with MNC of 100 micromol/l and CC50 of 548-5820 micromol/l included compounds in the following order: [Pt(HFoTsc)2] Cl2platinum complexes as well as [Pd(HFoTsc)2]Cl2 and [Pd(FoTsc)2] inhibited HSV- I infection following a structure-activity relationship but only [Pt(HFoTsc)2]Cl2 expressed a significant selectivity comparable to that of HFoTsc. However, [PdCl(FoTsc)] acting 48 hrs gave a higher infectious HSV-1 titer (170%) compared to control (100%, no compound). PMID:11719987

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

    PubMed

    Cobelo-Garcia, Antonio; Turner, Andrew; Millward, Geoffrey E; Couceiro, Fay

    2007-03-01

    The recovery of dissolved platinum group elements (PGE: Pd(II), Pt(IV) and Rh(III)) added to Milli-Q 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). 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. PMID:17386666

  8. Method for producing electricity using a platinum-ruthenium-palladium catalyst in a fuel cell

    DOEpatents

    Gorer, Alexander

    2004-01-27

    A method for producing electricity using a fuel cell that utilizes a ternary alloy composition as a fuel cell catalyst, the ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

  9. Palladium-platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction.

    PubMed

    Wang, Xue; Choi, Sang-Il; Roling, Luke T; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A; Mavrikakis, Manos; Xia, Younan

    2015-01-01

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability. PMID:26133469

  10. Extraction chromatography of palladium and platinum complexes with nitroso-R-salt.

    PubMed

    Flieger, A; Przeszlakowski, S

    1985-12-01

    The retention of palladium and platinum complexes with nitroso-R-salt on silica gel treated with Aliquat 336 has been investigated. The complexation of platinum with nitroso-R-salt (NRS) requires heating of H(2)PtCl(6) with an excess of NRS at 100 degrees . The affinity of the complexes for an Aliquat 336 stationary phase increases in the following order: PdCl(4)(2-) ~ Pt-NRS < PtCl(6)(2-) Pd-NRS. The complexes of palladium and platinum can be separated by column chromatography on silica treated with Aliquat 336 and eluted with 0.25M perchloric acid (Pt) and 1M perchloric acid (Pd). PMID:18963969

  11. Copper, Palladium, and Platinum-Containing Complexes of an Asymmetric Dinucleating Ligand

    PubMed Central

    Halvagar, Mohammad Reza; Neisen, Benjamin

    2013-01-01

    The coordination chemistry of an asymmetric dinucleating hexadentate ligand LH2 comprising neutral alkyltriamine and potentially dianionic dicarboxamido-pyridyl donor sets with copper, palladium, and platinum has been explored. Monometallic, dicopper, and heterodinuclear Cu-Pd and -Pt complexes have been prepared and characterized, including by NMR, EPR, UV-vis, and IR spectroscopy and X-ray crystallography. For example, the monometallic complexes [(LH2)MCl]X (M = Cu, X = OTf; M = Pd or Pt, X = Cl) were prepared, wherein the metal(II) ions is coordinated to the triamine portion and the pyridyldicarboxamide is unperturbed. Treatment of LH2 with [MesCu]x (Mes = mesityl) provided a monocopper(I) complex, again with the metal coordinated only to the trialkylamine donor set. Reaction of [(LH2)CuCl]OTf with NaOMe resulted in an unexpected migration of the copper(II)-chloride fragment to the pyridyldicarboxamide site to yield Na[LCuCl], from which a dicopper complex LCu2Cl2 and mixed-metal complexes LCu(Cl)M(Cl) (M = Pd, Pt) were prepared by addition of CuCl2 or MCl2, respectively. The heterodinuclear complexes were also prepared by addition of CuCl2 to [(LH2)MCl]Cl. PMID:23268657

  12. The adsorption of gold, palladium and platinum from acidic chloride solutions on mesoporous carbons.

    SciTech Connect

    Zalupski, Peter R.; McDowell, Rocklan; Dutech, Guy

    2014-08-05

    Studies on the adsorption characteristics of gold, palladium and platinum on mesoporous carbon (CMK-3) and sulfur-impregnated mesoporous carbon (CMK-3/S) evaluated the benefits/drawbacks of the presence of a layer of elemental sulfur inside mesoporous carbon structures. Adsorption isotherms collected for Au(III), Pd(II) and Pt(IV) on those materials suggest that sulfur does enhance the adsorption of those metal ions in mildly acidic environment (pH 3). The isotherms collected in 1 M HCl show that the benefit of sulfur disappears due to the competing influence of large concentration of hydrogen ions on the ion-exchanging mechanism of metal ions sorption on mesoporous carbon surfaces. The collected acid dependencies illustrate similar adsorption characteristics for CMK-3 and CMK-3/S in 1-5 M HCl concentration range. Sorption of metal ions from diluted aqueous acidic mixtures of actual leached electronic waste demonstrated the feasibility of recovery of gold from such liquors.

  13. The adsorption of gold, palladium and platinum from acidic chloride solutions on mesoporous carbons.

    DOE PAGESBeta

    Zalupski, Peter R.; McDowell, Rocklan; Dutech, Guy

    2014-08-05

    Studies on the adsorption characteristics of gold, palladium and platinum on mesoporous carbon (CMK-3) and sulfur-impregnated mesoporous carbon (CMK-3/S) evaluated the benefits/drawbacks of the presence of a layer of elemental sulfur inside mesoporous carbon structures. Adsorption isotherms collected for Au(III), Pd(II) and Pt(IV) on those materials suggest that sulfur does enhance the adsorption of those metal ions in mildly acidic environment (pH 3). The isotherms collected in 1 M HCl show that the benefit of sulfur disappears due to the competing influence of large concentration of hydrogen ions on the ion-exchanging mechanism of metal ions sorption on mesoporous carbon surfaces.more » The collected acid dependencies illustrate similar adsorption characteristics for CMK-3 and CMK-3/S in 1-5 M HCl concentration range. Sorption of metal ions from diluted aqueous acidic mixtures of actual leached electronic waste demonstrated the feasibility of recovery of gold from such liquors.« less

  14. Bioaccessibility of palladium and platinum in urban aerosol particulates

    NASA Astrophysics Data System (ADS)

    Puls, Christoph; Limbeck, Andreas; Hann, Stephan

    2012-08-01

    To evaluate potential health hazards caused by environmental Platinum Group Elements (PGEs), bioaccessibility of the metals in question needs to be assessed. To gain appropriate data, airborne particulate matter samples of different size fractions (total suspended particles as well as PM10 and PM2.5) were taken in downtown Vienna, an urban site primarily polluted by traffic. Total PGE concentrations in these samples were in the low picogram per cubic meter range, as determined by ID-ICP-MS after microwave digestion. For elimination of elements interfering with the accurate quantification, the digested samples were subjected to a cleaning procedure involving cation exchange. For determination of the bioaccessible fraction, it was assumed that inhaled particles are removed from the respiratory system by mucociliary clearance and subsequently ingested. Accordingly, the solubility of PGE in synthetic gastric juice was investigated by batch extraction of particulate matter samples followed by microwave assisted UV-digestion, cation exchange cleanup and ID-ICP-MS. The acquired data was used to calculate the bioaccessible fraction of Pd and Pt in airborne particulate matter. Average GIT-extractable fractions for Pd and Pt in TSP were 41% and 27%, in PM10 34% and 26%, respectively, thus exceeding previously determined values for bioaccessibility of PGE from ground catalyst materials by up to an order of magnitude.

  15. Exploring the photophysics and photocatalytic properties of platinum and palladium nanoparticles

    NASA Astrophysics Data System (ADS)

    Major, Kevin John

    Platinum and Palladium nanoparticles are important nanoscale materials for a variety of materials science and industrial applications. The presented research covers a broad spectrum of these unique nanoparticles, from their synthesis and characterization to their use in systems that examine their photophysical properties and as catalysts and photocatalysts. We developed a new synthetic method for producing well-defined platinum and palladium nanoparticles of less than 5 nm diameter. The nanoparticles are stabilized by long chain thioethers, which allow them to retain their stability in a variety of solvent environments. Stability and size control are critical to the application of these particles to experimental research in a variety of systems. After demonstrating the catalytic activity of these nanoparticles, we developed a method for linking them to magnetic cobalt ferrite nanoparticles. These linked particles were found to be highly recoverable when placed in a magnetic field, allowing for their reuse. In addition to traditional catalytic systems, platinum and palladium nanoparticles hold great potential as photocatalysts. We chose to study their use in two such systems. The first system explored involved utilizing platinum nanoparticles as charge transfer catalysts from titanium dioxide nanoparticles. We demonstrated the ability of this system for the degradation of an organic dye as well as for hydrogen production via water splitting, both under dark conditions. The final system explored involved studying the interaction between cadmium selenide quantum dots and palladium nanoparticles in solution. As a prelude to this research, we conducted an extensive study on the effects of stabilizing ligands on quantum dot fluorescence dynamics. We developed a model to define the dynamics of the dots based on changes in native ligand coverage upon sample dilution. These studies allowed us to take these effects into account before studying the interaction of the dots

  16. A simple one-pot strategy to platinum-palladium@palladium core-shell nanostructures with high electrocatalytic activity

    NASA Astrophysics Data System (ADS)

    Lv, Jing-Jing; Zheng, Jie-Ning; Wang, Ying-Ying; Wang, Ai-Jun; Chen, Li-Li; Feng, Jiu-Ju

    2014-11-01

    Well-defined platinum-palladium@palladium core-shell nanospheres (PtPd@Pd NSs) are synthesized by a facile one-pot solution approach using N-methylimidazole and poly(vinyl pyrrolidone) (PVP) as directing and capping agents, respectively, without using any seed, template, or organic solvent. The coexistence of the precursors, N-methylimidazole, PVP, and reaction temperature has great effects on the final morphology. Thus-prepared nanocomposites display an improved electrocatalytic activity for oxygen reduction reaction (ORR) in acidic media, methanol and ethylene glycol oxidation reaction in alkaline media, compared with Pt nanoparticles, Pd nanoparticles, commercial Pt black and Pd black catalysts. This method may direct a general orientation for shape control synthesis of functional bimetallic nanocrystals as promising electrocatalysts in direct alcohol fuel cells (DAFCs).

  17. Microwave-assisted synthesis of gold, silver, platinum and palladium nanostructures and their use in electrocatalytic applications.

    PubMed

    Safavi, Afsaneh; Tohidi, Maryam

    2014-09-01

    Microwave-assisted ionic liquid method was used for synthesis of various noble metals, such as gold, silver, platinum and palladium nanomaterials. This route does not employ any template agent, surface capping agents or reducing agents. The process is fast, simple and of high yield. Different metal precursors in various ionic liquids media (1-butyl-3-methylimidazolium tetrafluoroborate, octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate) were applied to produce metal nanomaterials. Silver, platinium and palladium nanoparticles exhibit spherical morphology while nanosheets with high aspect ratio were obtained for gold. These metal nanostructures were incorporated into a carbon ionic liquid electrode to investigate their electrocatalytic properties. It was found that synthesis in different ionic liquids result in different activity. Excellent electrocatalytic effects toward adenine, hydrazine, formaldehyde and ethanol were observed for the modified electrodes with different nanoparticles synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate. The high conductivity, large surface-to-volume ratio and active sites of nanosized metal particles are responsible for their electrocatalytic activity. In contrast, the carbon ionic liquid electrode modified with synthesized metal nanoparticles in octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate showed negligible activity for detection of these probes. PMID:25924389

  18. Californium--palladium metal neutron source material

    DOEpatents

    Dahlen, B.L.; Mosly, W.C. Jr.; Smith, P.K.; Albenesius, E.L.

    1974-01-22

    Californium, as metal or oxide, is uniformly dispersed throughout a noble metal matrix, provided in compact, rod or wire form. A solution of californium values is added to palladium metal powder, dried, blended and pressed into a compact having a uni-form distribution of californium. The californium values are decomposed to californium oxide or metal by heating in an inert or reducing atmosphere. Sintering the compact to a high density closes the matrix around the dispersed californium. The sintered compact is then mechanically shaped into an elongated rod or wire form. (4 claims, no drawings) (Official Gazette)

  19. Structural characterization and comparison of iridium, platinum and gold/palladium ultra-thin film coatings for STM of biomolecules

    SciTech Connect

    Sebring, R.; Arendt, P.; Imai, B.; Bradbury, E.M.; Gatewood, J.; Panitz, J.; Yau, P.

    1997-10-30

    Scanning tunneling microscopy (STM) is capable of atomic resolution and is ideally suited for imaging surfaces with uniform work function. A biological sample on a conducting substrate in air does not meet this criteria and requires a conductive coating for stable and reproducible STM imaging. In this paper, the authors describe the STM and transmission electron microscopy (TEM) characterization of ultra-thin ion-beam sputtered films of iridium and cathode sputtered gold/palladium and platinum films on highly ordered pyrolytic graphite (HOPG) which were developed for use as biomolecule coatings. The goals were the development of metal coatings sufficiently thin and fine grained that 15--20 {angstrom} features of biological molecules could be resolved using STM, and the development of a substrate/coating system which would allow complementary TEM information to be obtained for films and biological molecules. The authors demonstrate in this paper that ion-beam sputtered iridium on highly ordered pyrolytic graphite (HOPG) has met both these goals. The ion-beam sputtered iridium produced a very fine grained (< 10 {angstrom}) continuous film at 5--6 {angstrom} thickness suitable for stable air STM imaging. In comparison, cathode sputtered platinum produced 16 {angstrom} grains with the thinnest continuous film at 15 {angstrom} thickness, and the sputtered gold/palladium produced 25 {angstrom} grains with the thinnest continuous film at 18 {angstrom} thickness.

  20. Phonon anharmonicity and components of the entropy in palladium and platinum

    NASA Astrophysics Data System (ADS)

    Shen, Yang; Li, Chen W.; Tang, Xiaoli; Smith, Hillary L.; Fultz, B.

    2016-06-01

    Inelastic neutron scattering was used to measure the phonon density of states in fcc palladium and platinum metal at temperatures from 7 K to 1576 K. Both phonon-phonon interactions and electron-phonon interactions were calculated by methods based on density functional theory (DFT) and were consistent with the measured shifts and broadenings of phonons with temperature. Unlike the longitudinal modes, the characteristic transverse modes had a nonlinear dependence on temperature owing to the requirement for a population of thermal phonons for upscattering. Kohn anomalies were observed in the measurements at low temperature and were reproduced by calculations based on DFT. Contributions to the entropy from phonons and electrons were assessed and summed to obtain excellent agreement with prior calorimetric data. The entropy from thermal expansion is positive for both phonons and electrons but larger for phonons. The anharmonic phonon entropy is negative in Pt, but in Pd it changes from positive to negative with increasing temperature. Owing to the position of the Fermi level on the electronic DOS, the electronic entropy was sensitive to the adiabatic electron-phonon interaction in both Pd and Pt. The adiabatic EPI depended strongly on thermal atom displacements.

  1. Platinum-monolayer Electrocatalysts: Palladium Interlayer on IrCo Alloy Core Improves Activity in Oxygen-reduction Reaction

    SciTech Connect

    Gong, K.; Chen, W.-F.; Sasaki, K.; Su, D.; Vukmirovic, M.B.; Zhou, W.; Izzo, E.L.; Perez-Acosta, C.; Hirunsit, P.; Balbuena, P.B.; Adzic, R.R.

    2010-11-15

    We describe the synthesis and electrocatalytic properties of a new low-Pt electrocatalyst consisting of an IrCo core, a Pd interlayer, and a surface Pt monolayer, emphasizing the interlayer's role in improving electrocatalytic activity for the oxygen-reduction reaction on Pt in HClO{sub 4} solution. We prepared the IrCo alloys by decomposing, at 800 C, hexacyanometalate, KCoIr(CN){sub 6}, adsorbed on the carbon surfaces. The synthesis of Ir{sub 3}Co/C involved heating a mix of metal salts and carbon in hydrogen at 500 C. Thereafter, we placed a palladium and/or platinum monolayer on them via the galvanic displacement of an underpotentially deposited copper monolayer. The electrocatalysts were characterized using structural- and electrochemical-techniques. For PtML/PdML/IrCo/C, we observed a Pt mass activity of 1.18 A/mg{sub (Pt)} and the platinum-group-metals mass of 0.16 A/mg{sub (Pt, Pd, Ir)}. In comparison, without a Pd interlayer, i.e., Pt{sub ML}/IrCo/C, the activities of 0.15 A/mg{sub (Pt)} and 0.036 A/mg{sub (Pt, Pd, Ir)} were considerably lower. We consider that the palladium interlayer plays an essential role in achieving high catalytic activity by adjusting the electronic interaction of the platinum monolayer with the IrCo core, so that it accelerates the kinetics of adsorption and desorption of the intermediates of oxygen reduction. A similar trend was observed for Pt{sub ML}/Pd{sub ML} and Pt{sub ML} deposited on Ir{sub 3}Co/C alloy core. We used density functional theory to interpret the observed phenomena.

  2. Hydrogen-bonding pincer complexes with two protic N-heterocyclic carbenes from direct metalation of a 1,8-bis(imidazol-1-yl)carbazole by platinum, palladium, and nickel.

    PubMed

    Marelius, David C; Darrow, Evan H; Moore, Curtis E; Golen, James A; Rheingold, Arnold L; Grotjahn, Douglas B

    2015-07-27

    Pincer protic N-heterocyclic carbene (PNHC) complexes were synthesized by direct metalation, the formation of a metal carbon bond from an unfunctionalized CH bond in a single synthetic step. Significantly, direct metalation succeeded even for a first-row metal, nickel. The chloride complexes were isolated and then converted to the acetate, triflate, or in the platinum case, a hydride analogue. Crystal structures and (1) H, (13) C, and (15) N NMR data, as well as IR spectra, document the effects of intramolecular hydrogen bonding and the planar but flexible pincer framework. Anti-Markovnikov addition of OH bonds to alkynes, including catalyzed alkyne hydration, were demonstrated on the Pt triflate analog. PMID:26134355

  3. Electron photoemission from platinum and palladium microdeposits on glassy carbon into the solution

    SciTech Connect

    Yakushev, V.V.; Bagotskii, V.S.; Skundin, A.M.

    1984-08-01

    It was of interest to the authors to compare the electrocatalytic and photoemission properties of microdeposits in other systems. Platinum and palladium microdeposits on glassy carbon were selected as such systems in the present work. The procedure used in the photoemission measurements has been previously described. All measurements were conducted in 1 N KOH. A mercury-mercuric oxide electrode served as reference electrode. The true surface areas of the platinum microdeposits were measured potentiodynamically in terms of hydrogen adsorption and oxygen desorption, while that of the palladium microdeposits was measured in terms of oxygen desorption. The results of the present work yield the important conclusion that the changes which occur in the density of electronic states in the microdeposits because of their contact with the support depend on potential, i.e., on the position of the Fermi level. It is found that the enhancement of the photoemission currents is attended by an increase, and the depression of the photoemission currents is attended by a decrease in electrocatalytic activity.

  4. Highly Unsaturated Platinum and Palladium Carbenes PtC3 and PdC3 Isolated and Characterized in the Gas Phase

    PubMed Central

    Bittner, Dror M.; Zaleski, Daniel P.; Tew, David P.

    2016-01-01

    Abstract Carbenes of platinum and palladium, PtC3 and PdC3, were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and ab initio calculations confirm that both molecules are linear. The geometry of PtC3 was accurately determined by fitting to the experimental moments of inertia of twenty‐six isotopologues. The results are consistent with the proposal of an autogenic isolobal relationship between O, Au+, and Pt atoms. PMID:26879473

  5. Highly Unsaturated Platinum and Palladium Carbenes PtC3 and PdC3 Isolated and Characterized in the Gas Phase

    PubMed Central

    Bittner, Dror M.; Zaleski, Daniel P.; Tew, David P.

    2016-01-01

    Abstract Carbenes of platinum and palladium, PtC3 and PdC3, were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and ab initio calculations confirm that both molecules are linear. The geometry of PtC3 was accurately determined by fitting to the experimental moments of inertia of twenty‐six isotopologues. The results are consistent with the proposal of an autogenic isolobal relationship between O, Au+, and Pt atoms.

  6. Highly Unsaturated Platinum and Palladium Carbenes PtC3 and PdC3 Isolated and Characterized in the Gas Phase

    DOE PAGESBeta

    Bittner, Dror M.; Zaleski, Daniel P.; Tew, David P.; Walker, Nicholas R.; Legon, Anthony C.

    2016-02-16

    Carbenes of platinum and palladium, PtC3 and PdC3 , were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and abinitio calculations confirm that both molecules are linear. The geometry of PtC3 was accurately determined by fitting to the experimental moments of inertia of twenty-six isotopologues. In conclusion, the results are consistent with the proposal of an autogenic isolobal relationship between O, Au+ , and Ptatoms.

  7. Highly Unsaturated Platinum and Palladium Carbenes PtC3 and PdC3 Isolated and Characterized in the Gas Phase.

    PubMed

    Bittner, Dror M; Zaleski, Daniel P; Tew, David P; Walker, Nicholas R; Legon, Anthony C

    2016-03-01

    Carbenes of platinum and palladium, PtC3 and PdC3 , were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and ab initio calculations confirm that both molecules are linear. The geometry of PtC3 was accurately determined by fitting to the experimental moments of inertia of twenty-six isotopologues. The results are consistent with the proposal of an autogenic isolobal relationship between O, Au(+) , and Pt atoms. PMID:26879473

  8. Reactivity studies of pincer bis-protic N-heterocyclic carbene complexes of platinum and palladium under basic conditions

    PubMed Central

    Marelius, David C; Moore, Curtis E; Rheingold, Arnold L

    2016-01-01

    Summary Bis-protic N-heterocyclic carbene complexes of platinum and palladium (4) yield dimeric structures 6 when treated with sodium tert-butoxide in CH2Cl2. The use of a more polar solvent (THF) and a strong base (LiN(iPr)2) gave the lithium chloride adducts monobasic complex 7 or analogous dibasic complex 8. PMID:27559382

  9. Reactivity studies of pincer bis-protic N-heterocyclic carbene complexes of platinum and palladium under basic conditions.

    PubMed

    Marelius, David C; Moore, Curtis E; Rheingold, Arnold L; Grotjahn, Douglas B

    2016-01-01

    Bis-protic N-heterocyclic carbene complexes of platinum and palladium (4) yield dimeric structures 6 when treated with sodium tert-butoxide in CH2Cl2. The use of a more polar solvent (THF) and a strong base (LiN(iPr)2) gave the lithium chloride adducts monobasic complex 7 or analogous dibasic complex 8. PMID:27559382

  10. Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof

    DOEpatents

    Adzic, Radoslav; Mo, Yibo; Vukmirovic, Miomir; Zhang, Junliang

    2010-12-21

    The invention relates to platinum-coated particles useful as fuel cell electrocatalysts. The particles are composed of a noble metal or metal alloy core at least partially encapsulated by an atomically thin surface layer of platinum atoms. The invention particularly relates to such particles having a palladium, palladium alloy, gold alloy, or rhenium alloy core encapsulated by an atomic monolayer of platinum. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

  11. Platinum metals magmatic sulfide ores.

    PubMed

    Naldrett, A J; Duke, J M

    1980-06-27

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. PMID:17796685

  12. Anthropogenic platinum and palladium in the sediments of Boston Harbor

    USGS Publications Warehouse

    Tuit, C.B.; Ravizza, G.E.; Bothner, Michael H.

    2000-01-01

    Anthropogenic activity has increased recent sediment concentrations of Pt and Pd in Boston Harbor by approximately 5 times background concentrations. Surface sediments and downcore profiles were investigated to evaluate Pt and Pd accumulation and behavior in urban coastal sediments. There is no clear correlation between temporal changes in Pt and Pd consumption and sediment concentration. However, Pt/Pb and Pd/Pb ratios suggest that Pt and Pd flux into the Harbor may not be decreasing with cessation of sludge input as rapidly as other metals. This is supported by the large discrepancy between fluxes associated with sludge and effluent release and those calculated from surface sediment concentrations. This evidence supports catalytic converters as a major source of Pd and Pt to Boston Harbor but cannot preclude other sources. Pd does not exhibit signs of post-burial remobilization below the mixed layer in the sediment cores, although near-surface variability in Pd concentrations may indicate a labile Pd component. Pt displays an inverse correlation with Mn above the oxic/suboxic transition, similar to behavior seen in pristine sediments where Pt is thought to be chemically mobile. This study does not support the use of Pd and Pt as tracers of recent contaminated sedimentation. However, the possibility of a labile Pt and Pd in these sediments highlights the need for further study of the biological uptake of these metals.Anthropogenic activity has increased recent sediment concentrations of Pt and Pd in Boston Harbor by approximately 5 times background concentrations. Surface sediments and downcore profiles were investigated to evaluate Pt and Pd accumulation and behavior in urban coastal sediments. There is no clear correlation between temporal changes in Pt and Pd consumption and sediment concentration. However, Pt/Pb and Pd/Pb ratios suggest that Pt and Pd flux into the Harbor may not be decreasing with cessation of sludge input as rapidly as other metals. This is

  13. Palladium(II) and platinum(II) derivatives of benzothiazoline ligands: Synthesis, characterization, antimicrobial and antispermatogenic activity

    NASA Astrophysics Data System (ADS)

    Sharma, Krishna; Singh, R. V.; Fahmi, Nighat

    2011-01-01

    A series of Pd(II) and Pt(II) complexes with two N ∩S donor ligands, 5-chloro-3-(indolin-2-one)benzothiazoline and 6-nitro-3-(indolin-2-one)benzothiazoline, have been synthesized by the reaction of metal chlorides (PdCl 2 and PtCl 2) with ligands in 1:2 molar ratios. All the synthesized compounds were characterized by elemental analyses, melting point determinations and a combination of electronic, IR, 1H NMR and 13C NMR spectroscopic techniques for structure elucidation. In order to evaluate the effect of metal ions upon chelation, both the ligands and their complexes have been screened for their antimicrobial activity against the various pathogenic bacterial and fungal strains. The metal complexes have shown to be more antimicrobial against the microbial species as compared to free ligands. One of the ligands, 5-chloro-3-(indolin-2-one)benzothiazoline and its corresponding palladium and platinum complexes have been tested for their antifertility activity in male albino rats. The marked reduction in sperm motility and density resulted in infertility by 62-90%. Significant alterations were found in biochemical parameters of reproductive organs in treated animals as compared to control group. It is concluded that all these effects may finally impair the fertility of male rats.

  14. Three-dimensional distribution analysis of platinum, palladium and rhodium in auto catalytic converters using imaging-mode laser-induced breakdown spectrometry

    NASA Astrophysics Data System (ADS)

    Lucena, Patricia; Laserna, J. Javier

    2001-02-01

    Laser-induced breakdown spectrometry (LIBS) is reported here as an effective technique to describe the volume distribution of platinum, rhodium and palladium in catalytic converters installed in motor vehicles. Using the second harmonic output of a Nd:YAG laser and a CCD-based atomic emission spectrometer, LIBS is used in multielemental, imaging-mode to permit the simultaneous analysis of the several elements present in the converter, including the internal standard. The data are reported with a lateral resolution of 1.75 mm over a fresh catalytic structure which is 128 mm long. The concentrational variability of the platinum group metals (PGMs) varies in the range ˜3-23% relative standard deviation depending on the element, the substrate and the direction investigated. The causes of the dispersion observed are discussed.

  15. Stripping voltammetric determination of palladium, platinum and rhodium in freshwater and sediment samples from South African water resources.

    PubMed

    van der Horst, C; Silwana, B; Iwuoha, E; Somerset, V

    2012-01-01

    Stripping voltammetry as technique has proved to be very useful in the analysis of heavy and other metal ions due to its excellent detection limits and its sensitivity in the presence of different metal species or interfering ions. Recent assessments of aquatic samples have shown increased levels of platinum group metals (PGMs) in aquatic ecosystems, caused by automobile exhaust emissions and mining activities. The development of an analytical sensor for the detection and characterisation of PGMs were investigated, since there is an ongoing need to find new sensing materials with suitable recognition elements that can respond selectively and reversibly to specific metal ions in environmental samples. The work reported shows the successful application of another mercury-free sensor electrode for the determination of platinum group metals in environmental samples. The work reported in this study entails the use of a glassy carbon electrode modified with a bismuth film for the determination of platinum (Pt(2+)), palladium (Pd(2+)) or rhodium (Rh(2+)) by means of adsorptive cathodic stripping voltammetry. Optimised experimental conditions included composition of the supporting electrolyte, complexing agent concentration, deposition potential, deposition time and instrumental voltammetry parameters for Pt(2+), Pd(2+) and Rh(2+) determination. Adsorptive differential pulse stripping voltammetric measurements for PGMs were performed in the presence of dimethylglyoxime (DMG) as complexing agent. The glassy carbon bismuth film electrode (GC/BiFE) employed in this study exhibit good and reproducible sensor characteristics. Application of GC/BiFE sensor exhibited well-defined peaks and highly linear behaviour for the stripping analysis of the PGMs in the concentration range between 0 and 3.5 μg/L. The detection limit of Pd, Pt and Rh was found to be 0.12 μg/L, 0.04 μg/L and 0.23 μg/L, respectively for the deposition times of 90 s (Pd) and 150 s (for both Pt and Rh). Good

  16. Chemical Forms and Distribution of Platinum Group Metals and Technetium During Spent Fuel Reprocessing

    SciTech Connect

    Pokhitonov, Y.

    2007-07-01

    Amongst the fission products present in spent nuclear fuel of Nuclear Power Plants there are considerable quantities of platinum group metals (PGMs): ruthenium, rhodium and palladium. At the same time there are considerable amounts of technetium in the spent fuel, the problem of its removal at radiochemical plants being in operation encountering serious difficulties. Increased interest in this radionuclides is due not only to its rather large yield, but to higher mobility in the environment as well. However, the peculiarities of technetium chemistry in nitric acid solutions create certain problems when trying to separate it as a single product in the course of NPP's spent fuel reprocessing. The object of this work was to conduct a comprehensive analysis of platinum group metals and technetium behavior at various stages of spent fuel reprocessing and to seek the decisions which could make it possible to separate its as a single product. The paper will report data on platinum metals (PGM) and technetium distribution in spent fuel reprocessing products. The description of various techniques for palladium recovery from differing in composition radioactive solutions arising from reprocessing is given. (authors)

  17. Leaching platinum-group metals in a sulfuric acid/chloride solution

    NASA Astrophysics Data System (ADS)

    Mahmoud, M. H. H.

    2003-04-01

    A leaching process was established based on the ability of platinum-group metals to form stable chloro-complexes in acidic chloride solutions. Industrial catalyst losses were examined for the recovery of platinum, palladium, and rhodium by leaching with a mixture of sulfuric acid and sodium chloride to avoid using aqua regia or autoclave conditions. Extraction of platinum and rhodium in 60% H2SO4 at 135°C steadily increased with increasing NaCl concentrations reaching 95% and 85%, respectively, at 0.1 M NaCl after two hours. By comparison, palladium was dissolved more quickly but also reached 85% under the same conditions. Extraction of each metal increased with temperatures up to 125°C but plateaued at higher temperatures. Similar behavior was observed with increasing H2SO4 concentrations up to 60%. More than 99% extraction of each metal was obtained after ten hours using 0.1 M NaCl and 60% H2SO4 at 125°C.

  18. X-ray characterization of platinum group metal catalysts

    NASA Astrophysics Data System (ADS)

    Peterson, Eric J.

    Platinum group metals (PGMs) are used extensively as catalysts, employed in several sectors of the world energy economy. Fuel cells employing PGM catalysts show promise as power sources in the proposed hydrogen economy, using alcohols as hydrogen storage media. Currently, the most economically important application for PGMs is for the mitigation of emissions from internal combustion engines via catalytic converters. In all applications, efficient use of these expensive metals to fabricate robust catalysts is of the utmost importance. Understanding the catalyst structure/property relationship is the key to the improvement of existing catalysts and the discovery of new catalysts. For example, catalyst particle size can have profound effects on catalyst activity, as in the case of gold nanoparticles. Catalyst particle size control and stability is also important for the efficient use of PGM metals and catalyst deactivation prevention. The challenge is to identify and characterize structural features and determine if and how these features may relate to catalytic properties. The ultimate goal is to simultaneously measure catalyst structural characteristics and catalytic properties under operando conditions, unambiguously establishing the structure/property link. X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) are important techniques used for the characterization of PGM catalysts. Microstructural information such as crystallite size, as small as ~ 1 nm, and microstrain can be obtained from Bragg diffraction peak shapes in X-ray diffraction patterns, and long range crystal structure information is found in the intensities and positions of these peaks. In contrast, X-ray absorption spectroscopy provides information about the chemical state and local structure of selected atoms. From the average nearest neighbor coordination numbers, crystallite sizes can also be inferred, with particularly high sensitivity in the sub-nm size range. Electron microscopy

  19. Synthesis of Hollow Platinum-Palladium Nanospheres with a Dendritic Shell as Efficient Electrocatalysts for Methanol Oxidation.

    PubMed

    Lu, Qingqing; Wang, Hongjing; Eid, Kamel; Alothman, Zeid Abdullah; Malgras, Victor; Yamauchi, Yusuke; Wang, Liang

    2016-07-01

    Engineering the size, composition, and morphology of platinum-based nanomaterials can provide a great opportunity to improve the utilization efficiency of electrocatalysts and reinforce their electrochemical performances. Herein, three-dimensional platinum-palladium hollow nanospheres with a dendritic shell (PtPd-HNSs) are successfully fabricated through a facile and economic route, during which SiO2 microspheres act as the hard template for the globular cavity, whereas the triblock copolymer F127 contributes to the formation of the dendritic shell. In contrast with platinum hollow nanospheres (Pt-HNSs) and commercial platinum on carbon (Pt/C) catalyst, the novel architecture shows a remarkable activity and durability toward the methanol oxidation reaction (MOR) owing to the coupled merits of bimetallic nanodendrites and a hollow interior. As a proof of concept, this strategy is also extended to trimetallic gold-palladium-platinum hollow nanospheres (AuPdPt-HNSs), which paves the way towards the controlled synthesis of other bi- or multimetallic platinum-based hollow electrocatalysts. PMID:27283867

  20. Spectroscopic and structural properties of 2,2'-dipyridylamine and its palladium and platinum complexes

    NASA Astrophysics Data System (ADS)

    Yurdakul, Ş.; Bilkana, M. T.

    2015-10-01

    The structural features such as geometric parameters, vibration frequencies and intensities of the vibrational bands of 2,2'-dipyridylamine ligand (DPA), its palladium (Pd(DPA)Cl2) and platinum (Pt(DPA)Cl2) complexes were studied by the density functional theory (DFT). The calculations were carried out by DFT / B3LYP method with 6-311++G(d,p) and LANL2DZ basis sets. All vibrational frequencies assigned in detail with the help of total energy distribution analysis (TED). Optimized geometric bond lengths and bond angles were compared with experimental X-ray data. Using DPA, K2PtCl4, and Na2PdCl4, the synthesized complex structures were characterized by the combination of elemental analysis, FT-IR (mid and far IR) and Raman spectroscopy.

  1. Novel platinum-palladium bimetallic nanoparticles synthesized by Dioscorea bulbifera: anticancer and antioxidant activities.

    PubMed

    Ghosh, Sougata; Nitnavare, Rahul; Dewle, Ankush; Tomar, Geetanjali B; Chippalkatti, Rohan; More, Piyush; Kitture, Rohini; Kale, Sangeeta; Bellare, Jayesh; Chopade, Balu A

    2015-01-01

    Medicinal plants serve as rich sources of diverse bioactive phytochemicals that might even take part in bioreduction and stabilization of phytogenic nanoparticles with immense therapeutic properties. Herein, we report for the first time the rapid efficient synthesis of novel platinum-palladium bimetallic nanoparticles (Pt-PdNPs) along with individual platinum (PtNPs) and palladium (PdNPs) nanoparticles using a medicinal plant, Dioscorea bulbifera tuber extract (DBTE). High-resolution transmission electron microscopy revealed monodispersed PtNPs of size 2-5 nm, while PdNPs and Pt-PdNPs between 10 and 25 nm. Energy dispersive spectroscopy analysis confirmed 30.88% ± 1.73% elemental Pt and 68.96% ± 1.48% elemental Pd in the bimetallic nanoparticles. Fourier transform infrared spectra indicated strong peaks at 3,373 cm(-1), attributed to hydroxyl group of polyphenolic compounds in DBTE that might play a key role in bioreduction in addition to the sharp peaks at 2,937, 1,647, 1,518, and 1,024 cm(-1), associated with C-H stretching, N-H bending in primary amines, N-O stretching in nitro group, and C-C stretch, respectively. Anticancer activity against HeLa cells showed that Pt-PdNPs exhibited more pronounced cell death of 74.25% compared to individual PtNPs (12.6%) or PdNPs (33.15%). Further, Pt-PdNPs showed an enhanced scavenging activity against 2,2-diphenyl-1-picrylhydrazyl, superoxide, nitric oxide, and hydroxyl radicals. PMID:26719690

  2. Preparation and Characterization of Polymer-Stabilized Ruthenium-Platinum and Ruthenium-Palladium Bimetallic Colloids and Their Catalytic Properties for Hydrogenation of o-Chloronitrobenzene.

    PubMed

    Liu; Yu; Liu; Zheng

    1999-06-15

    Colloidal dispersions of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium-platinum and ruthenium-palladium bimetallic colloids were prepared by NaBH4 reduction of the corresponding mixed-metal salts at room temperature and characterized by TEM, XPS, and XRD. The resulting bimetallic colloids were used as catalysts for the selective hydrogenation of o-chloronitrobenzene (o-CNB) in methanol at 303 K under 0.1 MPa of hydrogen. It was observed that the catalytic performance of PVP-stabilized ruthenium-platinum colloids (PVP-Ru/Pt) and ruthenium-palladium colloids (PVP-Ru/Pd) was dependent on their compositions and could be remarkably affected by some added metal cations. In the presence of cobalt ion, nearly 100% selectivity to o-chloroaniline (o-CAN) was achieved over PVP-Ru/Pt colloids at 100% conversion of o-CNB, with an activity two orders of magnitude higher than that of monometallic PVP-Ru colloid. Copyright 1999 Academic Press. PMID:10339363

  3. Exhaust system having a gold-platinum group metal catalyst

    DOEpatents

    Ragle, Christie Susan; Silver, Ronald G.; Zemskova, Svetlana Mikhailovna; Eckstein, Colleen J.

    2011-12-06

    A method of providing an exhaust treatment device is disclosed. The method includes applying a catalyst including gold and a platinum group metal to a particulate filter. The concentration of the gold and the platinum group metal is sufficient to enable oxidation of carbon monoxide and nitric oxide.

  4. Exhaust system having a gold-platinum group metal catalyst

    DOEpatents

    Ragle, Christie Susan; Silver, Ronald G.; Zemskova, Svetlana Mikhailovna; Eckstein, Colleen J.

    2012-08-07

    A method of providing an exhaust treatment device is disclosed. The method includes applying a catalyst including gold and a platinum group metal to a particulate filter. The concentration of the gold and the platinum group metal is sufficient to enable oxidation of carbon monoxide and nitric oxide.

  5. Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

    PubMed

    Hung, Chang-Mao

    2009-04-15

    Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes. PMID:18657902

  6. Thermodynamic ground states of platinum metal nitrides.

    PubMed

    Aberg, Daniel; Sadigh, Babak; Crowhurst, Jonathan; Goncharov, Alexander F

    2008-03-01

    The thermodynamic stabilities of various phases of the nitrides of the platinum-metal elements are systematically studied using density functional theory. It is shown that for the nitrides of Rh, Pd, Ir, and Pt two new crystal structures, in which the metal ions occupy simple tetragonal lattice sites, have lower formation enthalpies at ambient conditions than any previously proposed structures. The region of stability with respect to those structures extends to 17 GPa for PtN2. Calculations show that the PtN2 simple tetragonal structures at this pressure are thermodynamically stable also with respect to phase separation. The fact that the local density and generalized gradient approximations predict different values of the absolute formation enthalpies as well different relative stabilities between simple tetragonal and the pyrite or marcasite structures are further discussed. PMID:18352720

  7. Thermodynamic Ground States of Platinum Metal Nitrides

    NASA Astrophysics Data System (ADS)

    Åberg, Daniel; Sadigh, Babak; Crowhurst, Jonathan; Goncharov, Alexander F.

    2008-03-01

    The thermodynamic stabilities of various phases of the nitrides of the platinum-metal elements are systematically studied using density functional theory. It is shown that for the nitrides of Rh, Pd, Ir, and Pt two new crystal structures, in which the metal ions occupy simple tetragonal lattice sites, have lower formation enthalpies at ambient conditions than any previously proposed structures. The region of stability with respect to those structures extends to 17 GPa for PtN2. Calculations show that the PtN2 simple tetragonal structures at this pressure are thermodynamically stable also with respect to phase separation. The fact that the local density and generalized gradient approximations predict different values of the absolute formation enthalpies as well different relative stabilities between simple tetragonal and the pyrite or marcasite structures are further discussed.

  8. Thermodynamic ground states of platinum metal nitrides

    SciTech Connect

    Aberg, D; Sadigh, B; Crowhurst, J; Goncharov, A

    2007-10-09

    We have systematically studied the thermodynamic stabilities of various phases of the nitrides of the platinum metal elements using density functional theory. We show that for the nitrides of Rh, Pd, Ir and Pt two new crystal structures, in which the metal ions occupy simple tetragonal lattice sites, have lower formation enthalpies at ambient conditions than any previously proposed structures. The region of stability can extend up to 17 GPa for PtN{sub 2}. Furthermore, we show that according to calculations using the local density approximation, these new compounds are also thermodynamically stable at ambient pressure and thus may be the ground state phases for these materials. We further discuss the fact that the local density and generalized gradient approximations predict different values of the absolute formation enthalpies as well different relative stabilities between simple tetragonal and the pyrite or marcasite structures.

  9. Platinum-palladium-gold mineralization in the Nkenja mafic-ultramafic body, Ubendian metamorphic belt, Tanzania

    NASA Astrophysics Data System (ADS)

    Evans, David M.; Barrett, Finn M.; Prichard, Hazel M.; Fisher, Peter C.

    2012-01-01

    Significant and widespread enrichment of platinum, palladium, and gold has been found within the Nkenja mafic-ultramafic body located in southern Tanzania in the central part of the Ubendian metamorphic belt. This body is dominated by partly serpentinized chromitiferous dunite, wehrlite and olivine clinopyroxenite, which are tectonically intercalated with amphibolitized metagabbro. The dunites contain both disseminated and seam-type chrome spinel with an Al-rich composition. The seams are thin, impersistent and, together with enclosing dunite, often show deformation at granulite facies conditions. Forsterite contents of olivine in the dunite range from 87 to 92 mol%. Clinopyroxene in wehrlite and clinopyroxenite is diopsidic with significant contents of Al and Na. Clinopyroxene forms irregular bands and crosscutting veins in the dunite, as well as occurring as weakly dispersed isolated grains in the dunite. Elevated levels of Pt, Pd and Au occur in all ultramafic rocks, but not amphibolitized metagabbro, and there is a weak correlation between high abundances of platinum-group element (PGE) and chromitites. PGE values are erratically distributed and are associated with trace to minor amounts of disseminated sulphides (pyrrhotite, pentlandite, heazlewoodite, chalcopyrite and bornite). The abundances of all PGE are consistently anomalous, suggesting a primary igneous control by sulphides in ultramafic rock. However, there has evidently been a strong metamorphic and/or hydrothermal overprint on what was probably an original magmatic concentration of PGE-bearing sulphides. Geological mapping and petrological evidence, as well as the style of PGE sulphide mineralization, are consistent with the Nkenja ultramafic body being part of the crustal section of a dismembered Palaeoproterozoic ophiolite.

  10. Outlooks of HLW Partitioning Technologies Usage for Recovering of Platinum Metals from Spent Fuel

    SciTech Connect

    Pokhitonov, Y. A.; Estimantovskiy, V.; Romanovski, v.; Zatsev, B.; Todd, T.

    2003-02-24

    The existing practice of management of high level waste (HLW) generated by NPPs, call for a task of selective separation of the most dangerous long-lived radionuclides with the purpose of their subsequent immobilization and disposal. HLW partitioning allows to reduce substantially the cost of vitrified product storage owing to isolation of the most dangerous radionuclides, such as transplutonium elements (TPE) into separate fractions of small volumes, intended for ultimate storage. By now numerous investigations on partitioning of HLW of various composition have been carried out in many countries and a lot of processes permitting to recover cesium, strontium, TPE and rare earth elements (REE) have been already tested. Apart from enumerated radionuclides, a fair quantity of palladium and rhodium presents in spent fuel, but the problem of these elements recovery has not yet been decided at the operating radiochemical plants. A negative effect of platinum group metals (PGM) occurrence is determined by the formation of separate metal phase, which not only worsens the conditions of glass-melting but also shortens considerably the service life of the equipment. At the same time, the exhaustion of PGMs natural resources may finally lead to such a growth of their costs that the spent nuclear fuel would became a substituting source of these elements industrial production. Allowing above mentioned, it is of interest to develop the technique for ''reactor'' palladium and rhodium recovery process which would be compatible with HLW partitioning and could be realized using the same facilities. In the report the data on platinum metals distribution in spent fuel reprocessing products and the several flowsheets for palladium separation from HLW are presented.

  11. Novel platinum(II) and palladium(II) complexes of thiosemicarbazones derived from 5-substitutedthiophene-2-carboxaldehydes and their antiviral and cytotoxic activities.

    PubMed

    Karaküçük-İyidoğan, Ayşegül; Taşdemir, Demet; Oruç-Emre, Emine Elçin; Balzarini, Jan

    2011-11-01

    A series of thiosemicarbazones and their platinum(II) and palladium(II) complexes have been synthesized. The chemical structures of ligands and their complexes were characterized by UV-Vis, IR, (1)H NMR, (13)C NMR, MS spectra, elemental analysis and TGA. The antiviral and cytotoxic activities of all compounds have been tested. Results of broad antiviral evaluation showed that none of the compounds evaluated endowed with anti-DNA or -RNA virus activity at subtoxic concentrations except for the palladium complex 1b. This compound exhibited slightly selective inhibition against cytomegalovirus. The platinum complex 4a exhibited the best cytostatic activities against human cervix carcinoma. Ligands 2, 4 and 5 showed cytostatic potential. The palladium complexes were in general less cytostatic than the corresponding platinum complexes or unliganded congeners. PMID:21993152

  12. Curious results with palladium- and platinum-carrying polymers in mass cytometry bioassays and an unexpected application as a dead cell stain.

    PubMed

    Majonis, Daniel; Ornatsky, Olga; Kinach, Robert; Winnik, Mitchell A

    2011-11-14

    We describe the synthesis of metal-chelating polymers (MCPs) with four different pendant polyaminocarboxylate ligands (EDTA, DTPA, TTHA, DOTA) and an orthogonal end-group, either a fluorescein molecule or a bismaleimide linker for antibody attachment. Polymer characterization by a combination of (1)H NMR, UV/vis absorption measurements, and thermal gravimetric analysis (TGA) indicated that each chain of the fluorescein-terminated polymers contained one dye molecule. These polymer samples were loaded with three different types of lanthanide ions as well as palladium and platinum ions. The numbers of metal atoms per chain were determined by a combination of UV/vis and conventional ICP-MS measurements. The experiments with lanthanide ions demonstrated that a net anionic charge on the polymer is important for water solubility. These experiments also showed that at least one type of lanthanide ion (La(3+)) is capable of forming a bimetallic complex with pendant DTPA groups. Conditions were developed for loading these polymers with palladium and platinum ions. While these polymers could be conjugated to antibodies, the presence of Pd or Pt ions in the polymer interfered with the ability of the antibody to recognize its antigen. For example, a goat anti-mouse (secondary) antibody labeled with polymers that contain Pd or Pt no longer recognized a primary antibody in a sandwich assay. In mass cytometry assays, these Pd- or Pt-containing MCPs were very effective in recognizing dead cells and provide a new and robust assay for distinguishing live cells from dead cells. PMID:21955116

  13. Triphenyl phosphine adducts of platinum(IV) and palladium(II) dithiocarbamates complexes: a spectral and in vitro study

    NASA Astrophysics Data System (ADS)

    Manav, N.; Mishra, A. K.; Kaushik, N. K.

    2004-11-01

    Triphenyl phosphine adducts of dithiocarbamate complexes of platinum(IV) and palladium(II) of the type [Pt(L) 2PPh 3Cl 2] and [Pd(L) 2PPh 3] [L: morpholine dithiocarbamate (L 1), aniline dithiocarbamate (L 2) and N-(methyl, cyclohexyl) dithiocarbamate (L 3)] were prepared and characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. Thermal studies of the complexes were carried out. In vitro antitumor activity has been screened towards human adenocarcinoma cell lines and showed significant inhibition even at very low concentration.

  14. Preparation and characterization of platinum (Pt) and palladium (Pd) nanoparticle decorated graphene sheets and their utilization for the elimination of basic fuchsin and indigo carmine dyes

    NASA Astrophysics Data System (ADS)

    Kurt, Belma Zengin; Durmus, Zehra; Durmus, Ali

    2016-01-01

    In this study, graphene nano sheets, prepared with chemical oxidation and reduction routes via modified-Hummer method, were successfully decorated with platinum (Pt) and palladium (Pd) nanoparticles. Structural and morphological features of resulted graphene-metal nanocomposites were characterized with FT-IR, XRD, SEM and TEM methods. Anti-oxidant activity (AOA) values of nanocomposites were determined. The IC50 values of Pt-graphene and Pd-graphene nanocomposites were found to be 46.1 and 90.2 μg/mL, respectively based on the ABTS method and 80.2 and 143.7 μg/mL according to the DPPH method. It was found that the graphene-metal nanocomposites exhibited superior free radical scavenging activity compared to several types of noble metal nano particles although the nanocomposites consist of much lower amount of active metal sites than the nano-crystalline metal powders. It was consequently reported that the graphene-metal nanocomposites could be successfully used for the photocatalytic elimination of fuchsin and indigo carmine dyes under light irradiation.

  15. Hydrodesulfurization and hydrogenation reactions on noble metal catalysts. 1. Elucidation of the behavior of sulfur on alumina-supported platinum and palladium using the {sub 35}S radioisotope tracer method

    SciTech Connect

    Kabe, Toshiaki; Qian, Weihua; Hirai, Yosiki; Li, Li; Ishihara, Atsushi

    2000-02-15

    Hydrodesulfurization (HDS) reactions of {sup 35}S-radioisotope-labeled dibensothiophene (DBT) were carried out over a series of {gamma}-Al{sub 2}O{sub 3}-supported noble-metal-containing catalysts at 5.00 MPa and at 260 and 280 C. The amount of sulfur (S{sub TOTAL}) accommodated on the catalyst and the amount of labile sulfur (S{sub 0}) participating in the reaction were determined using a direct method, the {sup 35}S radioisotope pulse tracer method, which has recently been developed by the authors. It was observed that both S{sub TOTAL} and S{sub 0} increased linearly with an increase in active metal loading. At the same time, it was found that the sulfided test noble metal catalysts corresponded to a S/Pt (Pd) ratio of 0.25 and that almost all the labile sulfur on these catalysts was mobile in the HDS reaction. Further, the activities of both HDS and hydrogenation reactions over the bimetallic catalyst (Pt-Pd) were higher than those of the monometallic catalysts tested together, whereas the synergetic effects observed on the Pt-Pd catalyst were not as significant as in typical Co-Mo catalyst cases.

  16. Microwave assisted synthesis, characterization and biological evaluation of palladium and platinum complexes with azomethines

    NASA Astrophysics Data System (ADS)

    Sharma, Krishna; Singh, Ritu; Fahmi, Nighat; Singh, R. V.

    2010-01-01

    Reactions of 3-acetyl-2,5-dimethylthiophene with thiosemicarbazide and semicarbazide hydrochloride resulted in the formation of new heterocyclic ketimines, 3-acetyl-2,5-dimethylthiophene thiosemicarbazone (C 9H 13N 3OS 2 or L 1H) and 3-acetyl-2,5- dimethylthiophene semicarbazone (C 9H 13N 3OS or L 2H), respectively. The Pd(II) and Pt(II) complexes have been synthesized by mixing metal salts in 1:2 molar ratios with these ligands by using microwave as well as conventional heating method for comparison purposes. The authenticity of these ligands and their complexes has been established on the basis of elemental analysis, melting point determinations, molecular weight determinations, IR, 1H NMR and UV spectral studies. These studies showed that the ligands coordinate to the metal atom in a monobasic bidentate manner and square planar environment around the metal atoms has been proposed to the complexes. Both the ligands and their complexes have been screened for their antimicrobial activities. The antiamoebic activity of both the ligands and their palladium compounds against the protozoan parasite Entamoeba histolytica has been tested.

  17. Microwave assisted synthesis, characterization and biological evaluation of palladium and platinum complexes with azomethines.

    PubMed

    Sharma, Krishna; Singh, Ritu; Fahmi, Nighat; Singh, R V

    2010-01-01

    Reactions of 3-acetyl-2,5-dimethylthiophene with thiosemicarbazide and semicarbazide hydrochloride resulted in the formation of new heterocyclic ketimines, 3-acetyl-2,5-dimethylthiophene thiosemicarbazone (C(9)H(13)N(3)OS(2) or L(1)H) and 3-acetyl-2,5- dimethylthiophene semicarbazone (C(9)H(13)N(3)OS or L(2)H), respectively. The Pd(II) and Pt(II) complexes have been synthesized by mixing metal salts in 1:2 molar ratios with these ligands by using microwave as well as conventional heating method for comparison purposes. The authenticity of these ligands and their complexes has been established on the basis of elemental analysis, melting point determinations, molecular weight determinations, IR, (1)H NMR and UV spectral studies. These studies showed that the ligands coordinate to the metal atom in a monobasic bidentate manner and square planar environment around the metal atoms has been proposed to the complexes. Both the ligands and their complexes have been screened for their antimicrobial activities. The antiamoebic activity of both the ligands and their palladium compounds against the protozoan parasite Entamoeba histolytica has been tested. PMID:19962340

  18. Platinum and Palladium Overlayers Dramatically Enhance the Activity of Ruthenium Nanotubes for Alkaline Hydrogen Oxidation

    SciTech Connect

    St. John, Samuel; Atkinson, Robert W.; Unocic, Kinga A.; Unocic, Raymond R.; Zawodzinski, Thomas A.; Papandrew, Alexander B.

    2015-10-18

    Templated vapor synthesis and thermal annealing were used to synthesize unsupported metallic Ru nanotubes with Pt or Pd overlayers. By controlling the elemental composition and thickness of these overlayers, we obtain nanostructures with very high alkaline hydrogen oxidation activity. For nanotubes with a nominal atomic composition of Ru0.90Pt0.10 display a surface-specific activity (2.4 mA/cm2) that is 35 times greater than that of pure Ru nanotubes at a 50 mV overpotential and 2.5 times greater than that of pure Pt nanotubes (0.98 mA/cm2). The surface-segregated structure also confers dramatically increased Pt utilization efficiency. We find a platinum-mass-specific activity of 1240 A/gPt for the optimized nanotube versus 280 A/gPt for carbon-supported Pt nanoparticles and 109 A/gPt for monometallic Pt nanotubes. Here, we attribute the enhancement of both area- and platinum-mass-specific activity to the atomic-scale homeomorphism of the nanotube form factor with adlayer-modified polycrystals. Subsurface ligand and bifunctional effects previously observed on segregated, adlayer-modified polycrystals are translated to nanoscale catalysts.

  19. Platinum and Palladium Overlayers Dramatically Enhance the Activity of Ruthenium Nanotubes for Alkaline Hydrogen Oxidation

    DOE PAGESBeta

    St. John, Samuel; Atkinson, Robert W.; Unocic, Kinga A.; Unocic, Raymond R.; Zawodzinski, Thomas A.; Papandrew, Alexander B.

    2015-10-18

    Templated vapor synthesis and thermal annealing were used to synthesize unsupported metallic Ru nanotubes with Pt or Pd overlayers. By controlling the elemental composition and thickness of these overlayers, we obtain nanostructures with very high alkaline hydrogen oxidation activity. For nanotubes with a nominal atomic composition of Ru0.90Pt0.10 display a surface-specific activity (2.4 mA/cm2) that is 35 times greater than that of pure Ru nanotubes at a 50 mV overpotential and 2.5 times greater than that of pure Pt nanotubes (0.98 mA/cm2). The surface-segregated structure also confers dramatically increased Pt utilization efficiency. We find a platinum-mass-specific activity of 1240 A/gPtmore » for the optimized nanotube versus 280 A/gPt for carbon-supported Pt nanoparticles and 109 A/gPt for monometallic Pt nanotubes. Here, we attribute the enhancement of both area- and platinum-mass-specific activity to the atomic-scale homeomorphism of the nanotube form factor with adlayer-modified polycrystals. Subsurface ligand and bifunctional effects previously observed on segregated, adlayer-modified polycrystals are translated to nanoscale catalysts.« less

  20. A combined experimental and theoretical investigation of a new imineoxime and its palladium(II) and platinum(II) complexes: Synthesis, structural characterization and spectroscopic properties

    NASA Astrophysics Data System (ADS)

    Kaya, Yunus; Icsel, Ceyda; Yilmaz, Veysel T.; Buyukgungor, Orhan

    2014-12-01

    A new imineoxime compound {(1E,2E)-(2-hydroxy-ethylimino)-naphthalene-2yl-ethanal oxime (heineoH)} and its palladium(II) and platinum(II) complexes ([M(heineo)2]) have been synthesized and characterized by IR, NMR, UV-vis, elemental analysis, mass spectra and X-ray single crystal diffraction. [Pt(heineo)2] was obtained as a single crystal, while [Pd(heineo)2] was synthesized as a polycrystalline powder. The X-ray diffraction analysis of the [Pt(heineo)2] indicated that the platinum(II) ion is coordinated by two heineo ligands in a distorted square-planar geometry. DFT (B3LYP/6-311++G(d,p) and LANL2DZ) calculations on the ligand and its complexes were carried out to correlate the geometry and vibrational and electronic properties. Additionally, heineoH is fluorescent in EtOH at room temperature, but the fluorescence is quenched in the case of the metal complexes.

  1. A combined experimental and theoretical investigation of a new imineoxime and its palladium(II) and platinum(II) complexes: synthesis, structural characterization and spectroscopic properties.

    PubMed

    Kaya, Yunus; Icsel, Ceyda; Yilmaz, Veysel T; Buyukgungor, Orhan

    2014-12-10

    A new imineoxime compound {(1E,2E)-(2-hydroxy-ethylimino)-naphthalene-2yl-ethanal oxime (heineoH)} and its palladium(II) and platinum(II) complexes ([M(heineo)2]) have been synthesized and characterized by IR, NMR, UV-vis, elemental analysis, mass spectra and X-ray single crystal diffraction. [Pt(heineo)2] was obtained as a single crystal, while [Pd(heineo)2] was synthesized as a polycrystalline powder. The X-ray diffraction analysis of the [Pt(heineo)2] indicated that the platinum(II) ion is coordinated by two heineo ligands in a distorted square-planar geometry. DFT (B3LYP/6-311++G(d,p) and LANL2DZ) calculations on the ligand and its complexes were carried out to correlate the geometry and vibrational and electronic properties. Additionally, heineoH is fluorescent in EtOH at room temperature, but the fluorescence is quenched in the case of the metal complexes. PMID:24929321

  2. Platinum(II) and palladium(II) metallomacrocycles derived from cationic 4,4'-bipyridinium, 3-aminopyrazinium and 2-aminopyrimidinium ligands.

    PubMed

    Schilter, David; Clegg, Jack K; Harding, Margaret M; Rendina, Louis M

    2010-01-01

    A series of cationic, ditopic N-donor ligands based on 4,4'-bipyridine (4,4'-bipy), 3-aminopyrazine (apyz) and 2-aminopyrimidine (apym), each incorporating two positively-charged N-heterocycles linked by a conformationally-flexible spacer unit, have been synthesised and treated with palladium(II) or platinum(II) precursors [M(2,2'-bipy)(NO(3))(2)] (M = Pd(II) or Pt(II)) to form highly cationic metallocyclic species. Treatment of 1,6-bis(4,4'-bipyridinium)hexane nitrate with [M(2,2'-bipy)(NO(3))(2)] in aqueous solution, followed by the addition of KPF(6), resulted in the formation of the [2+2] species [M(2)(2,2'-bipy)(2){4,4'-bipy(CH(2))(6)4,4'-bipy}(2)](PF(6))(8). Treatment of [Pd(PhCN)(2)Cl(2)] with 1,3-bis(4,4'-bipyridinium)propane hexafluorophosphate in MeCN afforded [Pd(2)Cl(4){4,4'-bipy(CH(2))(3)4,4'-bipy}(2)](PF(6))(4). When the cationic apyz or apym ligands were used in aqueous solution, the analogous metallomacrocycles did not form. Instead, deprotonation of the exocyclic amino group occurred upon coordination of the ligand to afford a tetranuclear [4+2] species in the case of platinum(II), with Pt(II)...Pt(II) bonding supported by strong UV-vis absorption at lambda = 428 nm which was assigned to a metal-metal-to-ligand charge transfer (MMLCT) band. Thus, treatment of 1,6-bis(3-aminopyrazinium)hexane nitrate with [Pt(2,2'-bipy)(NO(3))(2)], followed by the addition of KPF(6), led to the formation of the red species [Pt(4)(2,2'-bipy)(4){apyz(CH(2))(6)apyz-2H}(2)](PF(6))(8). No related products could be identified with palladium(II), consistent with the low propensity for this metal ion to form strong Pd(II)...Pd(II) bonding interactions. PMID:20023956

  3. MONTANA PALLADIUM RESEARCH INITIATIVE

    SciTech Connect

    Peters, John; McCloskey, Jay; Douglas, Trevor; Young, Mark; Snyder, Stuart; Gurney, Brian

    2012-05-09

    Project Objective: The overarching objective of the Montana Palladium Research Initiative is to perform scientific research on the properties and uses of palladium in the context of the U.S. Department of Energy's Hydrogen, Fuel Cells and Infrastructure Technologies Program. The purpose of the research will be to explore possible palladium as an alternative to platinum in hydrogen-economy applications. To achieve this objective, the Initiatives activities will focus on several cutting-edge research approaches across a range of disciplines, including metallurgy, biomimetics, instrumentation development, and systems analysis. Background: Platinum-group elements (PGEs) play significant roles in processing hydrogen, an element that shows high potential to address this need in the U.S. and the world for inexpensive, reliable, clean energy. Platinum, however, is a very expensive component of current and planned systems, so less-expensive alternatives that have similar physical properties are being sought. To this end, several tasks have been defined under the rubric of the Montana Palladium Research Iniative. This broad swath of activities will allow progress on several fronts. The membrane-related activities of Task 1 employs state-of-the-art and leading-edge technologies to develop new, ceramic-substrate metallic membranes for the production of high-purity hydrogen, and develop techniques for the production of thin, defect-free platinum group element catalytic membranes for energy production and pollution control. The biomimetic work in Task 2 explores the use of substrate-attached hydrogen-producing enzymes and the encapsulation of palladium in virion-based protein coats to determine their utility for distributed hydrogen production. Task 3 work involves developing laser-induced breakdown spectroscopy (LIBS) as a real-time, in situ diagnostic technique to characterize PGEs nanoparticles for process monitoring and control. The systems engineering work in task 4 will

  4. Concentration of some platinum-group metals in coal

    USGS Publications Warehouse

    Finkelman, R.B.; Aruscavage, P. J.

    1981-01-01

    New data on some platinum group metals in coal indicate that the concentration of Pt is generally less than about 5 ppb, that of Pd is generally less than 1 ppb, and that of Rh is generally less than 0.5 ppb. No conclusive evidence was obtained concerning the mode of occurrence of these elements in coal. ?? 1981.

  5. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    ERIC Educational Resources Information Center

    Duong, Hung Tuan

    2009-01-01

    The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

  6. Light-induced reduction of rhodium(III) and palladium(II) on titanium dioxide dispersions and the selective photochemical separation and recovery of gold(III), platinum(IV), and rhodium(III) in chloride media

    SciTech Connect

    Borgarello, E.; Serpone, N.; Emo, G.; Harris, R.; Pelizzetti, E.; Minero, C.

    1986-12-03

    Irradiation of aqueous TiO/sub 2/ dispersions containing palladium(II) or rhodium(III) chloride salts with AM1 simulated sunlight leads to the photoreduction of these metals, which are deposited on the semiconductor particle surface. Oxygen is detrimental to the photoreduction of rhodium(III) but not the photoreduction of palladium(II). However, in both cases the reduction process is most efficient if the solution contains CH/sub 3/OH, which acts to scavenge valence band holes of the illuminated TiO/sub 2/ semiconductor. The selective photoreduction and recovery of precious metals from a dilute solution (as might be found in industrial wastes) have been investigated for a mixture of gold(III), platinum(IV), and rhodium(III) chloride salts as a function of various parameters (pH, presence or absence of O/sub 2/, presence or absence of a hole scavenger, and the concentration of the semiconductor). At pH 0, gold is easily separated from platinum and rhodium. The rate of photoreduction of gold(III) on TiO/sub 2/ is nearly independent of the concentration of the semiconductor, under the experimental conditions employed; the limiting rate is 2.7 x 10/sup -7/ M s/sup -1/. The potential utility of this selective photochemical technique is discussed.

  7. Process for the separation and recovery of palladium and platinum from spent automobile catalyst leach liquor using LIX 84I and Alamine 336.

    PubMed

    Reddy, B Ramachandra; Raju, B; Lee, Jin Young; Park, Hyung Kyu

    2010-08-15

    Spent catalysts from automobile industry contain environmentally critical and economically valuable metals such as Pt, Pd, Fe, Ni, Mn, and Cr. In this paper, we present a process for the selective separation and complete recovery of palladium (Pd) and platinum (Pt) from hydrochloric acid leach liquors of spent automobile catalyst employing solvent extraction method. Typical composition of leach liquor used for the present study contains (mg/L): Pd-150, Pt-550, Mn-500, Ni-1000, Fe-1500, Cr-100 and 3 M HCl. Selective separation of Pd from the leach liquor is achieved with 0.5 vol.% LIX 84I (2-hydroxy-5-nonylacetophenone oxime in a mixture with a high flash point hydrocarbon diluent) in kerosene at an aqueous to organic (A/O) ratio of 3 in 2 stages, with an enrichment factor of three. Quantitative stripping of Pd from loaded organic is achieved with 0.5 M thiourea and 1 M HCl. Co-extraction of Fe and Pt with 5 vol.% Alamine 336 (tertiary amine of mixed tri-octyl/decyl amine) in kerosene followed by selective scrubbing of Fe with dilute HCl and complete stripping of Pt from loaded organic was proposed with 0.5 M thiourea and 0.1 M HCl. Purity of Pd and Pt strip solutions are 99.7%. Finally, the present process can solve environmental related issues and at the same time recover valuable metals in pure form. PMID:20435411

  8. Plasmonic enhancement of low cost mesoporous Fe2O3-TiO2 loaded with palladium, platinum or silver for dye sensitized solar cells (DSSCs)

    NASA Astrophysics Data System (ADS)

    Sanad, M. M. S.; Shalan, Ahmed E.; Rashad, M. M.; Mahmoud, M. H. H.

    2015-12-01

    In this article, a low cost mesoporous Fe2O3-TiO2 nanoparticles has been synthesized from Abu Ghalaga ilmenite ore, Egypt using simple hydrothermal route. Meanwhile, silver, platinum and palladium metals nanoparticles from spent catalysts have been extracted and deposited between the anatase TiO2 particles using in situ reduction step. The as-synthesized samples were characterized by X-ray diffraction (XRD), transmission electron microscopic (TEM), N2 adsorption-desorption isotherm (SBET) and X-ray photoelectron spectroscopy (XPS). The as-prepared materials were applied as photoanodes in dye-sensitized solar cells (DSSCs), whose photocurrent-voltage J-V characteristic curves measurements were consistently performed. The 0.5% precious metal doped samples NPs exhibit absorption enhancement over a broad wavelength range due to the excitation of localized surface plasmons (LSPs) at different wavelengths which also exhibited very good and enhanced photovoltaic performance as a result of the strong scattering lightresulting of noticeable enhancement of charge transfer rates. Indeed, the Ag@Fe2O3-TiO2 sample exhibited the maximum overall conversion efficiency (η % = 4.5%) and it can be considered as a cost-effective photoanode for DSSCs.

  9. Platinum trans-Bis(borirene) complexes displaying coplanarity and communication across a platinum metal center.

    PubMed

    Braunschweig, Holger; Damme, Alexander; Dewhurst, Rian D; Kelch, Hauke; Macha, Bret B; Radacki, Krzysztof; Vargas, Alfredo; Ye, Qing

    2015-02-01

    Ambient-temperature photolysis of the aminoborylene complex [(OC)5 Cr=B=N(SiMe3 )2 ] in the presence of a series of trans-bis(alkynyl)platinum(II) precursors of the type trans-[Pt(CCAr)2 (PEt3 )2 ] (Ar=Ph, p-C6 H4 OMe, and p-C6 H4 CF3 ) successfully leads to twofold transfer of the borylene moiety [:B=N(SiMe3 )2 ] onto the alkyne functionalities. The alkynyl precursors and resultant bis(borirene)platinum(II) complexes formed are of the type trans-[Pt(B{=N(SiMe3 )2 }C=CAr)2 (PEt3 )2 ] (Ar=Ph, p-C6 H4 OMe, and p-C6 H4 CF3 ). These species have all been successfully characterized by NMR, IR, and UV/Vis spectroscopy as well as by elemental analysis. Single-crystal X-ray diffraction has verified that these trans-bis(borirene)platinum(II) complexes display coplanarity between the twin three-membered rings across the platinum core in the solid state and stand as the first examples of coplanar conformations of twin borirene systems. These complexes were modeled using density functional theory (DFT), providing information helpful in determining the ability of the transition metal core to interact with each individual borirene ring system and allowing for the observed coplanarity of these rings in the solid state. This proposed transition metal interaction with the twin borirene systems is manifested in the electronic characterization of these borirene species, which display divergent photophysical UV/Vis spectroscopic profiles compared to a previously published mono(borirene)platinum(II) complex. PMID:25430871

  10. Composite metal membrane

    DOEpatents

    Peachey, Nathaniel M.; Dye, Robert C.; Snow, Ronny C.; Birdsell, Stephan A.

    1998-01-01

    A composite metal membrane including a first metal layer of Group IVB met or Group VB metals, the first metal layer sandwiched between two layers of an oriented metal of palladium, platinum or alloys thereof is provided together with a process for the recovery of hydrogen from a gaseous mixture including contacting a hydrogen-containing gaseous mixture with a first side of a nonporous composite metal membrane including a first metal of Group IVB metals or Group VB metals, the first metal layer sandwiched between two layers of an oriented metal of palladium, platinum or alloys thereof, and, separating hydrogen from a second side of the nonporous composite metal membrane.

  11. Composite metal membrane

    DOEpatents

    Peachey, N.M.; Dye, R.C.; Snow, R.C.; Birdsell, S.A.

    1998-04-14

    A composite metal membrane including a first metal layer of Group IVB met or Group VB metals, the first metal layer sandwiched between two layers of an oriented metal of palladium, platinum or alloys thereof is provided together with a process for the recovery of hydrogen from a gaseous mixture including contacting a hydrogen-containing gaseous mixture with a first side of a nonporous composite metal membrane including a first metal of Group IVB metals or Group VB metals, the first metal layer sandwiched between two layers of an oriented metal of palladium, platinum or alloys thereof, and, separating hydrogen from a second side of the nonporous composite metal membrane.

  12. Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

    DOE PAGESBeta

    Zhang, Lulu; Su, Dong; Zhu, Shangqian; Chang, Qiaowan; Yue, Jeffrey; Du, Zheng; Shao, Minhua

    2016-04-26

    Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

  13. Bio‐palladium: from metal recovery to catalytic applications

    PubMed Central

    De Corte, Simon; Hennebel, Tom; De Gusseme, Bart; Verstraete, Willy; Boon, Nico

    2012-01-01

    Summary While precious metals are available to a very limited extent, there is an increasing demand to use them as catalyst. This is also true for palladium (Pd) catalysts and their sustainable recycling and production are required. Since Pd catalysts exist nowadays mostly under the form of nanoparticles, these particles need to be produced in an environment‐friendly way. Biological synthesis of Pd nanoparticles (‘bio‐Pd’) is an innovative method for both metal recovery and nanocatalyst synthesis. This review will discuss the different bio‐Pd precipitating microorganisms, the applications of the catalyst (both for environmental purposes and in organic chemistry) and the state of the art of the reactors based on the bio‐Pd concept. In addition, some main challenges are discussed, which need to be overcome in order to create a sustainable nanocatalyst. Finally, some outlooks for bio‐Pd in environmental technology are presented. PMID:21554561

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

    USGS Publications Warehouse

    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

  15. The preparation of well-defined dendrimer-encapsulated palladium and platinum nanoparticles and their catalytic evaluation in the oxidation of morin

    NASA Astrophysics Data System (ADS)

    Ncube, Phendukani; Hlabathe, Thaane; Meijboom, Reinout

    2015-12-01

    The preparation of dendrimer-encapsulated platinum (Pt-DENs) and palladium (Pd-DENs) nanoparticles using generation 6-hydroxyl-terminated poly(amidoamine) (PAMAM) dendrimers as a templating agent is described. These nanoparticles were characterized using UV-vis spectrophotometry, spectrofluorophotometry, Fourier transform infrared spectrometry (FTIR), and high resolution transmission electron microscopy (HRTEM). The UV-vis spectra of palladium and platinum dendrimer-encapsulated nanoparticles gave a clear proof that nanoparticles were formed. It was found from FTIR spectra that there are shifts of peaks from higher wave numbers to lower wave numbers after reduction with sodium borohydride and these confirm the encapsulation of nanoparticles inside the voids of the dendrimer. The particle diameters were found to be 1.4 ± 0.2 and 1.6 ± 0.2 nm in diameter for palladium and platinum respectively from HRTEM. These nanoparticles were evaluated as catalysts in the oxidation of morin by hydrogen peroxide. The kinetic data was modeled to the Langmuir-Hinshelwood equation. The model allows relating apparent rate constant to the total surface area (S) of the nanoparticle. The Langmuir-Hinshelwood model also allows a direct relationship between the kinetic constant (k) and Kmorin and KH2O2 . The Arrhenius and Eyring equations were used to determine thermodynamic parameters for the oxidation of morin.

  16. Separation of platinum group metal ions by Donnan dialysis

    SciTech Connect

    Brajter, K.; Slonawska, K.; Cox, J.A.

    1985-10-01

    Separations of metal ions on the basis of Donnan dialysis across anion-exchange membranes should be possible if the receiver electrolyte composition favors the formation of selected anionic complexes of the sample metal ions. Moreover, such a separation has the possibility of being better suited from some applications than batch or column experiments with anion-exchange resins. The above hypothesis are tested on the platinum-group metal ions, Pt(IV), Rh(III), Pd(II), Ir(III), and Ir(IV). 13 references, 4 tables.

  17. International strategic minerals inventory summary report: platinum-group metals

    USGS Publications Warehouse

    Sutphin, David M.; Page, Norman J

    1986-01-01

    Major world resources of platinum-group metals are described in this summary report of information in the International Strategic Minerals Inventory {ISMI}. ISMI is a cooperative data-collection effort of earth-science and mineral-resource agencies in Australia, Canada, the Federal Republic of Germany, the Republic of South Africa, and the United States of America. This report, designed to be of benefit to policy analysts, contains two parts. Part I presents an overview of the resources and potential supply of platinum-group metals on the basis of inventory information. Part II contains tables of some of the geologic information and mineral-resource and production data that were collected by ISMI participants.

  18. Palladium, platinum, and rhodium contents of rocks near the lower margin of the Stillwater complex, Montana.

    USGS Publications Warehouse

    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.

  19. Platinum metals in magmatic sulfide ores

    USGS Publications Warehouse

    Naldrett, A.J.; Duke, J.M.

    1980-01-01

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example. Copyright ?? 1980 AAAS.

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

    PubMed

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

    2013-03-01

    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. PMID:23358311

  1. Preparation of fibrous palladium

    SciTech Connect

    Silver, G.L.; Seabaugh, P.W.; Leahy, B.T.; Werkmeister, D.W.; Martin, F.S.; Friedlander, H.N.

    1988-06-15

    Acrylic fibers (pan fibers) absorb palladium from a hot solution of palladium nitrate in nitric acid. When palladium-loaded acrylic fibers are burned, fibers consisting of palladium and palladium oxide are formed. Reduction of this mixture with hydrogen produces fibers of palladium metal. The fibers may be compressed into pellets which offer less resistance to flowing hydrogen than similar pellets prepared by compressing commercial palladium powder. 9 refs., 12 figs., 5 tabs.

  2. Bioaccumulation of palladium, platinum and rhodium from urban particulates and sediments by the freshwater isopod Asellus aquaticus.

    PubMed

    Moldovan, M; Rauch, S; Gómez, M; Palacios, M A; Morrison, G M

    2001-12-01

    The three-way catalytic converters introduced to oxidize and reduce gaseous automobile emissions represent a source of platinum group elements (PGEs), in particular platinum, palladium and rhodium, to the urban environment. Abrasion of automobile exhausts leads to an increase of the concentration of PGEs in environmental matrices such as vegetation, soil and water bodies. The bioaccumulation of Pd, Pt and Rh by the freshwater isopod Asellus aquaticus was studied in natural ecosystems and under laboratory conditions. Owing to the low concentration level (ng g(-1)) of PGEs in the animals studied. analyses were performed with a quadrupole inductively coupled plasma mass spectrometry (ICP-MS) and hafnium, copper, yttrium, rubidium, strontium and lead were monitored for spectral interference correction. Asellus aquaticus collected in an urban river showed a content (mean +/- s) of 155.4 +/- 73.4, 38.0 +/- 34.6, and 17.9 +/- 12.2 ng g(-1) (dry weight) for Pd, Pt and Rh, respectively. The exposure of Asellus aquaticus to PGE standard solutions for a period of 24h give bioaccumulation factors of Bf: 150, 85, and 7 for Pd, Pt and Rh, respectively. Exposure of Asellus aquaticus to environmental samples for different exposure periods demonstrated that PGE bioaccumulation is time dependent. and shows a higher accumulation for the materials with a higher PGE content. While all three elements have the same uptake rate for exposure to catalyst materials, for exposure to environmental materials they havc a different uptake rate which can be attributed to transformations of the PGE species in the environment. PMID:11791847

  3. Direct electron transfer of Phanerochaete chrysosporium cellobiose dehydrogenase at platinum and palladium nanoparticles decorated carbon nanotubes modified electrodes.

    PubMed

    Bozorgzadeh, Somayyeh; Hamidi, Hassan; Ortiz, Roberto; Ludwig, Roland; Gorton, Lo

    2015-10-01

    In the present work, platinum and palladium nanoparticles (PtNPs and PdNPs) were decorated on the surface of multi-walled carbon nanotubes (MWCNTs) by a simple thermal decomposition method. The prepared nanohybrids, PtNPs-MWCNTs and PdNPs-MWCNTs, were cast on the surface of spectrographic graphite electrodes and then Phanerochaete chrysosporium cellobiose dehydrogenase (PcCDH) was adsorbed on the modified layer. Direct electron transfer between PcCDH and the nanostructured modified electrodes was studied using flow injection amperometry and cyclic voltammetry. The maximum current responses (Imax) and the apparent Michaelis-Menten constants (K) for the different PcCDH modified electrodes were calculated by fitting the data to the Michaelis-Menten equation and compared. The sensitivity towards lactose was 3.07 and 3.28 μA mM(-1) at the PcCDH/PtNPs-MWCNTs/SPGE and PcCDH/PdNPs-MWCNTs/SPGE electrodes, respectively, which were higher than those measured at the PcCDH/MWCNTs/SPGE (2.60 μA mM(-1)) and PcCDH/SPGE (0.92 μA mM(-1)). The modified electrodes were additionally tested as bioanodes for biofuel cell applications. PMID:26323551

  4. Investigation of platinum and palladium as potential anodic catalysts for direct borohydride and ammonia borane fuel cells

    NASA Astrophysics Data System (ADS)

    Olu, Pierre-Yves; Deschamps, Fabien; Caldarella, Giuseppe; Chatenet, Marian; Job, Nathalie

    2015-11-01

    Platinum and palladium are investigated as anodic catalysts for direct borohydride and direct ammonia borane fuel cells (DBFC and DABFC). Half-cell characterizations performed at 25 °C using NH3BH3 or NaBH4 alkaline electrolytes demonstrate the lowest open-circuit potential and highest electrocatalytic activity for the NH3BH3 alkaline electrolyte for Pd and Pt rotating disk electrodes, respectively. Voltammograms performed in fuel cell configuration at 25 °C confirm this trend: the highest open circuit voltage (1.05 V) and peak power density (181 mW·cm-2) are monitored for DABFC using Pd/C and Pt/C anodes, respectively. Increasing the temperature heightens the peak power density (that reaches 420 mW·cm-2 at 60 °C for DBFC using Pt/C anodes), but strongly generates gas from the fuel hydrolysis, hindering the overall fuel cells performances. The anode texture strongly influences the fuel cell performances, highlighting: (i) that an open anode texture is required to efficiently circulate the anolyte and (ii) the difficulty to compare potential anodic catalysts characterized using different fuel cell setups within the literature. Furthermore, TEM imaging of Pt/C and Pd/C catalysts prior/post DBFC and DABFC operation shows fast degradation of the carbon-supported nanoparticles.

  5. Fuel cell performance of palladium-platinum core-shell electrocatalysts synthesized in gram-scale batches

    DOE PAGESBeta

    Khateeb, Siddique; Su, Dong; Guerreo, Sandra; Darling, Robert M.; Protsailo, Lesia V.; Shao, Minhua

    2016-05-03

    This article presents the performance of palladium-platinum core-shell catalysts (Pt/Pd/C) for oxygen reduction synthesized in gram-scale batches in both liquid cells and polymer-electrolyte membrane fuel cells. Core-shell catalyst synthesis and characterization, ink fabrication, and cell assembly details are discussed. The Pt mass activity of the Pt/Pd core-shell catalyst was 0.95 A mg–1 at 0.9 V measured in liquid cells (0.1 M HClO4), which was 4.8 times higher than a commercial Pt/C catalyst. The performances of Pt/Pd/C and Pt/C in large single cells (315 cm2) were assessed under various operating conditions. The core-shell catalyst showed consistently higher performance than commercial Pt/Cmore » in fuel cell testing. A 20–60 mV improvement across the whole current density range was observed on air. Sensitivities to temperature, humidity, and gas composition were also investigated and the core-shell catalyst showed a consistent benefit over Pt under all conditions. However, the 4.8 times activity enhancement predicated by liquid cell measurements was not fully realized in fuel cells.« less

  6. Structural, spectroscopic and quantum chemical studies of acetyl hydrazone oxime and its palladium(II) and platinum(II) complexes

    NASA Astrophysics Data System (ADS)

    Kaya, Yunus; Icsel, Ceyda; Yilmaz, Veysel T.; Buyukgungor, Orhan

    2015-09-01

    Acetyl hydrazone oxime, [(1E,2E)-2-(hydroxyimino)-1-phenylethylidene]acetohydrazone (hipeahH2) and its palladium(II) and platinum(II) complexes, [M(hipeahH)2] (M = PdII and PtII), have been synthesized and characterized by elemental analysis, UV-vis IR, NMR and LC-MS techniques. X-ray diffraction analysis of [Pd(hipeahH)2] shows that the two hipeahH2 ligands are not equal; one of the ligands loses the hydrazone proton, while the other one loses the oxime proton, resulting in a different coordination behavior to form five- and six-membered chelate rings. The molecular geometries from X-ray experiments in the ground state were compared using the density functional theory (DFT) with the B3LYP method combined with the 6-311++G(d,p) basis set for the ligand and the LanL2DZ basis set for the complexes. Comprehensive theoretical and experimental structural studies on the molecule have been carried out by FT-IR, NMR and UV-vis spectrometry. In addition, the isomer studies of ligand and its complexes were made by DFT.

  7. Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

    NASA Astrophysics Data System (ADS)

    Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

    2013-03-01

    A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

  8. Synthesis, Characterization, and In Vitro Cytotoxic Activities of Benzaldehyde Thiosemicarbazone Derivatives and Their Palladium (II) and Platinum (II) Complexes against Various Human Tumor Cell Lines

    PubMed Central

    Hernándeza, Wilfredo; Paz, Juan; Vaisberg, Abraham; Spodine, Evgenia; Richter, Rainer; Beyer, Lothar

    2008-01-01

    The palladium (II) bis-chelate Pd (L1−3)2 and platinum (II) tetranuclear Pt4(L4)4 complexes of benzaldehyde thiosemicarbazone derivatives have been synthesized, and characterized by elemental analysis and IR, FAB(+)-mass and NMR (1H, 13C) spectroscopy. The complex Pd(L2)2 [HL2 = m-CN-benzaldehyde thiosemicarbazone] shows a square-planar geometry with two deprotonated ligands (L) coordinated to PdII through the nitrogen and sulphur atoms in a transarrangement, while the complex Pt4(L4)4 [HL4 = 4-phenyl-1-benzaldehyde thiosemicarbazone] has a tetranuclear geometry with four tridentate ligands coordinated to four PtII ions through the carbon (aromatic ring), nitrogen, and sulphur atoms where the ligands are deprotonated at the NH group. The in vitro antitumor activity of the ligands and their complexes was determined against different human tumor cell lines, which revealed that the palladium (II) and platinum (II) complexes are more cytotoxic than their ligands with IC50 values at the range of 0.07–3.67 μM. The tetranuclear complex Pt4(L4)4, with the phenyl group in the terminal amine of the ligand, showed higher antiproliferative activity (CI50 = 0.07–0.12 μM) than the other tested palladium (II) complexes. PMID:19148285

  9. The separation of platinum, palladium and gold from silicate rocks by the anion exchange separation of chloro complexes after a sodium peroxide fusion: an investigation of low recoveries.

    PubMed

    Enzweiler, J; Potts, P J

    1995-10-01

    A series of experiments was undertaken to measure the recovery efficiency of platinum, palladium and gold from silicate rocks using a sodium peroxide fusion followed by anion exchange separation of the analytes as chloro complexes. Results obtained by graphite furnace atomic absorption spectrometric analysis of standard solutions prepared in dilute HCl or HCl-acidified sodium peroxide solution showed that recoveries were near quantitative. However, when standard solutions were added to an alkaline sodium peroxide solution, which was then acidified, low results were obtained for platinum and gold (46% and 76% respectively). Low and variable results were also obtained when standard solutions were added to a peridotite sample that had been dissolved by the state procedure, and in the analysis of the South African Bureau of Standards certified reference material, SARM 7. Various experiments were undertaken to investigate these low recoveries, but the reason proposed here is the formation of hydroxychloro compounds in alkaline solution which are not, on acidification with HCl, converted quantitatively to the chloro complex necessary for quantitative anion exchange separation. It is concluded that a sodium peroxide fusion followed by an anion-exchange separation does not appear to form the basis of a successful technique for the determination of platinum, palladium and gold in silicate rocks. PMID:18966370

  10. PALLADIUM, PLATINUM, RHODIUM, RUTHENIUM AND IRIDIUM IN PERIDOTITES AND CHROMITITES FROM OPHIOLITE COMPLEXES IN NEWFOUNDLAND.

    USGS Publications Warehouse

    Page, Norman J; Talkington, Raymond W.

    1984-01-01

    Samples of spinel lherzolite, harzburgite, dunite, and chromitite from the Bay of Islands, Lewis Hills, Table Mountain, Advocate, North Arm Mountain, White Hills Periodite Point Rousse, Great Bend and Betts Cove ophiolite complexes in Newfoundland were analyzed for the platinum-group elements (PGE) Pd, Pt, Rh, Ru and Ir. The ranges of concentration (in ppb) observed for all rocks are: less than 0. 5 to 77 (Pd), less than 1 to 120 (Pt), less than 0. 5 to 20 (Rh), less than 100 to 250 (Ru) and less than 20 to 83 (Ir). Chondrite-normalized PGE ratios suggest differences between rock types and between complexes. Samples of chromitite and dunite show relative enrichment in Ru and Ir and relative depletion in Pt and Pd.

  11. First palladium(II) and platinum(II) complexes from employment of 2,6-diacetylpyridine dioxime: synthesis, structural and spectroscopic characterization, and biological evaluation.

    PubMed

    Koumousi, Evangelia S; Zampakou, Marianthi; Raptopoulou, Catherine P; Psycharis, Vassilis; Beavers, Christine M; Teat, Simon J; Psomas, George; Stamatatos, Theocharis C

    2012-07-16

    Employment of the monoanion of 2,6-diacetylpyridine dioxime (dapdoH(2)) as a tridentate chelate in palladium(II) and platinum(II) chemistry is reported. The syntheses, crystal structures, spectroscopic and physicochemical characterization, and biological evaluation are described of [PdCl(dapdoH)] (1) and [PtCl(dapdoH)] (2). Reaction of PdCl(2) with 2 equivs of dapdoH(2) in MeOH under reflux gave 1, whereas the same reaction with PtCl(2) in place of PdCl(2) gave 2 in comparable yields (70-80%). The divalent metal center in both compounds is coordinated by a terminal chloro group and a N,N',N"-tridentate chelating (η(3)) dapdoH(-) ligand. Thus, each metal ion is four coordinate with a distorted square planar geometry. Characterization of both complexes with (1)H and (13)C NMR and UV-vis and electrospray ionization mass spectroscopies confirmed their integrity in DMSO solutions. Interaction of the complexes with human and bovine serum albumin has been studied with fluorescence spectroscopy, revealing their affinity for these proteins with relatively high values of binding constants. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that they can bind to CT DNA, and the corresponding DNA binding constants have been evaluated. Cyclic voltammograms of the complexes in the presence of CT DNA solution have shown that the interaction of the complexes with CT DNA is mainly through intercalation, which has been also shown by DNA solution viscosity measurements. Competitive studies with ethidium bromide (EB) have revealed the ability of the complexes to displace the DNA-bound EB, suggesting competition with EB. The combined work demonstrates the ability of pyridyl-dioxime chelates not only to lead to polynuclear 3d-metal complexes with impressive structural motifs and interesting magnetic properties but also to yield new, mononuclear 4d- and 5d-metal complexes with biological implications. PMID:22742945

  12. Square-planar coordinated polyanions of palladium, platinum, and gold stannaborate [SnB11H11]2- coordination chemistry.

    PubMed

    Marx, Thiemo; Mosel, Bernd; Pantenburg, Ingo; Hagen, Siegbert; Schulze, Herbert; Wesemann, Lars

    2003-09-22

    The tetrasubstituted polyanions of platinum, palladium, and gold [M(SnB(11)H(11))(4)](x-) (x=6, M=Pd, Pt; x=5, M=Au) have been prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR, Raman, (11)B, and (119)Sn heteronuclear NMR spectroscopy. In the case of the platinum derivative [Bu(3)MeN](6)[Pt(SnB(11)H(11))(4)] (2) (119)Sn Mössbauer spectroscopy has been carried out. The isolated salts are stable towards moisture and air and the complexes 2 and 3 were treated with 1,3-bis(diphenylphosphino)propane (dppp) to give the respective substitution products [Bu(3)MeN](2)[(dppp)M(SnB(11)H(11))(2)] (M=Pd, Pt). PMID:14502634

  13. Palladium, platinum, rhodium, iridium and ruthenium in chromite- rich rocks from the Samail ophiolite, Oman.

    USGS Publications Warehouse

    Page, N.J.; Pallister, J.S.; Brown, M.A.; Smewing, J.D.; Haffty, J.

    1982-01-01

    30 samples of chromitite and chromite-rich rocks from two stratigraphic sections, 250 km apart, through the basal ultramafic member of the Samail ophiolite were spectrographically analysed for platinum-group elements (PGE) and for Co, Cu, Ni and V. These data are reported as are Cr/(Cr + Al), Mg/(Mg + Fe) and wt.% TiO2 for most samples. The chromitite occurs as pods or lenses in rocks of mantle origin or as discontinuous layers at the base of the overlying cumulus sequence. PGE abundances in both sections are similar, with average contents in chromite-rich rocks: Pd 8 ppb, Pt 14 ppb, Rh 6 ppb, Ir 48 ppb and Ru 135 ppb. The PGE data, combined with major-element and petrographic data on the chromitite, suggest: 1) relatively larger Ir and Ru contents and highest total PGE in the middle part of each section; 2) PGE concentrations and ratios do not correlate with coexisting silicate and chromite abundances or chromite compositions; 3) Pd/PGE, on average, increases upward in each section; 4) Samail PGE concentrations, particularly Rh, Pt and Pd, are lower than the average values for chromite-rich rocks in stratiform intrusions. 2) suggests that PGEs occur in discrete alloy or sulphide phases rather than in the major oxides or silicates, and 4) suggests that chromite-rich rocks from the oceanic upper mantle are depleted in PGE with respect to chondrites. L.C.C.

  14. Structure analysis and photochemistry of adsorbates on platinum and palladium surfaces. [1,2-dichloroethene

    SciTech Connect

    Grassian, V.H.

    1987-05-01

    The vibrational spectra of benzene and toluene adsorbed on Pd(111) indicates at 180K these molecules weakly bond to the surface. The adsorption of benzene and toluene on Pt(111) is much stronger as indicated by large frequency shifts from gas phase values. Pyridine adsorption on both Pt(111) and Pd(111) was studied as a function of temperature. At room temperature pyridine decomposes on the surface to form an ..cap alpha..-pyridyl fragment (NC/sub 5/H/sub 4/) on Pt(111), whereas the molecule remains intact on Pd(111). The electron energy loss spectra of pyridine adsorbed on these surfaces is compared to the ir spectra of two osmium cluster compounds: Os/sub 3/(CO)/sub 11/(NC/sub 5/H/sub 5/), a pyridine complex, and HOs/sub 3/(CO)/sub 10/(NC/sub 5/H/sub 4/), a pyridyl complex. The stronger interaction of these molecules to the platinum surface is a consequence of the stronger bonding of the 5d orbitals as compared to the 4d orbitals. The uv photochemistry of 2-butene and 1,2-dichloroethene when adsorbed on Pt and Pd surfaces was also studied.

  15. Potentiometric titration of gold, platinum, and some other precious metals

    SciTech Connect

    Selig, W.S.

    1991-02-04

    Gold, platinum, and several other platinum metals can be determined by titration with cetylpyridinium chloride (CPC). CPC forms a precipitate with AuCl{sub 4}{sup {minus}} and PtCl{sub 6}{sup 2{minus}}. Differentiation of AuCl{sub 4{minus}} and PtCl{sub 6}{sup 2{minus}} with this titrant is not possible; however, their sum can be determined. Titration with tetraphenylarsonium chloride at pH 1 is selective for tetrachloroaurate, which thus can be determined in the presence of hexachloroplatinate. Hexachloroosmate(IV), tetrachloroplatinite(II), tetrachloropalladate(II), hexachloropalladate(IV), and hexachloroiridate(IV) can also be determined potentiometrically vs. CPC. The indicating electrode is prepared by coating a spectroscopic graphite rod with a solution of poly(vinyl chloride) (PVC) and dioctylphthalate (DOP) in tetrahydrofuran (THF). Gold in gold cyanide plating baths and in potassium aurocyanide can be determined by potentiometric titration vs standard silver nitrate, using a silver ion-selective indicating electrode. The monovalent gold need not be converted to the trivalent state with aqua regia, resulting in a considerable saving of time and effort. Free cyanide and aurocyanide can be titrated sequentially by this method. Chloride does not interfere and can, in fact, also be sequentially determined. 17 refs., 2 figs., 3 tabs.

  16. Tritium production from a low voltage deuterium discharge on palladium and other metals

    SciTech Connect

    Claytor, T.N.; Jackson, D.D.; Tuggle, D.G.

    1995-09-01

    Over the past year the authors have been able to demonstrate that a plasma loading method produces an exciting and unexpected amount of tritium from small palladium wires. In contrast to electrochemical hydrogen or deuterium loading of palladium, this method yields a reproducible tritium generation rate when various electrical and physical conditions are met. Small diameter wires (100--250 microns) have been used with gas pressures above 200 torr at voltages and currents of about 2,000 V at 3--5 A. By carefully controlling the sputtering rate of the wire, runs have been extended to hundreds of hours allowing a significant amount (> 10`s nCi) of tritium to accumulate. they show tritium generation rates for deuterium-palladium foreground runs that are up to 25 times larger than hydrogen-palladium control experiments using materials from the same batch. They illustrate the difference between batches of annealed palladium and as received palladium from several batches as well as the effect of other metals (Pt, Ni, Nb, Zr, V, W, Hf) to demonstrate that the tritium generation rate can vary greatly from batch to batch.

  17. A histopathological study of Hudson River crayfish, Orconectes virilis, exposed to platinum group metals.

    PubMed

    Wren, Melody; Gagnon, Zofia E

    2014-01-01

    Platinum group metals (PGMs), such as platinum (Pt), palladium (Pd), and rhodium (Rh), are of increasing concern due to rising anthropogenic input to aquatic systems. In this study, PGMs' effects on bioaccumulation and histopathological changes were investigated using Orconectes virilis, a native Hudson River crayfish, as a model. Organisms were exposed to varying concentrations of water-soluble PGM salts for 10 days. The following experimental treatments were established: 0.0, 1.0, 5.0, 10.0 ppm Pt(IV), 1.0 ppm Rh(III), 1.0 ppm Pd(II), and a PGM mix (1.0 ppm Pt(IV), Rh(III), Pd(II) each) dissolved in raw Hudson River water. Metal content in the tissue samples were analyzed by a Spectro Genesis ICP-OES. The relationship between Pt, Pd, and Rh concentrations in different treatments and observed behavioral changes during the experiment was analyzed through One-Way ANOVA Student-Newman-Keuls multiple comparison test (P ≤ 0.05). Paraffin sections, 6-μm-thick, were prepared in standard eosin-Y and hematoxylin-2 stain and examined for histological abnormalities within hepatopancreas, exoskeleton, brain, and ganglia tissue. Statistically significant differences in PGM bioaccumulation were observed in all organs, with highest concentrations found in the hepatopancreas, 81.68 mg g(-1) dw in 1.0 ppm Pd treatment, 20.03 mg g(-1) dw Rh in 1.0 ppm Rh treatment, and 81.58 mg g(-1) dw Pt in the 5.0 ppm Pt treatment. Pt bioaccumulation in the hepatopancreas and exoskeleton decreased at the highest Pt exposure treatment, suggesting severe structural damage to tissue. Hyper-segmentation of vacuoles and swelling of the vascular channels were observed in the hepatocyte structure of the hepatopancreas. Exoskeleton exhibited visible bands in the exocuticle indicating demineralization. Brain and ganglia demonstrated extensive vacuolization. Behavioral analysis showed an increase of maximum response intensity over the experimental period within each treatment

  18. Evidence for the Formation of Nitrogen-Rich Platinum and Palladium Nitride Nanoparticles

    SciTech Connect

    Veith, Gabriel M.; Lupini, Andrew R.; Baggetto, Loïc; Browning, James F.; Keum, Jong K.; Villa, Alberto; Prati, Laura; Papandrew, Alexander B.; Goenaga, Gabriel A.; Mullins, David R.; Bullock, Steven E.; Dudney, Nancy J.

    2013-12-03

    Here, we report evidence for the formation of nitrogen-rich precious metal nanoparticles (Pt, Pd) prepared by reactive sputtering of the pure metal in a N2 plasma. The composition of the nanoparticles varies as a function of particle size and growth conditions. For the smallest particles the nitrogen content appears to be as high as 6.7 N atoms for each Pd atom or 5.9 N atoms for each Pt atom whereas bulk films have nominal compositions of Pt7.3N and Pd2.5N. The nanoparticles are metastable in air and moisture, slowly decomposing over several years. This paper describes the synthesis of these materials along with experimental evidence of the composition, oxidation state, and growth modes. Moreover, the catalytic properties of these N-rich nanoparticles were accessed by rotating disk electrode electrochemical studies, the liquid phase oxidation of benzyl alcohol and gas phase CO oxidation and support the experimental evidence for the materials composition.

  19. Evidence for the Formation of Nitrogen-Rich Platinum and Palladium Nitride Nanoparticles

    DOE PAGESBeta

    Veith, Gabriel M.; Lupini, Andrew R.; Baggetto, Loïc; Browning, James F.; Keum, Jong K.; Villa, Alberto; Prati, Laura; Papandrew, Alexander B.; Goenaga, Gabriel A.; Mullins, David R.; et al

    2013-12-03

    Here, we report evidence for the formation of nitrogen-rich precious metal nanoparticles (Pt, Pd) prepared by reactive sputtering of the pure metal in a N2 plasma. The composition of the nanoparticles varies as a function of particle size and growth conditions. For the smallest particles the nitrogen content appears to be as high as 6.7 N atoms for each Pd atom or 5.9 N atoms for each Pt atom whereas bulk films have nominal compositions of Pt7.3N and Pd2.5N. The nanoparticles are metastable in air and moisture, slowly decomposing over several years. This paper describes the synthesis of these materialsmore » along with experimental evidence of the composition, oxidation state, and growth modes. Moreover, the catalytic properties of these N-rich nanoparticles were accessed by rotating disk electrode electrochemical studies, the liquid phase oxidation of benzyl alcohol and gas phase CO oxidation and support the experimental evidence for the materials composition.« less

  20. 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

    NASA Astrophysics Data System (ADS)

    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.

  1. Platinum and palladium complexes of thiosemicarbazones derived of 2-acetylthiophene: Synthesis and spectral studies

    NASA Astrophysics Data System (ADS)

    Neto, J. L.; de Lima, G. M.; Beraldo, H.

    2006-03-01

    The reaction of 2-acetylthiophene thiosemicarbazone (2-HATT) and 2-acetylthiophene 4-phenylthiosemicarbazone (2-HAT-4-FT) with Pd(COD)Cl 2 (COD = 1,5-cyclooctadiene) and trans-Pt 2PEt 3Cl 4 yielded four new metal complexes: [Pd(2-HATT)Cl 2] ( 1), [Pd(2-ATT) 2] ( 2), [Pd(2-AT-4-FT)Cl] ( 3) and [Pt(2-ATT)(PEt 3)Cl] ( 4). Apart from compound 3 all the others were characterised by 1H and 13C{ 1H} NMR, infrared spectroscopy, and elemental analysis. Multinuclear NMR experiments of 31P{ 1H} and 195Pt{ 1H} of complex 4 have revealed that the ligand 2-HATT behaves as a bidentate chelating agent towards Pd(COD)Cl 2 and trans-Pt 2PEt 3Cl 4 whereas ligand 2-HAT-4-FT forms a tridentate chelating complex with Pd(COD)Cl 2.

  2. High temperature silver-palladium-copper oxide air braze filler metal

    NASA Astrophysics Data System (ADS)

    Darsell, Jens Tommy

    The Ag-CuO system is currently being investigated as the basis for an air braze filler metal alloy to be used in SOFC components. The system is of interest because unlike most braze alloys, it is capable of wetting a variety of ceramic materials while being applied in an air. This thesis work examined modification of Ag-CuO filler metal system by alloying with palladium to increase the use temperature of the resulting air braze alloy. Thermal analysis was performed to track changes in the solidus and liquidus temperatures for these alloys and determine equilibrium phase present as a function of temperature and composition. Sessile drop experiments were performed to investigate the effect of palladium addition on braze wetability. The influence of copper-oxide and palladium contents on brazed joint strength was characterized by a combination of four-point bend testing and fractography. From combined thermal analysis and quenched data it was found that both the liquidus and solidus increase with increasing palladium content, and the silver-rich miscibility gap boundary could be shifted by the addition of palladium. This was employed as a tool to study the effects of two-liquid phase formation on wetting behavior. In addition, a mass loss likely attributable to silver volatilization is observed in the Pd-modified filler metals when heated over ˜1100°C. As volatilization should be avoided, the ternary alloys should be limited to 15mol% Pd. It was found by sessile drop wetting experiments that there is a definitive change in wetting behavior that corresponds directly to the miscibility gap boundary for the Pd-Ag-CuO system. The first order transition tracks with changes in the miscibility gap boundary that can be induced by increasing palladium content. This is the first experimental evidence of critical point wetting behavior reported for a metal-oxide system and further confirms that critical point wetting theory is universal. Four-point bend testing and

  3. Five-alkyl-two-thiopyrrolidones as ligands in platinum(II) and palladium(II) complexes

    SciTech Connect

    Shebaldova, A.D.; Bystrenina, V.I.; Bespalova, G.V.; Labunskaya, V.I.

    1985-09-01

    5-alkyl-2-thiopyrrolidones (TP, alkyl = C/sub 3/H/sub 7/, C/sub 4/H/sub 9/, C/sub 5/H/sub 11/) have been used for the first time as ligands for the synthesis of complex compounds. When they are reacted with solutions of Pt(II) and Pd(II) salts in a hydroalcoholic medium with a 2:1 ratio between the reactants, complexes with the general formula M(TP)/sub 2/Cl/sub 2/ are obtained. The composition of the complex compounds has been established on the basis of the data from elemental and thermographic analysis. The complex compounds are nonelectrolytes and have a trans configurations (one band with a frequency of 310-330 cm/sup -1/). With the aid of the methods of quantum chemistry and IR and NMR spectroscopy, it has been established that the coordination of TP with the metal is realized by means of the sulfur atom. A comparison of the electron-donor properties of the 5-substituted thiopyrrolidones and their oxygen-containing analogs has been made. All the complex compounds have moderate antiphage, antibacterial, and antifungal activities. The Pd(II) complexes are catalysts for the dehydrohalogenation of 1,2-dichloro-3-butene to chloroprenes.

  4. Investigation of palladium and platinum levels in food by sector field inductively coupled plasma mass spectrometry.

    PubMed

    Frazzoli, Chiara; Cammarone, Roberta; Caroli, Sergio

    2007-05-01

    Over the last two decades, there has been increased concern regarding the impact of some noble metals, such as Pd and Pt, on human health. These elements pollute the environment due to their widespread use as catalytic converters and in medical applications. The risk they pose to human health and the environment is still controversial; however, literature data point to diet as an important source of uptake by the human body. Within this context, the total Pd and Pt content of several Italian food commodities has been investigated. A total of 90 samples, including flour products, vegetables and foodstuffs of animal origin (meat, milk and eggs), were collected and freeze-dried. Samples were analyzed by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) after chopping or crushing followed by freeze-drying and microwave (MW)-assisted acid digestion in a Class-100 clean-room. A mathematical approach was adopted to correct the mass signals for still unresolved interference (mDeltam = 300, 10 000). The lowest and highest concentrations of Pt, i.e. 17 and 93 ng kg(-1) (dry weight, dw), were found in vegetables and flour products, respectively. The lowest Pd level (2830 ng kg(-1) dw) was found in eggs and the highest (47 800 ng kg(-1) dw) in vegetables. PMID:17487666

  5. Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications.

    PubMed

    Jiang, Kun; Zhang, Han-Xuan; Zou, Shouzhong; Cai, Wen-Bin

    2014-10-14

    Formic acid as a natural biomass and a CO2 reduction product has attracted considerable interest in renewable energy exploitation, serving as both a promising candidate for chemical hydrogen storage material and a direct fuel for low temperature liquid fed fuel cells. In addition to its chemical dehydrogenation, formic acid oxidation (FAO) is a model reaction in the study of electrocatalysis of C1 molecules and the anode reaction in direct formic acid fuel cells (DFAFCs). Thanks to a deeper mechanistic understanding of FAO on Pt and Pd surfaces brought about by recent advances in the fundamental investigations, the "synthesis-by-design" concept has become a mainstream idea to attain high-performance Pt- and Pd-based nanocatalysts. As a result, a large number of efficient nanocatalysts have been obtained through different synthesis strategies by tailoring geometric and electronic structures of the two primary catalytic metals. In this paper, we provide a brief overview of recent progress in the mechanistic studies of FAO, the synthesis of novel Pd- and Pt-based nanocatalysts as well as their practical applications in DFAFCs with a focus on discussing studies significantly contributing to these areas in the past five years. PMID:25144896

  6. Donnan dialysis of bromocomplexes of some platinum group metal ions

    SciTech Connect

    Brajter, K.; Slonawska, K. ); Cox, J.A. )

    1989-03-01

    The separation of bromocomplexes of platinum group metals by Donnan dialysis is demonstrated with both anion and cation exchange membranes. The inclusion of ethylenediamine (en) in the sample improves the separation of Pd(II) from Pt(IV) with experiments performed with an anion exchange membrane and decreases the amount of metal retained on the membrane phase. With a cation exchange membrane, the addition of a ligand such as en is required for transport. With 5.6 mM en in the sample at pH 10, 74% of Pd(II) is transported across an anion exchange membrane into 0.5 M NH{sub 4} Br after 6 hours while only 8% of the Pt(IV) is dialyzed. Rhodium(III) and iridium(III) behave like Pt(IV). Using a cation exchange membrane under the same conditions except with a 1 hour dialysis results in a 30-fold preferential preconcentration of Pd(II) relative to Pt(IV), and, based on the amount retained in the membrane, a preconcentration of Ir(III) which exceeds that of Pd(II) and Pt(IV) by factors of 40 and 20, respectively.

  7. Modeling platinum group metal complexes in aqueous solution.

    PubMed

    Lienke, A; Klatt, G; Robinson, D J; Koch, K R; Naidoo, K J

    2001-05-01

    We construct force fields suited for the study of three platinum group metals (PGM) as chloranions in aqueous solution from quantum chemical computations and report experimental data. Density functional theory (DFT) using the local density approximation (LDA), as well as extended basis sets that incorporate relativistic corrections for the transition metal atoms, has been used to obtain equilibrium geometries, harmonic vibrational frequencies, and atomic charges for the complexes. We found that DFT calculations of [PtCl(6)](2-).3H(2)O, [PdCl(4)](2-).2H(2)O, and [RhCl(6)](3-).3H(2)O water clusters compared well with molecular mechanics (MM) calculations using the specific force field developed here. The force field performed equally well in condensed phase simulations. A 500 ps molecular dynamics (MD) simulation of [PtCl(6)](2-) in water was used to study the structure of the solvation shell around the anion. The resulting data were compared to an experimental radial distribution function derived from X-ray diffraction experiments. We found the calculated pair correlation functions (PCF) for hexachloroplatinate to be in good agreement with experiment and were able to use the simulation results to identify and resolve two water-anion peaks in the experimental spectrum. PMID:11327912

  8. Crystal structures of di-chlorido-palladium(II), -platinum(II) and -rhodium(III) complexes containing 8-(di-phenyl-phosphan-yl)quinoline.

    PubMed

    Suzuki, Takayoshi; Yamaguchi, Hiroshi; Fujiki, Masayuki; Hashimoto, Akira; Takagi, Hideo D

    2015-05-01

    The crystal structures of di-chlorido-palladium(II), -platinum(II) and -rhodium(III) complexes containing 8-(di-phenyl-phosphan-yl)quinoline, (SP-4)-[PdCl2(C21H16NP)], (1) [systematic name: di-chlor-ido-(8-di-phenyl-phosphanyl-quinoline)-palladium(II)], (SP-4)-[PtCl2(C21H16NP)]·CH2Cl2, (2) [systematic name: di-chlorido-(8-di-phenyl-phos-phanyl-quinoline)-platinum(II) dichlorometh-ane monosolvate], and (OC-6-32)-[RhCl2(C21H16NP)2]PF6·0.5CH2Cl2·0.5CH3OH, (3) [systematic name: cis-di-chlor-ido-bis-(8-di-phenyl-phosphanyl-quinoline)-rhodium(III) hexa-fluorido-phos-phate di-chloro-methane/-methanol hemisolvate] are reported. In these complexes, the phosphanyl-quinoline acts as a bidentate ligand, forming a planar asymmetrical five-membered chelate ring. The palladium(II) and platinum(II) complex mol-ecules in (1) and (2), respectively, show a typical square-planar coordination geometry and form a dimeric structure through an inter-molecular π-π stacking inter-action between the quinolyl rings. The centroid-centroid distances between the stacked six-membered rings in (1) and (2) are 3.633 (2) and 3.644 (2) Å, respectively. The cationic rhodium(III) complex in (3) has a cis(Cl),cis(P),cis(N) (OC-6-32) configuration of the ligands, in which two kinds of intra-molecular π-π stacking inter-actions are observed: between the quinolyl and phenyl rings and between two phenyl rings, the centroid-centroid distances being 3.458 (2) and 3.717 (2) Å, respectively. The PF6 (-) anion in (3) is rotationally disordered, the site occupancies of each F atom being 0.613 (14) and 0.387 (14). The CH2Cl2 and CH3OH solvent mol-ecules are also disordered and equal site occupancies of 0.5 are assumed. PMID:25995852

  9. Near Infrared Phosphorescent, Non-oxidizable Palladium and Platinum Perfluoro-phthalocyanines.

    PubMed

    Łapok, Łukasz; Obłoza, Magdalena; Gorski, Alexandr; Knyukshto, Valeri; Raichyonok, Tamara; Waluk, Jacek; Nowakowska, Maria

    2016-04-18

    New Pd(II) and Pt(II) complexes with a highly electron-deficient ligand (H2 PcF64 ) were conveniently prepared in a three-step synthesis. This is the first time that the phosphorescence of phthalocyanines with a H2 PcF64 framework has been measured. Based on these measurements, the triplet-state energies (ET ) were directly determined. Transient absorption experiments revealed broad T1 →Tn absorption spanning from ca. 350 to ca. 1000 nm and allowed determination of the triplet-state lifetimes. Removal of the Pd or Pt from the perfluoro-phthalocyanine resulted in a significant increase of the triplet lifetime for H2 PcF64 . The very efficient intersystem crossing observed for both PdPcF64 and PtPcF64 leads to residual fluorescence and suppresses the fluorescence lifetimes to less than 50 ps. The absence of Pd and Pt in the perfluoro-phthalocyanine ligand, viz. H2 PcF64 , led to a recovery of fluorescence. Cyclic voltamperometry studies pointed to complete resistance of PdPcF64 and PtPcF64 to oxidation and very strong electron affinity, which rendered these materials very good electron acceptors (n-type materials). The presence of d-orbital metals such as Pd(II) and Pt(II) in the phthalocyanine ring stabilizes their reduced forms, as indicated by the spectroelectrochemical experiments. PdPcF64 and PtPcF64 easily sensitize singlet oxygen production with very high quantum yields. Both phthalocyanines presented resistance to photodegradation in the solid state under aerobic conditions and under intense irradiation. PMID:26817625

  10. Antimicrobial and antitumor activity of platinum and palladium complexes of novel spherical aramides nanoparticles containing flexibilizing linkages: structure-property relationship.

    PubMed

    Elhusseiny, Amel F; Hassan, Hammed H A M

    2013-02-15

    Square planar Pd (II) and octahedral Pt (IV) complexes with novel spherical aramides nanoparticles containing flexible linkages ligands have been synthesized and characterized using analytical and spectral techniques. The synthesized complexes have been tested for their antimicrobial activity using Kirby-Bauer disc diffusion method. The antitumor activity has been performed using liver carcinoma (HEPG2), breast carcinoma (MCF7) and colon carcinoma (HCT 116) cell lines. Palladium complexes of polyamides containing sulfones showed the highest potency as antibacterial and antifungal agents. Platinum complexes containing sulfone and ether flexible linkages and chloro groups exhibited high potency as antitumor and antimicrobial agents. The uniform sizes of these nanomaterials could find biological uses such as immune assay and other medical purposes. PMID:23261618

  11. Antimicrobial and antitumor activity of platinum and palladium complexes of novel spherical aramides nanoparticles containing flexibilizing linkages: Structure-property relationship

    NASA Astrophysics Data System (ADS)

    Elhusseiny, Amel F.; Hassan, Hammed H. A. M.

    2013-02-01

    Square planar Pd (II) and octahedral Pt (IV) complexes with novel spherical aramides nanoparticles containing flexible linkages ligands have been synthesized and characterized using analytical and spectral techniques. The synthesized complexes have been tested for their antimicrobial activity using Kirby-Bauer disc diffusion method. The antitumor activity has been performed using liver carcinoma (HEPG2), breast carcinoma (MCF7) and colon carcinoma (HCT 116) cell lines. Palladium complexes of polyamides containing sulfones showed the highest potency as antibacterial and antifungal agents. Platinum complexes containing sulfone and ether flexible linkages and chloro groups exhibited high potency as antitumor and antimicrobial agents. The uniform sizes of these nanomaterials could find biological uses such as immune assay and other medical purposes.

  12. Methanol-Triggered Turn-On-Type Photoluminescence in l-Cysteinato Palladium(II) and Platinum(II) Complexes Supported by a Bis(diphenylphosphine) Ligand.

    PubMed

    Yoshinari, Nobuto; Shimizu, Tsutomu; Nozaki, Koichi; Konno, Takumi

    2016-03-01

    The selective detection of methanol by photoluminescence under environmental conditions has been a great challenge for materials science. Herein, a reversible, turn-on-type photoluminescence triggered by methanol vapor in square-planar palladium(II) and platinum(II) complexes, newly prepared from [MCl2(1,3-bis(diphenylphosphino)propane)] and l-cysteine, is reported. Both the "turn-on" and "turn-off" states of the complexes were crystallographically characterized, which revealed the presence of intermolecular OH···O and CH···π interactions between methanol and the complex molecules in the turn-on state. These interactions prevent the vibrational quenching of the luminescence, leading to the turn-on-type luminescence in this system. PMID:26882289

  13. Complexes of platinum and palladium with β-diketones and DMSO: Synthesis, characterization, molecular modeling, and biological studies

    NASA Astrophysics Data System (ADS)

    do Couto Almeida, J.; Marzano, I. M.; de Paula, F. C. Silva; Pivatto, M.; Lopes, N. P.; de Souza, P. C.; Pavan, F. R.; Formiga, A. L. B.; Pereira-Maia, E. C.; Guerra, W.

    2014-10-01

    This work reports on the synthesis and characterization of new complexes of the type [MCl(L)DMSO], where L = 4,4,4-trifluoro-1-phenyl-1,3-butanedione (HTPB) or 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (HTTA) and M = Pt2+ or Pd2+. These complexes were characterized by elemental analyses, conductivity measurements, FT-IR, UV-Vis, high-resolution mass spectra (HRESIMS) and TG/DTA. In the complexes, the metallic ions bind to β-diketone via the oxygen atoms and to DMSO molecule via sulfur atom. The structures of complexes were optimized and theoretical data showed good agreement with the experimental results. The cytotoxic activity of the compounds was evaluated in a chronic myelogenous leukemia cell line. The platinum complexes were more cytotoxic than the free ligands and carboplatin and are promising candidates for further investigations. As example, the compound [PtCl(TPB)(DMSO)] inhibits the growth of K562 cells with an IC50 value equal to 2.5 μM. Furthermore, microbiological assays against Mycobacterium tuberculosis showed that all complexes exhibit low cytotoxicity against this bacterial strain while the free ligands exhibited MIC values of approximately 10 μg mL-1.

  14. Uptake and bioaccumulation of platinum group metals (Pd, Pt, Rh) from automobile catalytic converter materials by the zebra mussel (Dreissena polymorpha).

    PubMed

    Zimmermann, Sonja; Messerschmidt, Jürgen; von Bohlen, Alex; Sures, Bernd

    2005-06-01

    The uptake and bioaccumulation of the platinum group metals (PGM) platinum (Pt), palladium (Pd), and rhodium (Rh) by the zebra mussel (Dreissena polymorpha) were investigated in exposure studies using ground material from unused automobile catalytic converters as metal source. The mussels were exposed to the metals in tap water or humic water. In the soft tissue samples of exposed mussels mean Pt levels ranged in dependence on the type of tank water and the exposure period (6, 9, or 18 weeks) between 780 and 4300 ng/g, the Pd levels ranged between 720 and 6300 ng/g, and the Rh levels ranged between 270 and 1900 ng/g. In contrast, the control mussels had metal concentrations of <20 ng/g (Pt), <50 ng/g (Pd), and <40 ng/g (Rh). Considerably higher PGM levels were found in the exposed mussels of the humic water group than in those of the tap water group. Although there is a cumulative increase of the PGM concentrations in the environment since the introduction of the automobile catalyst more than 20 years ago, only little information about the PGM contamination in the biosphere, especially the fauna, is available. Due to the high capacity of D. polymorpha to accumulate PGM, this bivalve could be used as a potential sentinel for monitoring the noble metals in aquatic ecosystems. PMID:15820726

  15. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination

    NASA Astrophysics Data System (ADS)

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-06-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.

  16. Friction behavior of members of the platinum metals group with gold

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1975-01-01

    The adhesion and friction behavior of the platinum metals group was examined with clean surfaces and surfaces selectively contaminated with oxygen, vinyl chloride (C2H3Cl), and methyl mercaptan (CH3SH). A pin or disk specimen configuration was used with the pin being a single crystal of gold of the (111) orientation and with the platinum metal disks also being single crystals of the (111) or (0001) orientation. Loads applied ranged from 1 to 10 g and a sliding velocity of 0.7 mm/min was employed. Results indicate adhesion and transfer of gold to all of the platinum metals. Despite this observation friction differences existed among the metals in the group. These differences are related to surface chemical activity. Adsorption of various friction reducing species was selective. With some adsorbates present strong adhesive forces between metals were still observed.

  17. The platinum group metals in Younger Dryas Horizons are terrestrial

    NASA Astrophysics Data System (ADS)

    Wu, Y.; Wikes, E.; Kennett, J.; West, A.; Sharma, M.

    2009-12-01

    The Younger Dryas (YD) event, which began 12,900 years ago, was a period of abrupt and rapid cooling in the Northern Hemisphere whose primary cause remains unclear. The prevalent postulated mechanism is a temporary shutdown of the thermohaline circulation following the breakup of an ice dam in North America. Firestone et al. (2007) proposed that the cooling was triggered by multiple cometary airbursts and/or impacts that engendered enormous environmental changes and disrupted the thermohaline circulation. The evidence in support for this hypothesis is a black layer in North America and in Europe marking the YD boundary containing charcoal, soot, carbon spherules and glass-like carbon suggesting extensive and intense forest fires. This layer is also enriched in magnetic grains high in iridium, magnetic microspherules, fullerenes containing extraterrestrial He-3, and nanodiamonds. Whereas the nanodiamonds could be produced in an impact or arrive with the impactor, the cometary burst/impact hypothesis remains highly controversial as the YD horizon lacks important impact markers such as craters, breccias, tektites and shocked minerals. Firestone et al. (2007) contend that bulk of Ir found at the YD boundary is associated with magnetic grains. The key issue is whether this Ir is meteorite derived. We used Ir and Os concentrations and Os isotopes to investigate the provenance of the platinum group metals in the YD horizon. The bulk sediment samples from a number of North American YD sites (Blackwater Draw, Murray Springs, Gainey, Sheriden Cave, and Myrtle Beach) and a site in Europe (Lommel) do not show any traces of meteorite derived Os and Ir. The [Os] = 2 to 45 pg/g in these sediments and the 187Os/188Os ratios are similar to the upper continental crustal values (~1.3), much higher than those in meteorites (0.13). Higher [Os] is observed in Blackwater Draw (= 194 pg/g). However, the Os/Ir ratio in Blackwater Draw is 5 (not 1 as expected for a meteorite) and 187Os/188

  18. C-H Oxidation by Platinum Group Metal Oxo or Peroxo Species

    SciTech Connect

    Zhou, Meng; Crabtree, Robert H

    2011-01-01

    While C–H oxidation by ruthenium oxo compounds has been broadly applied in organic synthesis, examples of C–H oxidation by metal oxo complexes from the rest of the platinum group are still rare. We survey the preparation and reactivity of these late-transition metal oxo and peroxo complexes in this tutorial review.

  19. Coating Carbon Fibers With Platinum

    NASA Technical Reports Server (NTRS)

    Effinger, Michael R.; Duncan, Peter; Coupland, Duncan; Rigali, Mark J.

    2007-01-01

    A process for coating carbon fibers with platinum has been developed. The process may also be adaptable to coating carbon fibers with other noble and refractory metals, including rhenium and iridium. The coated carbon fibers would be used as ingredients of matrix/fiber composite materials that would resist oxidation at high temperatures. The metal coats would contribute to oxidation resistance by keeping atmospheric oxygen away from fibers when cracks form in the matrices. Other processes that have been used to coat carbon fibers with metals have significant disadvantages: Metal-vapor deposition processes yield coats that are nonuniform along both the lengths and the circumferences of the fibers. The electrical resistivities of carbon fibers are too high to be compatible with electrolytic processes. Metal/organic vapor deposition entails the use of expensive starting materials, it may be necessary to use a furnace, and the starting materials and/or materials generated in the process may be hazardous. The present process does not have these disadvantages. It yields uniform, nonporous coats and is relatively inexpensive. The process can be summarized as one of pretreatment followed by electroless deposition. The process consists of the following steps: The surfaces of the fiber are activated by deposition of palladium crystallites from a solution. The surface-activated fibers are immersed in a solution that contains platinum. A reducing agent is used to supply electrons to effect a chemical reduction in situ. The chemical reduction displaces the platinum from the solution. The displaced platinum becomes deposited on the fibers. Each platinum atom that has been deposited acts as a catalytic site for the deposition of another platinum atom. Hence, the deposition process can also be characterized as autocatalytic. The thickness of the deposited metal can be tailored via the duration of immersion and the chemical activity of the solution.

  20. Neutron emission and the tritium content associated with deuterium-loaded palladium and titanium metals

    NASA Astrophysics Data System (ADS)

    Wolf, K. L.; Packham, N. J. C.; Lawson, D.; Shoemaker, J.; Cheng, F.; Wass, J. C.

    1990-06-01

    An experimental investigation has been conducted on samples of palladium and titanium metals which have been loaded with deuterium through the electrolysis of D2O and by absorption of D2 gas. In approximately 200 experiments on 25 cells, statistically significant evidence for neutron emission was obtained in three separate experiments from one palladium cathode. Observed rates are 3-4 times the background rate and correspond to source strengths up to 50 neutrons/min. The pulse height response of the NE213 liquid scintillator-based detectors corresponds to that expected for 2.45 MeV neutrons. Tritium has been identified in nine Pd-Ni electrolytic cells, at levels corresponding 1012-1016 atoms. Activity buildup curves indicate that the apparent production occurs over a time period as short as a few hours.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Electrochemical metallization switching with a platinum group metal in different oxides

    NASA Astrophysics Data System (ADS)

    Wang, Zhongrui; Jiang, Hao; Hyung Jang, Moon; Lin, Peng; Ribbe, Alexander; Xia, Qiangfei; Yang, J. Joshua

    2016-07-01

    In a normal electrochemical metallization (ECM) switch, electrochemically active metals, such as Ag and Cu are used to provide mobile ions for the conducting filament. In both ECM and valence change memory (VCM) devices, platinum group metals, such as Pt and Pd, are typically used as the counter electrode and assumed to be chemically and physically inert. In this study, we explore whether the so-called inert metal itself can form a conducting filament and result in repeatable resistance switching. Pd and different oxide host matrices are used for this purpose. We have observed that the transport of oxygen anions dominates over Pd metal cations in ALD deposited AlOx and HfOx. However, in sputtered SiOx, Pd cation transport was revealed, accompanied by the formation of nano-crystalline Pd filament(s) in the junctions. Based on these observations, memristors with reversible and repeatable switching were obtained by using Pd doped SiOx as the switching material.In a normal electrochemical metallization (ECM) switch, electrochemically active metals, such as Ag and Cu are used to provide mobile ions for the conducting filament. In both ECM and valence change memory (VCM) devices, platinum group metals, such as Pt and Pd, are typically used as the counter electrode and assumed to be chemically and physically inert. In this study, we explore whether the so-called inert metal itself can form a conducting filament and result in repeatable resistance switching. Pd and different oxide host matrices are used for this purpose. We have observed that the transport of oxygen anions dominates over Pd metal cations in ALD deposited AlOx and HfOx. However, in sputtered SiOx, Pd cation transport was revealed, accompanied by the formation of nano-crystalline Pd filament(s) in the junctions. Based on these observations, memristors with reversible and repeatable switching were obtained by using Pd doped SiOx as the switching material. Electronic supplementary information (ESI) available

  3. Small palladium islands embedded in palladium-tungsten bimetallic nanoparticles form catalytic hotspots for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Hu, Guangzhi; Nitze, Florian; Gracia-Espino, Eduardo; Ma, Jingyuan; Barzegar, Hamid Reza; Sharifi, Tiva; Jia, Xueen; Shchukarev, Andrey; Lu, Lu; Ma, Chuansheng; Yang, Guang; Wågberg, Thomas

    2014-10-01

    The sluggish kinetics of the oxygen reduction reaction at the cathode side of proton exchange membrane fuel cells is one major technical challenge for realizing sustainable solutions for the transportation sector. Finding efficient yet cheap electrocatalysts to speed up this reaction therefore motivates researchers all over the world. Here we demonstrate an efficient synthesis of palladium-tungsten bimetallic nanoparticles supported on ordered mesoporous carbon. Despite a very low percentage of noble metal (palladium:tungsten=1:8), the hybrid catalyst material exhibits a performance equal to commercial 60% platinum/Vulcan for the oxygen reduction process. The high catalytic efficiency is explained by the formation of small palladium islands embedded at the surface of the palladium-tungsten bimetallic nanoparticles, generating catalytic hotspots. The palladium islands are ~1 nm in diameter, and contain 10-20 palladium atoms that are segregated at the surface. Our results may provide insight into the formation, stabilization and performance of bimetallic nanoparticles for catalytic reactions.

  4. Electrochemical metallization switching with a platinum group metal in different oxides.

    PubMed

    Wang, Zhongrui; Jiang, Hao; Hyung Jang, Moon; Lin, Peng; Ribbe, Alexander; Xia, Qiangfei; Yang, J Joshua

    2016-08-01

    In a normal electrochemical metallization (ECM) switch, electrochemically active metals, such as Ag and Cu are used to provide mobile ions for the conducting filament. In both ECM and valence change memory (VCM) devices, platinum group metals, such as Pt and Pd, are typically used as the counter electrode and assumed to be chemically and physically inert. In this study, we explore whether the so-called inert metal itself can form a conducting filament and result in repeatable resistance switching. Pd and different oxide host matrices are used for this purpose. We have observed that the transport of oxygen anions dominates over Pd metal cations in ALD deposited AlOx and HfOx. However, in sputtered SiOx, Pd cation transport was revealed, accompanied by the formation of nano-crystalline Pd filament(s) in the junctions. Based on these observations, memristors with reversible and repeatable switching were obtained by using Pd doped SiOx as the switching material. PMID:27166623

  5. Biocompatibility of platinum-metallized silicone rubber: in vivo and in vitro evaluation.

    PubMed

    Vince, V; Thil, M A; Veraart, C; Colin, I M; Delbeke, J

    2004-01-01

    Silicone rubber is commonly used for biomedical applications, including implanted cuff electrodes for both recording and stimulation of peripheral nerves. This study was undertaken to evaluate the consequences of a new platinum metallization method on the biocompatibility of silicone rubber cuff electrodes. This method was introduced in order to allow the manufacture of spiral nerve cuff electrodes with a large number of contacts. The metallization process, implying silicone coating with poly(methyl methacrylate) (PMMA), its activation by an excimer laser and subsequent electroless metal deposition, led to a new surface microtexture. The neutral red cytotoxicity assay procedure was first applied in vitro on BALB/c 3T3 fibroblasts in order to analyze the cellular response elicited by the studied material. An in vivo assay was then performed to investigate the tissue reaction after chronic subcutaneous implantation of the metallized material. Results demonstrate that silicone rubber biocompatibility is not altered by the new platinum metallization method. PMID:15109096

  6. Selective electroless coating of palladium nanoparticles on metallic single-walled carbon nanotube

    NASA Astrophysics Data System (ADS)

    Feng, Yiyu; Lv, Peng; Zhang, Xuequan; Li, Yu; Feng, Wei

    2010-08-01

    The selective electroless coating of palladium (Pd) nanoparticles on metallic single-walled carbon nanotube (SWNT) was studied. The remarkable increase in conductivity of SWNT/Pd films up to fourfold higher than pure SWNT was due to p-type doping and Ohmic contact. Metallic behavior of SWNT/Pd-Field effect transistor (on/off ratio=1.2) was attributed to more hole carriers and no electrostatic barrier between nanotube and Pd. G-band and radial breathing mode in Raman indicates a definitive increase in the proportion of metallic SWNT. Results indicate Pd are selectively coated on metallic SWNT with more negative potential allowing for the electroless Pd2+ reduction.

  7. Doped palladium containing oxidation catalysts

    DOEpatents

    Mohajeri, Nahid

    2014-02-18

    A supported oxidation catalyst includes a support having a metal oxide or metal salt, and mixed metal particles thereon. The mixed metal particles include first particles including a palladium compound, and second particles including a precious metal group (PMG) metal or PMG metal compound, wherein the PMG metal is not palladium. The oxidation catalyst may also be used as a gas sensor.

  8. Effective and selective recovery of gold and palladium ions from metal wastewater using a sulfothermophilic red alga, Galdieria sulphuraria.

    PubMed

    Ju, Xiaohui; Igarashi, Kensuke; Miyashita, Shin-Ichi; Mitsuhashi, Hiroaki; Inagaki, Kazumi; Fujii, Shin-Ichiro; Sawada, Hitomi; Kuwabara, Tomohiko; Minoda, Ayumi

    2016-07-01

    The demand for precious metals has increased in recent years. However, low concentrations of precious metals dissolved in wastewater are yet to be recovered because of high operation costs and technical problems. The unicellular red alga, Galdieria sulphuraria, efficiently absorbs precious metals through biosorption. In this study, over 90% of gold and palladium could be selectively recovered from aqua regia-based metal wastewater by using G. sulphuraria. These metals were eluted from the cells into ammonium solutions containing 0.2M ammonium salts without other contaminating metals. The use of G. sulphuraria is an eco-friendly and cost-effective way of recovering low concentrations of gold and palladium discarded in metal wastewater. PMID:27118429

  9. 21 CFR 872.3060 - Noble metal alloy.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Noble metal alloy. 872.3060 Section 872.3060 Food... DEVICES DENTAL DEVICES Prosthetic Devices § 872.3060 Noble metal alloy. (a) Identification. A noble metal alloy is a device composed primarily of noble metals, such as gold, palladium, platinum, or silver,...

  10. 21 CFR 872.3060 - Noble metal alloy.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Noble metal alloy. 872.3060 Section 872.3060 Food... DEVICES DENTAL DEVICES Prosthetic Devices § 872.3060 Noble metal alloy. (a) Identification. A noble metal alloy is a device composed primarily of noble metals, such as gold, palladium, platinum, or silver,...

  11. 21 CFR 872.3060 - Noble metal alloy.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Noble metal alloy. 872.3060 Section 872.3060 Food... DEVICES DENTAL DEVICES Prosthetic Devices § 872.3060 Noble metal alloy. (a) Identification. A noble metal alloy is a device composed primarily of noble metals, such as gold, palladium, platinum, or silver,...

  12. 21 CFR 872.3060 - Noble metal alloy.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Noble metal alloy. 872.3060 Section 872.3060 Food... DEVICES DENTAL DEVICES Prosthetic Devices § 872.3060 Noble metal alloy. (a) Identification. A noble metal alloy is a device composed primarily of noble metals, such as gold, palladium, platinum, or silver,...

  13. Metal-enhanced intrinsic fluorescence of nucleic acids using platinum nanostructured substrates

    NASA Astrophysics Data System (ADS)

    Akbay, Nuriye; Mahdavi, Farhad; Lakowicz, Joseph R.; Ray, Krishanu

    2012-10-01

    We investigated the feasibility of using platinum nanostructures to accomplish the metal-enhanced fluorescence (MEF) in the UV spectral region. We examine the possibility for detection of the intrinsic fluorescence from nucleotides and G-quadruplex DNA on platinum nanoparticles. Guanosine monophosphate (GMP) showed significant increases (˜20-fold) in fluorescence intensities in the presence of platinum nanostructures when compared to quartz controls. G-quadruplex DNA demonstrated ˜5-fold increase in fluorescence intensity and higher photostability in the presence of Pt nanostructures. We performed Finite Element Method simulations to explore how Pt nanoparticles interact with plane waves and conformed that the Pt nanostructures are promising for enhancing the fluorescence emission in the UV region.

  14. Photophysical investigation of palladium(II) ortho-metalated complexes

    SciTech Connect

    Craig, C.A.; Watts, R.J. )

    1989-01-25

    Syntheses and structural characterizations of four complexes of Pd(II) with ortho-metalated 2-phenylpyridinate (ppy{sup minus}) are reported. These complexes include a parent dimer, (Pd(ppy)Cl){sub 2}, and three derivative monomers, (Pd(ppy)(bpy))Cl, (Pd(ppy)(en))Cl, and (Pd(ppy)(CO)Cl), whereby = 2,2'-bipyridine and en = ethylenediamine. Photophysical characterizations of these species indicate low-energy absorption bands ({approximately}360 nm) and emission bands at 77 K ({approximately}460 nm) that are assigned to transitions located on the ppy{sup {minus}} ligand. Some evidence for low-energy charge-transfer states is found in trends in luminescence lifetimes. 2 tabs., 5 figs., 21 refs.

  15. Platinum Group Metal Recycling Technology Development - Final Report

    SciTech Connect

    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. Core-Protected Platinum Monolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes

    SciTech Connect

    K Sasaki; H Naohara; Y Cai; Y Choi; P Liu; M Vukmirovic; J Wang; R Adzic

    2011-12-31

    Platinum monolayers can act as shells for palladium nanoparticles to lead to electrocatalysts with high activities and an ultralow platinum content, but high platinum utilization. The stability derives from the core protecting the shell from dissolution. In fuel-cell tests, no loss of platinum was observed in 200,000 potential cycles, whereas loss of palladium was significant.

  17. Core-Protected Platinum Monolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes

    SciTech Connect

    Adzic, R.R.; Sasaki, K.; Naohara, H.; Cai, Y.; Choi, Y.M.; Liu, P.; Vukmirovic, M.B.; Wang, J.X.

    2010-11-08

    More than skin deep: Platinum monolayers can act as shells for palladium nanoparticles to lead to electrocatalysts with high activities and an ultralow platinum content, but high platinum utilization. The stability derives from the core protecting the shell from dissolution. In fuel-cell tests, no loss of platinum was observed in 200?000 potential cycles, whereas loss of palladium was significant.

  18. Hydrocarbon dissociation on palladium studied with a hydrogen sensitive Pd-metal-oxide-semiconductor structure

    NASA Astrophysics Data System (ADS)

    Dannetun, H.; Lundström, I.; Petersson, L.-G.

    1988-01-01

    The polycrystalline Pd surface of a hydrogen sensitive palladium-silicon dioxide-silicon [Pd-MOS (metal-oxide-semiconductor)] structure has been exposed to small unsaturated hydrocarbons in the temperature range 300-500 K. Apart from the hydrogen response of the Pd-MOS structure also work function (ΔΦ) and electron energy-loss studies were performed. At 500 K the hydrocarbons dissociate completely upon adsorption and produce a surface with atomically adsorbed carbon. The Pd-MOS structure can be used to observe both the dehydrogenation of the hydrocarbon molecules and the process of carbon adsorbing on the palladium surface. The sticking coefficient at this temperature for all hydrocarbons is close to unity. Furthermore, the hydrogen sensitivity of the structure is not drastically reduced by the adsorbed carbon. If the hydrocarbon adsorption is performed at 300 K there is still, at least on the initially clean surface, a large dehydrogenation. The dissociation is, however, not at all complete and there are considerable amounts of hydrocarbon species adsorbed for each gas. The induced work function shifts due to the different hydrocarbons vary from -1.0 to -1.7 eV. The hydrogen sensitivity of the Pd-MOS structure is reduced for growing hydrocarbon coverages and disappears completely for work function shifts of -1.7 eV.

  19. Platinum, palladium and rhodium release from vehicle exhaust catalysts and road dust exposed to simulated lung fluids.

    PubMed

    Colombo, Claudia; Monhemius, A John; Plant, Jane A

    2008-11-01

    The risk associated with the inhalation of platinum group element (PGE) emissions from vehicle exhaust catalysts (VECs) has been investigated by extracting road dust and milled auto catalyst with simulated lung fluids. Gamble's solution (representative of the interstitial fluid of the deep lung) and artificial lysosomal fluid (ALF) (representative of the more acidic environment within the lung) were employed as extraction fluids. The highest PGE release was observed in ALF, implying that inhaled particles would have to be phagocytized before significant amounts of PGEs dissolve. The greatest percentage (up to 88%) of PGEs was released from road dust, possibly due to the presence of mobile PGE species formed in the roadside environment. Pt showed the highest absolute bioavailability, due to its greater concentration in the environmental samples. Pd and Rh had higher percentage of release, however, because of their more soluble nature. From the toxicological perspective, the results demonstrate potential health risks due to the likely formation of PGE-chloride complexes in the respiratory tract, such species having well-known toxic and allergenic effects on human beings and living organisms. PMID:18206235

  20. Determination of platinum and palladium in road dust after their separation on immobilized fungus by electrothermal atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Woińska, Sylwia; Godlewska-Żyłkiewicz, Beata

    2011-07-01

    A flow solid phase extraction procedure based on biosorption of Pt(IV) and Pd(II) on Aspergillus sp. immobilized on cellulose resin Cellex-T was proposed for the separation and preconcentration of Pt and Pd before their determination by electrothermal atomic absorption spectrometry (ETAAS). The analytical conditions including sample pH, eluent type, flow rates of sample and eluent solutions were examined. The analytes were selectively retained on the biosorbent in acidic medium (pH 1) and subsequently eluted from the column with 1 mL of thiourea solution (0.25 mol L - 1 thiourea in 0.3 mol L - 1 HCl). The reproducibility of the procedure was below 5%. The limit of detection of the method was 0.020 ng mL - 1 for Pt and 0.012 ng mL - 1 for Pd. The method validation was performed by analysis of certified reference materials BCR-723 (tunnel dust) and SARM-76 (platinum ore). The developed separation procedure was applied to the determination of Pt and Pd in road dust samples by ETAAS. The applied biosorbent is characterized by high sorption capacity: 0.47 mg g - 1 for Pt and 1.24 mg g - 1 for Pd.

  1. Autocatalyst-derived platinum, palladium and rhodium (PGE) in infiltration basin and wetland sediments receiving urban runoff.

    PubMed

    Whiteley, J D; Murray, F

    2005-04-01

    The emission of platinum group elements (PGE) from automobile catalytic converters has led to rapid increases in Pt, Pd and Rh concentrations in roadside media. Significant quantities of the PGE may enter and accumulate in fluvial systems via road runoff. This paper examines the occurrence and spatial distribution of autocatalyst-derived PGE in surface sediments of infiltration basin and wetland sediments receiving road-runoff in Perth, Western Australia. Samples were analysed by ICP-MS following microwave digestion and cation exchange. PGE concentrations ranged between 1.5-17.2 Rh, 5.4-61.2 Pd and 9.0-103.8 ng g(-1) Pt. The highest levels of PGE were generally found at basin topographic low points and these concentrations were found to be strongly related to the area of road surface drained and the traffic volume. PGE ratios in infiltration basin and wetland sediments were within the typical range of catalytic converter compositions. However, comparisons of PGE ratios between parent road dusts and infiltration basin sediments revealed a systematic shift in Pt/Pd ratios, suggesting that PGE fractionation can occur during transport through the drainage system and that a small portion of Pd in road dust may be solubilised under natural conditions. PMID:15833252

  2. Virus templated metallic nanoparticles.

    PubMed

    Aljabali, Alaa A A; Barclay, J Elaine; Lomonossoff, George P; Evans, David J

    2010-12-01

    Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. ≤35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron. PMID:20877898

  3. Hydrogen storage studies on palladium-doped carbon materials (AC, CB, CNMs) @ metal-organic framework-5.

    PubMed

    Viditha, V; Srilatha, K; Himabindu, V

    2016-05-01

    Metal organic frameworks (MOFs) are a rapidly growing class of porous materials and are considered as best adsorbents for their high surface area and extraordinary porosity. The MOFs are synthesized by using various chemicals like triethylamine, terepthalic acid, zinc acetate dihydrate, chloroform, and dimethylformamide (DMF). Synthesized MOFs are intercalated with palladium/activated carbon, carbon black, and carbon nanomaterials by chemical reduction method for the purpose of enhancing the hydrogen adsorption capacities. We have observed that the palladium doped activated carbon on MOF-5 showed high hydrogen storage capacity. This may be due to the affinity of the palladium toward hydrogen molecule. The samples are characterized by X-ray diffraction, scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) surface area analysis. We have observed a clear decrease in the BET surface area and pore volume. The obtained results show a better performance for the synthesized sample. To our best knowledge, no one has reported the work on palladium-doped carbon materials (activated carbon, carbon black, carbon nanomaterials) impregnated to the metal-organic framework-5. We have attempted to synthesize carbon nanomaterials using indigenously fabricated chemical vapor deposition (CVD) unit as a support. We have observed an increase in the hydrogen storage capacities. PMID:26298339

  4. Synthesis of nanoscaled platinum particles (NSPP): their role in performance improvement of ionic polymer-metal composite (IPMC) artificial muscles

    NASA Astrophysics Data System (ADS)

    Kim, Kwang J.; Shahinpoor, Mohsen

    2001-07-01

    In this work the synthesis of nano-scaled platinum particles by a chemical reducing technique within an ion-exchange membrane has been performed. It is desirable to gain a fundamental knowledge and understanding of the properties of small nano-scaled platinum particles within ion-exchange membranes, which can affect the performance of Ionic Polymer-Metal Composite (IPMC) artificial muscles. In IPMC artificial muscle applications, the finite size of platinum particles is believed to strongly influence their properties. This might be related to a platinum surface effect originating from the electronic surface states of platinum particles that differ from the bulk states. In order to address this issue, we have attempted to synthesize small platinum particles having different size distributions by using protective agents. Further, we have characterized them as well. For IPMC artificial muscles, the presence of such nano-scale platinum particles minimizes the solvent- leakage from the surface electrodes. This in turn improves their performance dramatically. A successfully fabricated IPMC artificial muscle with nano-Platinum particles has shown a significantly improved force density as much as 100% than that of the conventional IPMC.

  5. Partitioning of palladium, iridium, platinum, and gold between sulfide liquid and basalt melt at 1200°C

    NASA Astrophysics Data System (ADS)

    Stone, W. E.; Crockett, J. H.; Fleet, M. E.

    1990-08-01

    Iron-nickel monosulfide and basalt glass containing trace amounts of PGE equilibrated at 1200°C, and fo2= 10 -9.2 (close to the wustite-magnetite buffer) and fs2= 10 -0.9, have been analyzed for noble metals by radiochemical and instrumental neutron activation analysis. The average contents of PGE in coexisting Fe-Ni sulfide and basalt glass, respectively, are Pd, 50 ppm and 0.5 ppb; Ir, 50 ppm and 0.5 ppb; Pt, 100 ppm and 10 ppb; and Au, 0.7 ppm and 0.8 ppb. The sulfide liquid-silicate melt partition coefficients ( D values) for the noble metals are (9 ± 7) × 10 4 for Pd, (1 ± 0.7) × 10 5 for Ir, (9 ± 6) × 10 3for Pt, and (1 ± 0.9) × 10 3 for Au. The noble metals are strongly partitioned into sulfide liquid, but the affinity of Pd and Ir for sulfide liquid is about 50 times greater than that of Pt and about 500 times greater than that of Au. The D values indicate that equilibrium partitioning between immiscible sulfide liquid and basalt magma would result in fractionation of the noble metals, which differs significantly from that generally observed in nature.

  6. Localization of alkali metal ions in sodium-promoted palladium catalysts as studied by low energy ion scattering and transmission electron microscopy

    SciTech Connect

    Liotta, L.F.; Deganello, G.; Delichere, P.

    1996-12-01

    Three series of palladium-based catalysts have been studied by Low Energy Ion Scattering (LEIS) and Transmission Electron Microscopy (TEM). The first series is comprised of Na-Pd/SiO{sub 2} catalysts, obtained by addition of palladium to a silica support and by further addition of sodium ions with a Na/Pd atomic ratio (R) equal to 0,6.4 and 25.6. The second series consists of palladium catalysts supported on natural pumice, in which, due to a different loading of supported palladium, R{prime}, the (Na+K)/Pd atomic ratio, is equal to 17.0 and 39.4. The third series is represented by two palladium-based catalysts supported on {open_quotes}model pumices,{close_quotes} synthetic silico-aluminates, obtained by sol-gel techniques, with a different amount of sodium, and R equal to 2.1 and 6.1 respectively. LEIS experiments and electron microscopy demonstrate a different location of alkali metal ions in the first two series: in the Na-Pd/SiO{sub 2} catalysts sodium is distributed in a way which is not uniform on the support and on the palladium metal, which is partly decorated with Na ions, whereas in the Pd/natural-pumice series the palladium surface is sodium-free. The results on the third series of catalysts, Pd/model pumice, are not definitive on the basis of the LEIS and TEM analyses, but by FTIR study of CO and CO{sub 2} adsorption, the decoration of palladium by sodium ions could be excluded. The results confirm the importance of the alkali metal ion location in alkali-promoted palladium catalysts and open new possibilities in the design of palladium-supported catalysts by a better control of promoter location. 18 refs., 5 figs., 2 tabs.

  7. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination

    PubMed Central

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-01-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon–nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation. PMID:26059552

  8. Palladium(II) and platinum(II) complexes containing benzimidazole ligands: Molecular structures, vibrational frequencies and cytotoxicity

    NASA Astrophysics Data System (ADS)

    Abdel Ghani, Nour T.; Mansour, Ahmed M.

    2011-04-01

    (1H-benzimidazol-2-ylmethyl)-(4-methoxyl-phenyl)-amine (L 1), (1H-benzimidazol-2-ylmethyl)-(4-methyl-phenyl)-amine (L 2) and their Pd(II) and Pt(II) complexes have been synthesized as potential anticancer compounds and their structures were elucidated using a variety of physico-chemical techniques. Theoretical calculations invoking geometry optimization, vibrational assignments, 1H NMR, charge distribution and molecular orbital description HOMO and LUMO were done using density functional theory. Natural bond orbital analysis (NBO) method was performed to provide details about the type of hybridization and the nature of bonding in the studied complexes. Strong coordination bonds (LP(1)N11 → σ *(M sbnd Cl22)) and (LP(1)N21 → σ *(M sbnd Cl23)) (M = Pd or Pt) result from donation of electron density from a lone pair orbital on the nitrogen atoms to the acceptor metal molecular orbitals. The experimental results and the calculated molecular parameters revealed square-planar geometries around the metallic centre through the pyridine-type nitrogen of the benzimidazole ring and secondary amino group and two chlorine atoms. The activation thermodynamic parameters were calculated using non-isothermal methods. The synthesized ligands, in comparison to their metal complexes were screened for their antibacterial activity. In addition, the studied complexes showed activity against three cell lines of different origin, breast cancer (MCF-7), Colon Carcinoma (HCT) and human heptacellular carcinoma (Hep-G2) comparable to cis-platin.

  9. Metallization of DNA and DNA Origami Using a Palladium Seeding Method

    NASA Astrophysics Data System (ADS)

    Geng, Yanli

    In this dissertation, I developed a Pd seeding method in association with electroless plating, to successfully metallize both lambda DNA and DNA origami templates on different surfaces. On mica surfaces, this method offered a fast, simple process, and the ability to obtain a relatively high yield of metallized DNA nanostructures. When using lambda DNA as the templates, I studied the effect of Pd(II) activation time on the seed height and density, and an optimal activation time between 10 and 30 min was obtained. Based on the Pd seeds formed on DNA, as well as a Pd electroless plating solution, continuous Pd nanowires that had an average diameter of ˜28 nm were formed with good selectivity on lambda DNA. The selected Pd activation time was also applied to metallize "T"-shape DNA origami, and Au coated branched nanostructures with a length between 200-250 nm, and wire diameters of ˜40 nm were also fabricated. In addition, I found that the addition of Mg2+ ion into the reducing agent and electroless plating solution could benefit the surface retention of Pd seeded DNA and Au plated DNA structures. This work indicated that DNA molecules were promising templates to fabricate metal nanostructures; moreover, the formation of Au metallized branched nanostructures showed progress towards nanodevice fabrication using DNA origami. Silicon surfaces were also used as the substrates for DNA metallization. More complex circular circuit DNA origami templates were used. To obtain high enough seed density, multiple Pd seeding steps were applied which showed good selectivity and the seeded DNA origami remained on the surface after seeding steps. I used distribution analysis of seed height to study the effect of seeding steps on both average height and the uniformity of the Pd seeds. Four-repeated palladium seedings were confirmed to be optimal by the AFM images, seed height distribution analysis, and Au electroless plating results. Both Au and Cu metallized circular circuit design

  10. Platinum metallization for MEMS application: focus on coating adhesion for biomedical applications.

    PubMed

    Guarnieri, Vittorio; Biazi, Leonardo; Marchiori, Roberto; Lago, Alexandre

    2014-01-01

    The adherence of Platinum thin film on Si/SiO 2 wafer was studies using Chromium, Titanium or Alumina (Cr, Ti, Al 2O 3) as interlayer. The adhesion of Pt is a fundamental property in different areas, for example in MEMS devices, which operate at high temperature conditions, as well as in biomedical applications, where the problem of adhesion of a Pt film to the substrate is known as a major challenge in several industrial applications health and in biomedical devices, such as for example in the stents. (1)(-) (4) We investigated the properties of Chromium, Titanium, and Alumina (Cr, Ti, and Al 2O 3) used as adhesion layers of Platinum (Pt) electrode. Thin films of Chromium, Titanium and Alumina were deposited on Silicon/Silicon dioxide (Si/SiO 2) wafer by electron beam. We introduced Al 2O 3 as a new adhesion layer to test the behavior of the Pt film at higher temperature using a ceramic adhesion thin film. Electric behaviors were measured for different annealing temperatures to know the performance for Cr/Pt, Ti/Pt, and Al 2O 3/Pt metallic film in the gas sensor application. All these metal layers showed a good adhesion onto Si/SiO 2 and also good Au wire bondability at room temperature, but for higher temperature than 400 °C the thin Cr/Pt and Ti/Pt films showed poor adhesion due to the atomic inter-diffusion between Platinum and the metal adhesion layers. (5) The proposed Al 2O 3/Pt ceramic-metal layers confirmed a better adherence for the higher temperatures tested. PMID:24743057

  11. Platinum metallization for MEMS application. Focus on coating adhesion for biomedical applications.

    PubMed

    Guarnieri, Vittorio; Biazi, Leonardo; Marchiori, Roberto; Lago, Alexandre

    2014-01-01

    The adherence of Platinum thin film on Si/SiO2 wafer was studies using Chromium, Titanium or Alumina (Cr, Ti, Al2O3) as interlayer. The adhesion of Pt is a fundamental property in different areas, for example in MEMS devices, which operate at high temperature conditions, as well as in biomedical applications, where the problem of adhesion of a Pt film to the substrate is known as a major challenge in several industrial applications health and in biomedical devices, such as for example in the stents. We investigated the properties of Chromium, Titanium, and Alumina (Cr, Ti, and Al2O3) used as adhesion layers of Platinum (Pt) electrode. Thin films of Chromium, Titanium and Alumina were deposited on Silicon/Silicon dioxide (Si/SiO2) wafer by electron beam. We introduced Al2O3 as a new adhesion layer to test the behavior of the Pt film at higher temperature using a ceramic adhesion thin film. Electric behaviors were measured for different annealing temperatures to know the performance for Cr/Pt, Ti/Pt, and Al2O3/Pt metallic film in the gas sensor application. All these metal layers showed a good adhesion onto Si/SiO2 and also good Au wire bondability at room temperature, but for higher temperature than 400 °C the thin Cr/Pt and Ti/Pt films showed poor adhesion due to the atomic inter-diffusion between Platinum and the metal adhesion layers. The proposed Al2O3/Pt ceramic-metal layers confirmed a better adherence for the higher temperatures tested. PMID:25482415

  12. The electrochemical recovery of metallic palladium from spent electroless plating solution

    NASA Astrophysics Data System (ADS)

    Warner, Nathan; Free, Michael L.

    2009-10-01

    Semiconductor bond pads are sometimes coated with palladium for good electrical properties and wire adhesion. The palladium is deposited by immersing the wafers in an electroless plating solution. When the plating solution is depleted and no longer achieves the desired results it is treated as waste. This work investigates the recovery of the remaining palladium in the waste solution by means of electrochemical deposition onto a high surface area cathode. Experiments show that the remaining palladium can be recovered economically and efficiently. This makes the process environmentally friendly and cost effective.

  13. Materials discovery by crystal growth: Lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt) from molten alkali metal hydroxides

    SciTech Connect

    Mugavero, Samuel J.; Gemmill, William R.; Roof, Irina P.; Loye, Hans-Conrad zur

    2009-07-15

    This review addresses the process of materials discovery via crystal growth, specifically of lanthanide metal containing oxides of the platinum group metals (Ru, Os, Ir, Rh, Pd, Pt). It provides a detailed overview of the use of hydroxide fluxes for crystal growth. The melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals are described. Furthermore, a general methodology for the successful crystal growth of oxides is provided, including a discussion of experimental considerations, suitable reaction vessels, reaction profiles and temperature ranges. Finally, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts, focusing on their crystal growth and crystal structures, is included. - Graphical abstract: A review that addresses the process of materials discovery via crystal growth using hydroxide fluxes. It provides a detailed overview of the use of hydroxide fluxes for crystal growth and describes the melt chemistry of hydroxide fluxes, specifically, the extensive acid base chemistry, the metal cation solubility, and the ability of hydroxide melts to oxidize metals. In addition, a compilation of complex platinum group metal oxides recently synthesized using hydroxide melts is included.

  14. Palladium metal nanoparticle size control through ion paired structures of [PdCl4]2- with protonated PDMAEMA.

    PubMed

    Tangeysh, Behzad; Fryd, Michael; Ilies, Marc A; Wayland, Bradford B

    2012-09-14

    The mean diameter of palladium metal particles produced by citrate reduction of the (H(+))(n) PDMAEMA/[PdCl(4)](2-) aqueous system increases from 1.4 nm to 5.0 nm as the pH decreases from 6.3 to 3.3 and the (H(+))(n) PDMAEMA/[PdCl(4)](2-) species undergo conversion from a cross linked polymer network to a single chain structure. PMID:22842614

  15. The reduction of platinum(IV) and palladium(IV) ions by 2,6-pyridinedihydroxamic acid.

    PubMed

    Griffith, Darren; Chopra, Atish; Müller-Bunz, Helge; Marmion, Celine J

    2008-12-28

    Reaction of K(2)[Pt(IV)Cl(6)] and K(2)[Pd(IV)Cl(6)] with 2,6-pyridinedihydroxamic acid (2,6-pyha) and its disodium salt, 2,6-pyhaNa(2), yielded not the desired Pt(IV) and Pd(IV) 2,6-pyridinedihydroxamato complexes, but rather the Pt(II) and Pd(II) 2,6-pyridinedicarboxylato complexes, trans-[Pt(II)(2,6-pyca(H-1))(2)].2H(2)O and trans-[Pd(II)(2,6-pyca(H-1))(2)].2H(2)O respectively (2,6-pyca = 2,6-pyridinedicarboxylic acid). Thus in the presence of Pt(IV) and Pd(IV), the dihydroxamic acid was adventitiously hydrolysed to the corresponding dicarboxylic acid and Pt(IV) and Pd(IV) reduced to Pt(II) and Pd(II) in situ. The X-ray crystal structures of 2,6-pyha, 2,6-pyhaNa(2).8H(2)O, trans-[Pt(II)(2,6-pyca(H-1))(2)].2H(2)O and trans-[Pd(II)(2,6-pyca(H-1))(2)].2H(2)O are reported, together with a possible mechanism for the metal-assisted hydrolysis of the dihydroxamic acid and reduction of Pt(IV) and Pd(IV) to Pt(II) and Pd(II) respectively. PMID:19050779

  16. Determination of platinum, palladium, and rhodium in automotive catalysts using high-energy secondary target X-ray fluorescence spectrometry.

    PubMed

    Van Meel, Katleen; Smekens, Anne; Behets, Marc; Kazandjian, Paul; Van Grieken, René

    2007-08-15

    A fast and direct determination procedure for precious metals in spent automotive catalyst was developed using the novel high-energy polarized-beam XRF. A sample preparation method working directly on the ground material was optimized. The material was pressed as a pellet using wax as a binder; no internal standard was added. The standards for this application were available spent automotive catalyst, previously analyzed by ICP-OES to verify their concentration, prepared in the same way as the unknown samples. The investigated concentration ranged from nearly 0 to approximately 2700 ppm for Pt, to 500 ppm for Rh, and to 7500 ppm for Pd. The repeatability of the XRF measurement appeared to be better than 0.5%, while the precision of the whole method was approximately 1%. The accuracy of the XRF method was verified with the well-established (but very time-consuming) ICP-OES method; a good agreement (no difference when using the 95% confidence interval) was found for the results. When using an irradiation time of 500 s for the CsI secondary target and the Zr secondary target, the detection limits for Pt, Pd, and Rh were found to be better than 5 ppm. PMID:17628117

  17. Design and synthesis of thin palladium membranes on porous metal substrate for hydrogen extraction

    NASA Astrophysics Data System (ADS)

    Shi, Z.; Szpunar, J. A.; Wu, S.

    2009-05-01

    Membrane separation is regarded nowadays as a preferred method for production of purified hydrogen. Palladium (Pd) is an attractive membrane material due to its ability to dissociate molecular hydrogen into atoms. It is usually deposited on the porous substrate that can provide good mechanical support and reduce the thickness of the membrane for maximizing hydrogen permeability. Pd membrane used for hydrogen separation must be thin enough to increase hydrogen flux and reduce cost while remaining thick enough to retain adhesion, attrition resistance and mechanical integrity during high temperature cycles. In this paper, the progress of electroless deposition of Pd around the pore area at surface of porous stainless steel was recorded and a bridge structure that was formed during the membrane deposition around the pore area of the substrate was illustrated. After that, the porous substrate was modified using micro-or nano-size metal or metal oxide particles in order to reduce pore size in the substrate surface. The experimental results obtained from hydrogen permeation through the Pd membranes having the thickness from 400 nm to 18 μm built on both modified and original porous stainless steel substrates demonstrate that these thin membranes are solid and they can be used at the temperature of 550°C and hydrogen pressure difference of 3.447x105 Pa. The proposed processing will allow optimizing the design and fabrication of thin Pd membranes on different porous substrates for hydrogen separation.

  18. Clinical utility of platinum chromium bare-metal stents in coronary heart disease

    PubMed Central

    Jorge, Claudia; Dubois, Christophe

    2015-01-01

    Coronary stents represent a key development for the treatment of obstructive coronary artery disease since the introduction of percutaneous coronary intervention. While drug-eluting stents gained wide acceptance in contemporary percutaneous coronary intervention practice, further developments in bare-metal stents remain crucial for patients who are not candidates for drug-eluting stents, or to improve metallic platforms for drug elution. Initially, stent platforms used biologically inert stainless steel, restricting stent performance due to limitations in flexibility and strut thickness. Later, cobalt chromium stent alloys outperformed steel as the material of choice for stents, allowing latest generation stents to be designed with significantly thinner struts, while maintaining corrosion resistance and radial strength. Most recently, the introduction of the platinum chromium alloy refined stent architecture with thin struts, high radial strength, conformability, and improved radiopacity. This review will provide an overview of the novel platinum chromium bare-metal stent platforms available for coronary intervention. Mechanical properties, clinical utility, and device limitations will be summarized and put into perspective. PMID:26345228

  19. Influence of platinum, palladium and rhodium as compared with cadmium, nickel and chromium on cell viability and oxidative stress in human bronchial epithelial cells.

    PubMed

    Schmid, Michael; Zimmermann, Sonja; Krug, Harald F; Sures, Bernd

    2007-04-01

    The platinum group elements (PGE) Pt, Pd and Rh are increasingly emitted into the environment by automobile catalytic converters. Whereas the biological availability of PGE to plants and animals has been demonstrated, only few studies concentrate on the influence of PGE on a cellular level. The effects of Pt, Pd and Rh compared with Cd, Ni and Cr on cell viability and oxidative stress response using soluble metal salts were studied in the human bronchial epithelial cell line BEAS-2B. Whilst Rh(III) showed little influence, both Pt(II) and Pt(IV) as well as Pd(II) had significant effects on cell viability at levels comparable to Cd(II) and Cr(VI). Arranging metal species in order of increasing toxicity as determined by LC50 yields: Rh(III)=1.2 mmol/L

  20. Interactions of the anticancer antibiotic altromycin B with copper(II), palladium(II) and platinum(II) ions and in vitro activity of the formed complexes.

    PubMed

    Nikolis, Nikolaos; Methenitis, Constantinos; Pneumatikakis, George; Fiallo, Marina M L

    2002-04-10

    Interaction of the anticancer antibiotic altromycin B with Cu(II), Pd(II) and Pt(II) ions was studied using 1H-NMR, EPR, electronic absorption and circular dichroism spectroscopy. The results derived from NMR studies where that the Pt(II) and Pd(II) ions interact with the nitrogen atom of the dimethylamino group of the C(10)-disaccharide, while the C(2)-epoxide group does not participate and remains intact. Cu(II) ions interact in a different way with altromycin B as was concluded by EPR and circular dichroism spectra. Altromycin B coordinates to the Cu(II) ions via the oxygen atoms of the C(11) phenolic and the C(12) carbonyl group while the nitrogen atom does not participate in the complexation. The presence of these metal ions improves the stability of altromycin B in solution. These complexes were studied in vitro against K562 leukemia sensitive and doxorubicin-resistant cells and GLC4 lung tumor cells, sensitive and doxorubicin-resistant. The activity of the complexes compared to the free drug is improved against resistant cells and is affected moderately against sensitive cells. Finally, 20% of platinum added as altromycin B metal complex entered GLC4 cells. PMID:11931973

  1. Fractionation of palladium and platinum in a Mesozoic diabase sheet, Gettysburg basin, Pennsyvania: implications for mineral exploration

    USGS Publications Warehouse

    Gottfried, D.; Froelich, A.J.; Rait, N.; Aruscavage, P. J.

    1990-01-01

    The York Haven diabase sheet displays clear-cut evidence of fractionation of Pd and Pt during differentiation of a high-Ti (about 1.1%) quartz-normative tholeiitic magma (York Haven type). At York Haven the sheet is about 750 m thick. It is characterized by abundant cumulus MgO-rich orthopyroxene (bronzite), and is markedly depleted in incompatible elements relative to the chilled margins. In contrast, at Reesers Summit, 16 km to the northwest, the sheet is about 500 m thick and consists of evolved rocks that have contents of incompatible elements two to three times greater than in the enclosing chilled margins. These evolved rocks represent complementary fractions to the cumulate rocks at York Haven. Mineralogic, petrologic and geochemical variations suggest considerable lateral migration and fractionation of the initial magma. Chilled margins of both sections have essentially the same Pd and Pt contents (10 ppb each) and similar Pd to Pt ratios (1.2). During differentiation, the cumulate rocks at York Haven were enriched in Pt and depleted in Pd, whereas at Reesers Summit, the low-MgO diabase and ferrogabbro zone were enriched in Pd relative to Pt. Anomalously high contents of Pd (to 165 ppb), Au (to 54 ppb), and Te (to 26 ppb) were found in an iron- (to 18%) and chlorine- (to 0.44%) rich ferrogabbro at Reesers Summit, suggesting possible late or post-magmatic enrichment of precious metals. Field relations, geochemical and petrographic data provide guides for further exploration for Pd and Pt in differentiated high-Ti quartz-normative diabase sheets. Based on present information, the most favorable sites for economic deposits are late-stage differentiates enriched in Fe and Cl. ?? 1990.

  2. Activity of phosphino palladium(II) and platinum(II) complexes against HIV-1 and Mycobacterium tuberculosis.

    PubMed

    Gama, Ntombenhle H; Elkhadir, Afag Y F; Gordhan, Bhavna G; Kana, Bavesh D; Darkwa, James; Meyer, Debra

    2016-08-01

    Treatment of human immunodeficiency virus (HIV) is currently complicated by increased prevalence of co-infection with Mycobacterium tuberculosis. The development of drug candidates that offer the simultaneous management of HIV and tuberculosis (TB) would be of great benefit in the holistic treatment of HIV/AIDS, especially in sub-Saharan Africa which has the highest global prevalence of HIV-TB coinfection. Bis(diphenylphosphino)-2-pyridylpalladium(II) chloride (1), bis(diphenylphosphino)-2-pyridylplatinum(II) chloride (2), bis(diphenylphosphino)-2-ethylpyridylpalladium(II) chloride (3) and bis(diphenylphosphino)-2-ethylpyridylplatinum(II) (4) were investigated for the inhibition of HIV-1 through interactions with the viral protease. The complexes were subsequently assessed for biological potency against Mycobacterium tuberculosis H37Rv by determining the minimal inhibitory concentration (MIC) using broth microdilution. Complex (3) showed the most significant and competitive inhibition of HIV-1 protease (p = 0.014 at 100 µM). Further studies on its in vitro effects on whole virus showed reduced viral infectivity by over 80 % at 63 µM (p < 0.05). In addition, the complex inhibited the growth of Mycobacterium tuberculosis at an MIC of 5 µM and was non-toxic to host cells at all active concentrations (assessed by tetrazolium dye and real time cell electronic sensing). In vitro evidence is provided here for the possibility of utilizing a single metal-based compound for the treatment of HIV/AIDS and TB. PMID:27246555

  3. Platinum-group element distribution in base-metal sulfides of the UG2 chromitite, Bushveld Complex, South Africa—a reconnaissance study

    NASA Astrophysics Data System (ADS)

    Osbahr, Inga; Oberthür, Thomas; Klemd, Reiner; Josties, Anja

    2014-08-01

    Two drill cores of the UG2 chromitite from the eastern and western Bushveld Complex were studied by whole-rock analysis, ore microscopy, SEM/Mineral Liberation Analysis (MLA), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. The top and base of the UG2 main seam have the highest bulk-rock Pd and Pt concentrations. Sulfides mostly occur as aggregates of pentlandite, chalcopyrite, and rare pyrrhotite and pyrite or as individual grains associated mostly with chromite grains. In situ LA-ICP-MS analyses reveal that pentlandite carries distinctly elevated platinum-group element (PGE) contents. In contrast, pyrrhotite and chalcopyrite contain very low PGE concentrations. Pentlandite shows average maximum values of 350-1,000 ppm Pd, 200 ppm Rh, 130-175 ppm Ru, 20 ppm Os, and 150 ppm Ir, and is the principal host of Pd and Rh in the studied ores of the UG2. Mass balance calculations were conducted for samples representing the UG2 main seam of the drill core DT46, eastern Bushveld. Pentlandite consistently hosts elevated contents of the whole-rock Pd (up to 55 %) and Rh (up to 46 %), and erratic contents of Os (up to 50 %), Ir (2 to 17 %), and Ru (1-39 %). Platinum-group mineral (PGM) investigations support these mass balance results; most of the PGM are Pt-dominant such as braggite/cooperite and Pt-Fe alloys or laurite (carrying elevated concentrations of Os and Ir). Palladium and Rh-bearing PGM are rare. Both PGE concentrations and their distribution in base-metal sulfides (BMS) in the UG2 largely resemble that of the Merensky Reef, as most of the Pd and Rh are incorporated in pentlandite, whereas pyrrhotite, chalcopyrite, and pyrite are almost devoid of PGE.

  4. Noble metal alloy clusters in the gas phase derived from protein templates: unusual recognition of palladium by gold.

    PubMed

    Baksi, Ananya; Pradeep, T

    2013-12-21

    Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd(+) in the gas phase. While a lysozyme-Au adduct forms Au18(+), Au25(+), Au38(+) and Au102(+) ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag(+), Pt(2+), Pd(2+), Cu(2+), Fe(2+), Ni(2+) and Cr(3+)) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38(+). While other metal ions like Cu(2+) help forming Au25(+) selectively, Fe(2+) catalyzes the formation of Au25(+) over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution. PMID:24146135

  5. Stable optical oxygen sensing materials based on click-coupling of fluorinated platinum(II) and palladium(II) porphyrins—A convenient way to eliminate dye migration and leaching

    PubMed Central

    Koren, Klaus; Borisov, Sergey M.; Klimant, Ingo

    2012-01-01

    Nucleophilic substitution of the labile para-fluorine atoms of 2,3,4,5,6-pentafluorophenyl groups enables a click-based covalent linkage of an oxygen indicator (platinum(II) or palladium(II) 5,10,15,20-meso-tetrakis-(2,3,4,5,6-pentafluorophenyl)-porphyrin) to the sensor matrix. Copolymers of styrene and pentafluorostyrene are chosen as polymeric materials. Depending on the reaction conditions either soluble sensor materials or cross-linked microparticles are obtained. Additionally, we prepared Ormosil-based sensors with linked indicator, which showed very high sensitivity toward oxygen. The effect of covalent coupling on sensor characteristics, stability and photophysical properties is studied. It is demonstrated that leaching and migration of the dye are eliminated in the new materials but excellent photophysical properties of the indicators are preserved. PMID:23576845

  6. Synthesis, characterization and antimicrobial activity of novel platinum(IV) and palladium(II) complexes with meso-1,2-diphenyl-ethylenediamine-N,N‧-di-3-propanoic acid - Crystal structure of H2-1,2-dpheddp·2HCl·H2O

    NASA Astrophysics Data System (ADS)

    Radić, Gordana P.; Glođović, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Garcia-Granda, Santiago; Roces, Laura; Menéndez-Taboada, Laura; Radojević, Ivana D.; Stefanović, Olgica D.; Čomić, Ljiljana R.; Trifunović, Srećko R.

    2012-12-01

    In the reaction of meso-1,2-diphenyl-ethylenediamine (1,2-dphen) with neutralized 3-chlor-propanoic acid, the new linear tetradentate edda-like ligand (edda = ethylenediamine-N,N'-diacetic ion) meso-1,2-diphenyl-ethylenediamine-N,N'-di-3-propanoic acid dihydrochloride monohydrate (H2-1,2-dpheddp·2HCl·H2O) was prepared. The corresponding platinum(IV) complex, s-cis-dichlorido-(meso-1,2-diphenyl-ethylenediamine-N,N'-di-3-propanoate)-platinum(IV) ([PtCl2(1,2-dpheddp)]) was synthesized by heating potassium-hexachloridoplatinate(IV) and H2-1,2-dpheddp·2HCl·H2O on steam bath for 12 h with neutralization by means of lithium-hydroxide. The palladium(II) complex, cis-dichlorido-(meso-1,2-diphenyl-ethylenediamine-N,N'-di-3-propanoate)-palladium(II) ([PdCl2(1,2-dpheddp)]) was obtained in the similar way using potassium-tetrachloridopalladate(II), H2-1,2-dpheddp·2HCl·H2O and lithium-hydroxide. The compounds were characterized by elemental analysis and infrared spectroscopy. The spectroscopically predicted structure of the synthesized tetradentate ligand was confirmed by X-ray analysis of the H2-1,2-dpheddp·2HCl·H2O. Antimicrobial activity of the ligand and corresponding palladium(II) and platinum(IV) complexes is investigated against 25 species of microorganisms. Testing is preformed by microdilution method and minimum inhibitory concentrations (MIC) and minimum microbicidal concentration (MMC) have been determined. The difference between antimicrobial activity of the ligand and corresponding platinum(IV) and palladium(II) complex is noticed and, in general, palladium(II) complex was the most active.

  7. Platinum group metal particles aggregation in nuclear glass melts under the effect of temperature

    NASA Astrophysics Data System (ADS)

    Hanotin, Caroline; Puig, Jean; Neyret, Muriel; Marchal, Philippe

    2016-08-01

    The viscosity of simulated high level radioactive waste glasses containing platinum group metal particles is studied over a wide range of shear stress, as a function of the particles content and the temperature, thanks to a stress imposed rheometer, coupled to a high-temperature furnace. The system shows a very shear thinning behavior. At high shear rate, the system behaves as a suspension of small clusters and individual particles and is entirely controlled by the viscosity of the glass matrix as classical suspensions. At low shear rate, above a certain fraction in platinum group metal particles, the apparition of macroscopic aggregates made up of chains of RuO2 particles separated by thin layers of glass matrix strongly influences the viscosity of the nuclear glass and leads, in particular, to the apparition of yield stress and thixotropic effects. The maximum size of these clusters as well as their effective volume fraction have been estimated by a balance between Van der Waals attractive forces and hydrodynamic forces due to shear flow. We showed experimentally and theoretically that this aggregation phenomenon is favored by an increase of the temperature, owing to the viscosity decrease of the glass matrix, leading to an unusual increase of the suspension viscosity.

  8. Versatile Oxidation Methods for Organic and Inorganic Substrates Catalyzed by Platinum-Group Metals on Carbons.

    PubMed

    Sawama, Yoshinari; Asai, Shota; Monguchi, Yasunari; Sajiki, Hironao

    2016-02-01

    Platinum-group metals on activated carbon catalysts, represented by Pd/C, Ru/C, Rh/C, etc., are widely utilized to accomplish green and sustainable organic reactions due to their favorable features, such as easy handling, recoverability, and reusability. The efficient oxidation methods of various organic compounds using heterogeneous platinum-group metals on carbons with or without added oxidants are summarized in this Personal Account. The oxidation of internal alkynes into diketones was effectively catalyzed by Pd/C in the presence of dimethyl sulfoxide and molecular oxygen or pyridine N-oxide. The Pd/C-catalyzed mild combustion of gaseous hydrogen with molecular oxygen provided hydrogen peroxide, which could be directly utilized for the oxidation of sulfide derivatives into sulfoxides. Furthermore, the Ru/C-catalyzed aerobic oxidation of primary and secondary alcohols gave the corresponding aldehydes and ketones, respectively. On the other hand, the dehydrogenative oxidation of secondary alcohols into ketones was achieved using Rh/C in water, and primary alcohols were effectively dehydrogenated by Pd/C in water under mildly reduced pressure to produce carboxylic acids. PMID:26666634

  9. Synthesis and spectral studies of platinum metal complexes of benzoin thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Offiong, Offiong E.

    1994-11-01

    The platinum metal chelates of benzoin thiosemicarbazone obtained with Ru(III), Rh(III), Ir(III), Pd(II) and Pt(II) were prepared from their corresponding halide salts. The complexes were characterized by elemental analysis, conductance measurement, IR, Raman, 1H-NMR, 13C-NMR and UV-visible spectra studies. Various ligand field parameters and nephelauxetic parameters were also calculated. The mode of bonding and the geometry of the ligand environment around the metal ion have been discussed in the light of the available data obtained. Complexes of Ru(III), Rh(III) and Ir(III) are six-coordinate octahedral, while Pd(II) and Pt(II) halide complexes are four-coordinated with halides bridging.

  10. Aurum and Platinum as Metal Contact to Amorphous Carbon Thin Films

    NASA Astrophysics Data System (ADS)

    Mohamad, F.; Suriani, A. B.; Noor, U. M.; Rusop, M.

    2010-07-01

    Amorphous carbon (a-C) thin films have been deposited on quartz substrates at different deposition temperatures ranging from 700 °C-800 °C. The objective of this work is to investigate several electrical contacts on a-C thin films and to find the suitable method to fabricate ohmic contact on a-C thin films that prepared from a natural product, camphor (C10H16O). The a-C thin films were prepared with a simple thermal CVD method. In this study, Aurum (Au) and Platinum (Pt) were selected as the metal contact to a-C thin films. I-V characteristics measurement was carried out to study the contact between metal and a-C thin films. It was found that increasing deposition temperature also contributes to the variation I-V characteristics of a-C thin films.

  11. Alkene epoxidation employing metal nitro complexes

    DOEpatents

    Andrews, M.A.; Cheng, C.W.; Kelley, K.P.

    1982-07-15

    Process for converting alkenes to form epoxides utilizes transition metal nitro complexes of the formula: M(RCN)/sub 2/XNO/sub 2/ wherein M is palladium or platinum, R is an alkyl or aryl group containing up to 12 carbon atoms, and X is a monoanionic, monodentate ligand such as chlorine, optionally in the presence of molecular oxygen.

  12. CONTROL ROD ALLOY CONTAINING NOBLE METAL ADDITIONS

    DOEpatents

    Anderson, W.K.; Ray, W.E.

    1960-05-01

    Silver-base alloys suitable for use in the fabrication of control rods for neutronic reactors are given. The alloy consists of from 0.5 wt.% to about 1.5 wt.% of a noble metal of platinum, ruthenium, rhodium, osmium, or palladium, up to 10 wt.% of cadmium, from 2 to 20 wt.% indium, the balance being silver.

  13. Virus templated metallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Aljabali, Alaa A. A.; Barclay, J. Elaine; Lomonossoff, George P.; Evans, David J.

    2010-12-01

    Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. <=35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron.Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. <=35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron. Electronic supplementary information (ESI) available: Additional experimental detail, agarose gel electrophoresis results, energy dispersive X-ray spectra, ζ-potential measurements, dynamic light scattering data, nanoparticle tracking analysis and an atomic force microscopy image of Ni-CPMV. See DOI: 10.1039/c0nr00525h

  14. Noble-metal minerals in ores of the black-shale type in the Voronezh Crystalline Massif, central Russia

    NASA Astrophysics Data System (ADS)

    Chernyshov, N. M.

    2009-12-01

    High-carbonaceous stratified formations and related metasomatic rocks of global abundance are among highly promising sources of gold and platinum-group metals (PGMs) in the 21st century. The Au-PGM mineralization of the black-shale type hosted in the Early Karelian Kursk and Oskol groups in central Russia is characterized by complex multicomponent and polymineralic composition (more than 60 ore minerals, including more than 20 Au and PGM phases) and diverse speciation of noble metals in form of (1) native elements (gold, palladium, platinum, osmium, silver); (2) metallic solid solutions and intermetallic compounds (Pt-bearing palladium, Fe-bearing platinum, gold-platinum-palladium, osmiridium, rutheniridosmin, platiridosmin, platosmiridium, Hg-Te-Ag-bearing gold, gold-silver amalgam, arquerite, palladium stannide (unnamed mineral), platinum-palladium-gold-silver-tin); (3) PGM, Au, and Ag sulfoarsenides, tellurides, antimonides, selenides, and sulfosalts (sperrylite, irarsite, hessite, Pd and Pt selenide (unnamed mineral)), testibiopalladinite, Pd antimonide (unnamed mineral), etc.; and (4) impurities in ore-forming sulfides, sulfoarsenides, tellurides, antimonides, and selenides. The chemical analyses of PGM and Au minerals are presented, and their morphology and microstructure are considered.

  15. Enhancement of palladium-porphyrin room temperature phosphorescence by alkaline earth metal in deoxycholate aggregates solution.

    PubMed

    Wang, Ying-Te; Wang, Xiang-Wei; Zhang, Yong

    2011-01-01

    Room temperature phosphorescence (RTP) of three palladium (Pd)-phorphyrins in air-saturated solution of sodium deoxycholate (NaDC) aggregates was measured. RTP of Pd-meso-tetrakis (4-carboxyphenyl) porphyrin (Pd-TCPP) was obviously enhanced in NaDC-aggregates mediated by alkaline earth metal (AEM). Under the same experimental conditions, Ca(2+), Ba(2+) and Mg(2+) induced 200, 90 and 24 times greater enhancement in RTP of Pd-TCPP, respectively. It is ascribed to form the complex of NaDC-aggregate/AEM/Pd-TCPP in the system. The positively charged AEM has a strong capability of co-ordination with negatively charged carboxyl groups of NaDC and Pd-TCPP. The phosphor Pd-TCPP is confined in rigid NaDC-aggregates/AEM system by the coordination which decreases the probability of collision of phosphor with quenchers such as dissolved oxygen molecules and prolongs the lifetime of the phosphor on the triplet state. Long excited-state lifetimes resulted in great enhancement of Pd-TCPP phosphorescence. Observations by optical microscope showed that specific fan-like structures of NaDC were formed under the influence of AEM. Surface tension measurements supported a close interaction between Ca(2+) ions and anion aggregates of NaDC with 1:1 stoichiometric ratio. Due to its outstanding RTP behavior in NaDC-aggregates induced by Ca(2+), Pd-TCPP was used as a RTP probe to detect bovine serum albumin (BSA). A broad linear range from 1.0 × 10(-9) to 9.0 × 10(-7) g mL(-1) was obtained. Detection limit is 2.6 × 10(-11) g mL(-1), the relative standard deviation (n = 6) is 2.3% for 2.0 × 10(-9) g mL(-1) BSA. PMID:21438880

  16. Platinum nanoparticles encapsulated metal-organic frameworks for the electrochemical detection of telomerase activity.

    PubMed

    Ling, Pinghua; Lei, Jianping; Jia, Li; Ju, Huangxian

    2016-01-21

    A simple and rapid electrochemical sensor is constructed for the detection of telomerase activity based on the electrocatalysis of platinum nanoparticle (Pt NP) encapsulated metal-organic frameworks (MOFs), which are synthesized by one-pot encapsulation of Pt NPs into prototypal MOFs, UiO-66-NH2. Integrating with the efficient electrocatalysis of Pt@MOFs towards NaBH4 oxidation, this biosensor shows the wide dynamic correlation of telomerase activity from 5 × 10(2) to 10(7) HeLa cells mL(-1) and the telomerase activity in a single HeLa cell was calculated to be 2.0 × 10(-11) IU, providing a powerful platform for detecting telomerase activity. PMID:26612011

  17. Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions.

    PubMed

    Esteruelas, Miguel A; López, Ana M; Oliván, Montserrat

    2016-08-10

    The preparation, structure, dynamic behavior in solution, and reactivity of polyhydride complexes of platinum group metals, described during the last three decades, are contextualized from both organometallic and coordination chemistry points of view. These compounds, which contain dihydrogen, elongated dihydrogen, compressed dihydride, and classical dihydride ligands promote the activation of B-H, C-H, Si-H, N-H, O-H, C-C, C-N, and C-F, among other σ-bonds. In this review, it is shown that, unlike other more mature areas, the chemistry of polyhydrides offers new exciting conceptual challenges and at the same time the possibility of interacting with other fields including the conversion and storage of regenerative energy, organic synthetic chemistry, drug design, and material science. This wide range of possible interactions foresees promising advances in the near future. PMID:27268136

  18. Noble metal alloy clusters in the gas phase derived from protein templates: unusual recognition of palladium by gold

    NASA Astrophysics Data System (ADS)

    Baksi, Ananya; Pradeep, T.

    2013-11-01

    Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution.Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster

  19. The catalytic inactivation of cellulase enzyme components by palladium complexes

    SciTech Connect

    Woodward, J.; Gooch, M.G.; Shultz, M.D.

    1993-10-01

    It has been discovered that sodium hexachloropalladate is a strong inhibitor of cellobiohydrolase I (CBH I) from Trichoderma reesei having an I{sub 50} of <50 {mu}M with p-nitrophenylcellobioside (PNPC) as the substrate. Similar complexes of the metals platinum, osmium, iridium, and rhodium have little effect on CBH I. Other cellulase activities (Avicelase, {beta}-glucanase) are also inhibited by the palladium complex, suggesting that inhibition of two major types of catalytic activity in cellulase are affected. Preliminary data on the kinetics of inhibition of CBH I by sodium hexachloropalladate indicate that the inhibition is reversible and, possibly, uncompetitive. It is anticipated that sodium hexachloropalladate and other palladium complexes will be useful for determining the effect of the binding of catalytically inactivated CBH I and other cellulase components on the structure of cellulose fibers.

  20. Thermally tolerant multilayer metal membrane

    DOEpatents

    Dye, Robert C.; Snow, Ronny C.

    2001-01-01

    A composite metal membrane including a first metal layer of a Group IVB or Group VB metal sandwiched between two layers of a Group VIIIB metal selected from the group consisting of palladium, platinum, nickel, rhodium, iridium, cobalt, and alloys thereof, and a non-continuous layer of a metal chalcogenide upon one layer of the Group VIIIB metal is disclosed together with a process for the recovery of hydrogen from a gaseous mixture using such a composite membrane and a process for forming such a composite metal membrane.

  1. The calculated solubility of platinum and gold in oxygen-saturated fluids and the genesis of platinum-palladium and gold mineralization in the unconformity-related uranium deposits

    NASA Astrophysics Data System (ADS)

    Jaireth, S.

    1992-01-01

    Thermodynamic calculations on the solubility of platinum and gold indicate that saline (1 m NaCl), fluids saturated with atmospheric oxygen can transport geologically realistic concentrations of platinum-group-elements (PGE), gold, and uranium as chloro-complexes. A number of calculations involving fluid-rock interaction suggest that the oxygen-saturated fluids flowing through rocks containing quartz, muscovite, kaolinite, magnetite and hematite, initially oxidize any magnetite to hematite, allowing subsequent batches of ore fluids to retain their high oxidation state. During their migration through the aquifer, the oxidizing fluids would move the oxidation-reduction interface deeper into the aquifer, leaching and redepositing platinum and gold. The redissolution of earlier precipitated platinum and gold depends on the fluid/ rock ratio and the associated increase in the oxidation state. Therefore, lowering of fluid/rock ratios and/or mixing of the oxidized fluids with a large amount of reduced fluid will precipitate uranium, PGE, and gold. It is suggested that this model can explain the genesis of gold and PGE mineralization in the unconformity-related uranium deposits of the Alligator Rivers Uranium Field in the Northern Territory, Australia.

  2. A Capped Octahedral MHC6 Compound of a Platinum Group Metal.

    PubMed

    Eguillor, Beatriz; Esteruelas, Miguel A; Lezáun, Virginia; Oliván, Montserrat; Oñate, Enrique; Tsai, Jui-Yi; Xia, Chuanjun

    2016-06-27

    A MHC6 complex of a platinum group metal with a capped octahedral arrangement of donor atoms around the metal center has been characterized. This osmium compound OsH{κ(2) -C,C-(PhBIm-C6 H4 )}3 , which reacts with HBF4 to afford the 14 e(-) species [Os{κ(2) -C,C-(PhBIm-C6 H4 )}(Ph2 BIm)2 ]BF4 stabilized by two agostic interactions, has been obtained by reaction of OsH6 (PiPr3 )2 with N,N'-diphenylbenzimidazolium chloride ([Ph2 BImH]Cl) in the presence of NEt3 . Its formation takes place through the C,C,C-pincer compound OsH2 {κ(3) -C,C,C-(C6 H4 -BIm-C6 H4 )}(PiPr3 )2 , the dihydrogen derivative OsCl{κ(2) -C,C-(PhBIm-C6 H4 )}(η(2) -H2 )(PiPr3 )2 , and the five-coordinate osmium(II) species OsCl{κ(2) -C,C-(PhBIm-C6 H4 )}(PiPr3 )2 . PMID:27123555

  3. Platinum-coated non-noble metal-noble metal core-shell electrocatalysts

    DOEpatents

    Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir

    2015-04-14

    Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.

  4. Changes in physical and chemical properties of a dental palladium-silver alloy during metal-porcelain bonding.

    PubMed

    Payan, J; Moya, G E; Meyer, J M; Moya, F

    1986-07-01

    The hardening ability of a dental palladium-silver (Pd-Ag-Sn-In) bonding alloy has been investigated, and the distribution of the elements along the metal-ceramic interface have been studied by microprobe analysis. The alloy was found to be highly heterogeneous in its 'as-cast' condition, but homogenized alloy was obtained after heating the alloy at 1000 degrees C for 2 h. Hardening occurred after annealing at 650 degrees C for 1 h. A longer thermal treatment caused the hardness to decrease (over-ageing). The change in hardness could be attributed to an internal oxidation phenomenon. The additional elements tin and indium segregated towards the ceramic-metal interface, with a diffusion of indium only into the porcelain. Diffusion of silver in the ceramics, supposed to be the cause of the 'greening' of dental porcelains baked on silver-rich alloys, has not been detected by the microprobe across the interface. PMID:3531444

  5. Stable palladium alloys for diffusion of hydrogen

    NASA Technical Reports Server (NTRS)

    Patapoff, M.

    1973-01-01

    Literature search on hydrogen absorption effect on palladium alloys revealed existence of alloy compositions in which alpha--beta transition does not take place. Survey conclusions: 40 percent gold alloy of palladium should be used in place of palladium; alloy must be free of interstitial impurities; and metallic surfaces of tube must be clean.

  6. Metal Bromide Controlled Interfacial Aromatization Reaction for Shape-Selective Synthesis of Palladium Nanostructures with Efficient Catalytic Performances.

    PubMed

    Dutta, Soumen; Ray, Chaiti; Roy, Anindita; Sahoo, Ramkrishna; Pal, Tarasankar

    2016-07-11

    Herein, the effect of diverse metal bromides for the shape evolution of palladium nanostructures (Pd NS) has been demonstrated. Aromaticity-driven reduction of bromopalladate(II) is optimized to reproducibly obtain different Pd NS at the water/organic layer interface. In this soft interfacial strategy, a redox potential driven reaction has been performed, forming the thermodynamically more stable (>10(4) -fold) PdBr4 (2-) precursor from PdCl4 (2-) by adding extra metal bromides. In the process, the reductant, Hantzsch dihydropyridine ester (DHPE), is aromatized. Interestingly, alkali metal bromides devoid of coordination propensity exclusively evolve Pd nanowires (Pd NWs), whereas in the case of transition metal bromides the metal ions engage the 'N' donor of DHPE at the interface, making the redox reaction sluggish. Hence, controlled Pd nanoparticles growth is observed, which evolves Pd broccolis (Pd NBRs) and Pd nanorods (Pd NRs) at the interface in the presence of NiBr2 and CuBr2 , respectively, in the aqueous solution. Thus, the effect of diverse metal bromides in the reaction mixture for tailor-made growth of the various Pd NS is reported. Among the as-synthesized materials, the Pd NWs stand to be superior catalysts and their efficiency is almost 6 and 2.5 times higher than commercial 20 % Pd/C in the electrooxidation of ethanol and Cr(VI) reduction reaction by formic acid, respectively. PMID:27294801

  7. 76 FR 67793 - Notification of Expanded Pricing Grid for Precious Metals Products Containing Platinum and Gold...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-11-02

    ... and Gold--Excluding Commemorative Gold Coins AGENCY: United States Mint, Department of the Treasury..., 2009, outlining the new pricing methodology for numismatic products containing platinum and gold. Since that time, the price of platinum and gold has increased considerably, and is approaching the...

  8. Platinum-nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving

    NASA Astrophysics Data System (ADS)

    Li, Zhi; Yu, Rong; Huang, Jinglu; Shi, Yusheng; Zhang, Diyang; Zhong, Xiaoyan; Wang, Dingsheng; Wu, Yuen; Li, Yadong

    2015-09-01

    Developing catalysts that provide the effective activation of hydrogen and selective absorption of substrate on metal surface is crucial to simultaneously improve activity and selectivity of hydrogenation reaction. Here we present an unique in situ etching and coordination synthetic strategy for exploiting a functionalized metal-organic framework to incorporate the bimetallic platinum-nickel frames, thereby forming a frame within frame nanostructure. The as-grown metal-organic framework serves as a `breath shell' to enhance hydrogen enrichment and activation on platinum-nickel surface. More importantly, this framework structure with defined pores can provide the selective accessibility of molecules through its one-dimensional channels. In a mixture containing four olefins, the composite can selectively transport the substrates smaller than its pores to the platinum-nickel surface and catalyse their hydrogenation. This molecular sieve effect can be also applied to selectively produce imines, which are important intermediates in the reductive imination of nitroarene, by restraining further hydrogenation via cascade processes.

  9. Palladium-mediated borylation of pentafluorosulfanyl functionalized compounds: the crucial role of metal fluorido complexes.

    PubMed

    Berg, Claudia; Braun, Thomas; Laubenstein, Reik; Braun, Beatrice

    2016-03-11

    Stoichiometric reactions of SF5 functionalized bromo or iodo aromatics at [Pd(PiPr3)2] (1) led to the oxidative addition products 3, 5 and 7. They were converted into their corresponding palladium fluorido complexes, which reacted readily with bis(pinacolato)diboron (B2pin2) to give the borylated SF5 aromatic compounds. Based on these studies a catalytic borylation of SF5 organyls was developed. PMID:26872070

  10. Platinum-group elements in the Eastern Deccan volcanic province and a comparison with platinum metals of the western Deccan

    NASA Astrophysics Data System (ADS)

    Crocket, James; Paul, Dalim; Lala, Trisha

    2013-08-01

    This study is the first detailed investigation of the platinum-group elements (PGE) at the eastern margin of the Deccan volcanic province of India. One of the PGE, osmium, is not included largely because of analytical problems. The study is focused on mafic volcanics and dykes from four areas including Amarkantak, Umaria, Shahdol and Chirimiri. The first two localities represent two lava piles of about 170 and 400 m thickness respectively. In Umaria, 16 flows have been demarcated based on petrography and field studies. The Shahdol samples are basal lava formations overlying Gondwana sediments (Carboniferous) and the Chirimiri samples are dykes. In this study, the western Deccan province is defined as the Western Ghats plus Kutch. On average, the PGE are ~20% higher in Amarkantak than Umaria and the flows are ~13% higher in PGE than the dykes. A Zr vs. Pd scattergram found a strong positive correlation for these two elements except for one Umaria sample which indicated severe Pd loss. A comparison of west and east parts of the Deccan volcanic province using primitive mantle normalization showed that higher values prevailed in the western province suite in the Ni-Ir-Ru-Pt region. In contrast, eastern province values dominated in the Pd-Au-Cu region at the `Cu' end of the profiles. A strong dominance of Pd in the eastern Deccan was also of interest. A number of factors, for example, percentage partial melting of the source rock and the temperature and pressure of partial melting strongly influence the character of these profiles. The observed PGE profile characteristics probably result in part from a long distance of subsurface transport of Deccan magma from the western to eastern regions.

  11. Metallization Process of a Polyimide Surface with Palladium-Free Activation for Electronic Field Applications

    NASA Astrophysics Data System (ADS)

    Li, Libo; Ma, Yue; Xie, Jingchen; Yang, Xiuchun; Wang, Heng; Tian, Haiyan; Mu, Hongjing; Wang, Wentao

    2015-10-01

    A new copper plating bath without Pd activation for electroless deposition on polyimide (PI) film is reported. The characteristics of Cu coatings on the PI via electroless plating and the effects of operating parameters on the coating coverage are discussed. The pre-treatment and plating processes are further optimized based on orthogonal experiment methods, involving variations of multiple process parameters. The electroless copper coating was characterized by scanning electron microscopy and atomic force microscopy, while the composition and crystalline structure are estimated by energy dispersive spectrometer and x-ray diffraction, respectively. These results show that the crystalline copper layer on the PI surface after electroless plating is dense, continuous and uniform. The joint tensile experiment is used to measure the adhesive strength of the coating with palladium-free and palladium activation, and the former is higher. Furthermore, the pre-treatment method proposed in this work without using palladium compounds is considered to be environmentally friendly. In addition, it provides a new concept of electroless Cu plating on the PI, which is generally difficult to plate due to its hydrophobic nature.

  12. Strong metal-support interaction and catalytic properties of anatase and rutile supported palladium catalyst Pd/TiO 2

    NASA Astrophysics Data System (ADS)

    Li, Yuanzhi; Fan, Yining; Yang, Hanpei; Xu, Bolian; Feng, Lingyun; Yang, Mingfeng; Chen, Yi

    2003-04-01

    In situ EPR investigation by using CO as probe molecules shows that even pre-reduced by H 2 at lower temperature results in SMSI for anatase titania supported palladium catalyst, but not for rutile titania supported palladium catalyst. The reason of the different behavior between rutile and anatase titania supported palladium catalyst is discussed. The very different catalytic properties between anatase and rutile titania supported palladium catalyst pre-reduced at lower temperature, and the rapid change of conversion and selectivity of titania supported palladium catalyst with the elevation of pre-reduction temperature further confirm the above-mentioned results.

  13. The Bioaccumulation and Toxicity of Platinum Group Metals in Developing Chick Embryos

    NASA Astrophysics Data System (ADS)

    Pavel, Ioana; Monahan, Jennifer; Markopoulos, Marjorie; Gagnon, Zofia; Nejame, Britney; Cawley, Jacob; Reens, David

    2008-10-01

    Recent studies showed that platinum group metals (PGMs) such as Pt, Pd, and Rh from automobile catalytic converters, can accumulate in the soft tissues of a variety of living organisms. However, the effects of PGMs on bone and organs development of animals are not clearly understood. To examine these aspects, developing chick embryos were injected with 0.1, 1.0, 5, or 10 ppm solutions of Pt, Rh, Pd, or with a PGMs mixture. 1) Pathological Changes: were observed for all PGM treatments above 1 ppm. Bone Cells Assesment: Chondrocyte cells in thibiotarsus showed decreased diameter and length. 2) PGMs Accumulation in Tissues: was quantified by GFAAS spectrometry on finely ground tissue powder. 3) Bone Demineralization: was detected by micro-Raman spectroscopy imaging on paraffin embedded bone sections. 4) DNA Damage in Cells: was determined by using a Comet assay and fluorescence spectroscopy. Oxidative Damage in Tissues: was analyzed using a glutathione peroxidase assay. The overall results indicated that PGMs presence in our environment raises concerns about their long-term health effects on all organisms.

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

    NASA Astrophysics Data System (ADS)

    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.

  15. Communication: Photoactivation of nucleobase bound platinum(II) metal complexes: probing the influence of the nucleobase.

    PubMed

    Sen, Ananya; Dessent, Caroline E H

    2014-12-28

    We present UV laser action spectra (220-300 nm) of isolated nucleobase-bound Pt(II)(CN)4(2-) complexes, i.e., Pt(CN)4(2-)⋅M, where M = uracil, thymine, cytosine, and adenine. These metal complex-nucleobase clusters represent model systems for identifying the fundamental photophysical and photochemical processes occurring in photodynamic platinum (II) drug therapies that target DNA. This is the first study to explore the specific role of the nucleobase in the photophysics of the aggregate complex. Each of the complexes studied displays a broadly similar absorption spectra, with a strong λmax ∼ 4.7 eV absorption band (nucleobase localized chromophore) and a subsequent increase in the absorption intensity towards higher spectral-energy (Pt(CN)4(2-) localized chromophore). However, strikingly different band widths are observed across the series of complexes, decreasing in the order Pt(CN)4(2-)⋅Thymine > Pt(CN)4(2-)⋅Uracil > Pt(CN)4(2-)⋅Adenine > Pt(CN)4(2-)⋅Cytosine. Changes in the bandwidth of the ∼4.7 eV band are accompanied by distinctive changes in the photofragment product ions observed following photoexcitation, with the narrower-bandwidth complexes showing a greater propensity to decay via electron detachment decay. We discuss these observations in the context of the distinctive nucleobase-dependent excited state lifetimes. PMID:25554122

  16. Noble metals in mid-ocean ridge volcanism: A significant fractionation of gold with respect to platinum group metals

    NASA Technical Reports Server (NTRS)

    Crocket, James H.

    1988-01-01

    Hydrothermal precipitates, black smoker particulate, and massive sulphide dredge samples from the Explorer Ridge on the Juan de Fuca Plate and the TAG hydrothermal area on the Mid-Atlantic Ridge were analyzed for selected noble metals including Au, Ir and Pd by radiochemical neutron activation analysis. The preliminary results indicate that gold contents may reach the ppm range although values in the neighborhood of 100 to 200 ppb are more typical. The platinum group elements (PGE) represented by Ir and Pd are typically less than 0.02 ppb and less than 2 ppb respectively. These abundances represent a significant enrichment of gold relative to the PGE in comparison with average noble metal abundances in mid-ocean ridge basalts (MORB). A partial explanation of this distinctive fractionation can be found in the concepts of sulfur-saturation of basic magma in mid-ocean ridge (MOR) settings, and the origin of MOR hydrothermal fluids. Experimental and petrological data suggest that MORBs are sulfur-saturated at the time of magma generation and that an immiscible sulfide component remains in the mantle residue. Hence, MORBs are noble metal-poor, particularly with respect to PGE. Consequently, black smoker fluids can be expected to reflect the low Ir and Pd contents of the rock column. The average Au content of MORB is 1.3 ppb, and so the rock column is not significantly enriched in Au. The generation of fluids which precipitate solids with 200 ppb Au is apparently dependent on highly efficient fluid chemistry to mobilize Au from the rock column, high Au solubility in seawater hydrothermal fluids and efficient precipitation mechanisms to coprecipitate Au on Fe, Zn and Cu sulfides. Significant differences in these parameters appear to be the ultimate cause of the strong Au-PGE fractionation in the MOR setting. It does not appear from the current data base that MOR hydrothermal fluids are significant contributors to the Ir enrichment seen in Cretaceous-Tertiary boundary

  17. Platinum porous nanoparticles hybrid with metal ions as probes for simultaneous detection of multiplex cancer biomarkers.

    PubMed

    Wang, Zifeng; Liu, Na; Ma, Zhanfang

    2014-03-15

    In this work, platinum porous nanoparticles (PtPNPs) absorbed metal ions as electrochemical signals were fabricated. Clean-surface PtPNPs were prepared by a surfactant-free method and decorated with amino groups via 2-aminoethanethiol. Amino capped PtPNPs complexation with Cd(2+) and Cu(2+) to form PtPNPs-Cd(2+) and PtPNPs-Cu(2+) hybrids, respectively. Anti-CEA and Anti-AFP separately labeled with PtPNPs-Cd(2+) and PtPNPs-Cu(2+) were used as distinguishable signal tags for capturing antigens. The metal ions were detected in a single run through differential pulse voltammetry (DPV) without acid dissolution, electric potentials and peak heights of which reflected the identity and concentrations of the corresponding antigen. Ionic liquid reduced graphene oxide (IL-rGO) modified glassy carbon electrode (GCE) was used as a substrate, which was rich in amino groups to immobilize antibodies by glutaraldehyde through cross-link between aldehyde groups and amino groups. Using the proposed probes and platform, a novel sandwich-type electrochemical immunosensor for simultaneous detecting carcinoembryonic antigen (CEA) and alpha-fetoprotein (AFP) was successfully developed. This immunoassay possessed good linearity from 0.05 ng mL(-1) to 200 ng mL(-1) for both CEA and AFP. The detection limit of CEA was 0.002 ng mL(-1) and that of AFP was 0.05 ng mL(-1) (S/N=3). Furthermore, analysis of clinical serum samples using this immunosensor was well consistent with the data determined by the enzyme-linked immunosorbent assay (ELISA). It suggested that the proposed electrochemical immunoassay provided a potential application of clinical screening for early-stage cancers. PMID:24176967

  18. Fabrication of a metal membrane on a perforated polymer substrate by palladium aerosol activation and subsequent electroless plating.

    PubMed

    Byeon, Jeong Hoon; Hwang, Jungho

    2009-02-01

    Fabrication of a metal membrane on a perforated flexible poly(tetrafluoroethylene) (PTFE) substrate was developed by employing spark-generated palladium (Pd) aerosol activation and the subsequent electroless plating of Pd. After aerosol activation, Pd agglomerates of spark-generated primary particles (approximately 2.6 nm in diameter) with a face-centered-cubic structure were deposited uniformly on the PTFE substrate. Homogeneous Pd particles with an average size of 188 nm were tightly packed together to form a Pd membrane after Pd plating. The average plating rate of Pd during 30 min of plating at an activation intensity of 25 microg/cm(2) was 14.2 microg/cm(2) x min. PMID:20353212

  19. Nickel(II) and palladium(II) thiaethyneporphyrins. Intramolecular metal(II)-η2-CC interaction inside a porphyrinoid frame.

    PubMed

    Nojman, Elżbieta; Berlicka, Anna; Szterenberg, Ludmiła; Latos-Grażyński, Lechosław

    2012-03-01

    3,18-Diphenyl-8,13-di-p-tolyl-20-thiaethyneporphyrin ([18]thiatriphyrin(4.1.1)), which formally contains an C1-C2 ethyne moiety instead of pyrrole embedded in the macrocyclic framework of 21-thiaporphyrin, was obtained in a modification of the "3 + 1" approach using the ethyne analogue of tripyrrane (1,4-diphenyl-1,4-di(pyrrol-2-yl)but-2-yne) and 2,5-bis(p-tolylhydroxymethyl)thiophene. The spectroscopic and structural properties of 20-thiaethyneporphyrin reflect its macrocyclic aromaticity, revealing a combination of the acetylene (≥C-C≡C-C≤) and cumulene (>C═C═C═C<) character of the C18-C1-C2-C3 linker. The magnetic manifestations of aromaticity and antiaromaticity of thiaethyneporphyrin and its two-electron-oxidized derivative were observed using (1)H NMR spectroscopy and were confirmed by density functional theory calculations involving chemical shifts and nucleus-independent chemical shift analysis. Protonation of 20-thiaethyneporphyrin yielded a nonaromatic tautomer of iso-20-thiaethyneporphyrin, locating the saturated meso carbon adjacent to thiophene. Insertion of palladium(II) and nickel(II) into 20-thiaethyneporphyrin afforded planar palladium(II) thiaethyneporphyrin and low-spin diamagnetic nickel(II) 20-thiaethyneporphyrin as determined by X-ray crystallography. 20-Thiaethyneporphyrin acts as a dianionic ligand that coordinates through the two nitrogen and one sulfur donors. Metal(II) ions are uniquely exposed to form an intramolecular metal(II)-η(2)-CC bond, whereas the organometallic fragment is coplanar with the whole macrocycle. Coordination of pyridine converts diamagnetic nickel(II) thiaethyneporphyrin into its paramagnetic counterpart as determined by (1)H NMR. PMID:22356285

  20. Global flows of critical metals necessary for low-carbon technologies: the case of neodymium, cobalt, and platinum.

    PubMed

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

    2014-01-01

    This study, encompassing 231 countries and regions, quantifies the global transfer of three critical metals (neodymium, cobalt, and platinum) considered vital for low-carbon technologies by means of material flow analysis (MFA), using trade data (BACI) and the metal contents of trade commodities, resolving the optimization problem to ensure the material balance of the metals within each country and region. The study shows that in 2005 international trade led to global flows of 18.6 kt of neodymium, 154 kt of cobalt, and 402 t of platinum and identifies the main commodities and top 50 bilateral trade links embodying these metals. To explore the issue of consumption efficiency, the flows were characterized according to the technological level of each country or region and divided into three types: green ("efficient use"), yellow ("moderately efficient use"), and red ("inefficient use"). On this basis, the shares of green, yellow, and red flows in the aggregate global flow of Nd were found to be 1.2%, 98%, and 1.2%, respectively. For Co, the respective figures are 53%, 28%, and 19%, and for Pt 15%, 84%, and 0.87%. Furthermore, a simple indicator focusing on the composition of the three colored flows for each commodity was developed to identify trade commodities that should be prioritized for urgent technical improvement to reduce wasteful use of the metals. Based on the indicator, we discuss logical, strategic identification of the responsibilities and roles of the countries involved in the global flows. PMID:24387330

  1. Extended Platinum Nanotubes as Fuel Cell Catalysts

    SciTech Connect

    Alia, S.; Pivovar, B. S.; Yan, Y.

    2012-01-01

    Energy consumption has relied principally on fossil fuels as an energy source; fuel cells, however, can provide a clean and sustainable alternative, an answer to the depletion and climate change concerns of fossil fuels. Within proton exchange membrane fuel cells, high catalyst cost and poor durability limit the commercial viability of the device. Recently, platinum nanotubes (PtNTs) were studied as durable, active catalysts, providing a platform to meet US Department of Energy vehicular activity targets.[1] Porous PtNTs were developed to increase nanotube surface area, improving mass activity for oxygen reduction without sacrificing durability.[2] Subsurface platinum was then replaced with palladium, forming platinum-coated palladium nanotubes.[3] By forming a core shell structure, platinum utilization was increased, reducing catalyst cost. Alternative substrates have also been examined, modifying platinum surface facets and increasing oxygen reduction specific activity. Through modification of the PtNT platform, catalyst limitations can be reduced, ensuring a commercially viable device.

  2. Real-time detection of hydrogen absorption and desorption in metallic palladium using vibrating wire method

    NASA Astrophysics Data System (ADS)

    Inagaki, Yuji; Nishimura, Atsuki; Yokooji, Honoka; Takata, Hiroki; Kawae, Tatsuya

    2015-09-01

    A vibrating wire (VW) method was applied to investigate the hydrogen absorption and desorption properties of palladium. At room temperature, a considerable shift in resonance frequency was successfully observed in VW spectra under H2 gas exposure. The shift is reversible in the initial stage of the exposure and is attributed to changes in the density and Young’s modulus of the VW sensor. Irreversibility of the shift because of embrittlement is detected after a sufficient exposure time. H absorption is slowed down enormously at T = 200 K owing to suppression of the thermal activation process.

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

    SciTech Connect

    Benavides, Pahola T.; Dai, Qiang; Sullivan, John L.; Kelly, Jarod C.; Dunn, Jennifer B.

    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.

  4. Problems, possibilities and limitations of inductively coupled plasma atomic emission spectrometry in the determination of platinum, palladium and rhodium in samples with different matrix composition

    NASA Astrophysics Data System (ADS)

    Petrova, P.; Velichkov, S.; Velitchkova, N.; Havezov, I.; Daskalova, N.

    2010-02-01

    The economic and geological importance of platinum group of elements has led to the development of analytical methods to quantify them in different types of samples. In the present paper the quantitative information for spectral interference in radial viewing 40.68 MHz inductively coupled plasma atomic emission spectrometry in the determination of Pt, Pd and Rh in the presence of complex matrix, containing Al, Ca, Fe, Mg, Mn, P and Ti as matrix constituents was obtained. The database was used for optimum line selections. By using the selected analysis lines the following detection limits in ng g - 1 were obtained: Pt 1700, Pd-1440, Rh-900. The reached detection limits determine the possibilities and limitation of the direct ICP-AES method in the determination of Pt, Pd and Rh in geological and environmental materials. The database for spectral interferences in the presence of aluminum can be used for the determination of platinum group of elements in car catalysts. The accuracy of the analytical results was experimentally demonstrated by two certified reference materials that were analyzed: SARM 7, Pt ore and recycled auto-catalyst certified reference material SRM 2556.

  5. Synthesis Dependent Core Level Binding Energy Shift in the Oxidation State of Platinum Coated on Ceria–Titania and its Effect on Catalytic Decomposition of Methanol

    SciTech Connect

    Karakoti, A. S.; King, Jessica; Vincent, Abhilash; Seal, Sudipta

    2010-11-20

    Synergistic interaction of catalyst and support has attracted the interest of the catalytic community for several decades. The decomposition/oxidation of alcohols for the production of hydrogen as a source of fuel requires such support catalyst interaction. Recent studies have suggested the active role of oxide based supports on the catalytic ability of noble metals such as gold, platinum and palladium. Herein, we report the effect of synthesis technique on the catalytic activity of platinum coated on mixed ceria-titania support system. Wet impregnation technique followed by calcination was compared with the chemical reduction of platinum during the coating over oxide support. Methanol decomposition studied using an in-house built catalytic reactor coupled to a mass spectrometer showed that catalyst prepared by thermal reduction of platinum demonstrated better catalytic ability than the catalyst prepared by chemical reduction of platinum. Transmission electron microscopy revealed that the size of both platinum and ceria-titania particles remained unchanged, while the X-ray photoelectron spectroscopy (XPS) revealed that the oxidation state of platinum was modified by different coating procedures. A shift in the core level binding energy of the Pt 4f towards lower binding energy was observed with chemical reduction. Based on the XPS data it was found that platinum (on ceria-titania supports) in mixed oxidation state outperformed the Pt in reduced metallic state. Results from catalysis and in situ Fourier transform infra red spectroscopy are presented and discussed.

  6. Boosting Photocatalytic Hydrogen Production of a Metal-Organic Framework Decorated with Platinum Nanoparticles: The Platinum Location Matters.

    PubMed

    Xiao, Juan-Ding; Shang, Qichao; Xiong, Yujie; Zhang, Qun; Luo, Yi; Yu, Shu-Hong; Jiang, Hai-Long

    2016-08-01

    Improving the efficiency of electron-hole separation and charge-carrier utilization plays a central role in photocatalysis. Herein, Pt nanoparticles of ca. 3 nm are incorporated inside or supported on a representative metal-organic framework (MOF), UiO-66-NH2 , denoted as Pt@UiO-66-NH2 and Pt/UiO-66-NH2 , respectively, for photocatalytic hydrogen production via water splitting. Compared with the pristine MOF, both Pt-decorated MOF nanocomposites exhibit significantly improved yet distinctly different hydrogen-production activities, highlighting that the photocatalytic efficiency strongly correlates with the Pt location relative to the MOF. The Pt@UiO-66-NH2 greatly shortens the electron-transport distance, which favors the electron-hole separation and thereby yields much higher efficiency than Pt/UiO-66-NH2 . The involved mechanism has been further unveiled by means of ultrafast transient absorption and photoluminescence spectroscopy. PMID:27321732

  7. Palladium/kieselguhr composition and method

    DOEpatents

    Mosley, W.C. Jr.

    1993-09-28

    A hydrogen-absorbing composition and method for making such a composition are described. The composition comprises a metal hydride, preferably palladium, deposited onto a porous substrate such as kieselguhr, for use in hydrogen-absorbing processes. The composition is made by immersing a substrate in a concentrated solution containing palladium, such as tetra-amine palladium nitrate. Palladium from the solution is deposited onto the porous substrate, which is preferably in the form of kieselguhr particles. The substrate is then removed from the solution, calcined, and heat treated. This process is repeated until the desired amount of palladium has been deposited onto the substrate.

  8. Palladium/kieselguhr composition and method

    DOEpatents

    Mosley, Jr., Wilbur C.

    1993-01-01

    A hydrogen-absorbing composition and method for making such a composition. The composition comprises a metal hydride, preferably palladium, deposited onto a porous substrate such as kieselguhr, for use in hydrogen-absorbing processes. The composition is made by immersing a substrate in a concentrated solution containing palladium, such as tetra-amine palladium nitrate. Palladium from the solution is deposited onto the porous substrate, which is preferably in the form of kieselguhr particles. The substrate is then removed from the solution, calcined, and heat treated. This process is repeated until the desired amount of palladium has been deposited onto the substrate.

  9. Extremely fast hydrogen absorption/desorption through platinum overlayers

    NASA Astrophysics Data System (ADS)

    Połczyński, Piotr; Jurczakowski, Rafał

    2016-02-01

    The hydrogen electrosorption in thin palladium films (50-1000 nm) was investigated at palladium electrodes covered with platinum overlayers. The results for this model system show that the rates of the hydrogen sorption/desorption are orders of magnitude higher for platinized samples with respect to pure palladium. The highest absorption kinetics have been observed for Pd electrodes fully covered with 1-3 platinum monolayers. By means of electrochemical impedance spectroscopy (EIS) we have shown that the process is diffusion limited at platinized Pd layers. Diffusion coefficient, DH, determined in EIS, is two orders of magnitude higher than that previously reported for thin palladium films and approaches DH for bulk palladium. The system stability after hydrogen absorption was assessed and the sorption mechanism was discussed. Surprisingly high durability of the platinized palladium enables its use in a variety of applications where fast and selective response in the presence of hydrogen is required.

  10. Novel Di- and Trinuclear Palladium Complexes Supported by N,N'-Diphosphanyl NHC Ligands and N,N'-Diphosphanylimidazolium Palladium, Gold, and Mixed-Metal Copper-Gold Complexes.

    PubMed

    Ai, Pengfei; Gourlaouen, Christophe; Danopoulos, Andreas A; Braunstein, Pierre

    2016-02-01

    The reaction of the trinuclear complex [Ag3(μ3-PC(NHC)P,κP,κC(NHC),κP)2](OTf)3 (Ag3; PC(NHC)P = N,N'-bis(di-tert-butylphosphanyl)imidazol-2-ylidene) with [Pd(dba)2] afforded the trinuclear palladium complex [Pd3(μ3-PC(NHC)P,κP,κC(NHC),κP)2](OTf)2 (Pd3) and the dinuclear palladium(I) complex [Pd2(μ2-PC(NHC)P,κP,κC(NHC),κP)2](OTf)2 (Pd2). The assignment of the oxidation state of the metals in the mixed-valence Pd3 chain as Pd(0)-Pd(II)-Pd(0) was based on the reactivity of the complex with 2,6-dimethylphenyl isocyanide and density functional theory calculations. Reaction of PCNHCP with [PdMe2(tmeda)] afforded the palladium(II) complex [PdMe2(PC(NHC)P,κP,κC(NHC))] (Pd-Me2), with PC(NHC)P acting as a bidentate ligand. The reaction of PC(NHC)P with [Pd(dba)2] led to a dinuclear palladium(0) complex [Pd2(μ2-PC(NHC)P,κP,κC(NHC),κP)](dba) (Pd2-dba); attempted replacement of the remaining dba by PC(NHC)P failed. The imidazolium triflate PCHP, precursor to PC(NHC)P, was reacted with [Pd2(dba)3]·CHCl3 to give the (2 + 2) metalla-mesocyclic cationic palladium(0) complex [Pd2(μ2-PCHP,κP,κP)2] (PCHP-Pd2), which resisted further deprotonation of the imidazolium cation. In contrast, PCHP reacted with [AuCl(tht)] to give [Au2Cl2(μ2-PCHP,κP,κP)] (PCHP-Au2), in which one Au-Cl moiety is bound to each P donor. Further reaction of PCHP-Au2 with [Au{N(SiMe3)2}(PPh3)] afforded a mixture of the trinuclear [Au3(μ3-PC(NHC)P,κP,κC(NHC),κP)2](OTf)3 (Au3) and [AuCl(PPh3)], while reaction with [CuMes]5, where Mes = 2,4,6-trimethylphenyl, resulted in a novel, centrosymmetric, heterometallic complex [Au2Mes2(Cu4Cl4)(PCHP,κP,κP)2] (PCHP-AuCu) featuring a new PCHP-AuMes metalloligand bridging a Cu···Cu diagonal of a Cu4Cl4 cubane via the P and AuMes functionalities. PMID:26790035